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.

     

Identification of the sources of metals and arsenic in river sediments by multivariate analysis and geochemical approaches

Purpose

Frequent mining activities and higher background values in soil have led to the contamination of the sediments of some rivers in southwest China by several metals and arsenic (As). This study combined multivariate analysis with geochemical approaches to differentiate mining activity from other sources, which may aid to evaluate the effectiveness of reducing mining release.

Materials and methods

Sixteen sediment samples were collected along the Yuan River, China. The total concentrations of lead (Pb), zinc (Zn), copper (Cu), cadmium (Cd), chromium (Cr), mercury (Hg), and As were measured by inductively coupled plasma-atomic emission spectrometer (ICP-AES). The Pb isotopic composition was measured using a thermal ionization mass spectrometer (TIMES). Both geochemical approaches and multivariate statistical analysis were used to identify the sources of these metals. The fractionation of Pb was determined through a Community Bureau of Reference (BCR) sequential extraction procedure to aid the identification of the sources.

Results and discussion

The concentrations and enrichment factors (EFs) of Pb, Zn, Cu, Cd, and As in the middle reach of the river were higher than those at the other sites, indicating anthropogenic sources. The factor analysis (FA) extracted “mining and smelting,” “mixture of anthropogenic and natural,” and “natural” factors. The Pb isotope composition of metal ores was similar (²⁰⁶Pb/²⁰⁷Pb?<?1.190 and ²⁰⁸Pb/²⁰⁶Pb?>?2.023) to that found in the sediments in the middle reach, indicating anthropogenic sources of mining activities. Compared with the narrow ranges of the δ³⁴S ratios in the bedrock (+8.5 to +9.3?‰) and the metal ores (?1.4 to +1.9?‰), the sediment samples presented a relatively wide range of δ³⁴S ratios from ?2.6 to +9.2?‰ with a mean of +2.6?‰, which suggests a mixed composition. The BCR sequential extraction procedure revealed that the proportion of the extractable fraction in the sediments in the middle reach was higher than that in other sites, suggesting anthropogenic sources as the cause of contamination in the study area.

Conclusions

Lead, Zn, Cu, Cd, Cr, Hg, and As are mainly derived from natural materials in the upstream region. In the middle reach, these elements are the result of anthropogenic activities, particularly activities associated with the mining industry. In the downstream region, the origin of these elements is considered to be a mixture of anthropogenic and natural sources. In addition to geochemical approaches and multivariate statistical analysis, the BCR sequential extraction method is an effective procedure for the identification of the anthropogenic sources of sediment-associated metals.     

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.     

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.     

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.     

Plant uptake of metals,transfer factors and prediction model for two contaminated regions of Kosovo

The bioavailability and plant uptake of heavy metals (HM), as well as finding the most reliable methods for the prediction of availability, continues to be one of the most crucial problems in agricultural and environmental studies. In agricultural soils from two regions in Kosovo, known for its metal pollution, we collected 60 soil and plant samples (wheat, corn, potatoes, and grass). Heavy metals were extracted from soil with aqua regia (pseudototal concentration), NH₄OAc‐EDTA (potential bioavailable), and NH₄NO₃ (mobile fraction), plant samples were digested with HNO₃/H₂O₂ (microwave assisted extraction). The pseudo total content of Cd, Pb, and Zn showed high value in Mitrovice (mean: Cd–2.92, Pb–570.15, and Zn–522.86 mg kg^?1), whereas in Drenas region Ni and Cr showed high value with a mean 258.54 and 203.22 mg kg^?1. Also, the potential bioavailability and mobile form of these metals were increased in Mitrovice (mean: Cd–1.59, Pb–217.05, Zn–522.86 mg kg^?1, respectively Cd–0.17, Pb–0.64, and Zn–15.45 mg kg^?1), compared to Drenas. Cd and Pb were elevated in potato tubers (mean Cd–0.48 and Pb–0.85 mg kg^?1). The TF was higher for micronutrients (Zn and Cu) than for non‐essential metals (Cd and Pb). Multiple regression analysis showed a good model for prediction of Cd, Pb and Zn content in plant with significance 99.9%, whereas this model was not significant for Cu, Cr, and Ni. Soil pH played a significant role in the content of Cd and Zn in wheat and potato plants. Clay content also showed significance in Cd concentration in wheat and potato plants, while carbon content was significant for Cd in grass plants, as well as for Zn in wheat and grass plants.     

Heavy Metals in Freshly Deposited Stream Sediments of Rivers Associated with Urbanisation of the Ganga Plain,India

Freshly deposited stream sediments from six urban centres of the Ganga Plain were collected and analysed for heavy metals to obtain a general scenery of sediment quality. The concentrations of heavy metals varied within a wide range for Cr (115–817), Mn (440–1 750), Fe (28 700–61 100), Co (11.7–29.0), Ni (35–538), Cu (33–1 204), Zn (90–1 974), Pb (14–856) and Cd (0.14–114.8) in mg kg^-1. Metal enrichment factors for the stream sediments were <1.5 for Mn, Fe and Co; 1.5–4.1 for Cr, Ni, Cu, Zn and Pb; and 34 for Cd. The anthropogenic source in metals concentrations contributes to 59% Cr, 49% Cu, 52% Zn, 51% Pb and 77% Cd. High positive correlation between concentrations of Cr/Ni, Cr/Cu, Cr/Zn, Ni/Zn, Ni/Cu, Cu/Zn, Cu/Cd, Cu/Pb, Fe/Co, Mn/Co, Zn/Cd, Zn/Pb and Cd/Pb indicate either their common urban origin or their common sink in the stream sediments. The binding capacity of selected metals to sediment carbon and sulphur decreases in order of Zn > Cu > Cr > Ni and Cu > Zn > Cr > Ni, respectively. Stream sediments from Lucknow, Kanpur, Delhi and Agra urban centres have been classified by the proposed Sediment Pollution Index as highly polluted to dangerous sediments. Heavy metal analysis in the <20-μm-fraction of stream sediments appears to be an adequate method for the environmental assessment of urbanisation activities on alluvial rivers. The present study reveals that urban centres act as sources of Cr, Ni, Cu, Zn, Pb and Cd and cause metallic sediment pollution in rivers of the Ganga Plain.     

Assessment of diffuse pollution associated with metals in urban sediments using the geoaccumulation index (Igeo)

Purpose

This study investigated the behavior of cadmium (Cd), lead (Pb), nickel (Ni), and zinc (Zn) in urban sediments collected in commercial, residential, and industrial areas of the city of Porto Alegre, Brazil, and evaluated different degrees of pollution in this urban subdrainage basin through the use of the geoaccumulation index (I_geo).

Materials and methods

Concentrations of Cd, Ni, Pb, and Zn were analyzed using acid digestion (EPA method 3050) in fractions <63 μm in 20 composite samples of urban sediment collected using a portable vacuum in 20 different sampling points on roads from three areas with diverse use: commercial, industrial, and residential.

Results and discussion

The values of I_geo were commercial area (3.35, Zn; 3.76, Cd; 3.60, Ni; 2.63, Pb) > residential area (3.34, Zn; 3.36, Cd; 2.94, Ni; 1.46, Pb) > industrial area (2.74, Zn; 1.78, Cd; 3.01, Ni; 1.45, Pb), indicating that the sediment was “highly contaminated” in the case of Zn and Ni, while for Cd, it was “moderately to highly contaminated,” and for Pb, it was “moderately contaminated.” The pollution is associated with traffic flow in all areas.

Conclusions

Research should be increased to make urban systems more sustainable, reducing their pollution potential and minimizing the delivery of potentially polluting particles into freshwater bodies. The I_geo allows for the determination of a simple index of diffuse pollution state associated with urban sediments.     

Evaluation and source identification of trace element contamination of soils in the Qixia lead-zinc mining area,Jiangsu, China

Purpose

The Qixia mine is one of the largest lead-zinc mines in Eastern China and has been operational for approximately 60 years. Source identification for trace element contamination of soils in the Qixia mining area has been lacking. This report details the evaluation and source identification of trace element contamination (including Cu, Zn, Pb, Cd, Hg, Cr, As, and Ni) of soils in this area.

Materials and methods

Thirty-three soil samples from roadsides and fields in the study area were collected and analyzed. The index of geo-accumulation (I _geo) was employed to evaluate contamination. Methods of multivariate statistical analysis were used to determine the probable sources of the pollutants.

Results and discussion

The analysis showed that the levels of contamination ranked in the following order: Cd > Pb/Zn> > As/Cu> > Hg > Cr/Ni. In the sampling area nearest the mine, soil samples collected from roadsides showed much higher levels of contamination than those collected from fields away from the roadways. Trace element contamination decreased as the distance from the mine increased. Contamination extended to a distance of approximately 700 m from mineral transportation routes, with the area of greatest impact at 200 m or less. Multivariate statistical analysis and ore composition data suggest that the Cu, Zn, Pb, Cd, and As found in the soil samples originate from anthropogenic sources. Ni and Cr are considered to be at natural background concentrations.

Conclusions

This study distinguished between natural and anthropogenic sources of trace element contamination in the soils of the Qixia mining area. The contamination of Cu, Zn, Pb, Cd, and As is linked to the mining activities and is likely due to the transportation of ore concentrates and tailings.     

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 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.

     

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.     

Digestion Methods for Total Heavy Metals in Sediments and Soils

The objectives of this study were to analyze the total contents of Cd, Cr, Cu, Ni, Pb, and Zn in the freshwater sediments and the arable and non-arable soils of Taiwan, and to compare the different digestion methods for their determination. Two hundred and thirty-nine freshwater sediments were collected from the Fei-Tsui Reservoir Watershed (FTRW) in northern Taiwan. Forty-two surface (0–15 cm) and subsurface (15–30 cm) soil samples were likewise collected from 21 representative arable soils derived from various parent materials and with varying weathered degrees in different regions of Taiwan. In addition, one hundred and ninety-four non-arable soils were collected from the different forest regions, industrial parks, resident areas, and commercial areas. Several digestion methods including the aquaregia and different combinations of concentrated acids (HClO₄, HNO₃, H₂SO₄, or HF) were compared. All samples were digested both by the aqua regia method and the Baker and Amacher method for Cd, Cr, Cu, Ni, Pb, and Zn. The Reisenauer method was used for Cr and the Burau method for Pb further. The results indicate that the best digestion methods to analyze the total contents of heavy metals in the sediments and soils were recommended as follows: the Baker and Amacher method for Cd, Cr,Cu, Ni, and Zn; the Reisenauer method for Cr, but for simplicity the Baker and Amacher method is also recommended as the flexible method for the total analysis of Cr; the aqua regia method for Cu, Ni, and Zn; and the Burau method for Pb.     

闽江大樟溪下游沿线湿地沉积物中重金属

基于2018年7月采集的大樟溪下游沿线湿地表层沉积物样品,探讨了6种重金属(Pb、Cr、Cu、Zn、Ni、Cd)的沿程分布特征,并运用地累积指数法(Igeo)和潜在生态风险指数法(RI)对其生态风险进行了评估。结果表明,湿地沉积物中重金属的平均含量整体表现为Zn>Pb>Cr>Cu>Ni>Cd,且其沿程变化较为一致,而这主要取决于沉积物粒度组成、磁学参数、pH、EC和有机质的沿程分布。湿地沉积物中的6种重金属含量均于桃花洲、耕櫵亭、方庄村和奥莱时代出现较低值,原因主要与4个采样点的采砂活动改变了河流水沙条件使得沉积物发生粗化有关。湿地沉积物中6种重金属之间均存在极显著正相关关系(P<0.01),说明其具有同源性,并可能代表了一个因采砂/采石活动以及建筑/生活垃圾堆放导致的复合污染源。大樟溪下游沿线湿地大部分样点的Pb处于轻度污染状态,而Cd处于中度污染状态。6种重金属平均单项潜在生态风险指数(E■)表现为Cd>Pb>Ni>Cu>Cr>Zn,Cd具有强生态风险。所有样点重金属的平均RI值为228.62,说明湿地整体处于中等生态风险。研究发现,尽管大樟溪下游沿线湿地沉积物中的重金属含量相比闽江上游其它支流和闽江中下游河段处于一个较低水平,但其Pb、Cd污染及生态风险(特别是Cd)仍较为突出,故下一步在加强对沿线湿地管控时应给予特别重视。     

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.     

汉江上游汉中段河流表层沉积物重金属污染风险评价

通过监测汉江上游汉中段河流表层沉积物重金属Pb,Cu,Zn,Cd,Cr的浓度,分析了各元素的含量分布特征,并选用Hakanson生态风险指数法对研究区进行了环境风险评价。结果表明,汉江上游汉中段各监测点重金属富集顺序为:Cd >Zn >Pb >Cr >Cu。单个重金属的污染指数C_fⁱ显示,汉江上游汉中段监测点仅有Cu的含量均值为0.83,小于1,为轻微污染;Pb,Zn,Cd,Cr的均值分别为1.06,1.25,1.33,1.02,略大于等于1,处于轻微污染以上水平,达到中度污染水平。综合分析多项重金属污染系数C_d,单项重金属的潜在生态风险系数E_rⁱ和多种重金属的生态系统的潜在生态风险指数I_R可知,汉江上游汉中段各监测点沉积物重金属污染属于轻微生态危害。     

Relationships of Heavy Metals in Natural Lake Waters with Physico-chemical Characteristics of Waters and Different Chemical Fractions of Metals in Sediments

The relationships between heavy metal concentrations and physico-chemical properties of natural lake waters and also with chemical fractions of these metals in lake sediments were investigated in seven natural lakes of Kumaun region of Uttarakhand Province of India during 2003–2004 and 2004–2005. The concentrations of Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb in waters of different lakes ranged from 0.29–2.39, 10.3–38.3, 431–1407, 1.0–6.6, 5.3–12.1, 12.6–166.3, 0.7–2.7 and 3.9–27.1 μg l^?1 and in sediments 14.3–21.5, 90.1–197.5, 5,265–6,428, 17.7–45.9, 13.4–32.0, 40.0–149.2, 11.1–14.6 and 88.9–167.4 μg g^?1, respectively. The concentrations of all metals except Fe in waters were found well below the notified toxic limits. The concentrations of Cr, Mn, Ni, Cu, Zn, Cd and Pb were positively correlated with pH, electrical conductivity, biological oxygen demand, chemical oxygen demand and alkalinity of waters, but negatively correlated with dissolved oxygen. The concentrations of Cr, Ni, Zn, Cd and Pb in waters were positively correlated with water soluble + exchangeable fraction of these metals in lake sediments. The concentrations of Zn, Cd and Pb in waters were positively correlated with carbonate bound fraction of these metals in lake sediments. Except for Ni, Zn and Cd, the concentrations of rest of the heavy metals in waters were positively correlated with organically bound fraction of these metals in lake sediments. The concentrations of Cr, Mn, Ni, Cu and Zn in waters were positively correlated with reducible fraction of these metals in lake sediments. Except for Cd, the concentrations of rest of the metals in waters were positively correlated with residual fraction and total content of these heavy metals in lake sediments.     

Geochemical monitoring of organic and inorganic pollutants in the sediment of the Eastern Posavina (Serbia)

Purpose

The aim of this study was to obtain a complete picture of the geochemical character of the sediment in the eastern Posavina region, Serbia, an area which has thus far not been systematically investigated. Geological mapping and impact assessment were thus carried out for this area.

Materials and methods

Sediments were sampled (from 0 to 0.5 m depth) in four locations in eastern Posavina between 2002 and 2014. Eight heavy metals (Ni, Zn, Cd, Cr, Cu, Pb, As and Hg) and a wide variety of organic parameters (16 EPA polycyclic aromatic hydrocarbons (PAHs), mineral oils, selected pesticides and polychlorinated biphenyls (PCBs)) were monitored. Metals were analysed by flame and graphite atomic absorption spectrometry, and gas chromatography with mass detection was used for the PAH analyses. The origins of the monitored substances were classified using geoaccumulation index (I _geo), ecological risk index (RI) and principal component analysis (PCA/FA).

Results and discussion

The sediments all contained higher heavy metals concentrations than the upper continental crust (UCC), suggesting dynamic natural and anthropogenic processes in this unique region. Significant variations (RSD values from 13 to 190) were observed for Cd (0.001–80.00 mg kg^?1), Hg (0.01–5.40 mg kg^?1), mineral oil (2.00–1851 mg kg^?1) and the sum of 16 EPA PAHs (0.003–5.57 mg kg^?1). The I _geo index classified the pollution risk due to Cr as strong, Cd, Zn and Hg as moderate to strong and Ni as moderate. Based on PCA/FA analysis, the parameters were grouped somewhat differently, with anthropogenic activity found to be responsible for much of the Hg, Cd and Cr pollution present in the sediments.

Conclusions

The analysis revealed eight heavy metals (Ni, Zn, Cd, Cr, Cu, Pb, As and Hg), the sum of 16 EPA PAHs and mineral oil as parameters of great interest for this unique region. These parameters must be the focus of future monitoring programs, in support of appropriate remediation techniques and/or dredging activities, which are required in order to comply with the new Serbian regulations and the relevant EU recommendations.

     

Anthropogenic Heavy Metal Pollution in the Surficial Sediments of the Keratsini Harbor, Saronikos Gulf, Greece

The contents of ten elements [Cd, Pb, W, Zn, Mn, As, Se, Cr, Cu, and organic carbon (C_org)] have been determined in the surficial sediments of Keratsini harbor, Saronikos Gulf, Greece. The contamination of the sediments was assessed on the basis of geoaccumulation index and to corresponding sediment quality guidelines (SQGs) effects range low/effects range median. The results revealed highly elevated Cd, Pb, W, Zn, As, Se, Cr, Cu, and C_org values (Cd, 190–1,763 mg kg^?1; Pb, 521–1,263 mg kg^?1; W, 38–100 mg kg^?1; Zn, 409–6,725 mg kg^?1; Mn, 95–1,101 mg kg^?1; As, not detectable–1,813 mg kg^?1; Se, not detectable–58 mg kg^?1; Cr, 264–860 mg kg^?1; Cu, 195–518 mg kg^?1; and C_org, 0.69–4.41%). The enrichment of metals in the sediments results from the contribution of the central Athens sewage outfall through which the waste of the Attica basin ends up in Keratsini harbor as well as from industrial and ship contaminants.     

抚仙湖重金属污染强度、历史及来源的沉积记录

This study focused on the concentration change of heavy metals of sediment cores in heavily polluted north area and less polluted middle area of Fuxian Lake in Southwest China.On the basis of the analysis of Cu,Ni,Ti,V,Pb,Cd,and Zn concentration-depth profiles,the pollution history of heavy metals was studied using ¹³⁷cesium (¹³⁷Cs) dating.The sources of heavy metals were distinguished by normalization of their profiles to aluminum and analysis of heavy metal concentrations of potential source materials.Geoaccumulation index (I_geo) was used to quantify their contamination intensity.The results showed that all the heavy metals found in the Fuxian Lake sediments originated naturally before 1980s.Cu,Ni,Ti,and V were still mainly natural in the north lake after 1980s,Cu,Ni,Ti,V,and Pb were mainly natural in the middle lake at all time,but the concentrations of Pb and Zn in the north lake were influenced by industrial wastes from the phosphorus fertilizer factory and cement plants.In all the lake,the contaminations of Cd and Zn were the results of agricultural cultivation using a large amount of fertilizers and the atmospheric fallouts of dusts from cement plants.At present,the geoaccumulation indices showed that the Fuxian Lake sediments were moderately to strongly polluted by Cd in the middle lake,and unpolluted to moderately polluted by Pb and Zn and strongly polluted by Cd in the north lake.Moreover,the pollution intensities of Cd,Zn,and Pb have been increased since 1980s.