Total and Methylmercury in Soft Tissues of White-Tailed Eagle (Haliaeetus albicilla) and Osprey (Pandion haliaetus) Collected in Poland

Mercury (Hg) contamination in piscivorous birds, especially methylmercury (MeHg), has been drawing much attention worldwide in regard to its bioaccumulation and biomagnification in food chains. In this study on Hg in the soft tissues of white-tailed eagles (n = 22) and ospreys (n = 2) from Poland, total Hg (THg) range was 0.15–47.6 while MeHg range was 0.11–8.05 mg kg⁻¹ dry weight. In both species, median THg and MeHg concentrations were lower in the muscle and brain than in the liver and kidney. Median nephric residues were just under 3 and 5 mgTHg kg⁻¹ or 0.9 and 3.7 mgMeHg kg⁻¹ for white-tailed eagle and osprey, respectively. In Norwegian data from the 1970s and in our results, MeHg in the muscle of white-tailed eagle was ~60 % THg (%MeHg = MeHg/THg × 100), lower than in other piscivorous birds. A clear similarity in THg tissue levels was found between Polish and German populations of white-tailed eagles.     

城市道路沉积物氮、磷溶出特性

国内外众多研究表明,城市不透水表面沉积物是雨水径流中污染物的重要来源。以北京市某道路沉积物为研究对象,对城市道路沉积物的粒径分布进行了分析,并通过批量实验,研究了不同粒径道路沉积物中氮、磷营养物及有机物(COD)的溶出特性。实验结果表明,粒径较大的沉积物中氮含量较高,而粒径较小的沉积物中磷含量较高;虽然TP、PO3-4、TN、NO-3、NH+4、COD的溶出浓度、溶出速率变化特征各不相同,但总体趋势是粒径越小氮、磷及COD溶出浓度和溶出速率越大,且最大溶出速率都出现在前5 min。因此,为实现对城市雨水径流污染的有效控制,应采用源头控制措施对小粒径道路沉积物和初期雨水进行有效控制。     

不同运行模式对同步脱氮除磷CAST工艺快速启动及其稳定维持的影响

以实际生活污水为处理对象,考察了传统进水/曝气和改良型分段进水的交替缺氧-好氧(A/O)2种运行模式对CAST工艺的快速启动及脱氮除磷性能稳定维持的影响。结果表明,传统进水/曝气运行模式下,系统达到最佳营养物去除性能所需启动时间30 d,稳定运行阶段TN平均去除80.66%,磷的去除率维持在66.30%左右;采用改良型交替运行模式,反应器达到稳定运行状态仅需18 d,系统稳定运行时TN平均去除81.36%,磷去除率稳定维持在90%以上,出水磷浓度在0.3 mg/L以下,出水水质达到国家污水综合排放标准一级A(GB8978-2002)。研究还发现,传统运行模式下,由低温引起的污泥沉降性能变差导致系统污泥严重流失,反应器几乎丧失污染物去除性能;而低温对交替运行模式下的反应器除磷性能几乎没有影响,总氮去除则因氨氮不完全硝化而大大降低。     

Use of cholinesterase activity in monitoring chlorpyrifos exposure of steer cattle after topical administration

The aim of this work was to study the pharmacokinetic behavior and the inhibitory effect of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities of chlorpyrifos (CPF) in steer cattle after pour-on administration. Determination of cholinesterase activity in plasma and erythrocyte was carried out according to Ellman kinetic method. CPF was analyzed by gas chromatography. AChE was the predominant form of cholinesterase analyzed, with low levels of BChE in plasma. Following the treatment with CPF, the maximum inhibitory effect on AChE or BChE were 50.88 ± 11.57 and 42.66 ± 12.01%, respectively. The chlorpyrifos plasma concentrations observed were low and they presented a high variability. Chlorpyrifos peak plasma concentration (10.42 ± 4.76 μ g/L) was reached at 8.42 ± 13.97 h. The pesticide was not detected in plasma after 48 h post treatment. The values of area under the curve (AUC) were 118.48 ± 87.46 μ g· h/L and mean resistance time (MRT) were 13.38 ± 10.41 h. The pour-on exposure to the organophosphate chlorpyrifos significantly reduced AChE and BChE activity in steer cattle and the recovery was not reached on 50 days post-treatment.     

The health risk assessment of organochlorine pesticides in smoked fish products available in Szczecin,Poland

The aim of this study was to determine the concentration of organochlorine pesticides [HCH and isomers (α, β, γ), aldrin, dieldrin, endrin, heptachlor and heptachlor epoxide and DDT and its metabolites (op’-DDD, pp’-DDD, op’-DDT, pp’-DDE, pp’-DDT] in smoked fish. Analysis was made of 12 typical smoked fish products that are the most popular among customers from the city of Szczecin, Poland. Pesticide residues were found in all samples of smoked fish. The smoked sprat and cold-smoked Baltic salmon were the most contaminated smoked fish products in terms of chlorine pesticides. The sum of DDT metabolites ranged from 1.48 (smoked mackerel) to 35.53 ng/g wet weight (smoked sprat), with the lowest concentrations found for op’-DDT and the highest for pp’-DDE. The level of heptachlor epoxide isomer B was low and ranged from 0.06 ± 0.01 (smoked eel) to 0.27 ± 0.07 ng/g w.w. (smoked sprat). The content of heptachlor was 0.48–1.99 ng/g w.w. Concentration of endrin was higher compared to other pesticides, ranged from 1.50 (cold-smoked salmon fillet) to 16.84 ng/g w.w (hot-smoked warehou). The contamination of smoked products was significantly low and poses no risk to the health of consumers provided that they eat a diverse diet. The concentration of organochlorine pesticides in the analysed products was below the standards accepted in European countries.     

Multiresidue determination of carbamate,organochlorine, organophosphorus,and dicarboximide pesticides in lettuce by GC/MS

An extraction method based on matrix solid-phase dispersion was developed to determine pirimicarb, methyl parathion, malathion, procymidone, α -endosulfan and β -endosulfan in lettuce using gas chromatography-mass spectrometry. The best results were obtained using 4.0 g of lettuce, 2.0 g of silica as dispersant sorbent, 0.1 g of activated carbon as clean up sorbent and acetonitrile as eluting solvent. The method was validated using lettuce samples fortified with pesticides at six different concentration levels (0.1 to 2.0 mg/kg). Average recoveries (7 replicates) ranged from 50 to 120 %, with relative standard deviations between 0.6 and 8.0 %. Detection and quantification limits for lettuce ranged from 0.01 to 0.02 mg/kg and 0.04 to 0.10 mg/kg, respectively.     

Pesticide dissipation curves in peach,pear and tomato crops in Uruguay*

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel®. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r²=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r²=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

Bioremediation of chlorinated pesticide–contaminated soil using anaerobic sludges and surfactant addition

Methanogenic granular sludge and wastewater fermented sludge were used as inocula for batch tests of anaerobic bioremediation of chlorinated pesticide contaminated soil. Results obtained for both types of biomass were similar: 80 to over 90% of γ -hexachlorocyclohexane (γ-HCH), 1,1,1-trichloro-2,2-bis-(4-methoxyphenyl)ethane (methoxychlor) and 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane (DDT) removed in 4–6 weeks. Residual fractions of these pesticides persisted till the end of the 16-week experiment. DDT was degraded through 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethane (DDD). Accumulation of this product corresponded stoichiometrically only to 34–53% of removed DDT, supposedly due to its further transformations, finally resulting in formation of detected 4,4′-dichlorobenzophenone (DBP). Addition of 0.5 mM Tween 80 nonionic surfactant resulted in about a twofold decrease of γ -HCH and methoxychlor residual concentrations, as well as considerably lower DDD accumulation (7–29%) and higher DBP production. However, 1.25 mM dose of this surfactant applied together with granular sludge brought DDD levels back to that observed for treatments with the sludge alone, also impairing DBP formation.     

Effect of phenobarbital and polychlorinated biphenyls on the toxicity and disposition of 1,2,4,5‐tetrachlorobenzene in the rat

Soil avoidance by earthworms has been generally considered a relevant and sensitive endpoint for assessing soil contamination by xenobiotics. However, when pesticide ecotoxicological assessment is concerned, the sensitivity of the recently standardized avoidance assay has been questioned. We hypothesized that this controversy may be due to the specific pesticide mode of action of the chemicals used rather than reveal inconsistencies in the test feasibility, i.e. provided that no pesticides interfering with neuronal pathways are tested, this bioassay should keep expected high levels of sensitivity. In this study, the avoidance behaviour of the earthworm Eisenia andrei under exposure to the carbamate insecticide methomyl [S-methyl N-(methylcarbamoyloxy)thioacetimidate] was linked to the corresponding acetylcholinesterase (AChE) inhibition. Significant AChE inhibition occurred at lower concentrations (from 0.86 mg Kg^?1 onwards) than significant avoidance of spiked soil (from 5.62 mg Kg^?1 onwards). This indicates that assessments regarding pesticides that have neurotoxic activity may be biased if behavioral endpoints are selected. Despite theoretical hypothesis that have been raised, this should be the first study providing preliminary experimental evidence on such a link between avoidance behavior and neuronal impairment levels in earthworms. Further studies are ongoing that should refine conclusions of this study.     

Concentrations and distributions of 18 organochlorine pesticides listed in the Stockholm Convention in surface sediments from the Liaohe River basin,China

Organochlorine pesticides (OCPs) were analyzed in 26 surface sediment samples from the Liaohe River basin, and the distributions of and potential environmental risks posed by OCPs in the basin were evaluated. Eighteen OCPs listed in the Stockholm Convention were determined using isotope-dilution gas chromatography–high resolution mass spectrometry. This is the first study of hexachlorobenzene (HCB) in the Liaohe River basin sediments. The total OCP concentrations were 0.39–68.06 ng g^?1 dry weight. The total α-, β-, γ-, and δ-hexachlorocyclohexane (HCH), the total dichlorodiphenyltrichloroethane (DDT – p,p′-dichlorodiphenyldichloroethane (DDD), p,p′-dichlorodiphenyldichloroethylene (DDE), o,p^'-DDT, and p,p′-DDT), and the HCB concentrations in the sediment samples were 0.1–28.48 ng g^?1 (mean 4.01 ng g^?1), 0.08–6.52 ng g^?1 (mean 3.07 ng g^?1), and 0.18–24.8 ng g^?1 (mean 4.38 ng g^?1), respectively. The HCB concentrations were higher than the concentrations of the other OCPs, and the HCHs and HCB together were the dominant OCPs. β-HCH was the most abundant HCH isomer. The concentrations of DDTs and other OCPs were relatively low, and the (DDE+DDD)/DDT ratios (>0.5) and DDD/DDE ratios (<1) indicated that no recent DDT inputs had occurred in the Liaohe River system. The main sources of HCHs were probably the historical production and agricultural use of HCH in the study area. The DDT and HCH concentrations were generally below or similar to the concentrations that have been found in other parts of the world. An ecotoxicological evaluation indicated that HCHs in surface sediments pose slight risks to human and ecological health in the Liaohe River basin.