Pesticide adsorption on a calcareous soil modified with sewage sludge and quaternary alkyl-ammonium cationic surfactants

BACKGROUND, AIM AND SCOPE: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate. METHODS: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations. RESULTS AND DISCUSSION: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides. CONCLUSIONS: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage. RECOMMENDATIONS AND PERSPECTIVES: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.     

In situ modification of an aquifer material by a cationic surfactant to enhance retardation of organic contaminants

Sorption of hexadecyltrimethylammonium chloride (HDTMA), a cationic surfactant, on aquifer material from Columbus AFB, Mississippi, U.S.A., was examined. Transport studies using flow-through columns and a box model aquifer showed that an almost stationary zone of HDTMA-modified aquifer material could be produced in situ without a significant decrease in hydraulic conductivity.Perchloroethylene (PCE) and naphthalene sorption isotherms on the HDTMA-modified aquifer material were linear, and sorption coefficients were increased by over two orders of magnitude relative to the unmodified material. The retardation of PCE by insitu emplaced HDTMA zones within a column was examined. Agreement between batch- and column-derived sorption coefficients and breakthrough curve symmetry indicates that local equilibrium was attained. Significant retardation of a naphthalene plume by an in situ emplaced surfactant zone was demonstrated in the box model aquifer system.The experimental results indicate that it is feasible to create in situ a sorbent zone within an aquifer using cationic surfactants. In most situations, the sorbent zone concept needs to be coupled with contaminant degradation processes for sorbent emplacement to be a practical tool in the remediation of groundwater contamination sites. Sorbent zones may be of benefit in the engineering of suitable environments for microbial or abiotic degradation reactions and by providing time slow reactions to occur.     

Influence of modified soils on the removal of diesel fuel oil from water and the growth of oil degradation micro-organism

Three soils were modified with two kinds of cationic surfactants in order to increase their sorptive capabilities for organic contaminants. Sorption of diesel fuel oil in water by these modified soils had been investigated. Modified soils can effectively sorb diesel fuel oil from water. The sorption capability of modified soils is: HDTMA-black soil > HDTMA-yellow brown soil > HDTMA-red soil > TMA-black soil > TMA-yellow brown soil > TMA-red soil. Sorption of diesel fuel oil by natural soils and HDTMA modified soils is via partition, the sorption isotherms can be expressed by Henry equation, and logK(SOM) is 2.42-2.80, logK(HDTMA) is 3.37-3.60. Sorption isotherms of TMA modified soils can be expressed by Langmuir equation, the saturation sorption capacities are 1150 (TMA-black soil), 750 (TMA-yellow-brown soil), 171 mg/kg (TMA-red soil), respectively. A diesel fuel oil degradation micro-organism (Pseudomonas sp.) was isolated in the lab. To test the influence of the modified soils on the micro-organism, various growth curves of Pseudomonas in different conditions were drawn. Pseudomonas can grow very well with natural soils and TMA modified soils. The acclimation period of Pseudomonas is reduced. As to HDTMA modified soils, HDTMA loading amount is very important. When HDTMA loading amount is no higher than 0.5 CEC, the micro-organism can grow very well after a long acclimation period.     

Simultaneous sorption of lead and chlorobenzene by organobentonite

Clays or organoclays have been used as a barrier to prevent the transport of hazardous contaminants in landfills. However, clays are known to effectively sorb mostly inorganic contaminants, while organoclays are mainly used for organic contaminants. Since the organoclays are basically clay particles modified with cationic surfactants, there might exist an optimal coverage of cationic surfactant on the clay particles to sorb both inorganic and organic contaminants. In order to determine the optimal mass of cationic surfactants on the bentonites, sodium bentonites were treated with various ratios of hexadecyltrimethylammonium (HDTMA) to bentonites. Chlorobenzene and lead were selected as representative contaminants. When either chlorobenzene or lead exists as a single contaminant, chlorobenzene sorption increased with increasing HDTMA to bentonite ratios, and lead sorption decreased with increasing HDTMA to bentonite ratios. Sorption of chlorobenzene was a function of HDTMA coverage on the bentonites, while lead sorption was much more influenced by the initial lead concentration rather than the mass of HDTMA added to the bentonites.     

Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient (K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.     

Sorption of hydrophobic organic compounds onto organoclays

The behavior and fate of nonionic hydrophobic organic compounds (HOCs) in the environment are mainly controlled by their interactions with various components of soils and sediments. Due to their large surface area and abundance in many soils, smectites may greatly influence the fate and transport of the contaminants in the environment. In our experiments, HOC sorption by hexadecyltrimethylammonium (HDTMA)-modified smectite linearly increased with the amount of HDTMA added to the clay. However, tetramethylammonium (TMA)- and dodecyltrimethylammonium (DTMA)-modified smectites showed not only inferiority in their sorption of HOC compared with the HDTMA-smectite, but also a partially decreased HOC sorption at specific surfactant loading levels. This means that the sorption of organoclays for organic contaminants was significantly influenced by the amount and size of the surfactants added on the clay. In addition, it seems that the interlayer structure (e.g., pore size) formed at each surfactant loading level plays an important role to adsorb HOC in different amount.     

Organo-modified sericite in the remediation of an aquatic environment contaminated with As(III) or As(V)

The aim of this investigation was to obtain the hybrid material precursor to the naturally and abundantly available sericite, a mica-based clay; the materials were further employed in the remediation of arsenic from aqueous solutions. The study was intended to provide a cost-effective and environmentally benign treatment technology. The hybrid organo-modified sericite was obtained using hexadecyltrimethylammonium bromide (HDTMA) and alkyldimethylbenzylammonium chloride (AMBA) organic surfactants by introducing regulated doses of HDTMA or AMBA. The materials were characterized using infrared and X-ray diffraction analytical data, whereas the surface morphology was discussed by taking its SEM images. These materials were employed to assess the pre-concentration and speciation of As(III) and As(V) from aqueous solutions. The batch reactor data showed that increasing the sorptive concentration (from 1.0 to 15.0 mg/L) and pH (i.e., pH 2.0 to 10.0) caused the percent uptake of As(III) and As(V) to decrease significantly. The kinetic data showed that a sharp initial uptake of arsenic reached its equilibrium state within about 50 min of contact time, and the sorption kinetics followed a pseudo-second-order rate law both for As(III) and As(V) sorption. A 1,000 times increase in the background electrolyte concentration, i.e., NaNO₃, caused a significant decrease in As(III) removal, whereas As(V) was almost unaffected, which inferred that As(III) was adsorbed, mainly by the van der Waals or even by the electrostatic attraction, whereas As(V) was adsorbed chemically and formed “inner-sphere” complexes at the solid/solution interface. The equilibrium state modeling studies indicated that the sorption data fitted well the Freundlich and Langmuir adsorption isotherms. Henceforth, the removal capacity was calculated under these equilibrium conditions. It was noted that organo-modified sericite possessed a significantly higher removal capacity compared to its virgin sericite. Between these two organo-modified sericite, the HDTMA-modified sericite possessed a higher removal capacity compared to the AMBA-modified sericite.     

Sorption of ametryn and imazethapyr in twenty-five soils from Pakistan and Australia.

Sorption of ametryn and imazethapyr in 25 soils from Pakistan and Australia was investigated using the batch method. The soils varied widely in their intrinsic capacities to sorb these herbicides as shown by the sorption coefficients, Kd, which ranged from 0.59 to 47.6 for ametryn and 0.02 to 6.94 for imazethapyr. Generally the alkaline soils of Pakistan had much lower Kd values of both herbicides than the soils of Australia. Both soil pH and soil organic carbon (SOC) were correlated significantly with the sorption of ametryn, whereas only soil pH was strongly correlated with imazethapyr sorption. No correlation was found between Kd values of the herbicides and the clay contents of the soils. Multiple regression analysis showed that Kd values were better correlated (r2=0.94 and 0.89 for ametryn and imazethapyr, respectively) if SOC and pH were simultaneously taken into account. The study indicated that sorption of these herbicides in the alkaline soils of Pakistan was low and consequently there is considerable risk of groundwater contamination.     

Influence of synthetic surfactants on the uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca

Uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca, has been studied in the presence of an anionic (sodium dodecyl sulphate, SDS), cationic (hexadecyltrimethylammonium bromide; HDTMA) and non-ionic (Triton X-100; TX) surfactant. Compared with the surfactant-free system, metal sorption was reduced in the presence of SDS or TX. Neither surfactant, however, had any measurable impact on cell membrane permeability, determined by leakage of dissolved free amino acids (DFAA), or on metal internalisation. We attribute these observations to the stabilisation of aqueous Cd and Pb by SDS and the shielding of otherwise amenable sorption sites by TX. Presence of HDTMA resulted in a reduction in the extent of both sorption and internalisation of all metals and a significant increase in the leakage of DFAA. Thus, by enhancing membrane permeability, HDTMA exerts the greatest influence on metal behaviour in the presence of U. lactuca.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.     

Sorption of triazoles to soil and iron minerals

Triazoles, additives in runway de-icers, are found in soil and groundwater at airport sites. To better understand the fate and transport of benzotriazole (BTA) and methylbenzotriazole (MeBTA) and to assess possible remediation options of contaminated groundwater, sorption to various soils and ferrous sorbents has been studied. In batch experiments, limited non-linear sorption of BTA to mineral subsoil from the Oslo International Airport, Gardermoen was observed. The sorption to soil could be described using a Freundlich isotherm. pH affected sorption of BTA to subsoil, although the effect was not strong. Increased sorption was observed to zerovalent iron (Fe(0)). MeBTA showed similar sorption behaviour as BTA although the sorption coefficient was generally higher. Sorption to Fe(0) seems to be controlled by multi-layer coverage. Our data suggest that sorption of triazoles to Fe(2)O(3) is negligible. However BTA sorption to 2-line and 6-line ferrihydrites showed strong sorption. The results demonstrate that triazoles are highly mobile in the subsurface environment, however zerovalent iron can be an effective medium for groundwater remediation. Without remediation, wide distribution of triazoles in the environment can be expected due to its extensive application and limited degradability.     

Sorption and degradation of pharmaceuticals and personal care products (PPCPs) in soils

Pharmaceuticals and personal care products (PPCPs) are one class of the most urgent emerging contaminants, which have drawn much public and scientific concern due to widespread contamination in aquatic environment. Most studies on the environmental fate and behavior of PPCPs have focused on nonsteroidal anti-inflammatory drugs. Some other compounds with high concentrations were less mentioned. In this study, sorption and degradation of five selected PPCPs, including bisphenol A (BPA), carbamazepine (CBZ), gemfibrozil (GFB), octylphenol (OP), and triclosan (TCS) have been investigated using three different soils. Sorption isotherms of all tested PPCPs in soils were well described by Freundlich equation. TCS and OP showed moderate to strong sorption, while the sorption of GFB and CBZ in soils was negligible. Degradation of PPCPs in three soils was generally fitted first-order exponential decay model, with half-lives (t _1/2) varying from 9.8 to 39.1 days. Sterilization could prolong the t _1/2 of PPCPs in soil, indicating that microbial activity played an important role in the degradation of these chemicals in soils. Degradation of PPCPs in soils was also influenced by the soil organic carbon (f _oc) contents. Results from our data show that sorption to the soils varied among the different PPCPs, and their sorption affinity on soil followed the order of TCS > OP > BPA > GFB > CBZ. The degradation of the selected PPCPs in soil was influenced by the microbial activity and soil type. The poor sorption and relative persistence of CBZ suggest that it may pose a high leaching risk for groundwater contamination when recycled for irrigation.     

A lysimeter experiment to investigate temporal changes in the availability of pesticide residues for leaching

Leaching of three pesticides (isoproturon, chlorotoluron and triasulfuron) and a tracer (bromide) were determined in four contrasting soils ranging in texture from sandy loam to clay. The compounds were applied to undisturbed columns of soil and four columns for each soil were randomly selected and leached with 24-mm equivalent of water at prescribed time intervals (3, 9, 24, 37 and 57 d after application). A rapid decline in leached loads of isoproturon and chlorotoluron as time from application to irrigation increased was observed in all soils. In contrast, triasulfuron and bromide loads only decreased rapidly in the clay soil. Bromide losses decreased with decreasing clay contents of the soil and therefore with a decrease in structural development. Magnitudes of pesticide losses varied from soil to soil, depending on structural development and the organic carbon content. Pesticide degradation experiments on disturbed and undisturbed soil samples showed that the rapid decline of leached loads with time was faster than could be explained by degradation alone. Five physico-chemical processes are put forward to explain the different patterns of pesticide leached loads observed in the soils: (1) relative extent of preferential flow, (2) sorption capacity of the compounds to the different soils, (3) extent of degradation of the compounds in the soil, (4) variation in sorption kinetics between compounds associated with pesticide diffusion into soil aggregates, and (5) protection of the compounds by a combination of intra-aggregate diffusion and the presence of preferential flow pathways.     

Transport and transformation of sulfadiazine in soil columns packed with a silty loam and a loamy sand

Concerning the transport of the veterinary antibiotic sulfadiazine (SDZ) little is known about its possible degradation during transport. Also its sorption behaviour is not yet completely understood. We investigated the transport of SDZ in soil columns with a special emphasis on the detection of transformation products in the outflow of the soil columns and on modelling of the concentration distribution in the soil columns afterwards. We used disturbed soil columns near saturation, packed with a loamy sand and a silty loam. SDZ was applied as a 0.57 mg L(-1) solution at a constant flow rate of 0.25 cm h(-1) for 68 h. Breakthrough curves (BTC) of SDZ and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline and 4-hydroxy-SDZ were measured for both soils. For the silty loam we additionally measured a BTC for an unknown transformation product which we only detected in the outflow samples of this soil. After the leaching experiments the (14)C-concentration was quantified in different layers of the soil columns. The transformation rates were low with mean SDZ mass fractions in the outflow samples of 95% for the loamy sand compared to 97% for the silty loam. The formation of 4-(2-iminopyrimidin-1(2H)-yl)aniline appears to be light dependent and did probably not occur in the soils, but afterwards. In the soil columns most of the (14)C was found near the soil surface. The BTCs in both soils were described well by a model with one reversible (kinetic) and one irreversible sorption site. Sorption kinetics played a more prominent role than sorption capacity. The prediction of the (14)C -concentration profiles was improved by applying two empirical models other than first order to predict irreversible sorption, but also these models were not able to describe the (14)C concentration profiles correctly. Irreversible sorption of sulfadiazine still is not well understood.     

Sorption and photolysis studies in soil and sediment of the herbicide napropamide

The influence of soil and sediment composition on sorption and photodegradation of the herbicide napropamide [N,N-diethyl-2-(1-naphthyloxy)propionamide] was investigated. Five soils and one sediment were selected for this study and the clay fractions were obtained by sedimentation. Sorption-desorption was studied by batch equilibration technique and photolysis in a photoreactor emitting within 300-450 nm wavelength with a maximum at 365 nm. Sorption increased with clay content and was not related to organic matter content. High irreversibility of sorption was related to the greater montmorillonite content. The presence of soil or sediment reduced photolysis rate due to screen effect and this process did not depend on solid composition but on particle size distribution.     

Evaluation of impacts of soil fractions on phenanthrene sorption

Phenanthrene sorption to soils and soil fractions was investigated using two contrasting soils with different clay mineral and organic carbon (OC) contents in an attempt to evaluate the contribution of each soil fraction to phenanthrene sorption and the applicability of the carbon-normalized distribution constant (K(OC)) in soils. Sorbents were characterized using surface analysis, solid-state (13)C NMR analysis, and glass transition temperature (T(g)) analysis to gain a insight into the chemical nature of OC in soils. Dissolved organic carbon (DOC) in the soil solution impeded the phenanthrene sorption, while humins accounted for the predominant phenanthrene sorption in soils. The contribution of OC to phenanthrene sorption in soil would be overestimated if only a K(OC)-approach was adopted, since clay minerals could account for much of the sorption, especially when OC was low in soils. Nitrogen gas was shown to be inappropriate for probing non-polar sorption capacity. The results obtained highlight the importance of clay minerals in governing the sorption of phenanthrene in soil, and emphasize the inapplicability of the carbon-normalized distribution coefficient K(OC) in soils.     

Effect of fly ash on metsulfuron-methyl sorption and leaching in soils

This investigation was undertaken to determine the effect of amendment of two fly ashes [Kota and Inderprastha (IP)] on sorption behavior of metsulfuron-methyl in three Indian soil types. Kota fly ash (5%) did not show any effect on herbicide sorption while IP fly ash significantly enhanced the sorption. Further studies on metsulfuron-methyl sorption-desorption behavior in 0.5, 1, 2, and 5% IP fly ash-amended soils suggested that effect of fly ash varied with soil type and better effect was observed in low organic carbon content soils. The sorption-desorption isotherms fitted very well to the Freundlich sorption equation and, in general, slope (1/n) values less than unity were observed. Metsulfuron-methyl sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to the Freundlich sorption constant (K _f), K _FA values (sorption normalized to fly ash content) showed less variation. Metsulfuron-methyl leaching studies suggested greater retention of herbicide in the application zone in IP fly ash-amended soils, but effect varied with soil type and no herbicide leaching was observed in 5% fly ash-amended soils. The study suggested that all coal fly ashes are not effective in enhancing the sorption of metsulfuron-methyl in soils. However, one which enhanced herbicide sorption, could play an important role in reducing its leaching losses.     

Effects of the antimicrobial agent sulfamethazine on metolachlor persistence and sorption in soil

Recent monitoring investigations have shown that antimicrobial agents used in veterinary medicine can cause non-point source contamination of soils through manure spreading. In the present study, the effect of the antimicrobial agent sulfamethazine (sulfadimidine) on degradation and sorption of the herbicide metolachlor in a sandy loam soil was studied. In soil samples treated with sulfamethazine at two concentrations (15 and 150 microg kg(-1) soil), metolachlor persistence was not different than of that observed in untreated samples. These results were supported by the absence of effects of both sulfamethazine concentration levels on the size of the culturable soil bacteria population. Equilibrating soil samples with metolachlor solutions containing equivalent sulfamethazine concentrations did not lead to any significant effects on metolachlor sorption, suggesting that, under the conditions of the present experiment, sulfamethazine did not affect metolachlor bioavailability in soil. This laboratory investigation showed that concentrations of sulfamethazine in the microg kg(-1) range did not cause significant effects on metolachlor degradation and sorption thus not affecting the main processes ruling its environmental fate in soil.     

Role of pH in partitioning and cation exchange of aromatic amines on water-saturated soils

Predicting the reversible interactions between aromatic amines and soil is essential for assessing the mobility, bioavailability and exposure from contaminated sites. Reversible sorption mechanisms of aniline and alpha-naphthylamine were investigated by using single and binary solute sorption to five soils at several pH values, and by applying a distributed parameter (DP) model. The DP model assumes linear partitioning of the neutral species into soil organic matter domains and organic cation binding on negative-charged sites with the exchange coefficients represented by a Gaussian probability distribution. Sorption nonlinearity was attributed to cation exchange with varying site affinities, which was adequately simulated using the DP model. Greater uptake by hydrophobic partitioning and selectivity for cation exchange sites was observed for alpha-naphthylamine compared to aniline. Sorption of alpha-naphthylamine was not impacted quantitatively by aniline under those conditions examined; however, aniline sorption was reduced by alpha-naphthylamine with the largest reduction occurring in the soil with the lowest pH. DP model simulations showed that although hydrophobic partitioning increases with soil-solution pH, cation exchange still contributes significantly to the total sorption even at soil-solution pH values greater than pKa + 2.