toxicity of tributyltins i/i antibiofouling … 224 acute toxicity of tributyltins and tributyltin...

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RO-0184 224 ACUTE TOXICITY OF TRIBUTYLTINS AND TRIBUTYLTIN i/I LEACHATES FROM MARINE ANTIBIOFOULING PAINTS(U) CALIFORNIA UNIV OAKLAND NAVAL BIOSCIENCES LAB UNCLASSIFIED R 8 LAUGHLIN ET AL 18 SEP 82 UC-NAL-875 F/G 6/11 NL EhlU Wli immI liw!llil UlEI!

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RO-0184 224 ACUTE TOXICITY OF TRIBUTYLTINS AND TRIBUTYLTIN i/ILEACHATES FROM MARINE ANTIBIOFOULING PAINTS(U)CALIFORNIA UNIV OAKLAND NAVAL BIOSCIENCES LAB

UNCLASSIFIED R 8 LAUGHLIN ET AL 18 SEP 82 UC-NAL-875 F/G 6/11 NL

EhlU Wli immIliw!llil UlEI!

ilL

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MICROCOPY RESOLUTION TEST CHARTNATIONAL BUREAU OF SIANDARP 1963 A

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224 ,DOCUMENTATION PAGE

~AD-A 18422 ouE , AGla. REPO 1 lb RESTRICTIVE MARKINGSu,- ..... -

NONE2a. SECURITY CLASSIFICATION AUIT . 3 DISTRIBUTION /AVAILABILITY OF REPORT

N/A Approved for public release;2b. OECJS,'FATON, I OWNGRA C EU -iE /A distribution unlimited

4. PERFORMING ORGANIZATION RE ,UMB0(S) 5. MONITORING ORGANIZATION REPORT NUMBER(S)

NBL No. 875

6a. NAME OF PERFORMING ORGANIZATION 6b. OFFICE SYMBOL 7a NAME OF MONITORING ORGANIZATION(If applicable)

University of California Otfice of Naval Research

6c, ADORE S(Cit , S ate, ano ZIPCode) 71. ADDRES City State, and ZIP Code)Cit, osc nces Laboratory Code 1141

Naval Supply Center 800 North Quincy AveOakland, California 94625 Arlington, VA 22217-5000

8a. NAME OF FUNDING/SPONSORING 8b OFFICE SYMBOL 9 PROCUREMENT INSTRUMENT IDENTIFICATION NUMBERORGANIZATION (If applicable)

Office of Naval Research N00014-81-C-0570Bc. ADDRE tS1 5ta.t,, ad ZIP CodV 10 SOURCE OF FUNDING NUMBERS

uuuiiortn .uincy Avenue PROGRAM I PROJECT ITASK IWORK UNIT

ELEMENT NO NO. No. ACCESSION NOArlington,Va 22217-5000 61153N RR041-05 R041-05-03 NR204-123

11 TITLE (Include Security Classification)(U) ACUTE TOXICITY OF TRIBUTYLTINS AND TRIBUTYLTIN LEACHATES FROM MARINE ANTIBIOFOULING

PAINTS12, PERSO A UHR

Laugin, Koy"., Linden, Olof and Guard, Harold E.

13 . TYPE OF RIEPORT, 13b. TIMEgcfiy6D 114 DATE CFgff.fORT (Year, Month, Day) 15. PA COUNT.un:narIy repurt I FROM MTO

8

16 SUPPLEMENTARY NOTATION

Bulletin De Liaison Du COIPM No. 13, 1982

17, COSATI CODES 8. SUBJECT TEtMS (Co on reverse if necess acd ftentify by block number)FIELD GROUP SUB-GROUP ywr

06 06

19 ABSTRACT (Continue on reverse if necessary and identify by block number)

Tributyitin compounds were shown to be slow-acting t~xins causing acute toxicity or twoamphipou species at concentrations as low as 10 g/L . Orchestia traskiana was exposed tobis (tributyltin) oxide (TBTO) or tributyltin flouride (TBTF) as sin le compounds. BothCompounds were acutely toxic in 10 days at concentrations of 10 g/L and above. bamnlarusoceanicus were exposed to tributyltin leachates from panel painted with two differentantifoullny paint formulations. Following 48 hr immersion, aqueous tributyltinconcentrations increased with increasing painted surface area, but one type of paintleached tributjltins about ten times faster than the other. Amphipod mortality in short-term tests was directly correlated with increases in painted surface area and leachingrates. Gammarus oceanicus was more sensitive than 0rchestia traskiana based on measuredtrinutyltins concentrations, with final leachate concentrations of 4.8 g/L- causing totalmortality in 5 days. The results of these experiments show that tributyltins compounds arevery toxic to som1e non-targeL organisms.

20 DISTRIBUTION / AVAILABILITY OF ABSTRACT 21 ABSTRACT SECURITY CLASSIFICATION[n(NCLASSIFIEDUNLIMITED [ SAME AS RPT El DTIC USERS UNCLASSIFIED

-~Di v, 2 2l 1"d Area Code) Rdd It

DO FORM 1473, 84 MAR 83 APR edition may be used until exhausted. SECURITY CLASSIFICATION OF THIS PAGEAll other editions are obsolete

%~

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BULLErIN DE LIAISON

DU

COI PM

N0 13 -1982

Table des mati~res /Table of contents

-Acute toxicity of tributyltins and tributyltin leachates

from marine antibiofouling paints,

by Roy B. Laughlin, Jr., Olof Lind~n, and H.E. Guard.

-Toxicit6 aigUe des tributy1dtains et des lixiviats de

tributyldtain provenant des pemntures antisalissures,

par Roy B. Laughlin, Jr., Olaf Lind6n, and H.E. Guard.

-Liste des publications diffusdes par ODEMA -

Acce- i"- In-List of publ icat ions distributed by ODE!IA NTIS C P ; XI

D-hfl Ti,' H

I P

87 8 28 2,72

Ixld 02 "p'11t

ACUTE TOXICITY OF TRIDUTYLTINS AND TRIBUTYLTIN LEACHATES

FRC MARINE ANTIBIOFOULING PAINTS.

by

Roy B. Laughlin, Jr. (1,2), Olof Lind6n (2), and H.E. Guard (1).

(1) University of California

Naval Biosciences Laboratory

Naval Supply Center

Oakland, California 94625 U.S.A.

(2) Institutet fbr Vtten och Luftvgrdsforskning (IVL)

Baltic Sea Laboratory

Utovagen 5

S 371 37

KarlsKrona, Swelen.

.,crte-Lr IQ , I

!%

V.

'

Triutitin Oj'cund3 were shown to be slow-acting toxins causing acute-1

to'scity to two ar;hipcr pecies at concentrations as low as 10 pg/L

r :t Jia trvJ!a3 was exposed to bis (tributyltin) oxide (TOTO) or tributyltin

Jiuor e ]T TF) as sing e compounds. Eoth compouncs were acutely toxic in I0-1

cos at concentraticns of lJ pg/L and above.

G2~a3~JO ooeacus .ere exposed to tributyltin leacnates from panels painted

with two diferent antifouling paint formulations. Following 48 hr immersion.

a~euS trioutltin concentrations increased with increasing painted surface

area. out one type of pairt leacheC trioutyltin about 10 times faster than the

ct'er. Arp'_ poj rrtality in snort-term tests was dirnctly correlated with

inireases in p3inteo surTace area and leaching rates.

T---arLJS 3Cet. was -ore sensitive than Orchestia tra'iKiana based on

measured tricu:Litin _onze-trations, with final leachate concentrations of

4. .-

a~&i- t mortality in S days. dThe results of these experimentsV.

hshM.. that tr. ., rc-cnis are very toxic to some non-target organisms.

Thi ta ! i-: - -- - - - dt_!hiooulin paint for-ulations depends upon

an anLz:t, 0':r lei tet n eulh rates, which arc ef'ctLve at the

'S

!./'i

t 3 _ , . t - :- ,

% %1

-6-

Resum6.

On d6montre que les compos~ii de tributyl~tain sont

des toxiques h~ action lente qui provuquent une toxicit6 aigne

chez deux esp?~ces d'amphipodes des concentrations aussi faibiles

que 10 pg/l. Orchestia traskiana a 6t6 exposoie h la fats a

I'oxy'de de tributyl~tain ou au fluorure de tributy1~tain en tant

que compos~~s simples, Les deUX compos~s 6taient extre'mement

toxiques en lespace de 10 jours bi des concentrations de 10 3jq/l

et 6 des concentrations sup~rieures.

Gammarus oceanicus a OtO expuf.6 h des lixiviats de tributyl~tain

provetnant. d'6prouvetteti peinteu avec deux formulations difftsrentes

de pevintUre antitoalis-,ure. Aprths 48 heures d'immersion, les

concentrations de tributyl~itain aqLeux ont auqment6 atvec un niveau

de surface peinte ac'cru. Totitefois, un type de peinture a ivd

lP trittttylr~tain 10 fois plusg vite que lautre. La mortalitL4

de'; amphipodes, lor de-; P,;sais h court terme, e6tait directement

line aux accrois;sementi de suirfaue peinte et aux taux de lixivia-

t I our.

Uamrartil' Vt iO tait p~u !nusible que Orchest ia t ra!J iana

1i Ifn ,v ba!,e u ir IVCi conctrt ations. de t mi utyl (t a in rstourOts

en av Ant Je:; cur -t: r t tiw di, l~vi at finajles, de 4,19 )jj,'l

qu i V, i o~oqw t lit mu rt al it6 ' (up Ie-t v en c1 jO~ o 0 ,. I vs r (' u It at 0

(IV CC r, v Cl Cuvct. munt renit qut 1 t ; ctmputis de t r itt 1nt a in

s io t t i t .to A i it -; p nok te vi ta i rt; i r qj r i i v! I v! m oi n : v o at ts.

1 L i o . 1 1 0 1 Xo 1 F) t VII I Q Vt i t (IeV f 01 MtU I att i Oil! de V e I)A ittoretsarit "i daIopsr S ~~ ettd d 'tini o"i I~l l a, t'( pt abl I e 1 esI t au x de

I I I I t t oil I A ,ot(wt A. ftC I aue it 1 veau de I a -otit A fa v peit, t e

o ,t I v- e f t t.t , ;,jr 1 v otp' r qe; I ,me Imo ki w, vo an t h

Con ,idrrat cL ef'ort has been expended in atte-;to to prevent biofouling

on :nIvs. 'rnt42' . important ,ot onij to proCtecLt the ship itself frum

damage. but also to instre efficient and dependdaile op:eration. The must

widely use! p aint forrr,l ,tons are based on coppr, hich leaches out as an

ion, the active antintofou'.ing material. Copper has several drawbacKs,

incl-dirg nut not litdto ohcrt paint l ife, and' ttoo fate of copper asi an

environ''entsl po. :tat. The most w~e-r~;t:and used substitutes conrtain

tri:!rganctin compoun:!d5 a toe active agent (Evans,. Ot ycKman. Ct al.,

l53 3. iowr !,ei<,rc ;enerai use, tn~tir act ,on on no ,r-target organisms

vis-3-4is their e~ _-eeir 1" d:erent, paint t-r-Ulations. has to bie

In~~~~ ~~~~~ t' ;-~~.wiu-eteot: - tr'tv-tyitin CCmpuuds,

-a t: f:.t, r in fokotriP- li * and the

t ~ '5, -->. : erootflo - ::- c,- :-omfls and con, -nitrat ions

,.: . , tr-'ktFun-rtfr&-n t

CuCpU ~ j-I

CI%

-8-

MATERIALS AND METHODS.

Experiments were conducted in the U.S., using Orchestia traskiana, and

in Sweden, with Gammarus oceanicus. In the experiments performed with

0. traskiana, we were interested in assessing the effect of TBTO and TBTF

added to the bioassay as single compounds. Experiments conducted in Sweden

were performed with plexiglass panels painted with either of two commercially-

available paint formulations. Specifics for each of the experimental protocols

follows.

Adult amphipods. 0. traskiana, were collected intertidally in a San

Francisco Bay marsh and in the laboratory were maintained in 30 o/oo S water

at 1B06. These were similar to ambient salinity a-d midday temperatures at

the time of collection. The experimentals were acclimated for 3 days before

toxicant exposure began.

bioassay : Five arnphipods were put into a 10 cm fingerbowl containing

15C ml of 30 o/oo S seawater. TBTO and TBTF solutions were prepared in

acetone arid ad!de to the seawater with thorough ixing. Three replicates of

each of the following toxicant concentrations wer. examined : acetone control

(67 ilJ ml seawater), C., 1, 3. 6, 10 or 15 pL-/L- 1.

Daily, the exposure

)raDs wero cOerv7u J , tra'nferrd to freshly prepa:-ed test media and fed pieces

of the preen alga cia and Art,"ia naLplii.

(' "ru< ':"anr~ .: wre coli:ectcd in Tvrrei Bay, 80 Km S of Stockholm.

n te,- 'I'l:rar,, ,aIt e re ,cp-irated from Fucus and put into aquaria

'r 2- .,- :r: tr- :r , ini the hiodssdys. The amihipods were fed

let r,-i- r ri j f , "rc dli ir this pret. ,t period, but no food was

, n ti it, It in (---it in from ,i- nt lea3chates.

t t" ; , , , t , t c irtnr :ch C *2 all-plans ,', uaria. The

.. . . . . . . , 1 : it

only TBTF as the active agent.

Chemical Analysis.

Time dependent loss of single compouds : Flasks containing 500 ml of-1

seawater with 50 wg/L TBTO were either plugged with cotton, without aeration,

or were not plugged and were aerated lightly. The control consisted of

seawater to which only acetone was added. The flasks were sampled at 0 and

24 hrs, and chemical analysis performed within 45 hrs.

Determination of tributyltin in paint leachates were performed on

samples collected in Sweden and analyzed in the U.S. Five hundred mls were

withdrawn directly from the aquaria during the bioassays, into 500 ml cleaned

brown-glass bottles. Subsequently, they were shipped to the U.S. and analyzed

within 2 months of collection. We have no information on the probable loss of

tributyltin during the period between collection and analysis. However,

given the amount measured, it appears that any loss which occurred was not

large.

Chemical Analysis : The following procedure was used to determine

tributyltin concentrations in the Orchestia traskiana experiment. TBTO concen-

trations, as the tributyltin hydride, were determined by gas chromatography

using a Varian 2400 gas chromatograph with a 15 % OV-101 on a 100/120 Chroma-

sorb G/HP column at 1C0C. To a 200 ml seawater sample containing TBTO,

80 mg of sodium borohycride was added. The solution was allowed to stand for

20-30 min after which 10 Ll of an internal standard solution containing

dicyclohexyl (0.8E mg/ml) in acetone was adoed. The tribultyltin hydride and

dicyclohexyl were extracte with 20 ml hexane. The hexane was dried (MgSO4 )

and evaporated to ca 10 pl, toirg careful not to take the sample to dryness.

The analyses reported in this paoer deal with the behavior of TBTO. On the

basis of a few additional sarples of the same concentration of TBTF collected

and anal>Zed in the sa'e fashion, it apcears that it displays identical behavior

with res:ect to time-d cenrient loss from seawater used in this bioassay.

The analysis of tributgltin-cnntaining paint leaczjtes was similar to the above

orotocol, with the following nc:ifications : only 4D mg of bodium borohydride

wa, aided. followed by 5tirrini fr" ')l ''__ The-r Ch3ones were necessitated by

the presenu of an unidentified interfering co-,0;ound r conpcunds which appeared

11 the %tared a-r .n n rtnr w3 c3erveJ in rof'rtnce samples

ae. e ,,, i n , o

- 10 -

RESULTS.

Persistence of TBTO in seawater : In seawater, tributyltin concentrations

remain stable for at least one day. The mean of three samples taken just after-1

TBTO addition was 43.66 + 1.27 pg/L (mean - standard deviation). The concen-

tration of TBTO in unaerated and aerated flasks 24 hrs later was not signifi--1

cantly different, 45.72 + 6.02 and 45.05 + 1.46 pg/L , respectively. The

acetone control had undetectable TBTO background levels (less than 0.2 Pg/L-

Table 1). The differences between nominal and measured concentrations may be

accounted for by slight inaccuracies in sampling methodology and probably by

adsorption into container walls. The lack of additional loss caused by

aeration indicates that volatilizatior was an insignificant loss route. The

assumption that actual exposure levels were within 10 % of nominal ones is

supported by the constancy of concentration with time.

Concentration of butyltins in paint leachates : For both paints, the

amount of tributyltins measured in the water after 24 or 48 hrs increased with

an increase in painted surface area. The data shown in Table 2 indicate that

the different paint formulations leach significantly different quantities of

butyltin within the period tested. Although the final tributyltin concentra-

tion ratio of the two paints showed no consistent value as the area of the

painted surface increased, at least 3 times as much tributyltin leached from(R) (R)

Interracing than from Micron 25 . Leach rates from larger plates may

have been inhibited as tributyltin concentrations approached the solubility-1

limit assumed to be below 5 mg/L

Toxicity of T13TO or TFTF to Orchestia traskiana : Both TBTO and TBTF

showed similar toxicity, with acute toxicity occurring at concentrations of-1

10 Wg/L and above. In this experiment, 80 % of the control amphipods

survived 9 day exposure to acetone (Fig. la). Amphipods exposed to 0.5 pg/L-1

TETO showed a slightly higher survival (87 %). Those in TOTO concentrations-1

between 1 and 6 pg/L exhibited a decline in viability, which was not consis--1

tently dose-dependent when compared to controls. Even in 6 pg/L , survival

was: at the on of ' days. The two highest concentrations, 10 and 15-1

W ',/L ,o esoic-.tly toxic. This Lecame apparent only after the fifth

day in 1 _ 2'L ,.an: aiftfr the fourth day in 15 pg/L-

. Final survival-1

v31ue3 were 2 2 and 7 2 in 1 and 15 jg/L TUTO, respectively. Concomitant

witn tne tnr j in tte latter t r cr'nu:;c "1 a loss of orientation and

f t"':.'..11,, 1i! cr :wirnirp rnoverrcnts were ataxic and very

PD~rll . ... ""

/ r1

-11 -

Similar to the results of the TBTO bioassay, the date for amphipods

exposed to TOTF cluster into two groups (Fig. 1). The first, comprised of

exposure concentrations below 6 pg/L 1, is above 50 % survival and does not

display a dose-dependent pattern. Survival values of the 10 and 15 pg/L-1

exposures were, respectively, 13 % (at the end of 9 days) and 0 % (at the end

fo 8 days). These values indicate that there is no significant difference of

toxicity between TBTF and TBTO to these non-target organisms. The behavioral

derangements caused by TBTF exposure were similar to those described for TBTO.

Toxicity of paint leachates to Gammarus oceanicus : The toxicity of the

two paint formulations shows a close correlation to the amount of tributyltin

leached. No amphipods survived 5 days exposure to leachates from Interracing2

paint. Panels with a painted surface area of 1720 and 480 cm caused 100 %

Vmortality within 24 hrs. In tanks containing a painted surface of 48 and2

5 cm , 100 % mortality occured in 2 and 5 days, respectively. Reference to

Table 2 will show that estimated tributyltin concentrations ranged from

0.98 to .0048 mg/L- 1

under the test conditions.

CR)The concentration of leachate from the Micron 25 painted surfaces

was shown to be much less than for the Interracing(R )

paint, from 0.153 down

to below 0.0014 mg/L. The mortality of the amphipods exposed to the leachate

was also lower. During the first 24 hrs exposure, all the amphipods died in

the tanks with a painted surface area of 1720 cm2

but it required 48 hrs for2

complete mortality to occur in the tanks with 480 cm painted surface. In thetanks containing 48 cm

2 of painted surface, 15 % of exposed aphipods survived

6 days, while those exposed to 5 cm2

had a mean survival value of 65 %, whichwas just slightly lower than that for the controls, 75

V N

.1..

'i--

12 -

DISCUSSION.

The data presented in this paper show that tributyltin compounds either

as single compounds or as leachates from antibiofouling paints are toxic to

aquatic organisms. Concentrations of single tributyltin compounds as low as-1

10 wg/L caused differential mortality of Orchestia traskiana. Gammarus

oceanicus appeared to be a bit more sensitive, with differential mortality

occurring in tributyltin concentrations between I and 5 pg/L-

. The increased

sensitivity of G. oceanicus is more obvious when one remembers that final and

time-averaged trialkyltin concentrations were different, with the latter being

much lower, since the alkyltins were slowly appearing in the water phase during

the 2 days between water changes.

Concentrations reported here are lower than ones widely reported to be-1

toxic. In a review ZucKerman et al. (1978) reported that 50 pg/L was a

common estimate of the LC of tributyltin compounds for aquatic organisms.

However, other lower values have been reported. Ritchie et al. (1974) reported

that TOTO levels as low as 1-10 ng/L significantly reduced maturation rates

and egg production in snails, Biomohalaria glabrata, which had been exposed

from hatching to these low levels. Lind6n et al. (1979] reported a LC50-1

(96 hrs) of 3 Wg/L for the copepod Nitocra soinioes exposed to TBTO.

Survival and growth of larval lobsters, Homarus americanus, were significantly-1

reduced in 1 jg/L TBTO. Exposure continued for ca. 21 days, the duration of

larval development (Laughlin and French, 19b0). Thus, it appears that the

sensitivity of these two amphipod species resembles that recently measured for

several other aquatic invertebrate species. It is probable that the actual

sensitivity of most marine species to chronic exposure is considerably lower-1

than the 50 ig/L generalization cited above.

The reason for the previous underestimation of toxicity occurs because

these materials are slow-acting. The toxicity of TBTO and TETF became apparent

only aft r the first 5 days of expomure durinp the tests with [rohuntia

trs3ian3. The o1ow action of thes e co-pounds has been acpreciated by indus-

trial hyrionizto (Err.25 and ? tnlnr, I ,):]ut the Kr olcdFe was not carried

over to onvironrrontal toxicoloc/ experi-ctstis5. zhsrt-tcrm toxicity tests

serlou:-1y u crost i'-utn to toxi.:ity ani iel vulues 5ich aro much hiner

than %ii-,,- acceptaile toxicant ccrajntr ti"

c iy77 .

aI

f.K

13 -

The chemical form of a material in seawater in seawater can exert a

profound effect on its biological behavior [Burton, 1979). The aqueous chemis-

try c- trialKyltin compounds is influenced by pH and the concentration of other

ions present (Tobias et al., 1978; Jewett, et al., 1979). In seawater which

I.% has a pH of ca. 3.0, and chloride and carbonate ions predominate under aerobic

conditions, several reactions products are formed when TETO is added. In

addition to the hydroxide, also present in varying proportions are the aquo

complex, the carbonate and the chloride (Guard et al., 1982). These findings

suggest that with the probable exception of sulfide (which binds very strongly

to trialKyltin compounds) a roughly similar proportion of tributyltin compounds

forms in seawater, regardless of the anion present or molecules originally

added. Thus this may explain why the anion in general exerts only a minor

effect on the toxicity of the trialKyltin cation. The pH strongly affects

the equilibrium mixture, at least for TBTO because the affinity for OH- is

about 10 greater than that for Cl-, the most abundant anion in seawater.

Thus, it should be expected that in areas such as estuaries or river mouths,

-where pH and ionic strenghs may be less than in the open sea, distinctly diffe-

rent equilibrium proportions of tributyltin compounds would be formed. The

possible effects on organisms due to shifts in the chemical equilibrium cannot

be predicted with certainty, but may be significant.

Differential tributyltin leaching rates, a function of paint type,

markedly affects the toxicity to non-target organisms. There is a direct corre-

lation between the toxicity of the formulation and the quantity of tributyltin

present ig the seawater. Furthermore, there is fairly close agreement between

the toxicity caused by a given quantity of single tributyltins dissolved in

seawater, and that observed when a similar (measured) amount of tributyltin

leaches from paints. Thus, at least with respect to biological activity,

paints leach toxic tributyltin cation regardless of the anion at a rate

influenced primarily by the paint type. Therefore any attempts to mitigate

the biological effects would most profitably be directed toward reducing the

amount of tributyltin leached commensurate with acceptable paint performance.

Since the stucies presented here snow that tributyltins are toxic at

fairly low levels, and are stable in seawater for periods of at least days,

additional studies of the c-vircn-ental effects are warranted.

Measure-cnt3 of nviron-ental conccntraticns, with particular attention to

the amaunt present as the :ulfide would Le most usefujl. At present, our

l-tor2tcri ccuct-o nx eriments to determine ciffercncos in Liological

-14-

activity of the tributyltin Rulfide and TBTO to determine if environmental

chemical modifications will mitigate effects.

ACKNOWLEDGMENTS : Portions of this work were supported by the Swedish

Institute of Water and Air Pollution Research during a visiting research

grant to R.L. and by the U.S. Office of Naval Research. We thank W. French,

L. Tenfelt, and J. Ng for their help with this study. We are grateful to

C. Hopper and S. Lynn For assistance in manuscript preparation.

15 -

Literature 2iteco

Barnes, J.r. and Stoner, H.B. 1959. The toxicology of tin compounds.

Phariacol. Re , 11, 211-231.

Burton, J.C., 1979. Physico-chemical limitations in experimental investiga-

tions. 2hil. Trans. Roy. Soc. Lond. B., 286, 443-456.

Cyckman. E.J., Tonte-arano, J.A., and Fischer, E.C., 1973. Environmentally

compatible antifouling materials : organometallic polymers. Naval

Engineers Journal, 85, 33.

Evans, C.J., 1970. The development of organotin-based antifouling paints.

Tin and Its Uses, 85, 3-7.

Guard, H.E., Coleman, W.M., and Cobet, A.B., 1982. Speciation of tributyltin

compounds in seawater and estuarine sediments (In press).

Jewett, R.L., Blair, W.R., and BrincKman,F.E., 1979. New methods for specia-

tion of bicantive organotin leachates from antifouling paints and

polymers. Sixti International Symposium on Controlled Release of

Bioactive "atter, New Orleans, Louisiana, Aug. 6-8, 1979, pp. II,

13-16 (Abstract).

Laughlin, R.B., Jr., and French, W., 1S91. Comparative study of the acute

toxicity of a homolcgous series of trialkyltins to larval shore crabs,

n Her'ira25us ncud, and lobster, nomarus americanus, Bull. Env. Contam.

Toxicol., 25, 802-522.

Lind6n, E., Bengtsson, B.-E., Svanberg, 0., and Sundstrom, G., 1979. The

acute toxicity of 75 chemicals and Pesticide formulations against two

bracKish water organisms, the bleaK (Alburnus olburnus) and the harpac-

ticoid %itrocra soinioes. Chemosohere, 11, 843-851.

McKim, J.r., i77. Evaluation of tests with early life stages of fish for

predicting long-term toxicity, J. Fish, Res. Ed. Can., 34, 148-154.

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% Consecucnces for antniocd distribution and abundance. J. Exp. mar.

• L: - - , 2Y--245.

Nreldon, '.'. , l27Th. The aofl~sco cstructural pattern in an eelgrass

(Zesteri '.ina) a- rcc ccr'--nity. J. Exp. mar. biol. Ecol., 3D,

231-26.

- - n -- - -- - - n - - - -

- 16-

Ritchie, L.S.. Lopez, V.A., and Cora, J.ri., 1974. Prolonged application of an

organotin against Biomphalaria glabrata and Schistosoma3 mansoni. In

tolluscicides in Schistosomiasis Control (ed.) Chang, T.C., Academic

Press, New YorK, 77-88.

Stoner, A.W., l9B0a. Perception and choice of substratum by epifaunal amphi-

pods associated with seagrasses. M'ar. Ecol., 3, 105-112.

Stoner, A.W. . 1980b. The role of seagrass biomass in the organization of

benthic macrofaunal assemblages. Bull. Miar. Sci., 30, 537-551.

Tobias, R.S., 1978. The chemistry of organometallic cations in aqueous media.

In :Organometals and organomretalloids :Occurence and Fate in the

Environment. (eds) erincKmran, F.E. and Bellama, J.fl. American Chemical

Society. Washington, D.C., 130-148.

ZucKerman, J.J., Reisdorf, R.P., Ellis, H.V., III, and WilKinson. R.R., 1978.

Organotins in biology and the environment. In :Organometals and

Organometalloids :Occurence and Fate in the Environment. (eds.)

Brinckman, F.E. and Bellama, J.tl. Amer. Chem. Soc., Washington. D.C.,

388-424.

... ... ..

".17 -

Tacle 1. TUT32 .onceitrations in seawater as me. sured by quantitative CE.-1

NoAiqal concentration was 50 .g/L Values are rean *1standard deviation.

Source. n Measured ioncentration

(Wg/L )

Acetone Control 1 0.2

30 o/oo Seawater

0 hr 3 43.E6 - 1.27

24 hrs

unaerated 4 45.72 * 6.C2

aerated 3 45.C5 1.46.

N

iS

Ir AF t 4 1. -~

J r ,- ___ t

-. 4 1

I4

bILM~g b'Al ILK ''- ~ ~K v. r

- 19 -

* LA

0 1 7IN3-,dn

N CY N N

E E E E

0~ 00 a: to

CI

U~ 4

C\ J

c c I r I I I I II I I I I IL

- - -- - - -

- -- - - N

0 a) CO r- '. Lk fq r) (\j -

V,, I A 6,-1--

I

g

r

eII

Utt~ 4' ft ne~'t w''

-2S

1.1 zab , rue GAtiiilie 64 , 11 KU lilt'ie I I est , lie 1 (11 [1ue 1983

L VPTE DEIS PIJI3ICAT IONSDI "' I ILWES PAR L'001 MA

([thpartement [UCRRUO5IO\ MARINE et SAL I ';HR[S)

P T f R! '.D 0I

1I1 1 t ( nqr~s International de la Corrosion Marineet des3 SaliSSures (Cannes, France, 1964) $70

12 -. ii r&,' International de la Corrosion Marineet ow0; 'lli ,-ures Antibes, France, 1976) $ 100

1 13. Tta~itjx dto la Table Runde de I OCDE sur lesperforant;, les cliampignons et les salissuresdu Pcris en milieu marin (Portsmouth, U.Y., 1968) $ 12

2.V~A ';(IV,-. princi )p!e Salisqrure; marines

*en Franqais en AnglaisBa 1 Baanes $ 11 $ 11

%'2 iir~ozoaires $ 15 6puisd

* photocople $27

0~ rpuo' tuicoes$ 15 06pUiS6photocople $ 19

%14 0cd1 1 puisdphotocopie $ 12

N0 ',pnqi;air es $13 $ 13N'6 AI;ques non 6ditd 35

Ri. F ', DF I I'11V". du; C7IP

Nl19n -0 Rapport qt~n6 ra1 de synthise sur 1'6.tat actuel

ot. recherches sur la pr~servit ion des mat6riauxon mil1ivu rar in (V . Horranovsy)

- Fr.'p,tritin de sajrface dans lern chantiers decowntrutt inn navale (P'. flaril Ion) $ 11

1021 L2 - ; r at~ i F" di ( om it rtovrma t i oria Pe rmanment pour

la Pe och ur la PrL6;orrvat iori des Mat~riaux enii ii Mir in Arme Wodn

-opt InRfe Pou de!n Otudels 'culogriquio' e ffectui~es*do- P0,8 6i 197J par le Groupo- do!; fbioloistos $ 15

NO$ -k.mtt do'; roinhercfro; (noip(rat ivon sur lec-i ,rt vri (-% pvirittjrf-, drtiInuo t

(I ,rw lrr .1 nt aj 0, dir.I c j - vi r,' t

r~t :**,. .

% A.

-- 24 -

N'6 (1975) - Mdthodes utilisables dans les chantiers deconstruction navale pour l'dtude de la contami-nation des surfaces de la calamine residuelleet du potentiel 6lectrochimique local destoles (par le Groupe de Travail des Etats deSurface). $ 11

N*7 (1975) - M0thode d'essai de l'action de la protectioncathodique sur les revttements protecteurssous-marins (par le Groupe de Travail sur laProtection Cathodique) $ 12

N'8 (1980) - Studies on Marine Algal Fouling Communitiesin the North Atlantic. The MacroAlgae ofFloating Marinas on the East & South Coasts ofthe British Isles , by R.L. Fletcher(en anglais avec un rdsum6 en frangais)

- The Colonization of Selected Naturally Durablelimbers by Marine Fungi & Borers,by S.E.J. Furtado & E.B. Gareth Jones $ 17

N*9 (1980) - Le COIPM, son historique, ses buts, ses objectifs" et l'activitd de ses Groupes de Travail $ 17

N'10(1981) - Biblioqraphy : Frictional Resistance of ShipBottoms, by 0. Hansen S 17

N11(1981) - Nouvelle mdthode de 1ixiviation des peinturesantisalissures pendant le vicillissementartificiel, par E. Mor

- Etude de quelques parambtres influenqant lalixiviation des peintures antisalissures,par E. Mor

- loxicit6 et ddgradation des compos6s orqano-mdtalliques de l'tain, par E. Mor $ 17

N\12l"Q2) - leneurs en cuivre dans les eaux portuaires etlittorales en France, Etats-Unis et Japon $ 20

N0I ill1 - Aculte Toxicity of Tributyltins and Tributltinteachates from Marine Antifouling Paints,tb Poy 8. [laughiln, l1af Linden and H.E. Guard

en ani a i a%.c un r~stJm6 en franaiis) $ 12

FL

"' , . . . e . ° -a'.",°°- ". * • * ' 4 el 4. "

I.

-25-

1983

ODEMA asbl, rue Gabrielle 64, Brussels, Belgium

LISTE OF PUBLICATIONSDISTRIBUTED BY ODEMA

(Department : MARINE CORROSION and FOULING)

1. PROCEEDINGS :

I.I. 1st International Congress on Marine Corrosion & Fouling(Cannes, France, June 1964) $ 70

1.2. 4th International Congress on Marine Corrosion & Fouling(Antibes, France, June 1976) $ 100

1.3. OECD Workshop on Marine Borers, Fungi and FoulingOrganisms of Wood. OECD Publication.(Portsmouth, U.K., March-April 1968) $ 12

2. CATALOGUES of Main Marine Fouling Organisms iin French in English

N0 1 Barnacles $ 11 $ 11

N0 2 Polyzoa $ 15 out of printphotocopy : $ 27

N0 3 Serpulids $ 15 out of print

photocopy $ 19

'W N0 4 Ascidians $ 11 $ 11

N0 5 Marine Sponges $ 13 $ 13N0 6 Algae $ 35

3. BULLETIN DE LIAISON du COIPM

N01 (1969) - Consolidated Progress Report on Research on thePreservation of Materials in the Marine Environ-ment (V. Romanovsky).

- Surface Preparation in Shipyards (P. Barillon). $ 11

0 N02(1972) - Activities of the Comit6 International Permanentpour la Recherche sur la Prdservation des Matdriauxen Milieu Marin (Anne Wodon).Report of the Ecological Studies carried out duringthe Years 1968 to 1970 by the Group of Biologists. $ 15

N13 (1973) - Results of Cooperative Research on the Behaviourof Antifouling Paints and the Corrosion of BareMetals in Sea Water. $ 40

N14 (1974) - lesting Stations-Caracteristics and Environment. $ 40

%. N0 5 (1974) - Results of an International Cooperative ResearchProramme on the Fouling of non loxic Panels byMarine Alqa- (R. Fletcher).

- Hvcnmandftions to Shipyards in ordor to AvoidStr: iv .urrents when fitting uit a ship (t,> theWor Ir,,j Sroup on Stray Currents). $ 37

k 1 N(, 1 ) - 4thjs ued in hip'arcd. for Studyinq Surfae(.C ont ,,t ir. cs iduaI p cale and Ic'al I lect to-( 'cbh 1- ' te tial of Platec (by WuIkirlrJ Group

no Grtu, Uinv). $ 11

- 26 -

N0 7 (1975) - A Method for Testing the Effect of CathodicProtections on Underwater Protective Coatings inin a Marine Environment (by the Working Groupon Cathodic Protection). $ 12

NO8 (1980) - Studies on Marine Algal Fouling Communities inthe North Atlantic. The Macro Algae of FloatingMarinas on the East & South Coasts of the BritishIsles, by R.L. Fletcher.

- The Colonization of Selected Naturally DurableTimbers by Marine Fungi & Borers,by S.E.J. Furtado & E.B. Gareth Jones. $ 17

N0 9 (1980) - The COIPM : its historical record, its aims,its activities, its working groups and itspublications. $ 17

N010(1981) - Bibliography : Frictional Resistance of Ship

Bottoms, by 0. Hansen. $ 17

N0 11(1981) - Methods of Leaching Rate Measurements,by E. Mor.

(in French with a large abstract in English)- Toxicity of Tin Organo-mettalic Compounds,

by E. Mor.

(in French with a large abstract in English) $ 17

N0 12(1982) - Copper Contents in Waters of some Harbours.by different authors(in English and in French) $ 20

N0 13(1982) - Acuite Toxicity of Tributyltins and TributyltinLeachates from Marine Antifouling Paints,by Roy B. Laughlin, Olaf Linden and H.E. Guard $ 12

Ii4

NA 111

9._