Lead in boreal soils and food plants

The soils of the boreal zone, characterized by acidic, low-organic-matter sands in uplands and organic deposits in lowlands, represent unique environments for heavy metals. The mobility and plant uptake of Pb can be substantially different than in other soils. A survey of natural levels of Pb in northern Ontario revealed concentrations of 26 mg kg^–1 dry soil and 1.3 mg kg^–1 dry blueberry leaf, with an apparent plant/soil concentration ratio (CR) of 0.051. In outdoor lysimeters with an acidic sand profile (pH 4.9) and under a boreal climate, 67% of a pulse of Pb, applied as Pb(NO₃)₂, was essentially immobile over 4 yr. The 33% that leached may have been mobilized by soluble organic ligands or the N0₃ ^– companion ion. The solid/liquid partition coefficient (K_d) for this soil, using either applied ²¹⁰Pb or stable Pb, was very low: 20 L kg^–1 The CR for ²¹⁰Pb in the same soil was correspondingly high: 0.10 for blueberry and 0.059 over all crops studied. In two organic soils, the K_d values were 9 × 10³ L kg^–1 (Sphagnum, pH 4.8) and 3 × 10⁴ L kg^–1 (sedge, pH 5.5) with corresponding CR values of 8 × 10^–4 and 0.0085 for blueberries (0.0027 overall in the latter soil). The CR was most closely related to soil cation exchange capacity, although organic matter content and pH were undoubtedly important related factors. In combination, the acidic sand and organic soils of boreal settings represent extremes for the mobility of Pb.     

The effects of clay,organic matter and time on adsorption and plant uptake of cadmium added to the soil

In a 2-yr pot experiment the effects of texture and organic matter content on adsorption in soil and uptake in Perennial ryegrass (Lolium perenne) and Winter rape (Brassica napus) of Cd added to the soil were studied. The soils used were a clay, a loamy sand and a sapric peat mixed in different proportions. One mg kg^?1 of Cd was added to each soil mixture. The organic matter showed a greater ability than clay to adsorb Cd in an unavailable form and thereby reduce plant uptake. The effect per unit of organic matter added was greatest at low organic matter content. Most of the Cd was adsorbed in a non-exchangeable form indicating the presence of strong organic complexing. The addition of organic matter reduced plant uptake more efficiently in sand than in clay even though the exchangeable Cd did not differ between the two soils. Increasing the clay content in sand from 9 to 63% led to slightly decreased water leachability but did not significantly decrease non-exchangeable Cd. Neither was plant uptake notably affected. The two crops showed a similar reaction to the different treatments. Uptake was correlated with Cd extractable in ammonium acetate at pH 7, but the relationship was different at each sampling occasion. No significant change in adsorption of the added Cd, fixation, was detected during the 2-yr period but seasonal variations in solubility and uptake were noticed.     

Cadmium sorption by two acid soils as affected by clearing and cultivation

Abstract

The objective of this study was to determine the effect of clearing and cultivation on the sorption of cadmium (Cd) by two acid soils from Zimbabwe with differing cultivation stories. In their original state, not cleared‐not cultivated (virgin soils), the two soils exhibited noticeable and similar capacities to sorb Cd. The Mazowe soil contains the highest level of organic matter (40 g kg^‐1) and a effective cation exchange capacity (ECEC) of 144 mmol_c kg^‐1. Yet, Bulawayo soil (23.5 g kg^‐1 organic matter and ECEC of 146 mmol_c kg^‐1) has higher pH and Mn and Fe oxide content and these characteristics seemed to counteract the effect of lower organic matter. After 50 years of cultivation, The Mazowe soil has lost 60% of its organic matter and ECEC, and consequently the ability of its soil matrix to bind Cd has proportionally decreased. In Bulawayo (cleared in 1983 and first ploughed in 1984), on the contrary, the organic matter and ECEC of the cultivated soil remains over 95% of the values on its virgin counterpart. In this soil, the retaining ability for Cd has not still been affected. In the two soils Cd sorption was highly pH‐dependent. The extent of sorption was minimal under acidic conditions and increased sharply as the pH was raised. The immediate reversibility of the sorption process proved to be very low. When sorption and desorption data were compared it was clear that soil characteristics like high organic matter and oxide content which showed to enhanced Cd sorption, contributed at the same time to slow down the backward reaction.     

Crop uptake of cadmium from phosphorus fertilizers: II. Relationship with extractable soil cadmium

In a greenhouse experiment, effects of different phosphate fertilizer applications on soil Cd extracted by DTPA and NH₄NO₃ in relation to plant uptake of Cd were investigated. The soils used were a sand and a loam treated with lime to achieve three pHs ranging from 4.77 to 5.94 for the sandy soil and 4.97 to 6.80 for the loam soil. Oat (Avena sativa L.), ryegrass (Lolium multiflorum L.), carrot (Daucus carota L.), and spinach (Spinacia oleracea L.), were used as test species. Application of the high-Cd NPK fertilizer (adding 12.5 μg Cd kg^?1 soil) significantly increased the extractable soil Cd, especially the DTPA-extractable Cd. Use of phosphate rock adding as much Cd as the high-Cd NPK fertilizer did not increase the extractable Cd in either of the soils. Both DTPA- and NH₄NO₃-extractable Cd decreased with the increases in soil pH. The Cd concentrations and total Cd uptake of plants were significantly correlated with the soil Cd extracted by DTPA and NH₄NO₃.     

The influence of pH,soil type and time on adsorbtion and uptake by plants of Cd added to the soil

Adsorption of Cd by two soils and its uptake by perennial ryegrass (Lolium perenne) and winter rape (Brassica napus) as a function of pH (pH 4 to 7) and the amount of Cd added to the soil (0 to 5 mg kg^?1 soil) were studied in a 2-yr pot experiment. In the soils, the more soluble fractions of Cd increased as the pH was lowered. Increasing the pH from 5 to 7 by adding CaO invariably reduced the Cd-content of ryegrass plants, but this decrease was less consistent where the pH had only been increased to 6. In some cases, acidifying the soil with S to reach a pH of 4 also led to a decrease in plant Cd-content. The Cd-content of rapeseed plants was markedly higher at pH 4 than at pH 5. Plant damage at low pH was observed in this crop. Water-leachable and CaCl₂-extractable soil Cd levels as well as plant uptake were higher in the sand soil than in the clay soil, whereas 1M NH₄AcO (buffered at pH 4.8 and 7) extracted roughly equal amounts from both soils. Adding more Cd to the soil did not change the relation between Cd levels in soil and those in plants; instead the amounts of Cd in both increased in direct proportion to the amounts added. Fixation of added Cd apparently did not occur continuously at any pH or Cd-level during the 2-yr period, but seasonal variations in solubility and uptake were observed.     

The ecological dose value (ED50) for assessing Cd toxicity on ATP content and dehydrogenase and urease activities of soil

Two soils of contrasting texture, organic matter content and pH were treated with CdSO₄ solutions to give a Cd concentration range of 0–4000 mg kg⁻¹ soil. The content of ATP and dehydrogenase and urease activities of soils were assayed after 3 h, and 7 and 28 days of Cd contamination. The relative ED₅₀ values were calculated by two kinetic models (model 1 and model 2) used by Speir et al. (1995) and by the sigmoidal dose–response model (model 3) employed by Haanstra et al. (1985). Model 1 was the most successful in calculating the ED₅₀ values for the ATP content, urease and dehydrogenase activities when both soils were contaminated by Cd. Similar ED₅₀ values were predicted by model 1 (describing the full inhibition) and model 3 only when the correlation coefficients r² were higher than 0.9. The ED₅₀ values of ATP calculated by model 1 were markedly higher than those calculated by model 2 (describing partial inhibition) when both models gave correlation coefficients higher than 0.9. This behavior was due to the high asymptote values obtained using model 2. According to model 2, some of the enzyme activities responsible for the ATP synthesis were probably not inhibited at the highest Cd concentrations. The inhibitory effect of Cd on the ATP content and both enzymatic activities was lower in the Castelporziano soil, which had the highest total organic carbon content.     

Development of QSAR's in soil ecotoxicology: Earthworm toxicity and soil sorption of chlorophenols,chlorobenzenes and chloroanilines

Soil adsorption and the toxicity of four chloroanilines for earthworms were investigated in two soil types. The toxicity tests were carried out with two earthworm species, Eisenia andrei and Lumbricus rubellus. LC₅₀ values in mg kg^?1 dry soil were recalculated towards molar concentrations in pore water using data from soil adsorption experiments. An attempt has been made to develop Quantitative Structure Activity Relationships (QSAR's) using these results and data on five chlorophenols and dichloroaniline in four soils and five chlorobenzenes in two soils published previously (Van Gestel and Ma, 1988, 1990; Van Gestel et al., 1991). Significant QSAR relationships were obtained between 1) adsorption coefficients (log K _om ) and the octanol/water partition coefficient (log k _ow ), and 2) LC₅₀ values (in itμmol L^?1 soil pore water) and log K _ow . It can be concluded that both earthworm species tested are equally sensitive to chlorobenzenes and chloroanilines, E. andrei is more sensitive than L. rubellus to chlorophenols.     

Displacement of Zn through acidic light-textured soils

In order to gain understanding of the movement of pollutant metals in soil, the chemical mechanisms involved in the transport of zinc were studied. The displacement of zinc through mixtures of sand and cation exchange resin was measured to validate the methods used for soil. With cation exchange capacities of 2.5 and 5.0 cmol_c kg⁻¹, 5.6 and 8.4 pore volumes of 10 mM CaCl₂, respectively, were required to displace a pulse of ZnCl₂ . A simple Burns-type model (Wineglass) using an adsorption coefficient (K_d) determined by fitting a straight line relationship to an adsorption isotherm gave a good fit to the data (K_d=0.73 and 1.29 ml g⁻¹, respectively).Surface and subsurface samples of an acidic sandy loam (organic matter 4.7 and 1.0%, cation exchange capacity (CEC) 11.8 and 6.1 cmol_c kg⁻¹, respectively) were leached with 10 mM calcium chloride, nitrate and perchlorate. With chloride, the zinc pulse was displaced after 25 and 5 pore volumes, respectively. The K_d values were 6.1 and 2.0 ml g⁻¹, but are based on linear relationships fitted to isotherms which are both curved and show hysteresis. Thus, a simple model has limited value although it does give a general indication of rate of displacement. Leaching with chloride and perchlorate gave similar displacement and K_d values, but slower movement occurred with nitrate in both soil samples (35 and 7 pore volumes, respectively) which reflected higher K_d values when the isotherms were measured using this anion (7.7 and 2.8 ml g⁻¹, respectively). Although pH values were a little higher with nitrate in the leachates, the differences were insufficient to suggest that this increased the CEC enough to cause the delay. No increases in pH occurred with nitrate in the isotherm experiments. Geochem was used to calculate the proportions of Zn complexed with the three anions and with fulvic acid determined from measurements of dissolved organic matter. In all cases, more than 91% of the Zn was present as Zn²⁺ and there were only minor differences between the anions. Thus, there is an unexplained factor associated with the greater adsorption of Zn in the presence of nitrate.Because as little as five pore volumes of solution displaced Zn through the subsurface soil, contamination of ground waters may be a hazard where Zn is entering a light-textured soil, particularly where soil salinity is increased. Reductions in organic matter content due to cultivation will increase the hazard.     

Statistical Modeling of the Partitioning of Nonylphenol in Soil

Partition coefficients K _P of nonylphenol (NP) in soil were determined for 193 soil samples which differed widely in content of soil organic carbon (SOC), hydrogen activity, clay content, and in the content of dissolved organic carbon (DOC). By means of multiple linear regression analysis (MLR), pedotransfer functions were derived to predict partition coefficients from soil data. SOC and pH affected the sorption, though the latter was in a range significantly below the pK_a of NP. Quality of soil organic matter presumably plays an important but yet not quantified role in sorption of NP. For soil samples with SOC values less than 3 g kg^?1, model prediction became uncertain with this linear approach. We suggest that using only SOC and pH data results in good prediction of NP sorption in soils with SOC higher than 3 g kg^?1. Considering the varying validity of the linear model for different ranges of the most sensitive parameter SOC, a more flexible, nonlinear approach was tested. The application of an artificial neuronal network (ANN) to predict sorption of NP in soils showed a sigmoidal relation between K _P and SOC. The nonlinear ANN approach provided good results compared to the MLR approach and represents an alternative tool for prediction of NP partitioning coefficients.     

Potassium fertilization on sandy soils in relation to soil test,crop yield and K-leaching

To study the influence of potassium (K) fertilizer rate on soil test K values, crop yield, and K-leaching in sandy soils, four long-term fertilizer experiments (0–60–120–180 kg K ha^?1 a^?1) were initiated in 1988 in northern Germany on farmers fields. Clay content of the plow layer was about 4%, and organic matter between 2% and 5%. Plant available soil K was estimated with the double lactate (DL) method. Small grain cereals (rye and barley) did not respond to K fertilization in the 7-year period even though the soil test value of the K-0 plots decreased from ca. 90 to ca. 30 mg K_DL kg^?1 within 3 years. This value remained almost constant thereafter. Crop removal (including straw) of 75 kg K ha^?1 a^?1 was therefore apparently supplied from nonexchangeable K fractions. Compared to the optimum, no K application reduced the yield of potato by up to 21%, and that of white sugar yield up to 10%. Maximum potato yield was obtained by annually applying 60 kg K ha^?1 which resulted in a test value of 60 mg K_DL kg^?1 soil. Maximum potato yield was also obtained at 40 mg K_DL kg^?1 soil, however, with a single application of 200 kg K ha^?1. Similar results were obtained with sugar beet. This indicates that for maximum yield, even for K demanding crops, it is not necessary to maintain K_DL values above 40 mg K kg^?1 soil throughout the entire crop rotation. Soil test values increased roughly proportional to the K fertilizer level. About 120 kg fertilizer K ha^?1 a^?1, markedly more than crop K removal, was required to maintain the initial K_DL of 90 mg kg^?1. The K concentration of the soil solution in the top soil measured after harvest was increased exponentially by K fertilizer level and so was K leaching from the plow layer into the rooted subsoil. The leached quantity increased from 22 kg K ha_?1 a_?1 in the plot without K application to 42.79 and 133 kg Kha^?1 a^?1 in plots supplied with 60, 120 and 180 kg K ha^?1 a^?1 respectively. Soil test values around 100 mg K_DL kg^?1 on sandy soils, as often found in the plow layer of farmers fields, lead to K leaching below the root zone that may exceed the critical K concentration of 12 mg K T^?1 for drinking water.     

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.     

Effect of organic matter on the distribution, extractability and uptake of cadmium in soils

Distribution and plant uptake of soil Cd as influenced by organic matter and soil type were investigated in a greenhouse experiment. Three soils (a sand, sandy loam and clay loam) were used. The rates of organic matter in its moist state added were 0,20,40, 80, 160 and 320 g kg^-1 of the air-dried soil on mass basis. Ryegrass (Lolium multörum L.) was used as a test crop. Soil Cd was analysed by a sequential extraction technique and by extraction with 1 M NH₄NO₃ and 0.005 M DTPA. The exchangeable fraction of Cd as determined by 1 M MgCl₂ in the sequential extraction procedure increased, whereas the Fe-Mn oxidebound fraction decreased, with increasing levels of organic matter addition in all three soils. The dry matter yields of ryegrass were not affected by the addition of organic matter, but the Cd concentrations in both cuts of ryegrass decreased with increasing amounts of organic matter added. The plant Cd was highly but negatively correlated to soil CEC. At any level of organic matter addition, the decrease in Cd concentration of ryegrass was in the order: sand > sandy loam > clay loam.     

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).     

Sorption behavior of copper,zinc, and cadmium in response to simulated changes in soil properties

Abstract

Environmental changes and management practices which alter soil properties may affect the capacity of soils to sorb trace metals, such as copper (Cu), zinc (Zn), and cadmium (Cd), and thus influence the bioavailability and leach ability of the metals. Two agricultural soils were treated to partially oxidize organic matter and to decrease soil pH for evaluating the effects of acidification and organic matter oxidation on trace metal sorption onto soils. For the one soil with a pH value of 6.74 and organic carbon (C) content of 46.9 g‐kg^‐1, loss of 11% of its organic matter reduced by 97, 72, and 62% the original sorption capacity for Cu, Zn, and Cd, respectively, while the corresponding values caused by acidifying the soil one pH‐unit were 32, 16, and 29%. For the another soil with a pH of 4.69 and organic C content of 16.3 g‐kg^‐1, a decrease in pH by one unit resulted in a loss of 43, 21, and 52% of the sorption capacity for Cu, Zn, and Cd, respectively.     

Phytotoxicity of some chloroanilines and chlorophenols, in relation to bioavailability in soil

Soil adsorption and the effect of four chlorophenols and three chloroanilines on the growth of lettuce (Lactuca sativa) were determined in two soil types differing in organic matter content and pH. Adsorption increased with increasing organic matter content of the soils. Phytotoxicity, based on dosed amounts, was significantly higher in the soil with the low level of organic matter. This difference could be reduced by recalculating the EC₅₀ values for the effect of the test substances on plant growth in mg kg-1 dry soil towards concentrations in mg L-1 pore water using data from soil adsorption experiments. For pentachlorophenol only this recalculation increased rather than decreased the difference between the two soils, however, when the EC50 values for pentachlorophenol were corrected for the difference in soil pH, almost the same values resulted for both soils. Calculated EC₅₀ values on the basis of pore water concentrations appeared to be in good agreement with values determined in nutrient solution tests. These results indicate that, for plants, the toxicity and therefore the bioavailability of organic chemicals in soil mainly depend on the concentration in the soil solution, and can be predicted on the basis of sorption data. Attempts to develop QSARs relating log EC₅₀ values in μmol L^?1 pore water with lipophilicity (expressed as the octanol/water partition coefficient: log K_ow,) of the test substances resulted in a statistically significant relationship. This relationship was further improved by correcting the chlorophenol data for dissociation effects.     

Initial results from a long-term, multi-site field study of the effects on soil fertility and microbial activity of sludge cakes containing heavy metals

In a long‐term study of the effects on soil fertility and microbial activity of heavy metals contained in sewage sludges, metal‐rich sludge cakes each with high Zn, Cu or Cd concentrations were applied annually for 4 years (1994–1997) to nine sites throughout Britain. These sites were selected to represent agricultural soils with a range of physical and chemical properties, typical of those likely to be amended with sewage sludge. The aim was to establish individual total Zn (approx. 60–450 mg kg^?1), total Cu (approx. 15–200 mg kg^?1) and total Cd (approx. 0.2–4 mg kg^?1) metal dose–response treatments at each site. Sludges with low metal concentrations were added to all treatments to achieve as constant an addition of organic matter as possible. Across the nine sites, soil pH was the single most important factor controlling Zn (P < 0.001; r² = 92%) and Cd extracted with 1 m NH₄NO₃ (P < 0.001; r² = 72%), and total iron content the most important factor controlling Cu extracted with 1 m NH₄NO₃ (P < 0.001; r² = 64%). There were also positive relationships (P < 0.001) between soil organic carbon (C) concentrations and soil biomass C and respiration rates across the nine sites. Oxidation of sludge C following land application resulted in approximately 45% of the digested sludge cake C and approximately 64% of the ‘raw’ sludge cake C being lost by the end of the 4‐year application period. The sludge cake applications generally increased soil microbial biomass C and soil respiration rates, whilst most probable numbers of clover Rhizobium were generally unchanged. Overall, there was no evidence that the metal applications were damaging soil microbial activity in the short term after the cessation of sludge cake addition.     

Effects of nitrogen-containing fertilizers on solubility and plant uptake of cadmium

In a pot experiment, three N-fertilizers, differing in NO^? ₃ and NH⁺ ₄; content, were compared in terms of their effects on the extractability of soil Cd in 1M ammonium acetate at pH 7 and on the uptake of native and added Cd by winter rape (Brassica napus L. var. oleifera Metzger). In another similar experiment the Cd-availability in soils receiving NPK-fertilizer applied in a concentrated, granulated form was compared to that in soils receiving a uniform application of dissolved NPK-fertilizer. Both loamy sand and clay soils were used. With the N-fertilizers levels of extractable soil Cd and plant Cd-contents were lowest in the nitrate of lime treatment, highest in the ammonium sulphate treatment and intermediate in the nitro-chalk treatment. The addition of 1 mg kg^?1 DW Cd to the soil increased Cd-levels but did not change the response pattern. There was a strong association between the effects of the various fertilizers on Cd availability and their effects on soil pH: the stronger the acidifying effect the higher the Cd availability. When applied at a low dose, granular NPK was more effective than dissolved NPK at enhancing plant uptake of Cd from both soils, but this was not the case when applied at a higher dose to the sand. The two forms of NPK differed little in their effect on extractable soil Cd. Plant uptake of Cd was greater from soils receiving granular NPK with a high Cd-content than from those receiving granular NPK low in Cd. In both experiments extractable Cd was taken up to a greater extent from the sand than from the clay. An increase in fertilizer dose generally resulted in an increase in levels of soil-Cd and in Cd concentrations in the plants.     

Determining critical limit of boron in soil for wheat (Triticum aestivum L.)

Abstract

Critical values of boron (B) for wheat nutrition in soil and plant were determined through a pot experiment with twenty-one surface soils of Alluvial flood plain and Red-latertic belt comprising three major soil orders (Entisols, Alfisols, Inceptisols) with four levels of boron. Application of boron significantly increased the dry matter yield as well as uptake of B by plants. Critical concentration of hot calcium chloride (CaCl₂) extractable B in soil for wheat was found to be 0.53?mg?kg^?1. The critical plant B concentration varied with growth stages and values were 7.4?mg?kg^?1 at panicle initiation and 4.18?mg?kg^?1 at maturity, respectively. The findings of this investigation also recommend the application of 2?kg?B^?1?ha^?1 for ensuring B sufficiency to wheat in Indo-gangetic alluvial and Red-Lateritic soils.     

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.