Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

Collaborative evaluation of the analytical state-of-the-art of platinum, palladium and rhodium determinations in road dust

In order to control the quality of platinum, palladium and rhodium determinations in road dust, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has started a project, the final aim of which is to certify a road dust reference material for its contents of platinum group elements. The first part of this project consisted of an interlaboratory study, which aimed to test the feasibility of the preparation of a candidate road dust reference material and to detect and remove most of the pitfalls observed in platinum, palladium and rhodium determinations. This paper presents the main results of this interlaboratory study carried out prior to the certification campaign. The concordance of the data obtained by the participating laboratories for the three elements was considered to reflect the state-of-the-art and was encouraging enough to decide on the organization of a certification campaign to be conducted during the year 2000. The progress made with respect to the analytical state-of-the-art for these elements will be of great benefit to the quality of measurements carried out in environmental monitoring in this particular field.     

Application of a modified BCR sequential extraction (three-step) procedure for the determination of extractable trace metal contents in a sewage sludge amended soil reference material (CRM 483), complemented by a three-year stability study of acetic acid and EDTA extractable metal content

This paper provides additional data on a sewage sludge amended soil certified reference material, CRM 483, which was certified in 1997 for its EDTA and acetic acid extractable contents of some trace metals, following standardised extraction procedures. The additional work aimed to test the long-term stability of the material and the applicability of an improved version of the BCR three-step sequential extraction procedure on the sewage sludge amended soil (CRM 483). The paper demonstrates the CRM 483 long-term stability for EDTA and acetic acid extractable contents of Cd, Cr, Cu, Ni, Pb and Zn and gives the results (obtained in the framework of an interlaboratory study) for the extractable contents of the same elements in the CRM 483, following the BCR three-step sequential extraction scheme. The aqua regia extractable contents following the ISO 11466 Standard are also given. The data are given as indicative (not certified) values.     

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators of urban and industrial impact on surface waters

The research focuses on the monitoring of trace metals and pharmaceuticals as potential anthropogenic indicators of industrial and urban influences on surface water. This study includes analysis of tracers use for the indication of water pollution events and discussion of the detection method of these chemicals. The following criteria were proposed for the evaluation of indicators: specificity (physical chemical properties), variability (spatial and temporal), and practicality (capacity of the sampling and analytical techniques). The combination of grab and passive water sampling (i.e., diffusive gradient in the thin film and polar organic chemical integrated samplers) procedure was applied for the determination of dissolved and labile trace metals (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) and pharmaceuticals (carbamazepine, diazepam, paracetamol, caffeine, diclofenac, and ketoprofen). Samples were analyzed using inductively coupled plasma mass spectrometry (MS; trace metals) and liquid chromatography–tandem MS electrospray ionization+/? (pharmaceuticals). Our results demonstrate the distinctive spatial and temporal patterns of trace elements distribution along an urban watercourse. Accordingly, two general groups of trace metals have been discriminated: “stable” (Cd and Cr) and “time varying” (Cu, Zn, Ni, and Pb). The relationship Cd???Cu?>?Ag?>?Cr?≥?Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the environment from point sources (municipal wastewaters) and the group Pb–Ni was discussed as a relevant fingerprint of the economic activity (industry and transport) mainly from non-point sources (runoff, atmospheric depositions, etc.). Pharmaceuticals with contrasting hydro-chemical properties of molecules (water solubility, bioaccumulation, persistence during wastewater treatment processes) were discriminated on conservative, labile, and with combined properties in order to provide information on wastewater treatment plant efficiency, punctual events (e.g., accidents on sewage works, runoff), and uncontrolled discharges. Applying mass balance modeling, medicaments were described as relevant socio-economic indicators, which can give a picture of main social aspects of the region.     

Homogeneity and stability study of the candidate reference material Adamussium colbecki for trace elements

The preparation of a new candidate certified reference material (CRM) for trace elements based on the antarctic bivalve Adamussium colbecki(IRMM 813) was carried out by the Istituto Superiore di Sanità(ISS, Rome, Italy) in cooperation with the Institute for Reference Materials and Measurements, Joint Research Centre of the European Commission (EC-JRC-IRMM), in the frame of the Italian National Programme of Research in Antarctica (Programma Nazionale di Ricerca in Antartide, PNRA). Samples were collected at Terra Nova Bay (Ross Sea) during the 2000-2001 expedition in Antarctica. The preparation of a material suitable for certification was performed by the EC-JRC-IRMM. Measurements for homogeneity and short-term stability tests were carried out by ISS. The elements selected for the certification project were As, Cd, Cu, Cr, Fe, Mn, Ni and Zn. For the above-mentioned tests, the determination of the elements of interest was performed on samples mineralised by microwave-assisted acid digestion. The analytical techniques employed to this end were inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma dynamic reaction cell quadrupole mass spectrometry (ICP-DRC-Q-MS). The candidate material was shown to be fit for purpose with regard to homogeneity and short-term stability, thus allowing the following phases of the certification project to be undertaken, in the first place the selection of expert laboratories for the accomplishment of the certification campaign.     

Collaborative study to improve the quality control of rare earth element determinations in environmental matrices

In order to control the quality of rare earth determinations in environmental matrices, the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference, BCR) of the European Commission has started a project, the final aim of which is to certify four types of matrices (tuna muscle, mussel tissue, aquatic plant and estuarine sediment) for their contents of a range of rare earth elements (Sc, Y and the lanthanides: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The elements U and Th were added to the study. The first part of this project consisted of an interlaboratory study which aimed to test the feasibility of preparation of environmental reference materials and to detect and remove most of the pitfalls observed in rare earth determinations. This paper presents the preparation of the four matrices for the intercomparison study and for the candidate reference material. The main results are presented of the interlaboratory study that was carried out prior to the certification campaign. This collaborative trial is the first attempt ever carried out at this scale to evaluate the state-of-the-art of rare earth determinations in the environment. Its impact on the improvement of chemical measurements will have positive effects on the comparability of data necessary for environmental monitoring.     

Trace Element Patterns and Seasonal Variability of Dust Precipitation in a Low Polluted City – The Example of Karlsruhe/Germany

Urban areas of different land uses can be distinguished by their specific patterns of atmospheric dust and trace element precipitation. Dusts emitted from industrial areas with fossil fuel processing, for instance, are enriched in V, Ni and Co. Cluster analysis groups sampling sites based on their specific element patterns. The resulting groups correspond to the surrounding land use: Urban sampling sites were identified showing similar patterns of dust and trace element precipitation as a reference site; dusts of other urban sites were influenced by diffuse pollution (caused by non-point and dispersed pollution sources), or by specific industrial emissions. Cluster analysis was also used to characterize the chemical dust composition. Three clusters of typical element associations were distinguished. These clusters represent the dust matrix, diffuse urban pollution and pollution due to fossil fuel processing. Dust precipitation and chemical dust composition show seasonal variations. Dust precipitation and concentrations of trace elements in the precipitated dust are negatively correlated during the annual courses. The highest concentrations of trace elements occur during winter, whereas the highest precipitations of dust were found during summer. This finding stresses that both, precipitation and concentration have to be addressed for the environmental assessment of urban dusts.     

Fast characterization of non domestic load in urban wastewater networks by UV spectrophotometry

Urban wastewater treatment plant efficiency, as well as biosolid quality, depends on urban wastewater quality, which can be affected by non domestic discharges (industrial, commercial etc.). The characterization of wastewater quality and non domestic discharge is complex, expensive and time consuming. However, these discharges must be controlled and reduced if possible. The development of a simple and fast methodology, namely based on alternative methods such as UV spectrophotometry, has been carried out and applied to different areas of a medium sized town of Southern Québec (Canada). Several autosamplers and on line/on site measurements have been used in critical control points of the network areas, for a dry weather campaign in four areas (industrial, commercial, hospital and university). The flow rate study, completed by the exploitation of conductivity measurements and the qualitative examination of UV spectra allows the discrimination of non domestic loads and their variability study from one point to another. The identification of critical discharges and organic shock loads has been possible with low investment, and mitigation actions have been proposed.     

水泥工业项目竣工环保验收监测中应关注的问题

根据建设项目竣工环境保护验收规范要求,结合工作实践,从验收监测工况的控制、废水监测、废气监测、噪声监测、环境质量监测几方面归纳了水泥工业项目竣工环境保护验收监测工作中应注意的技术问题,并从环保法律法规制度执行、污染防治设施、企业环境管理、排污口规范化、卫生防护距离、总量控制、淘汰落后设备、公众参与等几方面提出环境保护检...     

Heavy metals partitioning in sediments of the Kabini River in South India

Cu, Cr, Fe, Mn, Ni, Pb, and Zn in the sediments of the Kabini River, Karnataka, India was studied to determine the association of metal with various geochemical phases by sequential extraction. The variations of heavy metal concentration depend on the lithology of the river basin and partly on anthropogenic activities. The Kabini River sediments are dominated by Sargur supracrustals with amphibolites, gneisses, carbonates, and ultrabasic rocks weathering into gneissic and serpentine soils carrying a natural load of cationic heavy metals. The source of heavy metals in the Kabini riverbed sediments is normally envisaged as additional inputs from anthropogenic over and above natural and lithogenic sources. Geochemical study indicates the metals under study were present mostly in the least mobilizable fraction in the overlying water and it is concluded that heavy metals in these sediments are to a great extent derived from multisource anthropogenic inputs besides geochemical background contributions The results show that lead and chromium have higher potential for mobilization from the sediment due to higher concentration at the exchangeable ion and sulfide ion bounded, also Cu and Pb have the greatest percentage of carbonate fraction, it means that the study area received inputs from urban and industrial effluents. Association of the Fe with organic matter fraction can be explained by the high affinity of these elements for the humic substances. Further, Zn and Ni reveal a significant enrichment in sediment and it is due to release of industrial wastewater into the river. These trace metals are possible contaminants to enter into aquatic and food chain.     

Evaluation of the state-of-the-art of butyl- and phenyltin compound determinations in freshwater sediment prior to certification of a reference material

In order to control the quality of butyl- and phenyltin compound determinations in sediment, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has started a project, the final aim of which is to certify a freshwater sediment for its contents of a range of organotin compounds (mono-, di- and tributyltin, and mono-, di- and triphenyltin). The first part of this project involved an interlaboratory study which aimed to test the feasibility of preparation of candidate freshwater sediment reference material and to detect and remove most of the pitfalls observed in organotin determinations. This paper presents the main results of this interlaboratory study carried out prior to the certification campaign. The agreement obtained among laboratories for the six compounds determined was considered to reflect the state-of-the-art and was encouraging enough to decide upon the organisation of a certification campaign, which will be concluded in June 1999.     

Assessment of both environmental cytotoxicity and trace metal pollution using Populus simonii Carr. as a bioindicator

The level of environmental pollution in the city of Ivano-Frankivsk (Western Ukraine) has been assessed by means of roadside poplar trees as bioindicators. Dividable apical meristem cells of rudimentary leaves were quantitatively analysed for mitotic activity and distribution. Anaphases were further examined for chromosomal aberrations. Male catkins were also examined for sterile pollens. Accumulation of trace elements in vegetative buds was also evaluated in order to reveal source(s) of environmental pollution. Poplar trees growing in the urban environment proved to have increased chromosomal aberrations (up to 4-fold) and increased pollen sterility (up to 4-fold) as well as decreased mitotic activity (by factor 1.5) as compared to control sampling site. The biomarker data correlate moderately with increased (up to 4-fold) concentrations of Ni, Zn, Pb, Cd and Cu in vegetative tissues suggesting that probable cause of the environmental cytotoxicity may be vehicle emissions. The maximum increase in chromosomal aberrations (7-fold) and the minimum mitotic activity (half of the control one) were recorded in poplar trees growing in industrial suburb in vicinity of large cement production plant. Taking in mind insignificant bioaccumulation of trace elements in the industrial suburb, the high environmental toxicity has been ascribed to contamination in cement and asbestos particulates.     

Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure

Sequential extraction procedures have been used during the last decades to study and determine trace element mobility in aquatic sediments. However, the results obtained are operationally defined and, therefore, the significance of the analytical results is related to the extraction scheme used. So, there is a need for suitable reference materials for this type of study to enable the validation of the methodologies and to control the quality of the measurements. This paper describes the preparation of a sediment reference material, BCR-701, the homogeneity and stability studies and the analytical work performed for the certification of the extractable contents of some trace elements, following a collaboratively tested and optimised sequential (three-step) extraction procedure. The paper contains all the results and gives the methods used to certify the extractable contents (mass fractions expressed as mg kg-1 on a dry matter basis) of Cd, Cr, Cu, Ni, Pb and Zn in all steps. Moreover, indicative values are given for the aqua regia extractable contents of the six elements in the sediment and the residue obtained after sequential extraction.     

Lettuce plants as bioaccumulators of trace elements in a community of central Italy

A survey, based on the use of vascular plants to describe the distribution of selected elements (21 in total) was performed in 11 sites in the area of Castelfiorentino (Tuscany, Central Italy) differing for land use, from urban to industrial and rural areas. Lettuce plants grown under standardized conditions were positively used as biodeposimeters of airborne trace elements. Washing was found to be highly significant in reducing concentrations of many elements in the samples, suggesting a general surface contamination of leaves. The typical crustal element Al showed good correlations with Co, Fe, Li and V; on the contrary, Zn and Cd were intercorrelated and showed no connection with crustal indicators. Lead was still a relevant environmental presence, as the experiments were carried out before the ban of leaded gasoline. Source apportionment by factor analysis put in evidence a major contribution of crustal materials, followed by man-related activities; a minor role was ascertained for marine aerosol. A comparison was made between analytical data of lettuce plants grown in our experimental sites and a bulk of commercial lettuce purchased at a local supermarket. It should be stressed how Cu concentrations of commercial material were significantly higher than those found in our plants; this is likely caused by phytosanitary treatments.     

A decision-support system for sustainable urban metabolism in Europe

Urban metabolism components define the energy and material exchanges within a city and, therefore, can provide valuable information on the environmental quality of urban areas. Assessing the potential impact of urban planning alternatives on urban metabolism components (such as energy, water, carbon and pollutants fluxes) can provide a quantitative estimation of their sustainability performance. Urban metabolism impact assessment can, therefore, contribute to the identification of sustainable urban structures with regards, for example, to building types, materials and layout, as well as to location and capacity of transportation and infrastructural developments. In this way, it enables the formulation of planning and policy recommendations to promote efficient use of resources and enhance environmental quality in urban areas.The European FP7 project BRIDGE (sustainaBle uRban plannIng Decision support accountinG for urban mEtabolism) has developed a decision-support system (DSS) that systematically integrates urban metabolism components into impact assessment processes with the aim of accurately quantifying the potential effects of proposed planning interventions. The DSS enables integration of multiple spatial and non-spatial datasets (e.g. physical flows of energy and material with variables of social and economic change) in a systematic manner to obtain spatially defined assessment results and to thus inform planners and decision-makers. This multi-criteria approach also enables incorporation of stakeholders' perceptions in order to prioritise decisive assessment criteria. This paper describes the methodological framework used to develop the DSS and critically examines the results of its practical application in five European cities.     

Introduction of the Factor of Partitioning in the Lithogenic Enrichment Factors of Trace Element Bioaccumulation in Plant Tissues

Bioindicators are widely used in the study of trace elements inputs into the environment and great efforts have been conducted to separate atmospheric from soil borne inputs on biomass accumulation. Many monitoring studies of trace element pollution take into account the dust particles located in the plant surface plus the contents of the plant tissues. However, it is usually only the trace element content in the plant tissues that is relevant on plant health. Enrichment factor equations take into account the trace element enrichment of biomasses with respect soil or bedrocks by comparing the ratios of the trace element in question to a lithogenic element, usually Al. However, the enrichment equations currently in use are inadequate because they do not take into account the fact that Al (or whichever reference element) and the element in question may have different solubility-absorption-retention levels depending on the rock and soil types involved. This constrain will become critical when results from different sites are compared and so in this article we propose that the solubility factors of each element are taken into account in order to overcome this constrain. We analysed Sb, Co, Ni, Cr, Pb, Cd, Mn, V, Zn, Cu, As, Hg, and Al concentration in different zones of Catalonia (NE Spain) using the evergreen oak Quercus ilex and the moss Hypnum cupressiforme as target species. We compared the results obtained in rural and non industrial areas with those from the Barcelona Metropolitan Area. We observed differences in Al concentrations of soils and bedrocks at each different site, together with the differences in solubility between Al and the element in question, and a weak correlation between total soil content and water extract content through different sites for most trace elements. All these findings show the unsuitability of the current enrichment factors for calculating lithospheric and atmospheric contributions to trace element concentrations in biomass tissues. The trace element enrichment factors were calculated by subtracting the part predicted by substrate composition (deduced from water extracts from soils and bedrock) from total concentrations. Results showed that for most of the trace elements analysed, trace elements enrichment factors were higher inside the Barcelona Metropolitan Area than outside, a finding that indicates that greater atmospheric inputs occur in urban areas. The results show that the most useful and correct way of establishing a reference for lithospheric and atmospheric inputs into the plant tissues is, first, to analyse samples of the same plant species collected from a number of sites possessing similar environmental conditions (climate, vegetation type, soil type) and, second, to use this new enrichment factor obtained by subtracting from the total concentration in plant tissue the predicted contribution of soil or bedrock extracts instead of that of total soil or bedrock concentrations.     

Natural attenuation of coal combustion waste in river sediments

The weathering of coal combustion products (CCPs) in a lotic environment was assessed following the Tennessee Valley Authority (Kingston, TN) fly ash release of 2008 into surrounding rivers. Sampled materials included stockpiled ash and sediment collected from 180 to 880 days following the release. Total recoverable concentrations of heavy metals and metalloids in sediment were measured, and percent ash was estimated visually or quantified by particle counts. Arsenic and selenium in sediment were positively correlated with percent ash. For samples collected 180 days after the release, total concentrations of trace elements downstream of the release were greater than reference levels but less than concentrations measured in stockpiled ash. Total concentrations of trace elements remained elevated in ash-laden sediment after almost 2.5 years. A sequential extraction procedure (SEP) was used to speciate selected fractions of arsenic, copper, lead, nickel, and selenium in decreasing order of bioavailability. Concentrations of trace elements in sequentially extracted fractions were one to two orders of magnitude lower than total recoverable trace elements. The bulk of sequentially extractable trace elements was associated with iron-manganese oxides, the least bioavailable fraction of those measured. By 780 days, trace element concentrations in the SEP fractions approached reference concentrations in the more bioavailable water soluble, ion exchangeable, and carbonate-bound fractions. For each trace element, the percentage composition of the bioavailable fractions relative to the total concentration was calculated. These SEP indices were summed and shown to significantly decrease over time. These results document the natural attenuation of leachable trace elements in CCPs in river sediment as a result of the loss of bioavailable trace elements over time.     

工业废水毒性评估方法与应用研究进展

针对中国缺乏规范的工业废水毒性评估体系的现状，系统归纳了国外在毒性检测、毒性评价标准与方法方面的成功经验。在明确了工业废水急性毒性检测的重要性基础上，重点分析了美国全废水毒性测试法（WET）及其在工业废水评价中的应用；并结合对毒性评价标准的阐述，系统总结了发展较成熟的毒性鉴别评价法（TIE）和效应导向分析法（EDA）的流程与应用实例，以期为中国工业废水毒性检测评估和监管提供参考。     

水中汞监测存在的问题与解决办法

利用中日合作 (JICA)项目资金 ,对测定地表水中汞存在的主要问题 ,如水样的保存和处理 ,水样的消解 ,测汞的冷原子吸收法和原子荧光法等进行了研究。通过对 33个环境监测站的样品考核 ,发现测定结果与标准值相比 ,偏高的数据达 75 %以上。提出了用 1%H2 SO4 和 0 1%K2 Cr2 O7保存水样最好 ;高锰酸钾 -过硫酸钾消解法适用于消解含有机物、悬浮物和组成复杂的废水样 ,高锰酸钾 -硫酸消解法适用于消解被有机物轻度污染的废水 ,溴酸钾 -溴化钾消解法适用于消解地表水和含较少有机物的生活污水及工业废水。研究表明 :尤以硫酸 -高锰酸钾 -过硫酸钾消解体系消解地表水和废水效果良好。对冷原子吸收法和原子荧光法中影响汞测定的因素 ,如空白值高、干扰物的消除、载气种类和流量、反应瓶体积和气液比以及反应时间等提出了详尽的解决方法     

Spatial distribution and human contamination quantification of trace metals and phosphorus in the sediments of Chaohu Lake,a eutrophic shallow lake,China

Distinguishing and quantifying anthropogenic trace metals and phosphorus accumulated in sediment is important for the protection of our aquatic ecosystems. Here, anthropogenic proportion and potential sources of trace metals and phosphorus in surface sediments of Chaohu Lake were evaluated based on the exhaustive geochemical data. The analysis shows that concentrations of major and trace metals, and phosphorus, displayed significant spatial diversity and almost all elements were over the pre-industrial background value, which should be related to the variations of sediment composition partially. Therefore, conservative element normalization was introduced and calculated enrichment factors (EFs) of the elements were referenced highlighting the human contamination. EFs of the major and trace metals, except Zn, Pb, and Cu, were all nearly 1.0, indicating the detrital origin. The EFs of Zn, Pb, Cu and phosphorus were 1.0–10.4, 1.0–3.8, 1.0–4.9, and 1.0–7.6, respectively, showing moderate to significant contamination. Higher EFs of Zn, Pb and Cu occurred in the mouth areas of Nanfei River and Zhegao River, and they decreased to the lake center in the northwest and northeast lake areas, respectively. We deduced that anthropogenic Zn, Pb, and Cu were mainly from urban and industrial point sources and the non-point sources of atmospheric deposition contributed little to their contamination. The EFs of phosphorus showed similar spatial degradation with that of Zn, Pb, and Cu. Moreover, higher EFs (>1) of phosphorus also occurred in other areas adjacent to the river mouths besides Nanfei River and Zhegao River. This indicated that the non-point agricultural source may also be responsible for the contamination of phosphorus in Chaohu Lake in addition to the urban sewage sources. Anthropogenic phosphorus was mainly concentrated in the speciation of NaOH-P, which had higher potential biological effects than the detrital proportion. Concentrations of Zn, Pb and Cu surpassed the threshold effect concentrations (TEC) of consensus-based sediment quality guidelines of freshwater ecosystems, especially in the contaminated northwest area of Chaohu Lake. This highlighted the contributions of anthropogenic contamination to the elevated potential biological effects of trace metals. Though there had been no obvious human contamination of Cr and Ni in Chaohu Lake, concentrations were all over the TECs, which may be due to higher background levels in the parent materials of soils and bedrocks in Chaohu Lake catchment.