固相萃取小柱净化-气相色谱法测定土壤和沉积物中有机氯和拟除虫菊酯农药残留

建立了毛细管气相色谱法测定土壤和沉积物中α-六六六,β-六六六,γ-六六六,δ-六六六,硫丹,p,p'-DDE,p,p'-DDD,o,p'-DDT,p,p'-DDT,三氯杀螨醇,甲氰菊酯,氯氰菊酯,联苯菊酯,氟氯氰菊酯,氰戊菊酯,溴氰菊酯等16种农药残留量的方法.16种农药的残留组分在25min内能很好分离.标准加入回收率在81.2%-111.9%之间;方法变异系数2.9%-14.9%(0.01-0.1μg·ml-1,n= 6),检出下限在0.08-0.44μg·kg-1之间.     

南京市城郊蔬菜生产基地有机氯农药残留特征

以网格法在南京市无公害蔬菜生产基地八卦洲采集70个土壤样品,用加速溶剂萃取、固相萃取柱净化后GC-μECD测定土壤中有机氯农药(α-HCH,β-HCH,γ-HCH和δ-HCH以及o,p'-DDT,p,p'-DDT,o,p'-DDE,p,p'-DDE 和p,p'-DDD)残留量.结果表明,土壤中有机氯农药残留总量在6.18～84.72 μg·kg-1之间,平均18.63 μg·kg-1.DDT残留量高于HCH,为3.36～74.19 μg·kg-1,平均12.61 μg·kg-1.土壤中HCH残留量为2.48～17.80 μg·kg-1,平均6.02 μg·kg-1.DDT同系物中以p,p'-DDE和p,p'-DDT为主,而HCH中δ-HCH含量较低,其他3种异构体含量水平相当.所有土样中DDT和HCH残留量均远远低于GB/T 18407 无公害蔬菜产地土壤标准限定值500 μg·kg-1,但大多数土样中DDT和HCH残留量远远高于荷兰无污染土壤标准.     

太湖五里湖背角无齿蚌体内滴滴涕和六六六的残留

作为建立淡水"贝类观察"体系的初步尝试,选定2003年3月采自太湖五里湖水域的背角无齿蚌(Anodonta woodiana)为研究对象,测定其体内滴滴涕(DDT)和六六六(HCH)含量.除β型外,α型、γ型和δ型HCH异构体及p,p'-DDE,o,p'-DDT,p,p'-DDD,p,p'-DDT均在蚌样本中明显检出.∑DDTs湿重含量5.86～14.13 ng·g-1[平均(9.27±3.04) ng·g-1],高于∑HCHs湿重含量2.45～6.46 ng·g-1[平均(4.00±1.22) ng·g-1].p,p'-DDE、p,p'-DDD与α型、γ型HCH异构体分别为∑DDTs和∑HCHs的优势组分,说明太湖五里湖水域目前DDT的污染源可能很少,但存在较明显的新输入HCH.各蚌样的残留水平没有超过农业部、美国食品与药品管理局(FDA)和联合国粮农组织(FAO)颁布的最大限量.     

上海郊区表层土壤中DDT残留特征

为掌握上海市北部郊区农田表层土壤有机氯农药残留状况,在上海市宝山区的农田分布区域布设采样点,采集表层土壤样品,用美国EPA方法分析了土壤中DDT及其4种衍生物的残留量.结果表明,上海市宝山区农田土壤中平均DDT总残留量为0.057 mg·kg-1,DDT的4种衍生物p,p'-DDE,p,p'-DDD,p,p'-DDT,o,p'-DDT的平均残留量分别为0.032、0.007、0.018、0.000 mg·kg-1.该研究中大部分区域土壤DDT总残留量低于国家土壤环境质量二级标准限值,没有形成土壤DDT污染;但在DDT残留量最高的地块,土壤DDT总残留量达0.694 mg·kg-1,超过了国家土壤环境质量二级标准限值,形成了一定范围的土壤DDT污染.在所有采样点中,有4个点位的p,p′-DDT/p,p′-DDE比值大于1,且其DDT总残留量也较高,说明这几块区域村在禁用期间又被新施加了DDT的可能.该研究可为有针对性地开展区域土壤环境保护和污染防治提供重要参考依据.     

天津市郊农田土壤中有机氯农药残留的局地分异

在天津3处典型污灌与非污灌农田各采集了10个表土样品，测定了其中α-HCH，β-HCH，γ-HCH，δ－HCH、p,p'-DDE,p,p'-DDD,p,p'-DDT和p'-DDT等8种有机氯农药含量，籍以研究该地区有机氯农药在地块中的局部分异。结果表明，所研究地块中两类化合物含量均表现出显著的非均一特征。其中污灌土地中的（DDT）以及污灌农田中的HCH含量都具有与灌溉方向密切相关的空间分布特征。这样的规律性空间变异导致他们的空间波动幅度高于其他地块。鉴于上述趋势性和非趋势性空间分异，在开展相关时人有必要在目标地块中采集重复样或混合样。     

模拟胃肠液用Tenax提取法测定多溴联苯醚的生物有效性

以室内灰尘和鱼样为介质,利用Tenax提取,采用动态方法模拟污染物在人体肠道中的消化吸收,研究多溴联苯醚(PBDEs)的口服生物有效性.结果表明,在18 mL模拟胃肠液中,随着胃肠液中Tenax质量增加,Tenax吸附的PBDEs(BDE28、47、66、100、99、85、154、153、138、183和209)增加,当Tenax的质量达到200 mg后,增加Tenax的用量不会增加PBDEs在Tenax中的吸附总量.对于灰尘,3—7溴BDEs的生物有效性为50.8%,而添加Tenax后,随着Tenax质量的增大,其修正后的生物有效性从84.9%增大到101.1%;类似,对于鱼样,PBDEs修正后的生物有效性从43.7%升高到70.7%.这种修正后的生物有效性比未进行修正的结果更接近活体实验测得的PBDEs的生物利用度数据.因此,在18 mL模拟胃肠液中,采用200 mg的Tenax,用于模拟小肠对胃肠液中PBDEs的吸收,可以获得最差场景条件下PBDEs的生物有效性.     

食物粒径与混合方式对多溴联苯醚生物有效性的影响

多溴联苯醚(PBDEs)是一类典型的持久性有机污染物(POPs),口服摄入是其主要人体暴露途径。口服生物有效性是污染物健康风险评估中的关键因子。论文采用体外方法模拟食物在人体肠道中的消化过程,研究了食物粒径大小以及食物污染与混合方式对PBDEs生物有效性的影响。在150、150~212、212~250和250μm四个粒径范围的胡萝卜中,PBDEs同系物的平均生物有效性分别为48.8%±3.8%、45.2%±5.0%、38.6%±9.3%和37.3%±3.7%。测得菠菜和鲈鱼采用4种混合方式BY1、BY2、BY3和BY4中PBDEs同系物的平均生物有效性分别为17.1%±1.3%、48.3%±3.5%、36.4%±4.9%和44.4%±2.0%,比单纯菠菜(2.6%±0.2%)和鲈鱼(36.3%±4.3%)中的生物有效性高。结果表明,PBDEs的生物有效性随着胡萝卜粒径的增大而减小;不同污染方式再混合食品,比单一食品被污染时,PBDEs的生物有效性更高。     

采用一台气相色谱系统检测水质标准中四类有机化合物

本文采用1台Agilent 7890B气相色谱系统完成水中4类有机化合物的检测.水中4类有机化合物分别为:7种苯系物(BETX)包括苯、甲苯、乙苯、对二甲苯、间二甲苯、邻二甲苯、苯乙烯;5种挥发性卤代烃包括三氯甲烷、四氯化碳、三溴甲烷、三氯乙烯、四氯乙烯;8种有机氯农药包括α-六六六、β-六六六、γ-六六六、δ-六六六、p,p'-DDE、p,p'-DDD、o,p'-DDT、p,p'-DDT;7种有机磷农药包括敌敌畏、敌百虫、内吸磷、乐果、甲基对硫磷、马拉硫磷、对硫磷.优化顶空进样条件,采用微板流路分流器一次顶空进样同时完成水中苯系物及卤代烃分析.其中,对添加挥发性卤代烃(添加浓度分别为三氯甲烷4.00μg·L-1,四氯化碳2.00μg·L-1)及苯系物(添加浓度为400μg·L-1)的水样进行测定,各目标化合物的相对标准偏差RSD均小于2.5%.同时,对水中有机氯、有机磷农药进行分析,得到有机氯的相对标准偏差RSD范围为0.97%—3.7%,回收率范围为89.5%—104.9%.有机磷的相对标准偏差RSD范围为1.45%—2.94%,回收率范围为90.4%—98.8%.     

辽东半岛海域鱼贝中有机氯农药残留及其风险评估

2011年1月-2012年5月间采集了辽东半岛海域11种鱼类和2种贝类样品,分析了其可食部位中22种有机氯农药的残留量,评估了其中DDTs和HCHs的残留对人体健康的风险。在所调查样品中HCB、HCHs和DDTs是主要的污染物,样品中OCPs残留量为57.12~546.15μg·kg-1。利用污染指数计算法评估,旅顺海域小黄鱼、鳙鱼、中国斗鱼和偏口鱼未受到HCHs的污染,棒花鱼受到HCHs轻度污染,其它鱼种样品均受到重度污染,而对于DDTs,只有鲫鱼未受到污染,其它鱼种样品均受到重度污染。大黄鱼、梭鱼、黑鱼和鳙鱼体内HCHs残留量明显高于国标再残留限值,DDTs残留量符合国标标准。α-HCH、γ-HCH、β-HCH、p,p'-DDE、p,p'-DDD和p,p'-DDT的致癌风险指数范围为0.32×10-6~49.57×10-6,均低于10-4,为可接受的致癌风险;α-HCH、γ-HCH、β-HCH、p,p'-DDE的接触风险指数ERI为0.01×10-3~153.28×10-3,均小于1,为可接受的接触风险,但2012年4月的黑鱼样品上述六种农药的CRI总值高于10-4,存在潜在的致癌风险,因此,建议黑鱼的日均食用量应控制在50 g以下较为安全。     

In Vitro法评估铅污染土壤对人体的生物有效性

采用基于生理学的In Vitro实验，测定经口无意摄入的铅污染土壤在人体内的生物有效性。通过模拟人体的胃和小肠环境，研究土壤中铅被消化道吸收的最大量。结果表明，在铅污染土壤中施加羟基磷灰石后，铅对人体的生物有效性下降约20倍。     

Sorption of 1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane (DDT) by clays and organoclays

This study focused on the sorption isotherms of 1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane (p,p'-DDT) and 1,1-dichloro-2,2-bis(p-chlorophenyl) ethylene (p,p'-DDE) on different original clays (i.e., zeolite, montmorillonite and attapulgite) and organoclay complexes. Sorption of organic pollutants was determined using gas chromatographic (GC) techniques to investigate the sorption behavior, and characterize the effect of, different organic cations. The original clays only sorbed low amounts of p,p'-DDT and p,p'-DDE, and the sorptive curves can be classified as L-shaped. Organoclays exhibited higher amounts of p,p'-DDT and p,p'-DDE sorption. The p,p'-DDT and p,p'-DDE sorption increased with increasing total organic carbon (OC) content of the organoclays. For hexadecyltrimethylammonium (HDTMA)-modified organoclays, the dominant adsorptive medium showed the partitioning sorption of hydrophobic-hydrophobic interaction, indicating no competitive sorption. The sorptive curves can be classified as C-shaped of constant partition (CP). However, benzyltrimethylammonium (BTMA)-modified organoclays exhibited competitive sorption. The sorption isotherm curves can be classified as S-shaped. The sorptive capacity of the HDTMA-modified organoclays for p,p'-DDT were higher than those for p,p'-DDE, but the BTMA-modified organoclays showed a reverse trend. This can be attributed to the different structures and shapes of organic cations, giving different sorptive mechanisms. The p,p'-DDT and p,p'-DDE sorption onto HDTMA-modified organoclays were caused by chemical interaction, with the BTMA modified organoclays occuring due to physical sorption.     

The concentration and distribution of organochlorine pesticides in the air from the karst cave, South China

Organochlorine pesticides (OCPs) in the air of Dayan Cave in Guilin were analyzed, to investigate the source and contamination levels. Generally, air outside of the cave had much higher concentrations than inside air, and both outside and inside air showed much lower contamination levels than those observed in other regions in China and abroad. The ratios of α-/γ-HCHs and the percentages of β-(or δ-)HCH implied a residue of historical local technical HCH contamination. The DDT concentrations, o,p'-DDT/p,p'-DDT, and p,p'-DDE/p,p'-DDT suggested fresh DDT-containing products acted as the primary source of DDT for the air in Dayan Cave. An intermediate level concentration of α-endosulfan (156.00?pg/m(3)) was observed in the outside air, implying local source was dominant. Based on the similar sources of HCH and DDT and the relationships between outside and inside air, it appeared that outside air pollutants affected on inside HCH and DDT's distribution. For other OCPs, outside air might be major contributor to inside air contamination under conditions of high concentrations in outside air compared with low levels in inside air for semi-closed karstic caves.     

Persistent of Organochlorine Pesticides in the Green Lip Mussel (Perna Viridis) From Marine Estuaries in Thailand

Thailand has benefited from the availability of pest control chemicals for improving agricultural products and in public health like any other developing countries. in order to understand the distribution and contamination in the Gulf of Thailand, a Mussel Watch programme has been set up to monitor trace toxic substances of organochlorine pesticides along the Gulf of Thailand since 1989.

This paper focuses on the concentration of organochlorine pesticides in green lip mussels (Perna viridis) during 1989 to 1996. the mussel samples were used as a biological indicator and analyzed for 23 organochlorine compounds. the highest frequencies of organochlorine pesticide residues in Thailand were found in aldrin, dieldrin and DDTs in all samples and the highest concentration of DDT-isomer were p,p'-DDE and p,p'-DDT during 1989-1990 and 1991. the p,p'-DDE was only found during 1993-1995.

In 1996 the level of the DDT isomer (o,p-DDE) were found in the range of 11-16ppb(ngg^-1 wet weight), HCH isomer (a-HCH) was found ND -1.6ppb(ngg^-1 wet weight) and cis-chlordane found at ND - 3.4 ppb(ngg^-1 wet weight). Other organoichlorine pesticide compounds such as dieldrin, heptachlor, aldrin, endrin and endosulfan isomers were not detected. the detection limit of all organochlorine compounds were 1.3-8.2ppb(ngg^-1 wet weight). Trends of organochlorine pesticide residue in this area were found differently from the previous data during 1989-1991.     

离体培养植物细胞的表面与细胞粘连

对离体培养的胡萝卜（Ｄａｕｃｕｓｃａｒｏｔａ）细胞和普通烟草（Ｎｉｃｏｔｉａｎａｔａｂａｃｕｍ）细胞的表面进行了扫描电镜观察．观察表明，细胞的自由表面上有很多疣突和纤丝．疣突的大小不同、形状各异，主要含果胶质；有些细胞表面出现小坑，坑中集中有许多微小颗粒．疣突相互可融合成更大的疣突或连成桥；纤丝常与疣突结合．纤丝－纤丝的交织，纤丝－疣突的交联，及疣突－疣突的融合，在细胞壁外表面构成交织的网络．同种细胞之间及异种细胞之间均可通过纤丝、疣突的交织融合而粘连．疣突分布不均一，且与细胞的分散性有关．与疏松烟草愈伤组织比较，致密烟草愈伤组织细胞的自由表面上疣突显著较多．在分化再生时，烟草愈伤组织首先致密变绿，然后才见到芽的分化及植株再生．对疣突出现、壁物质沉积与细胞粘连、细胞分化、形态建成几者之间的关系进行了讨论．     

Satellite telemetry and prey sampling reveal contaminant sources to Pacific Northwest Ospreys.

Migratory behavior can be an important factor in determining contaminant exposure in avian populations. Accumulation of organochlorine (OC) pesticides while birds are wintering in tropical regions has been cited often as the reason for high concentrations in migrant populations. To explore this issue, we satellite tracked 16 Ospreys (Pandion haliaetus) over the period 1996-2003 from breeding sites in British Columbia, Canada, and integrated the results into a database on 15 Ospreys that were satellite tracked over the period 1995-1999, from breeding locations in Washington and Oregon, USA. Data on wintering sites of 31 Ospreys in Mexico and Central America were used for spatially targeted sampling of prey fish. Concentrations of the main organochlorine contaminant, p,p'-dichloro-diphenyl-dichloroethylene (DDE), in fish composites from Mexico ranged from 0.005 to 0.115 nicrog/g wet mass. Significant differences existed among fish families in p,p'-DDE, total dichloro-diphenyl-trichloroethane (sigmaDDT), sigmachlordanes, and total polychlorinated biphenyls (sigmaPCBs). Catfish (family Ariidae) generally had significantly higher levels of DDT metabolites and other organochlorine contaminants compared to other fish families collected. Differences in prey contaminant levels were detected among the collection sites around coastal Mexico, with fish from Veracruz State generally having higher levels of DDT metabolites, sigmachlordanes, sigmaPCBs, and hexachlorobenzene. Eggs collected from 16 nests throughout the Pacific Northwest (nine from British Columbia, seven from Oregon and Washington) where Ospreys had been satellite tagged, showed marked variation in levels of DDT metabolites (p,p'-DDE; range 0.02-10.14 microg/g). Wintering site had no significant effect on contaminant concentrations in sample eggs from those specific Ospreys; rather concentrations of p,p'-DDE, were predicted by breeding sites with highest levels in eggs of Ospreys breeding in the lower Columbia River, consistent with published reports of continued high concentrations of DDT and related compounds in that system.     

Interactive effects of prey and p,p'-DDE on burrowing owl population dynamics.

We used population models to explore the effects of the organochlorine contaminant p,p'-DDE and fluctuations in vole availability on the population dynamics of Burrowing Owls (Athene cunicularia). Previous work indicated an interaction between low biomass of voles in the diet and moderate levels of p,p'-DDE in Burrowing Owl eggs that led to reproductive impairment. We constructed periodic and stochastic matrix models that incorporated three vole population states observed in the field: average, peak, and crash years. We modeled varying frequencies of vole crash years and a range of impairment of owl demographic rates in vole crash years. Vole availability had a greater impact on owl population growth rate than did reproductive impairment if vole populations peaked and crashed frequently. However, this difference disappeared as the frequency of vole crash years declined to once per decade. Fecundity, the demographic rate most affected by p,p'-DDE, had less impact on population growth rate than adult or juvenile survival. A life table response experiment of time-invariant matrices for average, peak, and crash vole conditions showed that low population growth under vole crash conditions was due to low adult and juvenile survival rates, whereas the extremely high population growth under vole peak conditions was due to increased fecundity. Our results suggest that even simple models can provide useful insights into complex ecological interactions. This is particularly valuable when temporal or spatial scales preclude manipulative experimental work in the field or laboratory.     

江河中有机污染物挥发速率的模拟和预测

以第二松花江重点有机污染物－硝基芳烃为对象，模拟研究了它们在江河中的挥发过程，同时采用４种理论模式，预测了１６种硝基芳烃的挥发速率常数，并将其结果与模拟实测值进行比较评价，讨论了各种模式的优缺点。     

La在模拟水生态系统中的动力学行为

采用140La放射示踪技术,研究了稀土元素镧（La）在模拟水生态系统各组分中的迁移分布规律．并建立了相应的数学模型．结果表明,La在模拟水生态系统各组分中的积累率大小依次为：金鱼藻＞底泥＞螺蛳＞鱼,La在系统内的动态变化规律可用封闭分室模型来描述．     

黄河三角洲人工草场群落土壤盐分动态集成预报模型及其应用

提出了以ＧＭ（１，１）模型拟合发展的趋势、傅里叶变换撮周期分量ＡＲ（ｐ）模型模拟随机过程的集成预报模型，并用于黄河三角洲人工草场群落土壤盐分的定量研究中，经理论和应用检验证明：该模型能以较高的精度模拟或预报土壤盐分在较长时期内的动态变化过程，方法简单，计算工作量小，并优于传统的单一预报模型。     

水体中亚硝酸盐的光降解

一定浓度的亚硝酸盐溶液经太阳光模拟器照射一定时间后,观测溶液中亚硝酸盐的含量变化.改变溶液条件（介质、pH）和光照条件（时间、光强）等实验条件,同时进行黑暗对照实验,探求影响亚硝酸盐光解的因素和规律.结果表明,在光照的8 h内,时间越长亚硝酸盐的降解率越大,基本符合一级反应动力学曲线;光照强度越大亚硝酸盐的降解程度越大...