Modelling trace metal extractability and solubility in French forest soils by using soil properties

Soil/solution partitioning of trace metals (TM: Cd, Co, Cr, Cu, Ni, Sb, Pb and Zn) has been investigated in six French forest sites that have been subjected to TM atmospheric inputs. Soil profiles have been sampled and analysed for major soil properties, and CaCl₂‐extractable and total metal content. Metal concentrations (expressed on a molar basis) in soil (total), in CaCl₂ extracts and soil solution collected monthly from fresh soil by centrifugation, were in the order: Cr > Zn > Ni > Cu > Pb > Co > Sb > Cd , Zn > Cu > Pb = Ni > Co > Cd > Cr and Zn > Ni > Cu > Pb > Co > Cr > Cd > Sb , respectively. Metal extractability and solubility were predicted by using soil properties. Soil pH was the most significant property in predicting metal partitioning, but TM behaviour differed between acid and non‐acid soils. TM extractability was predicted significantly by soil pH for pH < 6, and by soil pH and Fe content for all soil conditions. Total metal concentration in soil solution was predicted well by soil pH and organic carbon content for Cd, Co, Cr, Ni and Zn, by Fe content for Cu, Cr, Ni, Pb and Sb and total soil metal content for Cu, Cr, Ni, Pb and Sb, with a better prediction for acidic conditions (pH < 6). At more alkaline pH conditions, solute concentrations of Cu, Cr, Sb and Pb were larger than predicted by the pH relationship, as a consequence of association with Fe colloids and complexing with dissolved organic carbon. Metal speciation in soil solutions determined by WHAM‐VI indicated that free metal ion (FMI) concentration was significantly related to soil pH for all pH conditions. The FMI concentrations of Cu and Zn were well predicted by pH alone, Pb by pH and Fe content and Cd, Co and Ni by soil pH and organic carbon content. Differences between soluble total metal and FMI concentrations were particularly large for pH < 6. This should be taken into account for risk and critical load assessment in the case of terrestrial ecosystems.     

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.     

Soil versus plant as indicators of agroecosystem pollution by potentially toxic elements

The major route of potentially toxic elements (PTEs) to humans is the intake through food. They enter the food chain principally by plants uptake from the soil and, to a less extent, through foliar deposition. The soil‐to‐plant transfer as part of the biogeochemical cycle of these elements is a complex and hardly predictable process. In this study, we investigated the capability of soils and plants to indicate PTEs inputs in an intermingled urban‐rural landscape of south Italy affected by legal and illegal waste disposal and dumping. For this aim, 172 agricultural soil and plant (edible part) samples were collected in pairs from 47 municipalities and analyzed for 12 PTEs (As, Be, Cd, Co, Cu, Cr, Ni, Pb, Se, Tl, V, Zn). Soil extractions with 1 M NH₄NO₃ and 0.05 M EDTA pH 7 were applied to assess PTEs bioavailability. Results were examined according to plant species and main soil chemical properties. For Pb and Cd, the soil‐to‐plant transfer factors (TF) and the corresponding soil benchmark concentrations were also investigated. Zinc, Cu, Cd, and Pb were the only PTEs of anthropic origin severely polluting from 10 to 16% of the soils, but only in a very few cases exceeded physiological or EU legal critical values in the edible part of the plants. An evaluation of human risk due to the ingestion of these elements was tried; no risk for consumers for Zn, Cu, and Pb, while for Cd three values slightly exceeded the tolerable daily intake. Therefore, we conclude that crops cultivated in the studied area could represent only a moderate risk for human health. No correlation was found between soil and plant data, which likely highlights different pollution inputs. A large variability characterized the Pb and Cd TF, making it difficult to establish a unique benchmark concentration for the studied agricultural soils.     

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.     

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.     

Sorption of lead,copper, zinc,and cadmium by soils: effect of nitriloacetic acid on metal retention

Abstract

Laboratory experiments were carried out to evaluate lead (Pb), copper (Cu), zinc (Zn), and cadmium (Cd) sorption‐desorption by three soils of contrasting characteristics. Talamanca (silt loam, montmorillonite, Calcic Haploxeralfs), Mazowe (clay, kaolinite, Rhodic Kandiustalf), and Realejos (sandy silt loam, allophane, Typic Hapludands). A second objective was to study the effect of nitriloacetic acid (NTA) on the sorption process. The Talamanca soil, which had a native pH of 6.4 and presented the highest effective cation exchange capacity (ECEC), sorbed more of each of the metal tested than did the other two soils. When the other two soils were compared metal sorption was also related to pH and ECEC. The very low sorption capacity showed by Realejos may be attributed to the low net surface negative charge density of this soil, arising from its allophanic nature. A common feature of the three soils was the relative strong sorption of both Pb and Cu relative to Cd and Zn with Pb showing the highest sorption levels. The selectivity sequences of metals retention were Pb>Cu>Zn>Cd for Talamanca soil, Pb>Cu>Zn≈Cd for Mazowe, and Pb>Cu>Cd>Zn for Realejos. Metal desorption values were low. The order of metal desorption (Cd≈Zn>Cu>Pb) was the same for the three soils studied. Quantitative differences observed in the extractability of the sorbed metals between the soils (Realejos>Mazowe>Talamanca) indicated that soil properties which enhanced metal sorption contributed at the same time to slow down the backward reaction. The addition of NTA to the soil suspension significantly depressed metal sorption by the three soils investigated. Compared with the free ligand system Pb, Cu, Zn, and Cd sorption in the presence of NTA decreased roughly 50%.     

A field study on the influence of soil ph on trace element levels in spring wheat (Triticum aestivum), potatoes (Solanum tuberosum) and carrots (Daucus carota)

Soil pH is one of the main factors influencing the solubility and availability of trace elements in arable soils. Thus pH can affect the trace element contents of agricultural crops and thereby indirectly influence human health. The aim of this study was to determine Cd, Ni, Zn, Cu, Mn, Cr, Al and Se contents in spring wheat, potatoes and carrots (Cd, Ni and Zn) and estimate their correlations with certain soil factors (surface and subsurface soil pH and organic matter content) governing the plant availability of these elements. Commercial fields were sampled in Sweden in order to cover a wide range of soil types with respect to pH, soil texture and organic matter content. Concentrations of Zn, Mn, Ni (grain) and Cd (straw) in spring wheat (n=43); Cd, Ni, Zn, Mn, Cu and Al in potatoes (n=69); and Cd, Ni and Zn in carrots (n=36) showed significant negative correlations with surface soil pH (0–25 cm). The Se content of potatoes and Cr content of spring wheat straw were positively correlated with soil pH. Stepwise multiple regressions including a combination of soil pHs (0–25 and 25–50 cm) and organic matter contents (0–25 cm) showed that the organic matter content as well as the surface and subsurface soil pH significantly influenced concentrations of several trace elements in one or more of the studied crops. It was concluded that, if acid deposition together with other acidifying processes (fertilisation, harvest of biomass, etc.) are not balanced by a sufficient amount of liming there might be a decrease in the pH of arable soils, which, in turn will lead to decreased levels of Se in edible crops but an overall increase concentrations of other trace elements.     

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.     

Pollution and Ecological Risk Assessment of Heavy Metals in Farmland Soils in Yanqi County,Xinjiang, Northwest China

A total of 50 farmland soil samples were collected from the Yanqi County, Xinjiang, China, and the concentrations of eight heavy metal elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn) were determined by standard methods. The spatial distribution, pollution level and ecological risk status of heavy metals were analyzed based on GIS technology, the Geo-accumulation Index (Igeo), the Pollution Load Index (PLI) and the Potential Ecological Risk Index (RI). Results indicated that: (1) The average contents of Cd, Cr, Ni, Pb, and Zn of farmland soils exceeded the background values of irrigation soils in Xinjiang by 1.5, 1.40, 1.33, 2.63, and 4.92 times, respectively. Cd showed a no-pollution level, Zn showed a partially moderate pollution level, Pb showed a slight pollution level, and Cr, Cu, As, Mn, and Ni showed no-pollution level, compared to the classification standard. The PLI values of heavy metal elements of farmland soils varied from 0.83 to 1.89, with an average value of 1.29, at the moderate pollution level. (2) The Individual Potential Ecological Risk Index for heavy metals in the study area was ranked in the order of: As > Ni > Cu > Cd > Pb > Cr> Zn. The RI values of heavy metals of farmland soils varied from 3.45 to 11.34, with an average value of 6.13, at the low ecological risk level. (3) Cu and Mn of farmland soils were mainly originated from the soil parent material and topography of the study area. As, Cd, Ni and Pb were mainly originated from human activities, and Cr and Zn may originated from both natural and anthropogenic factors in the study area.     

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).     

Der Einfluß der natürlichen organischen Substanzen auf die Metallverteilung zwischen Boden und Bodenlösung in einem sauren Waldboden

The influence of organic matter in the translocation of metals between soil and soil solution of an acid forest soil Water extracts were prepared from soil samples which were collected from a soil profile showing very little variation in the texture down to a depth of 120 cm and thus only little translocation of clay in the soil profile. The aim of the study was to describe the distribution between soil and soil solution of several metals like Cu, Pb, Cd, Zn, Al and Mn as a function of humic substances, electrolyte concentration and pH. From the experimental results the following hypothesis on the reaction mechanisms involving metals and humus derived substances has been deduced. The metals Cu, Fe, Al and Pb are mobilized through complexation by soluble humus substances in addition to the usual pH dependent desorption and dissolution of hydroxides. This mobilization determines the solution concentration of Cu and Fe at pH > 3.7 and Al and Pb at pH > 4.2. Al, Fe and Pb are complexed selectively by high molecular weight humus derived substances which undergo adsorption on soil mineral surfaces. Cu interacts with low molecular weight humus derived substances which are not easily adsorbed by the mineral surfaces. Zn, Cd and Mn primarily undergo sorption and are thus controlled by pH and electrolyte concentration of solutions because their complexation with humus derived substances seems to be weak or nonexistant. It is further postulated that the humus derived substances mobilize Al³⁺ and Fe³⁺ ions. By this, other metals like Cd, Zn, Mn, Ca and Mg can occupy the free exchange sites.     

Extractors for barium,cadmium, copper,nickel, and zinc in tropical soils

ABSTRACT

The accumulation of potentially toxic elements (PTEs) in the soil can pose risks to human health, and precise risk assessment dealing with the production and consumption of plants is required. The 0.43 M of nitric acid (HNO?) solution was suggested by the International Organization for Standardization for reactive fraction of PTEs in the soil. The efficiency of some extractors was evaluated in tropical soils. Contents of barium (Ba), cadmium (Cd), copper (Cu), nickel (Ni) and zinc (Zn) were extracted in accordance with the methods of Environmental Protection Agency (EPA) 3051A, Aqua Regia, Diethylenetriaminepentaacetic acid (DTPA), Mehlich-1, Mehlich-3, 0.43 M HNO? and 0.01 M of calcium chloride (CaCl?), and these contents correlated with the contents of PTEs in roots, shoots, and fruits of vegetables. Mehlich-3 had the highest correlation with Ni and Zn contents extracted by the plants. Contents extracted with 0.43 M HNO? had high correlation with the amounts extracted by DTPA and Mehlich-3, as well as with the amounts of PTEs accumulated by plants.     

Retention of copper, cadmium and zinc in soil and its textural fractions influenced by long-term field management

The present study investigated the impact of long‐term soil management on the metal retention capacity of soil. We examined the sorption behaviour of Cu, Cd and Zn in soils and in the various particle‐size fractions of these soils, which had been amended with farmyard manure, mineral fertilizers or were fallow for 38 years in a long‐term field experiment. The soils investigated contained different amounts and origins of organic matter and differed in soil pH, but the mineral phase showed less response to the different soil managements. Batch adsorption and desorption experiments as well as a sequential fractionation schema, which defines seven geochemical fractions, were used to investigate the retention properties of soil. Sequential extraction was conducted with original as well as with metal‐spiked soils. Results showed that amounts of Cu, Cd and Zn retained differed by a factor of more than 3 among the treatments in the long‐term field experiment, when a massive concentration of metal was added to soil. An increased sorption on smaller particle size fractions occurred (clay ≫ silt > fine sand ≥ coarse sand) due to the larger surface area as well as the greater carbon content in the smaller fractions. Soil sorption behaviour in another long‐term field experiment was estimated based on the present particle‐sorption data. Differences in the sorption behaviour were related to differences in soil mineralogy and amounts of Fe‐ and Mn‐oxides. Fractionation of the original and the metal‐spiked soil underlined the contribution of organic matter to sorption capacity (sequence: Cu ≫ Cd > Zn). Different organic matter contents and a different soil pH considerably changed the amounts of metals in the defined geochemical fractions. Freshly added Cu, Cd and Zn ions were found mainly in more mobile fractions. In contrast, metals in non‐spiked soils appeared in less‐mobile fractions reflecting their long‐term sorption behaviour.     

Residual heavy metal concentrations in sludge‐amended coastal plain soils ‐ I. Comparison of extractants

Abstract

The purposes for this research were: to examine the long‐term residual effects of farmland applications of municipal sludges from four treatment technologies on the total and extractable Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations in Coastal Plain soils; to investigate the effects of sludge sources and rates on the effectiveness of soil extractants to remove the various metals; and to determine correlation coefficients for soil extractable versus plant accumulation in tobacco. The extractants evaluated were Mehlich 1 and 3, and DTPA‐pH 7.3. Composite Ap horizon soil samples and tobacco leaf samples were obtained in 1984 from research plots at two sites in Maryland that were established in 1972 and 1976, respectively, using sludge materials from three wastewater treatment facilities in the Washington, D.C. metropolitan region. Similar application rates were used at both sites.

A wide range in soil pH values was found among treatments at each site. Significant (p ≤ 0.05) increases were observed in total Zn, Cu, Fe, Pb, Ni, and Cd for all sludge sources with increased rates; however, values for total soil Mn exhibited high variability in all cases. The rankings among the extractants varied for some elements depending on the sludge sources. For Zn, the rankings were Mehlich 1 > Mechlich 3 > DTPA‐pH 7.3 across all sources and rates. For Cu, Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was found for soils amended with Blue Plains digested (BPD) and Piscataway limeddigested (PLD) sludges but Mehlich 1 ≥ DTPA pH 7.3 > Mehlich 3 for Blue Plains limed compost (BPLC) and Annapolis Fe and heat treated (AFH) sludges. Concerning extractable Mn, Mehlich Mehlich 1 > Mechlich 3 > DTPH pH 7.3 was the order for BPLC and AFH sludges but Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was observed for BPD and PLD sludges. The rankings among extractants for Fe (Mehlich 3 > Mehlich 1 > DTPA‐pH7.3), Ni (Mehlich 3 ≥ Mehlich 1 > DTPA‐pH 7.3), Pb (Mehlich 3 > DTPA‐pH 7.3 > Mehlich 1) and Cd (Mehlich 1 > Mehlich 3 > DPTA‐pH7.3) were somewhat similar across all sludge sources. Significant correlation coefficients were obtained for all three extractants for soil extractable vs. plant Zn, Cu, Ni, and Cd at both sites; however, Mehlich 3 was not significant for Mn. Also, neither of the extractants produced significant coefficients for Fe and Pb.     

Does returning sites of historic peri‐urban waste disposal to vegetable production pose a risk to human health? – A case study near Manchester,UK

Urban waste disposal occurred on fenland to the west of Manchester, England, between 1900 and 1964. The reclaimed fenland, Chat Moss, is now used for mixed arable farming. A total of 1.92 Mt of waste including privy midden, street sweepings, clinkers and slaughterhouse refuse was incorporated into the moss resulting in a modified topsoil with raised pH and reduced organic matter content compared with the subsoil. Elevated levels of potentially toxic elements (PTEs) are observed in the topsoil beyond the typical depth of atmospheric contamination; Cd and As concentrations exceed soil guideline values (SGVs) at 1.8 and 43 mg/kg, respectively. Sequential extraction indicates that waste‐derived Pb, Zn and Ni remain predominantly in the residual fraction, whereas Cu was mainly organically bound. Arsenic was predominately found in oxide and organic matter fractions with Cd in carbonate, oxide, organic matter and residual fractions. Pot trials indicated limited uptake of PTEs by vegetables grown on the waste‐amended soil, with the exception of Cd uptake by lettuce (0.22 mg/kg FW) and Pb uptake by radish (0.16 mg/kg FW), which exceeded current EU limits of 0.2 and 0.1 mg/kg FW, respectively. Hazard quotients (HQs) identified no risks to adults from consumption of vegetables grown in these soils with the exception of lettuce consumption with a HQ of 1.4. Risks to children were slightly greater with HQs >1 for Cd in lettuce, spinach, carrots and onion, As in lettuce, parsley and onion and for Zn in spinach.     

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.     

Solubility control of Cu, Zn, Cd and Pb in contaminated soils

We developed a semiempirical equation from metal complextion theory which relates the metal activity of soil solutions to the soil's pH, organic matter content (OM) and total metal content (MT). The equation has the general form: where pM is the negative logarithm (to base 10) of the metal activity, and a, b and c are constants. The equation successfully predicted free Cu²⁺ activity in soils with a wide range of properties, including soils previously treated with sewage sludge. The significant correlation of pCu to these measured soil properties in long-contaminated soils suggests that copper activity is controlled by adsorption on organic matter under steady state conditions. An attempt was made from separate published data to correlate total soluble Cu, Zn, Cd and Pb in soils to soil pH, organic matter content and total metal content. For Cu, the total Cu content of the soil was most highly correlated with total soluble Cu. Similarly, total soluble Zn and Cd were correlated with total metal content, but were more strongly related to soil pH than was soluble Cu. Smaller metal solubility in response to higher soil pH was most marked for Zn and Cd, metals that tend not to complex strongly with soluble organics. The organic matter content was often, but not always, a statistically significant variable in predicting metal solubility from soil properties. The solubility of Pb was less satisfactorily predicted from measured soil properties than solubility of the other metals. It seems that for Cu at least, solid organic matter limits free metal activity, whilst dissolved organic matter promotes metal solubility, in soils well-aged with respect to the metal pollutant. Although total metal content alone is not generally a good predictor of metal solubility or activity, it assumes great importance when comparing metal solubility in soils having similar pH and organic matter content.     

Modelling the effects of ageing on Cd,Zn, Ni and Cu solubility in soils using an assemblage model

Ageing reactions can reduce trace metal solubility and can explain natural attenuation of contaminated soils. We modelled ageing reactions in soil with an assemblage model that considers slow reactions in Fe‐oxyhydroxides and reversible sorption on organic matter and clay minerals. Metal adsorption kinetics on Fe‐oxyhydroxides was obtained from data with synthetic oxyhydroxides. Metal solubility and isotopic exchangeability data were obtained from 28 soils amended with Ni, Zn, Cu and Cd metal salts and monitored for 850 days. The assemblage model was constructed in WHAM 6.0 and used soil properties and dissolved organic matter as input data. The model was first validated to predict dissolved metal concentrations, based on the concentration of isotopic exchangeable metals. The model overestimated metal solubility without parameter adjustment by mean factors of 4–7, and successful fits were obtained by increasing the specific surface area of Fe‐oxyhydroxides from measured values of synthetic systems to a value of 600 m² g^?1 recommended by other authors. The effect of ageing on the isotopic exchangeable metal fraction was subsequently modelled starting from the predicted fraction of metals present on Fe‐oxyhydroxides immediately after soil spiking. The observed isotopic exchangeable metal fractions of Ni, Zn and Cd agreed reasonably well with predicted values. The model predicts that ageing reactions are more pronounced at higher pH because metal sorption is increasingly directed to oxyhydroxide surfaces with increasing soil pH. Modelling fixation of Cu requires more information on fixation of that metal in organic matter.     

Metal‐Associated Forms and Speciation in Biosolid‐Amended Oxisols

Abstract

The objective of this study was to determine the effects of pH and ionic strength on the distribution and speciation of zinc (Zn), copper (Cu), and cadmium (Cd) in surface soil samples from two Brazilian Oxisols amended with biosolids. Soils and biosolids were equilibrated in an experimental dual‐chamber diffusion apparatus that permits the soils and biosolids to react through a solution phase via diffusion across a membrane. After equilibrium was reached, soil and biosolids samples were sequentially fractionated to identify various solid forms of Zn, Cu, and Cd. Metal concentrations in the solution phase were determined and mass balance calculated. Equilibrating pH had no major effect on Cu solubility from biosolids and, at pH range from 4 to 7, most Cu remained in the biosolids. Soluble Zn and Cd concentration increased with decreasing pH because of the increased solubility of the biosolids. Copper and Zn were primarily associated with the residual fraction and Fe oxides in one soil, but were primarily associated with chemically unstable fractions, or adsorbed to the surface of oxides, in the other soil. In both soils, Cd was primarily associated with readily bioavailable fractions. The effect of pH on the metal distribution was more evident than the ionic strength effect. Free ions were the predominant metal species in solution, especially at lower pH values.