Identification of heavy metal origins related to chemical and morphological soil properties using several non-destructive X-ray analytical methods

Soils are complex mixtures of organic, inorganic materials, and metal compounds from anthropogenic sources. In order to identify the pollution sources, their magnitude and development, several X-ray analytical methods were applied in this study. The concentrations of 16 elements were determined in all the soil samples using energy dispersive X-ray fluorescence spectrometry. Soils of unknown origin were observed by scanning electron microscopy equipped with a Si(Li) X-ray detector using Monte Carlo simulation approach. The mineralogical analyses were carried out using X-ray diffraction spectrometry. Due to the correlations between heavy metals and oxide compounds, the samples were analyzed also by electron probe microanalyzer (EPMA) in order to have information about their oxide contents. On the other hand, soil pH and salinity levels were identified owing to their influence between heavy metal and soil-surface chemistry. Moreover, the geoaccumulation index (I _geo) enables the assessment of contamination by comparing current and pre-industrial concentrations.     

Determination of total and EDTA extractable metal distributions in the colloidal fraction of contaminated soils using SdFFF-ICP-HRMS

Newly developed methods involving an on-line combination of sedimentation field-flow fractionation-inductively coupled plasma-high resolution mass spectrometry (SdFFF-ICP-HRMS) have been used to study the distributions of extractable heavy metals in a soil which had been treated with sewage sludge contaminated with Cu or Pb. The relationship of these metals with other elements in the colloidal fraction was also investigated. The colloidal fraction from the soil was obtained by repeated gravitational sedimentation and extracted with 0.11 M acetic acid, 0.1 M hydroxylamine hydrochloride, 0.05 M ethylenediaminetetraacetic acid disodium salt (EDTA) or aqua regia to assess the potential availability of the metals Cu and Pb. Large proportions of the Cu and Pb were extracted by EDTA, approaching that removed by aqua regia, whereas < 10% of the aqua regia extractable metals were removed by acetic acid and hydroxylamine chloride. The distributions of the heavy metals, the major mineral forming element (Al) and the elements forming sesquioxides (Fe and Mn) within different size classes (0.05-1 microm) of the colloidal fraction were measured using SdFFF-ICP-HRMS before and after extraction with EDTA. This information provides an insight into the composition of the colloids and the distributions of metal contaminants. In the contaminated soil colloids, the concentration of Fe, Mn and Pb is greatest in the smaller particles (<0.2 microm). In contrast, the Cu concentration is constant over the size range studied. Iron oxide surface coatings probably play a significant role in Pb adsorption on soil particles, but may be less important for Cu. The combination of selective chemical extraction, SdFFF and ICP-HRMS provides a means of determining the distribution of potentially available heavy metals within the colloidal fraction of contaminated soils.     

Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments

Several leaching tests were applied and compared to study metal remobilisation on various unpolluted and contaminated soils and on several contaminated sediments. The trace elements considered were Cd, Cr, Cu, Ni, Pb and Zn, and leaching tests consisted of the application of reagents with contrasting characteristics and strengths in order to assess the information provided. An extraction with aqua regia permitted the estimation of the pseudo-total metal content in the sample. Mild extractants such as H2O, CaCl2 and NaNO3 showed low and similar leaching capacities. Acid (CH3COOH) and complexing (EDTA) agents were more effective in remobilising trace metals from soils and sediments. Cd and Zn showed similar extraction characteristics under both extractant solutions, whereas Cu and Pb were more sensitive to complexation, and Ni and Cr to acidification processes. Sequential chemical extractions provided additional information on the association of the trace elements with the different soil and sediment phases. Cd and Zn showed the highest mobility, Pb was associated to reducible solid phases, Cu and Ni to oxidisable phases, and Cr remained mostly in the residual fraction. The results obtained in this paper provided valuable information for choosing a leaching test, which is an instrument of environmental analysis for the estimation of trace metal mobility.     

Optical and Chemical Methods of Metal Ash Analysis and Tin Recovery

‘Metal ash’ presents a waste disposal problem in most of the developing countries as the industries employ obsolete technologies. In this paper we describe analysis of tin ash, zinc ash and aluminium ash by means of optical methods, such as X-ray diffraction (XRD), inductively coupled plasma mass spectrometry (ICP-MS), electron probe micro analysis (EPMA), scanning electron microscopy (SEM) and chemical methods. The results of tin ash obtained by XRD method matched well with the cassiterite, a naturally occurring mineral of tin. ICP-MS studies reveal the presence of a large number of tracer metals, which may cause pollution by tertiary dispersion and this aspect is discussed. Conversely, the data generated by chemical methods are limited. However, the methods are simple and cost-effective. Then, they can easily be adopted by low-budget industries. Simple and cost-effective process to recover tin from tin ash is described. It is based on heating tin ash with sodium cyanide to about 900°C to separate tin component from the metal ash. The process recovers good quality tin and offers a very high yield. The process can be scaled up to small pilot plant.     

Concentrations of Cu, Fe, Mn, and Zn in tropical soils amended with sewage sludge and composted sewage sludge

Sewage sludge may be used as an agricultural fertilizer, but the practice has been criticized because sludge may contain trace elements and pathogens. The aim of this study was to compare the effectiveness of total and pseudototal extractants of Cu, Fe, Mn, and Zn, and to compare the results with the bioavailable concentrations of these elements to maize and sugarcane in a soil that was amended with sewage sludge for 13 consecutive years and in a separate soil that was amended a single time with sewage sludge and composted sewage sludge. The 13-year amendment experiment involved 3 rates of sludge (5, 10, and 20 t ha^?1). The one-time amendment experiment involved treatments reflecting 50, 100, and 200 % of values stipulated by current legislation. The metal concentrations extracted by aqua regia (AR) were more similar to those obtained by Environmental Protection Agency (EPA) 3052 than to those obtained by EPA3051, and the strongest correlation was observed between pseudo(total) concentrations extracted by AR and EPA3052 and bioavailable concentrations obtained by Mehlich III. An effect of sewage sludge amendment on the concentrations of heavy metals was only observed in samples from the 13-year experiment.     

土壤重(类)金属消解方法的研究进展

综述了目前国内外土壤重(类)金属的消解方法及相关标准,分析了各种方法的优缺点。指出传统的电热板消解法已逐渐被淘汰,微波消解法应用广泛却存在一定的局限性,全自动石墨消解法自动化程度高,适合大批量样品前处理,应用前景良好。提出相对于加入氢氟酸的混酸消解法获得的土壤重(类)金属全量,王水消解法获得的土壤重(类)金属总环境有效态与生物有效性相关性更好,研究者可根据需要选择合适的消解方法。     

Reference values for heavy metals in soils of the Brazilian agricultural frontier in Southwestern Amazônia

Guideline values are used to identify polluted or contaminated areas based on background values. Brazilian law establishes three guideline values for pollutants: a quality reference value (QRV), a prevention value, and an intervention value. Reference values refer to the natural concentration of an element or a substance in soils that have not been modified by anthropogenic impacts. These values inform assessments of soil quality and are used to establish maximum permissible limits. The objective of this study was to determine the natural levels and reference values for Cd, Co, Cr, Cu, Ni, Pb, and Zn in samples from the surface layer (0–20 cm) of 19 representative soils of the states of Mato Grosso and Rondônia, on Brazil’s agricultural frontier. Pseudo-total metal concentrations were obtained following microwave-assisted digestion using the aqua regia and EPA3051 methods. QRVs were calculated for each element as the 75th and 90th percentiles of the frequency distribution of the data. Natural levels of heavy metals in the soil samples followed the order: Cr?>?Zn?>?Cu?>?Co?>?Pb?>?Ni?>?and Cd (aqua regia) and Cr?>?Co?>?Cu?>?Pb?>?Zn?>?Ni?>?Cd (EPA3051). These values are generally lower than those reported in the Brazilian and international literature, which highlights the importance of establishing reference values for each state or for each soil type, taking into account the geomorphological, pedological, and geological diversity of the region under study.     

Investigation of trace elements in agricultural soils by BCR sequential extraction method and its transfer to wheat plants

In this study, soil samples were collected from Edirne, Turkey in both summer and winter seasons and subjected to the modified Community Bureau of Reference (BCR) sequential extraction procedure in order to investigate the chemical partitioning of metals in soils and to predict heavy metals uptake by wheat grains which grown at the same soils. The samples were subjected to a three stage extraction procedure proposed by the BCR. The three phases that were separated out in the following order: (1) carbonate, exchangeable, (2) Fe?CMn oxides, and (3) organic matter. Metal concentrations of soil fractions and grain samples were determined by inductively coupled plasma atomic emission spectroscopy. The wheat samples were prepared to analysis using microwave acid digestion procedure. The pseudo-total concentrations of metals were determined after aqua regia digestion. The analytical accuracy of the method was evaluated by using the Standard Reference Materials (BCR 142R Light Sandy Soil, NIST 2711 Montana Soil, and NIST 2704 Buffalo River Sediment). The sum of the metal contents obtained from the modified BCR sequential extraction procedure and pseudo-total metal contents for soil samples were used to calculate recovery values. In order to evaluate the bioavailability of metals, the relationships between the wheat-metal and soil-extractable metal concentrations were compared.     

Sediment load and bioconcentration of heavy metals by shrimp (Peaneus notalis) from Epe Lagoon, Nigeria

In many developing countries, surface waters, especially rivers and lagoons, have become deposition sites for all sorts of wastes. Three sampling sites located trigonally on Epe lagoon, Lagos, Nigeria were identified, and water, sediment, and commonly farmed shrimp, Peaneus notalis, were sampled and assessed for heavy metal concentrations. Zn, Pb, Ni, Cu, Cr, Cd, and Mn were determined in the aqua regia digests of the samples by means of Perkin Elmer AAnalyst 200 atomic absorption spectrophotometer. Heavy metals occurred above detection limits at all sites. The highest load of these trace elements was found in sediment samples followed by the water samples. The levels observed in the shrimp samples, however, were much lower than WHO levels. In the distribution, zinc was the highest metal found in the samples ranging from 17.94 ± 2.60 mg/L in water to 37.85 ± 9.35 μg/g in sediments. The least was Cd 0.03 ± 0.01 mg/L in water and 0.28 ± 0.04 μg/g in sediments. Lead was the most widely varied metal in shrimp with a 84.38% coefficient of variation. Apart from Cr, the metals appeared to be fairly and evenly distributed in the sediment, with coefficient of variation ranging from 14.29% (Cd) to 24.76% (Mn) The variations were between 14.49% (Zn) and 66.67% (Cr) in the water samples. The paired t test carried out between water and sediment, water and shrimp, and shrimp and sediment was significant at p?=?0.05. Three-factor analysis of variance did not reveal any significant difference in metal burdens among the trigonally located sites under investigation. Shrimp samples showed evidence of bioaccumulation but are still below internationally established levels.     

Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS)

Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured after aqua regia digestion), compared to approximately 10% for the control soil. This implies that the soils from the contaminated sites contained a large proportion of the U within more easily mobile soil fractions. Humic and fulvic acid fractions each gave characteristic peak maxima for analytes of interest (Mn, Fe, Cu, Zn, Pb and U), with the fulvic acid fraction eluting at a smaller diameter (approximately 2.1 nm on average) than the humic fraction (approximately 2.4 nm on average). DU in the fulvic acid fraction gave a bimodal peak, not apparent for other trace elements investigated, including natural U. This implies that DU interacts with the fulvic acid fraction in a different way to all other elements studied.     

Variation of Metals in Bed Sediments of Qaraaoun Reservoir, Lebanon

The Qaraaoun Reservoir (impoundment of the River Litani) is the only artificial surface water body in the country, Lebanon. Earlier study on the water quality of the Qaraaoun Reservoir identified three water quality zoning with a central distinct zone suitable for multipurpose water usage. The objective of this study was to extend the earlier work by considering the total metal content of reservoir bed sediments and hence to evaluate factors that control metal deposition or capture. Water samples were collected from 15 sampling sites and sediment samples were simultaneously collected from 9 sites. Water parameters analyzed were pH, Eh, DO and temperature. Sediment samples were dried and sieved and sediment < 75 μ m was retained for analysis. Sediments were subjected to a stepwise heating process with aqua regia to extract the metals, and their content in sediments determined by ICP-MS. The sediment data revealed higher metal contents where the river entered the reservoir which matched higher concentrations of water parameters at the influx site. Regression analysis of total metals in sediments with distance from the river Litani influx point to the dam revealed a log trend for Fe, Cr and Ni, whereas, the concentrations of Cu, Zn, Cd, Pb were better described by a polynomial regression. Three sediment zones were identified: entrance, oxidation (central) and reducing (near dam) zones. Sediment contents of Zn, Cu and Pb correlated with organic content, whereas sediment Cr and Ni were associated with iron. It was concluded that sediments act as a sink for metals and the deposition of metals is primarily related to sediment organic content and the level of dissolved oxygen in water.     

Energy-dispersive X-ray fluorescence analysis of moss and soil from abandoned mining of Pb-Zn ores

This research investigates heavy metal pollution around one of the most important mining areas in Turkey, the Sebinkarahisar (Giresun) lead–zinc mining, by means of analyzing moss and soil samples collected in the neighborhood of the copper mining at different distances. Energy dispersive X-ray fluorescence spectrometry (Epsilon 5, PANalytical, Almelo, The Netherlands) is utilized in the experiments. The results have indicated that the both moss and soil samples contain aluminum, vanadium, chromium, manganese, iron, nickel, copper, zinc, arsenic, barium, cerium, tungsten, and lead. The comparison of the heavy metal concentrations with the typical measurements in the world and with the limit values for the human health has revealed the critical heavy metal pollution levels in the region. The possible consequences of these results are briefly discussed from the point of potential hazards to ecology and human health.     

“基于质谱技术的全组分痕量重金属分析仪器开发和应用示范”项目进展

介绍了国家重大科学仪器设备开发专项"基于质谱技术的全组分痕量重金属分析仪器开发和应用示范"项目在电感耦合等离子体质谱仪(ICP-MS)研发、低温等离子体样品引入ICP-MS联用系统、ICP-MS监测汞的采样与预处理等方面的研究进展,并对ICP-MS应用发展及产业化前景进行了展望。     

Concentration of Cd, Cu, Pb, Zn, Al, and Fe in soils of Manresa, NE Spain

The aims of this study were to determine the contents of cadmium (Cd), copper (Cu), lead (Pb), zinc (Zn), aluminium (Al), and iron (Fe) (aqua regia-extractable) in 27 soil plots (54 samples) from Manresa, NE Spain, and to establish relationships between heavy metals and some soil properties. The main soil types were surveyed and the median concentrations (mg kg(-1)) obtained were Cd 0.28, Cu 20.3, Pb 18.6, Zn 67.4, Al 22,572, and Fe 21,551. Element concentrations for these soils were lower than the published values for the Valencia region (Spain) and Torrelles and Sant Climent municipal districts (Catalonia, Spain). In terms of soil properties, the results of this study suggest that, in Manresa soils, both trace element adsorption and retention are influenced by several properties such as clay minerals, carbonates, organic matter, and pH. All element contents were positively correlated with clay content. Pb and Zn were negatively correlated with pH and CaCO(3).     

Assessment of trace element contamination in sediment cores from the Pearl River and estuary,South China: geochemical and multivariate analysis approaches

Twenty-four major and trace elements and the mineralogical composition of four sediment cores along the Pearl River and estuary were analyzed using ICP-AES, ICP-MS, and X-ray diffraction (XRD) to evaluate contamination levels. The dominant minerals were quartz, kaolinite, and illite, followed by montmorillonite and feldspars, while small amounts of halite and calcite were also observed in a few samples. Cluster analysis (CA) and principal component analysis (PCA) were performed to identify the element sources. The highest metal concentrations were found at Huangpu, primarily due to wastewater treatment plant discharge and/or the surreptitious dumping of sludge, and these data differed from those of other sources. Excluding the data from Huangpu, the PCA showed that most elements could be considered as lithogenic; few elements are the combination of lithogenic and anthropogenic sources. An antagonistic relationship between the anthropogenic source metals (K, Ba, Zn, Pb, Cd, Ag, Tl, and U) and marine source metals (Na, Mg, Ti, V, and Ca) was observed. The resulting normalized Al enrichment factor (EF) indicated very high or significant pollution of Cd, Ag, Cu, Zn, Mo, and Pb at Huangpu, which may cause serious environmental effects. Conflicting results between the PCA and EF can be attributed to the background values used, indicating that background values must be selected carefully.     

Geochemical characterization and biomonitoring of reclaimed soils in the Po River Delta (Northern Italy): implications for the agricultural activities

This geochemical study is focused on the easternmost part of the Po River alluvial plain in Northern Italy, which is interested by widespread agricultural activities, investigating a reclaimed sector of the Province of Ferrara, known as “Valle del Mezzano” (Mezzano Low Land, hereafter reported as MLL) characterized by peat-rich soils. The chemical–mineralogical characterization of these reclaimed soils is important to compare the local geochemical backgrounds with those recorded in other sectors of the River Po plain and to monitor if the observed concentration exceeds critical thresholds. The reported analyses include (a) measurement of the soil salinity, (b) nutrient evaluation, (c) major and trace element concentrations carried out on bulk soils, (d) tests of metal extraction with both aqua regia and EDTA to highlight the distinct elemental mobility and (e) phyto-toxicological measurement of heavy metal concentrations in plants (Lactuca sativa acephala) grown on the studied soils. The results indicate (1) high soil salinity, often with drastic increase of sodium and chloride along the soil profiles, (2) high nitrogen content (in part related to anthropogenic activities) on superficial horizons and nitrate decrease along the soil profiles and (3) comparative enrichments in heavy metals with respect to other soils of the province, which indicate that peat deposits are effective in trapping metals from anthropogenic sources. This, in turn, implies potential geochemical risks for the agricultural activities. In this regard, specific concerns are related to the high nickel and arsenic content of MLL soils due to the mobility of these elements and their attitude to be taken up by plants.     

Spatial variation of salts in a Gyanpur canal command area

This study was aimed to establish background and reference values of total heavy metals in soils from a representative area of Albania (Tirana). Thirty-eight soil samples collected from genetic horizons of major soil types of Tirana were analyzed for important physicochemical properties by standard methods and for total contents of Cd, Cr, Ni, Pb, Zn, and Cu by atomic absorption spectrometer, after extraction with aqua regia. The results showed that the total contents of Cd, Cr, Ni, Pb, Zn, and Cu in surface horizons varied widely with respective mean values of 0.3 (??0.6), 174.2 (??63.7), 305.9 (??133.0), 19.7 (??12.4), 95.5 (??26.3), and 42.7 (??6.8) mg/kg. The highest metal contents were found in two soils developed in limestone. The depth distribution of metals showed a tendency for accumulation of Cd and Pb in the surface horizons of three soils, suggesting that these metals partially come from anthropogenic inputs. Correlation analysis indicated that the metal contents of soils were controlled by soil properties, including pH, CaCO₃, clay, organic matter, cation exchange capacity, and Fe oxides. The background values (given as the 90th percentile) were much higher than those reported in the literature, showing that the levels of respective metals were naturally higher. The total metal contents of some soils were above background levels, suggesting metal pollution. The reference values for all the analyzed metals were quite consistent with those of the Dutch system. The proposed background and reference values can be used to evaluate the soil pollution with these elements.     

Determination of trace heavy metals in harvested rainwater used for drinking in Hebron (south West Bank,Palestine) by ICP-MS

Rainwater samples harvested for drinking from the west part of Hebron (south of West Bank in Palestine), the largest city in the West Bank, were analyzed for the content of different trace heavy metals (Cr, Mn, Co, Ni, Cu, Zn, Mo, Ag, Cd, Bi, and Pb) by inductively coupled plasma mass spectrometry (ICP-MS). This study was conducted to determine the water quality of harvested rainwater used for drinking of south West Bank (case study, Hebron area). A total of 44 water samples were collected in November 2012 from 44 house cisterns used to collect rainwater from the roofs of houses. The samples were analyzed for their pH, temperature, electrical conductivity, total dissolved solids, and different heavy metal contents. The pH of all water samples was within the US Environmental Protection Agency limits (6.5–8.5), while some water samples were found to exceed the allowed WHO limit for total dissolved solids (TDSs) in drinking water. Results showed that concentrations of the heavy metals vary significantly between the 44 samples. Results also showed that the concentration of five heavy metals (Cr, Mn, Ni, Ag, and Pb) is higher than the WHO limits for these heavy metals in drinking water. Overall, our findings revealed that harvested rainwater used for drinking of this part of south West Bank is contaminated with heavy metals that might affect human health.     

Availability of geogenic heavy metals in soils of Thiva town (central Greece)

Potentially toxic metals in the urban chemical environment impose risks to both ecosystem and human health. Here, we evaluate the labile pools and availabilities of non-anthropogenic Ni, Cr, Co and Mn in soil samples from Thiva town (central Greece) and investigate their associations with common soil properties and geochemical data obtained by the aqua regia and single selective dissolutions. Experimental work included the initial application of the sequential extraction protocol proposed by the European Community Bureau of Reference and chemical extractions with ethylenediamine tetraacetic acid solution and a modified physiologically based extraction test with the aim to obtain the operationally defined fractions of plant availability and human bioaccessibility, respectively. The leachate results demonstrated that despite the significant contribution of residual metal species especially for Ni and Cr, the studied serpentine soils provide chemically labile pools for all the considered elements. Nickel was found to be the most available metal with the order being Ni?>?Cr?～?Co?～?Mn for plant uptake and Ni?>?Cr?>?Co?～?Mn for human bioaccessibility. The aqua regia extractable concentrations are not predictors of elemental availabilities except for Ni bioaccessible data interpreting however only a moderate percentage of the total variance. The incorporation of basic soil properties (mostly total organic carbon), geochemical data for the major elements Ca, Mg and Fe and ammonium oxalate extractable Cr significantly improved the estimations for individual elements entailing the strong influence of the chemistry and mineralogy of soil materials to the release of focus metals from the soil matrix. This study provides for the first time bioaccessible data for serpentine-derived soils that are more realistic for evaluating potential adverse effects on the human health.     

Total and available heavy metal concentrations in soils of the Thriassio plain (Greece) and assessment of soil pollution indexes

The Thriassio plain is located 25 km west of Athens city, the capital of Greece. Two major towns (Elefsina and Aspropyrgos), heavy industry plants, medium to large-scale manufacturing, logistics plants, and agriculture comprise the main land uses of the studied area. The aim of the present study was to measure the total and available concentrations of Cr, Zn, Ni, Pb, Co, Mn, Ba, Cu, and Fe in the top soils of the plain, and to asses soil contamination by these metals by using the geoaccumulation index (I _geo), the enrichment factor (EF), and the availability ratio (AR) as soil pollution indexes. Soil samples were collected from 90 sampling sites, and aqua regia and DTPA extractions were carried out to determine total and available metal forms, respectively. Median total Cr, Zn, Ni, Pb, Co, Mn, Ba, Cu, and Fe concentrations were 78, 155, 81, 112, 24, 321, 834, 38, and 16?×?10³ mg?kg^?1, respectively. The available fractions showed much lower values with medians of 0.4, 5.6, 1.7, 6.9, 0.8, 5.7, 19.8, 2.1, and 2.9 mg?kg^?1. Though median total metal concentrations are not considered as particularly high, the I _geo and the EF values indicate moderate to heavy soil enrichment. For certain metals such as Cr, Ni, Cu, and Ba, the different distribution patterns between the EFs and the ARs suggest different origin of the total and the available metal forms. The evaluation of the EF and AR data sets for the soils of the two towns further supports the argument that the EFs can well demonstrate the long-term history of soil pollution and that the ARs can adequately portray the recent history of soil pollution.