Surfactant solubilization of hydrophobic compounds in soil and water

Reductions in the apparent soil-water partition coefficients (K_d ^*) for 28 polychlorinated biphenyls (PCBs) caused by the surfactant sodium dodecylsulphate (SDS) in the aqueous phase were studied. Above the critical micelle concentration (CMC) of the surfactant, K_d ^* was reduced by 2–3 orders of magnitude, but even far below CMC at environmentally relevant surfactant concentrations significant reductions in K_d ^* were observed. The plot of the soil-water partition coefficient (K_d) divided by K_d ^* versus the concentration of SDS allowed for the calculation of monomer (K_mn ^oc) and micellar (K_mc ^oc) surfactant-water partition coefficients normalized to organic carbon for each PCB congener. K_mn ^oc values were comparable with published values for the partition of PCBs between natural dissolved organic matter and lake water. K_mc ^oc values were up to 30 times higher than K_mn ^oc values and comparable with published octanol-water distribution coefficients. The findings of the present study underline the potential of surfactants at concentrations below their CMC to mobilize otherwise strongly bound hydrophobic compounds in soil-water systems.     

Reaction rates and intermediates of chlorinated organic compounds in water and soil

Degradation reactions of thirteen chlorinated organic compounds were investigated in a water system and a water-soil system. Three compounds were degraded following the first order rate equation regardless of pH, and five compounds were degraded following the second order rate equation with a concentration of hydroxide ion in alkaline solution.The reaction rate constants and the activation energies of the reactions were obtained, and the intermediates were determined quantitatively for the eight compounds.From the result of the degradation of 1,1,1-trichloroethane in the water-soil system, it was found that 1,1,1 trichloroethane did not react on the soil surface and only reacted in the water phase.     

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) XYZ0 + mV(I)/100 + spi + bbetam + aalpham, was applied to analyze capacity factors (k'), soil organic partition coefficients (Koc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control logKoc, log P, and logk' (on soil and on C18) are the solute size (V(I)/100) and hydrogen-bond basicity (betam). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpham). Log k' on soil and log Koc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C18 and logP have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, logk' values on C18 have good correlations with logP (r > 0.97), while logk' values on soil have good correlations with logKoc (r > 0.98). Two Koc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC.     

挥发性有机物生物增溶性能及效果

选择二甲苯作为VOCs代表成分,在开放式自然培养条件下,研究VOCs增溶性能及增溶效果。结果表明,增溶菌具有明显的生长规律、增溶规律及发酵pH变化规律。培养32 h时,增溶菌数量及增溶活性最大,但发酵pH呈下降趋势。发酵液对二甲苯具有良好的增溶效果,其增溶能力是空白培养基的6倍。二甲苯与BST所形成的乳滴为水包油,易溶于水,有利于VOCs的生物降解。研究证明,对二甲苯的增溶是BST产生菌的贡献。     

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.     

老化石油污染土壤的清洗处理

以华北油田老化长达1年以上的石油污染土壤为研究对象,采用自行选配的清洗剂对该污染土壤进行了一次清洗和二次清洗处理.实验结果表明,一次清洗后,污染土壤样品的含油率从26.34%～29.90%降到6.34%～7.84%,洗油率达80.06%～81.06%;经二次清洗处理后,污染土壤样品的含油率从26.34%～29.90%降到4.05%～4.85%,洗油率达88.06%～88.19%.在一次清洗和二次清洗的基础上,通过模拟实验确定了洗油污水回用的最佳回用率为80%,最佳加药质量浓度为0.4 g/L,该条件下污水的最终产生量也较少.按照该参数对华北油田的石油污染土壤进行了清洗实验,洗油率达79.20%～80.51%.     

表面活性剂清洗处理重度石油污染土壤

为了优化表面活性剂清洗处理重度石油污染土壤的方法和具体洗脱条件参数,采集山东省东营市胜利油田污染土壤,研究了阴离子-非离子混合表面活性剂对该土壤中石油类污染物的去除效果。应用化学热洗原理,主要考查了表面活性剂配比、投加量、清洗温度及清洗助剂对去除效果的影响。实验得到的清洗处理最佳条件为：使用LAS与TX-100质量比为8∶2的组合表面活性剂,总表面活性剂浓度为3 g/L,助剂硅酸钠浓度为5 g/L,75℃条件下搅拌1 h。清洗后土壤含油量从20%下降到4.6%,去除率达到76.9%。废水回用实验表明,清洗处理的废水对土壤中石油烃类物质仍有一定的去除效果。废水回用比从30%到100%时,对土壤中石油烃的去除率都可达到55%以上。对废水进行二次回用时仍能去除18.8%的污染物。     

Critical evaluation of the measurement of the 1- octanol / water partition coefficient of hydrophobic compounds

Data on the experimental measurement of the octanol/water partition coefficient (K_ow) with hydrophobic compounds was assembled from the literature. The precision, characterised by the standard deviation of mean K_ow values based on five commonly used experimental methods, over an extended K_ow range was found to generally decline with compounds having log K_ow > 5.5. In the log K_ow range from 2.0 to 5.5 there was little difference between the mean values of log K_ow determined by the different methods but major differences occured with compounds having log K_ow > 5.5. The agreement between calculated ClogP values and K_ow values derived from individual experimental methods indicated that ClogP overestimates log K_ow from all experimental methods with compounds having values greater than 5.5.     

Sorption of hydrophobic organic pollutants in saturated soil systems

Sorption equilibria and rates were characterized for a matrix of four aquifer sands and two slightly to moderately hydrophobic organic solutes (nitrobenzene and lindane), and the effects of sorption on the behavior of these solutes in saturated systems of the soils were determined. Experimental data were used to test and evaluate a variety of mathematical models for predicting contaminant fate and transport in groundwater systems.Observed equilibrium relationships between soil and solution phase solute concentrations were found to be described best by the nonlinear Freundlich isotherm model. It was further determined that the sorption process in the systems tested is rate controlled, requiring several days to approach equilibrium in completely mixed batch reactors. Subsequent modeling of solute transport in continuous flow soil column reactors was found to be most successful when rate-controlled models were used, the best results were obtained with a dual-resistance model incorporating the coupled mass transport steps of boundary-layer and intraparticle diffusion.     

Occurrence and behaviour of selected hydrophobic alkylphenolic compounds in the Danube River

Six hydrophobic alkylphenolic compounds were investigated for the first time simultaneously in four different matrices in the Danube River. Maximum sediment concentrations were 2.83, 2.10, 0.28, and 0.035 mg kg⁻¹ for nonylphenol, nonylphenol monoethoxylate, nonylphenol diethoxylate and octylphenol. Maximum levels in suspended particulate matter (SPM) were 0.18, 0.12, 0.10, and 0.003 mg kg⁻¹. No correlation between concentrations in SPM and sediments was found. Octylphenol monoethoxylate and octylphenol diethoxylate were recorded only in sediment at one location. In mussels and water only nonylphenol and octylphenol were found. Nonylphenol concentrations in mussels (up to 0.34 mg kg⁻¹) correlate with concentrations found in SPM and indicate a slight bioaccumulation. Concentrations in water were close to the limit of quantification. We assume in situ formation of nonylphenol monoethoxylate and nonylphenol in sediments at some locations. In some cases nonylphenol in sediments exceeded the provisional EU environmental quality standards.     

Regression method of the hydrophobicity ruler approach for determining octanol/water partition coefficients of very hydrophobic compounds

A regression method was developed for the hydrophobicity ruler approach, which is an indirect method for determining the octanol/water partition coefficients of very hydrophobic compounds. Two constants introduced into the mathematical model were obtained by regression of the absorption data sampled before the partition equilibrium. A water miscible organic solvent was used to increase the solubility of the very hydrophobic compounds in the aqueous solution so that the hydrophobicity scale was reduced and the equilibration was accelerated. Polydimethylsiloxane/methanol aqueous solution and a series of 21 polychlorinated biphenyls (PCBs) were used to demonstrate the regression method. The PCB compounds with known experimental logK(o/w) values served as reference compounds, while the PCB compounds without known logK(o/w) values were determined. The distribution coefficients (logK(p/s)), uptake and elimination rate constants were obtained from the two regression constants for each compound (reference or unknown). The correlation of the logK(p/s) values of the reference PCB compounds with their logK(o/w) values was linear (logK(o/w)=2.69logK(p/s)+0.76, R(2)=0.97). The logK(o/w) values were compared with literature values and suggested that some values from the literature far off the calibration line could be inaccurate. The critical experimental factors, the merits of the regression method were discussed.     

Perfluorinated compounds in water, sediment, soil and biota from estuarine and coastal areas of Korea

Soil, sediment, water, and biota collected from the western coast of Korea were analyzed to determine occurrence and sources of perfluorinated compounds (PFCs). PFCs were significantly concentrations of PFCs were measured in some water and biological samples, while concentrations of PFCs in soils and sediments were relatively low. The most widely detected compound was found to be perfluorooctanesulfonate (PFOS), with a maximum concentration in water of 450 ng/L and in fish of 612 ng/g, dw. PFOS concentrations in water and biota were both less than those thought to cause toxicity. However, in both cases concentrations were within a factor of 10 of the toxicity threshold concentration. Concentrations of PFCs were significantly greater downstream than those upstream on the same river, suggesting point sources. Overall, the detection of PFCs at relatively great concentrations in various environmental matrixes from this region of Korea suggests that further studies characterizing PFCs and their potential risk to both humans and wildlife are needed.     

Bound residues of organic compounds in the soil: the significance of pesticide persistence in soil and water: a European regulatory view

The paper discusses key aspects of the European Union (EU) regulatory policy for persistence of agricultural pesticide active substances (a.s.) in soil, which is examined in the context of the EU Authorisations Directive (91/414/EEC). For agricultural pesticide regulation within EU Member States (MS), the Authorisations Directive will gradually replace existing national systems. Discussion is concentrated on this directive, looking in particular at the Uniform Principles therein and the possible ways that these decision-making guidelines could be developed into a regulatory framework. The aim in this process of negotiated development is to identify any questions or data requirements that will be needed for persistent pesticides, over and above those generally required for all compounds. The present European regulatory position on soil non-extractable or bound residues is discussed. Finally, a brief mention of pesticide persistence in water and sediment is made.     

Degradation and toxicity of phenyltin compounds in soil

Although the fate of organotins has been widely studied in the marine environment, fewer studies have considered their impact in terrestrial systems. The degradation and toxicity of triphenyltin in autoclaved, autoclaved-reinoculated and non-sterilised soil was studied in a 231 day incubation experiment following a single application. Degradation and toxicity of phenyltin compounds in soil was monitored using both chemical and microbial (lux-based bacterial biosensors) methods. Degradation was significantly slower in the sterile soil when compared to non-sterilised soils. In the non-sterilised treatment, the half-life of triphenyltin was 27 and 33 days at amendments of 10 and 20 mg Sn kg(-1), respectively. As initial triphenyltin degradation occurred, there was a commensurate increase in toxicity, reflecting the fact that metabolites produced may be both more bioavailable and toxic to the target receptor. Over time, the toxicity reduced as degradation proceeded. The toxicity impact on non-target receptors for these compounds may be significant.     

Influence of membrane permeation on biodegradation kinetics of hydrophobic compounds

The relationship between membrane permeation rate and biodegradation rate has been investigated for alkyl esters of p-aminobenzoic acid. The pseudo-first order biodegradation rate constants of these compounds increase with increasing alkyl chain length, and increasing hydrophobicity, until alkyl chain lengths of greater than five carbon atoms, for which the biodegradation rate constants remain constant. This relationship between biodegradation rate constant and hydrophobicity parallels that of the permeabilities of lipid membranes and aqueous diffusion layers towards these compounds. This indicates that the rate-determining step in the biodegradation of these esters is their diffusion into bacterial cells, and that they then undergo rapid transformation.     

Surfactant production accompanying the modified Fenton oxidation of hydrocarbons in soil

A hydrocarbon-contaminated soil was treated in laboratory slurry reactors using two types of modified Fenton (MF) chemistry. Liquid hydrogen peroxide (HP) with Fe(3+) was compared with a calcium peroxide (CaO(2))-based oxidant (Cool-Oxtrade mark). Bioslurry treatment served as a control. During oxidation, samples of slurry filtrate were tested to quantify hydrocarbon concentrations and bulk surfactant concentrations, using the critical micelle dilution method. The results showed that both oxidants resulted in the temporary accumulation of surfactants to maximum levels of four times the critical micelle concentration, but that surfactants were completely removed by the end of treatment. Removal of surfactants was complete within 2h for liquid HP treatment versus 2 days for the CaO(2)-based oxidant. For both MF oxidants, hydrocarbon concentrations in filtrate were 3-4 orders of magnitude greater than in the biological control. Both MF oxidants also showed enhanced removal of the high molecular weight fractions of the petroleum hydrocarbons relative to biological treatment, though this effect was considerably greater with the CaO(2)-based oxidant. The chemical treatments did not considerably reduce numbers of culturable hydrocarbon-degrading microorganisms relative to the bioreactor, suggesting that chemical and biological oxidation may have occurred simultaneously in the slurry.     

Desorption kinetics of neutral hydrophobic organic compounds from field-contaminated sediment

The chemical release rates from a field-contaminated sediment (Lake Charles, LA) using Tenax desorption were studied. Two dichlorobenzenes (m-, p-), hexachlorobutadiene, and hexachlorobenzene were investigated. Contrary to reports that sorption rates are inversely related to K(OW), the slow desorption rates were found to be similar for the four compounds. The data were modeled by a two-compartment irreversible adsorption and radial diffusion model. Desorption kinetics from the first irreversible compartment can be modeled by radial diffusion and assume an irreversible adsorption constant and soil tortuosity of 4.3. The desorption half-life is approximately 2-7 days. Desorption from the second irreversible compartment is very slow (half-life of approximately 0.32-8.62 years) presumably caused by entrapment in soil organic matter that increases the constrictivity of the solid phase to chemical diffusion. From the kinetic data, it is deduced that the diffusion pore diameter of the second irreversible compartment is approximately equal to the critical molecular diameter. The mass of chemicals in this highly constrictive irreversible compartment is approximately one-fourth of the maximum irreversible, or resistant, compartment. The slow kinetics observed in this study add additional support to the notion that the irreversibly sorbed chemicals are 'benign' to the environment.     

Sorption of hydrophobic organic compounds (HOC) in rapeseed oil bodies

Oil-bodies are minute plant organelles (0.5-2.0microm diameter) consisting of an oil core surrounded by a phospholipid monolayer/proteinaceous membrane. Oil-bodies have been isolated from rapeseed seeds and demonstrated to constitute a novel type of micro-capsule suitable for the extraction of hydrophobic organic compounds from aqueous environments. Three hydrophobic pesticides: atrazine (2-chlor-4-ethyl-amino-6-isopropylamino-1,3,5-triazine), carbaryl (1-naphthyl methylcarbamate) and parathion (O,O-diethyl O-(4-nitrophenyl) phosphorothioate), as well as naphthalene and 2-phenylethanol were successfully extracted from aqueous solutions, with absorption in the inner oily core of OB as sorption mechanism. The OB membrane does not represent a barrier for the mass transfer of the compound towards the inner oily core of OB. Moreover, due to very high surface area to volume ratio, oil-bodies exhibit very good mass transfer properties compared with larger synthetic microcapsules or two-phase liquid-liquid extraction (LLE) techniques, which diminishes the need for strong agitation and avoids the formation of difficult to separate stable emulsions.     

Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. Part II: hydrolysis reactions

The effect of dissolved humic acid (HA) on two types of hydrolysis reactions was investigated: (I) dehydrochlorination of gamma-hexachlorocyclohexane (HCH) and 1,1,2,2-tetrachloroethane (TeCA) as a reaction involving hydroxide ions (OH(-)) and (II) hydrolysis of 1-octyl acetate (OA) which is catalyzed by H(+) at the applied pH value (pH 4.5). The rate of TeCA hydrolysis was not affected by addition of 2 g l(-1) of HA at pH 10 (k' = 0.33 h(-1)) but HCH hydrolysis was significantly inhibited (k' = 4.6 x 10(-3) h(-1) without HA and 2.8 x 10(-3)h(-1) at 2 g l(-1) HA). HCH is sorbed by 51% whereas TeCA sorption is insignificant at this HA concentration. Sorbed HCH molecules are effectively protected due to electrostatic repulsion of OH(-) by the net negative charge of the HA molecules. In contrast, OA hydrolysis at pH 4.5 (k' = 1.6 x 10(-5) h(-1)) was drastically accelerated after addition of 2 g l(-1) HA (k' = 1.1 x 10(-3) h(-1)). The ratio of the pseudo-first-order rate constants of the sorbed and the freely dissolved ester fraction is about 70. H(+) accumulation in the microenvironment of the negatively charged HA molecules was suggested to contribute to the higher reaction rate for the sorbed fraction in case of this H(+)-catalyzed reaction. Analogous effects from anionic surfactants are known as micellar catalysis.     

Behavior of fenhexamid in soil and water

A study was conducted to investigate fenhexamid (FEX) behavior in soil and in water. FEX proved to be rather stable at acid pH but showed slight degradation at neutral and alkaline pH. After 101 days of FEX spiking of a soil sample, 94% at pH 4, 12% at pH 7 and 23% at pH 9 of the active ingredient was still present. In natural water the rate of FEX disappearance appeared to be slow which may be due to abiotic rather than biotic processes. The soil degradation tests showed low persistence of the active ingredient if a good microflora activity is guaranteed (DT₅₀ about 1 day). Moreover, in absence of microorganisms, FEX proved to be stable. Humidities of 25 and 50% of Water Holding Capacity (WHC) influenced in equal measure the rate of degradation. From the same soil, a bacterium was isolated and identified as Bacillus megaterium, which was able to metabolize FEX with the hydroxylation of the cyclohexane ring. Moreover, FEX showed an elevated affinity for humic acid (73%), smectite (31%), and ferrihydrite(20%) and low affinity for vermiculite (11%) and kaolinite (7%).