Influence of Increasing Soil Copper Concentration on the Susceptibility of Phosphomonoesterase and Urease to Heat Disturbance

The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO₄ ^2– and PO₄ ^3–, surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by K _f was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota.     

Specific sorption of trace amounts of cadmium by soils

Abstract

Sorption of trace quantities of Cd in four soils of different chemical and mineralogical properties, was studied. Initial Cd concentrations were between 15 to 150 μg. 1^?1. The sorption isotherms were linear and had a positive intercept in three of the soils, indicating a constant partition‐high affinity sorption isotherm (Giles et. al⁶). The data also followed the Freundlich sorption isotherm, and the Freundlich K parameter was taken as a measure of the relative affinity of the different soils for the Cd metal sorbed. Cadmium sorbed was extracted by IN‐NH₄C1 followed by 0.1N HC1, and the fraction remaining in the soils was considered specifically sorbed Cd. This fraction also followed a linear sorption isotherm, and was around 30% for the four soils studied. The sorption order for the amount of specifically sorbed Cd showed that the Boomer soil (kaolinite‐iron oxides) had the lowest affinity for specific sorption of this metal. This was taken as evidence that kaolinite and iron oxides have a lower capacity for retaining cadmium through specific sorption mechanism(s) than the materials present on the other soils (2:1 layer silicates and humic substances). The existence of specific mecha‐nism(s) responsible by the sorption of trace quantities of Cd in soil solutions has important implications on soil‐plant relationships, Cd mobility in soil profiles and control of Cd activity in soil solutions.     

Removal of Pb(II), Cr(III) and Cr(VI) from Aqueous Solutions Using Alum-Derived Water Treatment Sludge

The sorption of Pb(II), Cr(III) and Cr(VI) from aqueous solution using alum-derived water treatment sludge was investigated using the batch adsorption technique. Samples of sludge from two separate water treatment plants were used (one where alum was used alone and one where it was used in combination with activated C). The sorption characteristics of the two samples were generally very similar. Sorption isotherm data for all three ions fitted equally well to both Freundlich and Langmuir equations. Maximum sorption capacity and indices of sorption intensity both followed the order: Cr(III)?>?Pb(II)?>?Cr(VI). Kinetic data correlated well with a pseudo-second-order kinetic model suggesting the process involved was chemisorption. Sorption was pH-dependant with percentage sorption of Cr(III) and Pb(II) increasing from <30% to 100% between pH?3 and 6 whilst that of Cr(VI) declined greatly between pH?5 and 8. HNO₃ at a concentration of 0.1?M was effective at removing sorbed Cr(III) and Pb(II) from the sludge surfaces and regeneration was successful for eight sorption/removal cycles. It was concluded that water treatment sludge is a suitable material from which to develop a low-cost adsorbent for removal of Cr and Pb from wastewater streams.     

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

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

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.     

Einfluss eisenhaltiger Klärschlämme auf Kenngrößen der P‐Verfügbarkeit in Ackerböden

Influence of iron content in sewage sludges on parameters of phosphate availability in arable soils The use of iron salts for the P elimination in sewage plants is widely used. But it is not clear whether the P availability in arable soils is negatively influenced by iron compounds or not. The aim of the investigations was, therefore, to study the influence of two sewage sludges with a high and a low Fe content respectively on P sorption and phosphate concentration (P_i) in the soil solution after application of CaHPO₄ or sewage sludge to 5 loamy and 4 sandy soils (pot experiments and 1 silty loam (field experiment)). Soils were analyzed 1, 6, and 13 months after P application. Sludge Gö contained 12 kg P and 65 kg Fe (t DM)^—1 (P : Fe = 1 : 5.4) and sludge Sh 25 kg P and 39 kg Fe (t DM)^—1 (P : Fe = 1 : 1.5). The basic P application was 60 kg P ha^—1 (= 30 mg P (kg soil)^—1 in the pot experiment, as sludge or as CaHPO₄). P uptake by maize was determined in a separate pot experiment with a loamy soil and the same P application rate. The P sorption capacity remained similar in all soils after application of sludge Sh (P : Fe = 1:1.5) compared with soils without sludge, however, after application of sludge Gö the P sorption increased by 16% (0—59%). After application of sludge Sh the mean P_i concentration increased in loamy soils by 34% and in sandy soils by 15%. On the other hand the P_i concentration decreased after applying sludge Gö by 13% and 36% as compared to the controls of the respective soils. In the field experiment the P_i concentration of plots with a high P level (50 mg lactate soluble P (kg soil)^—1) was also significantly decreased after application of 10 t sludge Gö (126 kg P ha^—1) in comparison with triple phosphate. One month after the application of increasing amounts of sludge Gö (5, 10, 15 t DM ha^—1) both the concentration of oxalate‐soluble Fe in the soil and the P sorption were increased. The elevated relationship between these two parameters was highly significant (r² = 0.6 — 0.97). Plant uptake of P was less after application of sludge Gö than after application of sludge Sh and much less than P uptake from CaHPO₄. Sewage sludges with a P : Fe ratio of 1 : 5 should not be recommended for agricultural use, as the P availability is significantly reduced. Iron salts should not be used for conditioning of sludges.     

Predicting heavy metal transfer from soil to plant: potential use of Freundlich‐type functions

Soil‐plant transfer of metals is a nonlinear process. We therefore aimed at evaluating the potential of Freundlich‐type functions (c_Plant = b × c_Soil^a) to predict Cd, Cu, Pb, and Zn concentrations in wheat (Triticum aestivum L.) grain and leaf (c_Plant) from soil concentrations (c_Soil). Wheat plants and soil A horizons, mainly developed from Holocene sediments, were sampled at 54 agricultural sites in Slovakia. Metals were extracted from soils with 0.025 M EDTA at pH 4.6 and concentrated HNO₃/HClO₄ (3:1); plant samples were digested with concentrated HNO₃. Total metal concentrations of soil samples were 0.07—25 mg Cd kg^—1, 9.3—220 mg Cu kg^—1, 14—1827 mg Pb kg^—1, and 34—1454 mg Zn kg^—1. On average, between 20 % (Zn) and 80 % (Cd) of the total concentrations were EDTA‐extractable. The total metal concentrations of grain samples were < 0.01—1.3 mg Cd kg^—1, 1.3—6.6 mg Cu kg^—1, < 0.05—0.30 mg Pb kg^—1, and 8—104 mg Zn kg^—1. The leaves contained up to 3.2 mg Cd kg^—1, 111 mg Cu kg^—1, 4.3 mg Pb kg^—1, and 177 mg Zn kg^—1. Linear regression without data transformation was precluded because of the nonnormal data distribution. The Freundlich‐type function was suitable to predict Cd (grain: r = 0.71, leaf: 0.86 for the log‐transformed data) and Zn concentrations (grain: 0.69, leaf: 0.68) in wheat grain and leaf from the EDTA‐extractable metal concentrations. The prediction of Cu and Pb concentrations in grain (Cu: r = 0.44, Pb: 0.41) was poorer and in leaf only possible for Pb (0.50). We suggest to use the Freundlich‐type function for defining threshold values instead of linear regression because it is more appropriate to simulate the nonlinear uptake processes and because it offers interpretation potential. The results suggest that the coefficient b of the Freundlich‐type function depends on the intensity of metal uptake, while the coefficient a reflects the plants' capability to control the heavy metal uptake. The latter is also sensitive to metal translocation in plants and atmospheric deposition.<?show $6#>     

Characterization of soil heavy metal pools in paddy fields in Taiwan: chemical extraction and solid-solution partitioning

Background, aim, and scope  Ongoing industrialization has resulted in an accumulation of metals like Cd, Cu, Cr, Ni, Zn, and Pb in paddy fields across Southeast Asia. Risks of metals in soils depend on soil properties and the availability of metals in soil. At present, however, limited information is available on how to measure or predict the directly available fraction of metals in paddy soils. Here, the distribution of Cd, Cu, Cr, Ni, Zn, and Pb in 19 paddy fields among the total, reactive, and directly available pools was measured using recently developed concepts for aerated soils. Solid-solution partitioning models have been derived to predict the directly available metal pool. Such models are proven to be useful for risk assessment and to derive soil quality standards for aerated soils. Material and methods  Soil samples (0–25 cm) were taken from 19 paddy fields from five different communities in Taiwan in 2005 and 2006. Each field was subdivided into 60 to 108 plots resulting in a database of approximately 3,200 individual soil samples. Total (Aqua Regia (AR)), reactive (0.43 M HNO₃, 0.1 M HCl, and 0.05 M EDTA), and directly available metal pools (0.01 M CaCl₂) were determined. Solid-solution partitioning models were derived by multiple linear regressions using an extended Freundlich equation using the reactive metal pool, pH, and the cation exchange capacity (CEC). The influence of Zn on metal partitioning and differences between both sampling events (May/November) were evaluated. Results  Total metals contents range from background levels to levels in excess of current soil quality standards for arable land. Between 3% (Cr) and 30% (Cd) of all samples exceed present soil quality standards based on extraction with AR. Total metal levels decreased with an increasing distance from the irrigation water inlet. The reactive metal pool relative to the total metal content is increased in the order Cr << Ni = Zn < Pb < Cu < Cd and ranged from less than 10% for Cr to more than 70% for Cd. Despite frequent redox cycles, Cd, Pb, and Cu appear to remain rather reactive. The methods to determine the reactive metal pool in soils yield comparable results, although the 0.43 M HNO₃ extraction is slightly stronger than HCl and EDTA. The close correlation between these methods suggests that they release similar fractions from soils, probably those reversibly sorbed to soil organic matter (SOM) and clay. The average directly available pool ranged from less than 1% for Cu, Pb, and Cr to 10% for Ni, Zn, and Cd when compared to the reactive metal pool. For Cd, Ni, Zn, and to a lesser extent for Cu and Pb, solid-solution partitioning models were able to explain up to 93% (Cd) of the observed variation in the directly available metal pool. CaCl₂ extractable Zn increased the directly available pool for Ni, Cd, and Cu but not that of Pb and Cr. In the polluted soils, the directly available pool was higher in November compared to that in May. Differences in temperature, rainfall, and changes in soil properties such as pH are likely to contribute to the differences observed within the year. The solid-solution partitioning model failed to explain the variation in the directly available Cr pool, probably because Cr is present in precipitates rather than being adsorbed onto SOM and clay. Despite obvious differences in parent material, source of pollution, climate, and land use, solid-solution partitioning of Cd in paddy fields studied here was similar to that in soils from Belgium and the Netherlands. Discussion  To assess risks of metals in soils, both analytical procedures as well as models are needed. The three methods tested here to determine the reactive metal pool are highly correlated and either of these can be used. The directly available pool was predicted most accurately by the 0.43 M HNO₃ method. The similarity of metal partitioning in paddy soils compared to well-drained soils suggests that changing redox conditions in paddy fields have a limited effect on the geochemical behavior of metals like Cd, Ni, and Zn. Small but significant differences in the directly available metal pool during the year suggest that redox cycles as well as differences in rainfall and temperature affect the size of the directly available metal pool. The large observed spatial heterogeneity of contaminant levels requires ample attention in the setup of soil monitoring programs. Conclusions  The directly available pool (0.01 M CaCl₂) of Cd, Zn, and Ni in paddy fields can be described well by an extended Freundlich model. For Cu and Pb, more information on dissolved organic carbon is needed to obtain a more accurate estimate of the directly available pool. Recommendations and perspectives  Soil testing protocols and models used in risk assessment consider the availability of pollutants rather than the total metal content. Results from extensive testing indicate that approaches developed for nontropical regions can be applied in paddy fields as well for metals like Cd, Ni, and Zn. This study shows that the chemical behavior under drained conditions in paddy fields is comparable to that observed in soils across the European Union, which allows regions with large scale soil pollution including Taiwan to apply such concepts to derive meaningful experimental protocols and models to assess risks of metals in soils.     

Sorption of phosphorus by some surface soils from Quebec in relation to their properties

Abstract

Surface horizons from Podzolic and Gleysolic soils were collected in various parts of the province of Quebec, Canada, and equilibrated with various amounts of KH₂PO₄ in 0.01 M CaCl₂ for 48 hours. P sorption data conformed to the linear form of the Langmuir and Freundlich equations. P solubility isotherms showed evidence of hydroxyapatite formation in most samples studied, whereas equilibration solutions of only few samples were saturated with respect to either dicalcium phoshate dihydrate or octocalcium phosphate. These reaction products were associated to soil pH and levels of added phosphate. The average values of the Langmuir sorption maximum for these studied Gleysolic and Podzolic samples were 763 and 1096 μg/g respectively. These values were higher than those obtained by the segmented and modified Freundlich models.

Relationships between the soil characteristics and P sorption parameters were evaluated by regression analysis. Among all variables, oxalate‐extractable Fe plus Al content of the Podzolic samples and the ratio of oxalate—extractable Al to clay of the Gleysolic samples gave the best significant correlation coefficients. Furthermore, soil pH and various ratios such as pyrophosphate‐extractable Fe and Al, oxalate‐extractable Fe and organic matter to clay were found to be significantly correlated only with the P sorption parameters of the Gleysolic samples.     

The sorption of Cd and Zn by different soils in the presence of dissolved organic matter from sludge

Dissolved organic matter (DOM) is one of the important factors affecting metal mobility and phytotoxicity in the soils receiving sewage sludge. The aim of this study was to investigate the effects of DOM from anaerobically digested dewatered sludge on Cd and Zn sorption by three different soil types (calcareous clay loam, calcareous sandy loam and acidic sandy loam) of different physico-chemical properties through batch studies. The addition of DOM significantly reduced the Cd and Zn sorption capacity by a factor of 2.1–5.7 for Cd and 2.3–13.7 for Zn for these three soils as seen by their K values in the Freundlich equation compared to the control receiving no DOM, suggesting that DOM had a stronger inhibitory effect on Zn sorption than that of Cd. The reduction in metal sorption caused by DOM was very apparent in the pH range of 5 to 8, with a maximum inhibition on metal sorption occurring at pH 7–7.5 especially for Zn but the effect was minimal at lower pH. At a DOM concentration of < 200 mg C l^− 1, Cd and Zn sorption by all the three soils decreased with an increase in DOM concentration. At each given DOM concentration, the inhibition of metal sorption of the different soil types increased in the following order: acidic sandy loam < calcareous sandy loam < calcareous clay loam. DOM derived from sludge would significantly reduce metal sorption and increase its mobility through the formation of soluble DOM–metal complexes and poses risk of metal leaching and phytotoxicty in near-neutral and alkaline soils.     

Phosphordüngewirkung eisenhaltiger Klärschlämme

<?show $38#Bo;>Phosphorus fertilization effect of sewage sludges treated with iron compounds The result of waste water treatment with iron salts are sewage sludges with higher P but also Fe contents. The effect of such sludges on P availability in soils is not clear and was, therefore, compared with CaHPO₄ as a P mineral fertilizer. In experiments (Mitscherlich pots, 6 kg soil) two sandy soils (pH 4.3 and 4.9), two luvisols ( pH 6.3 and 7.2), a loess (13 % CaCO₃), and quartz sand all differing in their P status were treated with two sewage sludges which differed in their molar Fe:P ratios (sludge Gö: 1:0.3, sludge Sh: 1:1.2). For sludge Gö the P elimination had been carried out with FeSO₄ and the sludge was stabilized with FeCl₃ + Ca(OH)₂ (filter press). For sludge Sh P was eliminated by FeCl₃ in the aerobic basin. The first crop was maize (total shoot dry matter), the second red clover. In case of sludge Sh both crops took up in comparison to CaHPO₄ the same amount of P from all substrates with the exception of quartz sand. The effect of sludge Gö was quite different: from the neutral luvisol soils maize was able to take up only 64—82 % P and red clover 77—82 % P only as compared to CaHPO₄. On the sandy soils maize and red clover grew after sludge Gö as good or better than after CaHPO₄ application and P uptake was quite similar (83—106 %). This result was concomitant to an increase of pH values (from 4.3 to 4.9, 4.9 to 5.6, respectively). The negative efficiency of P uptake in heavy soils after application of sludge Gö resulted from an increase of P sorption and decrease of orthophosphate concentration in soil solution. This sludge contains a high proportion of iron hydroxides/oxides with free sorption sites for P. In future P elimination from waste water should be done without iron salts. At least during the process of conditioning no Fe salts should be used.<?show $6#>     

Spatial distribution of soil heavy metal concentrations as indicator of pollution sources at Mount Križna (Great Fatra,central Slovakia)

The objective of this study was to test the suitability of a simple approach to identify the direction from where airborne heavy metals reach the study area as indication of their sources. We examined the distribution of heavy metals in soil profiles and along differently exposed transects. Samples were taken from 10 soils derived from the same parent material along N-, S-, and SE-exposed transects at 0—10, 10—20, and 20—40 cm depth and analyzed for total Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn concentrations. The heavy metal concentrations at 0—10 cm were larger than background concentrations in German arable soils except for Cr (Cd: 0.6—1.8 mg kg^—1; Cr: 39—67; Cu: 40—77; Ni: 87—156; Pb: 48—94; Zn: 71—129; Fe: 26—34 g kg^—1; Mn: 1.1—2.4). Decreasing Cd, Cu, Mn, and Pb concentrations with increasing soil depth pointed at atmospheric inputs. Aluminum and Ni concentrations increased with soil depth. Those of Fe, Cr, and Zn did not change with depth indicating that inputs at most equalled leaching losses. The Pb accumulation in the surface layer (i.e. the ratio between the Pb concentrations at 0—10 to those at 20—40 cm depth) was most pronounced at N-exposed sites; Pb obviously reached Mount Križna mainly by long-range transport from N where several industrial agglomerations are located. Substantial Cd, Cu, and Mn accumulations at the S- and SE-exposed sites indicated local sources such as mining near to the study area which probably are also the reason for slight Cr and Zn accumulations in the SE-exposed soils. Based on a principal component analysis of the total concentrations in the topsoils four metal groups may be distinguished: 1. Cr, Ni, Zn; 2. Mn, Cd; 3. Pb (positive loading), Cu (negative loading); 4. Al, Fe, indicating common sources and distribution patterns. The results demonstrate that the spatial distribution of soil heavy metal concentrations can be used as indication of the location of pollution sources.     

Inhibitory effects of the total and water-soluble concentrations of nine different metals on the dehydrogenase activity of a loess soil

 This study focuses on a comparison of the microbial toxicity of nine metals, including As as a metalloid and two species of Cr. A loess soil [Ap horizon, clay 15.2%, organic C 1.12%, pH(CaCl₂) 7.02] was spiked with 8–12 geometrically increasing doses of the metals. The dehydrogenase assay (2-p-iodophenyl-3-p-nitrophenyl-5-phenyltetrazoliumchloride method) was combined with sorption and solubility experiments. The resulting dose-response curves and sorption isotherms were used to derive total doses that caused definite percentage inhibitions [i.e. effective doses (ED) causing a 10–90% reduction in dehydrogenase activity (dha)] as well as the corresponding toxic solution concentrations causing the same reductions in dha (i.e. effective concentrations; EC₁₀–EC₉₀). Based on total doses, the toxicity decreased in the following order with ED₅₀ values (mg kg^–1) given in brackets: Hg (2.0)>Cu (35)>Cr(VI) (71)>Cr(III) (75)>Cd (90)>Ni (100)>Zn (115)>As (168)>Co (582)>Pb (652). With regard to solution concentrations, toxicity decreased in the order (EC₅₀ in mg l^–1): Hg (0.003)>Pb (0.04)>Cu (0.05)>Cd (0.14)>Zn (0.19)>Cr(III) (0.62)>Ni (0.69)>Co (30.6)>As (55.5)>Cr(VI) (78.1). The retention of the metals by the soil differed strongly. Pb, Cu, and Hg exhibited the highest and Ni, As, and Cr(VI) the lowest sorption constants (Freundlich K values: 2455, 724, 348, 93, 13, and 0.06 mg kg^–1, respectively). The sorptivity of the metals and their microbial toxicity in the aqueous phase were characteristically related: metals with a strong toxic action in the soil solution were adsorbed by the soil to a high degree and vice versa. Therefore, especially for metals with a high inherent toxicity, sorption is an effective way of immobilizing them and temporarily detoxifying soil. Received: 2 July 1998     

Stabilization of chromium(VI) by hydroxysulfate green rust in chromium(VI)-contaminated soils

Chromium (Cr)-contaminated soils pose a great environmental risk, with high solubility and persistent leaching of Cr(VI). In this study, hydroxysulfate green rust (GR_SO4), with the general formula Fe(II)₄Fe(III)₂(OH)₁₂SO₄·8H₂O, was evaluated for its efficiency in Cr(VI) stabilization via Cr(VI) reduction to Cr(III) in four representative Cr(VI)-spiked soils. The initial concentrations of phosphate buffer-extractable Cr(VI) (Cr(VI)_b) in soils 1, 2, 3, and 4 were 382.4, 575.9, 551.3, and 483.7 mg kg^-1, respectively. Reduction of Cr(VI) to Cr(III) by structural Fe(II) (Fe(II)_s) in GR_SO4 in all studied soils was fast, wherein the application of GR_SO4 markedly decreased the amount of Cr(VI)_b at the Cr(VI)_b/Fe(II)_s stoichiometric mole ratio of 0.33. The kinetics of Cr(VI) reduction by GR_SO4 could not be determined as this reaction coincided with the release of Cr(VI) from soil during the experiment. The concentration of Cr(VI)_b decreased, as the Cr(VI)_b/Fe(II)_s ratio decreased from 0.46 to 0.20, generally to below 10 mg kg^-1. Back-transformation of the generated Cr(III) was examined in the presence of manganese oxide birnessite at the birnessite/initial Cr(III) mole ratio of 4.5. The results of batch tests showed that only 5.2% of the initial Cr(III) was converted to Cr(VI) after two months, while under field capacity moisture conditions, less than 0.05% of the initial Cr(III) was oxidized to Cr(VI) after six months. The results illustrated that remediation of Cr(VI)-contaminated soils would be fast, successful, and irreversible with an appropriate quantity of fresh GR_SO4.     

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

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

Short-term phosphorus sorption and desorption in contrasting cropped Vertisols

Vertisols are important cropping soils in tropical and subtropical areas, but in many regions, decades of cropping has substantially reduced concentrations of plant-available phosphorus (P), especially in the subsoil layers. Phosphorus behaviour in P-depleted Vertisols has received comparatively little attention, and the availability of P following the addition of inorganic P fertilisers at different concentrations is poorly understood. In this study, we evaluated short-term P sorption and desorption behaviour in cropped Vertisols in relation to specific soil physical and chemical properties. We collected the surface and subsurface of 15 Australian soils with a broad range of physical and chemical properties, comprising nine Vertisols, three Ferralsols, two Lixisols and one Calcisol. For each soil, we generated sorption and desorption curves (fitted with a Freundlich equation), determined soil physical and chemical properties likely to influence P sorption and evaluated the relationships between the measured soil properties and the Freundlich equation sorption coefficients. The P sorption curves differed drastically between soils, with the sorption equation coefficients (a_S × b) significantly correlated with the P buffering index (PBI) and clay content. Clay content itself was correlated with citrate-extractable Fe and Al oxides and BET surface area. Vertisols formed on basaltic parent materials had greater Fe and Al oxide concentrations, resulting in an overall greater P sorption capacity. Sorption and desorption hysteresis were mostly small. The reacting materials in these soils probably had limited ability to continue to react with P. The Vertisols differed in their capacity to replenish P in the soil solution by desorbing different proportions of previously sorbed P, although the proportion of desorbable P generally increased with greater concentrations of sorbed P. These results suggest that for fertiliser management in these soils, smaller volumes of P enrichment combined with higher P concentrations may result in a greater P recovery by the crop.     

Trace elements in Bangladesh paddy soils

Abstract

A study was carried out to investigate the status of four micronutrients, iron (Fe), copper (Cu), manganese (Mn), and zinc (Zn), and five other trace elements, cobalt (Co), chromium (Cr), nickel (Ni), lead (Pb), and strontium (Sr), in paddy soils of Bangladesh. Soil samples were digested by hydrofluoric acid (HF)‐nitric acid (HNO₃)‐perchloric acid (HClO₄) for determination of total contents of the nine elements, while DTPA, ASI and 0.1 Mhydrochloric acid (HC1) methods were used for determination of available Fe, Cu, Mn, and Zn. Total trace element contents were found to vary with physiography on which soils are distributed. In general, Ganges Tidal Floodplain soils had the highest content, whereas terrace soils had the lower content. Among the soil properties examined, clay content had a good relation with total trace element contents in the topsoil, except for Sr. Based on the variation with physiography or clay content, the nine trace elements could be grouped into six groups: Cu, Fe and Zn, Pb, Co and Cr and Ni, Mn, Sr. According to the extractable levels of four micronutrients, Bangladesh paddy soils had the medium to optimum amounts of Fe and Cu, but were deficient sporadically in Mn and extensively in Zn. It was indicated that paddy soils of Bangladesh are yet to be polluted with heavy metals.     

Predicting phosphorus sorption isotherm parameters in soil using data of routine laboratory tests

Knowledge of phosphorus(P) sorption dynamics across different soil types could direct agronomic and environmental management of P. The objective of this study was to predict P isotherm parameters for a national soil population using data of routine laboratory tests. Langmuir and Freundlich sorption parameters were calculated from two different ranges(0–25 and 0–50 mg P L~(-1)) using an archive of representative agricultural soil types from Ireland.Multiple linear regression(MLR) identified labile forms of aluminium(Al) and iron(Fe), organic matter(OM), cation exchange capacity(CEC), and clay as significant drivers. Langmuir and Freundlich sorption capacities, Freundlich affinity constant, and Langmuir buffer capacity were predicted reliably, with R~2 of independent validation 0.9. Sorption isotherm parameters were predicted from P sorbed at a single concentration of 50 mg P L~(-1)(S_(50)). An MLR prediction of P sorption maximum in the 0–50 mg P L~(-1) range was achieved, to an accurate standard, using S_(50), OM, and Mehlich-3 Fe(R~2 of independent calibration and validation being 0.91 and 0.95, respectively). Using Giles' four shapes of isotherms(C, L, H, and S), L non-strict-and C-shaped isotherm curves accounted for 64% and 27% of the soils, respectively. Hierarchical clustering identified a separation of isotherm curves influenced by two ranges of Mehlich-3 Al. Soils with a low range of Mehlich-3 Al(2.5–698 mg kg~(-1)) had no incidence of rapid sorption(C shape). Single point indices, Al, or available soil data make the regression approach a feasible way of predicting Langmuir parameters that could be included with standard agronomic soil P testing.     

Kinetic and Equilibrium Modeling for Cr(III) and Cr(VI) Removal from Aqueous Solutions by Citrus reticulata Waste Biomass

The pulp left after the extraction of juice from Citrus reticulate (kinnow), is a waste material, which was used as a potential sorbent for Cr(III) and Cr(VI) in the present study. The effect of experimental parameters such as pH, biosorbent dosage, biosorbent particle size, initial metal concentrations, temperature, shaking speed and sorption time on the Cr removal is apparent from the obtained results. The Freundlich isotherm and pseudo second order kinetic models fitted well to the data of Cr(III) and Cr(VI) biosorption by Citrus reticulata waste biomass. Effect of several pretreatments such as gases, natural coagulant and many other chemicals on Cr(III) and Cr(VI) sorption capacity of Citrus reticulata waste biomass was first time analyzed in the present study. The metal sorption capacity of Citrus reticulata waste biomass after a specific pretreatment was not only related to the nature of chemical but also strongly dependent on the oxidation state of the metal.     

Predicting Metal Uptake and Risk to the Human Food Chain from Leaf Vegetables Grown on Soils Amended by Long-Term Application of Sewage Sludge

The success of risk assessment of metal contaminated soils depends on how precisely one can predict the bio-availability of metals in soil and transfer to the human food chain. In the present investigation, we tested several formulations of the ‘free-ion activity model (FIAM)’ to predict uptake of Cd, Zn and Cu by perpetual spinach (Beta vulgaris, Cicla) grown on a range of soils amended with sewage sludge. The model was parameterised using data measured on samples of pore water extracted by centrifugation and with porous Rhizon samplers installed within the rhizosphere of the growing plants. Free ion activities (M²⁺) were estimated following speciation of solution data using version 6 of the ‘Windermere Humic Aqueous Model (WHAM-VI). For all three metals, the best formulation of the FIAM appeared to require only one hypothetical root sorption site without competition from protons. Values of (M²⁺) could also be predicted satisfactorily from a pH-dependent Freundlich relation. Thus, from a combined FIAM–Freundlich relation and population dietary information, it was possible to estimate risk (hazard quotients) to consumers from very simple soil measurements: extractable metal content (0.05 M EDTA (Zn and Cu) or 1 M CaCl₂ (Cd)), soil humus content and pH. The role of increased soil organic matter content and soil pH, in reducing risk to consumers, is illustrated for Cd in a hypothetical soil at the current UK statutory Cd limit for sludge application to agricultural land.