Effect of water treatment residuals on soil phosphorus, copper and aluminium availability and toxicity

Water treatment residuals (WTRs) are produced by the treatment of potable water with coagulating agents. Beneficial recycling in agriculture is hampered by the fact that WTRs contain potentially toxic contaminants (e.g. copper and aluminium) and they bind phosphorus strongly. These issues were investigated using a plant bioassay (Lactuca sativa), chemical extractions and an isotopic dilution technique. Two WTRs were applied to an acidic and a neutral pH soil at six rates. Reductions in plant growth in amended soils were due to WTR-induced P deficiency, rather than Al or Cu toxicity. The release of potentially toxic Al from WTRs was found to be mitigated by their alkaline nature and pH buffering capacity. However, acidification of WTRs was shown to release more soluble Al than soil naturally high in Al. Copper availability was relatively low in all treatments. However, the lability of WTR-Cu increased when the WTR was applied to the soil.     

Evaluating a drinking-water waste by-product as a novel sorbent for arsenic

Arsenic (As) carcinogenicity to humans and other living organisms has promulgated extensive research on As treatment technologies with varying levels of success; generally, the most efficient methods come with a significantly higher cost burden and they usually perform better in removing As(V) than As(III) from solution. In the reported study, a novel sorbent, a waste by-product of the drinking-water treatment process, namely, drinking-water treatment residuals (WTRs) were evaluated for their ability to adsorb both As(V) and As(III). Drinking-WTRs can be obtained free-of-charge from drinking-water treatment plants, and they have been successfully used to reduce soluble phosphorus (P) concentrations in poorly P-sorbing soils. Phosphate and arsenate molecules have the same tetrahedral geometry, and they chemically behave in a similar manner. We hypothesized that the WTRs would be effective sorbents for both As(V) and As(III) species. Two WTRs (one Fe- and one Al-based) were used in batch experiments to optimize the maximum As(V) and As(III) sorption capacities, utilizing the effects of solid:solution ratios and reaction kinetics. Results showed that both WTRs exhibited high affinities for soluble As(V) and As(III), exhibiting Freundlich type adsorption with no obvious plateau after 2-d of reaction (15000 mg kg-1). The Al-WTR was highly effective in removing both As(V) and As(III), although As(III) removal was much slower. The Fe-WTR showed greater affinity for As(III) than for As(V) and reached As(III) sorption capacity levels similar to those obtained with the Al-WTR-As(V) system (15000 mg kg-1). Arsenic sorption kinetics were biphasic, similar to what has been observed with P sorption by the WTRs. Minimal (<3%) desorption of sorbed As(III) and As(V) was observed, using phosphate as the desorbing ligand. Dissolved Fe2+ concentrations measured during As(III) sorption were significantly correlated (r2=0.74, p<0.005) with the amount of As(III) sorbed by the Fe-WTR. Lack of correlation between Fe2+ in solution and sorbed As(V) (r2=0.2) suggests reductive dissolution of the Fe-WTR mediating As(III) sorption. Results show promising potential for the WTRs in irreversibly retaining As(V) and As(III) that should be further tested in field settings.     

The impact of sequestration on the bioaccessibility of arsenic in long-term contaminated soils

Arsenic (As) contamination of soil poses a potential threat to human health, particularly for small children, through the incidental ingestion of soil from hand-to-mouth activity. In this study, we examined the relationship between As bioaccessibility using the simplified bioaccessibility extraction test (SBET) and the soil fractions that contribute to bioaccessible As in 12 long-term contaminated soils. Sequential fractionation of soils prior to As bioaccessibility assessment found that As was primarily associated with the specifically sorbed (3-26%), amorphous and poorly crystalline (12-82%), and the well crystalline (3-25%) oxyhydroxide Fe/Al phases with proportions varying depending on the mode of As input. Arsenic bioaccessibility in these soils ranged from less than 1% in the gossan soil to 48% in railway corridor soils. Soil fractions contributing to As bioaccessibility were found to be from the non-specifically (<1-11%), the specifically (<1-29%) sorbed and the amorphous and poorly-crystalline (30-93%) oxyhydroxide Fe/Al fractions. Significant correlations (p<0.05) were found between the As bioaccessible fraction and the amorphous and poorly-crystalline oxyhydroxide Fe/Al fractions indicating that this fraction is a key factor influencing As bioaccessibility in many anthropogenically contaminated soils.     

Influence of amendments on soil arsenic fractionation and phytoavailability by Pteris vittata L

Increasing availability of soil arsenic is of significance for accelerating phytoremediation efficiency of As-polluted sites. The effects of seven amendments, i.e., citrate, oxalate, EDTA, sodium polyacrylate (SPA), phosphate rock (PR), single superphosphate (SSP), and compost on fractionation and phytoavailability of soil As were investigated in lab culture experiment. The results showed that the addition of PR, SPA, EDTA or compost to soils significantly increased the concentration of NaHCO₃-extractable As over a 120 d incubation period compared with the control (amendment-free) soil. Then, the four amendments were selected to add to As-contaminated soil growing Pteris vittata. It was concluded that As accumulation by the fern increased significantly under the treatments of PR and SPA by 25% and 31%, respectively. For As fractionation in soil, SPA increased Fe-As significantly by 51% and PR increased Ca-As significantly by 18%, while both the two amendments reduced occluded-As by 16% and 19%, respectively. Adding PR and SPA in soil increased the activities of urease and neutral phosphatase resulting from the improvement the fertility and physical structure of the soil, which benefits plant growth and As absorption of P. vittata. The results of the research revealed that both PR and SPA were effective amendments for improving phytoremediation of As-contaminated sites by P. vittata.     

Adsorption and transport of arsenate in carbonate-rich soils: coupled effects of nonlinear and rate-limited sorption

The transport and fate of arsenate in carbonate-rich soil under alkaline conditions was investigated with multiple approaches combining batch, sequential extraction and column experiments as well as transport modeling studies. Batch experiments indicated that sorption isotherm was nonlinear over a wide range of concentration (0.1-200 mg L(-1)) examined. As(V) adsorption to the calcareous soil was initially fast but then continued at a slower rate, indicating the potential effect of rate-limited sorption on transport. Column experiments illustrated that transport of As(V) was significantly retarded compared to a non-reactive tracer. The degree of retardation decreased with increasing As(V) concentration. As(V) breakthrough curves exhibited nonideal transport behavior due to the coupled effects of nonlinear and rate-limited sorption on arsenate transport, which is consistent with the results of modeling studies. The contribution of nonlinear sorption to the arsenate retardation was negligible at low concentration but increased with increasing As(V) concentration. Sequential extraction results showed that nonspecifically sorbed (easily exchangeable, outer sphere complexes) fraction of arsenate is dominant with respect to the inner-sphere surface bound complexes of arsenate in the carbonate soil fraction, indicating high bioavailability and transport for arsenate in the carbonate-rich soils of which Fe and Al oxyhydroxide fractions are limited.     

Comparison of metals extractability from Al/Fe-based drinking water treatment residuals

Recycling of drinking water treatment residuals (WTRs) as environment amendments has attracted substantial interest due to their productive reuse concomitant with waste minimization. In the present study, the extractability of metals within six Al/Fe-hydroxide-comprised WTRs collected throughout China was investigated using fractionation, in vitro digestion and the toxicity characteristic leaching procedure (TCLP). The results suggested that the major components and structure of the WTRs investigated were similar. The WTRs were enriched in Al, Fe, Ca, and Mg, also contained varying quantities of As, Ba, Be, Cd, Co, Cr, Cu, K, Mn, Mo, Na, Ni, Pb, Sr, V, and Zn, but Ag, Hg, Sb, and Se were not detected. Most of the metals within the WTRs were largely non-extractable using the European Community Bureau of Reference (BCR) procedure, but many metals exhibited high bioaccessibility based on in vitro digestion. However, the WTRs could be classified as non-hazardous according to the TCLP assessment method used by the US Environmental Protection Agency (USEPA). Further analysis showed the communication factor, which is calculated as the ratio of total extractable metal by BCR procedure to the total metal, for most metals in the six WTRs, was similar, whereas the factor for Ba, Mn, Sr, and Zn varied substantially. Moreover, metals in the WTRs investigated had different risk assessment code. In summary, recycling of WTRs is subject to regulation based on assessment of risk due to metals prior to practical application.     

The ageing effect on the bioaccessibility and fractionation of arsenic in soils from China

Ingestion of contaminated soil has been recognized as an important exposure pathway of arsenic for humans, especially for children through outdoor hand-to-mouth activities. An improved sequential extraction procedure was employed in an attempt to reveal the relationship between bioaccessibility and fractionation of As in five soils from China. Arsenic bioaccessibility in acidic ( approximately pH 4.5) soils reached approximately stable levels after a sharp decline within one week of ageing. In contrast, As bioaccessibility in higher pH (>6.0) soils was found to be significantly higher and took two weeks of ageing to reach stable levels. The artificially added As was more labile than indigenous As. The main proportions of added As were found in the specifically sorbed and amorphous and poorly-crystalline hydrous Fe/Al oxide-bound fractions. Correlation analysis shows that the non-specifically and specifically sorbed As are likely to constitute the main proportion of bioaccessible soil As. The soil content of amorphous and crystalline Fe/Al oxides and soil pH appear to be the key factors controlling, not only the time needed to reach a steady state, but also the magnitude of the bioaccessibility of As added to the soils.     

Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution

Arsenic (As) is highly mobilized when paddy soil is flooded, causing increased uptake of As by rice. We investigated factors controlling soil-to-solution partitioning of As under anaerobic conditions. Changes in As and iron (Fe) speciation due to flooded incubation of two paddy soils (soils A and B) were investigated by HPLC/ICP-MS and XANES. The flooded incubation resulted in a decrease in Eh, a rise in pH, and an increase in the As(III) fraction in the soil solid phase up to 80% of the total As in the soils. The solution-to-soil ratio of As(III) and As(V) (R_L/S) increased with pH due to the flooded incubation. The R_L/S for As(III) was higher than that for As(V), indicating that As(III) was more readily released from soil to solution than was As(V). Despite the small differences in As concentrations between the two soils, the amount of As dissolved by anaerobic incubation was lower in soil A. With the development of anaerobic conditions, Fe(II) remained in the soil solid phase as the secondary mineral siderite, and a smaller amount of Fe was dissolved from soil A than from soil B. The dissolution of Fe minerals rather than redox reaction of As(V) to As(III) explained the different dissolution amounts of As in the two paddy soils. Anaerobic incubation for 30 d after the incomplete suppression of microbial activity caused a drop in Eh. However, this decline in Eh did not induce the transformation of As(V) to As(III) in either the soil solid or solution phases, and the dissolution of As was limited. Microbial activity was necessary for the reductive reaction of As(V) to As(III) even when Eh reached the condition necessary for the dominance of As(III). Ratios of released As to Fe from the soils were decreased with incubation time during both anaerobic incubation and abiotic dissolution by sodium ascorbate, suggesting that a larger amount of As was associated with an easily soluble fraction of Fe (hydr) oxide in amorphous phase and/or smaller particles.     

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.     

Arsenic mobility and speciation in a contaminated urban soil are affected by different methods of green waste compost application

Application of green waste compost (GWC) to brownfield land is now common practice in soil restoration. However, previous studies have demonstrated both beneficial and detrimental effects on arsenic and metal mobility. In this paper, trace element behaviour was investigated following GWC application, either as surface mulch to, or mixed into soil from a previously described brownfield site in the U.K. Significant differences in arsenic mobility were observed between treatments. Mulching caused most disturbance, significantly increasing soil pore water As, together with Fe, P, Cr, Ni and dissolved organic carbon, the latter was a critical factor enhancing As mobilization. Arsenate was the main inorganic As species in soil pore water, increasing in concentration over time. An initial flush of potentially more toxic arsenite decreased 4 weeks after compost application. Biological processes appeared to play an important role in influencing As mobility. The results point to the necessity for careful management of As-contaminated soils.     

Distribution of Al-, Fe- and Mn-pools and their correlation in soils from two acid deposition small catchments in Hunan, China

Distribution of Al-, Fe- and Mn-pools was investigated in five forest soil profiles (consisting of four horizons) in each of two Hunan catchments (BLT and LKS) where acid deposition has been considered critical. Al- and Fe-pools were higher in BLT than those in LKS, but Mn-pools much lower in BLT. Mn-pools vary from topsoils to bottom soils, but there are different trends for different Mn speciation. Al- and Fe-pools, except amorphous Fe_ox, were positively correlated to contents of soil organic matter (OM) showed by the loss on ignition in the two catchments. Accumulation of Al- and Fe-pools may occur in the area where soil organic matter was enriched (e.g. in top soil and rhizosphere soil). However, no direct correlation is observed between Mn and OM. Acidic atmospheric deposition may affect transforming among speciations of Al-, Fe- and Mn-pools and leaching of soil Al, Fe and Mn through formation of soluble organo-metal dissolved Al which was potentially toxic, increased. There were significant correlations between Al-pools complexes or change of oxidation–reduction conditions. Mn_ex (exchangeable Mn) and Mn_ox (amorphous and organic Mn) were highly linearly correlation with soil pH values at LKS but at BLT. Under acid deposition, the availability of the nutrient Fe increased with the amount of dissolved Al, which was potentially toxic, in the two catchments. There are no significant correlations between Al_ex (exchangeable Al) and Mn_ex, Fe_ex (exchangeable Fe) and Mn_ex in this work, indicating potentially toxic Mn increase seldom accompanying with Al increase in the two catchments.     

Effects of compost and phosphate amendments on arsenic mobility in soils and arsenic uptake by the hyperaccumulator,Pteris vittata L

Chinese brake fern (Pteris vittata L.), an arsenic (As) hyperaccumulator, has shown the potential to remediate As-contaminated soils. This study investigated the effects of soil amendments on the leachability of As from soils and As uptake by Chinese brake fern. The ferns were grown for 12 weeks in a chromated-copper-arsenate (CCA) contaminated soil or in As spiked contaminated (ASC) soil. Soils were treated with phosphate rock, municipal solid waste, or biosolid compost. Phosphate amendments significantly enhanced plant As uptake from the two tested soils with frond As concentrations increasing up to 265% relative to the control. After 12 weeks, plants grown in phosphate-amended soil removed >8% of soil As. Replacement of As by P from the soil binding sites was responsible for the enhanced mobility of As and subsequent increased plant uptake. Compost additions facilitated As uptake from the CCA soil, but decreased As uptake from the ASC soil. Elevated As uptake in the compost-treated CCA soil was related to the increase of soil water-soluble As and As(V) transformation into As(III). Reduced As uptake in the ASC soil may be attributed to As adsorption to the compost. Chinese brake fern took up As mainly from the iron-bound fraction in the CCA soil and from the water-soluble/exchangeable As in the ASC soil. Without ferns for As adsorption, compost and phosphate amendments increased As leaching from the CCA soil, but had decreased leaching with ferns when compared to the control. For the ASC soil, treatments reduced As leaching regardless of fern presence. This study suggest that growing Chinese brake fern in conjunction with phosphate amendments increases the effectiveness of remediating As-contaminated soils, by increasing As uptake and decreasing As leaching.     

Distribution coefficient of selenium in Japanese agricultural soils

In order to evaluate the selenium (Se) sorption level in Japanese soils, soil/soil solution distribution coefficients (K(d)s) were obtained for 58 agricultural soil samples (seven soil classification groups) using 75Se as a tracer. Although several chemical forms of Se are present in agricultural fields, selenite was used, because it is the major inorganic Se form in acid soils such as found in Japan. The Kd values obtained covered a wide range, from 12 to 1060l/kg, and their arithmetic mean was 315l/kg. Among the soil groups, Andosols had higher Kd values. The Kd values for all samples were highly correlated with soil active-aluminum (Al) and active-iron (Fe) contents. Thus, active-Al and active-Fe were considered to be the major adsorbents of Se. Then, a new sequential extraction procedure was applied to 12 soil samples in order to quantify the effect of soil components on Se adsorption. The sequential extraction results showed that 80-100% of the adsorbed Se was recovered as Al-bound Se and Fe-bound Se. The amount of Al-bound Se was the highest in the soils that showed high Kd values, though the relative contribution of Fe-bound Se tended to increase with decreasing Kd values. The high values of Kd seemed to be caused mainly by the adsorption of Se onto active-Al in Japanese soils.     

Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15-92%, whereas with the Kota fly ash an increase in sorption by 13-38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K(f)/K(d) values, K(FA) values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

Effect of clays, metal oxides, and organic matter on rhamnolipid biosurfactant sorption by soil

Rhamnolipids produced by Pseudomonas aeruginosa have been proposed as soil washing agents for enhanced removal of metal and organic contaminants from soil. A potential limitation for the application of rhamnolipids is sorption by soil matrix components. The objective of this study is to empirically determine the contribution of representative soil constituents (clays, metal oxides, and organic matter) to sorption of the rhamnolipid form most efficient at metal complexation (monorhamnolipid). Sorption studies show that monorhamnolipid (R1) sorption is concentration dependent. At low R1 concentrations that are relevant for enhancing organic contaminant biodegradation, R1 sorption followed the order: hematite (Fe(2)O(3))>kaolinite>MnO(2) approximately illite approximately Ca-montmorillonite>gibbsite (Al(OH)(3))>humic acid-coated silica. At high R1 concentrations, relevant for use in complexation/removal of metals or organics, R1 sorption followed the order: illite>humic acid-coated silica>Ca-montmorillonite>hematite>MnO(2)>gibbsite approximately kaolinite. These results allowed prediction of R1 sorption by a series of six soils. Finally, a comparison of R1 and R2 (dirhamnolipid) shows that the R1 form sorbs more strongly alone than when in a mixture of both the R1 and R2 forms. The information presented can be used to estimate, on an individual soil basis, the extent of rhamnolipid sorption. This is important for determining: (1) whether rhamnolipid addition is a feasible remediation option and (2) the amount of rhamnolipid required to efficiently remove the contaminant.     

Characterizing As(III,V) adsorption by soils surrounding ash disposal facilities

Leachate derived from unlined coal ash disposal facilities is a potential anthropogenic source of arsenic to the environment. To establish a theoretical framework for predicting attenuation of arsenic by soils subject to ash landfill leachate, which is typically enriched in calcium and sulfate, the adsorption of As(V) and As(III) was characterized from 1 mM CaSO₄ for 18 soils obtained down-gradient from three ash landfill sites and representing a wide range in soil properties. As(V) consistently exhibited an order of magnitude greater adsorption than As(III). As(V) adsorption was best described by coupling pH with 15 s DCB-Fe (R² = 0.851,  = 0.001), although pH coupled to clay, DCB-Fe, or DCB-Al also generated strong correlations. For As(III), pH coupled to Ox–Fe (R² = 0.725,  = 0.001) or Ox–Fe/Al (R² = 0.771,  = 0.001) provided the best predictive relationships. Ca²⁺ induced increases in As(V) adsorption whereas sulfate suppressed both As(V) and As(III) adsorption. Attenuation of arsenic from ash leachate agreed well with adsorption measured from 1 mM CaSO₄ suggesting that the use of 1 mM CaSO₄ in laboratory adsorption tests is a reasonable approach for estimating arsenic behavior in soils surrounding ash landfills. We also showed that the impact of leachate-induced changes in soil pH over time may not be significant for As(V) adsorption at pH < 7; however, As(III) adsorption may be impacted over a wider pH range especially if phyllosilicate clays contribute significantly to adsorption. The benefits and limitations of predicting arsenic mobility using linearized adsorption coefficients estimated from nonlinear adsorption isotherms or from the relationships generated in this study are also discussed.     

Sorption of imazaquin in soils with positive balance of charges

The herbicide imazaquin has both an acid and a basic ionizable groups, and its sorption depends upon the pH, the electric potential (psi0), and the oxide and the organic carbon (OC) contents of the soil. Sorption and extraction experiments using 14C-imazaquin were performed in surface and subsurface samples of two acric oxisols (an anionic "rhodic" acrudox and an anionic "xanthic" acrudox) and one non-acric alfisol (a rhodic kandiudalf), treated at four different pH values. Imazaquin showed low to moderate sorption to the soils. Sorption decreased and aqueous extraction increased as pH increased. Up to pH 5.8, sorption was higher in subsurface than in surface layers of the acric soils, due to the positive balance of charges resulted from the high Fe and Al oxide and the low OC contents. It favored electrostatic interactions with anionic molecules of imazaquin. For the subsurface samples of these highly weathered soils, where psi0 was positive and OC was low, it was not possible to predict sorption just by considering imazaquin speciation and its hydrophobic partition to the organic domains of the soil. Moreover, if Koc measured for thesurface samples were assumed to represent the whole profile in predictive models for leaching potential, then it would result in underestimation of sorption potential in subsurface, and consequently result in overestimation of the leaching potential.     

Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15–92%, whereas with the Kota fly ash an increase in sorption by 13–38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K_f/K_d values, K_FA values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

In-field variation in 2,4-D mineralization in relation to sorption and soil microbial communities

This study was undertaken to assess 2,4-D mineralization in an undulating cultivated field, along a sloping transect (458 m to 442 m above sea level), as a function of soil type, soil microbial communities and the sorption of 2,4-D to soil. The 2,4-D soil sorption coefficient (Kd) ranged from 1.81 to 4.28 L kg(-1), the 2,4-D first-order mineralization rate constant (k) ranged from 0.04 to 0.13 day(-1) and the total amount of 2,4-D mineralized at 130 days (M(130)) ranged from 24 to 39%. Both k and M(130) were significantly negatively associated (or correlated) with soil organic carbon content (SOC) and Kd. Both k and M(130) were significantly associated with two fatty-acid methyl esters (FAME), i17:1 and a18, but not with twenty-two other individual FAME. Imperfectly drained soils (Gleyed Dark Grey Chernozems) in lower-slopes showed significantly lesser 2,4-D mineralization relative to well-drained soils (Orthic Dark Grey Chernozems) in mid- and upper-slopes. Well-drained soils had a greater potential for 2,4-D mineralization because of greater abundance and diversity of the microbial community in these soils. However, the reduced 2,4-D mineralization in imperfectly drained soils was predominantly because of their greater SOC and increased 2,4-D sorption, limiting the bioavailability of 2,4-D for degradation. The wide range of 2,4-D sorption and mineralization in this undulating cultivated field is comparable in magnitude and extent to the variability of 2,4-D sorption and mineralization observed at a regional scale in Manitoba. As such, in-field variations in SOC and the abundance and diversity of microbial communities are determining factors that require greater attention in assessing the risk of movement of 2,4-D by runoff, eroded soil and leaching.