电子垃圾拆解区土壤中典型手性PCBs分布及对映体特征

龙塘镇位于广东省清远市,是国内最大的进口电子垃圾集中处理处置地之一.通过对龙塘镇土壤中7种手性PCBs对映体浓度和对映体百分数(enantiomer fractions,EF)值的测定,发现龙塘镇土壤样品除PCB45和PCB174外,其余5种手性PCBs在土壤中均有不同程度的检出.土壤中5种目标手性PCBs(PCB91、PCB95、PCB132、PCB136和PCB149)的总浓度为145.4—286.7 ng·g^-1,这与先前文献中测定清远市土壤中手性PCBs污染水平基本一致.5种同系物的含量排序为PCB95>PCB132>PCB136>PCB149>PCB91.在距离电子垃圾拆解区10km以外的区域也检测到手性PCBs,证实这些污染物已经迁移到周边地区.土壤中手性PCB91、PCB95、PCB132、PCB136和PCB149的EFs值分别为0.519±0.005、0.4443±0.006、0.427±0.003、0.379±0.016和0.494±0.008,其中PCB149具有双向选择性.在全部检出样品中26%的PCB91、78%的PCB95、100%的PCB132、86%的PCB136和53%的PCB149具有非外消旋特征,表明该地区土壤中手性对映体选择性降解的显著性.     

手性农药对映体选择性环境行为的研究进展

目前使用的农药中有25%是手性的,手性农药的生物活性存在对映体差异性,其活性往往只存在于一个或少数几个对映体中,而手性农药的对映体在环境中的消解和归趋往往也有明显的不同,即一个手性化合物的不同对映体具有不同的毒性.只有在对映体水平上研究手性农药的环境行为,考察手性农药的归趋和生态效应,才能更准确的评估其生态风险性以及对人类健康的影响,对手性农药的合理使用也有较好的指导作用.文章综述了近年来国际上有机氯、芳氧基羧酸和酰胺、有机磷和菊酯等手性农药对映体选择性环境行为的研究进展.提出今后的研究方向是拓展手性农药的研究种类、研究深度和广度,对映体选择性的毒理学研究,手性稳定性和手性转化,选择性的机制与相关微生物和酶学研究等.     

Chiralpak AS-H手性柱分离三唑醇对映体

利用Chiralpak型AS-H手性柱成功拆分三唑醇对映体,并通过气质联用和在线旋光检测器对四个对映体进行了定性,四个对映体按洗脱先后顺序依次分别为( )-三唑醇A、(-)-三唑醇A、( )-三唑醇B和(-)-三唑醇B.考察了流动相中异丙醇改性剂浓度对其对映体分离的影响.结果表明,在异丙醇含量为0-10%的范围内,随着异丙醇含量的增加,( )-三唑醇A和(-)-三唑醇A两个对映体的分离度呈波浪式下降,(-)-三唑醇A和( )-三唑醇B的分离度愈来愈小,而( )-三唑醇B和(-)-三唑醇B对映体的分离度愈来愈大.     

手性有机磷农药在土壤中对映体选择性降解特征

马拉硫磷和丙溴磷是2种常用的有机磷杀虫剂,均有一个手性中心存在2个对映体.采用室内避光培养的方法,在对映体水平上研究了马拉硫磷和丙溴磷在2种土壤中的降解情况.结果表明,2种农药在土壤中的降解均较快,马拉硫磷和丙溴磷的降解半衰期分别为:黄土中3.5 h和21.5 h,红土中4.3 h和29.4 h.进一步的手性测定表明2种农药的降解均存在一定的对映体差异,丙溴磷对映体的选择性明显高于马拉硫磷,在2种土壤中马拉硫磷的左旋对映体降解快于右旋对映体,丙溴磷的右旋体降解快于左旋体.研究有助于深入认识2种有机磷农药在环境中的归趋,并对其生态风险性进行更合理的评估.     

手性农药的环境行为研究进展

手性农药由于其对映体选择性,在环境中具有特殊的归宿.研究其环境行为有助于准确评价生态系统和人体健康的风险性.文章综述了手性农药的研究进展,指出高效液相和气质联用法是不同环境介质中手性农约的主要分离分析方法;利用手性农药的对映体分数可研究农约在土壤-大气,水体-大气间的迁移过程;一些手性农药在土壤、水体和动物体内中发生的选择性降解与累积与微生物或特异性的酶有直接关系,可利用此性质修复被污染的土壤;归纳了在手性农约污染环境风险研究中应注意的问题;加强手性农约在环境中的选择性降解动力学、对映体转化及毒理学机制研究,并最终深人到代谢机理、蛋白和基因水平上,阐述产生手性对映体选择性的根源将是未来研究的方向.     

环境水样中卤代甲基磺酸的高效液相色谱-串联质谱联用分析方法研究

利用高效液相色谱三重四极杆串联质谱(HPLC-MS/MS),建立了环境水样中卤代甲基磺酸的分析方法.通过对固相萃取、色谱柱、流动相和质谱条件的优化,确定了最佳萃取和分析条件.选用WAX固相萃取柱对卤代甲基磺酸进行富集,再依次用2 m L的5%氨水甲醇溶液、2%甲酸甲醇溶液和20%二氯甲烷甲醇溶液(均为体积比)进行洗脱.选用Acclaim HILIC-10为色谱分离柱,以乙腈和100 mmol·L~(-1)甲酸铵水溶液为流动相,分离目标化合物,采用串联质谱负离子扫描和多反应监测模式进行检测.方法对5种卤代甲基磺酸(三氟甲基磺酸、一氯甲基磺酸、二氯甲基磺酸、三氯甲基磺酸和一溴甲基磺酸)的线性范围为0.05—50μg·L~(-1),线性相关系数r0.99,各化合物的检出限(S/N=3)在0.005—0.039μg·L~(-1)之间.将建立的分析方法应用于实际样品中卤代甲基磺酸的测定,所得加标回收率在67.5%—95.4%之间,峰面积相对标准偏差(n=5)在8.5%—13.0%之间,可满足饮用水环境样品中痕量卤代甲基磺酸的分析.     

手性杀菌剂在有机蔬菜中的残留特征

本文建立了基于QuEChER-超高效液相色谱-串联质谱分析有机蔬菜中联苯三唑醇、苯霜灵、己唑醇、戊唑醇、粉唑醇、三唑酮、腈菌唑、甲霜灵和多效唑等9种手性杀菌剂的分析方法,该方法定量限为6.4—270.3 ng·kg~(-1)鲜重(fw),相对回收率为77.1%—110.3%.随后运用该方法对有机番茄、苦瓜、黄瓜和胡萝卜等4种有机蔬菜中的手性杀菌剂残留及其对映体特征进行了分析.研究结果显示,9种杀菌剂中,联苯三唑醇未检出,甲霜灵残留量最高,中值为4.9μg·kg~(-1) fw,有机黄瓜中的甲霜灵残留量(1.1—1.4 mg·kg~(-1) fw)超标(中国食品安全国家标准,最大残留限量0.5 mg·kg~(-1) fw).在4种有机蔬菜中,胡萝卜和黄瓜检测出的手性杀菌剂种类最多,且黄瓜的手性杀菌剂残留总量最高,达1.1—1.4 mg·kg~(-1) fw,主要为甲霜灵.不同蔬菜种类的杀菌剂残留有明显差异,但有机蔬菜的杀菌剂残留远低于常规蔬菜.手性杀菌剂对映体的残留与蔬菜种类有关.     

全氟辛烷磺酸和全氟辛烷羧酸异构体的高效液相色谱-串联质谱联用分析方法

建立了固相萃取-高效液相色谱-串联质谱(SPE-HPLC/MS/MS)联用测定全氟辛烷磺酸(PFOS)和全氟辛烷羧酸(PFOA)异构体的分析方法.以WAX固相萃取小柱为浓缩柱对样品中目标化合物进行富集浓缩,再用HPLC-MS/MS分离检测各异构体,串联质谱采用负离子扫描和多反应监测模式对样品进行分析检测.色谱分离采用梯度洗脱方式,流动相A相为甲醇,B相为60 mmol·L-1氨水/20 mmol·L-1甲酸水溶液(p H=4);选用AscentisExpress F5型色谱柱为分离柱.将建立的方法应用于河水、底泥和贝类中全氟化合物异构体的分析,对3种环境样品的方法检出限(S/N=3)分别为0.05—1.1 ng·L-1、0.025—0.56 ng·g-1和0.025—0.56 ng·g-1.以加标回收实验对建立的分析方法进行评价,自来水、底泥和贝类中11种PFOS和PFOA异构体的加标回收率平均值分别在90.8%—127%、74.0%—124%和76.7%—113%,相对标准偏差(n=5)分别为5.9%—17.2%、2.5%—17.0%和3.30%—11.5%.     

手性污染物与环境安全

本文就手性污染物在生命过程中对映体的差异作了简要评述,分析了手性污染物对映体的毒性差异及机理.同时指出了手性污染物今后研究的发展趋势.     

三重四极杆气质联用法测定熟肉及其制品中多组分β-受体激动剂残留量

通过未检出β-受体激动剂的熟肉作为空白样品,采用酶解法将动物组织彻底分解,以固相萃取小柱进行萃取净化,净化液经衍生剂后经毛细管色谱柱程序升温分离,利用GC-MS/MS多反应监测模式(MRM模式)对目标物进行采集,以氘代同位素化合物为内标进行内标法定量.采用质控样品和加标回收率评价方法的准确度,以回收率的相对标准偏差(RSD)评价方法的精密度.12种β-受体激动剂在0.20—50μg·kg-1范围线性关系良好,相关系数在0. 9925—0. 9995范围内,检出限为0. 2—0. 4μg·kg-1.空白样品在1. 00、10. 0、50.0μg·kg-1水平的回收率为65.5%—110.7%; RSD为1.16%—8.93%.此方法假阳性率低、准确、可靠.     

常规液相色谱柱测定早熟素Ⅱ的方法探讨

通过使用市售的常规C18液相色谱柱(规格:150mm×4.6mm,5 μm),探讨了早熟素Ⅱ的分析方法并对其进行了可行性论证.以V(甲醇):V(水)=80:20为流动相,流量1 mL·min~(-1),检测波长为224nm,柱温35℃.得出早熟素Ⅱ在8～108μg·mL~(-1)的范围内呈良好的线性关系(相关系数,为0.99997),最低检出限为1.0379μg·mL~(-1)(信噪比为3),加标回收率为93.3%～104.98%,变异系数为0.12%～4.41%.与使用非常规色谱柱分析早熟索Ⅱ的方法相比,该方法采用了市售常规柱,能够更大限度地满足实验条件,通用性更强.     

简易柱式无土栽培法

在立柱栽培技术发展过程中 ,简易柱式法最先是在 1994～ 1995年初发展起来的 ,并在当年推广到江苏张家港市和河北遵化市 ,后来在此基础上发展了现被广泛推广应用的标准型柱式无土栽培法[1～ 3] ,但该方法中的盆钵是由高强度抗老化的ＡＢＳ工程塑料铸塑而成 ,价格贵 ,安装 1亩 ( 6 6 6 .7ｍ2 )约需6万元人民币 ,在中小城市及农村推广使用不易 ,因此简易柱式无土栽培技术的优点值得重视 ,讨论如下 :1　简易立柱的组装简易柱是由包裹材料柱壁、柱体和栽培基质构成 .柱壁是新制丙烯 (ｐｏｌｙｐｒｏｐｙｒｅｎｅ)编织材料 (俗称“蛇皮”带 ) ,裁…     

分析人体弯腰提物时脊柱的受力情况预防腰椎间盘损伤

对人体脊柱不同情况的受力分析得出椎间盘受损伤的原因,结合现实生活中一些导致腰椎盘突出或损伤不良的力学行为,从而提出有效地预防腰椎间盘损伤的措施.     

酸阻滞法处理含酸及其相应盐的废液

本文主要介绍在含酸及其相应盐的废液中分离酸和盐的一种方法。将含酸及其相应盐的废液，通过装有强碱性阴离子交换树脂柱，其中的酸受到阻滞，而相应的盐能顺利通过，然后用水洗脱，则流出的是含酸的溶液，使酸和相应的盐得到了分离。经ＦｅＳＯ４－Ｈ２ＳＯ４和ＺｎＳＯ４－Ｈ２ＳＯ４两组废液的试验，均能使酸和金属得到回收。分离后的废水，可达标排放，废液得到了处理。酸阻滞法简单易行，易于投产使用，不受规模大小的限制。     

Chloride and atrazine transport through saturated soil columns

A possible contamination of water resources by the application of pesticides is a problem confronting many irrigated areas in arid and semi-arid areas. The best management practices have to be adopted to minimize pesticide transport and leaching under irrigated conditions. Atrazine dissipation in loam and sandy loam soils has been tested in the laboratory using disturbed soil columns under saturated flooding conditions. All the experiments were performed in replicates. The chloride transport was also studied to test its behavior as an inert tracer in both the soils. Atrazine and chloride breakthrough curves were analyzed with the parameter optimization program CXTFIT to determine transport parameters including pore-water velocity (v), retardation coefficient (R), hydrodynamic dispersion coefficient (D), and pulse duration (t _o ). The pore-water velocity and pulse duration of the solute were estimated from the experimental conditions and kept constant during the optimization procedure. The results indicated that the R of chloride was not significantly different from 1, indicating that chloride is an inert tracer for the types of soil tested in this study. The average R of atrazine was 4.56 and 3.15 for sandy loam and loam soils, respectively. Results also showed that the hydrodynamic dispersion coefficient was much higher in the case of sandy loam soil compared to the loam soil for the two solutes, thus indicating non-equilibrium transport conditions. In the case of chloride, D increased from 0.4 for the loam soil to 16.2?cm²/min for the sandy loam soil. Similar results were observed in the case of atrazine in which D for the sandy loam soil was 60% higher than that for the loam soil. More atrazine leaching is expected under field conditions due to the presence of soil cracks and macropores.     

模拟酸雨对土柱中稀土元素迁移的影响

模拟研究酸雨对土柱中稀土元素迁移的影响.结果表明,在雨水、酸雨淋溶下,对照组红壤土柱中所含稀土元素有向下迁移的趋势,并且随淋溶液pH值的降低,稀土元素向下迁移的能力增加.外源稀土迁移量的大小顺序为;Ce>La>Nd>Pr,其顺序与各稀土元素在稀土微肥中含量大小的顺序相同.表明外源稀土的迁移性与外源稀土的总量密切相关.外源稀土在土柱中的含量随着红壤深度的增加而减少,稀土元素主要在土柱中第一、二层持留;随着淋溶液酸度的下降,稀土元素向下迁移的能力增加.     

立柱无土栽培研究初报

立柱无土栽培研究初报龚颂福，李止正（中国科学院上海植物生理研究所上海２０００３２）关键词立柱无土栽培；蔬菜；花卉ＳＴＵＤＩＥＳＯＮＴＨＥＳＯＩＬＬＥＳＳＣＵＬＴＵＲＥＳＯＮＶＥＲＴＩＣＡＬＣＯＬＵＭＮＳ￥ＧｏｎｇＳｏｎｇｆｕａｎｄＬｉＺｈｉｓｈｅｎｇ...     

Mobilization of arsenic from technosols in a short-term dynamic column experiment

The release of arsenic from technosols was monitored using short-term dynamic leaching of homogeneous soil columns with native solution. Large amounts of readily available arsenic (16 mg kg^?1) were extracted from arsenic-rich ashy samples while representing less than 4 wt % of their total contents. In the first hour of leaching, the observed concentrations of water-soluble arsenic ranged from 650 to 830 μg L^?1, further increasing in the following leachates. The results showed that the concentrations of water-soluble arsenic were several times higher than the recommended limits for drinking water. Yet, most of arsenic is strongly bound to amorphous aluminosilicate phases. The contents of arsenic in the studied plant samples, including calculated transfer factors, confirmed that increased concentrations of arsenic in the soil of geological environment affected by dam failure of a coal ash pond may have a negative effect on crops since arsenic becomes part of the food chain.     

Dredged Material Disposal at the Edge of the Florida Current

A field data collection project was undertaken to investigate the short-term fate of dredged material discharged in the designated Miami Ocean Dredged Material Disposal Site (ODMDS) before dredging of the Miami River and the Miami Harbor Turning Basin begins. the designated ODMDS is located in relatively deep water for discharge sites with a typical bottom depth of 150 metres and is also located in the western boundary region of the Gulf Stream current off Miami. Acoustical backscattering, current, particulate, temperature and salinity data were gathered over a three day period from April 24, 1990 through April 26, 1990. the major generic features of shallow-water discharge plumes were observed to be present: (a) the presence of a rapid convective descending plume portion; (b) impact of that plume portion with the ocean bottom and concomitant generation of a bottom surge; (c) rapid horizontal width growth of the descending plume through entrainment; and (d) retention of a residual plume portion within the water column. A well-mixed upper water column layer extending to a depth of 40 to 60 metres below the surface of the ocean permitted measurements of the plume entrainment coefficient free from bottom boundary, water column density gradient, and vertical current shear effects which are usually present in relatively shallow, e.g. less than 40 metres bottom depth, coastal ocean discharge studies. Entrainment coefficient estimates obtained in this study were between 0.5 to 0.7. the residual water plume material was tracked over one-half hour during each of eight discharge events and was transported in a north-northeast direction.     

Dredged Material Disposal at the Edge of the Florida Current

A field data collection project was undertaken to investigate the short-term fate of dredged material discharged in the designated Miami Ocean Dredged Material Disposal Site (ODMDS) before dredging of the Miami River and the Miami Harbor Turning Basin begins. the designated ODMDS is located in relatively deep water for discharge sites with a typical bottom depth of 150 metres and is also located in the western boundary region of the Gulf Stream current off Miami. Acoustical backscattering, current, particulate, temperature and salinity data were gathered over a three day period from April 24, 1990 through April 26, 1990. the major generic features of shallow-water discharge plumes were observed to be present: (a) the presence of a rapid convective descending plume portion; (b) impact of that plume portion with the ocean bottom and concomitant generation of a bottom surge; (c) rapid horizontal width growth of the descending plume through entrainment; and (d) retention of a residual plume portion within the water column. A well-mixed upper water column layer extending to a depth of 40 to 60 metres below the surface of the ocean permitted measurements of the plume entrainment coefficient free from bottom boundary, water column density gradient, and vertical current shear effects which are usually present in relatively shallow, e.g. less than 40 metres bottom depth, coastal ocean discharge studies. Entrainment coefficient estimates obtained in this study were between 0.5 to 0.7. the residual water plume material was tracked over one-half hour during each of eight discharge events and was transported in a north-northeast direction.