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Dacthal and chlorophenoxy herbicides and chlorothalonil fungicide in eggs of osprey (Pandion haliaetus) from the Duwamish–Lake Washington–Puget Sound area of Washington state, USA
Abstract
Current-use chlorophenoxy herbicides including 2,4-dichlorophenoxyacetic acid, dicamba, triclopyr, dicamba, dimethyl tetrachloroterephthalate (DCPA or dacthal), and the metabolite of pyrethroids, 3-phenoxybenzoic acid (3-PBA), and the fungicide, chlorothalonil, were investigated in the eggs of osprey (Pandion haliaetus) that were collected from 15 sites from five study areas Puget Sound/Seattle area of Washington State, USA. DCPA differs from acidic chlorophenoxy herbicides, and is not readily hydrolyzed to free acid or acid metabolites, and thus we developed a new method. Of the 12 chlorophenoxy herbicides and chlorothalonil analyzed only DCPA could be quantified at six of these sites (2.0 to 10.3 pg/g fresh weight). However, higher levels (6.9 to 85.5 pg/g fresh weight) of the unexpected DCPA structural isomer, dimethyl tetrachlorophthalate (diMe-TCP) were quantified in eggs from all sites. diMe-TCP concentrations tended to be higher in eggs from the Everett Harbor area. As diMe-TCP is not an industrial product, and not commercially available, the source of diMe-TCP is unclear. Regardless, these findings indicate that DCPA and diMe-TCP can be accumulated in the food chain of fish-eating osprey, and transferred in ovo to eggs, and thus may be of concern to the health of the developing chick and the general reproductive health of this osprey population.
... Pyrethroids have not been detected (see Table 2 and figure 4), in any Osprey analyzed in this study. Given the extreme rarity of investigation of these compounds in the literature on wildlife, further studies are probably needed to really set the overall contamination of aquatic systems by pyrethroids, despite weaker toxicity compared to organophosphates and carbamates for mammals and wild birds [20,21]. ...
... As in the case of organochlorine pesticides and carbamates, herbicide concentrations remained low, and probably have very little impact on the conservation of the species, but the total sample size is too small for a definitive conclusion. Moreover, insofar as herbicides are rarely analyzed in comparable studies of the literature, very few items are available for comparison [21]. ...
... As in the case of the osprey, carbamates and pyrethroids pesticides were not detected in tissues of cormorants in this study. In this case also, the diet of cormorants, based on aquatic prey (fish and crayfish) probably explains the low or the absence of transfer of carbamates to the predator and seems to confirm the very low accumulation of pyrethroids in aquatic systems, at least in predators and top predators food compartments [20,21]. It is likely that these values situated below the detection limits of current analytical methods and not likely to increase in the future won't constitute a threat to the conservation of the species. ...
The basin of the Loire River in France, because of its size and its quite good conservation state, still houses a large variety of species in fresh and brackish waters, belonging to all components of food webs. However several species are threatened by habitat degradation, development of waterways, current climate change and the accumulation in the aquatic environment of toxic chemicals, especially pesticides, from human activities. By their respective trophic levels and requirements in terms of habitat, several animal species can be considered as good indicator species of global contamination, bioaccumulation and biomagnification of toxic contaminants in rivers, estuaries, reservoirs and lakes. Since the end of the eighties, scientific programs are conducted to enhance general knowledge on different species about ecology, new habitat foraging, diet, and contamination by xenobiotics in France, where pesticides use is one of the biggest in the world.
A specific standard measure method of various compounds was developed for domestic and wild animal tissues. 55 pesticides, including 9 organochlorine pesticides (Lindane, Endosulfan, DDE, DDD, DDT, Heptachlor, Heptachlor epoxyde, Aldrin and Metoxychlor), 20 organophosphate and carbamate pesticides (Dichlorvos, Carbofuran, Mevinphos, Phorate, Phorate oxon, Phorate sulfone, Methiocarbe, Terbufos, Diazinon, Disulfoton, Chlorpyriphos methyl, Chlorpyriphos ethyl, Fenitrothion, Pyrimiphos methyl, Malathion, Fenthion, Parathion, Methidathion, Disulfoton sulfone, Triazophos), 7 pyrethroids pesticides (Tefluthrin, cyhalothrin, permethrin, Cifluthrin 2, Cypermethrin 2, Fenvelarate cis and Deltamethrin), 11 Herbicides (Trifluralin, Atrazin, Atrazin-desethyl, Simazin, Terbuthylazin, Diuron, Linuron, Alachlor, Metolachlor, Cyanazin, Epoxyconazole) and 8 anticoagulant rodenticides (bromadiolone, chlorophacinone, difenacoum, difethialone, warfarin, coumatetralyl, brodifacoum, flocoumafen) were quantified in tissues by gas chromatography or GC/MS spectrometry. Sampled species were chosen among native and introduced species, in order to illustrate the current structure of main trophic webs in Western Europe. For ethical and legal reasons, sampling operations were conducted under appropriate authorizations using a non-invasive approach, especially concerning rare or declining species. Osprey (Pandion haliaetus), European otter (Lutra lutra), great cormorant (Phalacrocorax carbo), brown trout (Salmo trutta fario) and chub (Leuciscus cephalus) were chosen as representative of flagship or common native species, whereas catfish (Ameiurus melas), spiny-cheek crayfish (Orconectes limosus), signal crayfish (Pacifastacus leniusculus), red swamp crayfish (Procambarus clarkii) and asiatic clam (Corbicula fluminea) where chosen as representative of introduced and invasive species.
Organochlorine pesticides (mainly DDTs residues and lindane) were the most frequently detected compounds among almost all species, with moderate or quite high concentrations ranging between 0,5 and 8,2 ug.kg of fresh weight. This suggested recent uses of banned pesticides, e.g. DDTs. Some organophosphate pesticides (mainly dichlorvos) were also rarely detected. Concerning herbicides, Atrazin, Linuron and Terbuthilazin were detected in fish tissues but almost never found in tissues of predators or invertebrates species. These results suggest a variable transfer of pesticides with trophic level, between “recycling” species (invertebrates) “prey” species (fish) and “predator” species (otter, cormorant or osprey) depending on pesticides family. Anticoagulant rodenticides were only detected in otter tissues, with values ranging from 0,5 to 1,2 ug.kg of fresh weight, suggesting an intoxication risk of this species by secondary poisoning during control operations of rodent populations.
Significant variations were sometimes observed between sampling sites (i.e. geographical variations in concentrations) and between species. Our results confirm the status of several species as sentinels for aquatic environment quality evaluation and bioaccumulation of pesticides in food webs.
None of the studied species is currently threatened by extinction following contamination, as confirmed by regular monitoring. Nevertheless, toxicological consequences of pesticides contamination on individuals or little populations should not be totally excluded. Populations monitoring should be continued, to illustrate mid- or long-term effect of contamination, synergies or antagonisms between compounds and to evaluate toxicological effects of pesticides from fish on consumers or wild top-predators olike tters, cormorants or ospreys.
Chapter will describe field observations and laboratory measurements of pesticide concentrations in wild species of Loire River Catchment in France, and will analyse contamination and transfer ways, magnification of the compounds, detoxication ways and consequences on species conservation.
... Nevertheless, some studies demonstrated a direct effect of herbicides on herbivorous mammals or bird diversity or abundance during land use modifications (Santillo et al. 1989a,b). Bioaccumulation potential of herbicides to a top predator was recently confirmed by a study in Washington State (USA) on sediments, fish and ospreys (Chu et al. 2007). Furthermore, recent studies underlined a direct impact of herbicides, particularly triazines, on fish and amphibians' reproduction or survival (Langlois et al. 2009; Tillitt et al. 2010). ...
... These results lead to several hypotheses: - Pyrethroids pesticides may be quickly degraded or metabolized by animals; - Pyrethroids pesticides may be little concerned by bioaccumulation in aquatic food chains; - Global accumulation and transfer of recently used pyrethroids is very low for the moment, but is able to raise in the future with increasing uses. Metabolite of pyrethroids (3-phenoxybenzoic acid 3-PBA) was investigated in osprey eggs of the Washington State, USA (Chu et al. 2007) without being found. Complementary studies are needed to precisely evaluate general contamination of fauna by pyrethroids pesticides. ...
... particular intoxication sign. As for OP and CA pesticides, concentrations of herbicides measured in tissues and low frequency of herbicide detection leads to a probable weak impact of these compounds on species' conservation. Nevertheless, herbicides were very rarely searched in ospreys and very few data are available in literature for comparison. Chu et al. (2007) reported contamination of osprey eggs by a Dacthal structural isomer, indicating that some herbicides could be accumulated in ospreys with a potential reproductive impact on populations.Table 6. Contamination of ospreys by herbicides and fungicides (mg.kg -1 wet weight). ...
... DCPA has been classified as a group C-possible human carcinogen (US EPA 1998). It is a herbicide to control the overgrowth of annual grasses and some annual broad-leaved weeds (Chu et al. 2007). Terbuthylazine (TBA) was only detected in three composite mass groups of C. gariepinus. ...
Many of South Africa’s freshwater impoundments are compromised by pesticide pollution, and the Roodeplaat Dam, near Pretoria, is no exception. This paper is, to the best of our knowledge, the first report of the herbicides Dacthal, metribuzin, simazine, tebuthiuron, terbuthylazine, and the fungicides azoxystrobin, carbendazim, epoxiconazole, metalaxyl (Ridomil), propiconazole, pyrimethanil and thiabendazole in a South African freshwater impoundment. This short note reports on the screening results of water and muscle tissue samples against a comprehensive library of pesticides, herbicides and fungicides in the polluted Roodeplaat Dam. Muscle samples of Oreochromis mossambicus screened positive for p,p'-DDE and p,p'-DDD and for DCPA (chlorthal-methyl). The muscle tissue of Clarias gariepinus screened positive for p,p'-DDE and p,p'-DDD, chlorpyrifos, trans-chlordane, DCPA and terbuthylazine. The presence of these pesticides, herbicides and fungicides in this impoundment is of great concern as there is substantial evidence of adverse health effects in fish exposed to these chemicals.
... According to Karatas et al. (2015), in vegetable, tobacco, households, cotton, cereals, and other crops throughout the world, pyrethroids are widely used as insecticides. Also they are widely applied for the control of ectoparasites of domestic animals (Ural and Sağlam 2005, Chu et al. 2007, Enayati et al. 2010. For pyrethroids, the primary target sites are the voltage-gated sodium channels (VGSCs) (Jin et al. 2010, Rinkevich et al. 2012, Rinkevich et al. 2013, Karatas et al. 2015, Nieradko-Iwanicka and Borzecki 2016. ...
... Based on predicted chemical structure-activity relationships (SAR), 12 currently used chlorophenoxy herbicides along with the fungicide chlorothalonil were hypothesized to accumulate in osprey eggs. Of those compounds, chlorothalonil, the herbicide dacthal, and its isomer dimethyl tetrachlorophthalate (diMe-TCP) were consistently found, though at low picograms per gram (ww) concentrations (Chu et al., 2007). To our knowledge, this is the first time dacthal and diMe-TCP were reported in bird eggs. ...
... The term 'currently used pesticide' used here means pesticides which are not subject to worldwide restrictions. These CUPs attract our interest because of their continued high production volume and occurrence in aquatic biota, [10] [11] [12] osprey eggs, [13] human breast milk [14] and Arctic media (e.g. air, water and ice). ...
Surface seawater and air samples collected from the German Bight (North Sea) in March, May and July 2010 were analysed for hexachlorobenzene (HCB) and hexachlorocyclohexanes (HCHs), five currently used pesticides (CUPs) (trifluralin, endosulfan, chlorpyrifos, dacthal and quintozene) and pentachloroanisole (metabolite). Volatilisation from local surfaces was considered to be the main source of these chemicals to the air (excluding trifluralin). Long-range transport from Western Europe partly contributed to the higher air concentrations observed in July whereas riverine input was the main source for HCHs and pentachloroanisole in seawater in March. Air-sea gas exchange of HCB and alpha-HCH in the German Bight was found to be near equilibrium, probably reflecting the past use of these chemicals, their wide dispersal in the environment and lack of contemporary use. Deposition of target compounds from the air to seawater was observed to be much higher in July compared with depositional fluxes for March and May, except for chlorpyrifos (with volatilisation fluxes in all sampling periods: similar to 25 ngm (2) day (1)). Concentrations of trifluralin in seawater appear to have decreased since its restriction of use in European Union member states, with net volatilisation from seawater observed in March (flux: 6.3 +/- 7.2 ng m(-2) day(-1)). With the exception of chlorpyrifos, our results indicate that volatilisation from local sources combined with long-range transport from Western Europe and subsequent deposition are important pathways for these compounds to German Bight seawater during summer periods.
... The number of nests represented by eggs with concentrations >1,000 ppb was limited; thus, the 1,000-ppb effect level must be regarded as tentative. Current-use chlorophenoxy herbicides including 2,4-dichlorophenoxyacetic acid, dicamba, triclopyr, dicamba, dimethyl tetrachloroterphthalate (DCPA or dacthal) and the metabolite of pyrethroids, 3-phenoxybenzoic acid (3-PBA), and the fungicide chlorothalonil were investigated in the eggs of ospreys collected at 15 nests in Puget Sound, Washington (Chu et al., 2007). Dacthal was quantified in six eggs; however, an unexpected DCPA structural isomer, dimethyl tetrachlorophthalate (diMe-TCP), was quantified in eggs from all sites. ...
Osprey (Pandion haliaetus) populations were adversely affected by DDT and perhaps other contaminants in the United States and elsewhere. Reduced productivity, eggshell thinning, and high DDE concentrations in eggs were the signs associated with declining osprey populations in the 1950s, 1960s, and 1970s. The species was one of the first studied on a large scale to bring contaminant issues into focus. Although few quantitative population data were available prior to the 1960s, many osprey populations in North America were studied during the 1960s and 1970s with much learned about basic life history and biology. This article reviews the historical and current effects of contaminants on regional osprey populations. Breeding populations in many regions of North America showed post-DDT-era (1972) population increases of varying magnitudes, with many populations now appearing to stabilize at much higher numbers than initially reported in the 1970s and 1980s. However, the magnitude of regional population increases in the United States between 1981 (first Nationwide Survey, ∼8,000 pairs), when some recovery had already occurred, 1994 (second survey, ∼14,200), and 2001 (third survey, ∼16,000-19,000), or any other years, is likely not a simple response to the release from earlier contaminant effects, but a response to multi-factorial effects. This indirect "contaminant effects" measurement comparing changes (i.e., recovery) in post-DDT-era population numbers over time is probably confounded by changing human attitudes toward birds of prey (shooting, destroying nests, etc.), changing habitats, changing fish populations, and perhaps competition from other species. The species' adaptation to newly created reservoirs and its increasing use of artificial nesting structures (power poles, nesting platforms, cell towers, channel markers, offshore duck blinds, etc.) are two important factors. The timing of the initial use of artificial nesting structures, which replaced declining numbers of suitable trees at many locations, varied regionally (much later in the western United States and Mexico). Because of the increasing use of artificial nesting structures, there may be more ospreys nesting in North America now than ever before. Now, with the impact of most legacy organic contaminants (DDT, other organochlorine [OC] pesticides, polychlorinated biphenyls [PCB], polychlorinated dibenzo-p-dioxins [PCDD], polychlorinated dibenzofurans (PCDF]) greatly reduced or eliminated, and some osprey populations showing evidence of stabilizing, the species was proposed as a Worldwide Sentinel Species for evaluating emerging contaminants. Several emerging contaminants are already being studied, such as polybrominated diphenyl ethers (PBDE) and perfluorinated acids and sulfonate compounds (PFC). The many advantages for continued contaminant investigations using the osprey include a good understanding of its biology and ecology, its known distribution and abundance, and its ability to habituate to humans and their activities, which permits nesting in some of the potentially most contaminated environments. It is a top predator in most ecosystems, and its nests are relatively easy to locate and study with little researcher impact on reproductive success.
... Based on predicted chemical structure-activity relationships (SAR), 12 currently used chlorophenoxy herbicides along with the fungicide chlorothalonil were hypothesized to accumulate in osprey eggs. Of those compounds, chlorothalonil, the herbicide dacthal, and its isomer dimethyl tetrachlorophthalate (diMe-TCP) were consistently found, though at low picograms per gram (ww) concentrations (Chu et al., 2007). To our knowledge, this is the first time dacthal and diMe-TCP were reported in bird eggs. ...
In the United States, many fish and wildlife species have been used nationwide to monitor environmental contaminant exposure and effects, including carcasses of the bald eagle (Haliaeetus leucocephalus), the only top avian predator regularly used in the past. Unfortunately, bald eagles are sensitive to investigator intrusion at the nest. Thus, the osprey (Pandion haliaetus) is evaluated as a potential sentinel species for aquatic ecosystems. Several characteristics support the choice of the osprey as a sentinel species, including: (1) fish-eating diet atop the aquatic food web, (2) long-lived with strong nest fidelity, (3) adapts to human landscapes (potentially the most contaminated), (4) tolerates short-term nest disturbance, (5) nests spatially distributed at regular intervals, (6) highly visible nests easily located for study, (7) ability to accumulate most, if not all, lipophilic contaminants, (8) known sensitivity to many contaminants, and (9) nearly a worldwide distribution. These osprey traits have been instrumental in successfully using the species to understand population distribution, abundance, and changes over time; the effects of various contaminants on reproductive success; how contaminants in prey (fish on biomass basis) contribute to egg concentrations (i.e., biomagnification factors); and spatial residue patterns. Data summarized include nesting population surveys, detailed nesting studies, and chemical analyses of osprey egg, organ, blood, and feather samples for contaminants that bioaccumulate and/or biomagnify in aquatic food webs; and biochemical evaluations of blood and various organs. Studies in the United States, Canada, Mexico, Europe, and elsewhere have shown the osprey to be a useful sentinel species for monitoring selected environmental contaminants, including some emerging contaminants in lakes, reservoirs, rivers, and estuaries.
Agricultural practices are a major cause of the current loss of biodiversity. Among postwar agricultural intensification practices, the use of plant protection products (PPPs) might be one of the prominent drivers of the loss of wildlife diversity in agroecosystems. A collective scientific assessment was performed upon the request of the French Ministries responsible for the Environment, for Agriculture and for Research to review the impacts of PPPs on biodiversity and ecosystem services based on the scientific literature. While the effects of legacy banned PPPs on ecosystems and the underlying mechanisms are well documented, the impacts of current use pesticides (CUPs) on biodiversity have rarely been reviewed. Here, we provide an overview of the available knowledge related to the impacts of PPPs, including biopesticides, on terrestrial vertebrates (i.e. herptiles, birds including raptors, bats and small and large mammals). We focused essentially on CUPs and on endpoints at the subindividual, individual, population and community levels, which ultimately linked with effects on biodiversity. We address both direct toxic effects and indirect effects related to ecological processes and review the existing knowledge about wildlife exposure to PPPs. The effects of PPPs on ecological functions and ecosystem services are discussed, as are the aggravating or mitigating factors. Finally, a synthesis of knowns and unknowns is provided, and we identify priorities to fill gaps in knowledge and perspectives for research and wildlife conservation.
Graphical Abstract
In this study, about fifty otters from the basin of the Loire River (France) were analyzed in the context of a toxicological study funded by the Plan Loire Grandeur Nature. Individuals were recovered non-invasively, using a network of collection of otters killed by traffic collisions with vehicles. The chemical elements analyzed were the organochlorine and organophosphorus pesticides, carbamates, pyrethroids, herbicides, anticoagulants, PCBs and metals. Detectable levels of organochlorine pesticides and PCBs characterized all otters analyzed, with mean values reaching 2-15 mg.kg -1 , respectively. Concentrations of other analyzed pesticides remained very low. For metals, contamination of otters was systematic for lead and mercury, the latter being relatively abundant in tissues of several individuals. A significant trend to increasing concentrations of pesticides and PCBs by going towards the downstream parts of basins was shown. The inter-individual variations in concentrations were marked. Global values of contamination were below the toxicological threshold defined for the conservation of the species, and the current dynamics of populations within the basin of the Loire seems to confirm this. However, the potential effects of mixtures of compounds remain poorly studied.
In this paper, a pretreatment method for high-performance liquid chromatography (HPLC) determination of cypermethrin (CY) in microbial degradation systems was systemically studied, primarily to solve the problem of inaccurate determination of CY concentration caused by its uneven distribution in the systems. A suitable pretreatment method was established, including sampling, extraction and dehydration of CY. Partial sampling could be taken for bacterial and yeast systems in which CY was uniformly dispersed by an emulsifying agent, while total sampling was only suitable for mold systems with or without an emulsifying agent. CY could be fully extracted from the samples in which microbial cells were disrupted by ultrasonic treatment with acetonitrile under ultrasonic condition. The extract could be effectively dehydrated and purified by passing it through an anhydrous Na(2)SO(4) column followed by an elution with acetonitrile. The determination of CY in the pretreated sample by HPLC showed a high precision [relative standard deviation (RSD) = 1.14%, n = 5] and a good stability over a period of five days (RSD = 1.57%, n = 5). The recoveries of CY in microbial degradation systems at three different spiked levels ranged from 95.68 to 108.09% (RSD = 0.50-5.87%, n = 5).
In this study, osprey (Pandion haliaetus) tissues collected in France were used for contaminants analyses by a non-invasive approach. 53 pesticides (organochlorine, organophosphate, carbamate, pyrethroids, herbicides, anticoagulant rodenticides), 13 PCBs, and 5 metals (mercury, lead, cadmium, copper and arsenic) were quantified in liver of 14 individual samples. PCBs and mercury were frequent (mean 0.5 mg/kg, range < d.l.-2.6 mg/kg and mean 3.4 mg/kg, range < d.l.-16.3 mg/kg wet weight, respectively). Inter-individual variations in contaminant diversity and amounts were noticed. Immediate conservation of the species in the country does not seem to be threatened by global contamination.
An Osprey Pandion haliaetus population nesting along the lower 410 km of the Columbia River (94 occupied nests in 1997; increased to 103 in 1998) was studied to evaluate the merit in using the species for monitoring selected contaminants that biomagnify in food chains. We collected a "sample egg" from 29 Osprey nests and analyzed egg contents for residue concentrations of organochlorine pesticides, polychlorinated biphenyls, polychlorinated dibenzo- p-dioxins, polychlorinated dibenzofurans, and total mercury. Reproductive success was monitored at all nests, including those with an egg collected, to evaluate possible contaminant effects on reproductive success. For purposes of this investigation, the lower Columbia River study area was subdivided into four distinct reaches primarily based on locations of major industrial areas, urban boundaries and other known sources of pollution. Residue concentrations in Osprey eggs for most contaminants did not vary significantly among reaches. However, eggs collected from Reach II (immediately below the Bonneville Dam hydroelectric facility) contained significantly higher concentrations of PCB 105 (nearly all PCB congeners were higher) compared to eggs collected in Reach I (upstream) or Reach III (downstream), although three other large hydroelectric dams are located in Reach I. An historic landfill of electrical equipment containing PCBs was reported at Bonneville Dam in 2000, two years after completion of this field study. Elevated hexachlorobenzene in eggs collected from Reach III appeared to be associated with an aluminum smelter located nearby. Osprey eggs contained the highest concentrations of p, p'-DDE (DDE) (geometric mean 4872 µg kg-1 wet weight,
Osprey(Pandion haliaetus) eggs were collected during 1995 and 1996 at seven sites along the Fraser and Columbia River systems of British Columbia, Canada, and Washington and Oregon, USA. Fifty-four eggs were placed into a laboratory incubator. Thirty-eight of the hatched chicks were sacrificed within 24 h. Hatching success did not differ among sites and therefore between treatment and reference areas. Residual yolk sacs of eggs collected downstream of the large bleached-kraft pulp mill at Castlegar contained greater mean concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD, 2,930 ng/kg lipid) compared with reference sites such as the Nechako River, an upper tributary of the Fraser system (33.7 ng/kg). Total polychlorinated biphenyls (PCBs) in yolk sacs were also higher at Castlegar and in samples from the Columbia River downstream of Portland, Oregon, compared with those from the Nechako River. Concentrations of measured chemicals, including TCDD toxic equivalents (TEQs), total PCBs, p, p′-dichlorodiphenylethylene (p, p′-DDE), and other organochlorines were not different in eggs that failed to hatch compared with calculated whole-egg values for hatched eggs. There were significant biochemical responses; a hepatic cytochrome P4501A (CYP1A) cross-reactive protein was detected in all samples tested and correlated positively with ethoxyresorufin o-deethylase (EROD) activity and yolk sac concentrations of TEQs and total PCBs. Tissue concentrations of vitamin A compounds varied among sites and correlated positively with yolk sac concentrations of TEQs and PCBs. Morphological, histological, and other physiological parameters, including chick growth, edema, deformities, and hepatic and renal porphyrin concentrations, neither varied among sites nor showed concentration-related effects.
Sewage, a complex mixture of organic and inorganic chemicals, is considered to be a major source of environmental pollution. A random screen of 20 organic man-made chemicals present in liquid effluents revealed that half appeared able to interact with the estradiol receptor. This was demonstrated by their ability to inhibit binding of 17 beta-estradiol to the fish estrogen receptor. Further studies, using mammalian estrogen screens in vitro, revealed that the two phthalate esters butylbenzyl phthalate (BBP) and di-n-butylphthalate (DBP) and a food antioxidant, butylated hydroxyanisole (BHA) were estrogenic; however, they were all less estrogenic than the environmental estrogen octylphenol. Phthalate esters, used in the production of various plastics (including PVC), are among the most common industrial chemicals. Their ubiquity in the environment and tendency to bioconcentrate in animal fat are well known. Neither BBP nor DBP were able to act as antagonists, indicating that, in the presence of endogenous estrogens, their overall effect would be cumulative. Recently, it has been suggested that environmental estrogens may be etiological agents in several human diseases, including disorders of the male reproductive tract and breast and testicular cancers. The current finding that some phthalate compounds and some food additives are weakly estrogenic in vitro, needs to be supported by further studies on their effects in vivo before any conclusions can be made regarding their possible role in the development of these conditions.
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Eggs of ospreys (Pandion haliaetus) were collected over the period 1991 to 1997 at 111 nests in the Fraser and Columbia River drainage systems of British Columbia, Washington, and Oregon. Contents were analyzed for organochlorine (OC) pesticides, polychlorinated biphenyls (PCBs), and total mercury. Blood samples were taken from nestling ospreys at two time points during the 1992 breeding season on the Thompson River and analyzed for non-ortho PCBs. Concentrations of DDE and related compounds showed high variability among individual eggs within study areas and no significant differences in mean concentrations among study areas. Some eggs contained high concentrations of DDE, up to 20 mg/kg (wet weight), for which there were no evident local sources, suggesting that exposure occurred outside of the breeding grounds. Most other OC pesticides measured in osprey eggs showed a similar distribution, although mean concentrations of chlordane-related compounds were generally, and in some cases significantly, higher in samples collected from the Columbia River sites compared to elsewhere. Significantly greater concentrations of PCBs were found in eggs from the Columbia River basin compared to the Fraser. This was attributed to extensive development of hydroelectric generation and related industries on the Columbia system. Significant differences among sites were also found in the pattern of PCB congeners, e.g., eggs from the lower Columbia River site had proportionally greater concentrations of less chlorinated, Aroclor 1242-type PCBs compared to other sites. In contrast, eggs from upper reaches of the Columbia River had relatively greater amounts of Aroclor 1254 and 1260 congeners. Mercury concentrations in osprey eggs tended to be uniform among sites and comparable to those reported in the literature for ospreys nesting on naturally formed lakes and rivers. There were no significant temporal changes in mean concentrations of any of the measured compounds at sites monitored from 1991 to 1997.
A migratory population of 78 pairs of Osprey (Pandion haliaetus) nesting along the Willamette River in western Oregon was studied in 1993. The study was designed to determine contaminant concentrations in eggs, contaminant concentrations in fish species predominant in the Ospreys diet, and Biomagnification Factors (BMFs) of contaminants from fish species eaten to Osprey eggs. Ten Osprey eggs and 25 composite samples of fish (3 species) were used to evaluate organochlorine (OC) pesticides, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs). Mercury was also analyzed in fish. Geometric mean residues in Osprey eggs were judged low, e.g., DDE 2.3 microg g(-1) wet weight (ww), sigma PCBs 0.69 microg 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 presented by River Mile (RM) are discussed, e.g., higher PCDDs were generally found immediately downstream of paper mills and eggs from the Willamette River had significantly elevated PCBs and PCDDs compared to reference eggs collected nearby in the Cascade Mountains. Prey remains at nest sites indicated that the Largescale Sucker (Catostomus macrocheilus) and Northern Pikeminnow (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 fish biomass in the Osprey diet sampled for contaminants (and fish eaten 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 large series of contaminants. BMFs ranged from no biomagnification (0.42) for 2,3,7,8-TCDF to 174 for OCDD. Our findings for the migratory Osprey were compared to BMFs for the resident Herring Gull (Larus argentatus), and differences are discussed. We believe a BMF approach provides some basic understanding of relationships between contaminant burdens in prey species of fish-eating birds and contaminants incorporated into their eggs, and may prove useful in understanding sources of contaminants in migratory species although additional studies are needed.
Pesticide degradation by hydroxyl radicals produced in natural water is often cited as an important dissipation mechanism, yet its significance is rarely assessed with other dissipation processes occurring simultaneously in the aquatic environment. The computer model Exposure Analysis Modeling System (EXAMS) is useful for this purpose because it incorporates other dissipation processes and allows the assessment of their dynamics under different environmental conditions. Rate constants of reaction with photochemically generated hydroxyl radicals were measured for the herbicides sulfometuron, bensulfuron methyl, chlorsulfuron, triclopyr, dicamba, molinate, thiobencarb, 2,4-D, mecoprop, and oxadiazon, for the insecticides chlorpyrifos and imidacloprid, and for the fungicide chlorothalonil by competition kinetic methods and were used as the input value for second-order rate oxidation rate constant (KOX) in EXAMS. Hydroxyl radical degradation was estimated to be most significant in shallow water, where sunlight is less attenuated; however, in relatively clear water, it still could contribute to degradation at greater depths for compounds slowly degraded by other mechanisms. For carbaryl at shallow depths, degradation by hydroxyl radicals was predicted to contribute to less than 1% of the degradation profile at pH 8 to as much as 15% of the profile at pH 6. As unique degradation products may be generated by indirect photolysis mechanisms, it should be possible to use EXAMS to estimate when such products may occur for a particular chemical and environmental situation.
The triethylamine salt formulation of triclopyr was recent- ly registered for use in aquatic sites by the U.S. Environmen- tal Protection Agency for selective control of invasive aquatic and wetland weed species. Research shows that this herbicide and its metabolites have an environmentally compatible deg- radation scenario, an excellent toxicological profile, and the ability to selectively control a variety of exotic weed species, making it a valuable tool for restoring and managing aquatic ecosystems. Laboratory studies show that photolytic processes rapidly degrade triclopyr, indicating a major role in dissipa- tion from aquatic sites. However, subsequent field studies in- dicate that photolysis has a more limited role in the aquatic degradation, likely due to sunlight attenuation in natural wa- ters, and show that metabolic degradation processes assume a more important role. Laboratory investigations show aerobic and anaerobic degradation in hydrosoils is a slower process, and hydrolysis plays a minor role in triclopyr degradation. Field studies conducted in California, Georgia, Minnesota, Missouri, Texas and Washington have shown triclopyr and its TCP and TMP metabolites dissipated from water with half- lives ranging from 0.5 to 7.5, 4.2 to 10.0, and 4.0 to 8.8 days, respectively. Sediment dissipation half-lives ranged from 2.7 to 13.3 days for the same compounds. Half-lives for fish and shell fish ranged from 1.6 to 15.1 days. Results from laborato- ry and field studies indicate dissipation rates of the parent tri-
Residues of dimethyl, 2,3,5,6-tetrachloroterephthalate (DCPA) have been found repeatedly in recent years on a variety of produce grown in California to which this herbicide had not been applied. In response to this problem, drift, volatilization, and dissipation of DCPA were investigated in a circular plot seeded with bunch onions [Allium cepa (L.) var. White Lisbon], and off-site deposition was measured in a surrounding area seeded with parsley [Petroselinum crispum (Mill.) Mansf. var. Green Modified Curl Leaf]. Contamination by residual soil residues remaining on field after harvest was also examined by reseeding the circular plot with parsley. Atmospheric residues detected downwind on resin and filters indicated DCPA moved off-target as a vapor as well as on particles both during and up to 21 d after application. Volatilization flux, measured using the aerodynamic method, reached a maximum rate of 5.6 g ha-1h-1. An estimated 10% of the DCPA applied was lost to the atmosphere within 21 d of application. Deposition of DCPA outside the circular plot was evidenced by residues found on potted parsley plants and soil set out up to 23 m from the treated area. Parsley, seeded around the circular plot at the time of application and sampled 63 d later, contained residues ranging from 51 to 250 μg kg-1 indicating DCPA continued to move off-target in air up to 60 d after application. The mass of DCPA in soil exhibited a log-linear decline from which a 50 d dissipation half-life was calculated. Parsley planted in the circular plot after the onion harvest did not contain DCPA residues when sampled 217 and 336 d after the original application. Results indicated that drift during, and volatilization and subsequent atmospheric transport after, application are potentially important sources of DCPA contamination occurring on nontarget crops in California.
Two chlorinated pesticides, chlorothalonil and Dacthal, have been found at relatively high concentrations in air and precipitation samples taken from around the Great Lakes. Chlorothalonil is a fungicide used mainly on peanuts and potatoes; Dacthal is a pre-emergence herbicide used primarily on onions and broccoli. These compounds were identified using electron capture, negative ionization gas chromatographic mass spectrometry, and they were quantitated by electron capture gas chromatography. The concentrations of these compounds in Great Lakes air and precipitation were as high as or higher than those of other organochlorine pesticides now being measured by the Integrated Atmospheric Deposition Network. Long-term measurements of the atmospheric and precipitation concentrations of these two compounds is recommended.
Two simple and convenient methods are described for the extraction, analysis and clean-up of nine acidic herbicides in water and soil samples. The extracted acidic herbicides were converted into their methyl esters by a modified method using diazomethane. The methylated herbicides were analyzed by gas chromatography with electron-capture detection using a Restek Rtx-35 0.53 mm I.D. capillary column and simultaneously confirmed using an Rtx-5 capillary column. A simple clean-up procedure using a micro disposable Florisil column in also described. The mean recoveries for all herbicides from water were >95% and from soils >86%. The recoveries of herbicides after Florisil column clean-up were greater than 89%. Each sample run required about 25 min, including confirmation. The methods described are suitable as an initial screening procedure in the rapid simultaneous determination of nine acidic herbicides in large numbers of environmental samples at reasonable cost.
2,4-Dichlorophenoxyacetic acid decomposes rapidly in the presence of water and ultra-violet light. This decomposition results in the formation of 2,4-dichlorophenol, 4-chlorocatechol, 2-hydroxy-4-chlorophenoxyacetic acid, 1,2,4-benzenetriol, and, finally, polymeric humic acids. The results with artificial light and with sunlight are essentially identical.
Solid-phase extraction using strong anion exchange disks was evaluated as an alternative extraction method to conventional liquid-liquid extraction (LLE) for the quantitative analysis of the herbicide Dacthal (DCPA) and its mono- and dicarboxylic acid metabolites in ground water. The average recoveries of DCPA and its acid metabolites from deionized water were 93.7 +/- 2.6% and 85.6 +/- 2.5%, respectively. The detection limit of the SAX disk method is 0.05 mu g/L for a 100 mt water sample, While no DCPA was detected in ground water from the Malheur River Basin in eastern Oregon, the total concentrations of the acid metabolites of DCPA in 100 mt samples of ground water ranged from less than the detection limit (0.05 mu g/L) to 158.2 mu g/L and were in good agreement with those determined by means of conventional LLE.
Atmospheric deposition and air−water exchange of two semivolatile pesticides, Dacthal and chlorpyrifos, were compared in a small agricultural watershed in southern Manitoba, Canada, between 1994 and 1996. Dacthal was not used in the watershed nor in the surrounding region. Dacthal concentrations were derived from long-range transport and deposition processes and were lower than those of chlorpyrifos, which was applied locally each year of the study. Maximum concentrations of chlorpyrifos in air (103 ng/m3), precipitation (38 ng/L), and creek water (105 ng/L) were observed during local application periods. The highest Dacthal concentrations (4 ng/L) observed in precipitation occurred during intervals when its use in the U.S. was expected, although a seasonal relationship was not established. Precipitation and gas exchange across the air−water boundary were important pathways of movement for both chlorpyrifos and Dacthal. A net volatilization flux from the entire creek surface was observed for chlorpyrifos (1.4 g, 24 000 ng/m2) in 1995 and for Dacthal in both 1995 (0.37 g, 6300 ng/m2) and 1996 (0.15 g, 2600 ng/m2).
Suspended sediment was isolated from water samples collected from the Mississippi River at Thebes, IL, eight times over a 5-year period from May 1988 through September 1993 in order to evaluate the transport of lipophilic halogenated organic compounds associated with the suspended sedi ment. Two hydrologic extremes were includedthe 1988 drought and the 1993 flood. Halogenated organic compounds included polychlorinated biphenyls (PCBs), hexachlorobenzene, pentachloroanisole, DCPA (dacthal), trifluralin, aldrin, dieldrin, and chlordane components. Sedi ment transport of most of these organic compounds was substantially higher during the 1993 flood than at other sampling times. The extreme transports during the flood were due to unusually high concentrations of some contaminants on the suspended sediment, low to average concentrations of suspended sediment being transported, and unusually high water discharges.
Pesticide degradation by hydroxyl radicals produced in natural water is often cited as an important dissipation mechanism, yet its significance is rarely assessed with other dissipation processes occurring simultaneously in the aquatic environment. The computer model Exposure Analysis Modeling System (EXAMS) is useful for this purpose because it incorporates other dissipation processes and allows the assessment of their dynamics under different environmental conditions. Rate constants of reaction with photochemically generated hydroxyl radicals were measured for the herbicides sulfometuron, bensulfuron methyl, chlorsulfuron, triclopyr, dicamba, molinate, thiobencarb, 2,4-D, mecoprop, and oxadiazon, for the insecticides chlorpyrifos and imidacloprid, and for the fungicide chlorothalonil by competition kinetic methods and were used as the input value for second-order rate oxidation rate constant (KOX) in EXAMS. Hydroxyl radical degradation was estimated to be most significant in shallow water, where sunlight is less attenuated; however, in relatively clear water, it still could contribute to degradation at greater depths for compounds slowly degraded by other mechanisms. For carbaryl at shallow depths, degradation by hydroxyl radicals was predicted to contribute to less than 1% of the degradation profile at pH 8 to as much as 15% of the profile at pH 6. As unique degradation products may be generated by indirect photolysis mechanisms, it should be possible to use EXAMS to estimate when such products may occur for a particular chemical and environmental situation.
We analyzeds streambed sediment and fish in the Central Columbia Plateau in eastern Washington and Idaho for or ganochlorine pesticides and polychlorinated biphenyls (ΣPCB). Our objective was to assess the effects of land use on the occurrence and distribution of these compounds; land uses in the study area included forest, dryland and irrigated farming, and urban. We detected 16 organochlorine compounds in streambed sediment and fish tissue; fish usually had more compounds and a greater frequency of detection. The most frequently detected compound was ΣDDT (sum of six isomers), which was found in 52% of bed sediment samples and 94% of whole fish composite samples. The other commonly detected compounds were dimethyl tetrachloroterephthalate (DCPA), dieldrin, hexachlorobenzene, and Σchlordane (sum of cis- and trans-chlordane, cis- and trans-nonachlor oxychlordane, heptachlor, and heptachlor epoxide). Forest was the only land use with no detections of organochlorine compounds in either fish or bed sediment. Hexachlorobenzene was the only organochlorine pesticide detected at concentrations that differed significantly among land uses: concentrations were higher in the dryland farming areas than in the irrigated farming or urban areas. In agricultural areas irrigated by surface water, ΣDDT concentrations in both streambed sediment and fish tissue were related to the percentage of land irrigated by water delivered via furrows (gravity irrigation), although ΣDDT was not detectable in bed sediments until gravity irrigation exceeded 30%. Because of the relation between gravity irrigation and soil erosion, our study supports the importance of controlling soil erosion in order to reduce the overall loading of organochlorine compounds to surface waters.
Analyses of coho salmon from each of the Great Lakes by a single laboratory produced residue data on the accumulation of environmental contaminants which have been banned, severely restricted, or are currently permitted in the basin. Coho salmon from Lake Superior contained only trace amounts or low levels of most toxic substances quantified; Lake Erie fish were contaminated with low levels of a number of pesticides and industrial compounds; relatively higher residues were detected in coho from Lake Huron and Lake Michigan; and the highest concentrations for a number of compounds were found in fillets from coho from Lake Ontario. Contaminant concentrations in migratory coho salmon indicate open lake contaminant problems rather than point source or nearshore conditions. Tissue residues were less than USFDA action levels, used by many agencies in assessing the severity of fish contaminant problems. Only mirex concentrations in fish collected from Lake Ontario exceeded a USFDA action level. The data reported in this study generally agree with recent findings from individual state contaminant monitoring programs. Problems with varying analytical and sampling techniques preclude direct comparisons with previously published data of other studies.
An analytic method for the determination of phenoxy acid herbicides and 2,4-D esters in soil samples by GC-FID is described. The esterification reaction with MeOH and H(2)SO(4) as catalyst has been used, optimizing experimental variables by the 'Simplex method'. The recoveries in soil samples were between 76 and 97% with relative S.D.s between 4 and 7% (n=4) at level of concentration of 5 and 10 mug ml(-1) for phenoxy acids and 2,4-D esters, respectively.
The plastics industry utilizes a number of organic chemicals which have the potential of producing pulmonary reactions, particularly in susceptible individuals. Five workers are reported who were involved in the production of epoxy resins and developed recurrent respiratory symptoms and physiologic abnormalities following exposure to tetrachlorophthalic anhydride (TCPA). Inhalation challenge with TCPA reproduced their symptoms and demonstrated both an immediate and late (4-6 hours) physiologic response. Although the clinical picture strongly suggested a hypersensitivity reaction, immunologic studies failed to demonstrate precipitating or specific IgE antibody. Avoidance of exposure resulted in resolution of symptoms; however, three of the five individuals had residual functional impairment.
Eggs of wild birds collected for the purpose of measuring concentrations of pesticides or other pollutants vary from nearly fresh to nearly dry so that objective comparisons cannot be made on the basis of weight of the contents at the time of collection. Residue concentrations in the nearly dry eggs can be greatly exaggerated by this artifact.
Valid interpretation of residue data depends upon compensation for these losses. A method is presented for making adjustments on the basis of volume of the egg, and formulas are derived for estimating the volume of eggs of eagles, ospreys, and pelicans from egg measurements. The possibility of adjustments on the basis of percentage of moisture, solids, or fat in fresh eggs is discussed also.
Two metabolites of the herbicide dimethyl tetrachloroterephthalate, (DCPA), monomethyl tetrachloroterephthalate (MM) and tetrachloroterephthalic acid (TCPA), are assayed via high-performance liquid chromatography with ion paring. Samples are analyzed via direct injection, without preparation, and analyte detection is accomplished with an ultraviolet photodiode array detector. The metabolites are extracted from positive samples with a petroleum ether/diethyl ether mixture, derivatized with N,O-bis(trimethylsilyl) trifluoracetamide, and confirmed by way of gas chromatography/mass spectrometry. The HPLC analysis of 200 spiked drinking water samples yielded a recovery range of 92-106% with a mean recovery of 101% for TCPA and a recovery range of 92-101% with a mean recovery of 96% for MM. The minimum detection limits for TCPA and MM were 2.4 and 2.7 micrograms/L, respectively. In addition, the GC/MS analysis of spiked reagent water yielded mean recoveries of 91% for MM and 86% for TCPA. Twenty drinking water samples were split and analyzed by the HPLC and GC/MS methods and by USEPA Method 515.1. Comparable results were obtained. The HPLC method, which is amenable to automation, typically allows for the analysis of up to 40 samples overnight.
The described method permits the determination of the five most important metabolites of the pyrethroids permethrin, cypermethrin, deltamethrin, lambda-cyhalothrin, fenvalerate, phenothrin and beta-cyfluthrin in human urine in one run. The major urinary metabolites of these substances are cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (cis-Cl2CA), trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (trans-Cl2CA), cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (Br2CA), fluoro-3-phenoxybenzoic acid (F-PBA) and 3-phenoxybenzoic acid (3-PBA). After acidic hydrolysis to release the conjugated carboxylic acid metabolites, the analytes were separated from the matrix by means of solid-phase extraction using a reversed-phase column. The components of the eluate were converted to their methyl esters and extracted in hexane. Separation and quantitative analysis of the pyrethroid metabolites was carried out by capillary gas chromatography and mass selective detection. 2-Phenoxybenzoic acid served as an internal standard. The detection limits lay between 0.3 and 0.5 microg per litre urine. The relative standard deviations of the within-series imprecision were between 1% and 6%. The relative recovery rates ranged between 90% and 98%. Using this method we determined the elimination of pyrethroid metabolites in 24-h urine samples from eight pest controllers after indoor application of permethrin. The detected concentrations ranged from 1 to 70 microg g(-1) creatinine.
1. Nine male volunteers were exposed to the pyrethroid insecticide cyfluthrin. The study was performed in an exposure room, where an aerosol containing cyfluthrin was sprayed to obtain atmospheres with mean cyfluthrin concentrations of 160 and 40 micrograms/m3. Four volunteers were exposed for 10, 30 and 60 min at 160 micrograms/m3 and another five volunteers were exposed for 60 min at 40 micrograms/m3. For 160 micrograms/m3 exposure urine samples were collected before and immediately after exposure as well as for the periods 1-2, 2-3, 3-4, 4-5, 5-6, 6-12 and 12-24 h after exposure. For 40 micrograms/m3 exposure urine samples were collected before and 2 h after exposure. 2. The main urinary cyfluthrin metabolites, cis-/trans-3-(2,2-dichlorovinyl)-2,2-dimethylycyclopropane carboxylic acid (DCCA) and 4-fluoro-3-phenoxybenzoic acid (FPBA), were determined. The limit of detection (LOD) for all metabolites was 0.0025 microgram in an urine sample of 5 ml (0.5 microgram/l). After inhalative exposure of 40 micrograms cyfluthrin/m3 air for 60 min, the amount of metabolites in urine collected in the first 2 h after exposure was less than the LOD, namely 0.14 microgram for cis-DCCA, 0.15-0.28 microgram for trans-DCCA and 0.12-0.23 microgram for FPBA. 3. Of the metabolites, 93% was excreted within the first 24 h (peak excretion rates between 0.5 and 3 h) after inhalative exposure of 160 micrograms/m3. The mean half-lives were 6.9 h for cis-DCCA, 6.2 h for trans-DCCA and 5.3 h for FPBA. 4. The mean trans-:cis-DCCA ratio was 1.9 for the time course as well as for each subject. 5. The amount of metabolites in urine depends on the applied dose, on the exposure time and shows interindividual differences.
Osprey (Pandion haliaetus) eggs were collected during 1995 and 1996 at seven sites along the Fraser and Columbia River systems of British Columbia, Canada, and Washington and Oregon, USA. Fifty-four eggs were placed into a laboratory incubator. Thirty-eight of the hatched chicks were sacrificed within 24 h. Hatching success did not differ among sites and therefore between treatment and reference areas. Residual yolk sacs of eggs collected downstream of the large bleached-kraft pulp mill at Castlegar contained greater mean concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD, 2,930 ng/kg lipid) compared with reference sites such as the Nechako River, an upper tributary of the Fraser system (33.7 ng/kg). Total polychlorinated biphenyls (PCBs) in yolk sacs were also higher at Castlegar and in samples from the Columbia River downstream of Portland, Oregon, compared with those from the Nechako River. Concentrations of measured chemicals, including TCDD toxic equivalents (TEQs), total PCBs, p,p'-dichlorodiphenylethylene (p,p'-DDE), and other organochlorines were not different in eggs that failed to hatch compared with calculated whole-egg values for hatched eggs. There were significant biochemical responses; a hepatic cytochrome P4501A (CYP1A) cross-reactive protein was detected in all samples tested and correlated positively with ethoxyresorufin o-deethylase (EROD) activity and yolk sac concentrations of TEQs and total PCBs. Tissue concentrations of vitamin A compounds varied among sites and correlated positively with yolk sac concentrations of TEQs and PCBs. Morphological, histological, and other physiological parameters, including chick growth, edema, deformities, and hepatic and renal porphyrin concentrations, neither varied among sites nor showed concentration-related effects.
Twenty-four pesticides were tested for interactions with the estrogen receptor (ER) and the androgen receptor (AR) in transactivation assays. Estrogen-like effects on MCF-7 cell proliferation and effects on CYP19 aromatase activity in human placental microsomes were also investigated. Pesticides (endosulfan, methiocarb, methomyl, pirimicarb, propamocarb, deltamethrin, fenpropathrin, dimethoate, chlorpyriphos, dichlorvos, tolchlofos-methyl, vinclozolin, iprodion, fenarimol, prochloraz, fosetyl-aluminum, chlorothalonil, daminozid, paclobutrazol, chlormequat chlorid, and ethephon) were selected according to their frequent use in Danish greenhouses. In addition, the metabolite mercaptodimethur sulfoxide, the herbicide tribenuron-methyl, and the organochlorine dieldrin, were included. Several of the pesticides, dieldrin, endosulfan, methiocarb, and fenarimol, acted both as estrogen agonists and androgen antagonists. Prochloraz reacted as both an estrogen and an androgen antagonist. Furthermore, fenarimol and prochloraz were potent aromatase inhibitors while endosulfan was a weak inhibitor. Hence, these three pesticides possess at least three different ways to potentially disturb sex hormone actions. In addition, chlorpyrifos, deltamethrin, tolclofos-methyl, and tribenuron-methyl induced weak responses in one or both estrogenicity assays. Upon cotreatment with 17beta-estradiol, the response was potentiated by endosulfan in the proliferation assay and by pirimicarb, propamocarb, and daminozid in the ER transactivation assay. Vinclozolin reacted as a potent AR antagonist and dichlorvos as a very weak one. Methomyl, pirimicarb, propamocarb, and iprodion weakly stimulated aromatase activity. Although the potencies of the pesticides to react as hormone agonists or antagonists are low compared to the natural ligands, the integrated response in the organism might be amplified by the ability of the pesticides to act via several mechanism and the frequent simultaneous exposure to several pesticides.
Water samples from 30 lakes in Canada and the northeastern United States were analyzed for the occurrence of 27 current-use pesticides (CUPs). Eleven CUPs were frequently detected in lakes receiving agricultural inputs as well as in remote lakes hundreds of kilometers from known application areas. These included the triazine herbicide atrazine and its desethylated degradation product; the herbicides alachlor, metolachlor, and dacthal; the organophosphate insecticides chlorpyrifos, diazinon, and disulfoton; the organochlorine insecticides alpha-endosulfan and lindane; and the fungicides chlorothalonil and flutriafol. For six of the pesticides, empirical half-distances on the order of 560 to 1,820 km were estimated from the water-concentration gradient with latitude. For most of the pesticides, a suite of assessment models failed to predict such atmospheric long-range transport behavior, unless the effect of periods of lower hydroxyl radical concentrations and dry weather were taken into account. Observations and model results suggest that under the conditions prevailing in south-central Canada (relatively high latitude, low precipitation rates), many CUPs will be able to undergo regional-scale atmospheric transport and reach lakes outside areas of agricultural application. When assessing the potential of fairly reactive and water-soluble substances to undergo long-range transport, it is imperative to account for periods of no precipitation, to assure that degradation rate constants are correct, and to apply oxidant concentrations that are valid for the region and time period of interest.
Bed-sediments are a sink for many micro-organic contaminants in aquatic environments. The impact of toxic contaminants on benthic fauna often depends on their spatial distribution, and the fate of the parent compounds and their metabolites. The distribution of a synthetic pyrethroid, permethrin, a compound known to be toxic to aquatic invertebrates, was studied using river bed-sediments in lotic flume channels. trans/cis-Permethrin diagnostic ratios were used to quantify the photoisomerization of the trans isomer in water. Rates were affected by the presence of sediment particles and colloids when compared to distilled water alone. Two experiments in dark/light conditions with replicate channels were undertaken using natural sediment, previously contaminated with permethrin, to examine the effect of the growth of an algal biofilm at the sediment-water interface on diffusive fluxes of permethrin into the sediment. After 42 days, the bulk water was removed, allowing a fine sectioning of the sediment bed (i.e., every mm down to 5 mm and then 5-10 mm, then every 10 mm down to 50 mm). Permethrin was detected in all cases down to a depth of 5-10 mm, in agreement with estimates by the Millington and Quirk model, and measurements of concentrations in pore water produced a distribution coefficient (Kd) for each section. High Kd's were observed for the top layers, mainly as a result of high organic matter and specific surface area. Concentrations in the algal biofilm measured at the end of the experiment under light conditions, and increases in concentration in the top 1 mm of the sediment, demonstrated that algal/ bacterial biofilm material was responsible for high Kd's at the sediment surface, and for the retardation of permethrin diffusion. This specific partition of permethrin to fine sediment particles and algae may enhance its threat to benthic invertebrates. In addition,the analysis of trans/cis-permethrin isomer ratios in sediment showed greater losses of trans-permethrin in the experiment under light conditions, which may have also resulted from enhanced biological activity at the sediment surface.
Determination of 9 acidic herbicides in water and soil by gas chromatography using an electron-capture detector A review of the aquatic environmental fate of triclopyr and its major metabolites
- F Ngan
- T Ikesaki
- D G Petty
- K D Getsinger
- K B Woodburn
Ngan, F., Ikesaki, T., 1991. Determination of 9 acidic herbicides in water and soil by gas chromatography using an electron-capture detector. Journal of Chromatography 1991 (537), 385e395. Petty, D.G., Getsinger, K.D., Woodburn, K.B., 2003. A review of the aquatic environmental fate of triclopyr and its major metabolites. Journal of Aquatic Plant Management 41, 69e75. S. Chu et al. / Environmental Pollution 145 (2007) 374e381
Effects of currently used pesticides in assays for estrogenicity, androgenicity, and aromatase activity in vitro Pesticide hydroxyl radical rate constants: Measure-ments and estimates of their importance in aquatic environments
- H R Andersen
- A M Vinggaard
- T H Rasmussen
- I M Gjermandsen
- E C Bonefeld-Jorgensen
Andersen, H.R., Vinggaard, A.M., Rasmussen, T.H., Gjermandsen, I.M., Bonefeld-Jorgensen, E.C., 2002. Effects of currently used pesticides in assays for estrogenicity, androgenicity, and aromatase activity in vitro. Toxicology and Applied Pharmacology 179, 1e12. Armbrust, K.L., 2000. Pesticide hydroxyl radical rate constants: Measure-ments and estimates of their importance in aquatic environments. Environ-mental Toxicology and Chemistry 19, 2175e2180. Canadian Environmental Protection Act (1999), 2004. Government Notices, Department of the Environment 138, No. 7. <http://canadagazette.gc.ca/ partI/2004/20040214/html/notice-e.html>.
Degradation of Dacthal and its metabo-lites in soil Bulletin of Environmental Contamination and Toxicology 50, 226e231. World Health Criteria 192 Flame Retardants: A General Introduction
- A Wettasinghe
- I L Tinsley
Wettasinghe, A., Tinsley, I.L., 1993. Degradation of Dacthal and its metabo-lites in soil. Bulletin of Environmental Contamination and Toxicology 50, 226e231. World Health Criteria 192, 1997. Flame Retardants: A General Introduction. <http://www.intox.org/databank/documents/chemical/flame/ehc192.htm>.
- S Jobling
- T Reynolds
- R White
- M G Parker
- J P Sumpter
- S Va
- Chu
Jobling, S., Reynolds, T., White, R., Parker, M.G., Sumpter, J.P., 1995. A va S. Chu et al. / Environmental Pollution 145 (2007) 374e381
Government Notices, Department of the Environment
Canadian Environmental Protection Act (1999), 2004. Government Notices,
Department of the Environment 138, No. 7. <http://canadagazette.gc.ca/
partI/2004/20040214/html/notice-e.html>.
Determination of chlorinated acids in water using liquid-solid extraction and gas chromatography with an electron capture detector
- Us Epa Method
A variety of environmentally persistent chemicals, including some phthalate plasticizers, are weakly estrogenic
- Jobling