The influence of copper on tebuconazole sorption onto soils, humic substances, and ferrihydrite

The aim of this study is to investigate how the presence of Cu influences tebuconazole (Teb) sorption onto contrasting soil types and two important constituents of the soil sorption complex: hydrated Fe oxide and humic substances. Tebuconazole was used in commercial form and as an analytical-grade chemical at different Teb/Cu molar ratios (1:4, 1:1, 4:1, and Teb alone). Increased Cu concentrations had a positive effect on tebuconazole sorption onto most soils and humic substances, probably as a result of Cu?Teb tertiary complexes on the soil surfaces. Tebuconazole sorption increased in the following order of different Teb/Cu ratios 1:4?>?1:1?>?4:1?>?without Cu addition, with the only exception for the Leptosol and ferrihydrite. The highest K _f value was observed for humic substances followed by ferrihydrite, the Cambisol, the Arenosol, and the Leptosol. The sorption of analytical-grade tebuconazole onto all matrices was lower, but the addition of Cu supported again tebuconazole sorption. The Teb/Cu ratio with the highest Cu addition (1:4) exhibited the highest K _f values in all matrices with the exception of ferrihydrite. The differences in tebuconazole sorption can be attributed to the additives present in the commercial product. This work proved the importance of soil characteristics and composition of the commercially available pesticides together with the presence of Cu on the behavior of tebuconazole in soils.     

Potential contributions of clay minerals and organic matter to pentachlorophenol retention in soils

Sorption of pentachlorophenol (PCP) by pure minerals and humic acids were measured to obtain additional perspective on the potential contributions of both clay minerals and soil organic matter (SOM) to contaminants retention in soils. Four types of common soil minerals and two kinds of humic acids (HAs) were tested. The sorption affinity for PCP conformed to an order of HAs > K-montmorillonite > Ca-montmorillonite > goethite > kaolinite. Such a difference in sorption capacity could be attributed to the crucial control of HAs. Clay minerals also had their contribution, especially K-montmorillonite, which played an important, if not dominant, role in the controlling process of PCP sorption. By removing 80% (on average) of the organic carbon from the soils with H(2)O(2), the sorption decreased by an average of 50%. The sorption reversibility had been greatly favored as well. Considering the uncharged mineral fractions in soil before and after H(2)O(2)-treated, the main variation in sorption behavior of the soil might thus be related to the removed organic carbon and the reduced pH. This testified rightly the interactive effect of SOM and clay minerals on PCP sorption as a function of pH.     

Time and pH-dependent sorption of the veterinary antimicrobial sulfathiazole to clay minerals and ferrihydrite

Substantial amounts of sulfonamides, ionizable, polar veterinary antimicrobials, may reach the environment by spreading of manure. Sorption to soils and sediments is a crucial but not sufficiently understood process influencing the environmental fate of sulfonamides. Therefore, we investigated sorption of sulfathiazole to clay minerals (montmorillonite, illite) and ferrihydrite for varying pH values and two contact times (1d, 14 d) under sterile conditions. Results were compared to sulfathiazole sorption to organic sorbents. Sulfathiazole sorption to inorganic sorbents exhibited pronounced pH dependence consistent with sorbate speciation and sorbent charge properties. While sulfathiazole cations were most important for sorption to clay minerals, followed by neutral species, ferrihydrite was a specific anion sorbent, showing significant sorption only between pH 5.5-7. Experiments revealed a substantial increase of sorption with time for ferrihydrite (pH 5.5-7) and illite (pH<5.5). Reasons may be disaggregation of clay minerals and, for ferrihydrite, diffusion and sorption of sulfathiazole in micropores. Independent of contact time and pH, sorption to inorganic sorbents was more than an order of magnitude lower than to organic sorbents. This implies that in many topsoils and sediments inorganic sorbents play a minor role. Our results highlight the need to account for contact time and speciation when predicting sulfonamide sorption in the environment.     

Interaction of phenanthrene and its primary metabolite (1-hydroxy-2-naphthoic acid) with estuarine sediments and humic fractions

Experiments were conducted to compare the sorption and desorption of phenanthrene and its primary degradation product, 1-hydroxy-2-naphthoic acid (HNA), in estuarine sediment, humic acid (HA) and humin. Ionic composition, ionic strength (0.4 M) and pH (7.6) were employed to mimic native estuarine pore water at the sediment-water interface. Sorption to whole sediment and organic matter (OM) fractions was significantly lower for HNA than for phenanthrene. Whereas HNA did not sorb to HA, uptake to sediment and humin was observed, suggesting that HNA does not bind directly to OM. Phenanthrene uptake was characterized by hysteretic behavior and exhibited slow desorption. In contrast, HNA initially was more readily desorbed from sediment and humic fractions, but a significant fraction was not recovered in repeated desorption runs. The lower sorption of HNA reflects its greater polarity and water solubility, but the consistent retention of a non-desorbing fraction suggests strong binding and/or chemical transformation reactions may be important. It was postulated that abiotic transformation of HNA may occur in estuarine sediments, in part due to the presence of redox active minerals (Fe(III) and Mn(IV) oxides). The presence of Fe and Mn solids in the estuarine sediment was verified by sequential extraction and studies were then conducted to investigate the transformation of HNA in the presence of synthetic goethite (alpha-FeOOH) and birnessite (delta-MnO2) as model solids. Reaction with birnessite led to transformation of all HNA in solution within 24 h and resulted in the formation of partial oxidation products (POPs). Following reaction with goethite, HNA was present in solution and POPs were observed in the weakly bound fraction. This study indicates that degradation products of polycyclic aromatic hydrocarbons (PAHs) may have distinctly different sorption affinities and reactivities toward environmental surfaces than their parent compounds.     

Bioavailability and mass balance studies of a commercial pentabromodiphenyl ether mixture in male Sprague-Dawley rats

Cyanogenic glycosides are common plant toxins. Toxic hydrogen cyanide originating from cyanogenic glycosides may affect soil processes and water quality. In this study, hydrolysis, degradation and sorption of dhurrin (4-hydroxymandelonitrile-beta-d-glucoside) produced by sorghum has been studied in order to assess its fate in soil. The log K(ow) of dhurrin was -1.18+/-0.08 (22 degrees C). Hydrolysis was a first-order reaction with respect to dhurrin and hydroxyl ion concentrations. Half lives ranged from 1.2h (pH 8.6; 25 degrees C) to 530d (pH 4; 25 degrees C). The activation energy of hydrolysis was 112+9kJ. At pH 5.8 and room temperature, addition of humic acids (50gl(-1)) increased the rate of hydrolysis tenfold, while addition of kaolinite or goethite (100-250gl(-1)) both decreased the rate considerably. No significant sorption to soil components could be observed. The degradation rates of dhurrin in top and subsoils of Oxisols, Ultisols, Alfisols and Mollisols were studied at 22 degrees C (25mgl(-1), soil:liquid 1:1 (w:V), pH 3.8-8.1). Half-lives were 0.25-2h for topsoils, and 5-288h in subsoils. Hydrolysis in solution explained up to 45% of the degradation in subsoils whereas the contribution in topsoils was less than 14%, indicating the importance of enzymatic degradation processes. The highest risk of dhurrin leaching will take place when the soil is a low activity acid shallow soil with low content of clay minerals, iron oxides and humic acids.     

Sorption of 1-hydroxy-2-naphthoic acid to goethite, lepidocrocite and ferrihydrite: batch experiments and infrared study

The adsorption of naphthoic acids to iron oxides and hydroxides influences strongly their mobility in soils and sediments. Sorption of 1-hydroxy-2-naphthoic acid (HNA) to three iron oxides was examined over a wide range of conditions (pH, ionic strength, sorbate and sorbent concentrations). In the examination of HNA sorption, Tempkin model was performed to fit sorption data of HNA onto all iron oxides. The adsorption in the Henry law range increases in the order: goethite相似文献   

Investigating roles of organic and inorganic soil components in sorption of polar and nonpolar aromatic compounds

The main objective of the present study was to assess the roles of various soil components in sorption of organic compounds differing in polarity. Removal of the whole soil organic matter decreased sorption by approximately 86% for nonpolar 1,3,5-trichlorobenzene (TCB), but only 34-54% for highly polar 1,3,5-trinitrobenzene (TNB); however, removal of the extractable humic/fulvic acids did not much affect sorption of the two sorbates. With normalization of solute hydrophobicity, TNB exhibits several orders of magnitude stronger sorption compared with TCB to maize burn residue (black carbon), extracted humic acid and Na⁺-saturated montmorillonite clay, suggesting specific sorptive interactions for TNB with the individual model soil components. It was proposed that sorption of TCB to the bulk soil was dominated by hydrophobic partition to the condensed, non-extractable fraction of organic matters (humin/kerogen and black carbon), while interactions with soil clay minerals were an important additional factor for sorption of TNB.     

Sorption of thallium(I) onto geological materials: influence of pH and humic matter

The sorption behaviour of the severely toxic heavy metal thallium (Tl) as a monovalent cation onto three representative materials (goethite, pyrolusite and a natural sediment sampled from a field site) was examined as a function of pH in the absence and presence of two natural humic acids (HAs), using ²⁰⁴Tl(I) as a radiotracer. In order to obtain a basic understanding of trends in the pH dependence of Tl(I) sorption with and without HA, sorption of HAs and humate complexation of Tl(I) as a function of pH were investigated as well. In spite of the low complexation between Tl(I) and HAs, the presence of HAs results in obvious alterations of Tl(I) sorption onto pyrolusite and sediment. An influence on Tl(I) sorption onto goethite was not observed. Predictions of K_d (distribution coefficient) for Tl(I) on goethite in the presence of HAs, based on a linear additive model, agree well with the experimental data, while a notable disagreement occurs for the pyrolusite and sediment systems. Accordingly, it is suggested that HAs and goethite may act as a non-interacting sorbent mixture under the given conditions, but more complex interactions may take place between the HAs and the mineral phases of pyrolusite or sediment.     

Sorption of naphthalene and phenanthrene by soil humic acids

Humic acids are a major fraction of soil organic matter (SOM), and sorption of hydrophobic organic chemicals by humic acids influences their behavior and fate in soil. A clear understanding of the sorption of organic chemicals by humic acids will help to determine their sorptive mechanisms in SOM and soil. In this paper, we determined the sorption of two hydrophobic organic compounds, naphthalene and phenanthrene by six pedogenetically related humic acids. These humic acids were extracted from different depths of a single soil profile and characterized by solid-state CP/MAS 13C nuclear magnetic resonance (NMR). Aromaticity of the humic acids increased with soil depth. Similarly, atomic ratios of C/H and C/O also increased with depth (from organic to mineral horizons). All isotherms were nonlinear. Freundlich exponents (N) ranged from 0.87 to 0.95 for naphthalene and from 0.86 to 0.92 for phenanthrene. The N values of phenanthrene were consistently lower than naphthalene for a given humic acid. For both compounds, N values decreased with increasing aromaticity of the humic acids, such an inverse relationship was never reported before. These results support the dual-mode sorption model where partitioning occurs in both expanded (flexible) and condensed (rigid) domains while nonlinear sorption only in condensed domains of SOM. Sorption in the condensed domains may be a cause for slow desorption, and reduced availability and toxicity with aging.     

Effect of physical forms of soil organic matter on phenanthrene sorption

The sorption coefficient, K(OC), of phenanthrene (PHE) has been reported to vary with different types of organic matter, leading to uncertainties in predicting the environmental behavior of PHE. Among the studies that relate organic matter properties to their sorption characteristics, physical conformation of organic matter is often neglected. In this work, organic matter samples of different physical forms were examined for their sorption characteristics. Dissolved humic acids (DHA) showed significantly higher K(OC) than the corresponding solid humic acids (SHA) from which the DHAs were made. The K(OC) of DHAs was found to be related to polarity, whereas K(OC) of SHAs increased with aliphatic carbon content. Soil particles were treated with H(2)O(2) to remove organic matter, and humic acid was coated on H(2)O(2)-treated soil particles to make organo-mineral complexes at pH 4, 7 and 10. Although the nonlinear sorption was apparent for SHAs and H(2)O(2)-treated soil particles, the organo-mineral complexes formed using these two components at pH 4, 7 and 10 exhibited relatively linear sorption at organic carbon content, f(OC)>0.5%. These results indicate that organic matter of the same composition may have different sorption properties due to different physical forms (or conformations). Nonlinear sorption for the complexes formed at pH 4 with lower f(OC) (<0.5%) was also discussed.     

Sorption of humic substances on aquifer material at artificial recharge of groundwater

Experiments in batch equilibrium system were carried out to evaluate the importance of physical and chemical factors determining the sorption efficiency of humic substances (HS) on aquifer material, which has been used for artificial recharge of groundwater (ARG) in drinking water production. Results showed that an increase of the amount of clay in the aquifer material and a decrease of pH in water increased the sorption efficiency. The sorption of higher molecular weight, more hydrophobic and aromatic HS (Aldrich and forest soil humic acids) were greater than the sorption of acidic HS (river fulvic acids), either on the aquifer material or to its representative sorbing phases, clay and organic matter. The sorption on the aquifer material was largely due to physical sorption (hydrophobic attractions). This study showed the importance of HS composition on their removal during ARG and contributed to an understanding of the HS sorption mechanisms in this process.     

Effects of organic acids on adsorption of lead onto montmorillonite,goethite and humic acid

Adsorption isotherms for Pb onto six soil components (quartz, feldspar, kaolinite, montmorillonite, goethite and humic acid) were studied. The influence of pH, EDTA and citric acid on the adsorption of Pb onto montmorillonite, goethite and humic acid were considered. Results indicate that the experimental data fit the Langmuir Adsorption Isotherm. The adsorption capacity for Pb at pH 6 was found to be in the order: humic acid (22.7 mg g(-1)) > goethite (11.04 mg g(-1)) > montmorillonite (10.4 mg g(-1)) > kaolinite (0.91 mg g(-1)) > feldspar (0.503 mg g(-1)) > quartz (0.148 mg g(-1)). Generally, the amount of Pb adsorbed onto montmorillonite, goethite and humic acid decreased with increasing concentrations of EDTA and citric acid and with increases in alkality. However, there were two exceptions: (1) addition of citric acid increased the amount of Pb adsorbed onto humic acid; and (2) the amount of Pb adsorbed onto goethite decreased with increasing pH in the presence of EDTA. Some mechanisms involved in the adsorption reactions are discussed.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption-desorption processes. Four soils from Melozal (35° 43' S; 71° 41' W), Parral (36° 08' S; 71° 52' W), San Carlos (36° 24' S; 71° 57' W), and Panimavida (35° 44' S; 71° 24' W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g?1) and were related to soil pH. Molinate showed K(d) values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g?1 and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K(d) values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g?1. MCPA K(d) ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Desorption of cadmium from goethite: effects of pH, temperature and aging

Cadmium is perhaps environmentally the most significant heavy metal in soils. Bioavailability, remobilization and fate of Cd entering in soils are usually controlled by adsorption-desorption reactions on Fe oxides. Adsorption of Cd on soil colloids including Fe oxides has been extensively studied but Cd desorption from such soil minerals has received relatively little attention. Some factors that affect Cd adsorption on goethite include pH, temperature, aging, type of index cations, Cd concentrations, solution ionic strength and presence of organic and inorganic ions. This research was conducted to study the influence of pH, temperature and aging on Cd desorption from goethite. Batch experiments were conducted to evaluate Cd desorption from goethite with 0.01 M Ca(NO3)2. In these experiments Cd desorption was observed at 20, 40 and 70 degrees C in combination with aging for 16 h, 30, 90 and 180 d from goethite that adsorbed Cd from solutions containing initial Cd concentrations of 20, 80 and 180 microM. Following the adsorption step Cd desorption was measured by 15 successive desorptions after aging at various temperatures. At the lowest amount of initially adsorbed Cd and equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 17% with aging from 16 h to 180 d and the corresponding decrease at equilibrium pH 6.0 was from 32% to 3%. There was a substantial decrease in Cd desorption with increasing equilibration temperature. For example, in goethite with the lowest amount of initial adsorption at equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 31% with increase in temperature from 20 to 70 degrees C, even after 16 h. Dissolution of Cd adsorbed goethite in 1M HCl, after 15 successive desorptions with 0.01 M Ca(NO3)2, indicated that approximately 60% of the Cd was surface adsorbed. Overall, dissolution kinetics data revealed that 23% to 88% Cd could not be desorbed, which could possibly be diffused into the cracks and got entrapped in goethite crystals. At elevated temperature increased equilibrium solution pH favoured the formation of CaCO3 and CdCO3 which reasonably decreased Cd desorption. Cadmium speciation showed the formation of calcite and otavite minerals at 40 and 70 degrees C due to increase in pH (>9.5) during aging. X-ray diffraction analysis (XRD) of these samples also revealed the formation of CaCO3 at elevated temperatures with aging. While mechanisms such as Cd diffusion and/or entrapment into fissures and cracks in goethite structure with increase in temperature and aging are possible.     

Mechanochemical removal of organo-chlorinated compounds by inorganic components of soil

The purpose of this work is to evaluate the catalytic efficiency of two metal oxides, ferrihydrite and birnessite and of a ferruginous smectite, towards organic molecules such as 4-chloroaniline (4-CA), pentachlorophenol (PCP), and five polychlorinated biphenyls (PCBs) characterised by different number and position of chlorine atoms. Mechanochemical dry contacts with light grinding between catalytic surfaces and pollutants have been carried out.

The efficiency of the mechanochemical removal was compared with batch experiments for the soluble compounds (PCP and 4-CA). The removal of 4-CA and PCP by the mechanochemical procedure resulted more effective than by batch contact in the presence of birnessite and ferrihydrite, particularly at higher pH (100% removal of 4-CA by birnessite in 30 min at pH 8.6 after the mechanochemical contact compared to 20% removal using the batch interaction at the same pH).

The mechanochemical contact of PCBs and birnessite produced a removal of pollutant that was a function of the number of chlorine atoms (complete removal of 2,2^′-dichlorobiphenyl in 10 days and a removal of 30% and 20% of 2^′,3,4-trichlorobiphenyl and 3,3^′,4,4^′-tetrachlorobiphenyl, respectively in 90 days) and of the position of chlorine atoms about the biphenyl rings (100% of 2,2^′-dichlorobiphenyl in 10 days, 84% of 3,3^′-dichlorobiphenyl in 15 days and 40% of 4,4^′-dichlorobiphenyl in 27 days).     

Desorption of arsenic from clay and humic acid-coated clay by dissolved phosphate and silicate

Arsenic (As) contaminated aquifers contain iron minerals and clays that strongly bind As at their surfaces. It was suggested that As mobilization is driven by natural organic matter (including fulvic acids (FA) and humic acids (HA)) present in the aquifers either via providing reducing equivalents for reductive dissolution of Fe(III) (hydr)oxides or via competitive desorption of As from the mineral surfaces. In the present study we quantified sorption of As(III) and As(V) to Ca(2+)-homoionized illite (IL) and to kaolinite (Kao) as well as to HA-coated clays, i.e., illite-HA (IL-HA) and kaolinite-HA (Kao-HA) at neutral pH. Clay-HA complexes sorbed 28-50% more As than clay-only systems upon addition of 100μM As(III)/As(V) to 0.5g of clay or HA-clay with Ca(2+) probably playing an important role for HA binding to the clay surface and As binding to the HA. When comparing sorption of As(V) and As(III) to clay and HA-clay complexes, As(V) sorption was generally higher by 15-32% than sorption of As(III) to the same complexes. IL and IL-HA sorbed 11-28% and 6-11% more As compared to Kao and Kao-HA, respectively. In a second step, we then followed desorption of As from Kao, Kao-HA, IL and IL-HA by 100 and 500μM phosphate or silicate both at high (0.41-0.77μmol As/g clay), and low (0.04 to 0.05μmol As/g clay) As loadings. Phosphate desorbed As to a larger extent than silicate regardless of the amount of As loaded to clay minerals, both in the presence and absence of HA, and both for illite and kaolinite. At high loadings of As, the desorption of both redox species of As from clay-HA complexes by phosphate/silicate ranged from 32 to 72% compared to 2-54% in clay only systems meaning that As was desorbed to a larger extent from HA-coated clays compared to clay only systems. When comparing As(III) desorption by phosphate/silicate to As(V) desorption in high As-loading systems, there was no clear trend for which As species is desorbed to a higher extent in the four clay systems meaning that both As species behave similarly regarding desorption from clay surfaces by phosphate/silicate. Similarly, no significant differences were found in high As-loading systems in the amount of As desorbed by phosphate/silicate when comparing Kao vs. IL and Kao-HA vs IL-HA systems meaning that both clay types behave similarly regarding desorption of As by phosphate/silicate. At low As loadings, up to 80% of As was desorbed by phosphate and silicate with no noticeable differences being observed between different As species, different types of clay, clay vs clay-HA or the type of desorbant (phosphate and silicate). The results of this study showed that HA sorption to Ca(2+)-homoionized clay minerals can increase As binding to the clay although the As sorbed to the clay-HA is also released to a greater extent by competing ions such as phosphate and silicate. Desorption of As depended on the initial loadings of As onto the clay/clay-HA. Based on our results, the effect of humic substances on sorption of As and on desorption of As by phosphate and silicate has to be considered in order to fully understand and evaluate the environmental behavior of As in natural environments.     

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.     

Partitioning of selected environmental pollutants into organic matter as determined by solid-phase microextraction

Partitioning/sorption of selected environmental pollutants (PCBs, organochlorine insecticides, triazine and amide herbicides) into dissolved humic acids (HA), soil and mineral substances was evaluated by measuring their free concentrations by solid-phase microextraction (SPME). Compounds were chosen to cover a wide range of logK(ow) (2.2-7.6). Two different types of partitioning behaviour for dissolved HA were observed. Compounds with logK(ow)>5 partitioned almost instantly into HA fraction and the remaining free fraction remained rather constant. LogK(HA) and logK(DOC) were calculated and found to be similar for commercial HA, HA standard and isolated HA. The behaviour of these compounds in soil suspension was similar, but strong sorption on CaCO3 and Florisil was also noticed. For compounds with logK(ow)<5, we have not noticed significant changes in free concentrations in HA solutions over time. In soil suspension, however, some sorption/partitioning was observed over time for some compounds, but it was matching the sorption on CaCO3 and Florisil.     

Fractionation of heavy metals and distribution of organic carbon in two contaminated soils amended with humic acids

The effects of humic acids (HAs) extracted from two different organic materials on the distribution of heavy metals and on organic-C mineralisation in two contaminated soils were studied in incubation experiments. Humic acids isolated from a mature compost (HAC) and a commercial Spaghnum peat (HAP) were added to an acid soil (pH 3.4; 966 mg kg(-1) Zn and 9,229 mg kg(-1) Pb as main contaminants) and to a calcareous soil (pH 7.7; 2,602 mg kg(-1) Zn and 1,572 mg kg(-1) Pb as main contaminants) at a rate of 1.1g organic-C added per 100g soil. The mineralisation of organic-C was determined by the CO(2) released during the experiment. After 2, 8 and 28 weeks of incubation the heavy metals of the soils were fractionated by a sequential extraction procedure. After 28 weeks of incubation, the mineralisation of the organic-C added was rather low in the soils studied (<8% of TOC in the acid soil; <10% of TOC in the calcareous soil). Both humic acids caused significant Zn and Pb immobilisation (increased proportion of the residual fraction, extractable only with aqua regia) in the acid soil, while Cu and Fe were slightly mobilised (increased concentrations extractable with 0.1M CaCl(2) and/or 0.5M NaOH). In the calcareous soil there were lesser effects, and at the end of the experiment only the fraction mainly related to carbonates (EDTA-extractable) was significantly increased for Zn and decreased for Fe in the humic acids treated samples. However, HA-metal interactions provoked the flocculation of these substances, as suggested by the association of the humic acids with the sand fraction of the soil. These results indicate that humic acid-rich materials can be useful amendments for soil remediation involving stabilisation, although a concomitant slight mobilisation of Zn, Pb and Cu can be provoked in acid soils.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption–desorption processes. Four soils from Melozal (35° 43′ S; 71° 41′ W), Parral (36° 08′ S; 71° 52′ W), San Carlos (36° 24′ S; 71° 57′ W), and Panimavida (35° 44′ S; 71° 24′ W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g^?1) and were related to soil pH. Molinate showed K_d values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g^?1and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K_d values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g^?1. MCPA K_d ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g^?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.