United States Environmental Protection Agency Office of Water (4305) EPA-823-B-01-002 October 2001 

# Methods for Collection, Storage and Manipulation of Sediments for Chemical and T o xicological Analyses: T echnical Manual

### EPA-823-B

- 01-002 October 2001


# Methods for Collection, Storage and Manipulation of Sediments for Chemical and Toxicological Analyses: Technical Manual

Office of Science & Technolog y Office of W ater U.S. Environmental Protection Ag ency W a shing t on, DC 20460

### Disc laim e r T h is technical m a nual prov ides a com p ilation of cu rrent inform ation and recomme ndations for collecting , handling and m a nipulating sedime nt sam p les for phy sico chemical characteriz ation and biolog ical testing that are m o st likely to y i eld accurate, representa tiv e sedime nt quality data based on the experience of m a ny m onitoring prog ram s and researchers. T h is m a nual has no imme diate or direct reg u latory consequence. I tdoes not im pose leg a lly binding re quireme nts on EPA, States, T r ibes, other reg u latory authorities, or the reg u lated comm unity , and m a y notapply to a particular situation based upon the circum stances. EPA, State, T r ibal , and other decision m ake rs retain the discretion to adopt approaches on a case- by

- case basis that differ from those in th is m a nual where appropriate. EPA m a y update this m a nual in the future as better in form ation become s av ailable. T h is document has been approv ed for publication by the Office of Science and T echnolog y , Office of Water, U.S. Env i ronmental Protection Ag ency . Men tion of trade name s, products, or serv ices does not conv ey and should not be interpreted as conv ey ing , official USEPA a pprov al, endorseme nt, or recomme ndation for use.

The sug g e sted citation for this document is: U.S. EPA. 2001. Methods for Co llection, Storag e and Manipulation of Sedime nts for Chemical and T oxicolog i cal Analy s es: T echnical Manual. EP A 823- B- 01- 002. U.S. Env i ronmental Protection A g ency , O ffice of Water, Washing t on, D C
.Technical M anual 

## Acknowledgments

T h is document is a g e neral purpose m a nual intended to prov ide the user with sedime nt collection, storag e, and m a nipulation me thods that are m o st likely to y i eld accurate, representativ e sedime nt quality data for toxicity and chemical anlay s es ba sed on the experience of m a ny m onitoring prog ram s and researchers. T h e approaches described in th is m a nual represents a com p ilation of inform ation presented in m a ny publications, including Pug e t Sound Estuary Prog ram (PSEP, 1997), Washing t on State Departme nt of Ecolog y (1995), Env i ronment Canada (1994) , US Env i ronmental Protection Ag ency - US Arm y Corps of Eng i neers (USEPA

- U SACE, 1998), American Society for T e sting and Materials (AST M, 2000) , and USEPA (2000). The principal authors of this m a nual are Kathy Z i rbser, R i chard H ealy , L eanne S t ahl, B ill Tate (USEPA, Office of Science and T echnolog y ) , J e rry Diam ond (T etra T ech, I n c.), Allen Burton (Wrig h t State Univ ersity ), Michael J ohns (Windw ard Env i ronmental LLC), and J ohn Scott (SAI C). Rev i ew comme nts from the following indiv i duals led to substantial im prov ements in the m a nual for w h ich w e are g r ateful: T o m Ar mi t a g e USEPA- OST J u stine Barton USEPA – Reg i on 10 Brett Betts WA Dept of Ecolo g y : Sedime nt Manag e me nt Unit K a thry n Brag don- Cook T oxics Cleanup Pr og ram : Sedime nt Manag e me nt Unit J a me s Brannon Army Corps of Eng i neers – WES Robert Burg ess U SEPA – NHEERL A tlantic E c olog y D i v i sion Scott Carr USGS – Marine Ec otoxicolog y R e search Station Sc ot tCi e n i a ws ki USEPA – Re g i on 5 P h ilip C r ocke r U S E P A – R e g i on 6 Alan Crocke tt Consultant K a thleen Dadey U SEPA – Reg i on 9 Robert Eng l er Army Corps of Eng i neers – WES K e n Finkelstein U SEPA – Reg i on 1 M ar i aGome z- T a y l or USEPA – EAD T o m Gries W A Dept of Ecolog y Erik a Hoffm an USEPA – Reg i on 10 Se dime nt Manag e me nt Prog ram C h ris I n g e rsoll U S G S – C o lum b ia Env i ronmental R e search C e nter Laura J ohnson USEPA – OCPD As h J a i n EPRI Pe t e rLa ndrum NOAA – Gr e a tLake s Env
. Re s e ar c h Labor a t or y Shar on Li n U SEPA – OCPD/W D Ed Long NOAA Gui Lotufo Army Corps of Eng i neers – WES Don MacDonal d NOAA – Of f i ce of Response and Rest or at i o n J ohn Malek U SEPA – Reg i on 10 Se dime nt Manag e me nt Prog ram
Acknow ledgm ents iiiM e

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Cor n e l l Ros i u U SEPA – Re g i on 1 Brian Ross USEPA – Reg i on 9 Dredg i ng and Sed. Manag e me nt T i m o thy Sherm a n A rm y Corps of Eng i neers – Portland District Robert Shippen U SEPA- OST Mark S iipola A rmy C o rps of Eng i neers – Portland District J e rr y Sm r c hek U SEPA – OPPT / O PPT S M ark Spr e ng e r USEPA – OERR- ERT C Marc T u chm a n U SEPA – Reg i on 5 Ernest Waterm an USEPA – Reg i on 1 K a t h y Z i rb ser U SEPA- OST We are v e ry g r ateful to Sherw i n B eck (T etra T ech, I n c.) as w e ll as contributions from C armela Biddle, Marcus Bowersox, BrendaF o w l er, A bby Mark ow itz , P a tricia McC r eesh, Kristen P a v lik (T etra T ech, I n c.), and C o rinne Marino (VJ B A ssociates) to this m a nual. Front cov e r photog raphs prov ided by Allen Burton.

iv U S Environm ental Protection AgencyTechnical M anual 

## Acronym List

ACOE Ar my Corp s of Eng i ne e r s ARCS Assessment and Reme diation of Contaminated Sedime nts A S T M A merican Society for T e sting and Materials A V S A cid Volatile S u lfides B M Ps B e st Manag e me nt Practices B O D B iochemical O x y g e n D e m a nd C E C C ation Exchang e C apacity COD C hemi cal Oxy g e n Dem a nd C V C o efficient of Variation DOC Di s s o l v e dOr g a ni c Carbon D Q O D a ta Q u ality O b j ectiv es ED MI Electronic D i stance Measurement I n strume nt E M A P E n v i ronmental Monitoring & A ssessment P r og ram ERM E ffect Rang e Medium GC/MS G as Chrom a tog r aphy/Mass Spectrophotometry G C /F I D G a s C h rom a tog r aphy/F lame I oniz a tion D e tection G C /E C D G a s C h rom a tog r aphy/E lectron C apture D e tection GLNPO G r e a tLake s Na t i ona l Pr og r a m Of f i c e GPC G el Permeation Chrom a tog r aphy GPS G lobal Positioning Sy stem HPLC Hig h Perform ance Liquid Chrom a tog r aphy I C P- AES I nductiv ely Coupled Plasm aAtomic Emission Spectoscopy I C P- MS I nductiv ely Coupled Plasm aMass Spectrome try I R I n frared Spectrophotometer L O R A N L O n g R A n g eN a vi ga t i o n N A W Q A N a tional Water Q u ality A ssessment
Acronym List vM e

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NDI R N on- Di s p e r s i v e I n f r ar e d De t e c t or N E P N ational E s tuary P r og ram NOAA Nat i onal Oceani c and At m o spher i c Admi ni str a t i o n NSI N ational Sedime nt I n v e ntory NST N ational Status & T r ends ORP O xidation Reduction Potential O S H A O ccupational S a fety & H ealth A d mi nistration PC E P ow er C o st Efficiency PO C P articulate O r g a nic C arbon PSEP P ug et Sound Estuary Prog ram Q A Q u ality A ssurance Q A P P Q uality A ssurance P r oj ect P l an Q C Q u ality C ontrol RADAR RAdi o De t e c t i n g a nd Ra ng i n g R O V R em otely O p erated Vehicle R P D R elativ e Percent D i fference S A TN A V S A Tellite N A V ig ation SCV S econdary Chronic V a lue S E M S im ultaneously E x tracted Metals SI M S elected I on Monitoring SOC S uspended Org a nic Carbon SO D S ediment O x y g e n D e m a nd SOPs St andar dOper at i n g Pr ocedur es SPMD S emi- Permeable Mem b rane D e v i ce S R M S tandard R e ference Materials T I C T otal I norg a nic Carbon T M DLs T otal Maxim u m Daily Loads T O C T otal Org a nic Carbon T P H T otal Petroleum Hy drocarbons TVS T otal Volatile S o lids

vi U S Environm ental Protection AgencyTechnical M anual
U S EPA U nited States Env i ronmental Protection A g ency USGS Uni t e d St a t e s Ge ol og i c Sur v e y XR F X

- R ay Fluorescence

Acronym List vi iM e

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v iii U S Environm ental Protection AgencyTechnical M anual


## Foreword

Sedime nts prov ide essential habitat for m a ny freshwate r, estuarine, and m arine org a nism s. I n aquatic sy stem s, m o st anthropog enic chemicals and waste m a terials, particularly persistent org a nic and inorg a nic chemicals, m a y accum u late in sedime nts. T h ese sedime nts become repositories for m a ny of the m o re toxic chemicals that are introduced into surface w a ters. U n ited States Env i ronmental Protection Ag ency ’s National Se dime nt I n v e ntory (NSI ) (USE PA 1998), a biennial report to C ong ress on sedime nt quality in the U n ited S t ates, de m onstrates that sedime nt contamination exists in ev ery state of the country
. Contaminated sedi me nts represent a haz ard to aquatic life throug h direct toxicity as w e ll as to aquatic life, w ild life and hum an health throug h bioaccum u lation in the food chain. A ssessments of sedime nt quality comm only include analy s es of anthropog enic contaminants, benthic comm unity structure, phy sico chemical characteristics, and direct measures of whole sedime nt and pore water toxicity
. Accura te assessment of env i ronmental haz ards posed by sedime nt contamination depends in larg e part on the accuracy and representativ eness of these analy s es. T h e me thods described in this Manual are intended to prov ide the user with sedime nt collection, storag e, and m a nipulation me thods that are m o st likely to y i eld accurate, representativ e sedime nt quality data (e.g ., toxicity , chemical) based on th e experience of m a ny m onitoring prog ram s and researchers. This Manual represents a com p ilation of inform a tion presented in m a ny publications, including :
• A me rican Society for T e sting and Materials (AST M) 2000 document: Standard Guide for Storage, Characterization, and Manipulation of Se diments for Toxicological Testing, E1391- 94.
• E nv ironment Canada 1994 m a nual: Guidance Document on Co llection and Preparation of Sediments for Physicochemical Char acterization and Biological Testing , EPS 1/RM/29.
• U .S. Env i ronmental Protection Ag ency . 2000 m a nual: Methods for Measuring the Toxicity and Bioaccumulation of Sediment -Associated Contami nants with Freshwater Invertebrates. Second Edition
. EPA/600/R- 99/064.
• U .S. Env i ronmental Protection Ag ency / Army Corps of Eng i neers. 1998. Inland Testing Manual: Evaluation of Dredged Ma terial Proposed for Discharge in W a ters of the U.S. - Testing Manual
. EPA- 823- B- 98- 004.
• U .S. Env i ronmental Protection Ag ency / Army Corps of Eng i neers. 1991. Ocean Testing Manual: Evaluation of Dredged Material Proposed for Oce an Disposal: Testing Manual. EPA- 503/8- 91/001. I n addition to m a ny recent peer- r ev iew e d technical j ournal papers, other publications that w e re relied on extensiv ely include:

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• P ug et Sound Estuary Prog ram (PSEP) 1997 m a nual: R ecom m e nded G u idelines for Sam pling Marine Sediment, W a ter Column, and Tissue in Puget Sound
• W ashing ton Departme nt of Ecolog y 1995 Docume nt: G u idance on the D evelopm ent of Sediment Sampling and Analys is Plans Meeting the Requi rements of the Sediment Management Standards
• G reat Lake s National Prog ram Office (GLN PO) 1994 m a nual: Assessment and Remediation of Contaminated sedi ments ( ARCS) Program - Assessment Guidance EPA- 905- B94- 002.
• U .S. Env i ronmental Protection Ag ency . 2000 document: Estuarine and Near Coastal Marine W

a ters: Bioassessment and Bioc riteria Technical Guidance. EPA- 822- B- 00- 004. This Manual addresses sev e ral needs identifie d in EPA’s Contaminat ed Sedime nt Strateg y (U SEPA 1998) including : (1) an org a niz e d discussi on of activ ities inv o lv ed in sedime nt sam p ling and sam p le processing ; (2) im portant issues that need to be considered w ithin each activ ity ; and (3) recomme ndations on how to best address issu es such as sam p ling desig n , proper sam p ling procedures, and sam p le m a nipulati ons. T h roug hout this Manual, di fferent considerations pertaining to sam p ling and sam p le processing are presen ted depending on the prog ram need (e.g ., dredg e reme diation v e rsus status and trends m onitoring ). EPAalong w ith other ag encies, assesses aquatic sedime nt quality under a v ariety of leg i slativ e requireme nts including :
• N ational E n v i ronmental P o licy A c t (N E P A )
• C lean A i r A c t; the C o astal Z one Manag e me nt A c t (C Z M A )
• F ederal I n secticide, F ung icide, and R odenticide A c t (F I F R A )
• M arine Protection, R e search, and Sanctuaries A c t (MPR SA )
• R e s our c e Cons e r v a t i on a nd Re c o v e r y Ac t( RCRA)
• T oxic Substance Control Act (T SCA)
• C lean Water A c t (C WA )
• C om prehensiv e , E n v i ronmental and L i ability A c t (C E R C L A )
• G reat Lake s Critical Prog ram s Act of 1990. I n addition, m a ny EPA offices c oordinate sedime nt m onitoring st udies in specific g e og raphic areas, such as throug h the C h esapeake B a y Prog ram , the Great Lake s National Prog ra m , the G u lf of Mexico Prog ram , the Washing t on State Sedime nt Manag e me nt Standards Prog ram , and in the States of W a s h i n g t on, Fl or i d a , Ca l i f or ni a , Ne w York , Ne w J e rsey , South Carolina, T e xas, Massachusetts, and Wisconsin. T o address its responsibilities w ithin the abov e leg i slativ e acts, EPAhas sev e ral ong oing prog ram s that m a y inv o lv e sedime nt quality ev aluation as summ ariz e d below
.

x U S Environm ental Protection AgencyTechnical M anual Dredged Material Management T h e U
. S. A r my C o rps of Eng i neers (U SA C E ), the Federal ag ency desig n ated to m a intain nav i g able waters, conducts a m a j o rity of the dredg i ng proj ects and disposal under its Cong ressionally

authoriz ed civ il work s prog ram . T h e balance of dredg i ng and disposal is conducted by a num ber of local public and priv ate entities. I n either case, th e disposal is subj ected to a reg u latory prog ram admi nistered j o intly by the USACE and EPA under Section 103 of the Marine Protection, Research, and Sanctuaries A c t (MPRSA ) for ocean disposal , and Section 404 of the Clean Water A c t (CWA ) for discharg e at open w a ter sites, confined disposal facilities w ith return flow to w a ters of the U
. S
. , or for beneficial uses. EPAshares the responsibility of m a nag i ng dredg e d m a terial, principally in the dev e lopment of the env i ronmental criteria and g u idelines by which proposed discharg es are ev aluated and disposal sites are selected, and in th e exercise of its env i ronmental ov ersig h t authority
. J o int E P A/U S A C E g u idance m a nuals detailing the testing and analy s is protocols for dredg e d m a terial disposal are w e ll established. National Estuary P r ogram EPA admi nisters the National Estuary Prog ram , es tablished under the Clean Water Act to identify , restore, and protect nationally sig n ificant estuar ies in the U n ited S t ates. Within the existing 28 prog ram s , env i ronmental m onitoring is a ke y elemen t of watershed protection strateg i es dev e loped to m a intain the chemical, phy sical, a nd biolog ical properties of the es tuarine ecosy stem s. T h e Pug e t Sound Estuary Prog ram (PSEP), in particular, has been activ ely m onitoring ecolog i cal health, including sedime nt quality , in Pug e t Sound, Wash ing t on for m a ny y ears. PSEP, w h ich includes EPA , the Pug e t Sound Water Q u ality A u thority , and the Washing t on D e partme nt of Ecolog y , has dev e loped sedime nt sam p ling and analy s is procedur es in collaboration w ith local g o v e rnme nts and stakeholder g r oups (PSEP, 1997)
. T h e protocols are cited in and support the Washing t on Departme nt of Ecolog y ’ s (WDE) se dime nt m a nag e me nt standards reg u lation, and hav e serv ed as the foundation for m a ny other g u idance documents su ch as those produced by Env i ronment Canada (1994) and American Soci ety of T e sting Materials (AST M, 2000). T h is m a nual frequently refers to PSEP and WD E g u idance. Resource Conservat i o n and Recovery Act( RCRA) UnderRCRA, EPA assesses whet herr e l eases f r o m a haz ar dous wast e tr eat me nt , st or ag e, ordi sposal facility hav e contaminated sedime nts and requires correctiv e action, includi ng possible reme diation, if contamination is discov ered. I n m a ny cases, se dime nt sam p ling and analy s es, as discussed in this m a nual, are needed in RCRA facility assessments and RCRA facility inv e stig ations. Of f i ce of Water T h e Office of Water has been expanding prov isions for sedime nt m onitoring under the Clean Water Act, in the national m onitoring frame work dev e loped by the I n terg ov ernmental T a sk Force on Monitoring Water Q u ality (I T F M, 1995). T h roug h this frame w o rk , ag reements hav e been reached w ith other Federal, State, and local ag encies concerning incorporation of sedime nt m onitoring protocols, sedime nt m onitoring QA/QC procedures, and appropriate inform ation sy stem link a g e s into m onitoring prog ram s . T h e Office of Water and th e Office of I n form ation Resources Manag e me nt are also ensuring that the capability to store and use se dime nt data is enhanced as part of the ong oing m oderniz ation of the A g ency ’s w a ter quality data sy stem s (S TO R E T), and in coordination w ith the w a ter quality data elements procedures being recomme nded by the N a tional Methods and D a ta C o m p arability B o ard under the N a tional Water Q u ality Monitoring C ouncil. T h ese data elements include inform ation describing how sam p les were co llected, stored, and processed prior to analy s is.
Foreword xiM e

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Regional Environmenta l Moni t o ri ng and Assessm entP r ogram ( R EMAP ) R E MA P, w ithin the O ffice of R e search and D e v e lopment, g a thers chemi cal and biolog ical data describing sedime nt quality at m a ny EMA P sam p ling stations. D a ta collected under R E MA P are entered into the National Sedime nt I n v e ntory (NSI ). T h ese data are used to assess status and trends on a reg i onal scale, particularly for aquatic sy st em s that m a y hav e w a ter quality and/or sedime nt quality im pairme nt. C o mp reh en sive, E n viron m en tal an d L i ab ility A c t (C E R C L A ) U nder C E R C L A , EPAcarries out a detailed analy s is at a site, ev aluating the risk s posed by contaminants to hum an health and the env i ronmen t, and the feasibility of v arious response action alternativ es to reduce risk
. T h e Risk Assessment Guidance for Superfund (USEPA, 1997) prov ides a frame w o rk for the assessme nt of hum an health and env i ronmental im pacts. T h e C E R C L AProg ram is using the EPA- wide sedime nt testing me thods of the T i ered T e sting Framework in the Reme dial I n v e stig ation/F easibility S t udy (C R I /F S ) stag e of analy s is to help determine options for reme dial actions. Much of the g u idance presented in th is m a nual supports the T i ered T e sting Framework applicable to C E R C L A sites. G reat Lakes Critical P r ograms Act of 1990 A nnex 14 of the G r eat L ake s Water Q u ality A g reement betw een the U n ited S t ates and C a nada (as amended by the 1987 Protocol) stipulates that th e cooperating parties w ill identify the nature and extent of sedime nt contaminati on in the Great Lake s, dev e lop me thods to assess im pacts, and ev aluate the technolog ical capability of prog ra m s to reme dy such contamination. T h e 1987 amendments to the C l ean Water A c t authoriz ed the G r eat Lake s N a tional Prog ram O ffice (G LN PO ) to coordinate and conduct studies and dem onstrati on proj ects relating to the appropriate treatme nt of toxic contaminants in bottom sedime nts. To fulf ill the requireme nts of the A c t, G L N P O initiated the Assessment and Reme diation of Contaminated Sedime nts (ARCS) Prog ram to help address contaminated sedime nt concerns in the dev e lopm ent of Reme dial Action Plans (RAPs) for all 43 G r eat Lake s A r eas of C oncern (A O C s, as identified by the United States and Canadian g o v e rnme nts), as w e ll as similar concerns in the dev e lopment of Lake wide Manag e me nt Plans. T h is m a nual frequently relies on inform ation documented by the GLNPO and the ARCS prog ram .

xi i U S Environm ental Protection AgencyTechnical M anual TAB LE O F CO NTENTS P age A c know l edgments
............................................................... i i i A cronym L i st
................................................................... v F o rew ord
...................................................................... i x Tabl e of Cont ent s .............................................................. x i i i Li s tof Tabl e s ................................................................. x v i i List of F i gures ................................................................ x v i i L i st of R ecommendations
........................................................ x i x T echnical and G rammatical T erms ................................................ x x i Usi n g t h e Manual
.............................................................. x x i v 1. I N TRO DUCTI O N
....................................................... 1

- 1 1.1 B ack g r ound
....................................................... 1

- 1 1
. 2 S i g n i f i c a n c e a n d U s e o f t h i s M a n u a l
................................... 1

- 1 1.3 A pplicability and S cope of this Manual
................................. 1

- 2 2. SEDI M E NT M O NI TO RI NG AND ASSESSM ENT STUDY P L ANS
............. 2

- 1 2.1 D ata Q u ality O b j ectiv es P r ocess ....................................... 2

- 1 2
. 2 S t u d y P l a n C o n s i d e r a t i o n s ........................................... 2

- 5 2
. 2
. 1 D e f i n i t i o n o f t h e S t u d y A r e a a n d S t u d y S i t e ....................... 2

- 5 2.2.2 C ontrolling S ources of Variability
............................... 2

- 5 2
. 2
. 3 S a m p l i n g U s i n g a n I n d e x P e r i o d
................................ 2

- 6 2
. 3 S a m p l i n g D e s i g n s .................................................. 2

- 7 2.3.1 P robabilistic and R andom Sam p ling
............................. 2

- 7 2
. 3
. 2 T ar g e t e d S a m p l i n g D e s i g n s ................................... 2

- 1 0 2.4 Measurement Q u ality O b j ectiv es ..................................... 2

- 1 1 2
. 4
. 1 S a m p l e V o l u me ............................................ 2

- 1 2 2
. 4
. 2 N u m b e r o f S a m p l e s ......................................... 2

- 1 5 2
. 4
. 3 R e p l i c a t e a n d C o m p o s i t e S a m p l e s .............................. 2

- 1 5 2.5 S ite- S pecific Selection Consider ations for Selecting Sediment S a m p l i n g S t a t i o n s ................................................. 2

- 1 7 2
. 5
. 1 R e v i e w A v a i l ab l e D a t a ....................................... 2

- 1 9 2
. 5
. 2 S i t e I n s p e c t i o n ............................................. 2

- 1 9 2
. 5
. 3 I d e n t i f y S e d i me n t D e p o s i t i o n a n d E r o s i o n a l Z o n e s ................. 2

- 1 9 2.6 P ositioning Methods for Locating Sam p ling Stations
..................... 2

- 2 0 2
. 7 P r e p ar a t i o n s f o r F i e l d S a m p l i n g ...................................... 2

- 2 1 2
. 8 H e a l t h a n d S a f e t y ................................................. 2

- 2 3 3. CO LLECTI O N O F WH O LE SEDI M E NTS
.................................. 3

- 1 3
. 1 G e n e r a l P r o c e d u r e s ................................................. 3

- 1 3
. 2 T y p e s o f S e d i me n t S a m p l e r s .......................................... 3

- 5 3
. 2
. 1 G r ab S a m p l e r s .............................................. 3

- 5 3
. 2
. 2 C o r e S a m p l e r s .............................................. 3

- 9 3.3 S am ple A cceptability
.............................................. 3

- 1 3 3
. 4 E q u i p me n t D e c o n t a mi n a t i o n ......................................... 3

- 1 4 3
. 5 F i e l d M e a s u r e me n t s a n d O b s e r v a t i o n s ................................. 3

- 1 5 3
. 6 D o c u me n t a t i o n o f S a m p l e C o l l e c t i o n .................................. 3

- 1 7

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses TAB LE O F CO NTENTS ( C O N TI NUED) P age 4. F I ELD SAM P LE P R O C ESSI NG, TRANSP O RT, AND STO RAGE O F SEDI M ENTS
........................................................... 4- 1 4.1 S a m pl e C ont a i ne r s ................................................. 4- 1 4.1.1 C ont a i ne r M a t e r i a l
.......................................... 4- 3 4.1.2 C ont a i ne r P r e par a t i on ........................................ 4- 3 4.2 S ubsam pling and C om positing S am p les
................................ 4- 5 4.2.1 G e ne r a l P r oc e dur e s .......................................... 4- 5 4.2.2 G r ab S a m pl e s .............................................. 4- 6 4.2.3 C or e S a m pl e s .............................................. 4- 7 4.3 H om og e ni z a t i on .................................................. 4- 11 4.3.1 G e ne r a l P r oc e dur e s ......................................... 4- 11 4.4 S a m pl e T r a ns por t a nd S t or a g e ....................................... 4- 13 4.4.1 G e ne r a l P r oc e dur e s ......................................... 4- 13 4.5 S a m pl e H ol di ng T i me s ............................................ 4- 15 5. SEDI M E NT M ANI P U LATI O N S
.......................................... 5- 1 5.1 S i e v i ng .......................................................... 5- 1 5.1.1 S iev i ng Methods
............................................ 5- 3 5.1.2 A l t e r na t i v e s t o S i e v i ng ....................................... 5- 5 5.2 F orm u lated Sedim ent and Org anic Carbon Modification
................... 5- 6 5.2.1 G e ne r a l C ons i de r a t i ons ....................................... 5- 6 5.2.2 S e di me nt S our c e s ........................................... 5- 7 5.2.3 O rg anic Carbon Modification
.................................. 5- 7 5.3 S pi ki ng .......................................................... 5- 8 5.3.1 P r e par a t i on f or S pi ki ng ....................................... 5- 9 5.3.2 M ethods for Spiking
........................................ 5- 10 5.3.3 E quilibration Time s ........................................ 5- 12 5.3.4 U s e of O r g a ni c S ol v e nt s ..................................... 5- 13 5.4 P r e par a t i on of S e di me nt D i l ut i ons .................................... 5- 13 5.5 P r e par a t i on of S e di me nt E l utr i a t e s ................................... 5- 14 6. CO LLECTI O N O F I N TERSTI T I A L WATER
............................... 6- 1 6.1 G e ne r a l P r oc e dur e s ................................................ 6- 1 6.2 In-situ C ol l e c t i on .................................................. 6- 2 6.2.1 P eeper Methods
............................................ 6- 5 6.2.2 S uction Methods
............................................ 6- 7 6.2.3 P rocessing of F i eld- C o llected I n terstitial Water S a m p le
............. 6- 8 6.3 E x -situ E x traction of I n terstitial Water
................................. 6- 8 6.3.1 G e ne r a l P r oc e dur e s .......................................... 6- 8 6.3. 2 C e n tr i f u g a t i on ............................................. 6

- 10 6.3.3 S e di me nt S que e z i ng ........................................ 6- 12 6.3. 4 P r e s s u r i z e d a nd V a c uum D e v i c e s .............................. 6

- 12

xi v U S Environm ental Protection AgencyTechnical M anual TAB LE O F CO NTENTS ( C O N TI NUED) P age 7. Q UALI TY ASSURANCE AND Q UALI TY CO NTRO L
........................ 7

- 1 7
. 1 G e n e r a l P r o c e d u r e s ................................................. 7

- 1 7
. 2 Q A/ Q C P r o c e d u r e s f o r S e d i me n t C o l l e c t i o n a n d M a n i p u l a t i o n ............... 7

- 2 7.3 T he Q u ality A ssurance P r oj ect P l an (Q A P P )
............................. 7

- 2 7
. 4 S t a n d ar d O p e r a t i n g P r o c e d u r e s ........................................ 7

- 3 7
. 5 S e d i me n t S a m p l e D o c u me n t a t i o n ...................................... 7

- 3 7
. 6 S a m p l e T r a c ki n g D o c u me n t a t i o n ...................................... 7

- 4 7
. 7 R e c o r d K e e p i n g .................................................... 7

- 5 7
. 8 Q A A u d i t s ........................................................ 7

- 5 7
. 9 C o rr e c t i v e A c t i o n ( M a n a g e me n t o f N o n - c o n f o r m a n c e E v e n t s )
............... 7

- 5 7
. 1 0 D a t a R e p o r t i n g .................................................... 7

- 6 8. REF E RENCES
.......................................................... 8

- 1 A PP END I CES A EXAM P LES O F SEDI M ENT Q UALI TY SAM P LI NG DESI GNS USI N G TH E DATA QU A L IT Y OBJE C T IV E S (D QO) PR OC E S S B E XAM P LES O F M E ASUREM E NT Q UALI T Y O B JECTI V ES USED I N SEDI M ENT Q UALI TY M O NI TO RI NG STUDI ES C S TATI STI CAL CO NSI D ERATI O NS I N DETERM I NI NG TH E AP P R O P RI ATE NUM B ER O F REP LI CATE SAM P LES NEEDED AT EACH SAM P LI NG STATI O N D ADVANTAGES AND DI SADVANTAGES O F DI F F ERENT STATI O N P O SI TI O N I N G TECH N I Q UES E ADVANTAGES, DI SADVANTAGES AND I LLUSTRATI O NS O F GRAB AND CO RE SAM P LI NG DEVI CES USED I N SEDI M ENT M O NI TO RI NG STUDI ES F EXAM P LES O F F I ELD F O RM S USED TO DO CUM ENT STATI O N AND SAM P LE CH ARACTERI S TI CS AND SAM P LE TRACK I N G G P H Y SI CO - C H EM I CAL SEDI M ENT CH ARACTERI Z ATI O N

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xv i U S Environm ental Protection AgencyTechnical M anual LI ST O F TAB LES Tabl e P age

2- 1 S ug g estions for selecting an appropriate sam p ling desig n (from U S EPA 2000b)
........ 2

- 9 2- 2 C onv entional sediment v ariables and th eir use in sediment inv estig ations (Adapted from WDE, 1995)
........................................................ 2

- 1 3 2

- 3 T y p i c a l s e d i me n t v o l u me r e q u i r e me n t s f o r v ar i o u s a n a l y s e s p e r s a m p l e ............. 2

- 1 4 2- 4 P ractical considerations for site- speci fic selection of sam p ling stations in dev eloping a s a m p l i n g p l a n .......................................................... 2

- 1 8 4- 1 R ecommended sam p ling containers, hol ding times, and storag e conditions for c o mm o n t y p e s o f s e d i me n t a n a l y s e s .......................................... 4

- 4 6- 1 In Situ interstitial w a ter collection me thods
..................................... 6

- 5
LI ST O F F I GURES Fig u r e P age

1- 1 F l ow chart summ ariz i ng activ ities fo r collection, storag e, and m anipulation of sedime nts and interstitial w a ter .............................................. 1

- 3 2- 1 F low chart summ ariz i ng the process that should be im plemented in desig n ing and performing a m onitoring study (m odified from MacDonald et al. (1991)
.......... 2

- 2 2- 2 F low chart summ ariz i ng the D a ta Q u ality O b j ectiv es P r ocess (after U S E P A 2000a)
.................................................................. 2

- 3 2- 3 D escription of v arious sam p ling me thods (adapted from USEPA 2000c)
.............. 2

- 8 3- 1 G eneral ty pes of considerations or obj ectiv es that are appropriate for g r ab or core s a m p l i n g d e v i c e s ......................................................... 3

- 1 3- 2 F lowchart for selecting appropriate g r ab sam p lers based on site- specific or desig n f a c t o r s .................................................................. 3

- 2 3

- 3 F l o w c h ar t f o r s e l e c t i n g ap p r o p r i a t e c o r e s a m p l e r s b a s e d o n s i t e - s p e c i f i c f a c t o r s ........ 3

- 3 3- 4 I llustrations of acceptable and unacceptable g r ab sam p les
........................ 3

- 1 5 4

- 1 F l o w c h ar t o f s u g g e s t e d s e d i me n t p r o c e s s i n g p r o c e d u r e s .......................... 4

- 2 4- 2 A lternativ es for subsam pling and com positing sediment g r ab sam p les
................ 4

- 8 4- 3 A lternativ es for subsam pling and com positing sediment core sam p les
................ 4

- 9

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5- 1 F lowchart depicting relationshi ps between comm on sediment m anipulations i n c l u d i n g i m p o r t a n t c o n s i d e r a t i o n s ........................................... 5

- 2 6- 1 C onsiderations for selecting the appropriate ty pe of interstitial w a ter sam p ling me t h o d................................................................. 6

- 3 6- 2 F ront v i ew and com ponents of peepersam p ling dev i ces (top: plate dev i ce; bottom : c y l i n d r i c a l p r o b e )
........................................................ 6

- 6 6- 3 S umm ary of recommended procedures and considerations for laboratory isolation of interstitial w a ter ....................................................... 6

- 9

x

v iii U S Environm ental Protection AgencyTechnical M anual LI ST O F RECO M M ENDATI O N B O XES C h apter 2 P age

Bo x # 1 What ty pe of sam p ling strateg y should be used
.......................... 2

- 1 0 Bo x # 2 How m a ny sam p les and how m u ch sam p le v o lume should be collected
....... 2

- 1 4 Bo x # 3 H o w should station positioning be performed
........................... 2

- 2 0 Bo x # 4 What health and safety precautions should be follow ed
.................... 2

- 2 4 C h apter 3

Bo x # 1 What are appropriate sam p ling dev i ces g i v en different study o b

j e c t i v e s ......................................................... 3

- 9 Bo x # 2 How should sam p ling dev i ces be used
................................. 3

- 1 3 Bo x # 3 What inform ation should be documented for each sam p le collected
.......... 3

- 1 6 C h apter 4

Bo x # 1 S a m p l e c o n t a i n e r s .................................................. 4

- 1 Bo x # 2 How should sedime nt sam p les be subsam pled and com posited
............... 4

- 5 Bo x # 3 How should sam p les be hom og eniz ed
................................. 4

- 1 1 Bo x # 4 S a m p l e tr a n s p o r t a n d s t o r a g e ........................................ 4

- 1 4 Bo x # 5 How long should sam p les be stored before analy s is
....................... 4

- 1 5 C h apter 5

Bo x # 1 Should sediment be siev ed prior to analy s es .............................. 5

- 3 Bo x # 2 What ty pe of siev e should be used
..................................... 5

- 5 Bo x # 3 How should sedime nts be spiked with a chemical or other test m a terial
........ 5

- 9 Bo x # 4 How should sedime nt el utriates be performed
........................... 5

- 1 5 C h apter 6

Bo x # 1 In-situ interstitial w a ter collection
..................................... 6

- 2 Bo x # 2 E x traction of interstitial w a ter ........................................ 6

- 1 0

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## Technical Terms

T h e following definitions were deriv e d prim ar i l y f r o m AST M , USEPA, ACOE, a nd Env i r onme n t Canada sources. A c id V o latile S u l f i d e . T h e sulfides rem o v e d from sedime nt by cold acid extraction, consisting m a inly of iron sulfide. A V S is the principal binding phase in sedime nt for div a lent me tals. Ar t i f a c t . An undesirable, detectable f eature (e.g ., chemical or phy sical chang e ) in a sam p le, that has resulted from sam p ling , sam p le handling or storag e, or from m a nipulations of the sam p le. B e nt hi c. Associated with the bottom of a waterbody
. B i oaccumulation. T h e net accum u lation of a substance by an org a nism as a result of uptake from all env i ronmental sources. Bioavailability. T h e deg r ee to which a chemical is take n up by aquatic org a nism s. Chai n- of- c ust o dy. The documentation that establishes the control of a sam p le betw een the time it is collected and the time it is analy z ed. I tusually app lies to leg a l sam p les to dem onstrate that there w a s no tam p ering w ith, or contamination of, the sam p le during this time. Cl e a n . Denotes a sedime nt or water test sam p le determined to not contain concentrations of contaminants w h ich cause apparent and unacceptabl e harm (or effects) to the test org a nism s. C o mp osite samp le. Asam p le that is formed by com b ining m a terial from m o re than one sam p le or subsam ple. C o ncentration. The ratio of w e ig ht or v o lume of test m a terial(s) to the w e ig ht or v o lume of sedime nt or water. Cont am i n at ed sedi m e nt . Sedime nt containing ch emical substances at concentrations that pose a known or suspected threat to env i ronmental or hum an health. Cont rol sedi m e nt . Asedime nt that is essentially free of c ontaminants and is used routinely to assess the acceptability of a test. A n y contaminants in control sedime nt m a y orig inate from the g l obal spread of pollutants and do not reflect any s ubstantial input from local or non- point sources. Com p aring test sedime nts to control sedime nts is a measure of the toxicity of a test sedime nt bey ond inev itable back g r ound contamination. C o re sample. Asedime nt sam p le collected to obtain a v e rtical profile using a v ariety of instrume nts. D a ta Qu ality Ob jectives (D QOs). Q u alitativ e and quantitativ e statements that clarify the purpose of the m onitoring study , define the m o st appropriate ty pe of data to collect, and determine the m o st appropriate me thods and conditions under w h ich to collect them
. Decontamination. A process of washing or rinsing that re m o v e s chemicals adhering to equipment and supplies.

Term s xxiM e

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Ec ot oxThr e s hol d s ( ET) . B e nchm ark v a lues in ecolog i cal risk assessments defined as me diaspecific contaminant concentrations abov e w h ich there is sufficient concern reg arding adv e rse ecolog i cal effects to w arrant further site inv e stig ation. E l utriate. An aqueous solution obtained after adding w a ter to a solid substance or loose m a terial (e.g ., sedime nt, tailing s , drilling m ud, dredg e spo il), shaking the mi xture, then centrifug ing or filtering it or decanting the supernatant. E q u ilib ration . T h e condition in which a m a terial or contaminant is at steady state betw een the solid or particulate sedime nt and the interstitial w a ter. F o rm ul at ed Sedi m e nt . Mixtures of m a terials used to mi mi c a natural sedime nt. G l obal P o sitioning system (G P S ). A nav i g a tion sy stem that relies on satellite inform ation. I tcan g i v e continuous position reports(i.e., latitude and l ong itude) that v ary in accuracy depending on the sophistication of the receiv i ng unit. Gr a b . Any dev i ce desig n ed to “bite” or “scoop” into the bottom sedime nt of a lake , stream , estuary , ocean, and similar habitats to sam p le the benthos. G r abs are sam p lers w ith j a w s that are forced shut by weig hts, lev e r arm s , spring s or cables. Scoops are g r ab sam p lers that scoop sedime nt with a rotating container. H e ad Space
. T h e space in the storag e container betw een the top of the sam p le and the lid of the container. Hold in g time. T h e period of time during which a sedime ntor w a ter sam p le can be stored after collection, and before analy s is or use in a biolog i cal test. C h ang e s that occur in sedime nts or w a ter should be mi nim a l during this period and the integ r ity of the sam p le should not be com p romi sed to any substantial deg r ee w ith respect to its phy sical, chemical, or biol og ical characteristics. Homogeniz a tion
. T h e com p lete mi xing of sedime nt, e ither by hand or mechanical means, until phy sical, chemical, and /or biolog ical hom og eneity of the sam p le is achiev e d. IndexP eri od. S p ecific time period in w h ich sam p ling or in-situ analy s es are conducted. Generally pertains to an ecolog i cally im portant season a nd/or desired env i ronmental conditions under which sam p ling is performed. In S itu
. R e fers to the orig inal (field) location from w h ich test sam p les are collected, or at w h ich org a nism s are exposed to undisturbed wa ter or sedime nts for extended periods. Interf erences . Characteristics of sedime nts or sedime nttest sy stem s that can potentially affect analy tical results or test org a nism response aside from responses related to sedime nt contamination. T y pes of interferences include: non- contaminant char acteristics (e.g ., sedime nt texture or g r ain siz e , lig hting ) ; chang e s in chemical bioav a ilability due to sam p le handling or storag e (e.g ., amm onia g e neration); and the presence of indig e nous org a ni sm s. Also referred to as confounding factors. In terstitial w a ter. Water occupy ing space betw een sedime nt or soil particles. Measurement Quality Ob jectives (MQOs). Statements that describe the am ount, ty pe, and quality of data needed to address the ov erall proj ect obj ectiv es.

xxi i U S Environm ental Protection AgencyTechnical M anual Overlying w a ter. T h e w a ter placed ov er sedime nt in a test cham ber during a test. P eepers . D e v i ces that collect interstitial w a ter by diffusion throug h me m b ranes attached to collection cham bers. T h e cham bers are ty pically pl aced in the sedime nt for extended periods of time to allow for equilibration betw een the internal w a ter env i ronment of the peeper and the surrounding am bient sedime nt/interstitial w a ter m a trix. P o re w a ter. See in terstitial w a ter
. Quality A ssurance P r oject P l an . P r oj ect- s pecific document that specifies the data quality and quantity requireme nts needed for the study as w e ll as all procedures that w ill be used to collect, analy z e, and report those data. R e f erence sediment. A w hole sedime nt, collected near an area of concern, that is used as a point of com p arison to assess sedime nt conditions exclusiv e of the m a terial(s) or activ ities of interest. The reference sedime nt m a y be used as an indicator of localiz ed sedime nt conditions exclusiv e of the specific pollutant input of concern. Such sedime nt would be collect ed near the site of concern and w ould represent the back g r ound conditions resulting from any localiz ed pollutant inputs as w e ll as g l obal pollutant input. Prog ram - specific g u idance documents should be consulted, as some EPA prog ram s hav e specific definitions a nd requireme nts for reference sedime nt. Sampling P l atf o rm A w o rking space, such as the deck of a boat, from w h ich all sam p le collection activ ities are conducted. Sedi m e nt . P articulate m a terial that usually lies below w a ter, or form ulated particulate m a terial that is intended to lie below w a ter in a test. Sedi m e ntQ u al i t y Tri a d. A w e ig ht- o f- ev idence sedime nt quality assessment approach w h ich integ r ates data from sedime nt toxicity tests, ch emical analy s es, and benthic comm unity assessments. Si evi n g. S e lectiv ely rem o v i ng certain siz e fractions of the sedime nt sam p le by processing sedime nt throug h selected me sh siz e s. Si t e . Astudy area that can be com p rised of m u ltiple sam p ling stations. Spi ki ng. A ddition of a know n am ount of test m a terial to a sedime nt often used as a quality control check for bias due to interference or m a trix effects. St at i o n . A sam p ling location w ithin a study area or site, w h ere phy sical, ch emical, or biolog ical sam p ling and/or testing occurs. Supernatant. T h e w a ter separated from a sedime nt/w atermi xture following centrifug ation or other separation techniques. Tox i c i t y . T h e property of a chemical, or com b ination of chemicals, to adv e rsely affect org a nism s, tissues or cells. Whole sediment. S e dime nt and associated interstitial w a ter w h ich hav e had mi nim a l m a nipulation. A l so referred to as bul k sedi m e nt
.

Term s xx iiiM e

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## Grammatical Terms C onsistent w ith g u idance form ulated by the A mer ican Society for T e sting and Materials (A ST M), the follow i ng g r amm atical phrases, used in this m anual, are defined as follow s: T h e w o rds “m ust”, “should”, “m ay ”, “can”, and “mig ht” hav e specific meaning s in this m anual. “Must” is used to express an absolute requirement, that is, to produce accurate results, a sam p le oug ht to be handled or m anipulat ed in a specified m anner, unless the purpose of the study requires a different procedure. “Should” is used to state that the specified c ondition or procedure is recommended and oug ht to be met if possible. Althoug h v i olati on of one “should” is rarely a serious m atter, v i olations of sev eral w ill often render the results questionable. “D esirable” is used in connection w ith less im portant factors. “May ” is used to mean “is allow ed to.” “C an” is used to mean “is able to.” “Mig ht” is used to mean “could possibly
. ” T hus, the classi c distinction betw een “m ay ” and “can” is preserv ed, and “mig ht” is not used as a sy nony m for either “m ay ” or “can.” 

## Using the M **a**

**nual** T h roug hout this Manual, there are three categ ories of inform ation that are org aniz ed into text boxes as part of the effort to m ake this methods docum ent m o re useful and accessible to users. Each box alway s appears with the same icon throug hout the Manual:

Recommendations for procedures and equipment.

Consideration, or issues, that should be addressed

C h ecklists of inform ation

The full list of R ecomme ndation B oxes are identified on pag e xix as part of the T able of Contents.

xxi v U S Environm ental Protection AgencyTechnical M anual


## Introduction **CHA PT**  **ER** 

# 1

**1. 1**  **B ack**  **g round**  P r otecting sediment quality is an im portant part of restoring and m a intaining the biolog ical integ r ity of our Nation’s waters as well as protecting aquatic life, w ildlife and hum an health. S ediment is an integ r al com ponent of aquatic ecosy stem s, prov iding habitat, feeding , spawning , and rearing areas for m any aquatic org anism s. Sediment also serv es as a reserv oir for pollutants and therefore a potential source of pollutants to the w ater column , org ani sm s, and ultim ately hum an consumers of those org anism s. T h ese pollutants can arise from a num be r of sources, including m unicipal and industrial discharg es, urban and ag ricultural runoff, atm o spheric deposition, and port operations. C ontaminated sediment can cause lethal and subl ethal effects in benthic (sediment- dw elling ) and other sediment- associated org anism s. I n additi on, natural and hum an disturbances can release pollutants to the ov erly ing water, where pelag i c (w ater column ) org anism s can be exposed. Sediment pollutants can reduce or eliminate species of r ecreational, commercial, or ecolog i cal im portance, either throug h direct effects or by affecting the food supply that sustai nable populations require. Furtherm ore, some sediment pollutants can bio accum u late throug h the food chain and pose health risk s to w ildlife and hum an consumers ev en w h en sedime nt- dw e lling org a nism s are not them selv es im pacted. T h e extent and sev erity of sediment contaminati on in the U.S. has been documented in the National Sedime nt I nv e ntory (NSI ) 1 and throug h other historical inform ation. T h e N S I screening ev aluation of sediment contamination data i ndicates that associated adv erse e ffects are probable in thousands of locations throug hout the country
. T h e results em pha siz e the widespread need to address sediment contamination in the U .S
. 

### 1. **2 S**  **i g**  **ni fi**  **cance and Use of thi s Manual**  Sediment quality assessment is an im portant co m ponent of w ater quality protection prog ram s. Sediment assessments comm only include phy sicochemical characteriz ation, toxicity tests, and/or bioaccum u lation tests, as w ell as benthic comm unity analy s es. U S EPA ’ s N S I , for exam ple, collates this inform ation to dev e lop a biennial report to C ong ress on sediment quality in the U n ited S t ates, required under the Water Resources Dev elopment Ac t of 1992. T h e use of consistent sediment collection, m anipulation, and st orag e methods w ill help prov ide hig h quality sam p les w ith w h ich accurate data can be obtained for the national inv ent ory and for other prog ram s to prev ent, remediate, and m anag e contaminated sediment. I tis now widely known that the me thods used in sa m p le collection, transport, handling , storag e, and m a nipulation of sedime nts and interstitial w a ters can influence the phy sicochemical properties and

1 T h e Natio n a l Sed i me n t I n v e n t o r y , o rNSI , is th e d a tab a se o f sed i me n t q u alityin f o r m atio nu s ed to dev e l op EPA ’ s 1997 R e portt o C o n g r es s , T h e Incidence and Sever ity of Se diment Contami nation in Sur face W

a t e r s of th e U n i t e d St at es , Volume 1: N a tional Sediment Quality Sur vey (U .S . EPA , 1997a). T h e dat abas e i s u pd a t e d p e r i od i c a lly w ith n e w a v a il ab l e inf o r m a ti o n o n s e d i me nt q u a lity a t sit e s th r o ugh o ut the U
. S. h tt p : // www . e p a . gov /O ST/c s/re p o r t . h t ml C

hapter 1: Introduction 1-1M e

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses the results of chemical, toxicity , and bioaccum u la tion analy s es. A ddressing these v ariables in an appropriate and sy stem atic m a nner w ill help assure m o re accurate sedime nt quality data and facilitate com p arisons am ong sedime nt studies. T h is T echnical Manual prov ides current info rm ation and recomme ndations for collecting and handling sedime nts for phy sicochemical characteriz ati on and biolog ical testing , using procedures that are m o st likely to m a intain in situ conditions, m o st accurately represent the sedime nt in question, or satisfy particular prog ram needs, to help en sure consistent, hig h quality data collection. 

### 1 **. 3**  **A p**  **p lic**  **a b**  **ility a**  **n d**  **S c**  **o p**  **e o**  **f th**  **is M**  **a n**  **u a**  **l** T h is m a nual is intended to prov ide technical suppor t to those w ho desig n or perform sedime nt quality studies under a v ariety of reg u latory and non- re g u latory prog ram s . I n form ation is prov ided concerning g e neral sam p ling desig n considerati ons, field and laboratory facilities needed, safety , sam p ling equipment, sam p le storag e and trans port procedures, and sam p le m a nipulation issues comm on to chemical or toxicolog i cal analy s es. I n form ation contained in this m a nual reflects the knowledg e and experience of sev e ral internationa lly

- known sources including A merican Society for T e sting and Materials (AST M), Pug e t Sound Estuary Prog ram (PSE P), Washing t on State Departme nt of Ecolog y (WDE), U n ited States Env i ronmental Protection A g ency (U SEPA ), U S A r my Corp s of Eng i neer s ( A COE) , Nat i onal Oceani c and At m o spher i c Admi ni str a t i on ( NOAA) , and E n v i ronment C a nada. This m a nual attem p ts to pr esent a coherent set of recomme ndations on field sam p ling techniques and sedime nt/interstitial w a ter sam p le processing based on the abov e sources, as w e ll as extensiv e inform ation in th e current peer- r ev iew e d literature. A s the scope of this m a nual is broad, it is im po ssible to adequately present detailed inform ation on ev ery aspect of sedime nt sam p ling and processing for all situations or all prog ram s . N o r is such detailed g u idance w arranted because m u ch of this inform ation (e.g ., how to operate a particular sam p ling dev i ce or how to use a Geog raphical Pos itioning Sy stem (G PS) dev i ce) already exists in other published m a terials referenced in this m a nua l. Furtherm ore, m a ny prog ram s hav e specific sam p ling and sam p le processing procedures. While an attem p t is m a de to g i v e exam ples from different prog ram s , the m a nual repeatedly instruct s the reader to check their ow n specific prog ram requireme nts. G i v e n the abov e constraints, this m a nual: (1) pres ents an org a niz e d discussion of activ ities inv o lv ed in sedime nt sam p ling and sam p le processing ; (2) aler ts the user to im portant issues that need to be considered w ithin each activ ity ; and (3) g i v e s recomme ndations on how to best address the issues raised such that appropriate sam p les are collected a nd analy z ed. A n attem p t is m a de to alert the user to different considerations pertaining to sam p lin g and sam p le processing depending on the prog ram need (e.g ., dredg e reme diation v e rs us status and trends m onitoring ). F i g u re 1- 1 presents a flow chart of the g e neral ac tiv ities discussed in this m a nual. The org a niz a tion of these activ ities reflects the desire to g i v e fiel d personnel and m a nag e rs a useful tool for choosing appropriate sam p ling locations, characteriz e thos e locations, collect and store sam p les, and m a nipulate those sam p les for analy s es. C h apters are w r itten so that the reader could obtain inform ation on only one activ ity or set of activ ities (e.g ., subsam pling or sam p le processing ), if desired, w ithout necessarily reading the entire m a nua l. Many sections are cross- referenced so that the reader is alerted to relev a nt issues that mi g h t be cov e red elsew h ere in the m a nual. This is particularly im portant for certain chemical or toxi colog i cal applications in w h ich appropriate sam p le processing or laboratory proce dures are associated w ith speci fic field sam p ling procedures.

1-2 U S Environm ental Protection AgencyTechnical M anual

**F i**  **g u**  **r e 1-**  **1.** F l owc har t s um m ar i z i n g ac tivities f o rc o llec t ion, s t or a g e, and m anipulation of s edim ents and inter s titial w ater
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hapter 1: Introduction 1-3M e

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses T h e me thods contained in this m a nual are w i dely applicable to any entity w i shing to collect consistent, hig h quality sedime nt data. This m a nual does notprov ide g u idance on how to im plement any specific reg u latory requireme nt, or desig n a pa rticular sedime nt quality assessment, but rather it is a com p ilation of technical me thods on how to best collect env i ronmental sam p les that m o st appropriately address comm on sam p ling obj ectiv es. Althoug h the data from these sam p les mi g h t be used in env i ronmental decision- m aki ng at a v ariety of lev e ls, this m a nual does not address how data are to be used. T h e Foreword section summ ariz e s a v ariety of EPAprog ram s that assess sedime nt qua lity and m a y benefit from the me thods described in this m a nual. Other Ag encies and prog ram s are also encourag ed to consider these me thods in order to g e nerate consistent and hig h quality sedime nt data. T h e inform ation presented in this m a nual should notbe v i ewed as the final statement on all the recomme nded procedures. Some of the areas cov e re d in this document (e.g ., sedime nt holding time, form ulated sedime nt com position, interstitial w a te r collection and processing ) are being activ ely researched and debated. As data from sedime nt m onitoring and research become s m o re av ailable in the future, EPA m a y update this m a nual as necessary
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1-4 U S Environm ental Protection Agency**CHA PT**  **ER** 

# 2 Technical M anual 

## Sediment M **onitoring and Assessment Study Plans** 

Ev ery study site and proj ect are unique; therefore, sediment m onito ring and assessment study plans should be carefully prepared to best meet th e proj ect obj ectiv es (MacDonald et al., 1991; see Fig u re 2- 1). 

## Cons **ide r**  **a t**  **ions The initial issues that**  **need t o**  **be considered prior to preparing study**  **plans are...** ! def ine the potential pr oblem or g ener al pr oj ec t obj ec tive ! deter m i ne w hat r es our c es ( e. g ., tim e, m oney , per s onnel) ar e available f orthe pr oj ec t ! r eviewex is tin g inf o r m ation and identif y s pec if ic obj ec tives of the s t udy ! deter m i ne w hat data ar e lik ely to be needed to ans w erpr oj ec t obj ec tives , inc l udin g the r o le of s i te- s pec if ic c onditions and/oris s ues that m i g ht inf l uenc e the pr oc es s of data c ollec t ion and analy s es B e fore collecting any env i ronmental data, it is im portant to determine the ty pe, quantity , and quality of data needed to meet the proj ect obj ectiv es (e.g ., specific parameters to be measured) and support a decision based on the results of data collection and observ ation. Not doing so creates the risk of expending too m u ch effort on data collection (i.e., m o re data are collected than necessary ), not expending enoug h effort on data collection (i.e., m o re data are necessary than were collected), or expending the wrong effort (i.e., the wrong data are collected). 

### 2 **.1 D**  **a ta**  **Qu a**  **lity Ob**  **je c**  **tiv e**  **s Pr**  **ocess** Th e D a ta Qu ality Ob jectives (D QO) Process dev e loped by EPA (GLNPO, 1994; USEPA, 2000a) is a flexible planning tool that sy stem atically addresses the abov e issues in a coherent m anner. T h e purpose of this process is to im prov e the effectiv eness, efficiency , and defensibility of decisions m ade based on the data collected, and to do so in an effectiv e m anner (USEPA, 2000a). T h e info rm ation com p iled in the DQO pr oc e s s i s us e dt o de v e l op apr oj e c t
- s pe c i f i c Qu ality A ssu ran ce Pr oject P l an (QAP P ) (see C h apter 7 and U S EPA , 2000a) w h ich should be used to plan the m aj o rity of sediment quality m onitoring or assessment studies. I n some in stances, a prog ramm a tic QAPP m a y be prepared, as necessary , on a proj ect- by

- proj ect basis. T h e Data Quality Obj ectiv es (DQO) proce ss addresses the uses of the data (m ost im portantly , the decision(s) to be m ade) and othe r factors that w ill influence the ty pe and am ount of data to be collected (e.g ., the problem being addressed, exis ting inform ation, inform ation needed before a decision can be m ade, and av ailable resources). F r om these factors the qualitativ e and quantitativ e data needs are determined (see Fig u re 2- 2). DQOs are qua litativ e and quantitativ e statements that clarify the purpose of the m onitoring study , define th e m o st appropriate ty pe of data to collect, and determine the m o st appropriate methods and conditions under w h ich to collect them
. T h e products of the DQO process are criteria for data quality and a data collection desig n that ensures that data w ill meet the criteria.

C

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

**F i**  **g u**  **r e 2-**  **1.** F l owc har t s um m ar i z i n g the pr oc es s that s hould be im plem ented in des i g nin g and per f o r m in g a m onitor i n g s t udy ( m odif i ed f r om Mac D onald et al. ( 1991) )

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2-2 U S Environm ental Protection AgencyTechnical M anual

**F i**  **g u**  **r e 2-**  **2.** F l owc har t s um m ar i z i n g the Data Q uality O bj ec t ives Pr oc es s ( af t erUSEPA, 2000a)

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses 

## C **h ecklist**  **In the DQO process, the follo wing steps should be addressed:** 

� **Clearly st**  **at e t**  **h e p**  **r o**  **b lem:**  **p u**  **r p**  **o se an**  **d o**  **b ject**  **iv es, av**  **ailab le reso**  **u r**  **ces, memb ers**  **o f**  **t h**  **e p r**  **o ject**  **t eam:**  e. g ., T he pur pos e m i g ht be to evaluate c ur r ent s edim ent quality c onditions , his t or ic al c onditi ons , evaluate r em ediation ef f ec t s , orvalidate a s edim ent m odel. It is im por tant to r eviewand evaluate available his t or ic al data r e levant to the s t udy at this point in the pr oc es s . � **Id en**  **t if**  **y t**  **h e d**  **ecisio n**  **; t**  **h e q**  **u est**  **io n**  **s (**  **s )**  **t h**  **e st u**  **d y** **at t**  **e mp**  **t s**  **t o**  **ad d**  **r ess**  : e. g ., Is s i te A m or e tox i c than s i te B?; Ar e s edim ents in Lak e Y les s tox i c nowthan they us ed to be?; Does the s edim ent at s i te D need to be r em ediated? W hat point ornonpoint s our c es ar e c ontr i butin g to s edim ent c ontam ination? � **Identify inputs to the deci**  **sion: information and measu rements that need to be**  **obta i**  **ne d**  ; e. g ., analy s es of s pec if ic c ontam inants , tox i c i ty tes t r es ults , biolo g ic al as s es s m ents , bioac c um ulation data, habitat as s es s m ents , hy dr olo g y , and w aterquality c har ac ter i z ation. � **De fine**  **the s**  **t udy** **bounda r**  **i e**  **s (s**  **pa tia**  **l a**  **nd te mpor**  **a l**  **).** Identif y potential s our c es of c ontam ination; deter m i ne the loc ation of s edim ent depos ition z ones ; deter m i ne the f r equenc y of s a m p lin g and need f ora s eas onal s am plin g and/ors a m p lin g dur in g a s pec if ic index per iod; c ons iderar eas of pr evious dr ed g ed orf ill m a ter i al dis c har g es /dis pos al. Cons ider ation of hy dr aulic patter ns , f l owevent f r equenc y , and/or s edim entation r a tes c ould be c r itic al f o rdeter m i nin g s a m p lin g f r equenc y and loc ations

. � **De v**  **e lop a**  **de c**  **i s**  **i on r**  **u le**  **: de fine**  **pa r**  **a me**  **te r**  **s of inte**  **r e**  **s t**  **a nd de**  **te r**  **mine the**  **v a**  **lue of a**  **pa r**  **a me**  **te r**  **tha t**  **w ould c**  **a u**  **s e**  **follow -**  **up a c**  **t ion of s**  **o me**  **k i**  **nd** ; e. g ., ex c eedanc e of Sedim ent Q uality G u ideline value, NO AA Ef f e c t Ran g e Median ( E RM) value, ortox i c i ty e ffe c t ( e . g ., 50% m or t ality ) , r es ults in s om e ac tion ( Lon g et al., 1995)

. F orex am ple, in the G r eat Lak es As s es s m ent and Rem ediat ion of Contam inated Sedim ents ( A RCS) Pr o g r am , one dec is ion r ule w as : if total PCB c onc entr ation ex c eeds a par tic ularac tion level, then the s edim ents w ill be c l as s i f i ed as tox i c and c ons ider ed f orr em ediation ( G LNPO , 1994)

. Spec if y i n g dec is ion r u les orc r iter ia is es pec ially c r itic al in s edim ent r em ediation pr o g r am s and any s t udy in w hic h the r es ults c ould be s ubj ec t to le g al scru t i n y (e

. g ., s uper f und)

. � **Sp ecif**  **y limit**  **s o n**  **d ecisio**  **n erro**  **rs:** es tablis h the m eas ur em ent quality obj ec tives ( M Q O s ) w h ic h inc l ude deter m i nin g the level of c onf idenc e r equir ed f r om the data; pr ec is ion, bids , r epr es entativenes s , and c om pletenes s of data; the s am ple s i z e ( w ei g ht orvolum e) r equir ed to s atis f y the analy t ic al m ethods and Q A /Q C pr o g ra m f o r a l l analy t ic al tes t s ; the num berof s am ples r equir ed, to be w i thin lim its on dec is ion er r or s , and c o m pos itin g needed, if any . � **O p**  **t imiz**  **e t**  **h e d**  **esig n**  **:** c hoos e appr opr iate s am plin g and pr oc es s i n g m ethods ; s elec t appr opr iate m ethod f ordeter m i nin g the loc a tion of s a m p lin g s t ations ; s elec t an appr opr iate pos itionin g m ethod f orthe s i te and s t udy

. Cons ult his t or ic al data and a s t atis tic i an bef or e the s t udy be g ins r e g ar din g the s a m p lin g des i g n ( i .e., the f r equenc y , num ber , and loc ation of f i eld- c ollec t ed s am ples ) that w ill bes t s atis f y s t udy obj ec tives

.

2-4 U S Environm ental Protection AgencyTechnical M anual For m o st prog ram s , a Sam p ling and Analy s is Plan (SAP) is dev eloped prior to sam p ling which should describe the study obj ectiv es, sam p ling desi g n and procedures, and other aspects of the DQO process outlined abov e (see A ppendix B for an exam ple of S A P requirements recommended by Washing ton State Departmentof Ecolog y )
. T h e following secti ons prov ide g u idance on m a ny of the prim ary issues that should be addressed in the study plan. 

### 2. **2 S**  **t udy**  **Pl an Consi**  **derat i**  **ons** Monitoring and assessment studies are performed fo r a v ariety of reasons (I T F M, 1995) and sediment assessment studies can serv e m any different purpos es. Dev eloping an appropriate sam p ling plan is one of the m o st critical steps in m onitoring and assessment studies. T h e sam p ling plan, including definition of the site and sam p ling desig n, w ill be a product of the g eneral study obj ectiv es (Fig ure 2- 1). Station location, selection, and sam p ling me thods w ill necessarily follow from the study desig n. U ltim ately , the study plan should control extraneous sources of v ariability or error to the extent possible so that data are appropriately representativ e of the sedime nt and fulfill the study obj ectiv es. **2. 2.**  **1 D**  **ef i**  **ni t**  **i on of**  **t he St**  **udy A**  **r ea and St**  **udy Si**  **t e**  T h e study area refers to the body of water that contains the study site(s) to be m onitored and/or assessed, as well as adj acent areas (land or w a ter) that mi g h t affect or influence the conditions of the study site. T h e study site refers to the body of water and associated sediments to be m onitored and/or assessed. EMAP, for exam ple, often defines a site as an area of concern (AOC) which mi g h t extend sev eral miles in leng th, or m ay encom p ass larg e g eog raphical or coasta l areas. CERCLA defines a site in term s of a specific source of contamination such as a w aste disposal area. The siz e of the study area w ill g r eatly influence the ty pe of sam p ling desig n (see Section 2.3) and site positioning methods that are appropria te (see Section 2.6). T h e boundaries of the study area need to be clearly defined at the outset and should be outlined on a hy drog raphic chart or topog raphic m ap. **2.2.2 C**  **ontrolling S our**  **ces of V a**  **riability Co**  **mmo n**  **p u**  **r p**  **o ses o**  **f sed**  **imen t**  **qua lity** **s t**  **udie s**  **:**
• S tatus and tr ends • E valuatin g pr o g r a m orBMP ( bes t m ana g em ent pr ac tic e) ef f e c t ivenes s • V alidatin g s edim ent quality m odels • D e s i g nin g re g ulator y pr o g ra m s • I dentif y i n g w hethers i g nif i c ant c ontam ination ex is ts and ex tent of c ontam ination • I dentif y i n g so u r ce s o f c ontam ination • R ank in g ex is tin g and identif y i n g em er g in g pr oblem s • E s t ablis hin g g oals f o rs edim ent r e m ediation • E valuatin g dr ed g ed orf ill m a ter i al dis c har g es /dis pos al

A ke y factor in effectiv ely desig n ing a sedime nt quality study is controlling those sources of v ariability in w h ich one is not interested (U SEPA 2000a,b). T h ere are tw o m aj o r sources of v ariability that, w ith proper planning , can be mi ni mi z ed, or at least accounted for, in the desig n process, thereby ensuring a successful study
. I n st atistical term s, the tw o sources of v ariability are sam p ling error and measurement error (USEPA 2000b; Solom on et al., 1997). S a m p ling error is the error attri butable to selecting a certain sam p ling station that mi g h t not be representativ e of the site or population of sam p le units (e.g ., an estuary or a CERCLA site). Sam p ling error is controlled by either: (1) using unbiased methods to sel ect stations if one is performing g eneral m onitoring of a g i v en site (USE PA, 2000b); or (2) sev eral stations along a spatial g r adient if a specific location is being targ eted (see Section 2.3).

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Measurement error is the deg r ee to w h ich the inv e stig ator accurately characteriz es the sam p ling unit or station. T hus, measurement error includes com ponents of natural spatial and tem poral v ariability w ithin the sam p le unit as w e ll as actual errors of omission or commi ssion by the inv estig ator. Measurement error is controlled by using sta ndardiz ed and com p arable methods: standardiz ed methods include proper training of personnel and quality assurance procedures. T o help mi nimi z e measurement error, each station should be sam p led in the same w ay , w ithin a site or study , using a standardiz ed set of procedures and in the sa me time frame to mi nimi z e confounding sources of v ariability (see Section 2.2.3). I n analy tical laborat ory or toxicity procedures, measurement error is estim ated by duplicate determinations on some subset of sam p les (but not necessarily all). Similarly , in field inv estig ations, some subset of sam p le un its (e.g ., 10% of the sites) should be measured m o re than once to estim ate measurement error (see Replicate and Com posite Sam p les, Section 2.4.3). Measurement error can be reduced by analy z ing m u ltiple observ ations at each station (e.g ., m u ltiple g r ab sam p les at each sam p ling station, m u ltiple observ ations during a season), or by collecting depth- integ r ated, or spatially integ r ated (com posite) sam p les (see Section 2.4.3). O p timiz ing sam p ling desig n requires consideration of tradeoffs am ong the measures used, the effect that is considered meaning f ul, desired power, desired confidence, and resources av ailable for the sam p ling prog ram . S t atistical pow er is the ability of a g i v e n sam p ling desig n to detect an effect that 

## C **h ecklist**  **To minimize measurement error:** 
� Sam p le all s t ations s i m ilar l y w i thin a s t udy � Us e s t andar diz ed pr oc edur es � Sam p le dur in g the s am e tim e per iod � Collec t and analy z e m u ltiple s a m p les at a st a t i o n � Collec t and analy z e c om pos ited s am ples actually exists, and w ill be a product of the coll ection methods, analy tical procedures, and quality control processes used. P o w er is ty pically expr essed as the probability of correctly finding a difference am ong sites or between reference and test sites (e.g ., toxicity orbiolog ical im pairme nt) when one exists. For a fixed confidence lev el (e.g ., 90%), power can be increased by increasing the sam p le siz e or the num ber of replicates (see Sec tion 2.4.3 for m o re inform ation). Most prog ram s do not estim ate pow er of their sam p ling desig n because this g e nerally requires prior inform ation such as pilot sam p ling , w h ich entails further resources. O n e study (G ilfillan et al., 1995) reported pow er estim ates for a shoreline m onitoring prog ram fo llow i ng the Valdez oil spill in Prince William Sound, A l ask a. H o w ev er, these estim ates w ere com puted after the sam p ling took place. I tis desirable to estim ate pow er before sam p ling is performed to ensure credibility of non- sig n ificant results (see Appendix C). **2. 2.**  **3 S**  **ampl i**  **ng Usi ng an I**  **ndex Peri od**  Most m onitoring prog ram s do not hav e the resources to characteriz e v ariability or to assess sedime nt quality for all seasons. S am p ling can be restricted to an i ndexperi od when biolog ical and/or toxicolog i cal measures are expected to show th e g r eatest response to pollution stress and withinseason v ariability is sm all (H olland, 1985; B arbour et al., 1999). T h is ty pe of sam p ling mi g h t be especially adv a ntag eous for characteriz ing sedime nt toxicity , sediment chemistry , and benthic m acroinv ertebrate and other biolog ical assem b lag es (U SEPA , 2000c). I n addition, this approach is useful if sediment contaminati on is related to, or being separated from , hig h flow ev ents. By sam p ling ov erly ing waters during both low and hi g h flow conditions, the relativ e contribution of
2-6 U S Environm ental Protection AgencyTechnical M anual each to pollutant loads or sediment contaminati on can be better assessed, thereby better directing reme dial activ ities, or other w a tershed im prov ements. Those prog ram s that sam p le the same site ov er m u ltiple y ears (e.g ., m any E M A P and superfund studies), are interested in obtaini ng com p arable data w ith w h ich they can assess chang es ov er time, or following reme diation (GLNPO, 1994). I n these cases, index period sam p ling is especially useful because hy drolog ical reg i me (and th erefore biolog ical pro cesses) is likely to be m o re similar betw een similar seasons than am ong different seasons. 

### 2. **3 S**  **ampl i**  **ng Desi gns**  As mentioned in earlier sections of this chapter, the ty pe of sam p ling desig n used is a function of the study D ata Q u ality O b j ectiv es and m o re specifically , the ty pes of questions to be answered by the study
. A summ ary of v arious sam p ling desig n s is presented in Fig u re 2- 3 along with recommendations concerning the conditions under which a g i v en desig n is appropriate. Generally , sam p ling desig n s fall into tw o m a j o r categ ories: random or probabilistic, and targ eted (USEPA, 2000b). USEPA (2000b;c) present a thoroug h discussion of sam p ling desig n issues and detailed inform ation on different sam p ling desig n s. Some prog ram specific g u idance documents (e.g ., USEPA/ACOE 1991, 1998 for dredg e d m a terial disposal issues) also discuss relev a nt sam p ling desig n s. T able 2- 1 presents s u gge s t e d s a m p l i n g d e s i gn s gi ve nd i f f e r e n t **Samplin g**  **Desi g** **n** r ef er s to the ar r ay , ornetw or k , of s a m p lin g si t e s se l e ct e d f o r a m o n i t o ri n g pr o g r a m ; us ually tak i n g one of tw o f or m s : • Pr obabilis tic Des i gn — Netw or k that inc l udes s a m p lin g s i tes s elec t ed r andom ly in or derto pr ovide an unbias ed as s es s m ent of the c ondition of the w ater body at a s c ale above the individual s i te ors t r eam ; c an addr es s ques tions at m ultiple s c ales

. • T ar

geted Des i gn — Netw or k that inc l udes s a m p lin g s i tes s elec t ed bas ed on k now n ex is tin g pr oblem s , k now led g e of upc om in g events in the w ater s hed, ora s ur r oundin g ar ea that w ill adver s ely af f ec t the w ater body s uc h as developm ent ordef or es tation; or ins t allation of BMPs orhabitat r es t or ation that ar e intended to im pr ove w ater body quality ; pr ovides as s e s s m ents of individual s i tes or r eac hes

.

ov erall obj ectiv es and constraints. A ppendix A pr esents hy pothetical exam ples of sediment quality m onitoring desig n s g i v en different obj ectiv es or reg u latory applications. **2.3.1 P**  **robabilistic and R a**  **ndom S a**  **mpling** Probability-based or random sam p ling desig n s av oid bias in the results of sam p ling by randomly assig n ing and selecting sam p ling locations. Apr obability desig n requires that all sam p ling units hav e a k now n probability of being selected. B o th E P A ’ s E n v i ronmental Monitoring A ssessment Prog ram and NOAA’ s National Status and T r ends Prog ram use a probabilistic sam p ling desig n to infer reg i onal and national patterns w ith respectto contamination or biolog ical effects. Sites can be selected on the basis of a truly random scheme or in a sy stem atic way (e.g ., sam p le ev ery 10 meters along a randomly chosen transect). I n sim p le random sam p ling , all sam p ling units hav e an equal probability of selection. T h is desig n is appropriate for estim ating means and totals of env i ronmental v ariables if the population is hom og eneous. T o apply sim p le random sam p ling , it is necessary to identify all potential sam p ling times orlocations, then randomly select indiv i dual times or locations for sam p ling
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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses In grid or system atic sam p ling , the first sam p ling location is chosen randomly and all subsequent stations are placed at reg u lar interv als (e.g . 50m apart) throug hout the st udy area. Clearly , the num ber of sam p ling locations could be larg e if the study area is larg e and one desires “fine- g r ained” contaminant or toxicolog i cal inform ation. T hus, depending on the ty pes of analy s es desired, such sam p ling mi g h t become expensiv e unless the study area is relativ ely sm all and/or the density of stations (that is how closely spaced are the sta tions) is relativ ely low
. G r id sam p ling mi g h t be effectiv e for detecting prev iously unknow n “hot spots” in a limited study area.

**F i**  **g u**  **r e 2-**  **3.** Des c r iption of var i ous s a m p lin g m ethods

. Adapted f r om USEPA, 2000c

. In stratified designs , the selection probabilities mi g h t differ am ong strata. Stratified random sam p ling consists of div i ding the targ et populati on into non- ov erlapping part s or subreg ions (e.g ., ecoreg i ons, watersheds, or specific dredg i ng or reme diation sites) termed strata to obtain a better estim ate of the mean or total for the entire popul ation. T h e inform ation required to delineate the strata and estim ate sam p ling frequency m u st either be k nown prior to sam p ling using historic data, av ailable inform ation and k nowledg e of ecolog i cal function, or obtained in a pilot study
. Sam p ling locations are randomly selected from w ithin each of the strata. Stratified random sam p ling is often used in sediment quality m onitoring because certain env i ronmental v ariables can v ary by time of day , season, hy drody nami cs, or other factors. Maj o r env i ronmental m onitoring prog ram s that incorporate a stratified random desig n include EPA’s Mid- A tlantic I n teg r ated Assessment (MAI A). One disadv antag e of using random desig n s is the possi bility of encountering unsam pleable sites that w e re randomly selected by the com puter. Such problem s result in the need to reposition the v essel to an alternate location. Furtherm ore, if one is sam p ling to determine the percent spatial extent of

2-8 U S Environm ental Protection AgencyTechnical M anual deg r adation, it mi g h t be im portant to sam p le bey ond the boundaries of the study area to better ev aluate the limits of the im pacted area. Arelated desig n is m u ltistage sam p ling in w h ich larg e subareas w ithin the study area are first selected (usually on the basis of professional knowledg e or prev iously collected inform ation). Stations are then randomly located w ithin each suba rea to y i eld av erag e or pooled estim ates of the v ariables of interest (e.g ., concentration of a particular contaminant or acute toxicity to H y alella ) for each subarea. T h is ty pe of sam p ling is especially useful for statistically com p aring v ariables am ong specific parts of a study area. **T ab**  **l e 2-**  **1.** Su gg es tions f o rs e lec t in g an appr opr iate s a m p lin g des i g n ( f r o m USEPA 2000b)

. I f

y o u ar e . . . and y o u have . . . c o ns i d e r u s in g... ino r d e rto ... pe r f or mi ng as c r e e n ing pha s e of a n inv e stig ation a nd w ith a n unde r s ta nding of ar e lativ e l y sm al l

- scal e p r o b l em a limite d budg e ta nd/ora limite d s c he dule judg me nta l or t arget ed sa m p ling a sse ss w h e the r f u rthe r inv e stig ation is w arr a nte d thats hould inc l ude a statistic a l probabilistic sa m p ling de s i g n. de v e loping a n unde r s ta nding of w h en co n t ami n at i o n i s p r esen t a d e quate budg e tf o r

the num be r of

s a m p le s ne e d e d sy stem atic sa m p ling ha v e c o v e r a g e of the time pe r i ods of inte re st. de v e loping a n unde r s ta nding of w h ere co n t ami n at i o n i s p r esen t a d e quate budg e tf o r

the num be r of

s a m p le s ne e d e d gri d sam p l i n g h ave co verage o f th e area o f co n cern a nd ha v e ag i v e n le v e l of c onf ide n c e thaty ou w ould ha v e de te c t e d a hot s pot of ag i v e n s i z e . e s tim ating a population me a n a d e quate budg e t budg e tc ons tr a i nts a n d an al y t i cal co st s th atare h i gh co m p ared t o sam p l i n g co st s budg e tc ons tr a i nts a n d pr of e s s i ona l know le dg e or i n exp en s i v e screen i n g measu r emen t th atcan assess the r e lativ e a m ounts of the co n t ami n an tatsp eci f i c f i el d sa m p le loc ations sy stem atic o r g r id sa m p ling
c o m positing

ran k ed set sa m p ling a l s o pr oduc e inf o r m ation on s p atia l or te m por a l patte r n s . pr oduc e a n e qua llypr e c i s e oram o r e p r eci se est i m at e o f th e mean w i th f e w e r an al y ses an d l o w e r co st . red u ce th e n u m b e r o f an al y s es n eed ed f o rag i v e n le v e l of pr e c i s i on.

e s tim ating a population me a n or pr opor tion spatia l or te m pora l inf o r m ation on c onta mina n t patte rns stratif ie d sa m p ling i n crease th e p r eci si o n o f th e est i m at e w ith the s a me num be r of

s a m p le s , or ach i eve th e same p r eci si o n w i th f ew er sa m p le s a nd low e r c o st. de line ating the boundar i e s of a n area o f co n t ami n at i o n af i e l d sc re e n ing me thod stratif ie d sa m p ling sim u lta ne ouslyuse s a ll obse r v ations in e s tim ating the me a n . est i m at i n g th e p r eval en ce o f a rare trait an al y t i cal co st s th atare h i gh co m p ared t o sam p l i n g co st s r a ndom a n d c o m pos ite sa m p ling pr oduc e a n e qua llypr e c i s e orm o r e p r eci se est i m at e o f th e p r eval en ce w i th f e w e r an al y ses an d l o w e r co st . a s s e s s i ng w h e the ra population co n t ai n s a rare tr ai t the ab ilityto phy sic a llymi x a liquots f r om the s a m p le s a nd the n r e te s ta dditiona l a liquots c o m pos ite sa m p ling a n d re te sting cl assi f yal l sam p l e s atred u ced co st b y n o tan al y zi n g everysam p l e.

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## R **eco mmen**  **d a**  **tio n**  **B o**  **x #1 What type of sampling st**  **rategy should be used?**

� His t or ic al data, if available, s hould be c ons ider ed w hen s e lec t in g s a m p lin g s t ations

. � Loc ation of s edim ent depos itional z ones c an be im por tant in def inin g s ubar eas f or s a m p lin g o rf o r st ra t i f y i n g s a m p lin g in s om e pr o g ra m s . � If the obj ec tive of the s ur v ey is to identif y ar eas of tox i c and/orc ontam inated s edim ents on a quantitative s patial and/ortem por al bas is ( e. g ., s uper f und s i te) , a s y s t em atic orr e g ular g r i d- s a m p lin g s tr a te g y m i g ht be m os t appr opr iate ( U SEPA, 2000b)

. � If the m onitor i n g obj ec tive is to deter m i ne s edim ent c ontam ination or i g inatin g fr o m a s pec if ic s our c e ortr ibutar y , a tar g eted s i te loc ation des i g n m i g ht be m os t appr opr iate. Fa ct o r s a f f e ct i n g dis per s i on of s ubs tanc es orm ater i als f r om the point s our c e ( e. g ., c ur r ents ) s hould be c ons ider ed. � Str a tif i ed r andom s a m p lin g s hould be us ed w her e his t or ic al, s edim ent- m appin g data ar e available and ther e ar e w e ll- def ined z ones of dif f er ent s edim ent ty pes oradj ac ent land us es ( B ur ton, 1991)

. T his des i g n is c om m only us ed in NO AA National Status and T r ends (NS & T ) m o n i t o ri n g of s edim ent quality to ens ur e that the data c an be attr ibuted to the s t r ata in w hic h they w er e c ollec t ed ( Lon g et al., 1996)

. � F ordr ed g e m ana g em ent pr o g r a ms , mu l t i - s t a g e, s t r atif i ed- r andom , oreven tar g eted s a m p lin g is of ten appr opr iate, s i nc e the need is to r epr es ent s pec if ic ar eas to be dr ed g ed and dis pos ed. � F orw ater s hed orr e g ional as s es s m ent pr o g r a m s , a pr obabilis tic s a m p lin g des i g n m i g ht be m os t appr opr iate. � Sm all- s c a le, tar g eted s t udy des i g ns m i g ht r equir e m any s a m p les w i thin a s m all ar ea if f i ne s patial r e s o lution is needed ( e . g ., Super f und)

.
Use of random sam p ling desig n s mi g h t also mi ss relati onships am ong v ariables, especially if there is a relationship between an explanatory and a response v ariable. As an exam ple, estim ation of benthic response or contaminant concentration, in relation to a discharg e or landfill leachate stream , requires sam p ling targ eted around the potential contaminant s ource, including stations presum ably unaffected by the source (e.g ., Warwick and Cl arke , 1991). A sim p le random selec tion of stations is not likely to capture the entire rang e needed because m o st st ations w ould likely be relativ ely rem o v e d from the location of interest. **2. 3.**  **2 T**  **arget ed Sampl**  **i ng Desi**  **gns** In targeted ( also referred to as ju dgm en tal , or m odel-based) desig n s, stations are selected based on prior k nowledg e of other factors, such as contaminant loading , depth, salinity , and substrate ty pe. T h e sediment studies conducted in the Clark Fork Riv e r (Pascoe and DalSog lio, 1994; Brum baug h et al., 1994), in which contaminated areas were a focus, used a targ eted sam p ling desig n. T arg eted desig n s are useful if the obj ectiv e of th e inv e stig ation is to screen an area(s) for the presence or absence of contamination at lev els of concern, such as risk

- b ased screening lev els or toxicity , or to com p are specific se diments ag ainst reference conditions or biolog ical g u idelines. I n g e neral, targ eted sam p ling is appropriate for situa tions in which any of the following apply (USEPA, 2000b): 2-10 U S Environm ental Protection AgencyTechnical M anual

• T he site boundaries are well defined or the site phy sically distinct (e .g ., superfund or CERCLA site, proposed dredg i ng unit).
• S m a ll num bers of sam p les w ill be selected for analy sis/characteriz ation.
• I nform a tion is desired for a particular condition (e.g ., “worst case”) or location.
• T here is reliable historical and phy sical know ledg e about the feature or condition under inv e stig ation.
• T he obj ectiv e of the inv estig ation is to screen an area(s) for the presence or absence of contamination at lev els of concern, such as ri sk

- b ased screening lev els. (N ote that if such contamination is found, follow- up sam p ling is likely to inv o lv e one or m o re statistical desig n s to com p are specific sediments ag ainst reference cond itions, chemical or biol og ical g u idelines, or applicable sedime nt quality v a lues).
• S chedule or budg et limitations preclude the possi bility of im plementing a statistical desig n . • E xperimental testing of a k nown pollution g r adie nt to dev elop or v erify testing methods or m odels (i.e., as in ev aluations of toxicity tests, Long et al., 1990). B ecause targ eted sam p ling desig n s often can be qui ckly im plemented at a relativ ely low cost, this ty pe of sam p ling can often meet schedule a nd budg etary constraints that cannot be met by im plementing a statistical desig n. I n m a ny situ ations, targ eted sam p ling offers an additional im portant benefit of prov iding an appropriate le v e l- of- e ffort for meeting inv e stig ation obj ectiv es without excessiv e consum p tion of proj ect resources. Targ eted sam p ling , how ev er, limits the inferences m ade to the stations actually sam p led and analy z ed. Extrapolation from thos e stations to the ov erall population from which the stations were sam p led is subj ect to unknown selection bias. T h is bias mi g h t be unim portant for those reg u latory prog ram s in which inform ation is needed for a particular condition or location (e.g ., Dredg ed Manag ement Materials Prog ram or Superfund). 

### 2. **4 M**  **easurement Q u**  **al i**  **t y**  **O b**  **j ecti**  **v es**  As noted in Section 2.1, a key aspect of th e DQO process is specify ing measurement quality obj ectiv es (MQ O s): statements that describe the am ount, ty pe, and quality of data needed to address the ov erall proj ect obj ectiv es. Appendix B presents exam ples of MQOs and sam p ling desig n s that hav e been used in sev eral different prog ram s . Also included in Appendi x B is excerpted inform ation from Washing ton D epartment of Ecolog y ’ s Sam p ling and A n aly sis Plan G u idance (WD E , 1995). Similar to Q u ality Assurance Proj ect Plans (QAPP) mentioned earlier in Section 2.1, a Sam p ling and Analy s is Plan includes, am ong other thing s, m any of the elements of the D ata Q u ality O b j ectiv es P r ocess, including M QOs
. A key factor determining the ty pes of MQOs need ed in a g i v en proj ect or study is the ty pes of analy ses required because these w ill determine the am ount of sam p le required (see Section 2.4.1) and how sam p les are processed (see C h apter 4). The case exam ples presented in A ppendix B illustrate a v ariety of chemical, biol og ical, and toxicolog i cal analy s es that are often included in sediment quality m onitoring proj ects. Metals, org anic chemicals (including pesticides, PAHs, and PCBs), whole
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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses sediment toxicity , and org anism bioaccum u lati on of specific targ et chemicals, are frequently analy z ed in m any sediment m onitoring prog ram s . A num ber of other, m o re “conv entional” parameters, ar e also often analy z ed as w ell to help interpret chemical, biolog ical, and t oxicolog i cal data collected in a proj ect . T able 2- 2 summ ariz es m any of the comm only measured conv entional parameters and their uses in sedime nt quality studies (WD E , 1995). I tis im portant that conv entional parameters receiv e as m u ch careful attention, in term s of sam p ling and sam p le processing procedures, as do the contaminants or parameters of direct interest. T h e g u idance presented in Chapters 3 and 4 prov ides inform ation on proper sam p ling and sam p le processing procedures, respectiv ely , to ensure th at one has appropriate sam p les for these analy ses. T h is section concentrates on three aspects of MQ O dev elopment that are g enerally applicable to all sediment quality studies, reg ardless of the particul ar prog ram or obj ectiv es: sam p le v o lume, num ber of sam p les, and replication v s. com posite sam p ling
. 

## C **h ecklist**  **MQOs are defined in terms of the following attributes:** 

� **De te**  **c t**  **ion Limit** – T he low es t c onc entr ation of an analy t e that a s pec if ied analy t ic al pr oc edur e c an r eliably detec t. � **Bias** – T he dif f er enc e betw een an obs er ved value and the “ t r ue” value ( ork now n c onc entr ation) of the par am eterbein g m eas ur ed; bias is the f i r s t c om ponent of ac c ur ac y , w h ic h is the ability to obtain pr ec is ely a nonbias ed ( t r ue) value. � **Precisio n**  – T he level of a g r eem ent am on g m ultiple m eas ur em ents of the s am e c har ac ter i s t ic ; pr ec is ion is the s ec ond c om ponent of ac c ur ac y . � **Rep r**  **esen t**  **at i**  **v en**  **ess** – T he de g r ee to w hic h the data c ollec t ed ac c ur ately r epr es ent the population of inter es t ( e. g ., c ontam inant c onc entr ations )

. � **Comparabilit y** – T he s i m ilar i ty of data f r om dif f er ent s our c es inc l uded w i thin individual or m ultiple data s ets ; the s i m ilar i ty of analy t ic al m ethods and data f r om r elated pr oj ec ts ac r os s ar eas of c onc er n. � **Co mp**  **let e**  **n ess**  – T he quantity of data that is s uc c es s f ully c ollec t ed w i th r es pec t to the am ount intended in the ex per im ental des i g n.

**2. 4.**  **1 S**  **ampl e Vol**  **u me**  Before commencing a sam p ling prog ram , the ty pe and num ber of analy s es and tests should be determined, and the required v o lume of sediment per sam p le calculated. Each phy sicochemical and biolog ical test requires a specifi c am ount of sediment which, for ch emical analy s es, depends on the detection limits attainable and extraction efficien cy by the procedure and, for biolog ical testing , depends on the test org anism s and test method. T y pical sediment v o lume requirements for each end use are summ ariz ed in T able 2- 3. Specific prog ra m g u idance should be consulted reg arding sam p le v o lumes that mi g h t be required.

2-12 U S Environm ental Protection AgencyTechnical M anual **T ab**  **l e 2-**  **2.** Conventional s edim ent var i ables and theirus e in s edim ent inves t i g ations ( A dapted f r om W D E, 1995)

. Convent i onal Sedi m e ntVar i abl e Us e T o tal org anic carbon (T OC) • Norm aliz ation of the concentrations of nonioniz able org anic com pounds • I dentification of appropriate reference sediments for biolog ical tests A c id Volatile S u lfide (A VS ) • N o rm aliz ation of the concentrations of div a lent metals in anoxic sediments Sediment g r ain siz e • I dentification of appropriate reference sediments for biolog ical tests • I nterpretation of sedimenttoxicity test data and benthic m acroinv ertebrate abundance data • E v aluation of sediment transport and deposition • E v a luation of reme dial alternativ es T o tal solids • Expression of chemical concentrations on a dry

weig ht basis Amm onia • I n terpretation of sedime nt toxicity test data Total sulfides • I nterpretation of sedime nt toxicity test data
When determining the sam p le v o lumes necessary , one m u st k now what is required for all of the sam p le analy ses (considering adequate replicati on) and it is also helpful to k now the g eneral characteristics of the sedime nts being sam p led. F o r ex am ple, if interstitial w a ter analy ses or elutriate tests are to be conducted, the percent w ater (or per cent dry w e ig ht) of the sedime nt w ill g r eatly affect the am ount of w ater extracted. Many non- com p act ed, depositional sedime nts hav e interstitial w a ter contents rang ing from 30 to 70%. H o w ev er, inte rstitial w a ters are v e ry difficult to rem o v e from sandy or g r av el- r ich sediments. For benthic m acroinv ertebrate bioassessment anal y ses, sam p ling a prescribed area of benthic substrate is at least as im portant as sam p ling a g i v en v o lume of sediment. I n m any prog ram s , m acroinv ertebrates are sam p led using m u ltiple g r ab sam p les w ithin a g i v e n station location, ty pically to a standard sediment depth (e.g ., per 10- 20 cm of sediment; K l emm et al., 1990; GLNPO, 1994; Long et al., 1996; U S EPA 2000c ). More than 6 liters of sediment from each station mi g h t be necessary in order to hav e adequate num bers of org anism s for analy ses, especially in m any lakes, estuaries, and larg e riv ers (Barbouret al., 1999). Howev e r, this is v ery site specific and should be determined by the field sam p ling crew. T h is onl y applies to whole sediment sam p ling methods and not to surficial stream methods us ing methods such as ki ck

- n ets and Surber sam p lers. I f the sediment quality triad approach is used (i.e., biolog i cal, toxicolog i cal, and phy sicochemical analy ses performed on sam p les from the same sites), m o re than 10 liters of sediment from each site mi g h t be required depending on the specific analy s es conducted. NOAA routinely collects 7- 8 liters of sedime nt at each station for m u ltiple toxicity tests and chemical anal y s es (Long et al., 1996).

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**T ab**  **l e 2-**  **3.** T y pic a l s edim ent volum e r equir e m ents f o rvar i ous analy s es pers a m p le Sedi m e ntAnal ysi s Mi ni m u m Sam p l e Vol u m e I norg anic chemicals 90 m L Non- petroleum org anic chemicals 230 m L O t her chemical parame ters (e.g ., total org anic carbon, m o isture content) 300 m L Particle siz e 230 m L Petroleum hy drocarbons 1 250- 1000 m L Acute and chronic whole se dime nt toxicity tests 2 1- 2 L B i oaccum u lation tests 3 15 L Benthic m acroinv ertebrate assessments 8- 16 L P o re w a ter extraction 2 L Elutriate preparation 1 L 1 T h e m axim u m v o lume (1000 m L ) is required only for oil and g r ease analy sis; otherwise, 250 m

Lis sufficient. 2 Am ount needed per whole sedime nttest (i.e., one species) assumi ng 8 replicates per sam p le and test v o lume s specified in USEPA, 2000d 3 Based on an av erag e of 3 L of sedime nt per test cham ber and 5 replicates (USEPA, 2000d).



## R **eco mmen**  **d a**  **tio n**  **B o**  **x #2 How many samples and how much sample volume should be**  **collect ed?** 

� T he tes t in g labor ator y s hould be c ons ulted to c onf ir m the am ount of s edim ent r equir ed f o rall des ir ed analy s es . � T he am ount of s edim ent needed f r om a g iven s i te w ill depend on the num berand ty pes of analy s es to be per f or m ed. If biolo g ic al, tox i c o lo g ic al, and c hem ic al analy s es ar e r equir ed ( s edim ent tr iad appr oac h) , then at leas t 10 liter s of s edim ent m i g ht be r equir ed f r om eac h s t ation. � Sinc e s a m p lin g events m i g ht be ex pens ive and/ordif f i c ult to r eplic ate, it is us ef ul to c ollec t ex tr a s am ples if pos s i ble, in the event of pr oblem s enc ounter ed by the analy t ic al labor ator ies , f ailur e of per f or m anc e c r iter ia in as s ay s , orneed to ver i f y /validate r es ults

. � Cons iderc om pos itin g sa m p l e s f r o m a g iven s t ation orac r os s s i m ilars t ation ty pes to r educ e the num berof s am ples needed.

2-14 U S Environm ental Protection AgencyTechnical M anual **2. 4.**  **2 N**  **umber of Sampl**  **e s**  T h e num ber of sam p les collected directly affects the representativ eness and com p leteness of the data for purposes of addre ssing proj ect g o als. As a g eneral rule, a g r eater num ber of sam p les will y i eld better definition of the areal extent of contamination or toxicity
. Many prog ram s specify a certain num ber of sam p les per location (e.g ., CERCLA site or dredg i ng unit). According l y , sam p le requirements should be determined on a case- by

- case basis. T h e num ber of sam p les to be collected w ill ultim ately be an outcome of the questions asked. For exam ple, if one is interested in characteriz ing effects of a point source or a g r adient(e.g ., effects of certain tributaries or land uses on a lake or estuary ) , then m a ny sam p les in a relativ ely sm all area mi g h t need to be collected and analy z ed. I f, how ev er, 

### Considerations **The appropriate number of samples is usually**  **determined by...** ! s i z e of the s tudy s i te ! t y pe and dis t r i bution of the c ontam inants bein g m eas ur ed ! c har ac ter i s t ic s and hom o g eneity of the s edim ent ! c onc entr ations of c ontam inants lik ely to be f ound in the s edim ents ! s am ple volum e r equir e m ents ! des ir ed level of s t atis tic a l r e s o lution or pr ec is ion one is interested in screening “hot spots” or lo cations of hig h contamination within a watershed or w ater body , relativ ely few sam p les at reg u larly

- spaced locations mi g h t be appropriate. I n m o st m onitoring and assessment studies, the num ber of sam p les to be collected usually results from a com p romi se betw een the ideal and the practical. T h e m a j o r practical constraints are the costs of analy ses and log i stics of sam p le collection. T h e m aj o r costs associated w ith the collection of sedi me nt sam p les are those for trav el to the site and for sam p le analy sis. T h e costs of actual on- site sam p ling are mi nim al by com p arison. Consequently , it is g ood practice to collect an excess num ber of sam p les, and a subset equal to the mi nim u m num ber required is selected for analy sis. T h e arch iv ed replicate sam p les can be used to replace lost sam p les, for data v erification, to rerun analy ses y i elding questionable results, or for the independent testing of a posteriori hy potheses that mi g h t arise from screening the initial data. H o w e v e r, storag e of sedime nts mi g h t result in chang e s in bioav a ilability of chemical contaminants (see Section 4.5). T h erefore, follow- up testing of archiv ed sam p les should be done cautiously
. **2. 4.**  **3 R**  **epl i**  **cat e and Composi**  **t e Sampl**  **es** R e plicate Sa m p les A s mentioned in the prev ious section, the num ber of sam p les collected and analy z ed w ill alw ay s be a com p romi se betw een the desire of obtaining hig h quality data that fully addresses the ov erall proj ect obj ectiv es (MQOs) and the constraints im posed by analy tical costs, sam p ling effort, and study log i stics. T h erefore, ev ery sam p ling prog ram need s to find a balance between obtaining inform ation t o sat i s f y t he st at ed DQOs orstudy g o al s i n a cost
- e f f ect i v e m a nner , and y e thav e enoug h conf i d ence i n t he dat at o m ake appr opr i a t e deci si ons ( e .g ., r e me di at i on, dr edg i ng ; St ep 3 i n t he DQO pr ocess, Fig u re 2- 2). T w o different concepts are used to satisfy this challeng e: replication and sam p le com positing
. Replication is used to assess precision of a partic ular measure and can take m any form s depending on the ty pe of precision desired. For m o st prog ram s , analy tical replicates are the m o st frequently used form of replication because m o st MQ O s are concer ned w ith analy tical data quality (see exam ples in
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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Appendix B). T h e extent of anal y tical replication (duplicates) v a ries with the prog ram or study DQOs. Per f or mi ng dupl i cat e anal y s es on atl east10% of t h e sam p l e s col l ect ed i s consi d er ed satisfactory for m o st prog ram s (GLNPO, 1994; USEPA/ACOE, 1991; PSE P, 1997a; USEPA/ACOE, 1998). An MQO of 

### � 20 - 30% relativ e percent difference (R PD ) is comm only used for analy tical replicates depending on the analy t e. Field replicates can prov ide useful inform ation on the spatial distribution of contaminants at a station and the heterog e neity of sedime nt quality w ithin a site. Furtherm ore, field replicates prov ide true replication at a station (analy tical replicates and split sam p les at a station prov ide a measure of precision for a g i v en sam p le, not the station) and therefore can be used to statistically com p are analy ses (e.g ., toxicity , tissue concentration, whole sediment concentration) across stations. R e sults of field replicate analy sis y i eld the ov erall v ariability or precision of both the field and laboratory operations (as w e ll as the v ariability betw een the replicate sam p les them selv es, apart from any procedural error). B ecause field replicate analy ses integ r ate a num ber of different sources of v ariability , they mi g h t be difficult to interpret. A s a result, failure to meet a precision MQO 

## C **h ecklist**  **R**

**e**

**plicat ion can t**  **ake several forms**  **a nd s**  **a**

**t**

**is**

**fy diffe**  **re nt**  **purposes:** � Collec t f i eld r eplic ate s a m p les at a s t ation if ther e is a need to s t atis tic a lly c o m par e re su l t s a m o n g s t ations w i thin a s i te. � Analy t ic al r eplic ates : s epar ate labor ator y analy s es on s ubs am ples f r om the s am e f i eld s a m p le. � F i eld r eplic ates : s epar ate s a m p les c o llec t ed at a s t ation eac h of w hic h is analy z ed individually

. � F i eld- s p lit r eplic ates : a s i n g le f i eld s a m p le is s plit into s ubs am ples , eac h of w hic h is then analy z ed individually

. � C o m pos itin g s am ples is one w ay to r educ e the num berof r eplic ates needed f or analy s is

. for field replicates mi g h t or mi g h t not be a cause of concern in term s of the ov erall study obj ectiv es but would sug g est some uncertainty in the data. Many m onitoring prog ram s perform field replicates at 10% of the stations sam p led in the study as a quality control procedure. A n MQ O of 

### � 30 - 50% relativ e percent difference (R P D ) is ty pically used for field replicates depending on the analy t e (see exam ples in Appendix B). Many reg u latory prog ram s (e.g ., Dredg ed Disposal Manag ement within the Pug et Sound Estuary Prog ram ) routinely use 3- 5 field replicates pe r station. Appendix C summ ariz e s statistical considerations in determin ing the appropriate num ber of replicate sam p les g i v e n different sam p ling obj ectiv es. Split sam p le replication is less comm only performed in the field because m any prog ram s find it m o re useful to quantify data precision th roug h the use of analy tical and fi eld replicates described abov e. H o w e v e r, split sam p le replication is frequently used in the laboratory in toxicity and bioaccum u lation analy s es (USEPA, 2000d) and to v e rify hom og eneity of test m a terial in spiked sedime nt tests (see Section 5.3). I n the field, sam p les are comm only split for different ty pes of analy ses (e.g ., toxicity , chemistry , benthos) rather than to replicate a g i v en sam p le. This ty pe of sam p le splitting or subsam pling is further discussed in Section 4.2. C

o m posite Sa m p les A com posite sam p le is one that is formed by com b ining m aterial from m o re than one sam p le or subsam ple. Because a com posite sam p le is a co m b ination of indiv i dual aliquots, it represents an
2-16 U S Environm ental Protection AgencyTechnical M anual “av erag e” of the characteristics m ak i ng up the sam p le. C o m positing , therefore, results in a less detailed description of the v ariability w ithin the site as com p ared to taki ng field replicates at each station. Howev er, for characteriz ing a sing le station, com positing is g enerally considered an excellent w ay to prov ide quality data w ith relativ ely low uncertainty
. F u rtherm ore, m a ny prog ram s find it useful to av erag e the naturally heterog eneous phy sicochemical conditions that often exist w ithin a stati on (or dredg i ng unit, for exam ple), ev en w ithin a relativ ely sm all area (GLNPO, 1994; PSEP, 1997a; AST M , 2000a). Many prog ram s find it useful to com posite 3- 5 sam p les from a g i v en location or depth strata (PSEP, 1997a; GLNPO, 1994). 

## Cons **ide r**  **a t**  **ions C** 

**o**

**mposit e samples are**  **collect ed because**  **they...** ! Y ield a s i n g l e “a v e ra g e es tim ate f ora g iven s t ation w i th les s c o s t than us in g r eplic ates
. ! C an obtain us ef ul inf or m ation over m any s t ations at r educ ed analy t ic al co st s. ! A r e an ef f i c i ent w ay to pr ovide s uf f i c i ent s a m p le volum e f o rm u ltiple ty pes of analy s es , par tic u lar l y biolo g ic al/tox i c i ty analy s es . C o m positing is also a practical w a y to control an aly tical costs w h ile prov iding inform ation from a larg e num ber of stations. F o r exam ple, w ith relativ ely little m o re sam p ling effort, fiv e analy ses can be performed to characteriz e a proj ect seg ment or site by collecting 15 sam p les and com b ining sets of three into fiv e com posite sam p les. T h e increased cov erag e afforded by taki ng com posite sam p les mi g h t j u stify the increased time and cost of collecting the extra 10 sam p les in this case (U SEPA/A C O E, 1998). C o m positing is also an im portant w ay to prov ide the larg e sam p le v o lumes required for some biolog ical tests (see Table 2- 1) and for m u ltiple ty pes of analy ses (e.g ., phy sical, chemical, toxicity , and benthos). H o w ev er, com positing is not recommended w h ere com b ining sam p les could serv e to “dilute” a hig h ly toxi c but localiz ed sediment “hot spot” (WDE, 1995; USEPA/ACOE, 1998). Also, sam ples from stations with v e ry differe nt g r ain siz e characteristics or different stratig raphic lay e rs of core sam p les should not be com posited (see Section 4.3). 

## C **h ecklist**  **Before sampling:**

� Reviewavailable inf o r m ation about the s i te inc l udin g phy s i c al c onditions and potential c ontam inant s our c es . � Ins pec t the s i te to c onf ir m that the s am plin g des i g n and pr oc edur e c hos en ar e f eas ible. � Per f or m a pilot ors c r eenin g s a m p lin g , if pos s i ble, to ens ur e that s am plin g equipm ent and pr oc edur es ar e adequate f orthe ty pes of s t ations s elec t ed.


### 2. **5 S**  **i t**  **e-Speci fi**  **c Consi d**  **erati ons for Sel**  **e cti**  **ng Sedi ment Sampl**  **i n**  **g St**  **at i**  **ons** S e v e ral site- s pecific factors mi g h t ultim ately influe nce the appropriate location of sam p ling stations, both for larg e- scale m onitoring studies, in w h ich g e neral sediment quality status is desired, and for

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sm aller, targ eted studies, in determining the need fo r sedime nt reme diation. I f a targ eted or stratified random sam p ling desig n is chosen, it mi g h t be im portant to locate sediment depositional and erosional areas to properly identify contaminant re g i mes. T able 2- 4 presents a summ ary of sitespecific factors that should be considered when dev e loping a sam p ling plan. A com p rehensiv e rev i ew of such considerations is pr ov ided by Mudroch and MacK nig h t (1994).
**T ab**  **l e 2-**  **4.** Pr ac tic a l c ons ider ations f o rs i te- s pec if ic s e lec t ion of s a m p lin g s t ations in developin g a s a m p lin g plan. Activ i ty Co nsidera tio n Determin ationof areas w h ere se d i me nt c o nt a m i n a t i o n m i ght o c c u r Hy d r o l o g ic in f o r m atio n • q u a lityan d q u an tityo f r u n o f f • p o ten tial d e p o s itio n a l in p u ts o f to tal su sp en d e d so lid s • u p - w e llin g s • s eepag e pattern s Deter min atio no f d e p o s itio n a l an d eros ion a l areas Bath y metri c m aps an d h y drog raph i c ch art s • w ater depth • z o n es o f er o s io n , tr an sp o r t, an d d e p o s itio n • b a th y me tr y • d istr ib u tio n , th ickn e ss, an d ty p e o f sed i me n t • v elocityan d directionof cu rren ts • s ed imen tatio nr a tes Clim atic co n d itio n s • p r e va i l i ng w i nd s • s eas on al ch an g es intem p eratu r e, precipitation , s o lar radiation , etc. • tid es, seich e s • s eas on al ch an g e s i nan th ropog en i c an d n a tu ral l o adi n g s Deter min atio no f p o t en tial so u r ces of

con t amin ation A n th ropog en i c con s i d erat i o n s lo catio no f u rb a ncen ter s • h isto r i cal ch an g e s inlan d u s e • t yp es, d e n s ities, an d size o f in d u str i es • l ocat i o nof w a s t e di s pos al s i t e s • l o catio no f sew a g e tr eatme n t f

acilities • l ocationof s t ormw ater ou tf alls an d com b in ed s e w e r ov erf l ow s • l o catio n , q u an tity , an d q u alityo f ef f l u e n t s • p r e vi o u s m o ni t o r i ng a n da sse ssme n t o rge o c he mi c a l sur v e y s • l ocat i o nof dredg i n g an d open

- w a t e r dredg e d m a t e ri al di s pos al sites • l o catio no f h i sto r ical w a ste sp ills Factors af f ectin g con t am in an t b io a v a ilab ility Geoch e mi cal con s ideration s • t y p e o f b e d r o c k an d so il/sed imen t ch emistr y • p h y s i cal an d ch em ical properties of ov erly in g w a ter Deter min atio no f r e p r esen tativ en ess of

s a m p l e s • area to be ch aracterized • v olu me to be ch aracterized • d epthto be ch aracterized • pos s i ble s tratif icationof th e depos it to be ch aracterized

2-18 U S Environm ental Protection AgencyTechnical M anual **2. 5.**  **1 R**  **ev i**  **ew A**  **v ai**  **l abl**  **e Dat a**  Rev i ew of av ailable historical and phy sical data is critical in the sam p le selection process and subsequent data interpretation. Local experts should be consulted to obtain inform ation on site conditions and the orig in, nature, and deg r ee of contamination. Other potential sources of inform ation include g o v ernment ag ency records, m unicipal archiv es, harbor commi ssion records, past g eochemi cal analy s es, hy drog raphic surv ey s, bathy metric m aps, and dred g i ng/disposal history
. Potential sources of contamination should be identif ied and their locations noted on a m ap or chart of the proposed study area. I tis im portant that r ecent hy drog raphic or bathy metric data be used in identify i ng representativ e sam p ling locations, especi ally for dredg i ng or other sediment rem o v al proj ects. T h e m ap or chart s hould also note adj acent land and w ate r uses (e.g ., fuel dock s , storm drains, etc.). T h e quality and ag e of the av ailable data should be critically w eig hed. **2. 5.**  **2 S**  **i t**  **e I n**  **spect i**  **o n**  A phy sical inspection of the site is strong ly reco mmended when dev eloping a study plan, in order to assess the com p leteness and v alidity of the collected historical data, and to identify any sig n ificant chang es that mi g h t hav e occurred at the site or study area (Mudroch a nd MacK nig h t, 1994). A site inspection of the immediate drai nag e area and upstream watershed mi g h t also identify potential stressors (such as erosion), and help determine appropriate sam p ling g ear (such as corer v s. g r ab sam p lers and boat ty pe) and sam p ling log i stics. I f

resources allow, it is useful to perform some sc reening or pilot sam p ling and analy ses at this stag e to further refine the actual sam p ling desig n needed. P ilot sam p ling is particularly helpful in defining appropriate station locations for targ eted sam p ling or to identify appropriate strata or subareas in stratified or m u ltistag e sam p ling , respectiv ely
. **2. 5.**  **3 I**  **dent i**  **f y**  **Sedi ment**  **Deposi t**  **i on and Erosi**  **onal Zones**  W h e n s t udy DQOs di r e c ts a m p l i n g t o t h e hi g h e s tc ont a mi n a t i on l e v e l s ors p e c i f i c s ubar e a s of as i t e , it mi g h t be im portant to consider sedime nt depositi on and sediment erosional z ones, since g r ain siz e and related phy sicochemical charact eristics (including conv entional parameters such as total org anic carbon and acid v o latile sulfide, as w ell as contamin ants), are likely to v ary betw een these tw o ty pes of z ones. Depositional z ones ty pically contain fine

- g rained sediment deposits which are targ eted in some sam p ling prog ram s because fine- g rained sedi ments tend to hav e hig h er org anic carbon content (and are therefore a m o re likely repository for polluta nts) relativ e to larg er sedime nt particle siz e fractions (e.g ., sand and g r av el) (AST M, 2000a; Env i ronment Canada, 1994). Howev e r, for some prog ram s such as remediation dredg i ng ev alua tions or superfund, eroding sedime nt beds and nondepositional z ones mi g h t be of m o st concern as th ese could be a m aj o r source of pollutants in the water column and in org a nism s (USEPA/ACOE, 1991,1998). V arious non- disruptiv e technolog ies are av ailable to a ssist in the location of fine- g rained sediments rang ing from sim p listic to m o re adv anced. F o r exam ple, use of a steel rod or PV C pipe can be used in m any shallow areas to quickly and easily probe the sediment surface to find coarse (sand, g r av el) v s. fine sediments (silt, clay ). This technique can not, how ev er, determine sediment g r ain siz e at depth. Other m o re adv ance methods, including ac oustic surv ey techniques (e.g ., low frequency echo sounding , seismi c reflections, etc.) and side- s can sona r used with a sub- bottom profiler (Wrig h t et al., 1987), can prov ide useful inform ati on on surficial as well as deepersediment profiles. Howev er, these techniques are often limited in their accuracy and hav e hig h equipment costs (G uig n è et al., 1991).

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses A erial reconnaissance, w ith or w ithout satellite im ag ery , mi g h t assist in v i sually identify i ng depositional z ones where clear water conditions exis t. T h ese methods are not reliable, howev er, if w aters are turbid. O t her methods that can be us ed to locate sediment deposition z ones include g r ab sam p ling , inspection by div ers, or photog raphy us ing an underwater telev i sion camera or rem o tely operated v e hicle (Burton, 1992; AST M , 2000a). 

### 2. **6 P**  **osi t**  **i oni**  **ng Met hods f**  **or Locat i**  **ng Sampl i**  **ng St at**  **i ons**  T h e m o st im portant function of pos itioning technolog y is to determine the location of the sam p ling station (e.g ., latitude and long itude), so that th e user can later re- sam ple to the same position (USEPA, 1987). K nowing the precise location of sam p ling stations is also im portant so that reg u lators can determine if the area(s) of inte rest hav e been sam p led. T h ere are a v ariety of nav i g ation and/or position- fixing sy stem s av ailabl e, including optical orline- of- site techniques, electronic positioning sy stem s, a nd satellite positioning sy stem s. G l obal P o sitioning S y stem (G P S ) is g enerally reg arded as the positioning technique of choice as it is accurate, readily av ailable, and often less expensiv e than m any other com p arably sophisticated sy stem s. Giv en the rem o v al of selectiv e av ailability of satellite data by the U
. S. military , G PS is now capable of hig h accuracy positioning (1- 10 m )
. T h e characteristics, adv antag es, and disadv antag es of a v ariety of positioning sy stem s are summ ariz e d in Appendix D.


## R **eco mmen**  **d a**  **tio n**  **B o**  **x #3 How should station posit**  **ioning be performed?**

� Dependin g on level of ac c ur ac y needed, r e g ularc a libr a tion of the pos itionin g s y s t em by at leas t tw o m ethods m i g ht be r equir ed to ens ur e ac c ur ac y . � F orm onitor i n g and as s es s m ent s t udies of lar g e ar eas ( e. g ., lar g e lak es orof f s hor e m ar i ne envir onm ents ) , w her e an ac c ur ac y of ±100 m ty pic ally is s uf f i c i ent, eitherthe Lon g Ran g e Navi g ation ( LO R AN) orG l obal Pos i tionin g S y st e m (GP S ) sy st e m i s r ec om m ended. � F ornear - s hor e ar eas , orar eas w her e the s am plin g s t ations ar e num er ous orloc ated r e lativ e ly c l os e to g ether , G PS ora m i c r ow ave s y s t em s hould be us ed if the r equir ed pos ition ac c ur ac y is les s than 10 m

. W her e vis i ble ors uitable and per m anent tar g ets ar e available, RADAR c an be us ed if the r equi r ed pos ition ac c ur ac y is betw een 10 and 100 m. � F ors m all w aterbodies and ur ban w ater f r onts , G PS is of ten c apable of g ivin g pr ec is e loc a tion inf o r m ation. Alter natively , vis ual an g ularm eas ur em ents ( e. g ., s ex tant) by an ex per ienc ed oper ator , a dis t anc e line, ortaut w i r e c ould als o pr ovide ac c ur ate and pr ec is e pos itionin g data.
Reg ardless of the ty pe of sy stem selected, calibrati on of the sy stem is recommended by using at least tw o of these methods to ensure accuracy particular ly for stations that w ill be reoccupied. A teach sam p ling station, a fathometer or meter wheel can be used to determine the sam p ling depth. T h is w ill ensure that the w a ter is the desired depth and the bottom is sufficiently horiz ontal for proper operation of sam p ling equipment. I d eally , it is best to print out a copy of the ship’s location from the G P S m onitor nav i g ation chart, as w ell as the latitude / long itude, so the sam p ling station can be placed in a spatial context.
2-20 U S Environm ental Protection AgencyTechnical M anual 

### 2. **7 P**  **reparat i**  **ons f o**  **r Fi el**  **d S**  **a mp**  **lin g**  Proper preparation for any field sam p ling study is an essential part of Q u ality A ssurance that ensures a successful proj ect outcome and adherence to the obj ectiv es specified in the Q u ality A ssurance P r oj ect Plan (QAPP). Chapter 7 further discusses related Q u ality A ssurance/Q u ality C ontrol procedures that should be used in sediment quality studies. P r ior to performing field w o rk , characteristics of the site and accessibility of the indiv i dual sam p ling stations should be ascertained. Pictures of sam p ling stations both before as well as during sam p ling are often useful to ensure that the correct stations were sam p led and to docum ent weather and water conditions during sam p ling
. Adequate reconnaissance of stations prior to sam p ling is also v aluable for preparing ag ainst potential sam p ling haz ards or unforeseen difficulties. Such a reconnaissance can also help determine the necessary time needed to perform the desired sam p ling (i.e., time to g et from one station to the next). 

## C **h ecklist**  **Logistical Considerations:**  � si t e d e scri p t i o n � s t udy s i te ac c es s i bility � adequate s a m p lin g platf or m � qualif ied per s onnel � s pec if ic r e s pons ibilities of f i eld c r ew � loc a tin g and m a intainin g s t ations � adequate tim e f o rs a m p lin g � adequate s pac e and equipm ent � co m m u n i ca t i o n sy st e m � ac c es s to tem por ar y f i eld s t or a g e � health, s af ety , and w as t e m ana g em ent � em er g enc y plans and equipm ent � num berof s am ples to be c ollec t ed � s a m p le holdin g tim es

T h e appropriate v essel or sam p ling platform is one of the m o st im portant considerations in preparing for field sam p ling
. T h e v essel m u st be appropriate for the water body ty pe, and should prov ide sufficient space and facilities to allow collection, an y on- board m anipulation, and storag e of sam p les. I ce chests or refrig e ration mi g h t be required for sa m p le storag e, depending on the time course of the operation. T h e v essel should prov ide space for stor ag e of decontamination m aterials, as w ell as clean sam p ling g ear and containers to av oid c ontamination risk s associated with norm al v essel operations. Space for personal safety equipment is also required. Additionally , the v essel should be equipped with suffi cient winch power and cable streng th to handle the w eig ht of the sam p ling equipment, taki ng into account the additional suction pressure associated with extraction of the sediments. Larg e sam p ling dev i ces ty pically weig h between 50 and 400 k g em pty , and w h en filled w ith w et sediment mi g h t w eig h from 125 to ov er 500 k g . Care should be taken in operating the v essel to mi nimi z e disturbances of the sediment to be sam p led as well as sam p ling equipment. T h is would in clude phy sical disturban ce throug h propellar action and chemical contamination from eng i nes or stack emissions. For exam pl e, Pag e et al. (1995) reported that they positioned the ships’ stern into the wind to prev ent stack g ases from blowing onto sam p ling equipment during deploy ment, recov ery , and subsam pling of sediments in P r ince William Sound, Alask a .

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses T h e sam p ling plan and proj ected time schedule should be posted for v i ew by all personnel. T h e names, addresses, and telephone num bers of all pa rticipants inv o lv ed with the preparation and execution of the sam p ling prog ram should be av ailable to all participants, and the duties and responsibilities of each participant clearly documented. T h e study superv isor should ensure that the appropriate personnel clearly understand their role and are capable of carry ing out their assig n ed responsibilities and duties. C onting ency planning should address the need for back up personnel in the ev ent of accident or illness. A v ariety of sam p ling and sam p le handling equipm ent and supplies are often needed in sediment m onitoring studies. Besides the actual sam p lers them selv es (e.g ., g r ab or core dev i ce to be used), equipment is needed to rem o v e and process the sa m p les such as spatulas, scoops, pans or buckets, and g l ov es. I f it is im portant to m aintain anoxic conditions of the sam p le, a g l ov ebox and inert g as source (e.g ., nitrog en) is needed. Sam p le storag e and transport equipment and supplies need to be av ailable as well. T h ese include refrig eration, i ce chests, dry ice or ice, insulation m aterial to stabiliz e sam p les in transport, cust ody seals, and shipping airbills. T h e reag ents for cleaning , operating or calibrating equipment, and/or for collecting , preserv i ng or processing sam p les should be handled by appropr iately qualified personnel and the appropriate data for health and safety (e.g ., Material Safety D a ta Sheets) should be av ailable. Written approv ed protocols and standard operating procedures (i ncluding QA/QC requireme nts) should be readily accessible at all times, to ensure proper and safe operation of equipment. D ata form s and log book s should be prepared in adv a nce so that field notes and data can be quickly and efficiently recorded. Extra form s should be av ailable in the ev ent of a mi shap or loss. T h ese form s and book s should be waterproof and tear resistant. Under certain ci rcum stances audio or audio/v i deo recording s mi g h t prov e v aluable. All equipment used to collect and handle sam p les m u st be cleaned and all parts examined to ensure proper functioning before g o ing into the field. A repair k it should accom p any each m aj o r piece of equipment in case of equipment failure or loss of rem o v able parts. Back up equipment and sam p ling g ear should be av ailable. 

## C **h ecklist**  **Equipment and/or reagent**  **s needed:** 

� s a m p lin g equipm ent and s par e par ts � s a m p le handlin g equipm ent � s pec ial s a m p le handlin g equipm ent ( e. g ., g lovebox ors hielded c om par tm ent)

. � dec ontam ination and c l eanin g equipm ent � f i eld m eas ur em ent equipm ent and s upplies � sa m p l e st o r a g e s upplies / equipm ent � s am ple tr ans por t s upplies � per s onnel s upplies � m aps , navi g ation, and c om m unic ation equipm ent

2-22 U S Environm ental Protection AgencyTechnical M anual Storag e, transport, and sam p le c ontainers, including extra containers should be av ailable in the ev ent of loss or break ag e (see Section 4.2 for m o re in form ation on appropriate containers). T h ese containers should be pre- cleaned a nd labeled appropriately (i.e., with a waterproof adhesiv e label to w h ich the appropriate data can be added, using an indelible ink pen capable of w r iting on w et surfaces). T h e containers m u st hav e lids that are fastened securely , and if the sam p les are collected for leg al purposes, they should be transported to and from the field in a locked container with custody seals secured on the lids. S am p les to be froz e n before analy ses m u st not be filled to the lids. Leav e a 10% headspace to accomm odate expansion during freez ing
. Whether for leg al purposes or not, all sam p les should be accom p anied by a chain- of

- custody form that documents field sam p les to be submitted for analy ses (see C h apter 7). T r ans port supplies also include shipping airbills and addresses. A sam p le- i nv entory log and a sam p le- tracking log should be prepared in adv ance of sam p ling
. A sing le person should be responsible for these log s w ho w ill track the sam p les from the time they are collected until they are analy z ed and disposed of or archiv ed. 

### 2. **8 H**  **eal t**  **h and Saf et**  **y** Collection and processing of sedi me nts for analy ses and testing mi g h t inv o lv e substantial risk s to personal safety and health; particularly in situ ations inv o lv ing potentially haz ardous m a terials or challeng ing sam p ling conditions. I f a Q u ality A ssurance P r oj ect P l an (Q A P P ) or a S am p ling and Analy s is Plan (SAP) is prepared prior to sam p lin g , it should include or reference health and safety procedures. A health and safety field officer shoul d be appointed to ensure that personnel use safety precautions and equipment applicable to the opera tion of the v essel, the sam p ling equipment, and sam p le handling
. Personnel collecting or handling sediment sam p les should not work alone, and they should take all safety precautions necessary for the prev ention of bodily inj u ry and illness w h ich mi g h t result from sam p ling activ ities (e.g ., boat safety ), ing estion or inv asion of infectious ag ents, inhalation or absorption of corrosi v e or toxic substances throug h skin contact, or asphy xiation. Because sediment collection often occurs w ithout com p lete know ledg e of the source or deg r ee of haz ard, contact with sediment s hould to be mi nimi z ed by : (1) using g l ov es, laboratory coats, safety g l asses, face shields and respirators, as appropr iate, and (2) m anipulating sediments in open air, under a v entilated hood, or in an enclosed g l ov e box. U S EPA(1986a), Walters and J a me son (1984), and the Occupational Health and Safety Admi nistration (OSHA) standards prov ide g u idance on safe sediment handling
. Prog ram specific g u idance s hould be consulted first when av ailable (e.g ., Washing ton Department of Ecolog y ’ s Sam p ling and Analy s is Plan Guidance [WDE, 1995] or Pug e t Sound Estuaries Prog ram [PSEP, 1997a]). Othe r references (e.g ., AST M , 2000b; Waters, 1980) should also be consulted concerning special safe ty procedures for sam p ling and handling sam p les f r o m haz ar dous wast e si t e s. T h e NOAA Di v i ng Manual ( NOAA, 1991) ort h e EPA Di v i ng Saf e t y Manual (USEPA, 1997b) should be consulted for info rm ation reg arding div i ng safety plans and protocols.

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## R **eco mmen**  **d a**  **tio n**  **B o**  **x #4 W**  **h**

**at health and safety pr ecautions should be followed?** 

� F ollowCoas t G uar d appr oved s af ety pr oc edur es , inc l udin g us e of lif e ves t s . � All s a m p les m u s t be handled in a m annerthat s a tis f ies the Q uality As s u r anc e Pr oj ec t Plan, Standar d O per atin g Pr oc edur es , and DQ O s . � Sk in c ontac t w i th s edim ent s hould be m i nim i z ed to avoid potential c ontac t w i th haz ar dous s ubs tanc es . Pr otec tive c l othin g and equipm ent ( e. g ., g loves , boots , lab c oats orapr ons , s af ety g las s es , and r es pir ator ) ar e r ec om m ended dur in g s a m p lin g , s a m p le handlin g , and pr epar ation of tes t s ubs tanc es ors edim ents
. � Handlin g of s a m p les s hould be per f o r m ed in a w e ll- ventilated ar ea ( e . g ., outs i de, in a f um e hood, orin an enc los ed g love box ) to m i nim i z e the inhalation of s edim ent g as es s uc h as hy dr o g en s u lf ide if pr es ent. � A s p ill c ontr o l pr otoc ol s hould be in plac e in the s a m p lin g ves s e l and labor ator y . � Dis pos al of all haz ar dous w as t e s hould be in ac c or danc e w i th applic able law s , g uidelines , and r e g ulations

. � Pr ovide pr oc edur es r e g ar din g haz ar d as s es s m ent ( c hem ic al and phy s i c al haz ar ds )

. � Pr ovide pr oc edur es r e g ar din g dec ontam ination. � Meet the tr ainin g and m edic a l m onitor i n g r equir em ents
. � Pr ovide em er g enc y plannin g and em er g enc y c ontac ts
.

2-24 U S Environm ental Protection AgencyTechnical M anual 

## Collection of Whole Sediments **CHA PT**  **ER** 

# 3

Most sediment collection dev i ces are desig n ed to is olate and consistently retriev e a specified v o lume and surface area of sediment, from a required dept h below the sediment surface, w ith mi nim al disruption of the integ r ity of the sam p le and no contamination of the sam p le. Main tain ing th e in tegrity of the collected sediment, for the purposes of the measurements intended, is a prim ary concern in m o st studies becau se disruption of the sediment ’s structure could chang e its phy sicochemical and biolog ical characteristics, thereby infl uencing the bioav a ilability of contaminants and the potential toxicity of the sedi ment. T h is chapter discusses the factors to be considered in selecting a sediment collection de v i ce. A v ariety of sam p lers are described (and pictured in Appendix E), and recommendations are m ade reg arding their use in different situations. T h e flowchart in Fig u re 3- 1 shows recommended sam p ling g ear based on m onitoring obj ectiv e or site- s pecific issues of concern. Fig u res 3- 2 a nd 3- 3 prov ide recommended g r ab and core sam p lers, respectiv ely , based on site factors (such as depth and particle siz e), and sam p ling requirements (such as sam p le depth and v o lume of sam p le needed). 

### 3. **1 G**  **eneral Procedures**  T h e planned m ode of access to the sam p ling area (e.g ., by water, ov er land or ice, or from the air) play s an im portant role in the selection of sam p ling g ear. I f the sam p ling g ear needs to be transported to a rem o te area or shipped by air, its weig ht and **F i**  **g u**  **r e 3-**  **1.** G ener al ty pes of c ons ider ations orobj ec tives that v o lume mi g h t need to be taken ar e appr opr iate f or g r ab orc o r e s a m p lin g devic es . into account. I tis often the case that a specific v essel, hav i ng a fixed lifting capacity based on the config uration of its winch, crane, boom , A- frame , or other support equipment, is the only one av ailable for use. This w ill affect the ty pe of sam p ling equipment that can be safely operated from that v essel. Many sam p lers are capable of recov ering a re lativ ely undisturbed sam p le in soft, fine- g rained sedime nts, but few e r are suitable for sam p ling hard er sediments containing sig n ificant quantities of sand, g r av el, firm clay , or till (Mudroch and A z cue, 1995). O n e of the m o st im portant factors in determining the appropriate sam p ling dev i ce for the study are D a ta Qu ality Ob jectives
. Many m onitoring prog ram s , such as EPA’s Env i ronm ental Monitoring and A ssessment Prog ram (EMA P) and t h e NOAA Nat i onal St at us and T r ends pr og r a m , ar e pr i m ar i l y i nt e r e st ed i n char act er i z i ng r ecent env i ronmental im pacts in lakes, estuaries and coas tal w a ters and therefore sam p le surface sedime nts

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**F i**  **g u**  **r e 3-**  **2.** F l ow c har t f ors elec t in g appr opr iate g r ab s am pler s bas ed on s i te- s pec if ic ordes i g n f ac t or s

3-2 U S Environm ental Protection AgencyTechnical M anual

**F i**  **g u**  **r e 3-**  **3.** F l ow c har t f ors elec t in g appr opr iate c or e s am pler s bas ed on s i te- s pec if ic f ac t or s

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## Cons **ide r**  **a t**  **ions Although there is no**  **one sampler t h** 

**at sat**  **isf i**  **es all possible considerations, the**  **ideal sampler...** ! a voids a pr es s u r e w a ve ! penetr ates c l eanly to m i nim i z e dis t ur banc e ! cl o se s t i g htly ! a llow s f o rs ubs am plin g ! c an ac c om m odate w ei g htin g ! c ollec t s s u f f i c i ent s edim ent volum e ! r etr i eves s edim ent f r om a w i de r an g e of w aterand s edim ent depths ! does not c ontam inate the s am ple ! i s eas y and s af e to oper ate ! i s eas ily tr ans por ted/as s em bled at the si t e (e.g ., Long et al., 1996). Other prog ram s (e.g ., dredg e d m a terial characteriz ation studies conducted for EPA and the US Arm y Corps of Eng i neers), are concerned w ith the v ertical distribution of contaminan ts in sediment to be dredg ed and therefore seek to characteriz e a sediment column (U SEPA/ACOE, 1991,1998). Each prog ram would em ploy different sam p ling dev i ces. Related to study obj ectiv es, another im portant factor in selecting a sam p ler is desired depth of sediment penetration. For m onitoring and assessment studies w h ere historical contamination is not the focus, the upper 10 to 15 cm is ty pically the horiz on of interest. G e nerally , the m o st recently deposited sediments and m o st epifaunal and infaunal org anism s are found in this horiz on. T o ensure mi nim u m disturbance of the upper lay e r during sam p ling , a mi nim u m penetration depth of 6 to 8 cm is recommended, with a penetration depth of 10 to 15 cm being preferred. Howev er, if sediment contamination is being related to org anism exposures (e.g ., benthic m acroinv ertebrates and/orfish) then m o re precise sam p ling of sediment depths mi g h t be needed, such as w ith a core sam p ler. T h e life history and feeding habits of the org anism s (receptors) of c oncern should be considered. For exam ple, some org anism s (e.g ., shrim p , rotifers) mi g h t be epiben thic and are only exposed to surficial sediments (e.g ., 0 to 1 cm ) w h ile others (e.g ., am phipods, poly c haetes) that are infaunal irrig a tors mi g h t receiv e their prim ary exposure from sedime nts that are sev e ral centimeters in depth. Relating contaminant lev e ls that occur in sedime nt lay e rs other than where resident org anism s are exposed, mi g h t produce incorrect conclusions. Sam p ling of the surface lay e r prov ides inform ati on on the horiz ontal distri bution of parameters or properties of interest for the m o st recently deposite d m aterial. I n form ation obtained from analy sis of surface sediments can be used, for exam ple, to m a p the distribution of a chemical contaminant in sediments across a specific body of water (e.g ., la ke , em bay ment, estuary )
. A sedime nt column , including both the surface sediment lay er and the sedi ment underneath this lay er, is collected to study historical chang e s in parame ters of interest (as re v ealed throug h chang es in their v e rtical distribution) and to characteriz e sediment quality w ith depth. O n ce study obj ectiv es and the g eneral ty pe of sam p ler hav e been identified, a specific sam p ler is selected based on knowledg e of the bathy metry and areal distribution of phy sically different sedime nt ty pes at the sam p ling site. Therefore, it is strong ly recommended that this inform ation be g athered during the initial planning stag e of a ll sam p le collection efforts (see S ection 2.5.1). T h e quantity of sediment to be collected at each sam p ling site m ay also be an im portant consideration in the selection of a sam p ling dev i ce (see also S ection 2.4.1). The required quantity of sediment ty pically depends on the num ber and ty pe of phy sicochemical and biolog ical tests to be carried out (See T able 2- 3 for ty pical sedime nt v o lumes needed for different analy ses).
3-4 U S Environm ental Protection AgencyTechnical M anual R e g ardless of the ty pe of sam p ler used, it is im portant to follow the standard operating procedures specific to each dev i ce. Before retriev i ng the sam p le, the outside of the sam p ling dev i ce should be carefully rinsed w ith w a ter from the sam p ling sta tion. B etw een each sam p ling ev ent, the sam p ling dev i ce should be cleaned, inside a nd out, by dipping the sam p ler into and out of the water rapidly or by w ashing w ith w ater from the location being sam p led. More rig o rous betw een- sam ple cleaning of the sam p ler (e.g ., chemical decontamination or w a shing with soap) mi g h t be required, depending on the nature of the inv estig ation and specific prog ram g u idance (see Section 3.5). T o mi nimi z e cross- contamination of sam p les and to reduce the am ount of equipment decontamination required, it mi g h t be prudent to sam p le ref erence sites (i.e., relativ ely clean sites) first, follow e d by test stations. I f certain stati ons are known to be heav ily contaminated, it mi g h t be prudent to sam p le those stations last w h en sam p ling m any locations at one time. 

### 3. **2 T**  **y p**  **es of Sedi**  **ment Sampl**  **ers** T h ere are three m a in ty pes of sedime nt sam p ling dev i ces: grab samplers , core samplers , and dredge samplers
. Grab sam p lers (see Appendix E) are ty pi cally used to collect surficial sedime nts for the assessment of the horiz ont al distribution of sedi me nt characteristics. C o re sam p lers (see Appendix E) are ty pically used to sam p le thick sedi ment deposits, or to collect sediment profiles for the determination of the v e rtical distribution of sedimentcharacteristics or to characteriz e the entire sediment column . D r edg e sam p lers are used prim arily to collect benthos. D r edg es cause disruption of sedime nt and pore w a ter integ r ity , as w e ll as lo ss of fine- g rained sediments. For these reasons, only g r ab and core sam p lers are recommended for se diment phy sicochemistry ortoxicity ev aluations. Since m any g r ab sam p lers are appropriate for co llecting benthos as well (K lemm et al., 1990; AST M , 2000c), g r ab sam p lers are likely to be m o re useful than dredg es in sediment quality assessments. T h erefore, dredg es are not considered further in this document. Adv antag es and disadv antag es of v arious g r ab and core sam p lers are summ ariz ed in Appendix T ables E- 1 and E- 2, respectiv ely , and are discusse d briefly in the follow i ng sections. F i g u re 3- 1 prov ides recommendations reg arding the ty pe of sa m p ler that would be appropriate g i v en different study obj ectiv es. For m any study obj ectiv es either cores or g r ab sam p lers can be used, how ev er, in practice, one w ill often be preferred ov er the othe r depending on other constr aints such as am ount of sam p le required for analy ses and equipment av ailability
. **3. 2.**  **1 G**  **rab Sampl e**  **rs** G r ab sam p lers consist either of a set of j a w s th at shut w h en low ered into the surface of the bottom sediment or a bucket that rotates into the sedi ment w h en it reaches the bottom (see A ppendix E). G r ab sam p lers hav e the adv antag es of being relativ ely easy to handle and operate, readily av ailable, m oderately priced, and v e rsatile in term s of the rang e of substrate ty pes they can effectiv ely sam p le. O f the g r ab sam p lers, the Van Ve e n , Po n a r (see photog raph on pag e 3- 6), and P e tersen are the m o st comm only used. T h ese sam p lers are effectiv e in m o st ty pes of surface sediments and in a v ariety of env i ronments (e.g ., lakes, riv ers, estuaries, and m arine w aters). I n shallow , quiescent w ater, the Birg e- Ekm an sam p ler also prov ides acceptable sam p les and allow s for relativ ely nondisruptiv e sam p ling
. H o w e v e r, this sam p ler is ty pically limite d to soft sediments. T h e V an V een sam p ler, or the m odified V an- V een (T ed Young ), is used in sev e ral national and reg i onal estuarine m onitoring pr og r a m s , i n c l udi ng t h e NOAA Na t i ona l St a t us a nd T r e nds Pr og r a m , t h e EPA Env i r onme n t a l Monitoring and A ssessment Prog ram (EMA P), and the EPA N ational Estuary Prog ram because it can sam p le m o st ty pes of sediment, is less subj ect to block ag e and loss of sam p le than the Peterson or

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on of S edi ments for C hemi c al and T ox

i cologi cal A nal yses Exam pl es of gr ab sam pl ers P hot o c ourte s y of A lle n B urt on P hot o c ourte s y of A lle n B urt on

P o n a r Eckm an gr ab
P hot o c ourte s y of Ed Long P hot o c ourte s y of Sc ot tC a r r

Doubl e VanVeen gr ab Bi r ge- Eckm an gr ab

3-6 U S E

n vi ronmental P

r otecti on A gencyTechnical M anual

**P h**  **otos on th**  **i s**  **page, cou**  **r tesy** **of E d**  **Lon g**  **T a**  **k i**  **ng s ubs**  **a m**  **ple s**  **fr om a**  **T e**  **d Young mo**  **d if**  **ied Van**  **V een**  **samp ler** 

**S a**  **mpling us ing a**  **T e**  **d-Young modifie d**  **Van V**  **een .**  **L arg**  **e g r**  **ab samp**  **l ers su**  **ch as**  **t h**  **ese req u**  **i re w**  **i n**  **ch es an**  **d su**  **f f**  **i cien**  **t b**  **o at**  **s i**  **ze for**  **e ffi**  **c i**  **e n**  **t ope r**  **a ti**  **on.**

**T e**  **d-Young V a**  **nV e**  **e n**  **s a**  **mple r**  **in s uppor**  **ting f**  **r ame.**  **Illust rat**  **i ng mov**  **a bl**  **e cov e**  **r f l**  **ap t o**  **enable d**  **irect samp**  **lin g**  **f r**  **o m**  **t h**  **e g r**  **ab samp**  **ler. No**  **t e**  **t h**  **e o**  **v erly**  **in g**  **w at**  **er in t**  **h e samp**  **l er an**  **d ad**  **eq u**  **at e**  **v o**  **lu me, in**  **d icat**  **in g**  **an accep**  **t a**  **b le g**  **r ab**  **samp le.** 
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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses P onar sam p lers, is less susceptible to forming a bow w av e during descent, and prov ides g enerally hig h sam p le integ r ity (Klemm et al., 1990). T h e support frame further enhances the v e rsatility of the V anV een sam p ler by allowing the addition of e ither w e ig hts (to increase penetration in com p act sediments) or pads (to prov ide added bearing support in extremely soft sediments). Howev er, this sam p ler is relativ ely heav y and requires a pow er winch to operate safely (GLNPO, 1994). A s show n in A ppendix Table E

- 1, g r ab sam p ler capacities rang e from approxim ately 0.5 Lto 75 L
. I f

a sam p ler does not hav e sufficient capacity to m eet the study plan requirements, additional sam p les can be collected and com posited to obtain the requis ite sam p le siz e (see S ection 5.3). G r ab sam p lers penetrate to different depths depe nding on their siz e, weig ht, and the bottom substrate. Heav y , larg e v o lume sam p lers such as the Smith- M cI nty r e, larg e B i rg e- Ekm an, Van Veen, and Petersen dev i ces can effectiv ely sam p le to a depth of 30 cm
. T h ese sam p lers mi g h t actually sam p le sedime nts that are too deep for certain study obj ectiv es (i.e., not re flectiv e of recently deposited sediments). Sm aller sam p lers such as the sm all B i rg e- E k m an, standard and petite P onar, and standard S h ipek dev i ces can effectiv ely collect sedime nts to a m a xim u m depth of 10 cm
. T h e mi ni- S hipek can sam p le to a depth of 3 cm
. Another consideration in choosing a g r ab sam p ler is how well it protects the sam p le from disturbance and washout. Grab sam p les are prone to washout which results in th e loss of surficial, fine g r ained sedime nts that are often im portant from a biolog i cal and contaminant standpoint. T h e Ponar, T edYoung m odified g r ab, and V a n V een sam p lers ar e equipped with mesh screens and rubber flaps to cov e r the j a w s. This desig n allow s w a ter to pass throug h the sam p lers during descent, reducing disturbance from bow w av es at the sedime nt- w ater interface. T h e r ubber flaps also serv e to protect the sediment sam p le from washout during ascent. The use of sm all or lig htw eig ht sam p lers, such as the sm all B i rg e- E km an (see pag e 3- 6), petite P onar, and mi ni- S hipek , can be adv antag eous because of easy handling , particularly from a sm all v essel and/or using only a hand line. Howev er, these sam p lers are not recommended for use in strong currents or hig h wav es. T h is is particularly true for the B i rg e- E km an sam p ler, w h ich requires relativ ely calm conditions for proper perform ance. L i g h tw eig h t sam p lers g e nerally hav e the disadv antag e of being less stable during sediment pe netration. T h ey tend to fall to one side due to inadequate or incom p lete penetra tion, resulting in unacceptable sam p les. I n certain v ery shallow water applications, such as a stream assessment at a superfund site, it mi g h t be difficult to use ev en a lig htw e ig ht sam p ler to collect a sam p le. I n these cases, it mi g h t be acceptable to collect sediment from depositional ar eas, using a shov el or other hand im plement. H o w ev er, such sam p ling procedures are discourag ed as a g eneral rule and the use of a hand corer or similar dev i ce is preferred (see Section 3.2.2). Fig u re 3- 2 summ ariz es appropriate g r ab sam p lers based on two im portant site factors, depth and sediment particle siz e. T h is fig u re also indi cates appropriate g r ab sam p lers depending on certain comm on study constraints such as sam p le depth a nd v o lume desired, and the ability to subsam ple directly from the sam p ler (see also Section 4.3; AST M , 2000c). Based on all of these factors, the P onar or Van Veen sam p lers are perhaps the m o st v ersatile of the g r ab sam p lers, hence their comm o n usag e in sediment studies. C areful use of g r ab sam p lers is required to av oid problem s such as loss of fine- g rained surface sediments from the bow wav e during descent, mi xing of sediment lay ers upon im pact, lack of sediment penetration, and loss of sedimentfrom tilting or w ashout upon ascent (A ST M, 2000a; Env i ronment Canada, 1994; Baudo, 1990; Golterm an et al., 1983; Plum b,1981). When deploy ing a g r ab sam p ler, the speed of descent should be controlle d, with no “free fall” allowed. I n deep waters,
3-8 U S Environm ental Protection AgencyTechnical M anual use of a winching sy stem is recommended to cont rol both the rate of descent and ascent. A ballbearing swiv el should be used to attach the g r ab sam p ler to the cable to mi nimi z e twisting during descent. After the sam p le is collected, the sa m p ling dev i ce should be lifted slowly off the bottom , then steadily raised to the surface at a speed of about 30 cm /s (Env ironment Canada, 1994).



## R **eco mmen**  **d a**  **tio n**  **B o**  **x #1 W**  **h**

**at are appropriat**  **e sampling devices given dif**  **f**

**e**

**rent st**  **udy object**  **ives?**

� G r ab orc or e s am pler s ar e pr ef er r ed overdr ed g es f o rc o llec t in g s u r f ic ial s edim ents f o r phy s i c oc hem ic al ortox i c i ty analy s es . Dr ed g es m i g ht be ac c eptable f o rc o llec t in g m ac r oinver tebr ates
. � G r ab s am pler s ar e r ec om m ended f ors ur f ic ial s edim ent analy s es w her e ac c ur ate r es olution of s ur f ic ial s edim ent depths is not nec es s ar y . Cor e s am pler s ar e r ec om m ended f or : ( a) as s es s m ents r equir i n g ac c u r a te s u r f ic ial s edim ent depth r e s o lution, ( b ) his t or ic al s edim ent analy s es , ( c ) detailed s edim ent quality s t udies of ver t ic al s edim ent pr of iles , to c har ac ter i z e s edim ent quality at depth, ( d) w hen c har ac ter i z i n g thic k s edim ent depos its ( s uc h as s hoals to be ex c avated) , and/or( e) w her e it is im por tant to m aintain an ox y g en- f r ee envir onm ent. � In s and, g r a vel, f i r m c l ay , ortill s edim ents , g r a b s a mp l e r s mi g ht be pr ef er r ed overc or e s am pler s ( w hen only s ur f ac e m ater i al needs to be c ollec t ed and s am ples at depth ar e not nec es s ar y ) bec aus e the latterar e of ten les s ef f i c i ent in thes e s edim ent ty pes . � Ponar , VanVeen, orEk m an s am pler s ar e c om m only us ed and g ener ally pr ef er r ed f o r g r ab s a m p lin g . Ek m an s am pler s , how ever , ar e les s ef f i c i ent in deep w ater s . � T he Kaj a k - Br ink hur s t c o r e ris a c o m m on c o r e s a m p lerf o rs o f t, f i ne g r ained s edim ents w her e lar g e volum es ordeep c or es ar e not needed. T he Phle g erc o r e ris c o m m only us ed f ora var i ety of s edim ents inc l udin g peat and plant r oots but is not appr opr iate w her e lar g e volum es ordeep c or es ar e needed. � Box c or er s ar e es pec ially r ec om m ended f or : ( a) s t udies of the s edim ent- w aterinter f ac e; ( b ) c o llec t in g lar g ervolum es of s edim ent f r om a g iven depth ( g ener ally les s than one m eterdepth, how ever ) ; ( c ) f or in- s

itu s t udies involvin g inter s titial w aterc har ac ter i z ation; and ( d ) c o llec t in g s ubs am ples f ordif f er ent analy s es f r om the s am e s t ation. � Vibr ac or er s ar e r ec om m ended f ors t udies r equir i n g deep c or es ( > 1 m ) , orw her e s edim ent c ons is ts of ver y c om pac ted orlar g e g r ained m ater i al ( e. g ., g ra v e l ).

**3. 2.**  **2 C**  **ore Sampl e**  **rs** Core sam p lers (corers) are used: (1) to obtain sedi me nt sam p les for g e olog ical characteriz ations and dating , (2) to inv e stig ate the historical input of contaminants to aquatic sy stem s and, (3) to characteriz e the depth of contamination at a site. C o rers are an essential tool in sedime nts in w h ich 3- dimensional m aps of sediment contamination are necessary . Appendix T able E- 2 discusses some of the adv antag es and disadv antag es of comm on corers.

C

hapter 3: C o

llection of W hole Sedim ents 3-9Methods for C ol lecti on, S torage, and Mani pul ati

on of S edi ments for C hemi c al and T ox

i cologi cal A nal yses

Vi br acor er i n use showi ng ext r usi on of

t he core sam pl e for i nspect i on and Subsam pl i ng.

P hot os on t his pa ge , c ourte s y of A lle n B urt on

3-10 U S E

n vi ronmental P

r otecti on A gencyTechnical M anual C o re dev i ces are recommended for proj ects in w h ich it is critical to m a intain the integ r ity of the sediment profile, because they are considered to be less disruptiv e than dredg e or g r ab sam p lers. Core sam p lers should also be used where it is im portant to m aintain an oxy g en- free env i ronment because they limit oxy g en exchang e w ith the air m o re effectiv ely than g r ab sam p lers. Cores should also be used where thick sediment deposits m u stbe representativ ely sam p led (e.g ., for dredg i ng proj ects). O n e limitation of core sam p lers is that the v o lume of any g i v en depth horiz on w ithin the profile sam p le is relativ ely sm all. Thus, depending on the num ber and ty pe of analy ses needed, repetitiv e sam p ling at a site mi g h t be required to obtain the desired quantity of m aterial from a g i v en depth. Some core sam p lers are prone to “plug g i ng ” or “rodding ” where the friction of the sediment within the core tube prev ents it from passing freely and the core sam p le is com p ressed or does not sam p le to the depth required. This limitation is m o re likely w ith sm aller diameter core tubes and heav y clay sediments. Except for piston corers and v i braco rers, there are few core dev i ces that function efficiently in substrates w ith sig n ifican t proportions of sand, g r av el, clay , or till. C o ring dev i ces are av ailable in v arious desig n s, leng ths, and diameters (see Appendix E). With the obv ious exception of hand corers, there are only a few corers that can be operated without a mechanical w i nch. T h e m o re comm on of these include the standard K aj ak- B r i nkhurstcorer , suitable for sam p ling soft, fine- g rained sediments, and the P h leger corer , suitable for a w i der v ariety of sediment ty pes rang ing from soft to sandy , semi

- com pacted m aterial, as w ell as peat and plant roots in shallow lakes or m arshes (Mudroch and Az cue, 1995). T h e K aj ak

- Brink hurst corer uses a larg er core tube, and therefore recov ers a g r eater quantity of sediment, than the P h leg er corer. B o th corers can be used w ith different liner m a terials including stainless steel and PV C
. Stainless steel liners should not be used if trace metal contamination is an issue. G ravity corers are appropriate for recov ering up to 3 m long cores from soft, fine- g rained sediments. R ecent m odels include stabiliz ing fins on the upper part of the corer to prom ote v ertical penetration into the sediment, and weig hts that can be m ounted externally to enhance penetration (Mudroch and Az cue, 1995). A v ariety of liner m a terials are av ailable including stainless steel; Lexan®, and PV C. For studies in w h ich metals are a concern, stainless steel liners should not be used. V i bracorers are perhaps the m o st comm only used coring dev i ce in sam p ling prog ram s in the U
. S. because they collect deep cores in m o st ty pes of sediments, y i elding excellent sam p le integ r ity
. V i bracorers are one of the only sam p ling dev i ces that can reliably collect 

## C **h ecklist**  **Corers may consist of the following components (from**  **M**

**udroch and A z** 

**cue, 1995)** � A hollow m e tal ( o rplas tic ) pipe that s e r v es as the c or e bar r el � Eas ily r e m o ved plas tic liner s orc o r e tubes that f i t into the c or e bar r el and r etain the s edim ent s a m p le � A valve orpis t on m ounted on top of the c or e bar r el that is open and allow s w aterto f l ow thr ou g h the bar r e l dur in g des c ent, but s huts upon penetr ation of the c or erinto the s edim ent to pr event the s edim ent f r om s lidin g thr o u g h the c or erdur in g the as c ent � A c or e c atc herto r etain the s edim ent sa m p l e � A c or e c utterf orpenetr ation of the s edim ent � Rem o vable m e tal w e i g hts ( u s ually lead c oated w i th plas tic ) orpis t on- dr iven im pac t orvibr ation to inc r eas e penetr ation of the c or erinto the s edim ent � Stabiliz in g f i ns to ens ur e ver t ic al des c ent of the c or er
C

hapter 3: C o

llection of W hole Sedim ents 3-11M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses thick sediment sam p les (up to 10 meters or m o re). Some prog ram s that rely on v i bracorers include the Pug et Sound Estuary Prog ram , the Great Lake s ARCS Prog ram , and the Dredg e d Materials Manag ement Prog ram . Vibracorers hav e an electric- pow ered , mechanical v i brator located at the head end of the corer w h ich applies thousands of v ertical v i br ations per mi nute to help penetrat e the sedime nt. A core tube and rig i d liner (preferably of relativ ely inert m a terial such as cellulose acetate buty r ate) of v ary ing diameter depending on the specific v i brator head used, is inserted into the head and the entire assem b ly is low ered in the w ater. D epending on th e horsepower of the v i brating head and its weig ht, a v i bracorer can penetrate v ery com p act sediments and collect cores up to 6 m long
. For exam ple, the A R C S prog ram in the G r eat Lakes uses a Rossfelder® Model P- 4 V i bracorer (Rossfelder Corporation, La J o lla, CA) that produces a for ce of 7,000 lbs and a m ono- directional frequency of 3,400 v i brations per mi nute (GLNPO, 1994). Cores up to 6 m in leng th hav e been routinely collected using this v i bracorer. Howev er, this particular m odel is relativ ely heav y (113 k g as com p ared to 8.1 k g for the m o re portable Wacker® Model M3000 v i br acorers [GLNPO, 1994]). T h erefore, use of a heav y v i bracorer requires a larg e v e ssel to m a intainbalance and prov ide adequate lift to break the corer out of the sediment and re triev e it (GLNPO, 1994; PSEP, 1997a). When deploy ed properly , boxcorers can obtain undisturbed sedimentsam p les of excellent quality
. T h e basic box corer consists of a stainless steel box equipped w ith a frame to add stability and facilitate v ertical penetration on low slopes. B ox corers are recommended particularly for studies of the sediment- w ater interface or w h en there is a need to collect larg er v o lume s of sedime nt from the depth profile. Because of the heav y w eig ht and larg e siz e of alm o st all box corers, they can be operated only from a v e ssel w ith a larg e lifting capacity and sufficient deck space. Sediment inside a box corer can be subsam pled by inserting narrow co re tubes into the sediment. T hus, they are an ideal sam p ler for obtaining acceptable subsam ples for different analy ses at a g i v en station. C arlton and Wetz el (1985) describe a box corer that permits the sediment and ov erly ing water to be held intact as a laboratory mi crocosm under either the orig inal in situ conditions or other laboratory controlled conditions. A box corer was dev eloped th at enables horiz ontal subsam pling of the entire sedime nt v o lume recov e red by the dev i ce (Mudroch and Az cue, 1995). Fig u re 3- 3 summ ariz es the core sam p lers that are appropriate g i v en site factors such as depth and particle siz e and other study constraints such as sam p le depth and v o lume required, and lifting capacity needed to use the sam p ling dev i ce. G i v en the factors examined for g eneral m onitoring studies, the P h leg er, A l pine, and Kaj ak

- B r ink hurst corers mi g h t be m o st v ersatile. F o r dredg ed m aterials ev aluations, and proj ects requiring sediment profile char acteriz ations > 3 m in sediment depth, the v i bracorer or piston corer are the sam p lers of choice. Collection of core sam p les with hand- coring de v i ces should be executed with care to mi nimi z e disturbance and/or com p ression of sediment during collection. T o mi nimi z e disruption of the sediment, core sam p les should be kept as stationa ry and v i bration- free as possible during transport. T h ese cautions are particularly appli cable to cores collected by div ers. T h e speed of descent of coring dev i ces should be controlled, especially dur ing the initial penetration of the sediment, to av oid distur bance of the surface and to mi nimi z e com p ression due to frictional drag from the sides of the core liner (AST M, 2000d). I n deep waters, winches should be used where necessary to mi nimi z e tw isting and tilting and to c ontrol the rate of both descent and ascent. With the exception of piston corers or v i bracorers, that are equipped w ith their ow n mechanical im pact features, for other corers, only the weig ht or piston mechanism of the sam p ler should be used to force it into the sediment. T h e sam p ler should be raised to the surface at a steady rate, similar to that described for g r ab sam p lers. Where core caps are re quired, it is essential to quickly and securely cap
3-12 U S Environm ental Protection AgencyTechnical M anual the core sam p les when the sam p les are retriev ed. T h e liner from the core sam p ler should be carefully rem o v ed and kept in a stable position until the sam p les are processed (see C h apter 4). I f there is little to no ov erly ing w ater in the tube and the sediment s are relativ ely consolidated, it is not necessary to keep the core sam p le tubes v ertical. Core sam p le tubes should be quickly capped and taped to secure the sam p le. I f sediment oxidation is a concern (e.g ., due to potential chang es in metal bioav ailability or v o latile substances), then the head space of the core tube should be purg ed w ith an inert g as such as nitrog en or arg on.


## R **eco mmen**  **d a**  **tio n**  **B o**  **x #2 How should sampling devices be used?** 

� T he r ec om m ended depth of s edim ent s am plin g is dependent on the s t udy obj ec tives

. Is s ues that deter m i ne the appr opr iate depth of s am plin g inc l ude: r e g ulator y obj ec tives (e

. g ., depth of dr ed g in g f ors edim ent r em ediation) , need to c har ac ter i z e s edim ents at depth ( e. g ., m ater i als to be dr ed g ed ver s us s hallowdepos itional ar eas in s o m e s uper f und s i tes ) , his t or ic al c om par is ons , s edim ent depos ition r ates , and/ortim e per iod of c ontam ination. � Appr opr iate w i nc hin g s y s t em s ar e r equir ed to c ontr ol the r ate of as c ent and des c ent of the s am pler s . � T he s am plers hould be r i ns ed thor ou g hly w i th w aterat the s am plin g s t ation betw een and w i thin- s tation s am ples , and r i ns ed w i th w aterf r om the nex t s aplin g s t ation bef or e c o llec t in g a s am ple. Equipm ent us ed in the handlin g of s edim ent s hould als o be w as hed thor ou g hly betw een s am ples

. � M o re ri g or ous equipm ent dec ontam ination m i g ht be nec es s ar y if hi g hly c ontam inated s i tes ar e s a m p led orif lowlevel c ontam inants ar e a c onc er n. � T o r educ e the pr obability of c r os s - c ontam ination of s am ples , it is us ef ul to s am ple r ef er enc e orr elatively c l ean s i tes f i r s t and then s us pec ted c ontam inated s i tes
. 

### 3.3 **S ample A**  **cceptability** Only sediments that are correctly collected with g r ab or core sam p ling dev i ces should be used for subsequent phy sicochemical, biolog ical or toxicity testing
. A cceptability of g r abs can be ascertained by noting that the sam p lers w ere closed w h en retrie v e d, are relativ ely full of sedime nt (but not ov erfilled), and do not appear to hav e lost surficial fi nes. C o re sam p les are acceptable if the core w as inserted v ertically in the sediment and an adequate depth was sam p led. A sediment sam p le should be inspected as soon as it is secured. I f a collected sam p le fails to meet any of the acceptability conditions listed below for the respectiv e sam p ling dev i ce, then the sam p le mi g h t need to be rej ected and another sam p le collected at the site. T h e location of consecutiv e attem p ts should be as close to the orig inal attem p t as possible and located in the “upstream ” direction of any existing current. R ej ected sediment sam p les should be discarded in a m anner that w ill not affect subsequent sam p les at th at station or other possible sam p ling stations. I llustrations of acceptable and unacceptable g r ab sam p les are prov ided in Fig u re 3- 4.

C

hapter 3: C o

llection of W hole Sedim ents 3-13M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses


## C **h ecklist**  **Sample accept a** 

**bilit y f**  **o**

**r grab and core samples G** 

**r ab**  **samp les**  s hould be v i s

ually ins pec ted to ens ur

e that the following ac c

eptability c onditions ar

e s atis f ied ( U

SEPA, 1986b; Env i r onment Canada, 1994): � T he s a m p leris not over f illed s o that the s edim ent s u r f ac e is touc hin g the top of the sa m p l e r; � O v er ly in g w a teris pr es ent ( i ndic a tes m i nim a l leak a g e)

. T h is over ly in g w aters hould be r em oved pr iorto pr oc es s i n g and s t or a g e by s i phonin g , not dec antin g ( s ee Chapter6) ; � T he over ly in g w ateris c l earornot ex c es s i v ely tur bid; � T he s edim ent- w aterinter f ac e is intac t and r elatively f l at, w i th no s i g n of c hannelin g or s am ple w as hout; � T he des ir ed depth of penetr ation has been ac hieved; and � T her e is no evidenc e of s edim ent los s ( i nc om plete c l os ur e of the s am pler , penetr ation at an an g le, ortiltin g upon r e tr ieval)

. **Co re samp**  **les** s hould meet the following ac c

eptability c onditions : � T he c or e s am plerw as not ins er t ed at an an g le ortilted upon r etr ieval � T he c or e c ollec t ed the r equir ed depth to m eet the s t udy obj ec tives , w i th no los s of s edim ent.


### 3. **4 E**  **qui pment Decontami**  **n ati**  **o n**  F o r m o st sam p ling applications, site w a ter rinse of equipment in betw een stations is norm a lly sufficient (PSEP, 1997a). Howev er, if one is sam p ling m any stations, including some that could be heav ily contaminated, a site w a ter rinse mi g h t not be sufficient to mi nimi z e cross- contamination of sam p les am ong stations. I n these cases, it mi g h t be necessary to decontaminate all sam p ling m aterials in between stations. T h is would include the sam p ling dev i ce, scoop, spatula, mi xing bowls, and any other utensils that come in contact w ith sedime nt sam p les. An approach recomme nded by A S T M (2000a) for field sam p les of unk now n com position includes: (1) soap and w ater w ash, (2) distilled w ater rinse, (3) acetone or ethanol rinse, and (4) site w ater rinse. I n g eneral, org anic solv ents such as methy l ene chloride should not be us ed due to the associated health and safety risk s. Waste solv ents should be collected in labeled ha z ardous waste containers
. I f sedime nt can be collected from the interior of the sam p ling dev i ce, and aw ay from potentially contaminated surfaces of the sam p ler, it mi g h t be adequate to rinse w ith site w a ter betw een stations. I f

metals or other inorg anic com pounds are specifi cally of concern, sam p ling and handling equipment should be suspended ov er a tub and rinsed from the top down with 10 percent nitric acid using a pum p or squirt bottle (U SEPA , 1993; A S T M , 2000a). I f org anic com pounds are a specific concern, sam p ling equipment can be decontaminated using acetone follow ed by a site w ater rinse. Wash water from decontamination should be collected and disposed of properly
.

3-14 U S Environm ental Protection AgencyTechnical M anual Some specific prog ram s (like Superfund) hav e th eir own decontamination procedures, which are leg a lly required.

**F i**  **g u**  **r e 3-**  **4.** Illus t r ations of ac c eptable and unac c eptable g ra b sa m p l e s. 

### 3. **5 F**  **i e**  **l d**  **Measurements and O b**  **serv a**  **ti ons**  Field measurements and observ ati ons are critical to any sediment collection study , and specific details concerning sam p le documentation should be included in the study plan. Section 2.7 summ ariz es the ty pes of inform ation comm only reco rded in the field during sam p ling
. Sev eral prog ram s , referenced in this Manual, prov id e specific g u idance on field measurements and observ ations necessary (e.g ., see the Sam p ling a nd Analy s es Plan Guidance dev e lopment by the Washing ton Departme nt of Ecol og y in Appendix B [WDE, 1995 or PSEP, 1997a]). Measurements and observ ations should be documented clearly in a bound field log book (or on pre- printed sam p le form s). Preferably , a log book should be dedicated to an indiv i dual proj ect. T h e inv estig ator’s name, proj ect name, proj ect num ber, and book num ber (if m o re than one is required) should be entered on
C

hapter 3: C o

llection of W hole Sedim ents 3-15M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses the inside of the front cov er of the log book
. A ll entries should be w r itten in indelible ink , and the date and time of entry recorded. A dditionally , each pag e should be initialed and dated by the inv estig ator. A tthe end of each day ’ s activ ity , or entry of a particular ev ent if appropriate, the inv estig ator should enter his or her initials. A ll aspects of sam p le collection and handling as w ell as v i sual observ ations and field conditions should be documented in the field log book s at the time of sam p le collection. Log book entries should also include any circum stances that 

## C **h ecklist**  **Depending on program object**  **ives, f ield measurement**  **s might include the following:**  � tem per atur e and per haps pH of the s edim ent at the s edim ent- w aterinter f ac e; � c onc entr ation of dis s olved ox y g en in the w ater over ly in g the s edim ent in the s y s t em bein g s a m p led. � s a linity orc onduc tivity of the over ly in g w a ter
. potentially affected sam p ling procedures and/or an y field preparation of sam p les. D ata entries should be thoroug h enoug h to allow station relocati on and sam p le track ing
. Since field records are the basis for later w r itten reports, lang uag e should be obj ectiv e, factual, and free of personal opinions or other terminolog y which mi g h t appear inappropr iate. I n describing characteristics of sam p les collected (see below), some cautions should be noted. First, polariz ed g l asses are often worn in the field to reduce g l are, how ev er, they can also alte r color v i sion. T h erefore, v i sual examination or


## R **eco mmen**  **d a**  **tio n**  **B o**  **x #3 W**  **h**

**at information should be documented for each sample collect**  **ed? ( PSEP, 1997a;**  **A STM**  **, 2000a)**

� pr oj ec t title, tim e and date of c ollec t ion, s am ple num ber , r eplic ate num ber , s i te identif ic ation ( e . g ., nam e) ; s t ation num berand loc ation ( e. g ., pos itionin g inf o r m ation) ; � w aterdepth and the s am plin g penetr ation depth; � details per tainin g to unus ual events w hic h m i g ht have oc c u r r ed dur in g the oper ation of the sa m p l e r (e

. g ., pos s i ble s am ple c ontam ination, equipm ent f ailur e, unus ual appear anc e of s edim ent inte g r i ty , c ontr ol of ver t ic al des c ent of the s am pler , etc
. ) , pr es er vation and st o r a g e m ethod, analy s is ortes t to be pr ef or m ed; � es tim ate of quantity of s edim ent r ec over ed by a g r ab s am pler , orlen g th and appear anc e o f re co v e re d co re s; � des c r iption of the s edim ent inc l udin g tex t ur e and c ons is tenc y , c olor , pr es enc e of biota or debr is , pr es enc e of oily s heen, c han g es in s edim ent c har ac ter i s t ic s w i th depth, and pr es enc e/loc ation/thic k nes s of the r edox potential dis c ontinuity ( R PD) lay er( a vis ual indic ation of blac k is of ten adequate f ordoc um entin g anox ia) ; � photo g r aph of the s a m p le is des ir able, es pec ially lon g itudinally - s ec tioned c o r e s , to doc um ent s t r atif i c ation; � deviations f r om appr oved w o r k plans orSO Ps

. **NOT E**  **:** Som e g eolo g ic al c har ac ter i z ation m ethods m i g ht inc l ude an odorevaluation of the s edim ent as this c an pr ovide us ef ul inf o r m ation on phy s i c oc hem ic al c onditions

. How ever , s edim ent odorevaluation is potentially dan g er ous dependin g on the c hem ic als pr es ent in the s edim ent ( AST M 2000a) and s hould ther ef or e be done c autious ly , if at all.

3-16 U S Environm ental Protection AgencyTechnical M anual characteriz ation of sam p les should be perform ed without sung lasses (GLNPO, 1994). Second, descriptions of sediment textur e and com position should rely on a te xture- by

- f eel or “ribbon” test in addition to v i sual determinations (G LN PO , 1994). I n this test, a sm all piece of suspected clay is rolled betw een the fing ers w h ile w earing protectiv e g l ov es. I f the piece easily rolls into a ribbon it is clay ; if it break s apart, it is silt (G LN PO , 1994). 

### 3. **6 D**  **ocument at**  **i on of**  **Sampl e Col**  **l ect**  **i on**  Documentation of collection and analy sis of sediment and porewater sam p les requires all the inform ation necessary to: 1) trace a sam p le from the field to the final result of analy sis; 2) describe the sam p ling and analy tical methodolog y ; and 3) describe the QA/QC prog ram (Mudroch and Az cue 1995; K eith, 1993). Poor or incom p lete docum enta tion of sam p le collection can com p romi se the integ r ity of the sam p le(s) and thus, the study
. I n addition, stations thatcould not, or were not, sam p led should be docum ented w ith an explanati on. Sam p les should be accom p anied by chain- ofcustody form s that identify each sam p le collected and the analy s es to be conducted on that sam p le. S p ecific g u idance on quality assurance procedures re g arding sam p le chain- of- custody is summ ariz ed in C h apter 7.


## C **h ecklist**  **Project documentation should include...**
� ty pe of ves s el us ed ( e. g ., s i z e, pow er , ty pe of en g ine) ; � notation of the s y s t em us ed to def ine the pos ition of the s am plin g s i te; � notation of the s y s t em us ed to identif y and tr ac k s am ples ; � nam e of per s onnel c o llec t in g t h e sa m p l e s; � level of per s onal pr otec tive equipm ent w o r n ; � notation of any vis i tor s to the s i te; � sk e t ch o f sa m p l i n g ar ea w i th photo g r aphs , if pos s i ble; � am bient w eatherc onditions , inc l udin g w i nd s peed and dir ec t ion, w ave ac tion, c ur r ent, tide, ves s el tr af f i c , tem per atur e of both the airand w ater , thic k nes s of ic e if pr es ent; � ty pe of s edim ent c o llec t ion devic e and any m odif i c a tions m ade dur in g s a m p lin g ; � c a libr a tion data.

C

hapter 3: C o

llection of W hole Sedim ents 3-17Technical M anual 

## Field Sample Processing, Transport, **and Storage of Sediments CHA**  **PT ER**  

# 4

T h e way in which sediment sam p les are processed, transported, and stored mi g h t alter contaminant bioav ailability and concentration by introducing contaminants to the sam p le or by chang i ng the phy sical, chemical, or biol og ical characteristics of the sam p le. Manipulation processes often chang e av ailability of org anic com pounds because of disr uption of the equilibrium w ith org anic carbon in the pore water/sediment sy stem . Similarly , oxidation of anaerobic se dime nts increases the av ailability of certain me tals (D iT oro et al., 1990; A nkl ey et al., 1996). Materials and techniques should be selected to mi nimi z e s ources of contamination and v ariati on, and sam p le treatment prior to testing should be as consistent as possible. A flowchart is presented in Fig u re 4- 1 that summ ariz es comm on sediment processing procedures discussed in this section as w ell as issues a nd obj ectiv es relev ant to each processing step. 

### 4. **1 S**  **ampl e Contai**  **ners** A ny m a terial that is in contact w ith a field sa m p le has the potential to contaminate the sam p le or adsorb com ponents from the sam p le. For exam ple, sam p les can be contaminated by z i nc from g l assw are, metals from metallic containers, and or g anic com pounds from rubber or plastic m aterials. T h e use of appropriate m aterials, along with appropriate cleaning procedures, can mi nimi z e or mitig ate interferences from sam p le containers.


## R **eco mmen**  **d a**  **tio n B**  **o x #1**  **Sample Containers**

� Hi g h dens ity poly ethy l ene ( HDPE) orpoly t etr af l uor oethy lene ( P T F E) c ontainer s ar e s uitable and pr ef er r ed f orm os t analy t ic al m eas ur em ents bec aus e they ar e m ade of r e latively iner t m a ter i al and they ar e g ener ally unbr eak able. � All c ontainer s s hould be pr e- c l eaned pr iorto f illin g w i th s am ple. � Cons iderus in g c e r t if ied, pr e- c l eaned c ontainer s , c o m m e r c ially available f r om m any vendor s . � Pur g e c ontainer s w i th iner t g as ( e. g ., nitr o g en) pr iorto and af terf illin g if anox ic c onditions m us t be m aintained. � F ill c ontainer s c o m p letely if the s a m p le w ill not be f r oz en pr iorto analy s is

.

C

hapter 4: Field Sam p

ling Processing, Transport, and Storage of Sedim ents and Interstitial W a

ter 4-1M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

**F i**  **g u**  **r e 4-**  **1.** F l ow c har t of s u gg es ted s edim ent pr oc es s i n g pr oc edur es

4-2 U S Environm ental Protection AgencyTechnical M anual **4. 1.**  **1 C**  **ont ai**  **ner M a**  **t e**  **ri al**  Borosilicate Glass, and hig h

- d ensity poly ethy l en e, poly carbonate and fluor ocarbon plastics should be used w h enev er possible to mi nimi z e leachin g , dissolution, and sorption (A ST M, 2000a; A P H A , 1995). Direct contact betw een sediment sam p les and the followi ng substances should be av oided: PV C, natural or neoprene rubber, ny lon, talcum powder, poly s ty rene, g alv aniz ed metal, brass, copper, lead, other metal m aterials, soda g l ass, paper tissues, and painted surfaces. T able 4- 1 summ ariz es the appropriate ty pes of sam p ling cont ainers and allowable holding times for v arious ty pes of contaminants associated w ith sediments. I n g eneral, sediments and pore w aters w ith m u ltip le or unknow n chemical ty pes should be stored in containers m ade from hig h density poly ethy l en e plastic or poly t etrafluoroethy l ene (PT F E or Te flo n ® ) as these m a terials are least likely to add ch emical artifacts or interferences and they are m

u ch less frag ile than g l ass. Sam p les for org ani c contaminant analy s is should be stored in brown borosilicate g l ass containers w ith PT FE lid liners. I f v o latile com pounds w ill be analy z ed, containers should hav e a septum to mi nimi z e escape of v o latile g ases during storag e and analy sis. Extra containers should be prov ided for these analy s es in the ev ent that re- a naly sis of the sam p le is required. I f sam p les are contaminated w ith photoreactiv e com pounds such as PA H s , exposure to lig ht should be mi nimi z ed by using brown g l ass cont ainers or clear containers wrapped tig htly with an opaque m aterial (e.g ., clean aluminum foil). Plastic or acid- rinsed g l ass containers are recommended w h en the chemicals of concern are heav y metals. **4. 1.**  **2 C**  **ont ai**  **ner Preparat i**  **o n**  Many v endors hav e commercially av ailable pre- cleaned containers for a v ariety of applications. For chemical and toxicolog i cal analy s es, certified pre- cleaned containers are often a cost- e ffectiv e w a y to limit the potential for container contamination of sam p les. T hus, m anufacturer- s upplied pre- cleaned containers are often a prerequisite in QAPPs. I f

new containers are used, Env i ronment Cana da (1994) recomme nds that new g l assware and plasticware should be soaked in 1:1 concentrated acid prior to use. Soak ing ov ernig h t is adequate for g l assw are. For plasticw are, the recommended procedure inv o lv es soak ing for sev en day s in hy drochloric acid (HCl), followed by sev en day s in nitric acid (H N O 3 ), followed by sev en day s in deioniz ed water. Shorter soak ing times mi g h t be satisfactory in m o st instances (AST M, 2000a). Used sam p le containers should be washed followi ng these steps: (1) non- phosphate deterg ent wash, (2) triple w a ter rinse, (3) w a ter- mi scible org a ni c solv ent w ash (acetone follow ed by pesticide- g r ade hexane), (4) w ater rinse, (5) acid w ash (such as 5% concentrated H C l) and (6) triple rinse w ith deioniz e d- distilled w a ter. Adichrom a te- sulfuri c acid cleaning solution can g enerally be used in place of both the org anic solv ent and the acid (Ste ps 3 throug h 5), but it mi g h t attack any silicone adhesiv e present in the container. See AST M (2000a) and USEPA (2000d) for further inform ation. I f

a sam p le is to be refrig erated, the container should be filled to the brim to reduce oxy g en exposure. T h is is particularly critical for v o latile com pounds (e.g ., A V S). I f a sam p le is to be froz en, the container should be filled to approxim ately 90% of its v o lume (i.e., 10% headspace) to allow for expansion of the sam p le during freez ing
. See Sec tion 4.4 for preserv ation and storag e conditions for v arious ty pes of analy ses. For studies in which it is critical to m aintain the collected sediment under anoxic conditions (e.g ., w h ere metals are the polluta nts of concern), the c ontainer should be purg ed w ith an inert g as (e.g ., nitrog en) before f illing and then ag ain before capping tig htly
.

C

hapter 4: Field Sam p

ling Processing, Transport, and Storage of Sedim ents and Interstitial W a

ter 4-3M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses
**T ab**  **l e 4-**  **1.** Rec om m ended s am plin g c ontainer s , holdin g tim es , and s t or a g e c onditions f orc om m on ty pes of s edim ent analy s es ( U SEPA, 1983;1993; AST M, 2000a) . P=Plas tic ; G = G l as s ; PT F E =Poly t etr a f l uor oethy lene; R=r e f r i g er ate; F = f r eez e Contaminant C ontainer Hold ing Time Storage Condition Amm onia P ,G 28 day s R; F Sulfate P ,G 28 day s R; F Sulfide P ,G 28 day s R or NaOH; pH>9 Oil and Grease G 28 day s HCl, pH<2 Mercury P ,G 6 week s H 2 SO 4 , pH<2; R Metals (except Cr or Hg ) P ,G 6 m onths HNO 3 , pH<2; F Extractable org anics (including phthalates, airosami nes, org a nochlorine pesticides, PCBs arom atics, isophorone, PAHs, haloethers, chlorinated hy drocarbons, and T C DD) G, PT FE- l i n ed cap 7 day s (until extraction) 30 day s (after extraction) R; F

Purg ables (halocarbons and arom atics) G, PT FE- l i n ed septum 14 day s R; F
P e sticides G , P T F E

- lined cap 7 day s (until extraction) 30 day s (after extraction) R; F

Sediment T oxicity (acute and chronic) P, PT FE 2 week s* R, dark
B i oaccum u lation testing P , PT FE 2 w eek s* R , dark *Holding time mi g h t be long er depending on the m ag n itude and ty pe of contaminants present.

See Section 4.5.
All sediment containers should be properly labele d with a waterproof m arker prior to sam p ling
. C ontainers should be labeled on their sides in additi on to or instead of labeling the lids. Each label should include, at a mi nim u m , the study title, station location and/or sam p le identification, date and time of collection, sam p le ty pe, and name of coll ector. B lind sam p le labeling (i.e., a sam p le code) should be used, along w ith a sam p le log that id entifies inform ation about each sam p le (see Section 2.7) to mi nimi z e potential analy tical bias. Additi onal inform ation such as required analy s es and any preserv ativ e used mi g h t also be included on the labe l althoug h this inform ation is ty pically recorded on the chain- of- custody form (see Section 2.7 and 7. 6). Labeled containers should be stabiliz ed in an uprig ht position in the transport or storag e cont ainer (see Section 4.4 T r ansport and Storag e for further inform ation). Extra containers should be carried on each sam p ling trip.

4-4 U S Environm ental Protection AgencyTechnical M anual 

### 4. **2 S**  **ubsampl i**  **ng and Composi t**  **i ng Sampl**  **es** T h e decision to subsam ple and/or com posite sedime nt sam p les within or am ong stations depends on the purpose and obj ectiv es of the study , the nature and heterog eneity of the sediments, the v o lume of sedime nt required for analy tical a nd/or toxicity assessment, and the deg r ee of statistical resolution that is acceptable. Subsam pling and com positing mi g h t be accom p lished in the field, if facilities, space, and equipment are av ailable, or alterna tiv ely , in a laboratory setting follow i ng sam p le transport.


## R **eco mmen**  **d a**  **tio n**  **B o**  **x #2 How should sediment samples be subsampled and composited?** 

� O v er ly in g w aters hould be s i phoned of f , not dec anted, f r om g r ab s am pler s pr iorto s ubs am plin g . � All utens ils that ar e us ed to pr oc es s s am ples s hould be m ade of iner t m ater i als s uc h as T ef l on® hi g h quality s t ainles s s t eel, orHDPE. � Subs am ples s hould be c ollec t ed aw ay f r om the s i des of the s am plerto avoid potential c ontam ination. � Sedim ent s am ples s hould be pr oc es s ed pr iorto lon g - t er m s t or a g e, w i thin 72 hour s ( and pr ef er ably w i thin 24 hour s ) of c ollec t ion. � Suf f i c i ent s am ple hom o g eniz a tion, pr iorto plac in g in c ontainer s , is c r itic al f o rac c u r a te m eas ur em ents and c or r ec t s edim ent quality deter m i nations

. � If r i g or ous evaluation of m etal c ontam ination is a f oc us of the s t udy , orif anaer obic c onditions need to be m aintained f orotherr eas ons , it m i g ht be nec es s ar y to hom o g eniz e , s ubs am ple, and c om pos ite s am ples in an ox y g en- f r ee g lovebox orothers uitable appar atus
. � Sim ilardepth hor iz ons or g eolo g ic s t r a ta s hould be s ubs am pled w hen c o m pos itin g co re sa m p l e s.

**4. 2.**  **1 G**  **eneral Procedures**  S ubsam pling is useful for collecting sedime nt fro m a specific depth of a core sam p le, for splitting sam p les am ong m u ltiple laboratories, for obtaining replicates w ithin a sam p le, or for forming a com posite sam p le. C o m positing refers to com b ining aliquots from tw o or m o re sam p les and analy z ing the resulting pooled sam p le (Keith, 1993). C o m positing is often necessary w h en a relativ ely larg e am ount of sediment m u st be obtained at each sam p ling site (for instance, to conduct sev e ral different phy sical, chemical or biolog ical analy ses). C o m positing mi g h t be a practical, cost- e ffectiv e w a y to obtain av erag e sedime nt characteristics for a particular s ite (see T able 2- 2), but not to dilute a polluted sam p le. A l so, if an obj ectiv e of the study is to define or m odel phy sicochemical characteristics of the sediment, it mi g h t be im portant not to com pos ite sam p les because of m odel input requirements (EPRI , 1999).

C

hapter 4: Field Sam p

ling Processing, Transport, and Storage of Sedim ents and Interstitial W a

ter 4-5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses All utensils (e.g ., spoons, scoops, spatulas) which co me in direct contact with sediment sam p les during handling and processing should be m ade of non- contaminating m aterials (e.g ., g l ass, hig h

quality stainless steel and/or Teflon®). 

## Cons **ide r**  **a t**  **ions All handling procedures carry the**  **risk of sample cont**  **aminat ion.**  **Therefore, sediment sample ha ndling should be kept to a**  **minimum. Pot**  **e**

**nt ial sample cont**  **aminat ion can be caused by**  **the following common situations...** ! m a k i n g f i eld m eas ur em ents of s edim ents us in g c ontam inated pr obes , utens ils , orother i n st ru m e n t s. ! c ontam inated and unc ontam inated s t ations ar e s am pled w i thout appr opr iate dec ontam ination of equipm ent betw een s t ations

. ! t he par am eterof inter e s t is volatile ( e . g ., am m onia, ac id volatile s u lf ides , orvolatile or g anic s ) and s am ples ar e ex pos ed to air

. ! s am ples ar e ex pos ed to ves s el ex haus t f um es , lubr ic ants , orr us t
.
**4. 2.**  **2 G**  **rab Sampl es**  I f

a sediment g r ab sam p le is to be subsam pled in the laboratory , the sam p le should be released carefully and directly into a labeled container that is the same shape as the sam p ler and m ade of a chemically

- i nert m aterial (see Section 4.1 for recommendations on containers). T h e container m

u st be larg e enoug h to accomm odate the sediment sam p le and should be tig htly sealed w ith the air excluded. I f

the g r ab sam p le is to be subsam pled in the field, it is desirable to subsam ple from the sam p ler directly to mi nimi z e sedime nt handling and associated artifacts. T h erefore, the sam p ler should allow access to the surface of the sam p le without loss of water or fine- g rained sediment (see Section 3.1.1 for sam p ler descriptions). T h is ty pically dictates the use of a g r ab sam p ler w ith bucket cov ers that are either rem o v able or hing ed to allow access to the surface of the sediment sam p le (e.g ., Ponar, V a nV een). P r ior to subsam pling from the g r ab sam p ler, the ov erly ing water should be rem o v ed by slow siphoning using a clean tube near one side of the sam p ler (WDE, 1995; PSEP, 1997a). I f the ov erly ing w a ter in a sedime nt sam p ler is turbid, it should be allow ed to settle if possible. 

## Cons **ide r**  **a t**  **ions W**  **h**

**en working with grab samples...** 

! dec antin g the w ater , oropenin g the

ja w s l i g htly to let the w aterr un out is not r ec om m ended as thes e m ethods mi g ht r es ult in unac c eptable dis t ur banc e orlos s of f i ne- g r a ined s edim ent and or g anic m atter
. ! i f m etal c ontam ination ors edim ent ox y g en dem and ar e of c onc er n, ox idation of s edim ents c ould si g nif i c antly altertheirc har ac ter i s t ic s . Pr oc es s the s a m p le in a g lovebox or s i m ilarappar atus underan ox y g en- f r ee envir onm ent. ! f ors am ples that ar e s us pec ted of heavily elevated poly nuc learar om atic hy dr oc ar bons ( PAHs ) , pr oc es s im m ediately underlowli g ht upon r e tr iev a l to m i nim i z e ultr av iolet li g htac tivated tox i c i ty of PAHs ( A nk ley et al., 1994)

.

4-6 U S Environm ental Protection AgencyTechnical M anual The g eneral subsam pling and com positing process for g r ab sam p les is illustrated in F i g u re 4- 2. Subsam pling can be performed using a spoon or scoop m a de of inert, noncontaminating m a terial. Sediment which is in direct contact with the sides of the grab sam p ler should be excluded as a g eneral precaution ag ainst potential contamination from the dev i ce. Subsam ples m ay be com b ined or placed into separate clean, pre- labeled containers. I f the sam p le is to be froz en, it is adv i sable to leav e approxim ately 10% head space in the container to accomm odate expansion and av oid break ag e. There are tw o alternativ es for com positing sedime nt sam p les from g r ab sam p lers (see F i g u re 4- 2): (1) com positing and hom og eniz ing (mixing ) in the field and (2) com positing in the field and hom og eniz ing in the laboratory
. I n some studies (e.g ., w h ere metals are the pollutants of concern), it mi g h t be necessary to subsam ple a g r ab sam p le under oxy g en- free conditions to mi nimi z e oxidativ e chang es. I n these cases, it is recommended that a handcoring dev i ce be used for subsam pling
. T h e core should be inserted immediately upon retriev al of the sam p ler, then rem o v ed and placed into a g l ov e box or bag w h ich is flushed w ith a constant, controlled v o lume of inert g as. 

## C **h ecklist**  **Compositing samples involves** 

**I n**  **the fi**  **e l**  **d** � plac in g s ubs am ples f r om individual g r ab s am ples in a c l ean c ontainerto f o r m a c o m pos ite s a m p le � tr ans por tin g the c om pos ite to a labor ator y � hom o g eniz i n g the s am ple at the labor ator y to pr epar e it f ortes t in g (S e e Sec t ion 4.3 f o rf u r t herdetails ) **In t h**  **e lab** � plac in g s ubs am ples f r om m u ltiple g r abs in a c l ean c ontainer � mi x i n g the s ubs am ples to f or m a hom o g eneous c om pos ite s am ple � plac in g the c om pos ite s am ple in one orm or e c ontainer s , dependin g on the num berof analy s es to be per f or m ed � tr ans por tin g the c om pos ite s am ple to a labor ator y ( orlabor ator ies ) f or tes t in g

T h e sediment w ithin the core can then be extruded under oxy g en- free conditions into deaerated containers. T h e presence of oxy g en during hand ling and storag e mi g h t be relativ ely unim portant (Brum b aug h et al., 1994) or v ery im portant (Besser et al., 1995), depending on the sediment characteristics, the contaminants of concern, and the study obj ectiv es. **4. 2.**  **3 C**  **ore Sampl es**  Subsam pling sediment core sam p les is usually done to focus the assessment on a particular sediment horiz on or horiz ons and/or to ev al uate historical chang es or v er tical extent in contamination or sedimentation rates. Whenev er subsam pling of retr iev ed sediment cores is required, particularly for analy s is of contaminants, the sediment should be extruded from the core liners and subsam pled as soon as possible after collection. T h is can be acco m p lished in the field if appropriate facilities and equipment are av ailable, or in the laboratory after transport. Sy stem atic subsam pling (see Fig u re 4- 3) inv o lv es rem o v i ng the sediment from the core in sections of uniform thick n ess. Each incremental core sec tion corresponds to a particular sediment depth interv al. I n remedial dredg i ng and g eolog ical applications, long er sections (e.g ., 25- 50 cm ) are ty pically used to characteriz e a site.

C

hapter 4: Field Sam p

ling Processing, Transport, and Storage of Sedim ents and Interstitial W a

ter 4-7M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

**F i**  **g u**  **r e 4-**  **2.** Alter natives f o rs ubs am plin g and c o m pos itin g s edim ent g ra b sa m p l e s.

4-8 U S Environm ental Protection AgencyTechnical M anual

**F ig**  **u r**  **e 4- 3.**  Alter natives f o rs ubs am plin g and c o m pos itin g se d i m e n t co re sa m p l e s.

C

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thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses The depth horiz on(s) sam p led w ill depend on the study obj ectiv es as w ell as the nature of the substrate. For toxicolog i cal studi es, the biolog ically activ e lay e r and sedime ntation rates at the site mi g h t be im portant factors determining w h ich co re sections are sam p led. I n these studies, subsam pling depth interv als include the 0 to 2 cm lay er (for recent deposition) and the 0 to 5 cm or 0 to 15 cm lay ers (for biolog ical activ ity , depending on resident org anism s). Many prog ram s hav e proj ect- s pecific depths corresponding to study requirements, such as dredg i ng depths for nav i g ation or remediation dredg i ng . I n m any reg i onal or national env i ronmental m onitoring prog ram s (e.g ., EMA P ), the upperm ost surficial lay e r is sam p led because inform ation on the horiz ontal distribution of sediment contaminants is desired (USEPA, 2000d). T h ere are v arious methods for subsam pling sedimentcores including g r adual extrusion, dissection of a core using a j i g saw, reciprocating saws, use of a seg mented g r av ity corer, a hand corer, or scoops and spoons. C u tting dev i ces rang e from stainless steel k n iv es to teflon or ny lon string
. A piston- ty pe extruder that applies upward pressure on the sediment is an instrument comm only used to g r adually expose a core for sectioning in so me m onitoring prog ram s where specific sediment depths hav e been defined a priori (K em p et al., 1971). [Note: For dredg e d m a terial studies and other ty pes of remediation proj ects, where pre- determineddepth strata are not necessarily defined, it is usually im portant to v i ew the entire core prior to sectioning or com positing
. ] The capped core liner containing the sediment and ov erly ing w ater is uncapped at the low er end and placed v ertically on top of the piston. T h e top cap is rem o v ed and th e water is siphoned off to av oid disturbance of the sediment- w ater interface. T h e core liner is then pushed slow ly dow n until the surface of the sediment is at the upper end of the liner. Sediment sections are collected by pushing the liner down and cutting the exposed sediment into sections of the desired thickn ess using a stainless steel or T eflon® cutter (Env ironment Canada, 1994; Mudroch and Az cue, 1995). A 1- to 2- mm outer lay e r of sediment that has been in contact with the pl astic or metal liner should be rem o v ed and discarded, if possible, to av oid contaminati on. Each sedime nt subsam ple shoul d be placed into a labeled, clean and chemically

- i nert container, or, if subsam ples are being com posited, into an appropriately siz ed mi xing bowl. T h e siz e of the cont ainer should be as close to the v o lume of the sediment as possible to mi nimi z e the head space in the container. I f it is desirable to m aintain an oxy g en- free env i ronment during subsam pling , then all handling or m anipula tions should take place in a g l ov e box or bag filled w ith an inert g as and m odified to accomm odate the core liner throug h an opening (Env ironment Canada, 1994; Mudroch and MacK nig h t, 1994). Cores of m o re consolidated m aterial can be m ount ed onto a horiz ontal U- shaped rail and the liner cut using a saw m ounted on a depth- controlling j i g . T h e final cut can then be m ade w ith a sharp k n ife to av oid contamination of the sediment by liner m ateri al, and the core itself can be sliced w ith T eflon® or ny lon string
. T h e core then become s two D- shaped halv es that can be easily inspected and subsam pled (Mudroch and Az cue, 1995)
. Sediment in contact with the saw blade should not be used for toxicity tests or metals analy ses due to pot ential contamination from the saw blade. Another alternativ e for sectioning and subsam pling is a seg mented g r av ity corer described by Aanderaa I n struments of V i ctoria, BC, Canada
. T h e core tube of the sam p ler consists of a series of ring s placed on top of one another. Subsam pling is ca rried out by rotating the ring s around its other axis so that it cuts sedime nt lay e rs of similar thickn ess. This seg mented core tube is suitable for sam p ling fine- g rained sediments and allows one person in th e field to subsam ple the core into 1- cm sections (Mudroch and Az cue, 1995). Sediment from box- core sam p les can be effectiv el y subsam pled with a sm all hand corer after the ov erly ing water has been carefully siphoned off and discarded. Hand corers with sm all inner diameters less than 3 cm tend to com p act sediments, so they m u st be used with care. Spoons or

4-10 U S Environm ental Protection AgencyTechnical M anual scoops hav e also been used to subsam ple surf ace sediments from a box corer (Env ironment Canada, 1994). L i keg r ab s a mp l e s , c o r es a mp l e s ma y b ec o mp o s i t e d or subsam pled in the field or laboratory after ev aluating them for acceptability
. A lthoug h there mi g h t be occasions w h en it is desirable to com posite incremental core depths, it is recomme nded that only horiz ons of similar stratig raphy be com posited. Depending on the study obj ectiv es a nd desired sam p ling resolution, indiv i dual horiz ons w ithin a sing le core can be hom og eniz ed to create one or m o re “depth com posites” for that core, or corresponding horiz ons from two or m o re cores mi g h t be com posited (Fig ure 4- 3). Com posite sam p les m u st be hom og eniz ed prior to analy sis or testing
. 

### 4. **3 H**  **omogeni zat**  **i on**  Hom o g eniz ation refers to the com p lete mi xing of sediment to obtain consis tency of phy sicochemical properties throug hout the sam p le prior to using in analy ses. Hom o g eniz ation is ty pically performed on indiv i dual sam p les, as well as on com posited sam p les and can be done either in the field or the laboratory
. **4. 3.**  **1 G**  **eneral Procedures**  Prior to hom og eniz ation, unrepresentativ e m aterial s (e.g ., twig s, shells, leav es, stones, wood chips and seag rass) are often rem o v ed and documented in an appropriate field log (see Section 5.2 for techniques to rem o v e unrepresentativ e m aterial). T h e need for rem o v al of larg er m atter depends on the analy s es to be conducted. Mixing should be performed as quickly and effici ently as possible, because prolong ed mi xing can alter the particle- siz e distribution in a sam p le a nd cause oxidation of the se diments (Ditsworth et al., 1990; Stemmer et al., 1990a;b). T h is can alter th e bioav a ilability of contaminants, particularly metals, by increasing or decreasing their av ailability (A nkley et al., 1996). I f metal contaminants or v o latile chemicals are a concern, sam p les should be mi xed in a g l ov ebox under an inert atm o sphere and quickly partitioned into sam p le containers for analy sis.


## R **eco mmen**  **d a**  **tio n**  **B o**  **x #3 How should samples be homogenized?** 

� Us e a s uf f i c i ently lar g e, pr ec leaned g l a ss o rst a i n l e ss st e e l m i xi n g bow l to hom o g eniz e the s am ple. � Us e c l ean g las s poly e thy l ene, ors t ainles s s t eel im plem ents ( e . g ., s poon) to m i x s edim ent. � Mix i n g s hould be per f or m ed as quic k ly and ef f i c i ently as pos s i ble w hile attem ptin g to r educ e ox idation of the s am ple. � Intens ive m anual m i x i n g of w et s edim ent, in a s uitably lar g e c ontainer , is us ually s u f f i c i ent to hom o g eniz e the s am ple ( B ur ton et al., 1989; In g er s oll and Nels on, 1990; J ohns et al., 1991a; Car rand Chapm an, 1992)

. � Re g ar dles s of the m i x i n g m ethod s elec t ed, the ef f ec t ivenes s of the m ethod s hould be dem ons tr ated us in g a hom o g enate r eplic ate

.

C

hapter 4: Field Sam p

ling Processing, Transport, and Storage of Sedim ents and Interstitial W a

ter 4-11Methods for C ol lecti on, S torage, and Mani pul ati

on of S edi ments for C hemi c al and T ox

i cologi cal A nal yses

Ph ot o c ou rt es y of

N i l e K em b l e

Hom ogeni zi ng a com posi t ed sedi m ent Ph ot o c ou rt es y of

C h ri s I n g er s ol l sam pl e usi ng a m echani cal m i xer

Subsam pl i ng sedi m ent for t oxi ci t y t est i ng

4-12 U S E

n vi ronmental P

r otecti on A gencyTechnical M anual Mixing should be performed in a larg e, precleaned g l ass or stai nless steel bow l. T h e sediment should be thoroug hly stirred with a clean g l ass, hig h density poly ethy l ene, or stainless steel spoon until textural, color, and m o isture hom og eneity are achiev ed (Env ironment Canada, 1994; PSEP, 1995). Hand mi xing has also been performed by rolling the sediment out flat on a sheet of plastic or pre- com busted foil and tum b ling the sedime nt by alternately raising each corner of the sheet (Mudroch and Mack nig h t, 1994). T h is procedure, howev er, is not recommended w h ere the anaerobic integ r ity of the sediment m u st be m aintained. 

## Cons **ide r**  **a t**  **ions Homogenization of**  **anaerobic sediment s** 

**...**
! B ew ar e of over - m ix in g and/or intr oduc in g airto the s am ple. Suc h mi x i n g is lik ely to c han g e the c hem ic al c har ac ter i s t ic s of the s am ple and y i eld unr epr es entative r e s u lts

. T h is is es pec ially im por tant if s a m p les ar e initially anaer obic orif volatile orlabile c hem ic als ar e of inter e s t ( e . g ., AVS)

.
Mechanical mi xers hav e also been used to hom og eniz e sam p les (Ditsworth et al., 1990; Stemmer et al., 1990b; K em b le et al., 1993), incl uding portable cement mi xers (bare metal and T eflon- lined) and portable drills fitted w ith a v ariety of stai nless steel paddles (K em ble et al., 1994b). Hom o g enate replicates consist of two or m o re s ubsam ples, taken from different locations within a mi xed sam p le, and then com p aring analy tical results of the replicate sam p les. A f ter the sediment has been hom og eniz ed, it is g enerally partitioned am ong sam p le containers. P artitioning sediments for chemical or toxicity analy ses m ay be accom p lishe d using v arious me thods. I n one me thod, a num ber of sm all portions are rem o v ed from random locati ons in the mi xing c ontainer and distributed randomly in all sam p le j ars until the appropriate v o lume of sediment is contained in each sam p le j ar for each analy sis. D u ring distribution, the sedi ment is periodically mi xed using a g l ass rod or porcelain spatula to mi nimi z e stra tification effects due to differential settling , especially if the sediment is prone to rapid settling (A ST M, 2000a). A n alternativ e is to use a splitter box desig n ed to contain and then div i de the hom og eniz ed sediment. 

### 4. **4 S**  **ampl e T**  **r ansport and Storage**  T r ansport and storag e methods shoul d be desig n ed to m aintain structural and chemical qualities of sediment and pore water sam p les. Sediments collect ed using g r ab sam p lers are usually transferred from the sam p ler to containers that m ay or m ay notserv e as the storag e container. T h e containers mi g h t be stored tem porarily in the field or they mi g h t be transported imme diately to a laboratory for storag e. I f sediment core sam p les are not sectione d or subsam pled in the field, they m ay be stored uprig ht, in the core liner, for intact transportation to the laboratory
. I f sectioning or subsam pling takes place in the field, then the subsam ples m ay al so be transferred to sam p le containers and stored tem porarily
. T h e sam p le containers w ith the fi eld- collected sediments are then placed into a transport container and shipped to the laboratory
. **4. 4.**  **1 G**  **eneral Procedures**  Proper storag e conditions (see T able 4- 1) should be achiev ed as quickly as possible after sam p ling
. For those parame ters that are preserv e d v i a refrig e ration (e.g ., toxicity ) sam p les should be stored in the field in refrig erated units on board the sam p ling v e ssel or in insulated containers containing ice or froz en ice pack s. For sam p les that can be preserv ed v i a freez ing (e.g ., some metal and org anic chemical analy ses) dry ice can be used to fr eez e sam p les for tem porary storag e and transport (USEPA, 1983, 1993). Pelletiz ed dry ice has been used effectiv ely in the dredg e d m a terials m anag ement prog ram to store core sam p les. I tis im portant to know chilling capacities and
C

hapter 4: Field Sam p

ling Processing, Transport, and Storage of Sedim ents and Interstitial W a

ter 4-13M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses efficiencies to assure that tem p erature reg u lati on is adequate. Care should be taken to prev ent refrig e rated sam p les from freez ing and to keep fro z en sam p les from thaw ing
. F r eez ing chang es the sediment v o lum e depending on the water content, and it perm anently chang es the structure of the sedime nt and potentially alters the bioav a ilab ility of sedime nt associated contaminants. L o g i stics for sam p le transport w ill be specifically tailored to each study
. I n som e cases it is m o st efficient to transfer sam p les to a local storag e fac ility w h ere they can be either froz e n or refrig e rated. Depending on the log i stics of the operation, field personnel m a y transport sam p les to the laboratory them selv es or utiliz e an ov ernig h t courier serv ice. I f a freig ht carrier is em ploy ed, the user m u st be aw are of any potentially limiting reg u lations (e.g . reg a rding the use of ice or dry ice). S am p les that hav e a recommended storag e tem p erature should be c ooled to that tem p erature prior to placem ent in the transport container. Lig h t should be excluded from the transport container. Core sam p les should be transported as intact core lin ers (tubes). Prior to sam p le transport, the entire space ov er the sediment in the core liner should be filled w ith site w ater, and both ends of the core liner should be com p letely sealed to prev ent mi xi ng of the sediment inside. T h e cores should be m a intained in an uprig ht position particularly if th e sam p le is not hig h ly consolidated m aterial, and secured in either a transport container (e.g ., cooler or insulated box) with ice or ice pack s, or in a refrig e rated unit that can m a intain a tem p eratur e near 4° C (Env ironment Canada, 1994). I f the transport container cannot accomm odate long core sa m p les such as from v i bracorers or piston corers (core liners > 1 m ) , then the core sam p les can be cut into 1- m leng ths, and the ends securely capped such that no air is trapped inside the liners (see Section 4.3.3). I m preg nating unconsolidated sediment cores w ith e poxy or poly ester resins w ill preserv e sediment structure and texture (Ginsburg et al., 1966; Crev ello et al., 1981) but not sediment chemical characteristics. T h erefore, this procedure is not recommended for transporting or storing sediment sam p les for chemical characteriz ation or bi olog ical testing (Env ironment Canada, 1994).



## R **eco mmen**  **d a**  **tio n**  **B o**  **x #4 Sample Transport and Storage** 

� T he volum e of over ly in g w aterin s edim ent s am ples s hould be m i nim i z ed to r educ e the potential f o rr e s u s pens ion of s u r f ac e s edim ents dur in g tr ans por t. � Car e s hould be tak en to r e tain the s u r f ic ial f l oc over ly in g a co re sa m p l e . � Cor es s hould be s ec ur ed in an upr i g ht pos ition dur in g tr ans por t to m i nim i z e dis t ur banc e of the s edim ent. � Sedim ent s am ples c ollec t ed in the f i eld s hould be s t or ed in c ontainer s w i thout heads pac e at 4° C and in the dar k to m i nim i z e c han g es in c ontam inant bioavailability

. � Pr iorto tr ans por t, heads pac e in the c or e liners hould be f illed w i th s i te w aterand both ends of the liners hould be c om pletely s ealed.

4-14 U S Environm ental Protection AgencyTechnical M anual 

### 4. **5 S**  **ampl e Hol**  **di ng**  **Ti m**  **e s**  L i mits for effectiv e holding times are g o v erned by sediment ty pe and contaminant characteristics (A ST M, 2000a). B ecause these qualities are not alway s k nown, a g e neral recommendation is to store sediments and interstitial w a ter in the dark at 4 ° C (SET AC, 2001). Preserv a tion and recommended storag e times for v arious ty pes of analy ses are summ ariz ed in T able 4- 1. 

## R **eco mmen**  **d a**  **tio n**  **B o**  **x #5 How long should samples be**  **st ored bef**  **o**

**re analysis?**

� Unles s s i te- s pec if ic inf o r m ation is available, s edim ent s am ples s hould be s t or ed no lon g er than tw o w eek s pr iorto us in g in tox i c i ty tes t in g . � Pr es er ved s a m p les f o rc hem ic al analy s es s hould be s t or ed no lon g erthan the m ax i m um holdin g tim es as def ined by the par tic ular pr o g ra m .

Sam p les collected for toxicity tests should be us ed as quickly as possible. Recommended m axim u m hol di ng t i mes r a ng e f r om 10 day s ( NOAA) t o t w o week s ( A ST M, 2000a; USEPA, 2000d) , t o ei g h t week s (USEPA/ACOE, 1991, 1998). Preferred sam p le storag e tim es reported for toxicity tests hav e v aried substantially (Dillon et al., 1994; Becker and Ginn, 1990; Carr and Chapm a n, 1992; Moore et al., 1996; Sarda and Burton, 1995; Sij m et al., 1997; Defoe a nd Ankl ey , 1998), and differences appear to depend prim arily upon the ty pe orclass of contaminant(s) present. Extended storag e of sediments thatcontain hig h concentrations of labile contaminants (e.g ., amm onia, v o latile org anics) mi g h t lead to loss of these contaminants and a corresponding reduction in toxicity
. Under these circum stances, the sedi ment should be tested as soon as possible after collection, but not later than tw o week s (Sarda and Burton, 1995). Sediments that exhibit low to m oderate toxicity mi g h t exhibit hig h er v ariability in toxicity w h en tested follow i ng storag e of short duration (e.g
. two week s). T esting could actually be m o re reliable follow i ng long er storag e for these ty pes of sam p les if the long er storag e reduces potential interference associated with indig enous predators (DeFoe and Ankl ey , 1998). Sedime nt s contaminated with relativ ely stable com pounds (e.g . hig h m o lecular weig ht com pounds such as PCBs) or those that exhibit m oderate- t o- hig h toxicity , do not seem to v ary appreciably in toxi city with increased storag e time (Moore et al., 1996; D eFoe and A n kl ey , 1998). Long er term storag e mi g h t be acceptable in such cases. G i v en our incom p lete knowledg e on the chang es that occur, it is recommended that sediments should be stored no long er than tw o w eek s for toxicity testing unl ess site- specific inform ation indicates otherw ise. Periodic measurements of contaminants of concer n prov ide a useful context for interpretation of toxicity test results w h en sedime nts or interstitial w aters are stored for extended periods of time, but this is rarely cost- e ffectiv e. I tmi g h t be m o re efficient to conduct interstitial w a ter toxicity tests within two week s of sedi ment collection, corresponding with the start of sedime nt tests (I ng ersoll et al., 1993). I n g eneral, thoug h, interstitial w ater s hould be analy z ed as quickly as possible follow i ng sam p ling to mi nimi z e possible chan g e s in contaminant bioav a ilability
. Sedime nt cores collected for stratig raphical or g eolog ical studies can be stored at 4 ° C in a humidity

controlled room for sev eral m onths without any s ubstantial chang es in sediment properties (Mudroch and Az cue, 1995).

C

hapter 4: Field Sam p

ling Processing, Transport, and Storage of Sedim ents and Interstitial W a

ter 4-15M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

4-16 U S Environm ental Protection Agency**CHA PT**  **ER** 

# 5 Technical M anual 

## Sediment M **a**

**nipulations**

Manipulation of sediments in the laboratory is often required to achiev e certain desired characteristics or form s of m a terial for toxicity te sting and chemical analy sis. A s all m anipulation procedures alter some qualities of field sam p les, it is critical to ev aluate the effect that these chang e s mi g h t hav e on the study obj ectiv e and on each cr itical measurement endpoi nt. T h erefore, all procedures used to prepare sediment sam p les shoul d be explicitly described in the study plan and fully documented. Generally , m anipulation proce dures should be desig n ed to m aintain sam p le representativ eness in term s of toxicity and chemis try by mi nimi z i ng proce dural artifacts. Under certain prog ram s, some analy tical procedures a nd toxicity test protocols necessitate specific m anipulations (e.g ., seawater or solv ent extracti ons for effluent toxicity tests, USEPA/ACOE, 1991, 1998). T h e reader should alway s consult and follow any prog ram or test- s pecific g u idance. T h is chapter discusses me thods for sev e ral co mm on m anipulations performed in the laboratory including siev ing , spik ing , org a nic carbon m odification and form ulated sediments, sediment dilution, and elutriate preparati on. Other sediment m anipulations, su ch as salinity adj u stments or pretreatment of sediment amm onia or sulfides (often done in conj unction with toxicity testing in certain reg u latory prog ram s) are not discussed in this m anual as these are well documented elsewhere (e.g ., PSEP, 1995; USEPA/ACOE, 1998). T h e reader should consult these references for further inform ation on these procedures. Fig u re 5- 1 pr esents a flow chart summ ariz i ng the laboratory m anipulations discussed in this section, illustra ting im portant issues to be considered for each m anipulation. 

### 5. **1 S**  **i ev**  **i ng**  I n g eneral, siev ing is not recommended because it can substantially chang e the phy sicochemical characteristics of the sediment sam p le. For exam ple, wet siev ing of sediment throug h fine mesh ( 

### � 500 

### � m opening s) has been shown to result in decreased percent total org a nic carbon and decreased concentrations of total P C B s, w h ich mi g h t hav e been associated with fine suspended org anic m a tter lost during the siev ing process (Day et al., 1995). Siev ing can also disrupt the natural chemical equilibrium by hom og eniz ing or otherwise chang i ng the biolog ical activ ity w ithin the sedime nt (Env ironment Canada, 1994). I n some cases, how ev er, siev ing mi g h t be necessary to rem o v e indig enous org anism s, which can interfere with subsequent toxicity testing and confound 

## C **h ecklist**  **Sediment samples are**  **sieved f o** 

**r t h** 

**e f o** 

**llowing reasons:** 
� T o r em ove unr epr es entative m ater i al, s uc h as s hells , s t ones , tr as h, and tw i g s. � T o inc r eas e hom o g eneity and r eplic ability of sa m p l e s. � T o r e m o ve indi g enous or g anis m s pr iorto tox i c i ty tes t in g . � T o f a c ilitate or g anis m c ountin g , s edim ent handlin g , and s ubs am plin g . � T o ex am ine the ef f ec t s of par tic l e s i z e on tox i c i ty , bioavailability , orc ontam inant par titionin g ( AST M, 2000a)

.

C

hapter 5: Sedim ent M anipulations 5-1M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

**F i**  **g u**  **r e 5-**  **1.** F l ow c har t depic t in g r elations hips betw een c om m on s edim ent m anipulations inc l udin g im por tant c ons ider ations

.

5-2 U S Environm ental Protection AgencyTechnical M anual interpretations of analy tical results (USEPA , 1994; 2000d; AST M , 2000e). I ndig enous org anism s can be problem atic in toxicity testing because they mi g h t be similar in appearance to test org a nism s or they mi g h t prey on the test org anism s. I f

siev ing is performed, it should be done for all sam p les to be tested, including control and reference sediments if the obj ectiv e of the study is to com p are results am ong stations (AST M, 2000a). I tmi g h t be desirable to obtain certain measurements (e .g ., dissolv ed and total org anic carbon, acid v o latile sulfide [AV S ], and sim u ltaneously extracted meta ls [SEM]) both before and after m anipulation, to document chang es associated w ith siev ing (U SEPA , 2000d). I n addition, it mi g h t be desirable to document the effect of siev ing on the sediment sam p le by conducting com p arativ e toxicity tests using siev ed and unsiev ed sediment (Env ironment Canada, 1994).


## R **eco mmen**  **d a**  **tio n**  **B o**  **x #1 Should sediment be sieved prior to analyses?** 

� In g ener al, s i evin g is not r ec om m ended bec aus e it c an s ubs tantially c han g e the phy s i c oc hem ic al c har ac ter i s t ic s of the s edim ent s am ple. How ever , s i evin g mi g ht be nec es s ar y in pr epar in g sa m p l e s f o r so m e se d i m e n t t o xi ci t y t e st i n g ( i .e., m ar i ne am phipod tes t s ; USEPA, 1994)

. � Unw anted m ater i als ( e. g ., lar g e par tic l es and indi g enous or g anis m s ) c an be r e m o ved f r om the s edim ent s am ple us in g f or c eps as a pr ef er r ed alter native to s i evin g .
**5. 1.**  **1 S**  **i ev**  **i ng M**  **et hods**  Press Sieving I f

siev ing is necessary , press siev ing is the prefe rred method. I n this method, sediment particles are hand- pressed throug h a siev e using chemically iner t paddles (Giesy et al ., 1990; J ohns et al., 1991). Matter retained by the screen, such as org anism s, shell frag ments, g r av el, and debris, should be recorded in a log book and dis carded (USEPA/ACOE, 1991)
. Sam p les with hig h debris, v eg etation, or clay content mi g h t be difficult to press throug h a sing le siev e w ith a mesh siz e less than 1 mm ; such sam p les mi g h t need to be pressed throug h a series of siev es with prog ressiv ely sm aller opening s. Water should not be adde d to sediment when press siev ing , as this could result in chang es in contaminant concentration and bioav ailability
. S am p les that are g o ing to be used for both chemical analy sis and toxicity tests should be si ev ed tog ether, hom og eniz ed, and then split for their respectiv e analy ses. WetSi evi ng I f

sediments cannot be press siev ed w ithout the a ddition of pressure, w et siev ing mi g h t be required, howev er, this ty pe of siev ing increases the lik elihood of contaminant loss. Wet siev ing inv o lv es sw irling sedime nt particles w ithin a siev e using w a ter to facilitate the mechanical separation of sm aller from larg er particles. A slurry m a de w ith water that has separated from the sediment during storag e or transport mi g h t be sufficient to wash pa rticles throug h the siev e. Wet sam p les that mi g h t hav e settled during transit should be stirred to incor porate as m u ch field w ater as possible. I n some cases, addition of a sm all v o lume of running site or deioniz ed water mi g h t be required (AST M,
C

hapter 5: Sedim ent M anipulations 5-3Methods for C ol lecti on, S torage, and Mani pul ati

on of S edi ments for C hemi c al and T ox

i cologi cal A nal yses

P h ot o c ou rt es y of

A l l en B u rt on

S i evi n g a s e d i m e n ts a m p l e for tox i ci ty tes t i n g

5-4 U S E

n vi ronmental P

r otecti on A gencyTechnical M anual 2000a). Mechanical shakers or stirring w ith a ny lon brush can also facilitate w et siev ing (Mudroch and MacK nig h t, 1994). R ecom m e nded Sieves I n g eneral, sm aller mesh siev es are preferred to reduce loss of fines. Stainless steel, brass, or plastic wov en poly mer siev es (e.g ., poly ethy l ene, poly p ropy lene, ny lon, and T eflon) with mesh siz es that v ary from 0.24 to 2.0 mm hav e been used to siev e sediment for toxicity tests (Keilty et al., 1988a;b; Giesy et al., 1990; Ly dy et al., 1990; Stemmer et al., 1990a;b; J ohns et al., 1991; Landrum and Faust, 1991). Nonme tallic siev es are preferred if me tals are of interest. Stainl ess steel siev es are acceptable if org anic com pounds are of interest. Stainless steel (prov i ded the mesh is not soldered or welded to the frame), ny lon, or Nitex- ty pe plastic siev es are recommended w h en other inorg anic constituents are of concern or 

## Cons **ide r**  **a t**  **ions The mesh type and size**  **should be chosen based on the following**  **considerations...**
! T he ty pe of tox i c i ty tes t and tes t or g a n i sm s t o be us ed. ! P otential pr edator s and/orc om petitor s pr es ent in the s am ple. ! P otential ads or ption orc ontam ination of the c hem ic al of inter e s t due to s i evin g . ! T he natur e of the s am ple, inc l udin g i t s p a r t i cl e s i z e dis t r i bution, volum e, and s i z e of debr is

. are to be analy z ed (AST M, 2000a; PSEP, 1995). 

## R **eco mmen**  **d a**  **tio n**  **B o**  **x #2 W**  **h**

**at type of sieve should be used?** 

� Stainles s s t eel orbr as s s i eves ar e not r ec om m ended w hen m etals ar e a c onc er n or ar e analy z ed ( AST M, 2000a)

. � Sm allerm e s h s i eves ( � 2.0 m m m es h openin g s) ar e r ec om m ended to r educ e los s of f i ne par tic l e si z e s. � Ny lon ornitex m es h s i eves ar e r ec om m ended f o rinor g anic s analy s es ( e . g ., m etals )

.

**5. 1.**  **2 A**  **l t**  **ernat i**  **v es t**  **o Si**  **ev i**  **n g**  Generally , siev ing throug h a 10- mesh (2- mm opening s) siev e is acceptable as a basis to discrimi nate between sediment and other m aterials (AST M, 2000a). For toxicity testing , the m o st frequently used mesh siz e is 1.0 mm (Env ironment Canada, 1994), which w ill rem o v e m o st adult am phipods. Howev e r, a me sh of 0.25 mm mi g h t be needed to rem o v e imm ature am phipods and m o st m acrofauna (Landrum et al., 1992; Robinson et al., 1988; Day et al., 1995). I n m arine sediments, siev es with a mesh siz e of 0.5 mm are effectiv e in rem o v i ng m o st of the imm ature am phipods (Swartz et al., 1990; PSEP, 1995).

Unwanted m aterials (e.g ., larg e particles, trash, and indig enous org anism s), can be rem o v ed from the sediment sam p le using forceps, prior to or, as an a lternativ e to, siev ing
. I f anerobic integ r ity of the sam p le is not a concern, the sediment could be spr ead on a sorting tray m ade of cleaned, chemically

inert m aterial, and should be hand- picked with fo rceps. A stereomi croscope or m ag n ify i ng lens mi g h t facilitate the process, or m ay be used to determine if siev ing is necessary
. H and- picking is
C

hapter 5: Sedim ent M anipulations 5-5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses preferable to siev ing because it is less disruptiv e, but it ty pically is not practical for larg e v o lume s of sediment. O f course, this process oxidiz es the se dime nt and mi g h t alter contaminant bioav a ilability
. Autoclav ing , freez ing , and g amm a irradiation of se dime nts are alternativ es to phy sical rem o v a l for inhibiting endemi c biolog ical activ ity in field- collected sediments. These are not g enerally recomme nded procedures. Each me thod has unique effects on the phy sicoch emical and biolog ical characteristics of the sedime nt, and a careful ev aluation with respect to the study obj ectiv es is warranted when these methods are considered. 

## Cons **ide r**  **a t**  **ions In preparing formulated sediments, the following should be**  **noted...**
! S pec if ic m a ter i al s our c e s s hould be c a r e f u lly s e lec t ed, as c har ac ter i s t ic s c an var y si g nif i c antly am on g pr oduc t ty pes . A num berof s upplier s of var i ous s edim ent c om ponents ar e lis ted in AST M ( 2000a) and USEPA ( 2000d)

. ! Ac r itic al c om ponent of f or m ulated s edim ents is the s our c e of or g anic c ar bon. It is not c l ear that any one s our c e of or g anic c a r bon is r outinely s uper iorto another

. Alpha c e llulos e appear s to be a pr om is in g c ar bon s our c e f orf or m ulated s edim ents
. ! Avar i ety of f or m ulations have been us ed s uc c es s f ully in s edim ent tox i c i ty tes t in g (se e AST M [2000a] and USEPA [2000d])

. At this tim e, no one f or m ulation appear s to be univer s ally betterthan other s .



### 5. **2 Formul**  **at ed Sedi**  **ment and O**  **r gani**  **c Carbon Modi f**  **i cat**  **i on**  **5. 2.**  **1 G**  **eneral Consi**  **d erat**  **i ons**  Form ulated sediments (also called reconstituted, artificial, or sy nthetic sedime nts) are mi xtures of m a terials that mi mi c the phy sical com ponents of natural sediments. While they hav e not been used routinely , form ulated sedime nts potentially offer adv antag es ov er natural sediments for use in chemical fate and biolog ical effects testing
. Form ulated sedime nts also hav e limitations, howev er. T h ey do not possess the natural mi crobial, meiofaunal, and m acrofaunal comm unities or the com p lex org anic and inorg anic g r adients prev alent in natural sedime nts. T h e lack of biolog ical activ ity , diag enesis, and oxidation- reduction (redox) potential g r adients undoubtedly alters some sorption and desorption properties, which 

## C **h ecklist**  **A**

**d**

**vant a** 

**ges of Formulated Sediments** 
� T hey pr ovide a c ons is tent, r epr oduc ible m edium w h ic h f a c ilitates c o m par is ons betw een dif f er ent s ets of tes t s . � Elim inates inter f er enc es c aus ed by the pr es enc e of indi g enous or g a n i sm s. � Com ponents of the f or m ulated s edim ent c an be alter ed to m eas ur e the ef f ec t of c e r t ain phy s i c o c hem ic al c har ac ter i s t ic s on c hem ic al f a te and bioavailability

. � T hey ar e us ef ul in s p ik in g ex per im ents to obtain ef f ec t c onc entr ations f or c hem ic als

.

5-6 U S Environm ental Protection AgencyTechnical M anual

mi g h t in turn alter contaminant fate and effects. T h e current lack of understanding of phy sicochemical controls on bioav ailability in diffe rent sediment env i ronmen ts precludes broad- scale use of form ulated sediments in definitiv e ecolog i cal risk assessments. A form ulated sediment should: (1) support the surv iv al, g r owth, or reproducti on of a v ariety of benthic inv ertebrates, (2) prov ide consistent acceptable biolog ical endpoints fo r a v ariety of species, and (3) be com posed of m aterials that hav e consistent characteris tics (USEPA, 2000d; AST M ,



## C **h ecklist**  **D**

**isadvant a** 

**ges of Formulated Sediments** 
� T hey m i g ht be over ly s i m p lis tic biolo g ic ally and c hem ic ally

. � An appr opr iate f o r m ulation is not w e ll es tablis hed f o rall applic ations

.

**5. 2.**  **2 S**  **edi m**  **ent Sources**  2000a). Characteristics should include: (1) consistency of m a terials from batch to batch, (2) contaminant concentrations below concentrations of concern, and (3) av ailability to all indiv i duals and facilities (K em ble et al., 1999). Phy s icochemi cal characteristics that mi g h t be considered w h en ev aluating the appropriateness of a sediment form ulation include percent sand/clay/silt, org anic carbon content, cation exchang e capacity (CEC), redox potential, pH, and carbon:nitrog en:phosphorous ratios (USEPA, 2000d; AST M , 2000a).

T h e specific m aterial source should be carefully se lected, as characteristics can v ary sig n ificantly am ong product ty pes. For exam ple, USEPA ( 2000d) found that for three different sources of k aolinite clay , the percentag e of clay rang ed from 56.5 to 88.5%, depending on indiv i dual product specifications. T h ere are a num ber of suppliers of v arious sedimentcom ponents (see USEPA, 2000d). A critical com ponent of form ulated sediments is the source of org anic carbon. I tis not clear that any one source of org anic carbon is routin ely superior to another source. **5. 2.**  **3 O**  **rgani c Carbon M**  **odi f**  **i cat**  **i o**  **n** Org anic carbon content of natural as well as form ul ated sediments can be m odified to assess the effect on contaminant fate and bioav ailability
. Many studies em ploy se diment carbon m odifications because total org anic carbon (T O C ) content has been show n to be a m aj o r determinant of nonionic org a nic chemical bioav a ilability (D iT oro et al., 1991; D eWitt et al., 1992; a nd Kosian et al., 1999). While T O C m odifications mi g h t be necessary to achiev e study obj ectiv es, it should be recog n iz ed that org anic carbon m anipulations can chang e the particle com positi on and siz e distribution, thereby potentially affecting contaminant equilibrium
. T hus, results from such experiments should be interpreted w ith care. A l so, the sam p le need s to be equilibrated (see Section 5.3.3) follow i ng addition of the new source of org ani c carbon, prior to conducting analy s es. Many recipes hav e used peat as the source of org anic carbon, how ev er, the quality and characteristics of peat m o ss can v ary from bag to bag
. O t her sources of org anic carbon include hum us, potting soil, m aple leav es, com posted cow m a nure, rabbit chow, cereal leav es, chlorella, trout chow , T etramin®, Tetrafin®, and alpha cellulose. O f these, only peat, hum us, potting soil, com posted cow m anure, and alpha cellulose hav e been used successfully in se diment testing without fouling the ov erly ing water;

C

hapter 5: Sedim ent M anipulations 5-7M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses other sources hav e caused dissolv ed oxy g en concentr ations to fall to unacceptable lev e ls (Kem ble et al., 1999).
**M o**  **r e**  **a bout or**  **ga nic**  **c a**  **r bon modific**  **a t**  **ion:** F i ve s t udies c om par ed or g anic c ar bon s our c es in f or m ulated s edim ents
. A s t udy of 31 dif f er ent or g anic c ar bon r ec i pes by Envir onm ent Canada ( 1995) c om par ed ef f ec t s on s edim ent hom o g eneity , dens ity , and tur bidity

. Cer ophy ll and tr out c howw er e s elec t ed as the optim al or g anic c ar bon s our c es w i th hi g h c l ay ( k aolin at 50 or75% total c onc entr ation) and f i ne s and. Ribeir o et al. ( 1994) r ec om m ended us e of s y nthetic alpha- c ellulos e as a c ar bon s our c e am ended w i th hum ic ac id. T his c om pound has s i nc e been tes t ed by Kem ble et al ( 1999) , Saw y erand Bur t on ( 1994) , and F l em in g and Nix on ( 1996)

. Ribeir o et al. ( 1994) f ound that s or ption w as dependent on the am ount of or g anic c ar bon pr es ent. Kem ble et al. ( 1999) f ound that g r o w t h and s u r v ival of Chir onomus tentans and Hy alella az tec a w as betterin 10% than in 2% alpha- c ellulos e. Both alpha- c ellulos e and c onditioned r ed m aple leaves w er e f ound to be s uitable as or g anic c ar bon am endm ents f orr ef er enc e tox i c ant tes t in g w i th H y

allela az tec a (9 6 hr ) w hen s pik ed w i th c adm ium , z i nc , oranthr ac ene ( S aw y erand Bur t on, 1994)

. Us e of alpha c ellulos e as a c ar bon s our c e f ors edim ent- s pik i n g s t udies has not been adequately evaluated, but it appear s to be pr om is in g . Alpha c ellulos e is a c ons is tent s our c e of or g anic c a r bon that is r e latively biolo g ic ally inac tive and lowin c onc entr a tions of c hem ic als of c onc er n. F ur t her m or e, Kem ble et al. ( 1999) r epor ted that c onditionin g of f or m ulated s edim ent w as not nec es s ar y w hen alpha c ellulos e w as us ed as a c ar bon s our c e f ora ne g ative c ontr o l s edim ent. Com par ed w i th others our c es of or g anic c a r bon, alpha c e llulos e is hi g hly poly m er iz ed and w ould not s er v e as a f ood s our c e, but r atherw ould s er v e to add tex t ur e orpr ovide a par titionin g c om par tm ent f orc hem ic als

. Reductions in org anic carbon content hav e been ach iev ed by diluting sediment with clean sand (See Section 5.4; Clark et al., 1986; Clark et al., 1987; T a tem , 1986; K n ez ov ich and Harrison, 1988). H o w ev er, this can chang e sediment characteris tics resulting in non- linear responses in toxicity (Nelson et al., 1993). Com bustion has also been used to rem o v e fractions of org anic carbon (Adam s et al., 1985; IJ C, 1988). Howev e r, this method results in substantial m odification of the sediment characteristics, including oxidiz a ti on of some inorg anic com ponents. T h e ratio of carbon to nitrog en to phosphorous mi g h t be an im portant parameter to consider when selecting an org anic carbon source. T h is ratio can v ary widely am ong carbon sources (AST M, 2000a; USEPA, 2000d). For exam ple, carbon can rang e from 30 to 47%, nitrog en from 0.7 to 45 m g/g , and phosphorous from below detection limits to 11 μ g/g for sev eral different carbon sources (USEPA, 2000d). A v ariety of form ulations hav e been used successf ully in sediment toxicity testing (see AST M, 2000a and USEPA, 2000d). At this time, no one form ulati on appears to be univ ersally better than others. 

### 5. **3 S**  **pi ki**  **ng** S p ik ing inv o lv es adding one or m o re chemicals to sedime nt for either experime ntal or quality control purposes. Spik ing env i ronmental sam p les is used to document recov eries of an analy t e and thereby analy tical bias. Spiked sediments are used in toxicity tests to determine effects of m a terial(s) on test species. Spik ing tests can also prov ide inform ation concerning chemical interactions and transform ation rates. T h e desig n of spik ing expe riments, and interpretation of results, should alway s consider the ability of the sediment to sequester contaminants, recog n iz ing that this g o v erns m any chemical and biolog ical pro cesses (O’Donnel et al., 1985; Ste mme r et al., 1990a;b; AST M , 2000a;
5-8 U S Environm ental Protection AgencyTechnical M anual N o rthcott and J ones, 2000). I n preparation for toxicity and bioaccum u lation tests, references reg arding the choice of test concentrations should be consulted (USEPA, 2000d; AST M , 2000a; Env i ronment Canada, 1995). Prog ram specific g u idance docum ents should also be consulted as appropriate. Sev e ral issues reg arding sedime nt spiking are addre ssed in this section. First, sev eral methods hav e been used to spike sediments but the appropriate method needs to be selected carefully depending on the ty pe of m aterial being spiked (e.g ., soluble in water or not), its phy sical- chemi cal form , and obj ectiv es of the particular study
. Second, sp iked m a terial should be uniformly distributed throug hout the sediment. Otherwise, analy ses or toxicity tests are likely to y i eld hig h ly v ariable results, depending on the concentration of spiked m ate rial present. T h ird, the spiked m aterial needs to be at equilibrium betw een the sediment and the interstitial w a ter to en sure that all relev a nt exposure phases are appropriately considered in chemical analy ses or toxicity testing
. T h e time it take s to reach this equilibrium is a critical fact or that needs to be considered and documented.


## R **eco mmen**  **d a**  **tio n**  **B o**  **x #3 How should sediments be spiked**  **with a chemical or other test material?** 

� Re g ar dles s of the s p ik in g tec hnique us ed, c ar e s hould be tak en to ens ur e c om plete and hom o g enous m i x i n g . � Replic ate s ubs am ples s hould be analy z ed to c onf ir m hom o g eneous m i x i n g . � Mois tur e c ontent s hould be deter m i ned on tr iplic ates f oreac h s am ple s o that the s pik e c onc entr ation c an be nor m aliz ed on a dr y w ei g ht bas is

. � W e t s p ik in g is r e c o m m ended overdr y s p ik in g m ethods

. � G ener ally s peak in g , the j a rr o llin g m ethod is m or e s uitable than hand m i x i n g f o rs p ik in g lar g erbatc hes of s edim ent. � T o ens ur e c hem ic al equilibr i um betw een the s edim ent and por e w aterin tox i c i ty tes t in g , s pik e s edim ents s hould be s t or ed f orat leas t one m onth, unles s otherinf or m ation is available f o rthe s p ik in g m ater i al and s edim ent ty pe. � Dir ec t addition of or g anic s olvent c ar r i er s s hould be avoided bec aus e they m i g ht alter s edim ent c hem is tr y and af f e c t c ontam inant bioavailability

. Shell c oatin g m ethods s hould be us ed ins t ead as this elim inates m any of the dis advanta g es of s olvent c ar r ier s .
**5.3.1 P**  **reparation for S p**  **iking** Debris and indig enous org anism s s hould be rem o v ed from sediment sam p les as soon as possible after collection to reduce deterioration of sediment quality due to deco m position of org anic debris and dy ing infauna. I f sediments are to be stored prior to spik ing , they should be kept in sealed containers at 4 ° C
. Reg ardless of the spik ing technique used, care should be taken to ensure com p lete and hom ogenous mi x i ng (See Section 4.4). I tis recommended that ch emical analy ses be conducted to v erify that concentrations of the spiked contaminants are uni form throug hout the mi xed m aterial. T h ree or m o re subsam ples of the spiked sediment should be ra ndomly collected to determine the concentration of
C

hapter 5: Sedim ent M anipulations 5-9M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses the substance being tested. I n g eneral, th e coefficient of v ariation (CV ) should be 

### � 20% for hom og eneity of mi xing to be considered su fficient (AST M, 2000a; Northcott and J ones, 2000). T em p eratures should be kept cool during spiking preparation (e.g ., 4° C) due to rapid phy sicochemical and mi crobi olog ical alterations which mi g h t occur in the sediment that, in turn, mi g h t alter bioav ailability and toxicity (A ST M, 2000a; Env i ronment C anada, 1995). I f spik ing PA H com pounds, it mi g h t be im portant to conduct spik ing in the dark , or at least under low lig ht as PAH toxicity has been shown to increase unde r ultrav iolet lig ht (Ankley et al., 1994). I tis recommended that a subsam ple of the spiked sediment be analy z ed for at least the follow i ng parameters: m o isture content, pH , amm onia, total org anic carbon (T O C ), acid v o latile sulfide (AV S ), particle siz e distribution, and back g r ound lev e ls of the chemical(s) to be spiked. Further characteriz ation m a y include analy ses of total v o latile residue, pore w a ter salinity (before and after any siev ing ) , chemical oxy g en dem and, sedimentoxy g en dem and, oxidation- reduction potential (Eh), metals, total chlorinated org anic content, chlo rinated org anic com pounds, and poly cy clic arom atic hy drocarbons (see Appendix G for m o re inform ati on on phy sicochemical parameters often measured on sediments). I tis particularly im portant to de termine the TO C concentration if the sedime nt is to be spiked with a nonionic org anic com pound, as org a nic carbon is the prim ary binding phase for such com pounds (DiT oro et al., 1990). Similarly , the c oncentration of AV S (the prim ary binding phase for cationic metals in anoxic sediments) and T O C should be measured after spik ing with a cationic metal (Ankley et al., 1996; Leonard et al., 1999). T h e sediment m o isture content measurement is usedto standardiz e the am ount of chemical spiked on a dry weig ht basis (see Appendix G). Generally , the m o isture content should be determined on triplicates for each sam p le by measuring the w e ig ht lost follow i ng 24 h of ov en- d ry ing at 105 ° C
. A f ter dry i ng , the sam p les should be cooled to room tem p erature in a desiccator before taki ng dry weig ht measurements (Yee et al., 1992). T h e mean wet density , expressed as m g water/cm 3 , is measured by using the same dry i ng me thod on k nown sediment v o lumes. T h is allows spik ing to be norm aliz ed from a v o lume basis to an equiv alent dry weig ht basis. **5. 3.**  **2 M**  **et hods f**  **o r Spi**  **ki n**  **g** Spik ing of both w et and dry sediments is comm on, but w et spiking is recommended because dry i ng mi g h t reduce the representativ eness of the sam p le by chang i ng its phy sicochemical characteristics (AST M, 2000a). Methods differ m ainly in the am ount of water present in the mi xture during spik ing , the solv ent used to apply the toxicant, a nd the method of mi xing
. Generally speaking , the j ar rolling method is m o re suitable than hand mi xing for spik ing larg er batches of sediment. I n addition to the abov e techniques, sediments m ay be spiked by hand stirring using a scoop or spatula, as long as the hom og eneity of the mi xtur e is v erified. Eberbach and g y r o- rotary shakers hav e also been used effectiv ely to mi x spiked sediments (Stemmer et al., 1990a). Less comm only , chemical(s) are added to the w a ter ov erly ing th e sedime nt and allowed to sorb with no mi xing (Stephenson and Kane, 1984; O ’ N eill et al., 1985; C r o ssland and Wolff, 1985; Pritchard et al., 1986). S e dim e n tR o lling O n e of the recommended w et sediment rolling tec hniques requires a specific j ar- rolling apparatus, first described by D itsw o rth et al. (1990). Many other j ar- rolling apparatuses are av ailable, rang ing in siz e and options av ailable. T h is “rolling mill” method has been used to hom og eniz e larg e v o lumes of sediments spiked with metals and non- ionic or g anic com pounds. T h e prim ary disadv antag e of this method is that the mi xing apparatus m u st be constructed or purchased.
5-10 U S Environm ental Protection AgencyTechnical M anual T h e j ar- rolling apparatus used by D itsw o rth et al. (1990) consists of eig h t parallel, horiz ontal rollers powered by an electric m o tor throug h a reduction g ear, belts, and pulley s , which rotate cy lindrical v essels containing the substrate mi xtures. Mixing is accom p lished g r av imetrically by slow ly rolling the j ars (g allon- siz ed j ars can be rolled at a pproxim ately 15 rpm )
. Optim ally wetted, indiv i dual substrate particles adhere to each other and to the w a ll of the rev o lv ing j ar until they cascade or tum b le dow n the surface of the substrate m ass. D ilution w ater m ay be added to the substrate before rolling to adj u st the sedime nt- t o- w a ter ratio for optim al mi xing
. I f oxidation is a concern (for exam ple, if the sam p le w ill be analy z ed for me tals), 

## Cons **ide r**  **a t**  **ions** j ar contents mi g h t need to be m aintained in an inert 

### W **h**

**en rolling** atm o sphere. I f PAHs are of concern then j ars should 

### sediment **:** be shielded from lig ht (Ankley et al., 1994). Each j ar should be loaded with the required am ount of wet base sediment (with a calculated m ass of dry ! J ar s s hould not be over f illed, as sediment required for the test) prior to introduction of this w ill r educ e m i x i n g ef f i c i enc y . the toxicant. Sev eral 1- cm diameter holes of different ! P r o l o n g ed r o llin g (e

. g ., > 1 w k ) depths should be punched into the sediment to prov ide s hould be avoided to m i nim i z e m o re surface area for the initial distribution of the test phy s i c o c hem ic al c han g es to the s edim ent

. m aterial. Apredetermi ne d v o lume of the stock solution or a serial dilu tion of the stock should be used to spike each j ar load of sediment. A v o lumetric pipette should be used to dist ribute each aliquot onto the top su rface and into the holes of the sediment in each j ar. Sediments should be spiked sequentially , proceeding from low to hig h concentrations of test m aterial, to mi nimi z e cross- contamination. Control substrates should be prepared by adding an equiv alent v o lume of dilu tion water to a j ar loaded with unspiked sediment. After spiking , all j ars and their contents should be processed identically
. T y pically , j ars should be rolled for g r eater than two hours to achiev e sam p le hom og eneity
. J ars should be closely m onitored during the first hour of rolling to ensure proper mi xing of substrates. A f ter rolling for approxim a tely 15 mi n, mi xing efficien cies of the substrates can be j udg ed v i sually
. I f

a sediment display s excessiv e cohesiv eness, as indicated by ag g l omerating or balling , the j ars should be opened and an aliquot of appropriate dilution water ( 50 m Lof either saltwater or freshw ater depending on the source of the sediment) added to each substrate to increase the fluidity
. T h is procedure should be repeated as necessary un til the operator v i sually observ e s that all substrates are tum b ling without forming balls. Adding water in sm all rather than larg e aliquots can prev ent ov er- saturation of the sediment . O v er- saturation is undesirable because excess w ater m u st be decanted follow i ng rolling , prior to sediment testing
. A f ter rolling , the j ars should be g ently shaken to settle sediment that adhered to the w alls. T h ey m ay be set uprig ht and stored ov ernig h t in the dark atroom tem p erature or at an alternate tem p erature (e.g ., 4° C ) depending on the study obj ectiv es. A f ter equilibration (see Section 5.3.3) and prior to distributing the sam p le to test cham bers, a dditional rolling for tw o hours w ill help integ r ate interstitial w a ter into the sedime nt. Sedim e ntSuspensi on Spi ki ng T h e sediment suspension t echnique (Cairns et al. , 1984; Schuy tem a et al. , 1984; Stemmer et al. , 1990a; b; Landrum and Faust, 1991; Landrum et al., 1992) is the si m p lest of the three spiking techniques and requires the least equipment. T h e method inv o lv es placing dilution water and sediment tog ether in a 1- L beaker. T h e desired am ount of toxicant, dissolv ed in dilution water, is
C

hapter 5: Sedim ent M anipulations 5-11M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses added to the beaker. T h e mi xture should be stirred at a m oderate speed with a stir bar, or mechanical stirrer, for a mi nim u m of four hours. T h e sedime nt in the beakers should then be allow ed to settle and equilibrated at the appropriate test tem p erature as specified in the test method. T h e excess w ater ov erly ing the sediment is decanted and discarde d, and the sediment is distributed to the test containers (Env ironment Canada, 1995). Slurry Spi ki ng T h e slurry technique (Birg e etal., 1987; Francis et al., 1984; Landrum and Fa ust, 1991; Landrum et al., 1992) requires a mi nim u m of equipment and inv o lv es less water than the sediment suspension technique. A250- g dry w eig ht sam p le of sediment is placed in a 500- m LErlenmey er flask
. V i a a 25- m Laliquot of distilled, deioniz ed w ater, a suffici ent concentration of the m a terials of interest is added to obtain the desired sediment concentrati on (m g/k g , dry weig ht basi s). Control (unspiked) sediment receiv es a 25- m Laliquotof distilled, deioniz ed w ater hav i ng no added m aterials. T h e sealed flask m ay be mi xed using v arious methods such as continuous ag itation in a shaker for fiv e day s (Birg e et al., 1987) or v i g o rous shaking for 60 seconds, twice daily for sev en day s (Francis et al., 1984). Following mi xing , the se diment suspensions should be centr ifug ed to rem o v e water. T h e m o isture content of the sediment should be appr oxim ately 15% to 20% after centrifug ation. After rem o v al of excess w ater, the prepared sediment can be placed in the exposure cham bers and cov ered w ith dilution w a ter according to th e specific test methods. T h is procedure often y i elds sediment hav i ng its orig inal m o isture content. **5 .**  **3 .**  **3 E**  **q u**  **ilib ra**  **tio n**  **T i**  **me s**  Prior to distributing the spiked sediment to contai ners for toxicity testing or chemical analy ses, th e spiked sedim ents should be stored for a suffici ent tim e to approach chem ical equilibrium in the test m a terial betw een th e sedim e n tan d in terstitial w a ter. E quilibration times for spiked sedime nts v ary widely am ong studies (Burt on, 1991), depending on the spiking m ate rial and sediment ty pe. For metals, equilibration time can be as short as 24 h (J enne and Z achara, 1984; N ebecker et al ., 1986), but one to two week s is m o re ty pical (AST M, 2000a). For org a nic compounds with low octanolw a ter partition coefficients (K ow ), equilibration times as short as 24 h hav e been used (D ew itt et al ., 1989). Some org anic contaminants mi g h t underg o rapid mi crobiolog ical de g r adation depending on the mi crobial population present in the sam p le. I n these cases, k nowledg e of mi crobial effects mi g h t be im portant in defining an appropriate e quilibration period. O r g anic com pounds w ith a hig h partition coefficient mi g h t require tw o m onths or m o re to establish equilibrium (L andrum et al., 1992). B oundaries for the sorption time can be es tim ated from the partition coefficient, using calculations described by K arick hoff and Morris (1985a , b). I tis im portant to recog n iz e that the quantity of spiked chemical mi g h t exceed the cap acity of the test sedime nt sy stem , prohibiting equilibrium
. F o r research purposes, unless definitiv e inform ati on is av ailable reg arding equilibration time for a g i v en contaminant and sediment concentrati on, a one- m onth equilibration period is recommended, with consideration that two m onths mi g h t be needed in some instances (USEPA, 2000d). For reg u latory prog ram s, how ev er, sam p le holding time should not exceed 2 w eek s. T h erefore, for these prog ram s spiking equilibration time should not ex ceed 2 w eek s. Periodic m onitoring during the equilibration time is hig h ly recommended to em pi rically establish stability of interstitial w a ter concentrations (U SEPA , 2000d). Sediment and inte rstitial w a ter chemical concentrations should also be m onitored during long

- t erm bioassay tests to determine the actual chemical concentrations to which test org anism s are exposed, and to v erify th at the concentrations rem ain stable ov er the duration of the test.

5-12 U S Environm ental Protection AgencyTechnical M anual **5. 3.**  **4 U**  **se of O**  **r gani**  **c Sol v**  **ent s**  D i rect addition of org anic solv en ts should be av oided if possible, because they mi g h t dram atically affect sediment g eochemi stry and alter bioav a ilability (U SEPA , 2000d). H o w ev er, m any org anic m aterials require use of a solv ent to adequately mi x with the sediment. I f an org anic solv ent is to be used, the solv ent should be at a concentration th at does not affect testorg anism s and should be uniform across treatments. Further, both solv en t control and neg ativ e control sediments should be included in tests with solv ents. T h e solv ent concentration in the control should equal the treatment concentration and should be from the same batch used to m ake the stock solution (AST M, 2000a). T o reduce the possibility of solv ent- related artifacts, the spik ing process should include a step w h ich allow s the solv ent to ev aporate before addition of sediment and w ater follow ed by rolling (McL eese et al., 1980; Muir et al .,1982; A d am s et al., 1985). H i g h ly v o latile org anic com pounds hav e been spiked into sediments using co- solv ents followed by shaking in an aqueous slurry
. When hig h ly v o latile com pounds are used, immediate testing in cov ered flow

- t hroug h sy stem s is recommended (K nez o v i ch and Harrison, 1988). T h ere is some uncertainty concerning artifacts introdu ced by the use of solv ents. T h e use of a polar, w ater soluble carrier such as methanol w as found to hav e little effect on the partitioning of nonpolar com pounds to dissolv ed org anic m atter at concentra tions up to 15% carrier by v o lume (Webster et al., 1990). H o w ev er, another study show ed that chan g es in partitioning by a factor of approxim a tely tw o mi g h t occur w ith 10% methanol as a co- solv e nt for anthracene sorption (N kedi- K iz z a et al., 1985). T h e effect of carrier v o lu me on partitioning of org anic chemicals in sediments is equiv o cal. H o w ev er, because solv ents mi g h t be either directly or indirectly toxic to th e test org anism s, caution should be taken to mi nimi z e the am ount of carrier used. I n addition, the use of a carrier such as acetone mi g h t result in faster equilibration of spiked org anic com pounds (Schults et al., 1992). Shell coating techniques w h ich introduce dry chemical (s) to wet sediment hav e also been dev eloped, principally to eliminate the potential disadv antag e s of solv ent carriers. T h e chemical m ay be either coated on the inside walls of the container (Dits worth et al., 1990; Burg e ss et al., 2000) or coated onto silica sand (D riscoll et al., 1997; Cole et al., 2000). I n each shell coating method, the chemical is dissolv ed in solv ent, placed in a g l ass spik ing container (w ith or w ithout sand), and the solv ent is slowly ev aporated prior to addition of the wet sedi ment. Wet sediment then sorbs the chemical from the dry surfaces. I tis im portant that the solv ent be allow ed to ev aporate prior to adding sediment or wa t e r . 

### 5. **4 P**  **reparat i**  **on of Sedi**  **ment Di**  **l ut**  **i ons**  Spiked or field- contaminated sediments can be diluted with whole sediment to obtain different contaminant concentrations for concentration- eff ects testing
. T h e diluent sediment should hav e phy sicochemical characteristics similar to the te st sediment, including org anic carbon content and particle siz e, but should not c ontain concentrations of contaminants abov e back g r ound lev els (AST M, 2000a; Burton, 1991). Diluent sediment has in cluded form ulated sediment as well as known reference site sediment. D iluted sediment sam p les should be hom og eniz ed and equilibrated in accordance w ith procedures described in Sections 4.4 and 5.3.3, respectiv ely
. T h e diluent sediment should be com b ined with the test sediment in ratios determined on a dry weig ht basis to achiev e the desired nominal dilution se ries (D eWitt, personal comm unication). Volume to v o lume dilutions hav e also been performed (e.g ., Schlek at et al.,1995; J ohns et al., 1985), but weig ht to w eig ht dilutions are preferred because they prov ide m o re accurate control and enable a m o re straig htforward calculation of dose- response curv es. C

hapter 5: Sedim ent M anipulations 5-13M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Results from dilution experiments should be inte rpreted with care. T h ere are often non- linear responses due to non- equilibrium , non- linear sorpti on- desorption processes that cannot alw ay s be adequately controlled (Nelson et al., 1993). Nels on et al. (1993) found thatanaly ses of diluted sediments did not m atch nominal concentrations as estim ated by phy sical characteristics. T h ey sug g ested that chemical characteriz ation is need ed to determine effects of m anipulations (i.e., mi xing ) and resulting chang es (i.e., oxy g enation of com p lexing ag ents such as acid v o latile sulfides). 

### 5. **5 P**  **reparat i**  **on of Sedi**  **ment El**  **ut ri**  **at es**  Many studies of sediment toxicity hav e ev aluated aqueous extracti ons of suspended sediment called elutriates. T h e elutriate me thod w a s initially dev e l oped to assess the effects of dredg i ng operations on w ater quality (U .S. A C O E , 1976). Elutriate m anipul ations are also applicable to any situation where the resuspension of sediment
- bound toxicants is of concern, su ch as bioturbation and storm s , that mi g h t disturb sedim e nts and affect w a te r quality (U SEPA/A C O E, 1991, 1998; A n kl ey et al., 1991). USEPA/ACOE (1998) lists eig h teen freshwater and saltwater aquatic org anism s as candidates for elutriate toxicity testing
. Standa rd effluent toxicity test procedures are also appropriate for elutriates, incl uding tests with v arious v ascul ar and non- v ascular plant species (I ng ersoll, 1995). E l utriate tests are not intended to reflect the toxicity of interstitial w a ters or w hole sedime nts, as there are differences in contaminant bioav a ilability in the tw o ty pes of media (H arkey et al., 1994). I n g eneral, elutriates hav e been found to be less toxic than bulk sedime nts or interstitial w a ter fractions (Burg ess et al., 1993; Ankl ey et al., 1991), althoug h in some studies elutriates hav e been found to be m o re toxic (Hoke etal., 1990) or equally as toxic (Fleg e l et al., 1994) relativ e to interstitial w a ter. While there are sev e ral procedural v ariations, th e basic me thod for elutri ate preparation inv o lv es com b ining v arious mi xtures of water and sediment (usually in the ratio of 4 parts water to 1 part sediment, by v o lume) and shaking , bubbling or s tirring the mi xture for 1 hour (Ross and Henebry , 1989; Daniels et al., 1989; Ankl ey et al., 1991; Burg ess etal., 1993; USEPA/USACOE, 1991, 1998). I tis likely that chemical concentrations w ill v ary depending on the elutriate procedure used. S p ecific prog ram g u idance should be consulted as appropriate. T h e water phase is then separated from the sedime nt by settling and/or centrif ug ation (N ote: the dredg i ng re mediation prog ram does not alw ay s require centrifug ing elutriates). Once an elutriate has been prepare d, it should be analy z ed or used in biolog ical tests imme diatel y , or as soon as possible thereafter. I tshould be stored at 4 ° C for not long er than 24 h, unless the test method di ctates otherwise (Env ironment Canada, 1994; U S EPA/A C O E , 1991, 1998). For toxicity test expos ures exceeding 24 h, fresh elutriate should be prepared daily
. F iltering the elutriate is g e nerally discourag ed, but it mi g h t be prescribed for some toxicity tests. F iltration can reduce the toxicity of sediment elutriates due to sorp tion of dissolv ed chemicals on the filtration mem b rane and retention of colloids. I f colloidal m aterial needs to be rem o v ed, serial or double centrifug ation is g e nerally a preferred altern ativ e. I f an elutriate m u st be filtered, it is recommended that only pre- treated filters be used a nd that the first 10 to 15 m Lof the elutriate to pass throug h the filter be discarded (Env ironment C anada, 1994). T esting w ith a filtered elutriate should include an assessment to determine the exte nt of analy t e adsorption/desorption to/from the filter.

5-14 U S Environm ental Protection AgencyTechnical M anual


## R **eco mmen**  **d a**  **tio n**  **B o**  **x #4 How should sediment elutriates be performed?** 

� Com bine 1 par t s edim ent w i th 4 par ts w aterunles s a s pec if ic pr o g r a m s t ipulates other w i s e. � T he s edim ent- w aterm i x t ur e s hould be vi g or ous ly s hak en, bubbled ors t ir r ed f or1 hour

. � Centr i f u g ation is a us ef ul m eans f o ris olatin g the w aterphas e ( elutr iate)

. � O nc e pr epar ed, the elutr i ate s hould be analy z ed ortes t ed as s oon as pos s i ble. � Stor e elutr i ate at 4° C w i th little orno heads pac e until analy s is

. � F ilter in g the elutr i ate ( t o r e m o ve c o lloidal m a ter i al) is g ener ally not r ec om m ended. Us e double ( s er ial) c entr i f u g ation if appr opr iate.

C

hapter 5: Sedim ent M anipulations 5-15M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

5-16 U S Environm ental Protection AgencyTechnical M anual 

## Collection of Interstitial Water **CHA PT**  **ER** 

# 6

Sediment interstitial w ater, or pore w ater, is defined as the w ater occupy ing the spaces betw een sedime nt particles. I n terstitial w a ter mi g h t occupy about 50% (or m o re) of the v o lume of a depositional (silt- clay ) sedime nt. T h e interstitial w a ter is in contact w ith sedime nt surfaces for relativ ely long periods of time and therefore, mi g h t become contaminated due to partitioning of the contaminants from the surrounding sediments. I n addition, interstitial w aters mi g h t reflect g r ound w ater – surface w ater transition z ones in upw elling or dow nw elling areas. I n these areas their chemistry mi g h t be m o re reflectiv e of g r ound or surface w aters at the site. T h erefore, flow , residence time and other phy sicochemical factors (e.g ., pH, tem p erature, redox potential, org anic carbon, sulfides, carbonates, mi neralog y ) mi g h t hav e v ary in g roles in determining w h ether interstitial w a ters are contaminated. I n m a ny depositional sedime nts, interstitial w a ters ar e relativ ely static, and therefore contaminants in the interstitial w a ter and in the solid phase are exp ected to be at therm ody nami c equilibrium
. This m ake s interstitial w a ters useful for assessing contaminant lev e ls and associated toxicity . I n terstitial w a ter is often isolated to prov ide either a m a trix fo r toxicity testing and/or to prov ide an indication of the concentration and/or partitioning of c ontaminants w ithin the sediment m atrix. 

### 6. **1 G**  **eneral Procedures**  I n terstitial w a ter sam p ling has become especially im portant in reg u latory prog ram s because interstitial w a ter toxicity tests y i eld additional in form ation not currently prov ided by solid- phase, elutriate, or sedime nt extr act tests (Carr and Chapm an, 1992; SET A C, 2001). Furtherm ore, interstitial w a ter toxicity tests hav e prov en to be us eful in sedime nt toxicity identification ev aluation (T I E ) studies (e.g ., Burg ess et al., 1996; Carr, 1998; Burton, 2001) as test procedures and sam p le m anipulation techniques are g enerally cheaper, fast er, and easier to conduct than solid- phase tests (SET A C , 2001). T hus, the collection of interstitial w ater has become increasing l y im portant in sediment quality m onitoring and remediation prog ram s. I n terstitial w a ter sam p ling is m o st suitable for se diment ty pes rang ing from sandy to uncom pacted silt- clay s (Sarda and B u rton, 1995; SET A C , 2001). Such sam p ling is not ty pically performed on sediments with coarse particle siz e (such as g r avel) or on hard, com p acted clay s, as the potential for interstitial w a ter contamination in thes e sedime nt ty pes is relativ ely low
. A s w ith all sam p ling discussed in this m anual, the principle aim is to use procedures that mi nimi z e chang es to the in situ condition of the water. I tshould be r ecog n iz ed that m o st sedime nt collection and processing methods hav e been show n to alter interstitial w ater chemistry (e.g ., Schults et al., 1992; Bufflap and Allen, 1995; Sarda and Burton, 1995) , thereby potentially altering contaminant bioav a ilability and toxicity
. Laboratory

- based methods (e.g ., cen trifug ation, pressuriz ation, or suction) are comm only used as alternativ es to in-situ interstitial w ater collection (see Section 6.2). While these methods hav e been show n to alter interstitial w a ter chemistry , they ’re sometimes necessary or preferred, especially w h en larg er sam p le v o lum e s are required (e.g ., for toxicity testing )
.

C

hapter 6: C o

llection of Interstitial W a

ter 6-1M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses As both in-situ and laboratory

- based or ex-situ (e.g ., methods mi g h t be appropriate for m any study obj ectiv es, it is critical th at the sam e procedures are used for a ll station s sam p led in a stu d y, or program , so that appropriate sam p le com parisons can be m ade. Furtherm ore, the sedim ent depth at w h ich in terstitial w a ter is sam p led (eith er u s ing in -situ or ex-situ extraction m e th ods) sh ou ld m a tch th e depth of in terest in th e stu d y (SET AC, 2001). For exam ple, sam p les for dredg i ng remediation should be sam p led to the depth to be disturbed by dredg i ng activ ity , whereas sam p les for a status and trends surv ey should be collected at the biolog ically activ e depth (often < 15 cm ). Fig u re 6- 1 summ ariz es the m aj o r considerations for selecting in-situ or ex-situ procedures in a g i v en study
. The tw o m a j o r issues of concern reg arding interstitial w a ter sam p le integ r ity are: 1) the ability of the sam p ling dev i ce to m aintain phy sicochemical c onditions in the natural state by mi nimi z i ng adsorption/leaching of chemicals to/ from the dev i ce, and 2) the ability to m aintain the sam p le in the redox state existing at the site. Precautions require d to reduce the likelihood of sam p le artifacts w ill v ary w ith each study as indicated in the follow i ng sections. 

### 6. **2 In**  **-s itu**  **C o**  **lle c**  **tio n**  In situ methods mi g h t be superior to ex-situ me thods for collecting interstitial w a ter, as they are less subj ect to sam p ling/ extraction related artifacts and th erefore, mi g h t be m o re likely to m a intain the chemical integ r ity of the sam p le (Sardaand Burton, 1995; AST M 2000a; SET A C, 2001). Howe v e r , in situ m e thods hav e g e nerally produced relativ ely sm all v o lum e s of interstitial w a ter, and o ften limited to w a deable or div e r- accessible water depths. T h ese log i stical constraints hav e limited their use and applicability in sedime nt m onitoring 

## R **eco mmen**  **d a**  **tio n**  **B o**  **x #1** studies. 

### In-s **itu inte rs**  **titia l**  **wa te**  **r collect**  **ion** T h e principal me thods for in situ collection of interstitial w a ter inv o lv e either deploy ed “peepers” (B ufflap and � Us e peeper s f ors am plin g inter s titial w a ter s , r atherthan ( orin addition to) g r ab orc or e Allen, 1995; Brum baug h et al., 1994; s edim ent ex tr ac tions if s i te c onditions , volum e Adam s, 1991; Carig n an and Lean, 1991; r equir e m ents , and lo g is tic a l c ons ider ations allow

. Carig n an et al., 1985; Bottoml ey and Bay l y , 1984) or suction techniques � Reduc e potential f orox y g enation of s am ples (Watson and Frickers, 1990; K n ez ov ich by pr operdeploy m ent and r etr ieval and Harrison, 1988; Ho wes et al., 1985). pr oc edur es . A summ ary of these methods is � Allowadequate equilibr a tion of peeper s pr ior prov ided in T able 6- 1. Both me thods to s a m p lin g . hav e a hig h likelihood of m aintaining in situ conditions. I n cases where in situ � Minim i z e handlin g and pr oc es s i n g of f i eld- c o llec t ed inter s titial w a ter s . deploy ment is im practical, peepers or suction dev i ces can be placed in � F i eld c o llec t ed inter s titial w a ters a m p les s hould relativ ely undisturbed sedime nts be s t or ed in c ontainer s , w i thout heads pac e at 4° C in the dar k , until analy z ed/tes t ed. collected by core or g r ab sam p lers (see Sam p les f o rc e r t ain c hem ic al analy s es ( e . g ., Chapter 3). pes tic i des , phenols ) , s hould be f r oz en or pr es er ved im m ediately

.

6-2 U S Environm ental Protection AgencyTechnical M anual

**F i**  **g u**  **r e 6-**  **1.** Cons ider ations f ors elec t in g the appr opr iate ty pe of inter s titial w aters am plin g m ethod.

C

hapter 6: C o

llection of Interstitial W a

ter 6-3Methods for C ol lecti on, S torage, and Mani pul ati

on of S edi ments for C hemi c al and T ox

i cologi cal A nal yses

P h o t o a nd illus t ra tio n o n this pa ge , c o urte s y of

A lle n B u rt o n

Peepers depl oy ed i n t he f i el d

Gener a l peeper desi gn wi t h in -s itu sam pl e ext r act i on 6-4 U S E

n vi ronmental P

r otecti on A gencyTechnical M anual **6. 2.**  **1 P**  **eeper M et**  **hods** P eepers are sm all cham bers w ith mem b rane or mesh w a lls containing either distilled w a ter or clean water of the appropriate salinity or hardness. Sam p les are collected by bury i ng the dev i ces in sediments and allow i ng surrounding interstitial w aters to infiltrate. I n principle, dissolv ed solutes w ill diffuse throug h the porous w all into the peep er and the contained w ater w ill reach equilibrium w ith the am bient interstitial w a ter. The desig n concept for sediment peepers orig inated as m odifications of the dialy sis ba g technique used by May er (1976) and Hesslein (1976), and has been m odified successfully for use in laboratory sedime nt toxicity tests (Doi g and Liber, 2000). T h e initial desig n s consisted of either a flat base plat e or a cy lindrical dialy sis probe (B ottoml ey and Bay l y , 1984) with com p artments cov ered by dial y sis mem b ranes and a m anifold for collection of m

u ltiple sam p les at v arious depths in the sediment profile (F ig ure 6- 2). F u rther m odifications to these desig n s hav e incorporated sam p ling ports, larg e sam p le com p artments, and v arious ty pes of mem b ranes with different pore siz es. T h ese m odifications are usually required based on specific proj ect obj ectiv es reg arding sam p le v o lumes and contaminants of interest.
**T ab**  **l e 6-**  **1.** In- s

itu inter s titial w aterc ollec t ion m ethods ( S ar da and Bur t on, 1995; SET AC, 2001)

. D e v i c e Se dim e nt Dep th (cm ) Sa m p le Vol u m e

(L 3 ) Ad v an t age s D isad v an t age s

P e e pe r 0.2 - 10 � 0
. 5 M o s t accu rat e m eth o d , red u ced a r tifa c t s, no lab pro c e ssing ; rel a t i v el yfree o f effect s fro m t em p eratu r e, o x i d at i o n , an d pre ssure ; ine xpe nsiv e a nd e a s y to c o nstr uc t; so m e se le c tiv ity po ssible de pe nding o n na ture o f s am p l e v i a s p eci fi c m em b ran es ; w i de ra ng e o f m e m b ra ne /m e s h po re siz e s , a nd/o rinte rna l so lute s o rs u b s tr at es av ai l ab l e. Re quire s de plo y m e nt by ha nd, thus re quiring div i ng in > 0.6 m de pth w a te r; re quire s ho urs to da y s fo r e quilibr a tio n ( v a r ie s w ith site a n d c ha m be r); m e tho ds no t sta nda rdiz e d a nd use d infre que ntly ; s o me me mb r a n e s s u c h a s d i al y s i s / cel l u l o s e are s u b j ectt o b i of ou l i n g; mu s t d e ox y g e n a t e ch am b er an d m at eri al s t o p r ev en t o x ida tio n e f f e c t s; so m e c o nstruc tio n m a te r i a l s y i e l d ch emi cal art i f act s ; s o m e ch am b ers o n ly a llo w sm a ll sa m p le v o l um e s; care m u s tb e u s ed o n co l l ect i o n t o pr e v e n t sa m p le o x ida tio n. I n situ Suc tio n 0.2 - 30 � 0.25 Re duc e da r tifa c t s, g r a d ie nt de f i nitio n; r a pid c o lle c tio n, no lab p r o ces s i n g ; cl o s ed s y s t em w h i ch p r ev en t s co n t ami n at i o n ; m eth o d s inc l ude a i rsto ne , syring e s , pro be s , an dco re- typ e s am p l ers . Re quire s c usto m , no n- sta nda rd c o lle c tio n de v i c e s; sm a ll v o l um e s; limite d to so fte rse dim e nts; c o re a i r sto ne m e tho d ; dif f i c u lt in so m e se dim e nts a nd in de e pe rw a te r (>1 m ) ; m e tho d mi g ht re quire div i ng fo r de plo y m e nt in de e p w a te rs; m e tho ds use d infre que ntly a nd by limite d num be r o f labo ra to rie s . Note : I nc orporation of filtration into any c o lle c ti on me thod might re sult in loss of me tal and organic c ompounds. Various peeper dev i ces hav e been recently used eff ectiv ely to collect interstitial w a ter. For exam ple, a sim p lified desig n using a 1 μ m poly carbonate me m b rane ov er the opening of a poly ethy l ene v i al was successful in capturing elev ated lev els of copper and z i nc (Brum b aug h et al., 1994). Other

C

hapter 6: C o

llection of Interstitial W a

ter 6-5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

**F i**  **g u**  **r e 6-**  **2.** F r ont viewand c om ponents of peepers am plin g devic es ( t op: plate devic e; bottom : c y lindr ic al pr obe)

6-6 U S Environm ental Protection AgencyTechnical M anual desig n s hav e been used to collect nonpolar org a nic com pounds in a v ariety of aquatic sy stem s (Bennett et al., 1996; Axelm an etal., 1999) and in ov erly ing water (Hucki ns et al., 1990). Peepers hav e also been used to expose org anism s to sediments in situ (Burton et al ., 2001). Burton et al. (1999) successfully introduced org anism s to aer obic sediments using peepers. H o w ev er, anoxic sediments are not amenable to in situ org anism exposure. Different m aterials mi g h t be adv i sable in cons tructing peepers depending on the contaminants of concern. For exam ple, for m any contaminants, p eepers constructed from acry lic m a terial appear to y i eld interstitial w a ter sam p les w ith mi nim a l chemical artifacts (B urton etal., 2001). Some poly mer m a terials mi g h t be inappropriate for studies of certain nonpolar org anic com pounds. Cellulose mem b ranes are also unsuitable, as they decom pos e too quickly
. Plastic sam p lers can contaminate anoxic sediments with diffusibl e oxy g en (Carig nan et al., 1994). I n preparation for interstitial w a ter collection, peep er cham bers should be filled w ith deoxy g enated water, which can be prepared by nitrog en purg i ng for 24 hours prior to insertion. I f sediment oxidation is a concern, the peepers should be transported to the depl oy ment site in a sealed oxy g enfree w ater bath to av oid potential chang es to th e sediment- w ater equilibrium caused by dissolv ed oxy g en interactions. H o w ev er, during peeper equ ilibration periods, anoxic conditions are likely to be quickly reestablished. I n addition, when sam p le s are collected and processed, exposure to oxy g en should be mi nimi z e d. Follow i ng initial placement, the equilibration time for peepers m ay rang e from hours to a m onth, but a deploy ment period of one to two week s is m o stoften used (Adam s , 1991; Call et al., 1999; Steward and Malley , 1999). Equilibration time is a function of sediment ty pe, study obj ectiv es, contaminants of concern, and tem p erature (e.g ., Sk alski a nd Burton, 1991; Carr et al ., 1989; Howes et al., 1985; Sim on et al., 1985; May e r, 1976). Mem b rane pore siz e also affects equilibration time, w ith larg er pore siz es being used to achiev e reduced equilib ration times (Sarda and B u rton, 1995). For exam ple, using a peeper w ith a 149- μ m pore siz e, A d am s (1991) reported equilibration of conductiv ity w ithin hours of peeper insertion into the sediment. T hus , it appears that equilibration time is a function of the ty pe of contaminant, sediment ty pe, peeper v o lume, and mesh pore siz e. P eepers w ith larg e- pored mem b ranes, w h ile shorteni ng equilibration time, also allow particulates to enter the cham ber. The larg er so lids tend to settle to the bottom of the peeper cham ber, and caution should be used to av oid collecting the solids when retriev i ng the water sam p le from the cham ber. C o lloidal particles w ill rem a in suspended in the sam p le and thereby present an artifact, but the concentration of such particles is ty pically lower than that found in laboratory

- centrifug ed sam p les (Chin and Gschwend, 1991). I n sev e ral studies, analy sis of interstitial w a ter from replicate peepers has dem onstrated from low to hig h heterog e neity in w a ter quality characteris tics (Fraz i er et al., 1996; Sarda and B u rton, 1995). T h e potential for hig h v ariability in interstitial w a ter chemical characteristics should be take n into account when dev eloping the sam p ling desig n . **6. 2.**  **2 S**  **uct i**  **on M et**  **hods** There are a v ariety of suction dev i ces for collec ting interstitial w a ter. A ty pical suction dev i ce consists of a sy ring e or tube of v ary ing leng th, w ith one or m o re ports located at the desired sam p ling positions (AST M, 2000a). T h e dev i ce is inserted into the sediment to the desired depth and a m anual, spring

- operated, or v acuum g as suction is applied to directly retriev e the water sam p le. A

C

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ter 6-7M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

v ariation on this approach em ploy s a peeper- like por ous cup or perforated tube w ith filters. The unit is inserted into the sediment for a period of time, allow i ng interstitial w a ter to infiltrate the cham ber before suction is applied. T h e sam p les are then re triev ed by suction. Another v ariation that has been used successfully em ploy s an airstone em bedded in to the sedime nt w h ich forces interstitial w a ter upward where it can be collected v i a sy ring e or tube. All of these suction methods g enerally y i eld sm aller quantities of interstitial w a ter than peepers and chemical (toxicolog i cal) artifacts are m o re likely due to g r eater potential exposure of interstitial w ater to oxy g en (A ST M, 2000a). **6. 2.**  **3 P**  **rocessi ng of**  **Fi el**  **d- Col**  **l ect**  **ed I n**  **t erst**  **i t**  **i al**  **Wat er Sampl**  **e** F o llow i ng sam p le retriev a l, interstitial w a ter mi g h t need to be recov ered and stabiliz ed quickly to prev ent oxidativ e chang e s or v o latiliz ation (C arig nan, 1984). C ontainers should be filled, w ith no headspace to mi nimi z e chang es in dissolv ed oxy g en and contaminant bioav ailability
. Procedures for stabiliz ation are dependent on the analy s es to be performed. When non- v o latile com pounds are the targ et analy t es, acidification is often stipulated, w h ile org anic carbon and methane m ay be stabiliz ed with saturated mercury chloride (Mudroch and MacK nig h t, 1994). Sam p les to be analy z ed for toxicity , are norm ally c ooled to 4° C as soon as possible for transport to the laboratory
. EPA methods for toxicity tes ting of surface w aters and effluents (U SEPA 1991) recommend that sam p les not be froz en in storag e or transport. H o w e v e r, recent inform ation sug g ests that freez ing of interstitial w a ter m a y not affect toxicity in some cases (H o et al., 1997; C arr and C h apm an, 1995; SET A C , 2001). U n less a dem onstration of acceptability is m ade for the sites of interest, interstitial w a ter sam p les should not be fro z en prior to biolog ical testing
. Sam p les for chemical analy s es should be pres erv e d imme diately , if appropriate , or cooled to 4° C as soon as possible. 

### 6. **3 Ex-**  **s**

**i t** 

**u E**  **x tractio**  **n o**  **f In**  **terstitial Water** E

x -situ interstitial w a ter collection me thods are often necessary w h en relativ ely larg e v o lume s of interstitial w a ter are required (such as for toxicity testing ) , w h en in-situ collection is not v i able or when a brief sam p ling time is critical. While these extraction methods can be done in the field or in the laboratory , extraction in the laborat ory , j u st prior to analy sis or testing , is preferable so that the sam p le is m a intained as close to its orig inal st ate as m u ch as possible dur ing transport and storag e (SET A C , 2001). G u idance in this chapter reflect s recommendations presented in sev eral recent publications including proceeding s from tw o w o rk shops dev o ted entirely to interstitial w a ter extraction methods, water handling , and use in t oxicity applications: (1) a dredg e d m a terials m anag ement prog ram w o rk shop on interstitial w ater extraction methods and sam p le storag e in relation to tributy ltin analy sis (H offm an, 1998) and (2) a Pellston w o rk shop on interstitial w a ter toxicity testing including interstitial w a ter ex traction methods and app lications (SET A C , 2001). F i g u re 6- 3 summ ariz es m any of the issues associ ated w ith laboratory isolation of interstitial w a ter discussed in this section. **6. 3.**  **1 G**  **eneral Procedures**  C entrifug ation and squeez ing are the tw o m o st comm on techniques for collecting interstitial w a ter, and are g enerally preferred when larg e v o lumes ar e required. Other methods include pressuriz ation (e.g ., v acuum filtration) dev i ces, w h ich can be used to recov er sm all v o lumes of interstitial w ater. R e g ardless of the me thod used, interstitial w a ter should be preserv ed i mme diately for chemical analy s es, if appropriate, or analy z ed as soon as possible after sam p le collection if unpreserv ed (such as for toxicity testing ; Hoffm an, 1998; SET A C, 2001)
. Sig n ificant chemical chang es can occur ev en 6-8 U S Environm ental Protection AgencyTechnical M anual

**F i**  **g u**  **r e 6-**  **3.** Sum m ar y of r ec om m ended pr oc edur es and c ons ider ations f orlabor ator y is olation of inter s titial w a ter * *Note: Emphas is s hould be plac ed on minimiz i ng the dur ation of all s ample manipulations whenev er pos s

i ble

w h en interstitial w a ter is stored for periods as short as 24 h (H ulbert a nd B r indle, 1975; Watson et al., 1985; K e m b le et al., 1999; Sa rda and Burton, 1995; SET A C, 2001). I f

sediments are anoxic, as m o st depositional sedime nts are, sam p le processi ng , including mi xing of interstitial w ater that has separated from the sediment, should be conducted in an inert atm o sphere or with mi nim al atm o spheric contact. Exposure to ai r can result in oxidation of contaminants, thereby altering bioav ailability (B ray et al., 1973; Ly ons et al., 1979; H o w es et al ., 1985). A i r exposure can also result in loss of v o latile sulfides, w h ich mi g h t increase the av ailability of sulfide- bound me tals (A llen et al., 1993; B u fflap and A llen, 1995). I n addition, iron and m ang anese oxy hy droxides are quickly formed upon exposure to air. T h ese com pounds readily com p lex w ith trace metals, thus
C

hapter 6: C o

llection of Interstitial W a

ter 6-9M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses altering me tals- r elated toxicity (Bray et al., 1973; T r oup et al., 1974; Burton, 1991; Bufflap and A llen, 1995). Maintaining anoxic processing conditi ons is not necessary w h en study obj ectiv es are concerned with exposures to aerobic sediments, or if targ et contaminants are unaffected by oxidation in short- term toxicity or bioaccum u lation testing
. I n terstitial w a ter filtration should be av oided (S ET A C , 2001). N u me rous studies hav e show n that filters reduce toxicity and contaminant concentrati ons by retaining contaminant- associated particles and also by contaminant sorption onto the filter m atrix (B ray et al., 1973; T r oup et al., 1974; SassonB r ick s on and B u rton, 1991; Schults et al., 1992). I f f

iltration is stipulated by a test method, treated filters (e.g ., pre- soaked in distilled, deioniz ed w ater, or com busted at 400° C ov ernig h t for g l ass fiber filters) should be used, and an unfiltered sam p le shoul d also be tested for toxicity and contaminant concentrations. T h e characteristics of filters a nd the filtering apparatus should also be carefully considered, as different filters hav e different sorptiv e capacities for different contaminants.


## R **eco mmen**  **d a**  **tio n**  **B o**  **x #2 E** 

**x**

**tra c** 

**t**

**ion of inte rs**  **titia l**  **wa te**  **r**

� Centr i f u g ation is the g ener ally pr ef er r ed labor ator y m ethod f orthe ex tr ac tion of inter s titial wa t e r . � Ex tr ac tion of inter s titial w aters hould be c om pleted as s oon as pos s i ble. � Inter s titial w aterthat has ac c um ulated on the s ur f ac e of the hom o g eniz ed s edim ent s am ple s hould be m i x ed into the s edim ent bef or e the s am ple is par titioned am on g c entr i f u g e bottles

. � Unles s otherpr o g r a m - s pec if ic g uidanc e is available, s edim ents s hould be c entr i f u g ed at hi g h s peed ( e. g ., 8000- 10,000 x g ) f or30 m i nutes
. � U n les s s i te- s pec if ic inf o r m ation s u gg es ts other w i s e, c entr i f u g in g s hould be at 4° C to m i nim i z e tem per atur e- m ediated biolo g ic al and c hem ic al pr oc es s e s . � Inter s titial w aters hould be pr es er ved im m ediately f o rc hem ic al analy s es oranaly z ed as s oon as pos s i ble af terex tr ac tion, unpr es er ved. F ortox i c i ty tes t in g , inter s titial w ater s hould be s t or ed at 4° C f ornot lon g erthan 24 hour s , unles s the tes t m ethod dic t ates other w i s e. � F iltr ation s hould be avoided unles s r equir ed by a tes t m ethod bec aus e it m i g ht r educ e inter s titial w atertox i c i ty
. Double ( s er ial) c entr i f u g ation ( l ow s peed f ollow ed by hi g h s peed) s hould be us ed ins t ead. � If f ilter in g is r equir ed by a tes t m ethod, pr e- tr eated f ilter s s hould be us ed to r educ e potential c ontam ination.

**6. 3.**  **2 C**  **ent r**  **i f**  **ugat i**  **on** C e ntrifug a tion is the g e nerally preferred labor atory me thod for collection of interstitial w a ter (SET AC, 2001). I tis a relativ ely sim p le procedure that allows rapid collection of larg e v o lumes of interstitial w a ter. I talso fac ilitates the m aintenance of anoxic conditions (if required). H o w ev er, centrifug ation, like other ex-situ procedures mi g h t y i eld chemical and/or toxicolog i cal artifacts due to

6-10 U S Environm ental Protection AgencyTechnical M anual the extraction procedures them selv es, w h ich mi g h t alter the natural equilib rium betw een interstitial water and sediment. Prior to centrifug ation, the sediment sam p le is hom og eniz ed (see Section 4.3) and partitioned am ong centrifug e bottles. I f the hom og eniz ed sam p le is stored prior to centrifug ation, interstitial w a ter mi g h t accum u late on the surface of the sediment. T h is ov erly ing w ater should be mi xed into the sediment before subsam pling for centrifug ation. Sam p les are then partitioned am ong centrifug e bottles. I n g eneral, approxim ately 50% of sediment m o isture content can be extracted as interstitial w a ter. I f interstitial w a ter v o lum e requireme nts are low e r, sm aller sedime nt subsam ples m a y be used.

**For mor**  **e infor**  **ma t**  **ion a bout c**  **e n**  **tr ifuga**  **tion:** Inter s titial w ater s have been is olated overa r an g e of c entr i f u g al f or c es and dur ations ( Landr um et al., 1987; G i es y et al., 1988; Sc hults et al., 1992; Bur g es s et al., 1993; Ank l ey et al., 1990; Sc hubauer - B er i g an and Ank l ey , 1991; Ank l ey and Sc hubauer - B er i g an, 1994)

. F ortox i c i ty tes t in g of inter s titial w ater s , s om e s our c es r ec om m end that s edim ents be c entr i f u g ed at 10,000 x g f ora 30 m i n per iod ( AST M, 2000a; Envir onm ent Canada, 1994)

. Suc h hi g h s peed c entr i f u g ation is of ten nec es s ar y to r em ove m os t c olloids and dis per s i ble c l ay s ( A dam s , 1991; Chin and G s c hw end, 1991; Br ow naw ell and F ar r i n g ton, 1986; Ank l ey and Sc hubauer - B er i g an, 1994) , w hic h c an intr oduc e inter f er enc es to c hem ic al ortox i c olo g ic al analy s is

. How e ver , s u c h hi g h s peed c entr i f u g es ar e not c om m only available. F ur t her m or e, m any m ater i als ( g l a ss, plas tic ) ar e not able to w i ths t and hi g h c entr i f u g ation s peeds

. F i nally , it s hould be noted that tox i c i ty is ty pic ally r educ ed w i th hi g h s peed c entr i f u g ation due to the r em oval of par tic l eas s oc i ated c ontam inants ( S as s on- Br ic k s on and Bur t on 1991; Sc hults et al., 1992; Ank l ey and Sc hubauer - B er i g an, 1994; Buf f l ap and Allen, 1995)

. Based on research to date, both sl ower and faster centrifug ation sp eeds (and associated differences in colloid/suspended solids rem o v al) m ay be appropriate depending on the study obj ectiv es. For m any prog ram s that are interested in characteriz ing s ite toxicity , hig h speed centrifug ation m ay not be appropriate because one is interested in toxicity potential of the interstitial w a ter in its entirety (i.e., including colloidal m aterial). H o w ev er, if one is interested in co m p aring interstitial w a ter contaminant concentrations to specific sediment quality v alues, or m odel exposure com p artments for exam ple (EPR I , 2000), then hig h speed centrifug ati on mi g h t be necessary
. A s our k now ledg e is still limited in this area, it is perhaps m o st im portant to note that centrifug ation speed often has a dram atic effect on observ ed sam p le toxicity and chemical characteristics. T h erefore, in any sediment m onitoring study , one centrifugation protocol (including sp eed and tim e) should be identified and used t h roughoutf or al l sam pl e s . Centrifug ation has been performed at v arious te m p eratures. AST M (2000a) recommends that the centrifug ation tem p erature reflect the in situ sediment tem p erature to ensure that the equilibrium betw een the particulate and interstitial w a ter is not altered. A lternativ ely , a tem p erature of 4° C m a y be preferred to mi nimi z e tem p erature- mediated chemical and biolog ical processes (Env ironment Canada, 1994). When centrifug ing coarse sand, it mi g h t be desirable to use a m odified centrifug e bottle to aid interstitial w ater recov ery (U SEPA/A C O E, 1998). T h e m odified bottle is equipped w ith an internal filter that can recov e r 75% of the interstitial w a ter, as com p ared to 25 - 30% recov ery from squeez ing (Saag er et al ., 1990).

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hapter 6: C o

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses A s discussed in Section 4.2, all containers hav e limitations w ith reg ards to adsorption or leaching of chemicals, ease of use, and reliability
. F o r exam ple, poly t etrafluororthy l ene (P TF ) bottles hav e been used successfully up to 2500 x g w h en filled to 80% of capacity , but collapse at 3000 g (B urg ess et al., 1993). Poly carbonate bottles hav e been used succe ssfully for tributy tin analy ses in interstitial water (Hoffm an, 1998). I f sm all v o lumes of water are required for testing , hig h er speed centrifug ation can be performed with g l ass tubes (up to 10,000 g , Word et al., 1987). Larg er g l ass tubes, howev er, can not be centrifug ed at such hig h speeds. I f metal toxicity is not a concern, then hig h speed centrifug ation in larg er stainless steel centrifug e tubes is suitable. I f test sam p les are contaminated w ith photoreactiv e com pounds such as PA H s , exposure of the sam p le to lig ht should be mi nimi z e d to limit deg r adation or alterati on of potentially toxic com pounds. T h is can be accom p lished by using reduced lig hting
. **6. 3.**  **3 S**  **edi m**  **ent Squeezi**  **ng** I solation of interstitial w a ter by squeez ing has b een performed using a v ariety of procedures and dev i ces (R eeburg h, 1967; Kalil and G o ldhaker, 1973; J ahnke, 1988; C arr et al., 1989; Long et al., 1990; Watson and Frickers, 1990; Adam s, 1991; Carr and Chapm a n, 1995; Carr, 1998). I n expensiv e low pressure mechanical squeez ers can be constructed, and m ay prov ide specializ ed capacities such as collection of interstitial w a ter pr ofiles from core sam p les (B ender, et al , 1987). I n all cases, the interstitial w a ter is passed throug h a filter th at is a part of the squeez ing apparatus. S queez ing has been show n to produce a num ber of artifacts due to shifts in equilibrium from pressure, tem p erature, and g r adient chang es (e .g ., Froelich et al., 1979; Kr iuk o v and Manheim , 1982; B o lling er et al., 1992; Schults, 1992). Squeez ing can affect the electroly te concentration in the interstitial w a ter particularly w ith a decrease in chemical concentrations near the end of the squeez ing process. H o w ev er, others reported th at squeez ing did not produce artifacts in interstitial water toxicity studies (Carr and Chapm an, 1995; Carr, 1998; SET A C, 2001). I tis therefore recommended that if squeez ing is performed, m odera te pressures be applied along with electroly te (conductiv ity ) m onitoring during extraction (Kriuk ov and Manheim , 1982). Squeez ing should also be performed at in situ am bient tem p eratures, as sig n ificant alterations to interstitial w a ter com position can occur when squeez ing is conduc ted at tem p eratures different from am bient conditions (e.g ., Mang elsdorf et al., 1969; Bischoff et al., 1970; Say l es et al., 1973). O t her sources of interstitial w a ter alteration durin g squeez ing are: contamination from ov erly ing w a ter; internal mi xing of interstitial w a ter during ex trusion; and solid- solution reactions as interstitial w ater is expressed throug h the ov erly ing sediment. A s interstitial w aters are displaced into upper sediment z ones, they come in contact w ith solids w ith w h ich they are not in equilibrium
. This intermi xing causes solid- s olution reactions to occur. Most interstitial w a ter chemical species are rapidly transformed, as observ ed w ith amm onia and trace metals (Rosenfield, 1979; Santschi et al., 1997). B o lling er et al. (1992) found elev ated lev els of se v eral ions and dissolv ed org anic carbon in squeez ed sam p les as com p ared to sam p les collected by in situ peepers. T h e m ag n itude of the artifact w ill depend on the pollutant sediment characteristics and redox potential. **6. 3.**  **4 P**  **ressuri zed and Vacuum Dev**  **i ces**  O t her me thods for extraction of interstitial w a ter from sedime nt sam p les can include v acuum filtration (J enne and Z achara, 1987; Knez ov ich and H arrison, 1987; Wing erand Lasier, 1991), g a s pressuriz ation (Reeburg h, 1967), and displacement (A dam s , 1991). T h ese methods ty pically recov er only sm all v o lum e s of interstitial w a ter and are not comm only used.

6-12 U S Environm ental Protection AgencyTechnical M anual

P hoto courtesy of A l l en B u rton

**S e**  **dime nt s**  **que e**  **z ing a**  **ppa r**  **a tus**  **for e**  **x t**  **r a**  **c t**  **ing inte r**  **s titia**  **l w**  **a te**  **r**

C

hapter 6: C o

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses U s e of a hand v acuum w ith an aquarium stone is an effectiv e v acuum filtration me thod (Wing e r and Lasier, 1991; Sarda and Burton, 1995). T h e procedure ty pically inv o lv es attaching the air stone to a 50 m Lsy ring e v i a plastic tubing , inserting it into the sediment to the desired depth, and then apply i ng suction. T h is method can recov er relativ el y larg e v o lume s of interstitial w a ter; Santschi et al. (1997) used this procedure to extract up to 1,500 m Lfrom 4 L of sedime nt. Sarda and Burton (1995) found that amm onia concentra tions in water obtained by this procedure were similar to those collected by in situ peepers. D r aw back s to this method include loss of equilibrium betw een the interstitial w ater and the solids, filter clog g i ng , and oxidation (B rinkm an et al., 1982).

6-14 U S Environm ental Protection Agency**CHA PT**  **ER** 

# 7 Technical M anual 

## Quality Assurance and Quality **Control**
**7. 1**  **G eneral**  **Procedures** Q u ality assurance activ ities prov ide a form aliz ed sy stem for ev aluating the technical adequacy of sam p le collection and laboratory analy sis activ itie s. These quality assurance activ ities beg i n before sam p les are collected and continue after laborat ory analy s es are com p leted, requiring ong oing coordination and ov ersig h t. T h e quality assurance prog ram should integ r ate m anag ement and technical practices into a sing le sy stem to prov ide data that are sufficient, appropriate, and of known and documented quality
. D ev eloping and m aintaining a quality assurance (Q A ) prog ram requires an ong oing commitment by proj ect m anag ement and also includes the following : (1) appointment of a quality assurance officer w ith the responsibility and authority to dev elop and m a intain a QA prog ram , (2) preparation of a Q u ality A ssurance P r oj ect P l an w ith D a ta Q u ality O bj ectiv es, (3) preparation of w r itten descriptions of Standard Operating Procedures (SOPs) for sediment 

## C **h ecklist**  **QA pract**  **ices wit hin a**  **laboratory should address all act**  **ivit ies t**  **h**

**at af**  **f**

**ect t**  **h**

**e qualit y**  **of t**  **h**

**e f inal dat**  **a**

**, such as** ✓ s edim ent s a m p lin g and handlin g 

### ✓ c ondition and oper ation of equipm ent 

### ✓ ins t r u m ent c a libr a tion 

### ✓ r eplic ation 

### ✓ us e of s t andar ds 

### ✓ r ec or d k eepin g 

### ✓ data evaluation

sam p ling and m a nipulations, instrume nt calibrati on, sam p le chain- of- custody , laboratory sam p le track ing sy stem , and (4) prov ision of adequate , qualified technical staff and suitable space and equipment to assure reliable data. Prog ram specific g u idance for dev eloping and m aintaining a QA prog ram should be follow ed as appropriate. Exam ples of prog ram g u idance for dev eloping a quality assurance prog ram can be found in USEPA (1994; 1995; 2000d), PSEP ( 1997a), WDE (1995), and USEPA/ACOE (1991, 1998). Q u ality control (Q C ) practices consist of m o re focused, routine, day

- to- d ay activ ities carried out w ithin the scope of the ov erall Q A prog ram . Q C is the routine application of procedures for obtaining data that are accurate (precise and unbi ased), representativ e, com p arable, and com p lete. Q C procedures include activ ities such as iden tification of sam p ling and analy tical me thods, calibration and standardiz ation, and sam p le custody and record keeping
. A udits, rev i ew s, and com p lete and thoroug h documentation are used to v e rify com p liance w ith predefined Q C procedures. P r oj ect- specific Q Aplans (Q A P P ; see S ection 7.3 below ) prov ide a detailed plan for activ ities performed at each stag e of the study and outline the data quality obj ectiv es that should be achiev ed. Throug h periodic reporting , Q Aactiv ities prov ide a means to track prog ress and milestones, perform ance of measurement sy stem s, and data quality
. Acom p lete proj ect- specific Q A/ Q C effort has two m aj o r com ponents: a QA prog ram im plemented by the responsible ag ency (i.e., the data
C

hapter 7: Q uality Assu rance and Q uality C ontrol 7-1M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses user) and QC prog ram s im plements by the parties responsible for collection and analy ses (i.e., the data g e nerators). 

### 7. **2 Q**  **A /**  **Q C**  **Procedures f or Sedi**  **ment Col**  **l ect**  **i on and Mani**  **pul at**  **i on**  T o ensure the appropriateness of the sam p le collection protocol for sam p le integ r ity and data of suitable quality , a prog ram of scheduled field QC sam p les, such as field replicates (duplicates, splits, field spikes), field blank s (rinsate equipment), bottle, trip, and back g r ound (upg radient) sam p les is critical. A ll field QC sam p les should be handled exactly as the sediment sam p les and should be treated as blind sam p les so as to mi nimi z e bias in the analy s is. A random portion of the sam p les should also be analy z ed by a third party to ev aluate the prim ary laboratory ’ s perform ance. QC replicates (duplicates, splits) should be collected for analy sis by the prim ary laboratory to determine analy tical v ariability (U SEPA 1995). T h e procedures for sediment m anipulations described in Chapter 4 should m aintain the sam p le in a chemical condition as similar as possible to that at the time of collection. Q Aprocedures 

## C **h ecklist**  **QA/QC procedures for sample collection should**  **include the following principal element**  **s :**  ✓ im plem entin g a s ound s a m p lin g appr oac h bas ed on the intended us e of the data. 

### ✓ us e of s a m p lin g m ethodolo g ies w h ic h allow the c o llec t ion of r epr es entative s a m p les bas ed upon data needs

. 

### ✓ us e of s a m p lin g devic es that m i nim i z e the dis t ur banc e oralter ation to the m edia’s c hem ic al c o m pos ition. 

### ✓ em ploy in g dec ontam ination pr oc edur es w hic h r educ e c r os s - c ontam ination potential betw een s a m p lin g points

. 

### ✓ us e of pr opers am ple c ontainer s and pr es er vation tec hniques that m ax i m i z e the inte g r i ty of s am ples

.
are established to assure that SO Ps are follow ed and that contamination is neither introduced to nor lost from the m anipulated sam p le. For exam ple, sam p les to be analy z ed for trace metals should not come in contact w ith metal surfaces (except stainl ess steel). Sam p le track ing sheets should document date, time, and inv estig ator related to rem o v al and replacement of sam p les from storag e. Specific m anipulation procedures should follo w established SOPs that mi nimi z e chemical alteration of the sam p le (excepting chemical spiking ) , m aintain sedi ment phy sical properties, and include replication and blank sam p les. 

### 7. **3 T**  **he Q u**  **al i**  **t y**  **A ssurance Proj**  **ect Pl an (Q**  **A PP)**  The Q u ality A ssurance P r oj ect P l an (Q A P P ) is a proj ect- specific document that specifies the data quality and quantity requirements needed for the study as w e ll as all procedures that w ill be used to collect, analy z e, and report those data. T h e Q A PP uses input from the sam p ling desig n deriv ed from the D ata Q u ality O b j ectiv es Process (see C h apter 2 specifically Measurement Q u ality O b j ectiv es discussion, S ection 2.4, and U S E P A , 2000a) to specify the abov e elements. T h is Plan s hould be rev i ewed by an independent person (e.g ., quality assurance officer or staff me m b er not inv o lv ed in the proj ect directly ) for accuracy and com p leteness. A key element of a Q A PP is Sta ndard Operating Procedures (see Section 7.4). Further inform ation on preparing a QAPP and res ources necessary can be found in USEPA (2000e).

7-2 U S Environm ental Protection AgencyTechnical M anual 

### 7. **4 S**  **t andard O**  **p erat**  **i ng Procedures**  Standard operating procedures are w r itten descrip tions of routine methods and should be prov ided for all methods used. A larg e num ber of field a nd laboratory operations can be standardiz ed and presented as standard operating procedures. Genera l ty pes of procedures that benefit from standard operating procedures include field measurements ancillary to sam p le collection (e.g ., w ater quality measurements or mi xing m odel input measuremen ts); chain- of- custody , sam p le handling , and shipment; and routine analy tical methods for chemi cal analy ses and toxicolo g i cal analy s es. Standard operating procedures ensure that all persons conduc ting work are following the same procedures and that the procedures do not chang e ov er time. A ll personnel should be thoroug hly familiar w ith the standard operating procedures before w o rk is initiated. D ev i ations from standard operating procedures mi g h t affect data quality and integ r ity
. I f it is necessary to dev i ate from approv ed standard operating procedures, these dev i ations m u st be documented and approv ed throug h an appropriate chain- of- comm and. 

### 7. **5 S**  **edi m**  **ent Sampl e**  **Documentati o**  **n** Bound field log book s should be used for the m ainte nance of field records. All entries should be dated and time of entry recorded. A ll aspects of sam p le collection and handling as w ell as v i sual observ ations should be documented in the field log book s. Docume ntation should be recorded in prenum bered bound notebook s using indelible ink pens in sufficient detail so that decision log i c m a y be traced back , once rev i ew ed.


## C **h ecklist**  **Qualit y A**  **ssurance Project Plans vary in cont**  **ent depending on**  **program needs, but should address the following elements:**
✓ a des c r iption of the pr oj ec t or g aniz a tion and r e s pons ibilities 

### ✓ def inition of data quality obj ec tives ( s ee Sec t ion 2.1) 

### ✓ s a m p lin g , analy s is , and m eas ur em ent pr oc edur es 

### ✓ ins t r um ent c alibr ation pr oc edur es 

### ✓ pr oc edur es f orr ec or din g , r educ in g , validatin g , and r epor tin g data 

### ✓ pr oc edur es f orper f or m in g quality as s ur anc e ver i f i c ation and inter nal quality c ontr ol c hec k s 

### ✓ pr eventive m a intenanc e s c hedules 

### ✓ s pec if ic r outine pr oc edur es to evaluate pr ec is ion, ac c ur ac y , and c om pletenes s 

### ✓ def initions of deviations and appr opr iate c o r r e c t ive ac tions 

### ✓ inf or m ation on appr opr iate tr ainin g

C

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Proper field sheet, sam p le labeling , chain- of- cus tody , and sam p le tracking documentation should be m aintained as appropriate. Specific details concerning sam p le documentation and sam p le m anag ement should be included in planning documents and rev i ewed by the sam p ling team prior to initializ ing the sam p ling prog ram . 

### 7. **6 S**  **ampl e T**  **r acki**  **ng Documentati o**  **n** Sam p les deliv ered to the laboratory should be accom p anied by a chain- of- custody record that includes the name of the study , location of collecti on, date and time of collection, ty pe of sam p le, sam p le nam e or num ber, num ber of containers, an aly s is required, and the collector' s sig n atures. When turning ov er possession of sam p les, the relinqui sher and the receiv er sig n , date and record the time on the record sheet. T h e record sheet allows the transfer of a g r oup of sam p les at one time. When the laboratory takes possession of the sam p le s, each should be assig n ed a unique laboratory identification desig n ation. This assures a consistent sy stem for tracking w ithin the laboratory
. I f the sam p les arriv e at the laboratory w h en desig n ated personnel are not there to receiv e them , the sam p les are put into a secure location and the transfer is conducted when the appropriate personnel are present. Upon arriv al at the laboratory , sam p les are inspected for condition and tem p erature, and sam p le container labels are v e rified ag ainst the chain- of- custody record or sam p le tracking form
. S a m p le inform ation is entered on a laboratory log

- in data sheets used to m aintain inform ation reg arding sam p le: receipt, shipping , collection date, and storag e. T o allow for accurate identification of sam p les, inform ation contained on sam p le tracking form s m u st m a tch identically w ith inform ation contained on the sam p le container labels. The tracking form lists both the collector’s and the laboratory ’ s identification desig n ations. Verified tracking form s are sig n ed by the laboratory personnel with date and time in ink
. Missing and/or com p romi sed sam p les (e.g ., inappropriate preserv a tion to m a intain integ r ity , inappropriate containers, and unlabeled or mi slabeled containers) are documented on the tracking form s. When sam p les are rem o v ed from storag e, the sam p le tracking form accom p anies it and documents data, time, and inv estig ator associated w ith any m anipulations. T h e m anipulation ty pe is noted on the form in detail or by reference to an approv ed laboratory SOP. Any dev i ation from the SOP are also noted. Should the sam p le be 

## C **h ecklist**  **Sample documentation should include:** 
✓ pr oj ec t nam e, and analy s is ortes t to be per f or m ed 

### ✓ s a m p lin g loc a tions 

### ✓ dates and tim es 

### ✓ s a m p lin g per s onnel pr es ent 

### ✓ level of per s onal pr otec tive equipm ent wo r n 

### ✓ w eatherorany envir onm ental c ondition that m i g h t a f f e ct sa m p l e s 

### ✓ equipm ent us ed to c ollec t s am ples , and s am ple c ontainerpr epar ation 

### ✓ c a libr a tion data 

### ✓ deviations f r om appr oved w or k plans or SO Ps 

### ✓ sk e t ch o f sa m p l i n g ar ea 

### ✓ notation of the s y s t em identif y i n g and tr ac k i n g sa m p l e s 

### ✓ notation of any vis i tor s to the s i te 

### ✓ initials and date on eac h pa g e

7-4 U S Environm ental Protection AgencyTechnical M anual

m odified in such a way that additional subsam ples are created, additional tracking form s m u st also be created. 

### 7. **7 R**  **ecord Keepi n**  **g** P r oper record keeping is essential to the scie ntific defensibility of a sedime nt sam p ling and m anipulation prog ram . A separate file should be m aintained for each sam p ling/ m anipulation ev ent or closely related ev ents. T h is file should contain field log s, chain- of- custody form s, sam p le track ing form s, storag e records, and any QA/QC documenta tion and records. Orig inal documentation should be sig n ed and dated by the orig inator. 

### 7 **. 8**  **Q A Au**  **d i**  **t s**  

## C **h ecklist**  **Performance** I n addition to the QA/QC procedures conducted on a routine basis, quality audits (i.e., perform ance and 

### auditing procedures **are:** quality sy stem s audits) mi g h t be conducted. Perform ance audits refer to independent check s to ev aluate the quality of data produced during testing
. 

### ✓ s a m p le auditin g - the auditor T h ere are three ty pes of perform ance audits: us es a s epar ate s et of c alibr ated sam p ling ; test; and data processing
. These audits s t andar ds to c hec k the s am ple are independent of norm al quality control check s co l l e ct i o n sy st e m . performed by the operator. 

### ✓ tes t auditin g - the auditoris pr ovided w i th s et of a duplic ate A sy stem s audit is an on- site inspection and rev i ew s am ple ors plit por tion. of the quality assurance sy stem . The sy stem s audit is 

### ✓ data pr oc es s i n g audit - the performed to v e rify that the org a niz a tion is auditors pot c hec k s c alc ulations following the policies and procedures described in ora dum m y s et of r awdata is i t s QA/ QC pl a n a nd i n appropriate SOPs. Sy stem s ins e r t ed f o llow ed by r e viewof validated data

. audits are performed by an auditor ty pically from an accrediting body
. 

### 7. **9 C**  **orrecti v**  **e A c**  **ti on (Managemen**  **t of**  **Non- conf**  **ormance Ev ent**  **s)** T h e QA Officer and the responsible m anag er are res ponsible for rev i ewing the circum stances of all instances of occurrence of nonconformities, to dete rmine w h ether correctiv e action should be taken. T h e m anag er is responsible for determining if new sam p les are required, if the customer should be notified, if additional testing is necessary , or whether the results should be confirmed. A g ood comm unication plan is inv aluable in helping to iden tify interactions am ong labs, clients, and ag encies during correctiv e actions. C o rrectiv e action mi g h t take tw o form s: that of addressing technical problem s associated w ith proj ect activ ities and that of addressing Q A/ Q C infractions based upon perform ance. T echnical problem s in meeting proj ect obj ectiv es m ay rang e in m ag n itude from failure to meet mi nor procedural requirements, to m aj o r problem s associ ated with inappropriate methods or data loss. Established procedures for correctiv e action of mi nor technical problem s ar e often included in the SO Ps for cases w h ere perform ance limits or acceptance criteria hav e been exceeded. O n - t he- s pot correctiv e actions are noted on data sheets. Maj o r or recurrent QA/QC probl em s which require long

term correctiv e action, such as m odification of SOPs, are reported. Depending upon the nature and

C

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

sev erity of the problem , an approach mi g h t be dev eloped. Any correctiv e action is documented by ma na g e me nt . I n fractions of QA/QC policies by staff are iden tified and addressed by the m anag ement. Minor infractions are corrected throug h a dditional training and/or closer superv ision. Maj o r or recurrent infractions are corrected throug h re

- assig nment of technical personnel. C o rrectiv e actions relativ e to sam p le collection a nd m anipulation m ay include, but are not limited to, rev i ew of the data and calculations, flag g i ng and/ or qualification of suspectdata, or possible resam p ling
. Arev i ew that prov ides a preliminary check of all “out of limit” ev ents is performed as soon as the data for a g i v en parameter or test is tabulated and v erified for accuracy
. “O ut of limit” ev ents are flag g ed to determine w h ether new sam p les are required. 

### 7. **10 Dat**  **a Report i**  **ng** I n addition to reporting the raw data from a g i v en se diment quality study or analy sis, the data report should include additional quality assurance inform ation to ensure the data user that sam p le handling and analy s es are in accordance w ith the proj ectplan. T h e quality assurance inform ation also documents procedures taken to ensure accurate data collection. D ata are to be presented electronically as w ell as in hardcopy for m any reg u latory prog ram s. R equired electronic form at should be explicitly outlined as a data quality obj ectiv e during the planning process.


## C **h ecklist**  **Qualit y A**  **ssurance R e** 

**port ing** 

✓ A c opy of the s am ple c hain of c us t ody r ec or d, inc l udin g doc um entation of s am ple c o llec t ion date and tim e 

### ✓ Doc um entation of the labor ator y c er t if ic ation num ber 

### ✓ Doc um entation of the analy s is m ethod us ed 

### ✓ Doc um entation of analy s is date and tim e ( ortes t in g per iod in the c as e of tox i c i ty tes t s ) 

### ✓ Doc um entation that data f ors pik es , duplic ates , s t andar ds , etc m eets labor ator y Q A /Q C r equir e m ents f o rc hem ic al analy t es 

### ✓ Doc um entation that r ef er enc e tox i c ant tes t data m eets labor ator y Q A /Q C r equir em ents f o r t o xi ci t y t e st s. 

### ✓ Doc um entation of any deviations in s am ple pr epar ation oranaly s is pr otoc ols

7-6 U S Environm ental Protection AgencyTechnical M anual 

## References **CHA PT**  **ER** 

# 8

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llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses B r ow naw e ll, B
. J ., and J
. W. Farring ton. 1986. B i og eochemistry of PC B s in interstitial w a ters of a coastal m arine sedime nt. Geochimica et Co smochimica Acta. 50:157- 169. Brum baug h, W.G., C.G. I n g e rsoll, N.E. K e m b le, T
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. E. A llen. 1985. B i oav a ilability of trace me tals in natural w a ters. Aquatic T oxicol. And Haz ardAssessment: Sev e nth sy m posium
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thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Bidding er RG (editors). Ecolog i cal risk assessment of contaminat ed sedime nt. Pensacola FL: SET A C Press. p 271- 296. Stemme r, B.L., G.A. Burton, J r ., and S. Leibfritz

- F rederick . 1990a. Effects of sedime nt test v ariables on selenium toxicity to Daphnia magna
. Environmental Toxicology and Chemistry 9:381- 389. Stemme r, B.L., G.A. Burton, J r ., and S. Leibfr itz

- F rederick . 1990b. Effect of sedime nt spatial v ariance and collection me thod on Cladoceran toxicity and indig e nous mi crobial activ ity determinations. Environmental Toxicology and Chemistry 9:1035- 1044. Stephenson, R.R., and D.F. K a ne. 1984. Persistence and effects of chemicals in sm all enclosures in ponds. Arch. Environmental Toxicology and Chemistry 13:313- 326. Sternberg , R. W., and J
. S. Creag er. 1961. Com p arativ e Efficiencies of Siz e Analy s is by Hy drometer and Pipette Methods. Journal of Sedi ment Petrology 31:96- 100. Stewart, A.R., and D.F. Malley
. 1999. Effect of me tal mi xture (Cu, Z n , Pb, and Ni) on cadmi um partitioning in littoral sedime nts and its accum u lation by the freshw a ter m acrophy te Eriocaùlon septangùlare
. Environmental Toxicology and Chemistry 18(3):436- 447. Sw artz , R
. S., D
. W. Schults, T
. H
. D e Witt, G
. R
. D itsw o rth, and J
. O
. Lam b erson. 1990. T oxicity of fluoranthene in sedime nt to m arine am phipods: A te st of the equilibrium partitioning approach to sedime nt quality criteria. Environmental Toxicology and Chemistry 9:1071- 1080. Swift, D.J
. P., J
. R. Schubel, and R.W. Sheldon. 1972. Siz e analy s is of fine- g rained suspended sedime nts: A rev i ew. Journal of Sedi mentary Petrology 42:122- 134. T a tem , H
. E. 1986. Bioaccum u lation of poly c hlorin ated bipheny ls and me tals from contaminated sedime nt by freshwater prawns, Macrobracium rosenbergii , and clam s, Corbicula fluminea
. Archives of Environmental Contam ination & Toxicology 15:171- 183. T hurston, R.V ., R.C. Russo and G.A. V i nog radov . 1981. Amm onia toxicity to fi shes. Effect of pH on the toxicity of the unioniz e d amm onia species. Environmental Science and Technology 15:837- 840. T i nsley , I
. J
. 1979. Chemical Concepts in Polluti on Behav i or. Wiley

- I n terscience, New York , p. 92. T r oup, B.N., O.P. Bricke r, and J
. T
. Bray . 1974. Ox idation effect on the analy s is of iron in the interstitial w a ter of recent anoxic sedime nts. Nat u re 249:237. T ruax, D.D., A. Shindala and H. Sartain. 1995. Com p arison of two sedime nt oxy g e n dem a nd measurement techniques. Journal of Environmental Engineering , Septem ber, pp. 619- 624. T y e, R., R. J e psen and W. Lick . 1996. Effects of colloids, flocculation, particle siz e , and org a nic m a tter on the adsorption of hexachlorobenz ene to sedime nts. Environmental Toxicology and C

h em istry 15:643- 651. Uchrin, C.G. and W.K
. Ahlert. 1985. I n situ sedi me nt oxy g e n dem a nd determinations in the Passaic Riv e r (NJ ) during the late summe r/early fall 1983. W a ter Resources 19:1141- 1144.

8-18 U S Environm ental Protection AgencyTechnical M anual U.S. Army Corps of Eng i neers. 1976. Ecolog ical ev aluati on of proposed discharg e of dredg e d or fill m a terial into nav i g able w a ters. Miscellaneous Paper D- 76- 17, Waterway s Experime nt Station, V i ck sburg , MS. U.S. Env i ronmental Protection Ag ency . 1979. Ch emistry Laboratory Manual for Bottom Sedime nts and Elutriate T e sting
. EPA- 905- 4- 79- 014 (NT I S PB 294596) EPA Reg i on V , Chicag o, I L
. U.S. Env i ronmental Protection Ag ency . 1983. Met hods for the chemical analy s is of water and wastes. EPA 600/4- 79- 020. U.S. En v i ronmental Protection Ag ency , Env i ronmental Monitoring and Support Laboratory , Cincinnati, OH. 460pp. U.S. Env i ronmental Protection Ag ency . 1986a. Occ upational health and safety m a nual. Office of Admi nistration, Washing t on, DC. U.S. Env i ronmental Protection Ag ency . 1986b. T e stme thods for ev aluating solid waste (SW- 846): phy sical/chemi cal me thods. U.S. Env i ronmenta l Protection Ag ency , Office of Solid Waste, Washing t on, DC. U
. S. Env i ronmental Protection A g ency . 1987. Q u ality A ssurance/Q u ality C ontrol (Q A/ Q C ) for 301(h) Monitoring Prog ram s : Guidance on Fiel d and Laboratory Methods . U.S. EPA 430/9- 86- 004. U.S. Env i ronmental Protection Ag en cy . 1991. Methods for measuring the acute toxicity of effluents and receiv i ng w a ters to freshw a ter and m arine org a nism s. Fourth edition. EPA

- 600/4- 90/027F, Cincinnati, OH. U.S. Env i ronmental Protection Ag ency . 1993. U.S. EPA Contract La boratory Prog ram - statement of w o rk for org a nic analy s is, m u lti- me dia, m u lti- concentration. D o cume nt I L MO 1.0- I L MO

- 1 .9, 1993. U.S. Env i ronmental Protection Ag ency , Washing t on, DC. U.S. Env i ronmental Protection Ag ency . 1994. Met hods for measuring the toxicity of sedime ntassociated contaminants with estuarine and m a rine am phipods. EPA- 600/R- 94/ 025, Narrag a nsett, RI
. U.S. Env i ronmental Protection Ag ency . 1995. QA/QC Guidance for Sam p ling and analy s is of sedime nts, water, and tissues for dredg e d m a teri al ev aluations (chemi cal ev aluations). EPA 832- B95- 002. Office of Water, Washing t on, D.C. U.S. Env i ronmental Protecti on Ag ency . 1996. Eco Update Ecotox Thresholds . EPA 540- F- 95- 0380 U.S. Env i ronmental Protection Ag ency . 1997a. T h e incidence and sev e rity of sedime nt contamination in surface w a ters of the U n ited Stat es. Volume 1: N a tional Sedime nt Q u ality Surv ey . EPA 823- R- 97- 006. Office of Science and T echnolog y , Washing t on, DC. U.S. Env i ronmental Protection Ag ency . 1997b. EPA Div i ng safety m a nual - Aug u st, 1997. Prepared by the Office of Admi nistration and Resource Ma nag e me nt, Safety , Health, and Env i ronmental Manag e me nt Div i sion. U.S. Env i ronmental Protection Ag ency . 1997f. Ecolog ical Risk Assessment Guidance for Superfund: Process for Desig n ing and Conducting Ecol og ical Risk Assessments. EPA 540- R- 97- 006. U.S. Env i ronmental Protection Ag ency . 1998. Cont aminated sedime nt m a nag e me nt strateg y . EPA 823- R- 98- 001. Office of Water, Washing t on, DC.
C

hapter 8: R e

ferences 8-19M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses U
. S. Env i ronmental Protection A g ency . 1999. 1999 U pdate of A m bient Water Q u ality C r iteria for Amm onia. EPA- 823- F- 99- 013, Office of Water, Washing t on, DC. U
. S. Env i ronmental Protection A g ency . 2000a. G u idance for the D a ta Q u ality O b j ectiv es Process. EPA QA/G- 4. EPA/600/R- 96/055. Office of Env i ronmental I n form ation, Washing t on, D.C. U.S. Env i ronmental Protection Ag ency . 2000b. Guidance for Choosing a Sam p ling Desig n for E n v i ronmental D a ta C o llection. U.S. Env i ronmental Protection Ag ency . 2000c. Es tuarine and Near Coastal Marine Waters: Bioassessment and Biocriteria T echnical Guidance. EPA- 822- B- 00- 004. U.S. Env i ronmental Protection Ag ency . 2000d. Methods for measuring the toxicity and bioaccum u lation of sedime nt- a ssoci ated contaminants w ith freshw a ter inv e rtebrates. Second Edition. EPA/600/R- 99/064, Duluth, MN. U
. S. Env i ronmental Protection A g ency . 2000e. G u idance in the U s e and D e v e lopment of a Q u ality A ssurance Proj ect Plan. EPA Q A/ G

- 5S, O ffice of En v i ronmental I n form ation, Washing t on, D.C. I n Press. U.S. Env i ronmental Protection Ag ency/Army Corp s of Eng i neers. 1991. Ev aluation of dredg e d m a terial proposed for ocean disposal: T e s ting m a nual. EPA

- 503/8- 91/001, O ffice of Water, Waterway s Experime nt Station, V i ck sburg , MS. U.S. Env i ronmental Protection Ag ency/ Army Co rps of Eng i neers. 1998. Ev aluation of dredg e d m a terial proposed for discharg e in waters of the U.S. - testing m a nual. EPA- 823- B- 98- 004, Washing t on, DC. U.S. Geolog ical Surv ey . 1969. T echniques of Water- Resources I n v e stig ations of the U.S.G.S. Chp. C1, Harold P. Guy , p. 58, Laboratory T h eory and Methods for Sedime nt Analy s is; Book 5, Labor a t or y Ana l y s i s , U.S.G.S. Ar l i n g t on, V A
. V a nderpleog , H. A. 1981. Effect of the Alg a l Leng th/Aperture Leng th Ratio on Coulter Analy s es of Lake Seston. Canadian Journal of Fisheries & Aquatic Science 38:912- 916. V ecchi, M., T
. B. Rey noldson, A
. Pasteris and G
. Bonomi. 1999. T oxicity of copper- spiked sedime nts to T ubifex tubifex (Olig ochaeta, T ubificidae): Com p aris on of the 28- day reproductiv e bioassay with an early

- life- stag e biassay
. Environmental Toxicology and Chemistry 18(6):1144- 1148. Warwick , R.M., and K
. R. Clarke . 1991. A com p ar ison of some me thods for analy z ing chang e s in benthic comm unity structure. Journal of the Marine Biologica l Association of the United Kingdom 71:225- 244. Walters, D.B. and C.W. J a me son. 1984. Health and safety for toxicity testing
. Butterworth Publications, Woburn, MA. Washing t on Departme nt of Ecolog y (WDE). 1995. Sedime nt Sam p ling An aly s is Plan Appendix: Guidance on the Dev e lopment of Sedime nt Sam p lin g and A n aly s is Plans Meeting the R e quireme nts o f

th e S e d i me n tMan a g e me n tS t an d ard s. E c o l o g y P u b licatio n N o . 9 5

- XXX, Wash in g t o n D e p artme n t of E c olog y , S eattle, WA
.

8-20 U S Environm ental Protection AgencyTechnical M anual Waters, D.B. (Ed.). 1980. Safe handling of chemi cal carcinog ens, m u tag e ns, teratog e ns and hig h ly toxic substances. Ann ArborScience, Ann Arbor, MI
. Watson, P.G ., and T
. E. Fricke rs. 1990. A m u ltilev e l, in situ pore- w a ter sam p ler for use in intertidal sedime nts and laboratory mi crocosm s . Limnology and Oceanography 35:1381- 1389. Watson, P.G., P. Fricke rs, and C. Goodchild. 1985. Spatial and seasonal v ariations in the chemistry of sedime nt interstitial w a ters i the Tam ar estuary . Estuaries and Coastal Shelf Science . 21:105- 119. Watz in, M., A
. McI n tosh, E. B r ow n, R
. Lacey , D
. Lester, K. N e w b roug h, and A
. William s . 1997. A ssessing sedime nt quality in heterog e neous env i r onments: a case study of a sm all urban harbor in Lake Cham plain, V e rm ont USA. Environmental Toxicology and Chemistry 16:2125- 2135. Webster, G.R.B., M.R. Serv os, G.G. Choudhry , L. P. Sarna, and G.C.G. Muir. 1990. Methods for dissolv ing hy drophobics in water for studies of th eir interactions with dissolv ed org a nic m a tter. A d v a nces in C h emistry Series, Presented at the 193 rd N a tional Meeting of the A merican C h emical Society , Div i sion of Env i ronmental Chemistry
. Ex tended Abstracts. 28:191- 192. Welik y , K ., E. Suess and C.A
. U n g e rer. 1983. Problem s w ith accurate carbon measurements in m arine sedime nts and particulat e in seaw ater: a new approach. Limnology and Oceanography 28:1252- 1259. West, R.J
. and S.J
. Gonsior. 1996. Biodeg r adation of triethanolamine. Environmental Toxicology and C

h em istry 15:472- 480. Whitfield, M. 1969. Eh as an operational parame ter in estuarine studies. Limnology and Oceanography 14:547. Whitfield, M. 1978. T h e Hy droly s is of Amm onium I ons in Sea Water-

- E xperime ntal Confirm a tion of Predicted Constants at On e A t m o sphere Pressure. Journal of the Marine Biological Association of the United Kingdom 58:781- 787. Wing er, P.V
. and P.J
. Lassier. 1991. A v acuum - operated porewater extractor for estuarine and freshw a ter sedime nts. Archives of Environm ental Contamination & Toxicology 21:321- 324. Word, J
. Q ., J
. A
. Ward, L.M. Franklin, V.I
. C u llinan, and S.L. Kiesser. 1987. Ev aluation of the equilibrium partitioning theory for estim ating th e toxicity of the nonpolar org a nic com pound D D T to the sedime nt dw elling am phipod Rhepoxynius abronius . B a ttelle/Marine R e search Laboratory Report, T a sk 1, WA56, Sequim , WA. 60pp. Wrig ht, L.D., D.B. Prior, C.H. Hobbs, R.J
. By rn e, J
. D. Boon, L.C. Schaffner, and M.O. Green. 1987. S p atial v ariability of bottom ty pes in the low e r C h esapeake B a y and adj o ining estuaries and inner shelf. Estuarine, Coastal, and Shelf Sciences 24:765- 784. Yam a m u ro, M. and H. K a y a nne. 1995. Rapid direct determination of org a nic carbon and nitrog en in carbonate- b earing sedime nts with a Yanaco MT

- 5 CHN analy z er. Limnolology and Oceanography 40:1001- 1005.

C

hapter 8: R e

ferences 8-21M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Yee, S., M. V a n Rikxoort, and D. McL eay . 1992. T h e effect of holding time on Eohaustorius washingtonianus during ten- day sedime nt bioassay s and refe rence toxicant tests. R e port prepared for Env i ronment Canada and the I n ter- Gov e rnme ntal Aquatic T oxicity Group, North V a ncouv er, BC 53p.

8-22 U S Environm ental Protection Agency

# APPENDIX A **EXAMPLES OF SEDIMENT QUALITY SAMPLING DESIGNS USING THE DATA**  **QUALITY OBJECTIVES (DQO) PROCESS**Technical M anual T h e Data Quality Obj ectiv es (DQO) proce ss is a log i cal prog ression of steps that define the question to be answ ered and identifies qualitativ ely and qua ntitativ ely the procedures and decisions necessary t o addr ess t he quest i on posed. USEPA ( 2000a) di scusses a 7- st ep DQO pr ocess t hatl eads one throug h each of the decision points to help en sure a successful study or prog ram outcome. Sediment quality m onitoring studies, w h ether fo r reg u latory or non- reg u latory purposes, w ould be ne f i tf r o m f

o l l o wi ng USEPA’ s DQO pr oc e s s i n or de rt o :
• r educe the likelihood of collecting im proper or inappropriate sam p les
• i ncrease the likelihood of collecting representativ e sam p les for the question aske d
• d ecrease the chances of introduced measuremen t artifacts or interference due to sam p ling or sam p le processing techniques
• i ncrease the likelihood that data, and decisions based on those data, w ill be scientifically defensible and accepted by those inv o lv ed. T h e f o l l o wi ng t abl e s ar e hy pot he t i c a l e x a m pl e s de m ons tr a t i n g how t h e DQO pr oc e s s c oul d be us e d in addressing a few comm on purposes for collecting sediment quality data. The purpose of the study , orquest i on needi n g t o be answer ed, dr i v es t h e i nputf oral l subsequentst eps i n t he DQO pr ocess. T hus, sam p ling desig n, how sam p les are collected a nd m anipulated, and the ty pes of analy s es chosen, should all stem from the ov erall purpose of the st udy
. Many national and reg i onal prog ram s (e.g ., NOAA’ s St at us and T r ends, USEPA’ s Dr edg e Mat e r i al s Manag e me ntPr og r a m , orPug e tSound Estuary Prog ram ) already hav e a particular purpose identified, thus g i v i ng rise to the particular sam p ling protocols they each use.

Appendix A: Exam ples of Sedim ent Q uality Sam pling D esigns A-3M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **Examp l**  **e 1.** O bj ec t ive: Deter m ine w hetherc er t ain point and nonpoint s our c es ar e as s oc i ated w i th s edim ent c ontam ination in a lak e, es tuar y , orr i vers e g m ent DQ O Elem ent Issues/Co n cerns/Inf o rm a t io n 1. S t at e probl em / a v a i l abl e res o u r ces • C ertainpoin t an d n o n poin ts o u r ces of con cern • E no ugh r e so ur c e s fo r asm a l l

- m o d e r a t e sur ve yd e p e nd i ng o n num b e r of

an aly s es per s t ation 2
. I d en tif yq u estio n s to b e addres s e d • Ho wd o e s sed i me n t q u alityn earth ese so u r ces co m p ar e w itho th e r l o cat i o n s an d w i thEcot ox T h res h ol ds (U S E PA , 1996)? H o wt o x i c are th ey ? 3
. I d en tif yin f o r m atio n/ meas u r emen ts n eeded • Use av ailab l e d a ta, so u r ce in f o r m atio n , B P J to id en tif yco n t am in an ts of

con cern Meas u r emen ts cou l d in clu d e th e f o llow i n g : • 10d w h ol e s e di me n tt o x i ci t yt e s t s • A cu te o rch r o n i c to x i citytests u s in g in ter s titial w a ter • B en th ic m acroin v ertebrate an aly s es • C on tami n a n t an aly s es (e.g ., P A Hs , P C Bs , me tals , pes ticides ) • P ar ticle size, A VS ( i f me tals a co n cer n ) , T OC, % m o istu r e , p H, amm o n i a meas u r ed f o r eachs am p le • W ater, pH, ox y g en , con d u ctiv ity /s alin ityov erly in g s edimen t at each site 4
. Def i n e sp atial/tem p o r al b o und ar i e s • S am pl e du ri n g on e i n dex peri od • S u rf i ci al s e di me n t (t op 0 t o 2 or u p t o 15 cm ) of m o s ti n t e res t • C on cen trate s am p lin g n ear s u s p ected con t am in an t s o u r ces w iths o me ref e ren ce s t ation s (location s rem o v e d f r om poten tial s o u r ces ) as w e ll 5. D e f i n e th res h ol ds or decis i onru le f o r p ar a me ter s o f in ter e st • E cot o x T h res h ol ds (U S E PA , 1996), an d/ or oth e r s e di me n tth res h ol d v alu es f o r con t am in an ts • T o x icityef f ect lev e l: e.g ., sig n i f i can tlylo w e rsu r v iv al th anr e f e r e n c e statio n s o rsu r v iv al 

### � 50% 6. L i mi t s ondeci s i onerrors • P reci s i on : 

### � 40% C
. V. am on g f i eld replicates f o r con t amin an ts an d to x icity • T es t f o r dif f e ren ces betw eens u s p ect an d ref e ren ce s ites at p = 0.05 an d pow er = 80% • F ield b l an k s f o rco n t am in an ts < d e tectio nlim it • L ab du plicates f o r con t amin an ts y i eld 

### � 25% C
. V. T o x i citytes t replicates 

### � 35% C
. V
. • T ox tes t con trols meet EP Am i n i m u m perf orm a n ce requ iremen ts . 7. Optimize th e des i g n • C h oos e targ eted s am p lin g des i g nin clu d in g ref eren ce s t ation s • S am p l e w h enco n d itio n s m o st f av o r ab l e f o rg earef f i cien cyan d p e r s o n n e l saf e ty • U s e g r ab s a m p ler - P o n ar, Van V een , or P e ters en(s ee T able E- 1 f o r adv a n t ag es an d dis a dv an tag e s ) • U se GP S f o rsite p o s itio n i n g ( ± 1 0 m ) • C om pos ite s e v e ral (determ i n e d byn u m ber of con t am in an t an aly s es des i red) g r abs at eachs ite f o r a s i n g l e s a m p le • T ak e 3 replicate s a m p les at 10% of th e s ites , s elected at ran dom • S ee f l ow ch art f o r Selectin g a Grab Sam p ler B as ed onSite- S pecif i c F act ors (F i g u re 3- 2).

A-4 U S Environm ental Protection AgencyTechnical M anual **Examp l**  **e 2.** O bj ec t ive: Deter m ine the s t atus of s edim ent quality in a s i te ( e. g ., lak e, es tuar y , orr i v er se g m ent) DQ O Elem ent Issues/Co n cerns/Inf o rm a t io n 1. S t at e probl em / a v a i l abl e res o u r ces • S e d ime n t q u a lityunkno w no rsta tus w a s d e te r mine d in the p a st a n d th er e is a n eed to d e ter m in e h o wth e q u alitym a yh a v e ch an g e d
. • E no ugh r e so ur c e s fo r a

m o d e r a t e sur ve yd e p e nd i ng o n num b e r o f an aly s es per s t ation
. 2
. I d en tif yq u estio n s to b e addres s e d • Ho wd o e s sed i me n t q u alityco m p ar e w ithEco t o x T hr e sh o l d s ( USEP A , 1996)? H o wt o x i c are s e di me n t s n o was com p ared t o h i s t ori cal l y ? 3
. I d en tif yin f o r m atio n/ meas u r emen ts n eeded • Use av ailab l e d a ta, so u r ce in f o r m atio n , B P J to id en tif yco n t am in an ts of

con cern Meas u r emen ts cou l d in clu d e th e f o llow i n g : • 10d w h ol e s e di me n tt o x i ci t yt e s t s • A cu te o rch r o n i c to x i citytests u s in g in ter s titial w a ter • B en th ic m acroin v ertebrate an aly s es • C on tami n a n t an aly s es (e.g ., P A Hs , P C Bs , me tals , pes ticides ) • P ar ticle size, A VS ( i f me tals a co n cer n ) , T OC, % m o istu r e , p H, amm o n i a meas u r ed f o r eachs am p le • W ater, pH, ox y g en , con d u ctiv ity /s alin ityov erly in g s edimen t at each site 4
. Def i n e sp atial/tem p o r al b o und ar i e s • S am pl e du ri n g on e s eas on(i n d ex peri od) • S am ple s u rf icial as w ell as deeper s edimen t s to obtainh i s t orical record. • S am p l e statio n s r e p r esen tativ e o f th e en tir e site o r , if site co n t ain s d i ffe r e nt sub ar e a s o f i nt e r e st ( e . g. , ar e a s ha vi ng ve r yd i ffe r e nt sa l i ni t y zon e s or di f f e ren tg e ol og y / s e di me n t part i c l e s i ze), repres en t a t i v e s a m p les of eachs u barea. 5. D e f i n e th res h ol ds or decis i onru le f o r p ar a me ter s o f in ter e st • E cot o x T h res h ol ds (U S E PA , 1996), an d/ or oth e r s e di me n tth res h ol d v alu es f o r con t am in an ts • T o x icityef f ect lev e l: e.g ., sig n i f i can tlylo w e rsu r v iv al th anr e f e r e n c e statio n s o rsu r v iv al 

### � 50% 6. L i mi t s ondeci s i onerrors • P reci s i on : 

### � 40% C
. V. am on g f i eld replicates f o r con t amin an ts an d to x icity • T es t f o r dif f e ren ces betw eens u s p ect an d ref e ren ce s ites at p = 0.05 an d pow er = 80% • F ield b l an k s f o rco n t am in an ts < d e tectio nlim it • L ab du plicates f o r con t amin an ts y i eld 

### � 25% C
. V. T o x i citytes t replicates 

### � 35% C
. V
. • T ox tes t con trols meet EP Am i n i m u m perf orm a n ce requ iremen ts . 7
. Op tim ize th e d e sig n • C h o o s e p r o b ab ilistic sam p lin g d e sig n ; u s e str a tif ied r a n d o m o rm u ltistag e r a n d o m d e sig nif in ter e sted inco m p ar in g q u alityw ithr e sp ect to cer tainh ab itat f eatu r es o rsu b ar eas o f site, r e sp ectiv ely
. • U se a co r e rsam p lerto o b t ainv e r tical ( h isto r i cal) p r o f iiles o f sed i me n t at eachs t ation
. C o llect an d an aly ze s am p les of s trata of in teres t . Us e o f

a lar g erco r er( e.g ., b o x co r er ) w ill meanf ew erco r es n eed ed p er s t ation(s ee T able E- 2 f o r adv a n t ag es an d dis a dv an tag e s of dif f e ren t corers .) • U se GP S f o rstatio np o s itio n i n g ( ± 1 0 m )
. • T ak e 3 replicates f o r eachty pe of an aly s is at 10% of th e s t ation s . • S ee Flow ch art f o r Selectin g C o re Sam p lers B as ed onSite- S pecif i c F act ors (F i g u re 3- 3).
Appendix A: Exam ples of Sedim ent Q uality Sam pling D esigns A-5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **Examp l**  **e 3.** O bj ec t ive: Deter m ine the need f ororloc ations of s i te r em ediation ( e. g ., s uper f und) DQ O Elem ent Issues/Co n cerns/Inf o rm a t io n 1. S t at e probl em / a v a i l abl e res o u r ces • S ite kn o w nor s u s p ected to con t ai ncon t amin ated s edimen t s th at pos e anecolog i cal an d/or h u m anh ealthris k • R es ou rces are av ailable f o r a m oderate- i n t en s i v e s u rv ey 2
. I d en tif yq u estio n s to b e addres s e d • D oes th e s ite n eed to be remediated? W h ere at th e s ite is s edimen t reme di at i o n w arran t ed? 3
. I d en tif yin f o r m atio n/ meas u r emen ts n eeded • Use p r ev io u s lyco llected d a ta, if av ailab l e, to id en tif yco n t am in an ts o f con cern . If n o in f o rm ationis av ailable, a pilot s u rv ey , u s in g a ran dom sam p lin g d e sig n , m a yb e u s ef u l to id en tif yp o t en tial co n t amin an ts o f con cern . • M eas u r emen ts cou l d in clu d e:
– C o n tam i n a n t s o f co n cer ninw h o l e sed i me n t an d/ o rin ter s titial wa t e r
– 10 d w h ol e s e di me n tt o x i ci t yt e s t s
– A cu te o rch r o n i c in ter s titial w a terto x i citytests

– B en th ic m acroin v ertebrate an aly s es
– P ar ticle size, A VS ( i f me tals a co n cer n ) , T OC, % m o istu r e , p H, am m o n i a to h e lp in terp r e t ch em ical o rto x i co lo g i cal d a ta. 4
. Def i n e sp atial/tem p o r al b o und ar i e s • S am pl e ov er on e or m o re i n dex peri ods depen d i n g onas s u me d or meas u r ed rates of s e dime n t or con t amin an t m o v e me n t . • S u r f i cial as w ell as deeper s edimen t s m ayn eed to be s am p led depen d i n g ondepthof con t ami n at i o n . • S am plin g all areas of th e s ite m aybe n eces s aryto locate areas inn eed o f

r e me d i atio nu n l ess m o r e in f o r m atio nis av ailab l e. 5. D e f i n e th res h ol ds or decis i onru le f o r p ar a me ter s o f in ter e st • C on tami n a n t lev e ls ex ceed Ecotox T h res h olds (US EP A , 1996). • T o x icityef f ect lev e l: e.g ., sig n i f i can tlylo w e rsu r v iv al th anr e f e r e n c e s e di me n t an d < 50%
. 6. L i mi t s ondeci s i onerrors • P reci s i on : 

### � 40% C
. V. am on g f i eld replicates f o r con t amin an ts an d to x icity • T es t f o r dif f e ren ces betw eens u s p ect an d ref e ren ce s ites at p = 0.05 an d pow er = 80% • F ield b l an k s f o rco n t am in an ts < d e tectio nlim it • L ab du plicates f o r con t amin an ts y i eld 

### � 25% C
. V. T o x i citytes t replicates 

### � 35% C
. V
. • T ox tes t con trols meet EP Am i n i m u m perf orm a n ce requ iremen ts . 7
. Op timize th e d e sig n • C h o o s e sy stem atic o rg r id sam p lin g d e sig nif n o p r ev io u s in f o r m atio n av ailable onareas of con t amin ation
. • C h oos e targ eted des i g nif in f o rm ationis alreadyav ailable onareas of co n t amin atio nw ith inth e site. • C h o o s e m u lti- stag e d e sig nif m o r e th ano n e ar ea o f co n t am in atio n w ith inth e s ite is kn o w nbu t loca tion s of con t am in ationw ith ineach area are n o t precis elykn o w n . • U se g r ab sam p lerif r e me d i atio nw ill in v o lv e o n lysu r f icial sed i me n t s, or s e di me n t depthi s kn o w n t o be s h al l o w(s ee T abl e E- 1 an d F i g u re 3- 2). • Use co r e rif r e me d i atio nis lik elyto in v o lv e d eep ersed i me n t s. Fo r ar eas inw h ichr e me d i atio nm a yen tail v e r yd eep sed i me n t s ( > 2 m ) , con s ider u s in g a v i bracorer or pis t oncorer (s ee T able E- 2 an d th e Flo w ch ar t f o rSelectin g Co r e Sam p le rs B a s e d onSite- S pecif i c Factors (F i g u re 3- 3).

A-6 U S Environm ental Protection Agency

# APPENDIX B **EXAMPLES OF MEASUREMENT QUALITY OBJECTIVES USED IN SEDIMENT QUALITY**  **MONITORING STUDIES**Technical M anual I n the Data Quality Obj ectiv es (DQO) frame wo rk (discussed in Chapter 2 and exam ples presented in Appendix A of this Manual), a key element of this pr ocess is defining the thresholds or decision rules (Step 5, Fig u re 2- 2) and the limits on errors pertaini ng to those decisions (Step 6, Fig u re 2- 2). Both of these steps are critical to the DQO process, and the success of a study , because they explicitly define whether a particular result qualifies as an effect of interest, and w h en and w h ere something mi g h t need to be done to mitig ate or address a g i v en observ ed effect. A l so, these steps are critical factors in desig n ing a tiered or phased sam p ling pr og ram . Thresholds, for exam ple, can be initially set to identify problem areas w ith hig h accuracy (l ow decision error). T h is w ould be follow ed by a second sam p ling , with a lower threshold, to identif y emerg i ng or m o re subtle problem s in a costeffectiv e m a nner. The inform ation used to help deriv e meaning f ul th reshold or decision rules, and the tolerable errors associated w ith those rules, is collectiv ely refe rred to as Measurement Q u ality O b j ectiv es (MQ O s). MQ O s are qualitativ e or quantitativ e statements thatdescribe the ty pe of data quality needed to support or refute a g i v en decision. T h ese statemen ts explicitly define acceptable precision, bias, and sensitiv ity required of all analy ses in the study and therefore, should be consistent w ith the expected perform ance of a g i v en analy sis or test method (I T F M 1995). T hus, if a pa rticular whole sediment toxicity test is expected to y i eld 80% surv iv al am ong control replicates, the MQ O for control surv iv al should be 

### � 80% for that test. Further, if one intends to com p are sediment toxicity results betw een a reference station and test stations, it is im portant to set the num ber of replicates and the decision rule appropriately so that the study can determine w ith reasonable pow er and confidence w h ether a g i v en sediment sam p le is toxic to the test org anism s. The num ber of replicates performed w ill depend on the expected v ariability of a g i v en test endpoi nt and the sensitiv ity desired in the study
. T h e follow i ng summ ariz es four different exam ples of sediment quality studies or prog ram s, each w ith a different study purpose, and the ty pes of M Q O s they used. These exam ples are for illustrativ e purposes and are not meant to im ply that these are the only acceptable w ay s in w h ich MQ O s can be deriv ed. T h e exam ples prov ided are:
• S horeline ecolog y prog ram follow i ng the Exxon Valdez oil spill in A l ask a
• G reat Lakes Assessment and Remediation of Contaminated Sedime nt (ARCS) Prog ram
• A n exam ple of an EMAP study desig n in the S t . L ouis R i v er, Minnesota/Wisconsin
• Afocused assessment in Burling t on Harbor, V T in Lake Cham plain
• E xcerpts from Washing t on Department of Ecol og y ’ s Sam p ling and A n aly s is Plan G u idance (WDE, 1995). This latter g u idance dem onstrates how a particularprog ram addresses sam p ling and analy s is needs depending on the m onitoring obj ectiv e. T h e g u idance also prov ides an interesting com p arison of ov erall sam p ling procedures and sam p ling desig n considerations for two prog ram s : WDE’s Sediment Manag ement Standards Prog ram and the Pug et S ound Dredg e d Disposal Anal y s is Prog ram , both of which hav e some comm on m onitoring obj ectiv es.

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-3M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **E xample 1:**  **S horeline E**  **c ology**  **P r**  **ogram for P**  **r ince William S**  **ound, A l**  **aska, Follow i**  **ng th**  **e Exxon Val**  **dez Oil S**  **p ill**  Background A com p rehensiv e shoreline ecolog y prog ram w as de sig n ed to assess recov e ry in P r ince William Sound following the Exxon Valdezoil spill on March 24, 1989 (Pag e et al., 1995a; b; B o ehm et al., 1995; G ilfillan et al., 1995; G illfillan et al., 1999). T h e spill resulted in the release of about 258,000 barrels of Alask a North Slope crude oil into the m a rine env i ronment. Nearly 500 miles of shorelines in the sound were oiled to some deg r ee. Project O b jectives T h e shoreline ecolog y prog ram was desig n ed to assess the recov ery of hundreds of miles of oiled shorelines in Prince William Sound by using a limited num ber of sam p ling stations. T h e num ber of sam p ling stations had to be sm all enoug h for a surv ey to be accom p lished in the summer w eather w i ndow , but larg e enoug h to detect im portant spill eff ects. T h e study desig n consisted of tw o field com ponents: fixed sam p ling locations and stra tified random sam p ling locations. T h e 12 fixed locations prov ided inform ation on the chang es in am ount and com position of petroleum residues ov er the period 1989- 1991 to assess the rate of shoreline recov ery and oil loss. Stations chosen represented w o rst- case oiling conditions and referen ce sites. D a ta g a thered from these sites w e re used to assess oil loss, oil w eathering , and bi oav a ilability of oil residues to m u ssel comm unities. T h e stratified random sam p ling (SR S ) of 64 sam p le locations permitted results to be g eneraliz ed to the affected area of the sound. T h e SR S surv ey of the spill area shoreline w as div i ded into four habitats w h ich characteriz ed ov er 99% of the shor eline of interest, and four oiling lev els w h ich produced inform ation on all shoreline spill lev e ls. The m atrix of four habitats by four oiling lev els, w ith each cell containing four replicates, constitu ted a reasonable com p romi se betw een proj ect cost, the need to com p lete sam p ling w ithin the short A l ask an summer, and the need for statistical pow er. The principal obj ectiv e w a s to com p are m eans w ithin strata (habitat/oiling lev e l) and not to obtain ov erall estim ates (see T able B

- 1). Specific natural v ariables, including w av e exposure, percentag e sand, percentag e silt/clay , and total org anic carbon (T OC) were also quantified, and serv edas cov ariates in statistical analy ses of oil effects. Precautions w ere taken to mi nimi z e the possib ilities for petroleum hy drocarbon contamination of field sam p les by :
• positioning the ship’s stern into the w i nd to prev ent stack g ases from blowing onto the sam p ling equipment during deploy ment, recov ery , and subsam pling
• cleaning equipment j u st prior to arriv i ng on station
• ensuring that the sam p ling equipment was nev er deploy ed or recov ered throug h oil slick s or sheens
• closing the top access doors to the sam p ler w h en it w as not being deploy ed or cleaned
• f ield blank s w ere collected from each piece of equipment at reg u lar interv als

B-4 U S Environm ental Protection AgencyTechnical M anual

• potential sources of hy drocarbon contaminants were also collected to enab le their identification later Sam p le documentation included station log s and chai n- of- custody form s. All sediment sam p les were log g ed in on the chain- of- custody form s along with other im portant inform ation (station, date, time, sam p ling equipment and method, subsam pling method, and ty pe of sam p le.) A n y additional inform ation w as also noted. T h is form accom p anie d each sam p le during shipping to the analy tical lab and each sam p le cooler w as sealed w ith a custody seal w h ich w as initialed and dated by the packer. Sev eral analy tical laboratories w ere needed to process and analy z e the larg e num bers of sam p les collected. Alaboratory standard oil w as analy z ed w ith each analy tical batch to m onitor analy tical precision and to prov ide data for interlaboratory com p arisons. D uplicate precision for both subtidal sediment studies and 1991 deep sub tidal studies was ± 30%. Other M QOs are listed in the T able B- 1.
**T a**  **b le B-**  **1.** Meas ur em ent quality obj ec tives f o rs ubtidal s edim ent s t udies in Pr inc e W illiam Sound oil s p ill s t udy ( G ilf illan et al. 1995)

. P a rameter Subti d al Sedi ment Studi es 1991 Deep Subti d al Studi es U n its 

### � g/kg d r y w e i gh t 

### � g/kg d r y w e i gh t Practical Q u antification Limi t (P Q L ) 10 1.0 Estim ated Method Detection L i mit (MD L ) 1.0 0.1 Procedural Blank 5 x MDL 5 x MDL Field Blank 5 x MDL 5 x MDL Matrix Spike Recov ery 40 - 120% a 40 - 120% a Surrog a te Recov e ry 40 - 120% b 40 - 120% b Duplicate Precision ± 30% ± 30% EV C Control Oil Standard Precision ± 20% ± 20% Katalla C ontrol O il S t andard Precision NA ± 20% NI ST SRM 1941 Precision NA ± 25% NI ST SRM 1291 Accuracy NA ± 15%

a T h e av erag e percen t a g e recov e ri es f o r al l 16 com pou n d s m u s tf a l l bet w een40 an d 120%
. O n l yon e com pou n d canbe belowits m i n i m u m percen tag e recov e ry . T h is allow e d a dev i ation f o r a s i n g l e an aly t e of

n o tl e s s th an10% f o r ch ry s e n e an d ben z o(a) py ren e an d n o tl e s s th an20% f o r th e oth e rs . b S u rrog a te recov e ries m u s tf a ll betw een40 an d 120%
. T h e u pper con trol limit m a ybe ex ceeded byon e c o m p o und
. c T h e av erag e percen tag e dif f e ren ce f o r th e targ et com pou n d s s h ou ld n o t ex ceed 20% of th e meanof all prev i o u s v a l u es , an d n o s i n g l e com pou n d/i s omer g r ou pi n g s h ou l d dev i at e bym o re th an30% of i t s mean v a lu e o f all p r ev io u s d e ter min atio n s . d S R M = S t an dard ref e ren ce m a t e ri al
.

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **Exampl e 2:**  **M easurement**  **Q u**  **al i**  **t y**  **O b**  **ject i**  **v es used i**  **n t**  **h e G**  **r eat**  **Lakes A ssessment**  **and Remedi at**  **i on of**  **Cont ami**  **nat ed Sedi**  **ment (**  **A RCS)**  **Program** Background Althoug h toxic discharg es into the Great Lakes and elsewhere hav e been reduced in the last 20 y ears, persistent contaminants in sediments continue to pose a potential risk to hum an health and the env i ronment (GLNPO 1994). Elev at ed concentrations of contaminants in bottom sediments and associated adv erse effects hav e been found thr oug hout the Great Lakes and connecting channels. T h e extent of sediment contamination and its asso ciated adv erse effects hav e been the subj ect of considerable concern and study in the G r eat Lakes comm unity
. To address these concerns, A nnex 14 of the G r eat L akes Water Q u ality A g reement betw een the United States and Canada (as amended by the 1987 Pr otocol) stipulates that the cooperating parties w ill identify the nature and extent of sediment c ontamination in the G r eat Lakes, dev elop methods to assess im pacts, and ev aluate the technolog ical capab ility of prog ram s to remedy such contamination. T h e 1987 am endments to the Clean Water Act, au thoriz ed GLNPO to coordinate and conduct a 5- y ear study and dem onstration proj ects relating to th e appropriate treatment of toxic contaminants in bottom sedime nts. To fulfill the requireme nts of the A c t, G L N P O initiated the A ssessment and Remediation of Contaminated Sedi ments (A R C S ) P r og ram . A R C S is an integ r ated prog ram for the dev elopment and testing of assessment techniques a nd reme dial action alternativ es for contaminated sedime nts. I n form ation from A R C S P r og ram activ ities w ill help address contaminated sedime nt concerns in the dev elopment of Remedial Acti on Plans (R A P s) for all 43 G r eat Lakes A r eas of C oncern (A O C s, as identified by the U n ited States and Canadian g o v ernments), as well as similar concerns in the dev elopment of Lake wide Manag e me nt Plans. Program Objectives Sediments are associated w ith im pairment of be neficial uses at 42 of the 43 G r eat Lakes A O C s. P r ior to addressing the potential need for reme diati on of those sediments, th e following questions are addressed:
• A re the sedime nts sufficiently “contaminated” to warrant consideration for remediation? I n this context, “contaminated” refers to the pr esence of chemicals in the sediments that hav e the potential to cause adv erse effect s in hum ans or ecolog i cal receptors.
• I s there ev idence indicating that existing con centrations of sediment contaminants are adv ersely affecting ecolog i cal receptors? I n ot her w o rds, can it be show n that the presence of contaminants in the sediments is causing ad v e rse effects in org a nism s, either org a nism s naturally occurring in the env i ronment, or those exposed to sediments in controlled, laboratory toxicity tests?
• A re ecolog i cal receptors exposed to the sedi ments bioaccum u lating chemical contaminants to the extent that the resultant body burdens ar e adv e rsely affecting the org a nism s them selv es or other org anism s hig h er in the food chain, including hum ans?
• I f the sediments are j udg ed to be sufficiently c ontaminated to be causing such effects, w h at is the spatial extent (i.e., both horiz ontal and v er tical) of the contamination, and w h at are the im plications of the distribu tion of contaminants on possible remedial alternativ es?

B-6 U S Environm ental Protection AgencyTechnical M anual Early in the ARCS Prog ram , it was recog n iz ed thatthe current state of sediment assessment methods was rapidly ev olv i ng . T h e sediment assessment met hods currently av ailable consider a wide v ariety of endpoints and effects, w h ich differ in their su itability and sensitiv ity for inv e stig ating sedime nt contamination. T h erefore, assessment methods se lected in the ARCS Prog ram , reflect site- and prog ram - specific obj ectiv es of the study being conducted. The A R C S P r og ram dev e loped sev e ral measurement quality obj ectiv es (MQ O s) that it uses in the desig n and conduct of studies at AOCs. T able B- 2 summ ariz e s these MQOs. **T a**  **b le B-**  **2.** Ex am ples of the m eas ur em ent quality obj ec tives f orinor g anic and or g anic c hem is tr y analy s es of s edim ent us ed by the ARCS pr o g r am in the G r eat Lak es ( G LNPO , 1994)

. Pa r a me te r MD L a ( 

### � g/kg) A ccuracy b F requency P recision c F requency d T o tal org anic carbon 0.03% ± 20 percent 1 /batch d 

### � 20 percent 1 /batch Oil and g r ease 10,000 ± 20 percent 1 /batch 

### � 20 percent 1 /batch pH N/A ± 0.1 unit 1 /batch ± 0.1 unit 1 /batch A c id- v olatile sulfides 1,000 N/A N/A 

### � 20 percent 1 /batch Org a nohalog e ns e 0.03 ± 20 percent 1 /batch 

### � 20 percent 1 /batch T o tal sulfur 10,000 ± 20 percent 1 /batch 

### � 20 percent 1 /batch Total solids 1 ,000 N/A N/A 

### � 20 percent 1 /batch Volatile solids 2 ,000 N/A N/A 

### � 20 percent 1 /batch P article siz e f 1,000 windows 1 /batch 

### � 20 percent 1 /batch Solv ent extractable residue 1,000 ± 20 percent 1 /batch 

### � 20 percent 1 /batch Moisture content 1 ,000 N/A N/A 

### � 20 percent 1 /batch PAHs 200 ± 20 percent 1/batch 

### � 20 percent 1 /batch Pesticides 10 ± 20 percent 1 /batch 

### � 20 percent 1 /batch PC B / cong ener 0.5 ± 20 percent 1 /batch 

### � 20 percent 1 /batch PCB/Aroclor® 20 ± 20 percent 1 /batch 

### � 20 percent 1 /batch PCDDs/PCDFs 0.002 ± 20 percent 1/batch 

### � 20 percent 1 /batch Methy l mercury 1 0 ± 20 percent 1 /batch 

### � 20 percent 1 /batch Tributy ltin 10 ± 20 percent 1 /batch 

### � 20 percent 1 /batch Metals g 2,000 ± 20 percent 1 /batch 

### � 20 percent 1 /batch

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-7M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **T a**  **ble B-2**  **(c ontinue**  **d).** Ex am ples of the m eas ur em ent quality obj ec tives f orinor g anic and or g anic c hem is tr y analy s es of s edim ent us ed by the ARCS pr o g r am ( G LNPO , 1994)

. Pa r a me te r MD L a ( 

### � g/kg) A ccuracy b F requency P recision c F requency E x cept: Arsenic 100 ± 20 percent 1 /batch 

### � 20 percent 1 /batch Cadmium 100 ± 20 percent 1 /batch 

### � 20 percent 1 /batch Mercury 100 ± 20 percent 1 /batch 

### � 20 percent 1 /batch Not e : ARCS

- A ssessment and Reme diation of Contaminated Sediments MDL

- method detection limit N/A

- not applicable PAH

- poly nuclear arom atic hy drocarbon PCB

- poly chlorinated bipheny l PCDDs/PCDFs

- poly c hl orinated dibenz o- p - d ioxins/poly c hlorin ated dibenz ofurans

a U n its presented in the subheading are applicab le to all parameters unless otherwise noted. b A ccuracy is determined from a certified reference m aterial, standard reference m aterial, or standard and is m easured from the known concentration. c Precision is calculated as percent relativ e standa rd dev i ation. Precision requirements listed here are for analy tical replicates only ; field duplicates are required to hav e a relativ e percent difference 

### � 30 percent. dA batch is a sam p le g r oup (usually 10- 20 sam p les) that is carried throug h the analy tical scheme sim u ltaneously
. eT h e MDL for chlorine and bromine is 30 ng , while the MDL for iodine is 10 ng
. f A soil sam p le w ith acceptance w i ndow s per siz e fraction w as prov ided for use as an accuracy standard. g Metals include arsenic, cadmi um , chromi um , c opper, iron, lead, m ang anese, mercury , nickel, selenium , silv er, and z i nc. Exceptions are noted where different methodolog ies are used during the me tals quantification.

B-8 U S Environm ental Protection AgencyTechnical M anual **Exampl e 3:**  **Sedi ment**  **T oxi**  **ci t**  **y ,**  **Cont ami**  **nant Concent**  **r at**  **i ons and Bent**  **hi c Communi**  **t y**  **St ruct**  **ure as I ndi**  **cat ors of**  **Sedi ment**  **Q ual**  **i t**  **y i**  **n t he St**  **. Loui**  **s Ri v**  **er: A**  **T est**  **of EM**  **A P**  **Concept s A**  **ppl i**  **ed t o a G**  **r eat**  **Lakes A r**  **ea of Concern**  Background T h e I n ternational J o int Commi ssion (IJ C ) has desig n ated 43 areas of concer n (AOCs) throug hout the Great Lakes as threatened by conv entional po llutants, heav y metals, toxic org anic com pounds, habitat alterations, and introduction of undesirable sp ecies. Results of these disturbances hav e been biolog ical im pacts (e.g ., benthic m acroinv ertebrate and fish comm unity deg r adation), hum an health effects (fish consum ption adv i sories), and beach cl osing s . T h e g eog raphic areas associated w ith the AOCs contain a m aj o rity of th e population residing in the Gr eat Lakes basin, and com p rise approxim a tely 50% of all C a nadian citiz ens. T h e St. Louis Riv e r AOC, which drai ns a watershed of 3,634 square miles in northern Minnesota and Wisconsin, form s a larg e freshwater estuary that represents the second larg est tributary to Lake Superior. T h e 12,000- acre estuary is characteriz ed by a div ersity of habitat ty pes. T h e AOC is unique am ong the G r eat Lakes A O C s in that the rang e of habitat ty pes and contamination status is extreme: for exam ple, the lower estuary contains two federal Superfund sites located across the riv er from larg e, undisturbed tracts of forested land curren tly prov iding excellent habitat quality for a larg e v ariety of species. T h e outer ha rbor contains activ ely dredg ed sh ipping channels and a num ber of current or former m unicipal and industrial efflue nt discharg es, as well as the world’s larg est freshwater sand bar, which is home to numerous e ndang ered or threatened plants and anim als. T h is proj ect has a two- fold purpose: (1) determine if the E MA P intensified g r id prov ides a sam p ling framew o rk that can be used, w ith structural m odi fication, to assess AOCs; and (2) dev elop a set of g eneric env i ronmental indicator s based on biolog ical and chemical measures for long

- t erm assessment of A O C s using the EMA P

- G reat Lakes and Surface Water EMA P indicators. I n order to achiev e these stated purposes, the proj ect has four g o als: 1. To test the application of the G r eat L ake s- EMA P desig n features in the H arbors and Em bay ments resource class. 2. T o identify percentag e areas w ithin the St. Louis R i v er A O C hav i ng acceptable and subnominal quality w ith respect to sediment c ontamination, toxicity and benthic comm unity structure, and to associate statistically certain sediment contaminants w ith observ ed ecolog i cal effects. 3. T o serv e as a baseline status- and- trends m on itoring surv ey of the St. Louis R i v er ecosy stem health. 4. To determine the sam p ling intensity required to surv ey a com p lex G r eat L akes A O C in order to apply this k now ledg e to other A O C s w ithin R eg i on V. T h e proj ect w ill sam p le 120 sites w ithin three ha bitat classes in the St. Louis R i v er A O C for sediment toxicity , chemical contaminant concentra tions, and benthic comm unity structure. T h e three habitat classes are: (1) ship channels and areas in the low er estuary g r eater than 18 ft in depth, (2) areas of the estuary less than 18 ft in depth, a nd (3) T hom son, Forbay and Fond du Lac reserv oirs in the low e r S t . L ouis R i v e r.
Appendix B: Exam ples of M easurem ent Q uality O bjectives B-9M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses T h e distribution of sam p ling points in the three habita t classes is as follow s: 30 sites in ship channels and deep w ater areas, 30 sites in the reserv oirs, and 60 sites in the shallow

- w ater estuarine areas. Sam p ling locations w ere selected based on the G r eat Lakes- EMAP g r id for habitat classes 1 and 2, and a 7 5

- f old enhancement for habitat class 3. T h ese num bers were determined throug h consultation w ith E MA P statisticians at E R L

- C o rv allis. E ach site w ill be sam p led tw ice during the tw o- y ear proj ect period in order to estim ate the short- te rm tem poral v ariability for all three assessment me trics. Split- sam p le, surface sedime nts w ill be used for toxicity , chemistry and benthic assessment. Project O b jectives T h e questions to be answered by and/or obj ectiv es for this proj ect are the follow i ng : 1. What percentag e of the sediments in the St. Louis R i v er A O C hav e unacceptable lev els of sediment contamination, toxicity , and benthic comm unity disturbance? 2. Make statistical associations on an A O C

- w ide basis between contaminant lev els and sediment toxicity or sub- nominal benthic comm unity status. 3. H o w m a ny sam p ling sites and time points are necessary to characteriz e sedime nt quality , using the criteria determined in O b j ectiv e 1, in each of the identified habitat classes (i.e., ship channels and deep holes, shallow shoal orstream areas, and upstream reserv oirs)? 4. Establish a relev ant integ r ity index for bent hic comm unity assessment for the St. Louis R i v er using the E MA P sam p ling desig n . T h e requirements for precision, accuracy , com p letene ss, representativ eness and com p arability of the data in order to attain the proj ect obj ectiv es are described in T able B- 3. Obj ectiv e #1 has the least strict data quality requireme nts for toxicity and chemistry because the larg e num ber of sam p les w as desig n ed to prov ide an excessiv ely

- t horoug h site char acteriz ation. T h is was done in order to increase the likelihood of obtaining a wide v ariety of sediment ty pes with which to carry out Obj ectiv es #2 and #3. I n other words, the num ber of sites a nd sam p ling points is m o st likely ov erly abundant to address O b j ectiv e 1. H o w ev er, because this proj ectis intended as a pilot to actually establish the requisite num ber of sam p les on an areal basis for each habitat ty pe, an ov erestim ate w as required in the sam p le desig n . T hus, fewer sites should be required to answer Obj ectiv e #1 than to satisfy Obj ectiv es 2 and 3; therefore, the required data attr ibutes for O b j ectiv e #1 are slig htly less strict than for the other obj ectiv es. Obj ectiv e #4 does not require data for toxicity and chemistry
.

B-10 U S Environm ental Protection AgencyTechnical M anual **T a**  **b le B-**  **3.** Sum m ar y of m eas ur em ent quality obj ec tives f orthe St. Louis Riverar ea of c onc er n s edim ent quality as s es s m ent by s a m p lin g g oalObjectiveMetric P recision A ccuracy C o mpleteness R epresentativeness
Goal 1 40% RPD a N/A 80% 80% #1- T oxicity 40% RPD a N/A 80% 80% Benthos 30% RPD N/A 80% 80% Chemistry 50% RPD 50- 125% 90% 90% Goal 2 30% RPD N/A 90% 90% #2- T oxicity 30% RPD N/A 90% 90% Benthos 30% RPD N/A 90% 90% Chemistry 40% RPD 70- 125% 90% 90% Goal 3 30% RPD N/A 90% 90% #3- T oxicity 30% RPD N/A 90% 90% Benthos 30% RPD N/A 90% 90% Chemistry 40% RPD 70- 120% 90% 90% Goa l 4 N/A N/A N/A N/A #4- Toxicity N/A N/A N/A N/A Benthos 30% N/A 90% 90% C h emistry N/A N/A N/A N/A

a R e lativ e percent difference

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-11M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **Exampl e 4:**  **Ecol ogi**  **cal Ef**  **f ect**  **s of Sedi**  **ment -**  **A ssoci**  **at ed Cont**  **ami nant**  **s i n I**  **nner Burl**  **i ngt**  **on Harbor, Lake Champl**  **ai n**  Background I nner B u rling t on H arbor of Lake C h am plain has receiv ed numerous t oxicants from point and nonpoint sources in its watershed. Prev ious sediment sam p ling and analy s es (Watz i n et al., 1997) dem onstrated relativ ely hig h concentrations of silv er , lead, and PA H s in the harbor, especially in the southern end, com p ared to sites outside the break water. Much of this area corresponds to an old sewag e outfall and oil dolphins but could also re present mi g r ation of inputs from the old rail y ard and nonpoint sources in and around Bu rling t on. Because the surficial sediment (top 2- 3 cm ) at m o st sites had lower pollutant concentrations than se diments at g r eater depths , inputs of pollutants in recent history (past 30 y ears) m ay be declining
. H o w ev er, these studies also indicated substantial tem poral and spatial heterog e neity w ith respect to sediment contaminant concentrations and toxicity (Watz i n et al., 1997). Biolog ical assessments, using bent hic m acroinv ertebrates, w ere used in conj unction with other field and laboratory analy ses to help determine the eff ects of sediment contamin ation and other stressors on the biota of Burling t on Harbor. Project O b jectives The ov erall obj ectiv e of this proj ect w as to assess the haz ard resulting from toxic contaminants in the sediments of I nner B u rling t on H arbor using a se diment quality triad approach. B ecause certain potentially toxic contaminants are know n to occur in Burling t on Harbor, the obj ectiv e of this proj ect was div i ded into three m aj o r com ponent questions.
• H av e toxic sediments altered benthi c comm unities of B u rling t on H arbor? • C ould such chang es affect other ecolo g i cal com ponents of Lake Cham plain? • D o the toxic contaminants in Burling t on H arbor sediments accum u late up the food chain and cause risk s to hig h er terrestrial and aquatic trophic lev els and hum an health? Sampling Design Sam p ling locations in the present study were identified by reanaly z ing the 1993- 94 data from the harbor with a spatial statistical m odel known as k r ig ing (My ers, 1988) to estim ate contaminant concentrations and uncertainties throug hout the harbor. Kr ig ing is a g e ostatistical estim ation me thod w h ich incorporates a m odel of the spatial v ariability of data directly
. For each chemical, a v ariog ram w as calculated using U S EPA ’ s softw are G eo- EA S (v ersion 1.2.1) and fitted by a non- linear leastsquared procedure. T h e sam p ling sites selected for the present study w e re those w ith the g r eatest uncertainty (using existing data), and the hig h est likelihood of contamination. T en sites were sam p led in the harbor and 10 replicate sam p les from tw o different sites (refe rence sites) w ith relativ ely low contaminant concentrations and/or toxicity w ere sam p led to help assess sediment quality in the harbor, particularly w ith respect to bi olog ical and toxicolog i cal measur es. Fiv e replicate sam p les w e re collected from one site inside the harbor and 5 reference sam p les w ere collected from one site. T h e fiv e replicate sam p les collected at each reference s ite w e re tested separately for all toxicity and biolog ical analy s es, y i elding fiv e indiv i dual measures for t oxicity and m acroinv ertebrate comm unity structure at these tw o sites. Subsam ples from each of the fiv e sam p les collected at both sites w e re com posited into one sam p le from each site for phy sicochemical analy ses. T w o other sites w ere
B-12 U S Environm ental Protection AgencyTechnical M anual replicated once as w ell to obtain a measure of the v ariability surrounding chemical measures obtained in this study
. Atotal of eig h t sites w e re sam p led both in this study and in prev ious work
. Sediment Sampling and Analyses S ites w e re identified using differential g l obal pos itioning and checked frequently during sam p ling to ensure proper sam p ling location. E ach site w as sam p led using fiv e- sev en petite P onar g r abs, depending on the am ount of sedimentcollected in each g r ab sam p le. Contents of the Ponar samples from the site were composited and homogenized in the field using Teflon or high density plastic equipment to obtain a representative sample from each site for chemical, toxicological, and biological analyses. Table B

- 4 summ ariz es the analy ses performed in this study and the measurement quality obj ectiv es used. Sediment chemical analy s es included P A H s, sim u ltaneously extracted metals (S E M), total org anic carbon (% T O C ) , acid v o latile sulfides (A VS), total org anic nitrog en (T O N ) , amm onia, particle siz e, and pH. Fiv e metals (those prev i ously show ing the hig h est lev e ls: silv er, nickel, copper, lead, and z i nc) were measured. Z ebra m u ssels ( Dreissena polymorpha ) w e re collected from sev eral sites and analy z ed for tissue P A H s and percent lipid content on a com posite sam p le of org anism s collected at each site. A portion of the sam p le from three inner harbor sites were siev ed (stainless steel) to isolate the fine fraction less th an 63μ and also analy z ed for PA H s , total org anic carbon, and org anic nitrog en.

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-13M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **T a**  **b le B-**  **4.** Sum m ar y of m eas ur em ent quality obj ec tives f orpr ec is ion, ac c ur ac y , and c om pletenes s of biolo g ic al, tox i c o lo g ic al, s edim ent, or g anis m tis s ue, and f i eld c hem is tr y analy s es c onduc ted in Bur lin g ton Har bor( D iam ond et al., 1999)

. RPD = r elative per c ent dif f er enc e; C.V. = c oef f i c i ent of var i ation. Measurement Parameter Accuracy (% Recovery) Precision Completeness (%) Benthic macroinvertebrates
• Metric values • Metric scores • Bioassessment scores Field Water Quality Measurements
• Conductivity • Temperature • Dissolved Oxygen • p H Laboratory Sediment Analyses
• P A H • Ammonia • Total organic nitrogen • Total organic carbon • AVS/SEM • Particle size Sediment Toxicity Analyses
• Hyalella 10-day acute • Hyalella 28-day chronic • Pimephales 7-day chronic • Lumbriculus 28-day bioaccumulation Organism Tissue Analyses
• P A H • Lead Protein Expression Analyses N/A* N/A N/A

N/A N/A N/A N/A

± 25 ± 30 ± 20 ± 30 ± 30 N/A

N/A N/A N/A N/A

± 30 ± 30 N/A • RPD 

### � 20% • RPD 

### � 5% • RPD 

### � 5%

± 1% of rang e ± 0.15° C ± 0.2 m g /L ± 0.2 units

RPD 

### � 40% RPD 

### � 40% RPD 

### � 40% RPD 

### � 40% RPD 

### � 40% RPD 

### � 20%

C.V
. 

### � 30% C.V
. 

### � 40% C.V
. 

### � 30% C.V
. 

### � 40%

RPD 

### � 40% RPD 

### � 40% RPD 

### � 20% 100 100 100 85

85

85

85

85 * Not applicable except throug h use of routine standards and calibration.

B-14 U S Environm ental Protection AgencyTechnical M anual **Exampl e 5:**  **Washi ngt**  **on Depart ment**  **of Ecol**  **ogy Sampl**  **i ng and A**  **n al**  **y si**  **s Pl an**  **G ui**  **dance** Background T h e Washing t on Department of Ecolog y (WDE) prov ides technical g u idance for dev eloping sam p ling and analy sis plans for sediment inv estig ations to be conducted under the Washing t on Sediment Manag ement Standards (SMS) prog ram (WDE, 1995). T echnical g u idance on v arious aspects of sediment sam p ling and analy sis procedures that need to be considered in the desig n and im plementation of sedime nt inv e stig ations is m ade av ailable throug h the Pug et Sound Estuary Prog ram [PSEP] protocols. 1. Sediment Source C o ntrol P r ogram – Methods are described for controlling the effects of point and nonpoint source discharg es throug h the Nati onal Pollutant Discharg e Elimination Sy stem (N P D E S ) permit prog ram , state w a ter quality permit prog ram s, issuance of admi nistrativ e orders, or other m ans determined appropriate by WDE; and 2. Sedi m e ntCl eanup P r ogram – A d mi nistrativ e procedures and criteria are established to identify , screen, rank , and prioritiz e, and clean up contaminated surface sediment sites. ProjectObjecti ves: Sedim e ntInvesti gati ons Conducte d under t h e Sedim e ntSource Control Program Adverse effects of contaminated sediments on bi ological resources and threats to human health generally w ill only occur w h en there is a pathw ay to ecological or human recep tors. In most cases, such a pathw ay w ill only exist w h en surface sedime nts (defined by the SMS as those w ithin the biologically active zone) are contaminated. Contaminated sediments existing at depths below the biologically active zone are unlikely to result insuch effects unless the overlying sediments are removed by natural (e.g., erosion, sc ouring) or anthropogenic (e.g., dr edging, propeller scour) means, or there are other mechanisms for the release of sed iment contaminants such that exposure may occur. A dditionally, the surface sediment w ill be most lik ely to exhibit impacts from recent discharges of c o n t am i n an t s . H ence, the focus of sediment sa mpling in the sediment source control process is generally on the sediments within the biologically active zone. Table B-5 summarizes sediment management standards for biological effects criteria used by Washington Department of Ecology for Puget Sound marine sediments (WDE, 1995). These standards are, in effect, decision rules in a Data Quality Objectives context (Step 5, Figure 2-2, this Manual); cases where these standards are not met represent locations that are impaired and in need of some type of management action (e.g., remediation, follow-up sampling). WDE also has standards for many chemical contaminants (WDE, 1995) as does the Puget Sound Dredged Disposal Analysis Program (WDE, 1995).

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-15M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **T a**  **b le B-**  **5.** Sedim ent Mana g em ent Standar ds Biolo g ic al Ef f e c t s C r iter ia f o rPu g et Sound Mar i ne Sedim ents

B i o l o g ical T e st Sed i m e nt Qu ality Stan d a r d s a Se d i m e nt I m p a c t Zo ne M axi m um Le ve l s , Cl e anup Sc r e e n i ng Le ve l s , o r M i ni m um Cl e anup Le ve l s b Am p hi p o d

L a rv al

B e nt hi c i n fauna

J uve ni l e pol y c h aete

M i c r o t o x® T h e te st se d i m e nt ha s a si gni fi c antl y hi ghe r (t

- tes t , P 

### � 0
. 0 5 ) m ean mo rt ality th an th e ref e ren ce s e dim e nt , an d th e tes t s e dim e nt m ean mo rtality ex ceed s 2 5 p e rcent o n an ab so lu te bas i s T h ete st se d i m e nt ha s a m e an surv ivo r shipo f n o rmal larv ae th at is sig n i f i cantly less ( t
- test, P 

### � 0
. 0 5 ) th an th e m ean n o rmal surv iv o r ship in th e ref eren ce s edim ent , an d th e com b in ed ab n o rmality an d mo rt ality in

th e test sed i m e nt is mo re th an 15 percent g r eater, on an abs o lu te bas i s , th an th e ref eren ce s edim ent T h ete st se d i m e nt ha s le ss than 5 0p e r c e nt o f th e ref eren ce area s edim ent ' s m ean abu n d an ce o f

any o n e o f th e f o llo wi n gma j o r tax a : C r

u s tacea, Mollu s ca, or P o ly ch aeta, an d th e tes t s edim ent abu n d an ce is s i g n i f i cantly dif f erent(ttest, P 

### � 0.05) f rom t

h e ref e ren ce s e di m e nt abu n d an ce T h e m ean biomas s of poly ch aetes in th e tes t sed i m e nt is less th an 7 0p e r cent o f th e m ean biomas s of th e poly ch aetes in th e ref eren ce s e di m e nt , an d t h e te s t s e di m e nt bi omas s i s si gni fi c antl y d i ffe r e nt ( t -te s t , P 

### � 0.05) f r om t

h e ref e ren ce s e di m e nt bi omas s T he m e an l i ght o ut p ut o f t

hehi ghe st co n centr atio n o f th e test sed i m e nt is less th an 80 percent of t

h e m ean l i g ht ou t p u t of t

h e ref e ren ce s e dim e nt , an d th e tw o m ean s are si gni fi c antl y d i ffe r e nt ( t -te s t , P 

### � 0.05) T h e te st se d i m e nt ha s a si gni fi c antl y hi ghe r (t

- tes t , P 

### � 0
. 0 5 ) m ean mo rt ality th an th e ref e ren ce s e dim e nt , an d th e tes t s e dim e nt m ean mo rt ality is mo r eth an 3 0p e r cent g r eater , o n an abs o lu te bas i s , th an th e ref eren ce s edim ent m

ean mo rt ality T h ete st se d i m e nt ha s a m e an surv ivo r shipo f n o rmal larv ae th at is sig n i f i cantly less ( t
- test, P 

### � 0
. 0 5 ) th an th e m ean n o rmal surv iv o r ship in th e ref eren ce s edim ent , an d th e com b in ed ab n o rmality an d mo rt ality in

th e test sed i m e nt is mo re th an 30 percent g r eater, on an abs o lu te bas i s , th an th at in th e ref eren ce s edim ent T h ete st se d i m e nt ha s le ss than 5 0p e r c e nt o f th e ref eren ce area s edim ent ' s m ean abu n d an ce o f

any tw o o f th e f o llo wi n gma j o r tax a : C r

u s tacea, Mollu s ca, or P o ly ch aeta, an d th e tes t s edim ent abu n d an ce is s i g n i f i cantly dif f erent(ttest, P 

### � 0.05) f rom t

h e ref e ren ce s e di m e nt abu n d an ces T h e m ean biomas s of poly ch aetes in th e tes t sed i m e nt is less th an 5 0p e r cent o f th e m ean biomas s of th e poly ch aetes in th e ref eren ce s e di m e nt , an d t h e te s t s e di m e nt bi omas s i s si gni fi c antl y d i ffe r e nt ( t -te s t , P 

### � 0.05) f r om t

h e ref e ren ce s e di m e nt bi omas s No t ap p licab le

S o urce: WD E (1995).

a T h e s e dim e nt qu ality s t an dards are ex ceeded if on e tes t f

ails th e lis ted criteria [W A C 173- 204- 320(3)]. b T h e s edim ent im pact zon e max i m u m lev el, cleanup s c reen in g lev el, or m i n i m u m cleanup lev el is ex ceeded if o n e test f ails th e listedsed i m e nt im p act zo n e max i m u m lev e l, cleanup scr een in g lev e l, o r m i n i m u m cleanup lev e l criteria [W A C 173- 204- 520(3)] or if tw o tes t s f ail th e s e dim e nt qu ality s t an dards criteria [W A C 173- 204- 320(3)].

B-16 U S Environm ental Protection AgencyTechnical M anual WD E describes four g eneral types of sediment mon itoring(all of w h ich are the responsibilityof the discharg er) that m aybe conducted in support of the sediment source control process: (a) 

### B a sel i n e mon i tori n g —U sed to confirm the screening ev aluation for determining potential of a discharge to cause sediment impacts conducted prior to authorization of a sediment impact zone (S IZ ) to collect information that w ill be us ed in determining w h ether such an authorization is likely to be necessary, and to establish th e baseline conditions with which future conditions can be compared (b) 

### SIZ applic ation m o nit o r ing— Conducted to collect information to support application of the SIZ models (c) 

### SIZ m a int e nanc e m o nit o r i ng—C onducted during the term of a permit that includes an authorized SIZ, with the intent to determin e whether the SIZ should be renewed, reduced, or eliminated; w h ether areas of special importance have been adversely impacted by the discharge; and the conditions for SIZ reauthorization (d) 

### S I Z cl osu re mon i tori n g — Conducted follow i ng closure of anSIZ to demonstrate successful restoration of sediment quality. T h e monitoringobj ectiv es v arywith the type of monitoringbeingconducted, and the desig nof the monitoringprog ram v aries with both disc harg e- and site- specific characteristics. Proj ect Obj ect i ves: Sedi m e nt Invest i gat ions Conduct e d under t h e Sedi m e nt Cl eanup T h e Sedim ent Cleanup Standards set forth a decisi on process for identify i ngcontam inated sedim ent areas and determ iningappropriate cleanup respons es (WDE, 1995). T h e se dim ent cleanup decision process includes procedures for screeningand rank ingcontam inated areas of sufficient concern to warrant activ e cleanup, as well as procedures for sel ectingan appropriate cleanup alternativ e on a sitespecific basis. Because cleanup of contam inated sedim ents m ay require their remo v al, sedime nt sam p lingand analy s es, conducted in support of sediment cleanup studies, need to assess the total spatial extent (includingboth lateral and v e rtical ) of the sediment contam ination. Inthis respect, these sedim ent inv e stig ations differ from those prev iouslydescribe d under the sedim ent source control process, where the focus there is g enerallyonlyon sedime nts w ithin the biolog icallyactiv e z one. Inaddition to initial inv e stig ations and site char acteriz ation, w h ich are described in byWD E (1995), there are three g e neral types of monitoringthat m aybe conducted in support of the sedim ent cleanup process: (a) Source control monitorin g— Conducted prior to and followingsedim ent cleanup to determ ine how ong oingsources at or near a site m ay a ffect the success of activ e cleanup and/or natural recov e ry (b) Com p liance monitorin g— Long

- t erm monitoringconducted followingcleanup actions that include containment of contam in ated sediments, or to assess the prog ress of natural recov ery and/or to ev aluate recontam ination of the area

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-17M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses (c) C l osure monitoring— Conducted followingcom p letion of remo v al actions or com p liance monitoringto demonstrate successful cleanup of sediment contam inati on. Closure monitoring m

u st be performed before a site can be considered for delisting
. T h e prim aryobj ectiv es of sediment sam p lingand analy ses conducted as part of a prelim inary inv estig ation of a contam inated sediment site ar e to: (1) I d entify i ngsedime nt station clusters of potential concern, and (2) Rank ingidentified cleanup sites. Such sam p lingand analy ses m u st be sufficient to enable a determ ination of w h ether there are exceedances of the num erical chem ical criteria or biolog ical effects crite ria (T able B

- 5) at three or mo re stations within a specific area of concern. T hus, th e decision rules used byWDE in these studies (Step 5 of theDQO Pr oc e s s , Fi g ur e2- 2, thi s M anua l ) a r ede f i ne d by e xpl i c i t c ri t e ri a and thenum be r of the sam p les demonstratingexceedence of criteria. T h e sp atial extent of such exceedances is not required to be defined as part of a prelim inaryinv estig ation (WDE, 1995). G i v en the decision rules abov e, there are clear im pli cations for how sam p lingis desig n ed, as there need to be sev eral sam p les collected and analy z ed fro m a specific area of concern and some assurance of representativ e cov e rag eof the area. At sm aller site s of k nown or suspected se diment contam ination, the addition of a relativ elysm all num ber of stations or sam p les in a prelim inaryinv e stig ation is sug g e sted byWDE (1995) to allow assessm ent of the spatial ex tent of contam ination, g r adients toward or away from other sources, or other im portant details. Hen ce, a sing le studycould suffice, therebyprecluding the need for a second, focused inv estig ation. A lternativ ely , if there are no plans to dredg e or otherwise disturb the sediments, sam p ling and analy s es, conducted as part of a preliminary inv e stig ation, could focus only on surface sediments. After the need for cleanup has been identified, a m o re focused sediment sam p ling and analy sis prog ram would then be required by WDE to define the spatial extent of contamination (including its v e rtical extent) and to ev aluate cleanup alternativ es. Com parison of Data Requirem ents: Sedim e nt Managem e nt Standards (Sm s ) and the Dredged Material Managem e nt Program (DMMP) Inaddition to WDE’s Sedim ent Manag em ent Strate g y(S MS ), the other ma j o r fram e w o rk for sedim e nt m anag e me nt activ ities in the D r edg e d Material Manag e me nt Pr og ram (D MMP ). The S MS and D MMP prog ram s are v e rysim ilar in the suites of biolog i cal and chem ical ev aluations that are required, and in the ev aluation criteria that are applied. While th e two prog ram s hav e the same g o al, protection of sediment quality , the tw o prog ram s hav e different app lications and, as a result, som e differences in data requireme nts. Sedim ent sam p lingand analy s is is conducted under the SMS to determ ine whether, and to what extent, surface sedime nts are contam inate d, w h ether point or nonpoi nt source discharg es hav e contributed or m aystill be contributingto such contam inati on, and w h ether contam inat ed sediments should be rem ediated. Sedim ent sam p lingand analy s is is conducted under theDMMP prog ram to determ ine whether the sediment m atrix (v olum e) proposed for dredg i ng , when dredg ed and discharg ed at unconfined, open- w ater disposal sites w ithin Pug e t Sound, could cause or contribute to unacceptable adv erse effects on the aquatic env i ronm ent. B ecau se of these different purposes, sam p ling g ear and com positingtechniques w ill differ. H o w ev er, both theD MMPand S MS data requirements are based upon “exposure potential” and a “sediment unit” con cept. Indredg i ngsituations (DMMP), the exposure potential of concern is with the entire m ass of sedim ents released at the DMMP sites and the sedim ent unit of concern is the m i nim u m dredg e unit that can be effectiv ely m anag ed. InSMS

B-18 U S Environm ental Protection AgencyTechnical M anual situations, the exposure potential and sediment unit of concern is g e nerallythe surface, specificallythe “biolog i callyactiv e z one” (often the top 10 cm). D MMP sam p lingis desig n ed to characteriz e the bulk properties of the sediments to be dredg ed, transported, and discharg ed. Sedim ent core sa m p les (e.g ., v i bracorer) are typicallycollected to characteriz e the sediment m atrix to the depth of pr oposed dredg i ngfor disposal determ inations and to assure that the qualityof new l yexposed surfaces do not result in deg r adation. B ecause dredg i ng remo v e s the m aterial in bulk , the cores are typica llyseg m ented on a 4- foot basis and com posited across that seg ment (rather than further subdiv i ded) to define a “dredg ed m aterial m anag em ent unit.” Sediment sam p lingunder the sediment source contro l process of the SMS is g enerallydesig n ed to characteriz e conditions near the sedim ent surface. Incases w h ere the g o al is to characteriz e the exposure potential, such sam p ling m aytarg et the biolog icallyactiv e z one of the sedim ents. Inother cases, w h ere the g o al is to sam p le onlythe mo st recentlydeposited sedim ent, such sam p ling m aytarg et onlythe uppermost 0–2 cm of sedim ents. Sedim e nt sam p lingdesig n ed to identifycontam inated sediment sites under the sedim ent cleanup process of the SMS is also targ eted on the near- s urface, biolog icallyactiv e z one of the sediments. After a contam inated site is identified, howev er, collection of sedime nt cores w ill also g e nerallybe required to assess the v ertical extent of contam ination and to determ ine the sediment qualityof anynew surface to be exposed after cleanup. T h e process of com positingsam p les from a rang e of depth interv als below the sediment surface m ay dilute hig h er concentrations of contam inants as pointed out in Section 2.4.3 of this Manual and in U S EPA / A C O E(1998). C o m positingov er depth prov ides an assessment of the condition of the ov erall sedim ent m atrix, but does not prov ide an assessment of the sedime nts w ithin the biolog icallyactiv e z one. C o m positingof sam p les from a rang e of depth interv als is therefore appropriate for D MMP purposes, but is ordinarilynot performed for SMS in v estig ations. Inaddition, m any mo re sam p les m ay be needed for SMS purposes to establish patterns or g r adients of contam ination, to identifycontam inant sources, or to delim it the area of contam ination. D evelopm ent of Sedim ent Sa m p ling and A n alysis Plans Althoug h the specific details of indiv i dual sam p ling a nd analy sis plans m aybe v erydifferent, all such plans subm itted for rev i ew byWD Econtain certa in basic elem ents. F i g u re B

- 1 prov ides a recom mended outline for sediment sam p lingand analy sis plans that can also serv e as a check list for those preparingor rev i ew ingsuch plans. Each sedim ent sam p lingand analy s is plan, reg ardless of whether it is beingprepared under the sediment source control process or the sediment cleanup process, should in clude as part of the introduction a brief sum m aryof site backg r ound inform ation. T h e followingbackg r ound inform ation should be prov ided:
• S ite history
• R eg ulatoryframework (e.g ., NPDES; Model T oxics Control Act; SMS; Com p rehensiv e Env i ronm ental R esponse, C o m p ensation, and Liability A ct)
• S um m a ryof results of prev ious inv e stig ations, if any , of the site
• L ocation and characteristics of any current and/or histori cal w astew ater or stor m w ater discharg e(s) at the site

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-19M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

• L ocation and characteristics of any current and/or histori cal w astew ater or stor m w ater discharg e(s) in the local area
• Inform ation on onsite w aste dispos al practices or chem ical spills in the local area, if any
• S ite location, includinga location m ap s howingthe surroundingarea and a site m ap. T h e second section of a sam p lingand analy s is plan should describe the obj ectiv es of the sedim ent inv e stig ation in the context of the appropriate re g u latoryfram ework (e.g ., sedim ent source control process, sedim ent cleanup proce ss). WDE (1995) prov ides g u idan ce on appropriate field sam p ling methods; sam p le handlingprocedures; laboratory analy tical me thods; qualityassurance and quality control requirements; data analy sis, record k eeping , and reportingrequirements; health and safetyplan; schedule; and proj ect team and responsibilities.

B-20 U S Environm ental Protection AgencyTechnical M anual


## Sedim e nt Sam p ling and Analys is P l an Outline and C h ecklist (From WDE, 1995) 1. Int r oducti on and B ackground Inf orm ati on 

### � Site history 

### � Reg ulatoryframe work (e.g ., NPDES, MT CA, SMS, CERCLA) 

### � Sum m aryof prev ious inv estig ations, if any , of the site 

### � Location and characteristics of anycurrent and/ or historical wastew ater or storm water discharg e(s at the site 

### � Location and characteristics of anycurrent and/ or historical wastew ater or storm water discharg e(s) in the local area 

### � In form ation on on- site w aste disposal practices or chem ical spills in the local area, if any 

### � Site location m ap showingthe surroundingarea 

### � Site m ap showingsite features 2. Objectives and Design of the Sediment Investigation 

### � O b j ectiv es of the sedim e nt inv e stig ation 

### � Ov erall desig nof the sedime nt inv e stig ati on, includingrelated inv estig ations, if any 

### � C h em ical analy t es (including description of their relev ance to the obj ectiv es and the reg u latoryframe w o rk) 

### � Biolog ical tests (inc ludingdescription of their relev ance to the obj ectiv es and the reg u latoryframe w o rk) 

### � S am p ling S t ation L o cations 

### � R ationale for station locations 

### � S ite m a p(s) show ingsam p lingstations and other pertinent features (e.g ., bathy metryand current reg i me ; outfa ll(s)/diffuser(s); authoriz ed m i xing z one(s), if any ; sites of w a ste disposal, spills, or other activ ities that m ayhav e affected the sediments, such as sa ndblasting , boat repair, etc.; historical dredg i ngactiv ities) 

### � Proposed reference stations 

### � T able show ingthe w ater depth at each proposed station 

### � Proposed depth(s) below the sedim e nt surface w h ere sedime nts w ill be collected
**Figur e**  **B-1 .**  Sedim ent Sam p lin g and Analys is Plan O u tline and Chec k lis t Developed by W a s h in g ton Departm ent of Ec olo g y ( W DE, 1995)

.

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-21M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

3. F i eld Sampling Methods 

### � Station positioning m ethods 

### � Sam p lingequipment 

### � Decontam ination procedures 

### � Sam p le com positingstrateg yand methods 

### � Sam p le containers and labels 

### � Field docum entation procedures 

### � Procedures for disposal of contam inated sediments 4. Sample Handling P r ocedures 

### � Sam p le storag e requirements (e.g ., conditi ons, m axim u m holdingtimes) for each type of sam p le 

### � Chain- of- custodyprocedures 

### � D e liv eryof sam p les to analy tical laboratories 5. Laboratory Analytical Methods 

### � C h em ical analy ses and targ et detection lim its 

### � B i olog ical analy ses 

### � C o rrectiv e actions 6. Quality Assurance a nd Q u al i ty Cont rol Requi rem ent s 

### � Q A / Q C for chem ical analy ses 

### � QA/QC for biolog ical analy s is 

### � D ata qualityassurance rev i ew procedures 7. Data Analysis, Record Keeping, and R e porting R e quirements 

### � Analy sis of sediment chem istrydata 

### � Analy sis of biolog ical test data 

### � D ata interpretation 

### � R ecord k eepingprocedures 

### � Reportingprocedures

**Figur e**  **B-1 (c**  **ontinue d).**  Sedim ent Sam p lin g and Analys is Plan O u tline and Chec k lis t Developed by Wa s h i n g ton Departm ent of Ec olo g y ( W DE, 1995) ( c ont.)

.

B-22 U S Environm ental Protection AgencyTechnical M anual

8. H e al thand Saf e ty P l an ( requi red f or cl eanup i n vesti gati ons) 

### � Description of task s 

### � Keypersonnel and responsibilities 

### � Chem ical and phy sical haz ards 

### � Safetyand health risk analy sis for each task 

### � Air monitoringplan 

### � Personal protectiv e equipment 

### � Work z ones 

### � Decontam ination procedures 

### � Disposal procedures for cont am inated media and equipment 

### � Safe work procedures 

### � Standard operatingprocedures 

### � Conting encyplan 

### � Personnel trainingrequirements 

### � Medical surv eillance prog ram 

### � R ecord k eepingprocedures 9. Schedule 

### � T able or fig u re showing k

eyproj ect m ilestones 10. P roject T eam and R esponsibilities 

### � Description of sedim ent sam p lingprog ram personnel 

### � T a ble identify i ngthe proj ect team me m b ers and their responsibilities 11. R e f erences



### � L i st of references

F i gure B - 1 (continued). S ediment S am p lingand A n aly sis P l an O u tline and C h eck list D ev eloped by Washing t on Department of Ecolog y(WDE, 1995).

Appendix B: Exam ples of M easurem ent Q uality O bjectives B-23

# APPENDIX C **STATISTICAL CONSIDERATIONS IN**

**DETERMINING THE APPROPRIATE NUMBER OF REPLICATE SAMPLES**  **NEEDED AT EACH SAMPLING STATION**Technical M anual For certain prog ram s or ty pes of studies, it is de sirable (or necessary ) to determine if a particular location is sig n ificantly affected as com p ared to known non- im pacted or reference locations (e.g ., presence of toxicity and/or hig h contaminant concentrations in sedi me nts or interstitial w a ters). This ty pe of m onitoring obj ectiv e is used frequently in certain reg u latory prog ram s , such as the D r edg e d Materials Manag e me nt Prog ram and Superfund (C ERCLA), howev er, m a ny non- reg u latory prog ram s also hav e a similar obj ectiv e (see for exam ple the Burling t on Harbor ex am ple in Appendix B). I f

one is interested in determining statistical di fferences in certain measures (e.g ., toxicity to H y alella azteca ) am ong or betw een stations, then analy s is of replicate field sam p les m a y be necessary
. T h is entails collecting m u ltiple sam p les from the same sta tion (or other spatial unit of interest), processing each sam p le independently , and analy z ing separately each sam p le. For exam ple, if the purpose of a study is to determine w h ether the sedime nt in a specific location is toxic to the estuarine am phipod Rhepoxynius abronius as com p ared to sedime nt from a refe rence location, then it is desirable to collect m u ltiple sam p les from each location and perform a Rhepoxynius whole sedime nt toxicity test (including standard replication w ithin a test) for each sam p le collected. C l early , this ty pe of replication could entail substantial laboratory e ffort, as com p ared to com positing sam p les from a sing le location and performing a sing le analy s is or test (see Section 2.4.3 for a discussion of com positing v e rsus replication of sam p les). H o w e v e r, com positing does not prov ide any inform ation on the true v ariability of a g i v e n location and is rather, a form of pseudoreplication. For some prog ram s or studies, true fi eld replication is necessary
. T h e appropriate num ber of replicates needed for a g i v e n study depends on the statistical power and lev e l of confidence (i.e., measurement quality obj ectiv es; see A ppendix B for exam ples) one needs to support or refute a g i v e n decision (see D a ta Q u ality O b j ectiv es Process, Section 1.1 and A ppendix A )
. Pow e r is represented as 1- 

### � and is a measure of the Ty pe I Ierror rate: the probability of accepting the hy pothesis that the results from tw o diffe rent sam p les or stations are similar, w h en in fact they are not. C onfidence is represented as 1- 

### � and is a measure of the T y pe Ierror rate: the probability of rej ecting the hy pothesis that the re sults from tw o different sam p les or stations are different w h en in fact they are really the same . For exam ples, if the question is w h ether a g i v e n location should be dredg e d for reme diation purposes, the study w ill need to hav e a certain statistical pow er, to determine if the sedime nt sam p le from th e targ et location is m o re toxic or contaminated than the reference location sedime nt, w ith a certain deg r ee of confidence that one is m aki ng the correct decision. B o th pow er and confidence ar e dependent on the expected v ariability in the endpoint or parame ters of interest, both within a g i v e n location and within a g i v e n test or analy s is. T h e appropriate replication, then, is required so that one has sufficient statistical pow er and confidence to reliably m ake correct decisi ons about the status of a g i v e n location. T o determine the num ber of replicates require d, the following questions should be answered (Alldredg e, 1987): 1. What is being com p ared (i.e., t oxicity endpoint, parame ter v a lue)? 2. I s the sig n ificance criterion directional (is one only interested in w h ether a station is m o re toxic than another, not less toxic as w e ll; i.e., one- t ailed test)? 3. What is the lev e l of sig n ificance betw een the expected and actual v a lue of the parame ter being measured? 4. H o w larg e a difference is acceptable betw een the expected and actual v a lue of the criterion being measured, and w ith w h at lev e l of probability ? 5. What v ariability is expected in the data? Appendix C : Statistical C onsiderations in D e

term in

ing the Appropriate N u m ber of R eplicate Sam p

les C-3M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses T h ere are a num ber of approaches that can be used to determine the num ber of replicates required to achiev e a mi nim u m detectable difference at a sp ecific confidence lev e l and pow er (see Env i ronment Canada, 1995). While m a ny prog ram s specify a fixe d num ber of replicates per station (often 3- 5 replicates), in other cases, this could represent t oo m a ny or too few replicates for study data quality obj ectiv es. Sev e ral factors need to be defined to establish the appropriate num ber of replicates (see text box). U.S. EPA (2000c) presen ts a concise discussion of the relationships of these statistical considerations. T r aditionally , acceptable coefficien ts of v ariation v ary from 10 to 35%, the pow er from 80 to 95%, the confidence lev e l from 80 to 99%, and the mi nim u m detectable relativ e difference from 5 to 40% (Barth and Stark s , 1985). Sev e ral book s on sam p ling desig n (e.g ., K e ith 1993; USEPA 2000b) discuss me thods to determine the appropriate num ber of replicates needed for a g i v e n set of obj ectiv es. T able C- 1 summ ariz e s statistical approaches for determining the appropria te num ber of replicate sam p les needed per station g i v e n different study obj ectiv es.

**T a**  **b l**  **e C- 1.**  Statis tic a l F o r m ulae f o rD e ter m inin g Num berof Sam p les to be Collec t ed f o r Envir onm ental Monitor i n g and As s e s s m ent Study Objective F ormula R e f erence To determine the sam p le siz e required to detect an effect in an im pacted area v e rsus a control area ov er time: a) resam p ling same sites before and after im pact and testing if the mean chang e in the control area is the same as that in the im pacted area b) sam p ling different sites before and after im pact and testing if there is no interaction betw een area effect and time effect n = 2(t � + t � ) 2 (S / 

### � ) 2

n = 4(t � + t � ) 2 (S / 

### � ) 2

w h ere: n = num ber of sam p les for each of the control and im pact areas S = standard dev i ation 

### � = m ag nitude of chang e required to be a real effect w ith specified pow er (1- 

### � ) t � = tstatistic g i v e n a Ty pe I 1 error probability t � = tstatistic g i v e n a Ty pe I I 2 error probability Green, 1989

Green, 1989

C-4 U S Environm ental Protection AgencyTechnical M anual
**T a**  **ble C-1**  **(c ontinue**  **d).** Statis tic a l F o r m ulae f o rD e ter m inin g Num berof Sam p les to be Collec t ed f o rEnvir onm ental Monitor i n g and As s e s s m ent Study Objective F ormula R e f erence To determine if the mean v a lue for an im pacted area: a) differs sig n ificantly from a standard v a lue (e.g ., sedime nt g u ideline) b) differs sig n ificantly from the mean of a control site n 

### � (Z � + Z � ) 2 + 0. 5 Z � 2 d 2

n 

### � (Z � + Z � ) 2 + 0. 25 Z � 2 d 2

w h ere: n = num ber of sam p les Z � = Zstatistic for Ty pe I error probability (e.g ., 

### � =0.05) Z � = Zstatistic for Ty pe I I error probability (e.g ., 

### � =0.90) d = m a g n itude of the difference to be detected (i.e., effect lev e l) Alldredg e, 1987

T o determine the num ber of sam p les required to estim ate a mean v a lue (representativ e of the area) w ith a g i v e n statistical certainty y 

### � = t c S x (n- 1 ) 1⁄2

w h ere: y = accepted error as a proportion of the mean v a lue(e.g ., y = 0.10) 

### � = mean v a lue of x i (i = 1...n) S x = s tandard dev i ation t c = c onfidence coefficient (e.g ., 90% or t 0.95 n = num ber of sam p les Håk a nson, 1984

T o determine the num ber of sam p les required to estim ate a mean n = (Z � /2 ) 2 

### � 2 d 2

w h ere: n = num ber of sam p les Z = Zstatistic (standard norm a l curv e) 

### � 2 = v ar i a n c e 

### � /2 = p robability of a 95% confidence lev e l d = distance betw een the center of the low e r confidence and upper confidence bound Milton et al ., 1986

Appendix C : Statistical C onsiderations in D e

term in

ing the Appropriate N u m ber of R eplicate Sam p

les C-5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses
**T a**  **ble C-1**  **(c ontinue**  **d).** Statis tic a l F o r m ulae f o rD e ter m inin g Num berof Sam p les to be Collec t ed f o rEnvir onm ental Monitor i n g and As s e s s m ent Study Objective F ormula R e f erence T o determine the num ber of sam p les required for a particular power for a norm a l distribution (i.e., 

### � > s 2 ) n = 10 4 (t 2 s 2 ) K (R 2 

### � 2 )
w h ere: n = num ber of sam p les t = t statistic for a desired confidence lev e l 

### � = mean v a lue from preliminary sam p ling or historical data s = standard dev i ation of mean R 2 = p ercentag e coefficient of v ariation K = index of clum ping Kr atochv il and T a y l or, 1981

1 Ty p e I( 

### � ) error is the probability of rej ecting the hy pothesis being tested w h en it is true. 2 T y p e II ( 

### � ) error is the probability of not rej ecting th e hy pothesis being tested w h en it is false.
O

p tim izing Sa m p ling H a v i ng estim ated the v ariability in a g i v e n parame ter or endpoint, and the num ber of replicate sam p les per station that mi g h t be necessary to address data quality obj ectiv es, one can ev aluate the cost/benefit of collecting and analy z ing m o re or le ss sam p les in term s of the ov erall confidence in a g i v e n decision and the inform ation g a ined. T h is is referred to as optimiz ing the study desig n (S tep 7, F i g u re 2- 1). F e rraro et al . (1994, 1989) present a me thod for quantitativ ely ev aluating the optim um m acrobenthic sam p ling protocol, incl uding the num ber of replicates ( n ), which has relev a nce to other sedime nt quality studies as w e ll. T h eir approach helps answ er fundame ntal questions concerning the desig n of sedime nt quality studies such as:
• H ow larg e should the sam p ling unit be?
• H ow m a ny replicate sam p les should be take n? T h e procedure calculates the “pow er- c ost efficien cy ” (PCE), which incorporates both the num ber of sam p les ( n ), the cost (field collection effort and lab effort com b ined) and the expected statistical pow er for each alternativ e sam p ling scheme . T h e v arious sam p ling scheme s consist of different com b inations of sam p ling g ear, g ear area, and num be r of replicates. T h e me thod allows determining the optim um am ong a set of sam p ling scheme s for detecting differences betw een reference and test sites w h en the statistical m odel is a t- distribu tion for com p aring two means. T h e optim um scheme can be defined as the least costly one capable of reliably (e.g ., 

### � = 0.5, 1- 

### � = 0.95) detecting a desired difference in the means of particular m easure betw een tw o sites. T h e approach can be applied to each parame ter of interest and the resu lts ag g r eg ated to determine the optim um protocol.

C-6 U S Environm ental Protection AgencyTechnical M anual T h ere are four prim ary steps in assessing the P C E of a suite of alternativ e sam p ling scheme s: 1. For each scheme , collect replicate sam p les at pa ired reference and test sites. T h e observ e d difference in v a lues betw een the sites is opera tionally assume d to be the m a g n itude of the difference desired to be detected. Alternativ el y , a percentag e of the me dian (e.g ., 20%) for a g i v e n measure calculated across reference stati ons could be set as the m a g n itude of the difference to be detected. I n either case, this di fference, div i ded by the standard dev i ation, is the “effect siz e” (ES) of interest. 2. A ssess the “cost” (c i ), in time or m oney , of each sam p ling scheme i at each station. T h e cost can include labor hours for sam p ling , analy s is, and recording results. 3. Conduct statistical power analy s is to determine the mi nim u m num ber of replicate sam p les (n i ) needed to detect the E S w ith an acceptable probability of T y pe I( 

### � ) and T y pe I I( 

### � ) error (e.g ., 

### � = 

### � = 0.05). 4. C a lculate the pow er- c ost efficiency (PC E ) for each sam p ling scheme by : PCE i= (n x c) mi n / (n ix c i )
w h ere (n x c) mi n= mi nim u m v a lue of (n x c) am ong the i sam p ling scheme s. T h e reciprocal of PC E i is the factor by w h ich the optim al sam p ling sche me is m o re efficient than alternativ e scheme i
. When P C E is determined for m u ltiple me trics, the ov erall optim al sam p ling protocol m a y be defined as that w h ich rank s hig h est in P C E for m o st me trics in the test set.

Appendix C : Statistical C onsiderations in D e

term in

ing the Appropriate N u m ber of R eplicate Sam p

les C-7

# APPENDIX D **ADVANTAGES AND DISADVANTAGES OF DIFFERENT STATION POSITIONING**  **TECHNIQUES**Technical M anual Docume ntation of sam p ling station location or positi on is an im portant aspect of field operations to ensure that: (1) sam p ling occurs w h ere intended and (2) some one else (or another sam p ling team ) could re- s am ple the same location at a later date. This is particularly critical for trend m onitoring s u c h a s t h a tpe r f o r me dby NOAA’ s St a t us a nd T r e nds Pr og r a m . With current technolog y , a g l obal positioning sy stem (G PS) dev i ce is g e nerally the positioning me thod of choice because it is usually v e ry accurate, reliable, easy to use, and affordable. H o w e v e r, occasionally , other positioning me thods m a y be de sired or necessary
. T h e follow i ng tables, orig inally dev e loped under the Pug e t Sound Estuary Prog ram , summ ariz e m o st of the positioning me thods that hav e been used in m onitoring studi es, including their adv a ntag es and disadv antag e s.

Appendix D : Advantages and D i sadvantages of D i fferent Station Positioning Techniques D-3M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **T a**  **b l**  **e D- 1.**  Pos i tionin g m e thods appr opr iate f o rs m all w a terbodies ( s m a ll em bay m ent, s m all lak e s , r i ver s ) ( m odif i ed f r om PSEP 1997a)

. M e thod A ccuracy R a nge A dvantages D i s advantages G P S o rN a v s t ar ± 100 m (0. 1 to 1 m f

o r di f

f e re nt i a l GP S) n o limit ont h e rang e � C o n tin u o u s p o sitio n re p o rts av ailab l e w o rld w id e � Sy ste m s av ailableco mp rising a rang eo f accuracy and co st � Si t e -spe ci f i c pro b l e m s due to militaryscram b lin g

T h e o d o lite 1 0 to 3 0 s � ± 1 m 200 m t o 5 km � T r ad itio n a l m e th o d , m e asu r in g ho ri zo nt al ang l e s be t w e e n kno w n targ e t s � H i g h accuracy w h e n applie d succe ssf ully � Ine xpe nsi v e � Re qui re s tr i a ng ul at i o n be t w e e n t w o m a nne d sho r e site s o rtarg e t s � Re qui re s si mu l t a ne o u s mea s u r emen t s � R e q u i r e s goodvi s i b ility w h ich limits are a l co v e rag e � Re qui re s st at i o nary samp lin g p l atf o rm E l e c tro n ic D i stance M e a s u r emen t in stru m e n t (E D M I) 1. 5 t o 3. 0 cm 3 km w ith o u t mu ltip le pri s m s � H i g h accuracy � C o mp act, po rtable , rug g e d � R e lativ e l yin e x p e n s iv e � U s e able f o r o t he r surv e y ing pro j e c t s � Intro duce s e rro r and limitatio n s d u eto re f l e c to r m o v e m e n tan d d i re ctio n a lity as w e l l as g r o und w a v e re f

l e c tio n � R e q u i r e s good l i n e- of- s i g h t v i sib ility u n l e ss mi cro w av e u n it is av ailab l e � R e quire s tw o sho r esite s To t a l st at i o ns 5 t o 7 cm < 5 km � N o t lo g i sticallyco mp le x , re qui ri ng si ng l eo n sho r esi t e � C o mp atib le w ith o t h e r u s e s � In tro d u c e s limitatio n s d u eto re f

l e c to r m o v e m e nt and d i re ctio n a lity , p r ism co sts, a n d l i n e- of- s i gh t , op t i c a l or in f

r are dran g elimitatio n s Se xt ant ± 10 s ± 3 t o 5 m but var i ab l e 200 m t o 5 km � H i g h accuracy w h e n use d ne arsho r eby e xpe ri e n ce d op er a t or � P o rt abl e , i n v o l v i ng handhe l d de v i ce � Rapi d, e a sy t o i mpl e m e n t � E a sily o b tain ab le � N o sho r epartyne ce ssary � Ine xpe nsi v e � Re qui re s si mu l t a ne o u s m e a s u r em en tof t w o a n gl es � R e q u i r e s good t ar g et v i sib ility � Re qui re s l o cat i o n and m a in te n a n c e o f targ e t s f o r re lo catio n o f site � R e q u i re s calm co n d itio n s f o r be st re sults � O r ie n t atio n o f targ e taf f e cts accuracy � H a s limitatio n s o n acce ptableang l e s

D-4 U S Environm ental Protection AgencyTechnical M anual **T a**  **ble D-1**  **(c ontinue**  **d).** Pos i tionin g m e thods appr opr iate f o rs m all w a terbodies ( s m a ll em bay m ent, s m all lak e s , r i ver s ) ( m odif i ed f r om PSEP 1997a)

. M e thod A ccuracy R a nge A dvantages D i s advantages P e l o rus v ari abl e < 5 km � H i g h accuracy w h e n use d ne arsho r e � Rapi d, e a sy t o i mpl e m e n t � E a sily o b tain ab le � N o sho r epartyne ce ssary � Ine xpe nsi v e � Re qui re s si mu l t a ne o u s m e a s u r em en tof t w o a n gl es � R e q u i r e s good t ar g et v i sib ility � Re qui re s l o cat i o n and m a in te n a n c e o f targ e t s f o r re lo catio n o f site � R e q u i re s calm co n d itio n s f o r be st re sults � H a s limitatio n s o n acce ptableang l e s RADAR v ar i ab l e 3 0 t o 50 km � St andard e qui pm e n to n shi p s � E a s i l y op er a t ed � Y i e l ds rang eand re l a t i v e be ari n g to targ e t s � Re stri ct s appl i cat i o ns byno t be i n g po rt abl e � R e quire s a targ e tthat re f

l e c ts mi cro w av esig n als A u to tap e ± 0
. 5 m limite d � H i g h accuracyand pre c isio n � Po r t ab l e � Hi g hc o s t

Appendix D : Advantages and D i sadvantages of D i fferent Station Positioning Techniques D-5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **T a**  **b l**  **e D- 2.**  Pos i tionin g m e thods appr opr iate f o rlar g e w a terbodies ( o c ean, es tuar ies , lar g e lak e s ) ( m odif i ed f r om PSEP 1997a)

. C a tegory A ccuracy R a nge A dvantages D i s advantages G P S o rN a v s t ar ± 100 m (0 .1 to 1 m f

o r di f

f e re nt i a l GP S) n o limit o n t h erang e � C o n tin u o u s p o sitio n re p o rts av ailab l e w o rld w id e � Sy ste m s av ailableco mp rising a rang eo f accuracyand co st � Si t e -spe ci f i c pro b l e m s duet o militaryscram b lin g

Micro w av e n a vi ga t i o n sy ste m s (e .g ., Mi ni rang e r , Tri s po nde r, R acal Micro f i, De l No r t e ) ± 1 t o 3 m 25 t o 80 km ( d ep en d s on he i g hto f tran sce i v e r u n its) � N o v i sib ilityre strictio n s � Mu ltip le u s e r s � H i g h accuracy � R a d i o l i n e of s i gh t � P o rtable , e a sy sy ste m to op er a t e � Mo de rat e l y e xpe nsi v esy st e m � R e q u i re s mu ltip le o n sh o r esite s � C o st imp acts d u eto lo g i stics an dse cu rity o f th e n e ce ssary sh o r e u n its � P o te n tial so u r ce o f e rro r d u eto sig n al re f l e c tiv e n u lls � Li mi t e d rang eduet o l o w po w e re d sho r euni t s Sho r an ± 10 m � 80 km (sho rt rang e ) � H i g h accuracy � Li mi t e d rang e � R e q u i re s tw o sh o r etran smitte rs LORAN- C � ± 15m up t o 300 km (m e d ium rang e ) � N o v i sib ility o rran g e re strictio ns � R e q u i re s n o ad d itio n a l pe rso nne l � Exi s t i n g e qui pm e n t � R e lativ e l yin e x p e n s iv e � Incurs inte rf e r e n cein so m e are a s � U n i v er s a l c over a ge n o t av ailable � U s e d o n ly f o r re p o sitio n i n g af

t e r e mpl o y i ng a m o re g e o d e tically p r e c isesy ste m to id e n tif y lo catio n D e cca H I FIX/ 6 ± 1 m up to 300 km (m e d ium rang e ) � H i g h accuracyand pre c isio n � R e q u i re s mu ltip lesh o r esite s � Expe nsi v esy st e m
V ari abl erang e ± 0. 5 ° 16 t o 72 km � N o v i sib ilityre strictio n s � R e q u i re s n o ad d itio n a l pe rso nne l � Exi s t i n g e qui pm e n t � Ine xpe nsi v e � U s e s lin e - o f -sig h tm e th o d � R e lie s o n m ap accuracie s o f targ e t s � D e cre a se d accuracy w ith rang e scale D e cca Minif i x ± 2 m � 70 km � H i g h accuracyand pre c isio n � Li g h tw e i g hte qui pm e n t � Expe nsi v esy st e m Rang e - azi mu t h 0. 02 ° and 0. 5 m < 5 km (o ptical) 30 km (e le ct) � H i g h accuracy � S i n g lestatio n � C i r c u l ar c over a ge � U s e r-spe cif i c � U s e s lin e - o f -sig h tm e th o d � P o te n tial so u r ce o f e rro r d u eto sig n al re f l e c tiv e n u lls � Expe nsi v esy st e m S a te llite n a vi ga t i o n ( S ATNAV) 1 - 1 0 m n o limit o n t h erang e � H i g h accuracy � S i n g lesite w ith mi n i m a l lo g i stics � U s epo ssi bl ei n re stri ct e dand co ng e s t e d are a s � N o re quire m e nt f o r sho r esite s � C ap ab ility f o r in te g r atin g sate llite f i x e s w ith o t h e r d a ta so u r ce s to imp r o v e p r e c isio n � Co nt i nuo us co v e rag e unav a i l abl e � Intr o duct i o n o f e rro r duet o lo cal and atm o sphe ric e f f e cts � Di s t o r t e dwh e ns i g n a l p a t h cro sse s po lar icecaps � R e q u i re s h i g h in itial de v e l o pm e n te xpe ndi t u re s

D-6 U S Environm ental Protection Agency

# APPENDIX E **ADVANTAGES, DISADVANTAGES AND ILLUSTRATIONS OF GRAB AND CORE**  **SAMPLING DEVICES USED IN SEDIMENT MONITORING STUDIES** Technical M anual **T a**  **b l**  **e E- 1.**  Advanta g es and Dis advanta g es of Com m only Us ed G r ab Sam p ler s (modif i ed f r om Klemm et al. , 1990; Environment Canada, 1994; PSEP, 1997a; W D E, 1995)
. **Devi ce**  **Use Sa**  **mple D**  **e pt**  **h (cm**  **) Sa**  **mple Volume** 

**(L 3**  **) A** **d vantages**  **D i**  **sadvantages** Orange P eel M a ri ne w a t e rs , deep la k e s 0 t o 18 10 t o 20 • C om es i n a range of si z e s • N eed l a rge boat , pow ered w i nc h and c a l be l i n e • B l o c k i ng of j a w s m a y c aus e sa m p l e l o sss S m i t h-M c I n t y re Deep l a k e s , ri vers and es t uari e s 0 t o 4 (i n deep s and) 10 t o 20 • R eas onabl e quant i t at i v e sa m p l e s • T he t r i gger pl at es provi de added l e verage e s s e n t ia l to its penet rat i on of s ubs t r at e • H eavy, need boat and pow er wi n c h • S pri ng l oaded j a w s , hazardous • I nadequat e f o r deep burrow i ng organi s m s B i rge-E k m an, sm a l l Lak es and m a ri ne areas ; so ft s edi m ent s , s i l t and s and 0 t o 10 < 3. 4 • H andl es eas i l y w i t hout w i nc h or c r ane • C an be adapt ed f o r s h a l l o w wa t e r u s e • G ood f o r s o f t s edi m ent s , s and and s i l t • A l l o w s s ubs am pl i n g • R es t r i c t ed t o l o w c u rrent due t o l i ght w e i ght and m e s s enger a c tiv a tio n • M ay ex c eed t a rget penet rat i on dept h • S ubs am pl i ng m a y be res t ri c t ed by s i ze of t op f l aps B i rge-E k m an, la r g e Lak es and m a ri ne areas ; so ft s edi m ent s , s i l t and s and 0 t o 30 < 13. 3 • Can be adapt ed f o r s h a l l o w wa t e r u s e • G ood f o r s o f t s edi m ent s , s and and s i l t • A l l o w s s ubs am pl i n g • R es t r i c t ed t o l o w c u rrent c ondi t i ons • P enet rat i on dept h c an ex c eed des i r ed l e vel due t o w e i ght of sa m p l e r • H eavy; requi res w i nc h P O NA R, s t andard Deep l a k e s , ri vers and es t uari e s ; us ef ul on s and, s i l t or cl a y 0 t o 10 7. 25 • M os t uni vers al grab sa m p l e r • A dequat e on m o s t s ubs t r at es • Large s a m p l e obt ai ned in ta ct, p e r m i ttin g s ubs am pl i n g • G ood f o r c oars e and f i rm bot t o m s edi m ent s • M ay not c l os e c o m p l e t e l y , r e s u ltin g in s a m p le lo s s • M et al f r am e m a y c ont am i nat e sa m p l e • H eavy; requi res w i nc h

P O NA R, pet i t e D eep l a k e s , ri vers and es t uari e s ; us ef ul on s and, s i l t or cl a y 0 t o 10 1. 0 • A dequat e f o r m o s t s ubs t r at es t hat are not c o m pac t e d • M ay not penet rat e s edi m ent t o des i r ed dept h, es pec i a l l y i n c ons ol i dat ed s edi m ent s . • S u s c e p t ib le to in c o m p le te c l os ure and l o s s of s a m p l e . • R equi res m o re c a s t s t o obt ai n su ffi ci e n t sa m p l e i f m a n y anal ys es needed. V an V een Deep l a k e s , ri vers and es t uari e s ; us ef ul on s and, s i l t or cla y ; e ffe ctiv e in m a r i n e envi r onm ent s i n deep w a t e r and s t rong c u rrent s 0 t o 30 18 t o 75 • A dequat e on m o s t s ubs t r at es t hat are not c o m pac t e d • Large s a m p l e obt ai ned in ta ct, p e r m i ttin g s ubs am pl i n g • A vai l abl e i n s t ai nl es s s t eel • M ay not c l os e c o m p l e t e l y , r e s u ltin g in s a m p le lo s s • M ay c l os e prem at urel y i n rough w a t e rs • M et al f r am e m a y c ont am i nat e sa m p l e • H eavy; requi res w i nc h

M odi f i ed V a n V een (e. g . , “Ted-Y oung grab”) Lak es and m a ri ne areas 0 t o 15 < 18. 0 • Fl uoroc arbon pl as t i c l i ner c an hel p avoi d m e t a l c ont am i nat i o n • S c r eened buc k e t c o ver hel ps reduc e bow w a ve e ffe cts • R equi res w i nc h • R el at i v el y ex pens i v e

Appendix E: Illustrations of G r ab and C o

re Sam p

ling D e

vices E-3M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **T a**  **b l**  **e E- 1.**  Advanta g es and Dis advanta g es of Com m only Us ed G r ab Sam p ler s (modif i ed f r om Klemm et al. , 1990; Environment Canada, 1994; PSEP, 1997a; W D E, 1995)
. **Devi ce**  **Use Sa**  **mple D**  **e pt**  **h (cm**  **) Sa**  **mple Volume** 

**(L 3**  **) A** **d vantages**  **D i**  **sadvantages**
P e t e rs en Deep l a k e s , ri vers and es t uari e s ; us ef ul on mo s t s ubs t r at es 0 t o 30 9. 45 • P rovi des l a rge s a m p l e • P enet rat e s m o s t s ubs t r at es • S hoc kw a ve f r om des c ent m a y di s t urb f i ne-grai ned s edi m ent • L a cks l i d co v e r to p e r m i t s ubs am pl i n g • M ay not c l os e c o m p l e t e l y , r e s u ltin g in s a m p le lo s s • M et al f r am e m a y c ont am i nat e sa m p l e • R es t r i c t ed t o l o w c u rrent c ondi t i ons • M ay ex c eed t a rget penet rat i on dept h S h i pek , s t andard Us ed p r im a r ilyin ma r i n e w a te r s a n d l a rge i n l and l a ke s a n d res e rvoi rs ; not us ef ul f o r c o m pac t e d s andy c l ay or till s u b s tr a t e s 0 t o 10 3. 0 • S a m p l e buc k e t opens t o perm i t s ubs am pl i n g • R et ai ns f i ne-grai ned s edi m ent s ef f e c t i v el y • M et al f r am e m a y c ont am i nat e sa m p l e • H eavy; requi res w i nc h • C an res u l t i n t he l o s s of t h e t opm os t 2-3 c m of very f i ne, unc ons ol i dat ed s edi m ent

M i ni S h i pek Lak es , us ef ul fo rm o st s ubs t r at es t hat are s o f t 0 t o 3 0

. 5 • H andl es eas i l y w i t hout w i nc h or c r ane f r om m o st p l a tfo r m s • R equi res vert i c al penet rat i on • S am pl es s m al l vol u m e • M ay l o s e f i ne-grai ned s edi m ent • M ay c l os e prem at urel y

E-4 U S Environm ental Protection AgencyTechnical M anual **T a**  **b l**  **e E- 2.**  Advanta g es and Dis advanta g es of Com m only Us ed Cor e Sam p ler s (modif i ed f r om Klemm et al. , 1990; Environment Canada, 1994; PSEP, 1997a; W D E, 1995; USEPA/ ACO E , 1998) **Devi ce/**  **D i**  **m e**  **nsions Use**  **Dep t**  **h Sa**  **mple**

**(cm )**  **Volume Sa**  **mple**

**(L 3**  **) A** **d vantages**  **D i**  **sadvantages** Fl uoroc arbon pl as t i c or gl as s t ube (3. 5 t o 7. 5 c m i nner di am et er (I

. D

. ) ; � 120 c m l ong) Sh a llo w w adeabl e w a t e rs or deep w a te r s if S CUB A avai l abl e; s o f t or s e m i c ons ol i dat ed depos i t s 0 t o 10 0. 096- 0. 44 • P res e rves l a yeri ng and perm i t s hi s t ori c al s t udy of s edi m ent depos i t i o n • M in im a l r i s ko f c ont am i nat i o n • R api d; s a m p l e s i m m edi at el y ready f o r l aborat ory s h i p m ent • S m a ll s a m p le s i z e nec es s i t a t e s repet i t i v e s a m p lin g

Hand c o rer w i th r e m o v a b l e f l uoroc arbon pl as t i c or gl as s lin e r s ( 3 .5 to 7
. 5 cm I.D .; � 120 c m l ong Sa m e a s above ex c ept mo r e c ons ol i dat ed s edi m ent s c a n be obt ai ned 0 t o 10 0. 96-0. 44 • S am e advant ages as f l uoroc arbon pl as t i c or gl as s t ube • P enet rat e s s ubs t r at e w i t h great er eas e t h rough us e of handl es • S m a ll s a m p le s i z e nec es s i t a t e s repet i t i v e s a m p lin g • R equi res c a ref u l handl i n g t o prevent s p i l l age • R equi res rem o val of l i ners bef ore repet i t i v e s a m p l i n g • B arrel and c o re c u t t e r m e t a l m a y c ont am i nat e sa m p l e B o x c o rer S am e as above but t h e dept h of t h e unc ons o l i dat ed s edi m ent m u s t be at l eas t 1 m 0 t o 70 < 30. 0 • Col l e c t s l a rge, undi s t urbed s a m p l e ; opt i m al f o r obt ai ni ng i n t a c t s ubs am pl es • D i f f i c u l t t o handl e • R el at i v el y heavy; requi ri ng l a rger ves s e l and pow er w i nc h t o depl oy.

Gravi t y Corer, P h l eger Corer ( 3 .5 cm I.D ., � 50 c m l ong) Deep l a k e s and ri vers ; se m i c ons ol i dat ed s edi m ent s 0 t o 50 < 0. 48 • R educ es ri s kof s a m p l e c ont am i nat i o n • M ai nt ai ns s edi m ent in te g r ityr e la tiv e lyw e ll • P enet rat e s w i t h s harp c u t t i ng edge • R equi res c a ref u l handl i n g t o avoi d s edi m ent s p i l l age • R equi res repet i t i v e and t i m e -c ons um i ng operat i o n and rem o val of l i ners due to sm a l l sa m p l e si z e Gravi t y Corer, Kaja kB r i n k hurs t Corer (5 c m I.D ., � 70 c m l ong) Deep l a k e s and ri vers ; So ft fin e grai ned s edi m ent s 0 t o 70 < 1. 37 • C ol l e c t s great er vol u m e t han t he P h l eger Corer. • S am e as P h l eger Corer

B ent hos Grav it yCorer ( 6 .6 , 7
. 1 cm I.D

. � 3 m l ong) So ft, fin e grai ned s edi m ent s 0 t o 3 m < 10. 26 • R et ai ns c o m p l e t e s a m p l e f r om t ube bec aus e t h e co r e v a lv e is fitte d to th e c o re l i ner • F i n s prom ot e vert i c al penet rat i on • R equi res w e i ght s f o r deep penet rat i on s o t he requi red l i f t i ng c apac i t y i s 750 t o 1, 000 k g • R equi res vert i c al penet rat i on • C om pac t s s edi m ent sa m p l e A l pi ne Gravi t y Corer (3. 5 c m I.D .) So ft, fin e grai ned, s e m i c ons ol i dat ed s ubs t r at es < 2 m < 1. 92 • A l l o w s di f f e rent penet rat i on dept hs due t o i n t e rc hangeabl e s t eel barrel • L a cks sta b iliz in g fin s fo r vert i c al penet rat i on • M ay penet rat e nonvert i c al l yand i n c o m p l e t e l y • R equi res a l i f t i ng c apac i t y of 2, 000 k g • D i s t u rbs s edi m ent s t rat a s and i n t egri t y • C om pac t s s edi m ent sa m p l e P i s t on Corers Oc ean f l oor and l a rge deep l a k e s ; Mo s t s ubs t r at es 3 t o 20 m 5 - 40 • T ypi c al l yrec o vers a rel a t i vel yundi s t urbed s edi m ent c o re i n deep wa t e r s • R equi res l i f t i ng c apac i t y of >2, 000 k g • P i s t on and pi s t on pos i t i oni ng at penet rat i on ma y f a i l • D i s t u rbs s u rf ac e (0 t o 0. 5m ) l a yer

Appendix E: Illustrations of G r ab and C o

re Sam p

ling D e

vices E-5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses **T a**  **b l**  **e E- 2.**  Advanta g es and Dis advanta g es of Com m only Us ed Cor e Sam p ler s (modif i ed f r om Klemm et al. , 1990; Environment Canada, 1994; PSEP, 1997a; W D E, 1995; USEPA/ ACO E , 1998) **Devi ce/**  **D i**  **m e**  **nsions Use**  **Dep t**  **h Sa**  **mple**

**(cm )**  **Volume Sa**  **mple**

**(L 3**  **) A** **d vantages**  **D i**  **sadvantages**

B M H-53 P i s t on Corer Wa t e r s < 2 m deep w i t h ext ens i on rod; s o f t depos i t s � 2 m � 2 • P i s t on provi des f o r great er s a m p le r e te n t io n • C ores m u s t be ext r uded ons i t e t o ot her c ont ai ners • M et al barrel s i n t r oduc e ri s kof m e t a l c ont am i nat i o n B oom erang Corer (6. 7 c m I.D .) Oc ean f l oor (up t o 9, 000 m deep) 1 m 3

. 5 2 • Requri e s m i ni m a l s h i pboard equi pm ent s o s m al l ves s e l s c an be us ed • O nl y penet rat e s 1. 2 m • R equi res c a l m w a t e r f o r rec o very • Los es 10 t o 20% of sa m p l e V i brac orer (5. 0 to 7
. 5 cm I.D .) Cont i nent al s hel f of oc eans , l a rge l a k e s ; s and, s i l t y s and, gravel l y s and s ubs t r at es 3 t o 6 m 5
. 89 t o 13. 25 • F or deep prof i l e s i t e ffe cti v e l ysa m p l e s m o st s ubs t r at es w i t h m i ni m u m di s t urbanc e • C an be us ed i n over 20 m of w a t e r dept h • P ort abl e m odel s c an be operat ed f r om s m al l ves s e l s (e. g . 10 m l ong) • Labor i n t ens i v e • A sse m b l ya n d di s a s s e m b l y m i ght requi re di vers • D i s t u rbs s u rf ac e (0 t o 0. 5 m ) l a yer • S pec i a l generat or m a y be needed • H eavi e r m odel s requi re l a rger boat and pow er w i nc h t o depl oy

E-6 U S Environm ental Protection AgencyTechnical M anual

**Figur e**  **E -**  **1 .**  Som e r e c o m m ended devic es f o rc o llec t in g s u r f ic ial s edim ents ( d r a w i n g s f r o m Mur doc h and Az c ue 1995 and F r edette et al. 1990)

.

Appendix E: Illustrations of G r ab and C ore Sam pling D evices E-7M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

**Figur e**  **E -**  **2 .**  Som e r e c o m m ended devic es f o robtainin g s edim ent pr of iles ( dr aw i n g s f r om Mur doc h and Az c ue 1995 and F r edette et al. 1990)

.

E-8 U S Environm ental Protection Agency

# APPENDIX F **EXAMPLES OF FIELD FORMS USED TO DOCUMENT STATION AND SAMPLE** 

**CHARACTERISTICS AND SAMPLE**  **TRACKING**Technical M anual

Appendix F: Exam ples of Field Form s F-3M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses E x ample of f

i eld f o rm used by the G reat Lakes National P rogram Of f i ce:


## F i e l d Sa m p l i n g Lo g She e t **L o**  **cati o**  **n a n**  **d C**  **o r**  **e Info rmati**  **o n**  Sta ti o n N u m b er : Wa ter Su rf a c e El ev a ti o n Dat e W at e rDe p t h T i m e C o re tube L eng th Pr im a r y G PS L at it u d e D e p t hof Pe n e t r at i on Lo ng i t ud e Le n g t ho f R e t r i e v e dC o r e S e c on d a r y G PS L at it u d e L og g e r s I n it ia ls L on gi t u d e S a m p le r s In it ia ls


### S **a m**  **p le**  **In t**  **e r**  **v a**  **ls**
S a m p le N u mb e r S a m p le I n t e r v al Ph y s ic a l D e sc r it p io n o f S a mp le

F-4 U S Environm ental Protection AgencyTechnical M anual Ex ample of f

i eld f o rm used f o r site remediation samplin g at Naval bases:

Appendix F: Exam ples of Field Form s F-5

# APPENDIX G **PHYSICO-CHEMICAL SEDIMENT CHARACTERIZATION** Technical M anual **1 .**  **Ge n**  **e ra**  **l In fo**  **rma t**  **io n**  I tis often necessary or desirable to determine certain phy sico- c hemi cal ch aracteristics of sedime nts in the laboratory , in conj unction w ith toxicity tes ting or chemical analy s is for inorg a nic or org a nic contaminants. T h is characteriz ation should incl ude measurement of certain parame ters known to me diate the av ailability of contaminants in sedime nt (A ST M, 2000f). B u lk chemical concentrations alone should not be used to ev aluate bioav a ilab ility (U SEPA , 1998). T h e follow i ng parame ters are g e nerally measured:
• p H ( por e wa t e r ) • a mm onia (pore water) • t otal org a nic carbon • p article siz e distribution (e.g ., percent sand, silt and clay ) • p ercent w a ter content • s alinity and hardness of pore water • c onductiv ity of pore water Depending on the experime ntal desi g n and/or study obj ectiv es, m o re extensiv e characteriz ation m a y be necessary
. Sev e ral additional characteristics w h ich m a y assist in study im plementation, data interpretation or QA/QC (i.e., a ssessing sedime nt integ r ity , artif act production, optim al extraction and test procedures) include: sedime nt bioc hemi cal oxy g e n dem a nd (BOD), sedime nt chemical oxy g e n dem a nd (COD), sedime nt oxy g e n dem a nd (S O D ) , cation exchang e capacity (C EC ), R e dox (Eh) or oxidation- reduction potential (O R P ), total inorg a nic carbon, total v o latile solids, acid v o latile sulfides (AV S ), sim u ltaneously extracted me ta ls (SEM), me tals, sy nthetic org a nic com pounds (pesticides, PCBs, PAHs, and T C DD- dioxin), oil and g r ease, pe troleum hy drocarbons, dissolv ed org a nic carbon (DOC) in the pore water. Meas urem ents of m a ny sedime nt phy sicochemical characteristics use analy tical techniques orig inally dev e loped for soils and w a ters, and the literature should be consulted for details reg arding recomme nded me thodolog y (B lack , 1965; USGS, 1969; Plum b, 1981; Pag e et al., 1982). T h e follow i ng sec tions prov ide rationale for m aki ng each ty pe of sedime nt phy sicochemical measurement, along w ith brief descriptions of measurement techniques, and references for further inform ation and specific procedures. **2. pH**  S e dime nt pH is often one of the sing le m o st important factors controlling speciation and equilibria for m a ny chemicals including sulfides, amm onia, cy anide, and me tals, all of which ioniz e under the influence of pH
. The U S E P Aamm onia w a ter- quality criterion, for exam ple, is dependent in part on pH because amm onia toxicity is larg ely g o v e rned by the unioniz e d amm onia fraction w h ich is pH

dependent (U SEPA , 1999). Metal (C d, C u , N i , Pb , and Z n ) speciation and bioav a ilability are also known to be affected by pH (Schubauer- Beri g a n and Ankl ey , et al ., 1991; Ho et al. 1999). Generally , pH is measured using a pH me ter c onsisting of a potentiome ter, a g l ass electrode, a reference electrode, and a tem p erature com p ensating dev i ce. Acircuit is com p leted throug h the potentiome ter w h en the electrodes are submersed. General purpose process pH electrodes are av ailable in a wide v ariety of config urations for in- line and submersion applications. Generally , electrodes w ith g e l- filled references require le ss m a intenance than electrodes w ith liquid- filled references. T h e latest instrume nts hav e mi croproce ssors that autom a tically calculate and display the slope. Some older instrume nts hav e a percent- slope readout or (and) milliv olt readout. For instrume nts w ith a milliv olt readout, the measured electrode potential is calculated as the difference betw een milliv olts measured at the know n pH of tw o buffers.
Appendix G : Physico-C hem ical Sedim ent C haracteriz a

tion G-3M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses Plum b (1981) and Gonz alez (1995) described a me thod for meas uring pH in sedime nt using a pH probe and me ter. T h e probe was inserted into the se dime nt and pH directly measured after at least a 5 mi nute equibration time. Electr odes hav e also been used for direct measurements of pH in sedime nt pore water, or in a 1 to 1 mi xture of sedime nt to water (J ack son, 1958). Direct measurement of sedime nt pH is also possible usin g electrodes w ith “spear tip” desig n s allow i ng for g r eater penetration into the sam p le (Burg e ss, personal comm unication). Detailed me thods for measuring pH in water and sedime nt are al so described by USEP A (1983;1986b;1987), in USEPA (1979), and in USEPA (1987), respectiv ely
. **3 .**  **A mmo**  **n i**  **a in**  **P o**  **re Wa**  **te r**  N itrog en, a nutrient associated w ith ov er- e nrichm ent of aquatic env i ronments, exists in sev e ral form s, including amm onia. Amm onia is hig h ly so luble in water where it is found in an un- ioniz e d form (N H 3 ) and in an ioniz e d form as NH 4 +
. T h e extent of ioni z a tion is dependent on pH tem p erature, and salinity (in seaw ater). A mm onia in sedime nts and pore w a ter is g e nerally the result of mi crobial deg r adation of nitr og enous org a nic m a terial such as amino acids (Ank ely et al., 1990). Pore water concentrations of amm onia as hig h as 50 m g/L hav e been measured in otherwise uncontaminated sedime nts (Murra y et al., 1978; Kr istensen and Black burn, 1987), while amm onia in pore waters from contaminated sedime nts can rang e from 50 to m o re than 200 m g/L (Ankley et al., 1990; Schubauer- Berig a n and Ankl ey , 1991). T h e toxic effects of amm onia are g e nerally consider ed to be associated w ith the un- ioniz e d fraction (N H 3 ) rather than the ionic com ponents (NH 4 + and NH 4 SO 4 - ), w h ich co- e xist in equilibria. This equilibrium is hig h ly dependent on pH , tem p eratur e, pressure, salinity , and ionic concentrations of amm onia. T h e toxic un- ioniz e d amm onia fracti on can be calculated using known total amm onia v a lues and measurements of pH, pressure, salinity , and tem p erature as described by Whitfield (1978) and T hurston et al (1981). USEPA (1983), and APHA (1995) describe fiv e me thods av ailable to measure amm onia in the pore wa t e r :
• t he titrimetric me thod • t he amm onia- selectiv e electrode me thod • t he amm onia- selectiv e electrode me thod using know n addition • t he phenate me thod • t he autom a ted phenate me thod. Apreliminary distillation step m a y be require d if interferences are present (A PH A , 1995). I n terferences, e.g ., sam p le constituents that interact w ith procedural reag ents, are described in detail in the A P H A(1995) and A S T M (2000g ) me thods. O n ce distilled, the sam p le can be analy z ed using any of the me thods listed abov e. T h e distillation and titration me thods are frequently used w h en amm onia concentrations are g r eater than 5.0 m g/L. T h e amm onia- selectiv e electrode me thod is appropriate when concentrations rang e between 0.03 and 1400 m g NH 3 - N/L. A mm onia reading s are calibrated ag ainst amm onia standards. To v e rify me ter reading s , confirm a tory subsam ples can be preserv e d and analy z ed for amm onia using the standard Nessler technique described in APHA (1995). For the phe nate me thod, APHA (1995) recomme nds distillation w ith sulfuric acid w h en interferences are present (B ow er and H o lm

- H ansen, 1980). T h e autom a ted phenate me thod is suitable fo r pore waters with amm onia concentrations in the rang e of 0.02 and 2.0 m g NH 3 -N/L
.

G-4 U S Environm ental Protection AgencyTechnical M anual H ach C o m p any , I n c. (L ov eland, C O ) describes the U S E P A approv ed N e ssler/distillation me thod adapted from APHA (1995). T h is is a photometric procedure and has been m odified for use with Hach photometers. **4. T**  **o t**  **a l**  **O r**  **gani c Carbon Cont**  **ent (**  **T O**  **C )**  T h e total org a nic carbon (T OC) content of sedime nt is a measure of the total am ount of oxidiz able org a nic m a terial. T O C is the sum of dissolv ed org a nic carbon (DOC), particulate org a nic carbon (POC) or suspended org a nic carbon (S OC), and colloids. T O C is an im portant parame ter to measure in sedime nts because it is a m a j o r determinant of nonionic org a nic chemical bioav a ilability (D iT oro et al., 1991). Metal bioav a ilability is also affected by the am ount of T O C present in sedime nts. T O C is usually expressed as a percentag e of the bulk sedime nt and is used to norm a liz e the dry

- weig ht sedime nt concentration of a chemical to the org a nic carbon content of the sedime nt. USEPA E quilibrium P artitioning G u idelines estim ate bioav a ilability as a function of contaminant concentration sorbed to sedime nt org a nic carbon and contaminant concentration in the pore water under equilibrium conditions (U SEPA , 1998). R ecently , the presence of soot carbon from the com bustion of org a nic carbon (e.g ., fossil fuels) ha s been recog n iz ed as a fraction of the T O C in sedime nt. Soot carbon m a y alter the g e ochemi stry and bioav a ilability of some org a nic contaminants (Gustuffson et al., 1997). T h e org a nic carbon content of sedime nts has been measured using sev e ral me thods including : wet oxidation titration, m odified titra tion, and com bustion after rem o v a l of carbonate by the addition of HCl and subsequent dry i ng . USEPA me thods(1986b; 1987), including SW- 846 and 430/9- 86- 004, are often used to measure T O C. Plum b (1981) recomme nds one of tw o me thods to separate org a nic from inorg a nic carbon before analy z ing for T O C : (a) ig nition and using H C l as the acid for pretreating sedime nt, or (b) differential com bustion, wh ich uses therm a l com bustion to separate the tw o form s of carbon. EPA/ACOE g u idance (1998) recomme nds that T O C analy s es be based on hig h

- t em perature com bustion rather than on chemical oxidation, b ecause some classes of org a nic com pounds are not fully deg r aded by com b ined chemical and ultrav iolet oxidation techniques. I norg a nic carbon (e.g ., carbonates and bicarbonates) can be a sig n ificant pr oportion of the total carbon in some sedime nts. T h erefore, sam p les should be treated with acid to rem o v e the inorg a nic carbon prior to T O C analy s is. T h e procedure described by the Pug e t Sound Es tuary Prog ram (PSEP, 1997a) is recomme nded for T O C analy s is because this me thod uses hig h

- t emperature com bustion using an induction furnace. USEPA recomme nds a similar me thod using catal y tic com bustion and non- dispersiv e infrared detection (Leonard, 1991) for quantify i ng T O C. U.S. EPA acknowledg es that sev e ral me thods for measuring the total org a nic carbon (T OC) content of sedime nts exist (See N e lson and Somme rs 1996 for a rev i ew ). H o w e v e r, acceptable me thods m u st at a mi nim u m include the follow i ng steps: Sa m p le C o llection
• S ediment sam p les are collected a nd stored in non- org a nic containers Sa m p le P reparation
• E ach sedime nt sam p le m u st hav e m acr oscopic pieces of shells (e.g ., > 1 mm ) rem o v e d and then be pulv e riz e d and hom og eniz ed

Appendix G : Physico-C hem ical Sedim ent C haracteriz a

tion G-5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

• E ach sedime nt sam p le m u st be treated by direct addition with a strong non- oxidiz i ng acid (e.g ., HCL) for 

### � 18 hours to rem o v e inorg a nic carbon; sam p le pH should be 

### � 2 after acidification (Yam am uro and K a y a nne, 1995)
• E ach sedime nt sam p le m u st be ov en dr ied following acid treatme nt (60 - 70° C) (Welik y et al., 1983; Yam a m u ro and K a y a nne, 1995)
• E ach sedime nt sam p le m u st be st ored in a desiccator until analy s is
• A s noted, desiccation is hig h ly recomme nde d, howev er if not possible a pre- and post- acidification sam p le weig ht should be performed to correct for water uptake (Hedg e s and Stern, 1984). Sa m p le A n alysis
• E ach post- acidification sedime nt sam p le m u st be analy z ed using acceptable instrume ntation
• I nstrumentation should hav e a detection limit of approxim a tely 100 m g/K g
• Q uantification of org a ni c carbon should be based on a sam p le’s weig ht, measured before acidification. Sam p l e QA Arig o rous Q A prog ram should be in place to insure acceptable data quality , this m a y include:
• P erform ance of duplicate analy s is on a subset of sam p les w ith the relativ e percent difference (R P D ) betw een replicates below 30%
• P erform ance of analy s es on certified standard reference m a terials (SR M ) (e.g ., NI ST ) **5 .**  **P a**  **rtic le**  **S i**  **ze D**  **i s**  **t rib**  **u t**  **io n**  **(P e**  **r c**  **e n**  **t S a**  **n d**  **, S**  **ilt, a n**  **d C**  **l a**  **y )**  Particle siz e is used to characteriz e the phy sical characteristics of sedime nts. B ecause particle siz e influences both chemical and bi olog ical characteristics, it can be used to norm a liz e chemical concentrations and account for some of the v a riability found in biolog ical assem b lag e s (U SEPA 1998) or in laboratory toxicity testing (USEPA , 2000d; Hoss et al., 1999). Particle siz e can be characteriz ed in v ary ing detail. T h e broadest di v i sions that g e nerally are considered useful for characteriz ing particle siz e distributions are per centag e s of g r av el, sand, silt, and clay
. H o w e v e r, each of these siz e fractions can be subdiv i ded furt her so that additional characteristics of the siz e distribution are determined (PSEP, 1996). P article siz e determinations can either include or exclude org a nic m a terial. I f org a nic m a terial is rem o v e d prior to analy s is, the “true” (i.e., prim arily inorg a nic) particle siz e distribution is determined. I f org a nic m a terial is included in the analy s is, the “apparent” (i.e., org a nic plus inorg a nic) particle siz e distribution is determin ed. B ecause true and apparent distributions m a y differ, detailed com p arisons between sam p les analy z ed by these different me thods are questionable. T h erefore, if com p arisons am ong sam p les between st udies is desired, sedime nt particle siz e should be measured using consis tent me thods (PSEP, 1996).
G-6 U S Environm ental Protection AgencyTechnical M anual Sedime nt particle siz e can be measured by a num ber of different me t hods (Allen, 1975; Plum b,1981; PSEP, 1996; A S T M , 2000a). T h e best me thod w ill de pend on the particle properties of the sam p le (Sing e r et al., 1988). Particle siz e distribution is often determined by either wet siev ing the sam p le (USEPA, 1979; Plum b, 1981; PSEP, 1996; Sing er et al., 1988), th e hy drometer me thod (Day , 1965; Patrick , 1958), the pipet me thod (U SG S, 1969; R u k a v i na and D uncan, 1970), settling techniques (Sandford and Swift, 1971), and X

- ray absorption (Duncan and Lattaie, 1979; Ruk a v i na and Duncan, 1970). T h e pipet me thod m a y be superior to the hy drometer me thod (Ster nberg and Creag er, 1961). C o m b inations of m u ltiple me thods m a y prov ide refine d measurements of particle siz e distribution. G ee and B a uder (1986) used siev ing and pipetting afte r soluble salts w e re rem o v e d. G onz alez (1995) used a com b ination of siev e and hy drometer me t hods. Folk (1968) and Buchanan (1984) discuss additional me thods to measure particle siz e . Recomme nded me thods for measuring sedime nt par ticle siz e distribution are those of PSEP (1996) and U S EPA (1995). Percent g r av el, sand, silt, and cl ay are determined as apparent distribution using a mi nim u m sedime nt sam p le siz e of 100 g take n from a hom og eniz ed sedime nt sam p le (see Section 4.4). Org a nic m a tter should be rem o v e d prior to analy s is by oxidation us ing hy drog en peroxide. Wet- siev ing follow e d by dry siev ing (mechanical sh aking ) separates the tw o coarse particle siz e g r oups. T h e silt- clay fraction is subdiv i ded using a pipet technique that depends upon the differential settling rates of the tw o different particle siz e fracti ons. A ll fractions are dried to a constant w e ig ht. C ooled sam p les are stored in a desiccator and w e ig hed. T o obtain an accurate determination of particle siz e s for the fine fraction, the C oulter (particle siz e ) counter me thod m a y be em ploy ed (McCav e and J arv is, 1973; V a nderpleog , 1981). T h is me thod g i v e s the fraction of particles w ith an apparent s pherical diameter. I n a rev i ew of the av ailable me thods, Sw ift et al. (1972) found the C oulter c ounter me thod to be the m o st v e rsatile me thod ov erall; how ev er, it does not prov ide settling inform a tion. A nother potential me thod for determining the particle siz e distribution of a v e ry fine fraction is throug h the us e of electron mi croscopy (Leppard et al., 1988). Collection techniques for v e ry fine m a terial can result in ag g r eg ation of larg er colloidal structures (Leppard, 1986; Leppard et al., 1988). I n g e neral, particle settling me thods are preferred to sedime nt siz i ng me thods. **6. Percent**  **Wat e**  **r or M o**  **i s**  **t u**  **re Cont ent**  Water content is a measurement of sedime nt m o isture usually expressed as a percentag e of the whole sedime nt weig ht. I tis known to influence toxicity and is used to aid in the interpretation of sedime nt quality inv e stig ations. S e dime nt m o isture content is measured as the difference betw een w e t w e ig ht of the sedime nt and dry weig ht fo llowing ov en dry i ng at 50 to 105° C to a constant weig ht. Percent water is used to conv ert sedime nt concentrations of substances from wet- weig ht to a dry

- weig ht. Methods for determining m o isture content ar e described by Plum b (1981) and V ecchi (1999). Additional me thods are pr ov ided in USEPA (1987). **7 .**  **S a**  **lin ity**  **o f**  **th e**  **P o**  **re Wa**  **te r (Ma**  **r in**  **e S**  **e d**  **i me**  **n t**  **s )**  S a linity is a measure of the m a ss of dissolv ed salt in a g i v e n m a ss of solution. The m o st reliable me thod to determine the true or absolute salinity is by com p lete chemical analy s is. Howev e r, this is time consuming and costly
. T h erefore, indirect me thods are m o re suitable. I ndirect me thods include conductiv ity , density , sound speed, or refractiv e index (APHA, 1995). Salinity is then calculated from the em pirical relationship between salinity and the indirect measurement. Conductiv ity measurements hav e the g r eatest precision, but re spond only to ionic solutes (APHA, 1995). Density measurements respond to all solutes. APHA ( 1995) recomme nds the electrical conductiv ity me thod,
Appendix G : Physico-C hem ical Sedim ent C haracteriz a

tion G-7M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses because it is sensitiv e and easily performed. A P H A(1995) also recomme nds the density me thod, using a v i brating flow densitome ter. USEP A (1986) me thods should also be consulted. Asalinity refractometer can be used for quick reading s of salt density in solutions such as sea w a ter. T h ese refractometers are easy to read, non- corrosiv e and lig htweig ht. T h ey hav e dual scales and an adj u stable focus. T e m p erature and non- tem p eratur e com p ensating refractometers are av ailable. Most refractometers are accurate to 1 ppt and read speci fic g r av ity (1.000 to 1.070 in .001 div i sions) and parts per thousand (0- 100 in 1 ppt div i sions). **8. Conduct**  **i v**  **i t**  **y of**  **t h**  **e Pore Wat e**  **r ( F**  **resh Wat e**  **r Sedi ment**  **s)** C onductiv ity is a measure of the ability of an aqueous solution to carry an electric current. T h is ability is dependent on the presence of ions in th e solution, the concentration of the ions, their m obility and v a lence, and tem p erature. Solu tions of inorg a nic com pounds are usually g ood conductors while those of org a nic com pounds are usually poor conductors. Conductiv ity is enhanced by calcium , potassium , sodium , and m a g n esium chlorides and sulfides. Meters can be used to measure the deg r ee to w h ic h electrical current can trav el throug h w a ter. T h e unit of measure is 1 m S /m = 1 millisieme ns/meter or 1 

### � S/cm = 1 mi crosieme ns/cm
. T h e reading indicates the am ount of ions in the w a ter. While traditional chemical tests for hardness measure calcium and m a g n esium , they fail to prov ide an indication of other ions (e.g ., sodium ). T h e conductiv ity me ter prov ides a m u ch better measure of ionic streng th. **9 .**  **A c**  **id V**  **o la**  **tile S**  **u lfid**  **e (A** **V S**  **)** Measurement of acid v o latile sulfides (A VS ) and sim u ltaneously extracted div a lent me tal (S E M ) concentrations associated w ith A V S extraction can prov ide insig h t into the bioav a ilability of me tals in anaerobic (anoxic) sedime nts (D iT oro et al., 1990; A n kl ey et al., 1996). A V S is the reactiv e solidphase sulfide fraction that is extracted by cold hy drochloric acid. AV S appears to affect the bioav a ilability of m o st div a lent me tal ions as the sulf ide ions hav e a hig h affinity for div a lent me tals. This affinity results in the form ation of insolubl e me tal sulfides w ith g r eatly reduced bioav a ilability
. AV S concentrations in freshwater and m arine sedime nts can rang e between < 0.1 and > 50 μ m ol AV S/g of sedime nt (DiT oro et al., 1990). The bioav a ilability of me tals in sedime nts has been predicted by com p aring the m o lar concentration of AV S to the m o lar concentration of SEM (methods described below). I f AV S is g r eater than SEM, the me tals are bound in sulfide com p lexes w ith g r eatly limited bioav a ilability
. H o w e v e r, if A V S < S E M, me tals m a y or m a y not be toxic due to other controlling factors (e.g ., TO C )
. T h e easily extractable sulfide fraction can be measur ed using the acid purg e and trap technique. T h e sam p le sulfide is solubiliz ed in cold hy drochloric acid. T h e analy tical me thod inv o lv es conv ersion of sulfides to aqueous H 2 S
. This m a y be measured w ith a sulfide probe or by follow i ng a w e t chemistry me thod. I n the latter me thod, silv er sulfide is pr ecipitated in a g a s- tig ht assem b ly and flushed with nitrog en to eliminate oxidation. The precipitate is filtered, dried, and w e ig hed. The w e ig ht is com p ared with the weig ht obtained from a non- acidifi ed sam p le, and the difference is attributed to the AV S fraction (DiT oro et al., 1990). **10. Si**  **mul t**  **aneousl y**  **Ext r**  **act ed M**  **e t**  **a l**  **s** A m odel for predicting toxicity from div a lent tr ace me tals (D iT oro et al., 1990) is based on the binding of these me tals to AV S. Where the sum of the m o les of the SEM, including Ag , Cd, Cu, Ni,
G-8 U S Environm ental Protection AgencyTechnical M anual Pb, and Z n is exceeded by the m o lar concentrati on of A V S, the me tals are insoluble and larg ely unav a ilable to biota. T h e extraction of AV S and me tals should be achiev e d using a sing le me thodolog y to ensure that recov e ries associated w ith each measure are consistent. Sim u ltaneous extraction im prov es the efficiency of the me thodolog y . SEM can be measured in filtered aliquots by atomic absorption me thods (D iT oro et al., 1990). Recent SEM analy s is me thods use inductiv ely coupl ed plasm aatomic emission spectrome try (I CPAES; Berry et al., 1999). Other me thods for analy s is of me tals are described in Section 11 below. **1 1**  **. Me**  **ta ls**  Low lev e ls of trace me tals occur naturally in the en v i ronment but hig h ly elev ated lev e ls in sedime nt are g e nerally associated w ith anthropog enic contaminant loads. Metals are partitioned in sedime nts as soluble free ions, soluble org a nic and inorg a nic com p lexes, easily exchang eable ions, precipitates of me tal hy droxides, precipitates w ith colloidal ferric and m a ng anic oxy hy droxides, insoluble org a nic com p lexes, insoluble sulfides, and residual form s (Gam brell et al., 1976). Current instrume nt me thods av ailable for the analy s is of trace me tals include electrochemistry (e.g ., differential pulse polarog raphy ), spectrophotometry (e.g ., silv er diethy ldithiocarbam a te), atomic absorption spectrophotometry , atomic emission spectrophotometry , x- ray fluorescence (X RF), and neutron activ ation (PSEP 1997c). T h e m o st comm only used instrume ntal me thod to analy z e sedime nts for me tals is atomic absorption sp ectrophotometry (PSEP, 1997c ). I nductiv ely coupled p l a s mama s s s p e c tr o me tr y ( I C P -M S ) o rIC P

- A E S allow for sim u ltaneous determination of m a ny me tals at sub- ppb lev e ls w ith little pretreatme nt (C recelius et al., 1987; B e rry et al., 1999). T h e concentration of salt in m arine or estuar ine sam p les m a y interfere w ith me tals analy s es (USEPA/ACOE, 1998). T h erefore, acid dig e stion and atomic absorption spectroscopy should be coupled with an appropriate technique to contro l for this interference. Methods in USEPA (1986b) are recomme nded for the analy s is of me rcury in sedime nts and EPRI(1986) me thods are recomme nded for the analy s is of selenium and arsenic. EPA me thods for cadmi um , hexav a lent chromi um , copper, lead, me rcury , nickel, seleni um , silv er, and z i nc are described by USEPA (1986b). PSEP (1997c) sug g e sts that me rcury can be extracted using v acuum distillation and analy z ed by g a s chrom a tog r aphy/m ass spectrophotometry . **12. Sy**  **nt het**  **i c O**  **r gani**  **c Com pounds (**  **P est**  **i c**  **i d**  **es, PCBs,**  **T CDD-**  **Di oxi**  **n )**  Analy tical techniques for measuring org a nic com pounds require fiv e g e neral steps: dry i ng the sam p le, extraction, dry i ng the extract, clean up of the extract, and analy s is of the extract. PSEP (1997b) recomme nds centrifug ation orsodium sulfate to dry the sam p le and a solv ent extraction, w ith application of shaker/roller, or sonication. Sam p le dry i ng with sodium sulfate is recomme nded for sam p les w e ig hing approxim a tely 10 g r am s (after ov erly ing w a ter is decanted). T h e sedime nt and sulfate mi xture is extracted and the ex tract is processed (MacLeod et al., 1985). Soxhlet® extraction (U SEPA , 1986b) inv o lv es di stillation w ith a solv ent such as acetone, dichlorome thane/me thanol (2:1), dichlorome thane/me thanol (9:1), and benz ene/me thanol (3:2). USEPA (1983) recomme nds sonication with solv ent mi xtures and a 30- g r am s ubsam ple of sedime nt. D r y i ng the extract can be accom p lished throug h separatory funnel partitioning as needed to rem o v e water and sodium sulfate or by using a K udern a- Danish apparatus and rotary ev aporation with purified nitrog en g a s for concentration to sm a ller v o lume s (PSEP, 1997c). Using the separatory funnel partitioning me thod, the w e t sam p le is mi xed w ith me thanol and centrifug ed. T h e supernatant Appendix G : Physico-C hem ical Sedim ent C haracteriz a

tion G-9M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses is decanted and extracted later. Extraction of the sam p le is continued using less polar solv ents and the w a ter/me thanol and solv ent extracts are com b ined and dried. According to PSEP (1997c) elemental sulfur can be rem o v e d from the sedime nt sam p le with v i g o rous mechanical ag itation using a V o rtex or Genie® or using activ ated copper. Org a nic interferences can be rem o v e d w ith g e l permea tion chrom a tog r aphy (GPC) described in USEPA (1983), bonded octadecy l column s (PSEP, 1997c), hi g h perform ance liquid chrom a tog r aphy (HPLC) described by Metro (1981), silica g e l (PSEP, 1997c), or alumina (U SEPA , 1983). I n strume ntal analy s es for v o latiles and semi v o latiles and pesticides/P C B s are performed using g a s chrom a tog r aphy/m ass spectrophotometry (GC/MS ) and g a s chrom a tog r aphy/electron capture detection (GC/ECD), resp ectiv ely (PSEP, 1997b; Burg ess and McK i nney , 1997). **13. O**  **i l**  **and G r**  **ease** Oil and g r ease tests for sedime nts measure m a terial recov e red that is soluble in a nonpolar solv ent under acidic conditions. O il and g r ease com pounds ar e substances such as hy drocarbons, v e g e table oils, anim al fats, w a xes, soaps, and g r eases. Many solv ents can dissolv e other substances (e.g . sulfur com pounds, org a nic dy es, and chlorophy ll). T h erefore, oil and g r ease is operationally defined by the solv ent used and the analy tical me thod used to perform the analy s is. T h ere are two basic me thods used to analy z e oil and g r ease: the g r av imetric technique and the I R(i nfrared spectrophotometer) technique. Both are de scribed by PSEP (1996). **14. Pet**  **r ol**  **eum Hy drocarbons and Pol**  **y cy**  **cl i**  **c A**  **r omat**  **i c**  **Hy drocarbons**  Petroleum hy drocarbons are oil and g r ease constituen ts w h ich rem a in in solution after contact w ith silica g e l. Petroleum distillates, also called hy dro carbons or petrochemi cals, refer to a broad rang e of com pounds w h ich are extracted by distillation during th e refining of crude oil. D u ring the fractional distillation of petroleum , crude oil is heated to allow v arious com pounds to turn from liquid into g a s and then captured as they rise, cool, and condens e. Lig h ter, m o re v o latile com pounds rise hig h er before they condense and are collected on distillation tray s. H eav ier, less v o latile com pounds such as diesel fuel and oil are collected on low e r distillati on tray s. Waxes and asphalts are collected from the bottom after the other products hav e v o latiliz ed. Petroleum distillates contain both arom atic hy dr ocarbons (carbon ring s) a nd aliphatic hy drocarbons (straig h t carbon chains). T h e chemical structure of the hy drocarbon larg ely defines the nature and behav i or of these com pounds. Arom atic hy dr ocarbons are the m o st toxic com pounds found in petroleum products. Most arom atic hy drocarbons are chronic toxins and known carcinog ens. Arom atic com pounds are found in all crude oils and m o st petroleum products. Many arom atic hy drocarbons hav e a pleasant odor and include such substances as naphthalene, xy lene, toluene, and benz ene. Aliphatic hy drocarbons are flamm able and m a y be explosiv ely flamm able. Aliphatic hy drocarbons include me thane, propane, and ke rosene. Arom atic and aliphatic hy drocarbons were analy z ed in sedime nts by Pag e etal. (1995a, b). Sedime nt sam p les were spiked with the appropriate surrog a te s, mi xed with equal am ounts of sodium sulfate to dry the sam p les, and extracted w ith a me thy l ene chloride acetone mi xture (Method 3550, U S EPA , 1986b). T h e concentrated extracts w e re partitione d on an alumina column into saturated and unsaturated hy drocarbon fractions (Method 3611, USEPA, 1986b). T h e fractions were concentrated using the appropriate pre- inj ection v o lume , spiked w ith the appropriate internal standards, and analy z ed by g a s chrom a tog r aphy w ith flame ioni z a tion detection (GC/FI D) and g a s chrom a tog r aphy w ith m a ss spectrome try detection (G C /MS ) operating in the selected ion m onitoring (SI M ) m ode. T h e me thod of internal standards (Method 8000, US EPA, 1986b) using the av erag e relativ e response
G-1 0 U S Environm ental Protection AgencyTechnical M anual factors g e nerated from the linear initial calibration w a s used to quantify the targ et com pounds. A l l data were corrected for the recov e ry of the appropriate surrog a te com pound. T h eir relativ e abundances could then be used for id entification and quantification purposes. T P H (total petroleum hy drocarbons) and PAH (poly c y c lic arom atic hy drocarbons) hav e also been analy z ed by first acidify ing the sam p le w ith c oncentrated hy drochloric acid and then extracting hy drocarbons with a mi xture of me th anol and hexane. T h e hexane extracts were then spiked with an internal standard and analy z ed by G C

- F I D for T P H content and by G C /m ass spectrome try (MS) for PA H analy s is. K aplan et al. (1996) extracted hy drocarbons using anhy drous Na 2 SO 4 w ith me thy l ene chloride and sonication. The total solv ent extract w a s then c oncentrated with K uderna- Danish equipment. T h e concentrate was further concentrated using a g e n tle stream of dry nitrog en. An aliquot was then inj ected directly into the g a s chrom a tog r aphy
. **1 5**  **. T**  **o ta**  **l S u**  **lfid e**  **s** T o tal sulfides represent the com b ined am ount of acid- soluble H 2 S, HS - , and S 2- in a sam p le. S u lfides are often measured because they are comm on in some sedime nts, particularly those that are anoxic, and they can be toxic to aquatic org a nism s. PSEP (1996) describes a me thod to measure total sulfides in sedime nts. O x y g e n is rem o v e d from th e sam p le using nitrog en g a s, me thy l orang e and hy drochloric acid is added, and the mi xture is h eated. Amine solution and iron chloride are added to dev e lop a colorime tric reaction product and sam p le absorbance is measured spectrophotometrically
. Methods for measuring sulfides in aqueous sam p les include: potentiome tric me thods described by AST M (2000e) and APHA (Method 4500, 1995). Sulfid e ions are measured using a sulfide ionselectiv e electrode in conj unction w ith a double- j unc tion, sleev e ty pe reference electrode (Phillips et al., 1997). Potentials are read using a pH me ter or a specific ion me ter hav i ng a direct concentration scale for the sulfide ion. Sam p les are treated w ith sulfide anti- oxidant buffer w h ich fixes the solution pH at a hig h alk a line lev e l and retards air oxidation of sulfide ion in solution. This ensures that the sulfide measured represents total sulfides as S = ion and rather than the H S - or H 2 S found at lower pH v a lues (see pH, Section 2 in this Appendix). A P H A(Method 4500, 1995) prov ides qualitativ e as w e ll as quantitativ e me thods to determine aqueous sulfide concentrations. Q u alitativ e me thods include the antim ony test, the silv er- s ilv er sulfide electrode test, the lead acetate paper te st, and the silv er foil test. Q u antitativ e me thods include the photometric me thod, the autom a ted phot ometric me thy l ene blue colorime tric me thods, and the iodometric titration me thod fo r standardiz ing stock solutions. **16. Sedi**  **ment O**  **x y**  **g en Demand (**  **S O**  **D )**  Sedime nt can exhibit sig n ificant rates of oxy g e n upt ake attributable to either: (1) a benthic ecosy stem supported by soluble org a nic substances in the water column , (2) naturally occurring sedime nts deriv e d from aquatic plants and anim als, and (3) de tritus discharg ed into the water body by natural runoff. When numerical m odeling is required to pr edict dissolv ed oxy g e n concentrations, the rate of dissolv ed oxy g e n consumed by the benthic ecosy stem is defined as the sedime nt (benthic) oxy g e n dem a nd (SOD) in g O 2 /m2 -d a y . T w o approaches for measuring SOD were re v i ewed by T ruax et al. (1995) including in-situ respirometry and laboratory respirometry me thods. Nume rous techniques hav e been dev e loped for each approach. G e nerally , in- s itu me thods are considered m o re credible than laboratory Appendix G : Physico-C hem ical Sedim ent C haracteriz a

tion G-1 1M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses

measurements althoug h both apply th e same technique. A g i v e n am ount of sedime nt is enclosed in a cham ber w ith a know n w a ter v o lume and oxy g e n uptake is measured ov er time. T h e SO D rate is then calculated based on the area of the enclosed se dime nt, the v o lume of w a ter in the cham ber, and the rate of uptake. In situ sedime nt oxy g e n dem a nd measurement me thod we re described by Uchrin and Ahlert (1985). Acy lindrical respirometer, a dissolv ed oxy g e n pr obe with stirring mechanism , and a dissolv ed oxy g e n me ter were used. Am bient dissolv ed oxy g e n w a s measured using the probe/meter as w e ll as by using the Winkler me thod (APHA, 1995) in the laboratory to determine the effect of respiration on total dissolv ed oxy g e n uptake. T h e respirometer w a s deploy ed in a lev e l area at the bottom of the w a ter body
. D i ssolv ed oxy g e n w e re recorded in itially and at 15- mi nute interv als thereafter to determine the S O D rate. **17. Sedi**  **ment Bi**  **ochemi cal**  **O x**  **y g**  **en Demand ( B**  **O D**  **)** Biochemi cal oxy g e n dem a nd (BOD) is a measure of the dissolv ed oxy g e n consumed by mi crobial org a nism s while assimilating and oxidiz i ng the org a nic m a tter in a sam p le (PSEP, 1996). T h e test is an em pirical me thodolog y in which standardiz ed la boratory procedures are used to determine the relativ e oxy g e n uptake of env i ronmental sam p les. T h e test measures the am ount of m o lecular oxy g e n used during a specified incubation period to biochemi cally deg r ade org a nic m a terial and to oxidiz e reduced form s of nitrog en (APHA, 1995). Plum b (1981) described a me thod to analy z e BOD in sedime nts using freshwater bacteria as a “seed” and buffered distilled w a ter as dilution w a ter. PSEP (1996) described an alternativ e procedure to analy z e B O D in m arine sedime nts using m arine bacteria as the “seed” and filtered, oxy g e nated seawater as the dilution water. USEPA (1987) me thods should also be consulted. **18. Sedi**  **ment Chemi**  **cal O**  **x y**  **g en Demand (**  **C O**  **D )**  Chemical oxy g e n dem a nd (COD) is a measure of th e oxy g e n equiv a lent of org a nic m a tter content in a sam p le that is susceptible to oxidation by a str ong chemical oxidant at elev ated tem p erature and reduced pH
. T h e test w a s dev i sed to aug men t the biochemi cal oxy g e n dem a nd test. Chemical oxy g e n dem a nd can be related em pirically to bioc hemi cal oxy g e n dem a nd, org a nic carbon, or total v o latile solids (PSEP, 1996). PSEP (1996) described a me thod for analy z ing sedi me nt COD using a closed reflux/colorime tric me thod. DiChrom a te (Cr 2 O 7 ) ions are used to oxidiz e org a ni c m a tter to carbon dioxide and water and to prov ide oxy g e n. The dichrom a te ions rem a ining after the reaction are measured by titration and the am ount of oxy g e n consumed is then calculated. Four standards procedures for measuring COD in water are av ailable in APHA (1995): the open reflux me thod, the closed reflux me thod, the titrim etric me thod, and the closed reflux/colorime tric me thod. U S EPA(1983) me thods for the colorime tr ic and titrimetric me thod are described in U S EPA (1979). Semi

- a utom ated me thods are described in USEPA (1993). H ach (Lov eland, CO ) has m odified the EPA a pprov ed dichrom a te reflux me thod and the reactor dig e stion me thod. T h e me thods are photometric and are adapted for use with Hach photometers.

G-1 2 U S Environm ental Protection AgencyTechnical M anual **19. Cat**  **i on Exchange Capaci**  **t y**  **of Sedi**  **ment s**  C a tion exchang e capacity (C EC ) is a parame ter th at prov ides inform ation relev a nt to me tal bioav a ilability studies (B lack , 1965). C a tions orpositiv ely charg e d elements (such as calcium , m a g n esium , hy drog en, and potassium ), are attract ed to neg a tiv ely charg e d surfaces of clay and org a nic m a tter. T h ere is a continuous exchang e of cations between sedime nt and water. CEC is a measure of the sedime nt’s ability to retain cationic el ements. I tis also a measure of clay activ ity and mi neralog y , w h ich is used to calculate mi neraliz ati on rates, leaching rates, and to predict interactions w ith contaminants. T h e deg r ee of CEC is de pendent on the ki nd and am ount of suitable surfaces such as org a nic m a tter and clay
. H i g h cation ex chang e capacities are associated w ith hig h clay contents and hig h org a nic m a tter and chang e s in C E C are ty pically associated w ith chang e s in org a nic carbon content and pH of the sedime nt. Org a nic m a tter g e nerally supplies a g r eater num ber of exchang e sites than clay particles. V arious me thods hav e been recomme nded to determin e bioav a ilable fractions of me tals in sedime nts (Chao and Zhou, 1983; Crecelius et al., 1987; K e rs ten and Forstner, 1987; D i T o ro et al., 1990). C E C can be measured by treating sam p les w ith amm onium acetate so that all exchang eable sites are occupied by NH 4 + ion, dig e sting the sam p les w ith sodium hy droxide during distillation, and titrating to determine the amm onium ion concentration. T h e am ount of exchang eable cations are expressed as milliequiv a lents of amm onium ion exchang e d (meq) per 100 g of dried sam p le. More detailed me thods are prov ided in Bascom b (1964), Black (1965), K l ute ( 1986), and USEPA (1986b). **20. Redox Pot**  **e nt**  **i a**  **l (**  **E h)**  **of Sedi**  **ment s**  Redox (Eh) is a measure of the oxidation- reduction potential (ORP) of sedime nts. Measurements of E h are particularly im portant for me tal specia tion and for determining the extent of sedime nt oxidation. Eh v a lues below approxim a tely - 100 milliv olts w ould indicate biolog ically im portant sulfide concentrations. Some trace me tals form insoluble com p lexes w ith sulfides. T h ese me talsulfide com p lexes bind the me tals in a form that is not bioav a ilable. Si nce free ionic me tals are g e nerally thoug ht to possess the g r eatest toxicity potential, it is im portant to understand conditions which control binding dy nami cs, such as pH and Eh. P o tentiome tric measurements of E h using a m illiv olt reader can be obtained w ith a platinum electrode relativ e to a standard hy drog en electrode (Plum b , 1981)
. APHA (1995) does not recomme nd the standard hy drog en electrode as it is frag ile and im practical. I n stead, their me thod uses a silv er- s ilv er- c hloride or calomel refere nce electrode. APHA (1995) recomme nds a g r aphite rather than platinum electrode for sedime nts. O n ce the E h equilibrium is reached, the difference between the platinum or g r aphite electrode and th e reference electrode is equal to the redox potential of the sy stem . F o r a m o re detailed explanation on how to calculate the E h potential see A P H A (1995). Gonz alez (1995) also desc ribes a detailed me thod that can be used to measure sedime nt Eh. T h ere are a num ber of problem s associated w ith the accurate measurement and interpretation of Eh in sedime nts, particularly in m arine sedime nts. T h erefore, considerable attention should be paid to the use of proper equipment and techniques. So me of the problem s identified by Whitfield (1969) and Mudroch and A z cue (1995) include measurement inaccuracy due to disturbance of the sedime nt sam p le during insertion of the electrode, instability and poor reproducibility of the measurements and differential responses of platinum electrode s under different env i ronmental conditions. A com p rehensiv e description of the limitations of sedi me nt Eh measurement is bey ond the scope of this document. Rather, it is recomme nded that pub lished studies on the problem s associated with measuring and interpreting sedime nt Eh be consulted before any attem p t is m a de to measure these parame ters in sedime nt sam p les (Berner,1963; Morris and Stumm , 1967; Whitfield, 1969; T i nsley , Appendix G : Physico-C hem ical Sedim ent C haracteriz a

tion G-1 3M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses 1979; Bates, 1981). T h e recomme nded procedure for m easuring pH and Eh in the field are described in detail in the table below :

**T a**  **b l**  **e G -**  **1.** G ener al pr oc edur es f o rm eas ur em ent of Eh in bottom s edim ents ( f r o m Mur doc h and Az c ue 1995)

. Equi pm e n tand so l u t i o ns use di n t h em e asure m e n t s :

• Apo rt abl e , bat t e ry -o pe rat e d pH/E h m e t e r, ba tte rie s , and a po w e r co rd f o r re charg i ng the m e te r. • C o m bi nat i o n g l ass and pl at i num e l e c tr o d e s o ro t he r e l e c tr o d e s sui t abl ef o r t h em e asure m e n t s . • P lastic te st-tu b e -sh ap e dco n t ain e rs o ro t h e r co n t ain e rs f o r sto r in g th e e l e c tro d e s in so lu tio n s d u r in g tran sp o r t in th e fi el d
. • C o mm e rcially -av a ilab l e o rlab o rato ry -p re p are d p H b u f f e r so lu tio n s (p H 4 an d 7 ) in p l astic b o ttle s w ith lid s. • F re sh ly -p re p are dso lu tio n f o r calib ratio n o f E h e l e c tro d ein a p l astic b o ttle w ith a tig h tlid
. • F re sh ly -p re p are dso lu tio n o f satu rate d p o tassiu m ch lo rid e f o r sto r ag e o f th e e l e c tro d e s . • O th e rso lu tio n s n e ce ssary f o r p r o p e rf u n c tio n i n g o f e l e c tro d e s as o u tlin e d b y m a n u f actu r e r s. • D istille d w a te r an d w a sh b o ttle f o r sto r in g an drin s in g th e e l e c tro d e s b e tw e e n m e asu r e m e n ts. • S e v e r al sm all an dlarg e rp l astic b e ak e r s f o r h o ld in g so lu tio n s , rin s in g e l e c tro d e s , e t c.. • S uppo rtst ands, ro ds, cl amps t o se curee l e c tr o d e s i n so l u t i o ns and duri n g m e asure m e n t s . • L arg epl ast i c co nt ai ne rs f o r st o r ag eand tr anspo r to f use dbuf f e rs and Eh-cal i b rat i o n so l u t i o ns. • N o t eb o o k and pe ns, so f tpape r t i ssue . P r e p arat i o n o f e qui pm e n tbe f o ret h ef i e l d tr i p : • C he ck bat t e ri e s o f t h epo rt abl epH/E h m e t e r and re pl ace/r e c harg et h e m , i f ne ce ssary . • P re p arecalib ratio n so lu tio n s . • C he ck and t e stt h epH and Eh e l e c tr o d e s . • M ark th e e l e c tro d e s v e rticallyat d e sire din te rv als f o r in se rtio n in to th ese d i m e n tsamp le s. • S to rethe e l e c tro d e s acco rd ing them a nuf acture r s instructio ns. • P ack all e q u i p m e n t f o r tran sp o r t to th e f i e l dan dtak esp are e l e c tro d e s if av ailab l e . M e a s u r emen t s i nt h e fi el d :

• A llo catea sp ace w h e r e m e asu r e m e n ts w ill b ecarrie d o u t. W ith in th is sp ace , all e q u i p m e n t sh o u ld b easse m b le d , che c ke d f o r pro p e rf unct i o ni ng , and pre p are df o r m e asure m e n to f t h ef i rstsamp l e . • P lace g r ab samp le r an dse d i m e n tco re s w ith re co v e re dse d i m e n tin su ch a w a y th at th e y w ill re m a in ste a d y w ith o u t di st urbi ng t h ese di m e ntsamp l e s duri n g t h em e asure m e n t s . • I nse r te l e c tr o d e s care f ul l y i n t o t h eundi st urbe d se di m e nt samp l e s t o av o i d anyai r. co nt ami n at i o n, part i c ul arl y aro und t h e E h el ec tr od e. C ar emu s t b e t ak e nn o t t o gen e r a t e a n y op ens p a c e b e t w eent h e el ec tr od e a n d t h e s e d i men t . P r op er in se rtio n o f th e e l e c tro d e w ith o u t d i stu rb i n g th ese d i m e n tis th e m o st imp o rtan t ste p in m e asu r in g th e E h
. • I n s e r t e l e c tro d e s in to th ese d i m e n tto th e d e p t h m ark e d
. S w itch th e p H/E h m e te r to th e p H scalean dth e v a lu e re co rd e d w ith in 1 mi n u t eaf te r in se rtin g th e e l e c tro d ein to th esamp le
. S w itch th e m e te r to th e mV scale f o r re co rd in g th e E h v a lu e . T h e p o te n tial u s u a lly d r if ts co n s id e r ab ly o v e r th e f i rst 1 0 to 1 5 mi n u t e s , an dth e n stab ilize s . A f

te r stab ilizatio n , re co rdth e mV v a lu e . In m e asu r in g E h o f se d i m e n t s f r o mw a te rs w ith lo w io n i c stre n g th , su ch as m o st f r e s hw ate rbo die s , it is re co mm e nde d to “acclim atize ” the e l e c tro d e s in the w a te r prio r to m e asure m e n t, p articu l arly th e e l e c tro d e s th at w e resto r e din satu rate d p o tassiu m ch lo rid eso lu tio n . T h is w ill re d u c eth e d r if tin g o f th e p o te n tial af te r in se rtin g th e e l e c tro d ein to th ese d i m e n t . • R e m o v e b o th e l e c tro d e s , w a sh th e mw ith d i stille d w a te r to re m o v eall ad h e rin g se d i m e n tp article s, an d d r y th e m g e n tly w ith a so f tp ap e r tissu e . • C a l i b r a t e t h e el ec tr od es a f t e rea c h fi ve mea s u r emen t s . T h e el ec tr od es ma y n eed l e s s fr eq u e n t c a l i b r a t i o ni f p Ha n d Eh arebe i n g m e asure di n a se di m e ntco re . **21. T**  **o t**  **a l**  **I norgani**  **c Carbon** I norg a nic carbon has been measured as a com p leme ntto mi crobial activ ity (Breg n ard et al., 1996), to determine the fate of an org a nic contaminant in biodeg r adation studies (West and Gonsior, 1996), and to determine the % carbon unaccounted for in fate transport predictions of hy drophobic contaminants (T y e , et al., 1996). Often the total inorg a nic carbon (T I C ) fraction in sam p les is m a ny times g r eater than the T O C fraction and presents an interference in the measurement of T O C
. T h ere are sev e ral options to eliminate TI C interferences w h en try i ng to measure TO C
. O n e option is to com p ensate for the I C interference by measuring total carbon (T C) and total inorg a nic carbon (see Section 4 in this Appendix). T h e di fference betw een the tw o is the TO C
.
G-1 4 U S Environm ental Protection AgencyTechnical M anual T I C is determined by acidify ing the sam p le to conv ert the inorg a nic carbon (i.e., carbonates, bicarbonates, and dissolv ed CO 2 ) to carbon dioxide. Ca rbon dioxide is purg e d from the sam p le and then detected by a non- dispersiv e infrared detector (NDI R) calibrated to directly display the m a ss of carbon dioxide measured. T h is m a ss is proportional to the m a ss of T I C. Other instrume ntation for the analy s is of T I C is described in West and Gonsior (1996) a nd T y e et al. (1996). **2 2**  **. T**  **o ta**  **l V o**  **la tile**  **S o**  **lid s**  **(T V**  **S )**  Total v o latile solids represent the fraction of to tal solids that are lost on ig nition at a hig h er tem p erature than that used to dete rmine total solids. To tal v o latile solids are used as a crude estim ate of the am ount of org a nic m a tter in total solids (PSE P, 1996). I n this reg ard, total v o latile solids are often measured instead of, or in addition to, org a nic carbon content. Total v o latile solids are operationally defined by ig nition tem p erature. Total v o latile solids content does not alw a y s represent the org a nic content of a sam p le because some org a nic m a terial m a y be lost at the dry i ng tem p erature and some inorg a nic m a teri al (e.g , carbonates, chlorides) m a y be lost at the ig nition tem p erature. B ecause of the tem p erature dependence of total v o latile solids, v a lid interstudy com p arisons require the use of standardiz ed dry i ng and ig nition tem p eratures (PSEP, 1996). T o tal v o latile solids measurements are g e nerally m a de by ig niting the sedime nts at 550 ± 10 o C until a constant weig ht is achiev e d and reporting the percent ash- free dry weig ht (McLeese et al., 1980; A P H A , 1995; Keilty et al., 1988a). Plum b (1981) a nd PSEP (1996) describe standard me thods for determining the total v o latile solid content of sedime nts. A dditiona l me thods are prov ided in U S EPA (1987). **23. Di**  **ssol v**  **ed O r**  **gani c Carbon i**  **n Pore Wat**  **e r**  Dissolv ed org a nic carbon (DOC) often consists of humic substances and is the fraction of the org a nic carbon pool that is dissolv ed in w a ter and passed throug h a 0.45 μ m g l ass fiber filter. D O C is an indicator of the chemically reactiv e org a nic frac tion and accurately measures the dissolv ed org a nic load. Sedime nt pore waters can be rich in humic acids. Fifty to 90% of the pore w a ter D O C can be colloidal w h ich is a sig n ificant factor because or g a nic chemicals w ill preferentially partition to pore water DOC (Resendes et al ., 1992; Burg ess et al., 1996). Herm ann (1996) and Gilek et al . (1996) measured DOC using a T O C apparatus and infrared detection of CO 2 . Borg a et al. (1996) measured DOC us ing atomic emission spectrome try (ECPAES). T h e APHA (Method 5310, 1995) me thods for total org a nic carbon which can be applied to the measurement of DOC are (a) the com bustion- infrared me thod; (b) the persulfate- u ltrav iolet oxidation me thod; and (c) the wet- oxidation me thod. Adj u stme nts for inorg a nic carbon interference m a y be required (see Section 21 in this Appendix). **24. A**  **l kal**  **i n**  **i t**  **y and Hardness of**  **t h**  **e Pore Wat e**  **r ( F**  **resh Wat e**  **r Sedi ment**  **s)** A l k a linity is defined as the acid- neutraliz ing (i.e., proton- accepting ) capacity of w a ter. I tis the sum of all the titratable bases and a measure of the quality and quantity of constituents in the pore w a ter that result in a shift in the pH tow ard the alk a line side of neutrality
. The measured v a lue m a y v ary sig n ificantly w ith the pH end- point used. Studies hav e shown thateffects of certain contaminants such as me tals are influenced by alk a linity as it alters speciation and bioav a ilability
. A P H A(1995) recomme nds a color- chang e titration me thod to measure alk a linity w h ich is also described by A S T M (2000h). T h e sam p le is titrated w ith standard alk a li or acid to a desig n ated pH Appendix G : Physico-C hem ical Sedim ent C haracteriz a

tion G-1 5M e

thods for C o

llection, Storage, and M anipulation of Sedim ents for C hem ical and Toxicological Analyses and the endpoint is determined electrome trically or by the color chang e of an internal standard. I n addition, A S T M (2000h) describes tw o additional me thods: (1) a titration curv e is dev e loped to identify inflection points, a standard acid of alk a li is added to the sam p le by sm all increments and pH is recorded after each addition, and the total v o lume of acid or alk a li is plotted ag ainst the observ e d pH v a lues; and (2) pH is determined, standard aci d is added to lower the pH to 4.0 or less, the solution is boiled w ith hy drog en peroxide, and titr ated w h ile hot to the phenolphthalein endpoint or when cooled electrome trically with standard alk a li to pH 8.2, the desired endpoint. T h e color- chang e titration me thod is m o st comm only used. H ach (Method 8202) has dev e loped a portable w a ter chemistry kit based on the A P H A (1995) color- ch ang e titration me thod and an additional me thod using sulfuric acid w ith a dig ital titrator (H ach, Method 8203). H ardness is the concentration of me tallic cations, w ith the exception of alk a li me tals, present in w a ter sam p les. Generally , hardness is a measure of th e concentration of calcium and m a g n esium ions in water. Hardness is usually expressed as a calcium carbonate equiv a lent in m g/L. Like alk a linity , hardness alters speciation and bioav a ilability of cer tain contaminants particularly m a ny me tals. AHPA (Method 2340, 1995) describes tw o me thods to measure hardness: (1) the calculation me thod and (2) the ED T A titrimetric me thod. A S T M ( 2000i) describes the A P H A(1995) ED T Atitrimetric me thod. C a lcium and m a g n esium ions in w a ter are sequestered by the addition of ED T A
. T h e endpoint of the reaction is measur ed by means of Chrome Black T 3 , w h ich is red in the presence of calcium and m a g n esium and blue when both ar e sequestered. A P H Arecomme nds the calculation me thod because it is m o re accurate. T h e me thod uses direct determinations of calcium and m a g n esium to determine hardness. Hach has dev e loped portable water chemistry kits (Methods 8222, 8204, 8030, 8226, 8213, 8338, 8329) for a v ariet y of hardness determinations using a spectrophotometer or titrati on me thods w ith a decision tree for se lecting the appropriate procedure. T h ree of the Hach me thods (1992) were ad apted from APHA (Method 2340, 1995): the buret and 0.020 Ntitrant me thod (8222); the ManVer 2 buretand 0.020 Ntitrant me thod (8226); and the buret titration me thod (8338). T h e A P H AED T A titration me thod is m o st often used.

G-1 6 U S Environm ental Protection Agency