### MONITORING FOR INDICATORS OF ANTIFOULING PAINT P O LLUTIO N IN CALIFORNIA MARI NAS
Nan Singha semanon, Ellen Pyatt, and Juanita Bacey

June 2009

CALIF O R N IA ENVIR ONM ENT A L PROT ECTION AGE N CY En vi ro nm ent a l M oni t o ri n g B r anch Califo r n i a Departm en t o f Pest icid e Regu latio n 1 001 I St., Sacr am en to , Calif o r n i a 95 812
EH08-05

### ABSTRACT In the summer and fall of 2006, th e Department of Pesticide Regulation (DPR) sampled water and sediment from 23 marinas to assess the geographical scope and severity of pollution stemming from the use of antifouling paint (AFP) pesticides in California. Coppe r, zinc, Irgarol, M1 (the primary breakdown product of Irgarol), and aquatic toxicity were selected as potential indicators of AFP pollution. The highest dissolved copper concentrations were observed in larger salt water marinas along California’s Central and South Coast, the lowest were seen in freshw ater lake marinas. Copper and zinc concentrations were almost always higher in the marinas than in the adjacent local reference sites, indicating that significant sources of metals existed in the marinas. Concentrations of zinc never exceeded California’s water quality standards. In contrast, concentrations of dissolved copper in salt and brackish water marinas were frequently above California water quality standard s established for the protection of aquatic life. Developmental toxicity tests on the copper-sensitive embryo of the mussel Mytilus galloprovincialis were conducted on 47 marina water samples. Eight of these samples showed a statistically significant toxic response and copper was the likely cause of the toxicity. Several copper toxicity models that account forcopper bioavailability to aquatic organisms were used to predict toxicity for the 517 samples for which sitespecific water quality data were available. These mode ls were the freshwater Biotic Ligand Model (BLM), the saltwater BLM, and the Dissolved Organic Carb on Model. Model output indicated that copper sensitive aquatic organisms, particularly M. galloprovincialis in saltwater marinas, were occasionally exposed to toxic levels of copper. Forty-five marina water samples were collected and analyzed for Irgarol and M1. Irgarol and M1 were detected in all of these samples. Irgarol concentrations were often higher than sub-lethal toxicity thresholds for marine algae. In some saltwater marinas, Irgarol concentrations exceeded benchmark values used to determine if risk to aquatic plants exists. Source evaluation suggests that during dry periods, boat AFPs are a major sour ce of copper, Irgarol, and M1 to salt and brackish water marinas. The contribution of zinc AFPs to the total marina zinc load is likely to be less than the contribution of copper AFPs to the total marina copper load due to the input of zinc from the corrosion of sacrificial zinc anodes in salt water marinas and due to the much lower use of zinc AFPs compared to copper AFPs.

i

### ACKNOWLEDGEME NTS
Thi s st udy was co nd uct e d wi t h DPR reso u r c e s an d s u ppl e m ent a l fu ndi ng fr om th e U. S. En vi ro nm ent a l Pro t ection Ag en cy (U.S. EPA) an d fro m Cali forn ia ’s State Water Resou r ces Con tro l Bo ard (SWRCB).
The au th or s w oul d l i k e t o t h a n k th e f o l l o wi n g gr o ups an d i ndi vi d u al s f o r t h ei r c o ntri b u t i o n t o t h e success f ul c o mpletion of this study:

• Surface Water Program scientific stude nt ass i st ants: Catherine Cruge r-Ha nse n , Ste v e n Doo, and Michele Gibson for t h eir tir eless efforts in the field.

• DPR scien tist–Alb e rt W a ng fo r h is wo rk on th e Qu ality Assu ran ce Proj ect Plan

. • DPR scien tists– T erri Barry, Mark Pepp le, an d Frank Spu r l o ck fo r th eir inv a lu ab le inpu t an d revie w
. • Co pp er An tifou lin g Pain t Sub

- Work gro u p o f th e Marin aan d Recreation a l Bo atin g Work group o f th e Non

- Po i n t Sou r ce In teragen c y Coo r d in a t in g C o mmittee fo r t h eir i n pu t in th e stud y d e sign

. • R a y Ar nol d, ( C op per De vel o pm ent Associ a t i on) , Li n d a C a ndel ari a (Sa n t a A n a R e gi o n al Water Qu ality Co n tro l B o ard ) , Rich ard Looker (San Fran cisco Bay Reg i o n al W a ter Qu ality C ontr o l B o ar d) , Kel l y M o ran (TDC En vi r o n m ent a l ) , an d P a ul Sal o p ( A p p l i e d M a ri ne Scien ce) fo r their inp u t on th e stud y d e si g n
. • So uthe rn C a l i f or ni a C o a s t a l Wat e r R e sear c h P r o j ect st a ff: Ke n Sc hi f f a n d Dar r i n G r een st ei n for th ei r work o n tox i city an d to x i city id en tificatio n ev alu a tio n
. • Uni v ersi t y o f C a l i f or ni a, De part m e nt of A g ri cul tu ral an d Natu ral R e so ur ces Lab o r at ory ch em ists : Dirk Ho lsteg e and Tr acy Francis, and their analy tical chemists for their ha rd work on sam p le analysis.

• Natio n al Ocean i c and Atm o sp h e ric Ad m i n i stratio n , Ho lling s Mari n e Labo rat o ry staff: Ed Wo rth an d Yel e na Sap o zh ni k ova f

o r

th ei r wo rk on Irg aro l and M1 analys is.

• R obe rt Sa nt o re an d Adam R y an of Hy dr oq u a l , In c for th ei r assistan ce with th e salt water B i ot i c Li gan d M odel

. • Melen ee Em an u e l and Dian e Edward s o f SWRCB Non

- Po in t Sou r ce Pro g ram fo r th eir ro le as cont ract m a nagers.
• Th e Cen tral Valley Reg i o n a l Water Qu ality Co n tro l B o ard for th e use an d op eration o f their sam p l i ng vesse l fo r se di m e nt col l ect i on.
• City of L o ng B each Lifeguards for t h e use a n d ope ration of t h eir sam p ling vessels for t h e sam p l i ng of th e t w o L o n g B e ach m a ri nas.
• Particip atin g marin a s asso ciat ed with th e Calif or ni a Ass o ci at i on of Harb o rM a st ers an d P o rt C a pt ai ns (C A H M P C ) a n d t h e M a ri na R e c r eat i on Ass o ci at i on (M R A ) a n d th ei r m a ri na managers for their knowledge, cooperation, and assista n ce
. • Bill Krau se (APEX Group ), Eric End e rsb y (CAHMPC ), and Marian n Timm s (MRA) fo r facilitatin g commu n i catio n s with C AHMPC and MRA me m b ers.



### FEDE RAL DISCLOS U RE ST AT E M ENT
Fu ndi ng f o r th i s p r o j ect has b een pr o v i d e d , i n part , by U. S. EPA p u rs ua nt t o Assi st ance A g reem ent N o . C 9

­ 9 690 680 1 and an y am en d m en ts th ereto wh ich h a v e b e en award e d to SWRCB for th e im p le m en tatio n of Califo r n ia’s No npo in t Sou r ce (NPS) Po llu tio n Con tro l Pr og r a m
. Th e conten ts of th is docu m en t d o no t n ecessarily refl ect th e v i ews an d po licies of t h e U.S. EPA or SWRCB, n o r do es m e n tio n o f trad e n a m e s o r co mmercial p r o d u c ts con s titu te en dorsem e n t or reco mm en d a tio n for u s e.

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### TABLE OF CONTENTS
ABSTR A C T
....................................................................................................................... ............................ i
AC KN OWLE DG E M ENTS
............................................................................................................... .......... ii
FEDER A L DI SCLOS U RE STATEME N T
................................................................................................ ii
TABLE OF CO NTENTS
.............................................................................................................. .............. iii
LIST OF T A BLES
................................................................................................................. ....................... v LIST OF FIG URES
................................................................................................................ ..................... vi
LIST OF FR EQUENTL Y
- U SED ABB R EVIATI ON S AN D A C R O N Y M S
.......................................... vii
I. In tro duc tion
................................................................................................................ ............................... 1
II. Materials and Meth od s ...................................................................................................... ..................... 2 Sam p ling A p pr oach

.............................................................................................................. .................. 2 Ass u m p tions & Lim i tations

...................................................................................................... .............. 3 Site Selecti on Criteria

........................................................................................................ ..................... 3 Sam p ling Vess els

............................................................................................................... ..................... 8 Sam p ling Method a n d F r e q uency
.................................................................................................. ......... 8 Marina Sites - Copper , Zi nc, TSS, and BLM

- Ass o ciatedParam e ters

.............................................. 10 Marina Sites - Ir gar o l/M1

...................................................................................................... ........... 11 Marina Sites - To xicity and T I Es

............................................................................................... ....... 11 Local Refe re nc e Sites - C o ppe r, Zi nc, TS S , a n d BLM- Ass o ciated Param e ters

............................... 11 Local Refe re nc e Sites - Ir ga rol, Toxicity , and TIEs

......................................................................... 11 Sam p le Collect ion - Water

...................................................................................................... ............. 11 Sam p le Collection - Sedim e nt

................................................................................................... ........... 12 Field Quality Ass u ra n ce/Qua lity Control

........................................................................................ ..... 12 Sam p le Handli n g and C u stody

.................................................................................................... ......... 12 Sam p le An alys is

................................................................................................................ ................... 13 Water Sam p les - C o ppe r , Zi nc , TSS , a n d BL M-Ass o ciated Param e ters

.......................................... 13 Water Sam p les - Ir gar o l/M1

..................................................................................................... ........ 13 Water Sam p les - T o xicity an d TIEs

.............................................................................................. .... 13 Sedim e nt Samp les - Copper a n d Zinc

............................................................................................. . 1 3 Sedim e nt Samp les - I r gar o l/M1

.................................................................................................. ...... 14 Laboratory Quality Assu ra nc e/Quality Cont rol

................................................................................... . 1 4 Statistical Analys is

........................................................................................................... .................... 15 Pre d ictive T o xi city M odels

..................................................................................................... ............. 16 Biotic Ligand M odel - F r es hwater

............................................................................................... ..... 16 DOC M o del - Salt and Brac kish Water

............................................................................................ 17 Biotic Ligand Model - Sa lt a n d Brac kish Water

............................................................................... 17
III. Results
................................................................................................................... ................................ 18 Dissol v ed Copper

............................................................................................................... .................. 18 Total Co pper
................................................................................................................... ...................... 24 Dissol v ed Zinc

................................................................................................................. ..................... 28 Total S u spe nded S o lids

......................................................................................................... ............... 31 Cor r elations of Total S u s p ended S o lids and Dissol v ed O r ganic Car b on wi th Metals

.......................... 34 Ir gar o l a n d M1

................................................................................................................. ..................... 37 Total Copper - Sedim e nt

........................................................................................................ ............... 39 Total Zinc - Se dim e nt

.......................................................................................................... ................. 40 Toxicant I d e n tificati on Eval ua tion (TIE )

....................................................................................... ...... 42 Com p arisons to Water Quality St andards

......................................................................................... .... 42

iiiCTR Fres hwater CMC and C CC W ate r Qua lity Standa rds - Coppe r
............................................... 43 CTR Fres hwater CMC and C CC W ate r Qua lity Standa rds - Zinc

................................................... 43 CTR Saltwater CMC and CC C W ater Quality Standards - Copper

.................................................. 43 CTR Saltwater CMC and CC C W a te r Quality Standards - Z i nc
...................................................... 44 Com p arisons to T o xic ity Benchm ark Val u es
....................................................................................... 44 Com p arison of Sedim e nt Concentrations t o N O A A ’s Biological-Ef f ects G u idelines - C opper
....... 44 Com p arison of Sedim e nt Concentrations t o N O A A ’s Biological Ef fects G u idelines - Zinc

........... 45 C o m p ari s on o f Ir garol C once n tr at i o ns t o T o xi col o gi cal E n dp oi nt s an d A q uat i c To xi ci t y Benchm arks

..................................................................................................................... ................. 45 Com p arison of M1 C once n tra tions t o T oxic o logi cal E n dpoints

...................................................... 46 BLM-Ass o ciated Wa ter Quality Data

.............................................................................................. .... 46

Laboratory-Analy zed Cons tituents

............................................................................................... .... 46 In-Situ Meas ur em ents

........................................................................................................... ............ 46 Pre d ictive T o xi city M odels

..................................................................................................... ............. 49 Biotic Ligand M odel - F r es hwater

............................................................................................... ..... 49 DOC M o del - Salt and Brac kish Water

............................................................................................ 50 Biotic Ligand Model - Sa lt a n d Brac kish Water

............................................................................... 52
IV. Discus sion
................................................................................................................. ............................. 55 Occurre nce a n d Ma gnitude

....................................................................................................... ............ 55

Water C o lum n – C o ppe r
.......................................................................................................... ......... 55 Water C o lum n – Zinc

............................................................................................................ ........... 56 Water C o lum n – Ir garol/M1

...................................................................................................... ....... 57 Sedim e nt – Coppe r a n d Zinc

..................................................................................................... ....... 57 Com p arison to W ater Quality Standard s or Biological E ffe cts Thresh olds

.......................................... 57 Copper

......................................................................................................................... ..................... 57 Zinc

........................................................................................................................... ........................ 58 Ir gar o l/M1

..................................................................................................................... ................... 58 Marina vers us Local Refe re nc e Site

............................................................................................. ........ 59

Water C o lum n
................................................................................................................... ............... 59 Sedim e nt

....................................................................................................................... .................... 60 Marina S o urce s of C opper
....................................................................................................... ............. 60

Wood P r ese r va tives

............................................................................................................. ............. 60 Backgroun d L o ad

................................................................................................................ ............. 61 Marina Se dim e nt

................................................................................................................ .............. 61 Antif ouling Pa ints

............................................................................................................. ................ 61 Marina S o urce s of Zi nc
......................................................................................................... ............... 63 Antif ouling Pa ints

............................................................................................................. ................ 63 Wood P r ese r va tives

............................................................................................................. ............. 63 Sacrificia l A nod es
............................................................................................................. ............... 63 Toxicity/Toxicant I d e n tif ication E v aluation

.................................................................................... ..... 64 Pre d ictive Copper Toxicity Models

.............................................................................................. ........ 65
V. C o nclu sion s ................................................................................................................. ........................... 66
VI. Re ference s ................................................................................................................. ............................ 67 Appe ndix A : Marin a De scr i ption and Histor y .................................................................................... .... 71 Appe ndix B : An alytic al Me thods (A N R A n alytical L a b o rat o r y )
.......................................................... 81 Appe ndix C : SC CW RP ’s Toxici t y and Phase I TIE meth o ds
............................................................ 111 Appe ndix D : Method Valid ati o n Resul t s (ANR L a b o ra t o ry ) and Su m m ar y of L a b o rat o r y Q A / Q C Results ( A ll L a b o rat o ri es)
..................................................................................................... ................... 122 Appe ndix E : Field Qu ality Assur a nce/Q u a lity C o n t rol Results and D i scussion
................................ 128

i vA ppendix F: M e ta ls, TSS, & BLM -R elated Wa t e r Co lumn D ata (AN R La bo ra to ry a n d D P R Laborator y )
.................................................................................................................... ........................... 134 Appe ndix G: Water Q u ality Da t a (AN R La borat o ry and D P R) , Irgaro l/M 1 (N OAA HM L), & Toxicit y Resul t s ( S C C W R P )
...................................................................................................... .............. 153 Appe ndix H: Sediment Me t a ls D a ta ( A N R An alytic al Laborator y ) ................................................... 172 Appe ndix I: SC CW RP T o xici ty/TIE Dat a Rep o rt ............................................................................... 174 Appe ndix J : Com paris on o f Fres hw ater Dissol v ed C o p per Re sults t o CTR Ha rdnes s -Base d Freshw ater A c ute (C M C ) and Ch r o nic ( C C C ) S t and a rds
................................................................... 180 Appe ndix K: Com paris on of Fres hwater Dissol v ed Z i nc Resul t s to C a l i f or ni a T oxi cs Rul e H a rd nessBased Freshw ater Ac ute ( C MC ) and C h r o nic (C CC ) St and a rds
........................................................ 185 Appe ndix L: Freshw ater Biotic Ligan d M o de l O u t put ........................................................................ 190 Appe ndix M : Diss olved Or gani c C a rb on Mode l Ou tp ut ..................................................................... 193 Appe ndix N : Saltw a ter Bi ot ic Ligan d Mode l Ou tpu t ........................................................................... 205



### LIST OF TABLES
Tabl e 1. Li st of M a ri na Study Ar eas Tabl e 2. Sam p l i ng Sche m e /F reque ncy Tabl e 3. Sum m ary of A n al y t i cal M e thods a n d Det ect i on Li m i t s Table 4. Fres hwater BLM Operating Param eters Tab l e 5

. Saltwater BLM Op eratin g Param e ters Tabl e 6. R a nge o f M e t a l (i n μ g /L) and To tal Su sp ended So lid s (in mg /L) C o n cen t r atio n s i n Water b y Mar i n as Tabl e 7. M e di a n M e t a l (i n μ g / L) an d To tal Su spend e d So lids (in m g /L) Con cen t r atio n s in W a ter b y M a ri nas (ar r an ged i n a s cen di ng o r der o f m a ri na m e di an di ssol v e d c o ppe r co ncent r at i o n s ) Tabl e 8. Sum m a ry o f M e di an M e t a l C once n trat i ons (i n μ g / L) in W ater Tab l e 9

. Su mmary of Med i an Irg a ro l an d M1 Con cen trati o ns (in ng /L) in Water Sam p les Tabl e 10 . S u m m a ry of M e di a n M e t a l C o nce n tr at i o ns (i n m g / k g dry wei g h t ) i n Sedi m e nt Sam p l e s Tab l e 1 1

. Water Sam p les with Statisticall y Sig n i fican t Tox i c Endp o i n t s Tab l e 1 2

. Tox i can t Id en tificatio n Ev al u a tio n Treatm e n t Resu lts Tab l e 1 3 . Mari n a Med i an C o n cen t r atio n s o f Bio tic Lig a n d Mo d el-Related Con s titu en ts (in m g /L) Tab l e 1 4 . Ran g es of BLM

- Related Con s titu en t Co n cen tratio n s (i n m g /L) fo r Each Marina Area Tabl e 15 . F r es hwat e rB L M O u tp ut f

o r Sam p les with Pred icted To x icity Tab le 1 6

. D O C Mo del FCC an d FA C Ou tput Ran g e s Tab l e 1 7 . Salt water BLM Outp u t for Sam p les with Pred icted Tox i city Tabl e A- 1. M ari na GPS C o o r di nat e s Tab l e D-1

. Meth od Valid ation Resu lts (Low Lev e l Sp i k es) Tab le D-2

. Meth od Valid ation Resu lts (High Lev e l Sp ik es) Table D-3. Analyte-Specific Accuracy , Prec i s i on, an d R e c ove ry Li m i t s Tab l e D-4

. Sam p le Ho ld ing Ti m e Gu id elines and Calcu l at ed Av erag e Hold in g Tim es Tab le E- 1. D istr ibu tio n of D C u C o n c en tr ation s i n Field Q C Sam p les Table E

- 2. Fiel d a n d Rinse Bl ank Results Tab l e F-1. Met als, TSS, & BLM-Related Dat a Tab l e G-1

. Water Qu ality Data (ANR Labo rato ry an d DPR), Irg a ro l/M1 (N OAA HML), & Tox i city (SCC W R P) Resu lts Tabl e H- 1. Sed i m e nt Dat a– T C u a n d TZ n C once n tr at i o ns Table J

- 1. Com p arison of Freshwater DCu Results to CT R Hardness -Based Fres hwater Ac ute (CMC) and Ch ro n i c (CCC) Stand a rd s

vTabl e K- 1. C o m p ari s on of Fr eshw at er DZ n R e sul t s t o CT R Hardness -Based Fres hwater Ac ute (CMC) and Ch ro n i c (CCC) Stand a rd s Tabl e L

- 1 . F r e s hwat e rB L M Out put - Pre d i c t e d T oxi ci t y R e sul t s Tabl e M

- 1. D O C M o del Out put - Pre d i c t e d To xi ci t y R e sul t s Tab l e N-1

. Saltwater BLM Outp u t - Pred icted Tox i city to M. g a llop r o v incia lis



### LIST OF F I GURES
Fi gu re 1. St at ewi d e M ap of M a ri na Sam p l i n g A r eas Fi gu re 2. C l ose
- U p M ap of Sa n F r a n ci sco B a y Area M a ri na Sam p l i ng A r ea s Fi gu re 3. Di a g r a m of Sam p l i ng L o cat i o ns W i th i n M a ri n a s Fi gu re 4. Di stri but i o n o f Di ss ol ve d C o p p er C once n tr at i o ns i n F r es hwat e rM a ri na Areas Fi gu re 5. Di stri but i o n o f Di ss ol ve d C o p p er C once n trat i o ns i n B rac ki s h W a t e r M a ri na A r eas Fi gu re 6. Di stri but i o n o f Di ss ol ve d C o p p er C once n tr at i o ns i n Sal t w at e rM a ri na Areas ( S an Fra n ci sco B a y Area ) Fi gu re 7. Di stri but i o n o f Di ss ol ve d C o p p er C once n tr at i o ns i n Sal t w at e rM a ri na Areas ( C entr al an d So uth Co ast) Fi gu re 8. Di stri but i o n o f M a ri na M e di an Di s s ol ve d C o p p e r C once n trat i o ns by Wat e r Ty p e Fi gu re 9. Di stri but i o n o f T o t a l C o ppe r C once n tr at i o ns i n F r e s hwat e rM a ri n aA r eas Fig u r e 10

. D istr ibu tio n of To t a l Co pp er Con centrations i n Brackis h Water Mari na Areas Fig u r e 11

. D istr ibu tio n of To t a l Co pp er Concen tr atio ns i n Saltwater Mari na Areas (San Fra n cisco Bay Area ) Fig u r e 12

. D istr ibu tio n of To t a l Co pp er Concen tr atio ns i n Saltwater Mari na Areas (Ce n tral and South Co ast) Fi gu re 1 3

. Di stri b u t i o n o f M ari na M e di an T o t a l C o ppe r C o ncent r at i ons by W a t e r Ty pe Fi gu re 1 4 . C o r r el at i on Pl ot of Lo g Di ss ol ve dve rsus L o g T o t a l C o p p er C o n centr at i o ns Fi gu re 1 5

. Di stri b u t i o n o f Di s s ol ve d Zi nc C o ncent r at i ons i n Fres h w at er M a ri na Area s Fi gu re 1 6

. Di stri b u t i o n o f M ari na M e di an Di ssol v e d Zi nc C once n tr at i o ns i n B r ac ki s h Wa t e r M a ri na A r e a s Fig u r e 17 . D istr ibu tio n of Mar in a Med ian D i sso lv ed Zi n c C o n c en tration s in Saltw ate rMarina Area s (Sa n Fra n cisco Bay Area ) Fig u r e 18

. D istr ibu tio n of Mar in aMed ian D i sso lv ed Zin c C o n c en tration s in Saltwater Marin a Areas (C entr al a n d S out h C o ast ) Fi gu re 1 9

. Di stri b u t i o n o f M ari na M e di an Di ssol v e d Zi nc C once n tr at i o ns b y W a t e r Ty pe Fig u r e 20

. D istr ibu tio n of Mar in aMed ian To tal Susp end e d So lids Con c entratio n s (in m g /L) b y Water Typ e Fi gu re 2 1

. Di stri b u t i o n o f T o t a l Sus p e nde d S o l i d C once n tr a t i ons i n F r es h w at er M ari na Areas Fi gu re 2 2

. Di stri b u t i o n o f T o t a l Sus p e nde d S o l i d C once n tr a t i ons i n B r ac ki sh Wat e r M ari na Areas Fi gu re 2 3

. Di stri b u t i o n o f T o t a l Sus p e nde d S o l i d C once n tr a t i ons i n Sal t w a t er M a ri na A r e a s (Sa n Fra n ci s c o Bay Area) Fi gu re 2 4

. Di stri b u t i o n o f T o t a l Sus p e nde d S o l i d C onc en tr atio n s in S a ltw ate rMa r i n a Ar ea s ( C en tr a l a nd So uth C o ast ) Fi gu re 2 5 . C o r r el at i on of T o t a l Sus p e nde d S o l i d s a n d To tal Cop p e r C o n c en tration s in Brack ish W a ters Fi gu re 2 6 . C o r r el at i on of T o t a l Sus p e nde d S o l i d s vs. Di ss ol ved C o p p er C o ncent r at i ons at B e ni ci a an d Vallejo M a ri na Ar eas Fi gu re 2 7 . C o r r el at i on of T o t a l Sus p e nde d S o l i d s vs. Di ss ol vedZi nc C o nc entr at i o ns at B e ni ci a an d Val l e jo Marina Areas Fig u r e 28 . Marin aMed ian Irgar o l and M1 W a ter Con cen t r atio n s b y R o unds Fi gu re 2 9 . C o r r el at i on of I r g arol vs. M 1 C o n centr at i o ns i n M a ri na Wat e rs Fig u r e 30

. D istr ibu tio n of To t a l Co pp er Concen tr ation s i n Mar in a A r ea Sed im e n ts Fi gu re 3 1

. Di stri b u t i o n o f T o t a l Zi nc C o nce n tr at i ons i n M a r i na A r ea Sedi m e nt s Fi gu re 3 2 . B L M -Pre d i c t e d T oxi c U n i t s ( Ob s erve d DC u/ B L M -Pre d i c t e d M. g a llop r o v incia lis EC 50 ) v s
. Obse r v ed T oxi ci t y Fi gu re E

- 1. Fi el d B l an k R e s u l t s Ab o v e Det e ct i on Li m i t Fi gu re E

- 2. R i nse B l an k R e s u l t s A b ove Det ect i on Li m i t

vi

### LIST OF F R EQUENTLY-USED ABB R EVI A TIONS AND ACRO NYMS
AFP – an tifou lin g p a in t A NOV A – a n alys is o f v a r i an ce ANR – A g ric u lture a n d Nat u r a l Resou r ces B L M – B i ot i c Li gan d M odel C AHM PC – C a l i f or ni a A ssoc i at i on o f Har b o rM a st ers an d Port C a pt ai ns CCC –Criterion C o n tinuo u s Co n c en tration C D EC – C a l i f or ni a Dat aEx c h an ge C e nt er CI – confid en ce in terv al C M C – C ri t e ri on M a xi mu m C once n trat i o n C T R – C a l i f or ni a T oxi cs R u l e Cu Pt 2 – copp er p y r ith i o n e C W A – Clean Water Act DC u – di ss ol v e d c o p p e r DO – di ss ol ve d oxy gen DOC – di ss ol v e d or ga ni c car bo n DPR – Dep a rt m e nt of Pest i c i d e R e gul at i o n DZ n – di ssol v e d zi nc EC – electrical conductivity EC 50 – effective concent r ation (50% obse rve d e ffect) ERA – ec ological risk a ssess m e nt ERL – En vir o n m ental Risk Lim it (Irgar ol t o xicity thres hol d) ERL – Effects Ran g e Low (sed im en t q u ality g u i d elin e) ERM – E ffects Range Medi um FAC – Fi nal A c ut e C o nce n tr a t i on FA V – Fi nal A c ut e Val u e FC C – Fi nal C h r o ni c C o ncent r at i on GPS – gl obal p o si t i oni ng sy st em HML –Ho lling s Mari n e Labo rat o ry LC 50 –leth al co n c en tration (50 % m o rtality) LNB – L o wer New p ort Bay LOD – limit o f d e tection LOEC – l o wes t ob ser v ed ef fe ct conce n tr at i o n LRS – lo cal referen c e site M1 – pr im ar y d e gr ad e o f I r g ar o l M B YH – M ari na B a y Yacht Har b or (R i c hm on d M ari na ) M D L – m e thod det ect i o n l i m i t Md R – Mar in a d e l Rey MRA – Marina Recreation Association NO A A – Nat i o nal Ocea ni c a n d At m o spheri c A d m i ni strat i on N P S – non p o i n t so ur ce p p b –p arts p e r b illio n (eq u i v a len t to μ g/L ) ppm – part s pe r m i ll i on (e q u i v al ent t o m g /L or m g / kg) p p t –p arts p e r trillio n (equ iv alen t to n g /L) QA/ QC – qu ali t y assu ran ce/qu ality co n tro l QAPP –Qu ality Assu ran ce Pro j ect Plan RW QCB – Reg i on al W a ter Qu ality Con trol Bo ard SCC W RP – Southe rn California Coastal W at er Researc h Project SW RCB

–Stat e W a ter Resources C o n tro l B o ard TC u – t o t a l c o ppe r c o ncentr a t i ons TDS – t o t a l di s s ol ve d s o l i d s TIE

–Tox i city Id en tification Ev alu a tion TMDL

–To tal Max i mu m Daily Lo ad TSS

–t o tal su sp end e d so lid s TZn

–t o tal zinc U.S

. EP A – U n ited States E n v i ron m en tal Protectio n Ag en cy ZnPt 2 – zi nc p y r i t h i one

vii

### I. Introduction

In C a l i f or ni a, th e Depart m e nt o f Pest i c i d e R e gul at i o n (D P R ) re gi st ers a n t i fo ul i n g pai n t ( A FP ) pr o duct s sin ce th ey ar e p e sticid es. Like o th e r p e sticides, AFP pr oducts ar e f o r mu l ated b y co m b in in g p e sticid e activ e i n g redi e nt s wi t h ot he r c o m poun ds (e. g
. , s o l v ent s , a d ju va nt s, i n e rt i n gre d i e nt s) t o pr o duce usea bl e a n d ef

f ectiv e pr oducts. In A F P p r o d u c ts, activ e i n gr ed ien ts ar e o f ten r e f e rr ed t o as b i o c id es. Co pp er ox id e, cop p e r hy dr o x i d e, c o ppe r t h i o cy anate, zinc pyrithione (Z nPt 2 ), an d Irg a ro l are th e b i o c id es th at are m o st fre que nt l y f o r mul at ed i n t o A FP pr od uct s c u rre nt l y re g i stered in Calif or n i a (D PR, 20 08 a)

. A sing le AFP p r od u c t m a y actu a lly co n t ain mu lt ip le b i o c i d es. Copp er ox id e is th e m o st p opu lar o f th ese b i o c id es, ap p e ar ing i n mo r e th an 9 0 p e rcen t of Califo r n ia AFP pr oducts.
The leac hing of c o pper from AFPs u s ed o n r ecreat i onal b o a t s has bee n det e rm i n ed t o be t h e m a jor so u r c e of

co p p er p o l l u t i on i n a l a r g e boat basi n kn o w n as t h e S h el t e r I s l a n d Yacht B a si n (SI Y B ) i n Sa n Di eg o B a y (SDRWQC B , 20 0 5 )

. Wat e r col u m n l e vel s of di ss ol ve d c o ppe r (DC u ) at SIYB are hi gh eno u g h t o i m pai r bene ficial uses and e x ceed Ca lifor nia T oxics Rule (CTR ) st andards for c o ppe r (chronic value of 3.1 μ g/L and acute val u e of 4.8 μ g/L )

. More rece ntly, AFPs ar e s u s p ected as b e ing th e sign ifican t so urce of co pper i n t w o othe r l a r g e boat basi ns i n S out her n C a l i f or ni a: M a ri na del R e y an dLo wer Ne w p o r t B a y ( L A RW Q CB , 2 005 ; U.S. EPA , 20 02 ).
In th e p a st, m o n ito ri n g d a ta used i n th e ev al u a tio n of AFP p o llu tion i n Califo r n i a h a v e been larg ely gene rat e df r om th e Sa n Di eg o B a y regi on ( S i n g h as em anon, 2005). Rece n tly, an i n crease i n the devel opm ent of c o pper-relate d Total Maximum Daily Loads (TM D Ls) a n d the placem ent of additional cop p e r-i m p ai red wat e r b odi es on th e C l ea n Wat e r Act sect i on 3 0 3 ( d) l i s t chal l e ng es th e pres um pt i on th at th is issu e is on l y li mited to San Diego Bay.

Ir gar o l has bee n det ect ed wi t h i n creasi n g f r e que ncy at eco l o g i cally sen s iti v e lev e ls in coastal water worldwid e. In th e U.S., Irg a ro l (and its m a j o r m e tab o lite M1 ) h a s b e en d e tected i n th e waters of Chesapeake Ba y and Florid a (Hall and Gard i n ali, 200 4). Th e Un ited Stat es Env i ron m en tal Pro t ection Age n cy (U .S. EPA ) has e x pr essed c o ncer n ove r t h e pot e n t i a l phy t o t o xi c effect s of I r gar o l o n a q uat i c p l ant s and al gae ( U .S

. EP A, 2 0 03a ). I n 2 0 0 5 , th e Nat i onal Ocea ni c an d At m o sphe ri c Adm i ni strat i on ( N O A A ) con d u ct ed a n i nve st i g at i o n o f th e occu rre nce an d m a gni tu d e o f I r g ar ol an d M 1 i n a num ber o f m a ri nas i n San D i ego Bay ( S apo z hn ikova et al., 2 007 ). Ho w e v e r , t h is w a s t h e o n l y inv e stig ation th at h a s b e en co m p leted on t h ese con s titu ents in Californ i a th us far.
Zi nc f r o m th e use of A FP pr o duct s i s an othe r pot e n t i a l cont am i n ant i n m a ri nas. W i th th e use of Z n Pt 2 AFPs gro w i n g in recen t years an d th e po ssib i lity th at m o re zin c -b ased pro d u c ts co u l d en ter th e AFP mark et, zin c lev els in Californ i a m arin as n e ed to b e ev al u a ted

. Th ere is cu rren tly little d o cu m en tatio n o f zi nc co nce n tr at i ons i n m a ri nas
. For th i s stu d y , DPRc o l l ect ed wat e r a n d se di m e nt sam p l e s from a n u m b er of C a l i f or ni a m a ri nas an d analyzed t h em for indicators of AFP po llu tion

. Th e b io c id es of p a rticu lar in te r e s t ar e co pp e r ox id e, co pp e r h ydr ox id e, co pp er thiocya n ate, Z n Pt 2 , an d Ir gar o l. Th is m o nito r i ng stud y fo cused sp eci f i cally o n m a r i n a s because these areas harbor de nsely pac k e d recreationa l a nd comm ercial vessels, m o st of whic h have hul l s th at are p a in ted with AFPs. Mo reo v e r, m a r i n a s are purpo sefu lly con s tru c ted to sh elter bo ats fro m cu rren t s and wa ves t h us res u l t i ng i n po or fl u s hi ng i n t h e m a ri na. Th us, AF P pol l u t i on at t h ese l o c a t i ons s h oul d represen t so m e of th e wo rst water qu ality con d ition s resu ltin g fro m th e use of AFPs on bo ats.
Fin d i n g s fro m th is m o n ito ring stud y will h e l p DPR, State Water Resou r ces Con tro l Bo ard (SWRCB), Reg i on al W a ter Qu ality Co n t ro l Bo ards (RWQCBs), and o t h e r in terested ag en cies to m o re fu lly ev alu a t e th e po ten tial ad v e rse effects o f curren t AFP u s e on aq u atic org a n i sm s. Th ese find ing s will also h elp DPR d e term in e if mitig atio n actions (regu l ato r y an d/ o r vo lun t ary) are n e ed ed on a l o cal or a st atewid e scale.
Th e p r im ary ob j ective o f t

h is stud y is to :

• Determ ine the occurre nces and c once n trations of c opp er, zin c , an d Irg aro l and M 1 in th e water and sed i m en t o f sel ected Californ i a m arin as an d d eterm in e wh eth er t h ese lev els ex ceed water q u ality standards (e .g., CTR copper a n d zinc standards, s ite-speci fic objecti v es), c r iter ia ( e .g ., U

. S

. EPA’ s

1u p d a ted aqu a ti c life criteria fo r copp er), gu id elin es (e.g ., NOAA’s sed i m e n t qu ality gu idelin es), and othe r ec ol o g i cal l y rel e vant val u es (e. g ., LC 50 , EC 50 ).
Secondary objectives are to:

• Det e rm i n e i f c o p p e ra n d zi nc conce n tr at i o ns i n m a ri nas are si gni fi ca nt l y hi ghe r t h an co nc entr at i o ns i n the adjace nt local refe rence si tes (LRS).

• Determ in e wh eth e r AFP an alyte co n c en tration s d i ff er b etween salt water, br ackis h water, and fres h water m a rinas.

• Ap pl y U .S. EP A’s B i ot i c Li g a ndM o del (B LM ) or othe r s c i e nt i f i cal l y -rel e vant m odel s t o est i m at e b io a v a ilab ility an d tox icity o f co pp er.
• Measu r e th e t o x i city o f m a rina waters using me tal-sen s itiv e test sp ecies and en dpo in ts, com p are measu r ed tox i city with copper and zinc conc entr ation s and BLM-pred icted tox i city, and id en tify th e l i k el y cause of obs er ved t o xi ci t y usi n g T oxi ci t y Ide n t i f i cat i on E v al uat i o n ( T IE) p r oced ure s
.



### II. Materials and Methods Samplin g Ap proach
Co pp er, zin c , Irg aro l, and M 1 are t h e p r incipal AFP-re lated co nstitu en ts o f in terest. Water and sed i m e n t sam p l e s were t a ken f r om i n si de a n d o u t s i d e of m a ri na s and evaluate d for AFP analytes a s well as a num ber o f

o t h er water q u ality p a ram e ters. If m arin a lev els of th ese an alytes are con s isten tly and statistical ly h i g h er th an am bi ent l e vel s out si de t h e m a ri na, th i s w oul d pr o v i d e stro n g e v i d e n c e th at m a ri nas are a si gni fi can t so ur ce of A FP p o llu tan t s. Mor e ov er, if AFP so ur ces of AFP analytes ca n be s h own t o be large com p are d to othe r i n -m ari n a n o n
- AFP so u r ces, part i c ul ar l y du ri n g dry period s, t h en it is lik ely th at AFPs are th e pri m ary cause of el evat ed c once n tr at i o ns of th ese ana l y t es i n m a ri nas. T h i s ap pr oa ch doe s not ap pl y t o Ir gar o l s i nce AFPs are t h e m o st si gni fi can t use of t h i s bi oci d e i n s u rfac e waters

. He nce, sam p les col l ected for Irgarol and M1 analys is were all take n i n si de t h e m a ri nas. The sam p l i n g peri od was co n fi n e d t o C a l i fo rni a’ s s u m m e r m ont hs (J ul y t h r o ug h Oct o be r) t o a voi d con f ou n d i n g h y d r o l o gi c fact o r s th at c o ul d be i n tr od uce d by st orm event s
. Pro cesses s u c h as fl us hi n g , di l u t i o n , m i xi ng, a n d se di m e nt resu spe n si o n affect th e w a t e r a n dsedi m e nt conce n tr at i o ns of AF P i n di cat ors an d o th e r an al ytes. Mor e ov er , du r ing sto r m p e r iod s, o th e r n on- m a r in ain pu ts o f A F P an alytes in to th e marina could e x ceed AFP sources within t h e marina. Because DPR is interested in eval ua ting polluti on fr om AFP use, sam p l i ng fo r t h i s study was co nd uct e di n t h e dry s u m m er m ont hs.
D u e to t h e p opu larity o f copper-b a sed A FPs an d ex ceed an c es of co pp er water qu ality stan d ard s, t h is stud y foc u ses on c opper as a n AFP analyte. Particu l ar atten tion i s g i v en to t h e disso lv ed fraction o f copp er (i.e., DC u ) as t h e a f orem ent i one d s t anda rds are de fi ne d i n t h i s m a nne r. DC u c o ncent rat i ons at any gi ven t i m e are h eav ily influ e n c ed b y th e l e v e l of su sp end e d so lid s in the water co l u mn
. Copp er t h at b e co m e s b o u n d to so lid s will b e acco un ted fo r in th e to tal cop p e r (TCu) m easu r em en t. To im p r ov e th e und erstand i ng an d in terpretatio n of DC u resu lts, co n c en tration s o f TCu and t o tal sus p ende d s o lids (TS S) we re also assesse d.
To p r ov id e i n pu t in to U.S. EPA’s copp er BLM, a n u m b er of water q u ality p aram eters and con s titu en ts were measured for e ach water sam p le take n. T h e se includ e al k a lin ity, calciu m , salin ity (as ch lo ri d e), d i sso l ved or ga ni c car bo n , m a gnesi um , p H ( i n situ ), pot a ssium , sodi um , sulfate, and te m p erature ( in situ )

. A lth ough only the fres h water BLM wa s available at t h e onset of th is stud y, DPR measu r ed its i n pu t p aram e ters fo r all o f t

h e st u d y ’s am b i en t wat e r sam p les in an ticip atio n of t h e av ailab ility o f th e salt water BLM. Dev e l o p e rs of th e salt water BLM d i sclo sed th at sim i la r param e t e rs wo ul d be al s o be re qui redf o r

th e s a l t wat e r ver s i o n of t h e m odel ( R

. A r n o l d ., pe r s on al com muni cat i on, 2 0 0 6 )

. A su bset of sal t an d br ack ish mar in aw a ter sa m p les were as sessed for t o xicity using U.S. EPA’s m e thod for sh ort-term ch ro n i c t o x i city test on mu ssel ( Mytilu s ga llopro v in ci a lis ) embry o devel opm ent

. Si nce t h i s t e st is sen s itiv e t o co pp er, t h e results will h e lp estab lish wh eth e r lev e ls of DCu co rresp ond to sa m p le to x i city. Th e d eterm in atio n of actu al t o x i city will also b e u s efu l t o ward th e v alid ation o f th e salt water BLM.

2TIEs were u s ed to b e tter lin k ch em istry resu lts with a d verse bi ol ogi cal e ffe ct s. T I E pr oce d u r es we re conducted on a subset of toxic sam p les to con f irm th e cau s e of th e ob se rved toxicity. T I E treatm ents are designe d to selectively rem ove or neutralize classes of co mp oun d s an d th eir asso ciated tox icity to id en tify th e m o st lik ely cau se of th e tox i city. Resu lts fro m toxicity/TIE sam p les were c o m p ared t o DCu and pre di c t e d t oxi c i t y
. Th is st u d y was con d u c ted in acco rd an ce with th e Qu a lity Assu ran ce Proj ect Plan (QAPP) d o c u m en t, wh ich was p r ep ared an d approv ed p r io r t o th e on set of sam p lin g activ ities (DPR, 2 006 ).

Assum pti ons & Limita tions
C e rt ai n ass u mp t i o n s were m a de i n th e de vel opm ent o f th e study desi g n :

• A F P- p a i n ted bo ats ar e so ur ces of co pp er , zi n c , I r g a r o l, and M1 t o m a r in aw a ter s and sedi m e n ts.
• The pathways t h at introduce AFP pollutants to m arina wat e rs a n d se dim e nts are pa ssive leaching and u n d er wat e r hul l

- cl ea ni n g of AF P- pai n t e d boat s
. • AFP-p a i n ted bo ats in th e m a rin arep r esen t t h e m o st signi ficant s o urce of Ir garol a n d M1 detected in th e m arin a. C e rt ai n l i m i t a tions we re rec o g n i zed i n th e de vel o pm ent of t h e st udy desi g n :

• There are al so no n
- AF P s o urc e s o f c o p p e ra n d zi nc i n si de of m a ri nas
• DC u an d di ss o l ved zi nc (DZ n ) c once n tr at i o n s at any gi ve n si t e coul d vary ove r t i m e due t o a num ber of fact ors i n cl u d i n g t i dal i n fl ue nce, s i t e -speci fi c hy dr ol o g y , a n d fl uctu at i o ns i n t o t a l su sp end e d so lid lev e ls. Th e desig n of th is stu d y attem p ts to ad dress th ese li m i tatio n s ; howev er, th ese fact o r s may still h a v e some effects o n stu d y resu lts.

Site Selecti o n Criteria
Hu n d re ds o f C a l i for ni a m a ri nas we re e v al ua t e d u s i n g i n fo r m at i on p ro d u c e d by t h e M a ri na M a ppi ng S u bWork group o f th e Non

- Po i n t Sou r ce In teragen c y Coo r d in a t in g C o mmittee ’ s Mari n aan d Recreatio n a l Bo atin g Wo rkg r ou p. Th e poo l of cand id ate m a rin a s we re th en redu ced fro m th e larg e i n itial lis t with the use of m a ps an d appl i cat i o n o f th e f o l l o wi ng co nsi d e r at i o ns (i n desce n di n g o r de r of i m port a nce): 1) M a ri na c ont ai n s a rel a t i v el y hi gh n u m b er of s l i p s f o r

i t s wat e r bo dy t y pe. 2) Marina is l o cated in an area that receives poor fl ushing (t he likelihoo d of findi ng elevated levels of mar in a
- bor n e po llu tan ts ov er an ex tend ed per iod is h igh .) 3) M a ri nas ar e di stri but e d ove r vari ous re gi o n s o f t h e st at e.
Fo rty cand id at e m arin as rem a in ed after t h is i n itial redu ctio n. Aerial p h o t os and m o re-d et ailed m ap s were use d t o f u rt her eval uat e i ndi vi dual m a ri na l a y out s a n d rel e v a nt l o cal a n d re gi o n al ant h r o p oge ni c, ge ol o g i c, and hy dr ol o g i c featu r es. DPR st aff th e n vi si t e d m a ny of th e can di dat e m a ri nas t o gau g e c o l l abo rat i v e i n t e rest f

r om i ndi vi d u al m a rina m a nagers a n d t o di sc uss l ogi st i cal an d si t e -speci fi c c r i t e ri a wi th th em
. These c r iteria i n clude: 1) The m a ri na ow ner/ ope rat o r i s coo p e r at i v e. 2) The m a ri na ha s a boat o n -si t e th at can b e us ed fo r sam p l i ng. 3) The m a rina c o ntains slip area s that are s u fficien tly isolated from adjace nt o r surr ou nd ing sou r ces (e. g ., b o at y a rd s, i n d u stri al di s c har g es, m i ni ng di scharge s ). 4) Histo r ical and cu rren t acti v ities (e.g ., d r edg i n g , co nstru ction ) in t h e m arin a area will no t sig n i fican tly interfere with th e in terp retation o f resu lts.
Twe n ty-three marina areas were ultim ate ly chosen (T a b l e 1 a n d Fi g u r e 1)

. M a ny o f th e sel ect ed m a ri nas are locate d in the Sa n Fra n cis c o Bay Area (Figure 2).

3Ta ble 1
. List of M a rina S t udy A reas 1

Water Body County City To ta l Slips Percent Occupanc y Estima te 2 FRESHWAT ER 1) Fol s om Lak e M a ri na Fol s om Lake El D o ra do Fol s om 67 5 not a v ai l abl e 2) Tahoe Keys Marina Lake Tahoe El Dora do Lake Tahoe 25 0 10 0 3) Sacram ento City Marina Sacram ento River Sacram ento Sacram ento 54 7 97 4 ) Villag e West Marin a Sacram en to -San Jo aq u i n San Jo aqu i n Sto c k t o n 70 0 85 BRACKISH WATER 1) A n t i o c h M a ri na San J o a q ui n R i ver C ontra C o st a Ant i o c h 31 0 82 2 ) Pittsb u rg M arin a Sacram en to Riv er Co n tra Co sta Pittsb u r g 48 6 75 3) B e ni ci a M a r i na C a rq ui nez Stra i t Sol a n o B e ni ci a 32 0 95 4 ) Vallejo M u n i cip al Mari n a Mare Islan d St rait So lano Vallej o 80 0 60 SALTWATER 1 ) Clip p e r Yach t Harb or Rich ardson Bay Marin Sau s alito 73 5 90 2) Sa n F r a n ci s c o M a ri na San Fra n ci sco B a y San Fra n ci sco San Fra n ci sco 70 0 95 3) S out h B eac h Har b or San Fra n ci sco B a y W e st San Fra n ci sco San Fra n ci sco 70 0 95 4) B e rk el ey M a ri na San Fra n ci sco Bay East Alam eda Berkeley 1, 05 2 91 5) M a ri na B a y Yac h t Har b o r San Fra n ci sco B a y East C ontra C o st a R i chm ond 85 0 85 6) L o ch L o m ondM a ri na San Fra n ci sco B a y No rth M a ri n San R a fael 51 7 82 7) Ballena Isle Marina San Fra n cisco Bay East Alam eda Alam eda 50 4 75 8) C o y o t e P o i n t M a ri na San Fra n ci sco B a y W e st San M a t e o San M a t e o 56 5 85 9) Sa nt a C ruz Har b or Sant a C ruz Harb or Sant a C ruz Sant a C ruz 1, 00 0 10 0 10 ) M ont e r ey Har b or M ont erey B a y M ont erey M ont erey 4 13 8 5 - 90 11) Santa Barbara Harbor Santa Barbar a Channel Santa Barbar a Santa Barbar a 1, 13 3 95 12 ) M ari na del R e y B a si ns D, E, F M a ri na del R e y Har b or Los A ngel e s M a ri na del R e y ~ 3, 0 0 0 not a v ai l abl e 13 ) M ari na del R e y B a si ns A, B , C , G, H M a ri na del R e y Har b or Los A ngel e s M a ri na del R e y ~ 5 , 0 0 0 not a v ai l abl e 14) Alam itos Bay Marina Alamito s Bay Los Angeles Long Beach 1, 19 1 95 15) Downtown Shoreline Marina L. A. - L o ng Beach H. Los Angeles Long Beach 1, 80 0 90
1 Sour ce: Mar i na and Recr eational B o ating W o rkgr oup – M a pping Sub- W o rkgr oup 2 Per cent occupancy esti m a tes were p r ovided by indi vid u al m a rina m a nager s via e m ail sur v eys in 2007.

4Figure 1. Statewide Map of Marina Sampling Are a s

5Fi gure 2. Cl os e-Up Map of San Fr anci sco B a y A rea M a ri na S a m pl i ng Are a s

6Si nce c o p p e rl e vel s i n m a ri nas ha ve bee n do cum e nt ed t o s o m e ext e nt i n S a n Di eg o B a y , M i ssi on B a y , Oceanside Harbor, and Da na Point Ha rbor, th ese regi ons were e x cluded (Singh asem anon, 2005; Sc hiff, 2 007 ). M o reov er, th e San t a An a RW QCB i n itiated a m o n ito ring st u d y of metals in Newp ort Bay Area m a ri nas i n t h e sum m er of 20 0 6 (L. C a n d el ari a , pe rs onal c o m m uni cat i on, 20 0 6 )

. T h e r ef ore , th i s stu d y di d n o t i n clud e sites in t h e N e wpor t Bay Ar ea; ho w e v e r , f ind ing s fro m th ese stu d i es m a y b e referred to later in th is rep o rt.
DPR d o e s n o t req u i re u s e reportin g fo r m o st AFPs. Thu s , it is d i fficu lt to g e t a clear assessm en t o f lo cal and re gional us e of these pe sticides. Anec dotal evide n ce s u gge st that c o pper-base d AFPs are not as com m onl y app l i e d t o boat s i n fre sh wat e r ar eas because hard f oul i n g o r ga ni sm s (e.g. , bar n acl es, m o l l u s k s, an d tub e worm s ) , wh ich p r edomin an tly o ccurs in salt water, are not a m a jor pest c o ncern. AFPs (e .g., nonco pp er an d th i n -f il m Tef l on ® paints ) that are effecti v e a g ainst s o ft fo ul i n g o r ga ni sm s (e.g ., al gae an d aq u a tic weed s) are o f ten ad equ a te fo r use in fresh water. Furt herm ore, m a ny of t h e sm aller-sized boats that are used in fre s h water ar eas s p end a consi d e r able am ou nt o f t i m e out o f th e wat e r i n t h e of f-sea so n a n d m a y not ha ve AFPs o n t h ei r hul l s at al l

. Fi el d o b se rvat i o n s i n No rthe r n C a l i f or ni a an d con v e r sat i o n s wi th b o a ting i n du stry p r o f ession als sug gest th at co pp er-b ased AFPs are still u s ed to a lim i t ed ex ten t in fresh water ar eas. AFP u s e fo r boats m a in tain ed in salt and b r ack ish water area s tends to be hi ghe r t h an in fre sh water ar eas. In C a l i f or ni a, f oul i n g p r ess u re i s ge neral l y gr eat est on h u l l s of b o at s th at m o o r or sp en d a con s i d era b l e am ount o f t i m e i n m o re sal i n e wat e r
. Si nce t h e l a r g est m a ri nas a n d th e hi g h est am ount of AF P use occ u r s in saltwater are a s, the r e was a n em phasis on saltwaterm a rinas. F o r th e study , 1 5 s a l t w at er m a ri nas we r e chosen com p ared to four brac kish water m a rinas a n d four freshwater m a rinas.
Measure d elect rical conductivity (EC) data were usedt o det e rm i n e th e wat e r t y pes i n whi c h eac h m a ri na was l o cat ed. US GS a n d D W R gau g i n g st at i on dat aw e re ge neral l y use d t o veri fy fi el d

- crew m easured EC values

. T h ese measurem ents were com p ared to fre que n tly

- u se d ra n g es fo r EC o f t h e three water typ e s. Th e EC r a n g e s w e r e 0

– 1 , 50 0, 1 , 50 0–1 5,000 , and > 15 ,0 00 micr o Siem en s/cen ti m e ter ( μ S/cm ) fo r fresh water, brack i sh water, and salin e water, respectively. Sea water ha s an EC rea d i n g of abo u t 50 ,0 0 0 μ S/cm

. The four m a rinas situated i n t h e far nort h are aof the Sa n Francisco Bay Es tu ary (Vallejo , Ben i cia, Pittsb u r g , and An tio ch m arinas) were d i fficu lt to classi fy i n to water typ e s. Measu r ed EC d a ta at Vallej o an d Ben icia d u r ing th e stud y w e r e alm o st al w a ys ab ov e t h e 15 ,0 00 μ S/ c m EC th reshol d a n dco ul dar gua bl y be categorized as saltwater m arinas; althou gh , salin ity v a lues at th ese t w o marin a s are mu ch lower th an th o s e ob serv ed in San Fran cisco Bay Area an d co astal m ari n a s. Pittsbu rg Marin aex h i b ited salin ity th at is m o stl y in th e br ack ish r a ng e of 1 , 5 00– 15 ,00 0 μ S/cm ; howe v er, EC rea d ings there occa sionally dippe d bel o w th e f r es hwat e rth res h o l d o f 1, 5 0 0 μ S/c m
. Ev en An tio ch Marin a , wh ich exh i b ited salin ity th at is co nsid er ed t o be in th e h i gh en d of t

h e fr eshw ater r a ng e during th e en tire sam p lin g p e ri od , is d i fficu lt t o b e neatly categorized. T h e a n nual salinity profi l e from a g a ug i n g statio n d a ta ( CD E C, 200 8) n ear th e An tioch marin ashows t h at its salin ity lev e ls are in t h e br acki s h ran g e ab out si x m o n ths of t h e y ear
. For th e p u r p os e o f a n al y s i s and di sc ussi on , we have cl assified brac kish water m a rinas as those m a rinas that are ex po sed to salin ity th at is in th e brack ish EC r a n g e du r i ng so m e p a r t of th e year
. Th us, V a llejo , Ben i cia, Pittsbu rg , and An tioch m a rin a s are co nsid ered brack ish in n a ture.
Local R e fe re nc e Si t e s (LR S s) fo r eac h m a ri na we re i d e n t i f i e d t o hel p det e rm i n e whethe r conce n tr at i o ns of co pp eran d zinc in sid e of the mar in aw e r e attr ib u tab le to l o cal b ackgr oun d con cen t r atio ns, wh ich w e r e m easuredj u st out si de of eac h m a ri na. M a ri na ow ne rs, o p e r at or s, m a nage rs, a n d doc k m a st ers a n dharb or m a st ers (these i ndi vi dual s wi l l be c o l l ect i v el y refe rre d to f r o m here f o rth a s m a rina m a nagers ) were co nsu lted to d e termin e th e b est lo catio n s fo r th ese LR S sites at th eir resp ect iv e m arin a areas. LR Ss were in itially id en tified with th e marin am a n a g e rs’ h e lp an d th en selected b y DPR staff using th e fo llowing cri t e ri a (i n de s cendi ng o r der of i m port a nce) : 1) Th e site was l o cated ou tsid e th e influ e n ce of m a rin aactiv iti es and po ten tial sou r ces of AFPs, b u t adjace nt t o the marina area and with in t h e same b o d y of water. 2) The site was s u fficiently isolated from potent i ally co n f o und in g inp u ts ( e .g ., bo atyar d s, indu str ial

7di scharge s , a n d vari ous hi st o r i cal co nt am i n at i on)

. 3) Recent and c u rrent activities (e.g ., dre d ging, construction) i n the immediat e area woul d not sig n i fican tly interfere with th e in terp retation o f resu lts. 4) The si t e c ont ai ned u n d erl y i n g sedi m e nt that can be c o llected a n d analyze d

. 5) There wa s s u itable and safe a ccess to th e sit e
. The e x act locat ions of the LR Ss we re determined on t h e first day of sam p ling at eac h m a rina when the field crew we re a b le to e v aluate sit e -speci fic conditions

. On ce LRSs were d etermin ed in t h e first sam p lin g r oun d, th ey w e r e r e sam p led in th e seco nd an d th ird r oun d.
Mo re d e tailed i n fo rm atio n on th e stud y m a rin a s, in clud ing t h e descri pt i o n, hi st ory , an d Gl obal Po si t i oni n g Sy st em (GPS ) l o cat i ons can b e f o u n d i n A p p e ndi x A. M a ri na m a nagers p r ovi dedth i s m a ri na- s peci fi c inform ation vi a an em ail survey co ndu cted i n 2 007

. Su rv ey r e spon ses greatly aid e d D P R in th e in terpretatio n of stud y d a ta.
Sampling Ves sels Large rm a ri nas t e nd t o ha ve at l east o n e vess el fo r use by m a ri na st a ff. Du ri n g th e si t e sel ect i on pr ocess , DPRst af f e s t abl i s he d ver b al agreem ent s wi t h eac h m a ri na m a nager t o ve r i fy hi s or he r i n t e rest i n p a rticip ating in th e st u d y
. DPR staff also con f irm e d th e availab ility o f a sa m p lin g v e ssel and an o p e rator with the m a rina m a nager. In the case of the two L ong Beac h m a rinas, the City of L o ng B each life guards pr o v i d e d t h e n ecessary vessel s an d o p erat o r s t o m a ke sam p li ng at th ese l o c a t i ons p o ssi bl e
. DPRst af f e s t abl i s he d a sam p l i ng sc he dul e t o c o o r di nat e m a ri na vi si t s wi t h eac h m a ri na m a nager an d h i s or her st aff

. DPR ’ s sam p l i ng c r e w , w h o are bas e d i n Sa cram e n to , CA, tran spo r ted all n ecessar y supp lies an d sam p lin g equ i pmen t to each sa m p lin g site.

Samplin g Method and Fr eq uency Tabl e 2 pr ovi d e s an o v er vi ew o f th e sam p l i ng sc hem e and s a m p l i ng fre q u e n ci es. Whe n d e vi at i ons f r om th e o r i g i n al m oni t o ri ng pl a n o ccur r ed , th e pl anne d n u m b er of sam p l e s are sho w n i n pare n theses. T h ese devi at i o ns ar e not e d a n d di sc usse d th r o u g h o u t th i s M a t e ri al s an d M e th o d s Sect i on.

823451Table 2. SamplingScheme and NumberofSamplesTakenRound 1Round 2Round 3WaterWaterWaterSedimentSampling LocationWater Type1AbbreviatedSiteIDMetals/BLM2Irgarol/M1Metals/BLM2Toxicity/TIEMetals/BLM2Irgarol/M1Metals,TOC3, GrainSize4Irgarol/M1Folsom Lake MarinaFFL1 to FL88887(8)5Tahoe KeysMarinaFTK1 toTK8880(8)0(8)Sacramento City MarinaFSA1 to SA88888VillageWest MarinaFVW1 to VW87 (8)888Antioch MarinaBAM1 to AM88880(8)Pittsburg MarinaBPM1 to PM88284820(8)0(2)Benicia MarinaBBM1 to BM88284820(8)0(2)Vallejo Municipal MarinaBVM1 to VM88284820(8)0(2)ClipperYacht HarborSCY1 to CY88880(8)San FranciscoMarinaSSF1 to SF88284820(8)0(2)South Beach HarborSSH1 to SH88284820(8)0(2)BerkeleyMarinaSCB1 to CB88284820(8)0(2)Marina BayYacht HarborSMB1 to MB86(8)26(8)46(8)20(8)0(2)Loch Lomond MarinaSLL1 toLL88284820(8)0(2)BallenaIsle MarinaSBI1 to BI8828481(2)0(8)0(2)Coyote Point MarinaSCP1 to CP8880(8)0(8)Santa CruzHarborSSC1 to SC88880(8)MontereyHarborSMH1 to MH88880(8)Santa Barbara HarborSSB1 to SB88880(8)MdR Basins D,E, F(BackBasins)SBB1 to BB444(2)4442(2)0(4)0(2)MdR Basins A,B, C, G, H (FrontBasins)SFB1 to FB88880(8)Alamitos BayMarinaSAB1 to AB88284820(8)0(2)Downtown Shoreline MarinaSDS1 to DS880(2)8480(2)0(8)0(2)Total177(180)24(24)178(180)48162(180)21(24)23(180)0(24)Sampling sites located in F: Freshwater; B: Brackishwater;S: SaltwaterMetals and BLM parametersinclude: DCu,TCu,DZn,TSS,DissolvedOrganic Carbon (DOC),Salinity (Cl),Sulfate,Alkalinity,Mg,Ca, Na, andK.TOC= Total Organic CarbonForsediment samples,metalsparametersinclude TCu and TZnNumbersin parentheses indicate the numberofsamples planned in the original sampling plan.9Marina Sites - Copper, Zinc, TSS, an d B L M

- A ssoci at

ed Par a met e rs
Wat e r a n d se di m e nt sam p l e s were t a ke n by boat fr om fo ur poi nt s wi th i n e ach of th e 2 3 m a ri nas f o r

D C u, DZ n, TC u, TSS, and BLM-ass o ciated param e ters. W a te r sa m p les were col l ected about once a m onth at e ach site ove r a three-m onth pe riod.
Sed i m e n t sa m p les were on ly co llected in th e th ird sam p lin g roun d. Sed i m e n t sam p les were co llected after water sam p les at each sam p ling point t o hel p m i nimize co ntamination of the wate r sam p les. No te t h at sedim ent sa m p les were only co llected fro m th ree freshwater m arin a sites (Fo l so m Lak e Marin a, Sacramen to Marina, an d Villag e West Marin a). C onsi d erat i o n of safet y a n d l ogi st i cal co nce r ns res u l t e d i n th e deci si on t o not c o l l ect sedi m e nt sam p l e s for th e rem a i n i ng 20 m a ri nas as was pl an ne d i n th e o r i g i n al m oni t o ri ng pl a n a n d QA PP.
Past m oni t o ri n g st udi es o f c o ppe r i n m a ri nas su g g est e d th a t co pp er lev e ls in bo th water an d sed im e n t te n d to b e h igh est near the ar ea of m oore d vesse ls and lowest t o ward the en tran ce o f th e m a r i n a ( S D RW Q CB, 20 05 ; Pap , 20 04)

. Mar i na sam p ling sites were there f ore located i n area s where ve ssels were m o o r ed

. To m a in tain site-to

- site con s isten c y and to ens u re t h at sa m p l e s t a ken w e re not t o o cl os e t o boat h u l l s , DPR st af f c h os e sam p l i ng si t e s th at were l o c a t e d neart h e c e nt er of the fairway (comm on term for t h e c h anne ls betwee n t h e doc ks ) a n d adj acent to th e m i dway point of the doc k/pie r structure (see Figure 1, bel o w). Figure 3. Di agram of Sampli ng L o c a tions i n a Marina

L a nd D o c k s l i p s l i p
s l i p

D o c k D o c k D o c k D o c k X X X X

M a r i n a E n tr a n c e O p en W a t e r X = S a m p l i n g p o i n t is m i d d le o f f a i r w a y an d a d j a c e n t t o m i d - p o i n t of d o c k

Although each marina has a unique layout of docks a n d slips, DPR staff i d entified t h e ca ndi date fai r wa ys at each m a rina using m a rina l a yout diagram s and assi gne d num b ers to t h e fairways. Four fa irways we re random l y chos en in each m a rina as sam p lin g sites. Fairways th at were adj acen t to do cks w ith less th an 50% of th ei r slip s filled d u ring t h e first sam p lin g r oun d w e r e n o t selected an d an o t h e r f a irw a y w a s cho s en usin g th e sam e sel ectio n cr iter ia.

10To precisely re locate sam p ling sites duri ng subseque nt rounds, each sam p li ng location wa s initially identified using a GPS u n it to m a rk the ex act latitu d i n a l and l o ng itud i n a l co ord i n a t e s. Fiel d cre w also rec o rde d t h e ide n tification num bers of adjace nt docks

. If a m a rina or sam p ling site was i n accessible during a re vi sit, the sam p ling e v ent was res c heduled wit h in t h e s h o r t e st p o ssi bl e t i m e of th e ori g i n al sc h e dul e d dat e
. Marina Sites - Irgarol/M1

Wat e r sam p l e s we re c o l l ect ed f o r Ir garol a n a l y s i s from 12 o f th e 2 3 st udy m a ri nas. H o l d i ng t i m e constr ai nt s an d s h i p p i ng sche dul es l i m i t ed whi c h m a ri nas t h e DPR fi el d cre w c o ul d sam p l e for Ir garol

. T h e 12 ch ose n m a ri nas ar e i d e n t i f i e di n Tabl e 2.
The DPR field crew collected two s a m p les from each m a rina in the first and thi r d sam p ling rounds

. The first two sites with in t h e m a rin ath at were iden tified for t h e sam p lin g of co ppe r , zi nc, T S S, a n d BLM-as sociated parameters we re c hosen as Irg a ro l samp lin g sites.
In the st udy m onitoring plan, sedim e nt sa m p les were origi n ally to be c o llected from each of the 12 m a rinas during t h e third sam p lin g round

. Du e t o th e in ab ility o f fiel d crew to co llect sed i m en t sam p les at th ese lo catio n s , n o sed i m en t sa m p l es were t a ke n f o r Ir gar o l /M 1 a n a l y s i s
. Ma rina Sites - Tox i city a n d TIEs

Wat e r sam p l e s we re c o l l ect ed f o r t oxi ci t y t e st i ng fr om a sub s et of m a ri nas. Fo ur sam p l e s were t a ke n f r o m th e sam e 12 m a ri nas sel ect ed fo r Ir gar o l sa m p li ng (agai n due t o shi ppi n g c o n s tr ai nt s) i n th e sec o n d sa m p li ng ro u n d

. A t oxi ci t y samp l e was taken from each of t h e four sam p ling s ites within t h e marinas that were ide n tified for the sam p ling of copper, zinc, TSS, and BLM

- associated para m eters.
T I E p r o c ed ur es w e r e co ndu c t e d o n s e l ected toxic m arina water sam p les.
Lo ca l Reference Sites - C o p

p er, Zinc, TS S, an d B L M

- A s s o ci ated P

a ra m e te rs
Wat e r a n d se di m e nt sam p l e s were t a ke n by boat at

t

h e fo u r LR Ss o u t s i d e of th e sel ect e d m a ri nas. Wat e r sam p l e s were collected a b out once a m ont h at each site ove r a t h ree
- m onth peri od.
A limited nu mb er of sed i m en t sam p les wereco llected i n the th ird sam p lin g roun d. Recal l that the DPR field cre w we re o n l y ab le to collect sed i m en t sam p les fro m three freshwate rm a rina sites (Folso m Lake Marina, Sacra m ento Marina, and Villag e West Marin a ). Safety an d log i stical con cern s preven ted sed i m e n t sam p lin g at all 23 m a rin a s as o r i g in ally ou tlin ed in the m onitoring pla n
. Whe n sedim e nt sampling wa s done , it took place a f ter the collection of water sa m p les at each sam p lin g site to m i n i mize con t amin atio n o f th e water sam p les.
The field c r ew determ ined s p e c ific LRSs duri ng the first sa m p ling visit to each m arina. The c r iteria listed unde r the Si te Selectio n C r iteria sub-sectio n were u s ed t o determin e th e si tes.
Lo ca l Reference Sites - Irga r o l

, Tox i city, and TIEs

No sam p les were tak e n at LRSs fo r Irg a ro l, t o x i city, and TIE an alysis.

Sa mple Co llectio n - Water
Water sam p les we re c o llected from approxi m ately one m e ter be l o w the water s u rface. Schiff et al. (2007) doc um ented a dept h- rel a t e d g r adi e nt f

o r

co p p er i n m a ri nas wi th th e hi gh es t conce n tr at i o n s nearth e s u r f a ce. F u rtherm ore, t o a voi d AF P co n t am in atio n fro m th e sam p l i n g v essel itsel f, sam p les were tak e n ap p r o x i m a t e ly t w o m e t e rs f r om th e si de of t h e boat

.

11Th e water samp lin g app aratu s con s isted of a b a ttery-op e rated p e ristaltic pum p th at d r aws water t h ro ugh p o l yeth ylen e tu b i ng and d e po sits it d i rectly in to a co llectio n con t ain e r. On th e i n let end , t h e tub i ng is attach ed to a lo ng p l astic ex tend ab le po l e , wh ich allo ws for greater freedom of m ove m e nt and reac h.
Fo r m e tal sa mp les, U.S. EPA- certified, p r e-clean ed 25 0-ml p o l yeth ylen e p l astic bo ttles were u s ed

. For Irg aro l/M1 sam p les, U.S. EPA-certified, p r e-clean ed 1

- L am b e r g l ass b o ttles were u s ed

. Fo r TSS an d BLM-asso ciated p aram e te r sam p les, 2 5 0

- ml p o l yeth ylene bo ttles were u s ed

. For t o x i city sa m p les, 1-L p o l yeth ylene con t ain ers were u s ed.
Sam p l e s for D C u, DZ n, m a gnesi um , cal ci um , sodi um , an d pot assi um , anddi ss ol ve d o r gani c car b o n ( DOC ) a n al y s es we re filtered with an in -lin e 0.45

- μ m filter and the n acidi fied with Op tim a® u ltra-p u re n itric acid to a pH level o f < 2

. 0

. Sam p les fo r sulfate, ch l o ri d e, an d alk alin ity an alyses were si m p ly filtered (no sub s equ e n t acid i ficatio n). Sam p les for TCu an alysis were si m p ly acid i fied (n o filtratio n prio r to aci d i fica tio n )

. Sam p le s fo r TSS, Irg aro l/M1 , and t o x i city/TIE an al yses were no t filtered n o r aci d i fied.

Sample Collection - Sedime nt
Sedim e nt was collected using a Va n Vee n ® g r ab s a mp le r
. T h e j a w s an d do or s ar e co a t e d w ith T e f l on ® to p r ev en t contam ination from the sam p ler. Each gra b satisfi ed th e follo wing criteria to b e co nsid ered v a lid :

• Co m p lete clo s u r e of th e samp ler

• N o ev i d en ce of sign if ican t sedi m e n t w a shou t th ro ugh th e doo r s
• M i nimu m di stur ba nce of t h e sedi m e nt surfa ce Th e ov erlying water i n th e sam p ler was first drain e d b y s lig h tly op en ing t h e sam p ler su ch th at t h ere was m in i mal di stur ba nce of th e fi ne- g rai n e d t o p l a y e r o f s e di m e nt

. The t o p 2 cm of se d i m e nt were t h e n c o l l ect ed wi th a cl ea n Te fl o n ® coated scoop a n d place d int o a 4 oz., U.S. E P A-c ertified, pre-cleaned pol y ethylene co nt ai ner. T h i s c o l l ect i on p r oced ure was rep eated un til su fficien t sed i m e n t h a d b e en co llected to fill th e sam p le co n t ain e r.
Field Qua lity Assura nce/Qualit y Co nt ro l
Fi el d bl a n k s a n d e qui pm ent ri nse bl an ks (f r o m here o n re fer r ed t o as ri nse bl an ks) we re t aken t o a ssess p o t e nt i a l co n t am in atio n o f water sam p les in t h e fiel d

. Field b l ank s we re co llected by fillin g sam p le con t ain ers wi th d e -ion ized or d i stilled water at th e site of collectio n
. Rinse b l ank s were co llected b y ru nn ing d e -i o n i zed o r d i stilled water th rou g h t h e identical sam p ling ap parat u s t h at wa s used to co llect env i ron m en tal sa m p l es. Rinse b l ank s were tak e n after th e sam p lin g apparatu s ha d been cl eane d a t l east once th r o u g h th e sam p l i ng e v e n t

.
Sample H a ndl ing and Custody
Sin ce low (p art s p e r b illio n ) co n cen tration s of m etals in th e wa ter sam p les are ex p ected in th is stud y, sam p le co llectio n an d h a nd ling fo llowed U.S. EPA Meth od 1 669 –Sam p lin g of Am b i en t W a ter fo r Trace Metals at U.S. EPA Water Qu ality Criteria Levels (U .S. EP A, 1 9 96a ).
All sam p les were tra n s p orted in c oole r s with ice. Glass cont ainers we re placed in pre-form ed styrofoa m packs to m i nim i ze chance of bre ak age
. After tra n sport, sam p les we re refrigerated and store d at 4 o C u n til extractio n o r ch emical an alysis. Irg a ro l an d toxicity sa m p les were immed i at ely sh ipp e d to t h ei r res p ective analytical laborato r ies du e t o sh or t h o l d ing time requirem ents. These sam p les were care f u l l y packe d a n d s h i ppe d (th r o u g h th e U n i t e d Par cel Ser v i ce) i n st y r of oam packs and wel l

- i n sul a t e d co ol ers wi t h bl ue i ce. S o m e t oxi ci t y sam p l e s were pi c k ed u p di rect l y by t o xi ci t y -l ab orat ory pers o n n el

. Each sam p l e h a d a n acc om pany i n g D P Rc h a i n- of -cust ody f o rm , w h i c h c o nt ai ns sam p l e col l ect i on a n d i d ent i f i cat i o n in fo rm atio n as well as sam p lin g track i ng info rm atio n
. All i n d i v i d u a ls who co m e in to con t act with t h e sa m p le b o ttles were requ ired to sign an d d a te t h e form to ack nowledg e th ei r han d ling of th e sam p les.

12Sa mple Ana l ysis
Du e to t h e v a ri ety o f an alyses n e ed ed fo r th i s stud y, DPR u tilized sev eral l ab o ratories for th e an alytical work. A su m m ary o f

an alytical meth od s and th ei r citatio n s are p r ov id ed in th e sub s eq u e n t sub

- section s
. Water Sa m p les - C o pper , Zinc, T SS, an d BLM-Associ ated P a r

a meters
Th e Un iv ersity of Californ i a, Dav i s, Agricu l t u r e and Natu ral Resources (ANR ) Analytical Lab o rat o ry a n aly zed water sam p l e s for D C u, TC u, DZ n, TSS, m a gnesi um , cal ci u m , sodi um , pot assi um , sal i n i t y (as chl o ri de ), sul f at e, an d al kal i n i t y
. Not e t h at m a gnesi um , cal ci um , sodi um , pot assi um , chl o ri d e , s u l f at e, a n d al kal i n i t y are a l so m easured a s di ss ol ve d co n c en tration s
. The A N RLa b o rat o ry use d th e f o l l o wi ng m e th o d s (See A p pen d i x B f o r c o m p l e t e m e thods):

• ANR M e t h o d 83 7 wi th q u ant i fi cat i on by G r aphi t e F u rn ace Atom ic Abs o r p tion S p ectr o m e try (G FA AS ) fo r DCu.

• ANR M e th o d 89 1 wi t h q u ant i fi cat i on by G F AA S f o r TC u.
• ANR M e t h o d 87 0, em pl oy i ng gra v i m etri c anal y s i s f o l l o wi ng o v e n dry i n g f o r TSS.

• ANR M e t h o d 83 5 f o r DZ n, c a l c i u m , m a gnesi um , pot assi u m , sodi um wi t h qua nt i fi cat i o n by fl am e At o m i c Abs o rpt i o n, E m i ssi on S p ectr o m e tr y (AAS , AES ) , or I n duc t i v el y C o u p l e dPl asm aAt om ic Em i ssi on Sp ectrom e tr y (IC P

- AE S) de p e ndi ng o n t h e a n al y t e.
• ANR Met h od 8 8 0 , an ion ch ro m a to g r aph y co ndu ctiv ity m e th od for ch lorid e an d su lfate
DPRa n al y zed wat e r sam p l e s fo r DOC usi n g EPA M e th od 41 5. 3 (U .S. EP A, 2 0 0 5 )

. A s u m m a ry of t h i s m e thodcan al so be fo u nd i n A ppe ndi x B

. Wa ter Sa mp les - Irga ro l/M1

NO A A ’s H o llings M a ri ne La bo rato ry ( H M L ) in Cha r lesto n , So uth Carolina, a n alyzed water sam p les for Irgarol (als o know as Ir g ar o l 10 51 or 2

- m e th ylth i o -4

- tert

- b ut y l am i no- 6-cy cl o p r o p y l -am i no- s -tr iazin e ) and M1 ( a lso kn own as G S 26 575 o r 2­ meth ylth io -4- tert -b ut y l am i no-6 -am i no- s -tri a z i n e) usi n g a hi gh pe rf o r m a nce l i qui dch r o m a t o g r ap hy el ectro sp ray i o ni za t i on t a ndem m a ss spectr o m e tr y m e th o d as p u b l i s hedi n Th om as ( 2 0 0 2 ). A s u m m a ry of th i s m e thod i s p r es ent e d i n Ap pe n d i x B

. Wa ter Sa mp les - Tox i city a n d TIEs

Th e Sou th e rn Califo r n i a Co astal W a ter Res earch Proj ect’s (SCC W R P’s) lab o rato ry i n Westm i n s ter, Califo r n i a, test ed salt an d brack i sh water sam p les for su b-ch ro n i c dev e lop m en tal t o x i city on t h e mu ssel Myd u lis ga llop ro v i n cia lis base d o n m e t hods i n E P A/ 6 00/ R

- 9 5 / 1 3 6 (U. S

. EP A, 1 9 9 5 ). SC C W R P ’s c o m p l e t e t oxi ci t y m e t hod i s p rese n t e d i n A ppe n d i x C

. Thi s test m easu r es t h e redu ction in th e mu ssel’s ab ility to d e v e lop fertilized eg gs after a 4 8 -hou r expo sure t o water sam p les. Sam p les with salin ity co n c en tratio n s of less th an 30 g / kg were ad ju sted usin g h y p e rsalin e b r i n e. Th e tests were co ndu cted in glass s h ell vials containi ng 10 mL of s o lut i on at a tem p erature of 15°C

. Four re plicates we re tested for each sam p le. A seawater b l ank was i n clud ed as n e g a tiv e con tro l. A cop p e r referen ce t o x i can t test was inclu d e d as po sitiv e con tro l.
Aft e r a 48

- h o u re x p o s u re pe ri od , th e em bry o s we re prese r ved a n d exam ined with a m i cr osc ope t o as ses s n o rm al devel opm ent. The data a r e presented as p e rcen t norm a l-aliv e, wh ich was calcu l ated as t h e num b er of norm al e m bryos after ex po su re relativ e to th e nu m b er o f fertilized eg gs ad d e d at t h e b e g i n n i n g of th e expo sure. Sam p les were con s id ered toxic if th e di ffe rence bet w ee n m ean perce n t no rm al de vel o pm ent of th e sam p l e a n d th e c o ntr o l was st at i s t i cal ly si gni fi ca nt a n d i f th e sam p l e ’s m ean perce n t no rm al devel opm ent wa s less t h an 80% whe n c o m p ared t o the control.
SC C W R P al s o pe rf orm e d f o l l o w u p TIEs o n a s ubset o f t o x i c sam p l e s based on m e thods fr om EPA/ 6 00/ R

- 9 6 / 0 54 ( U

. S

. EPA , 1996 b)

. SCC W RP’ s Phase I TI E m e th o d is also pr esen ted i n A p p e nd ix C

. Th e t o xicity th r e sho l d th at tr igg e r e d a TIE was 50 % ab norm al e m b r y o d ev el o p m en t relativ e to contro l.
Sediment Sam p les - Copper an d Zinc

U CD AN R an alytical lab o r ator y an alyzed sed im e n t sa m p le s fo rt o tal copper(TCu) an d to tal zin c ( T Zn ) u s i n g AN R meth od

1339 0, w h i c h rel i es o n a n al y s i s by at om i c abso rpt i o n s p ectr o m e tr y
. In th e s tudy m oni t o ri n g pl an, D P R w a s t o a n al y ze s e di m e nt sam p les f o r grain size an d to t a l o r g a n ic carbo n ( T O C) using D P R m e th o d SOPMETH 00 4.00 ( D ietr ich, 200 5) and SOPMETH 0 0 5

. 00 ( G un asek ar a, 2 006 ) , re spect i v el y
. H o we ve r, DPRd eci ded t o not p r o cee d with grain size a n d T O C a n alyses due to li mited sed i m e n t sam p les th at were co llected

. Sedi ment Sa m p l

e s - Ir gar ol

/ M

1

In th e m oni t o ri ng pl a n , N O A A ’s HM L i n S out h C a r o l i n a was t o a n al y ze a su bset of samp l e s f o r I r g ar ol an d M 1 usi n g an accelerated s o l v ent e x traction liquid chro m atography - tande m m ass spectrom etry m e thod. Howe ver, DPR deci ded to not pr ocee d wi th t h e a n al y s i s o f I r garol i n se di m e nt d u e t o lim ited se dim e nt sam p les that were collected. .
The a n alytical param eters m e asure d , the m e th od s u s ed , and th e m e th o d d e tectio n limits a s rep o rted b y th e an alytical lab o rato ries are listed in Tab l e 3

. T a bl e 3. Sum mar y of An al yti c al Me th od s an d Detec t i o n L i mi ts (B L M
- a ss oci a ted par a meter s pr esented i n gre y )

An al yt es An alytic al Me tho d Met ho d D e tec t ion Limit ( M D L) or Limit of De tec t ion (LO D ) Di ssol v ed C o p p er ANR 8 37 0. 1 μ g/L Di ssol v edZi nc ANR 8 3 5 1. 0 μ g/L Ir gar o l Th om as, 20 02 1. 0 ng/L M 1 Th om as, 20 02 1. 0 ng/L Tot a l C o pp er ANR 8 91 0. 1 μ g/L To tal Su sp ended So lid s ANR 87 0 4 m g /L Dissol v ed Organic Carbon EPA 41 5.3 50 μ g/L or 5 0 m g /L * Ch lo ri d e (Salinity) ANR 8 80 0. 5 m g/L Sulfate A N R 88 0 0. 5 m g/L Alk a lin ity ANR 8 20 2 m g/L M a gnesi um A N R 83 5 0. 5 m g/L Calciu m A N R 83 5 0. 5 m g/L So di um ANR 8 35 0. 5 m g/L Potassium ANR 8 35 0. 5 m g/L Tot a l C o pp er ( s edi m ent ) ANR3 90 1 m g / kg ( d ry wei g ht ) Tot a l Zi nc (se d im ent ) ANR 3 90 1 m g / kg ( d ry wei g ht ) To xi ci t y EPA/ 60 0/ R

- 95 / 1 3 6 N/A To xi cant I d e n t i fi cat i on Eval ua t i on EPA/ 60 0/ R

- 96 / 0 5 4 N/A * T w o possible detection lim its depending o n the catalyst used.
Th e fo llowing in -situ field m easurem ents (s ome of which ar e re quire d for t h e BLM) we re collected using a variety of meter s an d appar a tu s:

• Water Dep th (v ari o u s bu ilt-in d e p th find er of sam p lin g b o a ts)

• Dissol v ed O x y g en ( D O ) (Y SI m e ter, m odel 85 )

• Electrical Co nd u ctiv ity (EC) (YSI m eter, mo d el 85 )

• p H (I Q Scien t if ic In stru m e n t )

• Tem p erature (YSI m e ter, m odel 85)

• Tu rb id ity (LaMo tte co lorimeter, m o d e l Smart II) During sam p lin g ev en ts, in form at io n o n site-sp eci fic activ itie s an d fact o r s (e.g ., activ e con s tru c tio n activ ities, po ssi b l e un de r wat e r hu l l

- cl eani n g o p e r at i ons , weathe r c o n d i t i ons ) w a s rec o r d e d

.

La borato ry Qua lity Assu r a nce/Quality Control
DPR requ ires th at an alytical lab o ratori es mu st co m p ly with a m i n i mu m st an d ard o f qu ality assu ran ce/qu ality co n tro l ( Q A /Q C) per D P R Stand a rd O p er ating Pr o c ed ur e nu m b erQ A Q C.0 01 .00 an d stud y Q A P P (D PR, 200 6).

14Earl y i n th e stu d y p r e p arat i o n st age, l a bo rat o ri es val i d at e d m e thods usi n g th e ap p r o p ri at e en vi r onm ent a l sam p l e m a tr i c es (e.g ., fresh wat er, salt water, sed i m en t ) o rt h ey altern ately p r o v i d e d do cu m e n tatio n t h at illustrated th e accu r acy and preci si o n o f th e m e thod s. Se e A ppe n d i x D fo r m e thod val i dat i on res u l t s fo r ANRLab o r at ory m e th o d s
. For o n goi n g Q A / Q C , l a b o rat o ri es em pl oy ed a vari et y of Q A / Q C sam p l e s as co nsi s t e nt w i th th e st udy Q A PP

.

Statistica l Ana ly s is
DPRst af f ge ne rat e d desc ri pt i v e or sum m ary st at i s t i c s t o he lp cha r acterize the res u lts. Va rious param e tric and nonparam e tr i c t e sts we re use d t o det e rm i n e whe ther di f f ere n ce s bet w een o ra m ong g r ou ps e x i s t e d. T o e x p l ore rel a t i ons hi ps b e tween d a ta group s, correlatio n an alysis wa s use d

. MINIT A B (Version 15) statistical software for statistical analysis and rel a t e d pl ot s w a s use d

. The Ry an -J oin e r a n d A n ders o n
- D arlin g tests we re used to t e st t h e no rm al it y of c o ncentr a t i on data. The s e tests indicated that the c o ncentrations of c o pper, zinc , a n d the rest of t h e st udy a n alytes were l o g- n o rm all y di stri but e d

. There f ore, su mm ary stat is tics were calculated u s i n g th e lo g-transfo r m e d d a ta. For e x a m ple, the 95% confi d ence i n tervals (C Is) were cal cul a t e d f r o m l og-tr a n s f o r m e d dat aa n d t h en bac k t

r ans f orm e d t o ori g i n al u n i t s
. Th u s , th e C I s ar e fr eque nt l y asy m m e tr i c
. Sim ilarly, the geom etric m e a n (instead of a n ar ithm etic mean) was the preferred estim a t e of the cent r al tende ncy a n d use d as th e basi s fo r co nd uct i n g hy pot hesi s t e st i n g t o det e rm i n e i f di f f ere n ces e x i s t am ong gr o ups
. Fo r si m p l i c i t y , th e ge om etri c mean is ro u t i n ely referred to in th is report as th e m e d i an
. No te, howev er, th at m a n y o f t

h e b oxp lo ts u s ed in th is report d i sp lay m e d i an lin es th at d e n o te th e 50 th p e rcen tile v a lu e of th e un tran sformed d a ta set. Th ese lin es are in tend ed to h e lp reade r s visuali ze the relative distr i bu tio n of th e un tr an sf ormed d a ta. Th e m e d i an v a lu es th at th ese lin es rep r esen t are b a sed th e m i ddl e val u e (o r ar i th m e ti c m ean o f th e m i ddl e t w o v a l u es fo r a n e v e n -n um bered dat aset ) of th e s o rt ed, u n tr a n sf o r m e d dat aset

. He nc e, th e m e di an v a l u es gene rat e d fr om th e t w o ap pr oac h es m a y not be i d e n t i cal

. I n th e en d, al l th e calcu latio n s and statistical tests in th is re po rt are base d on th e geom etric mean.
The four sam p les take n insi de each m a rina and the four sa mples take n for e ach LRS area duri ng each sampling eve n t rep r ese n t e d s u b-sam p l e s f o r

t h at part i c ul ar m a ri na an d LR S area

. In con t rast, th e three sa m p lin g ev en ts are con s id ered to b e rep licatio n o v e r tim e. Th e latter assu m p tio n is su ppo rte d by a n alyses of va riance (ANOVA) res u lts for DC u conce n tr at i o ns (an d si m i l a rl y fo r TC u, DZ n, andTS S) o v er th e th ree s u m m e r-m onth p e r i od t h at i n di cat ed no tr e nds o r m a jor cha n ge i n m a ri na m e dian c once n tr at i o ns.
Tw o A N O V A t e st s were co n duct e d fo r DC u, TC u, D Z n a n d TSS

. A o n e
- way AN O V A was use d t o t e s t fo r th e ef fect of wat e r b ody t y p e (i .e. , sal t , bra c ki sh , a n d f r es hwat e r) o n a n a l y t e conce n tr at i on dat a fr om the i n si de of m a ri nas. T h ese ANOVAs we re conducted wi th m e dian anal yte conce n trati ons from each sam p ling eve n t within a m a rina because t h e det e rm i n at i on of su b- sam p l e s ve rsus true rep l i cat es, as di sc usse d a b o v e. A sec o nd A N O V A was al s o con d u ct ed t o t e st fo r th e ef fect of t h e fact o r s of i n d i vi dual m a ri na, sam p l i ng l o cat i on (i nsi d e ver s us o u t s i d e t h e m a ri nas), an d s a m p l i ng e v e n t on analyte concentrations. T h is fu lly-n ested balan ced ANOVA was co ndu ct ed with in ea ch water type wit h m a rinas as t h e hi g h est nest i n g fact o r , f o l l o we d by i n si de ver s us o u t s i d e (i .e ., m a ri na ve rs u s LR S) , a n d th en sam p l i ng e v ent ( 1 st , 2 nd , and 3 rd ). A lev el of sign ifican ce ( α ) o f 0. 0 5 was use d f o r al l hy pot hesi s t e st i n g.
No te t h at resu l t s fro m Tah o e Keys Mari n aan d Co y o te Po in t Marin a were o m it ted fro m th e fu lly-n ested b a lan c ed ANOVA si nce sam p l e s f r om onl y t w o o u t o f t

h e th r ee events we re c o llected at these two site s. Ex clu s ion o f t

h ese d a ta allo wed the ANOVA tests to rem ain bala nced. On rare occasions, one or two sam p le results were m i ssing for a part icular e v ent. Whe n th is o c cu rred , t h e m i ssin g v a l u es were filled in using su bstitu tio ns b a sed on th e av erag ing o f th e resu lts of related su bsam p les from the sam e event. Only a sm all percenta ge of re sults we re below detection, thus t h e m e thod detection lim it value was use d as a s u bstitute for non-detects when m ean estimates were nee d ed for g r aph i cal d i sp lay. Fo r h ypo th esis test in g , th e v al u e t h at is 1⁄2 o f th e m e thod detection lim it was us ed as a s u bstitute for non-dete cts.

15Predictive Toxicity Models Th ree co m p u t er m o d e ls, wh ich p r ed ict th e t o x i city o f cop p e r b a sed on site-sp ecific water q u a lity d a ta, were u s ed fo r th i s study. T h ese ar e the freshwat er BLM, t h e DOC m o d e l, an d th e saltwat e r BLM. DPR’s staff use d the freshwater BL M to ev alu a te freshwater d a ta an d th e saltwater BLM to ev alu a te saltwater d a ta. Dep e n d i n g on th e site-sp ecifi c water qu ality ch aracteristics o f brack ish water sites, th ei r d ata were u s ed ineith er th e fresh water o r saltw ater BLM. The DOC m odel is usef ul fo r th e e v al uat i o n of sa l t and b r acki s h wat e r dat a
. B i ot i c Li ga nd M odel - F res h w at er In 2 0 0 7 , U .S. EPA i s s u e d re vi sed nat i o nal recom m ended fres h water aq uatic life criteria fo r cop p e r (U.S. EPA, 200 7). Th e revi se d c r i t e ri a u pdat e d U.S

. EPA ’ s pre v i o u s hard ness
- b as ed fres h wat e r c r i t e ri a, w h i c h h a ve not bee n c h an ge d si nce t h ey were estab lish e d in 198 4. Th e n e w criteria inco rpo r ated th e u s e of the BL M as a devel o pmental tool for site-specific water q u ality criteria. Th ese criteria co u l d p o t en tially b e used as fu ture fed e ra l or state water q u ality stan d a rd s (e.g ., v i a an upd ate of

the CTR )

. Th e cop p e r BLM is a m o d e l orig in ally d e v e l o p e d b y Hydroq u a l, In c. th at u tilizes d a ta on site-sp ecific water con s titu en ts to p r ed ict th e b i oav a ilab ility o f co pp er in n a t u ral waters and it s tox i city to aqu atic org a n i sms. It estab lish e s a sim p lified mechanistic fra mework t h at was or iginally based on the toxic effects of c o ppe r species on fish gills as t h e surface liga n d. Alth oug h th e BLM m a k e s a n u m b e r o f simp lifyin g assu mp tio ns (e.g ., t h e syste m is in eq u ilibriu m , sp eciatio n of m eta ls is co nstan t o v e r t i m e , an d catio n effects are limited to co m p eti tio n at the g ill site), its u s efu l n e ss will u ltimately b e prov en b y its ability to successfully pre d ict toxicity. Ea rly validation of the freshwate r m odel with re al-world toxicity data thus far h a s p r ov en th e BLM to b e a go od pr ed icto r of toxic effects t o fish (U.S. EPA, 20 07). In a n y case, th e acco un ting o f th e effect s of vari o u s phy si c o che m ical characteristics of t h e wa ter body on c o p p e r t o x i city is an im p r ov em e n t ov er th e pre v i o us m o re l i m i t e d, hard ne ss-ba sedap p r o ach. Th e fo llowing site-sp ecific d a ta were en tered in to t h e fre s h water BLM: te m p erature, pH, DOC, calcium , m a gnesium , sodi um , pot ass i um , sul f at e, c h l o ri de, an d al kal i n i t y
. T h e B L M v e rsion t h at was released in th e 20 07 U.S. EPA criteria u p d a te (v ersion 2

. 2

. 3 ) was operatio n a l on ly in th e tox i city pred iction m o d e
. Th e m e tal sp eciatio n m o d e was n o t av ailab l e. The fres h water BLM has a particular operating ra nge for wh ich it can g e nerate an ou tpu t (Tab le 4). Table 4. Fre shwater BL M Operating Par a meters

Model In put Lower Bou n d UpperBou n d
Tem p erature (  ̊ C ) 10 25 pH 4. 9 9. 2
DOC (m g/L) 0. 05 29 .6 5
Hum i c Aci d C ont e n t (% ) 10 60
C a l c i u m (m g/L) 0. 20 4 12 0. 2 4
M a gnesi um ( m g/L) 0. 02 4 51 .9
So di um (m g/L) 0. 16 23 6. 9
Pot a ssi um (m g/L) 0. 03 9 15 6 Sul fat e (m g/L) 0. 09 6 27 8. 4
C h l o ri de (m g/L) 0. 32 27 9. 7 2
Al kal i n i t y (m g/L) 1. 99 36 0
DIC (m m ol /L ) 0. 05 6 44 .9 2 Sul f i d e (m g/L) 0 0

16DOC M o d el - Sa lt and Bra c k i sh W a ter
The fres h water BLM was not devel ope d t o a ccurately account for t h e c h e m istry of c o pper in the sali ne envi ronm ent. Thus, n a tural waters with h i gh er salin ity lev e ls are b e yon d th e ac c e pt abl e op erat i onal ra nge o f t h e fres h wat e r B L M

. Furt herm ore, the responses of saltwater and estu arin e sp ecies to cop p e r mu st b e tak e n i n to co nsid erati o n to d e term in e relev a n t tox i c th resho l d s
. Since th e saltwater BLM was s till in d e v e lop m en t during th e early stag e o f this report’s syn th e sis, we in itially u tilized a reg r ession -based DOC m o d e l as an i n teri m ap p r o a ch for esti m a tin g th e p o t en tial to x i ci ty of copper i n marine a n d estuar ine waters

. T h e m odel ha s been field validated and is acc urate at pr edi c t i ng t oxi ci t y ( A rn ol d et al

. , 2005). (Note t h at an early version of t h e saltwater B LM ha s bee n recently release d

. Its use and out put for t h is study will b e d i scu ssed in th e n e x t su b-section

. )
The D O C m odel rep r ese n t s a reg r essi o n
- bas e d rel a t i ons hi p ( p o w er f

u nct i o n ) of D O C c o ncent r at i ons t o DC u EC 50 val u es fo r the mu ssel Mytilu s ga llopro v in ci a lis expo sed to copp er in sea water. Mo d e l ou tpu t s in clu d e : 1) an EC 50, 2) a fi nal acut e cri t e ri on (FAC ), a n d 3) a fi nal c h r o ni c cri t e ri on ( F C C )

. N o te that Arnol d et al., 2005 s p ecifically uses the ac rony m s : FC C an d F A C whe n refe rri ng t o th e D O C m odel ’ s cal cul a t e d t o xi ci t y th resh o l d s t h at were in tend ed to be equ i v a len t to th e CTR CCC an d CMC, resp ectiv ely.
B i ot i c Li ga nd M odel - Sa l t a n d B r ac ki sh W a t

e r
In 200 8, Hy d r oq u a l, In c. released a fu n c tion a l d r aft saltwat er BLM. A lthou gh U

. S. EPA d i d no t in cl u d e th e saltwater BLM with t h e fresh water BLM in its 200 7 rev i sion o f t

h e n a ti o n a l aqu a tic life criteria fo r copp er, the saltwater ve rsi o n of th e m o d e l will lik ely b e in co rp orated in to the n e x t rev i sion

. U.S. EPA an d Hydroqu al, Inc. h a v e b e en d i scu ssing t h e tech n ical asp e cts o f th e m o d e l and th e po ten tial fo r its im p l e m en tatio n (R

. Arn o l d , p e rso n al co mmu n i cat io n , 200 8). Until th en , th e ou tput o f th is d r aft m o d e l sh ou ld b e u s ed an d in t e rpreted accord ing ly un til it h a s un d e rgon e m o re ex ten s i v e revie w a n d gai n ed form al acceptance from th e scie ntific and regulatory c o mmunities.
At th is tim e, th e k e y o u t p u t of th is m o d e l in clu d e s pred icted cop p e r sp ecies and p r ed icted EC 50 fo r bot h M. g a llop r o v in ci alis and St r o n g y l ocent r ot us p u r pur at us (purpl e sea urc h in). Saltwater FAVs, CMC, a n d C CC are not yet gene rat e d by t h e versi o n o f t

h e m odel u s ed fo r th i s re po rt

. The r ef ore , th e m odel resul t s t h at are p r ese n t e d a n d di sc uss e d i n th e saltwater BLM resu lts sectio n w ill b e t h e pred icted site-sp ecific EC 50 fo r M. ga llo provin cia lis. T h e p r ed ic te d E C 50 results fo r S. p u rp ur at us are less relev a n t for d i scu ssion si nce th ey are abou t 2–4 tim es le ss sensitiv e when co m p ared t o th e Mytilu s species res u lts.
The i n puts nee d ed to operate the saltwater BLM are i d entic al to those for t h e fres h water BLM

. T h e op erating param e ters are, h o we ver , di ffe re nt (Ta b l e 5 ). Hy dr oq u a l , I n c. c o nd uc t e d m odel i n g runs o f o u r dat a t o pre d i c t t o xi ci t y
. Ta ble 5
. Sa ltw a ter BLM Operating P a r a meters

Model In put Lower Bou n d UpperBou n d Salin ity (p su ) 2 6 3 6 pH 7. 5 8. 3
DOC (m g/L) 0. 4 12 .0

17

### III. Results
The a n alytical results of accuracy and preci si on m easurem e n ts for the principal m eta l analytes (i.e., DCu, TCu, DZ n) were excel l e nt du ri n g m e thod val i d at i on (A p p en di x D). R e c ove r i es fo r t h ese a n al y t es were i n t h e ran g e of 9 0

– 1 0 7 % a n d 92 – 1 0 5 % fo r th e l o w and h i gh lev e l sp ik es, respectiv ely. Ong o in g b a tch QA/ Q C resu lts for all th e an alytes were alm o st always withi n accuracy a n d precision co ntrol limits with the exce ption of one rec o very result for the T C u standard refe rence m a terial. Copper and zi nc we re occasionally detect ed i n field a n d ri ns e blanks sam p les (Appe ndi x E). T w o of 21 rinse blank sam p l e s cont ai ned rel a t i v el y hi g h c once n tr a t i ons of DC u a n d TC u
. A f t e r pot e n t i a l co nt am i n ant so urc e s an d path way s were considere d , it appear e d that t h ese occ u rre n ce s we re likely is olat ed t o th ese t w o i n ci de nt s. Furt herm ore, th e pot e n t i a l of a si m ilar co n t amin atio n t o env i ro n m en tal sam p les wo u l d h a v e b e en ad d ition a lly red u c ed si nce th e co llectio n o f non fieldbl an k sam p l e s al so i n v o l v e d a ri g o r o us ri nsi n g wi th nat i v e water p r i o r to t h e co llectio n of each sam p le. Ov erall, ou r an alysis of labo rat o ry an d field QA/QC d a ta sug g ested t h at th e st u d y ’s che m istry resu lts (i.e., m eta ls and all o t h er an al yses) are h i gh ly reliab l e and reflecti v e o f real worl d co nd itio ns. Wh ile su mm ar y d a ta are presen ted i n th is sectio n , a co m p lete ta bul at i o n of anal y t i cal dat ai s in ap pendic es F–N. Analy t e c o n c en tr a tion s w e r e a l s o co mp a r ed to ap p licab le water q u a l ity stan d a rd s an d tox i city th resh o l d s
. Fi n a lly, m o d e ls th at account for the effect of vari ous fact ors on c o ppe r bioa vailability were us ed to estim a t e coppe rtoxicity.

Dissol v ed Copper
A to tal o f 346 , 9 6 and 88 water sam p les were co llected fro m salt, brackis h and fres hwater sites, res p ectively. DC u conce n tr at i o ns were ab o v e th e m e thod det ect i on l i m i t (M DL = 0. 1 μ g/L ) i n 49 3 o f 51 7 s a m p l e s (9 5% ) (A pp en di x F) . The range of DC u c once n trations for each m a ri na and its ass o cia t ed LRS is shown in Table 6. The sam p le with the highest conce n trat i o n of DC u ( 1 8. 4 μ g/L) cam e fr o m one o f M d R ’ s back ba si ns.
M e di an DC u c once n tr at i o ns f o r

i n di vi d u al m a ri nas ra n g ed fr om 0.5 μ g/L at Fol s om Lake M a ri na t o 13

. 6 μ g/L at M d R ’ s back ba si ns (T abl e 7 )

. T h e m e di an c o nce n tr at i ons fo r 2 1 of 2 3 m a ri nas we re bel o w 7 μ g/ L.
The fo u rf r es h w at er m a ri nas exhi bi t e d very l o w t o m oderat e m e di an DC u conce n tr at i o ns (Fi g ure 4 )

. M e di an co n c en tration s for th e ri v e rine Sacram en to an d Villag e West m a rin a s (3 .0 and 3

. 4 μ g/L , respectively) were c onsi d era b l y hi g h er th a n th e l a ke- b ou n d F o l s om Lake an d Tah o e Key s m a ri nas ( 0

. 5 a n d 0. 6 μ g /L, respectiv ely). Th e b oxp lo ts for water typ e s and reg i on s illu strate t h e m a rin a m e d i an (ho r izo n t al li n e insid e each b ox) as well as th e ind i v i du al sam p le resu lts (circles).
The fo u r brac k i sh w a t e r m a ri nas e x hi bi t e d l o w t o m ode rat e m e di an DC u conce n tr at i o ns (Fi g u r e 5)

. A m ong th e b r ac ki sh wat e r m a ri nas, m e di an co nce n tr at i ons we re h i ghest at Val l e j o M a ri na (3 .4 μ g /L) an d lowest at Pittsb u rg Marin a (2 .1 μ g/L)

. There ap pear s t o be s o m e vari at i on i n DC u c once n tr at i o ns a m ong b r ac ki sh wat e r m a ri nas al thou g h not as di st i n ct i v e a s i n the fres hwater case. The ei ght San Fra n ci sco B a y Area sal t w at er m a ri nas ex hi bi t e d l o w t o hi gh m e di an DC u c once n tr at i o ns ( F i g u r e 6)

. Am on g th ese m a ri nas, th e hi ghe st m e di an c o ncent r at i on was o b se rv ed at L o c h L o m ond M a ri na ( 5

. 8 μ g /L) an d th e lowest m e d i an conce n tr at i o n was ob ser v e d a t San Fra n ci sc o M a ri na (1 .1 μ g/L )

. T h e re m a i n i ng si x B a y Area m a ri nas ex hi bi t e d m e d i an DC u co nce n tr a t i ons t h at ra n g e d bet w ee n 2 a n d4 μ g/L.
The se ve n C e n tral an d S o uth C o ast sal t w at er m a ri nas exhi b i t e d l o w t o ve r y hi g h m e di an DC u co nce n tr a t i ons (Fi g u r e 7 )

. Am ong t h ese m a ri nas, DC u conce n tr at i o ns at M d R ’ s fr o n t an d back ba si ns (1 2. 4 a n d 1 3

. 6 μ g/L ) were mu ch hi g h e rt h an othe r m a ri nas i n th i s re gi o n
. I n fact , th e m e di an co nce n tr at i ons at M d R we re by far th e hi ghe st i n t h e e n t i r e stu d y
. Al am i t o s B a y M a ri na e xhi bi t e d th e l o west m e di an co nce n tr at i on (1 .2 μ g / L) in th is reg i on
. Th e rem a in in g fou rCen tral and So ut h C o ast m a ri nas e x hi bi t e d m e di an DC u conce n tr at i o ns th at ra nge d bet w een 4 an d 7 μ g/L.
The differe n ce s in DCu bet w een m a rinas a n d thei r ass o ciated LR S we re a l so not e w o r th y
. At al l 2 3 m a ri nas, t h e m e di an D Cu con c en tr atio n s w e r e gr eaterth an m e d ian co n c en tr ation s at t h eirassociated LRS. Th is d if f e r e n c e i s m o st p r o noun ced am ong th e sal t w at er m a ri nas al on g th e C e nt ral an d So uth C o ast w h e r e m a ri na m e di an c once n tr at i o ns were as hi g h as 5 7

18RangeofDissolvedCopperConcentrations1RangeofTotal CopperConcentrations1RangeofDissolvedZincConcentrations1Rangeof Total SuspendedSolidsConcentrations1Marina2MarinaLRS3MarinaLRSMarinaLRSMarinaLRSFolsomLakeMarina0.3 – 0.70.2 – 0.50.6 – 0.90.5 – 0.8<1.0 – 8.6<1.0 – 9.1<4<4Tahoe KeysMarina<0.1 – 0.9<0.1 – 0.71.1 – 1.40.1 – 0.3<1.0 – 4.4<1.0 – 5.0<4<4San Francisco Marina0.3 – 3.9<0.1 – 1.00.5 – 3.6<0.1 – 0.71.1 – 9.0<1.0 – 2.213 – 3211 – 32Alamitos Bay Marina0.4 – 3.4<0.1 – 1.2<0.1 – 4.4<0.1 – 1.22.9 – 22.31.6 – 20.3<4 – 2410 – 34Coyote PointMarina1.7 – 2.6 (n= 8)1.1 – 1.5 (n= 8)1.7 – 2.6 (n= 8)0.7 – 1.2 (n= 8)2.2 – 8.1 (n= 8)<1.0– 16.6 (n= 8)10 – 24 (n= 8)7– 20 (n= 8)PittsburgMarina1.7 – 3.61.4 – 1.62.4 – 4.92.5 – 3.31.2 – 7.1<1.0 – 6.4<4 – 1013 – 28AntiochMarina1.7 – 2.91.4 – 1.72.5 – 3.92.2 – 2.9<1.0 – 4.2<1.0 – 3.14 – 109 – 22South BeachHarbor1.9 – 3.00.4 – 1.01.1 – 3.2<0.1 – 1.53.3 – 6.2<1.0 – 2.28 – 258 – 29Clipper YachtHarbor1.3 – 6.60.3 – 1.20.8 – 9.00.6 – 2.32.4 – 12.7<1.0 – 6.39 – 2915 – 31MarinaBayYacht Harbor1.7 – 3.61.5 – 2.5 (n = 6)2.0 – 5.71.0 – 2.8 (n = 6)2.9 – 5.31.8 – 4.0 (n = 6)11 – 1712 – 21 (n = 6)Benicia Marina1.8 – 3.71.5 – 2.23.3 – 5.42.6 – 9.71.1 – 11.7<1.0 – 2.613 – 4622 – 150Ballena Isle Marina1.2 – 4.90.8 – 3.71.0 – 9.30.6 – 4.3<1.0 – 12.01.0 – 8.611 – 3710 – 33Sacramento Marina2.2 – 3.70.5 – 2.32.5 – 5.82.0 – 3.0<1.0 – 7.8<1.0 – 5.4<4 – 714 – 28Berkeley Marina1.8 – 6.80.2 – 2.02.4 – 7.00.4 – 3.22.9 – 8.8<0.1 – 9.58 – 258 – 25VillageWest Marina2.9 – 4.01.5 – 2.2 (n = 11)4.8 – 6.42.6 – 4.7 (n = 11)2.6 – 16.71.4 – 6.4 (n = 11)<4 – 2312 – 27 (n = 11)VallejoMarina2.3 – 4.71.3 – 1.73.1 – 5.63.0 – 7.93.3 – 9.9<1.0 – 3.810 – 35 (n = 11)28 – 112Santa CruzHarbor3.0 – 5.8<0.1 – 0.94.4 – 7.8<0.18.8 – 22.3<1.0 – 6.912 – 3110 – 26MontereyHarbor3.1 – 7.80.1 – 0.52.6 – 9.2<0.1 – 0.38.4 – 26.0<0.1 – 12.0<4 – 256 – 25Santa BarbaraHarbor2.3 – 8.2<0.1 – 0.53.6 – 8.6<0.16.4 – 22.8<1.0 – 4.810 – 3111 – 25LochLomondMarina3.2 – 10.31.3 – 2.22.8 – 10.61.9 – 3.14.9 – 13.8<1.0 – 3.710 – 3017 – 43Downtown ShorelineMarina2.4 – 10.90.4 – 1.22.6 – 11.5<0.1 – 1.29.9 – 40.12.1 – 7.611 – 266 – 22MarinadelReyFB8.9 – 16.20.3 – 4.79.2 – 17.0<0.1 – 4.638.2 – 66.6<1.0 – 22.19 – 2410 – 29Marinadel Rey BB8.1 – 18.40.3 – 4.79.0 – 20.2<0.1 – 4.633.3 – 59.5<1.0 – 22.110 – 2910 – 29Table 6. Rangeof Metal(μg/L)andTotal Suspended Solids(mg/L) Concentrations inWater(sorted byascendingorderof marina mediandissolved copperconcentrations)1The number of replicates (n)is12 unless otherwise indicated.2Marina names are colorcoded bywatertype.Green =freshwater,Yellow = brackish water, Blue = saltwater3LRS = localreference site19Table 7. Median Metal (μg/L)andTotal Suspended Solids(mg/L) Concentrations inWater(sorted byascendingorderof marina mediandissolved copperconcentrations)2LRS = localreference siteMedian Dissolved CopperConcentrationsMedian TotalCopperConcentrationsMedian DissolvedZincConcentrationsMedianTotal Suspended SolidsConcentrationsMarina1MarinaLRS2MarinaLRSMarinaLRSMarinaLRSFolsomLakeMarina0.50.30.70.62.82.5<4<4TahoeKeysMarina0.60.21.20.22.32.2<4<4SanFranciscoMarina1.10.40.90.22.71.621.919.8AlamitosBayMarina1.20.31.20.36.76.313.516.9CoyotePointMarina2.11.32.21.04.63.117.812.9PittsburgMarina2.11.53.02.92.91.77.317.9AntiochMarina2.21.53.02.61.91.66.813.7SouthBeachHarbor2.20.71.90.44.41.316.217.3ClipperYachtHarbor2.40.82.10.94.82.319.020.8Marina BayYachtHarbor2.61.72.71.74.12.813.016.4BeniciaMarina2.71.74.14.52.71.423.054.7BallenaIsleMarina2.81.43.31.15.22.420.116.7SacramentoMarina3.00.74.22.42.82.54.319.6BerkeleyMarina3.30.74.00.84.72.218.115.0VillageWestMarina3.41.85.63.65.13.212.519.4VallejoMarina3.41.54.13.94.31.216.055.0SantaCruzHarbor4.30.36.10.114.32.023.218.7MontereyHarbor4.90.25.30.118.51.714.116.3SantaBarbaraHarbor5.70.15.80.113.91.918.218.0LochLomondMarina5.81.76.32.47.92.018.926.9Downtown ShorelineMarina6.60.76.40.220.33.918.515.3MarinadelReyFB12.41.013.30.349.15.615.817.3MarinadelReyBB13.61.014.70.350.05.618.417.31Marina namesare colorcoded bywatertype.Green =freshwater, Yellow= brackish water,Blue = saltwater20Figure 4. Dis t ribution of Di ssolve d Coppe r Co ncentr ati o ns in Fres hwaterMarina Areas

V

i l l a g e W

e s t L R

S

V

i l l a g e W

e s t M

a r i n a

S

a c r a m

e n t o L R

S

S

a c r a m

e n t o M

a r i n a
F

o l s o m

L R

S

F

o l s o m

M

a r i n a

T

a h

o e K

e y s L R

S

T

a h

o e K

e y s M

a r i n a 4

3

2

1

0DCu Concentrations(μg/L)

Figure 5. Dis t ribution of Di ssolve d Coppe r Con cen tr ati o ns in Brac kis h W a terMari na Are a s

V

a l l e j o L R

S

V

a l l e j o M

a r i n a
B

e n i c i a L R

S

B

e n i c i a M

a r i n a

P i t t s b

u r g L R S

P i t t s b

u r g M

a r i n a
A

n t i o c h

L R S

A

n t i o c h

M

a r i n a 5

4

3

2

1DCu Concentrations(μg/L)

21Fi gure 6. Di s t ri buti o n of Di ssol v e d Coppe r Concentr ati o ns in Saltwater Marina Ar eas (San Fra n ci sco B a y Area)

C o y o t e P

o i n t L R S

C

o y o t e P

o i n t M

a r i n a

B

a l l e n a I s l e L R S

B

a l l e n a I s l e M

a r i n a

S

o u t h

B

e a c h

L R S

S

o u t h B

e a c h H

a r b

o r

S

a n F r a n c i s c o L R S

S

a n F r a n c i s c o M

a r i n a

B

e r k e l e y L R S

B

e r k e l e y M

a r i n a

C l i p p e r Y.

H .

L R S

C l i p p e r Y

a c h t H

a r b

o r

L

o c h L

o m

o n d L R S

L

o c h L

o m

o n d M

a r i n a

M

a r i n a B

a y Y.

H .

L R S

M

a r i n a B

a y Y

a c h t H

a r b

o r 10

8

6

4

2

0DCuConcentrations(μg/L)

Fi gure 7. Di s t ri buti o n of Di ssol v e d Coppe r Concentr ati o ns in Saltwater Marina Ar eas (Ce ntr al and S o u t h Co as t)

A l a m i t o s B

a y L R S

A l a m i t o s B

a y M

a r i n a

D

o w n t o w n S h o r e l i n e L R S

D

o w n t o w n S h o r e l i n e M

a r i n a M

d R

L R S

M

d R

F

r o n t B

a s i n s M

d R

L R S

M

d R

B

a c k B

a s i n s

S

a n t a B

a r b a r a L R S

S

a n t a B

a r b

a r a H

a r b o r
M

o n t e r e y L R S

M

o n t e r e y H

a r b

o r

S

a n t a C

r u z L R S

S

a n t a C

r u z H

a r b o r 20

15

10

5

0DCu Concentrations(μg/L)

22Table 8. Sum mar y of Medi an Me tal Con centr ations ( μ g/L ) i n Wa ter Median DCu Concentrations w/ 9 5 % C I Median T C u Concentrations w/ 9 5 % C I Median DZ n Concentrations w/ 95% CI Marin a Sites LRSs Marin a Sites LRSs Marin a Sites LRSs Saltwater Sites 3. 3 - 3. 7 - 4. 2 0. 5 - 0. 6 - 0

. 7 3. 3 - 3. 8 - 4

. 4 0. 2

- 0. 3 - 0

. 4 8. 0 - 9. 2 - 1 0. 7 2. 1

- 2. 4 - 2. 8

Bra ckish Water Site s 2. 4 - 2. 6 - 2

. 8 1. 5 - 1. 6 - 1

. 6 3. 3 - 3. 5 - 3

. 8 3. 1 - 3. 4 - 3

. 7 2. 4 - 2. 8 - 3

. 3 1. 3 - 1. 5 - 1. 7

Freshwater Sites 1. 1 - 1. 4

- 1

. 9 0. 4

- 0. 5 - 0

. 7 1. 7 - 2. 2 - 2

. 9 0. 8

- 1. 1 - 1

. 6 2. 5 - 3. 1 - 3

. 9 2. 1 - 2. 6 - 3. 2

All Water Sites 2. 7 - 3. 0 - 3

. 3 0. 6 - 0. 7 - 0

. 8 3. 1 - 3. 4

- 3

. 8 0. 5 - 0. 6 - 0

. 7 5. 4 - 6. 2 - 7

. 0 1. 9 - 2. 1 - 2. 4

Figure 8. Dis t ribution of Mari na Me dian Dissol v ed Cop per Conce ntr ati o ns by W a ter Type

S

a l t w

a t e r L R S

s

S

a l t w

a t e r M

a r i n a s

B

r a c k i s h

W

a t e r L R S

s

B

r a c k i s h

W

a t e r M

a r i n a s

F

r e s h

w

a t e r L R

S

s

F

r e s h

w

a t e r M

a r i n a s 14
12
10

8
6
4
2
0DCuConcentrations(μg/L)

23t i m e s th e LR S m e di an co nce n tr at i ons. B r a c k i sh w a t e r m a ri nas e x hi bi t e d t h e sm al l e st di ffere nce wi th m a ri na m e di an conce n tr at i o ns bei n g a b o u t t w i ce as hi gh as t h e LR S m e di an c once n tr at i o ns. Ove ral l , m e di an DC u co nce n trat i ons we re 3. 0 μ g/L f o r

al l m a ri na si t e s an d 0. 7 μ g/L f o r all LRSs (Ta b l e 8). Median DC u co nce n tr a t i ons i n wat e r were 3 .7 , 2. 6, a n d 1 .4 μ g/L for salt, brackis h, and fres hwat er m arin as, resp ectiv ely, wh ile th e res p ect i v e LR S m e di an D C u c once n tr at i ons we re 0. 6, 1 .6, an d 0. 5 μ g/L.
There we re si gnificant differe n ces i n m e dian DCu c once n tr at i ons am on g t h e th ree wat e r t y pes ( one
- w ay A N O V A , F 2, 64 = 8. 9 0 , p < 0 .0 0 0 5 ) , wi th fr eshw at er m a ri na m e di an DC u conce n tr at i o ns bei n g si gni fi ca nt l y l e ss th an t hos e i n sal t and b r ac kish w a ter m a rinas (T ukey ’ s Test, fa m i ly erro r rate =0. 0 5 ) (Fi g u r e 8, ). I n c o ntras t , th ere was n o si gni fi ca nt di ffe re nce bet w een m e di an DC u co nce n tr a t i ons i n sal t a n d brac ki sh wat e r m a ri nas. In Fi gu re 8, pl ot t e d ci rcl e s represe n t the median val u e for each m ari na and the horizontal line in si de the box represe n ts the water type m edian.
The ful l y
- n est e d bal a nce d AN OV A s h owe d s t at i s t i c al l y si gni fi cant di ffe ren ces bet w een m a ri nas a n d LR S DC u co n c en tration s in saltwater m a rin aar eas (fully-nested ba lanced A NOV A, F 14,56 = 22 .2 , p < 0

. 00 05 , Co y o te Po in t M a ri na om i t t e d) , brac ki sh wa t e r m a ri na area s (f ul l y -ne s t e d bal a nce d AN O V A , F 4,16 = 36 .3 , p < 0.000 5) , and fres h w a ter m a rina areas , (f ully -nested bala n ced AN O V A , F 3,12 = 3 3

. 9 , p < 0. 0 0 0 5 , Taho e Key s M ari na om it t e d).

To ta l Co pper As was t h e cas e for DC u, 346, 96, and 88 T C u water sam p les were collec t ed from salt, brackis h, a n d freshwater ar eas, respect i v el y
. TC u c once n tr a t i ons were ab o v e th e m e thod det ect i o n l i m i t (M DL = 0. 1 μ g/L) i n 45 5 o f 51 7 s a m p l e s (8 8% ), wi th c o ncent rat i ons ra ngi ng u p t o 20

. 2 μ g /L (App end i x F). Th e sam p le with th e h i gh est TC u con cen t r atio n cam e from on e o f M d R ’ s bac k basi ns (Ta b l e 6 )

. M e di an TC u c once n tr at i o ns f o r

i n di vi d u al m a ri nas ra n g edfr om 0.7 μ g/L at Fol s om Lake M a ri na t o 14

. 7 μ g/L at M d R ’ s bac k ba si ns ( T abl e 7 )

. The m e di an conce n tr at i o ns f o r 2 1 o f 2 3 m a ri nas were bel o w 7 μ g /L. Th e relativ e rank of

m a ri nas, bas e d on th e m a gn i tude of th ei r m e di an TC u c once n tr at i o ns , i s sl i ght l y di f f e r ent t

h an th at f o r

DC u. T h e com p ari s on o f m a ri na TC u co ncent r at i ons by wat e r t y pe a n dre gi o n re veal e d si m i l a r pat t e rns t o DC u (Fi g ures 9

– 1 2 ) wi th th e p r i m ary exce pt i o n of th e rel a t i ons hi p bet w ee n th e brac ki sh wat e r m a ri nas an d t h ei r LR Ss (Fi g u r e 10 ). Figure 9. Dis t ribution of T o tal Copper Con centr ati o ns in Freshw ater Marina Are a s

V

i l l a g e W

e s t L R

S

V

i l l a g e W

e s t M

a r i n a

S

a c r a m

e n t o L R

S

S

a c r a m

e n t o M

a r i n a
F

o l s o m

L R

S

F

o l s o m

M

a r i n a

T

a h

o e K

e y s L R

S

T

a h

o e K

e y s M

a r i n a 7
6
5
4
3
2
1
0TCu Concentrations(μg/L)

24Figure 10. Dis t ributi o n of T o tal Copper Concen tr ations in Brackish Water Marina Areas

V

a l l e j o L R

S

V

a l l e j o M

a r i n a
B

e n i c i a L R S

B

e n i c i a M

a r i n a

P i t t s b

u r g L R

S

P i t t s b

u r g M

a r i n a
A

n t i o c h

L R S

A

n t i o c h

M

a r i n a 10

9
8
7
6
5
4
3
2TCu Concentrations(μg/L)

Figure 11. Dis t ributi o n of T o tal Copp er Concentr ations in Sal t waterMari n a Are a s (S an Fra nci sc o B a y Are a )

C

o y o t e P

o i n t L R S

C

o y o t e P

o i n t M

a r i n a

B

a l l e n a I s l e L R S

B

a l l e n a I s l e M

a r i n a

S

o u t h

B

e a c h

L R S

S

o u t h B

e a c h H

a r b

o r

S

a n F r a n c i s c o L R S

S

a n F r a n c i s c o M

a r i n a

B

e r k e l e y L R S

B

e r k e l e y M

a r i n a

C l i p p e r Y

. H .

L R S

C l i p p e r Y

a c h t H

a r b

o r

L

o c h L

o m

o n d L R S

L

o c h L

o m

o n d

M

a r i n a

M

a r i n a B

a y Y

. H .

L R S

M

a r i n a B

a y Y

a c h t H

a r b

o r 12

10

8

6

4

2

0TCuConcentrations(μg/L)

25Figure 12. Di stributi o n of To ta l Co pper Concentrations in Sa ltw a ter Marina Are a s (Ce ntr al an d S o uth Coas t)

A l a m i t o s B

a y L R S

A l a m i t o s B

a y M

a r i n a

D

o w n t o w n S h

o r e l i n e L R S

D

o w n t o w n S h

o r e l i n e M

a r i n a M

d R

L R S

M

d R

F r o n t B

a s i n s M

d R

L R S

M

d R

B

a c k

B

a s i n s

S

a n t a B

a r b a r a L R S

S

a n t a B

a r b

a r a H

a r b o r
M

o n t e r e y L R S

M

o n t e r e y H

a r b o r

S

a n t a C

r u z L R S

S

a n t a C

r u z H

a r b o r 20

15

10

5

0TCu Concentrations(μg/L)

Figure 13. Dis t ributi o n of Marina Me dian To tal Copper Concentratio ns b y W a ter T y pe

S

a l t w

a t e r L R S

s

S

a l t w

a t e r M

a r i n a s

B

r a c k i s h

W

a t e r L R S

s

B

r a c k i s h

W

a t e r M

a r i n a s

F

r e s h

w

a t e r L R

S

s

F

r e s h

w

a t e r M

a r i n a s 16 14 12 10

8 6 4 2 0TCu Concentration(ug/L)

26Ove ral l , m e di an TC u c once n t rat i ons we re 3. 4 μ g/L f o r

al l m a ri na si t e s an d 0. 6 μ g/L f o r all LRSs (Ta b l e 8). Median TC u c once n tra t i ons i n wat e r were 3 .8 , 3. 5, a n d 2 .2 μ g/L for salt, brackis h, and fres hwat er m arin as, resp ectiv ely, wh ile th e res p ect i v e LR S m e di an T C u c once n tr at i ons we re 0. 3, 3 .4, an d 1. 1 μ g/L.
A t e st f

o r di ffe rences i n m a ri na TC u c once n tr at i ons am on g th e th ree wat e r t y pes f o u n d n o si gni fi ca nt di ffe rence b e tw een w a ter typ e s, altho ugh th e si g n if ican c e lev e l w a s o n l y slig h tly g r eater th an t h e cu to ff o f 0

. 0 5 (o ne- w ay A NOV A, F 2, 64 = 3 .1 , p = 0. 0 5 1 )

. TC u c o nce n tr at i o ns t e nd t o be si m i l a r am ong m a ri nas of th e t h ree wa t e r t y pes ( F igu r e 13)

. Th e TC u con c en tration s m easu r ed with in bo th freshwater an d saltwater marin a s were sig n i fican tly h i gh er th an tho s e measured in t h e associated L R S (fully -n ested b a lan c ed ANOVA; saltwater: F 14, 56 = 60 .8 , p < 0.000 5, C o yo te Po in t M a ri na om i t t e d; f r es hwat er: F 3,12 = 1 5

. 8 , p < 0. 0 0 0 5 , Taho e Key s M ari na om it t e d) (Fi g ur e 1 3 )

. In co ntr a st , th ere wa s no significant diffe re nce between m easur emen ts tak e n in b r ack i sh water mari na areas (fully-neste d balan ced ANO VA , F 4,16 = 0. 4, p = 0. 83 6 )

. M e di an TC u c once n tr at i o ns were al m o st alway s hi g h er i n si de of m a ri nas com p ared t o L R Ss. At B e ni ci a M a ri na, ho we ver , th e m e di an LR S T C u c once n tr at i o n was actual l y hi g h er th a n t h e m e di an m a ri na co nce n tr at i o n
. At B e ni ci a M a ri na, t h e c o r r esp o ndi ng TS S m easurem ents we re qui t e hi gh (m edi a n LR S TSS c once n t r at i o n 5 4

. 7 m g /L ) a n d co ul d p o ten tially serv e to exp lain th e h igh TC u co n c en tration s at the LRSs for Benicia Marina. At Vallejo Marina, where th e m e d i an LR S TSS co n c en t r atio n was also h i gh (5 5.0 m g /L), th e m e d i an LRS TC u co ncen tration (3.9 μ g/L ) was alm o st as high as the m e dian marina TCu concent r ation (4.1 μ g/L ).
Th er e w a s a st ro ng corr e lation b e tw een D C u an d TCu con c en tr ation s ( P earso n’ s r= 0.91 , p < 0

. 00 05 , Fi g u r e 14 )

. Ove r all analysi s of dissol v ed-t o-t o tal coppe r ratios s h owe d t h at abou t 92 % o f to tal copp er is DCu. Th is percen tag e is co nsisten t with th e co nv ersion factors (TCu to DCu) o f fered in th e U.S. EP A’s upd ated water qu ality criteria fo r cop p e r( U

. S

. E P A, 2 0 0 7 )

. T h e cri t e ri a doc u m ent su ggest s th at th e c o nve r s i o n fact o r s o f 0. 96 an d 0. 9 0 9 be use d fo r fresh water an d saltwater, respectiv ely. Thu s , th e ob serv ed co rrelatio n is a reflectio n of the fact that m o st of the c o ppe r i n t h e sy st em i s di ss ol ve d.

Figure 14. Correlation Pl ot of Log Dissol v ed ver sus L o g Total Copper Concentrations

3 2 1 0 -1 -2 -3 3

2

1

0

-1

-2

-3

l og T C ulogDCu P e a r s o n ’ s r =

0

. 91 , p < 0. 0005

27Dissol v ed Z i nc A to tal o f 346 , 9 6 , an d 88 wat er sam p les were co llected from salt, brac kis h , a n d fres h water area s, res p ec tively. DZ n co n c en tration s were abov e m e th od d e tectio n li mit (MDL = 1

. 0 μ g /L) in 465 o f 517 sam p les (9 0%) , w ith co n c en tration s rang ing up to 66 .6 μ g/L ( A p p e ndi x F ). T h e sam p l e wi t h t h e hi g h est DZ n conce n trat i o n c a m e from one of

M d R ’ s f r o n t basi ns (Tabl e 6)

. M e di an DZ n c once n trat i o ns f o r

i n di vi d u al m a ri nas ra n g ed fr om 1.9 μ g /L at An tio ch Marin ato 50 .0 μ g/ L at M d R ’ s back ba si ns (T abl e 7 )

. M e di a n DZ n c once n t r at i ons we re l e ss th a n 8 μ g /L in 17 of th e 23 mar in a s stud ied

. The fres h wat e r an d brac ki sh wat e r m a ri nas exhi bi t e d very l o w t o l o w m e di an DZ n c o nc entr at i o ns (Fi g ures 1 5 a n d 16 ). DZ n c once n tra t i ons were ge n e ral l y sim i l a r am ong f res hwat er m a ri nas an d am ong b rac ki sh wat e r m a ri na s. The ei ght San Fra n ci sco B a y Area sal t w at er m a ri nas ex hi bi t e d ve ry l o w t o m oderat e m e di an D Z n co nce n tr at i o ns (Fi g ure 1 7 )

. A m ong th ese m a ri nas, th e hi g h e s t m e di an conc entr at i o n was o b ser v e d at L o c h L o m ondM a r i na ( 7

. 9 μ g/L ) a n d th e l o w m e di an co n centr at i o n was obs er ved at Sa n F r a n ci sco M a ri na (2 .7 μ g /L)

. Th e r e m a in in g six Bay Area m a ri nas exhi bi t e d m e di an DC u co nce n tr at i ons th at ran g ed bet w een 4 and 6 μ g/L.
The se ve n C e n tral an d S o uth C o ast sal t w at er m a ri nas exhi b i t e d m oderat e t o very hi g h m e di an DZ n c o nc entrat i o ns (Fi g ure 1 8 )

. A m ong th ese m a ri nas, DC u c o n centr at i o ns at M d R ’ s fr o n t a n dbac k basi ns (4 9. 1 a n d 50 .0 μ g/L , respectively ) w e re by far the h i ghest. Alam itos Bay M a ri na exhi bi t e d t h e l o west m e di an conce n tr at i o n ( 6

. 7 μ g/L ) i n t h i s re gi o n
. T h e rem a i n i ng fo ur C e ntral a n d So ut h C o ast m a ri nas e x hi bi t e d m e di an DC u conce n trat i o ns t h at ra nge d bet w ee n 13 an d 20 μ g/L.

Figure 15. Dis t ributi o n of Dissolved Z i nc Co ncentrations in Fre shwater Marina Ar eas

V

i l l a g e W

e s t L R

S

V

i l l a g e W

e s t M

a r i n a

S

a c r a m

e n t o L R

S

S

a c r a m

e n t o M

a r i n a
F

o l s o m

L R

S

F

o l s o m

M

a r i n a

T

a h

o e K

e y s L R

S

T

a h

o e K

e y s M

a r i n a 18 16 14 12 10

8 6 4 2 0DZn Concentrations(μg/L)

28Figure 16. Dis t ributi o n of Marina Diss olve d Z i nc Con c e ntr ations in Brackish W a terMarina Are a s

V

a l l e j o L R

S

V

a l l e j o M

a r i n a
B

e n i c i a L R S

B

e n i c i a M

a r i n a

P i t t s b

u r g L R

S

P i t t s b

u r g M

a r i n a
A

n t i o c h

L R S

A

n t i o c h

M

a r i n a 12

10

8

6

4

2

0DZnConcentrations(μg/L)

Figure 17. Dis t ributi o n of Marina Diss ol ve d Z i nc Con c e n tr ati o ns i n S a l t w a ter Mari na Are a s (S an Fra n ci sco Ba y Area )

C o y o t e P

o i n t L R S

C

o y o t e P

o i n t M

a r i n a

B

a l l e n a I s l e L R S

B

a l l e n a I s l e M

a r i n a

S

o u t h

B

e a c h

L R S

S

o u t h B

e a c h H

a r b

o r

S

a n F

r a n c i s c o L R S

S

a n F

r a n c i s c o M

a r i n a

B

e r k e l e y L R S

B

e r k e l e y M

a r i n a

C l i p p e r Y .

H .

L R S

C l i p p e r Y

a c h t H

a r b

o r

L

o c h L

o m

o n d L R S

L

o c h L

o m

o n d M

a r i n a

M

a r i n a B

a y Y .

H .

L R S

M

a r i n a B

a y Y

a c h t H

a r b

o r 18 16 14 12 10

8 6 4 2 0DZnConcentrations(μg/L)

29Figure 18. Dis t ributi o n of Marina Di ss ol ve d Z i nc Con c e n tr ati o ns i n S a l t w a ter Mari na Are a s (Ce n tral an d Sou t h Coast)

A l a m i t o s B

a y L R S

A l a m i t o s B

a y M

a r i n a

D

o w n t o w n S h

o r e l i n e L R S

D

o w n t o w n S h

o r e l i n e M

a r i n a M

d R

L R S

M

d R

F

r o n t B

a s i n s M

d R

L R S

M

d R

B

a c k

B

a s i n s

S

a n t a B

a r b a r a L R S

S

a n t a B

a r b

a r a H

a r b o r
M

o n t e r e y L R S

M

o n t e r e y H

a r b o r

S

a n t a C

r u z L R S

S

a n t a C

r u z H

a r b o r 70
60
50
40
30
20
10

0DZnConcentrations(μg/L)

Figure 19. Dis t ributi o n of Marina Me dian Disso l v ed Z i nc Concen tr ati o ns by W a ter Type

S

a l t w

a t e r L R S

s

S

a l t w

a t e r M

a r i n a s

B

r a c k i s h

W

a t e r L R S

s

B

r a c k i s h

W

a t e r M

a r i n a s

F

r e s h

w

a t e r L R

S

s

F

r e s h

w

a t e r M

a r i n a s 50

40

30

20

10

0DZn Concentration(ug/L)

30Ove ral l , m e di an DZ n c once n t rat i ons i n wat e r w e re 6. 2 μ g/L f o r

al l m a ri na si t e s an d 2. 1 μ g /L fo r all LRSs (Tab le 8 )

. M e di an DZ n c once n trat i o ns were 9

. 2 , 2. 8, a n d 3

. 1 μ g/L for salt, brackis h, and fres h wa ter m arin as, respectiv ely, wh ile th e res p ect i v e LR S m e di an D Z n c o ncentr at i ons we re 3. 6, 1 .5, an d 2. 6 μ g/L.
There we re si g n i f i cant di f f ere n ces i n DZn co ncent r at i ons a m ong m a ri nas of th e t h ree wa t e r t y pes (o ne- w ay A N O V A , F 2, 64 = 1 5

. 5 , p < 0. 0 0 0 5 ) , wi th sal t wat e r m a ri na DZ n c onc entr at i o ns bei n g si gni fi ca nt l y hi g h er th a n th o s e f o r

b r acki s h and fres hwater m a rinas (Tuke y ’s Test, fam i ly error rate = 0.05 ) ( F i g ur e 19)

. In co n t r a st, t h er e w a s no sig n i f ican t diffe re nce between DZn concentrations i n brac ki sh an d fr eshw ater m a rinas.
At all 23 m arina areas, the m edian m arina DZn c o ncentrati ons we re greater tha n t h e m e dian LRS c onc entrations. In Fi gu re 1 8 , t h e m e di an f o r

Al a m i t o s B a y M a ri na ap pear s t o be l o we r th a n t h e m e di an f o r

i t s LR Ss. N o t e , h o we ve r, t h at th is is an artifact o f th e t w o d i fferen t app r o a ch es u s ed to calculate the sam p le m edian. R ecall that the geom etric m ean median val u e i s the one that i s use d fo r dat aanal y s i s an d di scussi o n
. The differe n ce in m a rina and LRS DZn conc entrations is st atistical ly sig n i fican t for saltwater m arin a areas (fu llynest ed bal a nce d AN O V A , F 14 ,56 = 2 2

. 9 , p < 0. 00 0 5 , C o y o t e Poi n t M a ri na om it t e d) an d b r acki s h wat e r m a ri na areas (fu lly-n ested balan ced ANOVA, F 4,16 = 5

. 4, p < 0

. 0 06) (Fig ur e 19 )

. Th ere is no statistically discerna bl e differe n ce for fres h w a ter m a rina areas ( f ully -neste d balanc ed AN O V A , F 3,12 = 0

. 3 , p = 0.79 3, Taho e Keys Marin a o m itted )

.

Total Sus pen d ed S o lids
TSS dat aare f r e que nt l y use f ul i n i m pro v i n g t h e un de rst a n d i n g o f m e t a l s dat a
. T hus , th e s e res u l t s are e v a l uat e d al on g with th e m e tals resu lts. TSS co n c en tration s were abov e th e d e tection limit(MDL = 4 m g /L) in 46 5 of 51 6 sam p les (9 0% ) wi th c o ncent rat i ons ra ngi ng u p t o 15 0 m g /L (A p p e ndi x F ). T h e s a m p l e wi t h t h e hi g h est T SS c once n trat i o n i n th i s stu d y wa s fr om one th e B e ni ci a M a ri na LR S (Ta b l e 6)

. M e di an T SS c once n tr at i o ns f o r

i n di vi d u al m a ri nas ra n g ed fr om bel o w th e det ect i o n l i m i t of 4 m g /L at Fol s om Lake and Tahoe Key s m a ri nas t o 23 .2 m g /L at Sa n t a C r uz Harb or (Ta b l e 7 )

. T h e m e di an co nc entr at i o ns of 1 8 of 2 3 m a ri nas w er e abov e 1 2 m g /L.
The fres h wat e r m a ri nas exhi b i t e d ve ry l o w t o l o w m e di an TSS c o ncentr at i ons (Fi g u r e 2 0 )

. The b r ac ki sh wat e r m a ri nas s h o w e d l o w t o m oder a t e m e di an TS S co nce n tr at i o ns (Fi g ur e 21 ). T h e 15 sal t w a t er m a ri nas al so s h o w e d l o w to m o d e r a te med ian TSS concen tr ation s ( F i g ur es 22 an d 23 ).
TSS con cen trat io n s were o f ten h i gh er ou tside of th e m a rin a th an in si d e (Fig ures 20–23). Since m arinas are co nstru c ted with th e prim ary goal o f pr ot ect i n g boat s f r om tu rb ul ence caus e d by wi nd, c u r r ent s , an d t i d es , th i s obs er vat i o n se em s l ogi cal

. M e di an T SS c once n tr at i o ns f o r

LR Ss we re hi g h er i n 1 3 ou t of 2 3 m a ri na areas. The t w o hi ghe st m e di an TSS conce n tr at i o ns –5 4. 7 a n d 55 .0 m g /L were do cum e nt ed f o r t h e B e ni ci a LR Ss an d t h e Vallejo LRSs , respectively. These high le vels of TSS at t h ese t w o areas can likely be attribute d to part icle flo c cu latio n , wh ich is a co mmo n ph en o m en on in estu arin e ar eas whe r e fres h wate r m eets m o re saline wa ter. At the o th e r two less-salin e brack ish water LRSs (Pittsb u r g an d An tio ch), th e TSS rang es are si milar to th ose o f th e t w o riv eri n e freshwater LRSs (Sacram en t o Ma rina and Villag e West Mari n a).
Ov erall, m e d i an TSS con cen t r atio n s in water were 13 .5 m g /Lfor all m arin a sites and 1 7 .4 m g /L for all LRSs (Tab le 8)

. M e di an TS S co nce n tr at i o ns i n w a t e r wer e 1 7

. 5 , 1 1

. 6 , a n d 5. 6 m g /L fo r sal t , brac ki s h , and f r es hwat er m a ri nas, respectively, while the respective LRS m edian T SS c o ncent rat i ons we re 1 7

. 6 , 2 9

. 3 , a n d 9. 3 m g /L

.

31Figure 20. Dis t ributi o n of T o tal Su spen de d S o lid Conce n tr ations in F reshwaterMarina Areas

V

i l l a g e W

e s t L R

S

V

i l l a g e W

e s t M

a r i n a

S

a c r a m

e n t o L R

S

S

a c r a m

e n t o M

a r i n a
F

o l s o m

L R

S

F

o l s o m

M

a r i n a

T

a h

o e K

e y s L R

S

T

a h

o e K

e y s M

a r i n a 30

25

20

15

10

5TSSConcentrations(mg/L)

Figure 21. Dis t ributi o n of T o tal Su spen de d S o lid Co nce n tr ations in Brackish W a terMarina Are a s

V

a l l e j o L R

S

V

a l l e j

o M

a r i n a
B

e n i c i a L R

S

B

e n i c i a M

a r i n a

P i t t s b

u r g L R

S

P i t t s b

u r g M

a r i n a
A

n t i o c h

L R

S

A

n t i o c h

M

a r i n a 16 0
14 0
12 0
10 0
80
60
40
20

0TSSConcentrations(mg/L)

32Figure 22. Dis t ributi o n of T o tal Su spen de d S o lid Conce n tr ati o ns i n S a l t w a ter Mari na Are a s (S an Fra nci sco B a y Area)

C o y o t e P

o i n t L R S

C

o y o t e P

o i n t M

a r i n a

B

a l l e n a I s l e L R S

B

a l l e n a I s l e M

a r i n a

S

o u t h

B

e a c h

L R S

S

o u t h B

e a c h H

a r b

o r

S

a n F r a n c i s c o L R S

S

a n F r a n c i s c o M

a r i n a

B

e r k e l e y L R S

B

e r k e l e y M

a r i n a

C l i p p e r Y.

H .

L R S

C l i p p e r Y

a c h t H

a r b

o r

L

o c h L

o m

o n d L R S

L

o c h L

o m

o n d

M

a r i n a

M

a r i n a B

a y Y.

H .

L R S

M

a r i n a B

a y Y

a c h t H

a r b

o r 45
40
35
30
25
20
15
10

5TSSConcentrations(mg/L)

Figure 23. Dis t ributi o n of T o tal Su spen de d S o lid Conce n tr ations in S a ltwater Mari na Are a s (Ce n tral an d S o u t h Co as t)

A l a m i t o s B

a y L R S

A l a m i t o s B

a y M

a r i n a

D

o w n t o w n S h

o r e l i n e L R S

D

o w n t o w n S h

o r e l i n e M

a r i n a M

d R

L R S

M

d R

F

r o n t B

a s i n s M

d R

L R S

M

d R

B

a c k

B

a s i n s

S

a n t a B

a r b a r a L R S

S

a n t a B

a r b

a r a H

a r b o r
M

o n t e r e y L R S

M

o n t e r e y H

a r b o r

S

a n t a C

r u z L R S

S

a n t a C

r u z H

a r b o r 35
30
25
20
15
10

5
0TSSConcentrations(mg/L)

33Figure 24. Dis t ributi o n of Marina Me dian Total Sus pen ded S o lids Concentr ati o ns b y W a ter Type

S

a l t w

a t e r L R S

s

S

a l t w

a t e r M

a r i n a s

B

r a c k i s h

W

a t e r L R S

s

B

r a c k i s h

W

a t e r M

a r i n a s

F

r e s h

w

a t e r L R

S

s

F

r e s h

w

a t e r M

a r i n a s 70
60
50
40
30
20
10

0TSSConcentration(mg/L)

There we re si g n i f i cant di f f ere n ces i n TS S c o ncent r at i ons a m ong m a ri nas of th e t h ree wa t e r t y pes (o ne- w ay A N O V A , F 2, 64 = 5 1

. 6 , p < 0. 0 0 0 5 ) , wi th T SS c o ncent r at i ons f r om m a ri nas o f eac h wat e r t y pes bei n g si g n i f i cant l y di ffe re nt th a n one an othe r (T ukey ’ s Test , fa m i ly erro r rat e = 0. 0 5 ) (Fi g u r e 2 4 )

. M e di an TSS c o ncentr at i ons i n m a ri nas we re i n th e order of saltwa t er > brac kish water > freshwater.
Th ere was n o statistica l d i fferen ce in m a rin aan d LRS TSS co n cen tration s for saltwater marin a areas (fu l ly-n ested b a lan c ed A NOV A, F 14, 56 = 0. 9, p = 0

. 6 0 1 , C o y o t e P o i n t M a ri na om i t t e d) (Figu r e 24). Ho wev e r, t h ere was a statistica l di ffe re nce i n m a ri na a n d LR S TSS c o ncentr at i ons f o r

b r acki s h wat e r m a ri n aareas (f ul l y -n est e d bal a nce d AN O V A , F 4,16 = 1 7

. 2 , p < 0. 0 0 0 5 ) a n d fo r fres h w a ter m a rina areas ( f u lly -nestedb a lancedA N O V A , F 3,12 = 17 .0 , p < 0.000 5, Tah o e Key s M a ri na om i t t e d). TSS co nce n tr a t i ons i n brac ki s h a n d f r es hwat er m a ri nas we r e l o we r t h an T SS co n c en tration s in th eir resp ect iv e LRSs.

Correl ati o ns of Total Sus pe nded Solids and Dissol v ed Organic Car b on with Metals
A c o rrelation a n alysis was conducted on t h e TSS, DOC, and m e tals d a ta to d e term in e th e presen ce of li n ear rel a t i ons hi ps a m ong th e vari abl e s. Al l pai r
- w i s e Pear s o n c o r r el at i on coe f fi ci ent s an d t h e n o n
- param e tr ic Spearm an’s ran k -c o rrelatio n c o ef ficients were com put ed f o r t h e l o g
- tr a n sf orm e d dat a set

. Acro ss all d a ta (all water typ e s co m b in ed), t h ere were n o si gni ficant c o rrelations betwee n TSS and a n y of the three m e t a l anal y t es (i .e., DC u, TC u, a n d DZ n). Furt herm ore, n o si gni fi ca nt c o r r el at i ons we r e o b ser v e d wh en th e dat a we r e eval uat e d se parat e l y as m a ri na an d LR S dat a set s
. W i t h in brackis h m a rina areas , a fe w si gni ficant but weak re l a tions hips we re observe d

. For e x am ple, there was a m odest l i n ear c o r r el at i on bet w een T SS a n d T C u i n b r acki s h water m a rina a r eas (m arina sites + LRSs ) (Pearson’s r = 0

. 5 6 , p < 0

. 00 05 ) (Fi g ure 25 ). A weak p o sitiv e lin ear as so ciatio n of TSS-TCu also ex ists in b r ack ish marin a s (Pearson ’ s r = 0

. 5 1 , p < 0

. 00 05 ). Howev e r, t h e m o st no tab l e of th e TSS-TCu co rrelatio n s is th e st rong po sitiv e lin ear associ at i o n i n brac ki sh LR Ss (Pear so n’s r = 0. 84 , p < 0. 0 0 0 5 ) (Fi g u r e 2 5 ).

34Figure 25. Correlation of T o tal Susp ende d Solids and Total Copper Con centrations in Br ackish LRSs

2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

lo g T C ulogTSS

P e a r s o n ’ s r = 0. 84, p < 0. 0005

It is po ssi b l e that th e ob serv ed po sitiv e relati o n s h i p b etwee n TSS and TC u for b r ack i sh wate r LR Ss is reflectiv e o f the t e nde ncy o f m e t a l s i n sol u t i o n t o bi nd t o sus p en de d s o l i d s i n th e wat e r c o l u m n
. T hus , w a t e r wi th hi gh am ount s o f sus p ende d s o lids will tend to also have hi gh am ounts of m e ta ls associated with them

. Re call that TSS at the Vallejo an d Ben i cia LRSs (b rack ish water sites) exh i b ited TSS load s t h at were mu ch h i gh er than an y o t h e r sites in t h is stud y (m ed ian TSS co n cen tration s > 50 m g /L).
TSS ca n al s o s e rve t o bi n d D C u a n dco n v ert i t

t o part i c ul at e co ppe r (M o rr i s, 1 9 86; Ac kr oy d et al

. , 19 8 6 )

. T h e m o re TSS t h ere ar e i n a sam p le, a highe r capacity gene rally exist s to l o wer th e DCu con c en tra tio n in th at sam p le. Th is bi n d i n g e ffect m a y pot ent i a l l y expl ai n th e n e gat i v e l i n ear r e l a t i onshi ps t h at are obse r ved f o r TSS an d D C u ( P ears o n’s r = -0 .7 8, p < 0

. 0 005 ) ( F i g ur e 2 6 ) and forTSS and D Z n ( P ear s on’ s r =
- 0 .64 , p < 0.000 5) ( F igu r e 27) at t h e Ben icia and Val l e jo m a ri na areas. T h us, a t l east fo r brac ki sh wat e r s , t h e m a gni tude of DC u m a y be si gni fi ca nt l y i n f l uence d by th e am ount o f part i c ul at e m a t t e r th at exi s t s i n t h ese wat e r s at a n y gi ven t i m e. B y co nve rt i n g di ss ol ve d m e tal s t o p a rticu l ate m e t a ls, su sp end e d so lid s i n n a tural water system s are m o d e ratin g b i o a v a ilab ility o f co pp er an d o t h e r m e ta l s to aqu atic o r g a n i sm s. No te t h at an y sign ifican t d ecreases in TSS c o ncentrat ions in t h ese brackish m a rinas could res u lt in a lower lev e l o f DC u co nv ersion p o t en tially lead i n g t o hi ghe r c o ncentr a t i ons of o b se rv ed DC u
. No sign ifican t co rrelatio n s b e tween TSS and m e tals were ob serve d for sal t water sam p les. C o rrelation of fres hwate r TSS a n d m e tals data was not conducted sinc e m o re than 50% of the fres hwater T SS data were b e low d e tectio n limits (<4 m g /L).

35Figure 26. Correlation of T o tal Suspende d Solids vs. Di sso lve d Coppe r Concentr ati o ns at Benicia and Vallejo Marin a Are a s

1.6 1.4 1. 2 1. 0 0.8 0.6 0. 4 0. 2 5.0

4.5

4.0

3.5

3.0

2.5

2.0

lo g D C ulog TSS P e a r s o n ’ s r = - 0. 78, p < 0. 0005

Figure 27. Correlation of T o tal Suspende d Solids vs. Di sso lve d Z i nc Concentrations at Benici a and Vallejo Marin a Are a s

2. 5 2. 0 1. 5 1. 0 0. 5 0. 0 5. 0

4. 5

4. 0

3. 5

3. 0

2. 5

2. 0

lo g D Z nlogTSS P e a r s o n ’ s r = - 0. 64, p < 0. 0005

36Si m ilar to th e case of TSS, acro ss all d ata (all water ty p es com b in ed ), t h ere were no si g n i fican t correlation s b etween DOC a n d a n y of the t h ree m etal analytes (i .e ., DC u, TC u, a n dD Z n )

. F u rt herm ore, n o si gni fi cant c o r r el at i ons were o b s erv e d wh en th e d a ta were ev alu a ted sep a rately as a m ari n a d ataset. Howev e r, th ere were weak po sitiv e co rrelatio n s b e tw een D O C an d D C u ( P earso n’ s r= 0.50 , p < 0

. 00 05) and also TC u (Pear s on’ s r = 0

. 64 , p < 0.000 5) f orth e LRS dat a
. B y wat e r t y pe, a weak c o r r el at i on was al so o b ser v e d bet w e e n DOC an d D C u i n sal t w at er LR Ss (Pearso n ’s r = 0

. 48 , p < 0

. 00 05)

. Buck et al. (2 007 ) and K u w a b a r a et al. (19 8 9 ) bo th fo und p o s it iv e corr e lations of D O C t o DCu co n c en tration s in th e am b i en t waters of San Fran cisco Bay. Th is asso ciatio n is su ppo rted b y th e fi n d i n g th at in a m b i en t water, th e m a j o rity of DC u ex ists as a co m p lex with d i sso l v ed organ i c m a tter (Bu c k and B r u l and , 20 05 ; Hurst andB rul an d, 2 0 0 5 )

. Thi s rel a t i ons hi p bet w e e n DOC an d D C u i s not l i k el y t o e x i s t i n m a ny sal t w at er m a ri nas si nce sig n i fican t inpu t of cop p e r b y m arin a so ur ces greatly d i stu r b s t h is equ ilib riu m th at su pp osed t o ex ist in a m b i en t water areas. M o reo v e r, si nce DC u conce n tr at i o ns at LR Ss c oul d pot e n t i a l l y be i m pact ed by co ppe r t h at i s g e n e rat e d fr om t h e m a ri nas, t h e D O C

- DC u re l a t i onshi p c oul d be weake n e d

. No co rrel a t i o n s we re obs er ve d bet w ee n DO C an d m e t a l s for b r acki s h or f

r esh w at er
.
Irgarol an d M1
Water sam p les f o r Ir garol a n dM 1 a n aly sis w e re take n i n th e first (J uly to A u g u st) an d t h ir d (Se p tem b er to No vem b er) sam p lin g r ound s. Fo r ty f iv e o u t of th e an ticip ated 4 8 w a tersam p les f o rt h ese an alyses w e r e co llected f r o m 1 1 m a ri nas. Thi r t y -three sam p l e s we re fr om eight sal t w at er m a ri nas an d 1 2 sam p l e s were fr om th ree b r a c ki sh wat e r m a ri nas. C o mp l e t e Ir ga rol a n d M 1 res u l t s a r e p resent e d i n Ap pe ndi x G. Irg a ro l an d M1 were d e tected in all 45 sam p les (limit o f q u a n tificatio n [LOQ] of 0

. 1 ng /L o r part s per tr i l l i on f o r

b o t h anal y t es). Ir garol det ect i o n s r a nge d fr om 12 t o 7 1 2 ng/L

. T h e hi g h est samp l e co nce n tr at i o n o f Ir gar o l w a s doc um ent e d at Loc h L o m ond M a ri na i n Sa n R a fael

. M 1 de t ect i ons ra n g e dfr om 1.6 t o 2 1 7

. 1 ng/L

. T h e hi g h est sam p l e concen tr at i on of M 1 was al s o doc u m ent e d at L o c h L o m ond M a r i na. M 1 c o nce n tr at i o ns were al way s l o wer th an Irg aro l i n th e sam e sa m p le.
M a ri na m e di an co ncent r at i o n s we re cal cul a t e d fo r Ir gar o l f o r bot h sam p l i ng ro u nds (Fi g u r e 28 ). F o r th e fi rst ro u n d , m a ri na m e di an co ncent r at i o n s we re hi g h est a t

Loc h L o m o n d M a ri na (5 3 9

. 0 ng/L ) , f o l l o w e d by M d R bac k basi n # 3 /4 (2 7 7

. 6 ng/L ) , a n dB e rk el ey M a ri na (1 9 7

. 6 ng /L ). The l o wes t m a ri na m e di an c once n tr at i o n was at B e ni ci a M a ri na (30.0 ng/L). For the t h ird roun d, Irgarol c o ncentrations were noticeably lower. Me dian c once n trations were hi ghest at Loc h L o m ond M a ri na (1 4 8

. 1 ng/L ), f o l l o we d by M a ri na B a y Yacht Harb or ( 1 1 1

. 9 n g /L ) , an d B a l l e na I s l e M a ri na (9 8. 9 n g /L ). T h e l o west m a ri na m e di an c o n centr at i o n was at Al am i t o s B a y M a ri na (2 1. 1 n g /L ).
Marina m e dian concent r ations we re also calc u lated fo r M 1 ( Figu r e 2 8 ). F o r the first r o u n d , m a rina m e dian conce n tr at i o ns were hi ghest at

Loc h L o m ondM a ri na ( 1 8 9

. 0 n g /L ), f o l l o we d by M d R bac k basi n # 3 /4 ( 1 04 .2 n g /L ) , and Berkeley Marina (75.6 ng/L). For the third round, M1 concen t r ations (like Irgarol c once n trations ) were noticeabl y l o we r. M e di an co ncent rat i o n s we re hi g h est a t Loc h L o m o n d (1 4 8

. 1 ng/L ), f o l l o we d by M d R bac k basi n #1/ 2 (2 2. 0 ng/L ), a n d M d R bac k basi n # 3 /4 ( 2 2 .0 n g /L )

. The o v eral l m e di an Ir garol a n d M 1 c once n tr at i ons fo r al l m a ri n asites w e re 66 .1 an d 15 .1 ng /L, r e sp ectiv ely ( T ab le 9 )

. M e di an Ir gar o l co ncent r at i o n s f o r t h e fi rst a n d th i r dsam p l i ng ro u nds we re 80 .5 an d 5 3

. 2 ng/L , re spect i v el y
. Table 9. Sum mar y of Medi an Ir gar o l a n d M 1 C o ncen t r ati o ns (n g/L) in W a terS a mples (S how n w i th b a ck
transformed lower and upper 95 % Confidence Inter val s)

An al yt e Ov era ll Media n C o ncentrat ion w/ 95 % C I 1 stRou nd (Jul y/Au gus t ) Me dian C o ncentrat ion w/ 95 % C I 3 rd Round (Se p tember/Oc tober) Median Conc entr ation w/ 95 % CI Irgarol 50.1 - 66 .1 - 87 .1 5 1

. 9 - 80 .5 - 12 4.8 3 8 .9 - 53 .2 - 74 .8 M1 10.3 - 15 .1 - 22 .0 2 0

. 2

- 31 .0 - 4 7. 8 4. 3 - 6. 8 - 10 .9

37Figure 28. Marina Median I r gar ol and M1 W a ter Conc en tr ations by Rounds (Rou nd 1 = Jul y /Augus t, Rou nd 3 = September/ October).

M 1 R o und 3 M 1 R ou nd 1 I r ga r olR oun d 3 I r ga r ol R o und 1 600

500

400

300

200

100

0Irgarol/M1Concentration(ng/L)

At alm o st all o f th e sam p lin g sites, Irg aro l an d M1 con c en tr ations we re hi ghe r i n the first round as c o m p ared to t h e th ird ro und

. Paired t-tests on lo g-tr an sf orm e d Ir gar o l a n d M 1 res u l t s y i el ded st at i s t i cal ly si gni fi ca nt di ffe rences b e tween th e fi rst and th ird ro un d of sam p lin g fo r bo th Irg arol co n c en trations (t 11 = 2. 4, p = 0. 0 3 6 ) a n d M 1 (t 11 = 13.1, p < 0. 0 0 0 5 ) c o ncent r at i ons
. ANOVA tests of res u lts also showe d t h at there was a sta tistically sig n i fican t d i fferen c e am ong m a ri nas (f ul l y -nest e d b a lan c ed A NOV A, F 11,23 = 5. 0, p = 0 .0 0 5 , w i t h M d R gr o u p e d i n t o 2 m a ri nas). T h at i s , Ir gar o l c once n tr at i ons vari e d con s i d era b l y a m ong th e m a ri nas t e st ed

. R e sul t s f o r

M 1 di d not sh o w a n y st at i s t i cal ly signi fi cant di ffe r e nce am ong marin a s (fu lly-n ested b a lan c ed A NOV A, F 11 ,23 = 1. 7, p = 0. 18 1, wi th M d R bei n g cat e g ori zed as 2 m a ri nas).
There wa s a si gni fi cant l o g
- l o g co rrel a t i o n bet w ee n Ir gar o l and M 1 co nc entr at i o ns (Pearso n ’ s r = 0. 85 , p < 0 .0 0 0 5 ) (Figu r e 29). Th is resu lt is exp ected b ecau s e M1 is t h e p r i m ary degradat e of Irgarol. Assu m i ng that there are no othe r app r eci abl e so urces o f M 1 , t h e am ount o f M 1 th at i s ge ne ra t e d i s depe n d e n t o n t h e am ou nt o f Ir gar o l th at i s pre s ent and on e n vironmental factors

. Fo r th e saltwater sites, t h e m e d i an con cent r at i ons f o r

I r garol an d M 1 w e re 83 .7 an d 2 0

. 1 ng/L , re spect i v el y
. Fo r b r ack i sh water sites (Ben icia, Vallej o , an d Pi ttsb u r g m arin a s), t h e m e di an conce n tr at i o ns fo r Ir gar o l a n dM 1 we re 3 3

. 2 an d 6.8 ng /L, resp ectiv ely. B a sed on th e r e su lts of two- sam p le t-tests o f lo g-transfo r m ed co n c en tration d a ta, saltwat er m a ri nas ex hi bi t e d hi ghe r c o n centrat i o ns of bot h Ir gar o l (t 22 = 2.7, p = 0

. 01 3) and M1( t 22 = 2.2, p = 0

. 037 ) as co m p ar ed to b r ac kish wat e r m a rinas.

38Figure 29. Correlation of Ir gar ol vs. M1 Concentrations at Marina Waters

6 5 4 3 2 1 0 7

6

5

4

3

2

l o g M 1 C o n cen t r at i o n slog IrgarolConcentrations P e a r s o n ’ s r = 0. 85, p < 0. 0005

Total Cop p er - Sedime nt
Twe n t y th ree o f th e ant i c i p at e d 18 0 s e di m e nt sam p l e s were anal y zed fo r T C u ( A ppe n d i x H). Se di m e nt col l ect i on was li mited to three freshwater m a rin a s: Fo lso m Lak e , Sacram en to Marin a , and Villag e West Marin a
. No sed i m e n t was co llected fro m th e rem a in in g 2 0 m a rin asites du e to log i stical an d safety issu es. At th e t h ree sites, DPR’s field crew u s ed a sam p l i n g v e ssel o w n e d b y th e Cen tral Valley Reg i on al W a ter Qu ality Co n tro l B o ard (CVRWQCB) with th e assistan ce o f its staff. Th is p articu l ar v e ssel was equ i pp ed with a man u a llyope rat e d wi nch , w h i c h al l o we d fi el d cre w t o col l ect sedi m e nt sam p l e s. I n st ead of ca ncel i ng t h e e n t i r e s e di m e nt collection, DPR chose to coll ect as m a ny sam p les as possi ble using this vessel.
Sedi m e nt TC u conce n trat i o ns were l o g- no rm al l y di stri but e d , an d ra nge d fr om 17 t o 1 6 7 m g / kg. Not e t h at TC u i n sed i m e n t refers to th e con c en t r atio n of to tal co pp er in th e sed i m e n t an d no t in th e in terstiti al o r po re water in th e sedi m e nt

. The hi g h est TC u c once n tr at i o n w a s d o c u m e nt ed at Sacram ento Marina a n d the lowe st was docum e nted at an LRS o f t

h at m a rina. Fo r th e three m a rinas w h ere sedim e nt sam p les were collected, m e dian TCu c o nc entrations i n sedi m e nt were 13 1. 5 m g / k g f o r th e th ree f r es hwat e rm a ri na si t e s and 4 8

. 5 m g / kg f o r t h ei r associ at ed LR Ss (T abl e 1 0 ).
Paired t-tests were use d t o te st the e qui valence of m a ri na and LRS sedi ment TCu c on centrations for each m a rina. There we re si gnificant differe n ces i n TC u c o ncent r ations be tween m a rin asites an d LRSs fo r all th ree m a r i n aareas: Fol s om M a ri na /L R S (t 5 = 8. 18 , p < 0. 00 0 5 ) , Sacram ent o M a ri na/L R S (t 6 = 4

. 31 , p = 0.005 ), an d Villag e W e st M a rina/LRS (t 6 = 4 .9 6 , p = 0. 00 3 )

. I n al l ca ses, TC u c once n tr at i o ns i n m a ri na se di m e nt were hi ghe r i n si de th e m a ri na th an i n th e ad j a cen t LRSs (Fi g u r e 30 ).

39T a bl e 10
. S u m m ar y of Medi an Me tal C o n centr ati o ns ( m g/k g dr y w e i g ht ) i n Sedi m e nt S a m p l e s Median T C u Concentrations w/ 95 % CI Median TZ n Concentrations w/ 95 % CI Marin a Sites LRSs Marin a Sites LRSs

3 Fres hwater Marin a Are a s 11 8. 2 - 13 1.5 - 14 6.3 3 6 .2 - 48 .5 – 6 4. 8 15 1. 3 - 18 2.5 - 22 0.2 4 9 .2 - 78 .3 - 12 4.7

Figure 30. Dis t ributi o n of T o tal Copper Con centr ations in Marina Ar ea Se diments

V

i l l a g e W

e s t L R

S

V i l l a g e W

e s t M

a r i n a

S

a c r a m

e n t o L R

S

S

a c r a m

e n t o M

a r i n a

F

o l s o m

L

a k

e L R

S

F

o l s o m

L

a k

e M

a r i n a 18 0 16 0 14 0 12 0 10 0 80 60 40 20

0TCuConcentrations(mg/kg dryweight)

Total Z i nc - S e diment
Twen ty th ree of th e an ticip ated 1 8 0 sed i m e n t sam p les were collected a n d a n alyzed fo r T Z n (A pp en dix H )

. TZn c o ncent r at i ons ra nge d fr o m 23 t o 27 3 m g / k g. T h e hi g h e st co ncentr at i ons we re d o cu m e nt ed at Vi l l age West M a ri na a n d th e l o we st at

an L R S ad jace nt t o th e F o l s om Lake M a ri na. F o r th e th ree m a rinas wh ere sedi m e nt was co llected , m e d ian TZn con c entr atio n s i n sed i men t w e r e 182.5 m g /k g fo r the m a r in asites an d 78 .3 m g /kg f o rth e associated LR Ss (T able 10).
Pai r ed t

- t e st s were use d t o t e st th e e qui val e nce of m a ri na and LR S sedi m e nt TZn co nc entr at i o ns fo r e ach m a ri na. Th ere were si gn ifican t TZn co n c en tra t i o n di ffe rences bet w een m a ri na an d LR S for all three m a rina area s–Folsom M a rina/LRS (t 5 = 1 2

. 5 6, p < 0. 00 0 5 ) , Sac r a m ent o M a ri n a /L R S (t 6 = 4

. 28 , p = 0

. 00 5), and Villag e West Marin a /LRS (t 6 = 6. 2 8 , p = 0 .0 0 1 )

. I n al l case s , TZ n c o ncent r at i ons i n m a ri na se di m e nt were hi g h er i n si de th e m a ri na th an i n t h e adjace nt LR Ss (Figure 31).

40Figure 31. Dis t ributi o n of T o tal Z i nc Con centr ations in Marina Are a Sediments

V

i l l a g e W

e s t L R

S

V i l l a g e W

e s t M

a r i n a

S

a c r a m

e n t o L R

S

S

a c r a m

e n t o M

a r i n a

F

o l s o m

L

a k

e L R

S

F

o l s o m

L

a k

e M

a r i n a 30 0

25 0

20 0

15 0

10 0

50

0Concentrations(mg/kg dry weight)

T oxi ci t y All of th e an ticip ated 4 8 tox i city sa m p les were co llected fo r to x i city tests on mu ssel em b r yo d e v e lop m en t. On e water sam p le (from Pittsburg Ma rina) was , howe ver, e x cluded from testing be cause it was not saline enough to m eet m i nimu m t e st requi rem e nt s. Ei ght of 4 7 sa m p l e s (17% ) e xhi bi t e d st at i s t i cal l y si gni fi can t to x i city (Tab le 11 ). Sev e n of th e eigh t tox i c sam p les cam e from M a ri na del R e y ( M dR ) i n L o s A ngel e s
. T h e re m a i n i ng t o xi c sam p l e ori g i n a t ed f r om M a ri n aB a y Yac h t Harbo r (MBYH) i n Rich m o nd

. Th e co m p le te to x i city test resu lts are av ai lab l e in App e nd ix G wh ile the to x i city d a ta rep o rt fr om SCC W RP is i n A ppe n d ix I.
T a bl e 11 . W a t er Sa mpl e s w i th S t ati s ti c a l l y Si gni f i c an t T oxi c E ndp oi nt s Sample Number Lo catio n C o ncentrat ion of DC u i n ass o ci ate d metal sam p le ( μ g/L ) Percent Norm al-Alive Sample Mea n Percent of Co ntr o l Stand a rd Devi ati o n Numberof Replicates 11 1 M B YH # 1 1. 7 72 88 5. 1 4 11 8 M dR FB #2 12 .5 55 64 11 .1 4 11 9 M dR B B # 3 12 .4 61 72 6. 9 4 12 0 M dR FB #1 13 .1 67 79 11 .8 4 12 1 M dR B B # 2 18 .4 4 4 1. 9 4 12 3 M dR B B # 4 14 .2 66 78 10 .8 4 17 8 M dR B B # 1 11 .5 37 44 7. 6 4 17 9 M dR FB #4 11 .9 49 57 7. 1 4

41Toxic a nt Ide n tifica ti on E v al uati on (T IE )
Tw o sam p l e s ( s am pl e num bers 1 2 1 a n d 1 7 9 ) we re t e st ed us i ng Pha s e I TI E p r oce d ures ( A p p e ndi x I). B o th of th e sel ect ed sam p l e s we re s u bject ed t o tr eat m e nts desi gne d t o s e l ect i v el y rem ove o r ne utral i ze cl asses of c o m pou nd s (Tab le 12 ). Treated sam p les were th en retested to d eterm ine whethe r c h anges i n toxicity occurre d a s a result of the tr eatm e nt s. A cont rol sam p l e , usi n g l ab o rat o ry sea w at er , was i n cluded with eac h type of tr eatm e nt to verify t h at the m a ni pul at i o n i t s el f wa s not causi n g t oxi ci t y
. Sam p l e s fo r e ach T I E m a ni p u l a t i on we re t e st ed at 10 0% s a m p l e stren g th

. Each sam p le was subjected t o four treatm ents:
• Ethylenediam i n etetraacetic a cid (EDTA) addition, which c h elates m eta ls and re duces the toxicity caused by them

. • Sod iu m th io su l f ate (STS) add i tio n , wh ich redu ces ox id an ts an d d e creases the to x i city of some m e tals, in cl u d i n g coppe r
. • C e ntri f ugat i o n, w h i c h rem ove s part i c l e s an d red u ces t h e t o x i ci t y associ at ed wi th sus p e nde d s o l i d s.
• C- 18 co lu m n ex tr action , wh ich r e m o v e s non- po lar or g a n i c co m p o u n d s and r e du ces t h e t o x i city cau sed b y th em
. T a bl e 12 . T o xi can tIde n ti fi c a ti on E val u a ti on T r e a t ment Resul t s

Sample Number Treatme nt Percent Norm al-Alive Sample Me an Percent of Co ntr o l Stand a rd Devi ati o n Numberof Replicates 12 1 B a sel i n e* 1 1 1. 1 4 12 1 EDT A 91 93 6. 8 3 12 1 STS 55 57 1. 3 3 12 1 C e ntri f uge 6 6 1. 5 3 12 1 C

- 1 8 C ol um n 80 82 3. 6 3 17 9 B a sel i ne* 14 14 4. 1 4 17 9 EDT A 92 92 10 .4 3 17 9 STS 82 83 1. 7 3 17 9 C e ntri f uge 37 38 8. 3 3 17 9 C

- 1 8 C ol um n 62 63 54 .0 3
* Results ar e differ e nt fr o m the analo gous sam p le in the pr evi ous table since baseline toxicity tests wer e r e done for the T I E s.

A d ecrease in sa m p le to x i city after th e E D T A a n d ST S trea tm ents suggest e d th at a cationic m etal was re sponsi ble for th e m a j o rity of th e tox i city. Id eally, if m e tal s were th e pri m ary cau se o f th e tox i city, th e C-18 co lu m n treatm e n t wo u l d h a v e h a d little effect o n th e ob serv ed tox i city o f th e b a seline sam p les; h o wev e r, th e i n term ed iate to x i city redu ctio n that was ob ser v e d i n th e C

- 18 res u l t s sug g est e d t h at n o n
- p ol ar o r ga ni cs were c a usi n g s o m e of th e t o xi ci t y
. F o l l o w u p discussi ons with SCC W RP pe rsonnel re veale d that t h e C

- 18 colum n s used by SC C W R P h a ve been d o c u m e nt ed t o also rem ove a sm all am ount of trace m e tals along with the non-polar orga nics. The se questration of m e tals by C-18 colum n s has been note d in a recent SCC W RP study (Schi ff et al., 2007 ). In t h at study, the col u m n s were estim ated to have rem ove d 45 % of t h e c o p p er o u t of t h e s a m p l e sol u t i o n
. T h i s l e vel o f cop p e rrem ova l coul d acc o unt f

o r t h e in term ed iate red u c tion of tox i city th at was ob serv ed for th e two C-1 8 TIE sam p les.
Ove r all, based on res u lts of t h e TIEs and t h e com p lications w ith th e C-1 8 co lu m n s, it is l i k e ly th at cation i c m e tals are the cause of t h e toxicity. C o ppe r c o ncentr a tions i n these s a m p les were hi gh enou gh t o e x ceed the t o xicity test’s range of

ef fects (i.e ., EC 50 ’s). Zi nc conce n tr at i o ns were bel o w i t s ran g e of ef fect s. T h e r ef ore , we bel i e ve t h at co ppe r i s t h e m o st lik ely cau se of tox i city in th e two TIE sam p les fro m Md R.

Com p ari s ons to W a ter Qu a l i t y S t a n d a rds
Two water q u a lity in d i cato r s o f AFP p o l l u tio n (cop p e r an d zin c ) were com p ared to av ai lab l e water qu ality stan d a rd s. Th ere are no ap p licab le water qu ality stan d a rd s fo r Irg a ro l o r M1 , howev er, t h ere are estab lish e d stand ard s for cop p e r an d zin c
. Th e m o st relev a n t water qu ality stan d ard s fo r cop p e r and zin c in th e State o f Califo r n i a are sp ecified in t h e C T R(U .S. EP A, 2 0 0 0 )

. The C T Rco nt ai ns t w o st an dar d s

– t h e c r i t e ri o n m a xi mu m concen tr at i on (C M C ), w h i c h i s th e acut e st an dard defi ned as th e hi g h est c once n tr at i on of a po llu tan t to wh ich aqu a tic life can b e ex po sed fo r a sh ort p eri o d of tim e with ou t d eleterio u s effects, and th e criteri o n co n tinuo us co ncen tration (CCC), wh ich is t h e chron i c

42st andard de fi ne d as th e hi g h es t conce n tr at i o n o f a p o l l u t a nt t o whi c h a quat i c l i f e can be ex pos ed f o r

an ex t e nde d peri od o f

ti m e with out d e leteriou s effects. For bo th cop p e r an d zinc, th e CMC and CCC are d e fi n e d as a 1-hou r av erag e and a 4-day a v era g e, res p ectively.
Consi d eri n g the specific way the CTR defi nes com p liance a ssessm ent for coppe r a n d zinc standards a n d the way t h e sam p les in th is stud y were taken , a d i rect com p ariso n o f th i s stu d y ’ s a n al y t i cal resul t s t o num eri c st an dards m a y not be th e m o st fittin g app r o a ch fro m a co m p lian ce stan dpo in t. Howev e r, sin ce t h e go al of t h is st u d y is water quality assessm en t an d no t regu lato ry co m p lian ce, such a co m p arison is still in fo rm ativ e in d e termin in g th e relativ e lev e l of metal p o llu tio n at a nu m b er o f sites acro ss Califo r n i a. CTR Freshwa t er CMC a n d C CC Wa ter Quality Sta n da rd s - Copp er
Fresh w ater DCu resu lts were co m p ared t o the CTR’s h a rdness-based CMC and CCC stan d ard s to d e termin e if th ere were an y ex ceed an ces (Ap p e n d i x J). CMC an d CCC equ a t i o n s and con v e rsion facto r s that are estab lished in th e C T R w e r e u s ed t o calcu late th e site- s p eci f ic copper w a ter q u a lity stan d ar d s (U .S. EPA , 200 0) u s ed for th e com p ar iso n
. Note t h at U

. S. EPA de fines f r e shw a ter as water th at co n t ains salin ity at 1 part p e rthou sand an d b e l o w at lo catio n s whe r e t h is occ u rs 95% or m o re of t h e tim e. In brackis h wat e r areas th at ar e bet w ee n 1 a n d 10 part s per th o u sa n d i n salin ity, th e fresh w ater criteria cou l d still ap p l y if th ey are m o re strin g e n t th an t h e saltwater criteria. Based on th ese d e fi n itio n s , fresh w ater CCC an d CMC were calcu lated for t h e fo llowing si x m arin as: Tah o e Keys, Fo lso m Lak e , Sacram en to , Villag e W e st, An tio ch, an d Pittsb u rg
. Ben i cia and Vallej o marin a s are lik el y to exp e rien ce salin ity th at is hi g h er th a n 10 part s pe r th o u s a ndf o r

m o st of th e y ear an d w e re th us l e ft o u t of th i s det e rm i n at i on.
No ne o f th e D C u c once n tr at i ons i n th e 1 3 5 fres h w a t e r sam p l e s c o l l ect ed f r om si x di ffe re nt m a ri na areas excee ded th e acute or c h roni c CTR standards for c o ppe r. CTR Freshwa t er CMC a n d C CC Wa ter Quality Sta n da rd s - Zinc
Fresh w ater DZn resu lts were co m p ared t o the CTR’s h a rdness-based CMC and CCC zinc stand a rd s t o d e term in e if there were any exceeda n ces (Appe ndi x K). CMC and CCC equations and c o nve r sion factors t h at are established in the CTR w e re used to calcu late t h e site-sp ecific zin c w a ter qu ality stan d a rd s (U .S. EPA , 2000 ) u s ed fo r t h e co m p ariso n
. The sam e sal i n i t y consi d e r at i ons as t h o s e pr esent e d i n t h e pre v i o us sect i o n fo r DC u ap pl y here

. Non e of th e DZn con cen tratio n s in th e 13 5 fresh water sam p les c o llected from six di ffe re nt m a rina areas excee ded the acute or c h roni c CTR standards for zi nc. CTR Sa ltwa t er CMC a n d CC C Wa ter Qua l i t y Sta n d a rd s - Co pp er
Salt an d brack i sh water DC u resu lts were com p ared to t h e CTR’s fi x e d saltwater CMC an d CCC stand ard s to determ ine if there were a n y e x ceeda n ces. The CTR states t h at the saltwater criteria ap ply at salinities of 10 parts per thousa nd and a b ove at l o cations whe r e t h is occu r 95 % or mo r e of th e tim e. Mo reove r , t h e saltwater c r iteria could also appl y at sal i n i t i e s bet w ee n 1 a n d 1 0 part s pe r th o u sa n d i f t

h ese criteria ar e m o re stringe nt than t h e fres h water c r iteria. There f ore, our evaluation of e x ceeda n ces of the saltwater standards incl udes th e salt a n d brac kish wate r marinas as classified b y this stu d y (see Tab l e 1). Th us, Taho e Keys M arin a, Fo lso m Marin a, Sacramen to Marina, an d Villag e West M a ri na were excl ude d fr om consi d e r a t i on a g ai nst s a l t w at er st an dard s.
Fo r salt and brack ish waters, th e CTR standard s fo r co p p er are fi xe d. T h e co ppe r C M C i s 4. 8 μ g /L an d r e pr esen ts a short-term (1-hour) ave r a g e that is not to be e x ceede d m o re t h an once e v e r y three years on the ave r a g e. T h e c o ppe r CCC is 3

. 1 μ g/ L and represe n ts a 4-day a v e r age that is not t o be e x ceeded m o re than onc e eve r y thre e y ears on the avera g e. In salt and brac kish water area s, DC u c o ncent r ations in 16 of 19 m a rinas ex ceeded the CCC. The m a rina areas where DCu conce n tra tions did not e x ceed the ch ronic standard (a nd thus not the acute sta nda rd either) we re Antioch, South Beach Harbor, and Coy o te Point. DCu conc entrations i n 10 of the 16 m a rinas thate x cee ded the CCC al so e x cee ded th e C M C

. T h e s e 1 0 m a ri nas were Loc h Lo m ond M a ri na , C l i pper Yac h t Har b or, B e rk el ey M a ri na, B a l l ena Isl e

43M a ri na, Sant a C r uz Harb or , M ont erey Harb or , Sa nt a B a r b ara Har b o r , M d R f r ont basi n s , M d Rbac k ba si ns, a n d Down town Sho r elin e Marin a
. Of t h e 388 samples take n from the 19 sa lt a n d brac kish wa ter m arina area s, 118 or 30% exceede d t h e C CC. Of t h ese 11 8 s a m p l e s, 6 7 had hi gh en o u g h DC u c onc entr at i o ns t o al so e x cee d th e C M C

. O v eral l , th i s n u m b er i s eq ui val e nt t o ab ou t 1 7 % o f all salt an d brack i sh water samp les fro m th is study that e x cee ded the CMC. Foc u sing s p eci fically on marin a sam p les, 114 o f 224 (5 1%) sam p les fro m salt an d brack ish water marin as ex ceed ed th e CCC. Fu rt h erm o r e, 67 of

2 2 4 ( 3 0%) o f sam p l e s fr om sal t an d brac ki sh wat e r m a ri n a s excee de d th e C M C

. Marina sam p les take n from MdR had the gre a test fre que ncy of CCC and C M C exceeda n c e s by far am ong all the m a rinas. In fa ct, all of the m a rina sam p les (12 of 12 sa m p les) fro m Md R’s Fron t and Back Basins were well abov e t h e C M C

. Fo u rm a ri nas e x hi bi t e d DC u co nce n tr at i ons th at we re ab ov e t h e C M C in m o re than h a lf o f th e sa m p les tak e n at th at part i c ul ar m a ri na. T h ese m a ri nas were Loc h L o m ond M a ri na (8 o f 1 2 sam p l e s), M ont e r ey Harb o r ( 8 of 1 2 sam p l e s), Sant a B a rbar a Har b or ( 9 of 1 2 sam p l e s), an d D o w n t o wn S h o r el i n e M a ri na ( 1 0 o f 12 sam p l e s).
On ly 4 o f th e 11 8 sam p les th at h a d DC u concen tration s abov e th e CCC were LRS sam p le s. DCu con c entratio n s i n th ese sam p l e s r a nge d bet w ee n 3. 4 a n d 3. 8 μ g /L. M o re ove r, three of these f o u rsam p les ca m e from M d R’ s LRS # 1 , wh ich after a t h oro ugh ev aluatio n o f m e ta ls d a ta, app eared to resem b le a marin asite rat h er th an an LR S. Of th e fo ur LRSs at Md R , th is LRS is t h e clo s est to th e Md R m a rin as ites. TC u , DCu, and DZn concen tration s from Md R LRS #1 ten d e d to b e at an in term ed iat e lev e l between Md R ’ s ei g h t basin sites and the three LRSs fart hest a w ay from the m a ri na area
. M e t a l conce n tr at i ons fr om MdR ’ s LR S # 2

– 4 we re typ i cally v ery l o w. The rem ain in g LRS sam p le th at exceede d t h e C CC was a sample take n from Ballena Isle M a rina’s LRS #7.
Note t h at site s p ecific objectives (SSO s ) tha t are higher t h a n the CTR are aw ai t i ng a p pr o v al by U. S. EP A (R . L o oke r, p e rson al co mmu n ication , 2008 ). Th e CCC, as propo sed in th e SSO s , is 6

. 0 μ g/L an d t h e C M C i s 9. 4 μ g/L. O n ce th ese SSOs are ado p t ed , t h ey will sup e rced e th e CTR criteri a as th e enforceab le water q u ality stan d ard s for mu ch o f San Fra n cisco Bay, where m a ny of t h e m a rinas in t h is study is lo cated. This m ean s th at DCu con c en tratio n s i n th ese marin a s will be in co m p lian ce with water qu ality stan d ard s m o re frequ ently. Th e estab l ish m en t o f SSOs will m ak e th is sectio n’s co m p ariso n of DCu resu lts wi th water q u ality stan d ards somewh at ob so lete. An up d a ted co m p arison with th e n e w SSOs will und ou b ted ly resu lt in a l o wer frequen c y of ex ceedan ces. CTR Sa ltwa t er CMC a n d CC C Wa ter Qua l i t y Sta n d a rd s - Zinc
Salt an d brack i sh water DZn resu lts were com p ared to t h e CTR’s fi x e d saltwater CMC an d CCC stand ard s to determ ine if there were a n y e x ceeda n ces
. For salt and brac kish waters, t h e CTR standards for zi nc are also fi xed values

. T h e zi nc CMC is 90 μ g/L and repre sents a short

- term (1-hour) a v er age that is not to be exc eede d m o re tha n o n c e ev ery three years o n th e av erag e. Th e zin c CCC is 81 μ g/L a n d re presents a 4-day avera g e t h at is not t o be exceede d m o re than once e v e r y th ree years on the ave r a g e. CTR saltwater CCC an d CMC for zi n c were n e v e r ex ceeded in an y of the 38 8 sam p les tak e n fro m th e 1 9 salt and brac ki sh wat e r m a ri nas. Eve n th o u g h D Z n c once n tr at i o ns a t M d Rm a ri na si t e s were som e o f th e hi ghest DZ n conce n tr at i o ns obs er vedi n t h i s stu d y , th e hi gh est DZn con c en tration d o c umen ted th ere (6 6.6 μ g/L) , di d n o t eve n exceed the CCC.

Com p ari s ons to T o xi ci ty B e nchma r k Val u es
In certain cases, water q u a lity stand a rd s do no t ex ist for com pariso n with measu r ed con c en tr ation s
. Fo r ex am p l e, th ere are c u rrently no num eric standards for m e tals in se dim ent and the r e are no stan dar d s fo r I r garol a n d M 1

. T h ere f o r e, no n -re gul at o r y t oxi ci t y th re sh ol ds o r benc h m arks ar e used i n st ead t o pr o v i d e refe re nce poi nt s t o hel p det e rm i n e th e pot e n t i a l im pact s of m easured c once n tr at i o ns. C

o m pari s on o f

Sedi me nt C

o n cen tra tio ns to NOAA’s Bio l og ica l -E

ffects Guid elines - C o pp er
Sin ce n o nu m e ric sed i m en t qu ality stan d a rds curren tly ex ists for m e tals, sed i m e n t TCu co n c en tration s were co m p ared t o N O A A ’ s E f fect s R a n g e L o w ( E R L ) an d E ffect s R a nge M e di um (ER M ) c once n tr at i o n s (L o n g an d M o r g a n , 1 9 9 1 ;

44Lon g et al., 199 5)

. ERLs and ERMs ar e scr e en ing lev e l tools d e v e lop e d by N OAA to assess th e po ten t i a l i m p acts o f sedi m e nt pol l u t a nt s. T h e ER L val u e re p r es ent s th e 1 0 th p e rcen tile of ranked d a ta fo r wh i c h th ere was an o b s erv e d effect for a sedim e nt polluta nt. T h e ERM va lue re pre sents t h e 50 th p e rcen t ile o f t

h e sam e rank ed d a taset. C once n tr at i o ns bel o w t h e ER L are n o t ex pe ct ed t o be t o xi c t o se di m e nt -d wel l i ng o r ga ni sm s. Toxi c e f f ect s m a y occasionally occur whe n m e a sure d c o ncent r ations a r e betw een the ERL a n d ERM thres h olds

. T h e likelihood of t oxic effects i n creas es significantly if a po llu tan t co n c en tration re gula r ly excee ds the ERM.
For c o p p er , th e ER L i s 34 m g /kg d r y w e i g ht and th e ER M i s 2 7 0 m g / kg dr y wei g ht

. O f t

h e 23 se di m e nt sam p l e s t a ken, TC u c o n centr at i o ns i n 22 o f t

h e sam p l e s excee ded th e co ppe r ER L

. Eve n t h o u g h TC u c once n tr a t i ons fr om i n si de t h e m a ri nas ar e gene ral l y hi ghe r t h an TC u c once n tr a t i ons fr om th e LR Ss, t h e LR S co ncent r at i o n s we re hi g h enough to als o exceed the copp er ERL. T h e only sam p le that did not e x ce ed this thre shol d was from an LRS associated with the Sac r am ento Mari na. None of the sedim ent sam p les collect ed exceede d the ERM. Pas t placem ents o f

sed i m e n t p o llu tan t d a ta on th e SWRCB’s C W A 303 d imp a ir ed water bo d i es list h a ve b een prim arily b a sed o n ERM exceeda n ces
. Alth oug h no sed i m e n t d a ta were g e n e rated in th is stud y f o r salt an d br ack i s h w a ter m a r inas, Calif or n ia’ s RW Q CBs co ndu cted sed i men t q u a lity assessm en ts in the 19 90’s, as p art of th ei r Califo r n i a Bay Pro t ectio n Tox i c C l ean Up Pro g r am s. A n u m b er o f m a ri nas al on g C a l i f or ni a’s C e ntral an d S o uth C o a s t (i ncl u di n g s o m e th at are i n cl ude d i n th i s study ) di d s h o w se di m e nt concent r at i ons th at were ab o v e t h e NO A A ER M val u es ( S i n g h asem anon , 20 05 ).
C

o m pari s on o f

Sedi me nt C

o n cen tra tio ns to NOAA’s Bio l og ica l Effects Guid elines - Zinc

NO A A ’s ER L and ER M val u es f o r

zi nc ar e 15 0 a n d 41 0 m g / k g dry wei g h t , res p ect i v el y
. Of th e 2 3 sam p l e s t a ke n, TZn c o ncent r ations in ei ght of the sam p les exceeded the zinc ERL. Interes tingl y, all eight sam p les were taken from marina sites (s pecifically, from Sacra m ento Marina a n d Vi l l age W e st M a r i na). No ne of th e sam p l e s t a k e n fr om Folsom Lake Marina e x cee ded the ERL. None of t h e samples e x ceede d t h e ERM.
C

o m pari s on o f

Irg ar

ol

C

o nce n t r at

i o ns t o To xi col ogi cal E n dp oi nt s an d A q u a t i c To xi cit y B e nchm ar ks

A vari et y o f t o xi col o gi cal e n d poi nt s (e .g ., E C 50 s and LC 50 s ) a n d aq uat i c t oxi ci t y be nc h m arks ar e a v ai l abl e i n t h e scien tific literatu re for co m p arison with m e a s u r ed Irg aro l co n c en tration s
. As an s -triazin e he rbicide , Ir g a rol te nds to b e mu ch m o re to x i c to th e aqu a tic flora t h an to th e aqu a tic fauna. T h us, t h e toxicity re ferred to in t h is su b-section foc u ses speci fically on s u b-le thal effe ct s on aquatic plants and algae.
Si nce Ir gar o l a c t s as an i n hi bi t o r of p h o t o sy n thesi s, gr o w th i nhi bi t i on o f ph y t opl an kt o n ap pears t o be o n e o f th e m o st comm only-obs erve d e ffects of Irgarol. For t h e gree n al gae Na vicu la p e llicu l o s a , an EC 50 o f 136 n g /L fo r gr ow th in h i b ition h a s b een do cu m e n t ed for Irg a ro l (Hugh es an d Alex and e r, 19 93 ). DeLo ren z o an d Serran o (200 6) d o c u m en ted si milar g r owth-rate in h i b ition fo r th e m a rin e ph yto p l an k t o n sp ecies Duna liella tertio lecta a t an EC 50 of 2 7 0 ng /L. Devilla et al. (20 05) d eterm in ed the EC 50 fo r growth i n h i b itio n o f Irg aro l t o b e 16 0 and 25 0 ng /L for th e phy t o pl an kt o n

– Sy nec hoc occ u s s p
. and Emil in ia h ux leyi , re spectively. Dahl and Bla n ck (1 996 ) do cu m e n ted a low e st obs er vedef fect s co nce n tr at i o n (L OEC ) o f 63 ng/L f o r

re duc ed ph ot o s y n th e t i c act i v i t y i n m a ri ne pe ri p h y t on co mmu n ities. Th ey also no ted an LOEC o f ab ou t 2 5 0 ng /L wh ere a ch ange in co mmu n it y stru cture was seen and an LO EC o f about 1 , 0 0 0 ng /L wh er e a r e du ction in b i o m ass w a s ob ser v ed

. I r g a ro l co n c en t r atio n s at m a n y o f th e m a r i n a s in t h is stud y ar e h i gh en ough to ex ceed some o f t

h e tox i co log i cal v a l u es cited he re. T h ese m a rinas we re Pittsburg M a rina, MB YH, Loc h L o m ond Marina, Be rk el ey Marina, South Beach Har b or, M d R f r o n t a n d bac k basi ns , a n d D o wnt o w n Sh or el i n e M a ri na
. I n co ntrast , Ir gar o l co nce n tr at i o ns at Val l e j o M a ri na, B e ni ci a M a ri na, Sa n Fra n ci sco M ari na, a n d Al am itos B a y M a ri na were al l bel o w th e l o west of t h ese t oxi col ogi cal v a l u es ( 6 3 ng/L )

. Hal l et al . ( 1 99 9) de ri ve d a n a quat i c
- p l a nt t o xi ci t y benc hm ark val u e of 1 3 6 n g /L f o r I r g ar ol i n a ecol o gi cal ri sk assessm ent (ERA) fo r Eu ro p ean waters. In ou r st udy , I r garol c o ncentr ations in 1 1 of th e 4 5 sam p les ( 2 4 % ) c o llected for Irgarol a n alysis exceede d t h is plant toxicity benc hm ark.
Hal l an d Gar d i n al i ( 2 0 0 4 ) c o n duct e d a si m i l a r ER A f o r U.S. wat e rs (C hesapeake B a y an d So utheast e r n F l ori d a )

. I n th is stud y, th e au tho r s used a larg er aqu a tic p l an t tox i city dataset (16 tox i co log i cal v a l u es) an d also i n clud ed

45to x i co l o g i cal data, wh ich con t ain e d m o rtality as en dpo in ts. Th e Irg a ro l b e n c h m ark v a lu e th at was d e rived (251 n g /L) w a s h igh er th an th e H a ll et al. (1 999 ) b e n c hmar k o f 13 6 ng/L. Fou r of th e 45 sam p les (9%) co llected forIrg aro l anal y s i s i n ou r study c o nt ai ne d c once n tr at i o ns t h at we re a b ove 2 5 1 ng/L

. Tw o of t h ese f o u rsam p l e s w e re c o l l ect ed fr om Loch L o m ond M a ri na
. The rem a i n i n g sam p l e s wi th I r garol c o ncent r at i ons a b ove 2 5 1 n g /L were c o l l ect ed f r o m Berkeley Mari na a n d MdR ’ s back ba sins.
In 2 0 0 7 , H a l l et al . ( 2 0 0 7 ) ge n e rat e d a n ot he r benc hm ark val u e of 1 9 3 ng/L

. C o m p ari s on of t h i s benc hm ark y i el ded t h e sam e resul t s as t h e c o m p ari s o n wi t h t h e 2 5 1 ng/L be nc hm ark val u e fr om Hal l and Gardi n al i (2 00 4)

. Ano th e r aqu a tic to x i city b e n c h m ark kno wn as th e Env i ro nmen tal Risk Limit (ERL) is bein g u tilized in th e Neth erland s. Th is ERL is al so b a sed o n a plan t to x i city d a taset an d is set at d a taset’s 5 th p e rcen tile v a lue (p ro tectiv e o f 95% of all a q uatic plant s p ecies). Va n Weze l and va n Vlaardi ng en (20 0 4 ) calcu lated an ERL fo r Irg aro l in water to b e 24 n g /L

. F o rt y o u t o f 4 5 samp l e s f r o m our s tudy (8 9% ) c o nt ai nedI r gar o l co ncent r at i o n s ab ove th e D u t c h ER L f o r Ir gar o l.
Co mp a riso n of M1 C o ncentra tio ns to Tox ico log ica l Endpo ints

M1 is mu ch less tox i c to aqu a tic p l an ts and an im a l s th an its p a ren t Irg aro l

. Hall and Gardin ali (200 4) est ab lish e d a pl ant a quat i c b e nchm ark fo r M 1 at 12 ,5 0 0 n g /L ( 1 0 th percen tile v a lu e or pro t ectiv e of 9 0 % of all aqu a ti c p l an t sp ecies) base d on 8 toxicological val u e s. None of the M1 res u lts from our study e x ceeded this t h reshold. T h e highe st M1 conce n tr at i o n doc um ent e d i n o u r stu d y wa s 21 7 n g /L s u g g e st i ng very l o w ec ol o g i cal ri sk fr om M 1 ex pos u r es at t

h es e sites.

BLM-Associated Wa ter Quality Data
Water qu ality d a ta th at are p r i m arily u s ed in th e sub s equ e nt sectio n s ’ m e t a l b i o a v a ilab ility an d t o x i city p r ed ictio n m odel s (the fre shwat e r B L M , DOC M o del , a n dsal t w at er B L M ) ca n be di vi de d i n t o t w o cat ego r i e s: l ab o rat o ry
an alyzed con s titu en ts an d in-situ m easu r em e n ts. Un lik e t h e presen ted results for m etals, TSS, t o x i city/ T IE, and Irgarol/M1, t h e BLM-ass o ciated param e ters were not s u mmarized and di scusse d as a narrative. Instea d, t h ese param e t e rs wer e si m p l y t abul at ed t o sh o w th e i r ra nge s a n d m e di an val u es on a m a ri na-ar ea speci fi c basi s. Lab o r a t

ory-A n a l yzed Constituents

Mo st of t h e BLM-asso ciated water qu ality co n s titu en ts were qu an tified u s in g lab o ratory in stru m e n t s. Th ese co nstitu en ts i n clu d e d alkalin ity, calciu m , ch lo rid e (salin ity), d i sso l v ed o r g a n i c carb on , mag n e siu m , potassiu m , so d i um , and s u lfate (c om ple t e results are in Appe nd i x G). Resu lts were with i n exp ected ran g e s fo r th e v a ri o u s water typ e s. Th e m a rin am e d i an and rang e for each co nstitu en t are p r esen ted i n Tab l e 13 an d Tab l e 14, resp ectiv ely.
In-Situ Mea s urements
In add itio n to t h e eigh t co nstitu en ts listed in th e p r ev iou s sectio n , t w o add i tio n a l water q u ality co n s titu ents– p H and te m p eratu r e were n eed ed t o ru n th e BLM

. Th ese t w o constitu en ts were d i rectly qu an tified in situ (probe placed d i rectly in th e water) using fi eld water q u ali ty m eters. Dat a of sev eral water qu ality co nstitu en ts th at were n o t n ecessarily n e ed ed fo r m o d e lin g inp u t bu t were n e v e rth e less co llected as gen e ral water qu ality an d water typ e in d i cators were DO, EC , an d tu rb id ity. In -situ m easurem ents res u lts are also s h own i n Appendix G.

46Table 13. Marina Median Concentrations ofBiotic LigandModel-Related Constituents(in mg/L)1DOCAlkalinityCalciumMagnesiumPotassiumSodiumChlorideSulfateMarina2MLRSMLRSMLRSMLRSMLRSMLRSMLRSMLRSFolsomLakeMarina1.31.222.422.24.74.71.51.50.60.61.51.81.11.11.51.5TahoeKeysMarina0.90.645.243.38.98.42.32.21.21.75.85.51.71.71.51.7SanFranciscoMarina0.91.01091093873971197123636937891669499179941820024862518AlamitosBayMarina0.90.9113113433437135613674114131048910595196701971826832701CoyotePointMarina1.71.61121113643681122113434835084948544166961673923562359AntiochMarina1.91.862.762.118.215.323.916.47.95.215092.327916344.629.3PittsburgMarina1.81.764.665.126.432.247.161.815.520.933143762386597.9126SouthBeachHarbor0.91.01081083803881176120336237090859255174061786323952463ClipperYachtHarbor1.01.11091083863851205120036636793929444175651752024042413MarinaBayYachtHarbor1.10.81041053753731150114835635787768847171831726223602388BeniciaMarina2.02.078.581.714718141151813516732824077668282798981121SacramentoMarina1.41.057.258.310.610.75.45.50.90.97.07.13.93.74.74.9BallenaIsleMarina1.41.41121113653671127113034234589498743167081659122632252VillageWestMarina3.73.670.071.318.218.48.78.82.52.528.929.532.733.129.529.8VallejoMarina2.22.287.485.1210197600563191180472544439379890412691207BerkeleyMarina1.01.01051063773771153115335635888548926170611737623452408SantaCruzHarbor1.01.0118115429433133813504104141039810430197181971526992694MontereyHarbor1.01.0115114437436136313614124101038210392197071978226902693SantaBarbaraHarbor0.80.7115113431430135113524074091042010447201182030927632777LochLomondMarina1.31.398.598.13253271001101131431477417803149301485520392041DowntownShorelineMarina1.01.411311643041513411284409394103359984194001847826662552MarinadelReyFB1.01.0117115431430135913584134141058410596197041961327132697MarinadelReyBB1.11.01171154284301347135841141410590105961969019613271826971Ordered by ascendingmarinamedian DCu concentrations.Values> 100 are rounded to thenearest one.Values < 100 areroundedto the nearest tenth.2Marina names are colorcoded bywatertype.Green =freshwater,Yellow = brackish water, Blue = saltwater.47Table 14. Ranges ofBLM-RelatedConstituentConcentrations (inmg/L)forEachMarinaArea1DOCAlkalinityCalciumMagnesiumPotassiumSodiumChlorideSulfateMarina2MLRSMLRSMLRSMLRSMLRSMLRSMLRSMLRSFolsomLakeMarina0.9 ­1.60.9 ­1.621 -2621 -244.5 ­4.94.5 ­4.91.4 ­1.61.4 ­1.50.6 ­0.60.6 ­0.61.8 ­1.91.8 ­1.91.1 ­1.11.0 ­1.11.4 ­1.51.4 ­1.5Tahoe KeysMarina0.7 ­1.20.5 ­0.742 -4939 -468.9 ­9.07.8 ­8.72.3 ­2.32.0 ­2.31.2 ­1.31.6 ­1.75.6 ­6.05.1 ­5.81.5 ­1.81.7 ­1.81.4 ­1.61.4 ­1.9San Francisco Marina0.6 ­2.10.6 ­1.5107 ­113107 ­113337 ­407387 –4141030 ­12501210 ­1280322 ­383365 ­3897690 ­95709210 ­983017614 ­1840017700 ­184822380 ­26632270 ­2672Alamitos Bay Marina0.8 ­1.10.8 ­1.0110 ­115110 ­117425 ­444429 ­4491340 ­13901350 ­1410399 ­429399 ­43810200 ­1070010320 ­1080019284 ­2040019258 ­204002507 ­28102589 ­2820Coyote PointMarina1.5 ­1.81.5 ­1.8110 ­114109 ­113353 ­378354 ­3811080 ­11701080 ­1180342 ­362337 ­3637680 ­92007980 ­912015993 ­1740016062 ­175002310 ­24102318 ­2420AntiochMarina1.6 ­2.31.4 ­2.456 -7356 -7016.5 ­20.413.5 ­18.320.3 ­31.013.2 ­22.46.2 ­11.74.4 ­6.9129 ­20168.0 ­137200 ­389123 ­24033.5 ­58.524.0 ­39.5PittsburgMarina1.5 ­2.31.5 ­2.361 -7258 -8021.8 ­38.719.8 ­192.135.6 ­86.829.0 ­554.611.5 ­29.512.4 ­180.7245 ­656182 ­4345426 ­1331391 ­841268.0 ­18057.9 ­1117South BeachHarbor0.7 ­1.50.6 ­1.5107 ­110106 ­110371 ­392376 ­3971150 ­12101170 ­1220351 ­370359 ­3778720 ­93109020 ­946017115 ­1788217468 ­185342210 ­25312300 ­2682Clipper YachtHarbor0.9 ­1.50.9 ­1.5107 ­111106 ­110374 ­403375 ­3991166 ­12501170 ­1240358 ­376356 ­3778780 ­97909250 ­970016800 ­1810016989 ­181002312 ­24762322 ­2480MarinaBayYacht Harbor0.7 ­6.40.6 ­1.299 ­10799 ­107369 ­382369 ­3781120 ­11701120 ­1160341 ­373345 ­3718320 ­93497860 ­917715994 ­1785716842 ­176362134 ­25132365 ­2406Benicia Marina1.7 ­2.31.6 ­2.374 -9276 -89139 ­157161 ­202379 ­444456 ­570129 ­141156 ­1903087 ­35203590 ­46936032 ­74587328 ­9311773 ­10201000 ­1238Sacramento Marina0.9 ­1.40.2 ­1.352 -6150 -7010.2 ­11.29.7 ­13.15.0 ­5.94.8 ­7.20.9 ­1.00.9 ­1.16.3 ­7.95.6 ­9.33.6 ­4.32.6 ­5.14.6 ­4.94.4 ­5.8Ballena Isle Marina1.3 ­1.61.2 ­1.6107 ­116107 ­115357 ­373356 ­3771110 ­11501110 ­1150333 ­350336 ­3528700 ­91408640 ­919016340 ­1800016364 ­170002150 ­23502140 ­2335VillageWest Marina3.3 ­4.43.2 ­3.859 -7662 -7615.8 ­20.016.2 ­19.87.2 ­9.87.3 ­9.92.1 ­3.02.2 ­2.724.4 ­32.325.3 –32.226.4 ­32.226.3 ­36.425.6 ­32.225.6 ­32.0VallejoMarina1.8 ­2.51.6 ­3.684 -9178 -92200 ­222181 ­216576 ­633523 ­614186 ­200172 ­1894511 ­49203996 ­47308739 ­103698048 ­103341162 ­14301065 ­1431Berkeley Marina0.8 ­1.20.7 ­2.799 ­109102 ­108372 ­380364 ­3851130 ­11701130 ­1180344 ­371347 ­3668152 ­91998606 ­918716362 ­1783316543 ­183022215 ­24712206 ­2521Santa CruzHarbor0.6 ­1.70.7 ­1.9113 ­127111 ­118413 ­447409 ­4551280 ­13801280 ­1400393 ­432404 ­43210100 ­107009900 ­1080019403 ­2005919300 ­201712650 ­27412600 ­2748MontereyHarbor0.7 ­1.60.5 –1.8111 ­120111 ­117422 ­454419 ­4561300 ­14201300 ­1420399 ­430393 ­42510100 ­108009900 ­1080019443 ­2010019298 ­205212650 ­27412608 ­2796Santa BarbaraHarbor0.7 ­1.00.6 ­0.9112 ­119111 ­115426 ­439413 ­4391330 ­13801300 ­1390389 ­433391 ­4379927 ­1100010057 ­1080019500 ­2083319400 ­212852550 ­30082600 ­3081LochLomondMarina1.0 ­1.71.2 ­1.692 ­10394 ­103313 ­344312 ­394969 ­1053957 ­1232304 ­332297 ­3796970 ­82107210 ­956014300 ­1612014417 ­156061912 ­21501911 ­2160Downtown Shoreline Marina0.9 ­1.20.9 ­2.9110 ­116109 ­128425 ­434345 ­4341330 ­13501010 ­1360402 ­417316 ­41410057 ­105307720 ­1050018971 ­1990014800 ­193002564 ­27502080 ­2670MarinadelReyFB0.7 ­1.10.7 ­1.7113 ­129112 ­118421 ­437417 ­4381340 ­13901320 ­1390401 ­421400 ­42810393 ­1070010400 ­1080019300 ­2041418468 ­201002635 ­27602454 ­2800Marinadel Rey BB1.0 ­1.90.7 ­1.7114 ­120112 ­118417 ­435417 ­4381320 ­13801320 ­1390394 ­421400 ­42810367 ­1100010400 ­1080019300 ­2040018468 ­201002604 ­27902454 ­28001Ordered by ascendingmarinamedian DCu concentrations.Values> 100 are rounded to thenearest one.Values < 100 areroundedto the nearest tenth.2Marina names are colorcoded bywatertype.Green =freshwater,Yellow = brackish water, Blue = saltwater.48Predictive Toxicity Models

B i ot i c Li ga nd M odel - F res h w at er
Sin ce relativ ely few of th e sam p les m e t th e o p e rating p a ra meter requ iremen ts for th e fr es h w a t er BL M (T ab le 4 ) (m ain l y p e rtain i n g t o th e salinity-related constitu en ts), on ly 53 sam p les were an alyzed u s i n g th is m o d e l. Mo st o f t

h ese sam p les were from the four freshwater sites; howe ver, so m e of th e sam p les cam e fro m th e An tio ch site, wh ich o n som e occasions containe d s o dium and c h l o ride conce n trations wit h in t h e BL M operating range. Recal l that the Ant i o c h M ari n ahas bee n cl as si fi ed i n th i s st udy a s a brac ki sh water site du e to th e ran g e of salin ity at th is lo cation o v e r t h e co urse of a year. Th e Pittsb u rg Mari n aan d sites wi th greater salinity th an Pittsburg h a d sod i u m an d ch l o ri d e co n c en tration s th at were ab ove th e o p e rating ran g e of th e fresh water BLM

. Th ey, ho wever, were ev al u a ted using th e in terim saltwat er BLM an d wi ll b e d i scu ssed in a later sub

- sectio n
. Appe ndi x L contains t h e fres hwater BLM res u lts for sam p le s th at m e t th e criteria of th e op erating p a rameter abov e. The B L M

- ge n e rat e d, u n i t

- l e s s , t o xi c uni t ( T U) val u es fo r f r esh w at er si t e s ra nge d fr om 0.0 3

– 9

. 4 2. T h e m odel pre d icted t h at s e ven of 53 fres hwate r sam p les eval uated wo uld m eet or e x ceed the 1-T U thres hol d (Tabl e 15). All seve n sam p les were collected from the Sacra m ento Marina area a n d the m o st significa n t exceeda n ces occurred during th e seco nd sam p lin g ev en t i n A ugu st 2006

. Th e BLM ou tpu t co l u m n s show n in clud e:

• Site an d sam p le in fo rm atio n (i.e., station n a me, sam p lin g date, site, and ev en t )

• The Fi nal Acut e Val u e ( F A V ) f o r c o ppe r (cal cul a t e d fr om the 4 l o we st ge nus m ean acute values adjusted to account for sit e-speci fic BL M input parameters)

• CMC (Calcu lated as 1⁄2 th e FA V and rounded to th e n e arest ten t h t o facilitate co m p ariso n w ith D C u.)

• Measure d DCu concent r ations

• TU (M eas ure d DC u/ C M C

. F o r TU eq ual t o or g r eat er t h an 1, t h e m odel pr edi c t s t o xi ci t y .)
The fres h wat e r B L M di d not pre d i c t acut e t oxi ci t y fr om DC u at the following m a rina areas: Tahoe Ke ys, Fols om Lak e , An tio ch , Pittsb u rg, an d Villag e West. No te t h at at th i s ti m e , to x i city th resho l d s g e nerated b y th e fresh water BLM are n o t en fo rceab l e wat er q u ality criteria or stan d ards.
Table 15. Fres hwaterBLM Output for S a mples w i th Pr edicted T oxici ty (TU ≥1) Station Nam e Sa mpling Da te Site 1 Ev ent FAV CM C Measured DC u ( μ g/L ) T oxi c Units
Sacram ent o M a ri na 7/ 2 1 / 2 00 6 1 1 7. 34 5 9 3. 7 3. 7 1. 00
Sacram ent o M a ri na 8/ 1 6 / 2 00 6 1 2 0. 81 7 8 0. 4 3. 0 7. 50
Sacram ent o M a ri na 8/ 1 6 / 2 00 6 2 2 0. 74 3 5 0. 4 3. 5 8. 75
Sacram ent o M a ri na 8/ 1 6 / 2 00 6 3 2 0. 61 2 9 0. 3 2. 8 9. 33
Sacram ent o M a ri na 8/ 1 6 / 2 00 6 4 2 0. 76 2 6 0. 4 2. 3 5. 75
Sacram ent o M a ri na 8/ 1 6 / 2 00 6 5 2 0. 69 7 1 0. 3 0. 6 2. 00
Sacram ent o M a ri na 9/ 1 2 / 2 00 6 8 3 1. 43 1 7 0. 7 0. 7 1. 00

1 Sites 1–4 ar e m a rina sites. Sites 5–8 ar e L R Ss.

Th e relativ ely larg e m a g n itu de of th e TU v a l u es for t h e seco nd ev en t su ggests th at copp erco n c en tr ations cou ld h a v e h a d a si g n i fican tly to x i c effect o n th e m o re sen s itiv e aq u a ti c org a n i sm s at th at site. BLM in pu t d ata for th e seco nd sam p ling eve n t at Sacram ento Marina do not app ear to exh i b it d i stin ctly d i fferen t ch aracteristics fro m d ata for th e fi rst sam p lin g ev en t, in wh ich on ly on e sam p le slig h tly ex ceed ed th e 1

- TU t h resh o l d , with t h e ex cep tion of the pH d ata. Upon m o re d e tailed ev al u a tion , it is lik ely that th e lower pH v a lu es reco rd ed during th e secon d sam p li n g ev en t (6.0– 6.5) com p ared to those during the firs t ev en t (7.3–7 .7 ) h a d a larg e im p act i n r e du cing t h e FAV an d CMC v a lu es fo r

49th at ev en t. Lower pH con d itio n s tend t o favo r th e p r esen ce o f m o re- b ioa v ailable free co ppe r i ons (s om etim es referre d t o as l a bi l e co p p er o r free di ss ol ve d c o p p e r), whi c h have g re a t e r i m pact on bi ot i c l i g a nds

. At hi g h er p H l e vel s , c o ppe r t e nds t o be b o u n d wi th b o th i n or ga ni c (e. g
. , c a rb o n at es) a n d or ga ni c (e. g
. , f u l v i c a n d h u m i c aci ds) com p l e xes i n so lu tion and is g en e rally less av ailab l e to in t eract with b i o tic lig and s
. An ev al u ation o f th e water quality field d ata sh eet for th e se co nd sam p lin g ev en t, howev er, rev ealed th at th e pH lev e ls were m easured usi n g p H st ri p s (i .e. , l i t mu s p a per ) si nce th e pH m e t e r was not f unct i o nal t h at day

. T h i s was t h e onl y ti m e w h en pH str i p s w e r e used in th e stud y. H i stor ical p H dat af r om a d o w nst r eam m onitoring station (Sacram ento R i ver at Ho o d ) sh owe d t h at p H l e vel s t y pi cal l y range d bet w een 6 .8 an d 7 .7 d u ri ng th e st udy ’s e n t i r e sa m p li ng peri od ( CD E C, 200 8)

. Th u s , th e pH r ead i n g s fo r the second sam p lin g ev en t is likely to b e less accu rate t h an the pH read i n g s m a de usi n g th e fre q u ent l y cal i b rat e d pH m e ters. C o nse que n tly, th e freshwater BLM ’ s t o x i city pred ictio n s fo r th e Sacram ento Marina for t h is particular e v en t are lik ely to b e less reliab l e as well.
Ev en if t h e t o xicity p r ed ictio ns fo r t h e second sam p lin g e v e n t at the Sacra m ento Marina were conside r e d to be u n reliab l e, t h ere are still pred i ctio n s o f tox i city fro m th e fi rst an d th ird sam p lin g ev en t. Ev en tho ugh th e pred icted TU s ar e r e latively lo w ( b o th at ar oun d 1 TU), th ese pr ed icti o n s su gg est t h at th e D C u cou ld b e b io a v a ilable en oug h at the Sac r am ento Mari na ar ea t o be occas iona lly toxic to fres h wate r organis m s.

DOC M o d el - Sa lt and Bra c k i sh W a ter Ap pe ndi x M c ont ai n s th e co m p l e t e resul t s fr om th e DOC m odel

. Tabl e 16 sh o w s t h e F C C andF A C o u tp ut ra n g es fo r th e 19 salt and b r ack i sh water marin a s ev al u a ted

. Ap p licab le saltwater CTR CCC/CMC a n d rang e o f m easu r ed DC u conce n tr at i o ns are al so s h o w n f o r c o m p ari s o n
. T h e DOC

- m odel gene rat e d FC C a n d F A C val u es are th resh ol d val u es that are use d t o predict toxic e ffects. T h ey are no t enforcea ble wate r quali ty objectives or standa rds

. Table 16. DO C Model F C C an d F A C Ou tput Ran g es ( μ g/L ) Station Nam e FC C Ra ng e FA C Ra ng e CTR C C C 1 CTR C M C 1 Ra nge D Cu
Al am i t o s B a y M a ri na 3. 0– 3. 8 4. 7– 5. 9 3. 1 4. 8 ND

– 3

. 6
Ant i oc h M a ri n a 4. 4– 6. 0 6. 9– 9. 4 3. 1 4. 8 1. 4– 3. 0
B a l l e na Isl e M a ri na 4. 0– 4. 8 6. 3– 7. 5 3. 1/ 6. 0 4. 8/ 9. 4 0. 1– 5. 0
B e ni ci a M a ri n a 4. 8– 5. 9 7. 5– 9. 3 3. 1/ 6. 0 4. 8/ 9. 4 ND

– 3. 7 C i t y of B e rkel ey 3. 0– 6. 5 4. 6– 1 0. 2 3. 1/ 6. 0 4. 8/ 9. 4 0. 2– 7. 2
C l i pper Yac ht Har b or 3. 1– 4. 7 4. 8– 7. 3 3. 1/ 6. 0 4. 8/ 9. 4 0. 3– 6. 6 C oy ot e P oi nt M a ri na 4. 6– 5. 2 7. 2– 8. 0 3. 1/ 6. 0 4. 8/ 9. 4 1. 0– 2. 6
Do w nt o wn S h orel i ne M a ri na 3. 3– 6. 9 5. 1– 1 0. 7 3. 1 4. 8 0. 4– 1 0. 9
Loc h L om ond M a ri na 3. 6– 5. 0 5. 6– 7. 8 3. 1/ 6. 0 4. 8/ 9. 4 1. 3– 1 0. 3
M a ri na B a y Y acht Har bo r 2. 8– 1 1. 0 4. 3– 1 7. 1 3. 1/ 6. 0 4. 8/ 9. 4 1. 3– 3. 6
M a ri na del R e y B ack B a si n 3. 6– 5. 3 5. 6– 8. 2 3. 1 4. 8 8. 1– 1 8

. 4
M a ri na del R e y Fro nt B a si n 2. 9– 5. 0 4. 5– 7. 8 3. 1 4. 8 0. 3– 1 6. 2
M ont erey Harb or 2. 5– 5. 1 3. 9– 7. 9 3. 1 4. 8 ND

– 7. 8 Pittsb u r g Marin a 4

. 5

– 6

. 0 7

. 1

– 9

. 3 3

. 1 4

. 8 1

. 4

– 3

. 2
San Fra n ci sco M a ri na 2. 6– 5. 5 4. 1– 8. 7 3. 1/ 6. 0 4. 8/ 9. 4 ND

– 3

. 9

50Station Nam e FC C Ra ng e FA C Ra ng e CTR C C C 1 CTR C M C 1 Ra nge D Cu
Sant a B a r b ara Har b or 2. 6– 3. 7 4. 0– 5. 7 3. 1 4. 8 ND

– 8

. 2
Sant a C ruz Harb or 2. 7– 4. 9 4. 2– 7. 6 3. 1 4. 8 ND

– 5. 8
So ut h B eac h H a rb or 2. 7– 4. 6 4. 2– 7. 1 3. 1/ 6. 0 4. 8/ 9. 4 0. 4– 3. 0 Val l e jo M u ni ci pal M a ri na 4. 7– 7. 8 7. 3– 1 2. 1 3. 1/ 6. 0 4. 8/ 9. 4 1. 3– 4. 7 1 CTR’s CCC and CMC f o r the San F r ancisco Ba y Are a Marinas will be re placed by Site Sp e c if ic Objectives pe nding U.S. EPA ap prova l. Once approved, the new chronic and acute water qualit y objec tives for these m a rinas will be 6.0 an d 9.4 μ g/L, respect ively.

Out o f th e 4 1 2 sal t and b r acki s h wat e r sam p les th at had D O C res u l t s , 8 6 c ont ai ne d hi gh eno u g h co nce n tr at i ons o f DC u to equal or exc eed the DOC-m odel pre d icted FCC a n d 54 of those als o e x ceede d t h e FAC. B o th FC C and FAC exceeda n ces are highlighted in Appe ndi x M. T h e m a jority of the sam p les that excee de d t oxicity thre sholds cam e from C e ntral an d So uth C o ast m a ri nas, m o st not a b l y M d R ’ s f r o n t an d bac k ba si ns, D o w n t o w n S h orel i n e M a ri na, Sa nt a B a rbar a Har b o r , M ont e r ey Harb or , a n d Sa nt a C r uz Har b o r
. B a y Area m a ri nas al s o had oc casi onal e x cee dance s , nam e ly Loch L o m ond M a ri na , C l i ppe r Yacht Ha rb or , B e rk e l ey M a ri na, a n d B a l l e na Isl e M a ri na. Ei ght y fi ve of th e 86 sam p l e s th at excee de d t h e l o we r FC C t h res h ol d cam e fr om i n si de o f m a ri nas. O n l y o n e LR S sam p le exceeded this sam e threshold. This s a m p le cam e from MdR’s LR S #1, which ha s be e n noted as an LRS site with ch aracteristics th at m a k e it m o re lik e a marin asite.
In co m p arison to th e CTR ’ s fix e d CCC and CMC fo r th e sa m e sites, th e DOC m o d el FCCs and FACs are g e n erally higher. T h us, measured DC u concent r ations tend to e x cee d CTR standards m o re fre quently than DOC-m odel pre d icted t oxic ity thresholds

. Occasi onally, the opposite is true. T h is is most noticeable at San Fra n cisc o Mari na, Sant a C ruz Harb or , M o nt erey Harb or , a n dS a nt a B a r b ara H a rb or
. Thi s p h e nom eno n i s l i kel y a re fl ect i o n of th e relativ ely lo w DOC con c en tratio n s at t h ese lo catio n s
. Du e to th e po ten tial o f DOC co n c en tration s t o fl u c tu ate at each si t e , a part i c ul arc once n tr at i o n o f m easuredD C u c oul d e x ce ed FC C s an d F A C s one day a n d be bel o w th em t h e ne xt

. A co m p ariso n o f th e Bay Area m arin as’ FC Cs and FACs t o water qu ality stand a rd s n e ed s t o b e d o n e with th e u n d e rstand ing th at site sp ecifi c ob j ecti v es (SSOs) co u l d b e ad op ted th at wo u l d resu lt in t h e CCC b e ing raised t o 6

. 0 μ g/L an d t h e C M C t o 9 .4 μ g / L. Sub s eq u e n t ly, DCu con c en tration s in Bay Area m a rin a s will lik ely ex ceed th e FCCs an d FACs m o re frequ en tly than th e SSOs.
Sin ce th e stud y ’ s tox icity tests in vo lv ed t h e ex act sam e test sp ecies, t o x ic en dpo in t, and ex po su re p e riod as th e tox icity tests o n wh ich th e DOC m o d e l’s fun c tio n is b a sed , it is p o ss ib le to d i rectl y co m p are m o d e l-p r ed icted resu lts to ou r to x i city resu lts. A co m p arison o f th e resu lts fro m th e DO C m o d e l with t h e stud y’s act u a l to x i city resu lts showed goo d ag reem en t in 42 o f 47 ou tco m es. In o t h e r wo rd s, th e DOC m o d e l p r ed icted acu t e tox i city wh en statistically sig n i ficant to x i city was observ e d i n tox i city tests, o rit pred icted th at no acu t e tox i city wou l d o c cur for sam p les wi th no ob serv ed to x i city. Fi v e i n con s isten t ou tco m es were, ho wev e r, ob served

. Th e m o d el pred icted acu t e to x i city at one Lo ch Lom ond M a ri n asi t e , o n e M d Rbac k basi n si t e , an d t w o D o wnt o w n Sh or el i n e M a ri na si t e s w h en n o acut e t oxi ci t y was obs erved for sa m p les tested from these sites. In one case, i n a Marin a Bay Yach t Harbo r sa m p le, th e m o d e l pred icted n o tox i city an d yet lo w lev e l acu t e tox i city was ob serv ed i n th e actu a l sam p le. Ov erall, t h e DOC m o d e l pred icted water c o lum n toxicity well (89% s u ccess rat e ) whe n c o m p ar ed to act ual re sult of ac ute toxicity tests on coppe r
sen s itiv e M . ga l l opr ovi n ci al i s
. Wh en th e m o d e l and t o x i city resu lts d i sagree, it is du e t o t h e tend en cy of th e m o d e l to o v e r-pred ict tox i city rath er than u n d e r-p r ed i c t.

51B i ot i c Li ga nd M odel - Sa l t a n d B r ac ki sh W a t

e r
Th e ou tpu t of t h e saltwater B L M is presen ted in App e nd ix N. Saltwater BLM res u lts that were greater than one t oxic uni t (TU ) ar e p r esent e d i n Ta bl e 1 7

. Si xt y s e ven o f 3 7 3 sa m p l e s (for w h i c h out put c o ul d be cal cul a t e d ) or 1 8 % of th e sam p les contained a high e n ough c o ncent r ation of DCu t o reach or excee d the 1-T U t h res hol d. Key BL M out put co lu m n s shown in cl u d e : p r ed icted EC 50 fo r M. g a l l opr ovi n ci al i s , ob served DCu con c en tration s , and TUs. No te t h at th e T U s cal cul a t e d f o r

th e sal t w at er B L M i n Tabl e 1 7 a n d Ap pe ndi x N ar e base d o n th e pre d i c t e d EC 50 ’s f o r M. g a llop r o v in ci alis and not on the CMC as wa s the cas e for the fres h water BLM. In t his c a se, e x ceeda n c e s over one TU, as determ ined by the saltwater BLM, s ugges ts that adverse risks t o M

. gal l opr ovi n ci al i s may ex ist fro m th e ex po su re o f

copp er. At th is tim e, th e p r ed icted EC 50 ’ s fo r M. g a llop r o v in cia lis t h at are gene rated by the saltwater BLM are not en fo rceab l e water qu ality cr iteria or stan d ards.
Table 17 . S a lt w a ter BL M O utpu t forS a m ples w i th Pre d icted To xicit y (TU ≥ 1)
Station Nam e Date Site Event Water Ty pe Obser v ed DC u ( μ g/L ) Predicted E C 50 M

. g

a llop r o v incia lis T oxi c Units Berkeley Mari na 7/ 2 4/ 2 00 6 1 1 Salt 6. 8 5. 2 1. 31 Berkeley Mari na 9/ 1 8/ 2 00 6 1 3 Salt 3. 8 3. 2 1. 19 Down town Sho r elin e Marin a 8/ 1/ 2 0 06 1 1 Salt 7. 4 3. 9 1. 90 Down town Sho r elin e Marin a 8/ 1/ 2 0 06 2 1 Salt 6. 3 3. 9 1. 62 Down town Sho r elin e Marin a 8/ 1/ 2 0 06 3 1 Salt 7. 7 4. 7 1. 64 Down town Sho r elin e Marin a 8/ 2 9/ 2 00 6 1 2 Salt 5. 3 5. 3 1. 00 Down town Sho r elin e Marin a 8/ 2 9/ 2 00 6 2 2 Salt 7. 4 4. 3 1. 72 Down town Sho r elin e Marin a 8/ 2 9/ 2 00 6 3 2 Salt 8. 9 4. 2 2. 12 Down town Sho r elin e Marin a 9/ 2 6/ 2 00 6 1 3 Salt 10 .9 4. 6 2. 37 Down town Sho r elin e Marin a 9/ 2 6/ 2 00 6 2 3 Salt 9. 5 4. 7 2. 02 Down town Sho r elin e Marin a 9/ 2 6/ 2 00 6 3 3 Salt 8. 6 4. 2 2. 05 Down town Sho r elin e Marin a 9/ 2 6/ 2 00 6 4 3 Salt 6 4. 8 1. 25 M a ri na del R e y B ack B a si n 8/ 2/ 2 0 06 1 1 Salt 18 .4 4. 8 3. 83 M a ri na del R e y B ack B a si n 8/ 2/ 2 0 06 2 1 Salt 17 .9 4. 5 3. 98 M a ri na del R e y B ack B a si n 8/ 2/ 2 0 06 3 1 Salt 14 .5 4. 5 3. 22 M a ri na del R e y B ack B a si n 8/ 2/ 2 0 06 4 1 Salt 14 .1 4. 8 2. 94 M a ri na del R e y B ack B a si n 8/ 3 0/ 2 00 6 1 2 Salt 11 .5 4. 5 2. 56 M a ri na del R e y B ack B a si n 8/ 3 0/ 2 00 6 2 2 Salt 18 .4 4. 6 4. 00 M a ri na del R e y B ack B a si n 8/ 3 0/ 2 00 6 3 2 Salt 12 .4 4. 7 2. 64 M a ri na del R e y B ack B a si n 8/ 3 0/ 2 00 6 4 2 Salt 14 .2 4. 6 3. 09 M a ri na del R e y B ack B a si n 9/ 2 7/ 2 00 6 1 3 Salt 12 .7 4. 6 2. 76 M a ri na del R e y B ack B a si n 9/ 2 7/ 2 00 6 2 3 Salt 13 .3 4. 6 2. 89 M a ri na del R e y B ack B a si n 9/ 2 7/ 2 00 6 3 3 Salt 8. 1 8. 1 1. 00 M a ri na del R e y B ack B a si n 9/ 2 7/ 2 00 6 4 3 Salt 12 4. 3 2. 79 M a ri na del R e y Fro n t B a si n 8/ 2/ 2 0 06 1 1 Salt 16 .2 4. 8 3. 38 M a ri na del R e y Fro n t B a si n 8/ 2/ 2 0 06 2 1 Salt 14 .5 4. 6 3. 15 M a ri na del R e y Fro n t B a si n 8/ 2/ 2 0 06 3 1 Salt 14 .9 4. 4 3. 39 M a ri na del R e y Fro n t B a si n 8/ 2/ 2 0 06 4 1 Salt 13 .8 3. 2 4. 31 M a ri na del R e y Fro n t B a si n 8/ 2/ 2 0 06 5 1 Salt 4. 7 4. 2 1. 12 M a ri na del R e y Fro n t B a si n 8/ 3 0/ 2 00 6 1 2 Salt 13 .1 4. 5 2. 91 M a ri na del R e y Fro n t B a si n 8/ 3 0/ 2 00 6 2 2 Salt 12 .5 4. 2 2. 98 M a ri na del R e y Fro n t B a si n 8/ 3 0/ 2 00 6 3 2 Salt 11 .8 4. 5 2. 62

52Station Nam e Date Site Event Water Ty pe Obser v ed DC u ( μ g/L ) Predicted E C 50 M

. g

a llop r o v incia lis T oxi c Units M a ri na del R e y Fro n t B a si n 8/ 3 0/ 2 00 6 4 2 Salt 11 .9 5 2

. 3 8 M a ri na del R e y Fro n t B a si n 9/ 2 7/ 2 00 6 1 3 Salt 12 .2 4. 3 2. 84 M a ri na del R e y Fro n t B a si n 9/ 2 7/ 2 00 6 2 3 Salt 11 .5 3. 9 2. 95 M a ri na del R e y Fro n t B a si n 9/ 2 7/ 2 00 6 3 3 Salt 8. 9 4. 6 1. 93 M a ri na del R e y Fro n t B a si n 9/ 2 7/ 2 00 6 4 3 Salt 10 4. 1 2. 44 M ont erey Ha rb or 8/ 1 0/ 2 00 6 1 1 Salt 6. 3 4. 7 1. 34 M ont erey Ha rb or 8/ 1 0/ 2 00 6 2 1 Salt 7. 1 4. 4 1. 61 M ont erey Ha rb or 8/ 1 0/ 2 00 6 3 1 Salt 4. 6 3. 9 1. 18 M ont erey Ha rb or 8/ 1 0/ 2 00 6 4 1 Salt 4. 8 4. 1 1. 17 M ont erey Ha rb or 9/ 8/ 2 0 06 1 2 Salt 3. 7 3 1. 23 M ont erey Ha rb or 9/ 8/ 2 0 06 2 2 Salt 3. 7 3. 2 1. 16 M ont erey Ha rb or 10/ 19/ 20 0 6 3 3 Salt 7. 8 6. 7 1. 16 Loc h L o m ond M a ri na 7/ 2 5/ 2 00 6 1 1 Salt 10 .3 5. 8 1. 78 Loc h L o m ond M a ri na 7/ 2 5/ 2 00 6 2 1 Salt 8. 4 5. 8 1. 45 Loc h L o m ond M a ri na 7/ 2 5/ 2 00 6 3 1 Salt 7. 2 5. 7 1. 26 Loc h L o m ond M a ri na 7/ 2 5/ 2 00 6 4 1 Salt 8 5. 5 1. 45 Loc h L o m ond M a ri na 8/ 2 2/ 2 00 6 1 2 Salt 7. 7 7. 5 1. 03 Loc h L o m ond M a ri na 9/ 1 9/ 2 00 6 1 3 Salt 6. 7 4. 5 1. 49 Santa Barbar a Harbor 8/ 3/ 2 0 06 2 1 Salt 6. 5 3. 6 1. 81 Santa Barbar a Harbor 8/ 3/ 2 0 06 3 1 Salt 6. 6 4. 2 1. 57 Santa Barbar a Harbor 8/ 3/ 2 0 06 4 1 Salt 4. 6 3. 3 1. 39 Santa Barbar a Harbor 8/ 3 1/ 2 00 6 1 2 Salt 5. 6 3. 5 1. 60 Santa Barbar a Harbor 8/ 3 1/ 2 00 6 2 2 Salt 6. 9 3. 2 2. 16 Santa Barbar a Harbor 8/ 3 1/ 2 00 6 3 2 Salt 8. 2 3. 4 2. 41 Santa Barbar a Harbor 8/ 3 1/ 2 00 6 4 2 Salt 7. 4 3. 3 2. 24 Santa Barbar a Harbor 9/ 2 8/ 2 00 6 1 3 Salt 4. 5 4. 3 1. 05 Santa Barbar a Harbor 9/ 2 8/ 2 00 6 2 3 Salt 7. 1 4. 1 1. 73 Santa Barbar a Harbor 9/ 2 8/ 2 00 6 3 3 Salt 6 4 1. 50 Santa Barbar a Harbor 9/ 2 8/ 2 00 6 4 3 Salt 5. 4 4. 6 1. 17 Sant a C ruz Harb or 8/ 9/ 2 0 06 3 1 Salt 4. 3 3. 5 1. 23 Sant a C ruz Harb or 9/ 7/ 2 0 06 1 2 Salt 5. 1 2. 7 1. 89 Sant a C ruz Harb or 9/ 7/ 2 0 06 2 2 Salt 5. 8 3 1. 93 Sant a C ruz Harb or 9/ 7/ 2 0 06 3 2 Salt 4. 4 3. 1 1. 42 Sant a C ruz Harb or 9/ 7/ 2 0 06 4 2 Salt 4. 5 2. 9 1. 55 C l i pper Yac h t Har b or 8/ 2 5/ 2 00 6 3 2 Salt 6. 6 4. 4 1. 50

For sam p les that equale d or e x ceede d t h e t o xicity thres hol d, TUs ra nged from 1.00–4.36. T h e m a jority of the sam p les that excee de d t h e M. g a llop r ovin cia lis site-sp ecific p r ed icted EC 50 s were fr om C e ntral andS out h C o ast m a ri nas. T h i s o b s erv atio n is si m ilar to th e DOC m o d el resu lts. M d R’s fron t a n d bac k basi ns ha d t h e m o st occur r enc e s o f sam p l e s t h at reac hed o r excee ded o n e TU. T h e m a gn i t ude of TU val u es ap peare d t o als o be highe st at MdR. TUs for M d R w e r e of ten 3– 4 ti m e s th e Mytilu s sp
. EC 50 va lues. Bay Are am a rinas also had occa sional excee dances, but th ese occurre nces were prim arily is olated to L o ch Lom ond M a ri n aan d B e rk el ey M a ri na. Six t y six sam p les with p r ed icted tox i city were co llected from m a rina sites and one sam p le was collected from an LRS. Th is sam p le is th e sam e sa m p le (Md R LR S # 1 ) t h at ex ceeded th e DOC m o d e l ’ s tox i city th resh o l d

. As p r ev iou s ly

53asserted, this L R S site has char acteristics that are m o re like a m arin a site th an an LRS. Ov erall, it is clear th at water sam p les fro m saltwater m arin as h a v e t h e p o t en tial to b e acutely to x i c to M. ga llo pro v i n cialis

. Pred ictio n s were fai r ly con s isten t b e twee n the saltwater BL M (i.e., excee dances of M. gallo p r

o v in cia lis EC 50 ) and t h e DOC m odel (i.e., e x ceedance s of FCCs or FACs). T h at is, bot h m odels te nd to predict a c ut e toxicity or the lack of to x i city for t h e sam e sa m p le. Th is is no t en ti rely surprising sin ce DOC, which is a m aj o r d eterm in an t in th e bioa vailability of copper i n sa line water, is a n input in both m odels. Note t h at chronic t o xicity cannot be com p ared h e re sin ce t h e d r aft saltwater BLM u s ed for th is rep o rt d o e s no t cu rren tly g e n e rate a CC C ou tpu t

. Th e saltwater BLM p r ed icted acu te tox i city m o re freq u e n tly than t h e DOC m odel. There we re 14 occa sions where the saltwater BLM predicted the e x ceeda n ce of a n ac ute toxicity thres hol d a n d the DOC m odel di d not. In cont rast, the r e were only two occasions where the DOC m odel pre d icted t h e e x ceedance of an acute t o xicity threshold and the saltwater BLM did not. T h is suggests t h at t h e DOC m odel is m o re con s erv a tiv e than th e saltwater BLM in p r ed ictin g acu te tox i city. Th ere is an assu m p tio n m a d e h e re th at bo th m o d e ls’ to x i city th resh o l d s (i.e., FACs and B L M pred icted EC 50 ’s) are si milar en ou gh t o allow th is com p ariso n
. Sin ce site-sp e cific CCCs and CMCs are n o t yet av ailab l e fro m th e saltwater BLM, it is no t po ssi b l e to accu rately co m p are th e curren t m o d el outp u t with the C T R’s water qua lity criteria. Howev er, c o n s id ering t h e im p o r tan ce o f D O C i n m ed i atin g t h e b i o a v ai l ab ility o f copper, it is lik ely t h at th e co m p ariso n of th e sa ltw ater BLM cri t eria to th e ex istin g CTR water qu ality criteria will b e si m i lar in resu lt to th e co m p ariso n of t h e DOC m o d el’s FACs and FCCs t o th e sam e criteria. In o t h e r word s, th e saltwat er BLM-p r ed icted CCCs and CMCs are lik el y to b e h i g h e r t h an th e fix e d acute (3.1 μ g/L ) a n d ch ro ni c ( 4

. 8 μ g/L ) CTRstandards for m a ny sites. Howe v e r, at sites wh ere DOC t en d s to b e low (i .e., Sa n F r anc i sco M a ri na, S a nt a C ruz Har b or , M o nt erey Har b or, an d Sa nt a B a r b ara Harb or ), i t i s p o ss i b l e th at th e saltwater BLM

- g e n e rated criteria cou l d b e lo wer t h an th e ex istin g stand a rd s. A s u bset of t h e saltwater BL M-predicted tox i city resu lts were d i rectly com p ared to t h e stu d y ’s tox i city resu lts. A com p ari s on o f sam p l e s th at h a d bot h pre d i c t e d a n dactual t oxi ci t y res u l t s sho w e d 35 of 4 0 m a t c hi ng o u t c om es. That is, th e saltwater BLM p r ed icted acu t e tox i city wh en statistically sig n i ficant to x i city was ob serv ed in tox i city tests, o rit pre d i c t e d t h at no t o xi ci t y wo ul d occ u r f

o r

s a m p l e s wi th n o o b ser v e d t o xi c i t y
. Fi ve c ont r a di ct i ng o u t c o m es were obs er ved

. The m odel pre d i c t e d ac ut e t o xi ci t y at a Loc h Lo m ond M a ri na s i t e , one M d R B ack B a si n si t e , an d t w o Down town Sho r elin e Marin a sites wh en no acu te tox i city wa s observe d i n the se sam p les. In one ca se, for a Ma rina Bay Yach t Harb or sam p le, th e m o d e l p r ed icted n o tox i city an d yet acu te t o x i city was observ e d i n th e sa m p le. Int e re st i ngl y , t h ese fi ve a n om al ous res u l t s ar e i d ent i cal t o thos e obse r ved bet w ee n th e D O C m odel p r e d i c t i ons an d actu a l tox i city resu lts.
Ov erall, th e sal t water BLM p r ed icted EC 50 ’ s fo r M. g a llop r o v in cia lis were g e n e rally in go od agreem en twith act u a l t oxi ci t y (8 8% s u ccess rat e ). L i ke th e D O C m odel , h o w eve r , th e saltwater BLM also tends to ov er-pred i ct to x i city on occasions. T h i s tendency ca n be see n when toxicity res u lts were pl otted a g ainst t h e BL M-predicted T U s (Figure 32). N o te t h e r e d v e r tical lin e on the gr aph , wh ich d e n o t es th e 1

- TU t h r e sho l d

. I n ter e stin g l y, sig n i f i can t abnor m a l d e v e l o p m en t (wh i ch in cl u d es larv al m o rtality) do es no t appear to tak e p lace un til th e p r edicted TU is greater th an 2

. Th is sug g e sts th at tox i city p r ed ictio n s b y t h e saltwater BL M , part i c ul arl y at l e vel s bet w ee n 1 a n d2 T U s, m a y not always translate to n o t ab le tox i city to M. gallo p r

o v in cia lis in labo rat o ry tests. W i t h th is in m i n d , o f th e 6 7 sam p les th at w e r e ab ove th e 1

- TU t h r e sh o l d , on ly 29 o f th em w e r e also ab ov e t h e 2- TU thr e sho l d. Th ese 29 samp les w e r e col l ect ed f r o m fo ur m a ri nas–S a nt a B a r b ara H a rb or , M d Rba ck basi ns , M d Rfr o n t basi ns, and D o wnt o w n Sh or el i n e Marina. T hus , if this s u bset of sa m p les were analyzed for t o xicity to M. gallo p r

o v in cia lis , th ey w o ul d l i k el y exhi bi t statistical ly sig n i fican t t o x i city. Fu ture in terp retation an d lin k a g e of BLM to x icity p r ed ictio n s to actu a l to x icity resu lts sh ou l d co n s i d er th is ob serv atio n.

54Figure 32. BL M-Pre dicted Toxic Units (Obser ved DCu/Predicted M
. ga llop r o v incia lis EC 50 ) v s . Observ ed T oxi ci t y

0 10 20 30 40 50 60 70 80 90 100

10Percent Abnormal Development

0. 1 1 L o g T o xic U n its



### IV. Discussion
Occurrence and Magni t ude
DC u, TC u, a n dDZ n were f r eq uent l y det ect e d

. T h e hi g h fre que ncy of det e ct i on i s n o t su r p ri si n g c o nsi d e r i n g ( 1 ) th e ubi qui t o us nat u re o f c o p p e ra n dzi nc ( 2 ) t h at m oni t o ri n g wa s co n duct e d i n m a ri na areas , whi c h have hi s t ori cal l y been k nown to exh i b it elev ated con cen t r atio n s o f m e tals, an d (3) th e relativ ely lo w d e tection l i m i ts u s ed fo r q u a n tificatio n.
W

a t

e r C o lu mn – C o pper
DC u co nce n tr a t i ons i n sal t a n d brac ki sh wat e r m a ri nas we r e fre q u ent l y hi ghe r t h an th ose f o u n d i n f r esh w at er m a ri nas. Thi s di ffe re nce i s st at i s t i cal ly si gni fi ca nt

. M a ri nas i n C a l i f or ni a’s S out h C o ast ex hi bi t e d l o w t o very h i gh m e di an DC u conce n tr at i o ns am ong res u l t s fo r al l th e m a ri nas. M d R ’ s fr ont a n d back b a si ns hadth e t w o hi ghe st m e di an conce n tr at i o ns at 12 .4 an d 1 3

. 6 μ g/L , re spect ively. T h e highest sam p le co n cen t r atio n of DCu was d e tected in t w o sam p l e s from the back ba si ns of M d R

. B o t h sam p l e s cont ai ned 1 8

. 4 μ g/L of DC u. D o w n t o wn S h o rel i n e M a ri na ha d th e th ird h igh est m e d ian co n c en tration in th e stud y at 6.6 μ g/L. The rem a i n i n g S out h C o ast m a ri na, Al a m i t o s B a y M a ri na, e x hi bi t e d a rel a t i v el y l o w m e di an D C u c once n tr at i o n o f 1. 2 μ g /L. Th is m arin a is lo cated on ly a few m iles fr om Dow n t o w n S h orel i n e M a ri na a n d i s si m i l a r i n si ze. Thi s devi at i o n, h o we ve r, c o ul d pot e n t i a l l y be creat edby t h e di l u t i o n ef fect cause d by th e r out i n e p u m p i n g of a hi g h vol um e of wat e r f r om th e m a ri na f o r c o ol i n g u s e at a ne ar by p o wer-g e n e ratin g facility (M. Sand ov al, p e rso n a l co mmu n i catio n , 20 07). During p e ak pu m p in g p e ri o d s, a vo lu m e th at i s ro u ghl y e qui val e nt t o th e capaci t y of Al am i t o s B a y co ul d be em pt i e d o u t fr om th e basi n
. Elevated DC u conce n trations in Sout h C o ast marinas ha ve a l so been doc u ment ed in t w o recent st udies

. In 2005, SC C W R P c o n duct e d a m oni t o ri ng st u d y o f 12 y acht basi n s i n fo u r S o ut h e rn C a l i for ni a har b ors ( D ana Poi n t Ha rb or , Oceanside Harbor, Mission B ay, and Sa n Di ego Bay) as part of SDRW QCB’s Harbor Monitoring Program (SC C W R P , 20 06 ). DC u c o nc entrat i o ns ran g e d fr om bel o w t h e det ect i o n l i m i t t o 21. 0 μ g /L with a m ean co n c en tration o f

7.0 μ g /L. In 20 06 , th e San t a An a RW QC B con d u c ted a metal m o n ito rin g stud y in LNB. DC u con c en tration s in th e m a ri nas sam p l e d ran g e d f r o m 1. 3

– 1 1 μ g/L with a m ean c o ncent r ation of 4.2 μ g/L

. T h e m a ri nas i n vest i g at ed i n bot h o f

55these studies a r e located fa rther s out h along th e Californ i a co ast th an t h e so u t h e rn m o st site in th is DPR stu d y
. If th e coppe r re sults from the three studies we re poole d toget h er , they would show that elev ated DCu conce n trations are com m on am ong C a l i f o r ni a S o ut h C o ast m a ri nas. Th e t h r ee Cen t r a l Co ast m a r in a s i n th is study ex h i b ited m o d e r a tely h i g h med ian D C u co n c en tr ation s
. San ta Barb ar a Har b or, M o nt e rey Ha rb o r, a n d Sa nt a C ruz H a rb or ha d m e di an c once n trat i o ns of 5 .7 , 4. 9, and 4 .3 μ g/L, respectively. These m e di an conce n tr at i o ns are th e fi ft h th r o u g h se ve nth h i ghest val u es d o cum e nt ed am on g t h e 23 m a ri nas stu d i e d

. The hi g h est D C u c once n tr at i o n d o c u m e nt ed am ong th e s e t h ree C e ntral C o ast m a ri nas w a s det ect ed i n a sam p l e from Sant a B a r b ar a Har b or at 8. 2 μ g/L.
Ei ght B a y Are am a ri nas were exam i n ed i n th i s stu d y a n d m o st of th em exhi bi t e d m oder a t e m e di an DC u c once n tr at i o ns bet wee n 2. 1– 3. 3 μ g/L

. T h e hi ghe r-e n d e x cep t i on t o th i s ra n g e i s L o c h L o m ond M a ri na i n Sa n R a fael w h ere th e m e di an co nce n tr at i on was 5. 8 μ g/L. The l o wer
- en d e x ce pt i on i s Sa n F r an ci sco M a ri na whe r e t h e m e di an conce n tr at i o n was 1. 1 μ g/L

. Th e b r ack i sh water m a rin a s–th e Vallej o , Ben i cia, Pittsbu rg , and An tio ch marin a s– ex h i bited lo w to m o d e rate m e d i an DC u co nce n tra t i ons of 3

. 4 , 2. 7, 2. 2 a n d 2. 1 μ g /L, resp ectively. Th e freshwater m arin as–th e Villag e W e st, Sacram en to , Fol s om Lake, andTahoe Key s m a ri nas–ex hi bi t e d m oderat e t o very l o w m e di an c o nce n tr at i ons of 3

. 4 , 3

. 0, 0

. 5 , 0. 6 μ g/L

. We obs e rve d t h e lowe st m e dian DCu concent r ations in th is stud y at th e two lak e marin a s at Taho e Keys an d Fol s om Lake.
The m e dian T C u a n d DC u c once n trations for each m a rina tend to be similar in m a gnitude. T h at is, m a rinas t h at exhi bi t hi g h D C u c once n trat i ons t e n d t o al s o e xhi bi t hi gh TC u c once n tra t i ons. S o , t h e r a nki ng o f m a ri nas fr om t h e l o west t o th e hi ghe st m e di an TC u c once n tr a t i ons cl osel y re sem b l e s th e ra nki ng f o r

DC u. T h i s o b se rvat i on i s l a rgel y explaine d by t h e fact that the TCu m eas ure m ent accounts for the DC u l o ad as well as t h e pa rticulate coppe r l o ad. U.S. EPA de ri ve d a recom m ended mu lt i p l i e r of 0

. 91 as a co n v ers i on fact o r of D C u f r o m TC u i n sal t w at er en v i ro nm ent s (U.S. EPA, 200 7). Th e freshwater mu ltip lie r is 0

. 9 6 (Stepha n , 19 95). In oth e r wo rd s, DC u tend s to m a k e up o v e r 90 % of TC u. The o v eral l rat i o o f DC u t o T C u f o r th i s stu d y i s 0. 92 , whi c h i s a g o o di n di cat or th at D C u a n dTC u w e re with in t h e expected rang e in th is stud y. Desp ite th is relation s h i p b e tween th e DC u and TCu , statistical an alysis (o n e
way A N O V A t e st s) of TC u da t aonl y s h owe d a m a rgi n al di f f ere n ce bet w ee n th e TC u co nc entr at i o ns of sa l t and fres h w a ter m a rinas.
Wa ter Co lumn – Zinc

DZ n c once n tr a t i ons were ge n e ral l y 2– 4 t i m es l a rge rt h an D C u a n dTC u co ncent r at i ons i n th e sam e sam p l e
. C onse q uent l y , m e di an D Z n c once n tr at i o ns were us ual l y hi ghe r t h an th ose f o r DC u o r T C u at eac h m a ri na. M d R ’ s fr ont a n d back basi ns ex hi bi t e d th e t w o hi g h e st m e di an DZ n c once n trat i o ns at 4 9

. 1 a n d 50 .0 μ g/L, res p ectively. The hi g h est DZn c once n tr at i o n d o cum e nt ed i n t h e st udy was detected in one of the fr o n t bas i ns of M d R at t

h e conce n tr at i o n of 6 6

. 6 μ g/L. The l o west m a ri na m e di an D Z n c o ncentr a tions are often a ssociat ed with the fres h a n d brac kish wate r sam p les. The diffe re nce between DZn concen tr at i o ns i n s a l t w at er m a ri nas an d DZ n c o ncent r at i ons i n brac ki sh an d fr eshw at er m arin as is statis tically significa nt.
The ran k i n g o f l o we st t o hi g h e st m e di an DZ n c once n tr at i o ns i s al s o very sim i l a r t o th e a n al o g o u s ra nki ng f o r

DC u a n d TC u. T h e pri m ary except i o n was Al am it os B a y w h i c h ra nke d mu ch hi g h er f

o r

zi nc t h a n c o p p e r
. N o t e , h o w eve r , th a t th e LR Ss at Al am i t o s B a y M a ri na (m edi a n D Z n of 6 .3 μ g/L ) e xhi bi t e d si m i l a r DZ n c onc e n trat i o ns as t h e m a ri na si t e s (m edi a n DZ n o f 6. 7 μ g/L )

. T hus , t h e fl us hi n g act i v i t y th at i s u n i q ue t o th i s m a ri na wo ul d not necessari l y ser v e t o effectiv ely d ilute th e DZn lo ad in th e m a rin a
. Th is c o u l d ex p lain wh y DZn co n c en tration s are still relativ ely h igh com p ared t o DCu a n d TCu concent r a t i ons i n Al am it os B a y M a ri na. Ov erall, larg er saltwater m ari n as ten d to rank h i gh ly fo r m etal co n cen tratio n s
. Sm aller saltwater m arin as and fresh and b r ack i sh water marin as tend t o m ak e up the in term ed iate andl o wer ra nki ngs
. Thi s o b se rvat i o n s u gge st s th at fact ors relatin g t o water typ e s and marin asize m a y p l ay a m a j o r role in d e term in i n g th e m a g n itud e o f copp er an d zin c i n m a rina wate rs. As pre v i o usl y not e d fo r Al am i t o s B a y M a ri n a , si t e speci fi c hy d r ol ogi cal fa ct ors (i .e. , fl us hi n g ) ap pear t o be a n i n fl ue nt i a l fact or ( K at z, 19 9 8 ) an d m a y serve t o e xpl ai n w h y Al am i t o s B a y M a ri na (af f e c t e d by i n d u str i al pum pi ng ) andSa n F r a n ci sco M ari na (l o cat ed at th e m outh o f Sa n Fra n ci sco B a y ) e x hi bi t e d rath e rl o w m e di an DC u a n dTC u

56conce n tr at i o ns rel a t i v e t o t h ei r si ze. Po or fl u s hi n g m a y al so ex pl ai n why L o ch L o m ond a n d B a l l e na I s l e m a ri nas, whi c h ar e bot h sm all e r m a ri nas, e xhi bi t e d hi ghe r c o ncentr a t i ons of co p p er an d zi nc w h e n com p aredt o l a rge rm a ri nas in th e Bay Area.
Wa ter Co lumn – Irga ro l/M1

The bi oci d e Ir gar o l a n d i t s p r im ary degra d e M 1 we re det e c t ed in all 45 sam p les. Irg a ro l an d M1 con c en tration s r a ng ed fro m 1 2 –71 2 and 2– 21 7 ng /L, r e sp ectiv ely. Th e h i g h e st Ir g ar o l an d M1 con cen tratio n s w e r e fou nd i n a sam p l e fr om Loch L o m ond M a ri na i n Sa n R a fael

. M 1 c once n tr at i ons we re al s o a l way s l o wer t h an Ir gar o l i n th e sam e sam p l e
. M 1 c once n tr at i ons al so co rrel a t e d wel l wi th Ir gar o l at eac h si t e reaffi rm i n g th e pare nt co m poun d- de gra d at e relations hip be tween t h e two analytes. Irgarol a n d M1 concent r ations we re high er i n saltwater m a rinas t h an bracki sh water m arinas. Sim ilar to o u r ev alu ation of

co p p er, I r garol c o ncentr at i ons i n a part i c u l ar m a ri na are l i kel y di ct at ed by th e am ou nt of use i n t h at m a ri na an d t h e lev e l of site-specific flu s h i ng at th at lo cation. DPR’s p r od u c t dat as h o w t h at 68 p r od uct s (i ncl u di n g se ve ral m a nufact uri n g use pr o duct s ) ar e re gi st ere d w i th DPR( D PR , 2 0 0 5 b )

. Al m o st al l of t h e e n d- use p r o d u ct s are f o r AFP u s e with bo at hu lls b e i n g th e m o st co mm o n ap p lication site. Irgarol a n d M1 concent r ations we re high er i n th e first v e rsu s th e th i r d sam p lin g roun d. Assu m i n g th at all of th e Irg a ro l in th e water co lu m n o r i g in ated from AFP sou r ces, th e n th e di ffe rence bet w een th e t w o sam p l i n g r o un ds ca n be attributed to t h e differe n ces i n the re lease of Irg aro l fro m b o a t hu lls (wh e th er th rou g h leach i ng o r und erwater hu llclean in g) du ri ng th e ti m e o f sa m p le co llectio n in th e first rou n d v e rsu s th e th ird ro und

. M a n y fact o r s could h a v e an in flu e n ce on the release rates b e tween th e two roun d s in cl uding use, elaps e d tim e from ap p lication an d h u ll clean ing , and seas onal c h an ges i n fl us h i ng a n d wat e r t e m p eratur e.
In 2 0 0 5 , Sap o z hni ko va et al . ( 2 0 0 7 ) co n duct e d a n asse ssm ent o f Ir gar o l a n d M 1 i n Sa n D i ego B a y Area m a ri nas. I r g a ro l an d M1 con cen t r atio ns in th at stud y ran g e d f r o m 1

– 3 0 4 ng /L an d 1– 68 ng /L, r e spectiv ely. In 2 0 0 6 , H a ll et al. (2 0 0 7 ) qua nt i f i e d Ir gar o l a n d M 1 c once n tr at i ons i n 1 5 C a l i f or ni a m a ri na ar eas. Al am it os B a y M a ri na, M d R , B a l l e na Isl e M a ri na , a n d B e rk el ey M ari na were al so studi e d i n Hal l et al . ( 2 0 0 7 ). I r garol a n d M 1 conce n tr at i o ns i n th i s st udy ran g e d f r o m 1–3 3 9 ng/L an d bel o w det ect i o n t o 7 4 n g /L , r e spec tively. Hall et al. (2007) also as sesse d l o cal re fere nce sites in add ition to m a rin asites. B o th Irg aro l and M 1 con cen tration s were mu ch lo wer at lo cal referen c e sites th an at m a ri na si t e s. Thi s s u pp ort s ou r pre v i o us as sert i o n th at t

h e m a i n so urce o f I r g ar ol an d M 1 are f r om AFP use
. Sedi ment – C o ppe r and Zi nc
On ly 2 3 of t h e an ticip ated 18 0 sed i m en t s samp les were tak e n in th is st u d y
. Th ese sam p les were tak e n from th ree fres h w a t e r m a ri nas. F o r TC u, b o t h t h e hi g h e s t (1 6 9 m g / kg dry wei g ht ) a n d l o west c o nce n trat i o ns (1 7 m g / k g dry weight) were detected at Sacra m ento Mari na and one of its associated LR Ss , respe c tively. For TZ n, t h e highest co n c en tration (2 73 m g /k g dry weigh t ) was d e tected at Villa ge W e st Marin aan d th e l o west co n c en tration (2 3 m g /k g d r y weigh t ) was d etected at an LRS o f Fo lsom Marin a. The av ailab ility of sed i m en t m et als d ata, p articu l arly tho s e fr om studi es w h ere sedi m e nt sam p l e s are n o t dept h-c o m p o s i t e d, i s very l i m i t e d for f

r es h w at er m a ri nas i n C a l i f o r ni a. Sed i m en t m eta ls d ata th at do ex ist are m ain ly fro m saltwat er m a ri nas. Pa p (2 0 0 4 ) doc u m ent e d t h e ra n g e of sedi m e nt TC u c once n tr a t i ons i n f o ur B a y Area m a ri nas (B al l e na Isl e , L o ch Lom o n d , B e rkel ey , a n d C o ri nt hi an C l ub ) t o be 3 8

. 2 – 15 1 m g / k g d ry wei g ht

. Sedi m e nt TZ n c o n c e n trat i o ns i n t h e Pap ( 2 00 4) st u d y ra n g ed f ro m 82.7

– 2 1 9 m g / k g dry weigh t

. Th ese rang es are fairl y si m ilar to th e ran g e s ob se rv ed fo r TC u a n d TZn at the thr ee fre sh water m a rinas in o u r study

. O r a nge C o u n t y C o ast Keepe r ’ s stu d y i n L N B doc u m ent e d se di m e nt TC u co nce n tr at i ons i n t h e r a nge o f 1 6

- 3 6 5 m g / kg d r y wei ght a n d TZ n co ncent r at i ons i n t h e ran g e of 6 9

– 6 9 2 m g / kg d r y wei ght (O ra nge C o u n t y C o ast Kee p er, 20 0 7 )

. T h ese r a nge s f r o m LNB m a ri nas are som e what hi gh er th a n t h e one s o b ser v e d i n P a p (2 0 0 4 ) a n d ou r st udy

.

Com p ari s on t o W a ter Q u al i t y St an dar d s or B i ol ogi c a l E ffect s T h res hol d s Co pp er
Th e CTR con t ain s th e enforceab le water q u ality stan d a rd s fo r co pp er in Califo r n i a. Th ese stand a rd s h a v e b een in place for California since 2000 when U.S. EPA promulgated th em in the absence of a stat e-established water quality standards.

57The c o m p arison of freshwater DCu res u lts to th e CTR’s h a rd n e ss-b a sed C CC (chron ic) an d CMC (acu te) stand ard s for coppe rs u ggest e d that DC u c o ncent r ations in fre shwater m a rin a areas (m arin as sites an d LRSs) were n o t lik ely to represen t a sign ifican t risk to fresh water aq uatic o r g a n i sm s. Bot h the CTR chronic a n d ac ute standards for DC u in fres h w a t e r wer e ne ver excee d e d i n th e 1 3 5 DC u sam p l e s eval uat e d f r om si x di ffe rent m a ri nas a n d ass o ci at ed LR Ss. No te t h at so m e sam p les fro m two of th e brack i sh water m ari nas c ont ai ne d l o w e n ou g h sal i ni t y th at i t

wa s p o ssi bl e t o evaluate t h em with the fres hwater sta ndards.
DCu resu lts fro m th e stu d y ’s salt an d brack i s h water m arina areas we re al so c o m p ared t o the CTR fixe d saltwater st andard s. O f t

h e 38 8 c o m b i n ed sal t a n db r a c ki sh wat e r sa m p l e s, DC u c o ncent r at i ons i n 3 0 % a n d 17% of th em exceede d t h e c h ronic and ac ute coppe rstandards , respec tively. Alm o st all of the sam p les that e x ceede d CTR st andard s were m a ri na sam p l e s. F o r m a ri na sam p l e s onl y , th e DC u co nce n tr at i o ns i n 5 1 % an d 3 0 % of th e sal t an d brac kish wate r marina sam p les com b ined exceeded th e chronic a n d ac ute standa rds, res p ectively.
DCu conce n tra tions i n 16 of 19 m a rina areas ex ceede d t h e c h ronic saltwate rCTR sta ndard of 3.1 μ g/L. The m a rina areas whe r e D C u c once n tr at i ons di d n o t exc eed th e ch r oni c st an dar d s wer e A n t i o ch M a ri na, So uth B eac h Har b or, an d Coyote Point Marina. Copper concentrations i n 10 of the 16 m arina areas that exceeded th e CCC also exceeded t h e C M C st anda rd of 4 .8 μ g/L. T h ese 10 m a rina areas we re L o ch L o m ond , C l i ppe r Yacht Harb or , B e rk el ey M a ri na, B a l l e na Isl e M a ri na, Sa nt a C ruz Har b or, M o nt erey Har b o r , Sant a B a r b ar a Har b or, M d R f r o n t basi ns , M d R back basi ns , a n dD o wnt o w n Sh or el i n e M a ri na
. As defi ned by th e C T R , excee dance s of C T Rsal t w at er st a n dar d s i ndi cat e th at co nce n tr at i ons o f DC u are hi g h e n ou g h to prese n t a si gnificant risk to the aquatic organism s and the i r use s. Th e exceedanc e of C TR stan dards for copper has h i sto r ically b e en u s ed to suppo r t t

h e d eclar at io n of b e n e f i cial u s e im p a ir men t s b y th e San D i ego RW Q C B. Th er ef or e, water bodies a c ross the state that ex ce ed thes e standards ca n certainly be pl aced on the C W A 303(d) impaire d water b o d i es list b y oth er RW QCBs as well. TMDL d e v elop m en t is a p o ssi b ility fo r all water bo d i es th at are on th e C W A 3 03(d) list. The ado p tion of a site-sp ecific ob j ectives for the San Fran cisco Ba y will, howev er, lik ely im p act th e fu ture 3 03( d) listin g p r o cess fo r Bay A r ea m a r in a s.
Zinc

Th e CTR also estab lish e d sp ecific water qu ality stan d a rd s fo r zin c
. Non e o f th e 13 5 fresh w ater DZn sam p les co llecte d in this st udy e x ceeded the CT R’s hardne ss-based fres h water c h ronic a n d a c ute standards fo r zinc

. M o re ove r, none of the 388 DZ n sa m p les from salt and brac kish water m a rinas containe d hi gh enough DZ n c once n trations to e x ceed the CTR’s saltwat er fi xed chroni c and ac ute sta nda rds of 81 a n d 90 μ g/L, res p ectively. T h e r efore , DZn concent r ations in all th e m arin a areas in th is st u d y were n o t li k ely to p r ese n t an a dve rse ri sk t o fres h wat e r aquat i c or ga ni s m s. Irg arol / M

1

Th ere are no water qu ality stan d a rd s for Irg a ro l o r M1. Thu s , a co m p ariso n of sam p le co n c en tration s to v a ri o u s bi ol o g i cal ef fe ct th res hol ds i s a m o re in formativ e way to p u t Irg a ro l an d M1 d a ta in to p e rsp ectiv e. Si n ce Irg a ro l acts as an i n hi bi t o r of p h o t o sy nt he si s, g r o w t h i n h i bi t i on of p h y t opl a nkt on ap pe ars t o be o n e o f i t s m o st com m onl y
obs er ved bi ol o g i cal eff ect s. I r garol c o ncent r at i ons at s o m e of th e m a ri nas i n th i s st udy ar e hi g h e n ou g h t o excee d so m e o f th e tox i co log i cal v a lu es for g r owth an d rep r od u c ti o n inh i b ition en dpo in ts. Th us, th ere are in st an ces wh ere sim p le risk quotients (EC 50 / o bser ve d c once n tr at i o n) w oul d be great er th an one
. Fo r a m o re com p le te assessmen t o f po ten t i a l risk s, it is mo re in form at iv e to co m p are en v i ron m en tal co n c en tration s to aquat i c be nch m ark val u es t h an t o EC 50 orLC 50 val u es. Ha l l et al . (1 9 9 9 ) deri ved an aq u a t i c -pl a nt t o xi c i t y benchm ark val u e f o r Ir gar o l i n a n ec ol og i cal ri sk asse ss m e nt (ER A ) fo r E u r o pean wat e rs. T h e benc h m ark th res hol d re prese n t s th e 10 th pe rcentile of the a v ailabl e and acce pted plant toxicity data set that contained nine toxi cological val u e s. For this part i c ul arasses s m e nt , th e be n c hm ark val u e was cal c u l a t e d t o be 1 3 6 ng/L

. Whe n c o m p ared wi th m easur ed envi ro nm ent a l conce n tr at i o ns (i .e., 9 0 th p e rcen tile v a lu e of variou s station ty p e s), v arying lev e ls of eco l og ical risks were est abl i s he d wi th ri sks i n m a ri nas bei n g th e hi ghe st am on g t h e st at i o n t y pes. Hal l et al . ( 1 9 9 9 ) det e r m i n ed th at Ir gar o l c once n t r at i ons at 2 4 % of t h e m a ri na s i t e s and 1 0 % o f al l t h e si t e s e v al uat e d e x cee ded t h e 1 3 6 n g /L be nchm ark. In o u r stu d y , Ir gar o l c once n tr at i ons i n 11 of th e 45 sam p l e s (also 24%) coll ected for Irga rol analysis e x c eeded this sam e pl ant t oxi ci t y benchm ark.

58Si m ilar ERAs were cond u c ted b y Hall an d Gard in ali (20 0 4 ) and Hall et al. (2 007 ). B o th th ese ER As u s ed a larg er aquat i c pl ant t oxi ci t y dat a set (1 6 t oxi c o l o gi cal val u es ) t h an t h e 1 9 9 9 asses s m e nt and al so i n cl u d ed LC 50 dat a
. The Ir gar o l benc hm ark val u es th at were de ri ve d i n Hal l an d Ga r d i n al i ( 2 00 4) a n dHal l et al

. ( 2 0 0 7 ) we re 25 1 ng/L an d 1 9 3 n g /L, r e sp ectively. Four o f t

h e 45 sam p les (9 %) co llected fo r Ir g ar o l an al ysis in ourstudy co n t ain e d I r gar o l co n c en tration s th at were ab ove th ese h i g h er and m o re r o b u s t be nchm arks. I n a ll three of these ER As, e cological ris k s f r o m I r g ar o l wer e assessed to b e g e n e r a lly low

. How e v e r , th e ER A s f ound th at r isks in mar in aar eas wer e n o tab ly hi g h er
. Fo r ad d ition a l p e rsp ectiv e, an aqu a tic tox i city b e n c h m ark kn own as t h e Env i ro n m en tal Risk Lim it (ERL) (no t to b e mistak en with th e id en tical abb r ev iatio n th at stan d s fo r Ef fe cts Range L o w that is used in the context of s e dim e nt q u a lity gu id eli n e) is used in t h e Neth erland s. Th e Du tch Irg a ro l ERL of 24 n g /L is also b a sed o n a p lan t tox icity d a taset and is set at d a taset’s 5 th pe rce n tile value (protective of 95% of al l aquatic pla n t species). Recall that the b e n c h m ark v a lu es u s e b y Hall et al. (19 9 9 ) an d Hall an d Gard i n ali (200 4) u tilized th e 10 th p e rcen tile v a l u e. Th e m o re p r o tectiv e p e rcen tile v a lu e u s ed for th e ERL and th e d i ffe ren ce in th e t o x i city d a taset an alyzed resu lted i n a si gni fi ca nt l y l o wer be nc hm ar k val u e. F o rt y out o f 45 sam p l e s fr om our st

udy ( 89% ) c o n t ai ned Ir gar o l c once n trat i o ns above t h e Dutc h ERL for Irgarol.
C onsi d eri n g t h e o v erl a p of m easure d m a ri na Ir ga rol c o ncen trat i ons wi t h p h y t opl a nkt on a n d pe ri p h y t o n EC 50 rang es an d aqu a tic b e n c h m ar k v a lu es, th er e ap p e ars to b e r isk fr om I r g aro l exposu r e to t h ese assem b lag e s in so m e o f th e saltw ater m ar i n as i n th is study. How ev e r , at th is p o i n t , it is no t clear wh at b i o l o g i cal and/o reco l og ical im p acts ar e occu rri ng d u e t o Ir gar o l e x p o s u re i n t h ese m a ri nas. A m o re foc u se d st udy on th e i m pact of I r garol t o m a ri na b i o l og ical assem b lag e s sh ou l d rev eal if ER A p r ed ic tio n s are represen tati v e o f real-wo r l d co nd itio ns.
M1 is co nsid erab ly less tox i c to aqu a tic o r g a n i sm s th an I r g a rol

. As a c o n s eq uence , i t s a quat i c ben c hm ark val u e (1 2, 5 0 0 n g /L ) i s mu ch hi ghe r th an t h at f

o r

I r g ar ol

. N o ne of th e sam p l e s i n th i s stu d y c ont ai ned M 1 c o nc entr at i o ns t h at were cl ose t o t h i s benc hm ark. T hus , ec ol o g i cal ri sks f r om M 1 ex p o su re t o aq uat i c pl a n t s i n th e m a ri nas i n th i s st udy are e x trem ely low.

Marina vers us Loc a l Re fere nce Site
Wa ter Co lumn Copper and zi nc concent r ations we re fre que n t l y hi ghe r i n m a ri na sam p l e s th an i n LR S sa m p l e s t a ken f r o m adjace nt areas. For DC u, t h is diffe rence is statisti cal ly si gni fi ca nt f

o r m a ri nas in all th ree water typ e s. Fo r TCu, th is d ifferen ce is statistical ly sig n i fican t in saltwater an d fre shwate r m a rinas. F o r DZn , th e differe n ce is statistically significant for sal t and b r acki s h wat e r m a ri n a s. T h e di scre pancy bet w ee n m a ri na and L R S co nce n tr at i ons o f c o ppe r a n d zi nc stro n g l y su ppo rt t h e assertio n th at sou r ces of m etals fro m in sid e of ma ri nas a n d/ o r f

act ors t h at are rel a t e d t o t h e r e si dence t i m e and fl ushi ng d y n am ics (as c o m p ared to LR S s ) a r e m a inly resp onsi b le f o r the o b se rve d di ffe rence
. Tw o basi c fact ors co ul d p o t e nt i a l l y expl ai n why el e v at ed m e t a l concentr at i ons oft e n e x i s t i n m a ny of t h e m a ri nas i n th is stud y. Metals lo ad ing from th e m a rin a ’s con f i n es co u l d serve as a loca lized source , which c o uld dist inctly elevate wat e r c o l u m n and se di m e nt conce n tr at i o ns o f c o p p er an d zi nc i n th e i m m e di at e vi ci ni t y o f th e m a ri na. M o re ove r, since the prim a r y basis of m arina placem en t, construction, a n d de sign is to pr ovide s h elter and protection for m o oring boat s f r om wi n d , c u rre nt s, a n d t i d es , m a ri na areas t e ndt o b e p o o r l y fl u s he d c o m p ared t o t h e l a r g er b ody o f w a t e r wi t h whic h they a r e associated.
In 2 0 0 5 , D P R con d u ct ed a re vi ew o f C a l i f o r ni a co p p er m oni t o ri ng stu d i e s th at c oul d ha ve rel e va nce t o th e e v al uat i o n of

co p p er AF P pol l u t i o n. T h e re vi ew s h owe d th at a

n u m b er o f st

ud ies h a d do cu m e n t ed el evated c o nce n trations of cop p e r(a s wel l as zi nc ) i n m a ri na wat e r a n d sedi m e nt vers u s th e l o cal bac k g r ou n d l e vel s (Si n g h asem anon , 20 0 5 )

. Two larg e m arin a stud ies that were r ece ntly conducted i n L N B an d alon g Califo r n i a’s Sou th C o ast (samp lin g sites bet w ee n Dana Poi n t Harb or a n d th e U. S./M e x i c o b o r d er ) al so do cum e nt ed th i s phe n o m e non ( O ra n g e C o unt y C o ast Keepe r , 2 0 07; Schi f f et

al ., 20 07 ).
Marina-related m e tal studies are typica lly co ndu cted du ri ng d r y p e ri o d s t o h e lp red u c e th e in terferen c e of m e tal contam inants a ssociated with rai n ru n o f f. St orm di scha rge dat af rom t h e LNB m e t a l s study d o cum e nt ed hi g h m e t a l co n c en tration s in run o ff water th at d isch a rg ed d irectly in to sev e ral m a rin a s (Oran g e Coun ty Co ast Keep er 200 7).

59Du ri n g peri od s o f w e t weat he r, i t i s l i k el y th at m e t a l l o ads i n tr od uce d vi a ru n o ff a n d se di m e nt di stur ba n ce an d tran sp ort o v e rsh a dow m e tal s o urces fro m with in th e m a rin a
. Whe n LRS a n d m a rina m e ta l concent r ations are no t statisti cally d i fferen t as in t h e cases of TCu in brac kish water mar in aar eas an d DZn in f r e sh w a term a r in a ar eas, t h is su ggests th at lo ad ing m ig h t no t be h igh en oug h in th e m a r in a s to b e d i stin ct fro m th e LRSs or th at site-sp eci fic flush i n g characteristics are go od eno ugh to k e ep m e tal co n c en tration s l o w. F o r th e c a se o f TC u i n brac ki sh wat e r m a ri na areas , t h e LR S m e di an c once n tr at i o ns ran g e d fr om 7 3

– 1 1 0 % of t h e associ at ed m a ri na m e di an TC u c once n tr at i o ns. B a se d on th e str o ng co rre l a t i on o f TC u t o T SS i n brac k i sh w a t e r marin aareas an d b a sed on t h e relatio n s h i p s estab lish e d in th e Equ ilib riu m Partitio n i n g Th eory, t h e h i gh TCu conce n tr at i o ns obs er ved i n t h e LR Ss ar e l i k el y l i nked t o t h e hi g h T SS c o nc entr at i o ns t h at co- o cc ur t h ere
. F o r DZ n, th e lack of statistical diffe re nce in fre shwa t e r m a ri na ar eas m a y pot e n t i a l l y be expl ai ne d by t h e l ack o f l o ad i ng wi th i n th e marin a s. Th is will b e furth e r ex p l o r ed i n th e n e x t su b-sectio n. Sediment

It is di fficult t o draw clear c o nclusion s fr om the se di m e nt dat acon s i d eri n g t h at o n ly three fres h w a ter m a rina areas were sam p l e d and th at se di m e nt f

r om sal t and b r ac ki sh wa t e r m a rina area s we re not c o llect ed and anal yzed. Sedim e nt conce n trations of TCu and T Z n in the t h ree freshwater m ari n as sam p led were statistically h i gh er th an t h e co n c en tration s in th eir resp ect iv e LRSs. Resu lts fro m Pap (2 004 ), wh ich l o ok ed at f iv e S.F. Bay Area (s altwater) m a ri na areas , a l so s h o w e d hi g h er sedi m e nt m e t a l concentr at i ons i n si de o f m a ri nas vers u s o u t s i d e. T h e sam e t w o factors that likely explain the diffe re nces in water co lu m n co n c en tration s may also p lay a m a j o r ro le i n th is ob serv ed di ffe re nce. T h e l o adi n g an d m a ri na fl u s hi n g dy nam i cs m a y be s o m e what di f f ere n t f

o r m e t a l s i n th e sed i m e nt vers us m e t a l s i n th e w a t e r col u m n
. F o r exam pl e, hi ghe r se di m e nt c o n c en tration s o f to tal m e ta ls in m a rin a s m a y b e an artifact of greater as sociation of particulate m eta ls with finer se d i men t p articles an d org an i c m atter th at is typically m o re p r ev alen t i n side of m arin as com p ared to t h e m o re well-flu s h ed LRSs, wh ere th e sed i m en t is lik ely to b e larg er-g rained.

Marin a Sourc e s of Copper
Wood Pr eserv a tives
There are m a ny pos si bl e m e tal so urces wi th i n a m a ri na. C o p p e r-c ont ai ni ng w o od p r ese r vat i v es th at ar e use d i n th e marin aenv i ronmen t represen t a po ten tia l c o p p er so u r ce. M a ri na s u rvey re spo n ses th at w e re pr ovi ded t o DPR by marin am a n a g e rs (Ap p e nd ix A) sugg ested th at p iling s and o t h e r m arin a-asso ciated stru ct u r es th at are con tin u a lly or occasionally immersed in t h e water could leach wood pre servative s int o marina wa te rs. Creosote, copper borate a zol (CBA), c h romated copper ars e nate (C C A ), Copper-Gree n ®, a n d amm oniacal co pper zinc ar senate (ACZA) we re id en tified as b e in g h i storically or cu rren tly u s ed in a few of t h e m a rinas. B e nicia Mari na , Vallejo Mari na , Berk eley M a ri na, B a l l e n aIsl e M a ri na, So uth B eac h H a rb or , a n dSa nt a B a rbar a Har b or al so re po rt ed th at t

h ere we re cre o s o t e
treated p iles in th eir m a rin a s, p a rticu l arly in asso ciatio n wit h ol de r c onst ru c t i on. C o nsi d e ri n g t h at c re o s o t e i s a pr o duct of coal tar disti llation, the leachate of c o ncern from creosot e use is polyarom atic hydroc arbons (PAHs ) , and does not contain copper in a n y appreciab le am ount (U.S . EP A, 2003).
CBA , CCA, C o pp er -G r e en ®, and A CZA, ho w e v e r , do leach co pp eran d h a v e th e po ten t ial to con tr ibu t e to co pp er levels in t h e marinas. Berkel ey Marina reported t h at lim ite d replacem ent piles for wood an d all other wood t r eated at the m a rina are treated with C B A. A n tioc h M a rina rep o rte d that som e of its wood is treated w i t h C C A al t hou g h no ne o f

th e wo od is su b m er g e d

. C o pp er -G r e en ®, a copp er n aph th en ate co m p oun d, is r e por ted l y u s ed forth e tr eatm e n t o f the ends of pre ssure -treate d wood i n M onterey Harbor. T h e survey res p onse s u ggests , howe ve r, t h at there is lim ited use of w o ode n m a t e ri al s i n th e m a ri na area a n d th at th e tr ea t e d m a t e ri al s are not s u bm erged i n m a ri na w a t e rs. Last l y , Santa Barbar a Harbor re ported that wood en w a le r s , s tr i ng er s , and d e c k boa r d s a t the m arina are treated with ACZA. Agai n, t h ese ar e above -water uses, and c o ntinuous a n d dire ct leaching int o the wate r c o lum n is unlikely although co n t am in atio n asso ciated with rain ev en ts o r stru ctural washin g and rin s ing is still p o ssi b l e. Co n s i d eri n g the wo od preservativ e u s e in formatio n th at we re su b m itted by m a rin am a n a g e rs v i a t h e m a rin asurv ey, it is unlikely that coppe r-t reated wood ha d a si gni fi cant di rect i n fl uence o n t h e wat e r c o l u m n concent r at i ons o f c o ppe r o b s erv e d dur ing th e stud y. No te th at su rv ey r e spon ses al s o suggest t h at the rece nt tre n d in m arina const r uction appear s t o be i n i n c o rp orat i n g m o re co ncret e an d pres su re-t reat ed w o o d ( w i th o u t a dde d prese r vat i v es) on ne we r structures.

60B a ck gr

oun d L o a d

A sizab le po r ti o n of t

h e co pperlo ad i n th e mar in a ’ s w a ter co lu m n can b e attrib u t ed to th e local background l o ad of cop p e r
. F o r e x am pl e, at th e B a l l e na Isl e M ar i na area , th e m easure d m e di an DC u co nce n tr at i ons we re 2. 8 μ g/L i n t h e m a ri na an d 1. 4 μ g/L f o r th e L R Ss. Ass u m i ng th at t

h e c o pp er l o a d m easur ed at th e LR Ss ori g i n at ed f r o m non-m a ri na so ur ces and not th e m a r in aitself , th en l o cal b ackgr oun d sou r ces of cop p e rfro m San Fr an cisco Bay could h a v e cont ributed a s mu ch as 50% of the loa d ch aracterized at Ballen aIsle Mari n a
. An i n v e rse p e rsp ectiv e to th is is th at co pp er so urces with in Ballen a Isle Mari n acau s ed th e c opp er co n c en trations to b e t w ice as h igh as th e lo cal background level. Thus, if l o ading fr om all the m a rina sources s u dde nly ceases, the n t h e m a rina conce n trations of co pp er sh ou ld ap pro ach tho s e of th e LRS c o ncent r ations

. Since the ba ckgrou nd m e tal load of eac h m a rina ar ea is u n i q u e , it was n ecessary to tak e LRS sam p les at all th e m a rin a s. Th is ob serv ation also assu m e s th at th e cop p e r conce n trations measured at the LRSs ar e a good ap prox im a tio n o f th e l o cal water bo d y ’s b ackgroun d load

. Marina Se dim e nt
Th e m arin a’s un d e rlyin g sed i men t also represen ts a po ten t ial in term ed iary so urce d esp ite th e p opu lar view th at it sim p ly acts as a sink for heavy m etals. A si zab le por tio n of co pp er in t h e mar i n ased i m e n t cou l d h a v e or ig in ated fro m sources withi n the m arina as well as fro m sources ext e rnal t o th e m a ri na th at are dep o si t e d vi a ( 1 ) wet d e po si t i on (rai n runo ff an d flows g e nerated fro m rain ev en t s ), (2) d r y d e po sitio n, an d (3 ) d e p o sitio n v i a cu rren ts or wav e action

. Once de p o si t e d, s e di m e nt -bo u n d c o ppe r ca n be rei n tr o duc e d i n t o t h e wat e r c o l u m n vi a di ff usi o n or pa rt i c l e resus p e n si o n a n d su bse q uent des o r p t i o n
. I n fact , deso r p t i o n fr om resus p e nde d part i c l e s coul d be a si g n i fi cant so u r ce of

DC u t o th e wat e r c o l u m n as dem onstr at e d by Gee an d B r ul an d ( 2 0 0 2 ) f o r t h e s o uther n po rt i o n of S. F. B a y
. I n th e Gee and Bruland (2002) study, even with the accounti n g of regional poi nt-s ource discharges, a si gnificant portion of DCu i n t h e Sou th Bay was still attrib u t ab le t o DCu t h at was released fro m su sp en d e d b a y sed i m e n t

. Thu s , a si gni fi ca nt net m ovem e nt of c o p p e rf r o m th e sedi m e nt t o th e wat e r col u m n i s t h ere f o r e p o ssi bl e. Before gene ral l y transposi n g the fi ndi ng for South S.F. Bay to the m a rina envi ronm ent, it is neces sary to conside rthe diffe re nces bet w een the open bay enviro nm ent an d t h e t y pi cal m a ri na en v i ro nm ent

. So u t h S. F. B a y i s a l a rge wat e r b o d y with a sign ifican tly larg e sed i m e n t -water co lu m n surface area for d i ffu sion and p a rtitio n i ng in teractio n
. Mo reo v e r, th e S.F. Bay is shallo w an d relativ ely vu ln erab l e t o pert ur

bat i o ns fr om th e wi ndan d wat e r m ovem e nt

. Th e scale of se diment-water c o lum n interface in a m arina is much sm aller and the m a rina se dim e nt bed is, by de sign, mu ch m o re pr ot ect ed fr om pertu rbat i ons com p ared t o th e e x po sed sedi m e nt i n th e o p en bay

. F u r therm ore, th ere i s a pote n tially substantial source of copper i n the m arina (i.e., boat a n tifouling paints t h at are desi gne d t o l each c o ppe r d i rectly in to t h e water co l u mn ) to factor int o the s o urce ca lculation.
So , alth oug h the m a rin ased i men t m a y n o t app ear to b e t h e ch ief con tribu tor to th e cop p e r co n c en tration s in th e m a rin a wat e r c o l u m n , i t does n o t m e an th at c o ntri b u t i ons f r om th e s e di m e nt are ne cessari l y fi xe d or th at se di m e nt co n t ribu tio n s will rem a in s m all. Sin ce copp er con c en tra tio n s in th e water co lu m n and sed i m e n t are con tin u a lly seek ing a state o f equ ilib ri u m , sed i m e n t d e sorp tion cou l d b e co m e a m o re si g n i fican t p a thway fo r copp er release in t o th e water co lum n if co pp er co n c en tration s in th e m a rin a se di m e nt are hi g h e n o u g h an d/ or i f l o a d i n g fr om t h e ot he r marin ainp u t s to th e water co lu m n sh arp l y declin ed

. Th is p o t en tial sh ift i n co n t ribu tio n s was sp eci fically n o t ed as a peer re view c o mment in the SI YB TM DL (S DRWQCB, 2 0 0 5 )

. Note t h at the background loa d of copper i n t h e LRS s h ould, to som e extent, account for c o pp e rthat is re leased through th e se di m e nt di ff usi o n a n d re s u sp ensi on p r oc ess, at l east f

o r

th e l a r g er wat e r bo dy i n w h i c h th e m a ri na r e si des. I n t h i s way , th e m a gni tude o f se di m e nt co ntri but i o n s m a y be part i a l l y account e d f o r

by t h e LR S resul t s
. Antifo u ling Paints

AFPs th at are ap p lied to bo at h u lls are o n e of th e m o st co mm o n l y id en tified m a j o r source s for copper i n the m a rina en v i r on m en t ( J o n e s an d Bo lam , 2 0 07 ; Sr in i v asan an d Sw ain , 2 007 ; Pap 20 04 ; H a ll and A nd e r s on , 1999 ; Matth iessen et al., 1999; Ha ll et al., 1998; Katz, 1 998 , Goh an d Chou , 199 7 ; McPh er so n and Peter s , 199 5 ; Claisse and A lzieu , 1 993 ; You n g et al., 197 9)

. There are o v e r 17 0 c o ppe r AF P p r o d u ct s (i nc l udi n g a fe w m a nu factu r i n g u s e p r o d u ct s) c u rre nt l y regi st er ed wi th DPR in 200 7. Ho wev e r, r e po r ting o f A F P a p p licatio n s (with th e ex cep tion of TBT sin ce it is a restricted u s e p e sticid e) is

61not re qui re d by DPR

. T h e ref o re, i t i s di ffi c u l t t o de vel o p a go o d un de rst a n d i n g of t h e use pat t e r n a n d us e am ount f

o r cop p e ror a n y othe r t y pes o f no n
- TB T AFP s
. R e searche r s ha ve at t e m p t e d t o est i m at e copper l o a d i n g f r o m AFP so urces
. In 1 9 7 9 , SC C W R P est i m ated t h at a s mu ch as 180 m e tric t o n s of cop p e r were app lied an nu ally to b o at hu lls in Sou ther n Calif o r n i a ( Y o ung et al., 1 979 ). Fu rt h erm o r e, it esti m ated th at th is lo ad represen ted at least t w ice th e am o u n t th at en ters th e Sou th e rn Califo r n i a co astal waters fro m sto r m run o ff and aerial d e po sitio n. At th at time, TBT AFPs were still co mm o n l y u s ed

. Th u s , t h is particula r c o pper AFP use estimate undoubte d ly re prese n ts a sm aller fracti o n tha n what is be ing use d i n recent year s. W i t h th e ad d itio n a l restrictions pu t o n TBT AFPs in t h e U. S. a n d abroad, coppe r AFPs ha ve becom e th e m o st po pul ar A F P fo r r e cr eatio n a l bo ats ( Y o ung et al., 197 9 ; Claisse and A lzieu , 199 3)

. To d a y, m o r e th an 95 % of A F Ps r e g ister ed fo r sal e a n d us e i n C a l i f o r ni a cont ai n co p p er bi oci d es.
In rece nt y ears, U. S. E P A ha s gene rat e da m o re c ont em porar y est i m a t e of c o p p e rl o a d i n g f r om AFP use i n th e L o we r New p ort B a y ( L NB ) area, w h i c h ha r b o rs a p pr o x i m at el y 10, 000 boats. T h e Agency e s timated that boa t AFPs co n t r ibu te m o r e th an 62 ,00 0 lb s. of co pp er (v ia p a ssi v e leach ing an d und erwater hu ll clean ing ) in to LNB waters an nu ally (U .S. EPA , 2002 )

. U

. S. EPA b e liev e d th at th is lo ad co u l d accoun t fo r as mu ch as 80 % of all co pp erinpu t in to LNB.
Tw o c o p p er s o urce l o a d i n g st udi es f o r

Sa n Di eg o B a y wer e co nd uct e d by th e U.S

. Navy an d by p r i v at e resear che r s i n th e l a t e 1 9 90s ( J oh ns o n et al ., 19 9 8 ; PR C , 1 9 9 7 )

. B o t h of th ese stu d i e s c o n c l ude d th at AF Ps acc ou nt ed f o r

th e maj o rity of DC u lo ad ing t o t h e Bay. Fo r SIYB, SDRW QCB esti m a ted t h at p a ssiv e leach ing an d und erwater hu ll clean in g of boat h u lls p a in ted with cop p e r AFPs co m b in e to co n t r i bu te 98% to t h e b a sin’s copp erl o ad (SD RW Q CB, 2 005 ).
Field obse rvati ons a n d anec dotal evidence sh ow t h at AFPs ar e r e gu lar l y used on b o a ts t h at o p e rate in salt an d brack ish waters. T h e us e of c o pper AFPs is necessary to c o m b at co ntin u a l hu ll-fou l in g pressu res (p articu larly h a rd fou ling ) th at ex ist in th e salt and b r ack i sh aqu a tic env i ron m en t. Mo reo v e r, th e largest m a rin a s in Califo r n i a tend to b e lo cated in saltwater are a s. T h us, we e xpecte d to see the hi ghe st c opp er con c en tratio n s in saltwater m a ri nas. T h e ei ght hi g h est m a ri na m e di an DC u c once n tr at i ons ar e fr om sal t w at er m a ri nas. T h e m a ri nas wi th t h e l a r g est assem b l a g e s o f boat s ( i.e., Md R f r ont an d b a ck b a si n s ) exh ib ited th e g r eatest m a r in am e d ian D C u an d TCu concen tr ation s
. An d alth oug h t w o s a l t w at er m a ri nas–Sa n F r anci sc o a n d A l am it os B a y m a ri nas

– ex hi bi t e d very l o w DC u c once n tr at i o ns, t h e hy d r aul i c fl us h i ng re gi m e s at th ese si t e s m a y ser v e t o ex pl ai n th i s de vi at i o n. Since hard foul ing is not a m a jor iss u e i n fres hwate r , boats in fresh water areas do no t n e ed to rely as h e av ily o n copp er AFPs to pro t ect th eir h u lls. Th ere f o r e, f r esh w at er m a ri nas, part i c ul ar l y th o s e th at are i n l a ndl ocke d wat e r b odi es , t e n d to h a v e v e ry few b o ats with hu lls p ai n ted wi th AFPs. Also, m arin as in fresh w ater tend t o b e sm al ler (con tain less slip s for m oori n g) e specially whe n com p ared to t h eir saltwate r co un terp ar ts. M o r e ov er , bo at s in fres hwater marinas m ay n o t sp end as mu ch ti m e in th e water du e t o trailerin g p r acti ces and t h e relat i ve ease of dry stora g e. Consi d eri n g these pote n tial loadi n g fact ors , we expecte d t o see the lowest c opp er conce n trations in freshwat er m a rinas. T h e two lake m a ri nas i n o u r study –Tah oe K e y s an d F o l s o m Lake–ex h i b i t ed th e t w o l o west m e di an D C u c once n tr at i ons by far a m o n g all th e marin as.
In ou r stud y, wh en all th e m arin a DC u d ata were sep a rate d by wat e r t y pes an d c o m p ared, DC u c once n tr at i ons i n sal t an d brack i sh water m a rin a s were statistically h i gh er th an DC u c once n tr at i ons i n f r esh w at er m a ri nas. T h i s fi n d i n g i s con s i s t e nt wi th o u r o b se rvat i o ns of A FP use and wat e r t y pe s si nce AF P us e ap pears t o be m o re pre v al e n t am ong b o at s that are m o ore d in salt and brackish waters.
It is im portant to note, howe ver, t h at boats t h at are m oor e d in s o m e freshwater m a rinas may occasiona lly spend tim e in salt o r brack ish water du ri n g th eir u s e. So, in s o m e cases, AFPs are em ployed on th ese b o a ts. So m e of th e bo ats o b s erv ed at Sacram en to and Villag e West marin as h a d AFPs o n th eir hulls. Th e use o f AFPs th ere is lik ely a reflection o f t

h e p e riod ic op eratio n o f th ese bo ats in th e adj a cen t salin e wat e rs o f S.F. Bay and b e yon d. Th is m a y expl ai n w h y th ese t w o f r es hw at er m a ri nas ex hi bi t e d m ode ra t e m a ri na m e dian DC u co nce n tr at i o ns a n d why conce n tr at i o ns of DC u a n dT C u w e re al s o d i st i n ct l y hi ghe r i n si de o f th e s e t w o m a ri nas com p ared t o th e i r LR Ss.
Th ere are lik ely o th e r n o t eworth y so urces of cop p e r t h at exist with in t h e marin aenv i ronmen t. In t h e en d, u n til an ex h au s tiv e source id en tificatio n and cop p e r mass lo ad ing stu d y in th e m a rin aenv i ron m e n t can b e don e, it will b e d i fficu lt to p r ecisely allo cate lo ad ing fro m all th e v ariou s marin asources. Su ch a stud y may p e rh ap s i d en tify

62ad d ition a l so urces. In 200 7, MEC Env i ro nmen tal in itiate d a m o n itoring stu d y o f v arious m a rin a -asso ciated po llu tan t s (in c lud i ng m e t a ls) in a pro t ected water area p r i o r t o th e co nstru c tion an d op eration o f a m a rin a facility (R. Sch o ttle, p e r s on al co mmu n ication , 2007 ). Th e f ind ing s f r o m th is stu d y sho u l d p r ov id e a clear er pictu r e o n th e eff ects of bo atasso ciated po llu tan ts on ex istin g b a ckg r ou nd con d ition s
. At th is tim e, co n s i d eri n g (1 ) th e stud y resu lt s fo r DC u an d TCu , (2 ) t h e availab l e scien tific literatu re, (3 ) field o b s erv a tio ns an d an ecdo tal ev id en ce (in c lud ing respon ses fr om the m a rina s u rvey), (4) the consi d erati o n of othe r likely sources of copper i n the m a rina envi ronm ent, and (5 ) th e predo m in an t use o f cop p er AFPs com p ared to othe r typ e s of AFPs in Californ i a, it is lik ely th at bo at AFPs ar e t h e m o st signi ficant s o urce of coppe rin salt a n d brac kish wat e r m a ri nas, part i c ul ar l y d u r i n g peri o d s o f dry weathe r. Th e lev e l of AFP co n t ribu tion will v a ry from marin ato marin a du e to site-sp eci fic fact ors. Howev e r, it is lik ely th at co n t ribu tio n s of AFPs to t h e marin a ’s water co lu m n lo ad of co pp er is h igh est in (1 ) sa ltwater m arinas whe r e AFP use i s hi g h , ( 2 ) l a r g er m a ri nas w h ere th ere i s a hi g h num ber o f A F P

- pai n t e d vessel s , an d (3 ) l o cat i o ns w h e r e c ontri but i o n s fr om non
- A FP m a ri na so u r ces are rel a t i v el y l o w
. In p a rt i c ul ar, t h e c once n t r at i ons o f c o pp er i n th e LR Ss of m a ny of th e ma r i n aa r ea s s ugg e s t th a t th e b a ckg r ou nd lo ad of co ppe rmu s t a l w a ys b e con s id er e d w h en ma r i n aco n c en tr a tion s of coppe r are evaluated, as t h ese load s cou l d represen t a sizab le po rtion o f wh at is ob serv ed in th e m a rin a
.

Marin a Sourc e s of Z i nc Antifo u ling Paints

Zi nc i s a c o m m on m a ri na p o l l u t a nt f

o u n d at elevated conc entrations i n marina wat e rs an d se di m e nt s (S i n g h asem anon , 2004). Som e AFPs contain a n d leach zi nc
. The s o le zinc biocide, c o ntained in AFPs sol d a n d use in California, is zi nc py ri t h i o ne (Z nPt 2 or tra d e nam e Zinc Omadine®). This chem ical i s use d as a b o o st er bi oci d e , whi c h s u ppl em ent s th e ant i f o u l i n g effect s of a pr o duct ’ s pri m ary bi oci d e t o be e ffect i v e o n a w i der ran g e o f f oul i n g pest s. Th us, Zn Pt 2 usu a l l y m a kes up a l o we r per cent a ge o f a n AFP p r o d u ct t h an the prim ar y active ingr e d ient. T h ere are 25 AFP pr o duct s (i ncl u di n g se veral m a nu factu r i n g- u s e p r o d u ct s) t h at cont ai n Z n Pt2 curre n tly regi stered with DPR for use i n C a l i for ni a. Zin c o x i d e is also a no n-b i o c id al co m p on en t in AFPs; ho wev e r, th e water qu ality i m p lic atio n s o f th is relativ ely wateri n sol ubl e c o m pou n d have n o t been wel l st udi ed. T h ere f o r e, at th is ti m e , it i s d i fficu lt to esti m a te o rev aluate th e cont ribution of zinc oxi de from leachin g or unde rwater hul l cleaning activities to the ove rall m a rina water c o lum n or sedi m e nt zi nc l o ad

. Fut u re ev al uat i ons o f zi nc i n m a ri nas s h o u l d i n vol ve t h e det e rm i n at ion o f c o ntri b u t i ons o f zi nc oxi de fr om AFP use

. Wood Pr eserv a tives

One w o od p r es ervat i v e , AC Z A , c o nt ai ns zi n c
. Ho we ver , o n l y th e m a ri na at Sant a B a r b ar a Har b o r rep o r t e d AC Z A use on som e of its above

- water st ruct ures
. T h e r efore, t h e very l i m i t e d use o f zi nc- b ased w o od p r ese r vat i v e m a kes t h em an unl i k el y m a jor sou r ce o f zi nc t o th e m a ri na envi ro nm ent

. Sa crificia l A n o d e s
Zinc is als o us ed in saltwater areas as sacrifi c ial anodes t h a t are attache d t o boat hulls and othe r m e tal s u rfaces t h at com e into cont act with saltwa t er. Zi nc a n odes protect less -corrodible m etals (e.g., coppe r) from decay while sacrificing th em se lv es in the p r o cess resu ltin g in a con tinua l release o f zi n c ion s in to th e surro und ing water.
Alum inum -based a n odes are pre f erred f o r

a n o d i c pr ot ect i o n i n b r ac ki sh w a t e rs, a n d m a gnesi um -base d ano d es i n fres h w a t e r. I n ou r st udy , D Z n co ncent r at i o n s t e ndt o be hi gh in saltwater marin a s, p a r ticu l arly th e larg er m arin as al on g th e C e nt ral an d So uth C o ast

. B r acki s h a n d f r es hwat er m a ri nas t e n d t o ex hi bi t l o wer DZ n c o nc entr at i o ns. T h i s di ffe re nce i n D Z n c o ncentr at i ons am ong wat e r t y pes (sal t w at er > f r es h a n d brac ki sh wat e r) was st at i s t i cal l y si gni fi ca nt

. Th eref ore , th e m a gni tu de o f DZ n c once n tr at i o ns i n th e stu d y m a ri nas i s c o n s i s t e nt wi th t h e ge neral use p a tter n of zi n c an od es. Bird et al. (1 996 ) and Matth iessen et al. (1999) esta blishe d that s a crificial zinc a n odes are t h e major source on zinc in t h e m a rina e n vironm ent. M o re over, bo th stud ies fo und th at em issio n s fro m sacrificial an od es

63are s o great t h a t they appear to be a m a j o r influ e n ce o n zin c lev els in th e larg er water bo dy in wh ich m arin as are a p art of

. At th is tim e, co n s i d eri n g (1 ) th e stud y resu lt s fo r DZn , (2 ) th e av ailab l e scien tific literatu re, (3) field o b serv ation s and anecdotal e v idence (including responses fr om the m arina survey), (4 ) the consideration of othe r likely s o urces of zinc i n th e m a ri na e nvi ro nm ent , an d (5 ) th e l i m i t e d use of zi nc A FPs in California, it is lik ely th at sacri f icial anodes are t h e m o st significant source of zinc in saltwater m a rinas d u ri ng p e rio d s of d r y w eather. I n Cali fo rnia ’s saltwa t er m a rinas, th e co ntri but i o n of AF Ps t o th e m a ri na zi nc l o adi s l i k el y t o be sm all e r th a n th e co ntri but i o n f r om ubi qui t ous zi nc anodes

. For fresh a n d brac kish water m a ri nas, th e sign ifican ce o f zin c ano d e s to th e m a rin alo ad o f zinc is lik ely to b e sm a ller d u e t o b o a ters’ reliance on n on-zin c sacrificial ano d es. Reg a rd less of th e relativ e rank ing o f th e so urces of zi nc i n m a ri nas acr oss di f f ere n t wat e r t y pe s, the curre nt zi nc load from the com b ined a pplications and s o urces of zinc in th e m a rin aen v i ron m en t is n o t sign ifican t en oug h to re sult in a water colu m n co n c en tratio n th at ex ceed s water q u a lity stand a rd s.

T oxi ci t y / T o x i c an t Ide n ti fi c a ti on E val u a ti on
Tox i city tests were cond u cted to asse ss th e p o t en tial adv e rse im p acts o f t

h e water sam p les to p r e-select ed test or ga ni sm s and t oxi c e n d p o i n t s
. T o xi ci t y t e sts are c o m m on t ool s th at are us ed by age n ci es, i n cl u d i n g t hos e th at regu late water q u ality (i.e., RW QCBs), t o determin e if b i olo g i cal im p a irmen t s ex ist. Eig h t o f th e 47 water sam p les were tox i c to co pp er-sen s itive mu ssel e m b r yo d e v e lop m en t b i o a ssays. Sev e n of t h ese ei ght t o xi c sam p l e s were c o l l e ct ed f r om M d R

. T h e DC u c once n tr at i o ns i n th e s e se ven s a m p l e s ran g e d fr om 11. 5– 1 8

. 4 μ g/L

. T h ese c once n tr at i o ns ar e wi th i n t h e ra nge o f d o cum e nt ed EC 50 v al u es fro m si m i lar to x i city tests as co m p iled anddi sc usse d i n Ar nol d et al

. (2 0 0 5 b )

. Th us , th ese t o xi ci t y resu lts were wi th in th e exp ect ed co n c en tration rang e. Th e to x i city th at was ob serv ed i n th e sam p le th at cam e from MBYH, however, was m o re s u r p risin g
. T h e D C u co n c en tration i n th e MBYH sa m p le in qu esti o n was on ly 1

. 7 μ g /L; ho wever, statistically sig n i fican t tox i city (alb eit relativ ely lo w) was o b serv ed

. It is p o ssib l e t h at a false po si tiv e ortyp e I erro r o c cu rr ed in th e an alysis o f th is sam p le.
Two of t h e toxic sam p les from MdR were s elected for TIE test s. Th e test s d eterm in ed t h at a trace m et al (m o s t lik ely co pp er) was the lik ely cau se o f tox i city in th ese sam p les. Co n s i d eri n g the TIE resu lts an d th e h i gh DC u co n c en tration s o f th e all th e sam p les tak e n at Md R, p e rsistent to x i city to M. ga llo pro v i n cialis m ay ex ist in th e waters of MdR. T h e regulare x ceeda n ces of the CT R acute c o ppe r st andard at t h is location als o strongly s u gge st that there may b e a sign ifican t risk to aqu a tic org a n i sms at Md R. If bi ological and ec ological im pac t s from copper are to be studi e d , M d R wo ul d be an ex cel l e nt can di da t e l o cat i o n bas e d on th e fre q u e nt occ u rre nce s an d hi g h m a gni t ude o f DC u and TC u co nce n tr at i o ns ob ser v ed t h e r e. DC u c once n tr ations docum ented at MdR ar e e v en higher tha n the conce n trat i o ns doc um ent e d at SIYB i n San D i ego B a y (S DRWQC B , 2 0 0 5 ). Although toxicity sam p les were also collecte d from Pittsburg, Be nicia, Vallejo, L o ch L o m ond, Berkele y , San Fra n cisco, South Beach Harbor , Downt o wn Shoreline , a n d Alamitos Bay ma rinas, none of the sam p les taken from th ese lo cation s exh i b ited an y statistical ly sig n i fican t t o x i city. Th e fi v e h i gh est DCu con c en tration s o u t si d e o f th e M B YH a n d M d R sam p l e s we re 8. 9, 7. 7, 7

. 4 , 5. 3, an d 5. 3 μ g/L. Th us , DC u c once n tr at i o ns as hi gh as 8. 9 μ g/L di d not in du ce a resp on se i n th e copper sen s itiv e toxicity test. A lth o ugh th e w a ter ch em istry o f each sam p le, p articu l arly tho s e facto r s th at regu late th e b i o a vailab ility o f cop p e r, mu st b e ta k e n in to con s i d eration (e.g ., DOC, pH), it is rem a rk ab le t o see th at DCu co n c en tration s th at are clo s e to two ti m e s h igh er th an th e C T R saltwater acu t e stand a rd were no t tox i c in th e copp er-sensitiv e M. gal l o pro v i n ci al i s test. Th is ob servatio n co nfirm s th e pro t ectiv e n a ture an d in ten t of t h e CTR stan d ards th at were orig in ally d e riv e d fro m U.S. EPA’s aqu atic life criteria d ev el o p m en t pro cess. In th is st u d y , we sp ecifically con s id ered th e to x i city of co pper to a mu ssel species. Howe ver, rece nt st udies s u ggest th at lo w p a rts-p e r-b illio n co ncen tration s o f d isso l v ed copper can n e g a tiv ely i m p act o lfacto r y sen s o r y n e u r on s an d pre d at o ra voi d a nce beha vi ors o f sal m oni ds t h at are cri t i cal for thei r s u rvival (McIntyre et al., 2007; Pyle and Mirza, 2 007 ; McPh er so n et al., 20 04). Th er efo r e, el evat ed c o pp er conce n tr at i o ns obs er ved i n m a ny m a ri nas i n t h i s stu d y , even at levels t h at m ay not affect mu ssel spe cies, could po t e n tially b e h a zardou s to salmo n i d s
. Fu t u re co nsid eration o f

th e aqu a tic im p acts o f coppermu st cer tainly ev alu a te th is asp ect o f tox i city.

64Predictive Copper T oxicity Models
Sin ce it is im p r actical an d expen s iv e to con d u c t tox i city tests on all th e st ud y sam p les, pred ictiv e tox i city m o d e ls of

fere d a n al t e r n at e way t o ge nerat e i n f o rm ati on o n pot e n t i a l b i o l og ical imp acts. Th e pred ictiv e tox i city m o d e ls (i.e., the fres hwater Biotic Ligand Model [B LM], saltwater BL M, and Dissol v ed Or ga ni c C a r b o n [D OC ] m odel ) em pl oy ed in th is st u d y focu sed o n th e po ten tial effects of co pp er on a quat i c t e st or ga ni sm s. These m odel s are n o t abl e i n t h at th ey all tak e into accoun t site-sp ecific water q u ality ch aracteristics th at affect th e b i o a v a ilab ility o f co pper to affect aquat i c or ga ni s m s. The fres h wat e r B L M has al re ady bee n a d opt ed by U .S. EP A as t h e recom m ended approa ch to calculate the national a m b i en t water q u a lity criteria for co pp er (U.S. EPA, 200 7). U.S. EPA is co n s i d eri n g th e ap p licab ility o f th e saltwater B L M as th e ba si s fo r a n u pdat e t o i t s sal t w at er cri t e ri a. C a l i for n i a ’s C T R st andard s were base d o n a n ol der ve rsi o n of th e fed eral criteria. Ulti m atel y , U.S. EPA con s id ers t h e cu rren t BLM

- b a sed ap pro ach to b e m o re scien t i f ically so un d th an t h e p r ev iou s app r o ach, wh ich d id no t adeq u a tely in te g r ate th e im p acts of b i o a v a ilab ility. Mo reo v e r, th e rev i sed criteria should replace t h e nee d for resource i n tensi v e site-s pecific a d ju stments for fres hwater usi n g the water e ffect ratio

. For our st udy, the fres hwater BLM pre d icted that se ven of 53 fres h water sa m p les woul d e x ceed the 1-T U thres hol d. A cl oser e v al u a t i o n o f t

h ese res u l t s str o n g l y su gge st ed t h at o n l y t w o of th ese seve n t oxi ci t y pre d i c t i ons we re rel i abl e (see the Freshwater BLM Results S ectio n). In com p ariso n , DC u con cen t r atio ns fro m all 5 3 sam p les ev alu a ted b y th e m odel neve r e x ceede d t h e C TR fre shwater CCC (chronic) an d CMC (ac u te) standards. Thus, t h e freshwater BLM p r ed icted t h at so m e risk (al b eit lo w) to aqu a tic life ex is ts due to th e expo sure to copp er, wh ile ex isting st an d ard s sug g est e d th at aquat i c or ga ni s m s are ful l y pr ot ect ed.
We al s o used a D O C

- base d m odel , as pre s en t e d i n A r n o l d e t al . ( 2 0 0 5 ) t o e v al uat e t h e pot ent i a l t oxi ci t y of sal t an d brac ki sh wat e r sam p l e s. Out of th e 4 1 2 sal t and b r ac ki sh w a t e r sam p l e s eval uat e d , 86 ( 2 1%) co nt ai ne d hi g h e n o u g h conce n trations of DC u to equa l or excee d t h e DOC -m odel predicted FCC a n d 54 of those also e x ceede d t h e FAC. Measure d DCu concent r ations tend to e x cee d CTR standards m o re frequ ently th an DOC-m o d e l p r ed icted tox i city thres hol ds. Oc casionally, the opposite is true

. T h is is m o st noticeable at San Fra n cisc o Marina, Santa Cruz Harbor, Monterey Harbor, a n d Sa nta Barbar a Harb or. Th is ph en omen o n is m o st lik ely a reflectio n of t h e relati v e ly lo w DOC co n c en tration s th at o c cu r at these lo cation s du ri n g ou r sam p lin g ev en ts. Ov erall, t h e DOC m o d e l p r ed i c ted water co lu m n to x i city well (8 9 % success rate) wh en co m p ared t o actu a l tox i city test resu lts from th is stu d y
. A d r aft saltwat er BLM was recen tly co m p let ed for u s e on salt an d brack ish water sam p les. At th is tim e, th e m o d el was onl y a b l e t o gene rat e pre d i c t e d EC 50 t h r e sh ol ds f o r M. g a llop r o v in ci alis and S. p u r pu ra t u s
. I t w a s no t po ssi b le to g e n e rate CCC an d CMC th resh o l d s with wh ich a m o re co mp lete ev al u a tion o f risk to aquatic o r g a n i sm s co u l d b e m a de. Ho we v e r, t h e c o m p ari s on o f pr edi c t e d ac ut e T U s fo r M. ga llop r o v in cia lis to actu a l to x i city resu lts still allo wed u s t o fact o r in t h e site-sp ecific b i o a v a ilab ility of co pp er to determin e if sam p les co u l d b e to x i c t o a copp er-sen sitiv e t e st or gani sm anden d poi nt

. S i xt y seve n of 3 7 3 sam p l e s (f o rw h i c h out put coul d be cal c u l a t e d) or 1 8 % o f th e sam p l e s containe d a high e n ough conc entration of DCu to reac h or exceed the 1-T U thre s hol d. R ecall that since the ac ute C M C th res hol ds c o ul d n o t be cal cul a t e d, a c o m p ari s on o f s a l t w at er B L M resul t s t o C T R st andard s i s no t po ssi bl e. Ov erall, th e sal t water BLM p r ed icted EC 50 ’ s fo r M. g a llop r o v in cia lis were in g ood ag reemen t with act ual to x icity (88% s u cces s rate). A c o m p arison was not done for S

. pu rp urat us si n ce t o x i city tests were no t cond u cted o n th em
. Th e fact th at ab ou t 9 8 % o f al l th e sam p les fo r wh ich tox i city was p r ed icted were m a rin asam p les stro ngly su gg ests t h at th e ex isting l o ad o f copp er (rep r esen ting the co m b in ed sou r ces with i n a m a rin a ) in m a n y o f th e st u d y ’s marin a s is h i gh en oug h to po se a risk to copp er-sen sitiv e aq uatic o r g a n ism s. Risk s fo r th e LRSs, wh ich were immed i atel y ad j acen t t o th e m a rin a s, app ear to b e mu ch lower. Thu s , th e st u d y o f co pp er tox i city an d im p acts o f co pp er to aqu a tic co mmu n ities i n m a rin a s sh ould b e an im p o r tan t area fo r fu t u re research.
Scien tific v alidatio n o f th ese m o d els with d a ta fro m o t h er st udi es has , th us far, bee n stro n g
. O v e r al l , ag r e em ent of m o d e l p r ed ictio n to ou r tox icity resu lts is also v e ry go od

. O urco m p ar ison o f th e DOC m odel’s and the saltwater BLM’s pred icted tox i city to actu al to x i city resu lts d i d show th at t h ese m o d e ls tend to sli ght l y o v er -p re di ct t oxi ci t y
. Ho we ver , c ons i d eri n g t h at th e use o f th e s e m odel s p r o v i d e a n in exp e nsiv e way to esti m a t e to x i city and a m o re p r ecise p r ed ictio n of bio l o g i cal effect s b y accou n ting for b i o a v a ilab ility , th ese mo d e ls app ear to b e reliab l e tools in th e fu ture ev alu a tion o f th e p o t en tial eco log i cal im pac t s from copper expos u re
.

65

### V. Conclusions
The e x t e nsi v e m oni t o ri ng o f m a ri na areas s h o w e d th at C a l i for n i am a ri nas ha ve el ev at ed conce n tr at i o ns of DC u, TC u, and DZn. Higher water col u m n concent r a tio n s of t h ese m etals ten d t o o c cu r in larg er saltwater m a rin a s su ch as tho s e al on g th e St at e ’ s C e ntral an d So uth C o ast

. Lo wer c o ncent r at i ons we re fo un d i n m a ri nas t h at are locate d in fres hwater l a kes or i n ar ea s th at are wel l

- fl us hed

. Despite being freque ntly elevated com p ar ed t o b ackgr oun d lev e ls, D Cu and D Z n con cen tratio n s i n fr eshw aterm a r in a s were always below CTR fres hwate rstandards for c o ppe r a n d zinc. Saltwater DZ n c o nc entrations were also al ways bel o w C T Rsal t wat e r zi nc st a ndar d s. H o we ver , i n m a ny sal t and b r acki s h wat e r m a ri nas, DC u co nce n tr a t i ons regu larly exceed CTR water qu ality stan d ards th at h a v e b e en estab lish e d fo r th e p r o t ection o f aqu a tic life. Tox i city tests showe d t h at m a rina wate r sam p les were som e tim e s disrup tiv e t o th e no rm al d e v e lopmen t o f mu ssel em b r yo s. An eval uat i o n of t w o o f t

h e t o xi c sam p l e s poi nt ed t o hi gh co nc entr at i o ns of D C u as t h e m o st l i k el y cause o f th e ob ser v ed toxicity. Predi ctive toxicity m odels, which accounted for bioa vailability, determ in ed that m any of the marina sam p les co llected were lik ely to b e toxic to copp er-sen sitiv e aq u a tic o r g a n i sm s. Ou r s o urce eva l uat i on a n d t h e co nsi d e r at i o n of past resear c h on m e t a l sou r ces i n m a ri nas su gg est th at fo r sal t an d brac ki sh wat e r m a ri nas, AFP s are l i k el y a m a jo r s o urce o f c o p p e r , part i c ul arl y d u ri n g pe r i ods o f dry we ather. T h e co n t ribu tio n of AFPs to th e total m a rin acopp er lo ad , ho wev e r, will v a ry fro m m a rin ato marin ad e p e n d in g on th e m a gni t ude of e ach wat e r b ody ’s back g r o u n dl o ad a n d othe r m a ri na so u r ces
. In b r acki s h wat e r m a ri nas and m a ny San Fra n cisco Bay Area m a rinas whe r e t h e background l o ad of cop p e rt e n d s t o be hi g h , A FP use c o ntri b u t e s l e ss t o t h e m a ri na co p p er l o ad t h an i n C e ntral a n d S out h C o ast m a ri nas w h ere th e bac k g r ou n d l o a d t e nd s t o be l o w. N o neth el ess, coppe rthat is generate d from leaching of AFPs and underwater hull cleani n g of t h ese paints clearly c ont ribute to t h e exceeda n ce of coppe rwater quality standards.
Consi d eri n g that water i n 16 of the m arinas in our study e x ceeded wate r quality standards fo r copper, it is possible t h at these area s will be placed on t h e C W A 303(d ) im paired wat e r bodies list. More ove r, rece nt studies of coppe r i n Lowe r New p ort B a y a n d al o n g C a l i f or ni a’s S out h C o ast ( D a n a P o i n t t o th e U. S. /M exi c o bo rde r) ha ve s h ow n t h at m a ny of th e marinas in t h es e areas als o e x ceeded the same standards. T h ere f ore, it is possible t h at m o re tha n 40 California m a rinas coul d be place d on the C W A 303(d) list due to elevate d DC u c once n trations. Placem ent on this list coul d e v ent u ally resu lt in TMDL d e v elop m en t.
I n r ecen t year s, th er e h a s b e en an i n cr ease in th e r e g istr a tion of AFP pr oducts w ith Zn Pt2 as the prim ary active in gred ien t

. If Zn Pt 2 pr o duct s gai n a l a r g e rf oot hol d on th e AFP m a rket (e. g ., as a re pl ace m e nt fo r c o p p e rA FPs ), co n t ribu tio n s of zin c AFPs t o th e m a rin azinc lo ad will in cr ease and po tentiall y lead to zi n c-related t o x i city. Fu ture eval uat i o ns o f ecol o gi cal ri s k s d u e t o zi nc A FP use s h oul d not rel y sol e l y on th e c o m p ari s on o f wat e r c o l u m n o r sedi m e nt conc entr at i o ns of zi nc t o st an dar d s an d gui del i n es , b u t al s o on th e spat i a l an d t e m poral di stri b u t i on of th e bi oci d e Z n Pt 2 and its trans-c h elation product CuPt 2 . CuPt 2 is m o re stab le an d m o re tox i c to aq u atic o r gan i sm s th an ZnPt 2 . Conv ersio n of Zn Pt 2 to C u Pt 2 tend s t o o ccur i n n a tural water wh ere cop p e r con c en tration s are h i g h lik e in so m e mar i n a s
. At th is tim e, U.S. EPA co n tinu es t o re fine its risk cha r acteri zations for a n tim icrobial uses of copper oxide and Z n Pt 2 . On ce th is ch aracterizatio n is co m p lete, th e Ag en cy will ev alu a te its risk man a g e m e n t op tio ns an d anno un ce its risk m a nagem e nt d eci si ons. U.S

. EPA i s al so de vel o pi n g di sch a rge pe rm i t s for rec r eat i o nal a n d com m erci al vessel s
. Disch a rg es from AFP u s e are curren tly in clud ed in t h ese p e rm i t s. Ov erall, th ese fed e ral activ ities m ay p o t en tially have a si gni fi c a nt i m pact on ho w St at es, i n c l udi n g C a l i f or n i a, re gul at e a n d use co p p er a n d zi nc A FPs i n th e fut u re.

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