水分调控下旱地土壤中毒死蜱的消解研究

为探讨水分调控下旱地土壤中毒死蜱的消解特性,通过盆栽试验及通径分析方法,研究了不同水分条件下旱地土壤中毒死蜱消解速率及其与土壤性质之间的关系.结果表明:①土壤中毒死蜱的消解速率随时间的延长而逐渐减缓,并且不同水分条件下土壤中毒死蜱的消解速率不同,施药45 d后,5个水分处理（20% FC、40% FC、60% FC、80% FC和100% FC,表示田间持水量依次为20%、40%、60%、80%和100%）下毒死蜱的消解率分别为65.58%~85.56%、70.71%~89.64%、76.30%~95.33%、72.53%~97.60%和70.57%~90.80%,其中以80% FC下的消解速率最快,60% FC下次之.②一级动力学方程能较好地描述土壤中毒死蜱的消解过程（R2>0.88）,消解速率常数（k）最大为0.099 0 d-1.③土壤中毒死蜱的消解速率与w（有机碳）、w（DOC）（DOC为可溶性有机碳）和w（MBC）（MBC为微生物量碳）均呈显著相关.通径分析结果显示,水分条件的改变致使土壤中w（有机碳）、w（DOC）和w（MBC）发生变化,进而对土壤中毒死蜱的消解速率产生较大影响.④大豆、玉米和小麦根际土壤中毒死蜱消解速率均快于非根际土壤,根际土壤中毒死蜱消解速率表现为大豆土壤（0.099 0 d-1）>玉米土壤（0.080 6 d-1）>小麦土壤（0.069 6 d-1）.研究显示,改变土壤水分含量可有效调节土壤中毒死蜱的消解,并为农业生产中毒死蜱的安全施用提供参考依据.      

Dissipation of chlorpyrifos on pakchoi inside and outside greenhouse

The dissipation of chlorpyrifos on pakchoi inside and outside greenhouse was studied. The decline curve of chlorpyrifos on pakchoi could be described as first-order kinetic. The experimental data showed that both the hermetic environment of greenhouse and season affected dissipation rates of chlorpyrifos on pakchoi. Chlorpyrifos declined faster outside greenhouse than inside greenhouse.Chlorpyrifos residues at pre-harvest time were below the maximum residue limits(MRLs) fixed in China, whereas the values inside greenhouse were higher than those outside greenhouse by almost 50%. The recommended pre-harvest time established under conditions of open field might not always fit to greenhouse production.     

Distribution of chlorpyrifos in rice paddy environment and its potential dietary risk

Chlorpyrifos is one of the most extensively used insecticides in China. The distribution and residues of chlorpyrifos in a paddy environment were characterized under field and laboratory conditions. The half-lives of chlorpyrifos in the two conditions were 0.9–3.8 days (field) and 2.8–10.3 days (laboratory), respectively. The initial distribution of chlorpyrifos followed the increasing order of water < straw < soil, and soil was characterized as the major absorber. The ultimate residues in rice grain were below the maximum residue limit (MRL) with a harvest interval of 14 days. The chronic exposure for chlorpyrifos was rather low compared to the acceptable daily intake (ADI = 0.01 mg/kg bw) due to rice consumption. The chronic exposure risk from chlorpyrifos in rice grain was 5.90% and 1.30% ADI from field and laboratory results respectively. Concerning the acute dietary exposure, intake estimated for the highest chlorpyrifos level did not exceed the acute reference dose (ARfD = 0.1 mg/kg bw). The estimated short-term intakes (ESTIs) were 0.78% and 0.25% of the ARfD for chlorpyrifos. The results showed that the use of chlorpyrifos in rice paddies was fairly safe for consumption of rice grain by consumers.     

基于旱地土壤环境风险的农药毒死蜱的施用限值研究

通过开展田间试验,研究毒死蜱在玉米、小麦和大豆3种作物田土壤中的降解及环境风险,基于毒死蜱及其降解产物TCP的残留特征和环境风险,计算毒死蜱施用限值.研究表明玉米田土壤中的毒死蜱残留量大于大豆田和小麦田;毒死蜱在农田土壤中的降解速率随着施用浓度的增加而提高.小麦、大豆、玉米3种作物种植土壤中毒死蜱及TCP的短期和长期生态风险均有差异.玉米、大豆和小麦3种作物农田中,当超过推荐剂量施用毒死蜱,毒死蜱及TCP均具有较高短期风险和长期生态风险,相对于毒死蜱,TCP对土壤的生态风险更高.基于旱地土壤的毒死蜱及TCP的环境风险,通过模型计算农药毒死蜱在大豆田中的施用限值为0.4412 kg·hm^-2,在小麦田中的施用限值为0.5034 kg·hm^-2,在玉米田中的施用限值为0.5487 kg·hm^-2.     

Residual dynamics of thiacloprid in medical herbs marjoram, thyme, and camomile and in soil

Thiacloprid is a new insecticide of the chloronicotinyl family. To assess its risk after application, residual characteristics of thiacloprid in marjoram, thyme, and camomile and in soil were studied under field conditions. The active ingredient was extracted from the plant material using a mixture of acetone-water. After filtration, the extract was concentrated to the aqueous phase, diluted with water, and portioned against ethyl acetate on a matrix solid phase dispersion column. Thiacloprid was extracted from soil using a mixture of methanol-water, filtered, and re.extracted （clean up） with dichloromethane. The residues were quantified using HPLC-MS-MS. The methods were validated by recovery experiments. Thiacloprid residues in marjoram, thyme, and camomile and in soil persisted beyond 10, 14, 14, and 21 d but no residues were detected after 14, 21, 21, and 28 d, respectively. The data obtained in this study indicated that the biexponential model is more suitable than the first-order function to describe the decline of thiacloprid in fresh marjoram, fresh thyme, and dried camomile flowers with half-life （t1/2） of 1.1, 0.7, and 1.2 d, respectively. However, both the first-order function and biexponential model were found to be applicable for dissipation of thiacloprid in soil with almost the same t1/2 values of 3.5 and 3.6 d. The results indicated that thiacloprid dissipates rapidly and does not accumulate in the tested herbs and in soil.     

乌梁素海硝酸盐来源的季节性变化

乌梁素海是典型农业灌区退水型湖泊,其水生态环境保护对黄河流域生态保护具有重要意义.该研究通过开展乌梁素海流域农业排干和湖体硝酸盐的δ15N和δ18O分析,应用IsoSource同位素模型估算流域生产生活污水、土壤氮源、化肥和大气沉降的贡献率.结果表明:①湖区δ15N-NO₃-和δ18O-NO₃-值范围分别为-2.50‰~18.17‰和-12.02‰~45.09‰,其中夏秋两季δ15N-NO₃-值偏正,冬季偏负,且秋季δ18O-NO₃-值偏正.②春季湖水硝酸盐主要源于化肥和土壤氮源相关的农业活动,其贡献率为43.7%;夏季、秋季和冬季主要源于生产生活污水,贡献率分别为51.3%、38.8%和40.2%,其中夏季农业活动贡献率超过40%,大气沉降主要体现在秋季湖水中.研究显示:春季湖区硝酸盐来源主要集中于七排干和八排干的受水区域,以上区域应在春季着重加强农业面源污染控制;夏季和秋季湖区硝酸盐来源主要集中于五排干和七排干所处城乡区域,以上区域应强化城乡生活污水处理.      

日光温室夏季休闲期间的土壤管理对可溶性氮的影响

日光温室夏季休闲期间大水漫灌和高温闷棚是普遍的土壤处理措施,该过程灌水多、温度高,对氮素循环影响大.为了探明休闲期间土壤管理对氮素保持与损失的影响,通过田间试验揭示夏季休闲期间大水漫灌、高温闷棚对不同灌溉施肥模式(滴灌、漫灌)和不同有机物料还田处理(单施有机肥、有机肥配施小麦秸秆、有机肥配施玉米秸秆)土壤可溶性氮的影响.结果表明:作物收获后,滴灌和漫灌各处理平均w(矿质氮)分别为103.9和68.6 mg/kg,大水漫灌使滴灌0~30 cm土层w(矿质氮)显著降低30%,漫灌w(矿质氮)变化不大.日光温室夏季休闲期w(SON)(SON为可溶性有机氮)为16.3~69.1 mg/kg,SON相对含量为15%~48%.大水漫灌使滴灌和漫灌w(SON)分别显著增加2.9和2.5倍;高温闷棚使滴灌和漫灌w(SON)显著降低107.1和72.4 kg/hm2,降幅分别为41%和34%,同时w(矿质氮)分别显著增加117.9和126.7 kg/hm2,土壤氮素矿化速率分别为1.7和1.8 mg/(kg·d).与单施有机肥相比,长期有机肥配施玉米或小麦秸秆可显著增加滴灌w(矿质氮),但对w(SON)无影响.综上,休闲期间的土壤管理对土壤表层氮素含量的影响较大,其中大水漫灌容易造成滴灌残留氮素的大量损失,而随后的高温闷棚加速了SON的矿化.      

黄海溶解无机氮时空变化及其水团对DIN总量的影响

本文根据2013~2016年4个航次调查资料,研究了黄海水体中溶解无机氮（DIN）的时空变化及其总量影响因素.结果表明：春、夏、秋和冬季黄海调查海域DIN平均浓度分别为（5.43±4.02）,（4.47±3.16）,（7.46±3.56）和（5.09±2.59）μmol/L.其中,秋季浓度最高,夏季最低;黄海调查海域各季节DIN的分布呈现近岸高、外海低的变化规律,近岸高值点多集中在长江口以北、山东半岛和辽东半岛等处.春~秋季影响DIN分布的因素主要是陆源输入和浮游植物的生长繁殖,冬季则主要是河流输入和沉积物再悬浮作用.四季在中央海域底层还存在一个高值区（>6μmol/L）,主要受黄海冷水团和黄海暖流等共同影响;通过聚类分析法对黄海四季水团进行了基本划分,调查海域主要包括5个水团：黄海混合水团、黄海冷水团、黄海暖流水、沿岸水团和黄东海混合水团,除黄海混合水团终年存在外,其他水团均为季节性存在;调查海域DIN总量四季差异不大,整体含量介于1.0×10⁶~1.5×10⁶t,春、夏、秋和冬季DIN总量分别约为1.2×10⁶,1.0×10⁶,1.5×10⁶和1.3×10⁶t.春季和夏季受浮游植物吸收影响,DIN总量略低,从水团对DIN总量的贡献上来看,春季以黄海暖流为主,夏季以黄海冷水团为主,秋、冬季以黄海混合水团为主.     

苯醚甲环唑在番茄和土壤中的残留动态研究

采用田间试验方法研究苯醚甲环唑在番茄和土壤中的残留与降解动态,应用超高效液相色谱-串联四级杆液质联用法(UPLC-MS/MS)进行定性和定量分析. 结果表明,苯醚甲环唑在番茄中的平均回收率为90.3%～107.1%,变异系数为0.7%～7.8%;在土壤中的平均回收率为80.1%～104.7%,变异系数为7.2%～9.1%. 动态研究结果表明:苯醚甲环唑在番茄中的降解比在土壤中快,在山东和河南两地番茄中的降解半衰期分别为3.3～3.8和3.3 d;在土壤中的降解半衰期分别为19.9～22.4和13.1～18.8 d. 10%苯醚甲环唑微乳剂在番茄上按照推荐剂量最多施药2次,采收期距最后一次施药3 d,番茄中苯醚甲环唑残留量小于0.158 mg/kg. 低于日本和澳大利亚规定的最高残留限量(MRL,0.5 mg/kg),说明苯醚甲环唑为低残留、易降解农药.      

Degradation of chlorpyrifos in laboratory soil and its impact on soil microbial functional diversity

Degradation of chlorpyrifos at different concentrations in soil and its impact on soil microbial functional diversity were investigated under laboratory conditions. The degradation half-lives of chlorpyrifos at levels of 4, 8, and 12 mg/kg in soil were calculated to be 14.3, 16.7, and 18.0 d, respectively. The Biolog study showed that average well color development (AWCD) in soils was significantly (P < 0.05) inhibited by chlorpyrifos within the first two weeks and thereafter recovered to the similar level as the control. A similar variation in the diversity indices (Simpson index 1/D and McIntosh index U) in chlorpyrifos-treated soils was observed, no significant difference in the Shannon-Wiener index H' was found in these soils. With increasing chlorpyrifos concentration, the half-lives of chlorpyrifos were significantly (P ≤ 0.05) extended and its inhibitory effects on soil microorganisms were aggravated. It is concluded that chlorpyrifos residues in soil had a temporary or short-term inhibitory effect on soil microbial functional diversity.     

水稻种植对黑土微生物生物量和碳源代谢功能的影响

采用磷脂脂肪酸方法和Biolog-ECO微平板检测法,以吉林省长春市双阳区农业技术推广站实验区的土壤为对象,研究了水稻种植对黑土微生物生态结构和功能的影响.结果表明空地中有机质含量最高,其次为田间土,根际土中有机质含量最低;在夏季的样品中有机质含量最高,土壤中全氮的变化趋势与土壤有机质比较相似.土壤微生物群落功能多样性指数则表现为夏季显著高于秋季和春季,春、秋两季差异不明显,冬季最低,空地中微生物群落的Shannon-Wiener指数和Pielou均匀度指数高于田间和根际.全部样品微生物生长步入稳定期时间和碳源的颜色平均变化率变化范围不同,时间分别为216、192、216、120 h,范围分别为0.52~0.84、0.82~1.28、0.40~0.84、0.05~0.48,表明春秋季微生物步入稳定期和对碳源的代谢量比较相似,夏季最大,冬季最小.研究结果为科学评价典型水稻种植黑土区土壤生境质量退化与恢复过程中微生物特征的变化提供参考.     

毒死蜱在小麦植株及土壤环境中的残留特性

通过盆栽试验,利用固相萃取和气相色谱氮磷检测器分析方法研究了有机磷农药毒死蜱在小麦植株及其生长土壤中的残留特性. 结果表明:毒死蜱在小麦植株中的降解较快,施药21 d降解率均已超过99%,其中分蘖期比拔节期降解更快,施药14 d降解率已达99.56%,降解规律用指数方程拟合得不够好;毒死蜱在盐碱土中的降解比在通常的生长土壤中快得多,平均半衰期为11.04 d,其中在拔节期比在分蘖期土壤中降解快,降解规律符合指数方程. 毒死蜱在低浓度下降解的半衰期相对更长.      

桂林盘龙洞土壤CO_2释放速率的分布状况和变化规律

以桂林盘龙洞岩溶实验场为例,选择岩溶洼地里的坡地灌木丛和洼地灌木丛2个样地,通过长期定时监测土壤CO2释放速率的季节变化、空间分布规律以及日动态变化。得知：⑴无论是坡地还是洼地,春季和夏季时土壤CO2释放速率表层土大于深层土,秋季和冬季时深层土大于表层土,且坡地大于洼地;⑵土壤CO2的释放速率具有明显的季节性变化特征,...     

江淮地区湿沉降对颗粒物清除能力的影响

为了解单次降水总量、降水时长、降水前颗粒物质量浓度对颗粒物清除能力的影响,对江淮地区2017年气象资料与颗粒物质量浓度资料展开分析.分析江淮地区2017年ρ（PM_2.5）、ρ（PM₁₀）及降水特征,综合对比各季节不同单次降水总量对颗粒物的清除能力,对比不同季节、不同降水时段对颗粒物清除能力的变化特征,以及不同季节降水前颗粒物质量浓度与清除率对应阈值关系.研究表明:江淮地区北部颗粒物质量浓度高于南部,南部单次降水总量和降水总时长较北部高.单次降水总量越大对颗粒物的清除率越高.当单次降水总量大于1.5 mm时,清除率提升最明显,并且秋、冬两季清除率高于春、夏两季;当单次降水总量低于1.5 mm时,春、夏两季清除率高于秋、冬两季.总体上,降水对PM₁₀的清除率高于对PM_2.5.降水时长对颗粒物的清除率具有明显的季节性变化特征.春、秋两季存在降水时长阈值,分别为10和20 h.春季低于该阈值（10 h）清除率为正清除率,高于该阈值清除率为负清除率;秋季低于该阈值（20 h）清除率为负清除率,高于该阈值为正清除率.夏、冬两季总体表现为正清除率.分析降水前颗粒物质量浓度对清除率的影响得知,降水对PM_2.5清除率由负转正的阈值较PM₁₀低,并且冬、春两季清除率阈值较夏、秋两季高,春季、夏季、秋季、冬季的ρ（PM_2.5）清除率阈值分别为35、15、25、30 μg/m3,ρ（PM₁₀）清除率阈值分别为60、50、60、60 μg/m3.单次降水过程中颗粒物所处高度由2 200 m降至1 000 m,并且此次降水对非球形粒子清除效果明显,粒径在2.5 μm以下粒子质量浓度显著下降,其中,粒径在0.7~1.2和1.5~2.5 μm粒子数浓度下降明显;另外,降水对颗粒物中NO₃-和NH₄+去除明显,并且降水后光学EC、光学OC及金属元素质量浓度和占比显著增长.研究显示,当冬季单次降水总量大于1.5 mm,降水前ρ（PM_2.5）大于30 μg/m3、ρ（PM₁₀）大于60 μg/m3时颗粒物的清除率最佳.      

Degradation of chlorpyrifos alone and in combination with chlorothalonil and their effects on soil microbial populations

In practice, pesticides are usually applied simultaneously or one after another for crop protection, and this type of pesticide application often leads to a combined contamination of pesticide residues in the soil environment. A laboratory study was conducted to investigate the influence of chlorothalonil on chlorpyrifos degradation and its effects on soil bacterial, fungal, and actinomycete populations. Under the experimental conditions here, the half-lives of chlorpyrifos alone, and in combination with chlorothalonil, at the recommended and double dosages, were measured to be 3.24, 2.77, and 2.63 d, respectively. Chlorpyrifos degradation was not significantly altered by its combination with chlorothalonil. However, the inhibitory effect of chlorpyrifos on soil microorganisms was increased by its combination with chlorothalonil, and the increase was related to the levels of chlorothalonil added. Compared to those in the controls, the populations of bacteria, fungi, and actinomycetes were significantly reduced by 44.1%, 61.1%, and 72.8%, respectively, on the first day after treatment (DAT) by chlorpyrifos alone. With the addition of chlorothalonil, the inhibition was increased to 55.2%, 79.3%, and 85.8% at the recommended dosage, and 86.0%, 94.1%, and 90.8% at the double dosage, at one DAT, respectively. The results suggested that combined effects should be taken into account to assess the actual impacts of pesticide applications.     

溶解性有机质对毒死蜱在土壤-植物系统中残留的影响

采用盆栽试验方法,研究了来源于绿肥(GM)、堆制过的猪粪(CP)、新鲜猪粪(PM)中的溶解性有机质(DOM)对农药毒死蜱消解及其在土壤-植物系统中残留的影响。结果表明:DOM能促进毒死蜱在土壤中的降解,显著降低植株对毒死蜱的吸收。在所研究的毒死蜱和DOM浓度范围内,添加GM、CP、PM处理可使土壤-植物系统中毒死蜱总残留量比对照处理(CK)分别减少10.6%、31.1%和36.0%,其中土壤中毒死蜱残留量降低了5.76%,16.39%和37.36%;植株中毒死蜱积累量降低了61.39%,35.12%和20.81%。研究结果可为有机肥的合理施用及农产品的质量安全控制提供参考。     

上海大气颗粒物中糖类的组成、粒径分布及来源

为更好地理解大气颗粒物中糖类的来源及其环境影响,利用微孔撞击式采样器(MOUDI)采集了上海市宝山区2012年11月—2013年8月四季节代表性时段18 μm以下11个不同粒径段的大气颗粒物样品,利用硅烷化衍生和GC-MS对10种脱水糖、单糖和糖醇类化合物进行了分析. 结果表明:上海大气颗粒物中所检测的10种糖类化合物的质量浓度之和在春、夏、秋、冬四季采样期的平均值分别为120.3、104.0、292.9和206.0 ng/m3,脱水糖在秋、冬季占主导地位,单糖和糖醇的质量浓度在冬季最低. 绝大部分脱水糖存在于粒径≤1.8 μm的颗粒中,冬、夏季质量浓度最高的粒径段(峰值粒径)为>0.32~0.56 μm,而春、秋季峰值粒径为>0.56~1.0 μm. 单糖和糖醇类化合物在春、夏季时主要存在于粒径>1.8 μm的颗粒中,而秋、冬季时在粒径≤1.8 μm的颗粒中质量浓度较高. 应用PMF(正定矩阵因子分析法)解析出了大气颗粒物中糖类的3个来源——生物质燃烧、植物源土壤有机质和微生物源土壤有机质. 脱水糖全部来源于生物质燃烧,单糖主要来源于植物源土壤有机质,而糖醇主要来源于微生物源土壤有机质;秋、冬季时生物质燃烧对山梨糖醇之外的单糖和糖醇有较大贡献.      

松花江上游金矿开采区环境中汞污染的空间分布特征

采用俄罗斯Lumex公司生产的RA-915+汞自动分析仪采集松花江上游桦甸金矿开采区环境中的气态总汞,并同步采集水体、土壤和植物样品,测定各环境要素中的汞含量,旨在研究金矿开采区周围大气汞的分布特征、影响因素及其与其它环境要素的相关性.结果表明,环境中大气汞污染的时间分布规律为夏季大于秋季,傍晚高于午间;空间分布规律以金矿开采和汞源为中心随距离加大而逐渐衰减;金矿开采区附近环境要素中汞污染的规律为:沉积物土壤植物水,植物中总汞污染特征为:根茎叶,秋季植物中汞的含量普遍大于夏季,这与植物随生长发育不断通过土壤向体内富集污染元素有关.无论夏季还是秋季,气汞与植物根部的相关性均最高,分别为0.83和0.97.     

沁河上游硝酸盐的定量源解析及其季节性差异

沁河流域人为源硝酸盐输入增加了河流富营养化的风险.为识别沁河上游硝酸盐来源,分别于2017年10月、2018年3月和2018年6月在沁河上游采集了28个河流表层水样,联合稳定同位素（δ15N-NO₃-和δ18O-NO₃-、δD-H₂O和δ18O-H₂O）和水化学参数（Cl-、NO₃--N、NH₄+-N）评估了沁河上游河流硝酸盐源与关键过程,并基于贝叶斯混合模型量化了不同硝酸盐来源的贡献.结果表明:①沁河上游溶解无机氮以NO₃--N为主,秋季[（2.40±1.17）mg/L]高于春季[（2.11±1.03）mg/L]和夏季[（1.50±0.61）mg/L];受积雪融化的影响,春季δ18O-NO₃-（13.0‰±3.13‰）显著高于夏季（2.90‰±3.12‰）和秋季（6.62‰±1.30‰）.②SIAR同位素模型结果表明,沁河上游硝酸盐主要来自土壤氮和化肥.在春、夏、秋3个季节,土壤氮的硝化对沁河上游硝酸盐的贡献比例分别为27.8%、39.5%和39.3%,化肥贡献比例分别为29.1%、40.2%和41.9%.春季（24.7%）大气沉降的贡献比例高于夏季（2.4%）和秋季（10.6%）.③沁河上游硝酸盐主要受硝化过程的影响,没有发生明显的反硝化过程.研究显示,春季、夏季和秋季沁河上游硝酸盐主要来自土壤氮和化肥的硝化,硝酸盐污染防治应考虑化肥的使用效率和抑制硝化过程的发生.      

北方典型灌区不同灌期农田系统中氮素迁移特征分析

以内蒙古河套灌区杭锦后旗解放闸灌域为研究区,分析2009年夏灌和秋浇前后土壤中、浅层地下水和土壤渗滤液中的硝态氮、总氮的分布特征,研究不同灌期农田系统中氮素的迁移规律及其影响因素.结果表明:夏灌对氮素的稀释作用明显,反硝化作用也会降低地下水中硝态氮的浓度,此外玉米地块的氮流失在夏灌时相对明显;秋浇是农田氮素淋失的主要阶段,一方面是硝态氮 (NO3-N) 在灌水作用下向下淋失,另一方面是土壤中的NO3-N 在反硝化作用下转变成N2O、N2和O2释放;夏灌与秋浇两次灌水前后地下水中总氮 (TN) 的峰值滞后于NO3-N,表明氮素的流失除以NO3-N的形式发生之外,部分氨氮以及有机氮等其他形式的氮素在灌溉驱动下也发生一定程度的纵向流失.