The transfer of heavy metals to barley plants from soils amended with sewage sludge with different heavy metal burdens

Purpose

Our main aim objective was to evaluate the transfer of Cd, Cr, Cu, Ni, Pb and Zn to barley (Hordeum vulgare) grown in various soils previously amended with two sewage sludges containing different concentrations of heavy metals. This allowed us to examine the transfer of heavv metals to barley roots and shoots and the occurrence of restriction mechanisms as function of soil type and for different heavy metal concentration scenarios.

Material and methods

A greenhouse experiment was performed to evaluate the transfer of heavy metals to barley grown in 36 agricultural soils from different parts of Spain previously amended with a single dose (equivalent to 50 t dry weight ha^?1) of two sewage sludges with contrasting levels of heavy metals (common and spiked sludge: CS and SS).

Results and discussion

In soils amended with CS, heavy metals were transferred to roots in the order (mean values of the bio-concentration ratio in roots, BCF_Roots, in brackets): Cu (2.4)?~?Ni (2.3)?>?Cd (2.1)?>?Zn (1.8)?>?Cr (0.7)?~?Pb (0.6); similar values were found for the soils amended with SS. The mean values of the soil-to-shoot ratio were: Cd (0.44)?~?Zn (0.39)?~?Cu (0.39)?>?Cr (0.20)?>?Ni (0.09)?>?Pb (0.01) for CS-amended soils; Zn (0.24)?>?Cu (0.15)?~?Cd (0.14)?>?Ni (0.05)?~?Cr (0.03)?>?Pb (0.006) for SS-amended soils. Heavy metals were transferred from roots to shoots in the following order (mean values of the ratio concentration of heavy metals in shoots to roots in brackets): Cr (0.33)?>?Zn (0.24)?~?Cd (0.22)?>?Cu (0.19)?>?Ni (0.04)?>?Pb (0.02) for CS-amended soils; Zn (0.14)?>?Cd (0.09)?~?Cu (0.08)?>?Cr (0.05)?>?Ni (0.02)?~?Pb (0.010) for SS-amended soils.

Conclusions

Soils weakly restricted the mobility of heavy metals to roots, plant physiology restricted the transfer of heavy metals from roots to shoots, observing further restriction at high heavy metal loadings, and the transfer of Cd, Cu and Zn from soils to shoots was greater than for Cr, Ni and Pb. Stepwise multiple linear regressions revealed that soils with high sand content allowed greater soil-plant transfer of Cr, Cu, Pb and Zn. For Cd and Ni, soils with low pH and soil organic C, respectively, posed the highest risk.     

Distribution of heavy metals in soils of the Yellow River Delta: concentrations in different soil horizons and source identification

Purpose

The Yellow River Delta, an active land-ocean interaction area, will develop into a large eco-economic region in East China during the coming decade. It is necessary to assess the geochemical features of heavy metals in the soils. The objectives of this research were to evaluate the concentrations and distribution of heavy metals (Cr, Ni, Cu, Zn, Pb, and Cd) in soil profiles of the area and to identify their sources.

Materials and methods

Horizon samples were collected based on pedogenic features from bottom to top in each profile to a depth of 120 cm and a total of 92 samples were collected. The sampling sites were grouped into four lines from inland to coastal area with three land use types (cotton field, cereal field, and wetland). The concentrations of Cr, Ni, Cu, Zn, Pb, and Cd were measured by inductively coupled plasma-mass spectrometry. Iron oxide fractions in the soil were extracted by oxalate-oxalic acid and dithionite-citrate-bicarbonate. X-ray diffraction (XRD) was used to determine the mineral composition of the soils. Multivariate statistical analysis and historical data were employed to identify the possible sources of these heavy metals.

Results and discussion

The mean concentrations of heavy metals were elevated along the Yellow River region and in the southern part of the delta; however, they were generally lower than the Chinese guideline values. As for the depth distribution of heavy metals in soil profiles, the maximum values of Cr, Ni, Cu, Zn, and Cd in middle horizon of cotton field were almost twice than those in surface horizon. The iron oxides and XRD analysis indicated that the trace elements accumulation appeared to be related with the contents of crystalline iron oxide and layer silicates. Historical data from suspended sediments of the Yellow River and principal component analysis (PCA) implied that most of the metals (Cr, Ni, Cu, and Zn) were sourced from natural alluviation and sedimentation.

Conclusions

The Yellow River Delta soils were slightly polluted by heavy metals the Yellow River Delta. The special pedogenic horizon characterized by higher iron oxides and layered silicates minerals in the middle and lower part of the soil profile was found with heavy metals enrichment, which required to be studied further. Suspended sediments transported by the Yellow River were suggested to be one of the major sources for the heavy metals accumulation in the basal soils of this region.     

Heavy metal distribution in different soil aggregate size classes from restored brackish marsh,oil exploitation zone,and tidal mud flat of the Yellow River Delta

Purpose

Heavy metal distribution in soils is affected by soil aggregate fractionation. This study aimed to demons trate the aggregate-associated heavy metal concentrations and fractionations in “sandy,” “normal,” and “mud” soils from the restored brackish tidal marsh, oil exploitation zone, and tidal mudflat of the Yellow River Delta (YRD), China.

Materials and methods

Soil samples were sieved into the aggregates of >2, 0.25–2, 0.053–0.25, and <0.053 mm to determine the concentrations of exchangeable (F1), carbonate-bound (F2), reducible (F3), organic-bound (F4), and residual fraction (F5) of Cd, Cr, Cu, Ni, Pb, and Zn.

Results and discussion

The 0.25–2 mm aggregates presented the highest concentrations but the lowest mass loadings (4.23–12.18 %) for most metal fractions due to low percentages of 0.25–2 mm aggregates (1.85–3.12 %) in soils. Aggregates <0.053 mm took majority mass loadings of metals in sandy and normal soils (62.04–86.95 %). Most soil aggregates had residual Cr, Cu, Ni, Zn, and reducible Cd, Pb dominated in the total Cd, Cr, Cu, Ni, Pb, and Zn concentrations. Sandy soil contained relatively high F4, especially of Cu (F4) in 0.25–2 mm aggregates (10.22 mg kg^?1), which may relate to significantly high organic carbon contents (23.92 g kg^?1, P?<?0.05). Normal soil had the highest total concentrations of metals, especially of Cu, Ni, and Pb, which was attributed to the high F3 and F5 in the <0.053 mm aggregates. Although mud soil showed low total concentrations of heavy metals, the relatively high concentrations of bioavailable Cd and Cu resulted from the relatively high Cd (F2) and Cu (F2) in the >2 mm aggregates indicated contribution of carbonates to soil aggregation and metal adsorption in tidal mud flat.

Conclusions

Soil type and aggregate distribution were important factors controlling heavy metal concentration and fractionation in YRD wetland soil. Compared with mud soil, normal soil contained increased concentrations of F5 and F3 of metals in the 0.053–0.25 mm aggregate, and sandy soil contained increased concentrations of bioavailable and total Cr, Ni, and Zn with great contribution of mass loadings in the <0.053 mm aggregate. The results of this study suggested that oil exploitation and wetland restoration activities may influence the retention characteristics of heavy metals in tidal soils through variation of soil type and aggregate fractions.

     

Identification of sources of heavy metals in agricultural soils using multivariate analysis and GIS

Purpose

Heavy metals in agricultural soils readily enter the food chain when taken up by plants, but there have been few investigations of heavy metal pressure in farming areas with low background concentrations. This study was carried out in a cultivation area of Northeast China that has undergone decades of intensive farming, with the aim of identifying the sources of accumulated heavy metals in agricultural soils using multivariate analysis and geographic information system (GIS).

Materials and methods

In 2011, concentrations of total iron (Fe), manganese (Mn), copper (Cu), nickel (Ni), lead (Pb), zinc (Zn), cadmium (Cd), chromium (Cr) and cobalt (Co), as well as soil pH and organic matter, were measured at 149 sites in arable soils in the study area. The principal component analysis (PCA) was employed to extract hidden subsets from the raw dataset in order to detect possible sources. Metal contents in soils from various croplands were further investigated using analysis of variance. With the Kriging interpolation method, GIS was used to display the PCA results spatially to explore the influence of land use on heavy metal accumulation.

Results and discussion

Most of the studied metals in arable soils of the study area were shown to have low concentrations, except for Cd (0.241 mg?kg^?1). According to the results of the PCA analysis, Fe, Mn, Pb, Zn, Cd, and Co formed the first component (PC1) explaining 40.1 % of the total variance. The source of these metals was attributed to farming practices (“anthropogenic” factor). Cu, Ni, and Cr fell into the second component (PC2), heavy metals that derived from parent rock materials (“lithogetic” factor). This component describes 24.6 % of the total variance. Compared to paddy lands, soils in drylands had greater accumulations of all the metals in PC1, which can be explained by a higher rate of phosphorus fertilizer application and a longer farming history.

Conclusions

Owing to the natural low backgrounds, soils in the study area were safe from heavy metal pollution with a contamination risk of Cd the only exception. Multivariate analysis and GIS were effective means in helping to identify the sources of soil metals and addressing the land use influence on soil metals accumulation. This work can support the development of strategy and policies to aid in the prevention of widespread heavy metal contamination in area with characteristics similar to those of the study area.     

Platinum-group and other traffic-related heavy metal contamination in road sediment, Guangzhou, China

Purpose

Human exposure to particulate matter emitted from on-road motor vehicles includes complex mixtures of heavy metals from tyres, brakes, part wear, and resuspended road sediment. The purpose of this study was to determine the concentrations of 14 platinum-group and other traffic-related heavy metals in road sediment within the metropolitan area of Guangzhou, China, with a view to identifying their sources and assessing the extent of anthropogenic influence on heavy metal contamination of road sediment.

Materials and methods

Thirty-five samples of road sediment were collected. The concentrations of Cr, Mn, Ni, Cu, Zn, La, Ce, Mo, Cd, Pb, Ba, and Rh were measured by inductively coupled plasma?Cmass spectrometry. Pt and Pd were analyzed by isotopic dilution?Cinductively coupled plasma?Cmass spectrometry. Multivariate statistical analysis and enrichment factor methods were employed to identify the sources of these heavy metals and to assess anthropogenic influences on their occurrence.

Results and discussion

The mean concentrations of Pt, Pd, Rh, Cr, Mn, Ni, Cu, Zn, La, Ce, Mo, Cd, Pb, and Ba in the road sediment samples were 68.24, 93.15, 23.85, 147.5, 712.3, 47.24, 177.5, 1254, 47.50, 96.62, 4.91, 3.00, 198.1, and 641.3?ng?g^?1, respectively. Very weak to significant linear positive correlations were found among the various heavy metals. The elemental composition of road sediment was dominated by five principal components. Three clusters were identified through cluster analysis, and enrichment factors were calculated relative to soils in China. The sources and degree of contamination of the heavy metals are discussed based on the results.

Conclusions

The mean concentrations of heavy metals are higher than background values, especially for Pt, Pd, Rh, Cd, and Zn. Four main sources are identified: (1) Pt, Pd, and Rh were derived from traffic sources; (2) La, Ce, Mn, and Ba were derived mainly from natural sources; (3) Cr, Ni, Cu, Mo, Cd, and Pb showed mixed traffic-industry sources; and (4) Zn originated mainly from industrial sources. Enrichment factor analysis supported this source identification and further indicated that contamination of road sediment in Guangzhou is extremely high for Pt, Pd, and Rh; moderate to very high for Cd, Zn, Pb, Cu, and Mo; and minimal for Cr, Ni, La, Ce, and Ba.     

Heavy metals in soils and sedimentary deposits of the Padanian Plain (Ferrara, Northern Italy): characterisation and biomonitoring

Purpose

This contribution investigates agricultural soils and sedimentary deposits in the province of Ferrara (Padanian alluvial plain, Northern Italy) in order to: examine their genesis; to define the geochemical background of the area; and to evaluate the existence of anthropogenic contamination. Moreover, environmental risk related to the presence of potentially toxic heavy metals that can be transferred into agricultural products (and consequently bio-accumulated in the food chain) was also assessed.

Materials and methods

The analyses (reported in an extensive supplementary dataset) include XRD, XRF and ICP-MS assessment of bulk sediments, tests of metal extraction with aqua regia, as well as analyses of local agricultural products, i.e. biomonitoring which is important in the evaluation of element mobility.

Results and discussion

Based on the results, GIS-based geochemical maps were produced and local background levels were defined. This approach demonstrated that high concentrations of Cr and Ni is a natural (geogenic) feature of the local alluvial terrains, which in turn is related to the origin and provenance of the sediments, as confirmed by the lack of top enrichment in all of the investigated sites. Tests of metal extraction and analyses of agricultural products provide guidelines for agricultural activities, suggesting that extensive use of sewage sludge, industrial slurry and manure (that are often rich in metals) should be minimised.

Conclusions

The dataset reported in this paper shows that the agricultural terrains of the studied alluvial plain are not characterised by anthropogenic heavy metal pollution. In spite of the elevated natural background of Cr and Ni, most of the local agricultural products do not show significant evidence of bio-magnification. Exceptions are represented by forage grass (alfalfa) and corn (maize) that tend to uptake As and Ni, respectively. This demonstrates that in agricultural areas, a geochemical risk assessment must include both soil and plant investigations.     

Contents and chemical forms of heavy metals in school and roadside topsoils and road-surface dust of Beijing

Purpose

The concentration of human activities in urban systems generally leads to urban environmental contamination. Beijing is one of ancient and biggest cities on the world. However, information is limited on Beijing’s soil contamination, especially for roadside and campus soils. Thus, the aims of this study were to investigate the contents and chemical forms of toxic heavy metals Cd, Cr, Cu, Ni, Pb, and Zn in the road-surface dust, roadside soils, and school campus soils of Beijing. In addition, enrichment and spatial variation of these toxic heavy metals in the soils and dust were assessed.

Materials and methods

Topsoil samples were collected from the schools and roadside adjacent to main ring roads, and dust samples were collected from the surface of the main ring roads of Beijing. These samples were analyzed for total contents and chemical forms of Cd, Cr, Cu, Ni, Pb, Sc, Zn, Al, and Fe. Enrichment factors (EFs, relative to the background content) were calculated to evaluate the effect of human activities on the toxic heavy metals in soils.

Results and discussion

Heavy metal contents in the road dust ranged from 0.16 to 0.80, 52.2 to 180.7, 18.4 to 182.8, 11.9 to 47.4, 23.0 to 268.3, and 85.7 to 980.9 mg kg^?1 for Cd, Cr, Cu, Ni, Pb, and Zn, respectively. In the roadside soil and school soil, Cd, Cr, Cu, Ni, Pb, and Zn contents ranged from 0.13 to 0.42, 46.1 to 82.4, 22.7 to 71.6, 20.7 to 29.2, 23.2 to 180.7, and 64.5 to 217.3 mg kg^?1, respectively. The average EF values of these metals were significantly higher in the dust than in the soils. In addition, the average EF values of Cd, Cu, Pb, and Zn in the soils near second ring road were significantly higher than those near third, fourth, and fifth ring roads. Anthropogenic Cd, Pb, and Zn were mainly bound to the carbonates and soil organic matter, while anthropogenic Cu was mainly bound to oxides. The mobility and bioavailability of these metals in the urban soils of Beijing generally decreased in the following order: Cd?>?Zn?>?Pb?>?Cu?>?Ni?>?Cr; while in the dust, they decreased in the following order: Zn, Cu, and Cd?>?Pb?>?Ni?>?Cr.

Conclusions

Both EF and chemical forms documented that Cr and Ni in the soils and dust mainly originated from native sources, while Cd, Cu, Pb, and Zn partially originated from anthropogenic sources. In overall, Beijing’s road dust was significantly contaminated by Cd and Cu and moderately contaminated by Cr, Pb, and Zn, while Beijing’s roadside soil and school soil were moderately contaminated by Cd and Pb. However, the maximal hazard quotients (HQs) for individual Cd, Cr, Cu, Ni, Pb, and Zn and comprehensive hazard index (HI) of these metals in the dust and soil were less than 1, indicating that the heavy metals in the dust and soil generally do not pose potential health effects to children, sensitive population.     

Anthropogenic environmental impact in the Mediterranean coastal area of Koper/Capodistria,Slovenia

Purpose

Heavy metal content in soils could be a consequence of geogenic and different anthropogenic sources. In ancient times, soils in the Mediterranean region were affected by agriculture and viticulture, whereas more recently, industry and traffic might contribute more to their pollution. The aim of the study is to determine the extent of multisource heavy metal pollution in soils within the Koper area.

Materials and methods

Along the northern Adriatic Sea coast, around the port city of Koper/Capodistria, 24 topsoil samples were collected; sets of six samples representing four possible pollution sources: intensive agriculture, viticulture, port activities and industry. The parent material of the soil is mainly derived from the Eocene flysch weathered marls and calcarenites and the soil types are eutric. The chemical composition of the samples was determined by ICP-ES for oxides and several minor elements and by ICP-MS for heavy metals. The mineral composition of the selected samples was checked using X-ray powder diffraction. Different statistical analyses were performed on the normally distributed data.

Results and discussion

The mean concentrations of all samples are: Cr 215 mg kg^?1, Ni 81 mg kg^?1, Zn 67 mg kg^?1, Cu 44 mg kg^?1 and Pb and Co 18 mg kg^?1. The ANOVA showed significant differences only in CaO, C/TOT, P₂O₅, Co and Pb between those locations within reach of the different contamination sources. The observed average values of heavy metals are well below Slovenia’s Directive limit for Cu, Pb and Zn, close to but not above it for Co and above the action value for Cr and Ni. According to Igeo, soils from all the sampling locations are uncontaminated with Co, Ni and Pb, and uncontaminated to moderately contaminated with Cu and Zn at one port location, and with Cr at all locations.

Conclusions

The very high Cr and Ni levels could still be geogenic because soils developed on Eocene flysch rocks are enriched in both metals. Cr and Ni are not correlated because of their different levels of sorption and retention in carbonate soils. Cr was retained and concentrated in the sand fraction but Ni has been mobilised in solution. The only serious threat to the environment seems to be an illegal waste dumping area near the port.     

Effect of biosolid application to Mollisol Chilean soils on the bioavailability of heavy metals (Cu,Cr, Ni,and Zn) as assessed by bioassays with sunflower (Helianthus annuus) and DGT measurements

Purpose

This study assessed the effect of biosolid application on the bioavailable fraction of some trace elements (Cu, Cr, Ni, and Zn) using a bioassay with sunflower (Helianthus annuus) and a chemical assay, diffusion gradient in thin films (DGT).

Materials and methods

Five surface soil samples (0–20 cm) were collected from an agricultural zone in Central Chile where biosolids are likely to be applied. Municipal biosolids were mixed with the soil at concentrations of 0, 30, 90, and 200 Mg ha^?1. The experiment to determine the bioavailability of metals in the soil using the bioassay was performed using sunflower. The DGT technique and Community Bureau of Reference (BCR) sequential extraction were used to determine the bioavailable fractions of the metals.

Results and discussion

The application of biosolids increased the phytoavailability of Zn, Ni, and Cr in most of the soils, as indicated by the increasing concentrations in sunflower plants as the biosolid application rate increased. In two of the soils, Codigua and Pelvín, this increase peaked at an application rate of 90 Mg ha^?1. Decreases in the bioavailable fractions of Zn, Ni, and Cr were observed with higher biosolid application rates. The bioavailability of metals was estimated through multiple linear regression models between the metals in the sunflower plants and the different chemical fractions of metals in the soils treated with different biosolid rates, which displayed a positive contribution of the labile (water soluble, carbonate, and exchangeable), oxide, and organic metal forms in the soil, particularly with respect to Ni and Zn at application rates of 30 and 90 Mg ha^?1. The bioavailable fraction of metals was determined in soils using the DGT technique. The effective concentration (C _E) results were compared with those in sunflower plants. The DGT technique could effectively predict the bioavailable fractions of Cr, Ni, and Zn in the Taqueral soil but only that of Zn in the Polpaico soil.

Conclusions

The application of biosolids significantly increased the labile fraction of most of the metals in the studied soils, particularly at the highest biosolid application rate. C _E increased as the concentration of biosolids increased for most of the metals. The effectiveness of the DGT technique for predicting the bioavailability of metals was dependent on the soil type and the metal. However, the C _E for soil Cu was not related to plant Cu for all soils studied.     

Remediation of an electroplating contaminated soil by EDTA flushing: chromium release and soil dissolution

Purpose

Remediation of soils contaminated with Cr (as Cr(III) complexes/precipitates and/or Cr(VI) oxyanion) and cationic metals (Cu, Ni, Zn, and Pb) by ethylenediaminetetraacetate (EDTA) flushing has been challenging and rarely investigated. This study aimed to evaluate the efficiency of EDTA flushing for metal extraction of soil from an electroplating site, with a specific focus on chromium release and soil dissolution.

Materials and methods

Column flushing tests were performed on a sandy soil contaminated by electroplating activities in the field. Three EDTA concentrations (5, 10, and 20 mM) and flow interruptions were employed to investigate the operation of EDTA flushing.

Results and discussion

Results demonstrated that Cr, Cu, and Ni were continuously released along with dissolution of Fe, Al, Mg, and Mn throughout the entire flushing process (up to 600 pore volumes), whereas Zn and Pb removal primarily occurred in the first 50–200 pore volumes. By comparing the Cr and Fe release patterns, the observed Cr release by EDTA flushing possibly resulted from a combination of dissolution of Fe oxides, dissolution of metal–chromate precipitates, and ligand competition for the surface sites (substitution reaction). The latter two mechanisms appeared to be more influential at the early stage. It was also revealed that soil dissolution was predominant, and metal extraction became inefficient at the later stage of flushing, especially with the concentrated EDTA solution. On the other hand, when the flushing process was temporarily paused (i.e., flow interruptions), Cr, Cu, Ni, and Zn concentrations elevated, whereas Pb levels in the effluent decreased, indicating the significance of rate-limited metal exchange of newly formed metal–EDTA complexes.

Conclusions

In consideration of EDTA utilization efficiency and potential ecological risks, diluted EDTA solution is recommended for field applications.     

Effects of iron ore tailings on growth and physiological activities of Tagetes patula L.

Purpose

Ornamentals can beautify the environment and resolve heavy metal pollution at the same time. Thus, the present study aimed at studying the growth and physiological response of Tagetes patula on iron ore tailings.

Materials and methods

Pot-culture experiments were conducted to investigate the effect of iron ore tailings both individually as well as in combination with soil (at different proportions) on the growth, pigment production as well as accumulation and translocation of various heavy metals from the tailings.

Results and discussion

The results suggested an increase in growth, chlorophyll content, as well as metal accumulation capacity of T. patula with increasing proportion of tailings in the soil. Furthermore, an increase in antioxidant activities in plants grown on tailings as compared to control was observed which suggests plant efficiency to overcome any stress generated due to excess of heavy metals. The order of accumulation of various heavy metals in the plant parts was observed to be Fe?>?Cr?>?Zn?>?Cu?>?Pb?>?Ni?>?Cd. Both bioaccumulation and translocation values were maximum for Fe and minimum for Ni and Cd, respectively.

Conclusions

The overall study clearly suggests plant ability to grow well on the tailings and survive excess of heavy metals present in the tailings. Thus, the plant qualifies well as a potential tool for phytostabilization of iron ore tailings and probably a source of income generation from wasteland owing to its multiple commercial values.     

Metal fluxes at the sediment–water interface in rivers in the Turvo/Grande drainage basin, S?o Paulo State, Brazil

Purpose

The Turvo/Grande drainage basin (TGDB), located in the northwestern region of S?o Paulo state, covers an area of 15,983?km². The region is typically regarded as agricultural by the S?o Paulo State Environmental Agency, but the industrial area is expanding, and some studies have shown that metal concentrations in water can be higher than the values regulated by Brazilian law. Therefore, the aim of this study was to assess the role of sediments as a source or a sink of metals for drainage basin management.

Materials and methods

Interstitial water from different sediment depths (0?C42?cm) and the sediment?Cwater interface and sediment core samples were collected in February and July 2010 from the Preto, Turvo, and Grande rivers. Quantification of Cr, Cu, Fe, Mn, Ni, and Pb in these samples was performed by graphite furnace or flame atomic absorption spectrometry. Metal diffusive flux estimation from sediment into the overlying water was calculated by Fick??s First Law of Diffusion.

Results and discussion

The fluxes of all metals for the three rivers were positive, indicating diffusion into the overlying water. Ni and Pb showed the lowest diffusive fluxes, which ranged from 2.4 to 3,978???g?m^?2?day^?1 for Ni and from ?0.1 to 1,597???g?m^?2?day^?1 for Pb. In turn, Cu and Cr were subject to the largest transfer to water, especially in the dry season (Cr, 4.5?C7,673???g?m^?2?day^?1; Cu, 1.3?C14,145???g?m^?2?day^?1). The Preto River (urban area) showed smaller fluxes than the Grande River (agricultural area), and the values of the latter were higher than those found in other impacted areas of the world.

Conclusions

The diffusive fluxes indicate that sediments from the TGDB act as a source of metals for the water column, with increased export of metals, particularly Cr and Ni, from the sediment into the overlying water during the dry season.     

Heavy metal pollution of the world largest antimony mine-affected agricultural soils in Hunan province (China)

Purpose  

The present work concerns the distribution of ten heavy metals (Sb, As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, and Zn) in the surrounding agricultural soils of the world largest antimony (Sb) mine in China. The objective is to explore the degree and spatial distribution of heavy metal pollution of the Sb mine-affected agricultural soils. The presented data were compared with metal concentrations in soils from mining and smelting sites in China and other countries.     

Influence of pH on the release and chemical fractionation of heavy metals in sediment from a suburban drainage stream in an arid mine-based oasis

Purpose

The objectives of this study were to explore the influences of pH on the release of Cu, Zn, Cd, Pb, Ni, and Cr in sediments derived from the upstream, middle, and downstream reaches of Dongdagou stream in Gansu Province, Northwest China, and to examine the fractionation changes of heavy metals in the sediments after reaching their release equilibrium under different pH conditions.

Materials and methods

Sediment samples were obtained using a stainless steel grab sampler to collect the uppermost 10 cm of sediment from the channel bed. The pH-dependent release experiment was conducted in the solid-to-liquid ratio of 1:20 at different pH values (2, 4, 6, 8, 10, and 12) at room temperature. The total Cu, Zn, Cd, Pb, Ni, and Cr concentrations in the sediments were digested using an acid digestion mixture (HNO₃ + HF + HClO₄) in an open system. Metal fractionation of selected sediments was obtained using the Tessier sequential extraction procedure. Heavy metal concentrations in the samples were determined using atomic absorption spectrophotometry.

Results and discussion

The mean concentrations of heavy metals in sediments decreased in the following order: Zn (1676.67 mg kg^?1) > Pb (528.65 mg kg^?1) > Cu (391.34 mg kg^?1) > Cr (53.48 mg kg^?1) > Ni (34.27 mg kg^?1) > Cd (11.53 mg kg^?1). Overall, the solubility of Cu, Zn, Cd, Pb, and Ni decreased with increasing pH, and they were strongly released at pH 2. Moreover, the solubility of Cr increased with increasing pH, and its release was highest at pH 12. After reaching the release equilibrium of heavy metals under different pH conditions, the percentages of organic Cu, Zn, Cd, and Fe-Mn oxyhydroxide Pb decreased, compared to their initial fractions. The residual fractions of Ni and Cr were dominant, regardless of pH.

Conclusions

The average concentrations of Cu, Zn, Cd, and Pb in sediments were highly elevated compared with the soil background values in Gansu Province, China. The results of this pH-dependent release experiment showed that the release behaviors of Cu, Zn, Pb, and Cr followed an asymmetric V-shaped pattern, whereas Cd and Ni followed an irregular L-shaped pattern. The changes in the release of heavy metals in sediments were related to their redistribution between chemical fractionations.

     

Trace metals in sediments and aquatic plants from the Xiangjiang River, China

Purpose

The metal concentrations and Pb isotopic composition in sediments and plants from the Xiangjiang River, China, were investigated to understand the contamination and potential toxicity of metals in sediments; to determine the accumulation and distribution of metals in plant tissues; and to trace the possible pollution source of Pb in sediments and plants.

Materials and methods

Sediments and plants were collected from 43 sampling sites in the study region. After sediments were air-dried and passed through a 63-??m sieve, they were acid-digested and DTPA-extracted for determination of total and bioavailable metals. The plants were separated into roots, leaves, and stems; dried; cut into pieces; and digested with HNO₃?CH₂O₂. Metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) and Pb isotopic composition were analyzed by inductively coupled plasma-mass spectrometry.

Results and discussion

Maximum As, Cd, Cr, Cu, Ni, Pb, and Zn concentrations in sediments were 47.18, 55.81, 129.5, 161.6, 160.4, 430.7, and 1,098.8?mg?kg^?1, respectively. The bioavailable fractions of As, Cd, Cu, Pb, and Zn had significant linear relationship with their corresponding total contents in sediments while no significant relationship was observed between bioavailable and total contents of Cr and Ni. In general, plant tissues showed higher As, Cd, Cu, Pb, and Zn concentrations and lower Cr and Ni concentrations compared with sediments. The ²⁰⁶Pb/²⁰⁷Pb ratios decreased in the order of total > bioavailable > stems ?? leaves > roots. A strong linear correlation was observed between the ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁷Pb ratios of the plant tissues, sediments, and the possible pollution sources of Pb in the Xiangjiang River.

Conclusions

As, Cd, Cu, Pb, and Zn demonstrated higher contamination levels in sediments and plants compared with Cr and Ni. Cd had highest potential ecological risk. The Pb from anthropogenic sources with low ²⁰⁶Pb/²⁰⁷Pb ratios was preferentially associated with the bioavailable fractions in sediments and accumulated in roots. The Pb in plant tissues is mainly derived from the Pb in sediment and is taken up through the sediment-to-root pathway.     

Pollution assessment and spatial variation of soil heavy metals in Lixia River Region of Eastern China

Purpose

The effect of soil heavy metals on crops and human health is an important research topic in some fields (Agriculture, Ecology et al.). In this paper, the objective is to understand the pollution status and spatial variability of soil heavy metals in this study area. These results can help decision-makers apportion possible soil heavy metal sources and formulate pollution control policies, effective soil remediation, and management strategies.

Materials and methods

A total of 212 topsoil samples (0–20 cm) were collected and analyzed for eight heavy metals (Cd, Hg, As, Cu, Pb, Cr, Zn, and Ni) from agricultural areas of Yingbao County in Lixia River Region of Eastern China, by using four indices (pollution index (PI), Nemerow pollution index (PI_N), index of geo-accumulation (I _geo), E _i /risk index (RI)) and cluster analysis to assess pollution level and ecological risk level of soil heavy metals and combining with geostatistics to analyze the concentration change of heavy metals in soils. GS+ software was used to analyze the spatial variation of soil heavy metals, and the semi-variogram model is the main tool to calculate the spatial variability and provide the input parameters for the spatial interpolation of kriging. Arcgis software was used to draw the spatial distribution of soil heavy metals.

Results and discussion

The result indicated that the eight heavy metals in soils of this area had moderate variations, with CVs ranging from 23.51 to 64.37 %. Single pollution index and Nemerow pollution index showed that about 2.7 and 1.36 % of soil sampling sites were moderately polluted by Cd and Zn, respectively. The pollution level of soil heavy metals decreased in the order of Cd?>?Zn?>?Pb?>?As?>?Cu?>?Cr?>?Ni?>?Hg. The I _geo values of heavy metals in this area decreased in the order of Zn?>?Cd?>?As?>?Pb?>?Cu?>?Cr?>?Hg?>?Ni. According to the E _i index, except Cd that was in the moderate ecological risk status, other heavy metals in soils were in the light ecological risk status, and the level of potential ecological risk (RI) of soil sampling sites of the whole area was light.

Conclusions

The results of four indices and the analysis of spatial variation indicated that the contents of Cd and Zn were contributed mainly by anthropogenic activities and located in the south-east of this study area. However, the contents of Hg, As, Cu, Pb, Cr, and Ni in soils were primarily influenced by soil parent materials.

     

Assessing the heavy metal contamination of soils in the water-level fluctuation zone upstream and downstream of the Manwan Dam,Lancang River

Purpose

The intersections of the terrestrial and aquatic systems (water-level fluctuation zones, WLFZs) suffer from the increasing pressure of hydroelectric construction and operation. Taking WLFZs upstream and downstream of Manwan Dam (first dam completed in Lancang River) as an example, the dam operation impacts on the heavy metals in soils in WLFZs were assessed.

Materials and methods

In December 2011, 117 soil samples were collected in the WLFZs and infralittoral reference zones (IRZs) with respect to heavy metal (Cd, Cr, Cu, Ni, Pb and Zn) and metalloid (As) concentrations. Their concentrations were determined with the application of inductively coupled plasma atomic absorption spectrometry, ICP-AES. Enrichment factor (EF), ecological risk index (RI) and principal component analysis (PCA) were employed for element contamination and ecological risk assessment and source identification, respectively. The multivariable statistic approaches, an analysis of variance (ANOVA) and a paired-samples T test were performed in the data analysis.

Results and discussion

Parts of element concentrations in the upstream were significantly higher than those in the downstream and significant differences existed between the WLFZs and IRZs. No significant difference was detected between the different water elevations in the WLFZs. Compared to the soil quality guidelines, As and Cd exceeded the standard in both the WLFZs and IRZs. In addition, the water-level fluctuation during the submergence increased the enrichment degree and risk level in the WLFZs. The sources of the studied elements could be divided into natural factors and anthropogenic inputs. In addition, the submergence changed the major contaminants in the upstream WLFZs.

Conclusions

The results verified that dam operation had an effect on the heavy metals in the soils in WLFZs. In addition, this study proposed a useful tool (modified enrichment factor) to assess the enrichment degree caused by the water-level fluctuation. Assessing the heavy metal contamination of soils in WLFZs could be an important first step to the rational management of the dam operation.     

The role of the smooth cordgrass Spartina alterniflora and associated sediments in the heavy metal biogeochemical cycle within Bahía Blanca estuary salt marshes

Background, aim, and scope

Bahía Blanca estuary is characterized by the occurrence of large intertidal areas, including both naked tidal flats and salt marshes densely vegetated with Spartina alterniflora. The estuary is strongly affected by human activities, including industrial and municipal discharges, harbor maintenance, cargo vessels and boat navigation, oil storage and processing, etc. Even numerous studies have reported the occurrence and distribution of heavy metals in sediments and biota from this estuary, although the function of the halophyte vegetation on metals distribution was at present not studied. The main objective of the present study was to understand the potential role of the salt marshes as a sink or source of metals to the estuary, considering both the obtained data on metal levels within sediments and plants from the studied areas at naked tidal as well as vegetated flats.

Materials and methods

The selected study area, named Villa del Mar, was located in the middle estuary coast. The sampling was carried out under low tide conditions, and the sampling area was divided into two parts: A (close to Villa del Mar) and B (north-westerly of Villa del Mar). In each part, two integrated samples of S. alterniflora (the first in the medium-salt marsh and the second in the higher one) were collected. Also sediments associated with the roots of S. alterniflora were taken at the same locations, in addition to another sediment sample from the naked zones of the tidal flats (without any vegetation). After corresponding treatment at the laboratory, plant and sediment samples were mineralized according to Marcovecchio and Ferrer, J Coast Res 21:826–834, 2005), in order to measure their metal concentrations by atomic absorption spectroscopy (AAS). Analytical quality (AQ) was checked against certified reference materials from NIES, Tsukuba (Japan).

Results

Most of the Spartina samples have shown highest Cd and Mn concentrations in the aerated parts of the plants, indicating an allocation process from the roots up to the leaves. Most of the samples have presented non-detectable Pb and Cr values. Cu, Fe, Ni, and Zn have presented highest concentrations in the underground parts of the plant, suggesting an accumulation process in the roots and rhizomes. In the case of sediments, samples from those sites located far away from Villa del Mar have presented greater concentrations on the sediments associated with underground parts of Spartina than those from the naked tidal flat, for almost all of the metals studied. Unlike this, the samples from the site close to Villa del Mar have shown the higher concentrations in sediments from the naked tidal flat.

Discussion

Marsh plants are known to absorb and accumulate metals from contaminated sediment, and this is one reason that allows wetlands to be used for wastewater treatment. It was observed that those sets of samples from the same salt marsh levels (e.g., A.1 and B.1, or A.3 and B.3) have shown similar heavy metal distribution trends, although even their corresponding concentrations could be different. Thus, the concentrations of Cu, Zn, Ni, and Fe in the medium-salt marshes were higher in the underground tissues (roots plus rhizomes), with the exception of Mn, which was seen to be higher in the aboveground parts. The same tendency occurs at high-salt marshes for these heavy metals, with the exception of Ni. This fact was sustained regarding the fact that the levels mentioned (medium-salt marsh and high-salt marshes) must have the same exposition to heavy metal sources, similar physical-chemical conditions regulating metal distribution within the compartments on the salt marshes or, simultaneously, both mentioned processes. Moreover, metals in this macrophyte can remain after the leaves have died and turned into detritus. The metals present in the detritus can be passed on to consumers (Quan et al., Mar Environ Res 64:21–37, 2007)). Keeping in mind that Bahía Blanca estuary’s salt marshes are inundated twice each day by tidal water for 3–4 h, macrophytes may act as a conduit for the movement of metals from the sediment to the estuarine body and near-coastal system.

Conclusions and recommendations

Considering the comments on the previous paragraphs, salt marshes from Bahía Blanca estuary are sources or sinks for metals? It can be sustained that both are the case, even if it is often stated that wetlands serve as sinks for pollutants, reducing contamination of surrounding ecosystems (Weis and Weis, Environ Int 30:685–700, 2004)). In the present study case, the sediments (which tend to be anoxic and reduced) act as sinks, while the salt marshes can become a source of metal contaminants. This is very important for this system because the macrophytes have been shown to retain the majority of metals in the underground tissues, and particularly in their associated sediments. This fact agreed well with previous reports, such as that from Leendertse et al., Environ Pollut 94:19–29, 1996) who found that about 50% of the absorbed metals were retained in salt marshes and 50% was exported. Thus, keeping in mind the large spreading of S. alterniflora salt marshes within Bahía Blanca estuary, it must be carefully considered as a re-distributor of metals within the system.     

Spatial distribution and source apportionment of the heavy metals in the agricultural soil in a regional scale

Purpose

Understanding the spatial distribution and sources of soil heavy metals (HMs) in a large city helps prevent and control soil pollution. This study aimed to investigate the spatial patterns of soil HMs and identify their main sources in a regional scale.

Materials and methods

A total of 110 topsoil samples were collected from Tai’an City, China. Cd, Cr, Cu, Hg, Ni, Pb, and Zn concentrations in each soil sample were determined. Geostatistics, geographic information system (GIS), and positive matrix factorization (PMF) were used to explore the spatial distribution of seven soil HMs and to reveal the main sources of soil HMs in Tai’an City, respectively.

Results and discussion

Soil Cd, Cr, Pb, and Zn generally showed slight pollution levels in the study area. However, soil Hg and Cu contents reached moderate to heavy pollution levels in some areas. Soil Hg content increased from north to south across the city, and the highest Hg concentration was detected in Ningyang County. Soil Cd, Cu, and Zn distributions exhibited a similar pattern, and their contents increased from west to east; the highest Cd, Cu, and Zn concentrations were found in Xintai County. The highest soil Ni concentration was obtained in the northeast of Feicheng and Xintai counties. PMF analysis revealed the following four potential sources of agricultural soil HMs in Tai’an City: industrial and mining activities, agricultural activities, residential living activities, and business activities. Soil Hg mainly originated from residential living activities, which accounted for 75.3% of the total source. The main sources of soil Ni were residential living activities, agricultural activities, and industrial and mining activities, which account for 38.2, 27.50, and 25.1% of the total source, respectively. Soil Cu was mainly produced by agricultural activities (36.6%), followed by residential living activities (29.8%) and industrial and mining activities (25.8%).

Conclusions

PMF combined with GIS could be effectively applied to determine the main sources of HMs in agricultural soils in a regional scale.

     

Occurrence of Cu and Cr in the sedimentary humic substances and pore water from a typical sugar cane cultivation area in São Paulo,Brazil

Purpose

The purpose of this paper is to study the interactions of sedimentary humic substances (SHS) from a sugarcane cultivation area with Cu(II) and Cr(III) and to evaluate the occurrence of these metals in the pore water and SHS.

Materials and methods

For this study, the northwestern region of the State of São Paulo, Brazil, which is considered the region with the highest production of sugar cane in the state, was selected. Samples of sediment were collected from four sampling sites in the Preto, Turvo, and Grande rivers. The SHS and pore water were extracted from the sediment using the method suggested by the International Humic Substances Society and centrifugation, respectively. The complexing capacity (CC) of the SHS for Cu(II) and Cr(III) was determined by individually titrating these metals with an ultrafiltration system using tangential flow. The total concentrations of Cr and Cu were determined for the pore water, sediments, and humic substances with graphite furnace atomic absorption spectrometry and Zeeman background correction after an acid digestion, according to the methods described in US EPA Method 3050B.

Results and discussion

The SHS from a site in the Turvo River, which is typically cultivated with sugarcane, possessed the highest concentration of Cu bound to SHS (25.0%), the largest CC (0.63 mmol Cu g^?1 HS) and the highest concentration of this metal in the pore water (1.38 mg Cu Kg^?1 sed.). For Cr, the SHS collected from a location on the Preto River dam had the largest CC (0.90 mmol Cr g^?1 HS) and the lowest Cr content in the pore water (0.29 mg Cr Kg^?1 sed.), indicating that there was an inverse relationship between the CC and the concentration of metal available in the pore water.

Conclusions

Sedimentary humic substances might be one of the regulatory factors controlling the availability of Cu and Cr in the sediments found in a typical region that has been planted with sugarcane. Distinct behaviors were observed between the two elements investigated; higher CC and a larger fraction of Cu(II) were found in the pore water of samples originating from sugarcane crops. The opposite behavior was observed for the Cr(III) species.