An interlaboratory comparison of sediment elutriate preparation and toxicity test methods

Elutriate bioassays are among numerous methods that exist for assessing the potential toxicity of sediments in aquatic systems. In this study, interlaboratory results were compared from 96-h Ceriodaphnia dubia and Pimephales promelas static-renewal acute toxicity tests conducted independently by two laboratories using elutriate samples prepared from the same sediment. The goal of the study was to determine if the results from the elutriate tests were comparable between two U.S. Environmental Protection Agency (USEPA) laboratories when different elutriate preparation procedures were employed by each lab. Complete agreement in site characterization was attained in 22 of the 25 samples for both bioassays amongst each lab. Of the 25 samples analyzed, 10 were found to be toxic to at least one of the species tested by either laboratory. The C. dubia elutriate tests conducted by the National Exposure Research Laboratory (NERL) indicated that 7 of the 25 sediment samples were toxic, while 8 sediment samples were characterized as such in testing conducted by USEPA Region 6 (Region 6). The P. promelas elutriate tests conducted by NERL determined 8 samples as toxic, while Region 6 tests displayed toxicity in 5 of the samples. McNemar's test of symmetry for C. dubia (S?=?0.33, p?=?0.5637) and P. promelas (S?=?3.0, p?=?0.0833) tests indicated no significant differences in designating a site toxic between NERL and Region 6 laboratories. Likewise, Cohen's kappa test revealed significant agreement between NERL and Region 6 C. dubia (K?=?0.7148, p?<?0.01) and P. promelas (K?=?0.6939, p?<?0.01) elutriate tests. The authors conclude that differences in interlaboratory elutriate preparation procedures have no bearing on the ability of either the C. dubia or P. promelas bioassay testing methods to detect toxicity while yielding similar results.     

Feasibility study of preparation and certification of reference materials for nitrogen dioxide and sulfur dioxide in diffusive samplers

This paper presents the results of a feasability study for the preparation and certification of reference materials (RMs) for nitrogen dioxide (NO(2)) and sulfur dioxide (SO(2)) in diffusive samplers. RMs for NO(2) were prepared by exposure to gas mixtures in a chamber while the RMs for SO(2) were prepared by liquid spiking. Certification of RMs for NO(2) was found feasible with a certified uncertainty of 5.8% and a proposed shelf life of 5 years. The uncertainty was calculated with contribution from the homogeneity of preparation, stability and transport of the CRMs and from an external verification of the certified value. To reach 5.8% of uncertainty, the contribution of the differences between the results of analysis by ion chromatography and colorimetry must be eliminated. It is proposed to solve this by pre-extracting the samplers with water before analysis. The results of this study indicate that the samplers are stable for at least two years before and after exposure when stored in a refrigerator. By contrast, the certification of RMs for SO(2) was found to not be feasible due to instability problems. This instability was attributed to reaction of sulfate on the walls of the samplers. Alternatively, the preparation of RMs by simultaneous exposure to SO(2) and NO(2) has been tested. Satisfying homogeneities has been reached both for NO(2) and SO(2).     

牡蛎中多环芳烃(PAHs)标准物质的研制

介绍了牡蛎中多环芳烃标准物质的研究、制备方法 ,进行了均匀性检验、稳定性检验 ,统计计算了检验结果 ,基本确定主要参数。检验结果表明 ,研制的牡蛎中难降解有机物标准物质均匀 ,在一年保存期间内稳定 ,可用于海洋环境监测中     

Field measurement of lead in workplace air and paint chip samples by ultrasonic extraction and portable anodic stripping voltammetry

On-site measurement of lead in workplace air filter samples and paint chip samples by ultrasonic extraction and anodic stripping voltammetry (UE-ASV) was evaluated in the field during renovation and remodeling activities in residences having leaded paint. Aerosol and paint samples were collected using standard techniques, and the samples were analyzed on-site for lead content by portable UE-ASV. Lead in sample extracts was subsequently determined by atomic absorption (AA) spectrometry in a fixed-site laboratory. The remaining sample extracts plus undissolved material (air filters or paint particles) were then subjected to hot plate digestion in concentrated nitric acid-30% hydrogen peroxide prior to AA analysis for lead. Field UE-ASV lead data were thereby compared to UE-AA and hot plate digestion-AA results from fixed-site laboratory lead measurement. Determination of lead in air filter samples by UE-ASV (over the range of 5 microg to approximately 800 microg Pb per sample) was extremely well correlated with lead measurement by UE-AA and hot plate digestion-AA procedures. However, a significant negative bias associated with ASV measurement was observed, and this was attributed to a matrix effect. Lead measurement in paint chip samples by UE-ASV (over the range of approximately 10 to approximately 550 microg Pb g(-1)) was well correlated with lead measurement by UE-AA and hot plate digestion-AA procedures. However, correlation and precision were lower for lead measurement in paint samples as compared to aerosol samples, and a negative bias was also observed. Lead measurements by UE-AA were compared to lead determinations by hot plate digestion-AA; these data were highly correlated and demonstrated no significant bias. Thus it was concluded that the ultrasonic extraction procedure performed equivalently to hot plate digestion. It was reasoned that matrix effects due to the preparation and analysis of paint chip particles resulted in greater imprecision as well as negative bias by ASV measurement. Despite significant negative bias in this sample set, UE-ASV offers promise for on-site measurement of lead in samples of interest in occupational and environmental health.     

牡蛎生物环境标准样品的研制

文章对我国环境保护系统研制出用于海洋和江河水域环境监测的牡蛎生物环境标准样品的一些情况做了详细介绍;尤其对牡蛎环境标样的制备过程,牡蛎标样的作用,均匀性、稳定性检测和分析定值进行了较为充分的论述。     

Ultrasonic extraction and portable anodic stripping voltammetric measurement of lead in paint, dust wipes, soil, and air: an interlaboratory evaluation

Recent studies have demonstrated the utility of ultrasonic extraction (UE), followed by portable anodic stripping voltammetry (ASV), for the on-site determination of lead in environmental and industrial hygiene samples. The aim of this work was to conduct an interlaboratory evaluation of the UE-ASV procedure, with a goal of establishing estimates of method performance based on results from collaborative interlaboratory analysis. In this investigation, performance evaluation materials (PEMs) with characterized lead concentrations were used for interlaboratory testing of the UE-ASV procedure. The UE-ASV protocol examined has been promulgated in the form of two separate national voluntary consensus standards (one for UE and another for electroanalysis, which includes ASV). The PEMs consisted of characterized and homogenized paints, soils, and dusts (the last of which were spiked onto wipes meeting national voluntary consensus standard specifications), and air filter samples (mixed cellulose ester membrane) generated using characterized paints within an aerosol chamber. The lead concentrations within the PEMs were chosen so as to bracket pertinent action levels for lead in the various sample matrices. The interlaboratory evaluation was conducted so as to comply with an applicable national voluntary consensus standard that can be used to estimate the interlaboratory precision of a given analytical test method. Based on the analytical results reported by the participating laboratories, relative standard deviations (RSDs) for repeatability and reproducibility were computed for three different lead contents of the four PEMs. RSDs for repeatability were 0.019-0.100 for paints; 0.030-0.151 for soils; 0.085-0.134 for dust wipes; and 0.095-0.137 for air filters. RSDs for reproducibility were 0.127-0.213 for paints; 0.062-0.162 for soils; 0.085-0.134 for dust wipes; and 0.114-0.220 for air filters. With the exception of one of the air filter samples and one of the paint samples, the precision estimates were within the +/- 20% precision requirement specified in the US Environmental Protection Agency National Lead Laboratory Accreditation Program (NLLAP). The results of this investigation illustrate that the UE-ASV procedure is an effective method for the quantitative measurement of lead in the matrices evaluated in this study.     

Fractionation of butyltin species during sample extraction and preparation for analysis

Solvent extraction and evaporative concentration steps are often used in procedures for the measurement of butyltins in environmental samples. As part of a larger study utilizing radiolabeled butyltins, the loss and fractionation of butyltins during sample preparation was investigated. TBT, DBT, and MBT were extracted from acidified seawater by hexane with efficiencies of about 95–99, 50–60 and 11% respectively. In addition, losses of about 70% of DBT were found during evaporative concentration of hexane. A variety of sediment extraction procedures were tested and none were found to be highly efficient for total butyltin extraction.     

A comparison of methods and materials for the analysis of leaded wipes

The purposes of this study are: (1) to determine whether proficiency analytical test (PAT) materials from the American Industrial Hygiene Association can be used to provide quality data for portable X-ray fluorescence analysis (XRF) of lead in dust wipe surface samples; (2) to provide data to determine whether the on-site analysis of field dust wipe samples by XRF and the laboratory method of inductively coupled plasma emission analysis (ICP) are comparable; and (3) to determine if differences exist between different wipe materials. Several wipes meet the ASTM E1792 performance requirements of lead background level less than 5 microg per wipe, be only one layer thick, yield recovery rates of 80- 120% from spiked samples, remain damp throughout the sampling procedure, and do not contain aloe. The wipes used in this study were Pace Wipes, which are used for the PAT materials, and, for the field samples, Palintest Wipes, which were supplied by the instrument manufacturer, and Ghost Wipes, which are popular because they digest in hot, concentrated acid, so that chemical analysis is simplified. Twenty PAT wipe samples were obtained from four different proficiency test rounds. Surface wipe samples were taken at three different locations representing different industry types. All samples were analyzed using a portable XRF spectrometer and by ICP. Strong linear relationships were found for the analysis of wipe samples by ICP and by portable XRF. For the PAT samples, the results from the ICP and XRF analysis were not statistically equivalent, which indicates a bias in the ICP analysis. The bias was not excessive, since all ICP analyses fell within the acceptable range for the proficiency samples. The good correlation between the proficiency sample reference values and the XRF determinations is not surprising considering similar proficiency samples were used to calibrate the instrument response. Users of this portable XRF analyzer could enroll in the proficiency test program as part of their quality assurance program. For field samples, the relationship was strongest for Palintest wipes, and the values found for all three industries could be combined. However, the results from the ICP and XRF analysis were not statistically equivalent using the correction factor in the calculation algorithm as supplied with the instrument, and a new coefficient was derived. The mean relative error for the XRF analysis versus the ICP analysis was greater than 25%, such that the method falls within the realm of screening procedures. For Ghost Wipe samples, the precision was different for different industries, and the results could not be pooled. Differences between the two wipe materials may be related to the number of folds required for analysis.     

环境治理工程验收监测存在问题及对策

本文论述了当前我国环境治理工程验收监测工作中存在的问题,提出了在验收监测中应严格遵守监测规范,适当增加监测频次,准确、客观地评价监测结果,充分地为企业服务的对策。     

Characterizing the intrinsic bioremediation potential of 1,4-dioxane and trichloroethene using innovative environmental diagnostic tools

An intrinsic biodegradation study involving the design and implementation of innovative environmental diagnostic tools was conducted to evaluate whether monitored natural attenuation (MNA) could be considered as part of the remedial strategy to treat an aerobic aquifer contaminated with 1,4-dioxane and trichloroethene (TCE). In this study, advanced molecular biological and stable isotopic tools were applied to confirm in situ intrinsic biodegradation of 1,4-dioxane and TCE. Analyses of Bio-Trap? samplers and groundwater samples collected from monitoring wells verified the abundance of bacteria and enzymes capable of aerobically degrading TCE and 1,4-dioxane. Furthermore, phospholipid fatty acid analysis with stable isotope probes (PLFA-SIP) of the microbial community validated the ability for microbial degradation of TCE and 1,4-dioxane. Compound specific isotope analysis (CSIA) of groundwater samples for TCE resulted in δ(13)C values that indicated likely biodegradation of TCE in three of the four monitoring wells sampled. Results of the MNA evaluation showed that enzymes capable of aerobically degrading TCE and 1,4-dioxane were present, abundant, and active in the aquifer. Taken together, these results provide direct evidence of the occurrence of TCE and 1,4-dioxane biodegradation at the study site, supporting the selection of MNA as part of the final remedy at some point in the future.     

Quantitative PCR analysis of fungi and bacteria in building materials and comparison to culture-based analysis

Prolonged moisture on building materials can lead to microbial growth on them. Microbes can emit spores, metabolites and structural parts into the indoor air and thus, cause adverse health effects of people living and working in these buildings. So far, culture methods have been used for assessment of microbial contamination of building materials. In this work, we used quantitative PCR (qPCR) for the detection of selected fungal and bacterial groups in 184 building materials of different types and compared the results with culture-based analysis. Nine either commonly found species, genera or groups of fungi, or those considered as moisture damage indicators, and one bacterial genus, Streptomyces, were determined using qPCR. Fungi and mesophilic actinomycetes were also cultivated using standard media and conditions of the routine analysis. The bacterial genus Streptomyces and the fungal group Penicillium/Aspergillus/Paecilomyces were the most prevalent microbial groups in all building material types, followed by Stachybotrys chartarum and Trichoderma viride/atroviride/koningii. The highest prevalences, concentrations and species diversity was observed on wooden materials. In general, the results of the two methods did not correlate well, since concentrations of fungi and streptomycetes were higher and their occurrence more prevalent when determined by qPCR compared to culture-based results. However, with increasing concentrations, the correlation generally increased. The qPCR assay did not detect Aspergillus versicolor and Acremonium strictum as often as culture.     

Persistence and vertical distribution of termiticide fipronil in modified ground board test

Fipronil termiticide belongs to phenyl-pyrazole class of chemical compounds. It has broad-spectrum activity particularly against house hold pests such as cockroaches, mosquitoes, locusts, ticks, and fleas at both larval and adult stages. At high dosage it can be used to control subterranean termites in building foundations. To evaluate long term efficacy against termites the persistence and vertical distribution of fipronil was studied under natural weather conditions of Dehradun, India. Fipronil was applied at four concentrations i.e. 0.05, 0.1, 0.25 and 0.5% a.i ha⁻¹ by drenching 17 × 17 in.² plot prepared as per modified ground board test. Soil samples were collected after 22, 38 and 56 months of treatment up to the depth of 75 cm. The soil core was cut into five distinct sections i.e. 0–15, 15–30, 30–45, 45–60 and 60–75 cm depth. The residues were extracted by shaking 20 g soil sample with acetone. The acetone extract was concentrated and cleaned-up over florisil column. Fipronil residues were estimated on GLC at 220, 260, and 300°C oven, injector and detector temperature respectively. Fipronil was found to persist beyond 56 months after application. Two metabolites viz. desulfinyl and sulfide-fipronil were detected in sampling after 22 months of application that also dissipated with time. Fipronil residues were found up to 60 cm depth. The residues in deeper layers dissipate slowly with time and after 56 months of treatment residues were detected only up to 30 cm depth.     

Exposure to anti-cancer drugs during preparation and administration. Investigations of an open and a closed system

Systems for the preparation and administration of drugs are designed to ensure that the drug is not contaminated. They do not necessarily consider the work environment for the medical staff and new techniques are therefore desirable. The aim of this work is to compare a new closed system for the preparation and administration of drugs with the traditional technique with regard to airborne emission and surface spillage of drugs. Platinum, determined using adsorptive voltammetry, was used as the tracer for airborne emission. Air samples were collected during the preparation and administration, and the collected platinum on the filters was determined by adsorptive voltammetry. For determination of spills and leakage onto surfaces the radioisotope 99m-technetium was used as a tracer. The radiation from the isotope was determined on protective gloves and bench covers after preparation and administration. The mean airborne emission was 6 ng m(-3) with the closed system and 15 ng m(-3) with the traditional pump technique. The average surface spillage using the closed technique was 0.005 microL. This is significantly smaller than with the traditional technique, which resulted in an average spillage of 64 microL. Our results also show that the dominant part of the leakage is surface spillage. Inexperienced nurses could also adequately handle the closed system.     

自制模拟样及留样复测的质控技术探讨

介绍了环境监测标准滤膜、标准滤筒、模拟降尘的制备方法、使用方法、实际效果。阐述了滤膜中铅、土壤样品、底泥（沉积物）、污水厂处理污泥等留样的来源、必要性及作用。探讨了滤膜中铅留样复测质控的评判依据。     

Optimal Selection of Priority Development Areas Considering Tradeoffs Between Hydrology and Development Configuration

Mixed-integer linear programs are proposed for siting development and conservation areas in watersheds, addressing economic objectives (development perimeter and proximity) and ecological objectives. Links between watershed hydrology and ecology need not be well defined. Parameters for the linear programs are obtained from linearization of the SWAT hydrologic model.     

Simultaneous extraction of bromide, chloride, fluoride and sulfate from soils, waste- and building materials

The simultaneous extraction of bromide, chloride, fluoride and sulfate was studied in soils, waste- and building materials. Acid, neutral and alkaline extractants were used; 0.01 mol l(-1) H(3)PO(4), milliQ-water and 0.01 mol l(-1) NaOH, respectively. The extracts were analysed by ion chromatography and ion selective electrode. Extracted concentrations were compared with the amount obtained by an alkaline smelt, as an approximation of the total extractable content. The results indicate that there is a significant difference in extraction behaviour between waste- and building materials and soils. Bromide and chloride were in general completely extracted from the former solid materials, but less than 10% and 50%, respectively, from soils. Fluoride is strongly bound in all investigated samples; less than 10% of the total content was extracted with any of the three extractants. The fraction of extracted sulfate varied between 4 and 87% of the total content, and was in general larger in waste- and building materials than in soils. Differences in extracted concentration between the 3 extractants occurred mainly for fluoride and sulfate. Extracted bromide was similar with all three extractants and extracted chloride showed differences for the various soil samples only. Increasing the NaOH concentration up to 1 mol l(-1) resulted mainly in an increase of extracted amount of fluoride and for soils also in extracted amounts of bromide and sulfate. Although, the results show that the composition of the solid material strongly influences the final pH of the extract and the extracted amount of investigated anions, application of Milli-Q water as an extractant might be a very fruitful option within the development of the Dutch Building Materials Decree.     

Preparation and evaluation of candidate certified reference materials (CRMs) for nutrients in seawater

Certified reference materials (CRMs) are an essential part of the quality assurance (QA) necessary for the reliable analytical measurement of nutrients in seawater. The CRMs currently available for these analyses are not matrix matched to marine samples. QUASIMEME routinely produces test materials for the nutrients in seawater and nutrients in estuarine water and low-salinity open water Laboratory Performance Studies (LPS) that are both homogeneous and stable. QUASIMEME, in conjunction with Eurofins Scientific, Denmark have produced two reference materials (RMs). The homogeneity testing and preliminary stability studies were carried out by QUASIMEME, and the results are presented in this article. Participants of the QUASIMEME LPS who demonstrated satisfactory long-term performance for the analysis of nutrients in seawater and nutrients in estuarine water and low-salinity open water were invited to take part in the certification exercise. Twenty laboratories returned data, a summary of which is also presented. The certification and long-term stability testing and additional data analysis were carried out by Eurofins Scientific, Denmark, and are outwith the scope of this article and not reported here. Eurofins Scientific, Denmark have marketed these RMs as part of their range of VKI Reference Materials (further information is available from eurofins@eurofins.dk).