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.     

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.     

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.     

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.     

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.     

Sorption of copper (II) and sulphate to different biochars before and after composting with farmyard manure

Biochar application has been suggested for reducing toxic levels of metals in contaminated soils and enhancing nutrient retention in agro‐ecosystems. We studied sorption of copper (Cu(II)) and sulphate‐sulphur (SO₄‐S) to charcoal, gasification coke and flash‐pyrolysis biochar in order to relate sorption to char properties. Furthermore, we investigated the effect of composting of charcoal and gasification coke on sorptive properties. Langmuir sorption affinity coefficients for Cu(II) for non‐composted biochars increased in the order flash‐pyrolysis char < charcoal < gasification coke. The sorption capacity for Cu(II) of the chars decreased in the order gasification coke (629 mg kg^?1) > flash‐pyrolysis char (196 mg kg^?1) > charcoal (56 mg kg^?1). Composting significantly increased the sorption affinity coefficient approximately by a factor of 5 for charcoal (up to 1.1 l mg^?1) and by a factor of 3–4 for gasification coke (up to 3.2 l mg^?1). Whereas Cu(II) sorption to gasification coke (composted or not) was largely irreversible, sorption to flash‐pyrolysis char and charcoal showed higher reversibility. Relationships between Cu(II) sorption and biochar properties such as cation exchange capacity, specific surface area or aromaticity suggest that sorption was largely determined by complexation with organic matter. Sorption of SO₄‐S was negligible by non‐composted and composted biochars. Composted gasification coke might be suited to reducing toxic Cu(II) concentrations in contaminated soils. Composted charcoal can potentially improve Cu(II) retention in a plant available form in acidic, sandy soils with small organic matter contents. Transient effects of biochars on soil pH can over‐ride the influence of sorption to biochars on concentrations of trace elements in soil solution and their availability to plants.     

General purpose Freundlich isotherms for cadmium,copper and zinc in soils

Assessing the accumulation and transport of trace metals in soils and the associated toxicological risks on a national scale requires generally applicable sorption equations. Therefore Freundlich equations were derived for Cd, Zn and Cu using multiple linear regression on batch sorption data from the literature with a wide variety of soil and experimental characteristics, and metal concentrations ranging over five orders of magnitude. Equations were derived based on both total dissolved metal concentrations and free metal activities in solution. Free metal activities were calculated from total metal concentrations taking into account ionic activity, and inorganic (all metals) and organic complexation (Cu only). Cadmium and Zn were present in solution predominantly as free ions, while Cu was present as organic complexes. Since actual dissolved organic carbon (DOC) concentrations were not available they were estimated using an empirical field relation between DOC and organic matter content. The logarithmic transformation of the Freundlich constant for Cd was regressed on the logarithmic transformations of cation exchange capacity (CEC) (H⁺) and dissolved Ca, and for Zn with CEC and (H⁺). For Cu the log–log regression model of the Freundlich constant included the solid:solution ratio of the batch to account for dilution of DOC in the batch as compared with the field. The explained variance for the fitted Freundlich equations was 79% for Cd, 65% for Cu and 83% for Zn, using log-transformed adsorbed concentrations and soil solution activities. The Freundlich adsorption models underestimated metal contents determined from 1 m HNO₃ digestion on field samples, up to a factor of 6 (Cd and Cu) or 10 (Zn).     

Zinc sorption by acid tropical soils as affected by cultivation

The sorption of zinc (Zn) by two acid tropical soils, Mazowe clay loam (kaolinitic, coarse, Rhodic Kandiustalf) and Bulawayo clay loam (coarse, kaolinitic, Lithic Rodustalf), was studied over a wide range of Zn solution concentrations. Samples of the two soils used in the experiments were collected at both uncleared, uncultivated (virgin) sites and cultivated sites. The two virgin soils showed similar abilities to bind Zn. Mazowe soil (40 g organic matter kg^?1) presented the highest affinity for Zn. Yet, Bulawayo soil (23.5 g organic matter kg^?1) sorbed almost the same amount. Bulawayo soil had higher pH and Fe and Mn-oxide content than Mazowe soil. Once cultivated, the two soils behaved quite differently. After 50 years, Mazowe soil had lost 60% of its organic matter and effective cation exchange capacity (ECEC). In this soil, Zn sorption capacity had also been decreased by 60%. Clearing and 10 years under cultivation had affected neither the organic matter content nor the ECEC of Bulawayo soil. For this soil, Zn sorption was even higher in the cultivated soil, presumably due to an increase in the amount of Fe and Mn oxide from subsoiling. Zinc sorption was dependent upon pH, with retention dramatically increasing in the pH range 6–7. Sorption occurred at pH values below the point of zero charge (PZC), indicating that the sorption reaction can proceed even in the presence of electrostatic repulsion between the positively charged soil surface and the cation. In the two soils, the reversibility of the sorption reaction was very low. More than 90% of the sorbed Zn was apparently strongly bonded.     

Relationship Between Extractable Metals in Acid Soils and Metals Taken Up by Tea Plants

Abstract

The accumulation of heavy metals in plants is related to concentrations andchemical fractions of the metals in soils. Understanding chemical fractions and availabilities of the metals in soils is necessary for management of the soils. In this study, the concentrations of copper (Cu), cadmium (Cd), lead (Pb), and zinc (Zn) in tea leaves were compared with the total and extractable contents of these heavy metals in 32 surface soil samples collected from different tea plantations in Zhejiang province, China. The five chemical fractions (exchangeable, carbonate‐bound, organic matter‐bound, oxides‐bound, and residual forms) of the metals in the soils were characterized. Five different extraction methods were also used to extract soil labile metals. Total heavy metal contents of the soils ranged from 17.0 to 84.0 mgCukg^?1, 0.03 to 1.09 mg Cd kg^?1, 3.43 to 31.2 mg Pb kg^?1, and 31.0 to 132.0 mg Zn kg^?1. The concentrations of exchangeable and carbonate‐bound fractions of the metals depended mainly on the pH, and those of organic matter‐bound, oxides‐bound, and residual forms of the metals were clearly controlled by their total concentrations in the soils. Extractable fractions may be preferable to total metal content as a predictor of bioconcentrations of the metals in both old and mature tea leaves. The metals in the tea leaves appeared to be mostly from the exchangeable fractions. The amount of available metals extracted by 0.01 mol L^?1 CaCl₂, NH₄OAc, and DTPA‐TEA is appropriate extractants for the prediction of metals uptake into tea plants. The results indicate that long‐term plantation of tea can cause sol acidification and elevated concentrations of bioavailable heavy metals in the soil and, hence, aggravate the risk of heavy metals to tea plants.     

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%.     

Competitivity,selectivity, and heavy metals-induced alkaline cation displacement in soils

Abstract

The simultaneous incorporation of heavy metals into the soil is still a matter of great concern. Interaction (competitive sorption) between these metals and the soil solid phase may result in a deterioration of soil quality which relies basically on amounts of alkaline cations saturating soils sorptive complex. Results of this study indicate that Pb, Cu, C d, and Zn have induced solution pH decreases which were more intensive at highest metal loading rates. Partition parameters (Kd)-based sequences showed that Pb and Cu were more competitive than Cd and Zn and the overall selectivity sequence followed: Pb > Cu > Cd > Zn. Metal loadings and their competitive sorption have led to a strengthened displacement of alkaline cations (i.e. Ca²⁺, Mg²⁺, K⁺, Na⁺), especially of Ca²⁺ as a factor “stabilizing” soil sorptive complex. Such metals impact jointly with soils acidification are of great environmental concern since tremendous amounts of alkaline cations (especially Ca²⁺) may be potentially leached out, irrespective of the degree of soil contamination, as evidenced in the current study. High and positive ΔG values implied that the studied soils were characterized by generally low concentrations of exchangeable potassium which required high energy to get displaced (desorbed). Further studies on heavy metal uncontaminated or contaminated areas should be undertaken to provide with data which should be used for predictions on changes related to soil buffering capacity as impacted by heavy metal inputs.     

Comparison of routine soil tests and EPA method 3050 as extractants for heavy metals in Delaware soils

Abstract

Agricultural use of sewage sludges can be limited by heavy metal accumulations in soils and crops. Information on background levels of total heavy metals in soils and changes in soil metal content due to sludge application are; therefore, critical aspects of long‐term sludge monitoring programs. As soil testing laboratories routinely, and rapidly, determine, in a wide variety of agricultural soils, the levels of some heavy metals and soil properties related to plant availability of these metals (e.g. Cu, Fe, Mn, Zn, pH, organic matter, texture), these labs could participate actively in the development and monitoring of environmentally sound sludge application programs. Consequently, the objective of this study was to compare three soil tests (Mehlich 1, Mehlich 3, and DTP A) and an USEPA approved method for measuring heavy metals in soils (EPA Method 3050), as extractants for Cd, Cu, Ni, Pb and Zn in representative agricultural soils of Delaware and in soils from five sites involved in a state‐monitored sludge application program.

Soil tests extracted less than 30% of total (EPA 3050) metals from most soils, with average percentages of total metal extracted (across all soils and metals) of 15%, 32%, and 11% for the Mehlich 1, Mehlich 3, and DTPA, respectively. Statistically significant correlations between total and soil test extractable metal content were obtained with all extractants for Cu, Pb, and Zn, but not Cd and Ni. The Mehlich 1 soil test was best correlated with total Cu and Zn (r=0.78***, 0.60***, respectively), while the chelate‐based extractants (DTPA and Mehlich 3) were better correlated with total Pb (r=0.85***, 0.63***). Multiple regression equations for the prediction of total Cu, Ni, Pb, and Zn, from soil test extractable metal in combination with easily measured soil properties (pH, organic matter by loss on ignition, soil volume weight) had R² values ranging from 0.41*** to 0.85***, suggesting that it may be possible to monitor, with reasonable success, heavy metal accumulations in soils using the results of a routine soil test.     

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.     

DISTRIBUTION AND SEQUENTIAL EXTRACTION OF SOME HEAVY METALS FROM SOILS IRRIGATED WITH WASTEWATER FROM MEXICO CITY

A sequential extraction procedure was used to fractionate Cu, Cd, Pb and Zn in 4 soil profiles into the designated forms of water soluble + exchangeable, organically bound, carbonate and Mn oxides bound. Soil profiles were obtained from the Rural Development District 063, State of Hidalgo, which have been irrigated with wastewater coming out of the basin of Mexico. The total heavy metal contents range as follows: Cu, 8.9 to 86.5 mg kg^-1 Cd, 0.86 to 5.07 mg kg^-1 Pb, 18.1 to 131.7 mg kg^-1 and Zn, 101 to 235.5 mg kg^-1. The highest concentrations of total heavy metals were found in the surface layers at all soil profiles. Sequential chemical fractionation indicated that the four metals were predominantly associated with the organic fraction at most soil samples. The contents in all fractions of the four metals showed a decrease with depth which has been explained by the variations in the organic matter and CaCO₃ contents in the different layers of soils. These soil properties were also the most important variables in the biological availability of the metals in these soils.     

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.     

中国原油污染区重金属空间分布模式及其潜在来源研究

Twenty-two soil samples were collected at the subregional scale （50 km2） around Gudao Town, a typical oil-producing region of the Shengli Oilfield in the Yellow River Delta, China to determine the spatial distribution patterns and potential sources of heavy metals in soils of crude oil-polluted regions. The concentrations of total petroleum hydrocaxbons （TPHs） and heavy metals as well as other soil properties were determined and the enrichment factor values were calculated for the heavy metals measured. Principal component analysis （PCA） and cluster analysis （CA） were used to estimate potential sources contributing to the concentrations of heavy metals in the soils. The results revealed that the soils were slightly alkaline （pH = 7.33-8.05） and high in salinity （1.43-41.30 g kg-1）, TPHs （0.51 28.40 g kg-1） and organic matter （1.74-31.50 g kg-1）. The mean concentrations of the measured heavy metals Cu, Zn, Pb, Cd, Cr, Ni and V were 18.4, 78.2, 20.8, 0.19, 56.6, 26.3 and 62.1 mg kg-1, respectively. Although the concentrations of all the metals measured in this study were not high enough to exceed the national control standards, there was a significant enrichment of Cd in the study area and Zn and Ni were in the category of deficiency to minimal enrichment. The spatial distribution patterns of Cu, Cr, Ni and V were similar and partially affected by oil exploitation and petroleum hydrocarbon spills. Potential sources of Cr, Ni, V and Cu in the soils were both natural sources and petroleum hydrocarbon spills, while Zn, Pb and Cd were probably from anthropogenic sources such as farming activities and traffic.     

Long-term changes in the Cu,Pb, and Zn content of forest soil organic horizons from North-East Scotland

Forest soil organic horizons from old and young plantations in the Alltcailleach Forest, N.E. Scotland were first sampled in 1949/50 and resampled in 1987. Copper, Pb and Zn in the soils were determined simultaneously on the original (stored) and the resampled soils. Overall mean Cu and Pb concentrations increased from 12.7 to 15.3 and 49.5 to 60.8 mg kg^?1 between 1949/50 and 1987. Zinc concentrations decreased from 76.4 to 60.7 mg kg^?1. Amounts of all 3 heavy metals increased because of increases in the thickness of organic horizons. Mean accumulation rates for Cu, Pb and Zn were 39.1, 186 and 114 g ha^?1 yr^?1, respectively. The rate of accumulation of Pb was significantly related to the rate of accumulation of organic matter. Copper and Zn concentrations were directly correlated with pH and inversely correlated with C/N ratio, whereas Pb was inversely correlated with pH and directly correlated with % C and C/N ratio. The more acidic soil organic horizons therefore contained higher concentrations of Pb and lower concentrations of Cu and Zn.     

Sorption-desorption behaviors of heavy metals by biochar-compost amendment with different ratios in contaminated wetland soil

Purpose

Heavy metal pollution in soils has become a global environmental concern. The combination of biochar and compost has already been proved to be an attractive method in contaminated soil. The objective was to study the sorption-desorption characteristics of Cd, Cu, and Zn onto soil amended with combined biochar-compost.

Materials and methods

In this study, the soil was amended with combinations of biochar and compost with different ratios at 10% (w/w). To determine the sorption-desorption behaviors of heavy metals by biochar-compost amendment with different ratios, we determine the effects of different ratios on soil properties and use batch experiments to investigate sorption-desorption behaviors of Cd, Cu, and Zn.

Results and discussion

The results show that the Langmuir and Freundlich model can well describe the adsorption isotherm of Cd, Cu, and Zn in the soils with or without biochar-compost combinations. The incorporation of amendment combinations into soil significantly promotes the sorption affinity of soil on metals. The sorption capacity of Cd and Zn was improved as the compost percentage rose in biochar-compost more likely due to the increase of organic matter and available phosphorus, while that of Cu was stronger with 10 and 20% biochar addition in biochar-compost combinations likely as the result of the formation of new specific adsorption sites and the mobile Cu adsorption in compost after adding a certain amount of biochar in amendment mixtures. Additionally, a certain proportion of biochar applied into amendment mixtures could suppress desorption of Cd and Cu by pH change, and the Zn desorption rate gradually decreased as the compost ratio increased in amendment mixtures.

Conclusions

The results indicated that the various ratios between biochar and compost have a significant effect on sorption-desorption of metals in soil, which helps us consider the effective combination of biochar and compost in soil.

     

Solubility,sorption and desorption of native and added cadmium in relation to properties of soils in New Zealand

Solution cadmium (Cd) concentrations and sorption and desorption of native and added Cd were studied in a range of New Zealand soils. The concentration of Cd in solution and the concentrations and patterns of native soil Cd desorbed and added Cd sorbed and desorbed varied greatly between the 29 soils studied. Correlation analysis revealed that pH was the most dominant soil variable affecting solution Cd concentration and sorption and desorption of native and added Cd in these soils. However, organic matter, cation exchange capacity (CEC) and total soil Cd were also found to be important. Multiple regression analysis showed that the log concentration of Cd in solution was strongly related to soil pH, organic matter and total Cd, which in combination explained 76% of the variation between soils. When data from the present study were combined into a single multiple regression with soil data from a previously published study, the equation generated could explain 81% of the variation in log Cd solution concentration. This reinforces the importance of pH, organic matter and total Cd in controlling solution Cd concentrations. Simple linear regression analysis could at best explain 53% of the total variation in Cd sorption or desorption for the soils studied. Multiple regression analysis showed that native Cd desorption was related to pH, organic matter and total Cd, which in combination explained 85% of the variation between soils. For sorption of Cd (from 2 μg Cd g^–1 soil added), pH and organic matter in combination explained 75% of the variation between soils. However, for added Cd desorption (%), pH and CEC explained 77%. It is clear that the combined effects of a range of soil properties control the concentration of Cd in solution, and of sorption and desorption of Cd in soils. The fraction of potentially desorbable added Cd in soils could also be predicted from a soil’s K_d value. This could have value for assessing both the mobility of Cd in soil and its likely availability to plants.     

Multi‐element stable isotopic dilution and multi‐surface modelling to assess the speciation and reactivity of cadmium and copper in soil

Chemical extraction, multi‐element stable isotopic dilution (ID) and multi‐surface modelling were used to investigate the lability of cadmium (Cd) and copper (Cu) in nine types of soil with different properties and contaminated or not with Cd and Cu. The chemical extraction and ID analyses both showed that Cd was more labile than Cu in all the soil types studied. From the ID results, 32.8–93.3% of total Cd and 14.7–71.8% of total Cu were isotopically exchangeable after 3 days of equilibration. A single extraction in 0.43 m HNO₃ gave similar results to the 3‐day ID assay for Cu in most of the soils and for Cd in the non‐calcareous soils. However, an eight‐step selective sequential extraction (SSE) procedure gave different results from the ID assay for both metals. Predictions of the multi‐surface model for the amounts of Cd and Cu adsorbed, based on measured metal ion activities in the soil solution and the concentrations of reactive surfaces in the soil, agreed with the ID results. The model predicted that soil organic matter was the predominant sorbent for Cd and Cu in the soils and that manganese oxide was the least important sorbent. The contributions of iron oxides to sorption were predicted to be small except in soil with a high pH and little organic matter. The predicted sorption on different soil components did not match SSE measurements.