The use of gas chromatography with ion-trap MS/MS detection for the determination of planar PCBs in biota and sediment

Combining capillary GC with ion-trap detection in the MS/MS mode allows the determination of trace levels of the highly toxic PCB congeners, CB 77, 126 and 169 in complex biological tissues, suspended matter and sediment. The high selectivity and sensitivity of MS/MS detection in the resonant and non-resonant modes yield detection limits of 60 fg, 300 fg and 200 fg for CB 77, 126, and 169, respectively.     

在重金属污染环境下散栖欧Ping的肾中毒效应

散栖欧Ｐinｇ的试验标本取自瑞典一硫化矿冶炼厂的污染区及对照区。试验山鼠放大代谢笼内，２４小时收集其尿液。对其血浆及整个肾脏分别进行了血浆肌酸酐和金属含量分析。对尿液体积，总蛋白质、肌酸酐和金属含量进行了分析。取纂我的山鼠，其肾的镉 一增加了３０－４０倍，出现多尿症和蛋白尿症。与匐元素不同，肾的其它金属含量在取自两个实验区的山鼠中是相似的，因为这些金属元素含量小球的功能有关。当整个肾的匐含量达到４ｍ     

A chemical and toxicological profile of Dutch North Sea surface sediments

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 μm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 μg kg⁻¹ dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 μg kg⁻¹ dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4–0.6 μg kg⁻¹ dw, decabromodiphenylether (BDE209) 1–32 μg kg⁻¹ dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt’s upper estuary. PCBs and PAHs were between 0.19–4.7 and 2.6–200 μg kg⁻¹ dw respectively and generally had highest concentrations at near-shore locations and river mouths.

Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX).

Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4–6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.     

Polybrominated diphenyl ethers in influents,suspended particulate matter,sediments, sewage treatment plant and effluents and biota from the Netherlands

Polybrominated diphenyl ethers (PBDEs) have been determined in 133 samples of suspended particulate matter (SPM), sediments, sewage treatment plant (STP) influents and effluents, fish and mussels from various locations in The Netherlands, as a part of a large Dutch national study on estrogenic contaminants in the aquatic environment (LOES project). Some PBBs were also analysed but not found in any of the samples at detectable levels. PBDEs and PBBs were included in this study because indications of long term effects on the balance of endocrine systems were found in the literature. High concentrations of decaBDE (up to 4600 g/kg dry weight) were found in SPM from the Western Scheldt. These levels are possibly related to spillage during use of PBDEs in industries upstream the river Scheldt in Belgium. SPM was identified as an important carrier for higher brominated diphenyl ethers in the aquatic environment. DecaBDE was not found at detectable levels in flounder, bream and mussels. The bioaccumulation of decaBDE in these fish and shellfish samples is apparently limited. Lower brominated PBDE congeners (tetra/penta) were also found in the Western Scheldt as well as in the Rhine delta and the river Meuse, but in much lower concentrations than the decaBDE. In contrast with decaBDE, the tetra and pentaBDEs were found in biota. It was concluded that at least a small part of the PBDE can pass STPs.     

Modelling and field application of the Chemcatcher passive sampler calibration data for the monitoring of hydrophobic organic pollutants in water

Passive sampling of dissolved pollutants in water has been gaining acceptance for environmental monitoring. Previously, an integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low density polyethylene membrane, was developed and calibrated for the measurement of time weighted average (TWA) concentrations of hydrophobic pollutants in water. In this study, the exchange kinetics were modelled to obtain a better understanding of the mechanism of the accumulation process and to enable the measurement of TWA concentrations of hydrophobic pollutants in the field. An empirical relationship that enables the calculation of in situ sampling rates of chemicals using performance reference compounds was derived and its application was demonstrated in a field study in which TWA aqueous concentrations estimated from sampler data for target analytes were compared with TWA concentrations obtained from spot samples of water collected regularly during the sampler deployment period.     

Behavior of Two Phenyl Urea Herbicides in Clayey Soils and Effect of Alternating Dry-Wet Conditions on their Availability

Adsorption and mobility of linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea) and diuron (3-(3,4-dichlorophenyl)-1, 1-dimethylurea) were studied in clayey soils from the Gharb area (Morocco). Soils A and B were planted with sun flower (Helianthus annuus) while soil C was planted with sugar cane (Saccharum offcinarum). Adsorption was studied for linuron in soils A and B, while mobility was studied only in soil B. Adsorption data were found to fit the Freundlich equation with correlation coefficients r² > 0.9. Freundlich coefficients (K_f, n_f) were in agreement with L and S isotherm types for soils A and B, respectively. Values of K_oc (195 and 102) indicate moderate adsorption. Desorption isotherms for linuron showed hysteresis for both soils. The pesticide would be more bound to soil A (H = 8.44) than to soil B (H = 4.01). The effect of alternating wet and dry conditions was tested for soils A and B. Results showed that retention would increase in soil subject to an additional wet and dry cycle. In the case of diuron isotherm was of type L in soil C. Desorption was noticeable at high concentrations and tended to decrease when concentrations diminished. Mobility of linuron was tested in polyvinyle chloride (PVC) columns, which received different treatments before their percolation. The pesticide was more mobile in a previously saturated column. In columns subject to a drying step after saturation with water, linuron mobility was greatly reduced.     

Toxicity of analytically cleaned pentabromodiphenylether after prolonged exposure in estuarine European flounder (Platichthys flesus), and partial life-cycle exposure in fresh water zebrafish (Danio rerio)

Residues of polybrominated diphenylethers (PBDEs), extensively applied as flame retardants, are widely spread in the aquatic environment and biota. The present study investigates effects of the environmentally relevant lower brominated diphenylethers in two fish species in vivo under controlled laboratory conditions. Euryhaline flounder (Platichthys flesus) and freshwater zebrafish (Danio rerio) were exposed to a range of concentrations of a commercial pentabromodiphenylether mixture, DE-71. Chemical analysis of exposed fish showed a pattern of PBDE congeners that was very similar to that in wild fish. The resulting range included environmentally relevant, as well as higher levels. Animals were investigated histopathologically with emphasis on endocrine and reproductive organs. In zebrafish, hatching of embryos and larval development were assessed. Biochemical parameters were investigated in flounder as markers for suggested dioxin-like activity (ethoxyresorufin-O-deethylase=EROD), and activation of endogenous estrogen synthesis (gonad aromatase activity). Thyroid hormones were analyzed in plasma in both species. Benchmark analysis using internal PBDE concentrations showed a mild dose-dependent decrease of hepatic EROD and ovarian aromatase activities, and plasma thyroxin levels in flounder, and an increase of plasma thyroid hormone levels in zebrafish. These trends did not result in statistically significant differences from control fish, and major histopathological changes were not observed. Reproduction in zebrafish appeared to be the most sensitive parameter with statistically significantly reduced larval survival and non-significant indications for decreased egg production at internal levels that were more than 55 times the highest environmental recordings. The present results indicate limited risk for endocrine or reproductive effects of current environmental PBDE contamination in fish.     

Cost‐Effectiveness of Using Small Vertebrates as Indicators of Disturbance

In species‐rich tropical forests, effective biodiversity management demands measures of progress, yet budgetary limitations typically constrain capacity of decision makers to assess response of biological communities to habitat change. One approach is to identify ecological‐disturbance indicator species (EDIS) whose monitoring is also monetarily cost‐effective. These species can be identified by determining individual species’ responses to disturbance across a gradient; however, such responses may be confounded by factors other than disturbance. For example, in mountain environments the effects of anthropogenic habitat alteration are commonly confounded by elevation. EDIS have been identified with the indicator value (IndVal) metric, but there are weaknesses in the application of this approach in complex montane systems. We surveyed birds, small mammals, bats, and leaf‐litter lizards in differentially disturbed cloud forest of the Ecuadorian Andes. We then incorporated elevation in generalized linear (mixed) models (GL(M)M) to screen for EDIS in the data set. Finally, we used rarefaction of species accumulation data to compare relative monetary costs of identifying and monitoring EDIS at equal sampling effort, based on species richness. Our GL(M)M generated greater numbers of EDIS but fewer characteristic species relative to IndVal. In absolute terms birds were the most cost‐effective of the 4 taxa surveyed. We found one low‐cost bird EDIS. In terms of the number of indicators generated as a proportion of species richness, EDIS of small mammals were the most cost‐effective. Our approach has the potential to be a useful tool for facilitating more sustainable management of Andean forest systems. Rentabilidad del Uso de Pequeños Vertebrados como Indicadores de Perturbaciones