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The influence of biochemical species differences on acute fish toxicity of organic chemicals.

1. Reported LC50s of hundreds of chemicals and data of many enzymes in many fishes have been reviewed in order to find the hypothesized influence of biotransformation on acute toxicity. 2. Biotransformation of carbaryl was correlated and biotransformation of endrin was inversely correlated with acute toxicity. 3. For most compounds no correlation was found which indicates that either biotransformation is not important in acute toxicity or enzyme activities are not representative parameters to quantify biotransformation reactions.

Animals↗

Lindane decreases forskolin-stimulated cyclic AMP accumulation but does not modify Gs in rat enterocytes.

Treatment of isolated rat enterocytes with the halogenated insecticide lindane (the gamma-isomer of hexachlorocyclohexane, HCCH) did not modify the general membrane fluidity (as estimated by a fluorescence polarization technique) nor the guanine nucleotide binding regulatory protein Gs (as studied by both ADP-ribosylation of its alpha subunit by cholera toxin and Gpp[NH]p stimulation of membrane adenylate cyclase activity). However, lindane decreased in a dose-dependent manner the effect of the diterpene forskolin on direct activation of the adenylate cyclase catalytic subunit. After 5 min of cell treatment with 0.5 mM lindane, the maximal stimulatory effect of forskolin (at 100 microM) decreased by about 50%. There was a certain degree of specificity since delta-HCCH was indeed more potent, whereas dieldrin and endrin (non-lindane related halogenated compounds) behaved as lindane, and alpha- and beta-HCCH were poorly efficient on the inhibition of forskolin stimulation of adenylate cyclase activity. A similar effect of lindane was observed on receptor-stimulated cyclic AMP accumulation by using vasoactive intestinal peptide instead of forskolin. The results on a non-receptor mediated effect of lindane on the adenylate cyclase catalytic subunit itself could be related to: (i) alterations of membrane microdomains surrounding this and other integral proteins which would result in modifications of their activities; and/or (ii) a reciprocal relation between the two main routes of signal transduction so that the activation of protein kinase C (or other Ca(2+)-dependent protein kinases) by lindane would lead to phosphorylation of the adenylate cyclase catalytic subunit.(ABSTRACT TRUNCATED AT 250 WORDS)

1-Methyl-3-isobutylxanthine↗

Pesticides and PCBs in sediments and fish from the Salton Sea, California, USA.

The Salton Sea, the largest manmade lake in California, is officially designated by the State of California as an agricultural drainage reservoir. The purpose of this study was to determine organochlorine and organophosphorous pesticides, as well as polychlorinated biphenyl (PCB) concentrations in sediments and fish tissues in the Salton Sea and evaluate the relative ecological risk of these compounds. Sediment samples were taken during 2000-2001 and fish tissues (Tilapia mossambique, Cynoscion xanthulu) were collected in May 2001. All samples were analyzed for 12 chlorinated pesticides, 6 organophosphorus pesticides, and 55 polychlorinated biphenyl (PCB) congeners. SigmaDichlorodiphenyltrichloroethane (SigmaDDT) and total PCB concentrations observed in sediments ranged from 10 to 40 and 116 to 304 ng/g dry wt, respectively. DDT/DDD ratios in sediments and fish tissues of the northern Sea in 2001 indicated recent DDT exposure. Lindane, dieldrin, dichlorodiphenylethane (DDE) and total PCB concentrations detected in sediments exceeded probable effect levels established for freshwater ecosystems, and pp-DDE and total PCB concentrations were higher than effect range-median values developed for marine and estuarine sediments. In fish liver, concentrations of endrin and SigmaDDT exceeded threshold effect level established for invertebrates. SigmaDDT concentrations detected in fish tissues were higher than threshold concentrations for the protection of wildlife consumers of aquatic biota. DDE concentrations in fish muscles tissues were above the 50 ng/g concentration threshold for the protection of predatory birds. Dimethoate, diazinon, malathion, chlorpyrifos, disulfoton varied from < or = 0.15 to 9.5 ng/g dry wt in sediments and from < or = 0.1 to 80.3 ng/g wet wt in fish tissues. Disulfoton was found in relatively high concentrations (up to 80.3 ng/g) in all organs from Tilapia and Corvina. These results demonstrate continued contamination of specific organochlorine compounds in sediments and resident fish species of the Salton Sea.

Analysis of Variance↗

Characterisation and analysis of persistent organic pollutants and major, minor and trace elements in Calabash chalk.

Analysis of Calabash chalk has been done using energy dispersive X-ray fluorescence spectroscopy (EDXRF), X-ray diffraction (XRD) and pressurised fluid extraction (PFE) followed by gas chromatography (GC) with mass selective detection (MSD). It was found by XRD that the composition of Calabash chalk was an aluminium silicate hydroxide from the kaolin clay group with the possible formula Al(2)Si(2)O(5)(OH)(4). Multi-elemental analysis by EDXRF was able to quantify 22 elements in Calabash chalk including lead at a mean concentration of approximately 40 mg/kg. A range of persistent organic pollutants were identified and quantified in Calabash chalk including alpha lindane, endrin, endosulphan II and p,p'-DDD using PFE-GC-MSD.

Aluminum Silicates↗

Analysis of some organochlorine pesticides in an urban atmosphere (Strasbourg, east of France).

High volume samples of urban air have been collected in Strasbourg, a big city situated in the east of France, for the evaluation of the contamination by organochlorine pesticides. Pesticides (p,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, dieldrin, endrin, gamma-HCH, cis-chlordane, trans-chlordane, alpha-endosulfan, beta-endosulfan, hexachlorobenzene, heptachlor and some of their metabolites: alpha-HCH, 2,4'-DDT, 2,4'-DDD and 2,4'-DDE) were analysed by GC-ECD. Prior to analysis, samples were Soxhlet extracted with a mixture of n-hexane/methylene chloride. The analysis of samples collected in 2001 (n = 6), 2002 (n = 7) and 2003 (n = 5) shows that alpha-HCH and gamma-HCH were detected in all samples (between 0.05 and 4 ng m(-3) and between 0.01 and 1 ng m(-3), respectively) along with aldrin and dieldrin at lower concentrations (between 0.01 and 0.08 ng m(-3) and between 0.02 and 0.09 ng m(-3), respectively). Other pesticides were detected very randomly at very low concentrations. The calculation of the alpha/gamma-HCH ratio shows that hexachlorocyclohexane measured in the atmosphere have a local origin and come probably from contaminated soil by volatilisation. alpha and beta-endosulfan were practically not detected in samples collected in 2001 and 2002 while they were always measured in the gas phase in samples from 2003. This observation can be explained by an increase of volatilisation with the increase of the air temperature. In July, temperature were higher (between 17 and 30 degrees C in climatic station) than in March-May 2001 and 2002 (between 2 and 19 and between 2 and 10, respectively).

Air Pollutants↗

Organochlorinated pesticides in sediments from the Lake Albufera of Valencia (Spain).

Bottom sediment samples from 121 sites of the Lake Albufera of Valencia were analyzed. Dieldrin, endrin, heptachlor and op'-DDT were not detected (<0.01 ng g(-1)) in 88-93% of the sites. Aldrin and HCB concentration ranges were between <0.01 and 0.1 ng g(-1) in 86% and 94% of the sites, respectively. Heptachlor-epoxide and lindane 95% confidence intervals were 0.2-0.5 and 0.06-0.12, respectively. The greatest average concentration corresponds to pp'-DDE, pp'-DDD and pp'-DDT. The sum of six isomers and derivatives of the DDT average concentration reaches 2.1 ng g(-1), as opposed to 2.7 ng g(-1) for the sum of 13 pesticides considered. In the site with a major contamination, 27.0 ng g(-1) of pp'-DDD and 12.8 ng g(-1) of pp'-DDT were accumulated. The DDE:DDT proportion average was 0.37, indicating an aged DDT contamination. Concentrations of pesticides in sediments were compared to three sediment quality guidelines, and indicated that a low biological effects level can be expected in either sediments or aquatic organisms.

DDT↗

Modification of UNIFAC parameter table Revision 5 for representation of aqueous solubility and 1-octanol/water partition coefficient for POPs.

In order to represent aqueous solubility and 1-octanol/water partition coefficient for POPs (persistent organic pollutants) by the UNIFAC model, two pairs of group interaction parameters in Revision 5 of the UNIFAC parameter table were modified. First, the pair of interaction parameters between the aromatic carbon-chloride (ACCl) and water (H2O) groups were corrected by minimizing the deviation between the experimental and calculated values of these properties for chlorinated benzenes, polychlorinated biphenyls, and polychlorinated dibenzo-p-dioxins and dibenzofurans. The corrected interaction parameters provided a better representation of both properties than the calculation results obtained in early works using the UNIFAC model. Second, the unknown pair of interaction parameters between the chloroalkene (Cl(C=C)) and H2O groups, which are required for calculating those properties of the other five POPs (aldrin, chlordane, endrin, dieldrin, and heptachlor), were newly determined from the experimental data on their properties. Finally, this study shows that Revision 5 could also predict solubility of POPs in some organic solvents. The modified parameter table is first suggested as the UNIFAC parameter table applicable to various phase equilibria including aqueous or nonaqueous solubility and partition coefficient of POPs.

1-Octanol↗

Residues of organochlorine pesticides in Hong Kong soils.

It was short of research on the organochlorine pesticides (OCPs) residues in the soils of Hong Kong. Sixty-six representative soil samples were collected from the 46 sites covering five types of land uses in Hong Kong. Hexachlorohexanes (HCH) and 7 Stockholm Convention OCPs were analyzed by gas chromatograph (GC) equipped with a Nickel 63 electronic capture detector (muECD). The results presented that HCH and 5 Stockholm Convention pesticides were detected in Hong Kong soils although the detectable ratio varies to a great extent. The concentration sequence of the five detectable OCPs was HCH > dichlorodiphenyltrichloroethane (DDT) > hexachlorobenzene (HCB) approximately = Endrin > alpha-endosulfan. Among the OCPs and their homologues or isomers, beta-HCH and p,p'-DDE were the two predominant substances according to the concentrations and detectable ratios, concentrations of which in soils were averagely 6.12 microg kg(-1) and 0.41 microg kg(-1) respectively. Soil horizon samples of 0-10 cm, 10-30 cm and >30 cm depth were selected from nine soil profiles to demonstrate the depth distributions of DDT and HCH in soil profiles. Concentrations of HCH tended to increase gradually from the topsoil to bottom layer while the lowest concentration of DDT is usually found in the subsoil (10-30 cm) in most sampling sites. In addition, close correlations of pH(KCl) and total organic carbon (TOC) with HCH indicated an effect on the residues of HCH caused by these two soils properties, but such relationships were not found with DDT or other OCPs.

DDT↗

Vertical distributions of persistent organic pollutants (POPs) caused from organochlorine pesticides in a sediment core taken from Ariake bay, Japan.

Persistent organic pollutants (POPs) of organochlorine pesticides such as dichlorodiphenyl trichloroethane (DDTs) and its metabolites, hexachlorobenzene (HCB), heptachlor, chlordane compounds (CHLs), aldrin, dieldrin, endrin, mirex and isomers of hexachlorocyclohexane (HCHs), were analyzed in sediment cores collected from Ariake Bay, Japan. Although Chikugo River has the largest flow in Ariake Bay, the total concentration of POPs in surface sediment was found in St.3, mouth of the Yabe River, where that level was two times higher than St.1, mouth of the Chikugo River. It could be assumed that the potential source of POPs contamination is relatively close to this study area. Relatively high residue levels of HCB, HCHs and DDTs in sediment core were found during the period from 1967 to 1970. In this layer, the HCB concentration investigated in sediment cores of Ariake Bay was maximum, 2.6 ng g(-1) dry weight and higher than that of Tokyo Bay and subsequently detected in deeper sediment cores. The ratio of (DDD+DDE)/SigmaDDTs was high in top sediments (0-2 cm). Although there was a concentration of DDTs in the top sediment, it was noticed that DDT emission did not cause direct input of DDT recently. The HCHs determined in upper sediment cores might be originated from long-range accumulation in environment after dispersing of technical-grade HCH. Moreover, the CHLs, dieldrin and heptachlor concentrations were detected and recently increased in sediment core. POPs in sediment cores of Ariake Bay based on the possibility of PCP contamination during the early 1960s were reflected.

DDT↗

Application of solid-phase microextraction to the study of the photochemical behaviour of five priority pesticides: "on-fiber" and aqueous photodegradation.

Solid-phase microextraction (SPME) is applied to study the photochemical degradation of five priority pesticides: atrazine, alachlor, aldrin, dieldrin, endrin. Analyses were carried out by gas chromatography-mass spectrometry. The possibility of studying the photochemical degradation of the target compounds in solid-phase microextraction fibers, "photo-SPME", is evaluated employing different SPME coatings. The target analytes were extracted from aqueous solutions using different commercial coatings and then, the fibers were exposed to UV light. Results indicated that on-fiber photodegradation takes place in a considerably major extent using PDMS coating for an irradiation time of 30min. On-fiber photodegradation kinetics of each analyte were determined by UV irradiation of the PDMS for different times. A large number of photoproducts were generated and they were tentatively identified by means of their mass spectra and with the aid of literature. In this way, main photodegradation mechanisms could be postulated. Aqueous photodegradation studies followed by SPME were performed and compared with photo-SPME. All the photoproducts detected in the aqueous experiments were previously found in the photo-SPME experiments. This study shows the potential of photo-SPME to evaluate the photo-transformation of organic pollutants.

Gas Chromatography-Mass Spectrometry↗

Development of a removable multi-column-switching system for gas chromatography.

A removable column-switching device for a commercially available gas chromatograph has been developed. To this end, the challenges of the equipment's high temperature stability, of the flow of gas through stand-by columns, of catalytically effective stainless steel surfaces, of the cooling trap effects within valves and the limited oven space are dealt with. The developed column-switching system was investigated in terms of dead volume (tailing factor), adsorption (Grob test) and degradation (Endrin test). This GC column-switching system shows comparable results with analyses that do not employ column switching. For example, it was possible to avoid effects, such as adsorption and decomposition. This system can automatically test the suitability of as many as eight separating columns to analyze unknown samples. The GC column-switching system thus serves to increase efficiency in the selection or screening of stationary phases with GC method developments.

Adsorption↗

Recombinogenic activity of 10 chemical compounds in male germ cells of Drosophila melanogaster.

The Drosophila melanogaster male germ cells are sensitive to the recombinogenic activity of chemical compounds. In our experiments, we have employed four recessive markers located on the 2nd chromosome: dumpy (dp, 13.0), black (b, 48.5), cinnabar (cn, 57.5), and brown (bw, 104.5); b and cn flank the centromere. Three-day-old larvae, heterozygous for these markers, were treated chronically by oral administration with the test compounds. The chemicals already shown to be positive or negative in the assay systems to test chemical agents in D. melanogaster are three carcinogens (4-nitroquinoline N-oxide, hydroxylamine HCl, and acrylamide), four herbicides (maleic hydrazide, alachlor, trifluralin, and amitrol), and three insecticides (endrin, piperonyl butoxide, and allethrin). In our study, some compounds induced recombinogenic effects in Drosophila premeiotic male germ cells, and comparison of our results with those reported in the literature with the Drosophila wing somatic mutation and recombination assay showed that the somatic cells and the germinal cells have a differential response to the defined compounds.

Animals↗

Evaluation of the concentration of HCH, DDT, HCB, PCB and PAH in the sediments along the lower stretch of Hugli estuary, West Bengal, northeast India.

Detailed analyses of persistent organic pollutants (POPs) such as hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs), hexachlorobenzene (HCB) and congeners of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in surface sediments from the coastal estuarine environment of West Bengal, northeast India allowed the evaluation of the contamination status, distribution and possible pollution sources. HCH, DDT, HCB, PCB and PAH were identified compounds in all the samples, whereas the concentrations of chlorinated pesticides (trans-eptachlorepoxide, dieldrin, endrin, metaoxychlor and mirex) were below the detection limits and were not of great concern. The pesticides did demonstrate markedly different distributions reflecting different agricultural and domestic usage in the region. The range of concentrations of HCH, HCB, DDT and PCBs in the sediments were 0.11-0.40, <0.05-0.98, 0.18-1.93 and 0.18-2.33 ng/g dry wt, respectively. Overall elevated levels of HCB, DDT and PCB were recorded at Babughat, a very closely located site of the metropolitan megacity Calcutta. Fluoranthene (flu) and pyrene (py), the dominant 4-ring PAHs, also showed an abrupt elevated concentrations at Babughat with values of 214 and 144 ng/g dry wt, respectively. Among the isomers and metabolites of HCH, DDT and PCB, alpha-HCH, pp'-DDT and PCB (101), PCB (118), PCB(153) and PCB (138) were found to be dominant. High ratios of metabolites of DDT to SigmaDDTs reveal recent use of DDT in this coastal environment. Fluoranthene, pyrene, 1,2-benzo(a)anthracene and chrysene formed the dominant congeners out of 19 identified PAHs. The sources of contamination are closely related to human activities such as domestic and industrial discharge, automobile exhausts, street runoff, slum sewage, agricultural chemicals and soil erosion due to deforestation as well as atmospheric transport. This study is compared to other coastal and estuarine environments in India and abroad. The baseline data can be used for regular ecological monitoring, considering the industrial and agricultural growth around this important estuarine ecosystem.

Agriculture↗

Organochlorine and organophosphorous pesticide residues in the Ouémé River catchment in the Republic of Bénin.

The Ouémé River is one of the most important rivers in the Republic of Bénin. It is 510 km long and its catchment drains 75% of the country. In this study, organochlorine and organophosphorous pesticide residues were measured in more than 35 sediment samples collected on nine locations along the Ouémé River from upstream to downstream. Except for one location, Tanéka-Koko, all areas were contaminated by more than 20 pesticides. Organochlorine pesticides identified in sediment samples included pp'-DDE, op'-DDD, pp'-DDD, op'-DDT, pp'-DDT, alpha-endosulfan, beta-endosulfan, endosulfan sulphate, alpha-HCH, beta-HCH, lindane, aldrin, dieldrin, endrin, telodrin, isodrin, cis- and trans-heptachlorepoxide, hexachlorbutadiene, hexachlorobenzene and octachlorostyrene. The organophosphorous pesticide chlorpyrifos, used in a new formulation to protect cotton, was also identified. In some areas, the concentrations of organochlorine pesticides in the sediment of the Ouémé River exceeded environmental quality standards and are reason for concern.

Benin↗

Determination of endocrine disruptors in Kafue lechwe (Kobus leche kafuensis) samples from the Lochinvar National Park of Zambia.

Analysis of serum, whole blood and liver tissue samples from Kafue lechwe in the Lochinvar National Park of Zambia for suspected endocrine disrupting compounds revealed high concentrations for some of the compounds. 45 samples of serum, whole blood and liver tissue were extracted by liquid-liquid extraction followed by an analysis using Gas Chromatography-Electron Capture Detection (GC-ECD). The following endocrine disruptors were analyzed: deltamethrin, aldrin, endosulfan, dieldrin, pp-DDD, heptachlor, d-t-allethrin, pp-DDE, endrin and pp-DDT. For all the samples, dieldrin showed the highest concentration ranging from 1.7 to 44.4 microg/ml in serum and whole blood sample extracts and 0.10-5.1 microg/g wet weight in liver sample extracts. The most frequently detected was deltamethrin in 62% of the samples. Percent recoveries in spiked laboratory blanks ranged between 60% and 100% while calculated detection limits ranged from 0.004 to 0.21 microg/ml for all the endocrine disruptors evaluated. Where endocrine disruptors were detected, the concentrations of most of them far exceeded the maximum residue limits (MRLs) and the extraneous maximum residue limits (EMRLs) set by the Codex Alimentarius of the United Nations (UN), Food and Agricultural Organization (FAO).

Animals↗

Residues of organochlorinated pesticides in soils from the Czech Republic.

National POPs inventories carried out currently in many countries as a part of the implementation of Stockholm Convention revealed the need for detailed information about a distribution of pollutants in various regions. Screening for the residues of selected organochlorinated pesticides (chlordane, heptachlor, dieldrin, aldrin, endrin, isodrin, endosulfan I, endosulfan II, methoxychlor, mirex) in soil and biotic samples from the Czech Republic was performed. Although these pesticides have never been used in large quantities in this region, results indicate that their residues still persist in the top layer soils more than 20 years after they have been banned. The fact that their soil concentrations in the mountains are generally higher than those in agricultural areas, and detection of the traces of pesticides that have never been used in this region suggest on their occurrence in soils due to the atmospheric redistribution rather than as a result of direct application.

Agriculture↗

A biomimetic absorbent for removal of trace level persistent organic pollutants from water.

A novel biomimetic absorbent containing the lipid triolein was developed for removing persistent organic pollutants (POPs) from water. The structural characteristics of the absorbent were obtained by SEM and a photoluminescence method. Under optimum preparation conditions, triolein was perfectly embedded in the cellulose acetate (CA) spheres, the absorbent was stable and no triolein leaked into the water. Dieldrin, endrin, aldrin and heptachlor epoxide were effectively removed by the CA--triolein absorbent in laboratory batch experiments. This suggests that CA-triolein absorbent may serve as a good absorbent for those selected POPs. Triolein in the absorbent significantly increased the absorption capacity, and lower residual concentrations of POPs were achieved when compared to the use of cellulose acetate absorbent. The absorption rate for lipophilic pollutants was very fast and exhibited some relationship with the octanol--water partition coefficient of the analyte. The absorption mechanism is discussed in detail.

Absorption↗

Consumption advisories for salmon based on risk of cancer and noncancer health effects.

The levels of dioxins/furans, polychlorinated biphenyls (PCBs), and chlorinated pesticides were determined in farmed salmon for eight regions in Europe, North America, and South America, in salmon fillets purchased in 16 cities in Europe and North America, and in five species of wild Pacific salmon. Upon application of US Environmental Protection Agency (USEPA) methods for developing fish consumption advisories for cancer from mixtures of all of these substance for which USEPA has reported a cancer slope factor, the most stringent recommendation, for farmed salmon from northern Europe, was for consumption of at most one meal every 5 months in order to not exceed an elevated risk of cancer of more than 1 in 100,000. Farmed salmon from North and South America triggered advisories of between 0.4 and one meal per month. Retail market samples, in general, reflected levels found in regionally farmed fish, although much of the US salmon comes from Chile, which had somewhat lower contaminant levels than the North American farmed samples. Upon consideration of all of these organochlorine compounds as a mixture, even wild Pacific salmon triggered advisories of between one and less than five meals per month. The advisories are driven by the non-dioxin-like PCBs and pesticides and not by dioxins/furans and coplanar PCBs. For noncancer effects for contaminants where USEPA has provided a reference dose only endrin and PCBs triggered any significant advisory. For both of these in the worst case, farmed salmon from northern Europe, the advice was not more than three meals per month.

Animals↗