7种农药对管氏肿腿蜂的毒性及初级风险评价

为评估农药对寄生类自然天敌昆虫的安全性,选择管氏肿腿蜂(Scleroderma guani Xiao et Wu)作为受试生物,采用管测药膜法测定了3种杀虫剂、2种除草剂、2种杀菌剂对其致死效应,并根据田间推荐剂量计算暴露量,采用风险商值HQ对杀虫剂进行风险评估。结果显示,与空白对照比较,3种杀虫剂均具明显毒性作用,其中丁硫克百威、吡虫啉和呋虫胺对管氏肿腿蜂的24 h半致死量(24 h-LR50)分别为5.11、2.92和0.06 g a.i.·ha-1,农田内风险商值分别为60.23、16.64和3 105。除草剂和杀菌剂在3倍最大田间推荐剂量作用下,24 h管氏肿腿蜂死亡率均小于50%。上述结果表明,在田间推荐用量下,3种杀虫剂对管氏肿腿蜂的初级风险评价为存在高风险,建议进一步开展高级阶段风险评估或者采取合理的风险管理措施来降低风险;除草剂和杀菌剂对管氏肿腿蜂的风险可接受。     

蔬菜常用农药在地下水中残留风险评估

为明确蔬菜常用农药在地下水中的环境风险,运用China-Pearl和SCI-GROW模型开展地下水环境暴露评估,并根据我国成人和儿童暴露参数推导25种农药预测无效应浓度(PNEC)。研究发现,25种农药PECgw为0~18.340μg·L-1,成年人PNECgw为0.003~19.654 mg·L-1,儿童PNECgw为0.001~23.253 mg·L-1。成年人和儿童的RQgw值均小于1,表明25种农药按照登记用量使用,我国成人和各年龄阶段儿童直接饮用施用农药区域地下水的环境风险可接受。     

Extraction and clean-up methods for organochlorine pesticides determination in milk

Organochlorine pesticides (OCPs) can cause environmental damage and human health risks since they are lipophilic compounds with high resistance to degradation and long half-lives in humans. As most persistent OCPs have been banned years ago, it is expected to find these compounds at trace levels in environment. Therefore, increasingly sensitive and reliable analytical techniques are required to ensure effective monitoring of these compounds. The aim of this review is to discuss extraction and clean-up methods used to monitor OCP residues in milk, reported in the last 20 years. To carry out this review, an exhaustive bibliographic review was conducted. Despite the disadvantages of conventional extraction and clean-up methods, such as liquid–liquid, solid-phase or Soxhlet extractions, these procedures are still used due to their reliability. New extraction methods, like solid-phase microextraction, matrix solid-phase dispersion or QuEChERS, have not been thoroughly evaluated for OCP determination in milk. Almost all the methodologies analyzed in this review presented good performance characteristics according to the performance acceptability criteria set in SANCO’s procedure. Comparison between limits of quantification (LOQ) and detection (LOD), for the reported methodologies, is not always possible due to the heterogeneity of the units. Thus, researchers should take into account an homogenization of LOD and LOQ units, according to the international regulations and MRLs established. Finally, more research is necessary to obtain the ideal methodology for OCPs determination in milk, which comprises the environmentally friendly characteristics of the new techniques and the reliability of the traditional methodologies.     

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.     

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.     

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.     

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.     

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.     

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.     

Watershed Regressions for Pesticides (warp) Models for Predicting Atrazine Concentrations in Corn Belt Streams1

Stone, Wesley W. and Robert J. Gilliom, 2012. Watershed Regressions for Pesticides (WARP) Models for Predicting Atrazine Concentrations in Corn Belt Streams. Journal of the American Water Resources Association (JAWRA) 48(5): 970‐986. DOI: 10.1111/j.1752‐1688.2012.00661.x Abstract: Watershed Regressions for Pesticides (WARP) models, previously developed for atrazine at the national scale, are improved for application to the United States (U.S.) Corn Belt region by developing region‐specific models that include watershed characteristics that are influential in predicting atrazine concentration statistics within the Corn Belt. WARP models for the Corn Belt (WARP‐CB) were developed for annual maximum moving‐average (14‐, 21‐, 30‐, 60‐, and 90‐day durations) and annual 95th‐percentile atrazine concentrations in streams of the Corn Belt region. The WARP‐CB models accounted for 53 to 62% of the variability in the various concentration statistics among the model‐development sites. Model predictions were within a factor of 5 of the observed concentration statistic for over 90% of the model‐development sites. The WARP‐CB residuals and uncertainty are lower than those of the National WARP model for the same sites. Although atrazine‐use intensity is the most important explanatory variable in the National WARP models, it is not a significant variable in the WARP‐CB models. The WARP‐CB models provide improved predictions for Corn Belt streams draining watersheds with atrazine‐use intensities of 17 kg/km² of watershed area or greater.