Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

The application of ICP-SMS, GF-AAS and HG-AFS to the analysis of water and sediment samples from a temperate stratified estuary

Three atomic spectrometry techniques, namely sector field inductively coupled plasma mass spectroscopy, graphite furnace atomic absorption spectrometry and hydride generation atomic fluorescence spectroscopy (ICP-SMS, GF-AAS and HG-AFS, respectively), housed at separate independent laboratories, were used to analyse water and sediment samples collected from the Huon River Estuary, SE Tasmania (Australia) in the Austral spring 1998. A dithiocarbamate-chelation/back-extraction technique was used to separate and preconcentrate Co, Ni, Cu, Zn, Cd and Pb from eight collected water samples prior to analysis by ICP-SMS and GF-AAS. A number of other elements in the waters were analysed directly (Mn, Fe and Zn by GF-AAS; As by HG-AFS), or following sample dilution (1 + 19: V, Mn, Fe, As, Mo, Ba and U by ICP-SMS). Where possible, previously corroborated GF-AAS and HG-AFS techniques were used to verify obtained ICP-SMS results. From the analysis of four reference waters (SLEW-1 and -2, SLRS-3 and NASS-5), good agreement, to within +/- 10-20%, was typically found between certified (or information only values) and measured results (irrespective of analytical technique). Exceptions included Zn (and sometimes Fe) that could not be quantified by ICP-SMS due to elevated blank signals, and As which was found to lie below ICP-SMS detection limits. For Huon Estuary water samples, inter-method agreement was within +/- 10-20% (for those elements amenable to analysis by more than one technique). Nitric acid extracts of two certified reference materials (Buffalo River Sediment and BCSS-1) and six Huon Estuary sediments were analysed by ICP-SMS (for Al, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd and Pb) and HG-AFS (for As). Results from the certified reference materials indicated extraction efficiencies of 60 70% (for most elements). A close correlation between ICP-SMS and HG-AFS was obtained for leachable As in the sediments. In terms of potential inorganic contaminants, the Huon Estuary was found to be a relatively 'clean' water system. The elemental concentrations measured in water and sediment samples from this region were found to lie within current Australian guidelines for estuaries. In general, no one analytical technique was able to accurately determine all elements in all samples from this relatively pristine estuarine environment. A combination of all three analytical techniques was necessary for the successful analysis of the elements considered in this study.     

微波消解法测定铅锌冶炼厂废旧除尘布袋及其飞灰中重金属的应用研究

以广东某铅锌冶炼厂的废旧除尘布袋及其布袋上的飞灰为实验材料,以HNO3-H2O2-HF对布袋及飞灰进行微波全量消解,采用BCR三步浸提法提取飞灰中Cu、Zn、Pb、Cr、Ni、Cd 6种重金属,并利用火焰原子吸收仪器检测布袋及飞灰中6种重金属的含量及飞灰中各形态含量。结果表明,铅锌冶炼厂废旧布袋和飞灰中重金属含量较高,远大于《国家土壤环境质量标准》(GB 15168—1995)三级标准值。不同重金属在飞灰中的形态分布差异较大,Ni主要以残渣态和酸可交换态为主,Cu和Pb以残渣态为主,Zn的4种形态分布都较均匀,Cd、Zn潜在的迁移性最强。     

Heavy metals and PCDD/Fs in solid waste incinerator fly ash in Zhejiang province,China: chemical and bio-analytical characterization

Fly ash samples were taken from solid waste incinerators with different feeding waste, furnace type, and air pollution control device in six cities of Zhejiang province. The solid waste incinerators there constitute one fifth of incinerators in China. Heavy metals and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in the fly ash. Moreover, the fly ash samples were extracted by toxicity characteristic leaching procedure (TCLP). The biotoxicity of the leachate was evaluated by Chlorella pyrenoidosa. High variation and contents were found for both the heavy metals and PCDD/Fs. The contents of Zn, Cu, As, Pb, Cd, Cr, Ni, and Hg in the fly ash samples varied from 300 to 32,100, 62.1–1175, 1.1–57, 61.6–620, 0.4–223, 16.6–4380, 1.2–94.7, and 0.03–1.4 μg g⁻¹ dw, respectively. The total contents of 17 PCDD/Fs varied from 0.1128 to 127.7939 μg g⁻¹ dw, and the 2,3,7,8-TeCDD toxic equivalents (TEQ) of PCDD/Fs ranged from 0.009 to 6.177 μg g⁻¹ dw. PCDF congeners were the main contributor to the TEQ. The leachate of the fly ash showed biotoxicity to C. pyrenoidosa. A significant correlation was found between the Cd and EC₅₀ values. Further research is required to investigate the environmental impact of the various pollutants in the fly ash.     

石河子燃煤电厂重金属排放研究

选取石河子市典型燃煤电厂,对其燃煤烟气重金属排放浓度及飞灰、底渣、脱硫石膏重金属的富集进行定量分析。结果表明,烟气中各重金属排放浓度从高到低依次为Zn、Ni、Cr、Pb、Cu、Hg、Co、Cd、As。各重金属元素在飞灰中的富集程度较高,除Hg、Cd、Ni外,其他重金属元素在飞灰的富集因均值均大于5。其中,As在飞灰的富集因子均值为5.76。研究结果可为石河子重金属污染控制提供基础数据。     

Evaluation of genotoxicity of coal fly ash in Allium cepa root cells by combining comet assay with the Allium test

Fly ash is a by-product of coal-fired electricity generation plants. Its utilization and disposal is of utmost importance. Using onion (Allium cepa) root tip system, the present study was carried out to evaluate the potential toxic and genotoxic effects of fly ash, collected from a thermal power plant in West Bengal, India. Prior to testing, the collected fly ash sample was mixed with sand in different proportions. Allium bulbs were allowed to germinate directly in fly ash and after five days the germinating roots were processed for the Allium test. Additionally, the Allium test was adapted for detecting DNA damage through comet assay. The results from the Allium test indicate that fly ash at 100% concentration inhibits root growth and mitotic indices; induces binucleated cells as a function of the proportion, but is not toxic at very low concentration. In the comet assay, a statistical increase for DNA strand breaks was found only at higher concentrations. The sample was analyzed by flame atomic absorption spectrometer for Zn, Pb, Cu, Ni, Cd and As, whose presence could partly be responsible for the toxicity of fly ash. The study concludes that the classical Allium test can give a more comprehensive data when done in combination with the comet assay, which is faster, simpler and independent of mitosis. Also when fly ash is used for other purposes in combination with soils, it should be judiciously used at very low concentrations in order to protect the ecosystem health from any potential adverse effects.     

Spatial variability of soil heavy metals in the three gorges area: multivariate and geostatistical analyses

There is a growing concern about environmental contamination in the three gorges area. The objectives of this study were to investigate the spatial variability and the possible influence factors of seven heavy metals (As, Cd, Cr, Cu, Hg, Pb, and Zn) in the center of this area based on multivariate and geostatistical approaches. All analyzed heavy metals were below their background levels, except Cd. The average concentrations of the analyzed elements in topsoil (0-20 cm) were 5.83 mg As kg(-1), 0.21 mg Cd kg(-1), 78.79 mg Cr kg(-1), 21.53 mg Cu kg (-1), 0.049 mg Hg kg(-1), 24.12 mg Pb kg(-1), and 68.5 mg Zn kg(-1). The concentration of As was mostly due to parent materials, whereas the source of Pb was mainly due to vehicle exhaust. The high concentration of Cd was resulted from agricultural practices and parent materials. The concentrations of Cr, Cu, Hg, and Zn were associated with parent materials and human activities.     

M3法测定土壤有效态Cd、Cr、Pb和Ni

通过M3法对耕地土壤重金属的联合测定,为土壤重金属污染监测应用提供快速联合测定的方法。用M3法测定北方耕地土壤的有效Cd、Cr、Pb和Ni,通过对M3法与其他方法进行有效重金属测定值差异性及其相关性比较,与全量的浸出率分析等探讨M3法对耕地土壤有效重金属测定的特征。结果表明,M3法在《土壤环境质量标准》(GB 15618—1995)的土壤重金属含量范围内可以测定土壤有效态重金属Cd、Cr、Pb和Ni,且呈线性极显著相关。M3法与其他方法有效Cd、Cr、Pb和Ni有较好的相关性,与DTPA法呈极显著相关;与NaNO₃法除有效Pb外,呈极显著和显著相关;与HCl法除褐土和潮土的有效Pb外,也呈极显著和显著相关。M3法的有效态Cd、Cr、Pb和Ni的测定值均为最大。M3法对4种耕地土壤有效Cd、Cr、Pb和Ni的浸出率,因土壤类型不同,有效重金属含量所占比率不同,但利用M3法测定的有效态Cd、Cr、Pb和Ni的浸出率最大。     

Bioaccumulation and translocation of metals in the natural vegetation growing on fly ash lagoons: a field study from Santaldih thermal power plant, West Bengal, India

A field study was conducted in the fly ash lagoons of Santandih Thermal Power Plant located in West Bengal (India) to find out total, EDTA and DTPA extractable metals in fly ash and their bioaccumulation in root and shoot portion of the naturally growing vegetation. Fly ash sample has alkaline pH and low conductivity. The concentration of total Cu, Zn, Pb and Ni were found higher than weathered fly ash and natural soil, where as Co, Cd and Cr were found traces. Five dominant vegetation namely, Typha latifolia, Fimbristylis dichotoma, Amaranthus defluxes, Saccharum spontaenum and Cynodon dactylon were collected in the winter months (November–December). Bioaccumulation of metals in root and shoot portions were found varied significantly among the species, but all concentration were found within toxic limits. Correlation between total, DTPA and EDTA extractable metals viz. root and shoot metals concentration were studied. Translocation factor (TF) for Cu, Zn and Ni were found less than unity, indicates that these metals are immobilized in the root part of the plants. Metals like Mn have TF greater than unity. The study infers that natural vegetation removed Mn by phytoextraction mechanisms (TF > 1), while other metals like Zn, Cu, Pb and Ni were removed by rhizofiltration mechanisms (TF < 1). The field study revealed that T. latifolia and S. spontaenum plants could be used for bioremediation of fly ash lagoon.     

Validation of a European standard for the determination of hexavalent chromium in solid material

A European standard for the determination of Cr(vi) in solid material has been elaborated in the framework of an international co-operation and finally validated in the course of an interlaboratory comparison. The procedure is based on the alkaline digestion prescribed by EPA method 3060A followed by ion chromatography and determines an operationally defined content of Cr(vi), including water-soluble and insoluble chromates. A preliminary robustness study was carried out in order to compare different extraction methodologies and to study the equivalency of different analytical methods for the determination of Cr(vi) in alkaline extracts of soil and waste materials. During an interlaboratory validation trial with 19 European laboratories a set of 4 samples (2 soil and 2 waste samples) was analysed to determine performance characteristics for different combinations of digestion and detection methods. With the procedures prescribed by the new European standard (EN 15192) acceptable results were obtained for both soil samples and one of the waste samples (sludge). However, for the second waste sample (fly ash) a large deviation in analytical results was observed. This indicates that particularly for waste materials a possible occurrence of strong matrix effects has to be considered and supplementary quality control data are needed in order to assess the validity of analytical results. The accuracy of the determination of Cr(vi) in solid matrices remains a challenging field in terms of maximum extraction efficiency and minimum species interconversion.     

Cadmium concentrations in human kidney in the UK: 1978-1993

Almost 2700 samples of human renal cortex have been collected from throughout the UK over a 16 year period from 1978 to 1993. The mean Cd concentration was 19 micrograms g-1 and the median 16 micrograms g-1. Smokers were, on average, about 5 micrograms g-1 higher than non-smokers. Cd increased from low concentration in the young to a maximum of 23 micrograms g-1 in middle age followed by a decrease in old age. Subjects who had died of renal disease had lower Cd concentrations. Geographical variations in the UK are small and the concentrations appear to be static over the 16 year period. Some 3.9% of the population had Cd concentrations > 50 micrograms g-1, the critical level at which beta 2-microglobulin appears in urine.     

Assessing the potential impact of fly ash amendments on Indian paddy field with special emphasis on growth, yield, and grain quality of three rice cultivars

Proper disposal and/or recycling of different industrial waste materials have long been recognized as a prime environmental concern throughout the world, and fly ash is major amongst them. In the present study, we tried to assess the feasibilities of possible effective and safe utilization of fly ash as soil amendment in Indian paddy field and its impact on rice plants, especially at growth and yield level. Our results showed that certain doses of fly ash amendments have significantly improved the physico-chemical and mineralogical properties of paddy field soil, and at lower level of amendments, fly ash induced the growth performances of three rice cultivars too. Grain yield and grain quality also responded similarly as per the growth responses. However, differential cultivar response was observed accordingly, and cultivar Sugandha-3 showed higher yield as compared with cultivars Sambha and Saryu-52. Based on the observed results, it was concluded that up to a certain level, fly ash amendments could be beneficial for Indian paddy field and can be utilized as feasible management strategy for the disposal of this major industrial waste.     

Monitoring the species of arsenic, chromium and nickel in milled coal, bottom ash and fly ash from a pulverized coal-fired power plant in western Canada

The concentration of As, Cr and Ni and their speciation (As3+;5+, Cr3+;6+ and Ni0;2+) in milled coal, bottom ash and ash collected by electrostatic precipitator (ESP) from a coal fired-power plant in western Canada were determined using HGAAS, ICP-AES and XANES. The chemical fractionation of these elements was also determined by a sequential leaching procedure, using deionized water, NH4OAC and HCI as extracting agents. The leachate was analyzed by ICP-AES. Arsenic in the milled coal is mostly associated with organic matter, and 67% of this arsenic is removed by ammonium acetate. This element is totally removed from milled coal after extraction with HCI. Arsenic occurs in both the As3+ and the As5+ oxidation states in the milled coal, while virtually all (>90%) of the arsenic in bottom ash and fly ash appears to be in the less toxic arsenate (As5+) form. Both Ni and Cr in the milled coal are extracted by HCI, indicating that water can mobilize Ni and Cr in an acidic environment. The chromium is leached by water from fly ash as a result of the high pH of the water, which is induced during the leaching. Ammonium acetate removes Ni from bottom ash through an ion exchange process. Chromium in milled coal is present entirely as Cr3+, which is an essential human trace nutrient. The Cr speciation in bottom ash is a more accentuated version of the milled coal and consists mostly of the Cr3+ species. Chromium in fly ash is mostly Cr3+, with significant contamination by stainless-steel from the installation itself.     

Study of heavy metals in some environmental samples

Fuels like coal and rubber are frequently used for brick burning. However, both coal and rubber contain heavy metals. These heavy metals may elutriate in the wake of fly ash or may adsorb or absorb in the product. The present work deals with the analysis of heavy metals in some samples collected from brick burning industries located in the vicinity of a metropolitan city, Peshawar, Pakistan. Samples from raw clay, product, chimney scale and fossil fuel & rubber were collected and leached with acid mixture. The leachates were concentrated and analyzed by atomic absorption spectrophotometer for the determination of chromium (Cr), lead (Pb), cadmium (Cd) and antimony (Sb). It was observed that heavy metals are present in clay, brick and chimney scale. However, significant amount of these metals was observed in chimney scale. It is inferred that such emanations laden with heavy metals are accompanying the stack gases which are being dumped in to the environment. In order to avoid environmental problems, strict environmental regulations shall be enforced and a constant check on these emanations to the environment must be made to ensure clean air act.     

Speciation of Cr and its leachability in coal by-products from spanish coal combustion plants

This study evaluates the behaviour of total Cr and Cr (VI) during coal combustion in two Spanish power stations. The content and distribution of Cr in the feed coal and combustion wastes was determined and the Cr contents were normalized using enrichment factor indexes. The speciation of Cr in the fly ash fractions from the different hoppers of the electrostatic precipitators was established and the possibility that the Cr (VI) might lixiviate when ashes are disposed of at landfill sites was assessed. Differences in the distribution and behavior of Cr in the two power stations were observed. According to European directive 1999/31/CEE, soluble Cr(VI) in the fly ashes studied would be unlikely to pose an environmental or health risk when the ash is disposed of.     

Fractionation and ecotoxicological implication of potentially toxic metals in sediments of three urban rivers and the Lagos Lagoon,Nigeria, West Africa

The potential environmental impact of sediment-bound Cd, Cr, Cu, Pb and Zn in three trans-urban rivers in Lagos state and in the Lagos Lagoon was assessed by use of the modified Community Bureau of Reference (BCR) sequential extraction. The quality of the data was checked using BCR CRM 143R and BCR CRM 701. Good agreement was obtained between found and certified/indicative values. Of the rivers, the Odo-Iyaalaro, was generally the most contaminated and the Ibeshe the least. Higher concentrations of metals were generally found in the dry season compared to the wet season. Cadmium and Zn were released mostly in the acid exchangeable step of the sequential extraction, indicating that they have the greatest potential mobility and bioavailability of the analytes studied. Chromium and Cu were associated mainly with the reducible and oxidisable fractions, and Pb predominantly with the reducible and residual fractions. Sediments with the highest pseudototal analyte concentrations also released higher proportions of analytes earlier in the sequential extraction procedure. The study suggests that, during the dry season, potentially toxic metals (PTM) may accumulate in sediments in relatively labile forms that are released and can potentially be transported or bioaccumulate in the rainy season. Application of risk assessment codes and Hankanson potential risk indices indicated that Cd was the element of greatest concern in the Lagos Lagoon system. The study indicated that there is a need to strengthen environmental management and pollution control measures to reduce risk from PTM, but that even relatively simple strategies, such as seasonal restrictions on dredging and fishing, could be beneficial.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

6项环境监测分析方法标准中钴、铬、钼、钛的不确定度分析及其在达标判定中的应用

研究依据测定不确定度的基本理论和ISO 21748：2017《采用重复性、再现性和正确度评估测量不确定度的导则》，提出了基于中国环境监测分析方法标准多家实验室验证中已获得的数据计算合成标准不确定度的方法，将方法标准中规定的重复性、再现性等指标与合成标准不确定度进行了衔接。分析了近年发布的6项水质监测分析方法标准中钴、铬、钼、钛等4种金属元素的相对合成标准不确定度，结果表明：被测量的浓度是影响方法标准测量不确定度的重要因素。对于火焰原子吸收分光光度法（FAAS）和石墨炉原子吸收分光光度法（GAAS），样品浓度为方法标准测定下限3倍左右时，测定结果的相对标准不确定度可保持在15%以下；对于电感耦合等离子体发射光谱法（ICP-AES），样品浓度为方法标准测定下限3~5倍时，测定结果的相对标准不确定度为12%~17%；对于电感耦合等离子体质谱法（ICP-MS），钛元素浓度为测定下限3倍左右时，相对标准不确定度在15%以下，而钴、铬、钼的浓度在测定下限40~100倍以上时，相对标准不确定度在15%以下。6项方法标准可分别用于《地表水环境质量标准》（GB 3838—2002）以及22项水污染物排放标准钴、铬、钼、钛的达标监测。     

Cross-border response of mosses to heavy metal atmospheric deposition in Southeastern Bulgaria and European Turkey

First cross-border atmospheric pollution of 11 heavy metals and toxic elements assessed by Hypnum cupressiforme was reported for a part of Southeastern Europe (Southeastern Bulgaria and European Turkey). Moss monitoring technique followed the main requirements of European Moss Survey. Moss samples were collected in April 2006 both in Bulgaria and Turkey. Concentration of Al, As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, V, and Zn were determined by ICP-AES. Interlaboratory parallel calibration (exchanged four moss samples from each country), standard reference moss materials (M2 and M3) results ensured the study. ANOVA showed no differences between measured results in both laboratories at the 99% confidence level. Principle Component Analyze proved two factors: F1 group of Al, As, Cd, Cr, Fe, Ni, and V and F2 of Cu, Pb, and Zn as main atmospheric pollutants. Results obtained showed approximately Cu and Pb high concentrations around Istanbul and Burgas and Zn pollution in Istanbul district. Arsenic cross-border atmospheric pollution in the study area of Southeastern Europe was found.