分散固相萃取-气相色谱-质谱法测定土壤中8种菊酯类农药的残留量

建立了气质联用同时检测土壤中8种菊酯类农药残留的方法。试样用1%乙酸-乙腈溶液提取,经QuEChERS(Quick、Easy、Cheap、Effective、Rugged、Safe)方法进行净化,用DB-5UI色谱柱(30m×0.25mm×0.25μm),外标法定量。考察了乙二胺-N-丙基硅烷(PSA)、氨基(NH2)和C18吸附剂对土壤中8种菊酯类农药的净化作用。结果发现,PSA吸附剂的净化效果最好并且对8种菊酯类农残的回收率效果最高。该方法在0.05~1μg/ml内相关系数大于0.99。对8种菊酯在土壤中3个添加水平(0.1、0.2、0.5mg/kg)下的回收率进行了测定,回收率为69.7%~107.2%,相对标准偏差(RSD)为2.4%~8.0%。该方法样品前处理简单、灵敏、可靠,灵敏度、准确度和精密度均符合农药残留检测要求,适用于土壤中菊酯类农残的检测。     

硅胶分离-气相色谱法测定海水样品中的有机氯农药及多氯联苯

建立了硅胶净化-具电子捕获检测器气相色谱(GC-ECD)测定海水样品中有机氯农药(OCPs)、多氯联苯(PCBs)的方法。海水样品经正己烷萃取,浓缩萃取液后过硅胶层析柱,通过梯度淋洗进行样品的净化和分离,采用GC-ECD进行分析测试。OCPs回收率达70.7%~109.2%,PCBs回收率达92.6%~119.2%。采用GC-MS进行辅助确证,结果表明,方法可行。     

超高效液相色谱-串联质谱法分析土壤及沉积物中氨基甲酸酯农药

利用超高效液相色谱-串联质谱,建立土壤和沉积物中痕量氨基甲酸酯农药的分析方法。该方法用体积比1:1的二氯甲烷/甲醇对土壤和沉积物样品进行加速溶剂萃取,GCB/PSA固相萃取小柱对萃取液进行净化,内标法定量,用超高效液相色谱-串联质谱法分析土壤和沉积物中20种氨基甲酸酯农药。20种氨基甲酸酯农药在0.02~1.0 μg/mL范围内线性良好(r≥0.99),检测限为0.20~0.60 ng/g。沉积物加标样品(20ng/g)和土壤加标样品(20ng/g)的回收率分别为33.2%~101.9%、38.8%~120.5%,相对标准偏差为6.1%~28.0%、2.3%~16.0%。沉积物加标样品(2.0 ng/g)回收率为43.0%~100.0%,相对标准偏差为2.1%~11.3%。     

气相色谱法同时测定水中28种多氯联苯单体

采用液液萃取-浓硫酸磺化净化-气相色谱电子捕获检测器同时测定水中28种多氯联苯单体,必要时利用质谱选择离子监测模式定性,考察了萃取溶剂种类和体积及盐析效应对测定的影响,比较了硫酸磺化和弗罗里硅土柱对萃取液的净化效果。方法在1.00μg/L~47.6μg/L范围内线性良好,当取样体积为200 mL时,方法检出限为0.001μg/L~0.002μg/L,基体加标回收率为95.8%~103%,相对标准偏差≤18.7%。     

分散液液微萃取气相色谱-质谱法测定水中15种硝基苯类化合物

建立了超声辅助基质分散液液微萃取（UA-DLLME）作为前处理联合气相色谱串联质谱（GC-MS）同时测定地下水和地表水中15种硝基苯类化合物的分析方法。萃取剂、分散剂、萃取温度、萃取时间和离子强度等影响因素采用Plackett-Burman设计,快速筛选出最显著影响因素,利用中心组合设计（CCD）简化实验步骤优化显著因素,结合响应曲面图最终确定最佳的萃取条件：5 mL水样在3%氯化钠条件下迅速加入40 μL四氯化碳（萃取剂）和0.5 mL乙腈（分散剂）,50 ℃下超声4 min,混合液4 000 r/min离心3 min。结果表明：15种硝基苯类化合物在50.0~1 000.0 μg/L的浓度范围内线性相关系数均大于0.995;采用超声辅助基质分散液液微萃取时,方法检出限（MDL）为0.018~0.039 μg/L;15种目标物的加标平均回收率为83.31%~99.08%,相对标准偏差均不高于5.0%（n=6）。     

废气中甲基对硫磷的比色测定

当选用弗罗里硅土和101白色酸洗担体作吸附剂,应选用丙酮淋洗,将淋洗液浓缩至干后,残留物加乙醇溶解,用盐酸萘乙二胺比色法测定;样品中的有机杂质用石油醚萃取而除去。本法适用于农药厂的排放尾气、生产过程的泄漏气、包装和使用时,甲基—E605浓度的测定。方法的最低检出限为0.34μg/5ml,样品测定的标准偏差<5％,总回收率达82％以上。     

乙腈盐析萃取HPLC-PDA同时测定水中11种苯胺类化合物

通过对色谱分析和样品萃取条件的选择和优化,建立了同时分析水中11种苯胺类化合物的HPLC方法。样品经乙腈盐析萃取后直接进样分析,采用 ODS色谱柱,以乙腈-水为流动相进行梯度洗脱,用PDA检测。结果表明,11种苯胺类化合物在0.20~100mg/L范围内其浓度和检测信号呈良好的线性关系,方法检出限为0.002~0.007mg/L,地表水和废水样品加标回收率为81.6%~97.4%,相对标准偏差为1.5%~5.5%。     

气相色谱-质谱法测定废酸油渣中的16种多环芳烃

建立了废酸油渣中16种多环芳烃超声萃取、Florisil萃取柱净化、气相色谱-质谱测定的方法。笔者对提取方式、提取剂类型和体积、提取时间和次数、净化方式等进行研究,采用无水硫酸钠分散,二氯甲烷作为提取剂超声40 min,提取液经纯水清洗、离心后取适量有机相经过3 g Florisil萃取柱净化,采用气相色谱-质谱选择离子模式(SIM),加入内标进行定量分析。结果表明:二氯甲烷提取效率比正己烷好,丙酮可能引起酸性样品中多环芳烃的降解,丙酮超声萃取时加入无水硫酸钠能在一定程度上防止目标物降解,但萃取效率不可控制,宜采用二氯甲烷作为萃取剂。分散提取能有效减少提取时间,超声清洗仪超声40 min提取效率为86.2%～104%。3g Florisil萃取柱净化比1 g Florisil萃取柱净化和GPC净化效果略好。方法检出限为0.4～1.3 mg/kg,6次空白加标的相对标准偏差为2.3%～15.3%,6个实际样品测定结果的相对标准偏差为1.2%～27.3%,基体加标回收率为51.3%～126%,连续校准稳定。该方法适用于废酸油渣样品中16种多环芳烃的检测,比直接溶解有效,比加速溶剂萃取、索氏提取、微波萃取和超声探头萃取简单、快捷,能有效减少设备污染和腐蚀,净化方法有效,测定结果准确可靠,是实现大批量样品检测的可行方法。     

弗罗里硅土净化和凝胶色谱净化在土壤苯并(a)芘测定中的应用

采用ASE萃取-弗罗里硅土净化-HPLC法和ASE萃取-GPC净化-HPLC法测定土壤中苯并(a)芘,并将2种方法的测定结果作比对。试验表明,方法在0.02 mg/L~0.500 mg/L之间线性良好,当取样量为10 g时,弗罗里硅土净化土壤样品方法检出限为8.93×10~(-5)mg/kg,平均加标回收率为72.7%~73.8%,3次测定结果的RSD为4.0%~4.5%;凝胶色谱净化土壤样品方法检出限为1.98×10~(-5)mg/kg,平均加标回收率为88.8%~90.2%,3次测定结果的RSD为2.1%~2.8%。     

饮用水中苯基脲除草剂的分子印迹固相萃取方法研究

以N-（4-异丙基苯基）-N-亚丁基脲分子印迹聚合物为吸附剂,建立了饮用水中苯基脲除草剂的分子印迹固相萃取方法。上样后固相萃取柱依次用2．5mL0．1mol／L盐酸和2．5mL去离子水淋洗,然后氮气吹干,再用1mL含8％乙腈的甲苯溶液淋洗,最后用2mL甲醇洗脱。将建立的方法用于自来水中异丙隆、非草隆、甲氧隆、绿麦隆、枯莠隆、灭草隆、伏草隆、草不隆等8种苯脲类除草剂的测定,除伏草隆和草不隆的回收率较低外,其余6种除草剂的回收率均〉60％。     

A New Mathematical Approach in Environmental and Life Sciences: Gene–Environment Networks and Their Dynamics

An important research area in life sciences is devoted to modeling, prediction, and dynamics of gene-expression patterns. As clearly understood in these days, this enterprise cannot become satisfactory without acknowledging the role of the environment. To a representation of past, present, and most likely future states, we also encounter measurement errors and uncertainties. This paper surveys and improves recent advances in understanding the foundations and interdisciplinary implications of the newly introduced gene–environment networks, and it integrates the important theme of carbon dioxide emission reduction into the networks and dynamics. We also introduce some operational and managerial issues of practical working and decision making, expressed in terms of sliding windows, quadrants (modules) of parametric effects, and navigating (controlling) between such effects and directing them. Given data from DNA microarray experiments and environmental records, we extract nonlinear ordinary differential equations that contain parameters that have to be determined. For this, we employ modern (Chebychevian) approximation and (generalized semi-infinite) optimization. After this is provided, time- discretized dynamical systems are studied. A combinatorial algorithm with polyhedra sequences allows to detect the region of parametric stability. Finally, we analyze the topological landscape of gene–environment networks with its structural (in)stability. By embedding as a module and investigating CO₂ emission control and figuring out game theoretical aspects, we conclude. This pioneering work is theoretically elaborated, practically devoted to health care, medicine, education, living conditions, and environmental protection, and it invites the readers to future research.      

微波消解-原子吸收光度法测定土壤中铜锌铅镉镍铬

用微波消解－原子吸收光度法测定土壤中铜，锌，铅，镉，镍和铬。通过硝酸－氢氟酸－过氧化氢体系消解液对土壤样品消解，选择出微波最佳消解条件。对硝酸－盐酸－过氧化氢体系消解液和硝酸－氢氟酸－过氧化氢体系消解液进行消解对比试验，发现前者不能将土壤样品完全消解，后者能将样品消解完全，但需将消解液中剩余的酸赶尽，否则测定结果将明显偏低。微波消解土壤与传统电热消解相比，操作简便快速，可提高工作效率。     

Topsoil and Housedust Metal Concentrations in the Vicinity of a Lead Battery Manufacturing Plant

The aim of the study was to determine the extent of heavy metal pollution in the vicinity of a lead battery manufacturing plant in the Czech Republic, both in the general environment and within homes. Topsoils (0–5 cm) were sampled from 100 sites along 4 transects which crossed the battery factory, the town centre and outlying rural areas. Housedust samples were collected from 15 plant-workers' homes and 15 non plant-workers' homes located at various distances from the factory. Samples were analysed for levels of Pb, Zn, Cd, Cu, As and Sb, using ICP-AES. Soil concentrations of Pb, Cd, As and Sb peaked at the perimeter fence of the battery factory with Pb levels of up to 12 650 g g> ^-1. Concentrations of these metals decreased exponentially within 500 m of the plant. Whilst the battery factory does appear to be a source of all the metals with the exception of Zn, emissions do not appear to be transported to any great extent over distances of more than 0.5 km. Topsoil and housedust concentrations of Pb, Zn, Cd, Cu, As and Sb in the general Mlada Boleslav area do not appear to be significantly different from those recorded in a large scale survey of urban soils in the United Kingdom. A comparison of housedust Pb concentrations in homes of plant workers and non-plant workers suggests that there may be a small input of Pb into the home environment by battery plant employees.     

An Overview of Contaminant-Related Issues Identified by Monitoring in San Francisco Bay

The San Francisco Estuary Regional Monitoring Program for Trace Substances (RMP) began in 1993 and is sponsored by 74 local, state, and federal agencies and companies through their discharge or Bay use permits. The RMP monitors water, sediment, toxicity, and bivalve bioaccumulation at 25 sites in the Bay that are considered to represent "background" conditions. Several major environmental issues have been identified by the RMP. Polychlorinated biphenyls and mercury were often above water quality guidelines, and often occurred in fish tissues above U.S. Environmental Protection Agency (U.S. EPA) screening values. Concentrations do not appear to be decreasing, suggesting continuing inputs. Episodes of aquatic toxicity often occurred following runoff events that transport contaminants into the Bay from urbanized and agricultural portions of the watershed. Sediment toxicity occurred throughout the Bay, and has been correlated with concentrations of specific contaminants (chlordanes, polynuclear aromatic hydrocarbons) at some locations; mixtures of contaminants were probably also important. Since the RMP does not monitor all ecosystem components, assessments of the overall condition of the Bay cannot be made. However, in terms of contamination, the RMP samples suggest that the South Bay, and North Bay sites are moderately contaminated.     

Biomagnification factors (fish to Osprey eggs from Willamette River,Oregon, U.S.A.) for PCDDs,PCDFs, PCBs and OC pesticides

A migratory population of 78 pairs of Osprey (Pandion haliaetus) nesting along the Willamette River in westernOregon was studied in 1993. The study was designed to determinecontaminant concentrations in eggs, contaminant concentrationsin fish species predominant in the Ospreys diet, andBiomagnification Factors (BMFs) of contaminants from fish specieseaten to Osprey eggs. Ten Osprey eggs and 25 composite samplesof fish (3 species) were used to evaluate organochlorine (OC)pesticides, polychlorinated biphenyls (PCBs), polychlorinateddibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans(PCDFs). Mercury was also analyzed in fish. Geometric meanresidues in Osprey eggs were judged low, e.g., DDE 2.3 g g^-1 wet weight (ww), PCBs 0.69 g g^-1, 2,3,7,8-TCDD 2.3 ng kg^-1, and generally well below known threshold values for adverse effects on productivity, and the population was increasing. Osprey egg residue data presentedby River Mile (RM) are discussed, e.g., higher PCDDs were generally found immediately downstream of paper mills and eggsfrom the Willamette River had significantly elevated PCBs and PCDDs compared to reference eggs collected nearby in the CascadeMountains. Prey remains at nest sites indicated that the Largescale Sucker (Catostomus macrocheilus) and NorthernPikeminnow (Ptychocheilus oregonensis) accounted for an estimated 90.1% of the biomass in the Osprey diet, and composite samples of these two species were collected from different sampling sites throughout the study area for contaminant analyses. With the large percentage of the fishbiomass in the Osprey diet sampled for contaminants (and fisheaten by Ospreys similar in size to those chemically analyzed),and fish contaminant concentrations weighted by biomass intake, a mean BMF was estimated from fish to Osprey eggs for the largeseries of contaminants. BMFs ranged from no biomagnification(0.42) for 2,3,7,8-TCDF to 174 for OCDD. Our findings for themigratory Osprey were compared to BMFs for the resident HerringGull (Larus argentatus), and differences are discussed. Webelieve a BMF approach provides some basic understanding ofrelationships between contaminant burdens in prey species offish-eating birds and contaminants incorporated into their eggs,and may prove useful in understanding sources of contaminants inmigratory species although additional studies are needed.     

Assessing health consequences in an environmental impact assessment: The case of Amsterdam Airport Schiphol

In this article a comprehensive approach for the evaluation of possible health effects in an environmental impact assessment (EIA) is described, illustrated with the example of Amsterdam Airport Schiphol. Unlike many EIAs, we estimated quantitatively the impact of aircraft-related pollution in terms of the number of affected people for aircraft noise annoyance, odour annoyance and hypertension. In addition, an analysis of health registry data on cardiovascular and respiratory diseases and a short survey on annoyance and risk perception were carried out. The scope of a health impact assessment depends on the situation, available knowledge and data, concern in the population about the impact and the number of people concerned. It is important to pay attention to the perception of risks and concerns from all parties involved. Moreover, the results demonstrate that far more people outside the area for which standards apply were affected than inside.     

Contaminant Profiles of Two Species of Shorebirds Foraging Together at Two Neighboring Sites in South San Francisco Bay, California

The San Francisco Bay estuary isused by over one million shorebirds during springmigration and is home to several hundred thousandduring the winter. Most shorebird use occurs in thesouthern reach of the estuary (South Bay). Thereduced water circulation and discharge fromindustrial sources in the South Bay are responsiblefor the highest levels of some trace elements in theestuary. Wintering shorebirds have been found to havestrong site fidelity to areas as small as a fewkilometers in the South Bay, which may increase theirexposure to contaminants near local point sources. Inaddition, different shorebird species foraging at thesame site have been shown to have differentcontaminant burdens. Thus, our objectives were totest whether contaminant burdens differed by species,or whether contaminant burdens differed in shorebirdscollected at adjacent sites. We examined thecontaminant profiles of two species of shorebirds,long-billed dowitchers (Limnodromus scolopaceus)and western sandpipers (Calidris mauri) thatforage together at two sites, Hayward and Newark,separated by 8 km in the South Bay. We usedmultivariate analysis of variance tests to compare thecomposition of 14 elemental analytes in their livertissues and estimated their molar ratios of Hg and Se. Composite samples were used for contaminant analysesbecause of the small body size of the shorebirds. Seven elemental analytes (Ag, Ba, Be, Cr, Ni, Pb, V)were below detection limits in a majority of thesamples so statistical analyses were precluded. Inthe measurable analytes (As, Cd, Cu, Hg, Mn, Se, Zn),we found no significant intra-site differences ofcontaminant profiles for the two species. We pooledthe samples to examine inter-site differences andfound significant differences in contaminant profilesbetween shorebirds at the neighboring sites (P = 0.03). Shorebirds at Newark had higher (P < 0.05) concentrations of As, Cd, and Se than those at Hayward. Dowitchers at Newark had concentrations of Hg and Se which were highly correlated (P < 0.003) in a mean molar ratio of 1:19, similar tothat reported in other birds. In the larger dowitcherspecies, we also examined exposure to 20organochlorine compounds. Organic analyses showedthat the dowitchers had been exposed to DDE, PCBs,dieldrin and trans-nonachlor, but with no significantdifferences in concentrations between Hayward andNewark (P > 0.05).     

An investigation on biological stability of product water generated by lab-scale and pilot-scale distillation systems

Material Disposal Area G is the primary low-levelradioactive waste disposal site at Los Alamos NationalLaboratory, New Mexico, and is adjacent to Pueblo of SanIldefonso lands. Pueblo residents and Los Alamos scientists areconcerned about radiological doses resulting from uptake of AreaG radionuclides by mule deer (Odocoileus hemionus) andRocky Mountain elk (Cervus elaphus), then consumption ofdeer and elk meat by humans. Tissue samples were collected fromdeer and elk accidentally killed near Area G and were analyzedfor ³H, ⁹⁰Sr, total U, ²³⁸Pu, ^{239, 240}Pu,²⁴¹Am, and ¹³⁷Cs. These data were used to estimatehuman doses based on meat consumption of 23 kg y^-1. Humandoses were also modeled using RESRAD, and dose rates to deer andelk were estimated with a screening model. Dose estimates tohumans from tissue consumption were 2.9 × 10^-3 mSv y^-1and 1.6 × 10^-3 mSv y^-1 from deer and elk, respectively,and RESRAD dose estimates were of the same order of magnitude. Estimated dose rates to deer and elk were 2.1 × 10^-4 mGyd^-1 and 4.7 × 10^-4 mGy d^-1, respectively. Allestimated doses were significantly less than established exposurelimits or guidelines.     

The Draft of the New German Guideline VDI 3782/8 to Model Automobile Exhaust Dispersion

The draft of the German guideline to calculate automobile exhaust dispersion is explained. It contains a two-stage-system: For first quick estimates the guideline contains the simple models MLuS and STREET. In case these models are not applicable or their results shows concentration levels close to the air quality standards, the more complex models PROKAS_V and MISKAM are recommended. PROKAS_V is a Gaussian plume model, MISKAM is a 3-dimensional microscale non hydrostatic flow model for built-up areas with an Eulerian dispersion model. The guideline comprises cases in rural areas without or with few adjacent buildings as well as urban areas with buildings near the roads. The contribution gives information about the models, typical results and some of the problems showing up presently.     

Hydrocarbon Utilization in Yeast Isolates Found to Grow in Association with Petroleum in a Polluted Ultisol of Midwestern Nigeria

The population counts of hydrocarbon-utilising yeasts weremonitored at six sampling stations in the Benin City municipalarea over a four-week period. Although the population countswere relatively constant in each locality, the highest countsoccurred in areas heavily polluted by domestic and industrialeffluents. A total of thirty-five hydrocarbon-degrading yeastswere isolated from soil at the sampling stations usingn-hexadecane as sole carbon source. The isolates were identifiedas belonging to the genera Candida (27 strains), Endomycopsis (4 strains). All the organisms grew on long-chainn-alkane, kerosene, diesel oil and crude oil but failed to growon short-chain n-alkane, aromatic and alicyclic hydrocarbons.Measurement of growth attributes of the isolates usingn-hexadecane, diesel oil and crude oil as substrates showed thatthe Candida species were better utilizers of hydrocarbonsubstrates relative to Endomycopsis and Schizosaccharomyces species.