Speciation of metals in contaminated sediments from Oskarshamn Harbor,Oskarshamn, Sweden

Bottom sediments in coastal regions have been considered the ultimate sink for a number of contaminants, e.g., toxic metals. In this current study, speciation of metals in contaminated sediments of Oskarshamn harbor in the southeast of Sweden was performed in order to evaluate metal contents and their potential mobility and bioavailability. Sediment speciation was carried out by the sequential extraction BCR procedure for As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn and the exchangeable (F1), reducible (F2), oxidizable (F3), and residual (R) fractions were determined. The results have shown that Zn and Cd were highly associated with the exchangeable fraction (F1) with 42–58 % and 43–46 %, respectively, of their total concentrations in the mobile phase. The assessment of sediment contamination on the basis of quality guidelines established by the Swedish Environmental Protection Agency (SEPA) and the Italian Ministry of Environment (Venice protocol for dredged sediments) has shown that sediments from Oskarshamn harbor are highly contaminated with toxic metals, especially Cu, Cd, Pb, Hg, As, and Zn posing potential ecological risks. Therefore, it is of crucial importance the implementation of adequate strategies to tackle contaminated sediments in coastal regions all over the world.     

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.     

Health risk assessment of heavy metals in soil-plant system amended with biogas slurry in Taihu basin,China

Biogas slurry is a product of anaerobic digestion of manure that has been widely used as a soil fertilizer. Although the use for soil fertilizer is a cost-effective solution, it has been found that repeated use of biogas slurry that contains high heavy metal contents can cause pollution to the soil-plant system and risk to human health. The objective of this study was to investigate effects of biogas slurry on the soil-plant system and the human health. We analyzed the heavy metal concentrations (including As, Pb, Cu, Zn, Cr and Cd) in 106 soil samples and 58 plant samples in a farmland amended with biogas slurry in Taihu basin, China. Based on the test results, we assessed the potential human health risk when biogas slurry containing heavy metals was used as a soil fertilizer. The test results indicated that the Cd and Pb concentrations in soils exceeded the contamination limits and Cd exhibited the highest soil-to-root migration potential. Among the 11 plants analyzed, Kalimeris indica had the highest heavy metal absorption capacity. The leafy vegetables showed higher uptake of heavy metals than non-leafy vegetables. The non-carcinogenic risks mainly resulted from As, Pb, Cd, Cu and Zn through plant ingestion exposure. The integrated carcinogenic risks were associated with Cr, As and Cd in which Cr showed the highest risk while Cd showed the lowest risk. Among all the heavy metals analyzed, As and Cd appeared to have a lifetime health threat, which thus should be attenuated during production of biogas slurry to mitigate the heavy metal contamination.     

Heavy metal (Cu, Zn, Cd and Pb) contamination of vegetables in urban India: a case study in Varanasi

The contributions of heavy metals in selected vegetables through atmospheric deposition were quantified in an urban area of India. Deposition rate of Zn was recorded maximum followed by Cu, Cd and Pb. The concentrations of Zn and Cu were highest in Brassica oleracea, Cd in Abelmoschus esculentus and B. oleracea, while Pb was highest in Beta vulgaris. Heavy metal pollution index showed that B. oleracea was maximally contaminated with heavy metals followed by A. esculentus and then B. vulgaris. The results of washing showed that atmospheric deposition has contributed to the increased levels of heavy metals in vegetables. Both Cu and Cd posed health risk to local population via test vegetables consumption, whereas Pb posed the same only through B. oleracea. The study concludes that atmospheric depositions can elevate the levels of heavy metals in vegetables during marketing having potential health hazards to consumers.     

Concentration and health risk evaluation of heavy metals in market-sold vegetables and fishes based on questionnaires in Beijing,China

Concentrations of heavy metals (As, Cd, Pb, Cu, Ni, Fe, Mn, and Zn) in market vegetables and fishes in Beijing, China, are investigated, and their health risk to local consumers is evaluated by calculating the target hazard quotient (THQ). The heavy metal concentrations in vegetables and fishes ranged from not detectable (ND) to 0.21 mg/kg fresh weight (f.w.) (As), ND to 0.10 mg/kg f.w. (Cd), and n.d to 0.57 mg/kg f.w. (Pb), with average concentrations of 0.17, 0.04, and 0.24 mg/kg f.w., respectively. The measured concentrations of As, Cd, Pb, Cu, Ni, Fe, Mn, and Zn are generally lower than the safety limits given by the Chinese regulation safety and quality standards of agriculture products (GB2762-2012). As, Cd, and Pb contaminations are found in vegetables and fishes. The exceeding standard rates are 19 % for As, 3 % for Cd, and 25 % for Pb. Pb contaminations are found quite focused on the fish samples from traditional agri-product markets. The paper further analyzed the health risk of heavy metals in vegetables and fishes respectively from supermarkets and traditional agri-product markets; the results showed that the fishes of traditional agri-product markets have higher health risk, while the supermarkets have vegetables of higher heavy metal risk, and the supervision should be strengthened in the fish supply channels in traditional agri-product markets.     

Heavy metals in coastal wetland sediments of the Pearl River Estuary, China

Sediment quality in coastal wetlands of the Pearl River Estuary was concerned since the wetlands were used for land reclamation, aquaculture and wildlife protection, and meanwhile served as one of the main ultimate sinks for large amount of heavy metals discharged from the rapidly developing Pearl River Delta. Total concentrations of heavy metal, such as Zn, Ni, Cr, Cu, Pb, and Cd, and their chemical speciation were investigated. Results showed that the sediments were significantly contaminated by Cd, Zn and Ni with concentration ranges of 2.79-4.65, 239.4-345.7 and 24.8-122.1mg/kg, respectively. A major portion (34.6-46.8%) of Pb, Cd, and Zn was strongly associated with exchangeable fractions, while Cu, Ni and Cr were predominantly associated with organic fractions, residual, and Fe-Mn oxide. Cd and Zn would be the main potential risk and the sediment quality is no longer meeting the demand of the current wetland utilization strategies.     

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.

     

Challenges with tracing the fate and speciation of mine-derived metals in turbid river systems: implications for bioavailability

The fast-flowing and highly turbid Lagaip River (0.5–10 g/L suspended solids) in the central highlands of Papua New Guinea receives mine-derived metal inputs in both dissolved and particulate forms. Nearest the mine, metal concentrations in suspended solids were 360, 9, 90, 740 and 1,300 mg/kg for As, Cd, Cu, Pb and Zn, while dissolved concentrations were 2.7, 0.6, 3.1, 0.1 and 25 μg/L, respectively. This creates a significant metal exposure source for organisms nearer the mine. However, because the Lagaip River is diluted by a large number of tributaries, the extent to which mine-derived metals may affect biota in the lower catchments is uncertain. To improve our understanding of the forms of potentially bioavailable metals entering the lower river system, we studied the partitioning and speciation of metals within the Lagaip River system. Dissolved and particulate metal concentrations decreased rapidly downstream of the mine due to dilution from tributaries. As a portion of the particulate metal concentrations, the more labile dilute acid-extractable forms typically comprised 10–30 % for As and Pb, 50–75 % for Cu and Zn, and 50–100 % for Cd. Only dissolved Cd, Cu and Zn remained elevated relative to the non-mine-impacted tributaries (<0.03, 0.5 and 0.3 μg/L), but the concentrations did not appreciably change with increasing dilution downriver. This indicated that release of Cd, Cu and Zn was likely occurring from the more labile metal phases of the mine-derived particulates. Chelex-labile metal analyses and speciation modelling indicated that dissolved copper and lead were largely non-labile and likely complexed by naturally occurring organic ligands, while dissolved cadmium and zinc were predominantly present in labile forms. The study confirmed that mine-derived particulates may represent a significant source of dissolved metals in the lower river system; however, comparison with water quality guidelines indicates the low concentrations would not adversely affect aquatic life.     

Speciation as a screening tool for the determination of heavy metal surface water pollution in the Guadiamar river basin

The Guadiamar river basin has traditionally received pollutants from two main sources: in its northern section of mining origin, and in its southern section (next to Do?ana National Park) from urban-industrial and agricultural sources. In April 1998, the spill of 6 million m3 of mining wastes (acidic waters and sludge) severely polluted the Guadiamar river basin with heavy metals, which caused serious damage to the local ecosystem. There is a direct association between the physicochemical speciation of an element and its toxicity, biological activity, bioavailability, solubility, etc. This work describes a distribution study of the metals Zn, Cd, Pb and Cu by speciation analysis of surface waters in eleven sampling points of the Guadiamar river basin. Four metal fractions were determined using anodic stripping voltammetry: labile metal forms, H+ exchangeable metal forms, strongly inert forms (associated with organic and inorganic matter in solution), and forms associated with suspended matter. Total concentrations in surface waters followed the trend Zn > Cu > Pb > Cd. The speciation study showed that Zn and Cd were present to a large extent in available forms (labile and H+ exchangeable), while Pb and Cu were found mostly in the less available forms (strongly inert). Moreover, the available forms were found in the northern section (mining pollution) and the strongly inert forms in the southern section (urban, industrial and agricultural pollution). These results can illustrate the potential value of speciation to discern between different sources of pollution.     

Metal accumulation in the greentail prawn, Metapenaeus bennettae, in Sydney and Port Hacking estuaries, Australia

Metal concentrations of the inshore greentail prawn, Metapenaeus bennettae, and surface sediments from locations within Sydney estuary and Port Hacking (Australia) were assessed for bioaccumulation and contamination. The current study aimed to assess metal concentrations in prawn tissue (tail muscle, exoskeleton, hepatopancreas and gills), relate whole body prawn tissue metal concentrations to sediment metal concentrations and animal size, as well as assess prawn consumption as a risk to human health. Metal concentrations were highest in sediment and prawns from contaminated locations (Iron Cove, Hen and Chicken Bay and Lane Cove) in Sydney estuary compared with the reference estuary (Port Hacking). Concentrations in sediments varied considerably between sites and between metals (As, Cd, Cr, Cu, Ni, Pb and Zn), and although concentrations exceeded Interim Sediment Quality Guideline-Low values, metals (As, Cd, Cr, Cu, Ni, Pb and Zn) were below Australian National Health and Medical Research Council human consumption guidelines in prawn tail muscle tissue. Metal concentrations in prawn tail muscle tissue were significantly different (p?≤?0.05) amongst locations for Pb, Zn and Cd, and metal concentrations were generally highest in gills tissue, followed by the hepatopancreas, exoskeleton and tail muscle. The exoskeleton contained the highest Sr concentration; the hepatopancreas contained the highest As, Cu and Mo concentrations; and the gills contained the highest Al, Cr, Fe and Pb concentrations. Concentrations of Pb, As and Sr were significantly different (p?≤?0.05) between size groups amongst locations.     

Heavy metal content and speciation in groundwater of the Guadiamar river basin

This work presents the conclusions of a speciation study concerning Zn, Cd, Pb and Cu in groundwater from ten wells in the alluvial aquifers of the Guadiamar river, affected by Aznalcollar mine tailing spill (April 1998). The sampling campaign took place in January 2000, almost two years after the mining accident. Four metal fractions were determined: labile metal forms, H+ exchangeable metal forms, strongly inert forms (associated with organic and inorganic matter in solution), and forms associated with suspended matter. Total metal concentration in groundwater followed the trend Cd < Pb < Cu < Zn. The speciation study showed that Zn and Cd were present to a great extent in available forms (labile and H+ exchangeable), while Pb and Cu were found mostly in the less available forms (strongly inert). These results can illustrate the potential value of the speciation tool for the follow-up of spill-induced pollution in the area.     

Accumulation of Al, Mn, Fe, Cu, Zn, Cd and Pb by the bryophyte Scapania undulata in three upland waters of different pH.

Measurements were made of the contents of Al, Mn, Fe, Cu, Zn, Cd and Pb in Scapania undulata in three streams (D2, D5, D11) in the English Lake District. The stream waters had average pH values of 5.35 (D2), 5.81 (D5) and 7.26 (D11), the main differences in other major chemical components being in Mg, Al, Ca and alkalinity. There was generally more metal accumulation in the older parts of the plants, but this was not significant in all cases. Extents of accumulation varied with stream pH and dissolved metal concentration. For Al, accumulation was greatest in streams D2 and D5. Mn accumulated most in D5 and Fe was without preference. Cu, Zn and Cd accumulated mostly in the plants in stream D11 and Pb accumulated more in D5 and D11. In terms of enrichment factors (amount of metal in the plants divided by stream water concentration) the sequence was Zn < Cd < Cu < Mn < Pb < Al < Fe. Laboratory experiments supported the findings of the field data, providing evidence that uptake increases with pH at constant total metal concentration. The results are interpreted qualitatively in terms of the chemical speciation of the metals in the stream water and competition between metal ions and protons at the plant-water interface. It is suggested that Al, Cu, Zn, Cd and Pb behave according to chemical complexation, whereas redox processes and/or colloidal interactions may be significant for Mn and Fe.     

Trace metal speciation and bioavailability in urban soils

Urban soils often contain concentrations of trace metals that exceed regulatory levels. However, the threat posed by trace metals to human health and the environment is thought to be dependent on their speciation in the soil solution rather than the total concentration. Three inactive railway yards in Montréal, Québec, were sampled to investigate the speciation and bioavailability of Cd, Cu, Ni, Pb and Zn. Soil solutions were obtained by centrifuging saturated soil pastes. In the soil solutions, up to 59% of the dissolved Cd was in its free ionic form. For Cu, Pb and Zn, organic complexes were the predominant species. Over 40% of Ni was present as inorganic complexes if the solution pH exceeded 8.1. Multiple regression analyses showed that pH and total metals in soil were significantly correlated with the activities of free metal ions, except for Cd(2+), which only had a weak correlation with soil pH. Free, dissolved and total soil metals were tested for their ability to predict metal uptake by plants in the field. However, none of these metal pools were satisfactory predictors. The results indicated that in these urban soils, trace metals were mainly in stable forms and bioavailability was extremely low.     

Heavy metal in sediments of Ziya River in northern China: distribution,potential risks,and source apportionment

The concentration partitioning between the sediment particle and the interstitial water phase plays an important role in controlling the toxicity of heavy metals in aquatic systems. The aim of this study was to assess the sediment quality in a polluted area of the Ziya River, Northern China. The contamination potential and bioavailability of six metals were determined from the concentrations of total metals and the bioavailable fractions. The results showed that the concentrations of Cr, Cu, Ni, Zn, and Pb exceeded the probable effect concentration at several sites. The high geoaccumulation indices showed that the sediments were seriously contaminated by Cd. The ratio of acid-volatile sulfide (AVS) to simultaneously extracted metal (SEM) was higher than 1, which indicated that the availability of metals in sediments was low. The risk assessment of interstitial waters confirmed that there was little chance of release of metals associated with acid-volatile sulfide into the water column. Values of the interstitial water criteria toxicity unit indicated that none of the concentrations of the studied metals exceeded the corresponding water quality thresholds of the US Environmental Protection Agency. Positive matrix factorization showed that the major sources of metals were related to anthropogenic activities. Further, if assessments are based on total heavy metal concentrations, the toxicity of heavy metals in sediment may be overestimated.     

Speciation of heavy metals in marine sediments vs their bioaccumulation by mussels.

Total contents and speciation of selected heavy metals, including Al, Fe, Co, Ni, Pb, Zn, Cu, Cr, were measured in sediment samples and mussels Mya arenaria and Astarte borealis collected in the Horsund Fjord off Spitsbergen (Norwegian Sea) and the Bay of Gdansk (Baltic Sea). The investigation aimed at revealing differences in the accumulation pattern of heavy metals in mussels inhabiting sediments characterized by varying metal bioavailability. The contents of metals adsorbed to sediments and associated with iron and manganese hydroxides, which were obtained by sequential extraction, were utilized as a measure of metal bioavailability. The contents of Cd, Pb, Zn, Cu and Cr in mussels collected off Spitsbergen were generally lower than those in mussels from the Baltic Sea. In sediments collected off Spitsbergen the bioavailable fraction represented a small proportion (0-3.7% adsorbed metals and 0-11% associated with metals hydroxides) of total heavy metal contents. In sediments from the Baltic Sea the percentages of metals adsorbed and bound to hydroxides were 1-46% and 1-13%, respectively. The differences in bioavailable metal contents measured in sediments were utilized to explain the different contents of metals in mussels collected in the corresponding sites.     

中国商品有机肥重金属分析

测定了来自10个地区不同生产原料的118个商品有机肥样品的重金属含量.结果表明:(1)商品有机肥样品中的Cd、Hg、Pb、Cr、As、Zn、Cu、Ni的平均值分别为0.600、0.120、7.34、84.30、9.45、202.91、91.06、11.01 mg/kg.(2)河南、湖北、上海的商品有机肥中8种重金属平均值均较高;内蒙古的商品有机肥中Cr平均值为20.32 mg/kg,广西的商品有机肥中Zn平均值为51.36mg/kg,远低于所有样品中Cr和Zn平均值.(3)以猪粪为主要生产原料的商品有机肥中重金属平均值最高.(4)Cr超过中国商品有机肥重金属限量标准、欧盟生态标志法的重金属限量标准、加拿大堆肥重金属限量标准(A级)和加拿大堆肥重金属限量标准(B级);As、Cd超过中国商品有机肥重金属限量标准、欧盟生态标志法的重金属限量标准和加拿大堆肥重金属限量标准(A级);Cu、Zn超过欧盟生态标志法的重金属限量标准和加拿大堆肥重金属限量标准(A级);Hg超过加拿大堆肥重金属限量标准(A级);Pb超过中国商品有机肥重金属限量标准;Ni均未超标.     

Accumulation of heavy metals in the mole in Finland

Metal concentrations (Cu, Ni, Zn, Cd, Cr, Hg, Pb and Mo) were analysed from the liver and kidneys of moles, Talpa europaea L. (Insectivora), trapped in southern Finland on both contaminated and rural areas. In rural areas the concentrations of Cd, Cu, Zn, Pb and Mo were lower in juveniles (individuals in their first summer), except for Zn in the liver, which was lower in adults. When the animals were divided into annual classes (0-6 years), Cd and Mo concentrations in the liver increased significantly with age, while concentrations of Cu, Zn and Cr tended to decrease. Female moles had higher Pb concentrations than males, especially adult females, which also had lower levels of Cu in the liver than adult males. Moles in the metropolitan area of Helsinki clearly differed from those in rural areas in that the concentrations of heavy metals in these moles were higher (especially for the most toxic metals: Cd, Pb and Hg), and their body weight was lower. The renal concentrations of Cd in most of the moles in Helsinki exceeded the threshold that has been shown to have a nephrotoxic effect in mammals. In one subsample from Helsinki, Pb and Zn concentrations in the mole liver decreased as the distance from the highway increased. Concentrations of Pb in earthworms and several heavy metals in soil also decreased similarly in the same area. Our data indicate that Pb accumulates in moles through their diet of earthworms.     

Evolution of heavy metal speciation during the aerobic composting process of sewage sludge

The contents of heavy metals and their bioavailability to the soil-plant system were the major limitation to the application of sewage sludge compost in soil. This study was conducted to determine the evolution of heavy metal speciation in the course of an aerobic composting, and investigate the influence of changes of composting process parameters including pH, temperature and organic matter (OM) content on distribution of heavy metal speciation in composted sludge. The sequential extraction procedure developed by Tessier et al. was used in sludge compost to determine the heavy metal speciation. Results showed that, during composting, (1) the contents of the residue fraction for Pb, Zn and Cd were decreased but those for Ni and Cr were increased; the Cu residue fraction was almost constant; (2) the contents of the total mobile fractions (including fractions 1-4) for Zn and Pb were significantly increased, but the increase of those for Cu and Ni were not so remarkable; (3) there were significant degrees of correlation between heavy metal fractions and changes of some selected parameters (for example, pH, composting temperature, and OM content). Only the content of the total mobile fractions for Cu could be predictable from its total content. For the prediction of the total mobile fractions of Zn, Ni, Cd and Cr, the R(2) value was significantly increased by the inclusion of other variables such as pH, temperature and OM content.     

Geofractionation of heavy metals and application of indices for pollution prediction in paddy field soil of Tumpat, Malaysia

The present study investigates the concentration of Pb, Cd, Ni, Zn, and Cu in the paddy field soils collected from Tumpat, Kelantan. Soil samples were treated with sequential extraction to distinguish the anthropogenic and lithogenic origin of Pb, Cd, Ni, Zn, and Cu. ELFE and oxidizable-organic fractions were detected as the lowest accumulation of Pb, Cd, Ni, Zn, and Cu. Therefore, all the heavy metals examined were concentrated, particularly in resistant fraction, indicating that those heavy metals occurred and accumulated in an unavailable form. The utilization of agrochemical fertilizers and pesticides might not elevate the levels of heavy metals in the paddy field soils. In comparison, the enrichment factor and geoaccumulation index for Pb, Cd, Ni, Zn, and Cu suggest that these heavy metals have the potential to cause environmental risk, although they present abundance in resistant fraction. Therefore, a complete study should be conducted based on the paddy cycle, which in turn could provide a clear picture of heavy metals distribution in the paddy field soils.     

Metal contents and potential health risk assessment of crops grown in a former mining district (Romania)

ABSTRACT

The Cd, Cu, Pb and Zn contents in home-grown crops in a former mining district were determined in order to evaluate the non-carcinogenic long-term potential health risk related to crop consumption. The potential health risk was investigated by estimating the daily intake and the hazard quotients. For all crop categories, the daily intake and the target hazard quotient were below the threshold values for Cd, Cu, and Zn. The daily intake of Pb exceeded the oral reference dose, while the target hazard quotient for vegetables was above 1, indicating a potential health risk. The total target hazard quotient for the individual metals decreased in the following order: Pb>Cd>Cu>Zn. This study confirmed that the daily consumption of crops grown in contaminated soils could pose health risks to humans.