Determination of synthetic musk compounds in sewage biosolids by gas chromatography/mass spectrometry

A review of sewage sludge regulations and land application practices by the United States National Research Council (2002) recommended development of improved analytical techniques to adequately identify and quantify new chemical contaminants, such as synthetic musk compounds in Class A sewage sludge (i.e., biosolids). This prompted the development of a rugged analytical method using gas chromatography coupled to mass spectrometry to detect this group of organic pollutants in biosolids. In this paper, the term "biosolids" is used interchangeably with "sewage sludge", which is defined in the regulations and used in the statue (Clean Water Act). Samples of Class A biosolids obtained from sewage treatment plants in Los Angeles, California, the City of Las Vegas, Nevada, and also in the form of a commercial fertilizer, were extracted using pressurized liquid extraction technique, subjected to gel permeation chromatography clean-up, and analyzed by GC/MS using the selected ion monitoring mode. The method developed has the potential to detect synthetic musk compounds in complex matrices, may provide accurate data useful in human health and environmental risk assessment, and may be useful in determining the efficacy of municipal sewage treatment plants for removing synthetic musk compounds.     

质谱及其联用技术在水中消毒副产物识别和分析中的应用

水中消毒副产物(DBPs)是在水消毒过程中消毒剂与水中溶解性有机物以及无机离子发生反应而产生,其对水环境生态安全和人体健康有不利影响。简述了DBPs的生成、种类、毒性和分析方法等,重点综述了气相色谱-质谱联用(GC-MS)、液相色谱-质谱联用(LC-MS)、离子色谱-质谱联用(IC-MS)以及超高分辨率质谱(UPMS)等质谱(MS)及其联用技术在水中DBPs识别和分析中的应用,分析了不同MS技术的特点和应用实例,提出了MS技术在DBPs研究领域的发展方向与挑战。     

Methodologies for determination of antimony in terrestrial environmental samples

Methodologies for the environmental analysis of total antimony and aqueous chemical speciation are critically reviewed, including preparation techniques for aqueous and solid matrices and the determination of solid state partitioning and recommendations are given for future research directions. Concentrations of total antimony commonly present in aqueous and solid environmental samples are readily determined using present day analytical techniques. This has resulted primarily from technological advances in microwave digestion for solid matrices and the development of plasma based analyte detection systems. ICP-AES and ICP-MS techniques are both utilised for the environmental analysis of total antimony concentrations. However, ICP-MS is increasingly favoured as a result of reduced spectral interferences and the potential for analyte detection in the pg mL(-1) range. Determination of aqueous antimony speciation presents a number of complex analytical challenges and highly selective separation and identification techniques are required prior to detection. The majority of published techniques including common applications of hydride generation are insufficiently selective for the determination of intrinsic chemical speciation and often only oxidation state data are obtained. The recent in-line applications of HPLC-ICP-MS offer the potential for highly selective separations of aqueous antimony species and determination of detailed chemical speciation data. However, considerable development work is required to optimise chromatographic separations and identify uncharacterised species resident in environmental systems. Analytical techniques to aid the determination of antimony's associations with solid environmental matrices include the application of chemical extraction procedures and leaching experiments. To date, this area of analytical research has received little attention and further studies are required to elucidate this aspect of antimony's environmental chemistry.     

Chromatographic techniques for pollution analyses

Pollution studies of air and water samples have been greatly enhanced by the use of chromatographic techniques. The selection of the proper detectors coupled with the various column types and substrates have broadened the capabilities of environmental analyses. Proper care in sampling protocols and sample treatment has steadily improved the sensitivity of these measurements. The recommended methods for air, wastewater, drinking water and solid waste samples all utilize some type of chromatographic analysis for the determination of organic contaminants. Three complimentary techniques: i.e., headspace sampling (dynamic and static methods), microextractions (liquid-liquid and/or liquid-solid) and solid-phase extractions have expanded the capabilities of such studies to permit the analytical chemist to perform fast in-the-field monitoring, concentrate low levels of analytes and determine solubilities of toxic substances. A discussion of other environmental areas which should be studied, along with the changes and/or modifications in analytical technology which should be investigated, will be presented.Plenary speaker.     

Assessing depleted uranium (DU) contamination of soil, plants and earthworms at UK weapons testing sites

Depleted uranium (DU) weapons testing programmes have been conducted at two locations within the UK. An investigation was therefore carried out to assess the extent of any environmental contamination arising from these test programmes using both alpha spectrometry and mass spectrometry techniques. Uranium isotopic signatures indicative of DU contamination were observed in soil, plant and earthworm samples collected in the immediate vicinity of test firing points and targets, but contamination was found to be localised to these areas. This paper demonstrates the superiority of the (235)U : (238)U ratio over the (234)U : (238)U ratio for identifying and quantifying DU contamination in environmental samples, and also describes the respective circumstances under which alpha spectrometry or mass spectrometry may be the more appropriate analytical tool.     

Determination of Steroid Estrogens in Wastewater Treatment Plant of A Controceptives Producing Factory

Steroid estrogens such as estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethynylestradiol (EE2) have been suspected to be the main contaminants, which can affect the endocrine system of animals. Many authors have investigated these chemicals in the domestic wastewater treatment plants (WTP). However, wastewater from industries producing steroid contraceptives has not got ample attention. From the environmental point of view, the four steroids are very significant because even very low concentrations (ng/L) can cause reproductive disturbances in human, livestock and wildlife. The main purpose of the present investigation was to develop an analytical method for the determination of the four steroid estrogens present in WTP of a pharmacy factory, mainly producing contraceptive medicine in Beijing, China. Analysis was performed by solid-phase extraction (SPE) system and liquid chromatography combined with tandem mass spectrometry (LC/MS/MS). The average recoveries from effluent samples ranged from 88% to 103% and the precision of the method ranged from 9% to 4%. Based on 0.5-L wastewater samples, the limit of quantification (LOQ) was determined at 0.7 ng/L for E1, 0.8 for E2, 0.9 ng/L for E3, and 0.5 ng/L for EE2 in influent, and 1.0 ng/L for E2 and EE2, and 2.0 ng/L for E1 and E3 in effluent. In the influent samples, average concentrations of 80, 85, 73 and 155 ng/L were determined for E1, E2, E3 and EE2, respectively, showing that they were removed in this WTP to the extent of 79, 73, 85 and 67%, respectively.     

Parasites of Fish as Indicators of Environmental Stress

During the 1994/1995 EMAP-Estauries program in the Carolinian Province we investigated the feasibility of using parasites of fish as response indicators. Parasites of fish are an indigenous component of healthy ecosystems. Within the EMAP-E design, the suite of environmental parameters which may affect parasite abundance, richness, prevalence, and diversity can be divided into three categories: 1) the physical and chemical characteristics of the water and sediment (including contaminants) external to the fish; 2) the internal environment defined by the physical condition (physiological) of individual fish; and 3) the presence and relative abundance of benthic macroinvertebrates, many of which serve as intermediate hosts. The biotic response of parasites to environmental stressors is also reflected in the health of fish. Parasite assemblages of silver perch Bairdiella chrysura respond to both natural and anthropogenic stressors. Our results showed that particular environmental stressors and specific parasites that respond include: temperature and monogeneans; contaminants and nematodes; low dissolved oxygen and protists; and salinity, together with a mixture of metal and organic contaminants and crustacea. Parasites of fish are useful biomarkers and appear to be more sensitive to environmental stressors than are the fish themselves. Parasite responses to selected environmental stressors may be used to discriminate polluted and unpolluted sites. The use of parasites of fish as biomarkers has relevant application to fisheries management and coastal monitoring programs.     

Multi-route risk assessment from trihalomethanes in drinking water supplies

The USA is entering an era of energy diversity, and increasing nuclear capacity and concerns focus on accidents, security, waste, and pollution. Physical buffers that separate outsiders from nuclear facilities often support important natural ecosystems but may contain contaminants. The US Nuclear Regulatory Commission (NRC) licenses nuclear reactors; the applicant provides environmental assessments that serve as the basis for Environmental Impact Statements developed by NRC. We provide a template for the types of information needed for safe siting of nuclear facilities with buffers in three categories: ecological, fate and transport, and human health information that can be used for risk evaluations. Each item on the lists is an indicator for evaluation, and individual indicators can be selected for specific region. Ecological information needs include biodiversity (species, populations, communities) and structure and functioning of ecosystems, habitats, and landscapes, in addition to common, abundant, and unique species and endangered and rare ones. The key variables of fate and transport are sources of release for radionuclides and other chemicals, nature of releases (atmospheric vapors, subsurface liquids), features, and properties of environmental media (wind speed, direction and atmospheric stability, hydraulic gradient, hydraulic conductivity, groundwater chemistry). Human health aspects include receptor populations (demography, density, dispersion, and distance), potential pathways (drinking water sources, gardening, fishing), and exposure opportunities (lifestyle activities). For each of the three types of information needs, we expect that only a few of the indicators will be applicable to a particular site and that stakeholders should agree on a site-specific suite.     

Accuracy and traceability in environmental monitoring--pitfalls in methylmercury determinations as a case study

The concepts of accuracy and traceability as applied to environmental analysis are still prone to misunderstandings. While accuracy refers to the closeness of analytical values to "true values" (trueness) and among various repetitions (precision), the term traceability implies a link of data obtained to established references through an unbroken chain of comparisons all with stated uncertainties. These misunderstandings, possibly occurring among the analytical community, may have consequences on environmental data interpretation. Recent discussions in the field of environmental speciation analysis illustrated that accuracy and traceability issues are still not firmly established within the environmental chemistry community. This paper discusses this issue, taking methylmercury as a case study.     

典型新兴环境污染物的研究进展

概述了内分泌干扰物(EDCs)、药物及个人护理品(PPCPs)等典型新兴环境污染物的主要类型、环境浓度、分析方法、来源与归趋以及国内外研究进展。内分泌干扰物、药物及个人护理品在世界各地的污水处理厂出水中检出,表明了污水处理技术的不完善性,亟需研究并应用更全面的污水处理技术,以从源头上阻断新兴环境污染物对环境的污染。     

Injectors for capillary gas chromatography and their application to environmental analysis

The application of different injectors in capillary gas chromatography (GC) analysis of semi-volatile organic contaminants in environmental samples prepared in organic solvents is reviewed. The injectors examined include a split/splitless injector in splitless mode (SS), cold on-column (COC), and programmable temperature vaporizer (PTV) and adaptations of these injector designs. Key issues when selecting an injector include properties of the analyte, such as potential for thermal degradation or discrimination of high boiling point compounds within the injector, and the ability of the GC systems to handle large volume injections (LVI) primarily to lower detection limits and allow direct coupling with sample preparation techniques such as at-line or on-line solid phase extraction (SPE). LVI also require consideration of matrix interference issues. This review examines only injector chamber modifications that are feasible with a standard GC configuration, however some modifications to the chromatographic system to extend the range of applicability of gas chromatography analysis for environmental samples are also noted.     

Quality assurance in measuring the elemental composition of the alga Fucus vesiculosus

Algae are increasingly used for the purpose of environmental biomonitoring, for instance in the long-term program of the Federal Environmental Specimen Bank of Germany. Therefore, for the studies presented here, freeze-dried samples of Fucus vesiculosus collected from the North Sea shores were analyzed for a broad range of elements by instrumental neutron activation analysis (INAA), while inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS) were carried out on digests. The entire analytical procedures, including field sampling, cleaning of material, sample handling, determination of blanks and instrumental parameters, are described. Certified reference materials analyzed in parallel with real samples and intermethod comparisons were used for assuring the accuracy of the analytical data. Reproducibility of INAA measurements was between 4 and 6% depending on the element considered. Possible sources of uncertainty and variation of the contaminant origins are discussed. Boundary conditions for the performance of algae sampling within environmental monitoring programs and the application of this marine bioindicator for the purpose of controlling time-dependent and local differences in element patterns are presented.     

Long-term ecosystem monitoring and assessment of the Detroit River and Western Lake Erie

Over 35 years of US and Canadian pollution prevention and control efforts have led to substantial improvements in environmental quality of the Detroit River and western Lake Erie. However, the available information also shows that much remains to be done. Improvements in environmental quality have resulted in significant ecological recovery, including increasing populations of bald eagles (Haliaeetus leucocephalus), peregrine falcons (Falco columbarius), lake sturgeon (Acipenser fulvescens), lake whitefish (Coregonus clupeaformis), walleye (Sander vitreus), and burrowing mayflies (Hexagenia spp.). Although this recovery is remarkable, many challenges remain, including population growth, transportation expansion, and land use changes; nonpoint source pollution; toxic substances contamination; habitat loss and degradation; introduction of exotic species; and greenhouse gases and global warming. Research/monitoring must be sustained for effective management. Priority research and monitoring needs include: demonstrating and quantifying cause-effect relationships; establishing quantitative endpoints and desired future states; determining cumulative impacts and how indicators relate; improving modeling and prediction; prioritizing geographic areas for protection and restoration; and fostering long-term monitoring for adaptive management. Key management agencies, universities, and environmental and conservation organizations should pool resources and undertake comprehensive and integrative assessments of the health of the Detroit River and western Lake Erie at least every 5 years to practice adaptive management for long-term sustainability.     

A small subsurface ion mobility spectrometer sensor for detecting environmental soil-gas contaminants

A small subsurface ion mobility spectrometer (SS-IMS) was constructed and tested with several environmental contaminants to determine its potential for monitoring gaseous volatile organic compounds in the vadose zone. Trichloroethylene (TCE) and tetrachloroethylene (PCE) were detected and separated in IMS for the first time. Detection limits as low as 1 part per billion volume-to-volume (ppb(v)) were observed. Reduced mobility (K(0)) values were reported for 11 environmental contaminants. These data demonstrated the potential of ion mobility spectrometry as a viable technology for detecting and separating environmental soil-gas contaminants in the field, which may lead to a practical and simple approach for long-term monitoring of contaminated soils.     

The relevance of speciation in the remediation of soils and sediments contaminated by metallic elements--an overview and examples from Central Scotland, UK

The environmental impact of metallic contaminants in soils and sediments is dependent both on the chemical speciation of the metal and the response of the matrix to biological and physicochemical conditions. These factors are responsible for the mobilisation of the metal from the solid into the aquatic phase and hence transport within the immediate vicinity, impacting on the rate of dispersal, dilution, uptake and transfer into living systems. The impact of changing environmental conditions on the contaminant inventory can be to enhance or moderate these phenomena, with subsequent consequences for the broader risk assessment of the contaminants. Remediation of metallic contaminants can only be brought about by their removal from the site or by establishing conditions which favour their retention in the solid phase. A wide range of in situ and ex situ approaches are available and a summary overview is presented. The examples show assessment at both the field and laboratory scale and demonstrate an equally wide range of success in achieving remediation targets. This can be attributed to limitations in ensuring that the desired conditions for the initial removal or immobilisation process are met and maintained over a suitable period of time. Three areas are reviewed which include: the transport and release of metallic contaminants in estuarine sediments and the assessment of their potential to impact on biota; terrestrial contamination systems involving the release of chromium from waste ore contaminating urban environments; the response of metal-contaminated wastes to changing environmental conditions and the impact of natural bioremediation. The focus of the discussion is to highlight the generation of reliable speciation information and the problems associated with impact and risk assessment. Particular issues of concern are the laboratory to field scale evaluation of contaminant behaviour and the approach used to assess the reliability of remediation options. In conclusion, part of a recent initiative in risk assessment and the development of pilot scale experimental systems to study long-term behaviour are addressed as future goals to fill gaps in current research.     

Reducing health risk assigned to organic emissions from a chemical weapons incinerator

Organic emissions from a chemical weapons incinerator have been characterized with an improved set of analytical methods to reduce the human health risk assigned to operations of the facility. A gas chromatography/mass selective detection method with substantially reduced detection limits has been used in conjunction with scanning electron microscopy/energy dispersive X-ray spectrometry and Fourier transform infrared microscopy to improve the speciation of semi-volatile and non-volatile organics emitted from the incinerator. The reduced detection limits have allowed a significant reduction in the assumed polycyclic aromatic hydrocarbon (PAH) and aminobiphenyl (ABP) emission rates used as inputs to the human health risk assessment for the incinerator. A mean factor of 17 decrease in assigned human health risk is realized for six common local exposure scenarios as a result of the reduced PAH and ABP detection limits.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Life cycle assessment as an analytical tool in strategic environmental assessment. Lessons learned from a case study on municipal energy planning in Sweden

Life cycle assessment (LCA) is explored as an analytical tool in strategic environmental assessment (SEA), illustrated by case where a previously developed SEA process was applied to municipal energy planning in Sweden. The process integrated decision-making tools for scenario planning, public participation and environmental assessment. This article describes the use of LCA for environmental assessment in this context, with focus on methodology and practical experiences. While LCA provides a systematic framework for the environmental assessment and a wider systems perspective than what is required in SEA, LCA cannot address all aspects of environmental impact required, and therefore needs to be complemented by other tools. The integration of LCA with tools for public participation and scenario planning posed certain methodological challenges, but provided an innovative approach to designing the scope of the environmental assessment and defining and assessing alternatives.     

固相萃取-超高效液相色谱-串联质谱法快速测定环境水样中30种极性农药

建立了固相萃取-超高效液相色谱-串联质谱快速测定环境水样中30种极性农药的方法。30种极性农药经过固相萃取(SPE)富集净化,以超高效液相色谱-串联质谱(UPLC-MS-MS)多级监测模式(MRM)外标法进行定性定量分析。结果表明:环境水样中30种极性农药的检出限为0.2～5 ng/L。对同一环境样品进行了低、中、高3个不同浓度水平的加标回收实验,平均回收率为63.7%～105.1%,相对标准偏差为4.4%～21.2%。该方法快速、灵敏、准确,可有效应用于环境水样中30种极性农药的快速监测。