Heavy metals and Pb isotopic composition of aerosols in urban and suburban areas of Hong Kong and Guangzhou,South China—Evidence of the long-range transport of air contaminants

Rapid urbanization and industrialization in South China has placed great strain on the environment and on human health. In the present study, the total suspended particulate matter (TSP) in the urban and suburban areas of Hong Kong and Guangzhou, the two largest urban centres in South China, was sampled from December 2003 to January 2005. The samples were analysed for the concentrations of major elements (Al, Fe, Mg and Mn) and trace metals (Cd, Cr, Cu, Pb, V and Zn), and for Pb isotopic composition. Elevated concentrations of metals, especially Cd, Pb, V and Zn, were observed in the urban and suburban areas of Guangzhou, showing significant atmospheric trace element pollution. Distinct seasonal patterns were observed in the heavy metal concentrations of aerosols in Hong Kong, with higher metal concentrations during the winter monsoon period, and lower concentrations during summertime. The seasonal variations in the metal concentrations of the aerosols in Guangzhou were less distinct, suggesting the dominance of local sources of pollution around the city. The Pb isotopic composition in the aerosols of Hong Kong had higher ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios in winter, showing the influence of Pb from the northern inland areas of China and the Pearl River Delta (PRD) region, and lower ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios in summer, indicating the influence of Pb from the South Asian region and from marine sources. The back trajectory analysis showed that the enrichment of heavy metals in Hong Kong and Guangzhou was closely associated with the air mass from the north and northeast that originated from northern China, reflecting the long-range transport of heavy metal contaminants from the northern inland areas of China to the South China coast.     

雷州半岛土壤重金属分布特征及其污染评价

在雷州半岛采集了106个土壤表层样品,分析了其中8种重金属元素(Cu、Pb、Zn、Cr、Ni、Cd、Hg和As)的全量.结果表明,雷州半岛土壤重金属污染由高到低排序为Ni＞Cr＞Hg＞Cu＞Zn＞Cd＞As＞Pb,Zn、Cd、As和Pb质量浓度均没有超标,Hg和Cu质量浓度超标率亦不高,但Ni和Cr平均质量浓度达49.81、87.13 mg/kg,高于国内外其他对照区域,超标率分别为25.47%和24.53%;重金属元素在雷州半岛各土壤利用类型中分布规律不明显,按4种主要土壤利用类型受重金属污染程度大小排序为甘蔗地＞果园土＞水田＞菜地;雷州半岛土壤综合污染指数总平均为0.970,土壤总体上尚清洁,重金属污染处于警戒水平;雷州半岛各区域中,徐闻、雷州两地土壤重金属质量浓度明显高于其他地区,其主要原因是徐闻、雷州两地成土母质主要为玄武岩,造成土壤Cr、Ni及其他重金属背景值较高.     

The study of metal contamination in urban soils of Hong Kong using a GIS-based approach

The study of regional variations and the anthropogenic contamination by metals of soils is very important for environmental planning and monitoring in urban areas. An extensive survey was conducted in the highly urbanized Kowloon area (46.9 km(2)) of Hong Kong, using a systematic sampling strategy with a sampling density of 3-5 composite soil samples (0-15 cm) per km(2). Geochemical maps of 'total' metals (Cd, Cr, Cu, Ni, Pb and Zn) from strong acid extraction in the surface soils were produced based on geographical information system (GIS) technology. A significant spatial relationship was found for Ni, Cu, Pb and Zn in the soils using a GIS-based analysis, suggesting that these metal contaminants in the soils of the Kowloon area had common sources. Several hot-spot areas of metal contamination were identified from the composite metal geochemical map, mainly in the old industrial and residential areas. A further GIS analysis revealed that road junctions, major roads and industrial buildings were possible sources of heavy metals in the urban soils. The Pb isotope composition of the contaminated soils showed clear anthropogenic origins.     

Distribution, availability, and sources of trace metals in different particle size fractions of urban soils in Hong Kong: Implications for assessing the risk to human health

The concentration and loading distribution of trace metals (Cu, Zn, Pb, Co, Ni, Cr, and Mn) and major elements (Al, Ca, Fe, and Mg) in different particle size fractions (2000-280, 280-100, 100-50, 50-10, 10-2, and <2 μm) of surface soils from highly urbanized areas in Hong Kong were studied. The enrichment of Pb, Cu, and Zn in the urban soils was strongly influenced by anthropogenic activities, and Pb accumulated in fine particles was mainly derived from past vehicular emissions as shown by Pb isotopic signatures. Trace metals primarily accumulated in clay, fine silt, and very fine sand fractions, and might pose potential health risks via the inhalation of resuspended soil particles in the air (PM₁₀ or PM_2.5), and ingestion of adhered soils through the hand-to-mouth pathway. The mobility, bioavailability, and human bioaccessibility of Pb and Zn in bulk soils correlated significantly with metal concentrations in fine silt and/or very fine sand fractions.     

Occurrence,speciation, and risks of trace metals in soils of greenhouse vegetable production from the vicinity of industrial areas in the Yangtze River Delta,China

The effect of industrial activities on trace metals in farmland of rapidly industrializing regions in developing countries has increasingly been a concern to the public. Here, soils were collected from 13 greenhouse vegetable production (GVP) farms or bases near industrial areas in the Yangtze River Delta of China to investigate the occurrence, speciation, and risks of Cr, Cu, Zn, Cd, Ni, and Pb in GVP soil. The results revealed that the main metal elements causing GVP soil pollution were Cd, Zn, Ni, and Cu, of which contamination levels were generally unpolluted to moderately polluted. Zinc pollution was mainly attributed to heavy fertilization, while Cd, Ni, and Cu pollution may be greatly ascribed to industrial effluents and coal combustion. Metal speciation studies showed that most of Cr, Ni, Cu, and Zn was present in residual fraction while more than half of Cd and Pb was present in non-residual fractions. Additionally, pollution of Cd, Cu, Ni, and Zn in GVP soil increased their corresponding mobile fractions. Risk assessment using potential ecological risk index and risk assessment code showed that Cd was the major risk contributor. Specifically, Cd generally posed moderate or considerable ecological risk as well as displayed medium or high mobility risk in GVP soil. Thus, great attention should be paid to the contribution of both industrial discharges and intensive farming to soil pollution by trace metals, especially Cd, because of its high mobility risk.

     

Assessing heavy metal pollution in the surface soils of a region that had undergone three decades of intense industrialization and urbanization

Heavy metals in the surface soils from lands of six different use types in one of the world’s most densely populated regions, which is also a major global manufacturing base, were analyzed to assess the impact of urbanization and industrialization on soil pollution. A total of 227 surface soil samples were collected and analyzed for major heavy metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn) by using microwave-assisted acid digestion and inductively coupled plasma–mass spectrometry (ICP-MS). Multivariate analysis combined with enrichment factors showed that surface soils from the region (>7.2?×?10⁴ km²) had mean Cd, Cu, Zn, and As concentrations that were over two times higher than the background values, with Cd, Cu, and Zn clearly contributed by anthropogenic sources. Soil pollution by Pb was more widespread than the other heavy metals, which was contributed mostly by anthropogenic sources. The results also indicate that Mn, Co, Fe, Cr, and Ni in the surface soils were primarily derived from lithogenic sources, while Hg and As contents in the surface soils were controlled by both natural and anthropogenic sources. The pollution level and potential ecological risk of the surface soils both decreased in the order of: urban areas?>?waste disposal/treatment sites?～?industrial areas?>?agricultural lands?～?forest lands?>?water source protection areas. These results indicate the significant need for the development of pollution prevention and reduction strategies to reduce heavy metal pollution for regions undergoing fast industrialization and urbanization.     

Trace element concentrations in soils along urbanization gradients in the city of Wien, Austria

Urban soil is an important component of urban ecosystems. This study focuses on heavy metal contamination in soils of Wien (Austria) and results are compared to those for a few large European cities. We analysed the elemental contents of 96 samples of topsoil from urban, suburban and rural areas in Wien along a dynamic (floodplain forest) and a stable (oak–hornbeam forest) urbanization gradient. The following elements were quantified using ICP-OES technique: Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Pb, P, S and Zn. For heavy metals PI (pollution index) values were used to assess the level of pollution. The PI values indicated high level of pollution by Pb in the suburban and rural area of stable gradient and in the urban area of dynamic gradient; moderate level of pollution was indicated for Cd in the urban area of stable gradient. The level of pollution was moderate for Co in the suburban and rural area of the stable gradient, and for Cu in suburban area of stable gradient, and urban area of dynamic gradient. The pollution level of Zn was moderate in all areas. Urban soils, especially in urban parks and green areas may have a direct influence on human health. Thus, the elemental analysis of soil samples is one of the best ways to study the effects of urbanization. Our results indicated that the heavy metal contamination was higher in Wien than in a few large European cities.     

Assessing heavy metal sources in agricultural soils of an European Mediterranean area by multivariate analysis

According to the European Thematic Strategy for Soil Protection, the characterization of the content and source of heavy metals in soils are necessary to establish quality standards on a regional level that allow the detection of sampling sites affected by pollution. In relation to this, the surface horizons of 54 agricultural soils under vegetable crops in the Alicante province (Spain), a representative area of the European Mediterranean region, were sampled to determine the content of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn. Analytical determinations were performed by atomic absorption spectroscopy after microwave sample digestion in acid solution. Results indicated that heavy metal levels were similar to those reported by authors working on agricultural soils from other parts of the Mediterranean region, with the exception of Cu and Pb in some samples. Multivariate analysis (principal component analysis and cluster analysis) was performed to identify a common source for heavy metals. Moreover, soil properties were determined in order to characterize agricultural soils and to analyze relationships between heavy metal contents and soil properties. The content of Co, Cr, Fe, Mn, Ni and Zn were associated with parent rocks and corresponded to the first principal component called the lithogenic component. A significant correlation was found between lithogenic metals and some soil properties such as soil organic matter, clay content, and carbonates, indicating an important interaction among them. On the other hand, elements such as Cd, Cu and Pb were related to anthropic activities and comprised the second (Cu and Pb) and third principal components (Cd), designated the anthropogenic components. Generally, Cd, Cu and Pb showed a lower correlation with soil properties due to the fact that they remain in available forms in these agricultural soils. Taking into account these results and other achieved in other parts of the European Mediterranean region, it can be concluded that soil quality standards are highly needed to declare soils affected by human induced pollution. This is particularly relevant for anthropogenic metals (Cd, Cu and Pb, and in some areas also Zn). Further research in other agricultural areas of the region would improve the basis for proposing such soil quality standards.     

Risk to breeding success of waterbirds by contaminants in Hong Kong: evidence from trace elements in eggs

Concentrations of 17 trace elements (As, Se, Rb, Sr, Ag, Sb, Cs, Tl, Pb, V, Cr, Mn, Co, Cu, Zn, Cd, and Hg) were determined in eggs of little egrets (Egretta garzetta), black-crowned night herons (Nycticorax nycticorax) and bridled terns (Sterna anaethetus) from northwestern and northeastern coastal areas of Hong Kong. Results indicated significant differences among the three species. Eggs of little egrets and black-crowned night herons appeared to be good bioindicators for monitoring selected elements (As, Pb, Zn Cr, Cu, and V) due to consistent correlations between metal concentrations in eggs and those in coastal marine sediments. Based on limited toxicological information, the predicted no effect concentrations (PNECs) of Hg and Se in the bird eggs were estimated as 0.5 to 1.8 and 0.90 to 1.45 mug g(-1), dry wt., respectively. Hazard quotients (HQs) indicated that Hg and Se might pose some risk to certain waterbirds in Hong Kong.     

Distribution,origin, and transformation of metal and metalloid pollution in vegetable fields,irrigation water,and aerosols near a Pb-Zn mine

Pollution of arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), and zinc (Zn) in vegetable fields was investigated near a Pb-Zn mine that has been exploited for over 50 years without a tailing reservoir. A total of 205 water, soil, and aerosol samples were taken and quantified by combined chemical, spectrometric, and mineral analytical methods. The pollution origins were identified by Pb isotopes and the pathways of transformation and transport of the elements and minerals was studied. The data showed that the vegetable fields were seriously polluted by As, Cd, and Pb. Some concentrations in the samples were beyond the regulatory levels and not suitable for agricultural activities. This study revealed that: (1) particulate matter is a major pollution source and an important carrier of mineral particles and pollutants; (2) the elements from the polluted water and soils were strongly correlated with each other; (3) Pb isotope ratios from the samples show that Pb minerals were the major pollution sources in the nearby vegetable fields, and the aerosols were the main carrier of mining pollution; (4) the alkaline, rich-carbonate, and wet conditions in this area promoted the weathering and transformation of galena into the secondary minerals, anglesite and cerussite, which are significant evidence of such processes; (5) the soil and the aerosols are a recycled secondary pollution source for each other when being re-suspended with wind. Highlights ? Mining activities generated heavy metal pollution in fields around a Pb-Zn mine ? The elements from water and soils are strongly correlated ? Anglesite and cerussite are evidence of galena transformation into secondary minerals ? Particulate matter is an important transport carrier of pollution     

Assessment of heavy metal pollution in surface soils of urban parks in Beijing, China

Assessing the concentration of potentially harmful heavy metals in the soil of urban parks is imperative in order to evaluate the potential risks to residents and tourists. To date, little research on soil pollution in China's urban parks has been conducted. To identify the concentrations and sources of heavy metals, and to assess the soil environmental quality, samples were collected from 30 urban parks located in the city of Beijing. Subsequently, the concentrations of Cu, Ni, Pb and Zn in the samples were analyzed. The investigation revealed that the accumulations of Cu and Pb were readily apparent in the soils. The integrated pollution index (IPI) of these four metals ranged from 0.97 to 9.21, with the highest IPI in the densely populated historic center district (HCD). Using multivariate statistic approaches (principal components analysis and hierarchical cluster analysis), two factors controlling the heavy metal variability were obtained, which accounted for nearly 80% of the total variance. Nickel and Zn levels were controlled by parent material in the soils, whereas Cu, Pb and, in part, Zn were accounted for mainly by anthropogenic activities. The findings presented here indicate that the location and the age of the park are important factors in determining the extent of heavy metal, particularly Cu and Pb, pollution. In addition, the accumulation of Zn did not appear to reach pollution levels, and no obvious pollution by Ni was observed in the soils of the parks in Beijing.     

Trace metal element pollution of soil and water resources caused by small-scale metallic ore mining activities: a case study from a sphalerite mine in North China

Trace metal element contamination in mining areas is always a huge environmental challenge for the global mining industry. In this study, an abandoned sphalerite mine near the Yanshan Mountains was selected as subject to evaluate the soil and water contamination caused by small-scale mining. The results show that (1) Pearson correlation matrix and principal component analysis (PCA) results reveal that Zn, Cu, Cd, and Pb were greatly affected by the operation of mines, especially mineral tailings. The contents of trace metal elements decrease with the increase of the distance from the mining area. Zinc, Pb, and Cd were discovered in almost all soil samples, and Zn accounted for about 80% of pollution of the topsoil. (2) The trace element pollution levels in the topsoil of the three villages were ranked as follows: Cd?>?Cu?>?Pb~Zn. The potential ecological risk of farmland around the mine ranges from lower to higher, with Cd being the most harmful. (3) Human health risk assessment results show that trace elements in the mining area pose obvious non-carcinogenic health risks to children while the risks to adults are not equally obvious. The carcinogenic risk of Cd and Cr is within a safe range and does not pose an obvious cancer risk to the population.

     

Metal concentrations in edible mushrooms following municipal sludge application on forest land

In the context of biosolids utilisation in forestry, effects of sludge application on mushroom metal concentration were studied in six sites of maritime pine forests in the South-West of France. Municipal sludge were applied at a rate of 6 T dry matter per hectare. Edible mushrooms were collected two years after sludge application. As, Cd, Cu, Hg, Pb, Se and Zn concentrations were determined. Results showed a high variability for trace element concentrations in mushrooms collected from control areas. No significant correlation was found between soil parameters (pH and trace elements concentrations) and mushroom trace element concentrations. Even if the concentration of trace metals increased in the soils, sludge application did not affect As, Cu, Se and Zn concentrations in carpophores but slightly increased Cd, Pb and Hg concentrations on some sites. This effect is dependent on sludge type and sites.     

Effects of incubation on solubility and mobility of trace metals in two contaminated soils

Much research has focused on changes in solubility and mobility of trace metals in soils under incubation. In this experiment, changes in solubility and mobility of trace metals (Pb, Cu and As) and Fe in two contaminated soils from Tampa, Florida and Montreal, Canada were examined. Soils of 30 g were packed in columns and were incubated for 3-80 days under water-flooding incubation. Following incubation, metal concentrations in pore water (water soluble) and in 0.01 M CaCl2 leachates (exchangeable+water soluble) were determined. While both soils were contaminated with Pb (1600-2500 mg kg(-1)), Tampa soil was also contaminated with As (230 mg kg(-1)). Contrast to the low pH (3.8) of Tampa soil, Montreal soil had an alkaline pH of 7.7 and high Ca of 1.6%. Concentrations of Fe(II) increased with incubation time in the Tampa soil mainly due to reductive Fe dissolution, but decreased in the Montreal soil possibly due to formation of FeCO3. The inverse relationship between concentrations of Pb and Fe(II) in pore water coupled with the fact that Fe(II) concentrations were much greater than those of Pb in pore water may suggest the importance of Fe(II) in controlling Pb solubility in soils. However, changes in concentrations of Fe(II), Pb, Cu and As in pore water with incubation time were similar to those in leachate, i.e. water soluble metals were positively related to exchangeable metals in the two contaminated soils. This research suggests the importance of Fe in controlling metal solubility and mobility in soils under water-flooded incubation.     

Risk assessment of heavy metal pollution for detritivores in floodplain soils in the Biesbosch, The Netherlands, taking bioavailability into account

Floodplains of the European rivers Rhine and Meuse are heavily polluted. We investigated the risk of heavy metal pollution (Cd, Cu, Pb, Zn) for detritivores living in a floodplain area, the Biesbosch, the Netherlands, affected by these rivers. Total soil, pore water and 0.01 M CaCl(2) extractable concentrations and concentrations in plant leaves, earthworms, isopods and millipedes were measured in two sites and compared with literature data to assess possible risks. Based on total metal concentrations in soil, serious effects on detritivores were expected. However, 0.01 M CaCl(2) extractable, pore water and plant leaf concentrations were similar to metal concentrations found in unpolluted areas. Concentrations of Cu and Cd in earthworms and Cu in millipedes were higher in the Biesbosch than in animals from reference areas. All other measured concentrations of heavy metals in earthworms, isopods and millipedes were similar to the ones found in reference areas. Despite high total soil concentrations, effects of Zn, Cu, Pb and Cd pollution on isopods are therefore not expected, while millipedes may only be affected by Cu. Since Cu and Cd levels in earthworms were increased compared to animals in unpolluted soils, this faunal group seems to be most at risk. Given the engineering role of earthworms in ecosystems, effects on the ecological functioning of floodplain soils therefore cannot be excluded.     

Landscape ecology of the Guanting Reservoir, Beijing, China: multivariate and geostatistical analyses of metals in soils

Surface soil samples were collected from 52 sites around Guanting Reservoir in Beijing, China, and contents of 'total' metals (Cu, Zn, Pb, Cd, As, Ni and Cr) were determined. The results indicate that the degree of heavy metal pollution in the soils declines in the order of Cd>Cr>Zn>As>Cu>Ni>Pb. Based on the results of a combination of multivariate statistics and geostatiscal analyses, it was concluded that land application of phosphate fertilizer, wastewater and sludge were the primary sources of Cd and Zn in soils. Whereas As, Cu, Cr and Ni in some soils were due to natural rock weathering. The sources of Pb in soils only partially originated from land application of phosphate fertilizer, but mainly from vehicle exhaust. The greatest concentrations of all metals, except for Pb, were found in Huailai County and the towns of Yanghedaqiao and Guanting.     

Trace metal distribution in sediments of the Pearl River Estuary and the surrounding coastal area, South China

Surface sediments and sediment cores collected at the Pearl River Estuary (PRE) and its surrounding coastal area were analysed for total metal concentrations, chemical partitioning, and Pb isotopic compositions. The distribution of Cu, Cr, Pb, and Zn demonstrated a typical diffusion pattern from the land to the direction of the sea. Two hotspots of trace metal contamination were located at the mixed zone between freshwater and marine waters. The enrichment of metals in the sediments could be attributed to the deposition of the dissolved and particulate trace metals in the water column at the estuarine area. The similar Pb isotopic signatures of the sediments at the PRE and its surrounding coastal area offered strong evidence that the PRE was a major source of trace metals to the adjacent coastal area. Slightly lower (206)Pb/(207)Pb ratios in the coastal sediments may indicate other inputs of Pb in addition to the PRE sources, including the inputs from Hong Kong and other parts of the region.     

Source identification and risk assessment of heavy metal contaminations in urban soils of Changsha,a mine-impacted city in Southern China

The urban soils suffered seriously from heavy metal pollutions with rapid industrialization and urbanization in China. In this study, 54 urban soil samples were collected from Changsha, a mine-impacted city located in Southern China. The concentrations of heavy metals (As, Cd, Co, Cu, Mn, Ni, Pb, and Zn) were determined by ICP-MS. The pollution sources of heavy metals were discriminated and identified by the combination of multivariate statistical and geostatistical methods. Four main sources were identified according to the results of hierarchical cluster analysis (HCA), principal component analysis (PCA), and spatial distribution patterns. Co and Mn were primarily derived from soil parent material. Cu, Pb, and Zn with significant positive relationships were associated with mining activities and traffic emissions. Cd and Ni might be affected by commercial activities and industrial discharges. As isolated into a single group was considered to have correlation with coal combustion and waste incineration. Risk assessment of heavy metals in urban soils indicated an overall moderate potential ecological risk in the urban region of Changsha.     

Modelling trace metal partitioning in forest floors of northern soils near metal smelters

Trace metal (TM) mobility and toxicity varies with changing soil conditions. Geochemical models can account for the influence of soil characteristics on TM behaviour. We tested the effectiveness of the Stockholm humic model (SHM), and the NICA-Donnan model (NDM) to estimate partitioning coefficients (logKd) in 26 forest floor horizons of podzolic soils enriched in trace metals from deposition by metal smelters. We wanted to know if a consistent approach could be applied to model metal partitioning in forest floors without optimizing each individual soil. When optimized, the SHM reproduced the partitioning of Cd, Cu and Zn but not Pb. It was necessary to revise the affinity constants for the NDM to simultaneously simulate the partitioning of the four metals. Revised affinity constants for the NDM model based on a fixed definition of soil organic carbon, i.e., a fixed ratio of fulvic and humic acids per unit carbon, reproduced metal partitioning more effectively in an independent data set of 16 soils than the use of generic affinity constants available for these models. From the perspective of the applicability of these models to risk assessment, this result suggests geochemical models using affinity constants that have been verified and/or modified against multiple soils from a region can provide good estimates of metal partitioning on a regional scale.     

Elevated levels of lead and other metals in roadside soil and grass and their use to monitor aerial metal depositions in Hong Kong

The Pb, Cu, Zn, Fe, Mn and Cd contents in roadside soils and grass from 36 sites on the Island of Hong Kong were determined by atomic absorption spectrometry. Results showed that both soil and grass contained elevated levels of the metals studied. Linear regression analysis between the logarithmic concentration of the metals in the samples and the logarithmic traffic volume of the sites revealed that, apart from Cd in soil, the two were strongly related (variance ratios' P values <0.001), thus indicating that the motor vehicle forms a major source of these metals in the roadside. The regional distribution of Pb and Cu in roadside soil and grass (presented in maps herein) shows high levels of contamination occurring mainly in the highly urbanised northern part of the Island where most of the traffic is concentrated. Apparently, both soil and grass could be utilised to reflect the extent of aerial deposition of metals in the roadside.