Residue dynamics of carbendazim and mancozeb in grape (Vitis Vinifera L.) berries

The residue dynamics of carbendazim and mancozeb in grape berries is reported. The fungicides were sprayed in accordance with the most critical use pattern i.e. 4 times at 15 days interval separately at recommended and double doses. The residues of each fungicide dissipated following 1st order rate kinetics. The half-lives of carbendazim and mancozeb were 7.3 and 8.1 days at recommended dose and 4.6 and 5.7 days at double dose. Ethylenethiourea (ETU), the toxic metabolite of mancozeb was detectable at harvest following four sprays of mancozeb at recommended dose. At double dose, however, the residues of ETU could be detected even after three sprays of mancozeb. The pre-harvest intervals for carbendazim and mancozeb were found to be 26 and 12 days at recommended dose and 33 and 17 days at double dose, respectively.     

香蕉镰刀菌枯萎病防治药剂的筛选

杀菌剂对香蕉尖孢镰刀菌的毒力测定筛选结果表明，绿亨一号 多菌灵、五氯硝基苯 多菌灵、多菌灵 普克、敌克松 普克等混配药剂对香蕉尖孢镰刀菌的抑制效果最佳，持效期长，可作为防治香蕉枯萎病的土壤消毒剂使用。     

12种杀菌剂制剂对半闭弯尾姬蜂的急性毒性及安全性评价

采用试管药膜法测定了12种杀菌剂制剂对半闭弯尾姬蜂成蜂的急性接触毒性,结合安全性系数评价了供试药剂对半闭弯尾姬蜂的安全性。急性毒性测定结果表明,氟硅唑和啶菌噁唑对半闭弯尾姬蜂成蜂的接触毒性最高,LC50值分别为220.022和223.115 mg·L-1;其次为多抗霉素、丙森锌和戊唑醇,LC50值分别为436.496、472.358和638.638 mg·L-1;其余7种杀菌剂制剂嘧霉胺、啶酰菌胺、苯醚甲环唑、多菌灵、嘧菌酯、嘧菌环胺和异菌脲对半闭弯尾姬蜂成蜂的触杀毒性都较低,LC50值均大于1 000 mg·L-1。安全性评价结果表明,丙森锌和啶菌噁唑对半闭弯尾姬蜂成蜂具有高风险性,安全系数分别为0.16和0.42;嘧霉胺、多抗霉素、氟硅唑和戊唑醇为中等风险性,安全系数分别为1.43、1.56、2.20和3.23;其余6种杀菌剂制剂啶酰菌胺、苯醚甲环唑、多菌灵、嘧菌酯、嘧菌环胺和异菌脲对半闭弯尾姬蜂表现为低风险性,安全系数均大于5。结果显示:甾醇脱甲基抑制剂氟硅唑、戊唑醇和啶菌噁唑以及苯胺基嘧啶类杀菌剂嘧霉胺、有机硫杀菌剂丙森锌和抗菌素多抗霉素对半闭弯尾姬蜂成蜂具有急性毒性风险,在有害生物综合治理中应谨慎使用,特别是啶菌噁唑和丙森锌,以免对半闭弯尾姬蜂造成不良影响和危害。     

南方茶园红壤施用PAM对土壤理化性质和茶叶安全的影响

传统的水土保持措施在坡地茶园上应用比较困难,而利用聚丙烯酰胺（PAM）来防治茶园土壤侵蚀的适宜性还有待研究。因此,在铁观音（Camellia sinensis）茶园设置6个不同PAM施用量的小区（0、2、4、6、8、10 g·m-2）,并采集春、夏、秋3个收获季节的土壤和茶叶样品,通过分析茶园土壤理化性质和茶叶中丙烯酰胺残留来评价PAM对土壤理化性质和茶叶安全品质的影响。结果表明：与对照小区相比,土壤容重在低PAM施用浓度小区中发生降低,土壤有机质在不同季节的各PAM处理之间差异不显著,而土壤速效磷、碱解氮和速效钾在3个收获季节中的流失下降明显,其中施用2 g·m-2 PAM的小区其土壤速效磷、碱解氮和速效钾含量最高。每个PAM处理的茶叶样品和土壤样品中单体丙烯酰胺的残留量分别为0.011~0.095μg·L-1和0.008~0.036μg·L-1,均远低于丙烯酰胺安全限值0.5μg·L-1。文章认为红壤茶园施用PAM不仅可以保持土壤肥力,而且对茶叶生产也是安全的。施用PAM是一种适宜的防治红壤茶园土壤侵蚀的水保措施,且最佳用量为2 g·m-2。     

4种甲氧基丙烯酸酯类杀菌剂对拟澳洲赤眼蜂成蜂的急性毒性及安全性评价

为甲氧基丙烯酸酯类杀菌剂合理使用提供科学依据,本研究采用试管药膜法测定了啶氧菌酯、吡唑醚菌酯、嘧菌酯和醚菌酯等4种药剂的原药及其制剂对拟澳洲赤眼蜂成蜂的急性毒性,并进行了安全性评价。对比原药结果发现,啶氧菌酯原药和醚菌酯原药毒性很高,LR50依次是2.66×10-4及7.32×10-4mg a.i.·cm~(-2),均属于高风险;而吡唑醚菌酯原药及嘧菌酯原药毒性较低,LR50分别为3.01×10-3和3.47×10-3mg a.i.·cm~(-2),均为中等风险药剂。对比制剂结果发现,啶氧菌酯悬浮剂毒性最高,LR50为5.02×10-5mg a.i.·cm~(-2),为极高风险药剂;其次是吡唑醚菌酯悬浮剂及乳油,LR50分别为3.78×10-3和5.80×10-3mg a.i.·cm~(-2),均为中等风险药剂;最低的是嘧菌酯水分散粒剂、悬浮剂和醚菌酯水分散粒剂,LR50均大于4.0×10-2mg a.i.·cm~(-2),均为低风险药剂。部分甲氧基丙烯酸酯类杀菌剂对天敌赤眼蜂存在较高风险,特别是啶氧菌酯,应避免田间使用,或通过避开赤眼蜂释放期来减少对赤眼蜂的伤害。     

江汉平原农村食品中农药残留研究

研究了湖北省潜江市农村６类食品中农药的残留情况,采样测定结果表明,在被检食品中有机氯农药污染普遍存在,但残留量均低于最大残留限量（ＭＲＬ）,以植物油残留量为最大;有机磷农药残留只在蔬菜中检出,检出率以根菜类为最大,叶菜类次之,果菜类和花菜类最小;菊酯类农药残留较少;杀菌剂多菌灵残留未检出。     

超声辅助乳化液相微萃取分析绿茶饮料和番茄汁中有机磷农药残留

农药施用于田间,必然会残留于环境中。农药残留的分析方法多种多样。为探究灵敏度高、重现性好的样品前处理方法,建立了超声辅助乳化液相微萃取,结合气相色谱和火焰光度检测器测定绿茶饮料和番茄汁中5种有机磷农药的方法,对萃取条件进行了优化,如萃取溶剂种类和体积、超声频率和时间、盐效应。在优化后的萃取条件下,5种有机磷农药实现良好分离,空白添加实验结果表明在0.1~10μg·L-1之间,线性相关系数在0.9985~0.9994之间,检测限在0.005~0.020μg·L-1之间,相对标准偏差(n=5)在4.3%~9.4%之间。在绿茶饮料和番茄汁实际样本检测中,目标分析物含量均低于检出限。样本添加回收试验的回收率均大于88.5%,相对标准偏差(n=3)在2.2%~9.8%之间,结果表明该方法用于液体样本中农药残留检测真实可靠。     

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.     

农药分配系数与其水溶解度的相关性

本文探讨了有机磷、有机氯和氨基甲酸酯等杀虫剂、杀菌剂和除草剂的各种不同类型以及所研究的全体农药在正辛醇与水中的分配系数与其水溶解度的相关关系,建立了相关经验方程。回归结果表明,除杀菌剂外两者间具有很好的线性关系。所有农药的回归方程中,分配系数和水溶解度均覆盖了10个数量级,两者间可很好地进行互算。     

Cytotoxicity of benalaxyl,metalaxyl, and triadimefon on Chinese hamster ovary cells

The cytotoxicity of the fungicides benalaxyl, metalaxyl, and triadimefon was evaluated in vitro using the Chinese hamster ovary (CHO-K1) cell line. The midpoint cytotoxicity values of neutral red (NR) incorporation (NRI₅₀), total cellular protein content (TCP₅₀), and the methyl tetrazolium assay (MTT₅₀) were estimated. Benalaxyl was the most cytotoxic fungicide, followed by metalaxyl and triadimefon. Fetal calf serum (10%) caused a reduction in benalaxyl, metalaxyl, and triadimefon cytotoxicity by factors of 1.8, 1.3, and 1.3. The effects of sublethal concentrations (NRI₂₅) of the three fungicides on the glutathione redox cycle components glutathione S-transferase, glutathione reductase, glutathione peroxidase, and total glutathione content were studied. The ameliorative effects of extracellular glutathione (1 mmol L^?1), vitamin C (70 µmol L^?1), and vitamin E (30 µmol L^?1) were also investigated. The three antioxidants led to significant effects on the glutathione redox cycle components.     

三叶虫茶茶多酚提取工艺研究

研究萃取-沉淀法从虫茶中提取分离茶多酚的影响因素.采用单因素循环法考虑各影响因素,得出三叶虫茶茶多酚的最优提取工艺.用回流法提取茶多酚,并用单因素循环法分别考察提取剂、沉淀剂、转溶酸、萃取次数对茶多酚提取率的影响,用紫外-可见分光光度法对提取液进行检测.用萃取-沉淀法从虫茶中提取分离茶多酚,以80%丙酮作提取剂,Zn Cl2作沉淀剂,盐酸转溶的效果较为理想.结论表明,萃取-沉淀法提取分离虫茶中茶多酚,所需要的有机溶剂少,能耗低,纯度高,具有可行性.图4,表5,参14.     

二氯喹啉酸在水稻、土壤和田水中消解动态及残留

为评价二氯喹啉酸在水稻及其土壤中的安全性,建立其在水稻上的使用规范,于2008、2009年在杭州、济南和铁力三地进行田间试验,研究了二氯喹啉酸在水稻、土壤和田水中消解动态及最终残留量。建立了二氯喹啉酸在水稻、土壤和田水中残留量的超高效液相色谱串联质谱测定方法。在添加水平5～100μg.kg-1范围内,二氯喹啉酸的平均回收率在81.6%～105.7%之间,相对标准偏差均低于17.9%。残留试验结果表明,二氯喹啉酸在植株、土壤和田水中消解均符合一级动力学方程,消解半衰期分别为16.4～18.6、16.6～21.9和15.4～16.9 d;二氯喹啉酸在植株、土壤、糙米和稻壳中最终残留量均未检出（〈5μg.kg-1）。若二氯喹啉酸在水稻中的最高残留限量推荐值为0.5 mg.kg-1,建议每年以有效成分25 g.mu-1的剂量,于水稻移栽后10 d喷施1次,用于防治水稻田中稗草。     

建立室内实验程序用于量化鸟类对种子消耗量的杀虫剂处理效应

种衣剂中使用的杀虫剂会影响鸟类对种子的消耗量,从而影响鸟类的实际暴露风险。虽然量化这种对消耗量的影响目前不被考虑在环境风险评估中,但这是一个潜在的选择,例如在比较不同农药的暴露风险时应予以考虑。这种方法可以突出用于防止鸟类服用致死或亚致死剂量的杀虫剂。为了制定一个标准,我们在已建立的笔试方法的基础上开发了一个室内测试程序,包括饥饿期的“两选择”和“无选择”阶段。测试期间采用动物福利的最高标准。利用统计方法确定最合适的重复次数并分析最终结果。杀虫剂对种子消耗量的影响用处理后种子与未处理种子消耗的比率表示。该消耗因子可作为种子处理的鸟类风险评估中的回避因子。 作为案例,我们提出了一个获得绿雀（Carduelis chloris）和日本鹌鹑（Coturnix japonica）对未处理和使用杀真菌剂处理的油菜籽（Brassica napus）的种子和特定物种消耗量因子的试验程序。总体来说,两种鸟类的体质都没有受到试验程序的负面影响。试验程序适用于显示预期消耗模式的差异,例如在“两选择”试验中比在“无选择”试验中对经过杀真菌剂处理的种子有更高的避免性。而种子消耗量在不同物种和杀真菌剂处理组有差别,这使得我们可以对不同杀真菌剂的规避效应进行排序。使用本文所提出的标准程序可以针对更多鸟类物种得到具有可比性的农药和物种特定的消费因子。     

聚乙烯醇精馏残渣组分分析及其环境风险评价

为评估聚乙烯醇生产中精馏残渣组分及其环境污染风险,为此类危险废物的环境管理提供技术支持,采集华东某聚乙烯醇生产企业的精馏残渣,分析其重金属以及有机污染物含量,并评估其环境风险。研究结果表明聚乙烯醇精馏残渣主要来自生产环节中的醋酸乙烯精制工段,残渣中的有机物组分主要为醋酸及其他有机酸类,其中醋酸的相对含量达到63.47%;残渣中的重金属主要包括Zn、Ni和Cr,其含量分别为404 537 mg·kg-1,8 654 mg·kg-1和5 084 mg·kg-1。环境风险评价的结果表明残渣中有机物污染物引起的环境风险在可接受范围内,而重金属污染严重,同时有很高潜在生态风险。精馏残渣中的主要环境污染风险因子为醋酸、Zn和Ni。     

菊花茶中砷含量特征及砷健康风险评价

菊花茶是深受人们喜爱的一种饮品,但其干燥过程及加工工艺不当会造成菊花茶的重金属污染,尤其是和硫磺矿伴生的重金属砷。以市售菊花茶为研究对象,采用硝酸-双氧水消解体系,高压密闭消解系统和原子荧光光谱法分析测定了其中砷(As)含量,对典型超标菊花茶样品进行不同冲泡方式的筛选,确定其适宜的饮用方式,并根据我国绿色代用茶行业标准和WHO砷最大日允许摄入量(ADI)对菊花茶中砷的人体健康风险做出评价。结果表明,菊花茶中砷的含量范围在0.01～3.52mg·kg-1,91.1%的样品符合绿色代用茶的《中华人民共和国农业行业标准》(0.5mg·kg-1),其中砷含量最高的为药用祁菊花达3.52mg·kg-1,所有样品中超标的8个菊花茶样品种类分别为祁白菊(2个),杭白菊(2个),黄山贡菊(1个)和野菊花(1个),怀菊和药用祁菊各1个,75%的超标样品为散装饮品;选择超标的2个典型菊花茶样品(杭白菊和药用祁菊花)进行冲泡方式筛选,得出适宜的饮用方式为:用水茶质量比例为25∶1的开水清洗菊花茶5min,然后用开水冲泡5～20min再饮用。随菊花茶进入人体的最大日摄入量(极限值)为43.7～169μg·d-1,其占ADI(allowable daily intake)的比值范围在34.1%～132%,其中随药用祁菊花进入人体的As最大日摄入量与ADI的比值超过100%,这表明砷经菊花茶饮品摄入人体内所潜在的健康风险不容忽视。砷超标的菊花茶经过冲泡后饮用,砷的人体日摄入量13.1～36.3μg·d-1,其占ADI的比值范围在10.3%～28.4%。因此,经过洗茶后再冲泡饮用,砷的日摄入量显著降低(P<0.01),建议饮用菊花茶时洗1次茶后再冲泡饮用。     

Determination of chlorothalonil residues in coffee

Coffee beans were treated with the fungicide chlorothalonil (2,4,5,6‐tetrachloro‐1,3‐benzene‐dicarbonitrile) and the residues were determined by high‐performance liquid Chromatograph (HPLC). Several techniques including Soxhlet extraction (SE), microwave‐assisted extraction (MAE) and accelerated solvent extraction (ASE) were compared for the extraction of residues. A column clean‐up procedure was developed to remove the co‐extractives in the extract before HPLC analysis. The overall mean recoveries from extracts obtained by SE, MAE and ASE were 89.2 ±3.9, 88.4 ±1.9 and 82.8 ±0.3, respectively. The results show that MAE followed by HPLC is a viable alternative to the commonly used SE and gas Chromatographic analysis for the determination of chlorothalonil in coffee.     

麻疯树核糖体失活蛋白(curcin)的化学修饰与其活性的关系

通过无细胞体系蛋白合成抑制活性的测定,结合荧光光谱和圆二色谱技术,对麻疯树核糖体失活蛋白(cur-c in)部分氨基酸残基进行特异性化学修饰,探讨维持curc in活性的必需氨基酸基团及修饰对curc in结构的影响.结果表明,组氨酸和半胱氨酸的修饰对活性没有影响.色氨酸和赖氨酸的修饰使curc in的活性分别下降了50%和100%,表明色氨酸和赖氨酸是维持curc in活性的重要残基.精氨酸修饰导致curc in的抑制活性完全丧失,内源荧光强度下降,最大发射波长发生红移,CD谱发生显著变化;表明精氨酸也是维持curc in活性的必需残基,并且对空间结构影响较大,推测对精氨酸的修饰破坏了精氨酸与其它基团的连接,导致curc in分子结构发生改变,失去和底物结合的能力,因而活性丧失.图3表1参34     

高效液相色谱-荧光检测法同时测定畜禽粪便中4种磺胺类药物残留

建立了高效液相色谱-荧光检测法测定畜禽粪便中4种磺胺药物(磺胺甲基嘧啶(SM1)、磺胺氯哒嗪(SCP)、磺胺邻二甲氧嘧啶(SDM’)、磺胺喹噁啉(SQ))的方法.样品用25 mL甲醇提取3次,合并提取液,浓缩干燥,用0.1 mol.L-1的HCL溶解残渣,经荧光胺衍生化后,用反相C18柱为分离柱,以乙腈∶0.5%乙酸=40∶60(V/V)为流动相进行洗脱,20 min内分离4种药物.在0.05—5.00μg.mL-1范围内,4种磺胺类药物的峰面积与质量浓度的线性关系良好(R2≥0.999),SM1、SCP、SDM’、SQ的定量限(LOQ)分别为2.3、6.3、4.3和9.6μg.kg-1;添加水平为50、100、1000μg.kg-1时,SM1、SCP、SDM’、SQ的回收率分别为74.91%—81.82%、78.45%—91.43%和86.10%—92.88%,RSD小于8.82%.     

Solid substrate fermentation of cassava fibrous residue for production of alpha-amylase, lactic acid and ethanol

There is serious concern about the disposal of solid residues left after large scale extraction of starch from cassava. Owing to the high starch content (55-65% on dry weight basis) and organic matter of these wastes, an attempt has been made to utilize it for the production of three bioproducts, i.e. alpha-amylase, lactic acid and ethanol in solid substrate fermentation by incubating the solid residue at different moisture holding capacity (40-80%) and incubation period (12- 60 hr for alpha-amylase, 24-144 hr for ethanol and 2-10 days for lactic acid). The highest product yield was obtained at 60% moisture holding capacity of the residue and period of incubation varied from 36 hr (alpha-amylase), 120 hr (ethanol) to 6 days (lactic acid). This study showed that the solid residues from cassava starch factories could serve as a low-cost substrate for bioproducts production.     

Assessing the potential of crop residue recycling in China and technology options based on a bottom-up model

Crop residues are an important biomass, and are significant in the sustainable development of China. This paper uses the Grey-Markov modeling approach, the cost-benefit analysis method, and the constraint optimiza- tion method to establish the potential of crop residue recycling in China （CRRC） using a bottom-up analysis. Taking 2010 as the baseline year, the CRRC model is used to determine the quantity trends of crop residue resources, simulating the recycling potential and selecting key crop residue recycling technologies for operation between 2010 and 2030. The results illustrate that the total residue output from different crops will gradually increase to 1062 million tons in 2030. The proportion of crop residue for field burning is expected to decrease as a result of guidance and support from the government. Market mechanisms are also improving the development of the crop residue recycling industry. The economic benefit of crop residue recycling is expected to be worth 132 billion CNY in 2030 according to technology structure options. Key crop residue recycling technologies preferred such as liquefaction, amination, silo, co-firing straw power and composting will account for more than 85% of the total benefits.