分散固相萃取-超高效液相色谱-串联质谱联用快速检测大豆及土壤中氟磺胺草醚残留

采用分散固相萃取(QuEChERS)样品前处理方法,建立了超高效液相色谱-串联质谱(UPLC-MS/MS)快速检测大豆和土壤中氟磺胺草醚的残留分析方法.大豆和土壤样品采用乙腈(含0.5%甲酸)提取,N-丙基乙二胺(PSA)或石墨化碳黑(GCB)净化,UPLC-MS/MS外标法检测定量.在0.005—0.5 mg.kg-1添加范围内,氟磺胺草醚在土壤、大豆和大豆植株中的平均回收率在79.4%—109.0%之间,变异系数在3.6%—10.1%之间.在山东、河南、吉林进行了氟磺胺草醚在大豆植株和土壤中的降解动态研究,结果表明,试验点中氟磺胺草醚在土壤中的降解半衰期为8.5—23.7 d;在大豆植株中的降解半衰期为2.7—9.8 d.     

Bioefficacy of insecticides against Leucinodes orbonalis on brinjal

Studies on bioefficacy of insecticides against brinjal shoot and fruit borer, Leucinodes orbonalis Guenee on brinjal were carried out during 2007 and 2008. The results on bioefficacy of insecticides showed that in terms of shoot infestation, emamectin benzoate (0.002%), endosulfan (0.05%), novaluron (0.01%) and lambda-cyhalothrin (0.004%) were found superior. The total number of drooping shoots was minimum (4.17) in emamectin benzoate followed by endosulfan (6.83) and novaluron (7.00), as compared to spinosad (9.17), deltamethrin (11.67) and Bacillus thuringiensis (13.17). In terms of reduction in fruit infestation, emamectin benzoate (0.002%) was highly effective followed by endosulfan (0.05%), agrospray oil T (0.2%) and spinosad (0.0024%). However, cost benefit ratio was highest in agrospray oil T (0.2%) followed by lambda-cyhalothrin (0.004%), endosulfan (0.05%) and deltamethrin (0.0028%).     

Field dissipation and health hazard assessment of Fenhexamid on Egyptian grapes

Dissipation behavior and hazard assessment of the fungicide fenhexamid applied to grapes were investigated under climatic conditions in Egypt. Fenhexamid residues were extracted from grape samples with ethyl acetate. The extract was cleaned up by QuEChERS (quick, easy, cheap, effective, rugged, and safe) method, and determined by gas chromatographic method (GC-μECD). The average recoveries ranged between 94.2% and 99.4% with associated relative standard deviation not exceeding 12%. The estimated limit of quantification for fenhexamid was 0.1 mg/kg. The field results showed that fenhexamid dissipated rapidly from grapes and had a half-life of approximately 4.21 days. Hazard assessment was evaluated by using the hazard quotient (HQ). Data showed that the HQ value was significantly less than HQ = 1. Results indicate that hazard of fenhexamid use in grape even at 1.5-fold higher than recommended dosage was negligible to humans. This study could provide guidance for safe and reasonable use of fenhexamid in grapes and prevent health problems to consumers. However, further hazard assessment studies are needed to ascertain the hazard of fenhexamid residues on grape to vulnerable groups, including children, pregnant women, and elderly consumers.     

Residues and dissipation of the pesticide emamectin benzoate under Egyptian field condition: a case study

A simple, rapid analytical procedure for the quantification of emamectin benzoate in tomato was developed using high performance liquid chromatography with fluorescence detector (HPLC-FLD). Emamectin benzoate residues were extracted from tomato samples with n-hexane:ethyl acetate (1:1, v/v). The method involved derivatization using trifluoroacetic anhydride and 1-methylimidazole, prior to analysis by HPLC-FLD. Limit of quantification of this method was found to be 0.01 mg/kg, while limit of detection was 0.005 mg/kg. The dissipation of emamectin benzoate on tomato was studied, and half-life (t_1/2) was estimated in a field study carried out at three different locations. Emamectin benzoate was sprayed on tomato at recommended dosage. Samples of tomato were collected at 0, 1, 3, 7, 10, and 15 days after treatment. The t_1/2 of emamectin benzoate when applied at the recommended doses in tomato was approximately 2.5 days. The residue of emamectin benzoate reached below the maximal residue limit (MRL) 10 days after spraying at the tested dosage. Hence, a safe pre-harvest interval of 10 days is suggested before harvesting of tomato. This study would also be helpful for the Egypt government to establish the MRL of emamectin benzoate in tomatoes and provide guidance on the proper and safe use of this insecticide.     

Full scale amendment of a contaminated wood impregnation site with iron water treatment residues

Iron water treatment residues are a free by-product with high concentration of iron oxides Iron water treatment residues has a large potential for arsenic sorption Soils are highly contaminated by arsenic at wood preservation sites Iron water treatment residues were added to hot spots contaminated with arsenic The addition led to significant decrease in leaching of arsenic from the contaminated soil Iron water treatment residues (Fe-WTR) are a free by-product of the treatment of drinking water with high concentration of iron oxides and potential for arsenic sorption. This paper aims at applying Fe-WTR to a contaminated site, measuring the reduction in contaminant leaching, and discussing the design of delivery and mixing strategy for soil stabilization at field scale and present a cost-effective method of soil mixing by common contractor machinery. Soil contaminated by As, Cr, and Cu at an abandoned wood impregnation site was amended with 0.22% (dw) Fe-WTR. To evaluate the full scale amendment a 100 m² test site and a control site (without amendment) were monitored for 14 months. Also soil analysis of Fe to evaluate the degree of soil and Fe-WTR mixing was done. Stabilization with Fe-WTR had a significant effect on leachable contaminants, reducing pore water As by 93%, Cu by 91% and Cr by 95% in the upper samplers. Dosage and mixing of Fe-WTR in the soil proved to be difficult in the deeper part of the field, and pore water concentrations of arsenic was generally higher. Despite water logged conditions no increase in dissolved iron or arsenic was observed in the amended soil. Our field scale amendment of contaminated soil was overall successful in decreasing leaching of As, Cr and Cu. With minor improvements in the mixing and delivery strategy, this stabilization method is suggested for use in cases, where leaching of Cu, Cr and As constitutes a risk for groundwater and freshwater.     

根际环境对除草剂扑草净环境归趋的影响评价

植物保护产品（PPP）需要经过严格的监管评估，以确保它们不会对环境造成不可接受的风险。阐明化学品在土壤中的命运和行为是环境风险评估的一个组成部分。土壤中PPP活性物质降解首先在实验室研究中进行评估（通常遵循OECD 307实验导则）。但指导性实验室研究中的条件与农业使用中的条件相差甚远，而目前还没有评估作物根系的贡献。在这里，我们将代表三种不同作物类型的有效植物根系整合到OECD 307实验设计中，以评估它们对除草剂PPP降解的影响。在所有三种种植体系中，母本残留的下降速度和不可提取残留的形成速度都显著加快。这导致50%降解时间（DT50）在黑麦草和辣椒的存在下降低约一半，在红三叶的存在下减少约三分之一。这些发现表明植物及其相关的根系网络对PPP降解有显著影响。基于这些数据，需要将植物根系纳入更高层次的研究，在标准化实验室研究设计中增加更大的环境现实性，进而有助于改进环境风险评估过程。     

Persistence and dissipation of dazomet in soil and tomato (lycopersicon esculentum mill) seedlings

The persistence and dissipation pattern of dazomet residues in nursery bed soil and tomato seedlings under field condition and in submerged soil and surface water under laboratory condition was studied. In nursery bed soil the half life (t _1/2) of dazomet ranged from 1.85 to 3.09 days indicating very rapid dissipation. No residues existed in tomato seedlings sown on the treated plots 3 weeks after application and the seedlings were healthy and devoid of any deformation. Under submerged condition dissipation was much faster both in soil and surface water, t_1/2 being 0.82–0.84 days only in water.     

苹果和土壤中丙森锌的消解动态及残留规律

研究了苹果和土壤中丙森锌残留的气相色谱分析方法,及其代谢物乙撑硫脲的高效液相色谱分析方法,并在天津、山东烟台和陕西咸阳进行了苹果和土壤中丙森锌及其代谢物乙撑硫脲残留消解动态和残留规律田间试验研究.结果表明,在0.05—2 mg.kg-1的加标水平下,苹果和土壤中丙森锌的加标回收率分别为77.12%—92.85%和9.24%—94.68%,变异系数分别为3.30%—6.56%和3.29%—5.29%;在0.05—1 mg.kg-1的加标水平下,苹果和土壤中乙撑硫脲的加标回收率分别为80.91%—97.47%和84.11%—99.97%,变异系数分别为3.23%—3.82%和2.80%—3.40%.苹果和土壤中丙森锌和乙撑硫脲的最小检出量分别为5.0×10-10g和1.0×10-10g,其中苹果和土壤中丙森锌的最低检出浓度为0.025 mg.kg-1,乙撑硫脲的最低检出浓度为0.005 mg.kg-1.按1.5倍推荐剂量600倍稀释液在苹果上施用65%戊唑醇.丙森锌可湿性粉剂1次,丙森锌在苹果和土壤中的残留消解半衰期分别为6.0—6.8 d和8.7—10.1 d.按推荐剂量和1.5倍推荐剂量在苹果上各施用65%戊唑醇.丙森锌可湿性粉剂3—4次,2次施药间隔为10 d,距最后一次施药21 d时,丙森锌在苹果中的最高残留量低于我国农业行业标准规定的最大残留限量2 mg.kg-1.     

噻苯隆在甜瓜和土壤中的残留及消解动态

建立了超高效液相色谱-串联质谱分析噻苯隆在甜瓜和土壤中残留的方法.本方法甜瓜中噻苯隆的平均回收率为90.2%—107.3%,变异系数为3.5%—12.9%;土壤中噻苯隆的平均回收率为81.4%—94.0%,变异系数为3.1%—8.8%.采用田间试验研究了噻苯隆在甜瓜和土壤中的残留动态.结果表明,河南和山东,噻苯隆在甜瓜中的消解半衰期为0.7—1.2d,土壤中的消解半衰期为4.1—7.6d.在甜瓜上使用0.1%的噻苯隆可湿性粉剂,按照最高推荐剂量和最高推荐剂量的1.5倍,施药一次,收获期距最后一次施药35d,噻苯隆在甜瓜和土壤中最终残留量均小于0.001mg.kg-1.说明噻苯隆为低残留,易降解农药.     

Dislodgeable residues of profenofos on jasmine and risk assessment of post application exposure to flower bud pickers

A field study was conducted to measure the dislodgeable residues of profenofos applied to jasmine (Jasminum sambac) and risk assessment was done for laborers engaged in picking of flower buds. Profenofos was applied at 0.10, 0.15, and 0.20% concentration and the jasmine bud samples were analysed for residues using GC. The initial deposit of 1.6–3.8, 3.8–7.1, and 5.2–7.6 µg cm^?2 was detected on jasmine buds at 0.10, 0.15, and 0.20% concentration, respectively. At the recommended dose of 0.10%, the half-life was 1–2 days and the dislodgeable residues disappeared within 7 days. The results indicate faster disappearance of dislodgeable residues on jasmine buds. Risk assessment was done based on dislodgeable foliar residues and exposure estimates based on surrogate data and expressed as Margin of Exposure (MOE). The entry restrictions for exposure of jasmine flower pickers to profenofos, would be at least, 1 day following application, for the recommended concentration of 0.10% (MOE = 106) and 3 days, at higher concentrations of 0.15% (MOE = 156) and 0.20% (MOE = 115).     

Residues,half-life times,dissipation, and safety evaluation of the acaricide fenpyroximate applied on grapes

A validated high-performance liquid chromatography–diode array detector method for simultaneous determination of the acaricide fenpyroximate on grape was developed. Estimated limit of detection and limit of quantification for fenpyroximate were 0.01 and 0.05 mg kg^?1, respectively. The intra- and inter-day precisions performed with relative standard deviation were better than 9.3% and 8%, respectively, while recoveries were in the range of 88.5%–100.4%. Residue levels of fenpyroximate in grape samples collected 10 days after field application were below the established maximum residue level values. The dissipation rates of fenpyroximate were described using first-order kinetics and its half-life, were approximately 3.5 days in grape. This study provides basic information for developing regulations to safeguard the use of fenpyroximate in grapes and prevent any potential health concerns for consumers.     

Quantifying the effect of wind on internal wave resonance in Lake Villarrica,Chile

Lake Villarrica, located in south central Chile, has a maximum depth of 167 m and a maximum fetch of about 20 km. The lake is monomictic, with a seasonal thermocline located at a depth of approximately 20 m. Field data show the presence of basin-scale internal waves that are forced by daily winds and affected by Coriolis acceleration. A modal linear and non-linear analysis of internal waves has been used, assuming a two-layer system. The numerical simulations show good agreement with the internal wave field observations. The obtained modes were used to study the energy dissipation within the system, which is necessary to control the amplitude growth. Field data and numerical simulations identify (1) the occurrence of a horizontal mode 1 Kelvin wave, with a period of about a day that coincides with the frequency of daily winds, suggesting that this mode of the Kelvin waves is in a resonant state (subject to damping and controlled by frictional effects in the field) and (2) the presence of higher-frequency internal waves, which are excited by non-linear interactions between basin-scale internal waves. The non-linear simulation indicates that only 10 % of the dissipation rate of the Kelvin wave is because of bottom friction, while the rest 90 % represents the energy that is radiated from the Kelvin wave to other modes. Also, this study shows that modes with periods between 5 and 8 h are excited by non-linear interactions between the fundamental Kelvin wave and horizontal Poincaré-type waves. A laboratory study of the resonant interaction between a periodic forcing and the internal wave field response has also been performed, confirming the resonance for the horizontal mode 1 Kelvin wave.     

Field evaluation and determination of four herbicides in a wheat ecosystem by a simple and versatile QuEChERS method with liquid chromatography-tandem mass spectrometry

Wheat products are consumed worldwide and every day; therefore, herbicides misuse in the wheat ecosystem has become a global food safety issue. Here, a simple and versatile method, QuEChERS (quick, easy, cheap, effective, rugged, and safe) with liquid chromatography-tandem mass spectrometry was developed to measure four herbicides in soil, wheat, and wheat straw – florasulam, carfentrazone-ethyl, fluroxypyr-meptyl, and fluroxypyr. By adjusting the amount of graphitized carbon black from 0 to 10 mg, the herbicides could be extracted with satisfactory recoveries of 80%–110%. Application of two water-dispersible granules showed first-order kinetics as well as half-lives between 1.2 and 5.1 d under open-field conditions. The dissipation kinetics of the four herbicides differed in the soil, wheat, and wheat straw, with residual concentrations in straw at 2 h after application being higher than in soil and faster degradation occurring in straw. The terminal residues in soil, wheat grain, and wheat straw were all below the maximum residue limits. The developed method was easy to handle and versatile; thus, it will facilitate regulation and inspection for possible misuse against Good Agriculture Practices. Moreover, the results of this study will contribute to global environmental protection as well as food safety issues.     

A simple approach to modeling microbial biomass in the rhizosphere

Microorganisms make an important contribution to the degradation of contaminants in bioremediation as well as in phytoremediation. An accurate estimation of microbial concentrations in the soil would be valuable in predicting contaminant dissipation during various bioremediation processes. A simple modeling approach to quantify the microbial biomass in the rhizosphere was developed in this study. Experiments were conducted using field column lysimeters planted with Eastern gamagrass. The microbial biomass concentrations from the rhizosphere soil, bulk soil, and unplanted soil were monitored for six months using an incubation–fumigation method. The proposed model was applied to the field microbial biomass data and good correlation between simulated and experimental data was achieved. The results indicate that plants increase microbial concentrations in the soil by providing root exudates as growth substrates for microorganisms. Since plant roots are initially small and do not produce large quantities of exudates when first seeded, the addition of exogenous substrates may be needed to increase initial microbial concentrations at the start of phytoremediation projects.     

多效唑在番茄和土壤中的残留与降解动态研究

研究了多效唑（paclobutrazol）在番茄（Lycopersicon eseulentum）和土壤中的残留分析方法及残留动态。建立番茄和土壤样品中多效唑残留的固相萃取-高效液相色谱（SPE-HPLC）检测方法,样品用乙腈提取,再用φ（甲醇-二氯甲烷）=5∶95混合溶剂经LC-NH2固相萃取柱净化,以φ（乙腈-水）=55∶45作流动相,Shiseido C18色谱柱（4.6 mm×250 mm,5μm）于222 nm波长检测,外标法定量。在0.1~5.0 mg·L-1范围内,多效唑峰面积与其质量浓度之间呈良好线性关系,相关系数为0.9995。采用田间试验方法,在番茄幼苗期施用不同多效唑质量分数50、100、200、600 mg·kg-1,研究在不同处理时间1、6 h,1、2、3、7、14、21、30、45、60 d,多效唑在番茄以及土壤中的残留动态变化。添加质量分数水平为0.05、0.1、0.5 mg·kg-1时,多效唑在果实、植株和土壤中的添加回收率分别为92.45%~103.70%、94.52%~98.85%和94.30%~102.10%,变异系数分别为3.69%~5.00%、1.58%~4.53%和1.28%~3.35%。结果表明：多效唑在番茄植株和土壤中的降解规律均符合一级动力学方程C=Coe-kt。当施用质量分数为600 mg·kg-1时,其在番茄植株中的残留半衰期为1.66 d,在土壤中的半衰期为2.78 d;在植株中的降解速率大于在土壤中的降解速率。按照推荐使用的施用浓度,采收时多效唑在番茄和土壤中无残留,证明推荐施用浓度是合理的。     

Evidence for DNA-diquat interaction and cytotoxicity in in vitro rat cells

Over 98% of sprayed insecticides and 95% of herbicides reach non-target species in air, soil, and water. Numerous studies have reported that pesticide residues can cause acute and chronic toxicity. Pesticide residues can be carcinogenic, mutagenic, and immunotoxic. There are actually too few studies that bridge the disciplines of chemobioanalysis and environmental toxicology. Here, we assessed the cytotoxicity of a bipyridilium herbicide diquat in rat adrenal pheochromocytoma cells (PC12). Our results show that diquat caused the decrease in cell viability with a lethal concentration 50 (LC₅₀) of 1.4 × 10⁻⁵ mol/L. This cytotoxicity may result from diquat-induced apoptosis, characterized by nuclear fragmentation and chromatin condensation by Hoechst 33324 staining. To explore the possible mechanisms, the interaction between herbicide diquat and calf thymus DNA (ctDNA) was further investigated using fluorescence quenching. The detection of static quenching showed that diquat was linked with ctDNA by electrostatic interaction with a binding constant of 9.288 × 10⁴ L/mol. This is the first study on the interaction of DNA with herbicide diquat by fluorometric method as well as on the evaluation of cytotoxicity by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and Hoechst staining. Given the widespread use of synthetic pesticides, the data would be valuable for the risk assessment of pesticide residues.     

Possible Use of Ash Residues for the Construction of Artificial Reefs at Sea

Utilization of ash residues, including coal ash, oil ash, and municipal solid waste combustion ash, for the construction of artificial reefs at sea has been investigated by many researchers throughout the world for nearly 20 years. Both laboratory and field studies have shown that an artificial reef made of stabillized ash-concrete (SAC) has had no adverse effect on the marine environment. Indeed, published studies have shown that fish counts increase around SAC reefs owing to an abundance of colonizing organisms and to protection provided by cavities within the reef structures. However, public and regulatory resistance to the use of SAC for artificial reef construction at sea is still very strong in certain countries due to concern for possible negative environmental impacts, primarily in the area of bioaccumulation of elements or compounds originating from the ash component of SAC.

In this paper, technological feasibility of using ash residues for artificial reef construction is presented, based on the available 20 years of scientific data, including engineering workability, physical integrity, chemical leaching potential and biological effects. More important, we also identify conceptual barriers for the acceptance of using SAC for the construction of ocean reefs and suggest approaches to overcome these barriers.     

Possible Use of Ash Residues for the Construction of Artificial Reefs at Sea

Utilization of ash residues, including coal ash, oil ash, and municipal solid waste combustion ash, for the construction of artificial reefs at sea has been investigated by many researchers throughout the world for nearly 20 years. Both laboratory and field studies have shown that an artificial reef made of stabillized ash-concrete (SAC) has had no adverse effect on the marine environment. Indeed, published studies have shown that fish counts increase around SAC reefs owing to an abundance of colonizing organisms and to protection provided by cavities within the reef structures. However, public and regulatory resistance to the use of SAC for artificial reef construction at sea is still very strong in certain countries due to concern for possible negative environmental impacts, primarily in the area of bioaccumulation of elements or compounds originating from the ash component of SAC.

In this paper, technological feasibility of using ash residues for artificial reef construction is presented, based on the available 20 years of scientific data, including engineering workability, physical integrity, chemical leaching potential and biological effects. More important, we also identify conceptual barriers for the acceptance of using SAC for the construction of ocean reefs and suggest approaches to overcome these barriers.     

3种人工草地不同植被覆盖度实地测量方法比较

植被覆盖度是植被垂直投影面积占统计区域面积百分比;理想覆盖度实地测量方法耗时短,工具简单,结果准确,受人为因素影响小.以结缕草(Zoysia japonica)、白三叶(Trifolium repens)和雀稗(Paspalum thunbergii)人工草地为研究对象,以照相法测量值为参考,比较样线法、目估法、样针法、点框架法、网格法1×1、网格法5×5、网格点法1×1和网格点法5×5等8种方法测量精度.结果表明:样线法误差小于5%,耗时短,工具简单.目估法误差大于样线法,适用于植被高度低且覆盖度较低或较高样方.样针法误差大于样线法和目估法,误差受植被高度和茎叶硬度影响,适用于植被高度低且硬度较小样方.点框架法、网格法和网格点法误差均较大,一般大于10%.网格法误差受覆盖度和小网格边长影响,误差峰值出现在覆盖度接近65%的样方,误差随着小网格边长增加而增加.8种方法测量值与照相法测量值均呈显著正相关(P <0.05),因此对于类似人工草地,这些方法测量值可通过本文提供的拟合公式转化为真实值.随着样方数量增加,8种方法误差均呈现出先降低后稳定趋势.本研究推荐样线法作为类似人工草地覆盖度实地测量方法;未来应根据覆盖度、植被高度和硬度等特征选择适合的测量方法.(图4表2参46)     

Abiotic control on the dissipation of chlorpyrifos spiked in an Udic Ferrisol at a lower dosage

The dissipation routes of chlorpyrifos spiked in an Udic Ferrisol at the dosage of 400 ng g^?1, which represents a residual level after an agricultural application, were studied in a laboratory, using the natural soil under three moisture regimes, sterilised, and organic matter-free soils in the dark at 20°C. The obtained results showed that higher soil moisture caused faster dissipation, and the abiotic and biotic contributions to the total dissipated amount of the applied chlorpyrifos in the soil accounted for 77.3–85.2% and 14.7–22.7%, respectively. In the sterilised soil, the contribution of organic matter to chlorpyrifos dissipation was noticed to account for 95% in the earlier two weeks, and was nearly equal to that of soil minerals two weeks after the incubation.