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 Toxicological Analyses:


Technical 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 & Technology


Office of Water


U.S. Environmental Protection Agency


Washington, DC 20460

Disclaimer 

This technical manual provides a compilation of current information and recommendations for collecting, 

handling and manipulating sediment samples for physicochemical characterization and biological testing 

that are most likely to yield accurate, representative sediment quality data based on the experience of 

many monitoring programs and researchers. This manual has no immediate or direct regulatory 

consequence. It does not impose legally binding requirements on EPA, States, Tribes, other regulatory 

authorities, or the regulated community, and may not apply to a particular situation based upon the 

circumstances. EPA, State, Tribal, and other decision makers retain the discretion to adopt approaches 

on a case-by-case basis that differ from those in this manual where appropriate. EPA may update this 

manual in the future as better information becomes available. 

This document has been approved for publication by the Office of Science and Technology, Office of 

Water, U.S. Environmental Protection Agency. Mention of trade names, products, or services does not 

convey and should not be interpreted as conveying, official USEPA approval, endorsement, or 

recommendation for use. 

The suggested citation for this document is: 

U.S. EPA. 2001. Methods for Collection, Storage and Manipulation of Sediments for Chemical and 

Toxicological Analyses: Technical Manual. EPA 823-B-01-002. U.S. Environmental Protection 

Agency, Office of Water, Washington, DC. 
Technical Manual 

Acknowledgments 

This document is a general purpose manual intended to provide the user with sediment collection,


storage, and manipulation methods that are most likely to yield accurate, representative sediment


quality data for toxicity and chemical anlayses based on the experience of many monitoring programs


and researchers. The approaches described in this manual represents a compilation of information


presented in many publications, including Puget Sound Estuary Program (PSEP, 1997), Washington


State Department of Ecology (1995), Environment Canada (1994), US Environmental Protection


Agency - US Army Corps of Engineers (USEPA-USACE, 1998), American Society for Testing and


Materials (ASTM, 2000), and USEPA (2000).


The principal authors of this manual are Kathy Zirbser, Richard Healy, Leanne Stahl, Bill Tate


(USEPA, Office of Science and Technology), Jerry Diamond (Tetra Tech, Inc.), Allen Burton


(Wright State University), Michael Johns (Windward Environmental LLC), and John Scott (SAIC).


Review comments from the following individuals led to substantial improvements in the manual for


which we are grateful:


Tom Armitage USEPA- OST


Justine Barton USEPA – Region 10


Brett Betts WA Dept of Ecology: Sediment Management Unit


Kathryn Bragdon-Cook Toxics Cleanup Program: Sediment Management Unit


James Brannon Army Corps of Engineers – WES


Robert Burgess USEPA – NHEERL Atlantic Ecology Division


Scott Carr USGS – Marine Ecotoxicology Research Station


Scott Cieniawski USEPA – Region 5


Philip Crocker USEPA – Region 6


Alan Crockett Consultant


Kathleen Dadey USEPA – Region 9


Robert Engler Army Corps of Engineers – WES


Ken Finkelstein USEPA – Region 1


Maria Gomez-Taylor USEPA – EAD


Tom Gries WA Dept of Ecology


Erika Hoffman USEPA – Region 10 Sediment Management Program


Chris Ingersoll USGS – Columbia Environmental Research Center


Laura Johnson USEPA – OCPD


Ash Jain EPRI


Peter Landrum NOAA – Great Lakes Env. Research Laboratory


Sharon Lin USEPA – OCPD/WD


Ed Long NOAA


Gui Lotufo Army Corps of Engineers – WES


Don MacDonald NOAA – Office of Response and Restoration


John Malek USEPA – Region 10 Sediment Management Program


Acknowledgments iii 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Cornell Rosiu USEPA – Region 1


Brian Ross USEPA – Region 9 Dredging and Sed. Management


Timothy Sherman Army Corps of Engineers – Portland District


Robert Shippen USEPA- OST


Mark Siipola Army Corps of Engineers – Portland District


Jerry Smrchek USEPA – OPPT/OPPTS


Mark Sprenger USEPA – OERR-ERTC


Marc Tuchman USEPA – Region 5


Ernest Waterman USEPA – Region 1


Kathy Zirbser USEPA- OST


We are very grateful to Sherwin Beck (Tetra Tech, Inc.) as well as contributions from Carmela


Biddle, Marcus Bowersox, Brenda Fowler, Abby Markowitz, Patricia McCreesh, Kristen Pavlik


(Tetra Tech, Inc.), and Corinne Marino (VJB Associates) to this manual.


Front cover photographs provided by Allen Burton.


iv US Environmental Protection Agency 
Technical Manual 

Acronym List 

ACOE Army Corps of Engineers


ARCS Assessment and Remediation of Contaminated Sediments


ASTM American Society for Testing and Materials


AVS Acid Volatile Sulfides


BMPs Best Management Practices


BOD Biochemical Oxygen Demand


CEC Cation Exchange Capacity


COD Chemical Oxygen Demand


CV Coefficient of Variation


DOC Dissolved Organic Carbon


DQO Data Quality Objectives


EDMI Electronic Distance Measurement Instrument


EMAP Environmental Monitoring & Assessment Program


ERM Effect Range Medium


GC/MS Gas Chromatography/Mass Spectrophotometry


GC/FID Gas Chromatography/Flame Ionization Detection


GC/ECD Gas Chromatography/Electron Capture Detection


GLNPO Great Lakes National Program Office


GPC Gel Permeation Chromatography


GPS Global Positioning System


HPLC High Performance Liquid Chromatography


ICP-AES Inductively Coupled Plasma Atomic Emission Spectoscopy


ICP-MS Inductively Coupled Plasma Mass Spectrometry


IR Infrared Spectrophotometer


LORAN LOng RAnge Navigation


NAWQA National Water Quality Assessment


Acronym List v 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

NDIR Non-Dispersive Infrared Detector


NEP National Estuary Program


NOAA National Oceanic and Atmospheric Administration


NSI National Sediment Inventory


NST National Status & Trends


ORP Oxidation Reduction Potential


OSHA Occupational Safety & Health Administration


PCE Power Cost Efficiency


POC Particulate Organic Carbon


PSEP Puget Sound Estuary Program


QA Quality Assurance


QAPP Quality Assurance Project Plan


QC Quality Control


RADAR RAdio Detecting and Ranging


ROV Remotely Operated Vehicle


RPD Relative Percent Difference


SATNAV SATellite NAVigation


SCV Secondary Chronic Value


SEM Simultaneously Extracted Metals


SIM Selected Ion Monitoring


SOC Suspended Organic Carbon


SOD Sediment Oxygen Demand


SOPs Standard Operating Procedures


SPMD Semi-Permeable Membrane Device


SRM Standard Reference Materials


TIC Total Inorganic Carbon


TMDLs Total Maximum Daily Loads


TOC Total Organic Carbon


TPH Total Petroleum Hydrocarbons


TVS Total Volatile Solids


vi US Environmental Protection Agency 
Technical Manual 

USEPA United States Environmental Protection Agency


USGS United States Geologic Survey


XRF X-Ray Fluorescence


Acronym List vii 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

viii US Environmental Protection Agency 
Technical Manual 

Foreword 

Sediments provide essential habitat for many freshwater, estuarine, and marine organisms. In aquatic 

systems, most anthropogenic chemicals and waste materials, particularly persistent organic and 

inorganic chemicals, may accumulate in sediments. These sediments become repositories for many 

of the more toxic chemicals that are introduced into surface waters. United States Environmental 

Protection Agency’s National Sediment Inventory (NSI) (USEPA 1998), a biennial report to 

Congress on sediment quality in the United States, demonstrates that sediment contamination exists 

in every state of the country. Contaminated sediments represent a hazard to aquatic life through 

direct toxicity as well as to aquatic life, wildlife and human health through bioaccumulation in the 

food chain. Assessments of sediment quality commonly include analyses of anthropogenic 

contaminants, benthic community structure, physicochemical characteristics, and direct measures of 

whole sediment and pore water toxicity. Accurate assessment of environmental hazards posed by 

sediment contamination depends in large part on the accuracy and representativeness of these 

analyses. 

The methods described in this Manual are intended to provide the user with sediment collection, 

storage, and manipulation methods that are most likely to yield accurate, representative sediment 

quality data (e.g., toxicity, chemical) based on the experience of many monitoring programs and 

researchers. 

This Manual represents a compilation of information presented in many publications, including: 

•	 American Society for Testing and Materials (ASTM) 2000 document: Standard Guide for 

Storage, Characterization, and Manipulation of Sediments for Toxicological Testing, E1391-94. 

•	 Environment Canada 1994 manual: Guidance Document on Collection and Preparation of 

Sediments for Physicochemical Characterization and Biological Testing, EPS 1/RM/29. 

• U.S. Environmental Protection Agency. 2000 manual: Methods for Measuring the Toxicity 

and Bioaccumulation of Sediment-Associated Contaminants with Freshwater Invertebrates. 

Second Edition. EPA/600/R-99/064. 

•	 U.S. Environmental Protection Agency / Army Corps of Engineers. 1998. Inland Testing 

Manual: Evaluation of Dredged Material Proposed for Discharge in Waters of the U.S. -

Testing Manual. EPA-823-B-98-004. 

•	 U.S. Environmental Protection Agency / Army Corps of Engineers. 1991. Ocean Testing 

Manual: Evaluation of Dredged Material Proposed for Ocean Disposal: Testing Manual. 

EPA-503/8-91/001. 

In addition to many recent peer-reviewed technical journal papers, other publications that were relied 

on extensively include: 

Foreword ix 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

•	 Puget Sound Estuary Program (PSEP) 1997 manual: Recommended Guidelines for Sampling 

Marine Sediment, Water Column, and Tissue in Puget Sound 

•	 Washington Department of Ecology 1995 Document: Guidance on the Development of 

Sediment Sampling and Analysis Plans Meeting the Requirements of the Sediment 

Management Standards 

•	 Great Lakes National Program Office (GLNPO) 1994 manual: Assessment and Remediation 

of Contaminated sediments (ARCS) Program - Assessment Guidance EPA-905-B94-002. 

•	 U.S. Environmental Protection Agency. 2000 document: Estuarine and Near Coastal Marine 

Waters: Bioassessment and Biocriteria Technical Guidance. EPA-822-B-00-004. 

This Manual addresses several needs identified in EPA’s Contaminated Sediment Strategy 

(USEPA 1998) including: (1) an organized discussion of activities involved in sediment sampling 

and sample processing; (2) important issues that need to be considered within each activity; and 

(3) recommendations on how to best address issues such as sampling design, proper sampling 

procedures, and sample manipulations. Throughout this Manual, different considerations pertaining 

to sampling and sample processing are presented depending on the program need (e.g., dredge 

remediation versus status and trends monitoring). 

EPA along with other agencies, assesses aquatic sediment quality under a variety of legislative 

requirements including: 

• National Environmental Policy Act (NEPA) 

• Clean Air Act; the Coastal Zone Management Act (CZMA) 

• Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) 

• Marine Protection, Research, and Sanctuaries Act (MPRSA) 

• Resource Conservation and Recovery Act (RCRA) 

• Toxic Substance Control Act (TSCA) 

• Clean Water Act (CWA) 

• Comprehensive, Environmental and Liability Act (CERCLA) 

• Great Lakes Critical Programs Act of 1990. 

In addition, many EPA offices coordinate sediment monitoring studies in specific geographic areas, 

such as through the Chesapeake Bay Program, the Great Lakes National Program, the Gulf of Mexico 

Program, the Washington State Sediment Management Standards Program, and in the States of 

Washington, Florida, California, New York, New Jersey, South Carolina, Texas, Massachusetts, and 

Wisconsin. To address its responsibilities within the above legislative acts, EPA has several ongoing 

programs that may involve sediment quality evaluation as summarized below. 

x US Environmental Protection Agency 
Technical Manual 

Dredged Material Management 

The U.S. Army Corps of Engineers (USACE), the Federal agency designated to maintain navigable 

waters, conducts a majority of the dredging projects and disposal under its Congressionallyauthorized civil works program. The balance of dredging and disposal is conducted by a number of 

local public and private entities. In either case, the disposal is subjected to a regulatory program 

administered jointly by the USACE and EPA under Section 103 of the Marine Protection, Research, 

and Sanctuaries Act (MPRSA) for ocean disposal, and Section 404 of the Clean Water Act (CWA) 

for discharge at open water sites, confined disposal facilities with return flow to waters of the U.S., 

or for beneficial uses. EPA shares the responsibility of managing dredged material, principally in the 

development of the environmental criteria and guidelines by which proposed discharges are 

evaluated and disposal sites are selected, and in the exercise of its environmental oversight authority. 

Joint EPA/USACE guidance manuals detailing the testing and analysis protocols for dredged 

material disposal are well established. 

National Estuary Program 

EPA administers the National Estuary Program, established under the Clean Water Act to identify, 

restore, and protect nationally significant estuaries in the United States. Within the existing 28 

programs, environmental monitoring is a key element of watershed protection strategies developed to 

maintain the chemical, physical, and biological properties of the estuarine ecosystems. The Puget 

Sound Estuary Program (PSEP), in particular, has been actively monitoring ecological health, 

including sediment quality, in Puget Sound, Washington for many years. PSEP, which includes 

EPA, the Puget Sound Water Quality Authority, and the Washington Department of Ecology, has 

developed sediment sampling and analysis procedures in collaboration with local governments and 

stakeholder groups (PSEP, 1997). The protocols are cited in and support the Washington 

Department of Ecology’s (WDE) sediment management standards regulation, and have served as the 

foundation for many other guidance documents such as those produced by Environment Canada 

(1994) and American Society of Testing Materials (ASTM, 2000). This manual frequently refers to 

PSEP and WDE guidance. 

Resource Conservation and Recovery Act (RCRA) 

Under RCRA, EPA assesses whether releases from a hazardous waste treatment, storage, or disposal 

facility have contaminated sediments and requires corrective action, including possible remediation, 

if contamination is discovered. In many cases, sediment sampling and analyses, as discussed in this 

manual, are needed in RCRA facility assessments and RCRA facility investigations. 

Office of Water 

The Office of Water has been expanding provisions for sediment monitoring under the Clean Water 

Act, in the national monitoring framework developed by the Intergovernmental Task Force on 

Monitoring Water Quality (ITFM, 1995). Through this framework, agreements have been reached 

with other Federal, State, and local agencies concerning incorporation of sediment monitoring 

protocols, sediment monitoring QA/QC procedures, and appropriate information system linkages into 

monitoring programs. The Office of Water and the Office of Information Resources Management are 

also ensuring that the capability to store and use sediment data is enhanced as part of the ongoing 

modernization of the Agency’s water quality data systems (STORET), and in coordination with the 

water quality data elements procedures being recommended by the National Methods and Data 

Comparability Board under the National Water Quality Monitoring Council. These data elements 

include information describing how samples were collected, stored, and processed prior to analysis. 

Foreword xi 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Regional Environmental Monitoring and Assessment Program (REMAP) 

REMAP, within the Office of Research and Development, gathers chemical and biological data 

describing sediment quality at many EMAP sampling stations. Data collected under REMAP are 

entered into the National Sediment Inventory (NSI). These data are used to assess status and trends 

on a regional scale, particularly for aquatic systems that may have water quality and/or sediment 

quality impairment. 

Comprehensive, Environmental and Liability Act (CERCLA) 

Under CERCLA, EPA carries out a detailed analysis at a site, evaluating the risks posed by 

contaminants to human health and the environment, and the feasibility of various response action 

alternatives to reduce risk. The Risk Assessment Guidance for Superfund (USEPA, 1997) provides a 

framework for the assessment of human health and environmental impacts. The CERCLA Program 

is using the EPA-wide sediment testing methods of the Tiered Testing Framework in the Remedial 

Investigation/Feasibility Study (CRI/FS) stage of analysis to help determine options for remedial 

actions. Much of the guidance presented in this manual supports the Tiered Testing Framework 

applicable to CERCLA sites. 

Great Lakes Critical Programs Act of 1990 

Annex 14 of the Great Lakes Water Quality Agreement between the United States and Canada (as 

amended by the 1987 Protocol) stipulates that the cooperating parties will identify the nature and 

extent of sediment contamination in the Great Lakes, develop methods to assess impacts, and 

evaluate the technological capability of programs to remedy such contamination. The 1987 

amendments to the Clean Water Act authorized the Great Lakes National Program Office (GLNPO) 

to coordinate and conduct studies and demonstration projects relating to the appropriate treatment of 

toxic contaminants in bottom sediments. To fulfill the requirements of the Act, GLNPO initiated the 

Assessment and Remediation of Contaminated Sediments (ARCS) Program to help address 

contaminated sediment concerns in the development of Remedial Action Plans (RAPs) for all 43 

Great Lakes Areas of Concern (AOCs, as identified by the United States and Canadian governments), 

as well as similar concerns in the development of Lakewide Management Plans. This manual 

frequently relies on information documented by the GLNPO and the ARCS program. 

xii US Environmental Protection Agency 
Technical Manual 

TABLE OF CONTENTS


Page 

Acknowledgments ............................................................... iii


Acronym List ................................................................... v


Foreword ...................................................................... ix


Table of Contents .............................................................. xiii


List of Tables ................................................................. xvii


List of Figures ................................................................ xvii


List of Recommendations ........................................................ xix


Technical and Grammatical Terms ................................................ xxi


Using the Manual .............................................................. xxiv


1.	 INTRODUCTION ....................................................... 1-1


1.1 Background ....................................................... 1-1


1.2 Significance and Use of this Manual ................................... 1-1


1.3 Applicability and Scope of this Manual ................................. 1-2


2.	 SEDIMENT MONITORING AND ASSESSMENT STUDY PLANS ............. 2-1


2.1 Data Quality Objectives Process ....................................... 2-1


2.2 Study Plan Considerations ........................................... 2-5


2.2.1 Definition of the Study Area and Study Site ....................... 2-5


2.2.2 Controlling Sources of Variability ............................... 2-5


2.2.3 Sampling Using an Index Period ................................ 2-6


2.3	 Sampling Designs .................................................. 2-7


2.3.1 Probabilistic and Random Sampling ............................. 2-7


2.3.2 Targeted Sampling Designs ................................... 2-10


2.4	 Measurement Quality Objectives ..................................... 2-11


2.4.1 Sample Volume ............................................ 2-12


2.4.2 Number of Samples ......................................... 2-15


2.4.3 Replicate and Composite Samples .............................. 2-15


2.5	 Site-Specific Selection Considerations for Selecting Sediment 


Sampling Stations ................................................. 2-17


2.5.1 Review Available Data ....................................... 2-19


2.5.2 Site Inspection ............................................. 2-19


2.5.3 Identify Sediment Deposition and Erosional Zones ................. 2-19


2.6 Positioning Methods for Locating Sampling Stations ..................... 2-20


2.7 Preparations for Field Sampling ...................................... 2-21


2.8 Health and Safety ................................................. 2-23


3.	 COLLECTION OF WHOLE SEDIMENTS .................................. 3-1


3.1 General Procedures ................................................. 3-1


3.2 Types of Sediment Samplers .......................................... 3-5


3.2.1 Grab Samplers .............................................. 3-5


3.2.2 Core Samplers .............................................. 3-9


3.3 Sample Acceptability .............................................. 3-13


3.4 Equipment Decontamination ......................................... 3-14


3.5 Field Measurements and Observations ................................. 3-15


3.6 Documentation of Sample Collection .................................. 3-17


Table of Contents xiii

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

TABLE OF CONTENTS (CONTINUED) 

Page 

4.	 FIELD SAMPLE PROCESSING, TRANSPORT, AND STORAGE OF


SEDIMENTS ........................................................... 4-1


4.1 Sample Containers ................................................. 4-1


4.1.1 Container Material .......................................... 4-3


4.1.2 Container Preparation ........................................ 4-3


4.2	 Subsampling and Compositing Samples ................................ 4-5


4.2.1 General Procedures .......................................... 4-5


4.2.2 Grab Samples .............................................. 4-6


4.2.3 Core Samples .............................................. 4-7


4.3 Homogenization .................................................. 4-11


4.3.1 General Procedures ......................................... 4-11


4.4 Sample Transport and Storage ....................................... 4-13


4.4.1 General Procedures ......................................... 4-13


4.5 Sample Holding Times ............................................ 4-15


5. SEDIMENT MANIPULATIONS .......................................... 5-1


5.1 Sieving .......................................................... 5-1


5.1.1 Sieving Methods ............................................ 5-3


5.1.2 Alternatives to Sieving ....................................... 5-5


5.2	 Formulated Sediment and Organic Carbon Modification ................... 5-6


5.2.1 General Considerations ....................................... 5-6


5.2.2 Sediment Sources ........................................... 5-7


5.2.3 Organic Carbon Modification .................................. 5-7


5.3	 Spiking .......................................................... 5-8


5.3.1 Preparation for Spiking ....................................... 5-9


5.3.2 Methods for Spiking ........................................ 5-10


5.3.3 Equilibration Times ........................................ 5-12


5.3.4 Use of Organic Solvents ..................................... 5-13


5.4 Preparation of Sediment Dilutions .................................... 5-13


5.5 Preparation of Sediment Elutriates ................................... 5-14


6.	 COLLECTION OF INTERSTITIAL WATER ............................... 6-1


6.1 General Procedures ................................................ 6-1


6.2 In-situ Collection .................................................. 6-2


6.2.1 Peeper Methods ............................................ 6-5


6.2.2 Suction Methods ............................................ 6-7


6.2.3 Processing of Field-Collected Interstitial Water Sample ............. 6-8


6.3	 Ex-situ Extraction of Interstitial Water ................................. 6-8


6.3.1 General Procedures .......................................... 6-8


6.3.2 Centrifugation ............................................. 6-10

6.3.3 Sediment Squeezing ........................................ 6-12


6.3.4 Pressurized and Vacuum Devices .............................. 6-12


xiv US Environmental Protection Agency 
Technical Manual 

TABLE OF CONTENTS (CONTINUED) 

Page 

7.	 QUALITY ASSURANCE AND QUALITY CONTROL ........................ 7-1 

7.1 General Procedures ................................................. 7-1 

7.2 QA/QC Procedures for Sediment Collection and Manipulation ............... 7-2 

7.3 The Quality Assurance Project Plan (QAPP) ............................. 7-2 

7.4 Standard Operating Procedures ........................................ 7-3 

7.5 Sediment Sample Documentation ...................................... 7-3 

7.6 Sample Tracking Documentation ...................................... 7-4 

7.7 Record Keeping .................................................... 7-5 

7.8 QA Audits ........................................................ 7-5 

7.9 Corrective Action (Management of Non-conformance Events) ............... 7-5 

7.10 Data Reporting .................................................... 7-6 

8. REFERENCES .......................................................... 8-1 

APPENDICES 

A EXAMPLES OF SEDIMENT QUALITY SAMPLING DESIGNS USING THE DATA 

QUALITY OBJECTIVES (DQO) PROCESS 

B	 EXAMPLES OF MEASUREMENT QUALITY OBJECTIVES USED 

IN SEDIMENT QUALITY MONITORING STUDIES 

C	 STATISTICAL CONSIDERATIONS IN DETERMINING THE APPROPRIATE 

NUMBER OF REPLICATE SAMPLES NEEDED AT EACH SAMPLING STATION 

D	 ADVANTAGES AND DISADVANTAGES OF DIFFERENT STATION 

POSITIONING TECHNIQUES 

E	 ADVANTAGES, DISADVANTAGES AND ILLUSTRATIONS OF GRAB AND CORE 

SAMPLING DEVICES USED IN SEDIMENT MONITORING STUDIES 

F	 EXAMPLES OF FIELD FORMS USED TO DOCUMENT STATION AND SAMPLE 

CHARACTERISTICS AND SAMPLE TRACKING 

G PHYSICO-CHEMICAL SEDIMENT CHARACTERIZATION 

Table of Contents xv 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

xvi US Environmental Protection Agency 
Technical Manual 

LIST OF TABLES


Table Page 

2-1 Suggestions for selecting an appropriate sampling design (from USEPA 2000b) ........ 2-9


2-2	 Conventional sediment variables and their use in sediment investigations (Adapted


from WDE, 1995) ........................................................ 2-13


2-3 Typical sediment volume requirements for various analyses per sample ............. 2-14


2-4	 Practical considerations for site-specific selection of sampling stations in developing


a sampling plan .......................................................... 2-18


4-1	 Recommended sampling containers, holding times, and storage conditions for


common types of sediment analyses .......................................... 4-4


6-1 In Situ interstitial water collection methods ..................................... 6-5


LIST OF FIGURES 

Figure Page 

1-1 	 Flow chart summarizing activities for collection, storage, and manipulation of


sediments and interstitial water .............................................. 1-3


2-1	 Flow chart summarizing the process that should be implemented in designing


and performing a monitoring study (modified from MacDonald et al. (1991) .......... 2-2


2-2	 Flow chart summarizing the Data Quality Objectives Process (after USEPA


2000a) .................................................................. 2-3


2-3 Description of various sampling methods (adapted from USEPA 2000c) .............. 2-8


3-1	 General types of considerations or objectives that are appropriate for grab or core


sampling devices ......................................................... 3-1


3-2	 Flowchart for selecting appropriate grab samplers based on site-specific or design


factors .................................................................. 3-2


3-3 Flowchart for selecting appropriate core samplers based on site-specific factors ........ 3-3


3-4 Illustrations of acceptable and unacceptable grab samples ........................ 3-15


4-1 Flowchart of suggested sediment processing procedures .......................... 4-2


4-2 Alternatives for subsampling and compositing sediment grab samples ................ 4-8


4-3 Alternatives for subsampling and compositing sediment core samples ................ 4-9


Table of Contents xvii

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

LIST OF FIGURES (CONTINUED)


Figure Page 

5-1	 Flowchart depicting relationships between common sediment manipulations


including important considerations ........................................... 5-2


6-1	 Considerations for selecting the appropriate type of interstitial water sampling


method................................................................. 6-3


6-2	 Front view and components of peeper sampling devices (top: plate device; bottom:


cylindrical probe) ........................................................ 6-6


6-3	 Summary of recommended procedures and considerations for laboratory isolation 


of interstitial water ....................................................... 6-9


xviii US Environmental Protection Agency 
Technical Manual 

LIST OF RECOMMENDATION BOXES 

Chapter 2 Page 

Box #1 What type of sampling strategy should be used .......................... 2-10


Box #2 How many samples and how much sample volume should be collected ....... 2-14


Box #3 How should station positioning be performed ........................... 2-20


Box #4 What health and safety precautions should be followed .................... 2-24


Chapter 3 

Box #1	 What are appropriate sampling devices given different study


objectives ......................................................... 3-9


Box #2 How should sampling devices be used ................................. 3-13


Box #3 What information should be documented for each sample collected .......... 3-16


Chapter 4 

Box #1 Sample containers .................................................. 4-1


Box #2 How should sediment samples be subsampled and composited ............... 4-5


Box #3 How should samples be homogenized ................................. 4-11


Box #4 Sample transport and storage ........................................ 4-14


Box #5 How long should samples be stored before analysis ....................... 4-15


Chapter 5 

Box #1 Should sediment be sieved prior to analyses .............................. 5-3


Box #2 What type of sieve should be used ..................................... 5-5


Box #3 How should sediments be spiked with a chemical or other test material ........ 5-9


Box #4 How should sediment elutriates be performed ........................... 5-15


Chapter 6 

Box #1 In-situ interstitial water collection ..................................... 6-2


Box #2 Extraction of interstitial water ........................................ 6-10


Table of Contents xix

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

xx US Environmental Protection Agency 
Technical Manual 

Technical Terms 

The following definitions were derived primarily from ASTM, USEPA, ACOE, and Environment 

Canada sources. 

Acid Volatile Sulfide. The sulfides removed from sediment by cold acid extraction, consisting 

mainly of iron sulfide. AVS is the principal binding phase in sediment for divalent metals. 

Artifact. An undesirable, detectable feature (e.g., chemical or physical change) in a sample, that has 

resulted from sampling, sample handling or storage, or from manipulations of the sample. 

Benthic. Associated with the bottom of a waterbody. 

Bioaccumulation. The net accumulation of a substance by an organism as a result of uptake from all 

environmental sources. 

Bioavailability. The degree to which a chemical is taken up by aquatic organisms. 

Chain-of-custody. The documentation that establishes the control of a sample between the time it is 

collected and the time it is analyzed. It usually applies to legal samples to demonstrate that there was 

no tampering with, or contamination of, the sample during this time. 

Clean. Denotes a sediment or water test sample determined to not contain concentrations of 

contaminants which cause apparent and unacceptable harm (or effects) to the test organisms. 

Composite sample. A sample that is formed by combining material from more than one sample or 

subsample. 

Concentration. The ratio of weight or volume of test material(s) to the weight or volume of 

sediment or water. 

Contaminated sediment. Sediment containing chemical substances at concentrations that pose a 

known or suspected threat to environmental or human health. 

Control sediment. A sediment that is essentially free of contaminants and is used routinely to assess 

the acceptability of a test. Any contaminants in control sediment may originate from the global 

spread of pollutants and do not reflect any substantial input from local or non-point sources. 

Comparing test sediments to control sediments is a measure of the toxicity of a test sediment beyond 

inevitable background contamination. 

Core sample. A sediment sample collected to obtain a vertical profile using a variety of instruments. 

Data Quality Objectives (DQOs). Qualitative and quantitative statements that clarify the purpose 

of the monitoring study, define the most appropriate type of data to collect, and determine the most 

appropriate methods and conditions under which to collect them. 

Decontamination. A process of washing or rinsing that removes chemicals adhering to equipment 

and supplies. 

Terms xxi 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Ecotox Thresholds (ET). Benchmark values in ecological risk assessments defined as mediaspecific contaminant concentrations above which there is sufficient concern regarding adverse 

ecological effects to warrant further site investigation. 

Elutriate. An aqueous solution obtained after adding water to a solid substance or loose material 

(e.g., sediment, tailings, drilling mud, dredge spoil), shaking the mixture, then centrifuging or 

filtering it or decanting the supernatant. 

Equilibration. The condition in which a material or contaminant is at steady state between the solid 

or particulate sediment and the interstitial water. 

Formulated Sediment. Mixtures of materials used to mimic a natural sediment. 

Global Positioning system (GPS). A navigation system that relies on satellite information. It can 

give continuous position reports(i.e., latitude and longitude) that vary in accuracy depending on the 

sophistication of the receiving unit. 

Grab. Any device designed to “bite” or “scoop” into the bottom sediment of a lake, stream, estuary, 

ocean, and similar habitats to sample the benthos. Grabs are samplers with jaws that are forced shut 

by weights, lever arms, springs or cables. Scoops are grab samplers that scoop sediment with a 

rotating container. 

Head Space. The space in the storage container between the top of the sample and the lid of the 

container. 

Holding time. The period of time during which a sediment or water sample can be stored after 

collection, and before analysis or use in a biological test. Changes that occur in sediments or water 

should be minimal during this period and the integrity of the sample should not be compromised to 

any substantial degree with respect to its physical, chemical, or biological characteristics. 

Homogenization. The complete mixing of sediment, either by hand or mechanical means, until 

physical, chemical, and /or biological homogeneity of the sample is achieved. 

Index Period. Specific time period in which sampling or in-situ analyses are conducted. Generally 

pertains to an ecologically important season and/or desired environmental conditions under which 

sampling is performed. 

In Situ. Refers to the original (field) location from which test samples are collected, or at which 

organisms are exposed to undisturbed water or sediments for extended periods. 

Interferences. Characteristics of sediments or sediment test systems that can potentially affect 

analytical results or test organism response aside from responses related to sediment contamination. 

Types of interferences include: non-contaminant characteristics (e.g., sediment texture or grain size, 

lighting); changes in chemical bioavailability due to sample handling or storage (e.g., ammonia 

generation); and the presence of indigenous organisms. Also referred to as confounding factors. 

Interstitial water. Water occupying space between sediment or soil particles. 

Measurement Quality Objectives (MQOs). Statements that describe the amount, type, and quality 

of data needed to address the overall project objectives. 

xxii US Environmental Protection Agency 
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Overlying water. The water placed over sediment in a test chamber during a test. 

Peepers. Devices that collect interstitial water by diffusion through membranes attached to 

collection chambers. The chambers are typically placed in the sediment for extended periods of time 

to allow for equilibration between the internal water environment of the peeper and the surrounding 

ambient sediment/interstitial water matrix. 

Pore water. See interstitial water. 

Quality Assurance Project Plan. Project-specific document that specifies the data quality and 

quantity requirements needed for the study as well as all procedures that will be used to collect, 

analyze, and report those data. 

Reference sediment. A whole sediment, collected near an area of concern, that is used as a point of 

comparison to assess sediment conditions exclusive of the material(s) or activities of interest. The 

reference sediment may be used as an indicator of localized sediment conditions exclusive of the 

specific pollutant input of concern. Such sediment would be collected near the site of concern and 

would represent the background conditions resulting from any localized pollutant inputs as well as 

global pollutant input. Program-specific guidance documents should be consulted, as some EPA 

programs have specific definitions and requirements for reference sediment. 

Sampling Platform A working space, such as the deck of a boat, from which all sample collection 

activities are conducted. 

Sediment. Particulate material that usually lies below water, or formulated particulate material that 

is intended to lie below water in a test. 

Sediment Quality Triad. A weight-of-evidence sediment quality assessment approach which 

integrates data from sediment toxicity tests, chemical analyses, and benthic community assessments. 

Sieving. Selectively removing certain size fractions of the sediment sample by processing sediment 

through selected mesh sizes. 

Site. A study area that can be comprised of multiple sampling stations. 

Spiking. Addition of a known amount of test material to a sediment often used as a quality control 

check for bias due to interference or matrix effects. 

Station. A sampling location within a study area or site, where physical, chemical, or biological 

sampling and/or testing occurs. 

Supernatant. The water separated from a sediment/water mixture following centrifugation or other 

separation techniques. 

Toxicity. The property of a chemical, or combination of chemicals, to adversely affect organisms, 

tissues or cells. 

Whole sediment. Sediment and associated interstitial water which have had minimal manipulation. 

Also referred to as bulk sediment. 

Terms xxiii 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Grammatical Terms 

Consistent with guidance formulated by the American Society for Testing and Materials (ASTM), 

the following grammatical phrases, used in this manual, are defined as follows: 

The words “must”, “should”, “may”, “can”, and “might” have specific meanings in this manual. 

“Must” is used to express an absolute requirement, that is, to produce accurate results, a sample 

ought to be handled or manipulated in a specified manner, unless the purpose of the study requires a 

different procedure. 

“Should” is used to state that the specified condition or procedure is recommended and ought to be 

met if possible. Although violation of one “should” is rarely a serious matter, violations of several 

will often render the results questionable. 

“Desirable” is used in connection with less important factors. 

“May” is used to mean “is allowed to.” “Can” is used to mean “is able to.” “Might” is used to mean 

“could possibly.” Thus, the classic distinction between “may” and “can” is preserved, and “might” is 

not used as a synonym for either “may” or “can.” 

Using the Manual 

Throughout this Manual, there are three categories of information that are organized into text boxes 

as part of the effort to make this methods document more useful and accessible to users. Each box 

always appears with the same icon throughout the Manual: 

Recommendations for procedures and equipment. 

Consideration, or issues, that should be addressed 

Checklists of information 

The full list of Recommendation Boxes are identified on page xix as part of the Table of Contents. 

xxiv US Environmental Protection Agency 
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Introduction


CHAPTER 

1 

1.1 Background 

Protecting sediment quality is an important part of restoring and maintaining the biological integrity 

of our Nation’s waters as well as protecting aquatic life, wildlife and human health. Sediment is an 

integral component of aquatic ecosystems, providing habitat, feeding, spawning, and rearing areas for 

many aquatic organisms. Sediment also serves as a reservoir for pollutants and therefore a potential 

source of pollutants to the water column, organisms, and ultimately human consumers of those 

organisms. These pollutants can arise from a number of sources, including municipal and industrial 

discharges, urban and agricultural runoff, atmospheric deposition, and port operations. 

Contaminated sediment can cause lethal and sublethal effects in benthic (sediment-dwelling) and 

other sediment-associated organisms. In addition, natural and human disturbances can release 

pollutants to the overlying water, where pelagic (water column) organisms can be exposed. Sediment 

pollutants can reduce or eliminate species of recreational, commercial, or ecological importance, 

either through direct effects or by affecting the food supply that sustainable populations require. 

Furthermore, some sediment pollutants can bioaccumulate through the food chain and pose health 

risks to wildlife and human consumers even when sediment-dwelling organisms are not themselves 

impacted. 

The extent and severity of sediment contamination in the U.S. has been documented in the National 

Sediment Inventory (NSI)

1

 and through other historical information. The NSI screening evaluation 

of sediment contamination data indicates that associated adverse effects are probable in thousands of 

locations throughout the country. The results emphasize the widespread need to address sediment 

contamination in the U.S. 

1.2 Significance and Use of this Manual 

Sediment quality assessment is an important component of water quality protection programs. 

Sediment assessments commonly include physicochemical characterization, toxicity tests, and/or 

bioaccumulation tests, as well as benthic community analyses. USEPA’s NSI, for example, collates 

this information to develop a biennial report to Congress on sediment quality in the United States, 

required under the Water Resources Development Act of 1992. The use of consistent sediment 

collection, manipulation, and storage methods will help provide high quality samples with which 

accurate data can be obtained for the national inventory and for other programs to prevent, remediate, 

and manage contaminated sediment. 

It is now widely known that the methods used in sample collection, transport, handling, storage, and 

manipulation of sediments and interstitial waters can influence the physicochemical properties and 

1

The National Sediment Inventory, or NSI, is the database of sediment quality information used to 

develop EPA’s 1997 Report to Congress, The Incidence and Severity of Sediment Contamination in Surface 

Waters of the United States, Volume 1: National Sediment Quality Survey (U.S. EPA, 1997a). The database is 

updated periodically with new available information on sediment quality at sites throughout the U.S. 

http://www.epa.gov/OST/cs/report.html 

Chapter 1: Introduction 1-1 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

the results of chemical, toxicity, and bioaccumulation analyses. Addressing these variables in an 

appropriate and systematic manner will help assure more accurate sediment quality data and facilitate 

comparisons among sediment studies. 

This Technical Manual provides current information and recommendations for collecting and 

handling sediments for physicochemical characterization and biological testing, using procedures that 

are most likely to maintain in situ conditions, most accurately represent the sediment in question, or 

satisfy particular program needs, to help ensure consistent, high quality data collection. 

1.3 Applicability and Scope of this Manual 

This manual is intended to provide technical support to those who design or perform sediment quality 

studies under a variety of regulatory and non-regulatory programs. Information is provided 

concerning general sampling design considerations, field and laboratory facilities needed, safety, 

sampling equipment, sample storage and transport procedures, and sample manipulation issues 

common to chemical or toxicological analyses. Information contained in this manual reflects the 

knowledge and experience of several internationally-known sources including American Society for 

Testing and Materials (ASTM), Puget Sound Estuary Program (PSEP), Washington State 

Department of Ecology (WDE), United States Environmental Protection Agency (USEPA), US Army 

Corps of Engineers (ACOE), National Oceanic and Atmospheric Administration (NOAA), and 

Environment Canada. This manual attempts to present a coherent set of recommendations on field 

sampling techniques and sediment/interstitial water sample processing based on the above sources, as 

well as extensive information in the current peer-reviewed literature. 

As the scope of this manual is broad, it is impossible to adequately present detailed information on 

every aspect of sediment sampling and processing for all situations or all programs. Nor is such 

detailed guidance warranted because much of this information (e.g., how to operate a particular 

sampling device or how to use a Geographical Positioning System (GPS) device) already exists in 

other published materials referenced in this manual. Furthermore, many programs have specific 

sampling and sample processing procedures. While an attempt is made to give examples from 

different programs, the manual repeatedly instructs the reader to check their own specific program 

requirements. 

Given the above constraints, this manual: (1) presents an organized discussion of activities involved 

in sediment sampling and sample processing; (2) alerts the user to important issues that need to be 

considered within each activity; and (3) gives recommendations on how to best address the issues 

raised such that appropriate samples are collected and analyzed. An attempt is made to alert the user 

to different considerations pertaining to sampling and sample processing depending on the program 

need (e.g., dredge remediation versus status and trends monitoring). 

Figure 1-1 presents a flow chart of the general activities discussed in this manual. The organization 

of these activities reflects the desire to give field personnel and managers a useful tool for choosing 

appropriate sampling locations, characterize those locations, collect and store samples, and 

manipulate those samples for analyses. Chapters are written so that the reader could obtain 

information on only one activity or set of activities (e.g., subsampling or sample processing), if 

desired, without necessarily reading the entire manual. Many sections are cross-referenced so that 

the reader is alerted to relevant issues that might be covered elsewhere in the manual. This is 

particularly important for certain chemical or toxicological applications in which appropriate sample 

processing or laboratory procedures are associated with specific field sampling procedures. 

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Figure 1-1. Flow chart summarizing activities for collection, storage, and manipulation of 

sediments and interstitial water. 

Chapter 1: Introduction 1-3

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

The methods contained in this manual are widely applicable to any entity wishing to collect 

consistent, high quality sediment data. This manual does not provide guidance on how to implement 

any specific regulatory requirement, or design a particular sediment quality assessment, but rather it 

is a compilation of technical methods on how to best collect environmental samples that most 

appropriately address common sampling objectives. 

Although the data from these samples might be used in environmental decision-making at a variety of 

levels, this manual does not address how data are to be used. The Foreword section summarizes a 

variety of EPA programs that assess sediment quality and may benefit from the methods described in 

this manual. Other Agencies and programs are also encouraged to consider these methods in order to 

generate consistent and high quality sediment data. 

The information presented in this manual should not be viewed as the final statement on all the 

recommended procedures. Some of the areas covered in this document (e.g., sediment holding time, 

formulated sediment composition, interstitial water collection and processing) are being actively 

researched and debated. As data from sediment monitoring and research becomes more available in 

the future, EPA may update this manual as necessary. 

1-4 US Environmental Protection Agency 
CHAPTER 

2 

Technical Manual 

Sediment Monitoring and


Assessment Study Plans


Every study site and project are unique; therefore, sediment monitoring and assessment study plans 

should be carefully prepared to best meet the project objectives (MacDonald et al., 1991; see 

Figure 2-1). 

Considerations 

The initial issues that 

need to be considered 

prior to preparing study 

plans are... 

!	 define the potential problem or general 

project objective 

!	 determine what resources (e.g., time, 

money, personnel) are available for the 

project 

!	 review existing information and identify 

specific objectives of the study 

!	 determine what data are likely to be 

needed to answer project objectives, 

including the role of site-specific 

conditions and/or issues that might 

influence the process of data collection 

and analyses 

Before collecting any environmental data, it is 

important to determine the type, quantity, and 

quality of data needed to meet the project 

objectives (e.g., specific parameters to be 

measured) and support a decision based on the 

results of data collection and observation. Not 

doing so creates the risk of expending too much 

effort on data collection (i.e., more data are 

collected than necessary), not expending enough 

effort on data collection (i.e., more data are 

necessary than were collected), or expending the 

wrong effort (i.e., the wrong data are collected). 

2.1	 Data Quality Objectives 

Process 

The Data Quality Objectives (DQO) Process 

developed by EPA (GLNPO, 1994; USEPA, 

2000a) is a flexible planning tool that 

systematically addresses the above issues in a 

coherent manner. The purpose of this process is 

to improve the effectiveness, efficiency, and defensibility of decisions made based on the data 

collected, and to do so in an effective manner (USEPA, 2000a). The information compiled in the 

DQO process is used to develop a project-specific Quality Assurance Project Plan (QAPP) (see 

Chapter 7 and USEPA, 2000a) which should be used to plan the majority of sediment quality 

monitoring or assessment studies. In some instances, a programmatic QAPP may be prepared, as 

necessary, on a project-by-project basis. 

The Data Quality Objectives (DQO) process addresses the uses of the data (most importantly, the 

decision(s) to be made) and other factors that will influence the type and amount of data to be 

collected (e.g., the problem being addressed, existing information, information needed before a 

decision can be made, and available resources). From these factors the qualitative and quantitative 

data needs are determined (see Figure 2-2). DQOs are qualitative and quantitative statements that 

clarify the purpose of the monitoring study, define the most appropriate type of data to collect, and 

determine the most appropriate methods and conditions under which to collect them. The products 

of the DQO process are criteria for data quality and a data collection design that ensures that data 

will meet the criteria. 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-1 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Figure 2-1. Flow chart summarizing the process that should be implemented in designing and 

performing a monitoring study (modified from MacDonald et al. (1991)). 

2-2 US Environmental Protection Agency 
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Figure 2-2. Flow chart summarizing the Data Quality Objectives 

Process (after USEPA, 2000a). 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-3

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Checklist 

In the DQO process, the following steps should be addressed: 

� Clearly state the problem: purpose and objectives, available resources, members 

of the project team: e.g., The purpose might be to evaluate current sediment quality 

conditions, historical conditions, evaluate remediation effects, or validate a sediment 

model. It is important to review and evaluate available historical data relevant to the 

study at this point in the process. 

� Identify the decision; the questions(s) the study attempts to address: e.g., Is site A 

more toxic than site B?; Are sediments in Lake Y less toxic now than they used to be?; 

Does the sediment at site D need to be remediated? What point or nonpoint sources are 

contributing to sediment contamination? 

� Identify inputs to the decision: information and measurements that need to be 

obtained; e.g., analyses of specific contaminants, toxicity test results, biological 

assessments, bioaccumulation data, habitat assessments, hydrology, and water quality 

characterization. 

� Define the study boundaries (spatial and temporal). Identify potential sources of 

contamination; determine the location of sediment deposition zones; determine the 

frequency of sampling and need for a seasonal sampling and/or sampling during a 

specific index period; consider areas of previous dredged or fill material 

discharges/disposal. Consideration of hydraulic patterns, flow event frequency, and/or 

sedimentation rates could be critical for determining sampling frequency and locations. 

� Develop a decision rule: define parameters of interest and determine the value of a 

parameter that would cause follow-up action of some kind; e.g., exceedance of 

Sediment Quality Guideline value, NOAA Effect Range Median (ERM) value, or toxicity 

effect (e.g., 50% mortality), results in some action (Long et al., 1995). For example, in 

the Great Lakes Assessment and Remediation of Contaminated Sediments (ARCS) 

Program, one decision rule was: if total PCB concentration exceeds a particular action 

level, then the sediments will be classified as toxic and considered for remediation 

(GLNPO, 1994). Specifying decision rules or criteria is especially critical in sediment 

remediation programs and any study in which the results could be subject to legal 

scrutiny (e.g., superfund). 

� Specify limits on decision errors: establish the measurement quality objectives 

(MQOs) which include determining the level of confidence required from the data; 

precision, bids, representativeness, and completeness of data; the sample size (weight 

or volume) required to satisfy the analytical methods and QA/QC program for all 

analytical tests; the number of samples required, to be within limits on decision errors, 

and compositing needed, if any. 

� Optimize the design: choose appropriate sampling and processing methods; select 

appropriate method for determining the location of sampling stations; select an 

appropriate positioning method for the site and study. Consult historical data and a 

statistician before the study begins regarding the sampling design (i.e., the frequency, 

number, and location of field-collected samples) that will best satisfy study objectives. 

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For most programs, a Sampling and Analysis Plan (SAP) is developed prior to sampling which 

should describe the study objectives, sampling design and procedures, and other aspects of the DQO 

process outlined above (see Appendix B for an example of SAP requirements recommended by 

Washington State Department of Ecology). The following sections provide guidance on many of the 

primary issues that should be addressed in the study plan. 

2.2 Study Plan Considerations 

Monitoring and assessment studies are performed for a variety of reasons (ITFM, 1995) and sediment 

assessment studies can serve many different purposes. Developing an appropriate sampling plan 

is one of the most critical steps in monitoring and assessment studies. The sampling plan, including 

definition of the site and sampling design, will be a product of the general study objectives 

(Figure 2-1). Station location, selection, and sampling methods will necessarily follow from the 

study design. Ultimately, the study plan should control extraneous sources of variability or error to 

the extent possible so that data are appropriately representative of the sediment and fulfill the study 

objectives. 

2.2.1 Definition of the Study Area and Study Site 

The study area refers to the body of water that contains 

the study site(s) to be monitored and/or assessed, as well 

as adjacent areas (land or water) that might affect or 

influence the conditions of the study site. The study site 

refers to the body of water and associated sediments to 

be monitored and/or assessed. EMAP, for example, 

often defines a site as an area of concern (AOC) which 

might extend several miles in length, or may encompass 

large geographical or coastal areas. CERCLA defines a 

site in terms of a specific source of contamination such 

as a waste disposal area. 

The size of the study area will greatly influence the type 

of sampling design (see Section 2.3) and site positioning 

methods that are appropriate (see Section 2.6). The 

boundaries of the study area need to be clearly defined at 

the outset and should be outlined on a hydrographic chart 

or topographic map. 

2.2.2 Controlling Sources of Variability 

Common purposes of sediment 

quality studies: 

• Status and trends 

•	 Evaluating program or BMP (best 

management practice) 

effectiveness 

• Validating sediment quality models 

• Designing regulatory programs 

•	 Identifying whether significant 

contamination exists and extent of 

contamination 

•	 Identifying sources of 

contamination 

•	 Ranking existing and identifying 

emerging problems 

•	 Establishing goals for sediment 

remediation 

•	 Evaluating dredged or fill material 

discharges/disposal 

A key factor in effectively designing a sediment quality study is controlling those sources of 

variability in which one is not interested (USEPA 2000a,b). There are two major sources of 

variability that, with proper planning, can be minimized, or at least accounted for, in the design 

process, thereby ensuring a successful study. In statistical terms, the two sources of variability are 

sampling error and measurement error (USEPA 2000b; Solomon et al., 1997). 

Sampling error is the error attributable to selecting a certain sampling station that might not be 

representative of the site or population of sample units (e.g., an estuary or a CERCLA site). 

Sampling error is controlled by either: (1) using unbiased methods to select stations if one is 

performing general monitoring of a given site (USEPA, 2000b); or (2) several stations along a spatial 

gradient if a specific location is being targeted (see Section 2.3). 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-5 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Measurement error is the degree to which the investigator accurately characterizes the sampling unit 

or station. Thus, measurement error includes components of natural spatial and temporal variability 

within the sample unit as well as actual errors of omission or commission by the investigator. 

Measurement error is controlled by using standardized and comparable methods: standardized 

methods include proper training of personnel and quality assurance procedures. To help minimize 

measurement error, each station should be sampled in the same way, within a site or study, using a 

standardized set of procedures and in the same time frame to minimize confounding sources of 

variability (see Section 2.2.3). In analytical laboratory or toxicity procedures, measurement error is 

estimated by duplicate determinations on some subset of samples (but not necessarily all). Similarly, 

in field investigations, some subset of sample units (e.g., 10% of the sites) should be measured more 

than once to estimate measurement error (see Replicate and Composite Samples, Section 2.4.3). 

Measurement error can be reduced by 

analyzing multiple observations at each 

station (e.g., multiple grab samples at 

each sampling station, multiple 

observations during a season), or by 

collecting depth-integrated, or spatially 

integrated (composite) samples (see 

Section 2.4.3). 

Optimizing sampling design requires 

consideration of tradeoffs among the 

measures used, the effect that is 

considered meaningful, desired power, 

desired confidence, and resources 

available for the sampling program. 

Statistical power is the ability of a given 

sampling design to detect an effect that 

Checklist 

To minimize measurement 

error: 

� Sample all stations similarly within a study 

� Use standardized procedures 

� Sample during the same time period 

� Collect and analyze multiple samples at a 

station 

� Collect and analyze composited samples 

actually exists, and will be a product of the collection methods, analytical procedures, and quality 

control processes used. Power is typically expressed as the probability of correctly finding a 

difference among sites or between reference and test sites (e.g., toxicity or biological impairment) 

when one exists. For a fixed confidence level (e.g., 90%), power can be increased by increasing the 

sample size or the number of replicates (see Section 2.4.3 for more information). Most programs do 

not estimate power of their sampling design because this generally requires prior information such as 

pilot sampling, which entails further resources. One study (Gilfillan et al., 1995) reported power 

estimates for a shoreline monitoring program following the Valdez oil spill in Prince William Sound, 

Alaska. However, these estimates were computed after the sampling took place. It is desirable to 

estimate power before sampling is performed to ensure credibility of non-significant results (see 

Appendix C). 

2.2.3 Sampling Using an Index Period 

Most monitoring programs do not have the resources to characterize variability or to assess sediment 

quality for all seasons. Sampling can be restricted to an index period when biological and/or 

toxicological measures are expected to show the greatest response to pollution stress and withinseason variability is small (Holland, 1985; Barbour et al., 1999). This type of sampling might be 

especially advantageous for characterizing sediment toxicity, sediment chemistry, and benthic 

macroinvertebrate and other biological assemblages (USEPA, 2000c). In addition, this approach is 

useful if sediment contamination is related to, or being separated from, high flow events. By 

sampling overlying waters during both low and high flow conditions, the relative contribution of 

2-6 US Environmental Protection Agency 
Technical Manual 

each to pollutant loads or sediment contamination can be better assessed, thereby better directing 

remedial activities, or other watershed improvements. 

Those programs that sample the same site over multiple years (e.g., many EMAP and superfund 

studies), are interested in obtaining comparable data with which they can assess changes over time, 

or following remediation (GLNPO, 1994). In these cases, index period sampling is especially useful 

because hydrological regime (and therefore biological processes) is likely to be more similar between 

similar seasons than among different seasons. 

2.3 Sampling Designs 

As mentioned in earlier sections of this 

chapter, the type of sampling design used is a 

function of the study Data Quality Objectives 

and more specifically, the types of questions 

to be answered by the study. A summary of 

various sampling designs is presented in 

Figure 2-3 along with recommendations 

concerning the conditions under which a 

given design is appropriate. Generally, 

sampling designs fall into two major 

categories: random or probabilistic, and 

targeted (USEPA, 2000b). USEPA (2000b;c) 

present a thorough discussion of sampling 

design issues and detailed information on 

different sampling designs. Some programspecific guidance documents (e.g., 

USEPA/ACOE 1991, 1998 for dredged 

material disposal issues) also discuss relevant 

sampling designs. Table 2-1 presents 

suggested sampling designs given different 

Sampling Design refers to the array, or network, 

of sampling sites selected for a monitoring 

program; usually taking one of two forms: 

•	 Probabilistic Design — Network that includes 

sampling sites selected randomly in order to 

provide an unbiased assessment of the 

condition of the waterbody at a scale above 

the individual site or stream; can address 

questions at multiple scales. 

•	 Targeted Design — Network that includes 

sampling sites selected based on known 

existing problems, knowledge of upcoming 

events in the watershed, or a surrounding 

area that will adversely affect the waterbody 

such as development or deforestation; or 

installation of BMPs or habitat restoration that 

are intended to improve waterbody quality; 

provides assessments of individual sites or 

reaches. 

overall objectives and constraints. Appendix A presents hypothetical examples of sediment quality 

monitoring designs given different objectives or regulatory applications. 

2.3.1 Probabilistic and Random Sampling 

Probability-based or random sampling designs avoid bias in the results of sampling by randomly 

assigning and selecting sampling locations. A probability design requires that all sampling units 

have a known probability of being selected. Both EPA’s Environmental Monitoring Assessment 

Program and NOAA’s National Status and Trends Program use a probabilistic sampling design to 

infer regional and national patterns with respect to contamination or biological effects. 

Sites can be selected on the basis of a truly random scheme or in a systematic way (e.g., sample every 

10 meters along a randomly chosen transect). In simple random sampling, all sampling units have 

an equal probability of selection. This design is appropriate for estimating means and totals of 

environmental variables if the population is homogeneous. To apply simple random sampling, it is 

necessary to identify all potential sampling times or locations, then randomly select individual times 

or locations for sampling. 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-7 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

In grid or systematic sampling, the first sampling location is chosen randomly and all subsequent 

stations are placed at regular intervals (e.g. 50m apart) throughout the study area. Clearly, the 

number of sampling locations could be large if the study area is large and one desires “fine-grained” 

contaminant or toxicological information. Thus, depending on the types of analyses desired, such 

sampling might become expensive unless the study area is relatively small and/or the density of 

stations (that is how closely spaced are the stations) is relatively low. Grid sampling might be 

effective for detecting previously unknown “hot spots” in a limited study area. 

Figure 2-3. Description of various sampling methods. Adapted from USEPA, 2000c. 

In stratified designs, the selection probabilities might differ among strata. Stratified random 

sampling consists of dividing the target population into non-overlapping parts or subregions (e.g., 

ecoregions, watersheds, or specific dredging or remediation sites) termed strata to obtain a better 

estimate of the mean or total for the entire population. The information required to delineate the 

strata and estimate sampling frequency must either be known prior to sampling using historic data, 

available information and knowledge of ecological function, or obtained in a pilot study. Sampling 

locations are randomly selected from within each of the strata. Stratified random sampling is often 

used in sediment quality monitoring because certain environmental variables can vary by time of day, 

season, hydrodynamics, or other factors. Major environmental monitoring programs that incorporate 

a stratified random design include EPA’s Mid-Atlantic Integrated Assessment (MAIA). One 

disadvantage of using random designs is the possibility of encountering unsampleable sites that were 

randomly selected by the computer. Such problems result in the need to reposition the vessel to an 

alternate location. Furthermore, if one is sampling to determine the percent spatial extent of 

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Technical Manual 

degradation, it might be important to sample beyond the boundaries of the study area to better 

evaluate the limits of the impacted area. 

A related design is multistage sampling in which large subareas within the study area are first 

selected (usually on the basis of professional knowledge or previously collected information). 

Stations are then randomly located within each subarea to yield average or pooled estimates of the 

variables of interest (e.g., concentration of a particular contaminant or acute toxicity to Hyalella) for 

each subarea. This type of sampling is especially useful for statistically comparing variables among 

specific parts of a study area. 

Table 2-1. Suggestions for selecting an appropriate sampling design (from USEPA 2000b). 

If you are... and you have... consider 

using... 

in order to... 

performing a screening phase of 

an investigation and with an 

understanding of a relatively 

small-scale problem 

a limited budget and/or a 

limited schedule 

judgmental or 

targeted 

sampling 

assess whether further investigation is 

warranted that should include a 

statistical probabilistic sampling 

design. 

developing an understanding of 

when contamination is present 

adequate budget for the 

number of samples needed 

systematic 

sampling 

have coverage of the time periods of 

interest. 

developing an understanding of 

where contamination is present 

adequate budget for the 

number of samples needed 

grid sampling have coverage of the area of concern 

and have a given level of confidence 

that you would have detected a hot 

spot of a given size. 

estimating a population mean adequate budget 

budget constraints and 

analytical costs that are high 

compared to sampling costs 

budget constraints and 

professional knowledge or 

inexpensive screening 

measurement that can assess 

the relative amounts of the 

contaminant at specific field 

sample locations 

systematic or 

grid sampling 

compositing 

ranked set 

sampling 

also produce information on spatial or 

temporal patterns. 

produce an equally precise or a more 

precise estimate of the mean with 

fewer analyses and lower cost. 

reduce the number of analyses needed 

for a given level of precision. 

estimating a population mean or 

proportion 

spatial or temporal 

information on contaminant 

patterns 

stratified 

sampling 

increase the precision of the estimate 

with the same number of samples, or 

achieve the same precision with fewer 

samples and lower cost. 

delineating the boundaries of an 

area of contamination 

a field screening method stratified 

sampling 

simultaneously uses all observations 

in estimating the mean. 

estimating the prevalence of a 

rare trait 

analytical costs that are high 

compared to sampling costs 

random and 

composite 

sampling 

produce an equally precise or more 

precise estimate of the prevalence with 

fewer analyses and lower cost. 

assessing whether a population 

contains a rare trait 

the ability to physically mix 

aliquots from the samples 

and then retest additional 

aliquots 

composite 

sampling and 

retesting 

classify all samples at reduced cost by 

not analyzing every sample. 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-9 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Recommendation Box #1 

What type of sampling strategy should be used? 

� Historical data, if available, should be considered when selecting sampling stations. 

� Location of sediment depositional zones can be important in defining subareas for 

sampling or for stratifying sampling in some programs. 

� If the objective of the survey is to identify areas of toxic and/or contaminated sediments on 

a quantitative spatial and/or temporal basis (e.g., superfund site), a systematic or regular 

grid-sampling strategy might be most appropriate (USEPA, 2000b). 

� If the monitoring objective is to determine sediment contamination originating from a 

specific source or tributary, a targeted site location design might be most appropriate. 

Factors affecting dispersion of substances or materials from the point source (e.g., 

currents) should be considered. 

� Stratified random sampling should be used where historical, sediment-mapping data are 

available and there are well-defined zones of different sediment types or adjacent land 

uses (Burton, 1991). This design is commonly used in NOAA National Status and Trends 

(NS&T) monitoring of sediment quality to ensure that the data can be attributed to the 

strata in which they were collected (Long et al., 1996). 

� For dredge management programs, multi-stage, stratified-random, or even targeted 

sampling is often appropriate, since the need is to represent specific areas to be dredged 

and disposed. 

� For watershed or regional assessment programs, a probabilistic sampling design might 

be most appropriate. 

� Small-scale, targeted study designs might require many samples within a small area if 

fine spatial resolution is needed (e.g., Superfund). 

Use of random sampling designs might also miss relationships among variables, especially if there is 

a relationship between an explanatory and a response variable. As an example, estimation of benthic 

response or contaminant concentration, in relation to a discharge or landfill leachate stream, requires 

sampling targeted around the potential contaminant source, including stations presumably unaffected 

by the source (e.g., Warwick and Clarke, 1991). A simple random selection of stations is not likely 

to capture the entire range needed because most stations would likely be relatively removed from the 

location of interest. 

2.3.2 Targeted Sampling Designs 

In targeted (also referred to as judgmental, or model-based) designs, stations are selected based on 

prior knowledge of other factors, such as contaminant loading, depth, salinity, and substrate type. 

The sediment studies conducted in the Clark Fork River (Pascoe and DalSoglio, 1994; Brumbaugh et 

al., 1994), in which contaminated areas were a focus, used a targeted sampling design. 

Targeted designs are useful if the objective of the investigation is to screen an area(s) for the 

presence or absence of contamination at levels of concern, such as risk-based screening levels or 

toxicity, or to compare specific sediments against reference conditions or biological guidelines. In 

general, targeted sampling is appropriate for situations in which any of the following apply (USEPA, 

2000b): 

2-10 US Environmental Protection Agency 
Technical Manual 

•	 The site boundaries are well defined or the site physically distinct (e.g., superfund or CERCLA 

site, proposed dredging unit). 

• Small numbers of samples will be selected for analysis/characterization. 

• Information is desired for a particular condition (e.g., “worst case”) or location. 

•	 There is reliable historical and physical knowledge about the feature or condition under 

investigation. 

•	 The objective of the investigation is to screen an area(s) for the presence or absence of 

contamination at levels of concern, such as risk-based screening levels. (Note that if such 

contamination is found, follow-up sampling is likely to involve one or more statistical designs to 

compare specific sediments against reference conditions, chemical or biological guidelines, or 

applicable sediment quality values). 

• Schedule or budget limitations preclude the possibility of implementing a statistical design. 

•	 Experimental testing of a known pollution gradient to develop or verify testing methods or 

models (i.e., as in evaluations of toxicity tests, Long et al., 1990). 

Because targeted sampling designs often can be quickly implemented at a relatively low cost, this 

type of sampling can often meet schedule and budgetary constraints that cannot be met by 

implementing a statistical design. In many situations, targeted sampling offers an additional 

important benefit of providing an appropriate level-of-effort for meeting investigation objectives 

without excessive consumption of project resources. 

Targeted sampling, however, limits the inferences made to the stations actually sampled and 

analyzed. Extrapolation from those stations to the overall population from which the stations were 

sampled is subject to unknown selection bias. This bias might be unimportant for those regulatory 

programs in which information is needed for a particular condition or location (e.g., Dredged 

Management Materials Program or Superfund). 

2.4 Measurement Quality Objectives 

As noted in Section 2.1, a key aspect of the DQO process is specifying measurement quality 

objectives (MQOs): statements that describe the amount, type, and quality of data needed to address 

the overall project objectives. 

Appendix B presents examples of MQOs and sampling designs that have been used in several 

different programs. Also included in Appendix B is excerpted information from Washington 

Department of Ecology’s Sampling and Analysis Plan Guidance (WDE, 1995). Similar to Quality 

Assurance Project Plans (QAPP) mentioned earlier in Section 2.1, a Sampling and Analysis Plan 

includes, among other things, many of the elements of the Data Quality Objectives Process, including 

MQOs. 

A key factor determining the types of MQOs needed in a given project or study is the types of 

analyses required because these will determine the amount of sample required (see Section 2.4.1) and 

how samples are processed (see Chapter 4). The case examples presented in Appendix B illustrate a 

variety of chemical, biological, and toxicological analyses that are often included in sediment quality 

monitoring projects. Metals, organic chemicals (including pesticides, PAHs, and PCBs), whole 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-11 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

sediment toxicity, and organism bioaccumulation of specific target chemicals, are frequently 

analyzed in many sediment monitoring programs. 

A number of other, more “conventional” parameters, are also often analyzed as well to help interpret 

chemical, biological, and toxicological data collected in a project. Table 2-2 summarizes many of the 

commonly measured conventional parameters and their uses in sediment quality studies (WDE, 

1995). It is important that conventional parameters receive as much careful attention, in terms of 

sampling and sample processing procedures, as do the contaminants or parameters of direct interest. 

The guidance presented in Chapters 3 and 4 provides information on proper sampling and sample 

processing procedures, respectively, to ensure that one has appropriate samples for these analyses. 

This section concentrates on three aspects of MQO development that are generally applicable to all 

sediment quality studies, regardless of the particular program or objectives: sample volume, number 

of samples, and replication vs. composite sampling. 

Checklist 

MQOs are defined in terms of the following attributes: 

� Detection Limit – The lowest concentration of an analyte that a specified analytical 

procedure can reliably detect. 

� Bias – The difference between an observed value and the “true” value (or known 

concentration) of the parameter being measured; bias is the first component of accuracy, 

which is the ability to obtain precisely a nonbiased (true) value. 

� Precision – The level of agreement among multiple measurements of the same 

characteristic; precision is the second component of accuracy. 

� Representativeness – The degree to which the data collected accurately represent the 

population of interest (e.g., contaminant concentrations). 

� Comparability – The similarity of data from different sources included within individual or 

multiple data sets; the similarity of analytical methods and data from related projects 

across areas of concern. 

� Completeness – The quantity of data that is successfully collected with respect to the 

amount intended in the experimental design. 

2.4.1 Sample Volume 

Before commencing a sampling program, the type and number of analyses and tests should be 

determined, and the required volume of sediment per sample calculated. Each physicochemical and 

biological test requires a specific amount of sediment which, for chemical analyses, depends on the 

detection limits attainable and extraction efficiency by the procedure and, for biological testing, 

depends on the test organisms and test method. Typical sediment volume requirements for each end 

use are summarized in Table 2-3. Specific program guidance should be consulted regarding sample 

volumes that might be required. 

2-12 US Environmental Protection Agency 
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Table 2-2. Conventional sediment variables and their use in sediment investigations (Adapted from 

WDE, 1995). 

Conventional Sediment Variable Use 

Total organic carbon (TOC) • Normalization of the concentrations of 

nonionizable organic compounds 

• Identification of appropriate reference sediments 

for biological tests 

Acid Volatile Sulfide (AVS) • Normalization of the concentrations of divalent 

metals in anoxic sediments 

Sediment grain size • Identification of appropriate reference sediments 

for biological tests 

• Interpretation of sediment toxicity test data and 

benthic macroinvertebrate abundance data 

• Evaluation of sediment transport and deposition 

• Evaluation of remedial alternatives 

Total solids • Expression of chemical concentrations on a dryweight basis 

Ammonia • Interpretation of sediment toxicity test data 

Total sulfides • Interpretation of sediment toxicity test data 

When determining the sample volumes necessary, one must know what is required for all of the 

sample analyses (considering adequate replication) and it is also helpful to know the general 

characteristics of the sediments being sampled. For example, if interstitial water analyses or elutriate 

tests are to be conducted, the percent water (or percent dry weight) of the sediment will greatly affect 

the amount of water extracted. Many non-compacted, depositional sediments have interstitial water 

contents ranging from 30 to 70%. However, interstitial waters are very difficult to remove from 

sandy or gravel-rich sediments. 

For benthic macroinvertebrate bioassessment analyses, sampling a prescribed area of benthic 

substrate is at least as important as sampling a given volume of sediment. In many programs, 

macroinvertebrates are sampled using multiple grab samples within a given station location, typically 

to a standard sediment depth (e.g., per 10-20 cm of sediment; Klemm et al., 1990; GLNPO, 1994; 

Long et al., 1996; USEPA 2000c ). More than 6 liters of sediment from each station might be 

necessary in order to have adequate numbers of organisms for analyses, especially in many lakes, 

estuaries, and large rivers (Barbour et al., 1999). However, this is very site specific and should be 

determined by the field sampling crew. This only applies to whole sediment sampling methods and 

not to surficial stream methods using methods such as kick-nets and Surber samplers. If the sediment 

quality triad approach is used (i.e., biological, toxicological, and physicochemical analyses 

performed on samples from the same sites), more than 10 liters of sediment from each site might be 

required depending on the specific analyses conducted. NOAA routinely collects 7-8 liters of 

sediment at each station for multiple toxicity tests and chemical analyses (Long et al., 1996). 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-13 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table 2-3. Typical sediment volume requirements for various analyses per sample 

Sediment Analysis Minimum Sample Volume 

Inorganic chemicals 90 mL 

Non-petroleum organic chemicals 230 mL 

Other chemical parameters 

(e.g., total organic carbon, moisture content) 

300 mL 

Particle size 230 mL 

Petroleum hydrocarbons1 250-1000 mL 

Acute and chronic whole sediment toxicity tests2 1-2 L 

Bioaccumulation tests3 15 L 

Benthic macroinvertebrate assessments 8-16 L 

Pore water extraction 2 L 

Elutriate preparation 1 L 

1	 The maximum volume (1000 mL) is required only for oil and grease analysis; otherwise, 250 

mL is sufficient. 2	 Amount needed per whole sediment test (i.e., one species) assuming 8 replicates per sample 

and test volumes specified in USEPA, 2000d 

3 Based on an average of 3 L of sediment per test chamber and 5 replicates (USEPA, 2000d). 

Recommendation Box #2 

How many samples and how much sample volume should be 

collected? 

� The testing laboratory should be consulted to confirm the amount of sediment required 

for all desired analyses. 

� The amount of sediment needed from a given site will depend on the number and types 

of analyses to be performed. If biological, toxicological, and chemical analyses are 

required (sediment triad approach), then at least 10 liters of sediment might be required 

from each station. 

� Since sampling events might be expensive and/or difficult to replicate, it is useful to 

collect extra samples if possible, in the event of problems encountered by the analytical 

laboratories, failure of performance criteria in assays, or need to verify/validate results. 

� Consider compositing samples from a given station or across similar station types to 

reduce the number of samples needed. 

2-14 US Environmental Protection Agency 
Technical Manual 

2.4.2 Number of Samples 

The number of samples collected directly affects 

the representativeness and completeness of the 

data for purposes of addressing project goals. As 

a general rule, a greater number of samples will 

yield better definition of the areal extent of 

contamination or toxicity. Many programs 

specify a certain number of samples per location 

(e.g., CERCLA site or dredging unit). 

Accordingly, sample requirements should be 

determined on a case-by-case basis. The number 

of samples to be collected will ultimately be an 

outcome of the questions asked. For example, if 

one is interested in characterizing effects of a 

point source or a gradient (e.g., effects of certain 

tributaries or land uses on a lake or estuary), then 

many samples in a relatively small area might 

need to be collected and analyzed. If, however, 

Considerations


The appropriate number


of samples is usually


determined by...


! size of the study site 

!	 type and distribution of the 

contaminants being measured 

!	 characteristics and homogeneity of the 

sediment 

!	 concentrations of contaminants likely to 

be found in the sediments 

! sample volume requirements 

!	 desired level of statistical resolution or 

precision 

one is interested in screening “hot spots” or locations of high contamination within a watershed or 

water body, relatively few samples at regularly-spaced locations might be appropriate. In most 

monitoring and assessment studies, the number of samples to be collected usually results from a 

compromise between the ideal and the practical. The major practical constraints are the costs of 

analyses and logistics of sample collection. 

The major costs associated with the collection of sediment samples are those for travel to the site and 

for sample analysis. The costs of actual on-site sampling are minimal by comparison. Consequently, 

it is good practice to collect an excess number of samples, and a subset equal to the minimum 

number required is selected for analysis. The archived replicate samples can be used to replace lost 

samples, for data verification, to rerun analyses yielding questionable results, or for the independent 

testing of a posteriori hypotheses that might arise from screening the initial data. However, storage 

of sediments might result in changes in bioavailability of chemical contaminants (see Section 4.5). 

Therefore, follow-up testing of archived samples should be done cautiously. 

2.4.3 Replicate and Composite Samples 

Replicate Samples 

As mentioned in the previous section, the number of samples collected and analyzed will always be a 

compromise between the desire of obtaining high quality data that fully addresses the overall project 

objectives (MQOs) and the constraints imposed by analytical costs, sampling effort, and study 

logistics. Therefore, every sampling program needs to find a balance between obtaining information 

to satisfy the stated DQOs or study goals in a cost-effective manner, and yet have enough confidence 

in the data to make appropriate decisions (e.g., remediation, dredging; Step 3 in the DQO process, 

Figure 2-2). Two different concepts are used to satisfy this challenge: replication and sample 

compositing. 

Replication is used to assess precision of a particular measure and can take many forms depending on 

the type of precision desired. For most programs, analytical replicates are the most frequently used 

form of replication because most MQOs are concerned with analytical data quality (see examples in 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-15 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Appendix B). The extent of analytical replication (duplicates) varies with the program or study 

DQOs. Performing duplicate analyses on at least 10% of the samples collected is considered 

satisfactory for most programs (GLNPO, 1994; USEPA/ACOE, 1991; PSEP, 1997a; USEPA/ACOE, 

1998). An MQO of � 20 - 30% relative percent difference (RPD) is commonly used for analytical 

replicates depending on the analyte. 

Field replicates can provide useful 

information on the spatial distribution of 

contaminants at a station and the 

heterogeneity of sediment quality within 

a site. Furthermore, field replicates 

provide true replication at a station 

(analytical replicates and split samples at 

a station provide a measure of precision 

for a given sample, not the station) and 

therefore can be used to statistically 

compare analyses (e.g., toxicity, tissue 

concentration, whole sediment 

concentration) across stations. 

Results of field replicate analysis yield 

the overall variability or precision of both 

the field and laboratory operations (as 

well as the variability between the 

replicate samples themselves, apart from 

any procedural error). Because field 

replicate analyses integrate a number of 

different sources of variability, they 

might be difficult to interpret. As a 

result, failure to meet a precision MQO 

Checklist 

Replication can take several 

forms and satisfy different 

purposes: 

� Collect field replicate samples at a station if 

there is a need to statistically compare 

results among stations within a site. 

� Analytical replicates: separate laboratory 

analyses on subsamples from the same 

field sample. 

� Field replicates: separate samples collected 

at a station each of which is analyzed 

individually. 

� Field-split replicates: a single field sample is 

split into subsamples, each of which is then 

analyzed individually. 

� Compositing samples is one way to reduce 

the number of replicates needed for 

analysis. 

for field replicates might or might not be a cause of concern in terms of the overall study objectives 

but would suggest some uncertainty in the data. Many monitoring programs perform field replicates 

at 10% of the stations sampled in the study as a quality control procedure. An MQO of � 30 - 50% 

relative percent difference (RPD) is typically used for field replicates depending on the analyte (see 

examples in Appendix B). Many regulatory programs (e.g., Dredged Disposal Management within 

the Puget Sound Estuary Program) routinely use 3-5 field replicates per station. Appendix C 

summarizes statistical considerations in determining the appropriate number of replicate samples 

given different sampling objectives. 

Split sample replication is less commonly performed in the field because many programs find it more 

useful to quantify data precision through the use of analytical and field replicates described above. 

However, split sample replication is frequently used in the laboratory in toxicity and bioaccumulation 

analyses (USEPA, 2000d) and to verify homogeneity of test material in spiked sediment tests (see 

Section 5.3). In the field, samples are commonly split for different types of analyses (e.g., toxicity, 

chemistry, benthos) rather than to replicate a given sample. This type of sample splitting or 

subsampling is further discussed in Section 4.2. 

Composite Samples 

A composite sample is one that is formed by combining material from more than one sample or 

subsample. Because a composite sample is a combination of individual aliquots, it represents an 

2-16 US Environmental Protection Agency 
Technical Manual 

“average” of the characteristics making up the 

sample. Compositing, therefore, results in a less 

detailed description of the variability within the 

site as compared to taking field replicates at each 

station. However, for characterizing a single 

station, compositing is generally considered an 

excellent way to provide quality data with 

relatively low uncertainty. Furthermore, many 

programs find it useful to average the naturally 

heterogeneous physicochemical conditions that 

often exist within a station (or dredging unit, for 

example), even within a relatively small area 

(GLNPO, 1994; PSEP, 1997a; ASTM, 2000a). 

Many programs find it useful to composite 3-5 

samples from a given location or depth strata 

(PSEP, 1997a; GLNPO, 1994). 

Considerations 

Composite samples are 

collected because 

they... 

!	 Yield a single “average estimate for a 

given station with less cost than using 

replicates. 

!	 Can obtain useful information over 

many stations at reduced analytical 

costs. 

!	 Are an efficient way to provide sufficient 

sample volume for multiple types of 

analyses, particularly biological/toxicity 

analyses. 

Compositing is also a practical way to control analytical costs while providing information from a 

large number of stations. For example, with relatively little more sampling effort, five analyses can 

be performed to characterize a project segment or site by collecting 15 samples and combining sets of 

three into five composite samples. The increased coverage afforded by taking composite samples 

might justify the increased time and cost of collecting the extra 10 samples in this case 

(USEPA/ACOE, 1998). Compositing is also an important way to provide the large sample volumes 

required for some biological tests (see Table 2-1) and for multiple types of analyses (e.g., physical, 

chemical, toxicity, and benthos). However, compositing is not recommended where combining 

samples could serve to “dilute” a highly toxic but localized sediment “hot spot” (WDE, 1995; 

USEPA/ACOE, 1998). Also, samples from stations with very different grain size characteristics or 

different stratigraphic layers of core samples should not be composited (see Section 4.3). 

Checklist 

Before sampling: 

� Review available information about the site including physical conditions and potential 

contaminant sources. 

� Inspect the site to confirm that the sampling design and procedure chosen are feasible. 

� Perform a pilot or screening sampling, if possible, to ensure that sampling equipment and 

procedures are adequate for the types of stations selected. 

2.5	 Site-Specific Considerations for Selecting Sediment Sampling 

Stations 

Several site-specific factors might ultimately influence the appropriate location of sampling stations, 

both for large-scale monitoring studies, in which general sediment quality status is desired, and for 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-17 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

smaller, targeted studies, in determining the need for sediment remediation. If a targeted or stratified 

random sampling design is chosen, it might be important to locate sediment depositional and 

erosional areas to properly identify contaminant regimes. Table 2-4 presents a summary of sitespecific factors that should be considered when developing a sampling plan. A comprehensive 

review of such considerations is provided by Mudroch and MacKnight (1994). 

Table 2-4. Practical considerations for site-specific selection of sampling stations in developing a 

sampling plan. 

Activity Consideration 

Determination of areas where 

sediment contamination might occur 

Hydrologic information 

• quality and quantity of runoff 

• potential depositional inputs of total suspended solids 

• up-wellings 

• seepage patterns 

Determination of depositional and 

erosional areas 

Bathymetric maps and hydrographic charts 

• water depth 

• zones of erosion, transport, and deposition 

• bathymetry 

• distribution, thickness, and type of sediment 

• velocity and direction of currents 

• sedimentation rates 

Climatic conditions 

• prevailing winds 

• seasonal changes in temperature, precipitation, solar radiation, 

etc. 

• tides, seiches 

• seasonal changes in anthropogenic and natural loadings 

Determination of potential sources 

of contamination 

Anthropogenic considerations 

location of urban centers 

• historical changes in land use 

• types, densities, and size of industries 

• location of waste disposal sites 

• location of sewage treatment facilities 

• location of stormwater outfalls and combined sewer overflows 

• location, quantity, and quality of effluents 

• previous monitoring and assessment or geochemical surveys 

• location of dredging and open-water dredged material disposal 

sites 

• location of historical waste spills 

Factors affecting contaminant 

bioavailability 

Geochemical considerations 

• type of bedrock and soil/sediment chemistry 

• physical and chemical properties of overlying water 

Determination of representativeness 

of samples 

• area to be characterized 

• volume to be characterized 

• depth to be characterized 

• possible stratification of the deposit to be characterized 

2-18 US Environmental Protection Agency 
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2.5.1 Review Available Data 

Review of available historical and physical data is critical in the sample selection process and 

subsequent data interpretation. Local experts should be consulted to obtain information on site 

conditions and the origin, nature, and degree of contamination. Other potential sources of 

information include government agency records, municipal archives, harbor commission records, 

past geochemical analyses, hydrographic surveys, bathymetric maps, and dredging/disposal history. 

Potential sources of contamination should be identified and their locations noted on a map or chart of 

the proposed study area. It is important that recent hydrographic or bathymetric data be used in 

identifying representative sampling locations, especially for dredging or other sediment removal 

projects. The map or chart should also note adjacent land and water uses (e.g., fuel docks, storm 

drains, etc.). The quality and age of the available data should be critically weighed. 

2.5.2 Site Inspection 

A physical inspection of the site is strongly recommended when developing a study plan, in order to 

assess the completeness and validity of the collected historical data, and to identify any significant 

changes that might have occurred at the site or study area (Mudroch and MacKnight, 1994). A site 

inspection of the immediate drainage area and upstream watershed might also identify potential 

stressors (such as erosion), and help determine appropriate sampling gear (such as corer vs. grab 

samplers and boat type) and sampling logistics. 

If resources allow, it is useful to perform some screening or pilot sampling and analyses at this stage 

to further refine the actual sampling design needed. Pilot sampling is particularly helpful in defining 

appropriate station locations for targeted sampling or to identify appropriate strata or subareas in 

stratified or multistage sampling, respectively. 

2.5.3 Identify Sediment Deposition and Erosional Zones 

When study DQOs direct sampling to the highest contamination levels or specific subareas of a site, 

it might be important to consider sediment deposition and sediment erosional zones, since grain size 

and related physicochemical characteristics (including conventional parameters such as total organic 

carbon and acid volatile sulfide, as well as contaminants), are likely to vary between these two types 

of zones. Depositional zones typically contain fine-grained sediment deposits which are targeted in 

some sampling programs because fine-grained sediments tend to have higher organic carbon content 

(and are therefore a more likely repository for pollutants) relative to larger sediment particle size 

fractions (e.g., sand and gravel) (ASTM, 2000a; Environment Canada, 1994). However, for some 

programs such as remediation dredging evaluations or superfund, eroding sediment beds and nondepositional zones might be of most concern as these could be a major source of pollutants in the 

water column and in organisms (USEPA/ACOE, 1991,1998). 

Various non-disruptive technologies are available to assist in the location of fine-grained sediments 

ranging from simplistic to more advanced. For example, use of a steel rod or PVC pipe can be used 

in many shallow areas to quickly and easily probe the sediment surface to find coarse (sand, gravel) 

vs. fine sediments (silt, clay). This technique can not, however, determine sediment grain size at 

depth. Other more advance methods, including acoustic survey techniques (e.g., low frequency echo 

sounding, seismic reflections, etc.) and side-scan sonar used with a sub-bottom profiler (Wright et al., 

1987), can provide useful information on surficial as well as deeper sediment profiles. However, 

these techniques are often limited in their accuracy and have high equipment costs (Guignè et al., 

1991). 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-19 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Aerial reconnaissance, with or without satellite imagery, might assist in visually identifying 

depositional zones where clear water conditions exist. These methods are not reliable, however, if 

waters are turbid. Other methods that can be used to locate sediment deposition zones include grab 

sampling, inspection by divers, or photography using an underwater television camera or remotely 

operated vehicle (Burton, 1992; ASTM, 2000a). 

2.6 Positioning Methods for Locating Sampling Stations 

The most important function of positioning technology is to determine the location of the sampling 

station (e.g., latitude and longitude), so that the user can later re-sample to the same position 

(USEPA, 1987). Knowing the precise location of sampling stations is also important so that 

regulators can determine if the area(s) of interest have been sampled. There are a variety of 

navigation and/or position-fixing systems available, including optical or line-of-site techniques, 

electronic positioning systems, and satellite positioning systems. Global Positioning System (GPS) 

is generally regarded as the positioning technique of choice as it is accurate, readily available, and 

often less expensive than many other comparably sophisticated systems. Given the removal of 

selective availability of satellite data by the U.S. military, GPS is now capable of high accuracy 

positioning (1-10 m). The characteristics, advantages, and disadvantages of a variety of positioning 

systems are summarized in Appendix D. 

Recommendation Box #3 

How should station positioning be performed? 

� Depending on level of accuracy needed, regular calibration of the positioning system by at 

least two methods might be required to ensure accuracy. 

� For monitoring and assessment studies of large areas (e.g., large lakes or offshore 

marine environments), where an accuracy of ± 100 m typically is sufficient, either the 

Long Range Navigation (LORAN) or Global Positioning System (GPS) system is 

recommended. 

� For near-shore areas, or areas where the sampling stations are numerous or located 

relatively close together, GPS or a microwave system should be used if the required 

position accuracy is less than 10 m. Where visible or suitable and permanent targets are 

available, RADAR can be used if the required position accuracy is between 10 and 100 

m. 

� For small water bodies and urban waterfronts, GPS is often capable of giving precise 

location information. Alternatively, visual angular measurements (e.g., sextant) by an 

experienced operator, a distance line, or taut wire could also provide accurate and 

precise positioning data. 

Regardless of the type of system selected, calibration of the system is recommended by using at least 

two of these methods to ensure accuracy particularly for stations that will be reoccupied. At each 

sampling station, a fathometer or meter wheel can be used to determine the sampling depth. This 

will ensure that the water is the desired depth and the bottom is sufficiently horizontal for proper 

operation of sampling equipment. Ideally, it is best to print out a copy of the ship’s location from the 

GPS monitor navigation chart, as well as the latitude / longitude, so the sampling station can be 

placed in a spatial context. 

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2.7	 Preparations for Field 

Sampling 

Proper preparation for any field sampling 

study is an essential part of Quality 

Assurance that ensures a successful project 

outcome and adherence to the objectives 

specified in the Quality Assurance Project 

Plan (QAPP). Chapter 7 further discusses 

related Quality Assurance/Quality Control 

procedures that should be used in sediment 

quality studies. 

Prior to performing field work, 

characteristics of the site and accessibility of 

the individual sampling stations should be 

ascertained. Pictures of sampling stations 

both before as well as during sampling are 

often useful to ensure that the correct stations 

were sampled and to document weather and 

water conditions during sampling. Adequate 

reconnaissance of stations prior to sampling 

is also valuable for preparing against 

potential sampling hazards or unforeseen 

difficulties. Such a reconnaissance can also 

help determine the necessary time needed to 

perform the desired sampling (i.e., time to get 

from one station to the next). 

Checklist 

Logistical 

Considerations: 

� site description


� study site accessibility


� adequate sampling platform


� qualified personnel


� specific responsibilities of field crew


� locating and maintaining stations


� adequate time for sampling


� adequate space and equipment


� communication system


� access to temporary field storage


� health, safety, and waste management


� emergency plans and equipment


� number of samples to be collected


� sample holding times


The appropriate vessel or sampling platform is one of the most important considerations in preparing 

for field sampling. The vessel must be appropriate for the water body type, and should provide 

sufficient space and facilities to allow collection, any on-board manipulation, and storage of samples. 

Ice chests or refrigeration might be required for sample storage, depending on the time course of the 

operation. The vessel should provide space for storage of decontamination materials, as well as 

clean sampling gear and containers to avoid contamination risks associated with normal vessel 

operations. Space for personal safety equipment is also required. 

Additionally, the vessel should be equipped with sufficient winch power and cable strength to handle 

the weight of the sampling equipment, taking into account the additional suction pressure associated 

with extraction of the sediments. Large sampling devices typically weigh between 50 and 400 kg 

empty, and when filled with wet sediment might weigh from 125 to over 500 kg. 

Care should be taken in operating the vessel to minimize disturbances of the sediment to be sampled 

as well as sampling equipment. This would include physical disturbance through propellar action 

and chemical contamination from engines or stack emissions. For example, Page et al. (1995) 

reported that they positioned the ships’ stern into the wind to prevent stack gases from blowing onto 

sampling equipment during deployment, recovery, and subsampling of sediments in Prince William 

Sound, Alaska. 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-21 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

The sampling plan and projected time schedule should be posted for view by all personnel. The 

names, addresses, and telephone numbers of all participants involved with the preparation and 

execution of the sampling program should be available to all participants, and the duties and 

responsibilities of each participant clearly documented. The study supervisor should ensure that the 

appropriate personnel clearly understand their role and are capable of carrying out their assigned 

responsibilities and duties. Contingency planning should address the need for backup personnel in 

the event of accident or illness. 

A variety of sampling and sample handling equipment and supplies are often needed in sediment 

monitoring studies. Besides the actual samplers themselves (e.g., grab or core device to be used), 

equipment is needed to remove and process the samples such as spatulas, scoops, pans or buckets, 

and gloves. If it is important to maintain anoxic conditions of the sample, a glovebox and inert gas 

source (e.g., nitrogen) is needed. Sample storage and transport equipment and supplies need to be 

available as well. These include refrigeration, ice chests, dry ice or ice, insulation material to 

stabilize samples in transport, custody seals, and shipping airbills. 

The reagents for cleaning, operating or calibrating equipment, and/or for collecting, preserving or 

processing samples should be handled by appropriately qualified personnel and the appropriate data 

for health and safety (e.g., Material Safety Data Sheets) should be available. Written approved 

protocols and standard operating procedures (including QA/QC requirements) should be readily 

accessible at all times, to ensure proper and safe operation of equipment. Data forms and log books 

should be prepared in advance so that field notes and data can be quickly and efficiently recorded. 

Extra forms should be available in the event of a mishap or loss. These forms and books should be 

waterproof and tear resistant. Under certain circumstances audio or audio/video recordings might 

prove valuable. 

All equipment used to collect and handle samples must be cleaned and all parts examined to ensure 

proper functioning before going into the field. A repair kit should accompany each major piece of 

equipment in case of equipment failure or loss of removable parts. Backup equipment and sampling 

gear should be available. 

Checklist 

Equipment and/or reagents needed: 

� sampling equipment and spare parts


� sample handling equipment


� special sample handling equipment (e.g., glovebox or shielded compartment).


� decontamination and cleaning equipment


� field measurement equipment and supplies


� sample storage supplies/equipment


� sample transport supplies


� personnel supplies


� maps, navigation, and communication equipment


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Storage, transport, and sample containers, including extra containers should be available in the event 

of loss or breakage (see Section 4.2 for more information on appropriate containers). These 

containers should be pre-cleaned and labeled appropriately (i.e., with a waterproof adhesive label to 

which the appropriate data can be added, using an indelible ink pen capable of writing on wet 

surfaces). The containers must have lids that are fastened securely, and if the samples are collected 

for legal purposes, they should be transported to and from the field in a locked container with 

custody seals secured on the lids. Samples to be frozen before analyses must not be filled to the lids. 

Leave a 10% headspace to accommodate expansion during freezing. Whether for legal purposes or 

not, all samples should be accompanied by a chain-of-custody form that documents field samples to 

be submitted for analyses (see Chapter 7). Transport supplies also include shipping airbills and 

addresses. 

A sample-inventory log and a sample-tracking log should be prepared in advance of sampling. A 

single person should be responsible for these logs who will track the samples from the time they are 

collected until they are analyzed and disposed of or archived. 

2.8 Health and Safety 

Collection and processing of sediments for analyses and testing might involve substantial risks to 

personal safety and health; particularly in situations involving potentially hazardous materials or 

challenging sampling conditions. If a Quality Assurance Project Plan (QAPP) or a Sampling and 

Analysis Plan (SAP) is prepared prior to sampling, it should include or reference health and safety 

procedures. A health and safety field officer should be appointed to ensure that personnel use safety 

precautions and equipment applicable to the operation of the vessel, the sampling equipment, and 

sample handling. Personnel collecting or handling sediment samples should not work alone, and they 

should take all safety precautions necessary for the prevention of bodily injury and illness which 

might result from sampling activities (e.g., boat safety), ingestion or invasion of infectious agents, 

inhalation or absorption of corrosive or toxic substances through skin contact, or asphyxiation. 

Because sediment collection often occurs without complete knowledge of the source or degree of 

hazard, contact with sediment should to be minimized by: (1) using gloves, laboratory coats, safety 

glasses, face shields and respirators, as appropriate, and (2) manipulating sediments in open air, 

under a ventilated hood, or in an enclosed glove box. USEPA (1986a), Walters and Jameson (1984), 

and the Occupational Health and Safety Administration (OSHA) standards provide guidance on safe 

sediment handling. Program specific guidance should be consulted first when available (e.g., 

Washington Department of Ecology’s Sampling and Analysis Plan Guidance [WDE, 1995] or Puget 

Sound Estuaries Program [PSEP, 1997a]). Other references (e.g., ASTM, 2000b; Waters, 1980) 

should also be consulted concerning special safety procedures for sampling and handling samples 

from hazardous waste sites. The NOAA Diving Manual (NOAA, 1991) or the EPA Diving Safety 

Manual (USEPA, 1997b) should be consulted for information regarding diving safety plans and 

protocols. 

Chapter 2: Sediment Monitoring and Assessment Study Plans 2-23 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Recommendation Box #4 

What health and safety precautions should be followed? 

� Follow Coast Guard approved safety procedures, including use of life vests. 

� All samples must be handled in a manner that satisfies the Quality Assurance Project 

Plan, Standard Operating Procedures, and DQOs. 

� Skin contact with sediment should be minimized to avoid potential contact with 

hazardous substances. Protective clothing and equipment (e.g., gloves, boots, lab coats 

or aprons, safety glasses, and respirator) are recommended during sampling, sample 

handling, and preparation of test substances or sediments. 

� Handling of samples should be performed in a well-ventilated area (e.g., outside, in a 

fume hood, or in an enclosed glove box) to minimize the inhalation of sediment gases 

such as hydrogen sulfide if present. 

� A spill control protocol should be in place in the sampling vessel and laboratory. 

� Disposal of all hazardous waste should be in accordance with applicable laws, 

guidelines, and regulations. 

� Provide procedures regarding hazard assessment (chemical and physical hazards). 

� Provide procedures regarding decontamination. 

� Meet the training and medical monitoring requirements. 

� Provide emergency planning and emergency contacts. 

2-24 US Environmental Protection Agency 
Technical Manual 

Collection of Whole Sediments


CHAPTER 

3 

Most sediment collection devices are designed to isolate and consistently retrieve a specified volume


and surface area of sediment, from a required depth below the sediment surface, with minimal


disruption of the integrity of the sample and no contamination of the sample. Maintaining the


integrity of the collected sediment, for the purposes of the measurements intended, is a primary


concern in most studies because disruption of the sediment’s structure could change its


physicochemical and biological characteristics, thereby influencing the bioavailability of


contaminants and the potential toxicity of the sediment. This chapter discusses the factors to be


considered in selecting a sediment collection device. A variety of samplers are described (and


pictured in Appendix E), and recommendations are made regarding their use in different situations.


The flowchart in Figure 3-1 shows recommended sampling gear based on monitoring objective or


site-specific issues of concern. Figures 3-2 and 3-3 provide recommended grab and core samplers,


respectively, based on site factors


(such as depth and particle size),


and sampling requirements (such


as sample depth and volume of


sample needed).


3.1	 General 

Procedures 

The planned mode of access to 

the sampling area (e.g., by water, 

over land or ice, or from the air) 

plays an important role in the 

selection of sampling gear. If the 

sampling gear needs to be 

transported to a remote area or 

shipped by air, its weight and Figure 3-1. General types of considerations or objectives that 

volume might need to be taken are appropriate for grab or core sampling devices. into account. It is often the case 

that a specific vessel, having a 

fixed lifting capacity based on the configuration of its winch, crane, boom, A-frame, or other support 

equipment, is the only one available for use. This will affect the type of sampling equipment that can 

be safely operated from that vessel. 

Many samplers are capable of recovering a relatively undisturbed sample in soft, fine-grained 

sediments, but fewer are suitable for sampling harder sediments containing significant quantities of 

sand, gravel, firm clay, or till (Mudroch and Azcue, 1995). One of the most important factors in 

determining the appropriate sampling device for the study are Data Quality Objectives. Many 

monitoring programs, such as EPA’s Environmental Monitoring and Assessment Program (EMAP) 

and the NOAA National Status and Trends program, are primarily interested in characterizing recent 

environmental impacts in lakes, estuaries and coastal waters and therefore sample surface sediments 

Chapter 3: Collection of Whole Sediments 3-1 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Figure 3-2. Flowchart for selecting appropriate grab samplers based on site-specific or design factors 

3-2 US Environmental Protection Agency 
Technical Manual 

Figure 3-3. Flowchart for selecting appropriate core samplers based on site-specific factors 

Chapter 3: Collection of Whole Sediments 3-3

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Considerations 

Although there is no 

one sampler that 

satisfies all possible 

considerations, the 

ideal sampler... 

! avoids a pressure wave 

!	 penetrates cleanly to minimize 

disturbance 

! closes tightly 

! allows for subsampling 

! can accommodate weighting 

! collects sufficient sediment volume 

!	 retrieves sediment from a wide range 

of water and sediment depths 

! does not contaminate the sample 

! is easy and safe to operate 

!	 is easily transported/assembled at the 

site 

(e.g., Long et al., 1996). Other programs (e.g., 

dredged material characterization studies 

conducted for EPA and the US Army Corps of 

Engineers), are concerned with the vertical 

distribution of contaminants in sediment to be 

dredged and therefore seek to characterize a 

sediment column (USEPA/ACOE, 1991,1998). 

Each program would employ different sampling 

devices. 

Related to study objectives, another important 

factor in selecting a sampler is desired depth of 

sediment penetration. For monitoring and 

assessment studies where historical 

contamination is not the focus, the upper 10 to 15 

cm is typically the horizon of interest. Generally, 

the most recently deposited sediments and most 

epifaunal and infaunal organisms are found in 

this horizon. To ensure minimum disturbance of 

the upper layer during sampling, a minimum 

penetration depth of 6 to 8 cm is recommended, 

with a penetration depth of 10 to 15 cm being 

preferred. However, if sediment contamination is 

being related to organism exposures (e.g., benthic 

macroinvertebrates and/or fish) then more precise 

sampling of sediment depths might be needed, 

such as with a core sampler. The life history and 

feeding habits of the organisms (receptors) of concern should be considered. For example, some 

organisms (e.g., shrimp, rotifers) might be epibenthic and are only exposed to surficial sediments 

(e.g., 0 to 1 cm) while others (e.g., amphipods, polychaetes) that are infaunal irrigators might receive 

their primary exposure from sediments that are several centimeters in depth. Relating contaminant 

levels that occur in sediment layers other than where resident organisms are exposed, might produce 

incorrect conclusions. 

Sampling of the surface layer provides information on the horizontal distribution of parameters or 

properties of interest for the most recently deposited material. Information obtained from analysis of 

surface sediments can be used, for example, to map the distribution of a chemical contaminant in 

sediments across a specific body of water (e.g., lake, embayment, estuary). A sediment column, 

including both the surface sediment layer and the sediment underneath this layer, is collected to study 

historical changes in parameters of interest (as revealed through changes in their vertical distribution) 

and to characterize sediment quality with depth. 

Once study objectives and the general type of sampler have been identified, a specific sampler is 

selected based on knowledge of the bathymetry and areal distribution of physically different 

sediment types at the sampling site. Therefore, it is strongly recommended that this information be 

gathered during the initial planning stage of all sample collection efforts (see Section 2.5.1). 

The quantity of sediment to be collected at each sampling site may also be an important 

consideration in the selection of a sampling device (see also Section 2.4.1). The required quantity of 

sediment typically depends on the number and type of physicochemical and biological tests to be 

carried out (See Table 2-3 for typical sediment volumes needed for different analyses). 

3-4 US Environmental Protection Agency 
Technical Manual 

Regardless of the type of sampler used, it is important to follow the standard operating procedures 

specific to each device. Before retrieving the sample, the outside of the sampling device should be 

carefully rinsed with water from the sampling station. Between each sampling event, the sampling 

device should be cleaned, inside and out, by dipping the sampler into and out of the water rapidly or 

by washing with water from the location being sampled. More rigorous between-sample cleaning of 

the sampler (e.g., chemical decontamination or washing with soap) might be required, depending on 

the nature of the investigation and specific program guidance (see Section 3.5). 

To minimize cross-contamination of samples and to reduce the amount of equipment 

decontamination required, it might be prudent to sample reference sites (i.e., relatively clean sites) 

first, followed by test stations. If certain stations are known to be heavily contaminated, it might be 

prudent to sample those stations last when sampling many locations at one time. 

3.2 Types of Sediment Samplers 

There are three main types of sediment sampling devices: grab samplers, core samplers, and 

dredge samplers. Grab samplers (see Appendix E) are typically used to collect surficial sediments 

for the assessment of the horizontal distribution of sediment characteristics. Core samplers (see 

Appendix E) are typically used to sample thick sediment deposits, or to collect sediment profiles for 

the determination of the vertical distribution of sediment characteristics or to characterize the entire 

sediment column. Dredge samplers are used primarily to collect benthos. Dredges cause disruption 

of sediment and pore water integrity, as well as loss of fine-grained sediments. For these reasons, 

only grab and core samplers are recommended for sediment physicochemistry or toxicity evaluations. 

Since many grab samplers are appropriate for collecting benthos as well (Klemm et al., 1990; ASTM, 

2000c), grab samplers are likely to be more useful than dredges in sediment quality assessments. 

Therefore, dredges are not considered further in this document. 

Advantages and disadvantages of various grab and core samplers are summarized in Appendix 

Tables E-1 and E-2, respectively, and are discussed briefly in the following sections. Figure 3-1 

provides recommendations regarding the type of sampler that would be appropriate given different 

study objectives. For many study objectives either cores or grab samplers can be used, however, in 

practice, one will often be preferred over the other depending on other constraints such as amount of 

sample required for analyses and equipment availability. 

3.2.1 Grab Samplers 

Grab samplers consist either of a set of jaws that shut when lowered into the surface of the bottom 

sediment or a bucket that rotates into the sediment when it reaches the bottom (see Appendix E). 

Grab samplers have the advantages of being relatively easy to handle and operate, readily available, 

moderately priced, and versatile in terms of the range of substrate types they can effectively sample. 

Of the grab samplers, the Van Veen, Ponar (see photograph on page 3-6), and Petersen are the most 

commonly used. These samplers are effective in most types of surface sediments and in a variety of 

environments (e.g., lakes, rivers, estuaries, and marine waters). In shallow, quiescent water, the 

Birge-Ekman sampler also provides acceptable samples and allows for relatively nondisruptive 

sampling. However, this sampler is typically limited to soft sediments. The Van Veen sampler, or 

the modified Van-Veen (Ted Young), is used in several national and regional estuarine monitoring 

programs, including the NOAA National Status and Trends Program, the EPA Environmental 

Monitoring and Assessment Program (EMAP), and the EPA National Estuary Program because it can 

sample most types of sediment, is less subject to blockage and loss of sample than the Peterson or 

Chapter 3: Collection of Whole Sediments 3-5 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Examples of grab samplers Photo courtesy of Allen Burton Photo courtesy of Allen Burton 

Ponar Eckman grab 

Photo courtesy of Ed Long Photo courtesy of Scott Carr 

Double VanVeen grab 

Birge-Eckman grab 

3-6 US Environmental Protection Agency 
Technical Manual 

Photos on this page, courtesy of Ed Long 

Taking subsamples from a Ted Young 

modified VanVeen sampler 

Sampling using a Ted-Young modified 

VanVeen. Large grab samplers such as 

these require winches and sufficient boat 

size for efficient operation. 

Ted-Young VanVeen sampler in supporting 

frame. Illustrating movable cover flap to enable 

direct sampling from the grab sampler. Note the 

overlying water in the sampler and adequate 

volume, indicating an acceptable grab sample. 

Chapter 3: Collection of Whole Sediments 3-7 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Ponar samplers, is less susceptible to forming a bow wave during descent, and provides generally 

high sample integrity (Klemm et al., 1990). The support frame further enhances the versatility of the 

VanVeen sampler by allowing the addition of either weights (to increase penetration in compact 

sediments) or pads (to provide added bearing support in extremely soft sediments). However, this 

sampler is relatively heavy and requires a power winch to operate safely (GLNPO, 1994). 

As shown in Appendix Table E-1, grab sampler capacities range from approximately 0.5 L to 75 L. 

If a sampler does not have sufficient capacity to meet the study plan requirements, additional samples 

can be collected and composited to obtain the requisite sample size (see Section 5.3). Grab samplers 

penetrate to different depths depending on their size, weight, and the bottom substrate. Heavy, large 

volume samplers such as the Smith-McIntyre, large Birge-Ekman, Van Veen, and Petersen devices 

can effectively sample to a depth of 30 cm. These samplers might actually sample sediments that are 

too deep for certain study objectives (i.e., not reflective of recently deposited sediments). Smaller 

samplers such as the small Birge-Ekman, standard and petite Ponar, and standard Shipek devices can 

effectively collect sediments to a maximum depth of 10 cm. The mini-Shipek can sample to a depth 

of 3 cm. 

Another consideration in choosing a grab sampler is how well it protects the sample from disturbance 

and washout. Grab samples are prone to washout which results in the loss of surficial, fine grained 

sediments that are often important from a biological and contaminant standpoint. The Ponar, TedYoung modified grab, and Van Veen samplers are equipped with mesh screens and rubber flaps to 

cover the jaws. This design allows water to pass through the samplers during descent, reducing 

disturbance from bow waves at the sediment-water interface. The rubber flaps also serve to protect 

the sediment sample from washout during ascent. 

The use of small or lightweight samplers, such as the small Birge-Ekman (see page 3-6), petite Ponar, 

and mini-Shipek, can be advantageous because of easy handling, particularly from a small vessel 

and/or using only a hand line. However, these samplers are not recommended for use in strong 

currents or high waves. This is particularly true for the Birge-Ekman sampler, which requires 

relatively calm conditions for proper performance. Lightweight samplers generally have the 

disadvantage of being less stable during sediment penetration. They tend to fall to one side due to 

inadequate or incomplete penetration, resulting in unacceptable samples. 

In certain very shallow water applications, such as a stream assessment at a superfund site, it might 

be difficult to use even a lightweight sampler to collect a sample. In these cases, it might be 

acceptable to collect sediment from depositional areas, using a shovel or other hand implement. 

However, such sampling procedures are discouraged as a general rule and the use of a hand corer or 

similar device is preferred (see Section 3.2.2). 

Figure 3-2 summarizes appropriate grab samplers based on two important site factors, depth and 

sediment particle size. This figure also indicates appropriate grab samplers depending on certain 

common study constraints such as sample depth and volume desired, and the ability to subsample 

directly from the sampler (see also Section 4.3; ASTM, 2000c). Based on all of these factors, the 

Ponar or Van Veen samplers are perhaps the most versatile of the grab samplers, hence their common 

usage in sediment studies. 

Careful use of grab samplers is required to avoid problems such as loss of fine-grained surface 

sediments from the bow wave during descent, mixing of sediment layers upon impact, lack of 

sediment penetration, and loss of sediment from tilting or washout upon ascent (ASTM, 2000a; 

Environment Canada, 1994; Baudo, 1990; Golterman et al., 1983; Plumb,1981). When deploying a 

grab sampler, the speed of descent should be controlled, with no “free fall” allowed. In deep waters, 

3-8 US Environmental Protection Agency 
Technical Manual 

use of a winching system is recommended to control both the rate of descent and ascent. A ballbearing swivel should be used to attach the grab sampler to the cable to minimize twisting during 

descent. After the sample is collected, the sampling device should be lifted slowly off the bottom, 

then steadily raised to the surface at a speed of about 30 cm/s (Environment Canada, 1994). 

Recommendation Box #1 

What are appropriate sampling devices given different study 

objectives? 

� Grab or core samplers are preferred over dredges for collecting surficial sediments for 

physicochemical or toxicity analyses. Dredges might be acceptable for collecting 

macroinvertebrates. 

� Grab samplers are recommended for surficial sediment analyses where accurate 

resolution of surficial sediment depths is not necessary. Core samplers are 

recommended for: (a) assessments requiring accurate surficial sediment depth 

resolution, (b) historical sediment analyses, (c) detailed sediment quality studies of 

vertical sediment profiles, to characterize sediment quality at depth, (d) when 

characterizing thick sediment deposits (such as shoals to be excavated), and/or (e) 

where it is important to maintain an oxygen-free environment. 

� In sand, gravel, firm clay, or till sediments, grab samplers might be preferred over core 

samplers (when only surface material needs to be collected and samples at depth are 

not necessary) because the latter are often less efficient in these sediment types. 

� Ponar, VanVeen, or Ekman samplers are commonly used and generally preferred for 

grab sampling. Ekman samplers, however, are less efficient in deep waters. 

� The Kajak-Brinkhurst corer is a common core sampler for soft, fine grained sediments 

where large volumes or deep cores are not needed. The Phleger corer is commonly 

used for a variety of sediments including peat and plant roots but is not appropriate 

where large volumes or deep cores are needed. 

� Box corers are especially recommended for: (a) studies of the sediment-water interface; 

(b) collecting larger volumes of sediment from a given depth (generally less than one 

meter depth, however); (c) for in-situ studies involving interstitial water characterization; 

and (d) collecting subsamples for different analyses from the same station. 

� Vibracorers are recommended for studies requiring deep cores (> 1 m), or where 

sediment consists of very compacted or large grained material (e.g., gravel). 

3.2.2 Core Samplers 

Core samplers (corers) are used: (1) to obtain sediment samples for geological characterizations and 

dating, (2) to investigate the historical input of contaminants to aquatic systems and, (3) to 

characterize the depth of contamination at a site. Corers are an essential tool in sediments in which 

3-dimensional maps of sediment contamination are necessary. Appendix Table E-2 discusses some 

of the advantages and disadvantages of common corers. 

Chapter 3: Collection of Whole Sediments 3-9 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Vibracorer in use showing extrusion 

of the core sample for inspection and 

Subsampling. 

Photos on this page, courtesy of Allen Burton 

3-10 US Environmental Protection Agency 
Technical Manual 

Core devices are recommended for projects in which it is critical to maintain the integrity of the 

sediment profile, because they are considered to be less disruptive than dredge or grab samplers. 

Core samplers should also be used where it is important to maintain an oxygen-free environment 

because they limit oxygen exchange with the air more effectively than grab samplers. Cores should 

also be used where thick sediment deposits must be representatively sampled (e.g., for dredging 

projects). 

One limitation of core samplers is that the volume of any given depth horizon within the profile 

sample is relatively small. Thus, depending on the number and type of analyses needed, repetitive 

sampling at a site might be required to obtain the desired quantity of material from a given depth. 

Some core samplers are prone to “plugging” or “rodding” where the friction of the sediment within 

the core tube prevents it from passing freely and the core sample is compressed or does not sample to 

the depth required. This limitation is more likely with smaller diameter core tubes and heavy clay 

sediments. Except for piston corers and vibracorers, there are few core devices that function 

efficiently in substrates with significant proportions of sand, gravel, clay, or till. 

Coring devices are available in various designs, lengths, and diameters (see Appendix E). With the 

obvious exception of hand corers, there are only a few corers that can be operated without a 

mechanical winch. The more common of these include the standard Kajak-Brinkhurst corer, 

suitable for sampling soft, fine-grained sediments, and the Phleger corer, suitable for a wider variety 

of sediment types ranging from soft to sandy, semi-compacted material, as well as peat and plant 

roots in shallow lakes or marshes (Mudroch and Azcue, 1995). The Kajak-Brinkhurst corer uses a 

larger core tube, and therefore recovers a 

greater quantity of sediment, than the 

Phleger corer. Both corers can be used 

with different liner materials including 

stainless steel and PVC. Stainless steel 

liners should not be used if trace metal 

contamination is an issue. 

Gravity corers are appropriate for 

recovering up to 3 m long cores from 

soft, fine-grained sediments. Recent 

models include stabilizing fins on the 

upper part of the corer to promote vertical 

penetration into the sediment, and 

weights that can be mounted externally to 

enhance penetration (Mudroch and 

Azcue, 1995). A variety of liner 

materials are available including stainless 

steel; Lexan®, and PVC. For studies in 

which metals are a concern, stainless 

steel liners should not be used. 

Vibracorers are perhaps the most 

commonly used coring device in 

sampling programs in the U.S. because 

they collect deep cores in most types of 

sediments, yielding excellent sample 

integrity. Vibracorers are one of the only 

sampling devices that can reliably collect 

Checklist 

Corers may consist of the 

following components (from 

Mudroch and Azcue, 1995) 

� A hollow metal (or plastic) pipe that serves 

as the core barrel 

� Easily removed plastic liners or core tubes 

that fit into the core barrel and retain the 

sediment sample 

� A valve or piston mounted on top of the core 

barrel that is open and allows water to flow 

through the barrel during descent, but shuts 

upon penetration of the corer into the 

sediment to prevent the sediment from 

sliding through the corer during the ascent 

� A core catcher to retain the sediment 

sample 

� A core cutter for penetration of the sediment 

� Removable metal weights (usually lead 

coated with plastic) or piston-driven impact 

or vibration to increase penetration of the 

corer into the sediment 

� Stabilizing fins to ensure vertical descent of 

the corer 

Chapter 3: Collection of Whole Sediments 3-11 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

thick sediment samples (up to 10 meters or more). Some programs that rely on vibracorers include 

the Puget Sound Estuary Program, the Great Lakes ARCS Program, and the Dredged Materials 

Management Program. 

Vibracorers have an electric-powered, mechanical vibrator located at the head end of the corer which 

applies thousands of vertical vibrations per minute to help penetrate the sediment. A core tube and 

rigid liner (preferably of relatively inert material such as cellulose acetate butyrate) of varying 

diameter depending on the specific vibrator head used, is inserted into the head and the entire 

assembly is lowered in the water. Depending on the horsepower of the vibrating head and its weight, 

a vibracorer can penetrate very compact sediments and collect cores up to 6 m long. For example, 

the ARCS program in the Great Lakes uses a Rossfelder® Model P-4 Vibracorer (Rossfelder 

Corporation, La Jolla, CA) that produces a force of 7,000 lbs and a mono-directional frequency of 

3,400 vibrations per minute (GLNPO, 1994). Cores up to 6 m in length have been routinely collected 

using this vibracorer. However, this particular model is relatively heavy (113 kg as compared to 8.1 

kg for the more portable Wacker® Model M3000 vibracorers [GLNPO, 1994]). Therefore, use of a 

heavy vibracorer requires a large vessel to maintain balance and provide adequate lift to break the 

corer out of the sediment and retrieve it (GLNPO, 1994; PSEP, 1997a). 

When deployed properly, box corers can obtain undisturbed sediment samples of excellent quality. 

The basic box corer consists of a stainless steel box equipped with a frame to add stability and 

facilitate vertical penetration on low slopes. Box corers are recommended particularly for studies of 

the sediment-water interface or when there is a need to collect larger volumes of sediment from the 

depth profile. Because of the heavy weight and large size of almost all box corers, they can be 

operated only from a vessel with a large lifting capacity and sufficient deck space. Sediment inside a 

box corer can be subsampled by inserting narrow core tubes into the sediment. Thus, they are an 

ideal sampler for obtaining acceptable subsamples for different analyses at a given station. Carlton 

and Wetzel (1985) describe a box corer that permits the sediment and overlying water to be held 

intact as a laboratory microcosm under either the original in situ conditions or other laboratory 

controlled conditions. A box corer was developed that enables horizontal subsampling of the entire 

sediment volume recovered by the device (Mudroch and Azcue, 1995). 

Figure 3-3 summarizes the core samplers that are appropriate given site factors such as depth and 

particle size and other study constraints such as sample depth and volume required, and lifting 

capacity needed to use the sampling device. Given the factors examined for general monitoring 

studies, the Phleger, Alpine, and Kajak-Brinkhurst corers might be most versatile. For dredged 

materials evaluations, and projects requiring sediment profile characterizations > 3 m in sediment 

depth, the vibracorer or piston corer are the samplers of choice. 

Collection of core samples with hand-coring devices should be executed with care to minimize 

disturbance and/or compression of sediment during collection. To minimize disruption of the 

sediment, core samples should be kept as stationary and vibration-free as possible during transport. 

These cautions are particularly applicable to cores collected by divers. 

The speed of descent of coring devices should be controlled, especially during the initial penetration 

of the sediment, to avoid disturbance of the surface and to minimize compression due to frictional 

drag from the sides of the core liner (ASTM, 2000d). In deep waters, winches should be used where 

necessary to minimize twisting and tilting and to control the rate of both descent and ascent. With 

the exception of piston corers or vibracorers, that are equipped with their own mechanical impact 

features, for other corers, only the weight or piston mechanism of the sampler should be used to force 

it into the sediment. The sampler should be raised to the surface at a steady rate, similar to that 

described for grab samplers. Where core caps are required, it is essential to quickly and securely cap 

3-12 US Environmental Protection Agency 
Technical Manual 

the core samples when the samples are retrieved. The liner from the core sampler should be carefully 

removed and kept in a stable position until the samples are processed (see Chapter 4). If there is little 

to no overlying water in the tube and the sediments are relatively consolidated, it is not necessary to 

keep the core sample tubes vertical. Core sample tubes should be quickly capped and taped to secure 

the sample. If sediment oxidation is a concern (e.g., due to potential changes in metal bioavailability 

or volatile substances), then the head space of the core tube should be purged with an inert gas such 

as nitrogen or argon. 

Recommendation Box #2 

How should sampling devices be used? 

� The recommended depth of sediment sampling is dependent on the study objectives. 

Issues that determine the appropriate depth of sampling include: regulatory objectives 

(e.g., depth of dredging for sediment remediation), need to characterize sediments at 

depth (e.g., materials to be dredged versus shallow depositional areas in some 

superfund sites), historical comparisons, sediment deposition rates, and/or time period of 

contamination. 

� Appropriate winching systems are required to control the rate of ascent and descent of 

the samplers. 

� The sampler should be rinsed thoroughly with water at the sampling station between and 

within-station samples, and rinsed with water from the next sapling station before 

collecting a sample. Equipment used in the handling of sediment should also be washed 

thoroughly between samples. 

� More rigorous equipment decontamination might be necessary if highly contaminated 

sites are sampled or if low level contaminants are a concern. 

� To reduce the probability of cross-contamination of samples, it is useful to sample 

reference or relatively clean sites first and then suspected contaminated sites. 

3.3 Sample Acceptability 

Only sediments that are correctly collected with grab or core sampling devices should be used for 

subsequent physicochemical, biological or toxicity testing. Acceptability of grabs can be ascertained 

by noting that the samplers were closed when retrieved, are relatively full of sediment (but not overfilled), and do not appear to have lost surficial fines. Core samples are acceptable if the core was 

inserted vertically in the sediment and an adequate depth was sampled. 

A sediment sample should be inspected as soon as it is secured. If a collected sample fails to meet 

any of the acceptability conditions listed below for the respective sampling device, then the sample 

might need to be rejected and another sample collected at the site. The location of consecutive 

attempts should be as close to the original attempt as possible and located in the “upstream” direction 

of any existing current. Rejected sediment samples should be discarded in a manner that will not 

affect subsequent samples at that station or other possible sampling stations. Illustrations of 

acceptable and unacceptable grab samples are provided in Figure 3-4. 

Chapter 3: Collection of Whole Sediments 3-13 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Checklist 

Sample acceptability for grab and core samples 

Grab samples should be visually inspected to ensure that the following acceptability conditions 

are satisfied (USEPA, 1986b; Environment Canada, 1994): 

� The sampler is not overfilled so that the sediment surface is touching the top of the 

sampler; 

� Overlying water is present (indicates minimal leakage). This overlying water should be 

removed prior to processing and storage by siphoning, not decanting (see Chapter 6); 

� The overlying water is clear or not excessively turbid; 

� The sediment-water interface is intact and relatively flat, with no sign of channeling or 

sample washout; 

� The desired depth of penetration has been achieved; and 

� There is no evidence of sediment loss (incomplete closure of the sampler, penetration at 

an angle, or tilting upon retrieval). 

Core samples should meet the following acceptability conditions: 

� The core sampler was not inserted at an angle or tilted upon retrieval 

� The core collected the required depth to meet the study objectives, with no loss of 

sediment. 

3.4 Equipment Decontamination 

For most sampling applications, site water rinse of equipment in between stations is normally 

sufficient (PSEP, 1997a). However, if one is sampling many stations, including some that could be 

heavily contaminated, a site water rinse might not be sufficient to minimize cross-contamination of 

samples among stations. In these cases, it might be necessary to decontaminate all sampling 

materials in between stations. This would include the sampling device, scoop, spatula, mixing bowls, 

and any other utensils that come in contact with sediment samples. An approach recommended by 

ASTM (2000a) for field samples of unknown composition includes: (1) soap and water wash, (2) 

distilled water rinse, (3) acetone or ethanol rinse, and (4) site water rinse. In general, organic 

solvents such as methylene chloride should not be used due to the associated health and safety risks. 

Waste solvents should be collected in labeled hazardous waste containers. If sediment can be 

collected from the interior of the sampling device, and away from potentially contaminated surfaces 

of the sampler, it might be adequate to rinse with site water between stations. 

If metals or other inorganic compounds are specifically of concern, sampling and handling equipment 

should be suspended over a tub and rinsed from the top down with 10 percent nitric acid using a 

pump or squirt bottle (USEPA, 1993; ASTM, 2000a). If organic compounds are a specific concern, 

sampling equipment can be decontaminated using acetone followed by a site water rinse. Wash 

water from decontamination should be collected and disposed of properly. 

3-14 US Environmental Protection Agency 
Technical Manual 

Some specific programs (like Superfund) have their own decontamination procedures, which are 

legally required. 

Figure 3-4. Illustrations of acceptable and unacceptable grab samples. 

3.5 Field Measurements and Observations 

Field measurements and observations are critical to any sediment collection study, and specific 

details concerning sample documentation should be included in the study plan. Section 2.7 

summarizes the types of information commonly recorded in the field during sampling. Several 

programs, referenced in this Manual, provide specific guidance on field measurements and 

observations necessary (e.g., see the Sampling and Analyses Plan Guidance development by the 

Washington Department of Ecology in Appendix B [WDE, 1995 or PSEP, 1997a]). Measurements 

and observations should be documented clearly in a bound field logbook (or on pre-printed sample 

forms). Preferably, a logbook should be dedicated to an individual project. The investigator’s name, 

project name, project number, and book number (if more than one is required) should be entered on 

Chapter 3: Collection of Whole Sediments 3-15 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

the inside of the front cover of the 

logbook. All entries should be written 

in indelible ink, and the date and time of 

entry recorded. Additionally, each page 

should be initialed and dated by the 

investigator. At the end of each day’s 

activity, or entry of a particular event if 

appropriate, the investigator should 

enter his or her initials. All aspects of 

sample collection and handling as well 

as visual observations and field 

conditions should be documented in the 

field logbooks at the time of sample 

collection. Logbook entries should also 

include any circumstances that 

Checklist 

Depending on program 

objectives, field measurements 

might include the following: 

� temperature and perhaps pH of the sediment 

at the sediment-water interface; 

� concentration of dissolved oxygen in the water 

overlying the sediment in the system being 

sampled. 

� salinity or conductivity of the overlying water. 

potentially affected sampling procedures and/or any field preparation of samples. Data entries 

should be thorough enough to allow station relocation and sample tracking. Since field records are 

the basis for later written reports, language should be objective, factual, and free of personal opinions 

or other terminology which might appear inappropriate. In describing characteristics of samples 

collected (see below), some cautions should be noted. First, polarized glasses are often worn in the 

field to reduce glare, however, they can also alter color vision. Therefore, visual examination or 

Recommendation Box #3 

What information should be documented for each sample 

collected? (PSEP, 1997a; ASTM, 2000a) 

� project title, time and date of collection, sample number, replicate number, site 

identification (e.g., name); station number and location (e.g., positioning information); 

� water depth and the sampling penetration depth; 

� details pertaining to unusual events which might have occurred during the operation of the 

sampler (e.g., possible sample contamination, equipment failure, unusual appearance of 

sediment integrity, control of vertical descent of the sampler, etc.), preservation and 

storage method, analysis or test to be preformed; 

� estimate of quantity of sediment recovered by a grab sampler, or length and appearance 

of recovered cores; 

� description of the sediment including texture and consistency, color, presence of biota or 

debris, presence of oily sheen, changes in sediment characteristics with depth, and 

presence/location/thickness of the redox potential discontinuity (RPD) layer (a visual 

indication of black is often adequate for documenting anoxia); 

� photograph of the sample is desirable, especially longitudinally-sectioned cores, to 

document stratification; 

� deviations from approved work plans or SOPs. 

NOTE: Some geological characterization methods might include an odor evaluation of the 

sediment as this can provide useful information on physicochemical conditions. However, 

sediment odor evaluation is potentially dangerous depending on the chemicals present in the 

sediment (ASTM 2000a) and should therefore be done cautiously, if at all. 

3-16 US Environmental Protection Agency 
Technical Manual 

characterization of samples should be performed without sunglasses (GLNPO, 1994). Second, 

descriptions of sediment texture and composition should rely on a texture-by-feel or “ribbon” test in 

addition to visual determinations (GLNPO, 1994). In this test, a small piece of suspected clay is 

rolled between the fingers while wearing protective gloves. If the piece easily rolls into a ribbon it is 

clay; if it breaks apart, it is silt (GLNPO, 1994). 

3.6 Documentation of Sample Collection 

Documentation of collection and analysis of sediment and porewater samples requires all the 

information necessary to: 1) trace a sample from the field to the final result of analysis; 2) describe 

the sampling and analytical methodology; and 3) describe the QA/QC program (Mudroch and Azcue 

1995; Keith, 1993). Poor or incomplete documentation of sample collection can compromise the 

integrity of the sample(s) and thus, the study. In addition, stations that could not, or were not, 

sampled should be documented with an explanation. Samples should be accompanied by chain-ofcustody forms that identify each sample collected and the analyses to be conducted on that sample. 

Specific guidance on quality assurance procedures regarding sample chain-of-custody is summarized 

in Chapter 7. 

Checklist 

Project documentation should include... 

� type of vessel used (e.g., size, power, type of engine); 

� notation of the system used to define the position of the sampling site; 

� notation of the system used to identify and track samples; 

� name of personnel collecting the samples; 

� level of personal protective equipment worn; 

� notation of any visitors to the site; 

� sketch of sampling area with photographs, if possible; 

� ambient weather conditions, including wind speed and direction, wave action, current, 

tide, vessel traffic, temperature of both the air and water, thickness of ice if present; 

� type of sediment collection device and any modifications made during sampling; 

� calibration data. 

Chapter 3: Collection of Whole Sediments 3-17 
Technical Manual 

Field Sample Processing, Transport, 

and Storage of Sediments 

CHAPTER 

4 

The way in which sediment samples are processed, transported, and stored might alter contaminant 

bioavailability and concentration by introducing contaminants to the sample or by changing the 

physical, chemical, or biological characteristics of the sample. Manipulation processes often change 

availability of organic compounds because of disruption of the equilibrium with organic carbon in 

the pore water/sediment system. Similarly, oxidation of anaerobic sediments increases the 

availability of certain metals (DiToro et al., 1990; Ankley et al., 1996). Materials and techniques 

should be selected to minimize sources of contamination and variation, and sample treatment prior to 

testing should be as consistent as possible. 

A flowchart is presented in Figure 4-1 that summarizes common sediment processing procedures 

discussed in this section as well as issues and objectives relevant to each processing step. 

4.1 Sample Containers 

Any material that is in contact with a field sample has the potential to contaminate the sample or 

adsorb components from the sample. For example, samples can be contaminated by zinc from 

glassware, metals from metallic containers, and organic compounds from rubber or plastic materials. 

The use of appropriate materials, along with appropriate cleaning procedures, can minimize or 

mitigate interferences from sample containers. 

Recommendation Box #1 

Sample Containers 

� High density polyethylene (HDPE) or polytetrafluoroethylene (PTFE) containers are 

suitable and preferred for most analytical measurements because they are made of 

relatively inert material and they are generally unbreakable. 

� All containers should be pre-cleaned prior to filling with sample. 

� Consider using certified, pre-cleaned containers, commercially available from many 

vendors. 

� Purge containers with inert gas (e.g., nitrogen) prior to and after filling if anoxic conditions 

must be maintained. 

� Fill containers completely if the sample will not be frozen prior to analysis. 

Chapter 4: Field Sampling Processing, Transport, and Storage of Sediments and Interstitial Water 4-1 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Figure 4-1. Flowchart of suggested sediment processing procedures 

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4.1.1 Container Material 

Borosilicate Glass, and high-density polyethylene, polycarbonate and fluorocarbon plastics should be 

used whenever possible to minimize leaching, dissolution, and sorption (ASTM, 2000a; APHA, 

1995). Direct contact between sediment samples and the following substances should be avoided: 

PVC, natural or neoprene rubber, nylon, talcum powder, polystyrene, galvanized metal, brass, 

copper, lead, other metal materials, soda glass, paper tissues, and painted surfaces. Table 4-1 

summarizes the appropriate types of sampling containers and allowable holding times for various 

types of contaminants associated with sediments. 

In general, sediments and pore waters with multiple or unknown chemical types should be stored in 

containers made from high density polyethylene plastic or polytetrafluoroethylene (PTFE or 

Teflon®) as these materials are least likely to add chemical artifacts or interferences and they are 

much less fragile than glass. Samples for organic contaminant analysis should be stored in brown 

borosilicate glass containers with PTFE lid liners. If volatile compounds will be analyzed, containers 

should have a septum to minimize escape of volatile gases during storage and analysis. Extra 

containers should be provided for these analyses in the event that re-analysis of the sample is 

required. If samples are contaminated with photoreactive compounds such as PAHs, exposure to 

light should be minimized by using brown glass containers or clear containers wrapped tightly with 

an opaque material (e.g., clean aluminum foil). Plastic or acid-rinsed glass containers are 

recommended when the chemicals of concern are heavy metals. 

4.1.2 Container Preparation 

Many vendors have commercially available pre-cleaned containers for a variety of applications. For 

chemical and toxicological analyses, certified pre-cleaned containers are often a cost-effective way to 

limit the potential for container contamination of samples. Thus, manufacturer-supplied pre-cleaned 

containers are often a prerequisite in QAPPs. 

If new containers are used, Environment Canada (1994) recommends that new glassware and 

plasticware should be soaked in 1:1 concentrated acid prior to use. Soaking overnight is adequate for 

glassware. For plasticware, the recommended procedure involves soaking for seven days in 

hydrochloric acid (HCl), followed by seven days in nitric acid (HNO3), followed by seven days in 

deionized water. Shorter soaking times might be satisfactory in most instances (ASTM, 2000a). 

Used sample containers should be washed following these steps: (1) non-phosphate detergent wash, 

(2) triple water rinse, (3) water-miscible organic solvent wash (acetone followed by pesticide-grade 

hexane), (4) water rinse, (5) acid wash (such as 5% concentrated HCl) and (6) triple rinse with 

deionized-distilled water. A dichromate-sulfuric acid cleaning solution can generally be used in 

place of both the organic solvent and the acid (Steps 3 through 5), but it might attack any silicone 

adhesive present in the container. See ASTM (2000a) and USEPA (2000d) for further information. 

If a sample is to be refrigerated, the container should be filled to the brim to reduce oxygen exposure. 

This is particularly critical for volatile compounds (e.g., AVS). If a sample is to be frozen, the 

container should be filled to approximately 90% of its volume (i.e., 10% headspace) to allow for 

expansion of the sample during freezing. See Section 4.4 for preservation and storage conditions for 

various types of analyses. For studies in which it is critical to maintain the collected sediment under 

anoxic conditions (e.g., where metals are the pollutants of concern), the container should be purged 

with an inert gas (e.g., nitrogen) before filling and then again before capping tightly. 

Chapter 4: Field Sampling Processing, Transport, and Storage of Sediments and Interstitial Water 4-3 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table 4-1. Recommended sampling containers, holding times, and storage conditions for common 

types of sediment analyses (USEPA, 1983;1993; ASTM, 2000a). P=Plastic; G=Glass; 

PTFE=Polytetrafluoroethylene; R=refrigerate; F=freeze 

Contaminant Container Holding Time Storage Condition 

Ammonia P,G 28 days R; F 

Sulfate P,G 28 days R; F 

Sulfide P,G 28 days R or NaOH; pH>9 

Oil and Grease G 28 days HCl, pH<2 

Mercury P,G 6 weeks H2SO4, pH<2; R 

Metals (except Cr or Hg) P,G 6 months HNO3, pH<2; F 

Extractable organics (including 

phthalates, airosamines, 

organochlorine pesticides, PCBs 

aromatics, isophorone, PAHs, 

haloethers, chlorinated 

hydrocarbons, and TCDD) 

G, PTFE-lined 

cap 

7 days (until 

extraction) 

30 days (after 

extraction) 

R; F 

Purgables (halocarbons and 

aromatics) 

G, PTFE-lined 

septum 

14 days R; F 

Pesticides G, PTFE-lined 

cap 

7 days (until 

extraction) 30 

days (after 

extraction) 

R; F 

Sediment Toxicity (acute and 

chronic) 

P, PTFE 2 weeks* R, dark 

Bioaccumulation testing P, PTFE 2 weeks* R, dark 

*Holding time might be longer depending on the magnitude and type of contaminants present. 

See Section 4.5. 

All sediment containers should be properly labeled with a waterproof marker prior to sampling. 

Containers should be labeled on their sides in addition to or instead of labeling the lids. Each label 

should include, at a minimum, the study title, station location and/or sample identification, date and 

time of collection, sample type, and name of collector. Blind sample labeling (i.e., a sample code) 

should be used, along with a sample log that identifies information about each sample (see Section 

2.7) to minimize potential analytical bias. Additional information such as required analyses and any 

preservative used might also be included on the label although this information is typically recorded 

on the chain-of-custody form (see Section 2.7 and 7.6). Labeled containers should be stabilized in an 

upright position in the transport or storage container (see Section 4.4 Transport and Storage for 

further information). Extra containers should be carried on each sampling trip. 

4-4 US Environmental Protection Agency 
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4.2 Subsampling and Compositing Samples 

The decision to subsample and/or composite sediment samples within or among stations depends on 

the purpose and objectives of the study, the nature and heterogeneity of the sediments, the volume of 

sediment required for analytical and/or toxicity assessment, and the degree of statistical resolution 

that is acceptable. Subsampling and compositing might be accomplished in the field, if facilities, 

space, and equipment are available, or alternatively, in a laboratory setting following sample 

transport. 

Recommendation Box #2 

How should sediment samples be subsampled and composited? 

� Overlying water should be siphoned off, not decanted, from grab samplers prior to 

subsampling. 

� All utensils that are used to process samples should be made of inert materials such as 

Teflon® hi gh quality stainless steel, or HDPE. 

� Subsamples should be collected away from the sides of the sampler to avoid potential 

contamination. 

� Sediment samples should be processed prior to long-term storage, within 72 hours (and 

preferably within 24 hours) of collection. 

� Sufficient sample homogenization, prior to placing in containers, is critical for accurate 

measurements and correct sediment quality determinations. 

� If rigorous evaluation of metal contamination is a focus of the study, or if anaerobic 

conditions need to be maintained for other reasons, it might be necessary to homogenize, 

subsample, and composite samples in an oxygen-free glovebox or other suitable 

apparatus. 

� Similar depth horizons or geologic strata should be subsampled when compositing core 

samples. 

4.2.1 General Procedures 

Subsampling is useful for collecting sediment from a specific depth of a core sample, for splitting 

samples among multiple laboratories, for obtaining replicates within a sample, or for forming a 

composite sample. 

Compositing refers to combining aliquots from two or more samples and analyzing the resulting 

pooled sample (Keith, 1993). Compositing is often necessary when a relatively large amount of 

sediment must be obtained at each sampling site (for instance, to conduct several different physical, 

chemical or biological analyses). Compositing might be a practical, cost-effective way to obtain 

average sediment characteristics for a particular site (see Table 2-2), but not to dilute a polluted 

sample. Also, if an objective of the study is to define or model physicochemical characteristics of 

the sediment, it might be important not to composite samples because of model input requirements 

(EPRI, 1999). 

Chapter 4: Field Sampling Processing, Transport, and Storage of Sediments and Interstitial Water 4-5 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

All utensils (e.g., spoons, scoops, spatulas) which come in direct contact with sediment samples 

during handling and processing should be made of non-contaminating materials (e.g., glass, highquality stainless steel and/or Teflon®). 

Considerations 

All handling procedures carry the risk of sample contamination. 

Therefore, sediment sample handling should be kept to a 

minimum. Potential sample contamination can be caused by 

the following common situations... 

! making field measurements of sediments using contaminated probes, utensils, or other 

instruments. 

!	 contaminated and uncontaminated stations are sampled without appropriate 

decontamination of equipment between stations. 

!	 the parameter of interest is volatile (e.g., ammonia, acid volatile sulfides, or volatile organics) 

and samples are exposed to air. 

! samples are exposed to vessel exhaust fumes, lubricants, or rust. 

4.2.2 Grab Samples 

If a sediment grab sample is to be subsampled in 

the laboratory, the sample should be released 

carefully and directly into a labeled container that 

is the same shape as the sampler and made of a 

chemically-inert material (see Section 4.1 for 

recommendations on containers). The container 

must be large enough to accommodate the 

sediment sample and should be tightly sealed 

with the air excluded. 

If the grab sample is to be subsampled in the 

field, it is desirable to subsample from the 

sampler directly to minimize sediment handling 

and associated artifacts. Therefore, the sampler 

should allow access to the surface of the sample 

without loss of water or fine-grained sediment 

(see Section 3.1.1 for sampler descriptions). This 

typically dictates the use of a grab sampler with 

bucket covers that are either removable or hinged 

to allow access to the surface of the sediment 

sample (e.g., Ponar, VanVeen). 

Prior to subsampling from the grab sampler, the 

overlying water should be removed by slow 

siphoning using a clean tube near one side of the 

sampler (WDE, 1995; PSEP, 1997a). If the 

overlying water in a sediment sampler is turbid, it 

should be allowed to settle if possible. 

Considerations 

When working with 

grab samples... 

!	 decanting the water, or opening the 

jaws lightly to let the water run out is 

not recommended as these methods 

might result in unacceptable 

disturbance or loss of fine-grained 

sediment and organic matter. 

!	 if metal contamination or sediment 

oxygen demand are of concern, 

oxidation of sediments could 

significantly alter their characteristics. 

Process the sample in a glovebox or 

similar apparatus under an oxygen-free 

environment. 

!	 for samples that are suspected of 

heavily elevated polynuclear aromatic 

hydrocarbons (PAHs), process 

immediately under low light upon 

retrieval to minimize ultraviolet lightactivated toxicity of PAHs (Ankley et al., 

1994). 

4-6 US Environmental Protection Agency 
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The general subsampling and compositing 

process for grab samples is illustrated in Figure 

4-2. Subsampling can be performed using a 

spoon or scoop made of inert, noncontaminating material. Sediment which is in 

direct contact with the sides of the grab 

sampler should be excluded as a general 

precaution against potential contamination 

from the device. Subsamples may be combined 

or placed into separate clean, pre-labeled 

containers. If the sample is to be frozen, it is 

advisable to leave approximately 10% head 

space in the container to accommodate 

expansion and avoid breakage. 

There are two alternatives for compositing 

sediment samples from grab samplers (see 

Figure 4-2): (1) compositing and homogenizing 

(mixing) in the field and (2) compositing in the 

field and homogenizing in the laboratory. 

In some studies (e.g., where metals are the 

pollutants of concern), it might be necessary to 

subsample a grab sample under oxygen-free 

conditions to minimize oxidative changes. In 

these cases, it is recommended that a handcoring device be used for subsampling. The 

core should be inserted immediately upon 

retrieval of the sampler, then removed and 

placed into a glove box or bag which is flushed 

with a constant, controlled volume of inert gas. 

Checklist 

Compositing samples 

involves 

In the field 

� placing subsamples from individual 

grab samples in a clean container to 

form a composite sample 

� transporting the composite to a 

laboratory 

� homogenizing the sample at the 

laboratory to prepare it for testing (See 

Section 4.3 for further details) 

In the lab 

� placing subsamples from multiple 

grabs in a clean container 

� mixing the subsamples to form a 

homogeneous composite sample 

� placing the composite sample in one 

or more containers, depending on the 

number of analyses to be performed 

� transporting the composite sample to 

a laboratory (or laboratories) for 

testing 

The sediment within the core can then be extruded under oxygen-free conditions into deaerated 

containers. The presence of oxygen during handling and storage might be relatively unimportant 

(Brumbaugh et al., 1994) or very important (Besser et al., 1995), depending on the sediment 

characteristics, the contaminants of concern, and the study objectives. 

4.2.3 Core Samples 

Subsampling sediment core samples is usually done to focus the assessment on a particular sediment 

horizon or horizons and/or to evaluate historical changes or vertical extent in contamination or 

sedimentation rates. Whenever subsampling of retrieved sediment cores is required, particularly for 

analysis of contaminants, the sediment should be extruded from the core liners and subsampled as 

soon as possible after collection. This can be accomplished in the field if appropriate facilities and 

equipment are available, or in the laboratory after transport. 

Systematic subsampling (see Figure 4-3) involves removing the sediment from the core in sections of 

uniform thickness. Each incremental core section corresponds to a particular sediment depth 

interval. In remedial dredging and geological applications, longer sections (e.g., 25-50 cm) are 

typically used to characterize a site. 

Chapter 4: Field Sampling Processing, Transport, and Storage of Sediments and Interstitial Water 4-7 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Figure 4-2. Alternatives for subsampling and compositing sediment grab samples. 

4-8 US Environmental Protection Agency 
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Figure 4-3. Alternatives for subsampling and compositing sediment core samples. 

Chapter 4: Field Sampling Processing, Transport, and Storage of Sediments and Interstitial Water 4-9

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

The depth horizon(s) sampled will depend on the study objectives as well as the nature of the 

substrate. For toxicological studies, the biologically active layer and sedimentation rates at the site 

might be important factors determining which core sections are sampled. In these studies, 

subsampling depth intervals include the 0 to 2 cm layer (for recent deposition) and the 0 to 5 cm or 0 

to 15 cm layers (for biological activity, depending on resident organisms). Many programs have 

project-specific depths corresponding to study requirements, such as dredging depths for navigation 

or remediation dredging. In many regional or national environmental monitoring programs (e.g., 

EMAP), the uppermost surficial layer is sampled because information on the horizontal distribution 

of sediment contaminants is desired (USEPA, 2000d). 

There are various methods for subsampling sediment cores including gradual extrusion, dissection of 

a core using a jig saw, reciprocating saws, use of a segmented gravity corer, a hand corer, or scoops 

and spoons. Cutting devices range from stainless steel knives to teflon or nylon string. 

A piston-type extruder that applies upward pressure on the sediment is an instrument commonly used 

to gradually expose a core for sectioning in some monitoring programs where specific sediment 

depths have been defined a priori (Kemp et al., 1971). [Note: For dredged material studies and other 

types of remediation projects, where pre-determined depth strata are not necessarily defined, it is 

usually important to view the entire core prior to sectioning or compositing.] The capped core liner 

containing the sediment and overlying water is uncapped at the lower end and placed vertically on 

top of the piston. The top cap is removed and the water is siphoned off to avoid disturbance of the 

sediment-water interface. The core liner is then pushed slowly down 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 thickness using a stainless steel or 

Teflon® cutter (Environment Canada, 1994; Mudroch and Azcue, 1995). A 1- to 2-mm outer layer 

of sediment that has been in contact with the plastic or metal liner should be removed and discarded, 

if possible, to avoid contamination. Each sediment subsample should be placed into a labeled, clean 

and chemically-inert container, or, if subsamples are being composited, into an appropriately sized 

mixing bowl. The size of the container should be as close to the volume of the sediment as possible 

to minimize the head space in the container. If it is desirable to maintain an oxygen-free environment 

during subsampling, then all handling or manipulations should take place in a glove box or bag filled 

with an inert gas and modified to accommodate the core liner through an opening (Environment 

Canada, 1994; Mudroch and MacKnight, 1994). 

Cores of more consolidated material can be mounted onto a horizontal U-shaped rail and the liner cut 

using a saw mounted on a depth-controlling jig. The final cut can then be made with a sharp knife to 

avoid contamination of the sediment by liner material, and the core itself can be sliced with Teflon® 

or nylon string. The core then becomes two D-shaped halves that can be easily inspected and 

subsampled (Mudroch and Azcue, 1995). Sediment in contact with the saw blade should not be used 

for toxicity tests or metals analyses due to potential contamination from the saw blade. Another 

alternative for sectioning and subsampling is a segmented gravity corer described by Aanderaa 

Instruments of Victoria, BC, Canada. The core tube of the sampler consists of a series of rings 

placed on top of one another. Subsampling is carried out by rotating the rings around its other axis 

so that it cuts sediment layers of similar thickness. This segmented core tube is suitable for sampling 

fine-grained sediments and allows one person in the field to subsample the core into 1-cm sections 

(Mudroch and Azcue, 1995). 

Sediment from box-core samples can be effectively subsampled with a small hand corer after the 

overlying water has been carefully siphoned off and discarded. Hand corers with small inner 

diameters less than 3 cm tend to compact sediments, so they must be used with care. Spoons or 

4-10 US Environmental Protection Agency 
Technical Manual 

scoops have also been used to subsample surface sediments from a box corer (Environment Canada, 

1994). 

Like grab samples, core samples may be composited or subsampled in the field or laboratory after 

evaluating them for acceptability. Although there might be occasions when it is desirable to 

composite incremental core depths, it is recommended that only horizons of similar stratigraphy be 

composited. Depending on the study objectives and desired sampling resolution, individual horizons 

within a single core can be homogenized to create one or more “depth composites” for that core, or 

corresponding horizons from two or more cores might be composited (Figure 4-3). Composite 

samples must be homogenized prior to analysis or testing. 

4.3 Homogenization 

Homogenization refers to the complete mixing of sediment to obtain consistency of physicochemical 

properties throughout the sample prior to using in analyses. Homogenization is typically performed 

on individual samples, as well as on composited samples and can be done either in the field or the 

laboratory. 

4.3.1 General Procedures 

Prior to homogenization, unrepresentative materials (e.g., twigs, shells, leaves, stones, wood chips 

and seagrass) are often removed and documented in an appropriate field log (see Section 5.2 for 

techniques to remove unrepresentative material). The need for removal of larger matter depends on 

the analyses to be conducted. 

Mixing should be performed as quickly and efficiently as possible, because prolonged mixing can 

alter the particle-size distribution in a sample and cause oxidation of the sediments (Ditsworth et al., 

1990; Stemmer et al., 1990a;b). This can alter the bioavailability of contaminants, particularly 

metals, by increasing or decreasing their availability (Ankley et al., 1996). If metal contaminants or 

volatile chemicals are a concern, samples should be mixed in a glovebox under an inert atmosphere 

and quickly partitioned into sample containers for analysis. 

Recommendation Box #3 

How should samples be homogenized? 

� Use a sufficiently large, precleaned glass or stainless steel mixing bowl to homogenize 

the sample. 

� Use clean glass polyethylene, or stainless steel implements (e.g., spoon) to mix sediment. 

� Mixing should be performed as quickly and efficiently as possible while attempting to 

reduce oxidation of the sample. 

� Intensive manual mixing of wet sediment, in a suitably large container, is usually sufficient 

to homogenize the sample (Burton et al., 1989; Ingersoll and Nelson, 1990; Johns et al., 

1991a; Carr and Chapman, 1992). 

� Regardless of the mixing method selected, the effectiveness of the method should be 

demonstrated using a homogenate replicate. 

Chapter 4: Field Sampling Processing, Transport, and Storage of Sediments and Interstitial Water 4-11 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Photo courtesy of Nile Kemble 

Homogenizing a composited sediment Photo courtesy of Chris Ingersoll 

sample using a mechanical mixer 

Subsampling sediment for toxicity testing 

4-12 US Environmental Protection Agency 
Technical Manual 

Mixing should be performed in a large, 

precleaned glass or stainless steel bowl. The 

sediment should be thoroughly stirred with a clean 

glass, high density polyethylene, or stainless steel 

spoon until textural, color, and moisture 

homogeneity are achieved (Environment Canada, 

1994; PSEP, 1995). Hand mixing has also been 

performed by rolling the sediment out flat on a 

sheet of plastic or pre-combusted foil and 

tumbling the sediment by alternately raising each 

corner of the sheet (Mudroch and Macknight, 

1994). This procedure, however, is not 

recommended where the anaerobic integrity of the 

sediment must be maintained. 

Considerations 

Homogenization of 

anaerobic sediments... 

!	 Beware of over-mixing and/or 

introducing air to the sample. Such 

mixing is likely to change the chemical 

characteristics of the sample and yield 

unrepresentative results. This is 

especially important if samples are 

initially anaerobic or if volatile or labile 

chemicals are of interest (e.g., AVS). 

Mechanical mixers have also been used to homogenize samples (Ditsworth et al., 1990; Stemmer et 

al., 1990b; Kemble et al., 1993), including portable cement mixers (bare metal and Teflon-lined) and 

portable drills fitted with a variety of stainless steel paddles (Kemble et al., 1994b). 

Homogenate replicates consist of two or more subsamples, taken from different locations within a 

mixed sample, and then comparing analytical results of the replicate samples. After the sediment has 

been homogenized, it is generally partitioned among sample containers. Partitioning sediments for 

chemical or toxicity analyses may be accomplished using various methods. In one method, a number 

of small portions are removed from random locations in the mixing container and distributed 

randomly in all sample jars until the appropriate volume of sediment is contained in each sample jar 

for each analysis. During distribution, the sediment is periodically mixed using a glass rod or 

porcelain spatula to minimize stratification effects due to differential settling, especially if the 

sediment is prone to rapid settling (ASTM, 2000a). An alternative is to use a splitter box designed to 

contain and then divide the homogenized sediment. 

4.4 Sample Transport and Storage 

Transport and storage methods should be designed to maintain structural and chemical qualities of 

sediment and pore water samples. Sediments collected using grab samplers are usually transferred 

from the sampler to containers that may or may not serve as the storage container. The containers 

might be stored temporarily in the field or they might be transported immediately to a laboratory for 

storage. If sediment core samples are not sectioned or subsampled in the field, they may be stored 

upright, in the core liner, for intact transportation to the laboratory. If sectioning or subsampling 

takes place in the field, then the subsamples may also be transferred to sample containers and stored 

temporarily. The sample containers with the field-collected sediments are then placed into a 

transport container and shipped to the laboratory. 

4.4.1 General Procedures 

Proper storage conditions (see Table 4-1) should be achieved as quickly as possible after sampling. 

For those parameters that are preserved via refrigeration (e.g., toxicity) samples should be stored in 

the field in refrigerated units on board the sampling vessel or in insulated containers containing ice or 

frozen ice packs. For samples that can be preserved via freezing (e.g., some metal and organic 

chemical analyses) dry ice can be used to freeze samples for temporary storage and transport 

(USEPA, 1983, 1993). Pelletized dry ice has been used effectively in the dredged materials 

management program to store core samples. It is important to know chilling capacities and 

Chapter 4: Field Sampling Processing, Transport, and Storage of Sediments and Interstitial Water 4-13 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

efficiencies to assure that temperature regulation is adequate. Care should be taken to prevent 

refrigerated samples from freezing and to keep frozen samples from thawing. Freezing changes the 

sediment volume depending on the water content, and it permanently changes the structure of the 

sediment and potentially alters the bioavailability of sediment associated contaminants. 

Logistics for sample transport will be specifically tailored to each study. In some cases it is most 

efficient to transfer samples to a local storage facility where they can be either frozen or refrigerated. 

Depending on the logistics of the operation, field personnel may transport samples to the laboratory 

themselves or utilize an overnight courier service. If a freight carrier is employed, the user must be 

aware of any potentially limiting regulations (e.g. regarding the use of ice or dry ice). Samples that 

have a recommended storage temperature should be cooled to that temperature prior to placement in 

the transport container. Light should be excluded from the transport container. 

Core samples should be transported as intact core liners (tubes). Prior to sample transport, the entire 

space over the sediment in the core liner should be filled with site water, and both ends of the core 

liner should be completely sealed to prevent mixing of the sediment inside. The cores should be 

maintained in an upright position particularly if the sample is not highly consolidated material, and 

secured in either a transport container (e.g., cooler or insulated box) with ice or ice packs, or in a 

refrigerated unit that can maintain a temperature near 4°C (Environment Canada, 1994). If the 

transport container cannot accommodate long core samples such as from vibracorers or piston corers 

(core liners > 1 m), then the core samples can be cut into 1-m lengths, and the ends securely capped 

such that no air is trapped inside the liners (see Section 4.3.3). 

Impregnating unconsolidated sediment cores with epoxy or polyester resins will preserve sediment 

structure and texture (Ginsburg et al., 1966; Crevello et al., 1981) but not sediment chemical 

characteristics. Therefore, this procedure is not recommended for transporting or storing sediment 

samples for chemical characterization or biological testing (Environment Canada, 1994). 

Recommendation Box #4 

Sample Transport and Storage 

� The volume of overlying water in sediment samples should be minimized to reduce the 

potential for resuspension of surface sediments during transport. 

� Care should be taken to retain the surficial floc overlying a core sample. 

� Cores should be secured in an upright position during transport to minimize disturbance 

of the sediment. 

� Sediment samples collected in the field should be stored in containers without 

headspace at 4° C and in the dark to minimize changes in contaminant bioavailability. 

� Prior to transport, headspace in the core liner should be filled with site water and both 

ends of the liner should be completely sealed. 

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4.5	 Sample Holding 

Times 

Limits for effective holding times are 

governed by sediment type and 

contaminant characteristics (ASTM, 

2000a). Because these qualities are 

not always known, a general 

recommendation is to store sediments 

and interstitial water in the dark at 4 

°C (SETAC, 2001). Preservation and 

recommended storage times for 

various types of analyses are 

summarized in Table 4-1. 

Recommendation Box #5 

How long should samples be 

stored before analysis? 

� Unless site-specific information is available, 

sediment samples should be stored no longer 

than two weeks prior to using in toxicity testing. 

� Preserved samples for chemical analyses 

should be stored no longer than the maximum 

holding times as defined by the particular 

program. 

Samples collected for toxicity tests should be used as quickly as possible. Recommended maximum 

holding times range from 10 days (NOAA) to two weeks (ASTM, 2000a; USEPA, 2000d), to eight 

weeks (USEPA/ACOE, 1991, 1998). Preferred sample storage times reported for toxicity tests have 

varied substantially (Dillon et al., 1994; Becker and Ginn, 1990; Carr and Chapman, 1992; Moore et 

al., 1996; Sarda and Burton, 1995; Sijm et al., 1997; Defoe and Ankley, 1998), and differences 

appear to depend primarily upon the type or class of contaminant(s) present. 

Extended storage of sediments that contain high concentrations of labile contaminants (e.g., 

ammonia, volatile organics) might lead to loss of these contaminants and a corresponding reduction 

in toxicity. Under these circumstances, the sediment should be tested as soon as possible after 

collection, but not later than two weeks (Sarda and Burton, 1995). Sediments that exhibit low to 

moderate toxicity might exhibit higher variability in toxicity when tested following storage of short 

duration (e.g. two weeks). Testing could actually be more reliable following longer storage for these 

types of samples if the longer storage reduces potential interference associated with indigenous 

predators (DeFoe and Ankley, 1998). Sediments contaminated with relatively stable compounds 

(e.g. high molecular weight compounds such as PCBs) or those that exhibit moderate-to-high 

toxicity, do not seem to vary appreciably in toxicity with increased storage time (Moore et al., 1996; 

DeFoe and Ankley, 1998). Longer term storage might be acceptable in such cases. Given our 

incomplete knowledge on the changes that occur, it is recommended that sediments should be stored 

no longer than two weeks for toxicity testing unless site-specific information indicates otherwise. 

Periodic measurements of contaminants of concern provide a useful context for interpretation of 

toxicity test results when sediments or interstitial waters are stored for extended periods of time, but 

this is rarely cost-effective. It might be more efficient to conduct interstitial water toxicity tests 

within two weeks of sediment collection, corresponding with the start of sediment tests (Ingersoll et 

al., 1993). In general, though, interstitial water should be analyzed as quickly as possible following 

sampling to minimize possible changes in contaminant bioavailability. 

Sediment cores collected for stratigraphical or geological studies can be stored at 4 °C in a humiditycontrolled room for several months without any substantial changes in sediment properties (Mudroch 

and Azcue, 1995). 

Chapter 4: Field Sampling Processing, Transport, and Storage of Sediments and Interstitial Water 4-15 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

4-16 US Environmental Protection Agency 
CHAPTER 

5 

Technical Manual 

Sediment Manipulations


Manipulation of sediments in the laboratory is often required to achieve certain desired 

characteristics or forms of material for toxicity testing and chemical analysis. As all manipulation 

procedures alter some qualities of field samples, it is critical to evaluate the effect that these changes 

might have on the study objective and on each critical measurement endpoint. Therefore, all 

procedures used to prepare sediment samples should be explicitly described in the study plan and 

fully documented. Generally, manipulation procedures should be designed to maintain sample 

representativeness in terms of toxicity and chemistry by minimizing procedural artifacts. Under 

certain programs, some analytical procedures and toxicity test protocols necessitate specific 

manipulations (e.g., seawater or solvent extractions for effluent toxicity tests, USEPA/ACOE, 1991, 

1998). The reader should always consult and follow any program or test-specific guidance. 

This chapter discusses methods for several common manipulations performed in the laboratory 

including sieving, spiking, organic carbon modification and formulated sediments, sediment dilution, 

and elutriate preparation. Other sediment manipulations, such as salinity adjustments or pretreatment of sediment ammonia or sulfides (often done in conjunction with toxicity testing in certain 

regulatory programs) are not discussed in this manual as these are well documented elsewhere (e.g., 

PSEP, 1995; USEPA/ACOE, 1998). The reader should consult these references for further 

information on these procedures. Figure 5-1 presents a flowchart summarizing the laboratory 

manipulations discussed in this section, illustrating important issues to be considered for each 

manipulation. 

5.1 Sieving 

In general, sieving is not recommended 

because it can substantially change the 

physicochemical characteristics of the 

sediment sample. For example, wet 

sieving of sediment through fine mesh 

(�500 �m openings) has been shown to 

result in decreased percent total organic 

carbon and decreased concentrations of 

total PCBs, which might have been 

associated with fine suspended organic 

matter lost during the sieving process 

(Day et al., 1995). Sieving can also 

disrupt the natural chemical equilibrium 

by homogenizing or otherwise changing 

the biological activity within the 

sediment (Environment Canada, 1994). 

In some cases, however, sieving might be 

necessary to remove indigenous 

organisms, which can interfere with 

subsequent toxicity testing and confound 

Checklist 

Sediment samples are 

sieved for the following 

reasons: 

� To remove unrepresentative material, such 

as shells, stones, trash, and twigs. 

� To increase homogeneity and replicability of 

samples. 

� To remove indigenous organisms prior to 

toxicity testing. 

� To facilitate organism counting, sediment 

handling, and subsampling. 

� To examine the effects of particle size on 

toxicity, bioavailability, or contaminant 

partitioning (ASTM, 2000a). 

Chapter 5: Sediment Manipulations 5-1 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Figure 5-1. Flowchart depicting relationships between common sediment manipulations including 

important considerations. 

5-2 US Environmental Protection Agency 
Technical Manual 

interpretations of analytical results (USEPA, 1994; 2000d; ASTM, 2000e). Indigenous organisms 

can be problematic in toxicity testing because they might be similar in appearance to test organisms 

or they might prey on the test organisms. 

If sieving is performed, it should be done for all samples to be tested, including control and reference 

sediments if the objective of the study is to compare results among stations (ASTM, 2000a). It might 

be desirable to obtain certain measurements (e.g., dissolved and total organic carbon, acid volatile 

sulfide [AVS], and simultaneously extracted metals [SEM]) both before and after manipulation, to 

document changes associated with sieving (USEPA, 2000d). In addition, it might be desirable to 

document the effect of sieving on the sediment sample by conducting comparative toxicity tests using 

sieved and unsieved sediment (Environment Canada, 1994). 

Recommendation Box #1 

Should sediment be sieved prior to analyses? 

� In general, sieving is not recommended because it can substantially change the 

physicochemical characteristics of the sediment sample. However, sieving might be 

necessary in preparing samples for some sediment toxicity testing (i.e., marine amphipod 

tests; USEPA, 1994). 

� Unwanted materials (e.g., large particles and indigenous organisms) can be removed 

from the sediment sample using forceps as a preferred alternative to sieving. 

5.1.1 Sieving Methods 

Press Sieving 

If sieving is necessary, press sieving is the preferred method. In this method, sediment particles are 

hand-pressed through a sieve using chemically inert paddles (Giesy et al., 1990; Johns et al., 1991). 

Matter retained by the screen, such as organisms, shell fragments, gravel, and debris, should be 

recorded in a log book and discarded (USEPA/ACOE, 1991). Samples with high debris, vegetation, 

or clay content might be difficult to press through a single sieve with a mesh size less than 1 mm; 

such samples might need to be pressed through a series of sieves with progressively smaller 

openings. Water should not be added to sediment when press sieving, as this could result in changes 

in contaminant concentration and bioavailability. Samples that are going to be used for both 

chemical analysis and toxicity tests should be sieved together, homogenized, and then split for their 

respective analyses. 

Wet Sieving 

If sediments cannot be press sieved without the addition of pressure, wet sieving might be required, 

however, this type of sieving increases the likelihood of contaminant loss. Wet sieving involves 

swirling sediment particles within a sieve using water to facilitate the mechanical separation of 

smaller from larger particles. A slurry made with water that has separated from the sediment during 

storage or transport might be sufficient to wash particles through the sieve. Wet samples that might 

have settled during transit should be stirred to incorporate as much field water as possible. In some 

cases, addition of a small volume of running site or deionized water might be required (ASTM, 

Chapter 5: Sediment Manipulations 5-3 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Photo courtesy of Allen Burton 

Sieving a sediment sample for toxicity testing 

5-4 US Environmental Protection Agency 
Technical Manual 

2000a). Mechanical shakers or stirring with a nylon brush can also facilitate wet sieving (Mudroch 

and MacKnight, 1994). 

Recommended Sieves 

In general, smaller mesh sieves are 

preferred to reduce loss of fines. 

Stainless steel, brass, or plastic woven 

polymer sieves (e.g., polyethylene, 

polypropylene, nylon, and Teflon) with 

mesh sizes that vary from 0.24 to 2.0 mm 

have been used to sieve sediment for 

toxicity tests (Keilty et al., 1988a;b; 

Giesy et al., 1990; Lydy et al., 1990; 

Stemmer et al., 1990a;b; Johns et al., 

1991; Landrum and Faust, 1991). Nonmetallic sieves are preferred if metals are 

of interest. Stainless steel sieves are 

acceptable if organic compounds are of 

interest. Stainless steel (provided the 

mesh is not soldered or welded to the 

frame), nylon, or Nitex-type plastic 

sieves are recommended when other 

inorganic constituents are of concern or 

Considerations 

The mesh type and size 

should be chosen based on 

the following 

considerations... 

!	 The type of toxicity test and test organisms to 

be used. 

!	 Potential predators and/or competitors present 

in the sample. 

!	 Potential adsorption or contamination of the 

chemical of interest due to sieving. 

!	 The nature of the sample, including its particle 

size distribution, volume, and size of debris. 

are to be analyzed (ASTM, 2000a; PSEP, 1995). 

Recommendation Box #2 

What type of sieve should be 

used? 

� Stainless steel or brass sieves are not 

recommended when metals are a concern or 

are analyzed (ASTM, 2000a). 

� Smaller mesh sieves (�2.0 mm mesh openings) 

are recommended to reduce loss of fine particle 

sizes. 

� Nylon or nitex mesh sieves are recommended 

for inorganics analyses (e.g., metals). 

5.1.2 Alternatives to Sieving 

Generally, sieving through a 10-mesh 

(2-mm openings) sieve is acceptable as 

a basis to discriminate between 

sediment and other materials (ASTM, 

2000a). For toxicity testing, the most 

frequently used mesh size is 1.0 mm 

(Environment Canada, 1994), which 

will remove most adult amphipods. 

However, a mesh of 0.25 mm might be 

needed to remove immature 

amphipods and most macrofauna 

(Landrum et al., 1992; Robinson et al., 

1988; Day et al., 1995). In marine 

sediments, sieves with a mesh size of 

0.5 mm are effective in removing most 

of the immature amphipods (Swartz et 

al., 1990; PSEP, 1995). 

Unwanted materials (e.g., large particles, trash, and indigenous organisms), can be removed from the 

sediment sample using forceps, prior to or, as an alternative to, sieving. If anerobic integrity of the 

sample is not a concern, the sediment could be spread on a sorting tray made of cleaned, chemicallyinert material, and should be hand-picked with forceps. A stereomicroscope or magnifying lens 

might facilitate the process, or may be used to determine if sieving is necessary. Hand-picking is 

Chapter 5: Sediment Manipulations 5-5 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

preferable to sieving because it is less disruptive, but it typically is not practical for large volumes of 

sediment. Of course, this process oxidizes the sediment and might alter contaminant bioavailability. 

Autoclaving, freezing, and gamma irradiation of sediments are alternatives to physical removal for 

inhibiting endemic biological activity in field-collected sediments. These are not generally 

recommended procedures. Each method has unique effects on the physicochemical and biological 

characteristics of the sediment, and a careful evaluation with respect to the study objectives is 

warranted when these methods are considered. 

Considerations 

In preparing formulated sediments, the following should be 

noted... 

!	 Specific material sources should be carefully selected, as characteristics can vary 

significantly among product types. A number of suppliers of various sediment components 

are listed in ASTM (2000a) and USEPA (2000d). 

!	 A critical component of formulated sediments is the source of organic carbon. It is not clear 

that any one source of organic carbon is routinely superior to another. Alpha cellulose 

appears to be a promising carbon source for formulated sediments. 

!	 A variety of formulations have been used successfully in sediment toxicity testing (see 

ASTM [2000a] and USEPA [2000d]). At this time, no one formulation appears to be 

universally better than others. 

5.2 Formulated Sediment and Organic Carbon Modification 

5.2.1 General Considerations 

Formulated sediments (also called 

reconstituted, artificial, or synthetic 

sediments) are mixtures of materials that 

mimic the physical components of natural 

sediments. While they have not been used 

routinely, formulated sediments potentially 

offer advantages over natural sediments for 

use in chemical fate and biological effects 

testing. 

Formulated sediments also have limitations, 

however. They do not possess the natural 

microbial, meiofaunal, and macrofaunal 

communities or the complex organic and 

inorganic gradients prevalent in natural 

sediments. The lack of biological activity, 

diagenesis, and oxidation-reduction (redox) 

potential gradients undoubtedly alters some 

sorption and desorption properties, which 

Checklist 

Advantages of 

Formulated Sediments 

� They provide a consistent, reproducible 

medium which facilitates comparisons 

between different sets of tests. 

� Eliminates interferences caused by the 

presence of indigenous organisms. 

� Components of the formulated sediment 

can be altered to measure the effect of 

certain physicochemical characteristics 

on chemical fate and bioavailability. 

� They are useful in spiking experiments 

to obtain effect concentrations for 

chemicals. 

5-6 US Environmental Protection Agency 
Technical Manual 

might in turn alter contaminant fate and effects. The current lack of understanding of 

physicochemical controls on bioavailability in different sediment environments precludes broad-scale 

use of formulated sediments in definitive ecological risk assessments. 

A formulated sediment should: (1) support the survival, growth, or reproduction of a variety of 

benthic invertebrates, (2) provide consistent acceptable biological endpoints for a variety of species, 

and (3) be composed of materials that have consistent characteristics (USEPA, 2000d; ASTM, 

Checklist 

Disadvantages of 

Formulated Sediments 

� They might be overly simplistic 

biologically and chemically. 

� An appropriate formulation is not well 

established for all applications. 

5.2.2 Sediment Sources 

2000a). Characteristics should include: 

(1) consistency of materials from batch to 

batch, (2) contaminant concentrations 

below concentrations of concern, and 

(3) availability to all individuals and facilities 

(Kemble et al., 1999). Physicochemical 

characteristics that might be considered when 

evaluating the appropriateness of a sediment 

formulation include percent sand/clay/silt, 

organic carbon content, cation exchange 

capacity (CEC), redox potential, pH, and 

carbon:nitrogen:phosphorous ratios (USEPA, 

2000d; ASTM, 2000a). 

The specific material source should be carefully selected, as characteristics can vary significantly 

among product types. For example, USEPA (2000d) found that for three different sources of 

kaolinite clay, the percentage of clay ranged from 56.5 to 88.5%, depending on individual product 

specifications. There are a number of suppliers of various sediment components (see USEPA, 

2000d). 

A critical component of formulated sediments is the source of organic carbon. It is not clear that any 

one source of organic carbon is routinely superior to another source. 

5.2.3 Organic Carbon Modification 

Organic carbon content of natural as well as formulated sediments can be modified to assess the 

effect on contaminant fate and bioavailability. Many studies employ sediment carbon modifications 

because total organic carbon (TOC) content has been shown to be a major determinant of nonionic 

organic chemical bioavailability (DiToro et al., 1991; DeWitt et al., 1992; and Kosian et al., 1999). 

While TOC modifications might be necessary to achieve study objectives, it should be recognized 

that organic carbon manipulations can change the particle composition and size distribution, thereby 

potentially affecting contaminant equilibrium. Thus, results from such experiments should be 

interpreted with care. Also, the sample needs to be equilibrated (see Section 5.3.3) following 

addition of the new source of organic carbon, prior to conducting analyses. 

Many recipes have used peat as the source of organic carbon, however, the quality and characteristics 

of peat moss can vary from bag to bag. Other sources of organic carbon include humus, potting soil, 

maple leaves, composted cow manure, rabbit chow, cereal leaves, chlorella, trout chow, Tetramin®, 

Tetrafin®, and alpha cellulose. Of these, only peat, humus, potting soil, composted cow manure, and 

alpha cellulose have been used successfully in sediment testing without fouling the overlying water; 

Chapter 5: Sediment Manipulations 5-7 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

other sources have caused dissolved oxygen concentrations to fall to unacceptable levels (Kemble et 

al., 1999). 

More about organic carbon modification: 

Five studies compared organic carbon sources in formulated sediments. A study of 31 different 

organic carbon recipes by Environment Canada (1995) compared effects on sediment 

homogeneity, density, and turbidity. Cerophyll and trout chow were selected as the optimal 

organic carbon sources with high clay (kaolin at 50 or 75% total concentration) and fine sand. 

Ribeiro et al. (1994) recommended use of synthetic alpha-cellulose as a carbon source 

amended with humic acid. This compound has since been tested by Kemble et al (1999), 

Sawyer and Burton (1994), and Fleming and Nixon (1996). Ribeiro et al. (1994) found that 

sorption was dependent on the amount of organic carbon present. Kemble et al. (1999) found 

that growth and survival of Chironomus tentans and Hyalella azteca was better in 10% than in 

2% alpha-cellulose. Both alpha-cellulose and conditioned red maple leaves were found to be 

suitable as organic carbon amendments for reference toxicant testing with Hyallela azteca (96 

hr) when spiked with cadmium, zinc, or anthracene (Sawyer and Burton, 1994). 

Use of alpha cellulose as a carbon source for sediment-spiking studies has not been adequately 

evaluated, but it appears to be promising. Alpha cellulose is a consistent source of organic 

carbon that is relatively biologically inactive and low in concentrations of chemicals of concern. 

Furthermore, Kemble et al. (1999) reported that conditioning of formulated sediment was not 

necessary when alpha cellulose was used as a carbon source for a negative control sediment. 

Compared with other sources of organic carbon, alpha cellulose is highly polymerized and would 

not serve as a food source, but rather would serve to add texture or provide a partitioning 

compartment for chemicals. 

Reductions in organic carbon content have been achieved by diluting sediment with clean sand (See 

Section 5.4; Clark et al., 1986; Clark et al., 1987; Tatem, 1986; Knezovich and Harrison, 1988). 

However, this can change sediment characteristics resulting in non-linear responses in toxicity 

(Nelson et al., 1993). Combustion has also been used to remove fractions of organic carbon (Adams 

et al., 1985; IJC, 1988). However, this method results in substantial modification of the sediment 

characteristics, including oxidization of some inorganic components. 

The ratio of carbon to nitrogen to phosphorous might be an important parameter to consider when 

selecting an organic carbon source. This ratio can vary widely among carbon sources (ASTM, 

2000a; USEPA, 2000d). For example, carbon can range from 30 to 47%, nitrogen from 0.7 to 45 

mg/g, and phosphorous from below detection limits to 11 μg/g for several different carbon sources 

(USEPA, 2000d). 

A variety of formulations have been used successfully in sediment toxicity testing (see ASTM, 2000a 

and USEPA, 2000d). At this time, no one formulation appears to be universally better than others. 

5.3 Spiking 

Spiking involves adding one or more chemicals to sediment for either experimental or quality control 

purposes. Spiking environmental samples is used to document recoveries of an analyte and thereby 

analytical bias. Spiked sediments are used in toxicity tests to determine effects of material(s) on test 

species. Spiking tests can also provide information concerning chemical interactions and 

transformation rates. The design of spiking experiments, and interpretation of results, should always 

consider the ability of the sediment to sequester contaminants, recognizing that this governs many 

chemical and biological processes (O’Donnel et al., 1985; Stemmer et al., 1990a;b; ASTM, 2000a; 

5-8 US Environmental Protection Agency 
Technical Manual 

Northcott and Jones, 2000). In preparation for toxicity and bioaccumulation tests, references 

regarding the choice of test concentrations should be consulted (USEPA, 2000d; ASTM, 2000a; 

Environment Canada, 1995). Program specific guidance documents should also be consulted as 

appropriate. 

Several issues regarding sediment spiking are addressed in this section. First, several methods have 

been used to spike sediments but the appropriate method needs to be selected carefully depending on 

the type of material being spiked (e.g., soluble in water or not), its physical-chemical form, and 

objectives of the particular study. Second, spiked material should be uniformly distributed 

throughout the sediment. Otherwise, analyses or toxicity tests are likely to yield highly variable 

results, depending on the concentration of spiked material present. Third, the spiked material needs 

to be at equilibrium between the sediment and the interstitial water to ensure that all relevant 

exposure phases are appropriately considered in chemical analyses or toxicity testing. The time it 

takes to reach this equilibrium is a critical factor that needs to be considered and documented. 

Recommendation Box #3 

How should sediments be spiked with a chemical or other test 

material? 

� Regardless of the spiking technique used, care should be taken to ensure complete and 

homogenous mixing. 

� Replicate subsamples should be analyzed to confirm homogeneous mixing. 

� Moisture content should be determined on triplicates for each sample so that the spike 

concentration can be normalized on a dry weight basis. 

� Wet spiking is recommended over dry spiking methods. 

� Generally speaking, the jar rolling method is more suitable than hand mixing for spiking 

larger batches of sediment. 

� To ensure chemical equilibrium between the sediment and pore water in toxicity testing, 

spike sediments should be stored for at least one month, unless other information is 

available for the spiking material and sediment type. 

� Direct addition of organic solvent carriers should be avoided because they might alter 

sediment chemistry and affect contaminant bioavailability. Shell coating methods should 

be used instead as this eliminates many of the disadvantages of solvent carriers. 

5.3.1 Preparation for Spiking 

Debris and indigenous organisms should be removed from sediment samples as soon as possible after 

collection to reduce deterioration of sediment quality due to decomposition of organic debris and 

dying infauna. If sediments are to be stored prior to spiking, they should be kept in sealed containers 

at 4 °C. 

Regardless of the spiking technique used, care should be taken to ensure complete and homogenous 

mixing (See Section 4.4). It is recommended that chemical analyses be conducted to verify that 

concentrations of the spiked contaminants are uniform throughout the mixed material. Three or more 

subsamples of the spiked sediment should be randomly collected to determine the concentration of 

Chapter 5: Sediment Manipulations 5-9 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

the substance being tested. In general, the coefficient of variation (CV) should be �20% for 

homogeneity of mixing to be considered sufficient (ASTM, 2000a; Northcott and Jones, 2000). 

Temperatures should be kept cool during spiking preparation (e.g., 4° C) due to rapid 

physicochemical and microbiological alterations which might occur in the sediment that, in turn, 

might alter bioavailability and toxicity (ASTM, 2000a; Environment Canada, 1995). If spiking PAH 

compounds, it might be important to conduct spiking in the dark, or at least under low light as PAH 

toxicity has been shown to increase under ultraviolet light (Ankley et al., 1994). 

It is recommended that a subsample of the spiked sediment be analyzed for at least the following 

parameters: moisture content, pH, ammonia, total organic carbon (TOC), acid volatile sulfide 

(AVS), particle size distribution, and background levels of the chemical(s) to be spiked. Further 

characterization may include analyses of total volatile residue, pore water salinity (before and after 

any sieving), chemical oxygen demand, sediment oxygen demand, oxidation-reduction potential (Eh), 

metals, total chlorinated organic content, chlorinated organic compounds, and polycyclic aromatic 

hydrocarbons (see Appendix G for more information on physicochemical parameters often measured 

on sediments). It is particularly important to determine the TOC concentration if the sediment is to 

be spiked with a nonionic organic compound, as organic carbon is the primary binding phase for such 

compounds (DiToro et al., 1990). Similarly, the concentration of AVS (the primary binding phase 

for cationic metals in anoxic sediments) and TOC should be measured after spiking with a cationic 

metal (Ankley et al., 1996; Leonard et al., 1999). 

The sediment moisture content measurement is used to standardize the amount of chemical spiked on 

a dry weight basis (see Appendix G). Generally, the moisture content should be determined on 

triplicates for each sample by measuring the weight lost following 24 h of oven-drying at 105 °C. 

After drying, the samples should be cooled to room temperature in a desiccator before taking dry 

weight measurements (Yee et al., 1992). The mean wet density, expressed as mg water/cm3

, is 

measured by using the same drying method on known sediment volumes. This allows spiking to be 

normalized from a volume basis to an equivalent dry weight basis. 

5.3.2 Methods for Spiking 

Spiking of both wet and dry sediments is common, but wet spiking is recommended because drying 

might reduce the representativeness of the sample by changing its physicochemical characteristics 

(ASTM, 2000a). Methods differ mainly in the amount of water present in the mixture during 

spiking, the solvent used to apply the toxicant, and the method of mixing. Generally speaking, the jar 

rolling method is more suitable than hand mixing for spiking larger batches of sediment. 

In addition to the above techniques, sediments may be spiked by hand stirring using a scoop or 

spatula, as long as the homogeneity of the mixture is verified. Eberbach and gyro-rotary shakers 

have also been used effectively to mix spiked sediments (Stemmer et al., 1990a). Less commonly, 

chemical(s) are added to the water overlying the sediment and allowed to sorb with no mixing 

(Stephenson and Kane, 1984; O’Neill et al., 1985; Crossland and Wolff, 1985; Pritchard et al., 1986). 

Sediment Rolling 

One of the recommended wet sediment rolling techniques requires a specific jar-rolling apparatus, 

first described by Ditsworth et al. (1990). Many other jar-rolling apparatuses are available, ranging 

in size and options available. This “rolling mill” method has been used to homogenize large volumes 

of sediments spiked with metals and non-ionic organic compounds. The primary disadvantage of this 

method is that the mixing apparatus must be constructed or purchased. 

5-10 US Environmental Protection Agency 
Technical Manual 

The jar-rolling apparatus used by Ditsworth et al. (1990) consists of eight parallel, horizontal rollers


powered by an electric motor through a reduction gear, belts, and pulleys, which rotate cylindrical


vessels containing the substrate mixtures. Mixing is accomplished gravimetrically by slowly rolling


the jars (gallon-sized jars can be rolled at approximately 15 rpm). Optimally wetted, individual


substrate particles adhere to each other and to the wall of the revolving jar until they cascade or


tumble down the surface of the substrate mass. Dilution water may be added to the substrate before


rolling to adjust the sediment-to-water ratio for


optimal mixing. If oxidation is a concern (for


example, if the sample will be analyzed for metals), Considerations


jar contents might need to be maintained in an inert When rolling
 atmosphere. If PAHs are of concern then jars should sediment:


be shielded from light (Ankley et al., 1994).


Each jar should be loaded with the required amount of


wet base sediment (with a calculated mass of dry ! Jars should not be overfilled, as


sediment required for the test) prior to introduction of this will reduce mixing efficiency.


the toxicant. Several 1-cm diameter holes of different ! Prolonged rolling (e.g., > 1 wk)


depths should be punched into the sediment to provide should be avoided to minimize


more surface area for the initial distribution of the test physicochemical changes to the


sediment. material. A predetermined volume of the stock 

solution or a serial dilution of the stock should be 

used to spike each jar load of sediment. A volumetric 

pipette should be used to distribute each aliquot onto the top surface and into the holes of the 

sediment in each jar. Sediments should be spiked sequentially, proceeding from low to high 

concentrations of test material, to minimize cross-contamination. Control substrates should be 

prepared by adding an equivalent volume of dilution water to a jar loaded with unspiked sediment. 

After spiking, all jars and their contents should be processed identically. 

Typically, jars should be rolled for greater than two hours to achieve sample homogeneity. Jars 

should be closely monitored during the first hour of rolling to ensure proper mixing of substrates. 

After rolling for approximately 15 min, mixing efficiencies of the substrates can be judged visually. 

If a sediment displays excessive cohesiveness, as indicated by agglomerating or balling, the jars 

should be opened and an aliquot of appropriate dilution water (50 mL of either saltwater or 

freshwater depending on the source of the sediment) added to each substrate to increase the fluidity. 

This procedure should be repeated as necessary until the operator visually observes that all substrates 

are tumbling without forming balls. Adding water in small rather than large aliquots can prevent 

over-saturation of the sediment. Over-saturation is undesirable because excess water must be 

decanted following rolling, prior to sediment testing. 

After rolling, the jars should be gently shaken to settle sediment that adhered to the walls. They may 

be set upright and stored overnight in the dark at room temperature or at an alternate temperature 

(e.g., 4° C) depending on the study objectives. After equilibration (see Section 5.3.3) and prior to 

distributing the sample to test chambers, additional rolling for two hours will help integrate 

interstitial water into the sediment. 

Sediment Suspension Spiking 

The sediment suspension technique (Cairns et al., 1984; Schuytema et al., 1984; Stemmer et al., 

1990a; b; Landrum and Faust, 1991; Landrum et al., 1992) is the simplest of the three spiking 

techniques and requires the least equipment. The method involves placing dilution water and 

sediment together in a 1-L beaker. The desired amount of toxicant, dissolved in dilution water, is 

Chapter 5: Sediment Manipulations 5-11 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

added to the beaker. The mixture should be stirred at a moderate speed with a stir bar, or mechanical 

stirrer, for a minimum of four hours. The sediment in the beakers should then be allowed to settle 

and equilibrated at the appropriate test temperature as specified in the test method. The excess water 

overlying the sediment is decanted and discarded, and the sediment is distributed to the test 

containers (Environment Canada, 1995). 

Slurry Spiking 

The slurry technique (Birge et al., 1987; Francis et al., 1984; Landrum and Faust, 1991; Landrum et 

al., 1992) requires a minimum of equipment and involves less water than the sediment suspension 

technique. A 250-g dry weight sample of sediment is placed in a 500-mL Erlenmeyer flask. Via a 

25-mL aliquot of distilled, deionized water, a sufficient concentration of the materials of interest is 

added to obtain the desired sediment concentration (mg/kg, dry weight basis). Control (unspiked) 

sediment receives a 25-mL aliquot of distilled, deionized water having no added materials. The 

sealed flask may be mixed using various methods such as continuous agitation in a shaker for five 

days (Birge et al., 1987) or vigorous shaking for 60 seconds, twice daily for seven days (Francis et 

al., 1984). Following mixing, the sediment suspensions should be centrifuged to remove water. The 

moisture content of the sediment should be approximately 15% to 20% after centrifugation. After 

removal of excess water, the prepared sediment can be placed in the exposure chambers and covered 

with dilution water according to the specific test methods. This procedure often yields sediment 

having its original moisture content. 

5.3.3 Equilibration Times 

Prior to distributing the spiked sediment to containers for toxicity testing or chemical analyses, the 

spiked sediments should be stored for a sufficient time to approach chemical equilibrium in the 

test material between the sediment and interstitial water. Equilibration times for spiked sediments 

vary widely among studies (Burton, 1991), depending on the spiking material and sediment type. For 

metals, equilibration time can be as short as 24 h (Jenne and Zachara, 1984; Nebecker et al., 1986), 

but one to two weeks is more typical (ASTM, 2000a). For organic compounds with low octanolwater partition coefficients (Kow), equilibration times as short as 24 h have been used (Dewitt et al., 

1989). Some organic contaminants might undergo rapid microbiological degradation depending on 

the microbial population present in the sample. In these cases, knowledge of microbial effects might 

be important in defining an appropriate equilibration period. Organic compounds with a high 

partition coefficient might require two months or more to establish equilibrium (Landrum et al., 

1992). Boundaries for the sorption time can be estimated from the partition coefficient, using 

calculations described by Karickhoff and Morris (1985a, b). It is important to recognize that the 

quantity of spiked chemical might exceed the capacity of the test sediment system, prohibiting 

equilibrium. 

For research purposes, unless definitive information is available regarding equilibration time for a 

given contaminant and sediment concentration, a one-month equilibration period is recommended, 

with consideration that two months might be needed in some instances (USEPA, 2000d). For 

regulatory programs, however, sample holding time should not exceed 2 weeks. Therefore, for these 

programs spiking equilibration time should not exceed 2 weeks. Periodic monitoring during the 

equilibration time is highly recommended to empirically establish stability of interstitial water 

concentrations (USEPA, 2000d). Sediment and interstitial water chemical concentrations should also 

be monitored during long-term bioassay tests to determine the actual chemical concentrations to 

which test organisms are exposed, and to verify that the concentrations remain stable over the 

duration of the test. 

5-12 US Environmental Protection Agency 
Technical Manual 

5.3.4 Use of Organic Solvents 

Direct addition of organic solvents should be avoided if possible, because they might dramatically 

affect sediment geochemistry and alter bioavailability (USEPA, 2000d). However, many organic 

materials require use of a solvent to adequately mix with the sediment. If an organic solvent is to be 

used, the solvent should be at a concentration that does not affect test organisms and should be 

uniform across treatments. Further, both solvent control and negative control sediments should be 

included in tests with solvents. The solvent concentration in the control should equal the treatment 

concentration and should be from the same batch used to make the stock solution (ASTM, 2000a). 

To reduce the possibility of solvent-related artifacts, the spiking process should include a step which 

allows the solvent to evaporate before addition of sediment and water followed by rolling (McLeese 

et al., 1980; Muir et al.,1982; Adams et al., 1985). Highly volatile organic compounds have been 

spiked into sediments using co-solvents followed by shaking in an aqueous slurry. When highly 

volatile compounds are used, immediate testing in covered flow-through systems is recommended 

(Knezovich and Harrison, 1988). 

There is some uncertainty concerning artifacts introduced by the use of solvents. The use of a polar, 

water soluble carrier such as methanol was found to have little effect on the partitioning of nonpolar 

compounds to dissolved organic matter at concentrations up to 15% carrier by volume (Webster et 

al., 1990). However, another study showed that changes in partitioning by a factor of approximately 

two might occur with 10% methanol as a co-solvent for anthracene sorption (Nkedi-Kizza et al., 

1985). The effect of carrier volume on partitioning of organic chemicals in sediments is equivocal. 

However, because solvents might be either directly or indirectly toxic to the test organisms, caution 

should be taken to minimize the amount of carrier used. In addition, the use of a carrier such as 

acetone might result in faster equilibration of spiked organic compounds (Schults et al., 1992). 

Shell coating techniques which introduce dry chemical(s) to wet sediment have also been developed, 

principally to eliminate the potential disadvantages of solvent carriers. The chemical may be either 

coated on the inside walls of the container (Ditsworth et al., 1990; Burgess et al., 2000) or coated 

onto silica sand (Driscoll et al., 1997; Cole et al., 2000). In each shell coating method, the chemical 

is dissolved in solvent, placed in a glass spiking container (with or without sand), and the solvent is 

slowly evaporated prior to addition of the wet sediment. Wet sediment then sorbs the chemical from 

the dry surfaces. It is important that the solvent be allowed to evaporate prior to adding sediment or 

water. 

5.4 Preparation of Sediment Dilutions 

Spiked or field-contaminated sediments can be diluted with whole sediment to obtain different 

contaminant concentrations for concentration-effects testing. The diluent sediment should have 

physicochemical characteristics similar to the test sediment, including organic carbon content and 

particle size, but should not contain concentrations of contaminants above background levels 

(ASTM, 2000a; Burton, 1991). Diluent sediment has included formulated sediment as well as known 

reference site sediment. Diluted sediment samples should be homogenized and equilibrated in 

accordance with procedures described in Sections 4.4 and 5.3.3, respectively. 

The diluent sediment should be combined with the test sediment in ratios determined on a dry weight 

basis to achieve the desired nominal dilution series (DeWitt, personal communication). Volume to 

volume dilutions have also been performed (e.g., Schlekat et al.,1995; Johns et al., 1985), but weight 

to weight dilutions are preferred because they provide more accurate control and enable a more 

straightforward calculation of dose-response curves. 

Chapter 5: Sediment Manipulations 5-13 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Results from dilution experiments should be interpreted with care. There are often non-linear 

responses due to non-equilibrium, non-linear sorption-desorption processes that cannot always be 

adequately controlled (Nelson et al., 1993). Nelson et al. (1993) found that analyses of diluted 

sediments did not match nominal concentrations as estimated by physical characteristics. They 

suggested that chemical characterization is needed to determine effects of manipulations (i.e., 

mixing) and resulting changes (i.e., oxygenation of complexing agents such as acid volatile sulfides). 

5.5 Preparation of Sediment Elutriates 

Many studies of sediment toxicity have evaluated aqueous extractions of suspended sediment called 

elutriates. The elutriate method was initially developed to assess the effects of dredging operations 

on water quality (U.S. ACOE, 1976). Elutriate manipulations are also applicable to any situation 

where the resuspension of sediment-bound toxicants is of concern, such as bioturbation and storms, 

that might disturb sediments and affect water quality (USEPA/ACOE, 1991, 1998; Ankley et al., 

1991). USEPA/ACOE (1998) lists eighteen freshwater and saltwater aquatic organisms as 

candidates for elutriate toxicity testing. Standard effluent toxicity test procedures are also 

appropriate for elutriates, including tests with various vascular and non-vascular plant species 

(Ingersoll, 1995). 

Elutriate tests are not intended to reflect the toxicity of interstitial waters or whole sediments, as 

there are differences in contaminant bioavailability in the two types of media (Harkey et al., 1994). 

In general, elutriates have been found to be less toxic than bulk sediments or interstitial water 

fractions (Burgess et al., 1993; Ankley et al., 1991), although in some studies elutriates have been 

found to be more toxic (Hoke et al., 1990) or equally as toxic (Flegel et al., 1994) relative to 

interstitial water. 

While there are several procedural variations, the basic method for elutriate preparation involves 

combining various mixtures of water and sediment (usually in the ratio of 4 parts water to 1 part 

sediment, by volume) and shaking, bubbling or stirring the mixture for 1 hour (Ross and Henebry, 

1989; Daniels et al., 1989; Ankley et al., 1991; Burgess et al., 1993; USEPA/USACOE, 1991, 1998). 

It is likely that chemical concentrations will vary depending on the elutriate procedure used. Specific 

program guidance should be consulted as appropriate. The water phase is then separated from the 

sediment by settling and/or centrifugation (Note: the dredging remediation program does not always 

require centrifuging elutriates). Once an elutriate has been prepared, it should be analyzed or used in 

biological tests immediately, or as soon as possible thereafter. It should be stored at 4 °C for not 

longer than 24 h, unless the test method dictates otherwise (Environment Canada, 1994; 

USEPA/ACOE, 1991, 1998). For toxicity test exposures exceeding 24 h, fresh elutriate should be 

prepared daily. 

Filtering the elutriate is generally discouraged, but it might be prescribed for some toxicity tests. 

Filtration can reduce the toxicity of sediment elutriates due to sorption of dissolved chemicals on the 

filtration membrane and retention of colloids. If colloidal material needs to be removed, serial or 

double centrifugation is generally a preferred alternative. If an elutriate must be filtered, it is 

recommended that only pre-treated filters be used and that the first 10 to 15 mL of the elutriate to 

pass through the filter be discarded (Environment Canada, 1994). Testing with a filtered elutriate 

should include an assessment to determine the extent of analyte adsorption/desorption to/from the 

filter. 

5-14 US Environmental Protection Agency 
Technical Manual 

Recommendation Box #4 

How should sediment elutriates be performed? 

� Combine 1 part sediment with 4 parts water unless a specific program stipulates 

otherwise. 

� The sediment-water mixture should be vigorously shaken, bubbled or stirred for 1 hour. 

� Centrifugation is a useful means for isolating the water phase (elutriate). 

� Once prepared, the elutriate should be analyzed or tested as soon as possible. 

� Store elutriate at 4° C with little or no headspace until analysis. 

� Filtering the elutriate (to remove colloidal material) is generally not recommended. Use 

double (serial) centrifugation if appropriate. 

Chapter 5: Sediment Manipulations 5-15 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

5-16 US Environmental Protection Agency 
Technical Manual 

Collection of Interstitial Water


CHAPTER 

6 

Sediment interstitial water, or pore water, is defined as the water occupying the spaces between 

sediment particles. Interstitial water might occupy about 50% (or more) of the volume of a 

depositional (silt-clay) sediment. The interstitial water is in contact with sediment surfaces for 

relatively long periods of time and therefore, might become contaminated due to partitioning of the 

contaminants from the surrounding sediments. In addition, interstitial waters might reflect ground 

water – surface water transition zones in upwelling or downwelling areas. In these areas their 

chemistry might be more reflective of ground or surface waters at the site. Therefore, flow, residence 

time and other physicochemical factors (e.g., pH, temperature, redox potential, organic carbon, 

sulfides, carbonates, mineralogy) might have varying roles in determining whether interstitial waters 

are contaminated. 

In many depositional sediments, interstitial waters are relatively static, and therefore contaminants in 

the interstitial water and in the solid phase are expected to be at thermodynamic equilibrium. This 

makes interstitial waters useful for assessing contaminant levels and associated toxicity. Interstitial 

water is often isolated to provide either a matrix for toxicity testing and/or to provide an indication of 

the concentration and/or partitioning of contaminants within the sediment matrix. 

6.1 General Procedures 

Interstitial water sampling has become especially important in regulatory programs because 

interstitial water toxicity tests yield additional information not currently provided by solid-phase, 

elutriate, or sediment extract tests (Carr and Chapman, 1992; SETAC, 2001). Furthermore, 

interstitial water toxicity tests have proven to be useful in sediment toxicity identification evaluation 

(TIE) studies (e.g., Burgess et al., 1996; Carr, 1998; Burton, 2001) as test procedures and sample 

manipulation techniques are generally cheaper, faster, and easier to conduct than solid-phase tests 

(SETAC, 2001). Thus, the collection of interstitial water has become increasingly important in 

sediment quality monitoring and remediation programs. 

Interstitial water sampling is most suitable for sediment types ranging from sandy to uncompacted 

silt-clays (Sarda and Burton, 1995; SETAC, 2001). Such sampling is not typically performed on 

sediments with coarse particle size (such as gravel) or on hard, compacted clays, as the potential for 

interstitial water contamination in these sediment types is relatively low. 

As with all sampling discussed in this manual, the principle aim is to use procedures that minimize 

changes to the in situ condition of the water. It should be recognized that most sediment collection 

and processing methods have been shown to alter interstitial water chemistry (e.g., Schults et al., 

1992; Bufflap and Allen, 1995; Sarda and Burton, 1995), thereby potentially altering contaminant 

bioavailability and toxicity. 

Laboratory-based methods (e.g., centrifugation, pressurization, or suction) are commonly used as 

alternatives to in-situ interstitial water collection (see Section 6.2). While these methods have been 

shown to alter interstitial water chemistry, they’re sometimes necessary or preferred, especially when 

larger sample volumes are required (e.g., for toxicity testing). 

Chapter 6: Collection of Interstitial Water 6-1 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

As both in-situ and laboratory-based or ex-situ (e.g., methods might be appropriate for many study 

objectives, it is critical that the same procedures are used for all stations sampled in a study, or 

program, so that appropriate sample comparisons can be made. Furthermore, the sediment depth 

at which interstitial water is sampled (either using in-situ or ex-situ extraction methods) should 

match the depth of interest in the study (SETAC, 2001). For example, samples for dredging 

remediation should be sampled to the depth to be disturbed by dredging activity, whereas samples for 

a status and trends survey should be collected at the biologically active depth (often < 15 cm). 

Figure 6-1 summarizes the major considerations for selecting in-situ or ex-situ procedures in a given 

study. 

The two major issues of concern regarding interstitial water sample integrity are: 1) the ability of the 

sampling device to maintain physicochemical conditions in the natural state by minimizing 

adsorption/leaching of chemicals to/from the device, and 2) the ability to maintain the sample in the 

redox state existing at the site. Precautions required to reduce the likelihood of sample artifacts will 

vary with each study as indicated in the following sections. 

6.2 In-situ Collection 

In situ methods might be superior to ex-situ methods for collecting interstitial water, as they are less 

subject to sampling/extraction related artifacts and therefore, might be more likely to maintain the 

chemical integrity of the sample (Sarda and Burton, 1995; ASTM 2000a; SETAC, 2001). However, 

in situ methods have generally produced relatively small volumes of interstitial water, and often 

limited to wadeable or diver-accessible 

water depths. These logistical 

constraints have limited their use and 

applicability in sediment monitoring Recommendation Box #1 

studies. In-situ interstitial water 

collection 

The principal methods for in situ


collection of interstitial water involve


either deployed “peepers” (Bufflap and 

� Use peepers for sampling interstitial waters,


rather than (or in addition to) grab or core 

Allen, 1995; Brumbaugh et al., 1994; sediment extractions if site conditions, volume 

Adams, 1991; Carignan and Lean, 1991; requirements, and logistical considerations 

allow. Carignan et al., 1985; Bottomley and


Bayly, 1984) or suction techniques � Reduce potential for oxygenation of samples


(Watson and Frickers, 1990; Knezovich by proper deployment and retrieval


and Harrison, 1988; Howes et al., 1985). procedures.


A summary of these methods is � Allow adequate equilibration of peepers prior


provided in Table 6-1. Both methods to sampling.


have a high likelihood of maintaining in


situ conditions. In cases where in situ � Minimize handling and processing of field-


collected interstitial waters. deployment is impractical, peepers or 

suction devices can be placed in � Field collected interstitial water samples should 

relatively undisturbed sediments be stored in containers, without headspace at 

4° C in the dark, until analyzed/tested. collected by core or grab samplers (see Samples for certain chemical analyses (e.g., Chapter 3). pesticides, phenols), should be frozen or 

preserved immediately. 

6-2 US Environmental Protection Agency 
Technical Manual 

Figure 6-1. Considerations for selecting the appropriate type of interstitial water sampling method. 

Chapter 6: Collection of Interstitial Water 6-3

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Photo and illustration on this page, courtesy of Allen Burton 

Peepers deployed in the field 

General peeper design with in-situ sample extraction 

6-4 US Environmental Protection Agency 
Technical Manual 

6.2.1 Peeper Methods 

Peepers are small chambers with membrane or mesh walls containing either distilled water or clean 

water of the appropriate salinity or hardness. Samples are collected by burying the devices in 

sediments and allowing surrounding interstitial waters to infiltrate. In principle, dissolved solutes 

will diffuse through the porous wall into the peeper and the contained water will reach equilibrium 

with the ambient interstitial water. The design concept for sediment peepers originated as 

modifications of the dialysis bag technique used by Mayer (1976) and Hesslein (1976), and has been 

modified successfully for use in laboratory sediment toxicity tests (Doig and Liber, 2000). The 

initial designs consisted of either a flat base plate or a cylindrical dialysis probe (Bottomley and 

Bayly, 1984) with compartments covered by dialysis membranes and a manifold for collection of 

multiple samples at various depths in the sediment profile (Figure 6-2). Further modifications to 

these designs have incorporated sampling ports, large sample compartments, and various types of 

membranes with different pore sizes. These modifications are usually required based on specific 

project objectives regarding sample volumes and contaminants of interest. 

Table 6-1. In-situ interstitial water collection methods (Sarda and Burton, 1995; SETAC, 2001). 

Device Sediment

Depth

(cm)

Sample

Volume

(L3

)

Advantages Disadvantages

Peeper 0.2 - 10 � 0.5 Most accurate method, reduced 

artifacts, no lab processing; 

relatively free of effects from 

temperature, oxidation, and 

pressure; inexpensive and easy to 

construct; some selectivity 

possible depending on nature of 

sample via specific membranes; 

wide range of membrane/mesh 

pore sizes, and/or internal solutes 

or substrates available. 

Requires deployment by hand, thus 

requiring diving in > 0.6 m depth 

water; requires hours to days for 

equilibration (varies with site and 

chamber); methods not 

standardized and used infrequently; 

some membranes such as 

dialysis/cellulose are subject to 

biofouling; must deoxygenate 

chamber and materials to prevent 

oxidation effects; some 

construction materials yield 

chemical artifacts; some chambers 

only allow small sample volumes; 

care must be used on collection to 

prevent sample oxidation. 

In situ 

Suction 

0.2 - 30 � 0.25 Reduced artifacts, gradient 

definition; rapid collection, no lab 

processing; closed system which 

prevents contamination; methods 

include airstone, syringes, probes, 

and core-type samplers. 

Requires custom, non-standard 

collection devices; small volumes; 

limited to softer sediments; core 

airstone method; difficult in some 

sediments and in deeper water (>1 

m); method might require diving for 

deployment in deep waters; 

methods used infrequently and by 

limited number of laboratories. 

Note:	 Incorporation of filtration into any collection method might result in loss of metal and organic 

compounds. 

Various peeper devices have been recently used effectively to collect interstitial water. For example, 

a simplified design using a 1 μm polycarbonate membrane over the opening of a polyethylene vial 

was successful in capturing elevated levels of copper and zinc (Brumbaugh et al., 1994). Other 

Chapter 6: Collection of Interstitial Water 6-5 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Figure 6-2. Front view and components of peeper sampling devices (top: plate device; 

bottom: cylindrical probe) 

6-6 US Environmental Protection Agency 
Technical Manual 

designs have been used to collect nonpolar organic compounds in a variety of aquatic systems 

(Bennett et al., 1996; Axelman et al., 1999) and in overlying water (Huckins et al., 1990). 

Peepers have also been used to expose organisms to sediments in situ (Burton et al., 2001). Burton et 

al. (1999) successfully introduced organisms to aerobic sediments using peepers. However, anoxic 

sediments are not amenable to in situ organism exposure. 

Different materials might be advisable in constructing peepers depending on the contaminants of 

concern. For example, for many contaminants, peepers constructed from acrylic material appear to 

yield interstitial water samples with minimal chemical artifacts (Burton et al., 2001). Some polymer 

materials might be inappropriate for studies of certain nonpolar organic compounds. Cellulose 

membranes are also unsuitable, as they decompose too quickly. Plastic samplers can contaminate 

anoxic sediments with diffusible oxygen (Carignan et al., 1994). 

In preparation for interstitial water collection, peeper chambers should be filled with deoxygenated 

water, which can be prepared by nitrogen purging for 24 hours prior to insertion. If sediment 

oxidation is a concern, the peepers should be transported to the deployment site in a sealed oxygenfree water bath to avoid potential changes to the sediment-water equilibrium caused by dissolved 

oxygen interactions. However, during peeper equilibration periods, anoxic conditions are likely to be 

quickly reestablished. In addition, when samples are collected and processed, exposure to oxygen 

should be minimized. 

Following initial placement, the equilibration time for peepers may range from hours to a month, but 

a deployment period of one to two weeks is most often used (Adams, 1991; Call et al., 1999; Steward 

and Malley, 1999). Equilibration time is a function of sediment type, study objectives, contaminants 

of concern, and temperature (e.g., Skalski and Burton, 1991; Carr et al., 1989; Howes et al., 1985; 

Simon et al., 1985; Mayer, 1976). Membrane pore size also affects equilibration time, with larger 

pore sizes being used to achieve reduced equilibration times (Sarda and Burton, 1995). For example, 

using a peeper with a 149-μm pore size, Adams (1991) reported equilibration of conductivity within 

hours of peeper insertion into the sediment. Thus, it appears that equilibration time is a function of 

the type of contaminant, sediment type, peeper volume, and mesh pore size. 

Peepers with large-pored membranes, while shortening equilibration time, also allow particulates to 

enter the chamber. The larger solids tend to settle to the bottom of the peeper chamber, and caution 

should be used to avoid collecting the solids when retrieving the water sample from the chamber. 

Colloidal particles will remain suspended in the sample and thereby present an artifact, but the 

concentration of such particles is typically lower than that found in laboratory- centrifuged samples 

(Chin and Gschwend, 1991). 

In several studies, analysis of interstitial water from replicate peepers has demonstrated from low to 

high heterogeneity in water quality characteristics (Frazier et al., 1996; Sarda and Burton, 1995). 

The potential for high variability in interstitial water chemical characteristics should be taken into 

account when developing the sampling design. 

6.2.2 Suction Methods 

There are a variety of suction devices for collecting interstitial water. A typical suction device 

consists of a syringe or tube of varying length, with one or more ports located at the desired sampling 

positions (ASTM, 2000a). The device is inserted into the sediment to the desired depth and a 

manual, spring-operated, or vacuum gas suction is applied to directly retrieve the water sample. A 

Chapter 6: Collection of Interstitial Water 6-7 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

variation on this approach employs a peeper-like porous cup or perforated tube with filters. The unit 

is inserted into the sediment for a period of time, allowing interstitial water to infiltrate the chamber 

before suction is applied. The samples are then retrieved by suction. Another variation that has been 

used successfully employs an airstone embedded into the sediment which forces interstitial water 

upward where it can be collected via syringe or tube. All of these suction methods generally yield 

smaller quantities of interstitial water than peepers and chemical (toxicological) artifacts are more 

likely due to greater potential exposure of interstitial water to oxygen (ASTM, 2000a). 

6.2.3 Processing of Field-Collected Interstitial Water Sample 

Following sample retrieval, interstitial water might need to be recovered and stabilized quickly to 

prevent oxidative changes or volatilization (Carignan, 1984). Containers should be filled, with no 

headspace to minimize changes in dissolved oxygen and contaminant bioavailability. Procedures for 

stabilization are dependent on the analyses to be performed. When non-volatile compounds are the 

target analytes, acidification is often stipulated, while organic carbon and methane may be stabilized 

with saturated mercury chloride (Mudroch and MacKnight, 1994). 

Samples to be analyzed for toxicity, are normally cooled to 4° C as soon as possible for transport to 

the laboratory. EPA methods for toxicity testing of surface waters and effluents (USEPA 1991) 

recommend that samples not be frozen in storage or transport. However, recent information suggests 

that freezing of interstitial water may not affect toxicity in some cases (Ho et al., 1997; Carr and 

Chapman, 1995; SETAC, 2001). Unless a demonstration of acceptability is made for the sites of 

interest, interstitial water samples should not be frozen prior to biological testing. Samples for 

chemical analyses should be preserved immediately, if appropriate, or cooled to 4° C as soon as 

possible. 

6.3 Ex-situ Extraction of Interstitial Water 

Ex-situ interstitial water collection methods are often necessary when relatively large volumes of 

interstitial water are required (such as for toxicity testing), when in-situ collection is not viable or 

when a brief sampling time is critical. While these extraction methods can be done in the field or in 

the laboratory, extraction in the laboratory, just prior to analysis or testing, is preferable so that the 

sample is maintained as close to its original state as much as possible during transport and storage 

(SETAC, 2001). Guidance in this chapter reflects recommendations presented in several recent 

publications including proceedings from two workshops devoted entirely to interstitial water 

extraction methods, water handling, and use in toxicity applications: (1) a dredged materials 

management program workshop on interstitial water extraction methods and sample storage in 

relation to tributyltin analysis (Hoffman, 1998) and (2) a Pellston workshop on interstitial water 

toxicity testing including interstitial water extraction methods and applications (SETAC, 2001). 

Figure 6-3 summarizes many of the issues associated with laboratory isolation of interstitial water 

discussed in this section. 

6.3.1 General Procedures 

Centrifugation and squeezing are the two most common techniques for collecting interstitial water, 

and are generally preferred when large volumes are required. Other methods include pressurization 

(e.g., vacuum filtration) devices, which can be used to recover small volumes of interstitial water. 

Regardless of the method used, interstitial water should be preserved immediately for chemical 

analyses, if appropriate, or analyzed as soon as possible after sample collection if unpreserved (such 

as for toxicity testing; Hoffman, 1998; SETAC, 2001). Significant chemical changes can occur even 

6-8 US Environmental Protection Agency 
Technical Manual 

Figure 6-3. Summary of recommended procedures and considerations for laboratory isolation of 

interstitial water* 

*Note: Emphasis should be placed on minimizing the duration of all sample manipulations whenever 

possible 

when interstitial water is stored for periods as short as 24 h (Hulbert and Brindle, 1975; Watson et 

al., 1985; Kemble et al., 1999; Sarda and Burton, 1995; SETAC, 2001). 

If sediments are anoxic, as most depositional sediments are, sample processing, including mixing of 

interstitial water that has separated from the sediment, should be conducted in an inert atmosphere or 

with minimal atmospheric contact. Exposure to air can result in oxidation of contaminants, thereby 

altering bioavailability (Bray et al., 1973; Lyons et al., 1979; Howes et al., 1985). Air exposure can 

also result in loss of volatile sulfides, which might increase the availability of sulfide-bound metals 

(Allen et al., 1993; Bufflap and Allen, 1995). In addition, iron and manganese oxyhydroxides are 

quickly formed upon exposure to air. These compounds readily complex with trace metals, thus 

Chapter 6: Collection of Interstitial Water 6-9 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

altering metals-related toxicity (Bray et al., 1973; Troup et al., 1974; Burton, 1991; Bufflap and 

Allen, 1995). Maintaining anoxic processing conditions is not necessary when study objectives are 

concerned with exposures to aerobic sediments, or if target contaminants are unaffected by oxidation 

in short-term toxicity or bioaccumulation testing. 

Interstitial water filtration should be avoided (SETAC, 2001). Numerous studies have shown that 

filters reduce toxicity and contaminant concentrations by retaining contaminant-associated particles 

and also by contaminant sorption onto the filter matrix (Bray et al., 1973; Troup et al., 1974; SassonBrickson and Burton, 1991; Schults et al., 1992). If filtration is stipulated by a test method, treated 

filters (e.g., pre-soaked in distilled, deionized water, or combusted at 400° C overnight for glass fiber 

filters) should be used, and an unfiltered sample should also be tested for toxicity and contaminant 

concentrations. The characteristics of filters and the filtering apparatus should also be carefully 

considered, as different filters have different sorptive capacities for different contaminants. 

Recommendation Box #2 

Extraction of interstitial water 

� Centrifugation is the generally preferred laboratory method for the extraction of interstitial 

water. 

� Extraction of interstitial water should be completed as soon as possible. 

� Interstitial water that has accumulated on the surface of the homogenized sediment 

sample should be mixed into the sediment before the sample is partitioned among 

centrifuge bottles. 

� Unless other program-specific guidance is available, sediments should be centrifuged at 

high speed (e.g., 8000-10,000 x g) for 30 minutes. 

� Unless site-specific information suggests otherwise, centrifuging should be at 4° C to 

minimize temperature-mediated biological and chemical processes. 

� Interstitial water should be preserved immediately for chemical analyses or analyzed as 

soon as possible after extraction, unpreserved. For toxicity testing, interstitial water 

should be stored at 4° C for not longer than 24 hours, unless the test method dictates 

otherwise. 

� Filtration should be avoided unless required by a test method because it might reduce 

interstitial water toxicity. Double (serial) centrifugation (low speed followed by high speed) 

should be used instead. 

� If filtering is required by a test method, pre-treated filters should be used to reduce 

potential contamination. 

6.3.2 Centrifugation 

Centrifugation is the generally preferred laboratory method for collection of interstitial water 

(SETAC, 2001). It is a relatively simple procedure that allows rapid collection of large volumes of 

interstitial water. It also facilitates the maintenance of anoxic conditions (if required). However, 

centrifugation, like other ex-situ procedures might yield chemical and/or toxicological artifacts due to 

6-10 US Environmental Protection Agency 
Technical Manual 

the extraction procedures themselves, which might alter the natural equilibrium between interstitial 

water and sediment. 

Prior to centrifugation, the sediment sample is homogenized (see Section 4.3) and partitioned among 

centrifuge bottles. If the homogenized sample is stored prior to centrifugation, interstitial water 

might accumulate on the surface of the sediment. This overlying water should be mixed into the 

sediment before subsampling for centrifugation. Samples are then partitioned among centrifuge 

bottles. In general, approximately 50% of sediment moisture content can be extracted as interstitial 

water. If interstitial water volume requirements are lower, smaller sediment subsamples may be 

used. 

For more information about centrifugation: 

Interstitial waters have been isolated over a range of centrifugal forces and durations (Landrum 

et al., 1987; Giesy et al., 1988; Schults et al., 1992; Burgess et al., 1993; Ankley et al., 1990; 

Schubauer-Berigan and Ankley, 1991; Ankley and Schubauer-Berigan, 1994). For toxicity 

testing of interstitial waters, some sources recommend that sediments be centrifuged at 10,000 

x g for a 30 min period (ASTM, 2000a; Environment Canada, 1994). Such high speed 

centrifugation is often necessary to remove most colloids and dispersible clays (Adams, 1991; 

Chin and Gschwend, 1991; Brownawell and Farrington, 1986; Ankley and Schubauer-Berigan, 

1994), which can introduce interferences to chemical or toxicological analysis. However, such 

high speed centrifuges are not commonly available. Furthermore, many materials (glass, 

plastic) are not able to withstand high centrifugation speeds. Finally, it should be noted that 

toxicity is typically reduced with high speed centrifugation due to the removal of particleassociated contaminants (Sasson-Brickson and Burton 1991; Schults et al., 1992; Ankley and 

Schubauer-Berigan, 1994; Bufflap and Allen, 1995). 

Based on research to date, both slower and faster centrifugation speeds (and associated differences in 

colloid/suspended solids removal) may be appropriate depending on the study objectives. For many 

programs that are interested in characterizing site toxicity, high speed centrifugation may not be 

appropriate because one is interested in toxicity potential of the interstitial water in its entirety (i.e., 

including colloidal material). However, if one is interested in comparing interstitial water 

contaminant concentrations to specific sediment quality values, or model exposure compartments for 

example (EPRI, 2000), then high speed centrifugation might be necessary. As our knowledge is still 

limited in this area, it is perhaps most important to note that centrifugation speed often has a dramatic 

effect on observed sample toxicity and chemical characteristics. Therefore, in any sediment 

monitoring study, one centrifugation protocol (including speed and time) should be identified and 

used throughout for all samples. 

Centrifugation has been performed at various temperatures. ASTM (2000a) recommends that the 

centrifugation temperature reflect the in situ sediment temperature to ensure that the equilibrium 

between the particulate and interstitial water is not altered. Alternatively, a temperature of 4° C may 

be preferred to minimize temperature-mediated chemical and biological processes (Environment 

Canada, 1994). 

When centrifuging coarse sand, it might be desirable to use a modified centrifuge bottle to aid 

interstitial water recovery (USEPA/ACOE, 1998). The modified bottle is equipped with an internal 

filter that can recover 75% of the interstitial water, as compared to 25 - 30% recovery from squeezing 

(Saager et al., 1990). 

Chapter 6: Collection of Interstitial Water 6-11 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

As discussed in Section 4.2, all containers have limitations with regards to adsorption or leaching of 

chemicals, ease of use, and reliability. For example, polytetrafluororthylene (PTF) bottles have been 

used successfully up to 2500 x g when filled to 80% of capacity, but collapse at 3000 g (Burgess et 

al., 1993). Polycarbonate bottles have been used successfully for tributytin analyses in interstitial 

water (Hoffman, 1998). If small volumes of water are required for testing, higher speed 

centrifugation can be performed with glass tubes (up to 10,000 g, Word et al., 1987). Larger glass 

tubes, however, can not be centrifuged at such high speeds. If metal toxicity is not a concern, then 

high speed centrifugation in larger stainless steel centrifuge tubes is suitable. If test samples are 

contaminated with photoreactive compounds such as PAHs, exposure of the sample to light should 

be minimized to limit degradation or alteration of potentially toxic compounds. This can be 

accomplished by using reduced lighting. 

6.3.3 Sediment Squeezing 

Isolation of interstitial water by squeezing has been performed using a variety of procedures and 

devices (Reeburgh, 1967; Kalil and Goldhaker, 1973; Jahnke, 1988; Carr et al., 1989; Long et al., 

1990; Watson and Frickers, 1990; Adams, 1991; Carr and Chapman, 1995; Carr, 1998). Inexpensive 

low pressure mechanical squeezers can be constructed, and may provide specialized capacities such 

as collection of interstitial water profiles from core samples (Bender, et al, 1987). In all cases, the 

interstitial water is passed through a filter that is a part of the squeezing apparatus. 

Squeezing has been shown to produce a number of artifacts due to shifts in equilibrium from 

pressure, temperature, and gradient changes (e.g., Froelich et al., 1979; Kriukov and Manheim, 1982; 

Bollinger et al., 1992; Schults, 1992). Squeezing can affect the electrolyte concentration in the 

interstitial water particularly with a decrease in chemical concentrations near the end of the 

squeezing process. However, others reported that squeezing did not produce artifacts in interstitial 

water toxicity studies (Carr and Chapman, 1995; Carr, 1998; SETAC, 2001). It is therefore 

recommended that if squeezing is performed, moderate pressures be applied along with electrolyte 

(conductivity) monitoring during extraction (Kriukov and Manheim, 1982). Squeezing should also 

be performed at in situ ambient temperatures, as significant alterations to interstitial water 

composition can occur when squeezing is conducted at temperatures different from ambient 

conditions (e.g., Mangelsdorf et al., 1969; Bischoff et al., 1970; Sayles et al., 1973). 

Other sources of interstitial water alteration during squeezing are: contamination from overlying 

water; internal mixing of interstitial water during extrusion; and solid-solution reactions as interstitial 

water is expressed through the overlying sediment. As interstitial waters are displaced into upper 

sediment zones, they come in contact with solids with which they are not in equilibrium. This intermixing causes solid-solution reactions to occur. Most interstitial water chemical species are rapidly 

transformed, as observed with ammonia and trace metals (Rosenfield, 1979; Santschi et al., 1997). 

Bollinger et al. (1992) found elevated levels of several ions and dissolved organic carbon in squeezed 

samples as compared to samples collected by in situ peepers. The magnitude of the artifact will 

depend on the pollutant sediment characteristics and redox potential. 

6.3.4 Pressurized and Vacuum Devices 

Other methods for extraction of interstitial water from sediment samples can include vacuum 

filtration (Jenne and Zachara, 1987; Knezovich and Harrison, 1987; Winger and Lasier, 1991), gas 

pressurization (Reeburgh, 1967), and displacement (Adams, 1991). These methods typically recover 

only small volumes of interstitial water and are not commonly used. 

6-12 US Environmental Protection Agency 
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Photo courtesy of Allen Burton 

Sediment squeezing apparatus for extracting interstitial water 

Chapter 6: Collection of Interstitial Water 6-13

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Use of a hand vacuum with an aquarium stone is an effective vacuum filtration method (Winger and 

Lasier, 1991; Sarda and Burton, 1995). The procedure typically involves attaching the air stone to a 

50 mL syringe via plastic tubing, inserting it into the sediment to the desired depth, and then 

applying suction. This method can recover relatively large volumes of interstitial water; Santschi et 

al. (1997) used this procedure to extract up to 1,500 mL from 4 L of sediment. Sarda and Burton 

(1995) found that ammonia concentrations in water obtained by this procedure were similar to those 

collected by in situ peepers. Drawbacks to this method include loss of equilibrium between the 

interstitial water and the solids, filter clogging, and oxidation (Brinkman et al., 1982). 

6-14 US Environmental Protection Agency 
CHAPTER 

7 

Technical Manual 

Quality Assurance and Quality 

Control 

7.1 General Procedures 

Quality assurance activities provide a formalized system for evaluating the technical adequacy of 

sample collection and laboratory analysis activities. These quality assurance activities begin before 

samples are collected and continue after laboratory analyses are completed, requiring ongoing 

coordination and oversight. The 

quality assurance program should 

integrate management and technical 

practices into a single system to 

provide data that are sufficient, 

appropriate, and of known and 

documented quality. 

Developing and maintaining a quality 

assurance (QA) program requires an 

ongoing commitment by project 

management and also includes the 

following: (1) appointment of a 

quality assurance officer with the 

responsibility and authority to develop 

and maintain a QA program, 

(2) preparation of a Quality Assurance 

Project Plan with Data Quality 

Objectives, (3) preparation of written 

descriptions of Standard Operating 

Procedures (SOPs) for sediment 

Checklist 

QA practices within a 

laboratory should address all 

activities that affect the quality 

of the final data, such as 

✓ sediment sampling and handling 

✓ condition and operation of equipment 

✓ instrument calibration 

✓ replication 

✓ use of standards 

✓ record keeping 

✓ data evaluation 

sampling and manipulations, instrument calibration, sample chain-of-custody, laboratory sample 

tracking system, and (4) provision of adequate, qualified technical staff and suitable space and 

equipment to assure reliable data. Program specific guidance for developing and maintaining a QA 

program should be followed as appropriate. Examples of program guidance for developing a quality 

assurance program can be found in USEPA (1994; 1995; 2000d), PSEP (1997a), WDE (1995), and 

USEPA/ACOE (1991, 1998). 

Quality control (QC) practices consist of more focused, routine, day-to-day activities carried out 

within the scope of the overall QA program. QC is the routine application of procedures for 

obtaining data that are accurate (precise and unbiased), representative, comparable, and complete. 

QC procedures include activities such as identification of sampling and analytical methods, 

calibration and standardization, and sample custody and record keeping. Audits, reviews, and 

complete and thorough documentation are used to verify compliance with predefined QC procedures. 

Project-specific QA plans (QAPP; see Section 7.3 below) provide a detailed plan for activities 

performed at each stage of the study and outline the data quality objectives that should be achieved. 

Through periodic reporting, QA activities provide a means to track progress and milestones, 

performance of measurement systems, and data quality. A complete project-specific QA/QC effort 

has two major components: a QA program implemented by the responsible agency (i.e., the data 

Chapter 7: Quality Assurance and Quality Control 7-1 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

user) and QC programs implements by the parties responsible for collection and analyses (i.e., the 

data generators). 

7.2 QA/QC Procedures for Sediment Collection and Manipulation 

To ensure the appropriateness of the 

sample collection protocol for sample 

integrity and data of suitable quality, a 

program of scheduled field QC samples, 

such as field replicates (duplicates, splits, 

field spikes), field blanks (rinsate 

equipment), bottle, trip, and background 

(upgradient) samples is critical. All field 

QC samples should be handled exactly as 

the sediment samples and should be 

treated as blind samples so as to 

minimize bias in the analysis. A random 

portion of the samples should also be 

analyzed by a third party to evaluate the 

primary laboratory’s performance. QC 

replicates (duplicates, splits) should be 

collected for analysis by the primary 

laboratory to determine analytical 

variability (USEPA 1995). 

The procedures for sediment 

manipulations described in Chapter 4 

should maintain the sample in a chemical 

condition as similar as possible to that at 

the time of collection. QA procedures 

Checklist 

QA/QC procedures for 

sample collection should 

include the following 

principal elements: 

✓	 implementing a sound sampling approach 

based on the intended use of the data. 

✓	 use of sampling methodologies which allow 

the collection of representative samples 

based upon data needs. 

✓	 use of sampling devices that minimize the 

disturbance or alteration to the media’s 

chemical composition. 

✓	 employing decontamination procedures 

which reduce cross-contamination potential 

between sampling points. 

✓	 use of proper sample containers and 

preservation techniques that maximize the 

integrity of samples. 

are established to assure that SOPs are followed and that contamination is neither introduced to nor 

lost from the manipulated sample. For example, samples to be analyzed for trace metals should not 

come in contact with metal surfaces (except stainless steel). Sample tracking sheets should document 

date, time, and investigator related to removal and replacement of samples from storage. Specific 

manipulation procedures should follow established SOPs that minimize chemical alteration of the 

sample (excepting chemical spiking), maintain sediment physical properties, and include replication 

and blank samples. 

7.3 The Quality Assurance Project Plan (QAPP) 

The Quality Assurance Project Plan (QAPP) is a project-specific document that specifies the data 

quality and quantity requirements needed for the study as well as all procedures that will be used to 

collect, analyze, and report those data. 

The QAPP uses input from the sampling design derived from the Data Quality Objectives Process 

(see Chapter 2 specifically Measurement Quality Objectives discussion, Section 2.4, and USEPA, 

2000a) to specify the above elements. This Plan should be reviewed by an independent person (e.g., 

quality assurance officer or staff member not involved in the project directly) for accuracy and 

completeness. A key element of a QAPP is Standard Operating Procedures (see Section 7.4). 

Further information on preparing a QAPP and resources necessary can be found in USEPA (2000e). 

7-2 US Environmental Protection Agency 
Technical Manual 

7.4 Standard Operating Procedures 

Standard operating procedures are written descriptions of routine methods and should be provided 

for all methods used. A large number of field and laboratory operations can be standardized and 

presented as standard operating procedures. General types of procedures that benefit from standard 

operating procedures include field measurements ancillary to sample collection (e.g., water quality 

measurements or mixing model input measurements); chain-of-custody, sample handling, and 

shipment; and routine analytical methods for chemical analyses and toxicological analyses. Standard 

operating procedures ensure that all persons conducting work are following the same procedures and 

that the procedures do not change over time. All personnel should be thoroughly familiar with the 

standard operating procedures before work is initiated. Deviations from standard operating 

procedures might affect data quality and integrity. If it is necessary to deviate from approved 

standard operating procedures, these deviations must be documented and approved through an 

appropriate chain-of-command. 

7.5 Sediment Sample Documentation 

Bound field logbooks should be used for the maintenance of field records. All entries should be 

dated and time of entry recorded. All aspects of sample collection and handling as well as visual 

observations should be documented in the field logbooks. Documentation should be recorded in prenumbered bound notebooks using indelible ink pens in sufficient detail so that decision logic may be 

traced back, once reviewed. 

Checklist 

Quality Assurance Project Plans vary in content depending on 

program needs, but should address the following elements: 

✓ a description of the project organization and responsibilities 

✓ definition of data quality objectives (see Section 2.1) 

✓ sampling, analysis, and measurement procedures 

✓ instrument calibration procedures 

✓ procedures for recording, reducing, validating, and reporting data 

✓	 procedures for performing quality assurance verification and internal quality control 

checks 

✓ preventive maintenance schedules 

✓ specific routine procedures to evaluate precision, accuracy, and completeness 

✓ definitions of deviations and appropriate corrective actions 

✓ information on appropriate training 

Chapter 7: Quality Assurance and Quality Control 7-3 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Proper field sheet, sample labeling, chain-of-custody, and sample tracking documentation should be 

maintained as appropriate. Specific details concerning sample documentation and sample 

management should be included in planning documents and reviewed by the sampling team prior to 

initializing the sampling program. 

7.6 Sample Tracking Documentation 

Samples delivered to the laboratory should be accompanied by a chain-of-custody record that 

includes the name of the study, location of collection, date and time of collection, type of sample, 

sample name or number, number of containers, analysis required, and the collector's signatures. 

When turning over possession of samples, the relinquisher and the receiver sign, date and record the 

time on the record sheet. The record sheet allows the transfer of a group of samples at one time. 

When the laboratory takes possession of the samples, each should be assigned a unique laboratory 

identification designation. This assures a consistent system for tracking within the laboratory. If the 

samples arrive at the laboratory when designated personnel are not there to receive them, the samples 

are put into a secure location and the transfer is conducted when the appropriate personnel are 

present. 

Upon arrival at the laboratory, samples are 

inspected for condition and temperature, and 

sample container labels are verified against 

the chain-of-custody record or sample 

tracking form. Sample information is 

entered on a laboratory log-in data sheets 

used to maintain information regarding 

sample: receipt, shipping, collection date, 

and storage. To allow for accurate 

identification of samples, information 

contained on sample tracking forms must 

match identically with information 

contained on the sample container labels. 

The tracking form lists both the collector’s 

and the laboratory’s identification 

designations. Verified tracking forms are 

signed by the laboratory personnel with date 

and time in ink. Missing and/or 

compromised samples (e.g., inappropriate 

preservation to maintain integrity, 

inappropriate containers, and unlabeled or 

mislabeled containers) are documented on 

the tracking forms. 

When samples are removed from storage, 

the sample tracking form accompanies it and 

documents data, time, and investigator 

associated with any manipulations. The 

manipulation type is noted on the form in 

detail or by reference to an approved 

laboratory SOP. Any deviation from the 

SOP are also noted. Should the sample be 

Checklist 

Sample documentation 

should include: 

✓	 project name, and analysis or test to be 

performed 

✓ sampling locations 

✓ dates and times 

✓ sampling personnel present 

✓	 level of personal protective equipment 

worn 

✓	 weather or any environmental condition 

that might affect samples 

✓	 equipment used to collect samples, and 

sample container preparation 

✓ calibration data 

✓	 deviations from approved work plans or 

SOPs 

✓ sketch of sampling area 

✓	 notation of the system identifying and 

tracking samples 

✓ notation of any visitors to the site 

✓ initials and date on each page 

7-4 US Environmental Protection Agency 
Technical Manual 

modified in such a way that additional subsamples are created, additional tracking forms must also be 

created. 

7.7 Record Keeping 

Proper record keeping is essential to the scientific defensibility of a sediment sampling and 

manipulation program. A separate file should be maintained for each sampling/manipulation event 

or closely related events. This file should contain field logs, chain-of-custody forms, sample tracking 

forms, storage records, and any QA/QC documentation and records. Original documentation should 

be signed and dated by the originator. 

7.8 QA Audits Checklist 

Performance In addition to the QA/QC procedures conducted on 

a routine basis, quality audits (i.e., performance and auditing procedures 

are: quality systems audits) might be conducted. 

Performance audits refer to independent checks to 

evaluate the quality of data produced during testing. ✓ sample auditing - the auditor 

There are three types of performance audits: uses a separate set of calibrated 

sampling; test; and data processing. These audits standards to check the sample 

are independent of normal quality control checks 

collection system. 

performed by the operator. ✓	 test auditing - the auditor is 

provided with set of a duplicate 

A systems audit is an on-site inspection and review sample or split portion. 

of the quality assurance system. The systems audit is ✓ data processing audit - the 

performed to verify that the organization is auditor spot checks calculations 

following the policies and procedures described in or a dummy set of raw data is 

its QA/QC plan and in appropriate SOPs. Systems	 inserted followed by review of 

validated data. audits are performed by an auditor typically from an 

accrediting body. 

7.9 Corrective Action (Management of Non-conformance Events) 

The QA Officer and the responsible manager are responsible for reviewing the circumstances of all 

instances of occurrence of nonconformities, to determine whether corrective action should be taken. 

The manager is responsible for determining if new samples are required, if the customer should be 

notified, if additional testing is necessary, or whether the results should be confirmed. A good 

communication plan is invaluable in helping to identify interactions among labs, clients, and agencies 

during corrective actions. 

Corrective action might take two forms: that of addressing technical problems associated with 

project activities and that of addressing QA/QC infractions based upon performance. Technical 

problems in meeting project objectives may range in magnitude from failure to meet minor 

procedural requirements, to major problems associated with inappropriate methods or data loss. 

Established procedures for corrective action of minor technical problems are often included in the 

SOPs for cases where performance limits or acceptance criteria have been exceeded. On-the-spot 

corrective actions are noted on data sheets. Major or recurrent QA/QC problems which require longterm corrective action, such as modification of SOPs, are reported. Depending upon the nature and 

Chapter 7: Quality Assurance and Quality Control 7-5 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

severity of the problem, an approach might be developed. Any corrective action is documented by 

management. 

Infractions of QA/QC policies by staff are identified and addressed by the management. Minor 

infractions are corrected through additional training and/or closer supervision. Major or recurrent 

infractions are corrected through re-assignment of technical personnel. 

Corrective actions relative to sample collection and manipulation may include, but are not limited to, 

review of the data and calculations, flagging and/or qualification of suspect data, or possible resampling. A review that provides a preliminary check of all “out of limit” events is performed as 

soon as the data for a given parameter or test is tabulated and verified for accuracy. “Out of limit” 

events are flagged to determine whether new samples are required. 

7.10 Data Reporting 

In addition to reporting the raw data from a given sediment quality study or analysis, the data report 

should include additional quality assurance information to ensure the data user that sample handling 

and analyses are in accordance with the project plan. The quality assurance information also 

documents procedures taken to ensure accurate data collection. Data are to be presented 

electronically as well as in hardcopy for many regulatory programs. Required electronic format 

should be explicitly outlined as a data quality objective during the planning process. 

Checklist 

Quality Assurance Reporting 

✓	 A copy of the sample chain of custody record, including documentation of sample 

collection date and time 

✓ Documentation of the laboratory certification number 

✓ Documentation of the analysis method used 

✓ Documentation of analysis date and time (or testing period in the case of toxicity tests) 

✓	 Documentation that data for spikes, duplicates, standards, etc meets laboratory QA/QC 

requirements for chemical analytes 

✓	 Documentation that reference toxicant test data meets laboratory QA/QC requirements 

for toxicity tests. 

✓ Documentation of any deviations in sample preparation or analysis protocols 

7-6 US Environmental Protection Agency 
Technical Manual 

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8-22 US Environmental Protection Agency 
APPENDIX A


EXAMPLES OF SEDIMENT QUALITY


SAMPLING DESIGNS USING THE DATA


QUALITY OBJECTIVES (DQO) PROCESS

Technical Manual 

The Data Quality Objectives (DQO) process is a logical progression of steps that define the question 

to be answered and identifies qualitatively and quantitatively the procedures and decisions necessary 

to address the question posed. USEPA (2000a) discusses a 7-step DQO process that leads one 

through each of the decision points to help ensure a successful study or program outcome. 

Sediment quality monitoring studies, whether for regulatory or non-regulatory purposes, would 

benefit from following USEPA’s DQO process in order to: 

• reduce the likelihood of collecting improper or inappropriate samples 

• increase the likelihood of collecting representative samples for the question asked 

•	 decrease the chances of introduced measurement artifacts or interference due to sampling or 

sample processing techniques 

•	 increase the likelihood that data, and decisions based on those data, will be scientifically 

defensible and accepted by those involved. 

The following tables are hypothetical examples demonstrating how the DQO process could be used 

in addressing a few common purposes for collecting sediment quality data. The purpose of the study, 

or question needing to be answered, drives the input for all subsequent steps in the DQO process. 

Thus, sampling design, how samples are collected and manipulated, and the types of analyses chosen, 

should all stem from the overall purpose of the study. Many national and regional programs (e.g., 

NOAA’s Status and Trends, USEPA’s Dredge Materials Management Program, or Puget Sound 

Estuary Program) already have a particular purpose identified, thus giving rise to the particular 

sampling protocols they each use. 

Appendix A: Examples of Sediment Quality Sampling Designs A-3 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Example 1. Objective: Determine whether certain point and nonpoint sources are associated with 

sediment contamination in a lake, estuary, or river segment 

DQO Element Issues/Concerns/Information 

1. State problem/available 

resources 

• Certain point and nonpoint sources of concern 

• Enough resources for a small-moderate survey depending on number 

of analyses per station 

2. Identify questions to be 

addressed 

• How does sediment quality near these sources compare with other 

locations and with Ecotox Thresholds (USEPA, 1996)? How toxic are 

they? 

3. Identify information/ 

measurements needed 

• Use available data, source information, BPJ to identify contaminants 

of concern 

Measurements could include the following: 

• 10d whole sediment toxicity tests 

• Acute or chronic toxicity tests using interstitial water 

• Benthic macroinvertebrate analyses 

• Contaminant analyses (e.g., PAHs, PCBs, metals, pesticides) 

• Particle size, AVS (if metals a concern), TOC, % moisture, pH, 

ammonia measured for each sample 

• Water, pH, oxygen, conductivity/salinity overlying sediment at each 

site 

4. Define spatial/temporal 

boundaries 

• Sample during one index period 

• Surficial sediment (top 0 to 2 or up to 15 cm) of most interest 

• Concentrate sampling near suspected contaminant sources with some 

reference stations (locations removed from potential sources) as well 

5. Define thresholds or 

decision rule for 

parameters of interest 

• Ecotox Thresholds (USEPA, 1996), and/or other sediment threshold 

values for contaminants 

• Toxicity effect level: e.g., significantly lower survival than reference 

stations or survival � 50% 

6. Limits on decision errors • Precision: � 40% C.V. among field replicates for contaminants and 

toxicity 

• Test for differences between suspect and reference sites at p = 0.05 

and power = 80% 

• Field blanks for contaminants < detection limit 

• Lab duplicates for contaminants yield � 25% C.V. Toxicity test 

replicates � 35% C.V. 

• Tox test controls meet EPA minimum performance requirements. 

7. Optimize the design • Choose targeted sampling design including reference stations 

• Sample when conditions most favorable for gear efficiency and 

personnel safety 

• Use grab sampler - Ponar, VanVeen, or Petersen (see Table E-1 for 

advantages and disadvantages) 

• Use GPS for site positioning (± 10m) 

• Composite several (determined by number of contaminant analyses 

desired) grabs at each site for a single sample 

• Take 3 replicate samples at 10% of the sites, selected at random 

• See flowchart for Selecting a Grab Sampler Based on Site-Specific 

Factors (Figure 3-2). 

A-4 US Environmental Protection Agency 
Technical Manual 

Example 2. Objective: Determine the status of sediment quality in a site (e.g., lake, estuary, or river 

segment) 

DQO Element Issues/Concerns/Information 

1. State problem/available 

resources 

• Sediment quality unknown or status was determined in the past and 

there is a need to determine how the quality may have changed. 

• Enough resources for a moderate survey depending on number of 

analyses per station. 

2. Identify questions to be 

addressed 

• How does sediment quality compare with Ecotox Thresholds (USEPA, 

1996)? How toxic are sediments now as compared to historically? 

3. Identify information/ 

measurements needed 

• Use available data, source information, BPJ to identify contaminants 

of concern 

Measurements could include the following: 

• 10d whole sediment toxicity tests 

• Acute or chronic toxicity tests using interstitial water 

• Benthic macroinvertebrate analyses 

• Contaminant analyses (e.g., PAHs, PCBs, metals, pesticides) 

• Particle size, AVS (if metals a concern), TOC, % moisture, pH, 

ammonia measured for each sample 

• Water, pH, oxygen, conductivity/salinity overlying sediment at each 

site 

4. Define spatial/temporal 

boundaries 

• Sample during one season (index period) 

• Sample surficial as well as deeper sediments to obtain historical 

record. 

• Sample stations representative of the entire site or, if site contains 

different subareas of interest (e.g., areas having very different salinity 

zones or different geology/sediment particle size), representative 

samples of each subarea. 

5. Define thresholds or 

decision rule for 

parameters of interest 

• Ecotox Thresholds (USEPA, 1996), and/or other sediment threshold 

values for contaminants 

• Toxicity effect level: e.g., significantly lower survival than reference 

stations or survival � 50% 

6. Limits on decision errors • Precision: � 40% C.V. among field replicates for contaminants and 

toxicity 

• Test for differences between suspect and reference sites at p = 0.05 

and power = 80% 

• Field blanks for contaminants < detection limit 

• Lab duplicates for contaminants yield � 25% C.V. Toxicity test 

replicates � 35% C.V. 

• Tox test controls meet EPA minimum performance requirements. 

7. Optimize the design • Choose probabilistic sampling design; use stratified random or multistage random design if interested in comparing quality with respect to 

certain habitat features or subareas of site, respectively. 

• Use a corer sampler to obtain vertical (historical) profiiles of sediment 

at each station. Collect and analyze samples of strata of interest. Use 

of a larger corer (e.g., box corer) will mean fewer cores needed per 

station (see Table E-2 for advantages and disadvantages of different 

corers.) 

• Use GPS for station positioning (± 10 m). 

• Take 3 replicates for each type of analysis at 10% of the stations. 

• See Flowchart for Selecting Core Samplers Based on Site-Specific 

Factors (Figure 3-3). 

Appendix A: Examples of Sediment Quality Sampling Designs A-5

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Example 3. Objective: Determine the need for or locations of site remediation (e.g., superfund) 

DQO Element Issues/Concerns/Information 

1. State problem/available 

resources 

• Site known or suspected to contain contaminated sediments that pose 

an ecological and/or human health risk 

• Resources are available for a moderate-intensive survey 

2. Identify questions to be 

addressed 

• Does the site need to be remediated? Where at the site is sediment 

remediation warranted? 

3. Identify information/ 

measurements needed 

• Use previously collected data, if available, to identify contaminants of 

concern. If no information is available, a pilot survey, using a random 

sampling design, may be useful to identify potential contaminants of 

concern. 

• Measurements could include: 

– Contaminants of concern in whole sediment and/or interstitial 

water 

– 10 d whole sediment toxicity tests 

– Acute or chronic interstitial water toxicity tests 

– Benthic macroinvertebrate analyses 

– Particle size, AVS (if metals a concern), TOC, % moisture, pH, 

ammonia to help interpret chemical or toxicological data. 

4. Define spatial/temporal 

boundaries 

• Sample over one or more index periods depending on assumed or 

measured rates of sediment or contaminant movement. 

• Surficial as well as deeper sediments may need to be sampled 

depending on depth of contamination. 

• Sampling all areas of the site may be necessary to locate areas in need 

of remediation unless more information is available. 

5. Define thresholds or 

decision rule for 

parameters of interest 

• Contaminant levels exceed Ecotox Thresholds (USEPA, 1996). 

• Toxicity effect level: e.g., significantly lower survival than reference 

sediment and < 50%. 

6. Limits on decision errors • Precision: � 40% C.V. among field replicates for contaminants and 

toxicity 

• Test for differences between suspect and reference sites at p = 0.05 

and power = 80% 

• Field blanks for contaminants < detection limit 

• Lab duplicates for contaminants yield � 25% C.V. Toxicity test 

replicates � 35% C.V. 

• Tox test controls meet EPA minimum performance requirements. 

7. Optimize the design • Choose systematic or grid sampling design if no previous information 

available on areas of contamination. 

• Choose targeted design if information is already available on areas of 

contamination within the site. 

• Choose multi-stage design if more than one area of contamination 

within the site is known but locations of contamination within each 

area are not precisely known. 

• Use grab sampler if remediation will involve only surficial sediments, 

or sediment depth is known to be shallow (see Table E-1 and Figure 

3-2). 

• Use corer if remediation is likely to involve deeper sediments. For 

areas in which remediation may entail very deep sediments (> 2 m), 

consider using a vibracorer or piston corer (see Table E-2 and the 

Flowchart for Selecting Core Samplers Based on Site-Specific Factors 

(Figure 3-3). 

A-6 US Environmental Protection Agency 
APPENDIX B 


EXAMPLES OF MEASUREMENT QUALITY


OBJECTIVES USED IN SEDIMENT QUALITY


MONITORING STUDIES

Technical Manual 

In the Data Quality Objectives (DQO) framework (discussed in Chapter 2 and examples presented in 

Appendix A of this Manual), a key element of this process is defining the thresholds or decision rules 

(Step 5, Figure 2-2) and the limits on errors pertaining to those decisions (Step 6, Figure 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 when and where something 

might need to be done to mitigate or address a given observed effect. Also, these steps are critical 

factors in designing a tiered or phased sampling program. Thresholds, for example, can be initially 

set to identify problem areas with high accuracy (low decision error). This would be followed by a 

second sampling, with a lower threshold, to identify emerging or more subtle problems in a costeffective manner. 

The information used to help derive meaningful threshold or decision rules, and the tolerable errors 

associated with those rules, is collectively referred to as Measurement Quality Objectives (MQOs). 

MQOs are qualitative or quantitative statements that describe the type of data quality needed to 

support or refute a given decision. These statements explicitly define acceptable precision, bias, and 

sensitivity required of all analyses in the study and therefore, should be consistent with the expected 

performance of a given analysis or test method (ITFM 1995). Thus, if a particular whole sediment 

toxicity test is expected to yield 80% survival among control replicates, the MQO for control survival 

should be � 80% for that test. Further, if one intends to compare sediment toxicity results between a 

reference station and test stations, it is important to set the number of replicates and the decision rule 

appropriately so that the study can determine with reasonable power and confidence whether a given 

sediment sample is toxic to the test organisms. The number of replicates performed will depend on 

the expected variability of a given test endpoint and the sensitivity desired in the study. 

The following summarizes four different examples of sediment quality studies or programs, each 

with a different study purpose, and the types of MQOs they used. These examples are for illustrative 

purposes and are not meant to imply that these are the only acceptable ways in which MQOs can be 

derived. The examples provided are: 

• Shoreline ecology program following the Exxon Valdez oil spill in Alaska 

• Great Lakes Assessment and Remediation of Contaminated Sediment (ARCS) Program 

• An example of an EMAP study design in the St. Louis River, Minnesota/Wisconsin 

• A focused assessment in Burlington Harbor, VT in Lake Champlain 

•	 Excerpts from Washington Department of Ecology’s Sampling and Analysis Plan Guidance 

(WDE, 1995). 

This latter guidance demonstrates how a particular program addresses sampling and analysis needs 

depending on the monitoring objective. The guidance also provides an interesting comparison of 

overall sampling procedures and sampling design considerations for two programs: WDE’s Sediment 

Management Standards Program and the Puget Sound Dredged Disposal Analysis Program, both of 

which have some common monitoring objectives. 

Appendix B: Examples of Measurement Quality Objectives B-3 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Example 1: Shoreline Ecology Program for Prince William Sound, Alaska, Following 

the Exxon Valdez Oil Spill 

Background 

A comprehensive shoreline ecology program was designed to assess recovery in Prince William 

Sound following the Exxon Valdez oil spill on March 24, 1989 (Page et al., 1995a; b; Boehm et al., 

1995; Gilfillan et al., 1995; Gillfillan et al., 1999). The spill resulted in the release of about 258,000 

barrels of Alaska North Slope crude oil into the marine environment. Nearly 500 miles of shorelines 

in the sound were oiled to some degree. 

Project Objectives 

The shoreline ecology program was designed to assess the recovery of hundreds of miles of oiled 

shorelines in Prince William Sound by using a limited number of sampling stations. The number of 

sampling stations had to be small enough for a survey to be accomplished in the summer weather 

window, but large enough to detect important spill effects. The study design consisted of two field 

components: fixed sampling locations and stratified random sampling locations. The 12 fixed 

locations provided information on the changes in amount and composition of petroleum residues over 

the period 1989-1991 to assess the rate of shoreline recovery and oil loss. Stations chosen 

represented worst-case oiling conditions and reference sites. Data gathered from these sites were 

used to assess oil loss, oil weathering, and bioavailability of oil residues to mussel communities. 

The stratified random sampling (SRS) of 64 sample locations permitted results to be generalized to 

the affected area of the sound. The SRS survey of the spill area shoreline was divided into four 

habitats which characterized over 99% of the shoreline of interest, and four oiling levels which 

produced information on all shoreline spill levels. The matrix of four habitats by four oiling levels, 

with each cell containing four replicates, constituted a reasonable compromise between project cost, 

the need to complete sampling within the short Alaskan summer, and the need for statistical power. 

The principal objective was to compare means within strata (habitat/oiling level) and not to obtain 

overall estimates (see Table B-1). 

Specific natural variables, including wave exposure, percentage sand, percentage silt/clay, and total 

organic carbon (TOC) were also quantified, and served as covariates in statistical analyses of oil 

effects. 

Precautions were taken to minimize the possibilities for petroleum hydrocarbon contamination of 

field samples by: 

•	 positioning the ship’s stern into the wind to prevent stack gases from blowing onto the sampling 

equipment during deployment, recovery, and subsampling 

• cleaning equipment just prior to arriving on station 

•	 ensuring that the sampling equipment was never deployed or recovered through oil slicks or 

sheens 

• closing the top access doors to the sampler when it was not being deployed or cleaned 

• field blanks were collected from each piece of equipment at regular intervals 

B-4 US Environmental Protection Agency 
Technical Manual 

•	 potential sources of hydrocarbon contaminants were also collected to enable their identification 

later 

Sample documentation included station logs and chain-of-custody forms. All sediment samples were 

logged in on the chain-of-custody forms along with other important information (station, date, time, 

sampling equipment and method, subsampling method, and type of sample.) Any additional 

information was also noted. This form accompanied each sample during shipping to the analytical 

lab and each sample cooler was sealed with a custody seal which was initialed and dated by the 

packer. 

Several analytical laboratories were needed to process and analyze the large numbers of samples 

collected. A laboratory standard oil was analyzed with each analytical batch to monitor analytical 

precision and to provide data for interlaboratory comparisons. Duplicate precision for both subtidal 

sediment studies and 1991 deep subtidal studies was ±30%. Other MQOs are listed in the Table B-1. 

Table B-1. Measurement quality objectives for subtidal sediment studies in Prince William Sound oil 

spill study (Gilfillan et al. 1995). 

Parameter Subtidal Sediment Studies 1991 Deep Subtidal Studies 

Units �g/kg dry weight �g/kg dry weight 

Practical Quantification Limit 

(PQL) 

10 1.0 

Estimated Method Detection 

Limit (MDL) 

1.0 0.1 

Procedural Blank 5 x MDL 5 x MDL 

Field Blank 5 x MDL 5 x MDL 

Matrix Spike Recovery 40 - 120%a 40 - 120%a 

Surrogate Recovery 40 - 120%b 40 - 120%b 

Duplicate Precision ± 30% ± 30% 

EVC Control Oil Standard 

Precision 

± 20% ± 20% 

Katalla Control Oil Standard 

Precision 

NA ± 20% 

NIST SRM 1941 Precision NA ± 25% 

NIST SRM 1291 Accuracy NA ± 15% 

a The average percentage recoveries for all 16 compounds must fall between 40 and 120%. Only one 

compound can be below its minimum percentage recovery. This allowed a deviation for a single analyte 

of not less than 10% for chrysene and benzo(a) pyrene and not less than 20% for the others. b	 Surrogate recoveries must fall between 40 and 120%. The upper control limit may be exceeded by one 

compound. c The average percentage difference for the target compounds should not exceed 20% of the mean of all 

previous values, and no single compound/isomer grouping should deviate by more than 30% of its mean 

value of all previous determinations. d SRM = Standard reference material. 

Appendix B: Examples of Measurement Quality Objectives B-5 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Example 2: Measurement Quality Objectives used in the Great Lakes Assessment 

and Remediation of Contaminated Sediment (ARCS) Program 

Background 

Although toxic discharges into the Great Lakes and elsewhere have been reduced in the last 20 years, 

persistent contaminants in sediments continue to pose a potential risk to human health and the 

environment (GLNPO 1994). Elevated concentrations of contaminants in bottom sediments and 

associated adverse effects have been found throughout the Great Lakes and connecting channels. 

The extent of sediment contamination and its associated adverse effects have been the subject of 

considerable concern and study in the Great Lakes community. 

To address these concerns, Annex 14 of the Great Lakes Water Quality Agreement between the 

United States and Canada (as amended by the 1987 Protocol) stipulates that the cooperating parties 

will identify the nature and extent of sediment contamination in the Great Lakes, develop methods to 

assess impacts, and evaluate the technological capability of programs to remedy such contamination. 

The 1987 amendments to the Clean Water Act, authorized GLNPO to coordinate and conduct a 5-

year study and demonstration projects relating to the appropriate treatment of toxic contaminants in 

bottom sediments. To fulfill the requirements of the Act, GLNPO initiated the Assessment and 

Remediation of Contaminated Sediments (ARCS) Program. ARCS is an integrated program for the 

development and testing of assessment techniques and remedial action alternatives for contaminated 

sediments. Information from ARCS Program activities will help address contaminated sediment 

concerns in the development of Remedial Action Plans (RAPs) for all 43 Great Lakes Areas of 

Concern (AOCs, as identified by the United States and Canadian governments), as well as similar 

concerns in the development of Lakewide Management Plans. 

Program Objectives 

Sediments are associated with impairment of beneficial uses at 42 of the 43 Great Lakes AOCs. 

Prior to addressing the potential need for remediation of those sediments, the following questions are 

addressed: 

•	 Are the sediments sufficiently “contaminated” to warrant consideration for remediation? In 

this context, “contaminated” refers to the presence of chemicals in the sediments that have 

the potential to cause adverse effects in humans or ecological receptors. 

•	 Is there evidence indicating that existing concentrations of sediment contaminants are 

adversely affecting ecological receptors? In other words, can it be shown that the presence 

of contaminants in the sediments is causing adverse effects in organisms, either organisms 

naturally occurring in the environment, or those exposed to sediments in controlled, 

laboratory toxicity tests? 

•	 Are ecological receptors exposed to the sediments bioaccumulating chemical contaminants to 

the extent that the resultant body burdens are adversely affecting the organisms themselves 

or other organisms higher in the food chain, including humans? 

•	 If the sediments are judged to be sufficiently contaminated to be causing such effects, what is 

the spatial extent (i.e., both horizontal and vertical) of the contamination, and what are the 

implications of the distribution of contaminants on possible remedial alternatives? 

B-6 US Environmental Protection Agency 
Technical Manual 

Early in the ARCS Program, it was recognized that the current state of sediment assessment methods 

was rapidly evolving. The sediment assessment methods currently available consider a wide variety 

of endpoints and effects, which differ in their suitability and sensitivity for investigating sediment 

contamination. Therefore, assessment methods selected in the ARCS Program, reflect site- and 

program-specific objectives of the study being conducted. 

The ARCS Program developed several measurement quality objectives (MQOs) that it uses in the 

design and conduct of studies at AOCs. Table B-2 summarizes these MQOs. 

Table B-2. Examples of the measurement quality objectives for inorganic and organic chemistry 

analyses of sediment used by the ARCS program in the Great Lakes (GLNPO, 1994). 

Parameter 

MDLa 

(�g/kg) Accuracyb Frequency Precisionc Frequency d 

Total organic carbon 0.03% ± 20 percent 1/batchd � 20 percent 1/batch 

Oil and grease 10,000 ± 20 percent 1/batch � 20 percent 1/batch 

pH N/A ± 0.1 unit 1/batch ± 0.1 unit 1/batch 

Acid-volatile sulfides 1,000 N/A N/A � 20 percent 1/batch 

Organohalogense 0.03 ± 20 percent 1/batch � 20 percent 1/batch 

Total 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 

Particle sizef 1,000 windows 1/batch � 20 percent 1/batch 

Solvent 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 

PCB/congener 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 

Methylmercury 10 ± 20 percent 1/batch � 20 percent 1/batch 

Tributyltin 10 ± 20 percent 1/batch � 20 percent 1/batch 

Metalsg 2,000 ± 20 percent 1/batch � 20 percent 1/batch 

Appendix B: Examples of Measurement Quality Objectives B-7 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table B-2 (continued). Examples of the measurement quality objectives for inorganic and organic 

chemistry analyses of sediment used by the ARCS program (GLNPO, 1994). 

Parameter 

MDLa 

(�g/kg) Accuracyb Frequency Precisionc Frequency 

Except: 

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 

Note: ARCS - Assessment and Remediation of Contaminated Sediments 

MDL - method detection limit 

N/A - not applicable 

PAH - polynuclear aromatic hydrocarbon 

PCB - polychlorinated biphenyl 

PCDDs/PCDFs - polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans 

a

 Units presented in the subheading are applicable to all parameters unless otherwise noted.


b

 Accuracy is determined from a certified reference material, standard reference material, or


standard and is measured from the known concentration.
 c

 Precision is calculated as percent relative standard deviation. Precision requirements listed here


are for analytical replicates only; field duplicates are required to have a relative percent difference


� 30 percent.


d

 A batch is a sample group (usually 10-20 samples) that is carried through the analytical scheme


simultaneously.
 e

 The MDL for chlorine and bromine is 30 ng, while the MDL for iodine is 10 ng.
 f

 A soil sample with acceptance windows per size fraction was provided for use as an accuracy


standard.


g

 Metals include arsenic, cadmium, chromium, copper, iron, lead, manganese, mercury, nickel,


selenium, silver, and zinc. Exceptions are noted where different methodologies are used during


the metals quantification.


B-8 US Environmental Protection Agency 
Technical Manual 

Example 3: Sediment Toxicity, Contaminant Concentrations and Benthic Community 

Structure as Indicators of Sediment Quality in the St. Louis River: A Test of EMAP 

Concepts Applied to a Great Lakes Area of Concern 

Background 

The International Joint Commission (IJC) has designated 43 areas of concern (AOCs) throughout the 

Great Lakes as threatened by conventional pollutants, heavy metals, toxic organic compounds, 

habitat alterations, and introduction of undesirable species. Results of these disturbances have been 

biological impacts (e.g., benthic macroinvertebrate and fish community degradation), human health 

effects (fish consumption advisories), and beach closings. The geographic areas associated with the 

AOCs contain a majority of the population residing in the Great Lakes basin, and comprise 

approximately 50% of all Canadian citizens. 

The St. Louis River AOC, which drains a watershed of 3,634 square miles in northern Minnesota and 

Wisconsin, forms a large freshwater estuary that represents the second largest tributary to Lake 

Superior. The 12,000-acre estuary is characterized by a diversity of habitat types. The AOC is 

unique among the Great Lakes AOCs in that the range of habitat types and contamination status is 

extreme: for example, the lower estuary contains two federal Superfund sites located across the river 

from large, undisturbed tracts of forested land currently providing excellent habitat quality for a large 

variety of species. The outer harbor contains actively dredged shipping channels and a number of 

current or former municipal and industrial effluent discharges, as well as the world’s largest 

freshwater sand bar, which is home to numerous endangered or threatened plants and animals. 

This project has a two-fold purpose: (1) determine if the EMAP intensified grid provides a sampling 

framework that can be used, with structural modification, to assess AOCs; and (2) develop a set of 

generic environmental indicators based on biological and chemical measures for long-term 

assessment of AOCs using the EMAP-Great Lakes and Surface Water EMAP indicators. 

In order to achieve these stated purposes, the project has four goals: 

1.	 To test the application of the Great Lakes-EMAP design features in the Harbors and 

Embayments resource class. 

2.	 To identify percentage areas within the St. Louis River AOC having acceptable and 

subnominal quality with respect to sediment contamination, toxicity and benthic community 

structure, and to associate statistically certain sediment contaminants with observed ecological 

effects. 

3.	 To serve as a baseline status-and-trends monitoring survey of the St. Louis River ecosystem 

health. 

4.	 To determine the sampling intensity required to survey a complex Great Lakes AOC in order 

to apply this knowledge to other AOCs within Region V. 

The project will sample 120 sites within three habitat classes in the St. Louis River AOC for 

sediment toxicity, chemical contaminant concentrations, and benthic community structure. The three 

habitat classes are: (1) ship channels and areas in the lower estuary greater than 18 ft in depth, (2) 

areas of the estuary less than 18 ft in depth, and (3) Thomson, Forbay and Fond du Lac reservoirs in 

the lower St. Louis River. 

Appendix B: Examples of Measurement Quality Objectives B-9 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

The distribution of sampling points in the three habitat classes is as follows: 30 sites in ship channels 

and deep water areas, 30 sites in the reservoirs, and 60 sites in the shallow-water estuarine areas. 

Sampling locations were selected based on the Great Lakes-EMAP grid for habitat classes 1 and 2, 

and a 75

-fold enhancement for habitat class 3. These numbers were determined through consultation 

with EMAP statisticians at ERL-Corvallis. Each site will be sampled twice during the two-year 

project period in order to estimate the short-term temporal variability for all three assessment 

metrics. Split-sample, surface sediments will be used for toxicity, chemistry and benthic assessment. 

Project Objectives 

The questions to be answered by and/or objectives for this project are the following: 

1.	 What percentage of the sediments in the St. Louis River AOC have unacceptable levels of 

sediment contamination, toxicity, and benthic community disturbance? 

2.	 Make statistical associations on an AOC-wide basis between contaminant levels and sediment 

toxicity or sub-nominal benthic community status. 

3.	 How many sampling sites and time points are necessary to characterize sediment quality, 

using the criteria determined in Objective 1, in each of the identified habitat classes (i.e., ship 

channels and deep holes, shallow shoal or stream areas, and upstream reservoirs)? 

4.	 Establish a relevant integrity index for benthic community assessment for the St. Louis River 

using the EMAP sampling design. 

The requirements for precision, accuracy, completeness, representativeness and comparability of the 

data in order to attain the project objectives are described in Table B-3. Objective #1 has the least 

strict data quality requirements for toxicity and chemistry because the large number of samples was 

designed to provide an excessively-thorough site characterization. This was done in order to increase 

the likelihood of obtaining a wide variety of sediment types with which to carry out Objectives #2 

and #3. In other words, the number of sites and sampling points is most likely overly abundant to 

address Objective 1. However, because this project is intended as a pilot to actually establish the 

requisite number of samples on an areal basis for each habitat type, an overestimate was required in 

the sample design. Thus, fewer sites should be required to answer Objective #1 than to satisfy 

Objectives 2 and 3; therefore, the required data attributes for Objective #1 are slightly less strict than 

for the other objectives. Objective #4 does not require data for toxicity and chemistry. 

B-10 US Environmental Protection Agency 
Technical Manual 

Table B-3. Summary of measurement quality objectives for the St. Louis River area of concern 

sediment quality assessment by sampling goal 

ObjectiveMetric Precision Accuracy Completeness Representativeness 

Goal 1 40% RPDa N/A 80% 80% 

#1-Toxicity 40% RPDa 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-Toxicity 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-Toxicity 30% RPD N/A 90% 90% 

Benthos 30% RPD N/A 90% 90% 

Chemistry 40% RPD 70-120% 90% 90% 

Goal 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% 

Chemistry N/A N/A N/A N/A 

a

 Relative percent difference 

Appendix B: Examples of Measurement Quality Objectives B-11 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Example 4: Ecological Effects of Sediment-Associated Contaminants in Inner 

Burlington Harbor, Lake Champlain 

Background 

Inner Burlington Harbor of Lake Champlain has received numerous toxicants from point and 

nonpoint sources in its watershed. Previous sediment sampling and analyses (Watzin et al., 1997) 

demonstrated relatively high concentrations of silver, lead, and PAHs in the harbor, especially in the 

southern end, compared to sites outside the breakwater. Much of this area corresponds to an old 

sewage outfall and oil dolphins but could also represent migration of inputs from the old rail yard 

and nonpoint sources in and around Burlington. Because the surficial sediment (top 2-3 cm) at most 

sites had lower pollutant concentrations than sediments at greater depths, inputs of pollutants in 

recent history (past 30 years) may be declining. However, these studies also indicated substantial 

temporal and spatial heterogeneity with respect to sediment contaminant concentrations and toxicity 

(Watzin et al., 1997). 

Biological assessments, using benthic macroinvertebrates, were used in conjunction with other field 

and laboratory analyses to help determine the effects of sediment contamination and other stressors 

on the biota of Burlington Harbor. 

Project Objectives 

The overall objective of this project was to assess the hazard resulting from toxic contaminants in the 

sediments of Inner Burlington Harbor using a sediment quality triad approach. Because certain 

potentially toxic contaminants are known to occur in Burlington Harbor, the objective of this project 

was divided into three major component questions. 

• Have toxic sediments altered benthic communities of Burlington Harbor? 

• Could such changes affect other ecological components of Lake Champlain? 

•	 Do the toxic contaminants in Burlington Harbor sediments accumulate up the food chain and 

cause risks to higher terrestrial and aquatic trophic levels and human health? 

Sampling Design 

Sampling locations in the present study were identified by reanalyzing the 1993-94 data from the 

harbor with a spatial statistical model known as kriging (Myers, 1988) to estimate contaminant 

concentrations and uncertainties throughout the harbor. Kriging is a geostatistical estimation method 

which incorporates a model of the spatial variability of data directly. For each chemical, a variogram 

was calculated using USEPA’s software Geo-EAS (version 1.2.1) and fitted by a non-linear leastsquared procedure. 

The sampling sites selected for the present study were those with the greatest uncertainty (using 

existing data), and the highest likelihood of contamination. Ten sites were sampled in the harbor and 

10 replicate samples from two different sites (reference sites) with relatively low contaminant 

concentrations and/or toxicity were sampled to help assess sediment quality in the harbor, 

particularly with respect to biological and toxicological measures. Five replicate samples were 

collected from one site inside the harbor and 5 reference samples were collected from one site. The 

five replicate samples collected at each reference site were tested separately for all toxicity and 

biological analyses, yielding five individual measures for toxicity and macroinvertebrate community 

structure at these two sites. Subsamples from each of the five samples collected at both sites were 

composited into one sample from each site for physicochemical analyses. Two other sites were 

B-12 US Environmental Protection Agency 
Technical Manual 

replicated once as well to obtain a measure of the variability surrounding chemical measures 

obtained in this study. A total of eight sites were sampled both in this study and in previous work. 

Sediment Sampling and Analyses 

Sites were identified using differential global positioning and checked frequently during sampling to 

ensure proper sampling location. Each site was sampled using five-seven petite Ponar grabs, 

depending on the amount of sediment collected in each grab sample. 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 summarizes the analyses performed in this study and the measurement quality objectives 

used. Sediment chemical analyses included PAHs, simultaneously extracted metals (SEM), total 

organic carbon (% TOC), acid volatile sulfides (AVS), total organic nitrogen (TON), ammonia, 

particle size, and pH. Five metals (those previously showing the highest levels: silver, nickel, 

copper, lead, and zinc) were measured. Zebra mussels (Dreissena polymorpha) were collected from 

several sites and analyzed for tissue PAHs and percent lipid content on a composite sample of 

organisms collected at each site. A portion of the sample from three inner harbor sites were sieved 

(stainless steel) to isolate the fine fraction less than 63μ and also analyzed for PAHs, total organic 

carbon, and organic nitrogen. 

Appendix B: Examples of Measurement Quality Objectives B-13 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table B-4. Summary of measurement quality objectives for precision, accuracy, and completeness of 

biological, toxicological, sediment, organism tissue, and field chemistry analyses conducted in 

Burlington Harbor (Diamond et al., 1999). RPD = relative percent difference; C.V. = coefficient of 

variation. 

Measurement Parameter Accuracy 

(% Recovery) 

Precision Completeness 

(%) 

Benthic macroinvertebrates 

• Metric values 

• Metric scores 

• Bioassessment scores 

Field Water Quality Measurements 

• Conductivity 

• Temperature 

• Dissolved Oxygen 

• pH 

Laboratory Sediment Analyses 

• PAH 

• 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 

• PAH 

• 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 range 

± 0.15° C 

± 0.2 mg/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 through use of routine standards and calibration. 

B-14 US Environmental Protection Agency 
Technical Manual 

Example 5: Washington Department of Ecology Sampling and Analysis Plan 

Guidance 

Background 

The Washington Department of Ecology (WDE) provides technical guidance for developing 

sampling and analysis plans for sediment investigations to be conducted under the Washington 

Sediment Management Standards (SMS) program (WDE, 1995). Technical guidance on various 

aspects of sediment sampling and analysis procedures that need to be considered in the design and 

implementation of sediment investigations is made available through the Puget Sound Estuary 

Program [PSEP] protocols. 

1.	 Sediment Source Control Program – Methods are described for controlling the effects of point 

and nonpoint source discharges through the National Pollutant Discharge Elimination System 

(NPDES) permit program, state water quality permit programs, issuance of administrative orders, 

or other mans determined appropriate by WDE; and 

2.	 Sediment Cleanup Program – Administrative procedures and criteria are established to identify, 

screen, rank, and prioritize, and clean up contaminated surface sediment sites. 

Project Objectives: Sediment Investigations Conducted under the Sediment Source 

Control Program 

Adverse effects of contaminated sediments on biological resources and threats to human health 

generally will only occur when there is a pathway to ecological or human receptors. In most cases, 

such a pathway will only exist when surface sediments (defined by the SMS as those within the 

biologically active zone) are contaminated. Contaminated sediments existing at depths below the 

biologically active zone are unlikely to result in such effects unless the overlying sediments are 

removed by natural (e.g., erosion, scouring) or anthropogenic (e.g., dredging, propeller scour) means, or 

there are other mechanisms for the release of sediment contaminants such that exposure may occur. 

Additionally, the surface sediment will be most likely to exhibit impacts from recent discharges of 

contaminants. Hence, the focus of sediment sampling 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: Examples of Measurement Quality Objectives B-15 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table B-5. Sediment Management Standards Biological Effects Criteria for Puget Sound Marine 

Sediments 

Biological Test Sediment Quality Standards

a	 Sediment Impact Zone Maximum Levels, 

Cleanup Screening Levels, or 

Minimum Cleanup Levels

b 

Amphipod 

Larval 

Benthic 

infauna 

Juvenile 

polychaete 

Microtox® 

The test sediment has a significantly higher 

(t-test, P�0.05) mean mortality than the 

reference sediment, and the test sediment mean 

mortality exceeds 25 percent on an absolute 

basis 

The test sediment has a mean survivorship of 

normal larvae that is significantly less (t-test, 

P�0.05) than the mean normal survivorship in 

the reference sediment, and the combined 

abnormality and mortality in the test sediment 

is more than 15 percent greater, on an absolute 

basis, than the reference sediment 

The test sediment has less than 50 percent of 

the reference area sediment's mean abundance 

of any one of the following major taxa: 

Crustacea, Mollusca, or Polychaeta, and the test 

sediment abundance is significantly different (ttest, P�0.05) from the reference sediment 

abundance 

The mean biomass of polychaetes in the test 

sediment is less than 70 percent of the mean 

biomass of the polychaetes in the reference 

sediment, and the test sediment biomass is 

significantly different (t-test, P�0.05) from the 

reference sediment biomass 

The mean light output of the highest 

concentration of the test sediment is less than 

80 percent of the mean light output of the 

reference sediment, and the two means are 

significantly different (t-test, P�0.05) 

The test sediment has a significantly higher 

(t-test, P�0.05) mean mortality than the 

reference sediment, and the test sediment mean 

mortality is more than 30 percent greater, on an 

absolute basis, than the reference sediment 

mean mortality 

The test sediment has a mean survivorship of 

normal larvae that is significantly less (t-test, 

P�0.05) than the mean normal survivorship in 

the reference sediment, and the combined 

abnormality and mortality in the test sediment is 

more than 30 percent greater, on an absolute 

basis, than that in the reference sediment 

The test sediment has less than 50 percent of 

the reference area sediment's mean abundance 

of any two of the following major taxa: 

Crustacea, Mollusca, or Polychaeta, and the test 

sediment abundance is significantly different (ttest, P�0.05) from the reference sediment 

abundances 

The mean biomass of polychaetes in the test 

sediment is less than 50 percent of the mean 

biomass of the polychaetes in the reference 

sediment, and the test sediment biomass is 

significantly different (t-test, P�0.05) from the 

reference sediment biomass 

Not applicable 

Source: WDE (1995). 

a

 The sediment quality standards are exceeded if one test fails the listed criteria [WAC 173-204-320(3)]. b

 The sediment impact zone maximum level, cleanup screening level, or minimum cleanup level is exceeded if 

one test fails the listed sediment impact zone maximum level, cleanup screening level, or minimum cleanup level 

criteria [WAC 173-204-520(3)] or if two tests fail the sediment quality standards criteria [WAC 173-204-320(3)]. 

B-16 US Environmental Protection Agency 
Technical Manual 

WDE describes four general types of sediment monitoring (all of which are the responsibility of the 

discharger) that may be conducted in support of the sediment source control process: 

(a)	 Baseline monitoring— Used to confirm the screening evaluation for determining potential of 

a discharge to cause sediment impacts conducted prior to authorization of a sediment impact 

zone (SIZ) to collect information that will be used in determining whether such an authorization 

is likely to be necessary, and to establish the baseline conditions with which future conditions 

can be compared 

(b)	 SIZ application monitoring— Conducted to collect information to support application of the 

SIZ models 

(c)	 SIZ maintenance monitoring—Conducted during the term of a permit that includes an 

authorized SIZ, with the intent to determine whether the SIZ should be renewed, reduced, or 

eliminated; whether areas of special importance have been adversely impacted by the discharge; 

and the conditions for SIZ reauthorization 

(d)	 SIZ closure monitoring— Conducted following closure of an SIZ to demonstrate successful 

restoration of sediment quality. 

The monitoring objectives vary with the type of monitoring being conducted, and the design of the 

monitoring program varies with both discharge- and site-specific characteristics. 

Project Objectives: Sediment Investigations Conducted under the Sediment Cleanup 

The Sediment Cleanup Standards set forth a decision process for identifying contaminated sediment 

areas and determining appropriate cleanup responses (WDE, 1995). The sediment cleanup decision 

process includes procedures for screening and ranking contaminated areas of sufficient concern to 

warrant active cleanup, as well as procedures for selecting an appropriate cleanup alternative on a sitespecific basis. 

Because cleanup of contaminated sediments may require their removal, sediment sampling and 

analyses, conducted in support of sediment cleanup studies, need to assess the total spatial extent 

(including both lateral and vertical) of the sediment contamination. In this respect, these sediment 

investigations differ from those previously described under the sediment source control process, where 

the focus there is generally only on sediments within the biologically active zone. 

In addition to initial investigations and site characterization, which are described in by WDE (1995), 

there are three general types of monitoring that may be conducted in support of the sediment cleanup 

process: 

(a)	 Source control monitoring— Conducted prior to and following sediment cleanup to determine 

how ongoing sources at or near a site may affect the success of active cleanup and/or natural 

recovery 

(b)	 Compliance monitoring— Long-term monitoring conducted following cleanup actions that 

include containment of contaminated sediments, or to assess the progress of natural recovery 

and/or to evaluate recontamination of the area 

Appendix B: Examples of Measurement Quality Objectives B-17 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

(c)	 Closure monitoring— Conducted following completion of removal actions or compliance 

monitoring to demonstrate successful cleanup of sediment contamination. Closure monitoring 

must be performed before a site can be considered for delisting. 

The primary objectives of sediment sampling and analyses conducted as part of a preliminary 

investigation of a contaminated sediment site are to: (1) Identifying sediment station clusters of 

potential concern, and (2) Ranking identified cleanup sites. 

Such sampling and analyses must be sufficient to enable a determination of whether there are 

exceedances of the numerical chemical criteria or biological effects criteria (Table B-5) at three or more 

stations within a specific area of concern. Thus, the decision rules used by WDE in these studies (Step 

5 of the DQO Process, Figure 2-2, this Manual) are defined by explicit criteria and the number of the 

samples demonstrating exceedence of criteria. The spatial extent of such exceedances is not required to 

be defined as part of a preliminary investigation (WDE, 1995). 

Given the decision rules above, there are clear implications for how sampling is designed, as there need 

to be several samples collected and analyzed from a specific area of concern and some assurance of 

representative coverage of the area. At smaller sites of known or suspected sediment contamination, the 

addition of a relatively small number of stations or samples in a preliminary investigation is suggested 

by WDE (1995) to allow assessment of the spatial extent of contamination, gradients toward or away 

from other sources, or other important details. Hence, a single study could suffice, thereby precluding 

the need for a second, focused investigation. 

Alternatively, if there are no plans to dredge or otherwise disturb the sediments, sampling and 

analyses, conducted as part of a preliminary investigation, could focus only on surface sediments. 

After the need for cleanup has been identified, a more focused sediment sampling and analysis 

program would then be required by WDE to define the spatial extent of contamination (including its 

vertical extent) and to evaluate cleanup alternatives. 

Comparison of Data Requirements: Sediment Management Standards (Sms) and the 

Dredged Material Management Program (DMMP) 

In addition to WDE’s Sediment Management Strategy (SMS), the other major framework for sediment 

management activities in the Dredged Material Management Program (DMMP). The SMS and DMMP 

programs are very similar in the suites of biological and chemical evaluations that are required, and in 

the evaluation criteria that are applied. While the two programs have the same goal, protection of 

sediment quality, the two programs have different applications and, as a result, some differences in data 

requirements. 

Sediment sampling and analysis is conducted under the SMS to determine whether, and to what extent, 

surface sediments are contaminated, whether point or nonpoint source discharges have contributed or 

may still be contributing to such contamination, and whether contaminated sediments should be 

remediated. Sediment sampling and analysis is conducted under theDMMP program to determine 

whether the sediment matrix (volume) proposed for dredging, when dredged and discharged at 

unconfined, open-water disposal sites within Puget Sound, could cause or contribute to unacceptable 

adverse effects on the aquatic environment. Because of these different purposes, sampling gear and 

compositing techniques will differ. However, both theDMMP and SMS data requirements are based 

upon “exposure potential” and a “sediment unit” concept. In dredging situations (DMMP), the 

exposure potential of concern is with the entire mass of sediments released at the DMMP sites and the 

sediment unit of concern is the minimum dredge unit that can be effectively managed. In SMS 

B-18 US Environmental Protection Agency 
Technical Manual 

situations, the exposure potential and sediment unit of concern is generally the surface, specifically the 

“biologically active zone” (often the top 10 cm). 

DMMP sampling is designed to characterize the bulk properties of the sediments to be dredged, 

transported, and discharged. Sediment core samples (e.g., vibracorer) are typically collected to 

characterize the sediment matrix to the depth of proposed dredging for disposal determinations and to 

assure that the quality of newly exposed surfaces do not result in degradation. Because dredging 

removes the material in bulk, the cores are typically segmented on a 4-foot basis and composited across 

that segment (rather than further subdivided) to define a “dredged material management unit.” 

Sediment sampling under the sediment source control process of the SMS is generally designed to 

characterize conditions near the sediment surface. In cases where the goal is to characterize the 

exposure potential, such sampling may target the biologically active zone of the sediments. In other 

cases, where the goal is to sample only the most recently deposited sediment, such sampling may target 

only the uppermost 0–2 cm of sediments. Sediment sampling designed to identify contaminated 

sediment sites under the sediment cleanup process of the SMS is also targeted on the near-surface, 

biologically active zone of the sediments. After a contaminated site is identified, however, collection of 

sediment cores will also generally be required to assess the vertical extent of contamination and to 

determine the sediment quality of any new surface to be exposed after cleanup. 

The process of compositing samples from a range of depth intervals below the sediment surface may 

dilute higher concentrations of contaminants as pointed out in Section 2.4.3 of this Manual and in 

USEPA/ACOE (1998). Compositing over depth provides an assessment of the condition of the overall 

sediment matrix, but does not provide an assessment of the sediments within the biologically active 

zone. Compositing of samples from a range of depth intervals is therefore appropriate for DMMP 

purposes, but is ordinarily not performed for SMS investigations. In addition, many more samples may 

be needed for SMS purposes to establish patterns or gradients of contamination, to identify contaminant 

sources, or to delimit the area of contamination. 

Development of Sediment Sampling and Analysis Plans 

Although the specific details of individual sampling and analysis plans may be very different, all such 

plans submitted for review by WDE contain certain basic elements. Figure B-1 provides a 

recommended outline for sediment sampling and analysis plans that can also serve as a checklist for 

those preparing or reviewing such plans. 

Each sediment sampling and analysis plan, regardless of whether it is being prepared under the 

sediment source control process or the sediment cleanup process, should include as part of the 

introduction a brief summary of site background information. The following background information 

should be provided: 

• Site history 

•	 Regulatory framework (e.g., NPDES; Model Toxics Control Act; SMS; Comprehensive 

Environmental Response, Compensation, and Liability Act) 

• Summary of results of previous investigations, if any, of the site 

•	 Location and characteristics of any current and/or historical wastewater or stormwater discharge(s) at 

the site 

Appendix B: Examples of Measurement Quality Objectives B-19 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

•	 Location and characteristics of any current and/or historical wastewater or stormwater discharge(s) in 

the local area 

• Information on onsite waste disposal practices or chemical spills in the local area, if any 

• Site location, including a location map showing the surrounding area and a site map. 

The second section of a sampling and analysis plan should describe the objectives of the sediment 

investigation in the context of the appropriate regulatory framework (e.g., sediment source control 

process, sediment cleanup process). WDE (1995) provides guidance on appropriate field sampling 

methods; sample handling procedures; laboratory analytical methods; quality assurance and quality 

control requirements; data analysis, record keeping, and reporting requirements; health and safety plan; 

schedule; and project team and responsibilities. 

B-20 US Environmental Protection Agency 
Technical Manual 

Sediment Sampling and Analysis Plan Outline and Checklist 

(From WDE, 1995) 

1. 	Introduction and Background Information 

� Site history 

� Regulatory framework (e.g., NPDES, MTCA, SMS, CERCLA) 

� Summary of previous investigations, if any, of the site 

� Location and characteristics of any current and/or historical wastewater or storm water 

discharge(s at the site 

� Location and characteristics of any current and/or historical wastewater or storm water 

discharge(s) in the local area 

� Information on on-site waste disposal practices or chemical spills in the local area, if 

any 

� Site location map showing the surrounding area 

� Site map showing site features 

2. 	Objectives and Design of the Sediment Investigation 

� Objectives of the sediment investigation 

� Overall design of the sediment investigation, including related investigations, if any 

� Chemical analytes (including description of their relevance to the objectives and the 

regulatory framework) 

� Biological tests (including description of their relevance to the objectives and the 

regulatory framework) 

� Sampling Station Locations 

� Rationale for station locations 

� Site map(s) showing sampling stations and other pertinent features (e.g., 

bathymetry and current regime; outfall(s)/diffuser(s); authorized mixing 

zone(s), if any; sites of waste disposal, spills, or other activities that may have 

affected the sediments, such as sandblasting, boat repair, etc.; historical 

dredging activities) 

� Proposed reference stations 

� Table showing the water depth at each proposed station 

� Proposed depth(s) below the sediment surface where sediments will be 

collected 

Figure B-1. Sediment Sampling and Analysis Plan Outline and Checklist Developed by Washington 

Department of Ecology (WDE, 1995). 

Appendix B: Examples of Measurement Quality Objectives B-21 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

3. 	Field Sampling Methods 

� Station positioning methods 

� Sampling equipment 

� Decontamination procedures 

� Sample compositing strategy and methods 

� Sample containers and labels 

� Field documentation procedures 

� Procedures for disposal of contaminated sediments 

4. Sample Handling Procedures 

� Sample storage requirements (e.g., conditions, maximum holding times) for each type 

of sample 

� Chain-of-custody procedures 

� Delivery of samples to analytical laboratories 

5. 	Laboratory Analytical Methods 

� Chemical analyses and target detection limits 

� Biological analyses 

� Corrective actions 

6. 	Quality Assurance and Quality Control Requirements 

� QA/QC for chemical analyses 

� QA/QC for biological analysis 

� Data quality assurance review procedures 

7. 	Data Analysis, Record Keeping, and Reporting Requirements 

� Analysis of sediment chemistry data 

� Analysis of biological test data 

� Data interpretation 

� Record keeping procedures 

� Reporting procedures 

Figure B-1 (continued). Sediment Sampling and Analysis Plan Outline and Checklist Developed by 

Washington Department of Ecology (WDE, 1995) (cont.). 

B-22 US Environmental Protection Agency 
Technical Manual 

8. 	Health and Safety Plan (required for cleanup investigations) 

� Description of tasks 

� Key personnel and responsibilities 

� Chemical and physical hazards 

� Safety and health risk analysis for each task 

� Air monitoring plan 

� Personal protective equipment 

� Work zones 

� Decontamination procedures 

� Disposal procedures for contaminated media and equipment 

� Safe work procedures 

� Standard operating procedures 

� Contingency plan 

� Personnel training requirements 

� Medical surveillance program 

� Record keeping procedures 

9. 	Schedule 

� Table or figure showing key project milestones 

10. Project Team and Responsibilities 

� Description of sediment sampling program personnel 

� Table identifying the project team members and their responsibilities 

11. References 

� List of references 

Figure B-1 (continued). Sediment Sampling and Analysis Plan Outline and Checklist Developed by 

Washington Department of Ecology (WDE, 1995). 

Appendix B: Examples of Measurement Quality Objectives B-23 
APPENDIX C


STATISTICAL CONSIDERATIONS IN


DETERMINING THE APPROPRIATE


NUMBER OF REPLICATE SAMPLES


NEEDED AT EACH SAMPLING STATION

Technical Manual 

For certain programs or types of studies, it is desirable (or necessary) to determine if a particular 

location is significantly affected as compared to known non-impacted or reference locations (e.g., 

presence of toxicity and/or high contaminant concentrations in sediments or interstitial waters). This 

type of monitoring objective is used frequently in certain regulatory programs, such as the Dredged 

Materials Management Program and Superfund (CERCLA), however, many non-regulatory programs 

also have a similar objective (see for example the Burlington Harbor example in Appendix B). 

If one is interested in determining statistical differences in certain measures (e.g., toxicity to Hyalella 

azteca) among or between stations, then analysis of replicate field samples may be necessary. This 

entails collecting multiple samples from the same station (or other spatial unit of interest), processing 

each sample independently, and analyzing separately each sample. For example, if the purpose of a 

study is to determine whether the sediment in a specific location is toxic to the estuarine amphipod 

Rhepoxynius abronius as compared to sediment from a reference location, then it is desirable to 

collect multiple samples from each location and perform a Rhepoxynius whole sediment toxicity test 

(including standard replication within a test) for each sample collected. Clearly, this type of 

replication could entail substantial laboratory effort, as compared to compositing samples from a 

single location and performing a single analysis or test (see Section 2.4.3 for a discussion of 

compositing versus replication of samples). However, compositing does not provide any information 

on the true variability of a given location and is rather, a form of pseudoreplication. For some 

programs or studies, true field replication is necessary. 

The appropriate number of replicates needed for a given study depends on the statistical power and 

level of confidence (i.e., measurement quality objectives; see Appendix B for examples) one needs to 

support or refute a given decision (see Data Quality Objectives Process, Section 1.1 and Appendix 

A). Power is represented as 1-� and is a measure of the Type II error rate: the probability of 

accepting the hypothesis that the results from two different samples or stations are similar, when in 

fact they are not. Confidence is represented as 1-� and is a measure of the Type I error rate: the 

probability of rejecting the hypothesis that the results from two different samples or stations are 

different when in fact they are really the same. For examples, if the question is whether a given 

location should be dredged for remediation purposes, the study will need to have a certain statistical 

power, to determine if the sediment sample from the target location is more toxic or contaminated 

than the reference location sediment, with a certain degree of confidence that one is making the 

correct decision. Both power and confidence are dependent on the expected variability in the 

endpoint or parameters of interest, both within a given location and within a given test or analysis. 

The appropriate replication, then, is required so that one has sufficient statistical power and 

confidence to reliably make correct decisions about the status of a given location. 

To determine the number of replicates required, the following questions should be answered 

(Alldredge, 1987): 

1. What is being compared (i.e., toxicity endpoint, parameter value)? 

2.	 Is the significance criterion directional (is one only interested in whether a station is more toxic 

than another, not less toxic as well; i.e., one-tailed test)? 

3.	 What is the level of significance between the expected and actual value of the parameter being 

measured? 

4.	 How large a difference is acceptable between the expected and actual value of the criterion being 

measured, and with what level of probability? 

5. What variability is expected in the data? 

Appendix C: Statistical Considerations in Determining the Appropriate Number of Replicate Samples C-3 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

There are a number of approaches that can be used to determine the number of replicates required to 

achieve a minimum detectable difference at a specific confidence level and power (see Environment 

Canada, 1995). While many programs specify a fixed number of replicates per station (often 3-5 

replicates), in other cases, this could represent too many or too few replicates for study data quality 

objectives. Several factors need to be defined to establish the appropriate number of replicates (see 

text box). U.S. EPA (2000c) presents a concise discussion of the relationships of these statistical 

considerations. Traditionally, acceptable coefficients of variation vary from 10 to 35%, the power 

from 80 to 95%, the confidence level from 80 to 99%, and the minimum detectable relative 

difference from 5 to 40% (Barth and Starks, 1985). 

Several books on sampling design (e.g., Keith 1993; USEPA 2000b) discuss methods to determine 

the appropriate number of replicates needed for a given set of objectives. Table C-1 summarizes 

statistical approaches for determining the appropriate number of replicate samples needed per station 

given different study objectives. 

Table C-1. Statistical Formulae for Determining Number of Samples to be Collected for 

Environmental Monitoring and Assessment 

Study Objective Formula Reference 

To determine the sample size 

required to detect an effect in 

an impacted area versus a 

control area over time: 

a) resampling same sites 

before and after impact 

and testing if the mean 

change in the control area 

is the same as that in the 

impacted area 

b) sampling different sites 

before and after impact 

and testing if there is no 

interaction between area 

effect and time effect 

n = 2(t� + t�)

2

 (S/�)

2 

n = 4(t� + t�)

2

 (S/�)

2 

where: 

n = number of samples for each of 

the control and impact areas 

S = standard deviation 

� = magnitude of change required 

to be a real effect with 

specified power (1-�) 

t� = t statistic given a Type I1

 error 

probability 

t� = t statistic given a Type II

2

 error 

probability 

Green, 1989 

Green, 1989 

C-4 US Environmental Protection Agency 
Technical Manual 

Table C-1 (continued). Statistical Formulae for Determining Number of Samples to be Collected 

for Environmental Monitoring and Assessment 

Study Objective Formula Reference 

To determine if the mean 

value for an impacted area: 

a) differs significantly from a 

standard value (e.g., 

sediment guideline) 

b) differs significantly from 

the mean of a control site 

n � (Z� + Z�)

2 + 0. 5 Z�2 

d2 

n � (Z� + Z�)

2 + 0. 25 Z�2 

d2 

where: 

n = number of samples 

Z� = Z statistic for Type I error 

probability (e.g., �=0.05) 

Z� = Z statistic for Type II error 

probability (e.g., �=0.90) 

d = magnitude of the difference to 

be detected (i.e., effect level) 

Alldredge, 1987 

To determine the number of 

samples required to estimate a 

mean value (representative of 

the area) with a given 

statistical certainty 

y� = tc Sx 

(n-1)

1⁄2 

where: 

y = accepted error as a proportion 

of the mean value(e.g., y = 

0.10) 

� = mean value of xi

 (i = 1...n) 

Sx = standard deviation 

tc = confidence coefficient (e.g., 

90% or t0.95 

n = number of samples 

Håkanson, 1984 

To determine the number of 

samples required to estimate a 

mean 

n = (Z�/2)

2

�2 

d2 

where: 

n = number of samples 

Z = Z statistic (standard normal 

curve) 

�2 = variance 

�/2 = probability of a 95% 

confidence level 

d = distance between the 

center of the lower 

confidence and upper 

confidence bound 

Milton et al., 1986 

Appendix C: Statistical Considerations in Determining the Appropriate Number of Replicate Samples C-5

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table C-1 (continued). Statistical Formulae for Determining Number of Samples to be Collected 

for Environmental Monitoring and Assessment 

Study Objective Formula Reference 

To determine the number of 

samples required for a 

particular power for a normal 

distribution (i.e., � > s2) 

n = 104

 (t2s2) K 

(R2

�2

) 

where: 

n = number of samples 

t = t statistic for a desired 

confidence level 

� = mean value from preliminary 

sampling or historical data 

s = standard deviation of mean 

R2 = percentage coefficient of 

variation 

K = index of clumping 

Kratochvil and 

Taylor, 1981 

1 Type I (�) error is the probability of rejecting the hypothesis being tested when it is true. 2 Type II (�) error is the probability of not rejecting the hypothesis being tested when it is false. 

Optimizing Sampling 

Having estimated the variability in a given parameter or endpoint, and the number of replicate 

samples per station that might be necessary to address data quality objectives, one can evaluate the 

cost/benefit of collecting and analyzing more or less samples in terms of the overall confidence in a 

given decision and the information gained. This is referred to as optimizing the study design (Step 7, 

Figure 2-1). Ferraro et al. (1994, 1989) present a method for quantitatively evaluating the optimum 

macrobenthic sampling protocol, including the number of replicates (n), which has relevance to other 

sediment quality studies as well. Their approach helps answer fundamental questions concerning the 

design of sediment quality studies such as: 

• How large should the sampling unit be? 

• How many replicate samples should be taken? 

The procedure calculates the “power-cost efficiency” (PCE), which incorporates both the number of 

samples (n), the cost (field collection effort and lab effort combined) and the expected statistical 

power for each alternative sampling scheme. The various sampling schemes consist of different 

combinations of sampling gear, gear area, and number of replicates. The method allows determining 

the optimum among a set of sampling schemes for detecting differences between reference and test 

sites when the statistical model is a t-distribution for comparing two means. The optimum 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 measure between two sites. The approach can be 

applied to each parameter of interest and the results aggregated to determine the optimum protocol. 

C-6 US Environmental Protection Agency 
Technical Manual 

There are four primary steps in assessing the PCE of a suite of alternative sampling schemes: 

1.	 For each scheme, collect replicate samples at paired reference and test sites. The observed 

difference in values between the sites is operationally assumed to be the magnitude of the 

difference desired to be detected. Alternatively, a percentage of the median (e.g., 20%) for a 

given measure calculated across reference stations could be set as the magnitude of the 

difference to be detected. In either case, this difference, divided by the standard deviation, is the 

“effect size” (ES) of interest. 

2. Assess the “cost” (ci

), in time or money, of each sampling scheme i at each station. The cost can 

include labor hours for sampling, analysis, and recording results. 

3.	 Conduct statistical power analysis to determine the minimum number of replicate samples (ni

) 

needed to detect the ES with an acceptable probability of Type I (�) and Type II (�) error (e.g., 

� = � = 0.05). 

4. Calculate the power-cost efficiency (PCE) for each sampling scheme by: 

PCEi

 = (n x c)min/ (ni x ci) 

where (n x c)min = minimum value of (n x c) among the i sampling schemes. The reciprocal of PCEi 

is the factor by which the optimal sampling scheme is more efficient than alternative scheme i. 

When PCE is determined for multiple metrics, the overall optimal sampling protocol may be defined 

as that which ranks highest in PCE for most metrics in the test set. 

Appendix C: Statistical Considerations in Determining the Appropriate Number of Replicate Samples C-7 
APPENDIX D


ADVANTAGES AND DISADVANTAGES OF


DIFFERENT STATION POSITIONING


TECHNIQUES

Technical Manual 

Documentation of sampling station location or position is an important aspect of field operations to 

ensure that: (1) sampling occurs where intended and (2) someone else (or another sampling team) 

could re-sample the same location at a later date. This is particularly critical for trend monitoring 

such as that performed by NOAA’s Status and Trends Program. 

With current technology, a global positioning system (GPS) device is generally the positioning 

method of choice because it is usually very accurate, reliable, easy to use, and affordable. However, 

occasionally, other positioning methods may be desired or necessary. The following tables, 

originally developed under the Puget Sound Estuary Program, summarize most of the positioning 

methods that have been used in monitoring studies, including their advantages and disadvantages. 

Appendix D: Advantages and Disadvantages of Different Station Positioning Techniques D-3 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table D-1.	 Positioning methods appropriate for small water bodies (small embayment, small lakes, 

rivers) (modified from PSEP 1997a). 

Method Accuracy Range Advantages Disadvantages 

GPS or Navstar ± 100 m (0.1 

to 

1 m for 

differential 

GPS) 

no limit 

on the 

range 

� Continuous position reports 

available worldwide 

� System s available comprising a 

range of accuracy and cost 

� Site-specific problems due 

to military scrambling 

Theodolite 10 to 30 s 

� ± 1 m 

200 m 

to 5 km 

� Traditional method, measuring 

horizontal angles between known 

targets 

� High accuracy when applied 

successfully 

� Inexpensive 

� Requires triangulation 

between two manned shore 

sites or targets 

� Requires simultaneous 

measurements 

� Requires good visibility 

which limits areal coverage 

� Requires stationary 

sampling platform 

Electronic 

Distance 

Measurement 

instrument 

(EDMI) 

1.5 to 3.0 cm 3 km 

without 

multiple 

prisms 

� High accuracy 

� Compact, portable, rugged 

� Relatively inexpensive 

� Useable for other surveying 

projects 

� Introduces error and 

limitations due to reflector 

movement and directionality 

as well as ground wave 

reflection 

� Requires good line-of-sight 

visibility unless microwave 

unit is available 

� Requires two shore sites 

Total stations 5 to 7 cm < 5 km � Not logistically complex, 

requiring single onshore site 

� Compatible with other uses 

� Introduces limitations due to 

reflector movement and 

directionality, prism costs, 

and line- of- sight, optical or 

infrared range limitations 

Sextant ± 10 s 

± 3 to 5 m but 

variable 

200 m to 

5 km 

� High accuracy when used 

nearshore by experienced 

operator 

� Portable, involving handheld 

device 

� Rapid, easy to implement 

� Easily obtainable 

� No shore party necessary 

� Inexpensive 

� Requires simultaneous 

measurement of two angles 

� Requires good target 

visibility 

� Requires location and 

maintenance of targets for 

relocation of site 

� Requires calm conditions for 

best results 

� Orientation of target affects 

accuracy 

� Has limitations on 

acceptable angles 

D-4 US Environmental Protection Agency 
Technical Manual 

Table D-1 (continued). Positioning methods appropriate for small water bodies (small embayment, 

small lakes, rivers) (modified from PSEP 1997a). 

Method Accuracy Range Advantages Disadvantages 

Pelorus variable < 5 km � High accuracy when used 

nearshore 

� Rapid, easy to implement 

� Easily obtainable 

� No shore party necessary 

� Inexpensive 

� Requires simultaneous 

measurement of two angles 

� Requires good target 

visibility 

� Requires location and 

maintenance of targets for 

relocation of site 

� Requires calm conditions for 

best results 

� Has limitations on 

acceptable angles 

RADAR variable 30 to 

50 km 

� Standard equipment on ships 

� Easily operated 

� Yields range and relative bearing 

to targets 

� Restricts applications by not 

being portable 

� Requires a target that 

reflects microwave signals 

Autotape ± 0.5 m limited � High accuracy and precision 

� Portable 

� High cost 

Appendix D: Advantages and Disadvantages of Different Station Positioning Techniques D-5

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table D-2.	 Positioning methods appropriate for large water bodies (ocean, estuaries, large lakes) 

(modified from PSEP 1997a). 

Category Accuracy Range Advantages Disadvantages 

GPS or Navstar ± 100 m 

(0.1 to 

1 m for 

differential 

GPS) 

no limit on 

the range 

� Continuous position reports 

available worldwide 

� System s available comprising 

a range of accuracy and cost 

� Site-specific problems due to 

military scrambling 

Microwave 

navigation 

systems (e.g., 

Miniranger, 

Trisponder, 

Racal Microfi, 

Del Norte) 

± 1 to 3 m 25 to 80 km 

(depends on 

height of 

transceiver 

units) 

� No visibility restrictions 

� Multiple users 

� High accuracy 

� Radio line of sight 

� Portable, easy system to 

operate 

� Moderately expensive system 

� Requires multiple onshore sites 

� Cost impacts due to logistics 

and security of the necessary 

shore units 

� Potential source of error due to 

signal reflective nulls 

� Limited range due to lowpowered shore units 

Shoran ± 10 m � 80 km 

(short range) 

� High accuracy � Limited range 

� Requires two shore transmitters 

LORAN-C �± 15m up to 300 km 

(medium 

range) 

� No visibility or range 

restrictions 

� Requires no additional 

personnel 

� Existing equipment 

� Relatively inexpensive 

� Incurs interference in some 

areas 

� Universal coverage not 

available 

� Used only for repositioning 

after employing a more 

geodetically precise system to 

identify location 

Decca HIFIX/6 ± 1 m up to 300 km 

(medium 

range) 

� High accuracy and precision � Requires multiple shore sites 

� Expensive system 

Variable range ± 0.5 ° 16 to 72 km � No visibility restrictions 

� Requires no additional 

personnel 

� Existing equipment 

� Inexpensive 

� Uses line-of-sight method 

� Relies on map accuracies of 

targets 

� Decreased accuracy with range 

scale 

Decca Minifix ± 2 m � 70 km � High accuracy and precision 

� Light weight equipment 

� Expensive system 

Range-azimuth 0.02 ° and 

0.5 m 

< 5 km 

(optical) 

30 km 

(elect) 

� High accuracy 

� Single station 

� Circular coverage 

� User-specific 

� Uses line-of-sight method 

� Potential source of error due to 

signal reflective nulls 

� Expensive system 

Satellite 

navigation 

(SATNAV) 

1 - 10 m no limit on 

the range 

� High accuracy 

� Single site with minimal 

logistics 

� Use possible in restricted and 

congested areas 

� No requirement for shore sites 

� Capability for integrating 

satellite fixes with other data 

sources to improve precision 

� Continuous coverage 

unavailable 

� Introduction of error due to 

local and atmospheric effects 

� Distorted when signal path 

crosses polar ice caps 

� Requires high initial 

development expenditures 

D-6 US Environmental Protection Agency 
APPENDIX E


ADVANTAGES, DISADVANTAGES AND 

ILLUSTRATIONS OF GRAB AND CORE 

SAMPLING DEVICES USED IN SEDIMENT 

MONITORING STUDIES 
Technical Manual 

Table E-1. Advantages and Disadvantages of Commonly Used Grab Samplers 

(modified from Klemm et al., 1990; Environment Canada, 1994; PSEP, 1997a; WDE, 1995). 

Device Use 

Sample 

Depth 

(cm) 

Sample 

Volume 

(L3

 ) 

Advantages Disadvantages 

Orange Peel Marine 

waters, deep 

lakes 

0 to 18 10 to 20 • Comes in a range of 

sizes 

• Need large boat, powered 

winch and calbe line 

• Blocking of jaws may cause 

sample losss 

Smith-McIntyre Deep lakes, 

rivers and 

estuaries 

0 to 4 (in 

deep 

sand) 

10 to 20 • Reasonable quantitative 

samples 

• The trigger plates 

provide added leverage 

essential to its 

penetration of substrate 

• Heavy, need boat and power 

winch 

• Spring loaded jaws, 

hazardous 

• Inadequate for deep 

burrowing organisms 

Birge-Ekman, 

small 

Lakes and 

marine areas; 

soft 

sediments, 

silt and sand 

0 to 10 < 3.4 • Handles easily without 

winch or crane 

• Can be adapted for 

shallow water use 

• Good for soft sediments, 

sand and silt 

• Allows subsampling 

• Restricted to low current due 

to light weight and messenger 

activation 

• May exceed target 

penetration depth 

• Subsampling may be 

restricted by size of top flaps 

Birge-Ekman, 

large 

Lakes and 

marine areas; 

soft 

sediments, 

silt and sand 

0 to 30 < 13.3 • Can be adapted for 

shallow water use 

• Good for soft sediments, 

sand and silt 

• Allows subsampling 

• Restricted to low current 

conditions 

• Penetration depth can exceed 

desired level due to weight of 

sampler 

• Heavy; requires winch 

PONAR, 

standard 

Deep lakes, 

rivers and 

estuaries; 

useful on 

sand, silt or 

clay 

0 to 10 7.25 • Most universal grab 

sampler 

• Adequate on most 

substrates 

• Large sample obtained 

intact, permitting 

subsampling 

• Good for coarse and firm 

bottom sediments 

• May not close completely, 

resulting in sample loss 

• Metal frame may contaminate 

sample 

• Heavy; requires winch 

PONAR, petite Deep lakes, 

rivers and 

estuaries; 

useful on 

sand, silt or 

clay 

0 to 10 1.0 • Adequate for most 

substrates that are not 

compacted 

• May not penetrate sediment 

to desired depth, especially in 

consolidated sediments. 

• Susceptible to incomplete 

closure and loss of sample. 

• Requires more casts to obtain 

sufficient sample if many 

analyses needed. 

Van Veen Deep lakes, 

rivers and 

estuaries; 

useful on 

sand, silt or 

clay; effective 

in marine 

environments 

in deep water 

and strong 

currents 

0 to 30 18 to 75 • Adequate on most 

substrates that are not 

compacted 

• Large sample obtained 

intact, permitting 

subsampling 

• Available in stainless 

steel 

• May not close completely, 

resulting in sample loss 

• May close prematurely in 

rough waters 

• Metal frame may contaminate 

sample 

• Heavy; requires winch 

Modified Van 

Veen (e.g., 

“Ted-Young 

grab”) 

Lakes and 

marine areas 

0 to 15 <18.0 • Fluorocarbon plastic 

liner can help avoid 

metal contamination 

• Screened bucket cover 

helps reduce bow wave 

effects 

• Requires winch 

• Relatively expensive 

Appendix E: Illustrations of Grab and Core Sampling Devices E-3

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table E-1. Advantages and Disadvantages of Commonly Used Grab Samplers 

(modified from Klemm et al., 1990; Environment Canada, 1994; PSEP, 1997a; WDE, 1995). 

Device Use 

Sample 

Depth 

(cm) 

Sample 

Volume 

(L3

 ) 

Advantages Disadvantages 

Petersen Deep lakes, 

rivers and 

estuaries; 

useful on 

most 

substrates 

0 to 30 9.45 • Provides large sample 

• Penetrates most 

substrates 

• Shock wave from descent 

may disturb fine-grained 

sediment 

• Lacks lid cover to permit 

subsampling 

• May not close completely, 

resulting in sample loss 

• Metal frame may contaminate 

sample 

• Restricted to low current 

conditions 

• May exceed target 

penetration depth 

Shipek, 

standard 

Used 

primarily in 

marine 

waters and 

large inland 

lakes and 

reservoirs; 

not useful for 

compacted 

sandy clay or 

till substrates 

0 to 10 3.0 • Sample bucket opens to 

permit subsampling 

• Retains fine-grained 

sediments effectively 

• Metal frame may contaminate 

sample 

• Heavy; requires winch 

• Can result in the loss of the 

topmost 2-3 cm of very fine, 

unconsolidated sediment 

Mini Shipek Lakes, useful 

for most 

substrates 

that are soft 

0 to 3 0.5 • Handles easily without 

winch or crane from 

most platforms 

• Requires vertical penetration 

• Samples small volume 

• May lose fine-grained 

sediment 

• May close prematurely 

E-4 US Environmental Protection Agency 
Technical Manual 

Table E-2. Advantages and Disadvantages of Commonly Used Core Samplers


(modified from Klemm et al., 1990; Environment Canada, 1994; PSEP, 1997a; WDE, 1995; USEPA/ACOE, 1998)


Device/ 

Dimensions Use 

Depth 

Sample 

(cm) 

Volume 

Sample 

(L3

 ) 

Advantages Disadvantages 

Fluorocarbon 

plastic or glass 

tube (3.5 to 7.5 

cm inner 

diameter (I.D.); 

� 120 cm long) 

Shallow 

wadeable 

waters or deep 

waters if 

SCUBA 

available; soft 

or semiconsolidated 

deposits 

0 to 10 0.096-

0.44 

• Preserves layering and 

permits historical study of 

sediment deposition 

• Minimal risk of 

contamination 

• Rapid; samples 

immediately ready for 

laboratory shipment 

• Small sample size 

necessitates repetitive 

sampling 

Hand corer 

with removable 

fluorocarbon 

plastic or glass 

liners (3.5 to 

7.5 cm I.D.; � 120 cm long 

Same as 

above except 

more 

consolidated 

sediments can 

be obtained 

0 to 10 0.96-0.44 • Same advantages as 

fluorocarbon plastic or 

glass tube 

• Penetrates substrate with 

greater ease through use 

of handles 

• Small sample size 

necessitates repetitive 

sampling 

• Requires careful handling 

to prevent spillage 

• Requires removal of liners 

before repetitive sampling 

• Barrel and core cutter 

metal may contaminate 

sample 

Box corer Same as 

above but the 

depth of the 

unconsolidated 

sediment must 

be at least 1 m 

0 to 70 < 30.0 • Collects large, undisturbed 

sample; optimal for 

obtaining intact 

subsamples 

• Difficult to handle 

• Relatively heavy; requiring 

larger vessel and power 

winch to deploy. 

Gravity Corer, 

Phleger Corer 

(3.5 cm I.D., � 50 cm long) 

Deep lakes 

and rivers; 

semiconsolidated 

sediments 

0 to 50 < 0.48 • Reduces risk of sample 

contamination 

• Maintains sediment 

integrity relatively well 

• Penetrates with sharp 

cutting edge 

• Requires careful handling 

to avoid sediment spillage 

• Requires repetitive and 

time-consuming operation 

and removal of liners due 

to small sample size 

Gravity Corer, 

KajakBrinkhurst 

Corer (5 cm 

I.D., � 70 cm 

long) 

Deep lakes 

and rivers; 

Soft finegrained 

sediments 

0 to 70 < 1.37 • Collects greater volume 

than the Phleger Corer. 

• Same as Phleger Corer 

Benthos 

Gravity Corer 

(6.6, 7.1 cm 

I.D. � 3 m 

long) 

Soft, finegrained 

sediments 

0 to 3 m < 10.26 • Retains complete sample 

from tube because the 

core valve is fitted to the 

core liner 

• Fins promote vertical 

penetration 

• Requires weights for deep 

penetration so the required 

lifting capacity is 750 to 

1,000 kg 

• Requires vertical 

penetration 

• Compacts sediment 

sample 

Alpine Gravity 

Corer (3.5 cm 

I.D.) 

Soft, finegrained, semiconsolidated 

substrates 

< 2 m < 1.92 • Allows different 

penetration depths due to 

interchangeable steel 

barrel 

• Lacks stabilizing fins for 

vertical penetration 

• May penetrate nonvertically and incompletely 

• Requires a lifting capacity 

of 2,000 kg 

• Disturbs sediment stratas 

and integrity 

• Compacts sediment 

sample 

Piston Corers Ocean floor 

and large 

deep lakes; 

Most 

substrates 

3 to 20 m 5 - 40 • Typically recovers a 

relatively undisturbed 

sediment core in deep 

waters 

• Requires lifting capacity of 

>2,000 kg 

• Piston and piston 

positioning at penetration 

may fail 

• Disturbs surface (0 to 

0.5m) layer 

Appendix E: Illustrations of Grab and Core Sampling Devices E-5

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Table E-2. Advantages and Disadvantages of Commonly Used Core Samplers


(modified from Klemm et al., 1990; Environment Canada, 1994; PSEP, 1997a; WDE, 1995; USEPA/ACOE, 1998)


Device/ 

Dimensions Use 

Depth 

Sample 

(cm) 

Volume 

Sample 

(L3

 ) 

Advantages Disadvantages 

BMH-53 Piston 

Corer 

Waters < 2 m 

deep with 

extension rod; 

soft deposits 

� 2 m � 2 • Piston provides for greater 

sample retention 

• Cores must be extruded 

onsite to other containers 

• Metal barrels introduce 

risk of metal contamination 

Boomerang 

Corer (6.7 cm 

I.D.) 

Ocean floor 

(up to 9,000 m 

deep) 

1 m 3.52 • Requries minimal 

shipboard equipment so 

small vessels can be used 

• Only penetrates 1.2 m 

• Requires calm water for 

recovery 

• Loses 10 to 20% of 

sample 

Vibracorer (5.0 

to 7.5 cm I.D.) 

Continental 

shelf of 

oceans, large 

lakes; sand, 

silty sand, 

gravelly sand 

substrates 

3 to 6 m 5.89 to 

13.25 

• For deep profiles it 

effectively samples most 

substrates with minimum 

disturbance 

• Can be used in over 20 m 

of water depth 

• Portable models can be 

operated from small 

vessels (e.g. 10 m long) 

• Labor intensive 

• Assembly and 

disassembly might require 

divers 

• Disturbs surface (0 to 

0.5 m) layer 

• Special generator may be 

needed 

• Heavier models require 

larger boat and power 

winch to deploy 

E-6 US Environmental Protection Agency 
Technical Manual 

Figure E-1.	 Some recommended devices for collecting surficial sediments (drawings from 

Murdoch and Azcue 1995 and Fredette et al. 1990). 

Appendix E: Illustrations of Grab and Core Sampling Devices E-7

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Figure E-2.	 Some recommended devices for obtaining sediment profiles (drawings from Murdoch 

and Azcue 1995 and Fredette et al. 1990). 

E-8 US Environmental Protection Agency 
APPENDIX F


EXAMPLES OF FIELD FORMS USED TO 

DOCUMENT STATION AND SAMPLE 

CHARACTERISTICS AND SAMPLE 

TRACKING 
Technical Manual 

Appendix F: Examples of Field Forms F-3

Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Example of field form used by the Great Lakes National Program Office: 

Field Sampling Log Sheet


Location and Core Information 

Station Number: Water Surface Elevation 

Date Water Depth 

Time Core tube Length 

Primary GPS Latitude Depth of Penetration 

Longitude Length of Retrieved Core 

Secondary GPS Latitude Loggers Initials 

Longitude Samplers Initials 

Sample Intervals 

Sample Number Sample Interval Physical Descritpion of Sample 

F-4 US Environmental Protection Agency 
Technical Manual 

Example of field form used for site remediation sampling at Naval bases: 

Appendix F: Examples of Field Forms F-5

APPENDIX G


PHYSICO-CHEMICAL SEDIMENT


CHARACTERIZATION

Technical Manual 

1. General Information 

It is often necessary or desirable to determine certain physico-chemical characteristics of sediments 

in the laboratory, in conjunction with toxicity testing or chemical analysis for inorganic or organic 

contaminants. This characterization should include measurement of certain parameters known to 

mediate the availability of contaminants in sediment (ASTM, 2000f). Bulk chemical concentrations 

alone should not be used to evaluate bioavailability (USEPA, 1998). The following parameters are 

generally measured: 

• pH (pore water) 

• ammonia (pore water) 

• total organic carbon 

• particle size distribution (e.g., percent sand, silt and clay) 

• percent water content 

• salinity and hardness of pore water 

• conductivity of pore water 

Depending on the experimental design and/or study objectives, more extensive characterization may 

be necessary. Several additional characteristics which may assist in study implementation, data 

interpretation or QA/QC (i.e., assessing sediment integrity, artifact production, optimal extraction 

and test procedures) include: sediment biochemical oxygen demand (BOD), sediment chemical 

oxygen demand (COD), sediment oxygen demand (SOD), cation exchange capacity (CEC), Redox 

(Eh) or oxidation-reduction potential (ORP), total inorganic carbon, total volatile solids, acid volatile 

sulfides (AVS), simultaneously extracted metals (SEM), metals, synthetic organic compounds 

(pesticides, PCBs, PAHs, and TCDD-dioxin), oil and grease, petroleum hydrocarbons, dissolved 

organic carbon (DOC) in the pore water. Measurements of many sediment physicochemical 

characteristics use analytical techniques originally developed for soils and waters, and the literature 

should be consulted for details regarding recommended methodology (Black, 1965; USGS, 1969; 

Plumb, 1981; Page et al., 1982). The following sections provide rationale for making each type of 

sediment physicochemical measurement, along with brief descriptions of measurement techniques, 

and references for further information and specific procedures. 

2. pH 

Sediment pH is often one of the single most important factors controlling speciation and equilibria 

for many chemicals including sulfides, ammonia, cyanide, and metals, all of which ionize under the 

influence of pH. The USEPA ammonia water-quality criterion, for example, is dependent in part on 

pH because ammonia toxicity is largely governed by the unionized ammonia fraction which is pHdependent (USEPA, 1999). Metal (Cd, Cu, Ni, Pb, and Zn) speciation and bioavailability are also 

known to be affected by pH (Schubauer-Berigan and Ankley, et al., 1991; Ho et al. 1999). 

Generally, pH is measured using a pH meter consisting of a potentiometer, a glass electrode, a 

reference electrode, and a temperature compensating device. A circuit is completed through the 

potentiometer when the electrodes are submersed. General purpose process pH electrodes are 

available in a wide variety of configurations for in-line and submersion applications. Generally, 

electrodes with gel-filled references require less maintenance than electrodes with liquid-filled 

references. The latest instruments have microprocessors that automatically calculate and display the 

slope. Some older instruments have a percent-slope readout or (and) millivolt readout. For 

instruments with a millivolt readout, the measured electrode potential is calculated as the difference 

between millivolts measured at the known pH of two buffers. 

Appendix G: Physico-Chemical Sediment Characterization G-3 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

Plumb (1981) and Gonzalez (1995) described a method for measuring pH in sediment using a pH 

probe and meter. The probe was inserted into the sediment and pH directly measured after at least a 

5 minute equibration time. Electrodes have also been used for direct measurements of pH in 

sediment pore water, or in a 1 to 1 mixture of sediment to water (Jackson, 1958). Direct 

measurement of sediment pH is also possible using electrodes with “spear tip” designs allowing for 

greater penetration into the sample (Burgess, personal communication). Detailed methods for 

measuring pH in water and sediment are also described by USEPA (1983;1986b;1987), in USEPA 

(1979), and in USEPA (1987), respectively. 

3. Ammonia in Pore Water 

Nitrogen, a nutrient associated with over-enrichment of aquatic environments, exists in several 

forms, including ammonia. Ammonia is highly soluble in water where it is found in an un-ionized 

form (NH3) and in an ionized form as NH4

+

. The extent of ionization is dependent on pH 

temperature, and salinity (in seawater). Ammonia in sediments and pore water is generally the result 

of microbial degradation of nitrogenous organic material such as amino acids (Ankely et al., 1990). 

Pore water concentrations of ammonia as high as 50 mg/L have been measured in otherwise 

uncontaminated sediments (Murray et al., 1978; Kristensen and Blackburn, 1987), while ammonia in 

pore waters from contaminated sediments can range from 50 to more than 200 mg/L (Ankley et al., 

1990; Schubauer-Berigan and Ankley, 1991). 

The toxic effects of ammonia are generally considered to be associated with the un-ionized fraction 

(NH3) rather than the ionic components (NH4

+

 and NH4SO4

-

), which co-exist in equilibria. This 

equilibrium is highly dependent on pH, temperature, pressure, salinity, and ionic concentrations of 

ammonia. The toxic un-ionized ammonia fraction can be calculated using known total ammonia 

values and measurements of pH, pressure, salinity, and temperature as described by Whitfield (1978) 

and Thurston et al (1981). 

USEPA (1983), and APHA (1995) describe five methods available to measure ammonia in the pore 

water: 

• the titrimetric method 

• the ammonia-selective electrode method 

• the ammonia-selective electrode method using known addition 

• the phenate method 

• the automated phenate method. 

A preliminary distillation step may be required if interferences are present (APHA, 1995). 

Interferences, e.g., sample constituents that interact with procedural reagents, are described in detail 

in the APHA (1995) and ASTM (2000g) methods. Once distilled, the sample can be analyzed using 

any of the methods listed above. 

The distillation and titration methods are frequently used when ammonia concentrations are greater 

than 5.0 mg/L. The ammonia-selective electrode method is appropriate when concentrations range 

between 0.03 and 1400 mg NH3-N/L. Ammonia readings are calibrated against ammonia standards. 

To verify meter readings, confirmatory subsamples can be preserved and analyzed for ammonia using 

the standard Nessler technique described in APHA (1995). For the phenate method, APHA (1995) 

recommends distillation with sulfuric acid when interferences are present (Bower and Holm-Hansen, 

1980). The automated phenate method is suitable for pore waters with ammonia concentrations in 

the range of 0.02 and 2.0 mg NH3-N/L. 

G-4 US Environmental Protection Agency 
Technical Manual 

Hach Company, Inc. (Loveland, CO) describes the USEPA approved Nessler/distillation method 

adapted from APHA (1995). This is a photometric procedure and has been modified for use with 

Hach photometers. 

4. Total Organic Carbon Content (TOC) 

The total organic carbon (TOC) content of sediment is a measure of the total amount of oxidizable 

organic material. TOC is the sum of dissolved organic carbon (DOC), particulate organic carbon 

(POC) or suspended organic carbon (SOC), and colloids. TOC is an important parameter to measure 

in sediments because it is a major determinant of nonionic organic chemical bioavailability (DiToro 

et al., 1991). Metal bioavailability is also affected by the amount of TOC present in sediments. TOC 

is usually expressed as a percentage of the bulk sediment and is used to normalize the dry-weight 

sediment concentration of a chemical to the organic carbon content of the sediment. USEPA 

Equilibrium Partitioning Guidelines estimate bioavailability as a function of contaminant 

concentration sorbed to sediment organic carbon and contaminant concentration in the pore water 

under equilibrium conditions (USEPA, 1998). Recently, the presence of soot carbon from the 

combustion of organic carbon (e.g., fossil fuels) has been recognized as a fraction of the TOC in 

sediment. Soot carbon may alter the geochemistry and bioavailability of some organic contaminants 

(Gustuffson et al., 1997). 

The organic carbon content of sediments has been measured using several methods including: wet 

oxidation titration, modified titration, and combustion after removal of carbonate by the addition of 

HCl and subsequent drying. USEPA methods(1986b; 1987), including SW-846 and 430/9-86-004, 

are often used to measure TOC. Plumb (1981) recommends one of two methods to separate organic 

from inorganic carbon before analyzing for TOC: (a) ignition and using HCl as the acid for pretreating sediment, or (b) differential combustion, which uses thermal combustion to separate the two 

forms of carbon. 

EPA/ACOE guidance (1998) recommends that TOC analyses be based on high-temperature 

combustion rather than on chemical oxidation, because some classes of organic compounds are not 

fully degraded by combined chemical and ultraviolet oxidation techniques. Inorganic carbon (e.g., 

carbonates and bicarbonates) can be a significant proportion of the total carbon in some sediments. 

Therefore, samples should be treated with acid to remove the inorganic carbon prior to TOC analysis. 

The procedure described by the Puget Sound Estuary Program (PSEP, 1997a) is recommended for 

TOC analysis because this method uses high-temperature combustion using an induction furnace. 

USEPA recommends a similar method using catalytic combustion and non-dispersive infrared 

detection (Leonard, 1991) for quantifying TOC. 

U.S. EPA acknowledges that several methods for measuring the total organic carbon (TOC) content 

of sediments exist (See Nelson and Sommers 1996 for a review). However, acceptable methods must 

at a minimum include the following steps: 

Sample Collection 

• Sediment samples are collected and stored in non-organic containers 

Sample Preparation 

•	 Each sediment sample must have macroscopic pieces of shells (e.g., > 1 mm) 

removed and then be pulverized and homogenized 

Appendix G: Physico-Chemical Sediment Characterization G-5 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

•	 Each sediment sample must be treated by direct addition with a strong non-oxidizing 

acid (e.g., HCL) for �18 hours to remove inorganic carbon; sample pH should be �2 

after acidification (Yamamuro and Kayanne, 1995) 

•	 Each sediment sample must be oven dried following acid treatment (60 - 70° C) 

(Weliky et al., 1983; Yamamuro and Kayanne, 1995) 

• Each sediment sample must be stored in a desiccator until analysis 

•	 As noted, desiccation is highly recommended, however if not possible a pre- and 

post-acidification sample weight should be performed to correct for water uptake 

(Hedges and Stern, 1984). 

Sample Analysis 

•	 Each post-acidification sediment sample must be analyzed using acceptable 

instrumentation 

• Instrumentation should have a detection limit of approximately 100 mg/Kg 

•	 Quantification of organic carbon should be based on a sample’s weight, measured 

before acidification. 

Sample QA 

A rigorous QA program should be in place to insure acceptable data quality, this may include: 

•	 Performance of duplicate analysis on a subset of samples with the relative percent 

difference (RPD) between replicates below 30% 

•	 Performance of analyses on certified standard reference materials (SRM) (e.g., 

NIST) 

5. Particle Size Distribution (Percent Sand, Silt, and Clay) 

Particle size is used to characterize the physical characteristics of sediments. Because particle size 

influences both chemical and biological characteristics, it can be used to normalize chemical 

concentrations and account for some of the variability found in biological assemblages (USEPA 

1998) or in laboratory toxicity testing (USEPA, 2000d; Hoss et al., 1999). Particle size can be 

characterized in varying detail. The broadest divisions that generally are considered useful for 

characterizing particle size distributions are percentages of gravel, sand, silt, and clay. However, 

each of these size fractions can be subdivided further so that additional characteristics of the size 

distribution are determined (PSEP, 1996). 

Particle size determinations can either include or exclude organic material. If organic material is 

removed prior to analysis, the “true” (i.e., primarily inorganic) particle size distribution is 

determined. If organic material is included in the analysis, the “apparent” (i.e., organic plus 

inorganic) particle size distribution is determined. Because true and apparent distributions may 

differ, detailed comparisons between samples analyzed by these different methods are questionable. 

Therefore, if comparisons among samples between studies is desired, sediment particle size should 

be measured using consistent methods (PSEP, 1996). 

G-6 US Environmental Protection Agency 
Technical Manual 

Sediment particle size can be measured by a number of different methods (Allen, 1975; Plumb,1981; 

PSEP, 1996; ASTM, 2000a). The best method will depend on the particle properties of the sample 

(Singer et al., 1988). Particle size distribution is often determined by either wet sieving the sample 

(USEPA, 1979; Plumb, 1981; PSEP, 1996; Singer et al., 1988), the hydrometer method (Day, 1965; 

Patrick, 1958), the pipet method (USGS, 1969; Rukavina and Duncan, 1970), settling techniques 

(Sandford and Swift, 1971), and X-ray absorption (Duncan and Lattaie, 1979; Rukavina and Duncan, 

1970). The pipet method may be superior to the hydrometer method (Sternberg and Creager, 1961). 

Combinations of multiple methods may provide refined measurements of particle size distribution. 

Gee and Bauder (1986) used sieving and pipetting after soluble salts were removed. Gonzalez (1995) 

used a combination of sieve and hydrometer methods. Folk (1968) and Buchanan (1984) discuss 

additional methods to measure particle size. 

Recommended methods for measuring sediment particle size distribution are those of PSEP (1996) 

and USEPA (1995). Percent gravel, sand, silt, and clay are determined as apparent distribution using 

a minimum sediment sample size of 100 g taken from a homogenized sediment sample (see Section 

4.4). Organic matter should be removed prior to analysis by oxidation using hydrogen peroxide. 

Wet-sieving followed by dry sieving (mechanical shaking) separates the two coarse particle size 

groups. The silt-clay fraction is subdivided using a pipet technique that depends upon the differential 

settling rates of the two different particle size fractions. All fractions are dried to a constant weight. 

Cooled samples are stored in a desiccator and weighed. 

To obtain an accurate determination of particle sizes for the fine fraction, the Coulter (particle size) 

counter method may be employed (McCave and Jarvis, 1973; Vanderpleog, 1981). This method 

gives the fraction of particles with an apparent spherical diameter. In a review of the available 

methods, Swift et al. (1972) found the Coulter counter method to be the most versatile method 

overall; however, it does not provide settling information. Another potential method for determining 

the particle size distribution of a very fine fraction is through the use of electron microscopy 

(Leppard et al., 1988). Collection techniques for very fine material can result in aggregation of 

larger colloidal structures (Leppard, 1986; Leppard et al., 1988). In general, particle settling methods 

are preferred to sediment sizing methods. 

6. Percent Water or Moisture Content 

Water content is a measurement of sediment moisture usually expressed as a percentage of the whole 

sediment weight. It is known to influence toxicity and is used to aid in the interpretation of sediment 

quality investigations. Sediment moisture content is measured as the difference between wet weight 

of the sediment and dry weight following oven drying at 50 to 105°C to a constant weight. Percent 

water is used to convert sediment concentrations of substances from wet-weight to a dry-weight. 

Methods for determining moisture content are described by Plumb (1981) and Vecchi (1999). 

Additional methods are provided in USEPA (1987). 

7. Salinity of the Pore Water (Marine Sediments) 

Salinity is a measure of the mass of dissolved salt in a given mass of solution. The most reliable 

method to determine the true or absolute salinity is by complete chemical analysis. However, this is 

time consuming and costly. Therefore, indirect methods are more suitable. Indirect methods include 

conductivity, density, sound speed, or refractive index (APHA, 1995). Salinity is then calculated 

from the empirical relationship between salinity and the indirect measurement. Conductivity 

measurements have the greatest precision, but respond only to ionic solutes (APHA, 1995). Density 

measurements respond to all solutes. APHA (1995) recommends the electrical conductivity method, 

Appendix G: Physico-Chemical Sediment Characterization G-7 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

because it is sensitive and easily performed. APHA (1995) also recommends the density method, 

using a vibrating flow densitometer. USEPA (1986) methods should also be consulted. 

A salinity refractometer can be used for quick readings of salt density in solutions such as sea water. 

These refractometers are easy to read, non-corrosive and lightweight. They have dual scales and an 

adjustable focus. Temperature and non-temperature compensating refractometers are available. Most 

refractometers are accurate to 1 ppt and read specific gravity (1.000 to 1.070 in .001 divisions) and 

parts per thousand (0-100 in 1 ppt divisions). 

8. Conductivity of the Pore Water (Fresh Water Sediments) 

Conductivity is a measure of the ability of an aqueous solution to carry an electric current. This 

ability is dependent on the presence of ions in the solution, the concentration of the ions, their 

mobility and valence, and temperature. Solutions of inorganic compounds are usually good 

conductors while those of organic compounds are usually poor conductors. Conductivity is enhanced 

by calcium, potassium, sodium, and magnesium chlorides and sulfides. 

Meters can be used to measure the degree to which electrical current can travel through water. The 

unit of measure is 1 mS/m = 1 millisiemens/meter or 1 �S/cm = 1 microsiemens/cm. The reading 

indicates the amount of ions in the water. While traditional chemical tests for hardness measure 

calcium and magnesium, they fail to provide an indication of other ions (e.g., sodium). The 

conductivity meter provides a much better measure of ionic strength. 

9. Acid Volatile Sulfide (AVS) 

Measurement of acid volatile sulfides (AVS) and simultaneously extracted divalent metal (SEM) 

concentrations associated with AVS extraction can provide insight into the bioavailability of metals 

in anaerobic (anoxic) sediments (DiToro et al., 1990; Ankley et al., 1996). AVS is the reactive solidphase sulfide fraction that is extracted by cold hydrochloric acid. AVS appears to affect the 

bioavailability of most divalent metal ions as the sulfide ions have a high affinity for divalent metals. 

This affinity results in the formation of insoluble metal sulfides with greatly reduced bioavailability. 

AVS concentrations in freshwater and marine sediments can range between < 0.1 and > 50 μmol 

AVS/g of sediment (DiToro et al., 1990). 

The bioavailability of metals in sediments has been predicted by comparing the molar concentration 

of AVS to the molar concentration of SEM (methods described below). If AVS is greater than SEM, 

the metals are bound in sulfide complexes with greatly limited bioavailability. However, if AVS < 

SEM, metals may or may not be toxic due to other controlling factors (e.g., TOC). 

The easily extractable sulfide fraction can be measured using the acid purge and trap technique. The 

sample sulfide is solubilized in cold hydrochloric acid. The analytical method involves conversion of 

sulfides to aqueous H2S. This may be measured with a sulfide probe or by following a wet chemistry 

method. In the latter method, silver sulfide is precipitated in a gas-tight assembly and flushed with 

nitrogen to eliminate oxidation. The precipitate is filtered, dried, and weighed. The weight is 

compared with the weight obtained from a non-acidified sample, and the difference is attributed to 

the AVS fraction (DiToro et al., 1990). 

10. Simultaneously Extracted Metals 

A model for predicting toxicity from divalent trace metals (DiToro et al., 1990) is based on the 

binding of these metals to AVS. Where the sum of the moles of the SEM, including Ag, Cd, Cu, Ni, 

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Technical Manual 

Pb, and Zn is exceeded by the molar concentration of AVS, the metals are insoluble and largely 

unavailable to biota. The extraction of AVS and metals should be achieved using a single 

methodology to ensure that recoveries associated with each measure are consistent. Simultaneous 

extraction improves the efficiency of the methodology. 

SEM can be measured in filtered aliquots by atomic absorption methods (DiToro et al., 1990). 

Recent SEM analysis methods use inductively coupled plasma atomic emission spectrometry (ICPAES; Berry et al., 1999). Other methods for analysis of metals are described in Section 11 below. 

11. Metals 

Low levels of trace metals occur naturally in the environment but highly elevated levels in sediment 

are generally associated with anthropogenic contaminant loads. Metals are partitioned in sediments 

as soluble free ions, soluble organic and inorganic complexes, easily exchangeable ions, precipitates 

of metal hydroxides, precipitates with colloidal ferric and manganic oxyhydroxides, insoluble 

organic complexes, insoluble sulfides, and residual forms (Gambrell et al., 1976). 

Current instrument methods available for the analysis of trace metals include electrochemistry (e.g., 

differential pulse polarography), spectrophotometry (e.g., silver diethyldithiocarbamate), atomic 

absorption spectrophotometry, atomic emission spectrophotometry, x-ray fluorescence (XRF), and 

neutron activation (PSEP 1997c). The most commonly used instrumental method to analyze 

sediments for metals is atomic absorption spectrophotometry (PSEP, 1997c). Inductively coupled 

plasma mass spectrometry (ICP-MS) or ICP-AES allow for simultaneous determination of many 

metals at sub-ppb levels with little pretreatment (Crecelius et al., 1987; Berry et al., 1999). 

The concentration of salt in marine or estuarine samples may interfere with metals analyses 

(USEPA/ACOE, 1998). Therefore, acid digestion and atomic absorption spectroscopy should be 

coupled with an appropriate technique to control for this interference. Methods in USEPA (1986b) 

are recommended for the analysis of mercury in sediments and EPRI (1986) methods are 

recommended for the analysis of selenium and arsenic. EPA methods for cadmium, hexavalent 

chromium, copper, lead, mercury, nickel, selenium, silver, and zinc are described by USEPA 

(1986b). PSEP (1997c) suggests that mercury can be extracted using vacuum distillation and 

analyzed by gas chromatography/mass spectrophotometry. 

12. Synthetic Organic Compounds (Pesticides, PCBs, TCDD-Dioxin) 

Analytical techniques for measuring organic compounds require five general steps: drying the 

sample, extraction, drying the extract, clean up of the extract, and analysis of the extract. PSEP 

(1997b) recommends centrifugation or sodium sulfate to dry the sample and a solvent extraction, 

with application of shaker/roller, or sonication. Sample drying with sodium sulfate is recommended 

for samples weighing approximately 10 grams (after overlying water is decanted). The sediment and 

sulfate mixture is extracted and the extract is processed (MacLeod et al., 1985). 

Soxhlet® extraction (USEPA, 1986b) involves distillation with a solvent such as acetone, 

dichloromethane/methanol (2:1), dichloromethane/methanol (9:1), and benzene/methanol (3:2). 

USEPA (1983) recommends sonication with solvent mixtures and a 30-gram subsample of sediment. 

Drying the extract can be accomplished through separatory funnel partitioning as needed to remove 

water and sodium sulfate or by using a Kuderna-Danish apparatus and rotary evaporation with 

purified nitrogen gas for concentration to smaller volumes (PSEP, 1997c). Using the separatory 

funnel partitioning method, the wet sample is mixed with methanol and centrifuged. The supernatant 

Appendix G: Physico-Chemical Sediment Characterization G-9 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

is decanted and extracted later. Extraction of the sample is continued using less polar solvents and 

the water/methanol and solvent extracts are combined and dried. 

According to PSEP (1997c) elemental sulfur can be removed from the sediment sample with 

vigorous mechanical agitation using a Vortex or Genie® or using activated copper. Organic 

interferences can be removed with gel permeation chromatography (GPC) described in USEPA 

(1983), bonded octadecyl columns (PSEP, 1997c), high performance liquid chromatography (HPLC) 

described by Metro (1981), silica gel (PSEP, 1997c), or alumina (USEPA, 1983). Instrumental 

analyses for volatiles and semivolatiles and pesticides/PCBs are performed using gas 

chromatography/mass spectrophotometry (GC/MS) and gas chromatography/electron capture 

detection (GC/ECD), respectively (PSEP, 1997b; Burgess and McKinney, 1997). 

13. Oil and Grease 

Oil and grease tests for sediments measure material recovered that is soluble in a nonpolar solvent 

under acidic conditions. Oil and grease compounds are substances such as hydrocarbons, vegetable 

oils, animal fats, waxes, soaps, and greases. Many solvents can dissolve other substances (e.g. sulfur 

compounds, organic dyes, and chlorophyll). Therefore, oil and grease is operationally defined by the 

solvent used and the analytical method used to perform the analysis. There are two basic methods 

used to analyze oil and grease: the gravimetric technique and the IR (infrared spectrophotometer) 

technique. Both are described by PSEP (1996). 

14. Petroleum Hydrocarbons and Polycyclic Aromatic Hydrocarbons 

Petroleum hydrocarbons are oil and grease constituents which remain in solution after contact with 

silica gel. Petroleum distillates, also called hydrocarbons or petrochemicals, refer to a broad range of 

compounds which are extracted by distillation during the refining of crude oil. During the fractional 

distillation of petroleum, crude oil is heated to allow various compounds to turn from liquid into gas 

and then captured as they rise, cool, and condense. Lighter, more volatile compounds rise higher 

before they condense and are collected on distillation trays. Heavier, less volatile compounds such as 

diesel fuel and oil are collected on lower distillation trays. Waxes and asphalts are collected from the 

bottom after the other products have volatilized. 

Petroleum distillates contain both aromatic hydrocarbons (carbon rings) and aliphatic hydrocarbons 

(straight carbon chains). The chemical structure of the hydrocarbon largely defines the nature and 

behavior of these compounds. Aromatic hydrocarbons are the most toxic compounds found in 

petroleum products. Most aromatic hydrocarbons are chronic toxins and known carcinogens. 

Aromatic compounds are found in all crude oils and most petroleum products. Many aromatic 

hydrocarbons have a pleasant odor and include such substances as naphthalene, xylene, toluene, and 

benzene. Aliphatic hydrocarbons are flammable and may be explosively flammable. Aliphatic 

hydrocarbons include methane, propane, and kerosene. 

Aromatic and aliphatic hydrocarbons were analyzed in sediments by Page et al. (1995a, b). Sediment 

samples were spiked with the appropriate surrogates, mixed with equal amounts of sodium sulfate to 

dry the samples, and extracted with a methylene chloride acetone mixture (Method 3550, USEPA, 

1986b). The concentrated extracts were partitioned on an alumina column into saturated and 

unsaturated hydrocarbon fractions (Method 3611, USEPA, 1986b). The fractions were concentrated 

using the appropriate pre-injection volume, spiked with the appropriate internal standards, and 

analyzed by gas chromatography with flame ionization detection (GC/FID) and gas chromatography 

with mass spectrometry detection (GC/MS) operating in the selected ion monitoring (SIM) mode. 

The method of internal standards (Method 8000, USEPA, 1986b) using the average relative response 

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factors generated from the linear initial calibration was used to quantify the target compounds. All 

data were corrected for the recovery of the appropriate surrogate compound. Their relative 

abundances could then be used for identification and quantification purposes. 

TPH (total petroleum hydrocarbons) and PAH (polycyclic aromatic hydrocarbons) have also been 

analyzed by first acidifying the sample with concentrated hydrochloric acid and then extracting 

hydrocarbons with a mixture of methanol and hexane. The hexane extracts were then spiked with an 

internal standard and analyzed by GC-FID for TPH content and by GC/mass spectrometry (MS) for 

PAH analysis. 

Kaplan et al. (1996) extracted hydrocarbons using anhydrous Na2SO4 with methylene chloride and 

sonication. The total solvent extract was then concentrated with Kuderna-Danish equipment. The 

concentrate was further concentrated using a gentle stream of dry nitrogen. An aliquot was then 

injected directly into the gas chromatography. 

15. Total Sulfides 

Total sulfides represent the combined amount of acid-soluble H2S, HS-

, and S2- in a sample. Sulfides 

are often measured because they are common in some sediments, particularly those that are anoxic, 

and they can be toxic to aquatic organisms. PSEP (1996) describes a method to measure total 

sulfides in sediments. Oxygen is removed from the sample using nitrogen gas, methyl orange and 

hydrochloric acid is added, and the mixture is heated. Amine solution and iron chloride are added to 

develop a colorimetric reaction product and sample absorbance is measured spectrophotometrically. 

Methods for measuring sulfides in aqueous samples include: potentiometric methods described by 

ASTM (2000e) and APHA (Method 4500, 1995). Sulfide ions are measured using a sulfide ionselective electrode in conjunction with a double-junction, sleeve type reference electrode (Phillips et 

al., 1997). Potentials are read using a pH meter or a specific ion meter having a direct concentration 

scale for the sulfide ion. Samples are treated with sulfide anti-oxidant buffer which fixes the solution 

pH at a high alkaline level 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 HS- or H2S found at lower pH 

values (see pH, Section 2 in this Appendix). 

APHA (Method 4500, 1995) provides qualitative as well as quantitative methods to determine 

aqueous sulfide concentrations. Qualitative methods include the antimony test, the silver-silver 

sulfide electrode test, the lead acetate paper test, and the silver foil test. Quantitative methods 

include the photometric method, the automated photometric methylene blue colorimetric methods, 

and the iodometric titration method for standardizing stock solutions. 

16. Sediment Oxygen Demand (SOD) 

Sediment can exhibit significant rates of oxygen uptake attributable to either: (1) a benthic ecosystem 

supported by soluble organic substances in the water column, (2) naturally occurring sediments 

derived from aquatic plants and animals, and (3) detritus discharged into the water body by natural 

runoff. When numerical modeling is required to predict dissolved oxygen concentrations, the rate of 

dissolved oxygen consumed by the benthic ecosystem is defined as the sediment (benthic) oxygen 

demand (SOD) in g O2/m2

-day. 

Two approaches for measuring SOD were reviewed by Truax et al. (1995) including in-situ 

respirometry and laboratory respirometry methods. Numerous techniques have been developed for 

each approach. Generally, in-situ methods are considered more credible than laboratory 

Appendix G: Physico-Chemical Sediment Characterization G-11 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

measurements although both apply the same technique. A given amount of sediment is enclosed in a 

chamber with a known water volume and oxygen uptake is measured over time. The SOD rate is 

then calculated based on the area of the enclosed sediment, the volume of water in the chamber, and 

the rate of uptake. 

In situ sediment oxygen demand measurement method were described by Uchrin and Ahlert (1985). 

A cylindrical respirometer, a dissolved oxygen probe with stirring mechanism, and a dissolved 

oxygen meter were used. Ambient dissolved oxygen was measured using the probe/meter as well as 

by using the Winkler method (APHA, 1995) in the laboratory to determine the effect of respiration 

on total dissolved oxygen uptake. The respirometer was deployed in a level area at the bottom of the 

water body. Dissolved oxygen were recorded initially and at 15-minute intervals thereafter to 

determine the SOD rate. 

17. Sediment Biochemical Oxygen Demand (BOD) 

Biochemical oxygen demand (BOD) is a measure of the dissolved oxygen consumed by microbial 

organisms while assimilating and oxidizing the organic matter in a sample (PSEP, 1996). The test is 

an empirical methodology in which standardized laboratory procedures are used to determine the 

relative oxygen uptake of environmental samples. The test measures the amount of molecular 

oxygen used during a specified incubation period to biochemically degrade organic material and to 

oxidize reduced forms of nitrogen (APHA, 1995). 

Plumb (1981) described a method to analyze BOD in sediments using freshwater bacteria as a “seed” 

and buffered distilled water as dilution water. PSEP (1996) described an alternative procedure to 

analyze BOD in marine sediments using marine bacteria as the “seed” and filtered, oxygenated 

seawater as the dilution water. USEPA (1987) methods should also be consulted. 

18. Sediment Chemical Oxygen Demand (COD) 

Chemical oxygen demand (COD) is a measure of the oxygen equivalent of organic matter content in 

a sample that is susceptible to oxidation by a strong chemical oxidant at elevated temperature and 

reduced pH. The test was devised to augment the biochemical oxygen demand test. Chemical 

oxygen demand can be related empirically to biochemical oxygen demand, organic carbon, or total 

volatile solids (PSEP, 1996). 

PSEP (1996) described a method for analyzing sediment COD using a closed reflux/colorimetric 

method. DiChromate (Cr2O7) ions are used to oxidize organic matter to carbon dioxide and water 

and to provide oxygen. The dichromate ions remaining after the reaction are measured by titration 

and the amount of oxygen consumed is then calculated. 

Four standards procedures for measuring COD in water are available in APHA (1995): the open 

reflux method, the closed reflux method, the titrimetric method, and the closed reflux/colorimetric 

method. USEPA (1983) methods for the colorimetric and titrimetric method are described in USEPA 

(1979). Semi-automated methods are described in USEPA (1993). 

Hach (Loveland, CO) has modified the EPA approved dichromate reflux method and the reactor 

digestion method. The methods are photometric and are adapted for use with Hach photometers. 

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19. Cation Exchange Capacity of Sediments 

Cation exchange capacity (CEC) is a parameter that provides information relevant to metal 

bioavailability studies (Black, 1965). Cations or positively charged elements (such as calcium, 

magnesium, hydrogen, and potassium), are attracted to negatively charged surfaces of clay and 

organic matter. There is a continuous exchange of cations between sediment and water. CEC is a 

measure of the sediment’s ability to retain cationic elements. It is also a measure of clay activity and 

mineralogy, which is used to calculate mineralization rates, leaching rates, and to predict interactions 

with contaminants. The degree of CEC is dependent on the kind and amount of suitable surfaces 

such as organic matter and clay. High cation exchange capacities are associated with high clay 

contents and high organic matter and changes in CEC are typically associated with changes in 

organic carbon content and pH of the sediment. Organic matter generally supplies a greater number 

of exchange sites than clay particles. 

Various methods have been recommended to determine bioavailable fractions of metals in sediments 

(Chao and Zhou, 1983; Crecelius et al., 1987; Kersten and Forstner, 1987; DiToro et al., 1990). 

CEC can be measured by treating samples with ammonium acetate so that all exchangeable sites are 

occupied by NH4

+ ion, digesting the samples with sodium hydroxide during distillation, and titrating 

to determine the ammonium ion concentration. The amount of exchangeable cations are expressed as 

milliequivalents of ammonium ion exchanged (meq) per 100 g of dried sample. More detailed 

methods are provided in Bascomb (1964), Black (1965), Klute (1986), and USEPA (1986b). 

20. Redox Potential (Eh) of Sediments 

Redox (Eh) is a measure of the oxidation-reduction potential (ORP) of sediments. Measurements of 

Eh are particularly important for metal speciation and for determining the extent of sediment 

oxidation. Eh values below approximately -100 millivolts would indicate biologically important 

sulfide concentrations. Some trace metals form insoluble complexes with sulfides. These metalsulfide complexes bind the metals in a form that is not bioavailable. Since free ionic metals are 

generally thought to possess the greatest toxicity potential, it is important to understand conditions 

which control binding dynamics, such as pH and Eh. 

Potentiometric measurements of Eh using a millivolt reader can be obtained with a platinum 

electrode relative to a standard hydrogen electrode (Plumb, 1981). APHA (1995) does not 

recommend the standard hydrogen electrode as it is fragile and impractical. Instead, their method 

uses a silver-silver-chloride or calomel reference electrode. APHA (1995) recommends a graphite 

rather than platinum electrode for sediments. Once the Eh equilibrium is reached, the difference 

between the platinum or graphite electrode and the reference electrode is equal to the redox potential 

of the system. For a more detailed explanation on how to calculate the Eh potential see APHA 

(1995). Gonzalez (1995) also describes a detailed method that can be used to measure sediment Eh. 

There are a number of problems associated with the accurate measurement and interpretation of Eh 

in sediments, particularly in marine sediments. Therefore, considerable attention should be paid to 

the use of proper equipment and techniques. Some of the problems identified by Whitfield (1969) 

and Mudroch and Azcue (1995) include measurement inaccuracy due to disturbance of the sediment 

sample during insertion of the electrode, instability and poor reproducibility of the measurements and 

differential responses of platinum electrodes under different environmental conditions. A 

comprehensive description of the limitations of sediment Eh measurement is beyond the scope of this 

document. Rather, it is recommended that published studies on the problems associated with 

measuring and interpreting sediment Eh be consulted before any attempt is made to measure these 

parameters in sediment samples (Berner,1963; Morris and Stumm, 1967; Whitfield, 1969; Tinsley, 

Appendix G: Physico-Chemical Sediment Characterization G-13 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

1979; Bates, 1981). The recommended procedure for measuring pH and Eh in the field are described 

in detail in the table below: 

Table G-1.	 General procedures for measurement of Eh in bottom sediments (from Murdoch and 

Azcue 1995). 

Equipment and solutions used in the measurements: 

• A portable, battery-operated pH/Eh meter, batteries, and a power cord for recharging the meter. 

• Combination glass and platinum electrodes or other electrodes suitable for the measurements. 

• Plastic test-tube-shaped containers or other containers for storing the electrodes in solutions during transport in the 

field. 

• Commercially-available or laboratory-prepared pH buffer solutions (pH 4 and 7) in plastic bottles with lids. 

• Freshly-prepared solution for calibration of Eh electrode in a plastic bottle with a tight lid. 

• Freshly-prepared solution of saturated potassium chloride for storage of the electrodes. 

• Other solutions necessary for proper functioning of electrodes as outlined by manufacturers. 

• Distilled water and wash bottle for storing and rinsing the electrodes between measurements. 

• Several small and larger plastic beakers for holding solutions, rinsing electrodes, etc.. 

• Support stands, rods, clamps to secure electrodes in solutions and during measurements. 

• Large plastic containers for storage and transport of used buffers and Eh-calibration solutions. 

• Notebook and pens, soft paper tissue. 

Preparation of equipment before the field trip: 

• Check batteries of the portable pH/Eh meter and replace/recharge them, if necessary. 

• Prepare calibration solutions. 

• Check and test the pH and Eh electrodes. 

• Mark the electrodes vertically at desired intervals for insertion into the sediment samples. 

• Store the electrodes according the manufacturers instructions. 

• Pack all equipment for transport to the field and take spare electrodes if available. 

Measurements in the field: 

• Allocate a space where measurements will be carried out. Within this space, all equipment should be assembled, 

checked for proper functioning, and prepared for measurement of the first sample. 

• Place grab sampler and sediment cores with recovered sediment in such a way that they will remain steady without 

disturbing the sediment samples during the measurements. 

• Insert electrodes carefully into the undisturbed sediment samples to avoid any air. contamination, particularly around 

the Eh electrode. Care must be taken not to generate any open space between the electrode and the sediment. Proper 

insertion of the electrode without disturbing the sediment is the most important step in measuring the Eh. 

• Insert electrodes into the sediment to the depth marked. Switch the pH/Eh meter to the pH scale and the value 

recorded within 1 minute after inserting the electrode into the sample. Switch the meter to the mV scale for 

recording the Eh value. The potential usually drifts considerably over the first 10 to 15 minutes, and then stabilizes. 

After stabilization, record the mV value. In measuring Eh of sediments from waters with low ionic strength, such as 

most freshwater bodies, it is recommended to “acclimatize” the electrodes in the water prior to measurement, 

particularly the electrodes that were stored in saturated potassium chloride solution. This will reduce the drifting of 

the potential after inserting the electrode into the sediment. 

• Remove both electrodes, wash them with distilled water to remove all adhering sediment particles, and dry them 

gently with a soft paper tissue. 

• Calibrate the electrodes after each five measurements. The electrodes may need less frequent calibration if pH and 

Eh are being measured in a sediment core. 

21. Total Inorganic Carbon 

Inorganic carbon has been measured as a complement to microbial activity (Bregnard et al., 1996), to 

determine the fate of an organic contaminant in biodegradation studies (West and Gonsior, 1996), 

and to determine the % carbon unaccounted for in fate transport predictions of hydrophobic 

contaminants (Tye, et al., 1996). Often the total inorganic carbon (TIC) fraction in samples is many 

times greater than the TOC fraction and presents an interference in the measurement of TOC. There 

are several options to eliminate TIC interferences when trying to measure TOC. One option is to 

compensate for the IC interference by measuring total carbon (TC) and total inorganic carbon (see 

Section 4 in this Appendix). The difference between the two is the TOC. 

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TIC is determined by acidifying the sample to convert the inorganic carbon (i.e., carbonates, 

bicarbonates, and dissolved CO2) to carbon dioxide. Carbon dioxide is purged from the sample and 

then detected by a non-dispersive infrared detector (NDIR) calibrated to directly display the mass of 

carbon dioxide measured. This mass is proportional to the mass of TIC. Other instrumentation for 

the analysis of TIC is described in West and Gonsior (1996) and Tye et al. (1996). 

22. Total Volatile Solids (TVS) 

Total volatile solids represent the fraction of total solids that are lost on ignition at a higher 

temperature than that used to determine total solids. Total volatile solids are used as a crude estimate 

of the amount of organic matter in total solids (PSEP, 1996). In this regard, total volatile solids are 

often measured instead of, or in addition to, organic carbon content. 

Total volatile solids are operationally defined by ignition temperature. Total volatile solids content 

does not always represent the organic content of a sample because some organic material may be lost 

at the drying temperature and some inorganic material (e.g, carbonates, chlorides) may be lost at the 

ignition temperature. Because of the temperature dependence of total volatile solids, valid interstudy 

comparisons require the use of standardized drying and ignition temperatures (PSEP, 1996). 

Total volatile solids measurements are generally made by igniting the sediments at 550 ± 10o

C until a 

constant weight is achieved and reporting the percent ash-free dry weight (McLeese et al., 1980; 

APHA, 1995; Keilty et al., 1988a). Plumb (1981) and PSEP (1996) describe standard methods for 

determining the total volatile solid content of sediments. Additional methods are provided in USEPA 

(1987). 

23. Dissolved Organic Carbon in Pore Water 

Dissolved organic carbon (DOC) often consists of humic substances and is the fraction of the organic 

carbon pool that is dissolved in water and passed through a 0.45 μm glass fiber filter. DOC is an 

indicator of the chemically reactive organic fraction and accurately measures the dissolved organic 

load. Sediment pore waters can be rich in humic acids. Fifty to 90% of the pore water DOC can be 

colloidal which is a significant factor because organic chemicals will preferentially partition to pore 

water DOC (Resendes et al., 1992; Burgess et al., 1996). 

Hermann (1996) and Gilek et al. (1996) measured DOC using a TOC apparatus and infrared 

detection of CO2. Borga et al. (1996) measured DOC using atomic emission spectrometry (ECPAES). The APHA (Method 5310, 1995) methods for total organic carbon which can be applied to 

the measurement of DOC are (a) the combustion-infrared method; (b) the persulfate-ultraviolet 

oxidation method; and (c) the wet-oxidation method. Adjustments for inorganic carbon interference 

may be required (see Section 21 in this Appendix). 

24. Alkalinity and Hardness of the Pore Water (Fresh Water Sediments) 

Alkalinity is defined as the acid-neutralizing (i.e., proton-accepting) capacity of water. It is the sum 

of all the titratable bases and a measure of the quality and quantity of constituents in the pore water 

that result in a shift in the pH toward the alkaline side of neutrality. The measured value may vary 

significantly with the pH end-point used. Studies have shown that effects of certain contaminants 

such as metals are influenced by alkalinity as it alters speciation and bioavailability. 

APHA (1995) recommends a color-change titration method to measure alkalinity which is also 

described by ASTM (2000h). The sample is titrated with standard alkali or acid to a designated pH 

Appendix G: Physico-Chemical Sediment Characterization G-15 
Methods for Collection, Storage, and Manipulation of Sediments for Chemical and Toxicological Analyses 

and the endpoint is determined electrometrically or by the color change of an internal standard. In 

addition, ASTM (2000h) describes two additional methods: (1) a titration curve is developed to 

identify inflection points, a standard acid of alkali is added to the sample by small increments and pH 

is recorded after each addition, and the total volume of acid or alkali is plotted against the observed 

pH values; and (2) pH is determined, standard acid is added to lower the pH to 4.0 or less, the 

solution is boiled with hydrogen peroxide, and titrated while hot to the phenolphthalein endpoint or 

when cooled electrometrically with standard alkali to pH 8.2, the desired endpoint. The color-change 

titration method is most commonly used. Hach (Method 8202) has developed a portable water 

chemistry kit based on the APHA (1995) color-change titration method and an additional method 

using sulfuric acid with a digital titrator (Hach, Method 8203). 

Hardness is the concentration of metallic cations, with the exception of alkali metals, present in water 

samples. Generally, hardness is a measure of the concentration of calcium and magnesium ions in 

water. Hardness is usually expressed as a calcium carbonate equivalent in mg/L. Like alkalinity, 

hardness alters speciation and bioavailability of certain contaminants particularly many metals. 

AHPA (Method 2340, 1995) describes two methods to measure hardness: (1) the calculation method 

and (2) the EDTA titrimetric method. ASTM (2000i) describes the APHA (1995) EDTA titrimetric 

method. Calcium and magnesium ions in water are sequestered by the addition of EDTA. The 

endpoint of the reaction is measured by means of Chrome Black T3

, which is red in the presence of 

calcium and magnesium and blue when both are sequestered. APHA recommends the calculation 

method because it is more accurate. The method uses direct determinations of calcium and 

magnesium to determine hardness. Hach has developed portable water chemistry kits (Methods 

8222, 8204, 8030, 8226, 8213, 8338, 8329) for a variety of hardness determinations using a 

spectrophotometer or titration methods with a decision tree for selecting the appropriate procedure. 

Three of the Hach methods (1992) were adapted from APHA (Method 2340, 1995): the buret and 

0.020 N titrant method (8222); the ManVer 2 buret and 0.020 N titrant method (8226); and the buret 

titration method (8338). The APHA EDTA titration method is most often used. 

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