高效液相色谱-串联质谱法测定废水中5种喹诺酮类抗生素

建立高浓度有机废水中5种喹诺酮类抗生素的高效液相色谱-串联质谱测定方法。水样经HLB固相萃取小柱富集净化,12 ml甲醇洗脱、浓缩并加入内标溶液后,定容至1 mL待测。以C18柱为分离柱,含0.01%甲酸的甲醇-含0.01%甲酸的水溶液为流动相,目标物质在10 min内分离。在0.25~1 250 ng/mL范围内,目标物质线性关系良好(R20.99)。基质加标试验结果表明,纯水中的回收率为61.40%~91.92%,废水中的回收率为54.92%~101.87%,检出限为0.25~2.5 ng/L,方法定量限为0.36~3.99 ng/L。应用该方法对21家猪场的64份废水样品进行分析,5种喹诺酮类抗生素的检出频率为47%~95%,平均检出浓度为980~5 734 ng/L。该方法快速、准确,适用于高浓度有机废水中喹诺酮类抗生素的同时测定。     

加速溶剂萃取-凝胶净化色谱-气相色谱质谱法测定农用地土壤中有机氯农药方法研究

通过对加速溶剂萃取、平行蒸发及净化方法等环节的优化实验,建立了加速溶剂萃取-凝胶净化色谱-气相色谱质谱法测定农用地土壤中23种有机氯农药的检测方法。结果表明,方法检出限为0.0034~0.0052 mg/kg;对化合物质量分数为0.25 mg/kg的土壤加标样品进行平行实验,回收率为82.0%~93.7%;测定结果的相对标准偏差（RSD）≤8.7%。对土壤有证标准质控样品进行分析,测定结果均在验收范围之内。该方法准确可靠,灵敏度较高,样品净化效果较好,能够满足农用地土壤中有机氯农药残留痕量分析的要求。     

固相萃取-超高效液相色谱法检测地表水中7种氯酚类化合物

建立了一种能够测定地表水中7种氯酚类化合物的固相萃取-超高效液相色谱方法。调节水样p H=2,经固相萃取柱富集后,用丙酮和二氯甲烷洗脱,浓缩定容后分析。以甲醇-水溶液(含0.2%乙酸)为流动相,柱温为30℃,紫外检测波长为分段检测(285、290、300、304 nm)。结果表明,检测方法对7种氯酚类化合物具有良好的线性相关性,相关系数≥0.999 7。当水样萃取体积为1 L,浓缩至1 m L,进样量为5μL时,方法检出限为12.7~32.1 ng/L,测定下限为50.8~128.4 ng/L;高低两组浓度的平均加标回收率为79.2%~108.4%,相对标准偏差为4.6%~13.3%。     

固相萃取-UPLC-MS/MS法测定水中全氟化合物

水样中全氟辛酸、全氟辛烷磺酸钾、全氟丁酸、全氟丁烷磺酸经弱阴离子交换固相萃取柱富集净化后,用超高效液相色谱-串联质谱法测定。通过优化样品前处理条件和仪器条件,使4种全氟化合物在0.05μg/L~10.0μg/L范围内线性良好,相关系数为0.998 9~0.999 9,方法检出限为0.27 ng/L~0.96 ng/L。空白水样3个质量浓度水平的加标回收率为73.1%~91.3%,6次测定结果的RSD为7.4%~14.3%。     

鱼类样品中有机磷阻燃剂分析方法的优化研究

建立了鱼类组织样品中有机磷阻燃剂（OPFRs）的分析方法,优化了萃取条件、净化条件、液相色谱条件和质谱检测参数。确定了生物样品经冷冻干燥后,以1∶1（V/V）的正己烷/二氯甲烷混合溶液进行加速溶剂萃取,利用氨基固相萃取柱进行净化,以1∶1（V/V）的正己烷/二氯甲烷、二氯甲烷和9∶1（V/V）的二氯甲烷/甲醇为洗脱液,最后用超高效液相色谱-串联质谱同时对9种OPFRs进行定性定量检测。结果表明,各物质的基质加标回收率均为56.5%~108%,方法的测定下限为0.016~0.104 ng/g （以脂重计）,满足了生物样品中OPFRs的分析检测要求。利用该方法测定了北京和广州市养殖和野生鲫鱼肌肉组织样品,主要的OPFRs同族体为磷酸三正丁酯（TNBP）、磷酸三乙基己基酯（TEHP）、磷酸三（1-氯-2-丙基）酯（TCIPP）和磷酸三氯乙基酯（TCEP）,质量比为5.94~33.7 ng/g（以脂重计）,显示出良好的适用性。     

SPE-GC-MS/MS法测定水源水中多种有机氯EDCs

采用C 18柱固相萃取(SPE)-三重四级杆气相色谱-质谱法同时测定水中18种含有机氯的环境内分泌干扰物,方法在0.500μg/L^100μg/L范围内线性良好,方法检出限为0.04 ng/L^0.8 ng/L,空白水样的加标回收率为61.3%~108%,6次测定结果的RSD为3.8%~18.0%。将该方法用于饮用水源水监测,18种目标化合物的测定值为未检出~1.5 ng/L,平均加标回收率为71.9%~109%,平行测定结果的RSD<15%。     

固相萃取-超高效液相色谱/三重四极杆质谱法同时测定地表水中8种亚硝胺类化合物

建立了固相萃取（SPE）-超高效液相色谱/三重四极杆串联质谱（UPLC-MS/MS）同时测定地表水中8种亚硝胺类化合物的方法。水样中目标物经椰壳活性炭固相萃取小柱吸附富集,小柱经氮气吹干后采用二氯甲烷洗脱。待测样品采用Atlantis T₃柱,以水-甲醇作为流动相进行梯度洗脱,大气压力化学电离源（APCI）正离子模式多反应监测方式（MRM）进行检测,内标法定量分析。8种目标物在相关线性范围内线性良好(r≥0.9950),地表水加标回收率为55.4%~90.4%,相对标准偏差为3.1%~14.3%,方法检出限为1.1 ~1.8 ng/L。本方法准确度和灵敏度高,适用于快速测定地表水中8种亚硝胺类化合物含量。     

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%。     

典型药物污染物的SPE-UPLC-MS-MS检测方法

采用固相萃取-高效液相色谱-串联质谱法(SPE-UPLC-MS-MS)测定自然水体中的10种典型药物污染。比较了2种萃取柱HLB和C18的富集效果,并对水样pH、萃取柱的淋洗溶剂及水样体积进行了优化。结果表明,采用HLB小柱进行富集净化,水样体积为500 mL,调节pH=3.0,95%甲醇洗脱,在0~200μg/L范围内10种药物的标准曲线线性关系良好(r≥0.999),方法检出限0.5~2.0 ng/L,精密度高(RSD10%),加标回收率为64.3%~100.7%。经过对太湖和某污水厂排水口水样的测试,表明该方法适用于自然水体药物的快速检测,同时大部分药物被检出,说明选择的10种目标药物及建立的检测方法对研究中国水体药物污染具有一定的参考价值。     

加速溶剂萃取-气相色谱/串联质谱法测定土壤中20种有机氯农药

建立了用加速溶剂萃取法（ASE）提取、气相色谱-串联质谱法分析土壤中20种有机氯农药的方法。用正己烷和丙酮（1∶1,V/V）的混合溶剂为提取剂,萃取温度100℃,压力1 500 psi,静态提取10 min,循环提取2次,提取液经石墨化碳黑固相萃取柱净化,浓缩后进行GC-MS/MS测定,外标法定量。试验结果表明,采用串联质谱多反应监测模式,降低了背景干扰,当取5 g土壤时,有机氯农药的检出限在0.1~3.0μg/kg之间,低浓度水平（8μg/kg）的基体加标回收率为70.3%~134%,相对标准偏差〈23%。测定方法背景干扰低,灵敏度高,适合土壤中20种有机氯农药残留的同时测定。     

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.     

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.     

火焰原子吸收光谱法测定苏州开发区26种蔬菜中铜锌铁锰镍

用火焰原子吸收光谱法测定了苏州开发区26种蔬菜中的铜、锌、铁、锰和镍的含量。蔬菜样品用硝酸高氯酸混合酸进行消解。4次测定值的相对标准差<5%,加标回收率在92%～107%之间。26种蔬菜中铜、锌、铁、锰、镍的含量基本均在世贸组织规定的范围内。     

Using Multiple Taxonomic Groups to Index the Ecological Condition of Lakes

Biological indicators of communitiestypically reflect a common environmental signalreflecting the general condition of the ecosystem, as well asindividual signals by indicators differentiallysensitive to particular environmental conditions. Wedescribe here a method of integrating and interpretingsuch indicators from 19 New England lakes for fivetaxonomic groups (diatoms, benthos, zooplankton, fish,and birds). Our approach provides a systematicstandardized way to integrate multiple metrics fromdifferent taxonomic groups by addressing four elementscrucial to analyzing data from multiple indicators: covariate control, re-scaling of data, standardizing the sign of responses, and dimensional reduction. We evaluated the biologicalmetrics against individual environmental stressors andagainst multivariate physicochemical metricscharacterizing general anthropogenic stress among thelakes. The method detected a response to variationin the gross environmental condition of the lakes thatwas correlated across taxa and metrics. In addition,a differential response to near shore conditions wasdemonstrated for fish. The success of the approach inthis study lends support to its general application toecological monitoring involving complex data sets.     

Concentrations of Cadmium, Mercury and Selenium in Blood, Liver and Kidney of Common Eider Ducks from the Canadian Arctic

We determined concentrations of selected trace elements inlivers, kidneys and blood samples from common eiders (Somateria mollissima borealis) from the eastern Canadianarctic during 1997 and 1998. Concentrations of totalmercury and organic mercury were generally low in the liversof these birds (less than 6 and 4 g g^–1 dry wt,respectively). Selenium ranged between 11–47 g g^–1 inlivers. Renal cadmium concentrations were among the highestever published for this species (range: 47–281 g g^–1). The regressions of log-transformed concentrations ofthese trace elements in blood samples on those in liver orkidney were significant (all P-values < 0.05) andpositive. However, except for organic mercury (RM ² = 0.83), the co-efficients of determination were low tomoderate (range of R ²: 0.26–0.52), suggesting poorto moderate predictive capability. Furthermore, therelationships between total mercury in blood and liverchanged between 1997 and 1998, suggesting that it would notbe possible to predict consistently, concentrations ofmercury in blood from those in liver based on samples takenin one year. Blood samples can be used to determineconcentrations of these trace elements in common eiders (andprobably other sea duck species as well). The use of bloodsamples is especially warranted when it is undesirable tokill the animal such as when working with rare or endangeredsea duck species or when the objective is to relate traceelement exposure to annual survival rates. However, thepredictive equations developed here should not be used topredict expected concentrations in one type of tissue fromthose in the other.     

Impact of Pollution Caused by Uranium Production on Soil Macrofauna

Thirty years of mining and milling activities of the Priargunsky Mining-Chemical Production Company (South-Eastern Siberia, Russia) have resulted in an enrichment of uranium in adjacent steppe soils by a factor of up to 600. A number of attendant pollutants (thorium, arsenic and heavy metals) also have high concentrations in the soil. To estimate the effects of this pollution on soil-living macroinvertebrates, pitfall trapping and core sampling were applied. The element composition of four beetle species was analysed. Soil macroinvertebrates had 3–37 times lower abundance and biodiversity at the contaminated sites compared with the control. Ground beetle communities at the contaminated sites were reduced compared to the control site. The concentrations of uranium and arsenic in beetles collected at the contaminated sites were 2–41 and 2–26 times higher, respectively, than at the control site. There is strong evidence that the contamination caused by uranium production has severe negative biological effects on important groups of the soil food web.     

Eutrophication and Sedimentation Patterns in Complete Exploitation of Water Resources Scenarios: An Example from Northwestern Semi-arid Mexico

Water requirements to supply human needs lead water stakeholders to store more water during surplus periods to fulfil the demand during – not only – scarcity periods. At the reservoirs, mostly those in semi-arid regions, water level then fluctuates extremely between rises and downward during one single year. Besides of water management implications, changes on physical, chemical and biological dynamics of these drawdown and refilling are little known yet. This paper shows the results, throughout a year, on solids, nutrients (N and P), chlorophyll-a, and sedimentation changes on the dynamics, when the former policy was applied in a reservoir from the semi-arid Northwestern Mexico. Water level sinusoidal trend impinged changes on thermal stratification and mixing, modifying nutrient cycling and primary producer responses. According to nitrogen and phosphorus concentration as well as chlorophyll-a, reservoir was mesotrophic, becoming hypertrophic during drawdown. Nutrient concentrations were high (1.22 ± 0.70 and 0.14 ± 0.12 mg P l⁻¹), increasing phosphorus and lowering N:P significantly throughout the study period, although no intensive agricultural, no urban development, neither industrial activities take place in the watershed. This suggests nutrient recycling complex mechanisms, including nutrient release from the sediment–water interface as the main nutrient pathway when shallowness, at the same time as mineralization, increases. Outflows controlled nitrogen and phosphorus availability on the ecosystem while organic matter depended on river inflows. As on other subtropical aquatic ecosystems, nitrogen limited primary productivity (Spearman correlation R = 0.75) but chlorophyll-a seasonal pattern showed an irregular trend, prompting other no-nutrient related limitants. Shallowness induced a homogeneous temporal pattern on water quality. This observed temporal variability was mainly explained statistically by changes on solids (mineral and organic), chlorophyll-a and flows (62.3%). Annual sedimentation rates of total solids ranged from 11.73 to 16.29 kg m⁻² year⁻¹ with organic matter comprising around 30%. N:P ratio on sedimentation rates were as high as could be expected in a resuspension dominated ecosystem, and spatially inverse related with N:P ratio on bottom sediments. Distance from river inlet into the reservoir reveals a marked spatial heterogeneity on solid and nitrogen sedimentation, showing the system dependence on river inflows and supporting resuspension as the main phosphorus pathway. Accretion rates (2.19 ± 0.40 cm year⁻¹) were not related to hydrological variability but decreased with the distance to the river input. Total sediment accumulation (9,895 tons km⁻² year⁻¹) denotes siltation as other serious environmental problem in reservoirs but possibly not related with operational procedures.