Professional Documents
Culture Documents
www.elsevier.com/locate/marpolbul
Baseline
Abstract
In January and February 2002, the presence of certain agricultural pesticides throughout the coastline of the Caribbean island of
Martinique was investigated. The tropical climate of the French West Indies is suitable for banana production, which requires inten-
sive use of pesticides. An inventory of all pesticides used on the island (compounds and tonnage) was compiled. Surveys and analyses
revealed the presence of pesticides in the plumes of seven rivers. The organochlorine chlordecone and metabolites of aldicarb were
detected at nearly all of the monitored sites, even though the use of chlordecone has been prohibited since 1993. Two triazines (amet-
ryn and simazine) were also identified. The concentrations of carbamates and triazines detected in the water and sediment samples
from Martinique are comparable to those reported for mainland France. Chlordecone concentrations in the sediment and partic-
ulate matter samples were, however, particularly high in the samples from Martinique. Toxicological implications are discussed. Of
particular concern are the high levels of chlordecone (which is bioaccumulating and carcinogenic) and further monitoring of this
compound is recommended, especially in fish and other sea-food products.
2005 Elsevier Ltd. All rights reserved.
0025-326X/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2005.06.026
G. Bocquené, A. Franco / Marine Pollution Bulletin 51 (2005) 612–619 613
Fig. 1. Location of sampling sites in the plumes of rivers along the coastline of Martinique Island.
2.3. Analyses Solvent extracts from eluted SPE cartridges and ASE
were evaporated to near dryness (using a gentle stream of
The most widely used pesticides that might be present nitrogen), and the residue dissolved in 1 ml solvent, the
in the environment were selected for analysis (Table 2). nature of which was specified by the chosen chromato-
For the dissolved phase, analyses were directed towards graphic technique. Analyses were performed as follows:
more soluble compounds such as some triazines, Organophosphorus pesticides/triazine herbicides/tria-
fungicides, aldicarb and its metabolites, as well as zole compounds. Gas-chromatography with thermoionic
compounds with a more hydrophobic behaviour, such nitrogen/phosphorus detector or ion trap mass spec-
as some organophosphorus compounds. In the particu- trometer: GC conditions were as follows: DB5 column,
late phase and in sediments adsorption properties 60 m length, 0.25 mm diameter. The GC oven was held
guided the focus of analyses: organophosphorus com- at 50 C for 5 min, then ramped to 200 C at
pounds, aldicarb (and its primary metabolites) and 20 C min1, held at 200 C for 10 min, then ramped
chlordecone. to 300 C at 30 C min1 and finally held at 300 C for
G. Bocquené, A. Franco / Marine Pollution Bulletin 51 (2005) 612–619 615
3. Results
5 min. The GC inlet was operated in splitless mode at
250 C, with a 1 ll injection volume. The detector was Results are presented in Table 3. At 3 of the 9 mon-
held at 300 C. itored sites, no pesticide contamination was detected un-
Chlordecone. Gas-chromatography with electron der the described sampling and analysis conditions.
capture detector or ion trap mass spectrometer column: These sites included the two sampling sites located along
GC conditions were as follows: DB5 column, 60 m the salinity gradient of the Baie du Robert (6, S = 25&
length, 0.25 mm diameter. The GC oven was held at and 7, S = 35&), Fig. 1 and the sampling site located in
60 C for 4 min, then ramped to 200 C at 20 C min1, the estuary of the Carbet river (8) on the Caribbean Sea
held at 200 C for 20 min, then ramped to 320 C at coast. Samples from the other six monitored sites sam-
5 C min1 and finally held at 320 C for 10 min. The ples were all contaminated by pesticides, often by more
GC inlet was operated in splitless mode at 250 C, with than one compound. At these sites, the pesticides
a 1 ll injection volume. The detector was held at 300 C. detected and quantified were chlordecone, aldicarb,
Confirmation was undertaken using a DB1701 column, and triazines.
60 m length, 0.25 mm diameter. Here the GC oven was
held at 60 C for 2 min, then ramped to 200 C at 3.1. Chlordecone
20 C min1, held at 200 C for 20 min, then
ramped to 280 C at 5 C min1 and finally held at Levels of each compound found within this study in
280 C for 16 min. Inlet and detector conditions were Martinique were compared with concentrations re-
as above. ported for the same or closely-related compounds from
Carbamates. High-performance liquid chromatogra- mainland France.
phy with diode array detector, and fluorescence detector In Martinique, chlordecone was frequently found in
after post column derivatization with PICKERING particulate matter isolated from river water and in sed-
system (HPLC/fluo. KOK method) (column: Supelco iments. It was quantified in sediment samples from the
LC-8; 250 mm · 4.6 mm and LC-ABZ; 250 mm · Lorrain (1, 44 lg kg1), François (4, 38 lg kg1), and
4.6 mm). Column temperature was 40 C. Lézarde (9, 31 lg kg1) rivers, as well as in particulate
The detection limits were 2 lg kg1 for chlordecone matter samples collected in the plume of the François
in sediment and particulate matter, 2 ng l1 for ametryn (4, 57 lg kg1), the Galion (3, 52 lg kg1), Lézarde (9,
616 G. Bocquené, A. Franco / Marine Pollution Bulletin 51 (2005) 612–619
Table 3
Levels of pesticides in water, suspended particulates and sediments from different locations of the Martinique Island in January and February 2002
Chlordecone Chlordecone Aldicarb Aldicarb Simazine Ametryne
(in particulate (in sediment) sulfoxide sulfone
matter)
Capot river <10 <10 0.043 0.083 <0.010 <0.010
Lorrain river <10 44 <0.030 <0.030 <0.010 <0.010
Galion river 52 <10 0.052 0.032 0.016 0.017
Cacao river 22 <10 <0.030 <0.030 0.015 0.010
Baie du Robert (25& sea water) <10 <10 <0.030 <0.030 <0.010 <0.010
Baie du Robert (35& sea water) <10 <10 <0.030 <0.030 <0.010 <0.010
Du François river 57 38 <0.030 <0.030 0.018 0.300
Lézarde river 45 31 <0.030 <0.030 <0.010 <0.010
Results are expressed as lg l1 (water) and lg kg1 (particulate matter and sediment samples).
45 lg kg1) and Cacao (5, 22 lg kg1) rivers. Although This is the case for the estuaries of the Sèvre Niortaise
chlordecone has never been used in mainland France, (0.030 lg l1) and the Charente (0.040 lg l1) rivers. In
levels can be compared with DDT, another OC insecti- other European estuaries, simazine levels can reach
cide with similar biogeochemical behaviour. Chlorde- higher values, e.g. up to 3 lg l1 (Tauler et al., 2001;
cone levels in sediment samples from Martinique were Garmouma et al., 2001; Drevenkar et al., 2004).
far greater than those measured for DDT in mainland
France, where DDT levels in sediment generally range
between 0 and 2 lg kg1. The chlordecone levels were 4. Discussion
also much higher than DDT levels measured on the
French Mediterranean coast, where they reach This study builds upon 2 earlier surveys carried out in
10 lg kg1 (RNO, 1998). the upstream reaches of the rivers of Martinique. In
1999 and 2001, the DIREN conducted three surveys
3.2. Carbamates based on samples collected at 33 sites located in the riv-
ers of Martinique. Nineteen pesticide active ingredients
Carbamates were detected in the dissolved phase were identified and found to be present at various
samples from the northeastern part of the island. Aldi- concentrations and frequencies (DIREN, 2001). The
carb metabolites (sulfone and sulfoxide) were found in DIREN reported the recurring presence of chlordecone
the plumes of the Capot (2) and Galion (3) rivers. Levels in waters of the Galion (1.20 lg l1, in October 2000),
reached 0.043 and 0.052 lg l1 for the sulfoxide metab- Rouge (2.13 lg l1, in August 2001) and Pocquet
olite and 0.083 and 0.032 lg l1 for the sulfone metabo- (2.07 lg l1, in August 2001) rivers. These rivers are
lite in these rivers respectively. Although aldicarb is not located in the north and middle-east parts of the island,
used in mainland France, comparisons could be made very close to the banana fields. Contamination of river
with related compounds such as carbofuran and carba- waters by chlordecone may reflect the presence of resid-
ryl. These compounds are rather regularly found in ual levels of this compound in treated soils. Although
streams and rivers and are present at concentrations of the use of chlordecone has been prohibited since 1994,
the order of 0.020 lg l1. Carbofuran levels in the Seu- levels reaching 5000 lg kg1 were recorded in the soils
dre river of up to 0.200 lg l1 were observed in May of the Gradis farm located near the river Rouge in
2001, while carbaryl levels of 0.250 lg l1 in the Vilaine August 1999 (DSDS, 2001).
river were reported in 1997 (GRAP, 2002; CORPEP, The assessment of river water quality conducted by
2000, 2001). the DSDS showed that 36 pesticide active ingredients
were present in all drinking water sources. The insecti-
3.3. Triazines cide chlordecone was ubiquitous, being found in 95%
of samples collected by the DSDS from January 1999
Triazines partition primarily to the dissolved phase. to May 2000 and in 100% of samples in June and July
Simazine and ametryn were detected in the Galion (3), 2000, together with HCH beta, another prohibited orga-
François (4), and Cacao (5) rivers. Levels of ametryn nochlorine insecticide. The highest values were observed
measured in the François (4) river, in brackish water in the Capot river, with a maximum level of 3 lg l1 in
(S = 11&), were high (0.300 lg l1). Existing data on the Gradis source (unfiltered water). Chlordecone still
simazine levels in European estuaries show that concen- chronically contaminates most water resources, notably
trations found in Martinique and mainland France are the drinking water inlet of the Capot river. Chlordecone
of the same order of magnitude, i.e. a few tens of ng l1. was also found at levels reaching 2.51 lg l1 in the
G. Bocquené, A. Franco / Marine Pollution Bulletin 51 (2005) 612–619 617
Rouge river and 2.13 lg l1 in the Pocquet river (unfil- exposure to only 0.08 lg l1 chlordecone. Goodman
tered water). The following herbicides were also identi- et al. (1982) showed that the lethal concentration in
fied: bromacil, diuron, simazine, atrazine, and sheepshead minnow embryos was 0.02 lg l1 after a
ametryn. In August 2001, diuron (2.47 lg l1) was de- 21-day exposure. Chlordecone has estrogenic activity,
tected in the François river and ametryn (1.14 lg l1) i.e. it can affect the reproductive system in many species
in the Pilote river. In the DSDS surveys, ametryn and including humans (Okubo et al., 2004; Donohoe and
simazine were present in 16% and 13% of samples, Curtis, 1996). Chlordecone was also shown to be carcino-
respectively. genic in trout (Donohoe et al., 1998) and rats (Guzellian
Aldicarb is rapidly degraded. However, according to et al., 1992). According to the International Agency for
the DSDS surveys, the presence of its more stable Research on Cancer (IARC, 1979), chlordecone is ‘‘pos-
metabolites was frequently detected. Aldicarb sulfone sibly carcinogenic to humans’’ and is therefore consid-
concentrations, measured at the drinking water inlet of ered as a Group 2B compound.
the Capot river, reached 0.162 lg l1 in June and July Aldicarb, a highly toxic pesticide (WHO, 1991), and
2000. The water quality survey of the Capot river also its two main metabolites do not accumulate in the suc-
revealed the presence of the insecticides oxamyl and cessive trophic levels of the food chain. The LC5096
cadusafos. Runoff of water from an area of cropland for many fish species ranges between 80 and 600 lg l1
treated with aldicarb was analyzed by the Centre de (Mayer and Ellersleck (1986) and Mayer (1987) both
Coopération Internationale en Recherche Agronomique in WHO, 1991), but the LOEC (lowest observed effects
pour le Développement (CIRAD) in 1999 (CIRAD/ concentration) has been shown to be as low as 4.5 lg l1
IRD, 2001). Results showed that aldicarb sulfoxide for the fathead minnow (Moore et al., 1998). The same
and aldicarb sulfone levels were 11.5 times higher than authors showed that crustaceans are much more sensi-
aldicarb levels 10 days after treatment. tive to aldicarb, as shown by a LOEC of 0.5 lg l1 in
Organophosphorous compounds were not detected the water flea Daphnia magna. Bivalve molluscs are
during the current study, despite terbufos, cadusafos, apparently insensitive to the presence of this compound
isazofos, and phenamiphos accounting for 700 of the in their environment (LC5048 for oysters is 8800 lg l1,
1816 tonnes of insecticides imported in 1998. The DSDS Mayer (1987) in WHO, 1991). Aldicarb is not consid-
reported the presence of tetrachlorvinphos and cadusa- ered carcinogenic. As is the case with organophospho-
fos, while the DIREN reported the presence of methyl rous insecticides, aldicarb and its metabolites are
parathion. The biogeochemical behaviour of these com- acetylcholinesterase inhibitors and as such are consid-
pounds is complex and understanding this requires a ered neurotoxic. Moreover, salinity appears to be an
better knowledge of the metabolism of these neurotoxic aggravating factor for the neurotoxic effect of aldicarb.
molecules. El-Alfy and Schlenk (1998) established a direct correla-
Fungicides were also not detected in the current tion between salinity and aldicarb toxicity to the meda-
study. The monitoring network implemented by the DI- ka fish, which may be due to a higher absorption of the
REN recorded the presence of the fungicides tebuconaz- compound and a greater production of the sulfoxide
ole, propiconazole and thiabendazole at levels of nearly metabolite at higher salinity. The use of aldicarb has
1 lg l1 in the north-eastern part of the island in March been prohibited in the French West Indies since January
2000. 2003.
Chlordecone is considered hazardous to the aquatic Portmann and Wilson (1971) report the LC5048 for
environment and human health due to its stability, per- the triazine ametryn in the common shrimp (Crangon
sistence and potential to bioaccumulate in the food crangon) as being between 33 and 100 lg l1. Fish, on
chain (WHO, 1984). Its bioconcentration factor can the other hand, appear to be less sensitive: the LC5048
reach 9350 in the oyster Crassostrea virginica, 11,425 was estimated at 5800 lg l1 for the sheepshead min-
in the shrimp Palaemonetes pugio, and 16,600 in the fat- now, 5000 lg l1 for the medaka fish, and 5700 lg l1
head minnow Pimephales promelas (Bahner et al. (1977) for the fathead minnow (EPA, 2000). Simazine toxicity
in WHO, 1984; Huckins et al., 1982). The LC5096 for the is of the same order of magnitude. LC5048 values were
blue crab (Callinectes sapidus) has been reported as estimated at 10,000 lg l1 for the European green crab
210 lg l1 and the LC5048 for the brown shrimp (Paen- (Carcinus maenas) and 100,000 lg l1 for the common
eus aztecus) as 85 lg l1 (EPA, 2000). Chlordecone is shrimp. Hashimoto and Nishiuchi (1981) reported a
acutely toxic to the fathead minnow and sea lamprey, LC5048 of 10,000 lg l1 for the medaka fish. According
with LC5096 values of 69.5 and 414 lg l1 respectively to the EPA (2000), LC5096 for the sheepshead minnow is
(EPA, 2000; Mallatt and Barron, 1988). Sublethal effects 6400 lg l1.
occur at much lower concentrations in long-term (36 Triazines are potent photosystem II inhibitors and
day) exposure experiments. Hansen et al. (1976) in ametryn is known to impact photosynthesis of the endo-
(WHO, 1984) reported reduced growth of juvenile symbiotic zooxanthellae of corals at low (ng l1) concen-
sheepshead minnows (Cyprinodon variegatus) following trations (reviewed in this issue by Jones, in press). A
618 G. Bocquené, A. Franco / Marine Pollution Bulletin 51 (2005) 612–619
recent study (Jones and Kerswell, 2003) on the effects of in suspended matter and sediment samples were far
herbicides on zooxanthellae within the host tissues of the greater in Martinique than, for example DDT levels in
coral Seriatopora hystrix also reported that the concen- mainland France. Chlordecone is a carcinogenic and
tration of ametryn required to reduce chlorophyll con- bioaccumulating pesticide which has a strong potential
tent by 50% was 1.7 lg l1. Simazine has also been for causing endocrine disruption. Monitoring of this
shown to impact coral zooxanthellae photosynthesis, compound should therefore be one of the priorities of
although it appears to be less toxic when compared to any pollution monitoring network such as the Réseau
ametryn and diuron (Jones, in press). Herbicides have National dÕObservation, which has been implemented
also been associated with damage exhibited by man- in mainland France. Use of chlordecone has been pro-
grove trees in the NE region of Australia (Duke et al., hibited since 1993, but as chlordecone appears to be
2005). ubiquitous, important areas of cropland may still con-
Data reported herein were obtained from samples tain residual contamination today. There is a high risk
collected after a five month period characterised by daily that runoff and seeping water will continue to contami-
tropical rainfall events. Rainfall during the 2001–2002 nate the aquatic and marine environments of the island
winter season was exceptional in terms of duration. for years to come. Considering the fact that chlordecone
The dry season usually lasts from October to June, how- is extremely stable and given the lipophilic properties of
ever, in December 2001 precipitation reached 240 mm this molecule, as well as its capacity to bioaccumulate,
(the monthly average for 2001 was 117 mm). For effi- transfer of this compound to other trophic levels of
ciency/economic reasons, pesticide application is limited the food chain, notably marine species, such as fish
during the rainy season. The observed precipitation may and crustaceans, which are consumed in large quantities
have caused a significant leaching of pesticides from by the local population, should be investigated.
soils. Consequently, the most soluble molecules, such The presence of any contaminant that inhibits photo-
as fungicides and many herbicides, may have been read- synthesis of corals, which are of fundamental importance
ily transported to coastal waters and dissipated, which for the structure and function of reef environments,
may account for the fact that they were not detected could have serious ecological consequences (Owen
in this study during January and February. Under such et al., 2002). Given reports of contamination of both riv-
conditions, identification of simazine and ametryn in ers and their coastal plumes by herbicides in this and pre-
surface waters may suggest recent application. For the vious studies and growing evidence of the low level effects
same reasons, maximum potential pesticide concentra- of these chemicals on coral photosynthesis, further inves-
tions within the plumes may have been missed. Only tigation of the distribution of these herbicides and their
compounds such as chlordecone, which binds more impacts in the reef ecosystems adjacent to catchments
readily to soil particles, are leached in a more regular with significant agricultural activity in Martinique is
way throughout the erosion process of the catchment recommended.
area. Data reported in this study may underestimate
the pesticide loads to the marine environment.
References
Drevenkar, V., Fingler, S., Mendas, G., Stipicevic, S., Vasilic, Z., 2004. IARC, 1979. Some halogenated hydrocarbons. International Agency
Levels of atrazine and simazine in waters in the rural and urban for Research on Cancer. Monographs on the evaluation of the
areas of north-west Croatia. International Journal of Environmen- carcinogenic risk of chemicals to human, vol. 20. Geneva,
tal Analytical Chemistry. 84 (1–3), 207–216. Switzerland.
DSDS, 2001. Pesticides et alimentation en eau potable en Martinique. Jones, R., in press. The ecotoxicological effects of Photosystem II
Etat des lieux et position sanitaire. Bilan actualisé en octobre 2001. herbicides on corals. Marine Pollution Bulletin, doi:10.1016/
Direction de la Santé et du développement Social de la Martinique, j.marpolbul.2005.06.027.
Fort-de-France. Martinique Island, France, 11p. Jones, R., Kerswell, A., 2003. Phytotoxicity of photosystem II (PSII)
Duke, N.C., Bell, A.M., Pederson, D.K., Roelfsema, S.M., Nash, S.B., herbicides to coral. Marine Ecology Progress Series 261, 149–
2005. Herbicides implicated as the cause of severe mangrove 159.
dieback in the Mackay region, NE Australia: consequences for Mallatt, J., Barron, M.G., 1988. High tolerance of Lampreys to
marine plant habitats of the GBR World Heritage Area. Marine Kepone toxicity. Archives of Environmental Contamination and
Pollution Bulletin 51, 308–324. Toxicology 17 (1), 73–80.
El-Alfy, A., Schlenk, D., 1998. Potential mechanisms of the enhance- Moore, M.T., Huggett, D.B., Gillespie Jr., W.B., Rodgers Jr., J.H.,
ment of aldicarb toxicity to japanese medaka (Oryzias latipes) at Cooper, C.M., 1998. Comparative toxicity of chlordane, chlor-
high salinity. Toxicology and Applied Pharmacology 152, 175–183. pyrifos, and aldicarb to four aquatic testing organisms. Archives
EPA, 2000. US Environmental Protection Agency. Pesticide ecotox- of Environmental Contamination and Toxicology 34 (2), 152–
icity database (Environmental Effects Database (EEDB)). Office of 157.
Pesticide Programs. Environmental Fate and Effects Division, US Okubo, T., Yokoyama, Y., Kano, K., Soya, Y., Kano, I., 2004.
EPA, Washington, DC, AQUIRE Reference No: 344. Estimation of estrogenic and antiestrogenic activities of selected
Garmouma, M., Blanchoud, H., Teil, M.J., Blachard, M., Chevreuil, pesticides by MCF-7 cell proliferation assay. Archives of Environ-
M., 2001. Triazines in the Marne and the Seine rivers (France): mental Contamination and Toxicology 46 (4), 445–453.
longitudinal evolution and flows. Water, Air and Soil Pollution 132 Owen, R., Knap, A., Toaspern, M., Carbery, K., 2002. Inhibition of
(1–2), 1–17. coral photosynthesis by the antifouling herbicide Irgarol 1051.
Goodman, L.R., Hansen, D.J., Manning, C.S., Faas, L.F., 1982. Marine Pollution Bulletin 44, 623–632.
Effects of Kepone on the sheepshead minnow in an entire life-cycle Portmann, J.E., Wilson, K.W., 1971. Shellfish Information Leaflet No.
toxicity test. Archives of Environmental Contamination and 22 (second ed.), Ministry of Agriculture Fishery and Food, Fishery
Toxicology 11, 335–342. Laboratory, Burnham-on-Crouch, Essex, and Fish Experimental
GRAP, 2002. Réseau régional de suivi de la qualité des eaux vis à vis Station, Conway, North Wales, Burnham-on-Crouch, United
des produits phytosanitaires. Années 1999, 2000 et 2001. DIREN Kingdom, 12p.
Poitou-Charente, Poitiers, France, 74p. R.N.O, 1998. Réseau National dÕObservation de la qualité du milieu
Guzellian, P.S., Chambers, P.L., Chambers, C.M., Bolt, H.M., marin. Surveillance du milieu marin. Travaux du RNO. IFR-
Preziosi, P., 1992. The clinical toxicology of Chlordecone as an EMER et Ministère français de lÕaménagement du Territoire et de
example of toxicological risk assessment for man. Toxicology from lÕEnvironnement. Nantes, France, 50p.
discovery and experimentation to the human perspective. Toxicol- Tauler, R., Azevedo, D., Lacorte, S., Cespedes, R., Viana, P., Barcelo,
ogy Letters 64–65, 589–596. D., 2001. Organic pollutants in surface waters from Portugal using
Hashimoto, Y., Nishiuchi, Y., 1981. Establishment of bioassay chemometric interpretation. Environmental Technology 22 (9),
methods for the evaluation of acute toxicity of pesticides to 1043–1054.
aquatic organisms. Journal of Pesticide Sciences 6 (2), 257–264. WHO, 1984. Environmental Health Criteria 43. Chlordecone. World
Huckins, J.N., Stalling, D.L., Petty, J.D., Buckler, D.R., Johnson, Health Organization. Geneva, Switzerland, 57p.
B.T., 1982. Fate of Kepone and mirex in the aquatic environment. WHO, 1991. Environmental Health Criteria 121, Aldicarb. World
Journal of Agriculture and Food Chemistry 30, 1020–1027. Health Organization. Geneva, Switzerland, 130p.