Toxaphene chemistry: separation and characterisation of selected enantiomers of the Polychloropinene mixtures

The primary goal for the study presented here was the preparation and characterisation of enantiomeric pure chlorobornane standards (Toxaphene). In this context, we partially modeled the procedure for Polychloropinene production in the former USSR. The initial reaction was ionic addition of hydrogen chloride to (1S)-alpha-pinene resulting predominantly in (1S)-2-endo-chlorobornane. Further photochlorination gave mixtures of chlorinated terpenes with different average content of Cl per molecule. The resulting mixtures were separated on a silica-gel column and a number of known hepta to decachlorobornanes were identified in fractions with the help of NMR and GC (using electron capture and mass spectrometric detection)--but in very unusual ratios as compared to the technical Toxaphene mixture formerly produced by Hercules (USA). Also several previously unknown congeners were isolated or detected. Three of the isolated congeners were obtained in crystalline state and X-ray crystallography showed their enantiomeric purity.     

Bioaccumulation of per- and polyfluorinated alkyl substances (PFAS) in selected species from the Barents Sea food web

The present study reports concentrations and biomagnification potential of per- and polyfluorinated alkyl substances (PFAS) in species from the Barents Sea food web. The examined species included sea ice amphipod (Gammarus wilkitzkii), polar cod (Boreogadus saida), black guillemot (Cepphus grylle) and glaucous gull (Larus hyperboreus). These were analyzed for PFAS, polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs) and polybrominated diphenyl ethers (PBDEs). Perfluorooctane sulfonate (PFOS) was the predominant of the detected PFAS. Trophic levels and food web transfer of PFAS were determined using stable nitrogen isotopes (delta(15)N). No correlation was found between PFOS concentrations and trophic level within species. However, a non-linear relationship was established when the entire food web was analyzed. Biomagnification factors displayed values >1 for perfluorohexane sulfonate (PFHxS), perfluorononanoic acid (PFNA), PFOS and SigmaPFAS(7). Multivariate analyses showed that the degree of trophic transfer of PFAS is similar to that of PCB, DDT and PBDE, despite their accumulation through different pathways.     

Influence of Substrate on Bioaccumulation of 14C-Paraquat in Compost Worms Eisenia foetida

Contamination of soil with pesticides can be evaluated using toxicity tests with worms because their ecological niche makes them good bioindicators. Bioaccumulation in compost worms of [methyl- ¹⁴C] paraquat (1,1′-dimethyl-4,4′-bipyridinium dichloride) was measured after three-month exposure in two substrates with differing physicochemical characteristics, in particular their organic matter and clay contents. The treatments were 1.2, 12, and 120 μg paraquat g^?1 substrate. The action of the worms did not influence the loss of ¹⁴C from the substrates, as the ¹⁴C-recovered was essentially quantitative at the end of the study in both the presence and absence of the worms. The organic matter and clay contents of the substrates determined the extent of the paraquat uptake by the worms; worms from the substrate with smaller amounts of clay and organic matter had the higher values of the bioconcentration factor (BCF), these being about 5 (fresh-weight basis) and independent of the application rate. The BCF values in the substrate containing more organic matter and clay were smaller but increased from 1.1 to 3.8 with the increasing rates of application. However, in both substrates the amounts of paraquat bioaccumulated in the worms was always less than 1% of that applied, indicating the very strong binding of paraquat to the substrates and hence low availability to the worms.     

PCBs and other organochlorines in human tissue samples from the Welsh population: I--Adipose

The general exposure of humans to polychlorinated biphenyls (PCBs) and SigmaDDT (i.e., p,p'-DDT + p,p'DDE = p,p'-DDD) in Wales (UK) was determined through the analysis of adipose tissue samples collected from 75 individuals during post-mortem examinations in 1990-1991. Fifty PCB congeners were screened, of which 29 were identified in most of the samples. Congener IUPAC numbers 138, 153 and 180 were the most abundant compounds, accounting for an average of 55% of the SigmaPCB congeners analysed. SigmaPCB concentrations varied between 0.2 and 1.8 microg g(-1) of adipose tissue and were positively correlated with the donors age and negatively associated with the percentage of lipid in the adipose tissue. A progressive change in the congener pattern was noted with increasing subject age. Tissue from older individuals generally contained a relatively high proportion of the more persistent and higher chlorinated congeners. SigmaDDT concentrations ranged from 0.11 to 5.6 microg g(-1) adipose tissue, with p,p'-DDE contributing 96% towards the SigmaDDT concentration. SigmaDDT levels were also positively correlated with age. No significant differences in the SigmaPCB and SigmaDDT concentrations were noted between males and females, between people living in rural and urban locations or with the subjects' body weight at the time of their death.     

PCBs and other organochlorines in human tissue samples from the Welsh population: II--Milk

Polychlorinated biphenyl (PCB) and SigmaDDT (i.e. p,p'-DDT + p,p'-DDE = p,p'-DDD) concentrations were determined from the analysis of 115 Welsh breast milk samples collected in 1990 and 1991. Fifty PCB congeners were screened, of which 24 were identified in most samples. The PCB congener pattern was consistent between individual milk samples, with IUPAC congeners 28, 138, 153 and 180 being the most abundant and accounting for an average of 50% of the SigmaPCB concentrations determined. PCB concentrations varied between 2 and 70 ng g(-1) whole milk, were positively correlated with age, and negatively correlated with the total lactation period and with the percent lipid content of the milk. PCB pattern distributions differed between milk and adipose tissue samples. Human milk had a higher proportion of tri- (18 and 28), tetra- (44, 52 and 66) and pentachlorinated biphenyls (101) compared to human adipose tissue. SigmaDDT concentrations ranged from 0.3 to 71 ng g(-1) of whole milk, with p,p'-DDE contributing towards an average of 92% of the SigmaDDT concentrations. SigmaDDT levels were also positively correlated with age and negatively associated with the lactation period, though these correlations were rather weak. No significant differences in the SigmaPCB and SigmaDDT concentrations were noted between milk samples from donors living in rural and urban locations, or between the subjects' body weight, smoking habits or diet.     

Electrokinetic remediation of organochlorines in soil: enhancement techniques and integration with other remediation technologies

Electrokinetic remediation has been increasingly used in soils and other matrices for numerous contaminants such as inorganic, organic, radionuclides, explosives and their mixtures. Several strategies were tested to improve this technology effectiveness, namely techniques to solubilize contaminants, control soil pH and also couple electrokinetics with other remediation technologies. This review focus in the experimental work carried out in organochlorines soil electroremediation, aiming to systemize useful information to researchers in this field. It is not possible to clearly state what technique is the best, since experimental approaches and targeted contaminants are different. Further research is needed in the application of some of the reviewed techniques. Also a number of technical and environmental issues will require evaluation for full-scale application. Removal efficiencies reported in real contaminated soils are much lower than the ones obtained with spiked kaolinite, showing the influence of other factors like aging of the contamination and adsorption to soil particles, resulting in important challenges when transferring technologies into the field.     

Bioaccumulation and catabolism of prometryne in green algae

Investigation on organic xenobiotics bioaccumulation/biodegradation in green algae is of great importance from environmental point of view because widespread distribution of these compounds in agricultural areas has become one of the major problems in aquatic ecosystem. Also, new technology needs to be developed for environmental detection and re-usage of the compounds as bioresources. Prometryne as a herbicide is widely used for killing annual grasses in China and other developing countries. However, overuse of the pesticide results in high risks to contamination to aquatic environments. In this study, we focused on analysis of bioaccumulation and degradation of prometryne in Chlamydomonas reinhardtii, a green alga, along with its adaptive response to prometryne toxicity. C. reinhardtii treated with prometryne at 2.5-12.5 μg L(-1) for 4 d or 7.5 μg L(-1) for 1-6 d accumulated a large quantity of prometryne, with more than 2 mg kg(-1) fresh weight in cells exposed to 10 μg L(-1) prometryne. Moreover, it showed a great ability to degrade simultaneously the cell-accumulated prometryne. Such uptake and catabolism of prometryne led to the rapid removal of prometryne from media. Physiological and molecular analysis revealed that toxicology was associated with accumulation of prometryne in the cells. The biological processes of degradation can be interpreted as an internal tolerance mechanism. These results suggest that the green alga is useful in bioremediation of prometryne-contaminated aquatic ecosystems.     

Accumulation features of persistent organochlorines in resident and migratory birds from Asia

Concentrations of organochlorine contaminants including polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene (HCB) were determined in the resident and migratory birds, which were collected from India, Japan, Philippines, Russia (Lake Baikal) and Vietnam. Accumulation patterns of organochlorine concentrations in resident birds suggested that the predominant contaminants of each country were as follows: Japan--PCBs Philippines--PCBs and CHLs, India--HCHs and DDTs, Vietnam--DDTs, and Lake Baikal--PCBs and DDTs. The migratory birds from Philippines and Vietnam retained mostly the highest concentrations of DDTs among the organochlorines analyzed, indicating the presence of stopover and breeding grounds of those birds in China and Russia. On the other hand, migratory birds from India and Lake Baikal showed different patterns of organochlorine residues, reflecting that each species has inherent migratory routes and thus has exposure to different contaminants. Species which have breeding grounds around the Red Sea and Persian Gulf showed high levels of PCBs, indicating the presence of areas heavily polluted by PCBs in the Middle East.     

Coronaviruses in humans and animals: the role of bats in viral evolution

Environmental Science and Pollution Research - Bats act as a natural reservoir for many viruses, including coronaviruses, and have played a crucial epidemiological role in the emergence of many...     

Influence of nocturnal vertical stability on daytime chemistry: A one-dimensional model study

Nocturnal chemistry can play an important role in determining the initial morning conditions for daytime chemistry in urban areas. However, the impact on daytime O₃ levels is difficult to assess as the suppression of vertical trace gas transport leads to highly altitude dependent nocturnal chemistry, in particular with respect to the removal and conversion of nitrogen oxides (NO_x) and volatile organic compounds (VOC). One-dimensional (1-D) chemical transport model calculations for different nighttime vertical stabilities and different ozone formation regimes (i.e. NO_x- vs. VOC-sensitive) were performed assuming a 1000 m high daytime boundary layer and a growing nocturnal boundary layer reaching 200 m height at the end of the night. Exclusion of NO₃ chemistry from the model leads to daytime O₃ concentration changes from ?4% to +16% for different O₃ sensitivities. In all cases strong nocturnal vertical concentration profiles of NO_x, O₃, NO₃ and N₂O₅ and a dependence of these profiles on vertical stability were found at night. The nocturnal NO_x loss averaged over the lowest 1000 m changes by 9–24% for different vertical stabilities and ozone sensitivities. The impact of nocturnal vertical stability leads to 7–12% difference in O₃ concentration in the morning and ～0–2.5% in the afternoon.     

Interlaboratory analysis of high molecular weight organochlorines in ambient air

High volume air samples were collected in Boston, MA, and Columbia, SC using a glass fiber filter — polyurethane foam trap, and the pooled sample extracts from each location were distributed among nine laboratories for organochlorine analysis. Polychlorinated biphenyls (PCB) were reported by all laboratories, with relative standard deviations (RSDs) ranging from 26–39 % for total PCB. The total PCB concentration in Boston was 7.1 ng m⁻³, compared to 4.4 ng m⁻³ in Columbia. Other organochlorines identified by three or more laboratories included hexachlorobenzene and the pesticides DDT, DDE, chlordane, dieldrin, endrin, hexachlorocyclohexane, and polychloroterpenes. RSDs for most pesticides ranged from 35–75% and as high as 116% for polychloroterpenes (quantified as toxaphene). In general, pesticide levels were an order of magnitude higher in Columbia than in Boston.     

NMR and molecular modeling in environmental chemistry: prediction of 13C chemical shifts in selected C10-chloroterpenes employing DFT/GIAO theory

Accurate predictions of 13C NMR chemical shifts (standard error approximately 1.7 ppm) are achieved for a subset of chlorinated bornanes by empirical scaling of shifts from GIAO calculations with geometries obtained from HF/6-31G* calculations. The optimized molecular geometries were compared with X-ray structures for three of the toxaphene components most frequently detected in environmental samples (Parlar nos. 26, 50 and 62), and the concordance between the experimental and calculated values was found to be satisfactory. Taken overall, the results indicate that theoretical methods hold great promise for rationalizing 13C NMR chemical shifts in organohalogen compounds. However, it appeared that the DFT/GIAO shifts need to be empirically scaled to achieve good numerical agreement with experimental shifts in chlorinated bornanes. Obviously, there is a need to develop new computational methods to describe the large deshielding effects of chlorine atoms properly.     

Atmospheric deposition of organochlorines (PCBs and pesticides) in northern France

Bulk deposition measurements were made in northern France for a number of organochlorines (PCBs, HCB, pp'DDE, alpha-HCH and gamma-HCH) over a 1-y period, at urban, semi-rural, rural and forest sites located in accordance with prevailing wind direction. The west-east rise of PCB bulk deposition (average annual values as sigma 7) ranged from 12.2 to 46.8 ng l(-1) and showed the anthropogenic influence arising from towns, industries, storage areas and landfills over continental areas. The values were maximal at the urban site 3, Paris (122 ng l(-1)) and were still high at the eastern site 6, Abreschviller near landfills (62 ng l(-1)). Also, the highest annual deposits were found at sites 3 and 6 (Paris and Abreschviller), 38.6 and 47.3 microgm-2, respectively, i.e. 3.6 and 4 times higher than the western site value: Pleumeur. A temporal trend was observed, at the urban site where a rise occurred (up to 441 ng l(-1)) in March and April. PCB distribution according to the chlorination degree displayed high proportions of 3 Cl and 4 Cl congeners, particularly in the forest area. Annual gamma-hexachlorocyclohexane (gamma-HCH) concentration values at sites 1 (Ouessant) and 2 (Pleumeur) were close to the background noise (1.7 ng l(-1)). At the agricultural (4) and the urban (3) sites, values were maximal (19.2 and 15.9 ng l(-1)) with peaks in spring and autumn. At Pleumeur, without any local input, negative correlations were found between PCB/temperature (r = -0.503, p < 0.05), HCB/temperature ( r = -0.549, p < 0.01) and gamma-HCH/temperature ( r = -0.675, p < 0.01). A clear influence of south-west winds upon the magnitude of PCB fluxes throughout the sites was noticed. Whereas there was no global decrease of PCB contamination since 1986, the general trend of gamma-HCH total deposits was a 10-time fall, as a result of the restricting legislation in use.     

Reproductive transfer of organochlorines in viviparous surfperch, Ditrema temmincki

To discuss the maternal-fetal transfer of persistent organic pollutants (POPs) in viviparous fish, the whole-body burdens of POPs were determined in gravid surfperches from Otsuchi Bay, Japan, and in their fetuses. The concentrations were 2.75-15.5 times higher in the maternal tissue. To compare the characteristics of the maternal-fetal transfer between species with different gestation systems, reports on the striped dolphin and long-finned pilot whales were studied. The transfer rates of POPs in surfperches were 0.6-6.0%, while in marine mammals they were 3.0-9.4%. The difference in transfer rates may derive from the difference in their reproductive systems. On the other hand, as in marine mammals, selective transfer of POPs was seen in surfperches. The transfer rates were higher in less hydrophobic compounds such as dieldrin, and lower in more hydrophobic compounds such as DDTs. A new transfer factor is also discussed which instantly indicates the difference in the concentrations between mother and fetus.     

Bioaccumulation of decamethylcyclopentasiloxane in perch in Swedish lakes

Decamethylcyclopentasiloxane (D5), a high production volume chemical used in personal care products, enters the environment both via air and sewage treatment plant (STP) recipients. It has been found in fish, and there is concern that it may be a bioaccumulative substance. In this work D5 was analyzed in perch from six Swedish lakes that did not receive STP effluent, and in perch and sediment from six lakes that received STP effluent. In the lakes receiving the STP effluent, the D5 concentrations in sediment varied over three orders of magnitude and were correlated with the number of persons connected to the STP normalized to the surface area of the receiving body. In the lakes not receiving effluent, the D5 levels in perch were all below the LOQ, while D5 was above the LOQ in almost all perch from lakes that received effluent. The D5 concentrations in perch and sediment from the lakes receiving STP effluent were correlated. This shows that STP effluent is a much more important source of D5 to aquatic ecosystems than atmospheric deposition, and that the risk of adverse effects of D5 on aquatic life will be greatest in small recipients receiving large amounts of STP effluent. The bioaccumulation of D5 was compared to that of PCB 180 on the basis of multimedia bioaccumulation factors (mmBAFs), which describe the fraction of the contaminant present in the whole aquatic environment (i.e. water and surface sediment) that is transferred to the fish. In four of the six lakes the mmBAF of D5 was >0.3 of the mmBAF of PCB 180. Given that PCB 180 is a known highly bioaccumulative chemical, this indicates that the bioaccumulation of D5 in perch is considerable.     

Bioaccumulation and physiological effects of mercury in Sesbania drummondii

The accumulation of mercury and its effect on growth, photosynthesis and antioxidative responses were studied in Sesbania drummondii seedlings. Mercury concentration in shoots as well as in the roots increased with increasing Hg concentrations in the growth solution. The accumulation of Hg was more in roots than shoots. At 100 mg l-1 Hg concentration, shoots accumulated 998 mg Hg kg -1 dry weight (dw) while roots accumulated 41,403 mg Hg kg-1 dw. Seedlings growth was not significantly affected at lower concentrations of Hg. A concentration of 100 mg l-1 Hg inhibited growth by 36.8%, with respect to control. Photosynthetic activity was assessed by measuring chlorophyll a fluorescence by determination of Fv/Fm and Fv/Fo values. Photosynthetic integrity was not affected up to 50 mg l-1 Hg concentration, however, concentrations higher than 50 mg l-1 affected photosynthetic integrity. Sesbania responded to Hg induced oxidative stress by modulating non-enzymatic antioxidants [glutathione (GSH) and non-protein thiols (NPSH)] and enzymatic antioxidants: superoxide dismutase (SOD), ascorbate peroxidase (APX) and glutathione reductase (GR). Glutathione content and GSH/GSSG ratio increased up to a concentration of 50 mg l-1 while slight down at 100 mg l-1 Hg. The content of NPSH significantly increased with increasing Hg concentrations in the growth medium. The activities of antioxidative enzymes, SOD, APX and GR followed the same trends as antioxidants first increased up to a concentration of 50 mg l-1 Hg and then slight decreased. The results of present study suggest that Sesbania plants were able to accumulate and tolerate Hg induced stress using an effective antioxidative defense mechanisms.     

Bioaccumulation of PCBs in Arctic seabirds: influence of dietary exposure and congener biotransformation

Four seabird species and their prey (zooplankton or fish) were collected in the Barents Sea to determine how dietary exposure, cytochrome P450 (CYP) enzyme activities and sex influenced their hepatic PCB concentrations and accumulation patterns. Five males and five females from each seabird species (little auk (Alle alle), Brunnich's guillemot (Uria lomvia), black guillemot (Cepphus grylle) and black-legged kittiwake (Rissa tridactyla)) were analysed. PCB concentrations could not be explained directly by carbon source (delta13C) or trophic position (delta15N), but by a combination of dietary parameters (delta13C, delta15N, migratory pattern, age) and contaminant metabolism. Contrary to previous studies, the PCB pattern differed among seabirds, with a higher proportion of persistent congeners (% of PCB-153, RPCB-153) in black-legged kittiwake than in auks. The PCB pattern also differed among auks, with little auk as the most efficient biotransformer (highest RPCB-153 values of persistent congeners). Based on high RPCB-153 values, Brunnich's guillemot poorly metabolised ortho-meta-unsubstituted congeners, whereas black guillemot poorly metabolised meta-para unsubstituted congeners. Species-specific differences in PCB biotransformation were confirmed by metabolic indices, where PCB patterns in seabirds were adjusted for PCB pattern in prey. The relative contribution of ortho-meta-unsubstituted congeners to SigmaPCBs decreased with increasing EROD activity. There were no differences in PCB concentrations, PCB patterns or cytochrome P450 enzyme activities between males and females. CYP P450 activities (CYP1A- and CYP2B/3A-like: EROD and testosterone 6beta-hydroxylation, respectively) were low and did not correlate with concentrations of non- or mono-ortho Cl-substituted PCBs (NO- and MO-PCBs), or with total toxic equivalent concentrations (TEQs) for dioxin-like effects of NO- and MO-PCBs.     

Contamination status of persistent organochlorines in human breast milk from Japan: recent levels and temporal trend

Contamination levels of persistent organochlorines (OCs) such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), and chlordane compounds (CHLs) was examined in human breast milk collected during 2001-2004 from Fukuoka prefecture in Japan. The concentrations of OCs such as dioxins and related compounds, DDTs, CHLs and HCB in human breast milk from primiparae were comparable to or slightly higher than the data obtained during 1998, indicating that the levels of these contaminants in Japanese human breast milk have not decreased since 1998 and Japanese are continuously exposed to these chemicals, presumably via fish intake. In addition, OC levels in human breast milk from primiparae were significantly higher than those from multiparae, implying elimination of OCs via lactation. Furthermore, significant positive correlations were observed between levels of OCs in human breast milk and the age of primiparae. These results indicate that the mothers with higher age may transfer higher amounts of OCs to the first infant than to the infants born afterwards through breast-feeding, and hence the first born children might be at higher risk by OCs.     

Bioaccumulation and uptake routes of perfluoroalkyl acids in Daphnia magna

Perfluoroalkyl acids (PFAs), one kind of emerging contaminants, have attracted great attentions in recent years. However, the study about their bioaccumulation mechanism remains scarce. In this research, the bioaccumulation of six kinds of PFAs in water flea Daphnia magna was studied. The uptake rates of PFAs in D. magna ranged from 178 to 1338 L kg^?1 d^?1, and they increased with increasing perfluoroalkyl chain length; the elimination rates ranged from 0.98 to 2.82 d^?1. The bioaccumulation factors (BAFs) of PFAs ranged from 91 to 380 L kg^?1 in wet weight after 25 d exposure; they increased with increasing perfluoroalkyl chain length and had a significant positive correlation with the n-octanol/water partition coefficients (log K_ow) of PFAs (p < 0.05). This indicated that the hydrophobicity of PFAs plays an important role in their bioaccumulation. The BAFs almost kept constant when the PFA concentrations in aqueous phase increased from 1 to 10 μg L^?1. Scenedesmus subspicatus, as the food of D. magna, did not significantly affect the bioaccumulation of PFAs by D. magna. Furthermore, the body burden of PFAs in the dead D. magna was 1.08–2.52 times higher than that in the living ones, inferring that the body surface sorption is a main uptake route of PFAs in D. magna. This study suggested that the bioaccumulation of PFAs in D. magna is mainly controlled by their partition between organisms and water; further research should be conducted to study the intrinsic mechanisms, especially the roles of protein and lipid in organisms.     

Influence of selected fixed parameters on pulse-jet fabric filter operation

The effect of (a) fixing the time interval between cleaning pulses or (b) fixing the maximum pressure drop at which cleaning is started, on the performance of the fabric filter was investigated.A maximum pressure drop value of 2500 Pa:

• 1.(a) minimized the effect of the filter medium resistance;
• 2.(b) reduced the energy consumption by the filter;
• 3.(c) minimized the dust emission from the fabric filter to the surrounding atmosphere.