噻虫啉在水稻中的残留消解动态及风险评估

为了评价19.8%噻虫啉悬浮剂在水稻上使用的安全性,于2011—2012年在福州、天津和南京三地进行了为期2年的田间试验,采用超高效液相色谱法(UPLC)研究了噻虫啉在水稻秆、稻米和稻壳中的消解动态和最终残留.结果表明:噻虫啉在水稻植株中的消解规律符合一级动力学模型,在三地的半衰期为3.8~17.3 d.在推荐使用剂量86.4 g·hm-2(以有效成分计)下,距最后一次施药30 d后收获的稻米中噻虫啉的残留量未超过日本规定的最大残留限量(MRL)值(0.1 mg·kg-1).通过计算得出每人每天从稻米中所摄入的噻虫啉为0.121 mg,风险商值(RQ)为0.192,处于安全水平.     

灭幼脲Ⅲ号杀虫剂在大白菜和土壤中持久性及残留的研究

本文报道灭幼脲Ⅲ号杀虫剂在大白菜和土壤中的残留试验结果.经在南北两地连续两年的田间试验表明,灭幼脲Ⅲ号属非持久性农药,在作物和土壤中都较快地消失,在大白菜上的半衰期为3.8—14.0d,在土壤中为8.8—27.0d.用25％灭幼脲Ⅲ号胶悬剂稀释2500倍,每亩每次按常规用药10g或加倍药量20g(有效成分)施药,喷施2或3次,距最后一次施药三周时,灭幼脲Ⅲ号杀虫剂在大白菜的最大残留量为2.67ppm,在土壤中为13.81ppm.建议该农药在大白菜上的最高允许残留量(MRL)为3ppm,安全间隔期为21d.     

黄土高原区不同植物凋落物可溶性有机碳的含量及生物降解特性

以黄土高原区刺槐、小叶杨、沙棘、沙柳、苜蓿和长芒草等6种植物凋落物为研究对象,利用2种浸提剂(水和0.01 mol·L^-1CaCl₂)浸提了不同大小(2 mm粉碎样和1 cm长)植物凋落物,测定了其中可溶性有机碳(SOC)的含量,并利用室内培养试验(25℃)评价了可溶性有机碳的生物降解特性.结果表明,不同植物凋落物可溶性有机碳含量在4.21～76.25 g·kg^-1之间,占其全碳的比例在0.99%～19.84%之间.平均来看,乔木凋落物可溶性有机物含量及其占全碳的比例大于灌木,而灌木又高于草本.经过7 d的培养,不同凋落物可溶性有机碳的生物降解率在34.7%～75.1%之间,平均56.3%,不同种类凋落物的生物降解率相比为乔木＞灌木＞草本.紫外及荧光光谱法测定法表明,培养结束后SOC溶液中结构较为复杂的可溶性有机物的比例呈显著上升,这与其中易降解组分的降解有关.     

Residue analysis and dissipation of monosulfuron in soil and wheat

HPLC-UV residue analytical method for monosulfuron [ N-[( 4‘-methyl ) pyrimidin-2‘-yl ]-2-nitrophenylsulfonyl urea] in soil and wheat was developed. Monosulfuron residues were recovered by solvent extraction, followed by liquid-liquid partition, and C18 cartrige clean-up. Excellent method recoveries ranging from 95%-104% for both fortified soil and wheat grain were obtained with coefficients of variation 1.5%-11.8%. The minimum detectable quantities in soil and wheat were both 4 ng, the limit of detection was 0.02 mg/kg. When monosulfuron was applied according to double dosage of maximum recommended use direction(120 g ai/hm^2 of 10% monosulfuron wettable powder sprayed for once during development of wheat ) in field studies conducted in Shandong Province and near Beijing, monosulfuron residues was not detected in soil and wheat samples collected 75 d after application. Laboratory soil degradation studies showed that monosulfuron degraded faster in acidic soil and strong alkaline soil than in neutral or weak alkaline soil. Half lives in Jiangxi soil, Shijiazhuang soil, Jiangsu soil and Heilongjiang soil were 41, 48, 87 and 84 d respectively. Monosulfuron residues dissipated rapidly in Shandong and Beijing field test sites with half-lives of less than 14 d.     

Determination of respiration, gross nitrification and denitrification in soil profile using BaPS system

A facility of BaPS （Barometric Process Separation） was used to determine soil respiration, gross nitrification and denitrification in a winter wheat field with depths of 0-7, 7--14 and 14-21 cm. N2O production was determined by a gas chromatograph. Crop root mass and relevant soil parameters were measured. Results showed that soil respiration and gross nitrification decreased with the increase of soil depth, while denitrification did not change significantly. In comparison with no-plowing plot, soil respiration increased significantly in plowing plot, especially in the surface soil of 0-7 cm, while gross nitrification and denitrification rates were not affected by plowing. Cropping practice in previous season was found to affect soil gross nitrification in the following wheat-growing season. Higher gross nitrification rate occurred in the filed plot with preceding crop of rice compared with that of maize for all the three depths of 0-7, 7-14 and 14-21 cm. A further investigation indicated that the nitrification for all the cases accounted for about 76% of the total nitrogen transformation processes of nitrification and denitrification and the N2O production correlated with nitrification significantly, suggesting that nitrification is a key process of soil N2O production in the wheat field. In addition, the variations of soil respiration and gross nitrification were exponentially dependent on root mass （p〈0.00l）.     

水稻土中外源Cd老化的动力学特征与老化因子

选择5种不同性质的水稻土,通过外源添加制备了6个不同浓度梯度的Cd污染土壤,研究了外源Cd在几种水稻土中的老化动力学特征与影响因子;同时利用盆栽实验,结合Log-logistic分布模型,研究了5个不同老化时间(14、30、60、90和180d)与土壤中Cd对二种不同Cd敏感性水稻生长毒性的影响.结果表明,不同浓度外源Cd进入土壤后,0.05mol/L EDTA-2Na浸提的有效态Cd含量随着老化时间的增加而逐渐下降;与14d处理相比,老化30d后土壤中有效态Cd降幅达21.5%(红壤)~38.0%(黑土);老化90d后,土壤中Cd进入慢反应阶段. 基于二级动力学方程的拟合参数显示,土壤中Cd的老化特征表现为有效态Cd含量在30~60d内快速降低,随后变化减缓,经过90d的老化后,土壤中有效态Cd含量逐渐趋于平衡.基于老化动力学方程参数(C∞及K2)与土壤性质间的相关性分析表明,土壤pH值是影响Cd有效态含量变化的主控因子,其次是土壤CEC和OC含量.在不同性质土壤中,随着老化时间的增加,土壤中外源Cd对水稻生长毒性的半抑制浓度(EC50)值显著升高;与14d老化处理相比,经过180d老化后土壤中Cd对水稻生长毒性的EC50增加72.1%~195.0%;在大于90d的长期老化过程中,土壤pH值对Cd老化过程的影响逐渐降低,而CEC的影响逐渐上升,尽管如此,土壤中Cd老化过程的主要影响因子仍然是土壤pH,而与测试的2种水稻品种无关.     

基于不同土壤数据单元法的DNDC模型对太湖地区水稻土CH4排放模拟研究

利用农业土壤痕量气体排放模型DNDC(DeNitrification-DeComposition),以整个太湖地区37个县234万hm2水稻土为例,分析了3种不同土壤数据单元法对CH4排放模拟的影响.其中,1∶5万图斑单元法土壤属性来自1∶5万土壤数据库,图斑为最小模拟单元;1∶5万"县级"单元法土壤属性也取自1∶5万土壤数据库,"县"为最小模拟单元;1∶1 400万"县级"单元法土壤属性取自国内同类研究使用最多的1∶1 400万土壤图和《中国土种志》,"县"为最小模拟单元.结果表明,虽然1∶5万图斑单元法大多数县的CH4排放量都在1∶5万"县级"单元法最大与最小值范围之间,但整个地区总排放量(以C计,下同)相差达到1 680 Gg;而1∶1 400万"县级"单元法CH4排放量与1∶5万图斑单元法相比,尽管整个地区总排放量只相差180 Gg,但各"县级"单元之间的估算差异却很大,这一方面说明了土壤数据的详细程度是保证地球生物化学模型模拟精度的重要因子,另一方面也说明在区域CH4排放量估算模拟中使用更详细的土壤资料是非常必要的.     

Effects of combination of plant and microorganism on degradation of simazine in soil

The degradative characteristics of simazine （SIM）, microbial biomass carbon, plate counts of heterotrophic bacteria and most probably number （MPN） of SIM degraders in uninoculated non-rhizosphere soil, uninoculated rhizosphere soil, inoculated non- rhizosphere soil, and inoculated rhizosphere soil were measured. At the initial concentration of 20 mg SIM/kg soil, the half-lives of SIM in the four treated soils were measured to be 73.0, 52.9, 16.9, and 7.8 d, respectively, and corresponding kinetic data fitted first-order kinetics. The experimental results indicated that higher degradation rates of SIM were observed in rhizosphere soils, especially in inoculated rhizosphere soil. The degradative characteristics of SIM were closely related to microbial process. Vegetation could enhance the magnitude of rhizosphere microbial communities, microbial biomass content, and heterotrophic bacterial community, but did little to influence those community components responsible for SIM degradation. This suggested that rhizosphere soil inoculated with microorganisms-degrading target herbicides was a useful pathway to achieve rapid degradation of the herbicides in soil.     

Differences of cadmium absorption and accumulation in selected vegetable crops

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涕灭威在烟草及土壤中残留动态研究

烟草,土壤中涕灭威总有毒残留分别用丙酮、丙酮与水混合液提取,过氧乙酸氧化,液-液分配和柱层析净化后,气相色谱检测。方法回收率在83~105%之间,土壤、鲜烟叶和干烟叶中的最小检出浓度分别为0.0135ppm,0.0169ppm和0.0339ppm。      

江汉平原中部表层土壤中有机氯农药分布及来源

以GC/ECD测定江汉平原中部24个表层土壤中25种有机氯农药的含量。所有有机氯农药均有检出,其中含量最高的是DDT类农药,HCHs类农药含量规律为δ-HCH>α-HCH>β-HCH>γ-HCH。研究区域农药含量较国内其他地方来说污染较低。通过成分的不同含量比较,发现该地区农药除了早期污染外,近期也有新的污染源。     

厌氧和好氧条件下土壤中六氯乙烷降解的动态研究

通过在实验室模拟不同的环境条件,研究常用有机氯化合物——六氯乙烷(Hexachloroethane,HCE)在好氧和厌氧环境条件中的土壤生物降解动态及其影响因素。结果表明,HCE在水稻土中的降解遵循一级反应动力学方程。相对于好氧条件,厌氧条件下土壤微生物对HCE的降解影响较大。在厌氧条件下,在30⁶0 mg/kg的浓度范围内,HCE的降解随土壤中HCE起始浓度增加而加快,当浓度≥60 mg/kg时,随HCE起始浓度增加而减慢。而在好氧条件下,HCE的降解速率变化较小,表明相对于好氧条件,厌氧条件下土壤微生物可以利用HCE生长,在未达到其毒性耐受浓度时,HCE降解速率随着其浓度的增加而提高,但当浓度超过微生物的耐受极限浓度时,微生物活动将受到抑制,HCE的降解速率呈下降趋势。     

深圳市表层土中氟化物组成及分布

为探究深圳市表层土中氟化物的组成及其与土壤性质参数(有机碳和pH值)的相关关系,应用氟离子选择电极法测定了深圳市表层土中总氟(TF)、可萃取有机氟(EOF)的含量,用固相萃取分离富集与高效液相色谱串联质谱的方法分析了深圳市表层土中全氟化合物(PFCs)的残留水平.结果表明,深圳市表层土中氟化物主要以无机态存在,呈TF>>EOF>> IF(可鉴别F,即以氟计量的总PFCs)的分布规律; EOF仅占TF的0.04%,IF占EOF的0.32%,显示近99.7%的EOF仍属未知.深圳市表层土中PFOA、PFOS分别占∑PFCs的43%(18%~100%)和20%(n.d.~44%),是表层土中主要的PFCs污染物,就空间分布而言,∑PFCs呈西高东低的趋势.表层土中EOF和∑PFCs含量受土壤性质参数的影响,pH值与EOF(P<0.05)、∑PFCs(P<0.01)含量呈负相关,有机碳则与EOF、∑PFCs呈正相关(P<0.01).     

三峡水库消落区土壤、植物汞释放及其在斑马鱼体的富集特征

利用室内模拟试验,探讨了三峡水库消落区淹没后土壤、植物汞释放特征及其在斑马鱼体的富集水平.结果表明,随淹水时间的延长,淹没土壤中总汞(THg)含量下降;水体THg浓度总体明显升高.淹没土壤及水体中甲基汞(MMHg)含量总体明显上升,其中稗草+土壤处理水体中增加尤为明显,淹水21 d后,其浓度是土壤处理的2.52倍.表明消落区土壤、植物是水库水体汞的一个重要来源.供试稗草淹水分解造成水体pH及溶解氧(DO)含量下降、溶解性有机碳(DOC)含量上升,对土壤MMHg含量无明显影响,对水体MMHg影响较大.供试斑马鱼头部、内脏及肌肉中THg含量总体明显上升,与水体中THg浓度具有显著相关性(P<0.01).鱼体头部、内脏及肌肉中均出现不同程度的MMHg富集现象,以头部与肌肉最为明显.淹水21 d后,添加土壤处理的鱼体头部、内脏及肌肉MMHg增加的含量分别是对照的1.75~6.25、3.53~8.38、2.22~3.36倍;稗草+土壤处理的分别是土壤处理的3.57、2.37、1.52倍.可见,淹没土壤是鱼体MMHg增加的重要来源,淹没植物改变原水环境条件影响其向水体释汞过程能提高鱼体中MMHg含量.     

Degradation of 14C-glyphosate and aminomethylphosphonic acid (AMPA) in three agricultural soils

Glyphosate (N-phosphonomethyl glycine) is the most used herbicide worldwide. The degradation of 14C-labeled glyphosate was studied under controlled laboratory conditions in three di erent agricultural soils: a silt clay loam, a clay loam and a sandy loam soil. The kinetic and intensity of glyphosate degradation varied considerably over time within the same soil and among di erent types of soil. Our results demonstrated that the mineralization rate of glyphosate was high at the beginning of incubation and then decreased with time until the end of the experiment. The same kinetic was observed for the water extractable residues. The degradation of glyphosate was rapid in the soil with low adsorption capacity (clay loam soil) with a short half-life of 4 days. However, the persistence of glyphosate in high adsorption capacity soils increased, with half-live of 19 days for silt clay loam soil and 14.5 days for sandy loam soil. HPLC analyses showed that the main metabolite of glyphosate, aminomethylphosphonic acid (AMPA) was detected after three days of incubation in the extracts of all three soils. Our results suggested that the possibility of contamination of groundwater by glyphosate was high on a long-term period in soils with high adsorption capacity and low degrading activities and/or acid similar to sandy loam soil. This risk might be faster but less sustainable in soil with low adsorption capacity and high degrading activity like the clay loam soil. However, the release of non-extractable residues may increase the risk of contamination of groundwater regardless of the type of soil.     

淮河流域土壤中全氟化合物的空间分布及组成特征

为了阐明淮河流域土壤中全氟化合物(PFCs)的暴露特征和潜在来源,2008年10月在淮河安徽段共采集了18个表层土壤样品,通过离子燃烧色谱(CIC)测定总氟(TF)和可提取有机氟(EOF),以及采用高效液相色谱/质谱联用(HPLC/MS-MS)分析了16种PFCs,其中11种PFCs有不同程度的检出.PFCs含量为n.d.～1.22 ng·g-1,其中全氟辛酸(PFOA)、全氟壬酸(PFNA)和全氟辛烷磺酸(PFOS)是主要的PFCs.在这些土壤样品中,PFCs含量相差不大,但组成不一,主要来源于周边小型化工厂的排放以及大气的干湿沉降.利用氟原子质量平衡原理,分析得出PFCs占EOF比例为0.3%,EOF占TF比例为0.02%,一方面说明除PFCs外仍有很大一部分可提取有机氟难以定性和定量,且离子态氟及未提取出的有机氟是TF的主要成分,另一方面受现有标准物质和检测技术限制,尚不能完全甄别和分析出PFCs的含量及未知的有机氟.     

Microencapsulated chlorpyrifos: Degradation in soil and influence on soil microbial community structures

Degradation kinetics of microencapsulated chlorpyrifos （CPF-MC） in soil and its influence on soil microbial community structures were investigated by comparing with emulsifiable concentration of chlorpyrifos （CPF-EC） in laboratory. The residual periods of CPF-MC with fortification levels of 5 and 20 mg/kg reached 120 days in soil, both of the degradation curves did not fit the first-order model, and out-capsule residues of chlorpyrifos in soil were maintained at 1.76 （±0.33） and 5.92 （±1.20） mg/kg in the period between 15 and 60 days, respectively. The degradation kinetics of CPF-EC fit the first-order model, and the residual periods of 5 and 20 mg/kg treatments were 60 days. Bacterial community structures in soil treated with two concentrations of CPF-MC showed similarity to those of the control during the test period, as seen in the band number and relative intensities of the individual band on DGGE gels （p 〉 0.05）. Fungal community structures were slightly affected in the 5 mg/kg treatments and returned to the control levels after 30 days, but initially differed significantly from control in the 20 mg/kg treatments （p 〈 0.05） and did not recover to control levels until 90 days later. The CPF-EC significantly altered microbial community structures （p 〈 0.05） and effects did not disappear until 240 days later. The results indicated that the microcapsule technology prolonged the residue periods of chlorpyrifos in soil whereas it decreased its side-effects on soil microbes as compared with the emulsifiable concentration formulation.     

基于梯度薄膜扩散技术评估黑麦草吸收Cd的研究

分别采用固态结合相(Chelex100)和液态结合相(聚丙烯酸钠,PAAS)的梯度薄膜扩散技术(DGT)对盆栽黑麦草实验中的土壤有效态Cd进行了提取,结果表明2种不同结合相的DGT技术提取的土壤有效态Cd含量与黑麦草地上部和地下部的Cd含量都呈显著相关关系,其相关系数分别为0.90,0.89(Chelex100-DGT)和0.90,0.87(PAAS-DGT).运用多元统计分析方法研究土壤pH值、阳离子交换量(CEC)、有机质(OM)和土壤颗粒组成等理化指标的影响,提取出2种主成分因子,建立逐步回归模型.第1主成分与OM和黏粒组成之间呈显著相关,定义为代表土壤中影响重金属生物有效性的“有机指标”,第2主成分则土壤pH值和CEC相关程度较高,定义为代表土壤中影响重金属生物有效性的“无机指标”.研究表明Chelex100-DGT和PAAS-DGT技术均能较好预测黑麦草对Cd的吸收,且包含了土壤理化性质的影响.     

离子液体支撑液膜萃取分离双酚A、辛基酚和壬基酚

本研究以离子液体1-甲基-3-丁基咪唑六氟磷酸盐([BM IM][PF6])作膜溶剂,利用支撑液膜分离技术,用0.1mol/L的氢氧化钠溶液作萃取溶液将三种环境内分泌干扰物壬基酚、辛基酚和双酚A进行分离。研究结果显示该支撑液膜分离技术对双酚A的萃取效果最好,其次是辛基酚,而壬基酚不被萃取。利用该技术能将三种混合物选择性地进行萃取分离,但萃取时间不宜超过46小时。     

Effect of methamidophos on soil fungi community in microcosms by plate count, DGGE and clone library analysis

Methamidophos was widely used a pesticide in northern China. The potential influences of methamidophos on soil fungal community in black soil were assessed by plate count, 28S rDNA-PCR-DGGE, and clone library analysis. Three methamidophos levels (50, 150, and 250 mg/kg) were tested in soil microcosms. Results from plate count during a 60-d microcosm experiment showed that high concentrations of methamidophos (250 mg/kg) could significantly stimulate fungal populations. DCGE (denaturing gradient gel electrophoresis) fingerprinting patterns showed a significant difference between the responses of culturable and total fungi communities under the stress of methamidophos. Shannon diversity indices calculated from DGGE profiles indicated that culturable fungi in all microcosms with methamidophos treatment increased after 1 week of incubation. However, the diversity indices of total fungi decreased in the first week, as compared to the stimulation of culturable fungi. At the 8th week, however, all the microcosms treated by methamidophos were similar to the control microcosms in community structure as suggested by the Shannon diversity indices for both culturable and total fungi. In contrast, after 1 week the fungal structure of culturable and unculturable both were disturbed to different extent under the stresses of methamidophos by clustering analysis. Clone sequencing analysis indicated the stimulation of pathogenic and unculturable fungal populations by methamidophos treatment, suggetsing potential risks of plant disease outbreak.