Metal Extractability in Binary and Multi-metals Spiked Calcareous Soils

In the present study, a laboratory experiment was designed to compare the 0.01 M calcium chloride (CaCl₂) and diethylenetriaminepentaacetic acid (DTPA) extraction methods for their ability to predict cadmium (Cd), copper (Cu), iron (Fe), Manganese (Mn), nickel (Ni), and zinc (Zn) availability and mobility in five calcareous soils. The soils were spiked with different amounts of metals (0, 50, 100, 200, and 400 mg kg^?1) both in binary (Cu and Zn; Ni and Cd; Fe and Mn) and in multi-systems (Cd, Cu, Fe, Mn, Ni, and Zn) and incubated for 1 months at field capacity. In metal-spiked soils, both extraction methods showed a linear relationship of extractable to total metals for all soils. The fraction of total metals extracted by DTPA was much higher than the fraction extracted by CaCl₂, which was attributed to the formation of soluble metal-complexes in the complexing extracts calculated by the Visual Minteq program. DTPA extraction method showed higher selectivity for Cu over other metals both in binary and in multi-systems. Different order of metals extractability was found in binary and multi-systems for both extraction methods. Solid/solution distribution coefficient (K_d) was calculated by the ratio of the solid phase to soil solution concentration of metals extracted by CaCl₂ or DTPA extraction methods. Both in binary and in multi-systems, the average K_d (l kg^?1) of metals by soils were in the order of Mn (5398) > Fe (4413) > Zn (3376) > Cu (2520) > Ni (969) > Cd (350) in the CaCl₂-extractable metals and Fe (35) ≥ Ni (34) > Zn (18) > Mn (11.2) > Cu (6.3) > Cd (4) in the DTPA-extractable metals. Results showed that among the six studied metals, Cd had the lowest K_d, implying a relative higher mobility in these calcareous soils. The Visual Minteq indicated that in the CaCl₂-extraction method and in both binary and multi-systems the dominant species for Cu, Mn, Ni, and Zn were Cu²⁺, Mn²⁺, Ni²⁺ and Zn²⁺, respectively, while for Cd and Fe, the dominant species were CdCl⁺ and Fe(OH)²⁺, respectively.     

Heavy‐Metal Inhibition of Nitrification in Selected Iowa Soils Treated with Stay‐N 2000

Abstract

Heavy‐metal inhibition of nitrification in soils treated with reformulated nitrapyrin was investigated. Clarion and Okoboji soils were treated with ammonium sulfate [(NH₄)₂SO₄] and a nitrification inhibitor. Copper(II) (Cu), Zinc(II) (Zn), Cadmium(II) (Cd), or Lead(II) (Pb) were added to each soil. A first‐order equation was used to calculate the maximum nitrification rate (K _max), duration of lag period (t′), period of maximum nitrification (Δt), and the termination period of nitrification (t _s). In the Clarion soil, the K _max decreased from 12 mg kg^?1 d^?1 without the nitrification inhibitor to 4, 0.25, 0.86, and 0.27 mg kg^?1 d^?1, respectively, when the inhibitor and Cu, Zn, Pb, or Cd were applied. In the Okoboji soil, K _max decreased from 22 mg kg^?1 d^?1 with no inhibitor to 6, 3, 4, and 2 mg kg^?1 d^?1, respectively, when an inhibitor and Cu, Zn, Pb, or Cd were added. The t′ varied from 8 to 25 d in the Clarion soil and from 5 to 25 d in the Okoboji soil, due to addition of Cu, Zn, Pb, or Cd and the inhibitor.     

Differential Sorption Behavior of Cadmium,Lead, Zinc,and Copper in Some Tropical Soils and Their Environmental Implications

This study evaluated cadmium (Cd), lead (Pb), zinc (Zn), and copper (Cu) sorption characteristics of three tropical soils. Data obtained conformed to Freundlich sorption model and the S-shaped isotherm curve. Sorption efficiency of Zn and Pb were highest in alkaline soil while slightly acid soil had the highest Cd and Cu sorption efficiency for monometal sorption. In competitive sorption, metals were more sorbed in slightly acid soil while the least efficiency was recorded in acid soil. Distribution coefficient; K_d (average across soil types) in monometal sorption followed the order: Pb > Zn > Cd > Cu. For competitive sorption, the order was Zn > Pb > Cu > Cd. When in competition, Cd was preferentially sorbed in slightly acid and alkaline soils and Zn for acid soil. Conclusively, lead is more in equilibrium solution when in competition with Cd, Zn and Cu making it potential agent of soil and groundwater pollution.     

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.     

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.

     

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.     

Adsorption isotherms of copper and zinc in clay minerals of calcareous soils and their effects on X-ray diffraction

Reactions of elements with the water mineral interface are important and affect their bioavailability and transportation within soil. Effects of metal sorption on X-ray-diffraction (XRD-photographs) of clay minerals have been not studied. Therefore, sorption experiments were done on clay fractions of two calcareous soils using 12 concentrations of 0–2000 mg L^?1 Zn(NO₃)₂ and Cu(NO₃)₂. Langmuir and Freundlich isotherms’ coefficients were determined. After sorption, XRD-diffraction were prepared and compared with those of initial samples. Langmuir (R² = 0.996–0.999 and SE = 0.001–0.002) and Freundlich equation were the best-model for Zn and Cu-sorption, respectively. Sorption energy was higher for Zn than Cu, whereas the maximum concentration of sorbed-Cu was higher than that of Zn. Distribution coefficient (K_d) of Cu were more (threefold) than that of Zn. The K_d values representing the slope of Freundlich isotherms decreased according to linear regression equations (R² = 0.72–0.91) as the equilibrium concentrations of metals increased. No significant differences were observed among XRD-photographs of applied concentrations (some negligible differences were found in position/sharpness of peaks). Dry-XRD-method resulted in omission of intensity peaks at 2θ which may interfere in recognition of clays that show a maximum intensity >1.4 nm in the mentioned 2θ. Zinc can become more leachable especially in Shekarbani-soil-series, whereas, Cu highly adsorb on clay minerals and can show less tendency to transportation.     

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.

     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

Heavy‐Metal Contamination of Soil and Vegetables in Wastewater‐Irrigated Agricultural Soil in a Suburban Area of Hanoi,Vietnam

The To Lich and Kim Nguu Rivers, laden with untreated waste from industrial sources, serve as sources of water for irrigating vegetable farms. The purposes of this study were to identify the impact of wastewater irrigation on the level of heavy metals in the soils and vegetables and to predict their potential mobility and bioavailability. Soil samples were collected from different distances from the canal. The average concentrations of the heavy metals in the soil were in the order zinc (Zn; 204 mg kg^?1) > copper (Cu; 196 mg kg^?1) > chromium (Cr; 175 mg kg^?1) > lead (Pb; 131 mg kg^?1) > nickel (Ni; 60 mg kg^?1) > cadmium (Cd; 4 mg kg^?1). The concentrations of all heavy metals in the study site were much greater than the background level in that area and exceeded the permissible levels of the Vietnamese standards for Cd, Cu, and Pb. The concentrations of Zn, Ni, and Pb in the surface soil decreased with distance from the canal. The results of selective sequential extraction indicated that dominant fractions were oxide, organic, and residual for Ni, Pb, and Zn; organic and oxide for Cr; oxide for Cd; and organic for Cu. Leaching tests for water and acid indicated that the ratio of leached metal concentration to total metal concentration in the soil decreased in the order of Cd > Ni > Cr > Pb > Cu > Zn and in the order of Cd > Ni > Cr > Zn > Cu > Pb for the ethylenediaminetetraaceitc acid (EDTA) treatment. The EDTA treatment gave greater leachability than other treatments for most metal types. By leaching with water and acid, all heavy metals were fully released from the exchangeable fraction, and some heavy metals were fully released from carbonate and oxide fractions. The concentrations of Cd, Cr, Cu, Ni, Pb, and Zn in the vegetables exceeded the Vietnamese standards. The transfer coefficients for the metals were in the order of Zn > Ni > Cu > Cd = Cr > Pb.     

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.

     

Comparison of single and competitive metal adsorption by pepper stem biochar

Carbon-based sorbents have been proven to be cost-effective in removing pollutants from wastewater. Biochar from plant residue and agricultural waste is an emerging treatment technology. However, there is a limited number of studies on the effects of various biochar sources on metal adsorption. The aim of this study was using batch experiment to evaluate the adsorption of heavy metals in single- and multi-metal conditions onto pepper stem biochar. The maximum adsorption capacities (mg g^?1) of metals by pepper stem biochar were in the order of Pb (131) ? Cr (76) > Cd (67) > Cu (48) > Zn (31) in the single-metal adsorption isotherm and Pb (91) ? Cu (39) > Cr (29) > Zn (20) > Cd (13) in the multi-metal adsorption isotherm. Lead was the most retained cation, whereas Cr and Cd could be easily exchanged and substituted by other metals (Pb or Cu). For pepper stem biochar, the Langmuir model provided a slightly better fit than the Freundlich model. Results from the batch experiments show that competitive adsorption among metals increases the mobility of these metals. Particularly, Cd adsorption capacity in multi-metal conditions was significantly reduced. Overall, the results suggested that competitive adsorption studies are necessary for obtaining an accurate estimation of the metal retention capacity of pepper stem biochar in natural environments.     

Soil solution concentration of Cd and Zn canbe predicted with a CaCl2 soil extract

Risk assessment of heavy metals in soil requires an estimate of the concentrations in the soil solution. In spite of the numerous studies on the distribution of Cd and Zn in soil, few measurements of the distribution coefficient in situ, K_d, have been reported. We determined the K_d of soils contaminated with Cd and Zn by measuring metal concentrations in the soil and in the soil solution and attempted to predict them from other soil variables by regression. Soil pH explained most of the variation in logK_d (R² = 0.55 for Cd and 0.70 for Zn). Introducing organic carbon content or cation exchange capacity (CEC) as second explanatory variable improved the prediction (R² = 0.67 for Cd and 0.72 for Zn), but these regression models, however, left more than a factor of 10 of uncertainty in the predicted K_d. This large degree of uncertainty may partly be due to the variable degree of metal fixation in contaminated soils. The labile metal content was measured by isotopic dilution (E value). The E value ranged from 18 to 92% of the total metal content for Cd and from 5 to 68% for Zn. The prediction of K_d improved when metals in solution were assumed to be in equilibrium with the labile metal pool instead of the total metal pool. It seems necessary therefore to discriminate between ‘labile’ and ‘fixed’ pools to predict K_d for Cd and Zn in field contaminated soils accurately. Dilute salt extracts (e.g. 0.01 m CaCl₂) can mimic soil solution and are unlikely to extract metals from the fixed pool. Concentrations of Cd and Zn in the soil solution were predicted from the concentrations of Cd and Zn in a 0.01 m CaCl₂ extract. These predictions were better correlated with the observations for field contaminated soils than the predictions based on the regression equations relating logK_d to soil properties (pH, CEC and organic C).     

Adsorption and solubility of ten metals in soil samples of different composition

We conducted batch experiments for ten metals [Mg, Cr(III), Fe(III), Co, Ni, Cu, Zn, Sr, Cd, Pb] and four soil samples of different composition to determine the relation of the soluble fraction (’intensity’︁) to an adsorbed or precipitated metal pool (’quantity’︁) and, thus, to investigate the buffer function of soils. The soil samples were spiked with 6 to 12 exponentially increasing metal doses added as metal nitrates. The native metal pool involved in sorption processes was characterized by an extraction with 0.025 M (NH₄)₂EDTA (pH 4.6). The quantity-intensity (Q/I) relations of eight metals [except Cr(III) and Fe(III)] were governed by sorption and complexation processes and can be fitted by Freundlich isotherms. Q/I relations for Cr(III) and two soils indicate a sorption maximum, which can be approximated with the Langmuir isotherm. In a calcareous soil high Cr doses induced the precipitation of a Cr oxide. The solution concentrations of Fe are primarily a function of the pH-dependent solubility of ferrihydrite. For all metals pH was the predominant factor controlling the partitioning between the solid and the liquid phase. Drastic losses in the buffer function of soils primarily occurred in the slightly acidic range. Furthermore, adsorption was also metal specific. On the basis of median Freundlich K values, adsorption increased in the order [median K_F values and K_F range (mg kg^—1) in brackets]: Mg (2.9: 0.9—19) < Sr (4.7: 0.6—21) << Co (17.7: 1.1—143) < Zn (26.7: 1.8—301) = Ni (27.6: 2.4—120) < Cd (71: 2.5—405) << Cr(III) (329: 45—746) < Cu (352: 30—1200) < Pb (1730: 76—4110).     

Metal removal from and microbial property improvement of a multiple heavy metals contaminated soil by phytoextraction with a cadmium hyperaccumulator Sedum alfredii H.

Purpose

Effects of phytoextraction by Sedum alfredii H., a native cadmium hyperaccumulator, on metal removal from and microbial property improvement of a multiple heavy metals contaminated soil were studied under greenhouse conditions.

Materials and methods

A rhizobox experiment with an ancient silver-mining ecotype of S. alfredii natively growing in Zhejiang Province, China, was conducted for remediation of a multiple heavy metals contaminated soil. The rhizobox was designed combining the root-shaking method for the separation of rhizospheric vs near-rhizospheric soils and prestratifying method for separation of sublayers rhizospheric soils (0–10 mm from the root) and bulk soil (>10 mm from the root). Soil and plant samplings were carried out after 3 and 6 months of plant growth.

Results and discussion

Cadmium (Cd), zinc (Zn), and lead (Pb) concentrations in shoots were 440.6, 11,893, and 91.2 mg kg^?1 after 6 months growth, and Cd, Zn, and Pb removed in the shoots were 0.862, 25.20, and 0.117 mg/plant. Microbial biomass C, basal respiration, urease, acid phosphatase, and invertase activities of the rhizospheric soils were significantly higher than that of unplanted soils after 6 months growth. Microbial biomass carbon (MBC) of 0–2 mm and basal respiration (BR) rate of 0–8 mm sublayer rhizospheric soils were significantly higher than that of bulk soil after 6 months growth. So were the three enzyme activities of 0–4 mm sublayer rhizospheric soils. BR rate and urease were significantly negatively correlated with soluble Cd, so were MBC, acid phosphatase, and intervase activities with soluble Zn, MBC, BR rate, and three enzyme activities with soluble Pb.

Conclusions

Harvesting shoots of S. alfredii could remove remarkable amounts of Cd, Zn, Pb, and lower water-soluble Cd, Zn, and Pb concentrations in the rhizospheric soils. MBC, BR rate, and enzyme activities of the metal polluted soil, especially the rhizospheric soils increased with phytoextraction process, which is attributed to the stimulation of soil microbes by planting as well as the decrease in soil-soluble metal concentration.     

Role of soil constituents in fixation of soluble Zn, Cu, Ni and Cd added to soils

Slow immobilization of trace metals in soil, termed ‘fixation’, affects their natural attenuation but it is still unclear which reactions occur. Twenty‐eight soils were selected to assess the role of Fe oxides and carbonates on fixation of Cu, Cd, Zn and Ni. Soils included samples from 2 toposequences (Vietnam, Spain) and 13 European topsoils with different soil characteristics (pH 3.4–7.7). Samples were amended with 250 mg Zn kg⁻¹, 100 mg Cu kg⁻¹, 80 mg Ni kg⁻¹ and 2.5 mg Cd kg⁻¹ as metal salts and incubated for 850 days. Fixation was measured as the increase of the fraction of added metals that were not isotopically exchangeable. Fixation increased with time and was, averaged over all the soils, 43% (Cu), 41% (Zn), 41% (Ni) and 28% (Cd) after 850 days. Metal fixation within samples from each toposequence was generally positively related to total Fe oxide concentration (Fe_d) for Zn, Ni and Cd. However, the fixation of Cd, Zn and Ni was mainly explained by pH and not by Fe_d when considering all soils. Fixation of Zn and Cd in soils with pH >7.0 increased with increasing concentrations of carbonates at initial ageing times. Fixed fractions of Zn, Ni and Cd were significantly released when experimentally removing 50% of carbonates by acidification. Fixation of Cu was most poorly related to soil properties. Our data suggest that fixation of Cd, Zn and Ni is related to a pH‐dependent diffusion into oxides and that of Cd and Zn also to diffusion and/or coprecipitation in carbonates. Fixation of Ni at neutral pH may also be related to stabilization of precipitates that form readily in soil.     

Single and competitive adsorption isotherms of some heavy metals onto a light textured calcareous soil amended with agricultural wastes-biochars

This study investigated the adsorption behavior of selected heavy metals (Pb, Cu, and Ni) under single and multi-metal conditions by a light textured calcareous soil amended with plant residue biochars (corn straw, wheat straw, rice husk and licorice root pulp each at 3% w/w). The Freundlich isotherm best described the heavy metal adsorption suggesting multilayer adsorption. For all treatments under both adsorption conditions, the heavy metal adsorption capacity followed the order of Pb > Cu > Ni, which was associated with the hydrolysis constant, ionic radius, and electronegativity of these metals. Simultaneous presence of multiple metals decreased the adsorption capacity for each metal and the sequence was in the order of Ni > Pb > Cu. The corn straw biochar (CSB) had the highest adsorption capacity (Freundlich K_f (mg g^?1) for Ni = 0.23, Cu = 1.41 and Pb = 2.73) and medium distribution coefficient (K_{d medium}(L kg^?1) for Ni = 59.30, Cu = 1961.00 and Pb = 2602.00), indicating the CSB is the best treatment for stabilization of heavy metals in the soil. This was associated with the chemical characteristics of the CSB (high amounts of CaCO₃ and P) and the greatest increase in soil pH value.     

Competitive adsorption of zinc,cadmium, copper,and lead in three highly‐weathered Brazilian soils

Abstract

Equilibrium adsorption experiments on zinc (Zn), cadmium (Cd), copper (Cu), and lead (Pb) were conducted in three horizons of two Ultisols and one Oxisol with and without liming, from Viçosa‐MG (Brazil). Equilibrium solutions were applied as a “cocktail”; containing 700 mg L^‐1 of Zn, 20 mg L#lb¹ of Cd, 200 mg L^‐1of Cu, and 300 mg L^‐1 of Pb and its dilutions of 1:5 and 1:20. After shaking, the mixture was centrifuged, the supernatant collected and the pH and the concentrations of metals in the mixture were determined. Soil order, soil horizon, and liming had significant effects on the metal adsorption. Some important changes in the adsorption characteristics of the metals, especially in Zn and Cd, were observed due to competition between the different cations present in the solution. Also, desorption of Zn and Cd was observed with an increasing concentration of the solution. The adsorption data for Zn and Cd did not fit the linear, Langmuir, Freundlich, and Temkin isotherm equations for most situations, as these equations do not consider the possibility of a decrease in the amount of metal adsorbed with increasing metal competition for the adsorption sites. Due to the competition with other metals, the equations, which offered the best fit for Zn and Cd, were quadratic polynomial models. On the other hand, for Cu and Pb, the equations, which showed the best fit were linear, Langmuir, and Temkin, for different situations. The reasons for this behavior were related to the strong competitive forces for the adsorption sites presented by these two metals.     

在法国前铅和锌冶炼厂附近的城市土壤重金属的污染、分离和利用

smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical Soil contamination by metals from anthropogenic activities （e.g., mining and smelting） is a major concern for the environment and human health. Environmental availability of cadmium （Cd）, lead （Pb）, zinc （Zn）, copper （Cu）, and indium （In） in 27 urban soils located around two former Pb and Zn smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical procedure. Metal partitioning was conducted using a four-step sequential extraction procedure. The results showed that Cd and Zn were mainly in the acid-extractable and reducible forms in the urban soils studied. In contrast, Pb and In were largely in the reducible fraction. However, in some samples, the amount of In extracted in the residual or exchangeable fraction was higher than that in the reducible fraction. Copper was mainly found in the reducible and residual fractions. A pot experiment was conducted in a glasshouse with seven soils （six contaminated and one uncontaminated） and two plant species, ryegrass and lettuce. The results showed transfer of metals from the contaminated soils to the shoots of ryegrass and the edible part of lettuce. The metal bioconcentration factor was in the order of Cd Cu > In > Zn Pb for lettuce leaves, whereas for ryegrass shoots, three orders were found, Cd > Zn > Cu In > Pb, Cd ≥ In > Zn > Cu Pb, and Zn > Cd > Cu > In > Pb, depending on the physico-chemical properties of the soils, such as pH, cation exchange capacity, carbonates, and organic matter. It was established that the metal toxicity was related to the contamination levels and the physico-chemical properties, including pH, organic matter, and in a lesser extent, Ca, Mg, and phosphorus contents, of the soils. However, it was shown that lettuce could grow on soils having high Cd and CaCO₃ contents. Cadmium was one of the most available metals while Pb was always the least available in the soils studied.     

Extractability and plant uptake of heavy metals in alum shale soils

Abstract

Fifty soil samples (0–20 cm) with corresponding numbers of grain, potatoes, cabbage, and cauliflower crops were collected from soils developed on alum shale materials in Southeastern Norway to investigate the availability of [cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), and manganese (Mn)] in the soil and the uptake of the metals by these crops. Both total (aqua regia soluble) and extractable [ammonium nitrate (NH₄NO₃) and DTPA] concentrations of metals in the soils were studied. The total concentration of all the heavy metals in the soils were higher compared to other soils found in this region. Forty‐four percent of the soil samples had higher Cd concentration than the limit for application of sewage sludge, whereas the corresponding values for Ni, Cu, and Zn were 60%, 38%, and 16%, respectively. About 70% the soil samples had a too high concentration of one or more of the heavy metals in relation to the limit for application of sewage sludge. Cadmium was the most soluble of the heavy metals, implying that it is more bioavailable than the other non‐essential metals, Pb and Ni. The total (aqua regia soluble) concentrations of Cd, Cu, Zn, and Ni and the concentrations of DTPA‐extractable Cd and Ni were significantly higher in the loam soils than in the sandy loam soils. The amount of NH₄NCyextractable metals did not differ between the texture classes. The concentrations of DTPA‐extractable metals were positively and significantly correlated with the total concentrations of the same metals. Ammonium nitrate‐extractable metals, on the other hand, were not related to their total concentrations, but they were negatively and significantly correlated to soil pH. The average concentration of Cd (0.1 mg kg^‐1 d.w.) in the plants was relatively high compared to the concentration previously found in plants grown on the other soils. The concentrations of the other heavy metals Cu, Zn, Mn, Ni, and Pb in the plants were considered to be within the normal range, except for some samples with relatively high concentrations of Ni and Mn (0–11.1 and 3.5 to 167 mg kg‘¹ d.w., respectively). The concentrations of Cd, Cu, Zn, Ni, and Mn in grain were positively correlated to the concentrations of these respective metals in the soil extracted by NH₄NO₃. The plant concentrations were negatively correlated to pH. The DTPA‐extractable levels were not correlated with plant concentration and hence DTPA would not be a good extractant for determining plant availability in these soils.