Determination of anthropogenic boundary depth in industrially polluted soil and semi-quantification of heavy metal loads using magnetic susceptibility

This study focuses on magnetic susceptibility processing and analysis towards fast and cost-efficient discrimination and semi-quantification of anthropogenic heavy metal loads in soil. Spatial variability of magnetic susceptibility was investigated on sets of soil cores from both “polluted” and “less polluted” forest soil close to a steel mill near Leoben, Austria. Test sites of ∼10 m² represent “site scale” dimensions. Statistical analysis of magnetic data provides a boundary depth indicating the transition from the “polluted” to the deeper, “unpolluted” zone in contaminated natural soil. Introduction of a block master curve simplifies the complex variations of individual curves, and represents magnetic susceptibility at “site scale”. For linking the block master curve to heavy metals we only require magnetic susceptibility data from one soil core and heavy metal data from two sub-samples from the same core. Our optimized magnetic susceptibility data processing scheme provides an applicable tool to semi-quantify anthropogenic heavy metal loads in soil.     

Geochemical partitioning of Co, Cr, Fe, Sc and Zn in polluted and non-polluted marine sediments

The partitioning of Co, Cr, Fe, Sc and Zn into three fractions (reducible by acidified hydroxylamine hydrochloride, oxidizable by acidified hydrogen peroxide, and the residual after the previous extractions) of Saronikos Gulf surface sediments was determined by using a sequential extraction technique. The metal concentrations were determined by Instrumental Neutron Activation Analysis. With the exception of Sc, the metal content in the reducible and oxidizable fractions increases in the polluted sediments near the Athens Sewage Outfall (ASO) and a Fertilizer Plant (FP). In the non-polluted sediments, the residual fraction is the most important carrier for all metals examined. Oxidizable Cr and Zn correlate well with the organic carbon content of the sediments, but the reducible fraction (mainly Fe/Mn hydroxides) is the most important sink for Co, Cr, Fe and Zn in the polluted sediments near the ASO. The pyrite-rich wastes from the FP are influencing the geochemical partitioning of the metals examined in the sediments in front of the FP and, partially, in the sediments near the ASO.     

Transfer functions for solid-solution partitioning of cadmium for Australian soils

To assess transport and ecotoxicological risks of metals, such as cadmium (Cd) in soils, models are needed for partitioning and speciation. We derived regression-based “partition-relations” based on adsorption and desorption experiments for main Australian soil types. First, batch adsorption experiments were carried out over a realistic range of dissolved Cd concentrations in agricultural soils in Australia. Results showed linear sorption relationships, implying the adequacy of using Kd values to describe partitioning. Desorption measurements were then carried out to assess in-situ Kd values and relate these to soil properties The best transfer functions for solid-solution partitioning were found for Kd values relating total dissolved Cd concentration to total soil Cd concentrations, accounting for the variation in pH, SOM contents and DOC concentrations. Model predictions compared well with measurements of an independent data set, but there was a tendency to underestimate dissolved Cd concentrations of highly polluted soils.     

Multispecies transport of metal–EDTA complexes and chromate through undisturbed columns of weathered fractured saprolite

Laboratory-scale tracer experiments were conducted to investigate the geochemical and hydrological processes that govern the fate and transport of organically chelated radionuclides and toxic metals in undisturbed saturated columns of weathered, fractured shale saprolite. Three long-term, reactive contaminant injections were pulsed onto three separate soil columns, with the following influent mixtures: (1) ¹⁰⁹CdEDTA²⁻, (2) ¹⁰⁹CdEDTA²⁻ and ^57,58Co(II)EDTA²⁻, and (3) ¹⁰⁹CdEDTA²⁻, ⁵⁷Co(III)EDTA⁻, and H⁵¹CrO₄⁻. Both single and multiple species experiments were conducted to determine the importance of interaction between the contaminants and competition for surface sites. Flow interruption was used to identify physical and chemical non-equilibrium (PNE and CNE) which were caused by multiple pore-region flow and rate-limited chemical reactions, respectively. Reactive contaminant transport through the fractured, weathered shale was affected by sorption, redox, and dissociation reactions, which were mediated by soil organic matter and surficial oxides of Fe, Mn, and Al. The transport of CdEDTA²⁻ was significantly influenced by ligand-promoted dissolution of subsurface Fe and Al sources, resulting in the liberation of Cd²⁺, Al(III)EDTA⁻ and Fe(III)EDTA⁻. Flow interruption confirmed that the surface-mediated dissociation reaction was time-dependent, with the stability of the CdEDTA²⁻ complex dependent on its residence time within the soil. The migration of Co(II)EDTA²⁻ was dominated by oxidization to the highly stable Co(III)EDTA⁻ species, and elevated effluent Mn²⁺ suggested that surficial Mn(IV) oxides likely catalyzed the redox reaction, though Fe-oxides may have also contributed to the reaction. Dissociation (12%) of the Co(II)EDTA²⁻ complex was first observed during flow interruption, indicating that rate-limited dissociation of the complex by Fe-oxides may be significant under equilibrium conditions. The transport of HCrO₄⁻ was significantly altered by the reduction of mobile Cr(VI) to irreversibly bound Cr(III). The reduction reaction was catalyzed by surface-bound natural organic matter and flow interruption confirmed that the reaction was time-dependent. There was little evidence of competitive effects between the various contaminants in the multispecies experiments, since each was influenced by a different geochemical process during transport through the soil. The results of this study further support research findings that suggest anionic toxic metals and radionuclide–organic complexes can be significantly influenced by soil geochemical processes that can both enhance and impede the subsurface migration of these contaminants.     

天津市典型河网区沉积物中重金属分布及生态风险评价

选择天津市典型河网区为研究对象,分析了沉积物中6种重金属(Cr、Cu、Mn、Ni、Pb和Zn)的分布特征,并采用富集系数法和潜在生态危害指数法分析了重金属的来源,进而评价了其生态风险。结果表明,表层沉积物中Cr、Cu、Mn、Ni、Pb和Zn的平均含量分别是58.18、23.52、524.60、22.93、25.24和49.51 mg/kg,其中Cr、Mn和Ni含量均低于天津市土壤背景值,而Cu、Pb和Zn含量在部分样点高于背景值;在垂直分布上,沉积物中Cr和Ni的含量相对稳定,而Cu、Mn、Pb和Zn的含量从底层到表层均先增加后降低。重金属富集系数(EF)分析显示,河网区表层沉积物中Cu和Zn在个别样点以及Pb在近一半样点存在人为输入过程(EF1.5),与接纳上游及区域的生活污水、农田退水有关,而Cr、Mn和Ni均来自自然源。重金属综合潜在生态危害指数(RI)评价表明,整个河网区表层沉积物为轻微生态危害水平,对区域的水环境质量不构成威胁。     

In situ measurements of concentrations of Cd, Co, Fe and Mn in estuarine porewater using DGT

Vertical profiles of metals were measured by the in situ application of DGT (diffusive gradients in thin films). Well-defined laboratory systems ensured the good reproducibility and precision DGT accumulated metals on a chelex resin after diffusional transport through a layer of hydrogel. Three kinds of DGT probes (with three thicknesses of diffusive gel: 0.40 mm, 0.80 mm and 1.92 mm) measured interfacial concentration and induced flux from solid to solution phase which had intricate variations with depth. The DGT induced flux and interfacial concentration of four metals belonged to “partially sustained” state, indicating a labile equilibrium of metals between solid phase and porewater. The concentration profiles showed the good correlation between Mn and Co and peak concentrations of Mn and Fe between −2.00 cm and −5.25 cm with depth.     

Influence of soil pH on the fractionation of Cr, Cu and Zn in solid phases from a landfill site

The spatial variability of soil pH for engineered Weathered Oxford Clay is described using 35 samples collected from the base of a new cell in an existing landfill. Soil pH variability influences the reactivity of Cr, Cu and Zn in the site. The reactivity of these metals as natural components was determined using a sequential extraction method. The total concentration of Cr, Cu and Zn and the mineralogical composition were also determined. The results showed that due to the presence of a layer rich in pyrite in the base, a natural acidification may occur which can produce a soil pH as low as 2.7. The spatial variability of soil pH in this area has been described with an anisotropical variogram model and the estimation of its values at unsampled locations was carried out using the ordinary kriging algorithm. From the spatial modelling of the soil pH, it was found that the metals in the soil solid phases follow a similar distribution.     

The biological responses and metal phytoaccumulation of duckweed Spirodela polyrhiza to manganese and chromium

The phytoaccumulation ability of duckweed Spirodela polyrhiza on manganese (Mn) and chromium (Cr) was assessed by exposing the plant to various concentrations of single or dual metals (5–70 mg L^?1 Mn, 2–12 mg L^?1 Cr(VI)) under laboratory conditions. The results showed that S. polyrhiza can tolerate Mn at high concentrations of up to 70 mg L^?1, and its growth rate was barely affected by Mn. The effects of Cr on S. polyrhiza growth were dose-dependent, and the growth was completely inhibited in the presence of 12 mg L^?1 Cr. Analysis of metal content in the plant biomass revealed a high accumulation of Mn (up to 15.75 mg per g of duckweed dry weight). The Cr bioaccumulation (from below detection limit to 2.85 mg Cr (11.84 mg Cr₂O₇ ^2?) per g of duckweed dry weight) increased with cultivation time and metal concentration in the medium. Further study with the concurrence of Mn and Cr showed increased toxicity to plant growth and photosynthesis. The metal accumulations in the dual metal treatments were also significantly decreased as compared to the single metal treatments. Nevertheless, the phytoaccumulation of these two metals in S. polyrhiza in the dual metal treatments were still comparable to or higher than in previous reports. Thus, it was concluded that duckweed S. polyrhiza has the potential to be used as a phytoremediator in aquatic environments for Mn and Cr removal.

     

Acidification Remediation Alternatives: Exploring the Temporal Dimension with Cost Benefit Analysis

Acidification of soils and surface waters caused by acid deposition is still a major problem in southern Scandinavia, despite clear signs of recovery. Besides emission control, liming of lakes, streams, and wetlands is currently used to ameliorate acidification in Sweden. An alternative strategy is forest soil liming to restore the acidified upland soils from which much acidified runoff originates. This cost–benefit analysis compared these liming strategies with a special emphasis on the time perspective for expected benefits. Benefits transfer was used to estimate use values for sport ffishing and nonuse values in terms of existence values. The results show that large-scale forest soil liming is not socioeconomically profitable, while lake liming is, if it is done efficiently—in other words, if only acidified surface waters are treated. The beguiling logic of “solving” an environmental problem at its source (soils), rather than continuing to treat the symptoms (surface waters), is thus misleading.     

Metal partitioning and uptake in central Ontario forests

Evaluation of the potential environmental risk posed by metals depends to a great extent on modeling the fate and mobility of metals with soil-solution partitioning coefficients (Kd). However, the effect of biological cycling on metal partitioning is rarely considered in standard risk assessments. We determined soil-solution partitioning coefficients for 5 metals (Cd, Zn, Pb, Co and Ni) at 46 forested sites that border the Precambrian Shield in central Ontario, where soil pHaq varied from 3.9 to 8.1. Foliage from the dominant tree species and forest floor samples were also collected from each site to compare their metal levels with Kd predictions. Analogous to other studies, log Kd values for all metals were predicted by empirical linear regression with soil pH (r2=0.66-0.72), demonstrating that metal partitioning between soil and soil solution can be reliably predicted for relatively unpolluted forest mineral soils by soil pH. In contrast, whereas the so-called bioavailable water-soluble metal fraction could be predicted from soil pH, metal concentrations in foliage and the forest floor at each site were not consistently related to pH. Risk assessment of metals should take into account the role of biota in metal cycling and partitioning in forests, particularly if metal bio-accumulation and chronic toxicity in the food chain, rather than metal mobility in soils, are of primary concern.     

Levels and Composition of Atmospheric Particulates (PM10) in a Mining-Industrial Site in the City of Lavrion,Greece

Abstract

The present work focuses on the characterization of air quality and the identification of pollutant origin at a former mining site in the city of Lavrion, Greece. A historical metallurgy complex is reused for establishing the Lavrion Technology and Cultural Park (LTCP). A serious problem with this is the severe soil contamination that resulted from intensive mining and metallurgical activities that has taken place in the greater area for the past 3000 years. Among other consequences, surface-polluted depositions, rich in heavy and toxic metals, are loose and easily wind-eroded, resulting in transportation of particu-late matter (PM) in the surrounding atmosphere. On the other hand, there are a number of industries relatively close to the site that are potential sources of PM air pollution. The current study deals with the collection and analysis of PM₁₀ samples with respect to their concentration in heavy metals, such as Pb, Cd, Cu, Fe, Zn, Mn, Cr, and Ni. Though not a heavy metal, As also is included. Furthermore, the source of these elements is verified using statistical correlation and by calculating enrichment factors (EFs), considering that some substances are certainly of contaminated soil origin. Results show that PM₁₀ and element concentrations are relatively low during winter but significantly increase during summer. Fe, Pb, Zn, Mn, and Cu may be considered of contaminated soil origin, while As, Ni, Cd, and Cr are very much enriched with respect to contaminated soil, indicating another possible source attributed to the adjacent industrial plants.     

Multidimensional modeling of aerosol monitoring data

The present study deals with the application of N-way factor analysis for modeling and interpretation of a three-dimensional environmental data set acquired from monitoring of particulate matter (PM) collected at four different sampling locations in Lower Austria region (Central Europe). In the study the Tucker3 algorithm for N-way modeling was used. It was statistically validated that the Tucker3 model offered having the dimensionality [222] is appropriate for correct interpretation of the relationships between chemical parameters, sampling locations and sampling period. The Tucker3 model allowed to distinguish three major sources of pollution in the region of interest conditionally named “soil dust”, “combustion” and “street dust” latent factors as responsible for chemical profile of PM and to identify seasonal variability. Additionally, some specificity of the sampling locations was also pointed out.     

层次分析法与地理信息系统在农田土壤重金属污染评价中的应用

以《土壤环境质量标准》(GB 15618—1995)二级标准作为评价标准,采用以改进层次分析法确定权重的加权平均法对南京市郊典型蔬菜地的土壤重金属污染状况进行了评价。结果表明,研究区土壤中Cu、Pb、Cr的单因子污染指数平均值均小于1,含量超标率均不超过10.32%,而Cd的单因子污染指数平均值达2.15,含量超标率为84.13%,急需对该区土壤和受体做进一步的Cd污染深入调查或风险评估;研究区土壤重金属综合污染指数平均值为1.28,属玷污水平;利用ArcGIS 8.3软件进行土壤重金属污染的空间分布特征分析结果表明,研究区各元素的污染程度为Cd>Pb>Cu>Cr,各元素的污染格局较为相似,城市化活动对土壤污染贡献较大;研究区有81.16%的土壤重金属污染级别为玷污,3.78%处于本底级,15.06%处于安全级。     

Changes in trace metal concentrations in lake water and biota during experimental acidification of Little Rock Lake, Wisconsin, USA

Little Rock Lake, a small (18 ha), low-alkalinity (25 microeq litre(-1), pH 6.1) seepage lake in northern Wisconsin, was divided into two basins by a flexible, inert barrier and, beginning in spring 1985, the north basin was acidified in three 2-year steps to pH 5.6, 5.1 and 4.7. The annual average pH of the reference basin remained near 6.1. As part of a comprehensive programme to determine the chemical and biological responses to acidification, minor metals (Al, Fe, Mn) and trace metals (Cd, Cu, Pb, Zn) in lake water (0.4 microm pore filtered samples), periphyton, zooplankton, and yellow perch (Perca flavescens) were measured. At pH 5.6, dissolved Mn and Fe increased in the acidified basin. At pH 5.1 and 4.7, dissolved Al, Fe, Mn, Cd and Zn were elevated in the acidified basin. At pH 4.7, dissolved Pb in the acidified basin became elevated over reference basin levels. Dissolved Cu remained similar in both basins down to pH 4.7. Cd burdens in periphyton collected on artificial substrates were lower in the treatment basin at pH 5.1 (1.8 microg g(-1) dry wt.) than in the reference basin at pH 6.1 (7.5 microg g(-1) dry wt.), but Al and Fe burdens in periphyton were similar in both basins. Likewise, Cd levels in muscle tissue of perch from the treatment basin at pH 4.7 were lower (26 ng g(-1) dry wt.) than in the reference basin at pH 6.1 (36 ng g(-1) dry wt.); Al and Fe burdens were similar in perch muscle tissue from both basins. Levels of Cd and Fe in zooplankton from the acidified basin at pH 4.7 were approximately equal to 2x higher than in animals from the reference basin. In both basins of the lake, Al and Cd levels in lake biota decreased with increasing trophic level, demonstrating that food chain biomagnification does not occur for these metals.     

An ozone flux-response relationship for wheat

The concentrations of heavy metals in the fine fraction (<63 microm) of 19 surficial sediment samples from the border region of Baja California (Mexico) and California (USA) were determined. The concentration ranges (in microg g(-1)) of the metals were: Cu, 4.9-23; Zn, 39-188; Ni, 16-44; Cr, 56-802; Pb, 6-21; Cd, 0.08-0.64; Ag, 0.01-0.28; and Mn, 392-1506; the intervals (percentage) for Fe and Al were 1.36-4.6 and 3.61-8.55, respectively. The heavy metals in these sediments indicate a relative enrichment of Cr (>3000%), Zn (>350%), Ni (>300%) and Cu (>150%) off the wastewater outfall at Punta Bandera in Tijuana, Baja California, with respect to non-polluted sediments of the region. Pb, Cd and Ag have low concentrations off the same outfall and enrichment factors are generally lower than 300% (Pb) and lower than 150% (Cd and Ag). This suggests that these metals have a different origin, or that they are controlled by a different geochemical mechanism than the former. The concentrations of Mn, Fe and Al occurred within ranges typical for coastal areas and probably reflect the mineralogical composition of the sediments of the region.     

Levels and composition of atmospheric particulates (PM10) in a mining-industrial site in the city of Lavrion,Greece

The present work focuses on the characterization of air quality and the identification of pollutant origin at a former mining site in the city of Lavrion, Greece. A historical metallurgy complex is reused for establishing the Lavrion Technology and Cultural Park (LTCP). A serious problem with this is the severe soil contamination that resulted from intensive mining and metallurgical activities that has taken place in the greater area for the past 3,000 years. Among other consequences, surface-polluted depositions, rich in heavy and toxic metals, are loose and easily wind-eroded, resulting in transportation of particulate matter (PM) in the surrounding atmosphere. On the other hand, there are a number of industries relatively close to the site that are potential sources of PM air pollution. The current study deals with the collection and analysis of PM10 samples with respect to their concentration in heavy metals, such as Pb, Cd, Cu, Fe, Zn, Mn, Cr, and Ni. Though not a heavy metal, As also is included. Furthermore, the source of these elements is verified using statistical correlation and by calculating enrichment factors (EFs), considering that some substances are certainly of contaminated soil origin. Results show that PM10 and element concentrations are relatively low during winter but significantly increase during summer. Fe, Pb, Zn, Mn, and Cu may be considered of contaminated soil origin, while As, Ni, Cd, and Cr are very much enriched with respect to contaminated soil, indicating another possible source attributed to the adjacent industrial plants.     

Elemental distribution in the edible leaves of Celosia trigyna from the western and northern regions of Nigeria

Celosia trigyna, which belongs to the plant family Amaranthaceae, is a plant used in traditional medicine to treat several conditions such as sores, chest pains, diarrhoea and menstrual cramps in many countries in Africa. It is also consumed by the local people in Nigeria as soups, sauces and stews. In this study, the distribution and bioaccumulation of the elements in C. trigyna species and growth soil from the western and northern regions of Nigeria was investigated to determine the effects of geographical location on the uptake of elements by the plant. Elemental concentrations in the leaves from the western region were found to be in decreasing order of Ca?>?Mg?>?Fe?>?Mn?>?Zn?>?Cu?>?Pb?>?As?>?Ni. Concentrations of elements in the leaves from the northern region were found to be in decreasing order of Ca?>?Mg?>?Fe?>?Mn?>?Zn?> Cu?>?As?>?Pb?>?Ni?>?Co?>?Cd. Proximate analysis of leaves from both regions compared well with the recommended dietary allowance making the leaves safe for human consumption. Principal component analysis was used to group elements having the same sources irrespective of their geographical locations. Cd, Co and Cr were not detected in the leaves from the western region. Concentrations of As and Pb were above maximum permissible limits in both regions, while Ayegunle and Bida (in the northern region) had the highest concentrations of Cd. The high level of these toxic metals may be attributed to anthropogenic activities. It is therefore important that the Nigerian agricultural extension system emphasizes the dangers of heavy metal contamination in leafy vegetables to farmers. Activities of the manufacturing industries in the study area should be adequately monitored under standard environmental protection laws.     

Geochemical fractionation and pollution assessment of Zn,Cu, and Fe in surface sediments from Shadegan Wildlife Refuge,southwest of Iran

This research focuses on the fractionation and distribution patterns of heavy metals (Zn, Cu, and Fe) in surficial sediments collected from Shadegan Wildlife Refuge, the biggest wetland in southern part of Iran, to provide an overall classification for the sources of metals in the study area using a sequential extraction method. For this purpose, a four-step sequential extraction technique was applied to define the partitioning of the metals into different geochemical phases of the sediment. The results illustrated that the average total level of Zn, Cu, and Fe in surface sediments were 55.20 ± 16.04, 22.86 ± 5.68, and 25,979.01 ± 6917.91 μg/g dw, respectively. On the average, the chemical partitioning of all metals in most stations was in the order of residual >oxidizable-organic > acid-reducible > exchangeable. In the same way, the results of calculated geochemical indices revealed that Cu, Zn, and Fe concentrations are mainly influenced by lithogenic origins. Compared with consensus-based SQGs, Cu was likely to result in occasionally harmful biological effects on the biota.

     

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.