Optimization of a multielement sequential extraction method employing an experimental design approach for metal partitioning in soils and sediments

The optimisation of a simple multielement extraction method employing an experimental design approach is described. The method uses centrifugation to pass one extractant solution at varying pH through a contaminated soil sample. The nature and concentration of the acid, rate of centrifugation and time, number of sequential leachates and the ratio of extractant volume: sample weight have been studied in order to obtain the optimum conditions for extraction. A fractional factorial experimental design was performed, and the results were used to identify significance which was then evaluated by carrying out a central composite experimental approach. Once optimum conditions had been obtained, sequential leaches were analysed by ICP-AES and chemometrics were employed to identify the composition of each component. Comparisons have been made with previous studies and tentative assignments, based on well defined separated fractions and percentage compositions for individual elements, used to identify the different physico-chemical components in the sample.     

Assessment of vehicular pollution in Kolkata, India, using CALINE 4 model

Michigan water quality standards for public bathing beaches require local health departments to collect and analyze a minimum of three water samples for Escherichia coli during each sampling event. The geometric mean number of E. coli colonies is then compared to the 300 colonies per 100 ml standard to determine compliance. This article compares the results of the currently mandated procedure to a composite sampling method, whereby the three samples are mixed in equal volumes and analyzed once. This effectively replaces the geometric mean of the individual sample results with an arithmetic mean. Although arithmetic means are more affected by outliers, this sensitivity to high concentrations is more health conservative than the geometric mean. During the 2007 sampling season, nine bathing beaches were monitored once each week. Three individual point samples and a composite sample were analyzed for each sampling event. No statistically significant differences in bacteria concentrations were found between composite sample analysis and the arithmetic mean of individual point sample analyses. No violations were detected in the 2007 sampling season, so using historical data, a retrospective analysis was performed on samples gathered at nine bathing beaches in Kalamazoo County, Michigan during the years 2001–2007. The arithmetic mean of the three samples taken at each site served as a surrogate composite sample. The benefits of compositing the three samples were investigated assuming a 2/3 reduction in analytical costs. In the traditional sampling method, three individual samples were obtained and analyzed once in every 3-week period during the summer season, whereas compositing was simulated by taking the arithmetic mean of each week’s results. The results of this retrospective cost analysis indicates that ten to 14 violations would have been missed using the less frequent traditional sampling and analysis methodology. Composite sampling is a cost-saving alternative to traditional sampling techniques that can be more protective of public health, particularly when the savings are applied to increased numbers of samples in time or space.     

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.     

Fixed wavelength fluorescence to detect PAH metabolites in fish bile: Increased statistical power with an alternative dilution method

Polyaromatic hydrocarbons (PAHs) are a group of environmental toxicants mainly emitted from diffuse sources. Fixed wavelength fluorescence of fish bile is a simple screening method that allows environmental monitoring of PAH exposure to fish. One drawback with this method is that the results can be biased by the presence of a so-called inner filter effect. This effect can be reduced by dilution of the bile samples. However, bile samples differ in density and extensive dilution may cause increased measurement error. An alternative method is to adjust the dilution rate to the density of each bile sample. Here, both methods have been applied to bile samples collected from caged rainbow trout. The bile density was estimated using biliverdin. The results show that the variance within experimental groups is reduced when the dilution rate is adjusted to the bile density, resulting in increased statistical power to detect differences when applied for environmental monitoring.     

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).     

Total organic carbon analysis as a precursor to disinfection byproducts in potable water: oxidation technique considerations

In recent years, an increasing number of regulations and methodologies have begun to utilize total organic carbon (TOC) analysis for monitoring microbial contamination and/or disinfectant byproduct (DBP) precursors. This paper highlights some analytical differences and similarities between the two widely used TOC oxidation techniques: UV persulfate and high temperature combustion (HTC). Previous papers have come to different and sometimes contradictory conclusions on this subject. However, these studies either compared instruments with significantly different flow paths or TOC systems from different eras. Unlike previous studies, this paper compares two modern TOC analyzers with nearly identical flow paths for sample recovery, detection limits, and analysis of real world samples. On average, both persulfate and HTC oxidation yielded good recoveries for 10 hard to oxidize compounds and potable water samples from 5 different locations across the USA. In general, persulfate yielded more precise results because of its lower background response relative to sample response while HTC gave slightly higher results (roughly 2% to 3%) for surface water samples.     

The role of Raman spectroscopy in the analytical chemistry of potable water

Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of chemical applications. For example, many recalcitrant industrial process monitoring problems have been solved in recent years with in-line Raman spectrometers. Raman is attractive for these applications for many reasons, including remote non-invasive sampling, minimal sample preparation and tolerance of water. To a lesser extent, Raman spectroscopy is beginning to play a significant role in environmental analysis for the same reasons. At present, the environmental applications typically apply only to the most contaminated situations due to the still relatively high limits of detection. However, some emerging sampling technologies hold out the promise that Raman may soon be more widely applicable to the analytical chemistry of potable water. Herein we discuss these recent advances, summarize some examples of environmental applications to aqueous systems and suggest avenues of future developments that we expect to be most useful for potable water analysis. Also, a simplified, but detailed, theory of normal Raman scattering is presented. While resonance-enhanced Raman spectroscopy, surface-enhanced Raman spectroscopy and non-linear Raman techniques are briefly discussed, their theories and instrumental configurations are not addressed. Also, this article deals primarily with the modern dispersive Raman experiment (as opposed to the Fourier transform Raman experiment), because it seems most suited for potable water analysis. The goal of this article is to give the environmental scientist with no specialized knowledge of the topic just enough theory and background to evaluate the utility of this rapidly developing analytical tool.     

Comparison of bioassessment results and costs between preserved and unpreserved macroinvertebrate samples from streams

The choice to use or not use a preservative before sorting macroinvertebrate samples (i.e., dead specimens vs. living specimens) is based on studies not solely focused on the effects of preservation. Using identical sample processing protocols, we compared preserved and unpreserved samples for the following parameters: (1) the number of taxa and individuals for each major macroinvertebrate group, (2) ecological quality classes calculated with a multimetric index developed for the assessment of small Dutch lowland streams, and (3) costs of sample processing. We collected macroinvertebrate samples from three lowland streams in the Netherlands. At each site, we collected six replicate samples, of which three samples were preserved and three were not. Significantly different numbers of Ephemeroptera individuals and Hydracarina taxa and individuals were collected from preserved samples compared to unpreserved samples. In assessments based on these individual metrics, standardization of sample processing will be required. In streams with Ephemeroptera, the preservation of samples is necessary to optimize the number of Ephemeroptera individuals collected. In streams that contain Hydracarina, the preservation of samples will result in an underestimation of the number of Hydracarina taxa and individuals present. In only one instance there was a difference in ecological quality between preserved and unpreserved samples, indicating that assessing small Dutch lowland streams does not require standardization of sample preservation as part of the sample processing protocol. We detected no significant differences in sample processing costs between preserved and unpreserved samples.     

River evaluation using ecotoxicological and microbiological procedures

One of the many problems researchers and managers face is to try and interpret data collected from various river studies. There is an underlying awareness of the incompleteness of most data bases due to a variety of problems outside of those concerning sample processing.In this study we have attempted, by using the battery of tests approach (12 tests) and the examination of different types of samples such as water, Milli-Q water extracted sediments, and organic solvent extracted sediments, to explore the implication of spacial and temporal sampling programmes.The results obtained were not unexpected: there were spatial and temporal influences, sometimes so great that it would appear that you were examining samples from different parts of the country. However, data arising from solvent extracted sediments were found to be much less influenced by temporal sampling than by spatial variation. Another interesting and important observation was that sediment composition appeared to have no relationship to toxicant content.In this study, the first field application of the Mutatox test (genotoxicity) was carried out and it was found to be a very responsive test in all three types of samples. This test shows great promise as laboratory studies indicate it is sensitive to many of the chemicals which trigger the Ames test.     

测定水中铁、锰、汞时前处理问题探讨

基于大量实测数据统计,比较了测定水中铁、锰、汞3种重金属时,样品是否过滤、加酸保存等前处理方式对测定结果的影响,提出铁、锰水样需过滤检测,汞水样不能过滤检测,且3种金属的水样均需加酸保存,这样测定的结果才能根据现行水环境质量标准进行评价。     

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.     

Integration of multi-disciplinary geospatial data for delineating agroecosystem uniform management zones

The aim of this study was the development of analytical methods for the simultaneous determination of 25 selected pharmaceuticals, metabolites, and pesticides, belonging to the various chemical classes, in river sediments and their corresponding surface and ground water with the purpose of monitoring the contamination levels. The methods were based on the solid-phase extraction as the sample preparation method for water samples, and the ultrasonic solvent extraction for the sediment samples, followed by the liquid chromatography–tandem mass spectrometry. High recoveries were achieved for extraction from both water and sediment samples for the majority of analytes. Low limits of detection were achieved for all investigated compounds in the water sample (1–5 ng L^?1) as well as in the sediment (1–3 ng g^?1). Applicability of the developed methods was demonstrated by determination of pharmaceutical and pesticide residues in 30 surface water, 44 groundwater, and 5 sediment samples from the Danube River Basin in Serbia. Sixty percent of target compounds were detected in environmental samples. The most frequently detected analytes in river sediments were the pesticides dimethoate and atrazine, while carbamazepine and metamizole metabolites 4-AAA and 4-FAA were the most frequently found in water samples.     

固相微萃取技术在环境监测分析中的应用进展

样品前处理是整个样品分析过程中的关键一环,其目的在于减少杂质对待测物的干扰及对目标物进行富集。固相微萃取技术是集采样、萃取、富集、进样于一体的样品前处理新技术。近年来,固相微萃取技术在环境污染物监测分析领域得到了广泛应用,该文章系统地综述了固相微萃取技术在不同环境基质(水体、大气、土壤及沉积物)预处理的方法,比较了不同类型涂层材料(如纳米材料、离子液体等)与装置形式(如内部冷却固相微萃取、箭形固相微萃取等)的优缺点及应用范围。针对现阶段固相微萃取技术应用于不同环境基质中存在的问题和不足,提出进一步研究的方向。     

Application of Microwave Plasma Atomic Emission Spectrometry (MP-AES) for environmental monitoring of industrially contaminated sites in Hyderabad City

Recently introduced microwave plasma-atomic emission spectroscopy (MP-AES) represents yet another and very important addition to the existing array of modern instrumental analytical techniques. In this study, an attempt is made to summarize the performance characteristics of MP-AES and its potential as an analytical tool for environmental studies with some practical examples from Patancheru and Uppal industrial sectors of Hyderabad city. A range of soil, sediment, water reference materials, particulate matter, and real-life samples were chosen to evaluate the performance of this new analytical technique. Analytical wavelengths were selected considering the interference effects of other concomitant elements present in different sample solutions. The detection limits for several elements were found to be in the range from 0.05 to 5 ng/g. The trace metals analyzed in both the sectors followed the topography with more pollution in the low-lying sites. The metal contents were found to be more in ground waters than surface waters. Since a decade, the pollutants are transfered from Patancheru industrial area to Musi River. After polluting Nakkavagu and turning huge tracts of agricultural lands barren besides making people residing along the rivulet impotent and sick, industrialists of Patancheru are shifting the effluents to downstream of Musi River through an 18-km pipeline from Patancheru. Since the effluent undergoes primary treatment at Common Effluent Treatment Plant (CETP) at Patanchru and travels through pipeline and mixes with sewage, the organic effluents will be diluted. But the inorganic pollutants such as heavy and toxic metals tend to accumulate in the environmental segments near and downstreams of Musi River. The data generated by MP-AES of toxic metals like Zn, Cu, and Cr in the ground and surface waters can only be attributed to pollution from Patancheru since no other sources are available to Musi River.     

地表水监测误差分析与对策

分析和探讨了地表水环境监测过程中存在的误差。在13家监测站同步采样、同步分析的基础上，筛选出地表水监测实验室间比对结果偏差较大的石油类、挥发酚、氨氮、五日生化需氧量、化学需氧量、高锰酸盐指数和总磷等7个监测指标。从方法误差、仪器误差、试剂误差、操作误差、环境误差、过失误差和质控选择不当造成的误差等各方面探讨误差成因。根据实样测定结果，提出合理选择并统一分析方法、增加平行测定次数、加强质控措施和修改允许相对偏差等切实可行的对策和措施，为地表水监测和水环境管理提供技术依据。     

Determination of gaseous polycyclic aromatic hydrocarbons by a simple direct method using thermal desorption–gas chromatography–mass spectrometry

In the last decade, the development of novel analytical methodologies enabled the identification of several environmental pollutants responsible for health problems associated with indoor exposure. Polycyclic aromatic hydrocarbons (PAHs) are among the potential hazardous chemicals present in ambient air. Due to their bioaccumulation potential and carcinogenic/mutagenic effects, 16 PAHs are currently listed as priority air pollutants. The main goal of this work was to implement a new and simple method for sampling and determination of PAHs in air by using a thermal desorption (TD) technique followed by gas chromatography coupled with mass spectrometry analysis. A detailed study was carried out to optimise the experimental method in each of its phases, including (active) sampling, TD and chromatographic analysis. The results demonstrate that this approach allowed the detection and quantification of the six more volatile PAHs, namely, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, and anthracene. Acceptable precision and good linearity over the explored range were obtained. No carry-over was observed during experimental tests and the method provided a reproducible answer. The applicability of the novel methodology was tested in real environment, namely, on the roof of a building in an urban area, in a domestic kitchen and in a collective car garage. The method enabled the identification of two PAHs in the field samples, specifically, naphthalene (two rings) and phenanthrene (three rings). With regard to PAHs sample composition, the most abundant PAH found, in the three different locations, was naphthalene, accounting for about 84–100 % of the total PAH mass detected.     

植物油烟组分的色质联机分析

将植物油烟采集在玻璃纤维滤筒中 ,用环己烷处理样品 ,样品经过净化处理 ,然后进行色质联机分析。对油烟化学成分的分析有助于人们研究油烟对人体健康的影响     

The biological behaviour and bioavailability of aluminium in man, with special reference to studies employing aluminium-26 as a tracer: review and study update

Until 1990 biokinetic studies of aluminium metabolism and biokinetics in man and other animals had been substantially inhibited by analytical and practical difficulties. Of these, the most important are the difficulties in differentiating between administered aluminium and endogenous aluminium-especially in body fluids and excreta and the problems associated with the contamination of samples with environmental aluminium. As a consequence of these it was not possible to detect small, residual body burdens of the metal following experimental administrations. Consequently, many believed aluminium to be quantitatively excreted within a short time of uptake in all, but renal-failure patients. Nevertheless, residual aluminium deposits in a number of different organs and tissues had been detected in normal subjects using a variety of techniques, including histochemical staining methods. In order to understand the origins and kinetics of such residual aluminium deposits new approaches were required. One approach taken was to employ the radioisotope (67)Ga as a surrogate, but this approach has been shown to be flawed-a consequence of the different biological behaviours of aluminium and gallium. A second arose from the availability, in about 1990, of both (26)Al-a rare and expensive isotope of aluminium-and accelerator mass spectrometry for the ultra-trace detection of this isotope. Using these techniques the basic features of aluminium biokinetics and bioavailability have been unravelled. It is now clear that some aluminium is retained in the body-most probably within the skeleton, and that some deposits in the brain. However, most aluminium that enters the blood is excreted in urine within a few days or weeks and the gastrointestinal tract provides an effective barrier to aluminium uptake. Aspects of the biokinetics and bioavailability of aluminium are described below.     

Fluorescent screening of phytoplankton and organic compounds in sea water

The flow-through spectrofluorometers, FLUO-IMAGER, were developed to measure the abundance of phytoplankton, including the analysis of pigment composition and concentration of organic pollution and dissolved organic matter (DOM), in continuous mode. The measurements can be carried out without the time-consuming pretreatment of water samples. The analytical concept uses the technique of spectral fluorescent signatures (SFS), based on the systematized spectral library comprising the SFS of major phytoplankton species and chemical pollution. The SFS technique has been applied for several years in qualitative and quantitative screening of organic compounds and phytoplankton in the Baltic, North and Norwegian Seas. The results of the analysis of phytoplankton pigments, the dynamic processes of bloom development, DOM and oil pollution are presented.     

Leaching Characteristics of Fly Ash from Thermal Power Plants of Soma and Tunçbilek, Turkey

Use of lignite in power generation has led to increasing environmental problems associated not only with gaseous emissions but also with the disposal of ash residues. In particular, use of low quality coal with high ash content results in huge quantities of fly ash to be disposed of. The main problem related to fly ash disposal is the heavy metal content of the residue. In this regard, experimental results of numerous studies indicate that toxic trace metals may leach when fly ash contacts water. In this study, fly ash samples obtained from thermal power plants, namely Soma and Tunçbilek, located at the west part of Turkey, were subjected to toxicity tests such as European Committee for standardization (CEN) and toxicity characteristic leaching (TCLP) procedures of the U.S. Environmental Protection Agency (U.S. EPA). The geochemical composition of the tested ash samples from the power plant show variations depending on the coal burned in the plants. Furthermore, the CEN and TCLP extraction results showed variations such that the ash samples were classified as `toxic waste' based on TCLP result whereas they were classified as `non-toxic' wastes based on CEN results, indicating test results are pH dependent.