Downward movement of cadmium and phosphorus from phosphatic fertilisers in a pasture soil in New Zealand

Total cadmium (Cd) and phosphorus (P) concentrations in a pastoral soil, amended annually for 10 years with four forms of P fertilisers, decreased with soil depth. Single superphosphate (SSP) and North Carolina phosphate rock (NCPR) which had higher Cd contents (32 and 41 mg kg(-1), respectively) produced higher total soil Cd than diammonium phosphate (DAP-10 mg kg(-1)), Jordan phosphate rock (JPR-5 mg kg(-1)) and control treatments to a depth of 120 mm. Total soil P in SSP treated plots to a depth of 120 mm and NCPR treated plots to a depth of 75 mm was also higher than the control plots. No significant fertiliser P and Cd moved below 120 mm depth. Approximately 90% of the applied Cd was recovered in the soil of which 93% remained within the top 120 mm. Plant recovery of applied Cd was 1.5-4.5%. Plant available P (Olsen P) also decreased with depth. Plant available Cd (0.01 M CaCl2 extractable Cd) was higher in the 30-75 and 75-120 mm soil depths compared to 0-30 mm soil depth. This may be due to strong adsorption of Cd by the surface soils which have a higher organic matter content and higher pH; factors which are known to increase Cd adsorption in soils     

Phosphate-induced lead immobilization from different lead minerals in soils under varying pH conditions

This study investigated phosphate-induced lead immobilization from different Pb minerals in soils under varying pHs. Four soils were used, including one Pb-contaminated soil (NC-Soil) and three soils spiked with litharge (PbO), cerrusite (PbCO3), or anglesite (PbSO4), referred to as PbO-soil, PbCO3-soil, and PbSO4-soil, respectively. The soils were equilibrated with KCl and Ca(H2PO4)(2).H2O under pH of 3-7. At low pH (3 and 5), Pb solubility followed PbO-soil>PbCO3-soil>PbSO4-soil; while at pH=7, it was PbSO4-soil>PbO-soil>PbCO3-soil. Phosphate decreased Pb dissolution time from >180 to <60 min and reduced soluble Pb by 67-100%. This was mostly via transformation of Pb minerals into chloropyromorphite [Pb(5)(PO(4))(3)Cl]. Our results indicated that P addition can effectively transform various Pb minerals into insoluble chloropyromorphite in soils. This transformation was more significant at acidic condition (e.g., pH相似文献   

In situ immobilization of Cu(II) in soils using a new class of iron phosphate nanoparticles

This study tested the feasibility of using a new class of iron phosphate (vivianite) nanoparticles synthesized using sodium carboxymethyl cellulose (NaCMC) as a stabilizer for in situ immobilization of Cu(II) in soils. Transmission electron microscopy measurements demonstrated that the particle size was about 8.4+/-2.9 nm. Batch tests showed that nano-sized vivianite particles can effectively reduce the leachability and in vitro bioaccessibility of Cu(II) in three representative soils (calcareous, neutral, and acidic) at the low doses of 0.61 and 3.01 mg PO(4) g(-1) soil. The Cu leachability was evaluated by the toxicity characteristic leaching procedure and in vitro bioaccessibility was evaluated by the physiological based extraction test. In the case of soil amendment with nanoparticles in 3.01 mg PO(4) g(-1) soil, Cu leachability reduced 63-87% and Cu concentrations in TCLP extract decreased from 1.74-13.33 mg l(-1) to 0.23-2.55 mg l(-1) after those soils were amended for 56 d. Meanwhile, the bioaccessibility of Cu was reduced by 54-69%. Sequential extraction procedures showed the significant decrease of water soluble/exchangeable Cu(II) and carbonate bound fractions and concomitant increase of Cu residual fraction after the soils were amended with the nanoparticles, suggesting that the formation of copper phosphate minerals through precipitation and adsorption was probably responsible for the decrease of Cu availability in soils. Visual MINTEQ modeling further revealed that Cu(3)(PO(4))(2) and Cu(5)(PO(4))(3)OH were formed in the vivianite-solid Cu(II) system, resulting in the decreased solubility of the Cu(II) in the acidic pH range.     

桂林会仙湿地沉积物中磷形态及分布特征

沉积物中磷的含量及其形态是影响水体营养化进程的重要因素,对研究湿地水体富营养化具有重要意义。应用蒋柏藩等石灰性土壤无机磷提取方法,调查了桂林会仙岩溶湿地5个典型区域柱状沉积物中的磷形态分布、垂向上的变化特征,分析了各形态磷之前的相关性。结果表明,桂林会仙湿地柱状沉积物中w(TP)为161.14~555.48 mg/kg,活性较高的Ca2-P(5.27~51.45 mg/kg)、Ca8-P(7.76~37.57 mg/kg)均较低。沉积物中的磷以Ca-P(42.92%)为主,Ca-P中的Ca10-P所占比例较高(>70.3%),导致内源磷不易释放,有利于减缓桂林会仙湿地水体富营养化进程。在空间分布上,Ca2-P、Ca8-P、Al-P、Fe-P与TP分布趋势相似,从沉积物表层至底层逐渐降低并趋于稳定。Pearson相关系数表明,TP与总氮(TN)、有机质(OM)、Ca2-P、Ca8-P、Al-P、Fe-P极显著相关,与Ca10-P显著相关。     

Improving ecological risk assessment by including bioavailability into species sensitivity distributions: an example for plants exposed to nickel in soil

The variability of species sensitivity distribution (SSD) due to contaminant bioavailability in soil was explored by using nickel as metal of concern. SSDs of toxicity test results of Avena sativa L. originating from different soils and expressed as total content and available (0.01 M CaCl2) extractable concentration were compared to SSDs for terrestrial plants derived from literature toxicity data. Also the 'free' nickel (Ni2+) concentration was calculated and compared. The results demonstrated that SSDs based on total nickel content highly depend on the experimental conditions set up for toxicity testing (i.e. selected soil and pH value) and thus on metal bioavailability in soil, resulting in an unacceptable uncertainty for ecological risk estimation. The use in SSDs of plant toxicity data expressed as 0.01 M CaCl2 extractable metal strongly reduced the uncertainty in the SSD curve and thus can improve the ERA procedure remarkably by taking bioavailability into account.     

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.     

The effect of pH on zinc adsorption equilibria and exchangeable zinc pools in soils

Zinc adsorption equilibria were measured in soils differing in pH but with similar textures and total zinc concentrations, using adsorption isotherm and isotopic exchange techniques. The results suggested that the equilibrium between solution and exchangeable zinc was strongly pH dependent and the active zinc species in adsorption was single charged (e.g. Zn(OH)(+)). The size of the exchangeable zinc pool was not strongly pH dependent. Similar results were obtained when zinc was added to the soils, either as Zn(NO(3))(2) or in sewage sludge.     

Recovery of phosphates from wastewater using converter slag: Kinetics analysis of a completely mixed phosphorus crystallization process

A phosphorus crystallization process for recovering phosphates was developed using a completely mixed reactor and powdered converter slag as a seed crystal. This completely mixed phosphorus crystallization process achieved a stable and high phosphorus recovery: the average PO4-P removal efficiency during 200 d of operation was 87%, with a range of 70-98%. The apparent volume of the slag doubled due to crystal growth during the long-term phosphorus-removal experiments. The Ca2+ concentration, slag dosage, and temperature were found to govern the phosphorus recovery system for a given condition of pH and hydraulic retention time. The equations for the rate constant and reaction order were obtained by evaluating the model parameters. The model developed in this study was observed to successfully simulate the behavior of effluent PO4-P in a completely mixed phosphorus crystallization reactor over a wide variety of operating conditions of temperature, Ca2+ concentration, and influent PO4-P. Model investigations of design factors suggest that the completely mixed phosphorus crystallization process with influent PO4-P concentrations of less than 10 mg l(-1) could ensure effluent PO4-P concentrations of less than 0.5 and 1.0 mg l(-1) during summer and winter in Korea, respectively.     

Evaluation of plant availability of soil trace metals by chemical fractionation and multiple regression analysis

Soil samples with a range of chemical and physical properties were collected from 10 different rural regions of China. Trace metals (Ni, Co, Cu, and Pb) in the soils were partitioned by a sequential extraction procedure into Mg(NO(3))(2) extractable (F1), CH(3)COONa extractable (F2), NH(2)OH.HCl extractable (F3), HNO(3)?H(2)O(2) extractable (F4), and residual (F5) fractions. Chemical fractionation showed that F1 fraction of the metals was less than 1% and residue was the dominant form for Cu and Ni in all samples, and for Co in most of the samples. Significant interrelationships of the fractions varied considerably with the different metals. Winter wheat (Triticum aestivum L.) and alfalfa (Medicago sativa L.) had been grown on the soils in a pot-culture experiment under greenhouse conditions for 40 days. Metal availability to the plants was evaluated by simple and multiple regression analysis. The Mg(NO(3))(2) extractable Co (F1) was significantly correlated with Co concentrations in different parts of wheat and in the whole of alfalfa. For the other metals, the independent variables of the multiple regression models, chosen by stepwise selection, were given as: F1 and F2 + F3 + F4 for Ni; F1, F2 + F3 and F4 for Cu; and F3 + F4 for Pb. The results of this study demonstrate that the sequential extraction procedure, in conjunction with multiple regression models using a combination of correlated fractions as an independent variable, may be useful for the prediction of plant absorption of trace metals in soils.     

腐殖质纳米颗粒对镉污染土壤的修复

外源腐殖质可改变土壤镉（Cd）的含量和状态。以风化煤为原料制备的不溶性胡敏酸为吸附剂,对比研究了其对冶炼厂周边污染土壤及人工模拟污染土壤中Cd的钝化效果。再以泥炭为原料,制备富里酸钾为主的水溶性腐殖酸钾为淋洗剂,用于活化、去除上述2种土壤中的Cd。结果表明,胡敏酸在砂质的人工模拟污染土壤中钝化效果更好,2%的剂量可使土壤中CaCl2提取态Cd的浓度（0.103 mg·L-1）降低19.7%。腐殖酸钾去除土壤Cd的效率随淋洗剂浓度增加而提高,在10 g·L-1的浓度时,单次淋洗可去除高达38.1%的Cd。傅里叶变换红外光谱分析表明,腐殖质与Cd反应后形成了羧酸盐。因此,腐殖质纳米颗粒既可以钝化土壤中的Cd,也可以活化土壤中的Cd,从而达到修复Cd污染土壤的目的。其关键在于根据钝化或活化的目标,选择溶解度适当的腐殖质材料。     

Phosphate-induced metal immobilization in a contaminated site

To assess the efficiency of P-induced metal immobilization in soils, a pilot-scale field experiment was conducted at a metal contaminated site located in central Florida. Phosphate was applied at a P/Pb molar ratio of 4.0 with three treatments: 100% of P from H3PO4, 50% of P from H3PO4+ 50% of P from Ca(H2PO4)2, and 50% of P from H3PO4+5% phosphate rock in the soil. Approximately 1 year after P application, soil and plant samples were collected to determine mobility and bioavailability of selected metals (Pb, Zn, and Cu) using sequential extraction procedure and mineralogical characterization using X-ray diffraction (XRD) and scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis. Phosphorus distribution and soil pH effects were also evaluated. Phosphate was more effective in transforming soil Pb (to 53%) from the non-residual to the residual phase than soil Zn (to 15%) and soil Cu (to 13%). This was because Pb was immobilized by P via formation of an insoluble pyromorphite-like mineral in the surface and subsurface of the soil, whereas no phosphate mineral Zn or Cu was identified. While P amendment enhanced metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it significantly reduced metal translocation from root to shoot, especially Pb via formation of a pyromorphite-like mineral on the membrane surface of the root. A mixture of H3PO4 and phosphate rock was effective in metal immobilization, with less soil pH reduction and less soluble P. Although H3PO4 was effective in immobilizing Pb, its use should be limited to minimize soil pH reduction and potential eutrophication risk.     

Relation of enhanced Pb solubility to Fe partitioning in soils

It is well documented that Pb solubility may be related to Fe chemistry in soils and enhanced Pb solubility may occur under certain reducing conditions; however, quantification of such relationships is unavailable. Based on metal classification, Pb (II) and Fe (II) are similar in some chemical characteristics. Thus, competition between Pb and Fe for ligands in soils may be important in determining Pb solubility. In this paper, Pb solubility was examined in a sandy soil after spiking with Pb and incubating for 40 days under water-flooded or non-water-flooded conditions. Solution chemistry in soil columns was adjusted using different concentrations of NaCl, CaCl(2) and deionized water of varying pH before incubation. The results showed that Pb solubility in the soil was not correlated well with pH, dissolved organic C or aqueous Fe concentrations. However, an index of Fe partition behavior using the ratio of aqueous Fe to sorbed Fe was related to Pb solubility. Enhanced Pb solubility occurred only when the index was < approximately 2 kg l(-1). The index can be a simple measure of Fe's ability to compete with Pb for ligands in solution. The ability of Fe to compete with Pb decreases as the index decreases and as the ratio approached its minimum, substantial increases in Pb solubility will be expected. In general, the index was not sensitive to changes in solution chemistry. A similar trend was observed using one data set published in the literature.     

A model for evaluation of the phytoavailability of trace elements to vegetables under the field conditions

Currently, several single extraction methods are used for the evaluation of the phytoavailability of metals using pot experiments. A systematic comparison, however, is lacking. It is especially true for the field studies. This study was to investigate the phytoavailability of trace elements to vegetables grown on metal-contaminated soils under the field conditions. All soils collected were typical calcareous soils in northern China. Four frequently used methods using CaCl2, diethylenetriaminepentaacetic acid (DTPA), CH3COOH, and water as extractants were compared for phyto-availability. The concentrations of metals extracted by these four extraction methods ranged from 3.42 to 815, 1.51- 6965, 0.732-24473, 0.688-7863, 0.246-685, 1.99-5337 0.203-4649 ng/g for Cr, Ni, Zn, Cu, Cd, Pb and REEs, respectively. Simple correlation analysis indicated that a significant correlation (Cr: r = 0.5411**; Zn: r = 0.6352**; Cd: r = 0.6979**; Pb: r = 0.5537** and REEs: r = 0.5185** -0.6684**) was observed between the CaCl2-extractable metals in soil solution and that in Chinese cabbage. In addition, soil pH, organic matter (OM), and cation exchange capacity (CEC) also affect the phytoavailability. An empirical model was developed to express the combined effect of soil properties on the phytoavailability. The stepwise multiple regression analysis demonstrated that the phytoavailability of trace elements strongly correlated with the extractable fraction by CaCl2, total metal concentration in soils, and soil pH, OM, CEC. This model can describe approximately 75-95% of the variability of metal uptake and the r2 values ranged from 0.741** to 0.954**, which were much better than the single correlation analysis. For celery and cole, a strong correlation was obtained for Cr, Ni, Zn, Cu, Cd, La, Ce, Pr and Nd. For spinach and Chinese cabbage, however, a positive correlation was only observed for 1 and 3 metals, respectively. Generally, the developed empirical model can integrate the combined effects of soil properties, extractable metal fractions in soil solutions and plant species on the phytoavailability of metals to vegetables in the field conditions.     

Distribution, speciation and availability of antimony (Sb) in soils and terrestrial plants from an active Sb mining area

Here, we present one of the first studies investigating the mobility, solubility and the speciation-dependent in-situ bioaccumulation of antimony (Sb) in an active Sb mining area (Xikuangshan, China). Total Sb concentrations in soils are high (527-11,798 mg kg⁻¹), and all soils, including those taken from a paddy field and a vegetable garden, show a high bioavailable Sb fraction (6.3-748 mg kg⁻¹), dominated by Sb(V). Elevated concentrations in native plant species (109-4029 mg kg⁻¹) underpin this. Both chemical equilibrium studies and XANES data suggest the presence of Ca[Sb(OH)₆]₂, controlling Sb solubility. A very close relationship was found between the citric acid extractable Sb in plants and water or sulfate extractable Sb in soil, indicating that citric acid extractable Sb content in plants may be a better predictor for bioavailable Sb in soil than total acid digestible Sb plant content.     

Effects of incubation on solubility and mobility of trace metals in two contaminated soils

Much research has focused on changes in solubility and mobility of trace metals in soils under incubation. In this experiment, changes in solubility and mobility of trace metals (Pb, Cu and As) and Fe in two contaminated soils from Tampa, Florida and Montreal, Canada were examined. Soils of 30 g were packed in columns and were incubated for 3-80 days under water-flooding incubation. Following incubation, metal concentrations in pore water (water soluble) and in 0.01 M CaCl2 leachates (exchangeable+water soluble) were determined. While both soils were contaminated with Pb (1600-2500 mg kg(-1)), Tampa soil was also contaminated with As (230 mg kg(-1)). Contrast to the low pH (3.8) of Tampa soil, Montreal soil had an alkaline pH of 7.7 and high Ca of 1.6%. Concentrations of Fe(II) increased with incubation time in the Tampa soil mainly due to reductive Fe dissolution, but decreased in the Montreal soil possibly due to formation of FeCO3. The inverse relationship between concentrations of Pb and Fe(II) in pore water coupled with the fact that Fe(II) concentrations were much greater than those of Pb in pore water may suggest the importance of Fe(II) in controlling Pb solubility in soils. However, changes in concentrations of Fe(II), Pb, Cu and As in pore water with incubation time were similar to those in leachate, i.e. water soluble metals were positively related to exchangeable metals in the two contaminated soils. This research suggests the importance of Fe in controlling metal solubility and mobility in soils under water-flooded incubation.     

Solubility of lead, zinc and copper added to mineral soils

Elevated levels of heavy metals in soils are a result of industrial activities, atmospheric deposition, and the land application of sewage sludges and industrial by-products. Their persistence in the soil environment has created interest in the possible changes in solubility. In this study, total dissolved concentrations of Pb, Zn, and Cu were monitored in seven metal-amended soils (a calcareous and six acid mineral soils). Single metal solutions were added to soils and equilibrated (aged) for 40 days. During the 40 days the soil was allowed to air-dry and was rewetted in cycles of about 5 days. At the end of this reaction period, metal solubility was measured (by atomic absorption spectrometry and direct current plasma spectrometry) at the initial soil pH and at decreased pH values which were induced by addition of small aliquots of acid. As expected, solubility of added Pb, Zn, and Cu increased with a decrease in pH. Furthermore, the results showed that the solubility relationship with pH was similar in all non-calcareous soils. This suggests that metal solubility may be controlled by similar soil components, presumably involving soil characteristics such as pH, organic matter content, and soil mineralogy. For each metal, an approximate pH value was found at which solubility deviated from the solubility of metals when they occur in soils at typical (natural) values. This pH was about (pH+/-0.2): 5.2 for Pb, 6.2 for Zn, and 5.5 for Cu. Thus, pH values below these thresholds may enhance metal mobility, biological availability and toxicity in soils. Metals dissolved at higher pH in the calcareous soil (18.8 g kg(-1) inorganic carbon, initial pH 8.2). In a calcareous soil, a significant fraction of these metals react with carbonates, and decreased pH results in much higher metal dissolution. Yet, metal solubility in soils is not determined by the formation and dissolution of single metal compounds.     

Effect of soil on microbial responses to metal contamination

An experiment was conducted to investigate microbial responses to metal inputs in five soils with varying clay and organic contents; one soil had also a higher pH. These soils were treated with a low metal, sewage sludge control or with this sludge contaminated to achieve Cu=112, Ni=58 and Zn=220 mg kg(-1) in medium and Cu=182, Ni=98 and Zn=325 mg kg(-1) in high metal soils. CO(2) evolution rates were measured at 1 week and at 4-5-day intervals thereafter until the end of the incubation (7 weeks). Extractable metals (CaCl(2) and water), biomass C, metabolic quotient, ergosterol, bacterial-fungal phospholipid fatty acid (PLFA-3 weeks only) ratio and mineral N were measured at 3 and 7 weeks. Metal inputs caused a marked increase in metal availability in the slightly acidic sandy loams, a smaller increase in slightly acidic clays and had little effect in the alkaline loam. After an initial increase in CO(2) evolution with metal inputs in all soils, the high metal treatment alone caused a significant decrease at later stages, mainly in sandy loams. Although biomass C and metabolic quotient decreased in all soils with higher metal inputs, the effect was more pronounced in the sandy loams. Metal inputs increased ergosterol and decreased bacterial-fungal PLFA ratios in most soils. Larger mineral N contents were found in all high metal soils at 3 weeks but, after 7 weeks, metals caused a significant decrease in sandy loams. CaCl(2) and water-extractable Cu, Ni and Zn contents were closely correlated with microbial indices in sandy loam but not in clay soils. Overall, the effect of treatments on microbial and extractable metal indices was greater in loams. Within a single series, higher organic soils showed less pronounced responses to metal inputs, although this trend was not always consistent.     

Comparison of a rhizosphere-based method with other one-step extraction methods for assessing the bioavailability of soil metals to wheat

There is no method recognized as a universal approach for evaluation of bioavailability of heavy metals in soil. Based on the simulation of the rhizosphere soil conditions and integration of the combined effects of root-soil interactions as a whole, a rhizosphere-based method has been proposed. Wet fresh rhizosphere soil was extracted by low-molecular-weight organic acids (LMWOAs) to fractionate metal fractions of soil pools, which were then correlated with the metal contents of wheat roots and shoots. The rhizosphere-based method was compared with other one-step extraction methods using DTPA, EDTA, CaCl2, and NaNO3 as extractants and the first step of the Community Bureau of Reference (BCR) method. Simple correlation and stepwise multiple regression analysis were used for the comparison. Simple correlation indicated that the extractable Cu, Zn, Cr, and Cd of soils by the rhizosphere-based method were significantly correlated with the metal contents of wheat roots. For DTPA, BCR1 and EDTA methods there was a relatively poor correlation between the extractable Cu, Zn and Cd of soil and metal contents of wheat roots. Stepwise multiple regression analysis revealed that the equation of the rhizosphere-based method was the simplest one, and no soil properties variables needed to be added. In contrast, the equations of other one-step extraction methods were more complicated, and soil properties variables needed to be entered. The most distinct feature of the rhizosphere-based method was that the recommended method was suitable for acidic, neutral and near alkaline soils. However, the DTPA and EDTA extraction methods were suitable for calcareous soils only-or-only for acidic soils. The CaCl2, and NaNO3 extraction methods were only suitable for exchangeable metals. In short, the rhizosphere-based method was the most robust approach for evaluation of bioavailability of heavy metals in soils to wheat.     

Cadmium availability to wheat grain in soils treated with sewage sludge or metal salts

Grain Cd concentrations were determined in wheat (Triticum aestivum L.) grown in 1999, 2001 and 2003, at six sludge cake field experiments. Three of these sites also had comparisons with Cd availability from metal amended liquid sludge and metal salts. Grain Cd concentrations in all years and at all sites were significantly linearly correlated with NH4NO3 extractable Cd and soil total Cd (P<0.001). Soil extractability was greater in the liquid sludge and metal salt experiments than in the cake experiments, as were grain Cd concentrations. Across all the sites, NH4NO3 extractable soil Cd was no better at predicting grain Cd than soil total Cd. Stepwise multiple linear regression analysis showed that soil total Cd, pH and organic carbon were the only significant (P<0.001) variables influencing wheat grain Cd concentrations, explaining 78% of the variance across all field experiments (1408 plots). This regression predicted that the current UK soil total Cd limit of 3 mg kg(-1) was not sufficiently protective against producing grain above the European Union (EU) grain Cd Maximum Permissible Concentration (MPC) of 0.235 mg Cd kg(-1) dry weight, unless the soil pH was > 6.8. Our predictions show that grain would be below the MPC with > 95% confidence with the proposed new EU draft regulations permitting maximum total Cd concentrations in soils receiving sludge of 0.5 mg kg(-1) for soils of pH 5-6, 1 mg kg(-1) for soils of pH 6-7, and 1.5 mg kg(-1) for soils of pH > or = 7.     

Effect of the cationic composition of sorption solution on the quantification of sorption-desorption parameters of heavy metals in soils

We obtained the sorption isotherms of Cd, Cu, Pb and Zn in clay, clay saline and organic soils. The distribution coefficients (K(d)) were determined in 0.02 eq l(-1) CaCl(2) and in a solution that simulated the soil solution cationic composition. The K(d) values greatly varied with the composition of the sorption solution and the initial metal concentration. The sorption experiments were complemented with the quantification of the extractable metal, to estimate the reversibility of metal sorption. The extraction yields depended on the metal-soil combination, and the initial metal concentration, showing no correlation with previous K(d) values. The effect of the solution composition in mobility predictions was estimated through a Retention Factor, defined as the ratio of the K(d) versus the extraction yield. Results showed that risk was over- or underestimated using the CaCl(2) medium in soils with a markedly different soil solution composition.