Trends in hazardous trace metal concentrations in aerosols collected in Beijing, China from 2001 to 2006

Daily observations of hazardous trace metal concentrations in aerosols in Beijing, China were made in the period from 2001 to 2006. We considered coal combustion as a major source of some anthropogenic metals by achieving a correlation analysis and by investigating enrichment factors and relative composition of metals. A possible extra source of some specific metals, such as Cu and Sb, was brake abrasion particles, however, we did not think the transport-related particle was a major source for the hazardous anthropogenic metals even though they could originate from vehicle exhaust and brake/tire abrasion particles. A time-trend model was used to describe temporal variations of chemical constituent concentrations during the five-year period. Several crustal elements, such as Al, Ti, V, Cr, Mn, Fe, and Co, did not show clear increases, with annual rates of change of -15.2% to 3.6%. On the other hand, serious increasing trends were noted from several hazardous trace metals. Cu, Zn, As, Cd, and Pb, which are derived mainly from anthropogenic sources, such as coal combustion, showed higher annual rate of change (4.9-19.8%, p<0.001) according to the regression model. In particular, the Cd and Pb concentrations increased remarkably. We hypothesize that the trend towards increasing concentrations of metals in the air reflects a change that has occurred in the process of burning coal, whereby the use of higher temperatures for coal combustion has resulted in increased emissions of these metals. The increasing use of low-rank coal may also explain the observed trends. In addition, nonferrous metal smelters are considered as a potential, albeit minor, reason for the increasing atmospheric concentrations of anthropogenic hazardous metals in Beijing city.     

Current and future emissions of selected heavy metals to the atmosphere from anthropogenic sources in Europe

Current atmospheric emissions of As, Cd, Cr, Ni, and Pb (reference year 2000) from major anthropogenic sources in Europe are presented in this paper. Combustion of fuels in stationary sources was the main emission source for As, Cd, Cr, and Ni (more than a half of the total anthropogenic emissions), while combustion of gasoline was the main source of for lead. There is a continuous reduction of heavy metal emissions in Europe during the last 40 years. Better knowledge of heavy metal sources, emissions, pathways, and fate in the environment, and progress in developing efficient emission control equipment has resulted in more efficient regulatory efforts to curb heavy metal emissions from anthropogenic sources very substantially. There is a potential for further reduction of these emissions until the year 2010 up to about 40% for As, Cd, Cr, and Ni and about 57% for Pb, as estimated within various emission scenarios presented in the paper.     

Parametrization of groundwater quality of the Quaternary aquifer in N’Djamena (Chad), Lake Chad Basin: application of numerical and multivariate analyses

The urban groundwater of the Quaternary aquifer of the Lake Chad basin in N’Djamena has been subject to many hydrochemical studies. However, the results are often not presented in a way that enables water quality managers to make an appropriate decisions, which restrict development and poverty reduction efforts. The objective of the present study was to contribute the improved management of the local groundwater resources. A total of 85 groundwater samples were interpreted using hydrochemical techniques associated with integrated numerical indices and multivariate statistical analysis. The hydrochemical results coupled with the relative residence time of water have shown that the chemical composition of these waters is linked to geogenic and anthropogenic factors and to their proximity to the Chari-Logone rivers. These investigations showed that the groundwater quality in N’Djamena is characterized by a high spatial variability. This study also assessed the suitability of groundwater for user needs and identified areas which are more/less favorable for a specific use. The evaluation of water quality and its suitability for human consumption is also a problem of optimizing data acquisition strategy, and this study used the correlation between water quality index (WQI) and electrical conductivity (EC) to orientate future data acquisition strategies. This parametrization can assist the decision makers and water management professionals in evaluating groundwater availability and setting up a robust water quality management plan in areas with similar hydrogeological and climatic conditions.

     

大气汞的来源及其浓度分布特征研究进展

大气汞是全球性的污染物,其来源有自然源和人为源,亚洲地区是最大的人为大气汞排放源,占全球人为排汞量的67％(质量分数),其中又以中国为最.燃煤和有色金属冶炼对中国大气汞排放的贡献最大.环境界面的释汞通量是全球大气汞预算的重要组成部分,也是目前的研究热点之一.综述了不同环境界面的释汞通量及其影响因素,并比较了不同地区大气...     

Assessment and Distribution of Antimony in Soils around Three Coal Mines,Anhui, China

ABSTRACT

Thirty-three soil samples were collected from the Luling, Liuer, and Zhangji coal mines in the Huaibei and Huainan areas of Anhui Province, China. The samples were analyzed for antimony (Sb) by inductively coupled plasma-optical emission spectrometry (ICP-OES) method. The average Sb content in the 33 samples was 4 mg kg^?1, which is lower than in coals from this region (6.2 mg kg^?1). More than 75% of the soils sampled showed a significant degree of Sb pollution (enrichment factors [EFs] 5–20). The soils collected near the gob pile and coal preparation plant were higher in Sb content than those collected from residential areas near the mines. The gob pile and tailings from the preparation plant were high in mineral matter content and high in Sb. They are the sources of Sb pollution in surface soils in the vicinity of coal mines. The spatial dispersion of Sb in surface soil in the mine region shows that Sb pollution could reach out as far as 350 m into the local environment conditions. Crops in rice paddies may adsorb some Sb and reduce the Sb content in soils from paddyfields. Vertical distribution of Sb in two soil profiles indicates that Sb is normally relatively immobile in soils.

IMPLICATIONS This work was carried out to analyze the pollution situation and environmental distribution of Sb in three important mines in Anhui Province of China. A detailed concentration analysis of Sb was used to indicate the anthropogenic source of human operation such as coal mining and depositing, coal cleaning, and electricity generation by coal power plants in the mine region. The investigation provides special useful information on the environmental behavior characteristics of Sb for environmental scientists and policy-makers.     

潞城市大气PM_（10）中化学元素分布特征

利用ICP-AES分析了潞城市采暖期和非采暖期4个不同功能区PM10样品中16种化学元素,对不同元素的时空分布特征进行了研究,并采用富集因子和主成分分析初步研究了潞城市PM10中元素的主要来源。结果表明,潞城市PM10中重金属污染较为严重,且各元素在采暖期的平均浓度均明显高于非采暖期。PM10中Ca、V、Cr、As、Ni、Mn、Cu、Zn、Al和Pb的富集因子EF〉10,主要来源于人为污染;而Na、Mg、Si、Fe和K的EF〈10,除部分来自人为活动外,主要来自土壤风沙等自然来源。主成分分析结果显示,潞城市PM10中元素的主要来源按贡献率大小依次为：煤烟尘和工业粉尘50.39%,自然源34.37%和机动车尾气15.24%。     

Origin of middle rare earth element enrichment in acid mine drainage-impacted areas

The commonly observed enrichment of middle rare earth elements (MREE) in water sampled in acid mine drainage (AMD)-impacted areas was found to be the result of preferential release from the widespread mineral pyrite (FeS₂). Three different mining-impacted sites in Europe were sampled for water, and various pyrite samples were used in batch experiments with diluted sulphuric acid simulating AMD-impacted water with high sulphate concentration and high acidity. All water samples independent on their origin from groundwater, creek water or lake water as well as on the surrounding rock types showed MREE enrichment. Also the pyrite samples showed MREE enrichment in the respective acidic leachate but not always in their total contents indicating a process-controlled release. It is discussed that most probably complexation to sulphite (SO₃ ^2?) or another intermediate S-species during pyrite oxidation is the reason for the MREE enrichment in the normalized REE patterns.     

Size distribution and anthropogenic sources apportionment of airborne trace metals in Kanazawa, Japan

Aerosol samples were collected from Kanazawa, Japan to examine the size distribution of 12 elements and to identify the major sources of anthropogenic elements. Key emission sources were identified and, concentrations contributed from individual sources were estimated as well. Concentrations of elements V, Ca, Cd, Fe, Ba, Mg, Mn, Pb, Sr, Zn, Co and Cu in aerosols were determined with ICP-MS. The results showed that Ca, Mg, Sr, Mn, Co and Fe were mainly associated with coarse particles (>2.1 μm), primarily from natural sources. In contrast, the elements Zn, Ba, Cd, V, Pb and Cu dominated in fine aerosol particles (<2.1 μm), implying that the anthropogenic origin is the dominant source. Results of the factor analysis on elements with high EF_Crust values (>10) showed that emissions from waste combustion in incinerators, oil combustion (involving waste oil burning and oil combustion in both incinerators and electricity generation plants), as well as coal combustion in electricity generation plants were major contributors of anthropogenic metals in the ambient atmosphere in Kanazawa. Quantitatively estimated sum of mean concentrations of anthropogenic elements from the key sources were in good agreement with the observed values. Results of this study elucidate the need for making pollution control strategy in this area.     

Polycyclic aromatic hydrocarbons in suspended particulate matter and sediments from the Pearl River Estuary and adjacent coastal areas, China

The spatial distribution, composition, and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments and suspended particulate matter (SPM) from the Pearl River Estuary and adjacent coastal areas were examined. Total PAH concentrations varied from 189 to 637 ng/g in sediments and 422 to 1,850 ng/g in SPM. PAHs were dominated by 5,6-ring compounds in sediments and by 2,3-ring compounds in SPM samples. Assessment of PAH sources suggested that biomass and coal combustion is the major PAH source to the outer part of the estuary sediments and that petroleum combustion is the major PAH source to the inner part of estuary sediments. As for SPM samples, PAH isomer pair ratios indicated multiple (petroleum, petroleum combustion, and biomass and coal combustion) PAH sources, and significant temporal variations could exist for the sources of water column PAHs in the study area. The distribution of perylene in SPM samples indicated that the river was the dominant source of perylene in SPM and that perylene could be taken as an index to assess the contribution of river inflow to the total PAHs in SPM samples. The high concentration of perylene in the sediment was indicative of an in situ biogenic origin.     

Distribution and sources of polycyclic aromatic hydrocarbons in the middle and lower reaches of the Yellow River, China

In this study, concentrations, distribution between different phases, transition along the Middle and Lower reaches of the Yellow River and possible sources of PAHs were assessed. Results demonstrated that the relative proportions of 15 PAHs in all stations of the main River were similar, with concentrations of benzo[a]pyrene all above drinking water standards in most of the stations sampled. PAHs concentrations in tributaries were higher than those in the corresponding sites in the main River. PAHs concentrations of suspended particles were mainly correlated with contents of total organic carbon. However, PAHs concentrations in sediments were mainly correlated to the volume of particles with size smaller than 0.01 mm. The distribution of PAHs in all media sampled indicated that sediments could act as a sink/source for PAHs in different sections and source analysis revealed that PAHs mainly originated from coal burning, although in some tributaries PAH inputs could come from combustion of petroleum.     

Active methods of mercury removal from flue gases

Due to its adverse impact on health, as well as its global distribution, long atmospheric lifetime and propensity for deposition in the aquatic environment and in living tissue, the US Environmental Protection Agency (US EPA) has classified mercury and its compounds as a severe air quality threat. Such widespread presence of mercury in the environment originates from both natural and anthropogenic sources. Global anthropogenic emission of mercury is evaluated at 2000 Mg year⁻¹. According to the National Centre for Emissions Management (Pol. KOBiZE) report for 2014, Polish annual mercury emissions amount to approximately 10 Mg. Over 90% of mercury emissions in Poland originate from combustion of coal.

The purpose of this paper was to understand mercury behaviour during sub-bituminous coal and lignite combustion for flue gas purification in terms of reduction of emissions by active methods. The average mercury content in Polish sub-bituminous coal and lignite was 103.7 and 443.5 μg kg⁻¹. The concentration of mercury in flue gases emitted into the atmosphere was 5.3 μg m⁻³ for sub-bituminous coal and 17.5 μg m⁻³ for lignite. The study analysed six low-cost sorbents with the average achieved efficiency of mercury removal from 30.6 to 92.9% for sub-bituminous coal and 22.8 to 80.3% for lignite combustion. Also, the effect of coke dust grain size was examined for mercury sorptive properties. The fine fraction of coke dust (CD) adsorbed within 243–277 μg Hg kg⁻¹, while the largest fraction at only 95 μg Hg kg⁻¹. The CD fraction < 0.063 mm removed almost 92% of mercury during coal combustion, so the concentration of mercury in flue gas decreased from 5.3 to 0.4 μg Hg m⁻³. The same fraction of CD had removed 93% of mercury from lignite flue gas by reducing the concentration of mercury in the flow from 17.6 to 1.2 μg Hg m⁻³. The publication also presents the impact of photochemical oxidation of mercury on the effectiveness of Hg vapour removal during combustion of lignite. After physical oxidation of Hg in the flue gas, its effectiveness has increased twofold.

     

Size distribution and anthropogenic sources apportionment of airborne trace metals in Kanazawa,Japan

Aerosol samples were collected from Kanazawa, Japan to examine the size distribution of 12 elements and to identify the major sources of anthropogenic elements. Key emission sources were identified and, concentrations contributed from individual sources were estimated as well. Concentrations of elements V, Ca, Cd, Fe, Ba, Mg, Mn, Pb, Sr, Zn, Co and Cu in aerosols were determined with ICP-MS. The results showed that Ca, Mg, Sr, Mn, Co and Fe were mainly associated with coarse particles (>2.1 μm), primarily from natural sources. In contrast, the elements Zn, Ba, Cd, V, Pb and Cu dominated in fine aerosol particles (<2.1 μm), implying that the anthropogenic origin is the dominant source. Results of the factor analysis on elements with high EF_Crust values (>10) showed that emissions from waste combustion in incinerators, oil combustion (involving waste oil burning and oil combustion in both incinerators and electricity generation plants), as well as coal combustion in electricity generation plants were major contributors of anthropogenic metals in the ambient atmosphere in Kanazawa. Quantitatively estimated sum of mean concentrations of anthropogenic elements from the key sources were in good agreement with the observed values. Results of this study elucidate the need for making pollution control strategy in this area.     

Grain size partitioning of platinum-group elements in road-deposited sediments: implications for anthropogenic flux estimates from autocatalysts

Twelve road-deposited sediment samples were analyzed for platinum-group elements (PGEs) and Pb in the <63 microm fraction of an urban watershed in Hawaii. Three samples were further fractionated into five size classes, from 63-125 microm to 1000-2000 microm, and these were analyzed for PGEs and Pb. Concentrations in the <63 microm fraction reached 174 microg/kg (Pt), 101 microg/kg (Pd), 16 microg/kg (Rh), and 1.3 microg/kg (Ir). Enrichment ratios followed the sequence Rh>Pt=Pd>Ir. Iridium was geogenic in origin, while the remaining PGEs indicated significant anthropogenic contamination. Palladium, Pt and Rh concentrations and enrichment signals were consistent with PGE bivariate ratios and PGE partitioning in three-way catalysts. Size partitioning indicated that the <63 microm fraction had the lowest PGE concentrations and mass loading percentages. These data suggest that autocatalyst PGE flux estimates into the environment will be significantly underestimated if only a fine grain size fraction is analyzed.     

Survey of heavy metal pollution and assessment of agricultural soil in Yangzhong district, Jiangsu Province, China

We investigated concentrations of Hg, Cd, Pb, Zn, Cu, As, Ni, and Cr in samples of soil, cereal, and vegetables from Yangzhong district, China. Compared to subsoils, the sampled topsoils are enriched in Hg, Cd, Cu, Pb, Zn, and As. High levels of Cd and Hg are observed in most agricultural soils. Concentrations of Cr and Ni show little spatial variation, and high Cu, Pb, and Zn contents correspond well to areas of urban development. High As contents are primarily recorded at the two ends of the sampled alluvion. The contents of Cd, Hg, and total organic carbon (TOC) increase gradually to maximum values in the upper parts of soil profiles, while Cr and Ni occur in low concentrations within sampled profiles. As, Pb, Cu, and Zn show patterns of slight enrichment within the surface layer. Compared to data obtained in 1990, Cd and Hg show increased concentrations in 2005; this is attributed to the long-term use of agrochemicals. Cr and Ni contents remained steady over this interval because they are derived from the weathering of parent material and subsequent pedogenesis. The measured As, Cu, Pb, and Zn contents show slight increases over time due to atmospheric deposition of material sourced from urban anthropogenic activity. Low concentrations of heavy metals are recorded in vegetables and cereals because the subalkaline environment of the soil limits their mobility. Although the heavy metal concentrations measured in this study do not pose a serious health risk, they do affect the quality of agricultural products.     

Spatial variability of arsenic and chromium in the soil water at a former wood preserving site

Contamination of industrial sites by wood preservatives such as chromated copper arsenate (CCA) may pose a serious threat to groundwater quality. The objective of this study was to characterise the spatial variability of As and Cr concentrations in the solid phase and in the soil water at a former wood impregnation plant and to reveal the fundamental transport processes. The soil was sampled down to a depth of 2m. The soil water was extracted in situ from the vadose zone over a period of 10 months at depths of 1 and 1.5m, using large horizontally installed suction tubes. Groundwater was sampled from a depth of 4.5m. Results showed that arsenic and chromium had accumulated in the upper region of the profile and exhibited a high spatial variability (As: 21-621 mg kg(-1); Cr: 74-2872 mg kg(-1)). Concentrations in the soil water were high (mean As 167 microg L(-1); Cr: 62 microg L(-1)) and also showed a distinct spatial variability, covering concentration ranges up to three orders of magnitude. The variability was caused by the severe water-repellency of the surface soil, induced by the concurrent application of creosote wood preservatives, which leads to strong preferential flow as evident from a dye experiment. In contrast to soil water concentrations, only low As concentrations (<12 microg L(-1)) were detected in the groundwater. High Cr concentrations in the groundwater (approx. 300 microg L(-1)), however, illustrated the pronounced mobility of chromium. Our study shows that at sites with a heterogeneous flow system in the vadose zone a disparity between flux-averaged and volume-averaged concentrations may occur, and sampling of soil water might not be adequate for assessing groundwater concentrations. In these cases long-term monitoring of the groundwater appears to be the best strategy for a groundwater risk assessment.     

Seasonal variability and source apportionment of metals in the atmospheric deposition in Belgrade

The primary objective of this study is to assess anthropogenic impacts on the environment by determination of element atmospheric depositions. Bulk depositions were collected monthly, from June 2002 to December 2006, at three urban locations in Belgrade. Concentrations of Al, V, Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb were analyzed by atomic absorption spectrometry and the current deposition fluxes of atmospheric metals were established. Fourier analysis was applied in order to investigate seasonal variation of the monthly data set. Nickel, V, Fe and Al showed pronounced seasonal dependence, while seasonal variation of the other elements was not evident. The enrichment factors of Pb, Zn, Cd and Cu were obviously above those who could have been caused by natural processes, indicating a mainly anthropogenic origin. Nickel was intermediately enriched suggesting participation of both natural and anthropogenic sources. The multivariate receptor model, Unmix, was used to analyze a 5-yr element atmospheric depositions data set. Three main source profiles (mixed road dust, oil combustion and metal processing) were identified and the overall average percentage source contributions determined.     

Formation of fine particles enriched by V and Ni from heavy oil combustion: Anthropogenic sources and drop-tube furnace experiments

The present study attempts to investigate the emission characteristics of fine particles with special emphasis on nickel and vanadium metal elements emitted from the heavy oil combustion in industrial boilers and power plant, which are typical anthropogenic sources in Korea. A series of combustion experiments were performed to investigate the emission characteristics of particles in the size range of submicron by means of drop-tube furnace with three major domestic heavy oils. Cascade impactors were utilized to determine the size distribution of particulates as well as to analyze the partitioning enrichment of vanadium and nickel in various size ranges. Experimental results were compared with field data of particle size distribution and metal partitioning at commercial utility boilers with heavy oil combustion. Such data were interpreted by chemical equilibrium and particle growth mechanism by means of computational models. In general, fine particles were the major portion of PM₁₀ emitted from the heavy oil combustion, with significant fraction of ultra-fine particles. The formation of ultra-fine particles through nucleation/condensation/coagulation from heavy oil combustion was confirmed by field and experimental data. Vanadium and nickel were more enriched in fine particles, particularly in ultra-fine particles. The conventional air pollution devices showed inefficient capability to remove ultra-fine particles enriched with hazardous transition metal elements such as vanadium and nickel.     

The anthropogenic atmospheric elements fraction: A new interpretation of elemental deposits on tree barks

The superficial deposit on the bark surface of several trees (mainly Fraxinus excelsior L.) was sampled in the experimental station of the university campus in Grenoble (France). Its composition was studied by scanning electron microscopy–energy dispersive X-ray emission (SEM–EDX) and, after digestion, by inductively coupled plasma-mass spectrometry (ICP-MS). The deposit was composed of 81.3% ± 7.4 organic matter, 9.4% ± 4.9 of geogenic minerals issued from the atmosphere (atmospheric geogenic fraction: AGF) and 9.3% ± 2.7 of a mixture of elements which was called anthropogenic atmospheric elements fraction (AAEF). The SEM–EDX analysis showed the presence of particles of geogenic compounds such as different types of silicates, phosphates, carbonates, sulphates, oxides and also particles of metals such as iron or of alloys of Fe–Zn, Fe–Ni, Ni–Cr and Ca sulphates or phosphates. Typical spheres of “fly ashes” composed of pure iron or Al-silicates were detected. Using the SEM–EDX analysis of the deposit and the average local soil composition, an empiric formula for the AGF (without polluting elements) was chosen, which presented a clear analogy with the global formula of the upper continental crust. In the same way, a formula for the pure organic matter fraction was chosen. Withdrawing the elements corresponding to these two fractions allows a tentative estimation of the content of the AAEF which was supposed to better represent the elemental anthropogenic contamination issued from the atmosphere. In the station, most of Sb, Cd, Sn, Pb, Cu, V and Zn were found in the AAEF. This AAEF composition was compared to that of the deposit in a highway tunnel where Pb and Cu were at a very high level. The meaning and the limits of the AAEF concept were critically discussed.     

Anthropogenic platinum fluxes: Quantification of sources and sinks, and outlook

Employing the data available to date, anthropogenic Pt fluxes are calculated for Germany with special emphasis on the Pt emitted by cars equipped with catalytic converters. Pt fluxes are quantified using five different methods (street deposition, automobile emission rate, sewage sludges, atmospheric load, industrial consumption). During the first and the second methods, approx. 100 kg of emitted Pt are seen to result for both for the mid 1990’s. Up to the year 2018, a total of 2100 kg of Pt will be emitted by cars equipped with catalytic converters. The diffuse atmospheric Pt deposition amounts to 0.73 – 4.4 μg/m²y or 260 kg Pt/year. Industrial sources emitting Pt into the atmosphere are likely but difficult to quantify. The enrichment of Pt in soils during agriculture fertilization with sewage sludges and during diffuse atmospheric deposition result in a level of 46 – 460 ng/kg up to the year 2018. Although this is slightly below the geogenic background, a comparison with the pollution history of Pb implies that forthcoming environmental Pt enrichment should not be neglected.     

Assessment and distribution of antimony in soils around three coal mines, Anhui, China

Thirty-three soil samples were collected from the Luling, Liuer, and Zhangji coal mines in the Huaibei and Huainan areas of Anhui Province, China. The samples were analyzed for antimony (Sb) by inductively coupled plasma-optical emission spectrometry (ICP-OES) method. The average Sb content in the 33 samples was 4 mg kg(-1), which is lower than in coals from this region (6.2 mg kg(-1)). More than 75% of the soils sampled showed a significant degree of Sb pollution (enrichment factors [EFs] 5-20). The soils collected near the gob pile and coal preparation plant were higher in Sb content than those collected from residential areas near the mines. The gob pile and tailings from the preparation plant were high in mineral matter content and high in Sb. They are the sources of Sb pollution in surface soils in the vicinity of coal mines. The spatial dispersion of Sb in surface soil in the mine region shows that Sb pollution could reach out as far as 350 m into the local environment conditions. Crops in rice paddies may adsorb some Sb and reduce the Sb content in soils from paddyfields. Vertical distribution of Sb in two soil profiles indicates that Sb is normally relatively immobile in soils.