高效液相色谱-串联质谱法同时检测地表水中13种药物及个人护理品

采用高效液相色谱-串联质谱(HPLC-MS/MS)检测,建立了地表水中13种药物及个人护理品的测定方法。水样用盐酸与氢氧化钠溶液调p H值至7.0左右,过固相萃取小柱进行富集,用14 m L甲醇洗脱。以C18柱为分离柱,0.01%甲酸的甲醇-0.01%甲酸水溶液为流动相,目标物在10 min内分离,在0.50~250μg/L范围内,13种化合物峰面积与内标物质峰面积之比与质量浓度的线性关系良好(0.99),检出限在0.05~0.5 ng/L范围内。基质加标实验结果表明,13种化合物在水中的回收率分别在56.2%~123.2%之间(加标水平5 ng/m L)和58.0%~107.8%(加标水平50 ng/m L),相对标准偏差在1.60%~19.9%(n=6)之间。应用该方法测定了从2条纳污河流采集的10份水样,结果表明,除美托诺尔和普洛萘尔未被检出外,其余11药物的检出频率在30%~100%之间。在13种目标物质中,咖啡因的检测浓度最高达287.5ng/L,舒必利次之,为277.5 ng/L。本方法快速、准确,适用于地表水中PPCPs类的快速测定。     

超声波提取-恒波长同步荧光法测定淡水藻中叶绿素a的含量

针对绿藻,采用超声波提取,以荧光激发-发射波长差216nm,建立了同步荧光法测定绿藻叶绿素a含量的新方法,其线性范围为0.02～1.25 mg/L,检出限为1.6ug/L,加标回收率在97.0%～104%之间。与分光光度法测定叶绿素a的对比试验结果表明,两者无显著性差异,但该方法具有快速、灵敏,其他常见色素不干扰测定的优点,能够满足供水中绿藻叶绿素a含量快速检测的需要。     

固相萃取-超高效液相色谱-串联质谱测定水中痕量苯甲地那铵

苯甲地那铵是一种广泛使用的苦味剂,近年来被发现在欧洲水体中普遍存在。建立灵敏可靠的环境样品前处理分析方法对评价其环境行为具有重要意义。通过优化关键前处理过程参数,建立了水中苯甲地那铵的固相萃取-超高效液相色谱串联质谱分析方法,系统考察了该方法的准确度、精密度、基质效应、检出限以及线性范围。研究表明：当调节水样pH至8以上,采用混合型阳离子交换小柱(200 mg, 3 mL)富集水样,采用含体积分数2%甲酸的甲醇溶液洗脱时,该方法可获得最佳回收率;纯水和环境水样中加标回收率分别为97%～105%和89%～119%,相对标准偏差小于7%;基质效应均在24%以内;方法检出限为0.07 ng/L,线性范围为0.01～50μg/L。该方法可用于环境水体中苯甲地那铵的痕量检测。     

Solid‐phase extraction and GC analyses of select agricultural pesticides and metabolites in stream water

Abstract

The occurrence of agricultural pesticides in surface waters around the USA has created a concern over the status of safe drinking water. Solid‐phase extraction (SPE) or liquid‐liquid extraction (LLE) is usually employed to concentrate trace levels of pesticides in water samples to concentrations that are measurable with advanced chromatographic instruments. We describe here a SPE and capillary gas chromatographic (GC) procedure to extract and concentrate trace levels of select agricultural pesticides and metabolites from stream water. Our SPE and GC method provides high sensitivity, with recoveries between 85% to 95%, and high reproducibility for 9 of the pesticides studied. The described method provided marginal recoveries of 19 and 60% for the atrazine metabolites.     

U型工作面上隅角埋管瓦斯抽采数值模拟研究

传统的U型通风工作面上隅角瓦斯积聚现象经常出现，严重制约着矿井正常生产能力的有效发挥，对矿井安全生产造成重大威胁。基于前人对采空区非均质多孔介质气体运移理论的研究，采用Fluent软件数值模拟研究了U型和上隅角埋管条件下U型通风系统的静压力场和瓦斯浓度场。研究结果表明：在相同的模型参数条件下，U型通风容易造成上隅角瓦斯积聚，上隅角瓦斯超限问题十分严重；采空区5m处埋管，治理上隅角瓦斯积聚的效果欠佳，达不到安全开采的条件；15m处埋管可以较好的解决上隅角瓦斯超限问题，工作面没有出现瓦斯积聚现象，工作面和回风巷的瓦斯浓度始终处于1％以下；25m处埋管的效果与15m基本相同，没有表现出更好的瓦斯治理效果。综合数值模拟的结果，确定了上隅角埋管抽放采空区瓦斯的理想抽放位置为距离地板垂高1．2m、沿走向深入采空区15m处。     

Ecotoxicological effects assessment in the Netherlands: Recent developments

In a recently published annex to the National Environmental Policy Plan of the Netherlands (1989), attention was paid to ecotoxicological effects assessment. The proposed procedure was based on the advice of the Health Council of the Netherlands (1989) on risk assessment of toxic chemicals for ecosystems. The various extrapolation methods described by the Health Council are critically discussed in this paper. The extrapolation method of Van Straalen and Denneman (1989) is evaluated for eight chemicals and 11 aquatic species. Conclusions are drawn about the quality and quantity of the ecotoxicological data needed for aquatic effects assessment. For the soil—a compartment that is often at risk—ecotoxicological effects assessment is not possible because suitable ecotoxicological test methods still have to be developed.     

Evaluation of tidal marsh restoration: Comparison of selected macroinvertebrate populations on a restored impounded valley marsh and an unimpounded valley marsh within the same salt marsh system in Connecticut,USA

Macroinvertebrates were examined on an impounded valley marsh in Stonington, Connecticut, that has changed from aTypha-dominated system to one with typical salt-marsh vegetation during 13 years following the reintroduction of tidal exchange. Animal populations on this restored impounded marsh were evaluated by comparing them with populations on a nearby unimpounded valley marsh of roughly the same size. Populations of the high marsh snail,Melampus bidentatus Say, were quantitatively sampled along transects that extended from the water-marsh edge to the upland; those of the ribbed mussel,Geukensia demissa Dillwyn, were sampled in low marsh areas on transects along the banks of creeks and mosquito ditches. The occurrence of other marsh invertebrates also was documented, but their abundance was not measured. The mean density ofMelampus was 332±39.6 SE/m² on the restored impounded marsh and 712±56.0 SE/m² on the unimpounded marsh. However, since snails were larger on the restored impounded marsh, the difference in snail biomass was less pronounced than the difference in snail density. MeanMelampus biomass was 4.96±0.52 SE g dry wt/m² on the restored impounded marsh and 6.96±0.52 SE g dry wt/m² on the unimpounded marsh. On the two marshes, snail density and biomass varied in relation to plant cover and other factors. The density and biomass ofGeukensia at the edge of the marsh were comparable on the restored impounded and unimpounded marshes. Mean mussel densities ranged from 80 to 240/m² and mean mussel biomass varied from 24.8–64.8 g dry wt/m² in different low marsh areas. In contrast, below the impoundment dike, meanGeukensia density was 1100±96.4 SE/m² and meanGeukensia biomass was 303.6±33.28 SE g dry wt/m². A consideration of all available evidence leads to the conclusion that the impounded marsh is in an advanced phase of restoration.     

BAYESIAN MODELS OF FORECASTED TIME SERIES1

Bayesian Processor of Forecasts (BPF) combines a prior distribution, which describes the natural uncertainty about the realization of a hydrologic process, with a likelihood function, which describes the uncertainty in categorical forecasts of that process, and outputs a posterior distribution of the process, conditional upon the forecasts. The posterior distribution provides a means of incorporating uncertain forecasts into optimal decision models. We present fundamentals of building BPF for time series. They include a general formulation, stochastic independence assumptions and their interpretation, computationally tractable models for forecasts of an independent process and a first-order Markov process, and parametric representations for normal-linear processes. An example is shown of an application to the annual time series of seasonal snowmelt runoff volume forecasts.     

GEOLOGIC INFERENCE FROM “FLOW NET” TRANSMISSIVITY DETERMINATION: THREE CASE STUDIES1

A graphical inverse method for determining the regional transmissivity distribution was applied to three field problems. The study areas were the Hanford Site, Washington; the Rocky Mountain Arsenal, Colorado; and the Nevada Test Site, Nevada. This method can aid in flow system conceptualization by revealing the location of bedrock controls for groundwater flow. It is a valuable tool for aiding the hydrogeologist in asking questions about the nature of trends in the pattern of transmissivity values. Quantitative estimates of regional transmissivities can be used as starting points for further parameter refinement. Sensitivity analysis using Monte Carlo simulation shows that quantitative estimates of transmissivity can be obtained when measurement error in the hydraulic head does not cause a large error in the hydraulic gradient.     

Groundwater mapping: An analysis of the United States Hydrological Investigation Atlas Series

Groundwater mapping is a critical component of efficient water resource management today. Difficulties arise when highly specialized and complex groundwater data are collected and presented in map form. This is an analysis of the map content and its presentation in the USGS Hydrological Investigation Atlas Series. This analysis reveals the problems to be surmounted in mapping groundwater information. The technical nature of the groundwater data requires special design considerations.