Spatial distribution of organochlorine contaminants in soil, sediment, and fish in Bikini and Enewetak Atolls of the Marshall Islands, Pacific Ocean

Several nuclear tests were performed at Enewetak and Bikini Atolls in the Marshall Islands between 1946 and 1958. The events at Bikini Atoll involved several ships that were tested for durability during nuclear explosions, and 24 vessels now rest on the bottom of the Bikini lagoon. Nine soil samples were collected from different areas on the two islands of the atoll, and eighteen sediment, nine fish, and one lobster were collected in the vicinity of the sunken ships. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polychlorinated terphenyls (PCTs) in these samples were analyzed using gas chromatography/ion trap mass spectrometry (GC/ITMS). The average recoveries ranged from 78% to 104% for the different PCB congeners. The limits of detection (LOD) for PCBs, PCTs, DDE, DDT, and dieldrin ranged 10-50 pg g⁻¹. Some fish from Enewetak contained PCBs at a concentration range of 37-137 ng g⁻¹, dry weight (dw), and most of the soils from Enewetak showed evidence of PCBs (22-392 ng g⁻¹ dw). Most of the Bikini lagoon sediment samples contained PCBs, and the highest was the one collected from around the Saratoga, an aircraft carrier (1555 ng g⁻¹ dw). Some of the fish samples, most of the soil samples, and only one of the sediment samples contained 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and PCBs. In addition to PCBs, the soils from Enewetak Atoll contained PCTs. PCTs were not detected in the sediment samples from Bikini Atoll. The results suggest local pollution sources of PCBs, PCTs, and OCPs.     

pp´DDT and pp´DDE Accumulation in a Food Chain of Lake Maggiore (Northern Italy): Testing Steady-State Condition

- DOI: http://dx.doi.org/10.1065/espr2006.01.010 Background, Aims and Scope Although pp'DDT usage was strongly limited or banned in most parts of the world during the last three or four decades, the parent compound, its homologues and their metabolites still occur at levels which might pose a risk for many ecosystem components. A case of DDT pollution of industrial origin was discovered in 1996 in Lake Maggiore, the second largest (212 km2) and deepest (370 m) lake in Italy, causing concern for wildlife and human health. The extensive monitoring of many biotic and abiotic compartments which followed from 1998 in order to assess the pollution level and its trend in time, provided a great availability of data referring to DDT contamination of the different fish species of the lake. In this study, the recent contamination levels in selected fish species were compared to those measured in 1998 to evaluate the temporal pollution trend of the lake and its natural recovery, given that no remediation measures were carried out on the contaminated soils and sediments in this time span. Moreover, a modelling approach to test the equilibrium condition between water and pelagic fish species was used. Analytical results of pp'DDT and pp'DDE concentrations in lake water were used as input data in the bioenergetic model by Connolly & Pedersen (1988) to calculate concentrations in two fish species and to compare the predicted and the measured contamination. Methods Sampling and analytical determination of DDT homologues in lake water: Five water sampling campaigns were carried out from May 2002 to February 2004 in three sampling sites of Lake Maggiore. Suspended and dissolved pollutants were determined separately. Quantitative DDT homologue analyses were performed by HRGC coupled with ECD detection by the external standard method. Single water extracts were put together in correspondence with the stratification zones of the water column inferred on the basis of the temperature profile to improve analytical sensitivity. Selection of fish data: Concentrations of DDT and DDE in fishes were selected from recent literature (CIPAIS 2003, 2004). Bioaccumulation model: The bioenergetic model proposed by Connolly & Pedersen (1988) was used to assess the bioaccumulation of pp'DDT and pp'DDE of Alosa fallax (landlocked shad) and Coregonus spp. (whitefish), selected among the different species as representative of a secondary consumer level. Results and Discussion The average concentrations of pp'DDT and pp'DDE in water to be used as input data in the bioenergetic model were obtained considering all the concentrations measured at the three sampling stations in the epylimnion where the fish species considered in this study spend most of their life. The resulting values were 0.05 and 0.16 ng/L for pp'DDT and pp'DDE, respectively. Average measured pp'DDT and pp'DDE concentrations in landlocked shad were 0.81 +/- 0.39 and 1.69 +/- 0.71 mg/kg lipids, respectively, and were 0.29 +/- 0.12 and 1.06 +/- 0.41 mg/kg lipids for the whitefish. Calculated and measured values turned out to be in quite good agreement for pp'DDT, while measured pp'DDE concentrations were higher than expected on the basis of the bioenergetic model in both species. Probably metabolic transformations of pp'DDT accumulated in fish tissues in the past are responsible for the observed differences between calculated and expected pp'DDE concentrations in fish. Conclusions Pelagic fishes of Lake Maggiore seem to maintain the DDT accumulated during their life time and the most efficient mechanism responsible for the fish population recoveries is probably their generation changes; for this reason, equilibrium models cannot be used until negligible pp'DDT concentrations are reached in fish tissues. Recommendations and Outlook The limit proposed for pp'DDT in water by the EU Directive 2000/60, which will come in force in 2008, is 0.2 ng/L, four times higher than the average concentration measured in Lake Maggiore waters. Nevertheless, concentrations measured in Lake Maggiore fish were very close and sometimes exceeded the Maximum residue limits (MRLs) settled by the Italian legislation for foods (0.1 mg/kg w.w. for fish containing 5–20% lipid). It seems, therefore, that the 'environmental quality standard' of 0.2 ng/L cannot guarantee the suitability of fish for human consumption.     

Residues of Organochlorinated Pesticides in Eggs of Water Birds from Tai Lake in China

The levels of organochlorine compounds in eggs of water birds from the colony on Tai Lake in China were studied. The eggs were collected in 2000 and belonged to the following species: 65 samples of black-crowned night heron (Nycticorax nycticorax), 36 samples of little egret (Egretta garzetta), 26 samples of cattle egret (Bubulcus ibis) from 13 clutches and 43 samples of Chinese pond heron (Ardeola bacchus) from 17 clutches. Dichlorodiphenyltrichloroethane (DDT) and its derivates (DDE and DDD), hexachlorocyclohexane (HCH) and its isomers (-HCH, -HCH, -HCH, -HCH), heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, endrin aldehyde, -endosulfan, -endosulfan, and endosulfan sulfate were determined in the laboratory by gas chromatography. The data showed that DDE had the highest levels in all the samples, followed by -HCH. The mean levels of DDE among the water bird species were in the order as follows: black-crowned night heron (5464.26ng/g, dry weight) > Chinese pond heron (2791.12ng/g, dry weight) > little egret (1979.97ng/g, dry weight) > cattle egret (660.11ng/g, dry weight). DDT and its metabolites accounted for 90% of the total organochlorines, except that it was only 73% for cattle egret. The differences of the residue among the bird species were statistically significant and could be attributed to their variations in prey and habitat. Although the DDE burdens in Tai Lake were much lower than 8 g/g (wet weight) which are thought to have significant adverse effects on black-crowned night herons, they would be expected to increase the risk of adverse effects on survival of chicks of herons and egrets, particularly black-crowned night heron, based on the critical value of 1 g/g (wet weight) DDE. The burdens of HCHs in this study were higher and the cyclodienes were lower than those found elsewhere.     

PESTICIDE ACCUMULATION IN A NEW IMPOUNDMENT IN IOWA1

ABSTRACT: Estimates were made of the amounts of selected pesticides entering and leaving Saylorville Reservoir, a new partly filled impoundment on the Des Moines River. Samples were collected at 1– or 2-week intervals at stations above, in, and below the reservoir. Atrazine, alachlor, and cyanazine were found only in the dissolved state, and dieldrin and p, p′ -DDE in both the, dissolved and suspended state. Heptachlor epoxide, p,p-DDT. p, p′ -DDD, 2,4-D, 2,4,5-TP, endrin, lindane, methoxychlor, propachlor, and toxaphene were not detected or were at very low concentrations. Estimated deposition in the reservoir from September 1977 to October 1978 was 281 kg atrazine, 251 kg alachlor, 26 kg cyanazine, 16 kg dieldrin, and 20 kg p, p′ -DDE.     

Study of Fishes in the Chung-Kung Stream: Species Distribution and Organochlorine Pesticide Residues

Abstract

In this study, we investigated the potential for reductive dechlorination of 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) by municipal sewage sludge adapted to 2,4-DCP at different concentrations. 2,4-DCP was completely dechlorinated within 4 weeks. After 18 weeks' incubation, 2,4,6-TCP was also completely dechlorinated and the residue of PCP was 0, 44.46, 51.96% at 0.5, 5, and 50 μg ml¹ respectively. the 2,4-DCP adapted communities initially removed the ortho-chlorine from PCP of 5.0, 50 μg ml¹, following an ortho < para < meta order of chlorine removal. Intermediate products were 3,4,5-TCP, 3,5-DCP, 3-CP (3-chlorophenol), phenol, benzoate and hexanoic acids, whereas PCP (0.5 μg ml¹) indicated a preference for meta-chlorine removal. the intermediate product of 2,4,6-TCP at three concentrations were 2,4-DCP, phenol, benzoate and hexanoic acid. These products were identified by GC-MASS spectrometry. the effects of supplements, including sodium citrate (0.08 mM), sodium pyruvate (0.18 mM), sodium sulphate (0.14 mM) had a direct stimulatory effect on the dechlorination of 2,4,6-TCP and PCP after treatment for 4 weeks, but dechlorination was inhibited after 8 weeks.     

Use of the p,p'-DDD: p,p'-DDE Concentration Ratio to Trace Contaminant Migration from a Hazardous Waste Site

For approximately 50 years, beginning in the 1920s, hazardous wastes were disposed in an 11-hectare area of the Marine Corps Base (MCB) Quantico, Virginia, USA known as the Old Landfill. Polychlorinated biphenyls (PCBs) and DDT compounds were the primary contaminants of concern. These contaminants migrated into the sediments of a 78-hectare area of the Potomac River, the Quantico Embayment. Fish tissue contamination resulted in the MCB posting signs along the embayment shoreline warning fishermen to avoid consumption. In this paper, we interpret total PCB (t-PCBs) and total DDT (t-DDT, sum of six DDT, DDD, and DDE isomers) data from monitoring studies. We use the ratio of p,p'-DDD to p,p'-DDE concentrations as a tracer to distinguish site-related from regional contamination. The median DDD/DDE ratio in Quantico Embayment sediments (3.5) was significantly higher than the median ratio (0.71) in sediments from nearby Powells Creek, used as a reference area. In general, t-PCBs and t-DDT concentrations were significantly higher in killifish (Fundulus diaphanus) and carp (Cyprinus carpio) from the Quantico Embayment compared with Powells Creek. For both species, Quantico Embayment fish had mean or median DDD/DDE ratios greater than one. Median ratios were significantly higher in Quantico Embayment (4.6) than Powells Creek (0.28) whole body carp. In contrast, t-PCBs and t-DDT in channel catfish (Ictalurus punctatus) fillets were similar in Quantico Embayment and Powells Creek collections, with median ratios of 0.34 and 0.26, respectively. Differences between species may be attributable to movement (carp and killifish being more localized) and feeding patterns (carp ingesting sediment while feeding). We recommend that environmental scientists use this ratio when investigating sites with DDT contamination.     

Biomagnification factors (fish to Osprey eggs from Willamette River,Oregon, U.S.A.) for PCDDs,PCDFs, PCBs and OC pesticides

A migratory population of 78 pairs of Osprey (Pandion haliaetus) nesting along the Willamette River in westernOregon was studied in 1993. The study was designed to determinecontaminant concentrations in eggs, contaminant concentrationsin fish species predominant in the Ospreys diet, andBiomagnification Factors (BMFs) of contaminants from fish specieseaten to Osprey eggs. Ten Osprey eggs and 25 composite samplesof fish (3 species) were used to evaluate organochlorine (OC)pesticides, polychlorinated biphenyls (PCBs), polychlorinateddibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans(PCDFs). Mercury was also analyzed in fish. Geometric meanresidues in Osprey eggs were judged low, e.g., DDE 2.3 g g^-1 wet weight (ww), PCBs 0.69 g g^-1, 2,3,7,8-TCDD 2.3 ng kg^-1, and generally well below known threshold values for adverse effects on productivity, and the population was increasing. Osprey egg residue data presentedby River Mile (RM) are discussed, e.g., higher PCDDs were generally found immediately downstream of paper mills and eggsfrom the Willamette River had significantly elevated PCBs and PCDDs compared to reference eggs collected nearby in the CascadeMountains. Prey remains at nest sites indicated that the Largescale Sucker (Catostomus macrocheilus) and NorthernPikeminnow (Ptychocheilus oregonensis) accounted for an estimated 90.1% of the biomass in the Osprey diet, and composite samples of these two species were collected from different sampling sites throughout the study area for contaminant analyses. With the large percentage of the fishbiomass in the Osprey diet sampled for contaminants (and fisheaten by Ospreys similar in size to those chemically analyzed),and fish contaminant concentrations weighted by biomass intake, a mean BMF was estimated from fish to Osprey eggs for the largeseries of contaminants. BMFs ranged from no biomagnification(0.42) for 2,3,7,8-TCDF to 174 for OCDD. Our findings for themigratory Osprey were compared to BMFs for the resident HerringGull (Larus argentatus), and differences are discussed. Webelieve a BMF approach provides some basic understanding ofrelationships between contaminant burdens in prey species offish-eating birds and contaminants incorporated into their eggs,and may prove useful in understanding sources of contaminants inmigratory species although additional studies are needed.     

PBDEs, PCBs, and DDE in eggs and their impacts on aplomado falcons (Falco femoralis) from Chihuahua and Veracruz, Mexico

Eggs from aplomado falcons (Falco femoralis septentrionalis) nesting in Chihuahua and Veracruz, Mexico, were analyzed for organochlorine pesticides, PCBs, and PBDEs. p,p′-DDE was the only organochlorine found in all eggs at concentrations ranging from 0.13 to 7.85 μg/g wet weight. PCBs ranged from 0.04 to 2.80 μg/g wet weight and PBDEs from 62 to 798 ng/g lipid weight. DDE concentrations in eggs were not significantly different among regions; however, PCBs were significantly greater (P = 0.015) in Tinaja Verde, Chihuahua than in the other three regions. Also, PBDEs were significantly higher (P < 0.0001) in eggs from Veracruz than in those from Chihuahua. DDE concentrations in eggs were much lower than those associated with eggshell thinning. PBDEs and PCBs were lower than those reported in raptors from industrialized countries. Overall, contaminant concentrations observed suggest no likely impact on hatching success. The PBDE concentrations are among the first to be reported in raptor species in Mexico.     

Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.