The effect of surfactants on the distribution of organic compounds in the soil solid/water system

The efficiency of soil remediation by surfactant washing was evaluated via the measured distribution coefficients of a number of nonpolar compounds in several soil-water mixtures. The studied compounds (contaminants) are BTEX (benzene, toluene, ethylbenzene, and p-xylene) and three chlorinated pesticides (lindane, alpha-BHC, and heptachlor epoxide), which span several orders of magnitude in water solubility (S(w)). A peat, and two natural soils were used that comprise a wide range in soil organic matter (SOM) content. The surfactants tested included cationic, anionic and nonionic types, with concentrations up to five to six times the critical micelle concentration (CMC). The K(d)(*)/K(d), values were used to evaluate the remediation efficiency under various operation conditions. For relatively water soluble BTEX compounds, the surfactant adsorption on the soil surface is the deciding factor on contaminant desorption from soil. For the less-soluble pesticides, surfactant micelles in solution influence the contaminant desorption more. The contaminants partitioning to SOM or adsorbed surfactants lowers the desorption efficiency. Anionic surfactants are found to be a better choice on soil remediation because they do not form admicelle on soil surface that enhances the SOM content. Cationic surfactant, which adsorb onto soil surfaces, leads to poor remediation efficiency. An improper selection of surfactant would result in inefficiency in soil remediation by surfactant washing.     

Use of farming and agro-industrial wastes as versatile barriers in reducing pesticide leaching through soil columns

Increased interest has been recently focused on assessing the influence of the addition of organic wastes related to movement of pesticides in soils of low organic matter (OM) content. This study reports the effect of two different amendments, animal manure (composted sheep manure) and agro-industrial waste (spent coffee grounds) on the mobility of 10 pesticides commonly used for pepper protection on a clay-loam soil (OM = 0.22%). The tested compounds were azoxystrobin, cyprodinil, fludioxonil, hexaconazole, kresoxim-methyl, pyrimethanil, tebuconazole, and triadimenol (fungicides), pirimicarb (insecticide), and propyzamide (herbicide). Breakthrough curves were obtained from disturbed soil columns. Cumulative curves obtained from unamended soil show a leaching of all pesticides although in different proportions (12-65% of the total mass of compound applied), showing triadimenol and pirimicarb the higher leachability. Significant correlation (r = 0.93, p<0.01) was found between the observed and bibliographical values of GUS index. The addition of the amendments used drastically reduced the movement of the studied pesticides. Only two pesticides were found in leachates from amended soils, pyrimethanil (<1%) for both, and pirimicarb (44%) in the soil amended with spent coffee grounds. A decrease in pesticide leaching was observed with the increase in dissolved organic matter (DOM) of leachates. The results obtained point to the interest in the use of organic wastes in reducing the pollution of groundwater by pesticide drainage.     

Solubility enhancement of PCDD/F in the presence of dissolved humic matter

From previous studies, we, the authors collected and arranged the octanol-water partition coefficients (K(ow)), water solubility (S0), and dissolved humic matter (DHM)-water partition coefficients (K(oc)) for 95 organic compounds, and presented the correlations between each physical property. The K(oc) and K(ow) of dioxins estimated were significantly increased while S0 was decreased on increasing the chlorine number. In the presence of DHM, solubility enhancement (Sw/S0, Sw is the actual solubility in the presence of DHM) in highly chlorinated PCDD/F such as HpCDDs and OCDD is higher than that in low chlorinated ones. It means that dioxins abundant wastes (fly ash) should not be codisposed with organic abundant wastes (sewage sludge, food waste or bottom ash, etc.) to minimize the leachability of dioxins.     

Degradation of polycyclic aromatic hydrocarbons (PAHs) in contaminated soils by Fenton's reagent: a multivariate evaluation of the importance of soil characteristics and PAH properties

In this study, we investigated how the chemical degradability of polycyclic aromatic hydrocarbons (PAHs) in aged soil samples from various contaminated sites is influenced by soil characteristics and by PAH physico-chemical properties. The results were evaluated using the multivariate statistical tool, partial least squares projections to latent structures (PLS). The PAH-contaminated soil samples were characterised (by pH, conductivity, organic matter content, oxide content, particle size, specific surface area, and the time elapsed since the contamination events, i.e. age), and subjected to relatively mild, slurry-phase Fenton's reaction conditions. In general, low molecular weight PAHs were degraded to a greater extent than large, highly hydrophobic variants. Anthracene, benzo(a)pyrene, and pyrene were more susceptible to degradation than other, structurally similar, PAHs; an effect attributed to the known susceptibility of these compounds to reactions with hydroxyl radicals. The presence of organic matter and the specific surface area of the soil were clearly negatively correlated with the degradation of bi- and tri-cyclic PAHs, whereas the amount of degraded organic matter correlated positively with the degradation of PAHs with five or six fused rings. This was explained by enhanced availability of the larger PAHs, which were released from the organic matter as it degraded. Our study shows that sorption of PAHs is influenced by a combination of soil characteristics and physico-chemical properties of individual PAHs. Multivariate statistical tools have great potential for assessing the relative importance of these parameters.     

Enhanced solubilization and removal of naphthalene and phenanthrene by cyclodextrins from two contaminated soils

The development of innovative methods for cleaning contaminated soils has emerged as a significant environmental priority. Herein, are investigated the effectiveness of cyclodextrin (CD) to solubilize and to extract organic pollutants from soils. The interactions in the cyclodextrin/pollutant/soil system have been studied "step by step" using two kinds of polycyclic aromatic hydrocarbons (PAH), naphthalene (Nap) and phenanthrene (Phe), cyclodextrins and soils. Inclusion complex formation of PAH with beta-cyclodextrin (beta-CD) and hydroxypropyl-beta-cyclodextrin (HPCD) has been investigated and was proposed as a way to facilitate the pollutant removal from soil. Little effect of ionic strength was observed on CD complex formation for both compounds. The solubility of PAH in 50 g L(-1) of HPCD was enhanced 20- and 90-fold for naphthalene and phenanthrene, respectively. Batch experiments were performed to study the adsorption-desorption of two PAH on two soils and the influence of CDs over these processes. These experiments were also conducted with a mixture of two PAH. The batch desorption results indicate that removal capacity of HPCD was higher than that of beta-CD. Phenanthrene was strongly sorbed on soils, this led to low desorption rates compared to that of naphthalene, whatever the extracting agent used. When HPCD solution was used as a flushing agent, 80% of naphthalene and 64% of phenanthrene recovery from soil were observed. For both compounds, the slowest desorption rate was found for the soil that had the greatest content of organic matter. CD sorption on soils, was relatively low and depended on soil type. The soil organic matter (SOM) could favor the retention of both CD and pollutant involving the extraction rate to be decreased. A competitive hydrophobic interactions of pollutant between SOM and CD molecules, and co-sorption were expected to be the mechanism for the inhibited desorption.     

Highly dealuminated Y zeolite as efficient adsorbent for the hydrophobic fraction from wastewater treatment plants effluents

In this work we report that highly dealuminated zeolite Y is a hydrophobic material that is able to remove selectively fatty acids and hydrocarbon compounds from the effluent of an urban wastewater treatment plant (UWTP). This adsorbent capability of zeolite Y could lead to an improved quality of UWTP effluents. Typical domestic wastewaters contain detergents, soaps and surfactants that are only partially removed in conventional UWTP. In the present work using an effluent from a UWTP located at Ribarroja del Turia (Valencia, Spain) containing 10 ppm of total organic carbon, we have been able to retain by adsorption on the dealuminated Y zeolite up to 16 and 60% of the organic matter of the effluent at pH values 7.2 and 4, respectively. Characterization of the adsorbed organic matter by Fourier transformed infrared (FT-IR), ¹H NMR and GC–MS after derivatization has shown that the zeolite adsorbs selectively the hydrophobic compounds of the effluent.     

Evaluation of persulfate oxidative wet scrubber for removing BTEX gases

Soil vapor extraction (SVE) coupled with air sparging of groundwater is a method commonly used to remediate soil and groundwater contaminated with volatile organic petroleum contaminants such as gasoline. These hazardous contaminants are mainly attributable to the compounds-benzene, toluene, ethylbenzene, and xylenes (known collectively as BTEX). Exhaust gas from SVE may contain BTEX, and therefore must be treated before being discharged. This study evaluated the use of iron-activated persulfate chemical oxidation in conjunction with a wet scrubbing system, i.e., a persulfate oxidative scrubber (POS) system, to destroy BTEX gases. The persulfate anions can be activated by citric acid (CA) chelated Fe(2+) to generate sulfate radicals (SO(4)(*-), E degrees =2.4V), which may rapidly degrade BTEX in the aqueous phase and result in continuous destruction of the BTEX gases. The results show that persulfate activation occurred as a result of continuous addition of the citric acid chelated Fe(2+) activator, which readily oxidized the dissolved BTEX. Based on initial results from the aqueous phase, a suitable Fe(2+)/CA molar ratio of 5/3 was determined and used to initiate activation in the subsequent POS system tests. In the POS system, using persulfate as a scrubber solution and with activation by injecting Fe(2+)/CA activators under two testing conditions, varying iron concentrations and pumping rates, resulted in an approximate 50% removal of BTEX gases. During the course of the tests which in corporate activation, a complete destruction of BTEX was achieved in the aqueous phase. It is noted that no removal of BTEX occurred in the control tests which did not include activation. The results of this study would serve as a reference for future studies into the practical chemical oxidation of waste gas streams.     

Association of radionuclides with components of fulvic acids isolated from soils

The distribution of Pu and Am between specific and nonspecific components of various groups of the organic matter of soil was studied. For chernozem and soddy podzolic soil, 63 and 53% of Pu and only 1 and 8% of Am, respectively, are bound with fulvic acid purified to remove low-molecular-weight compounds by fractionation on BAU activated charcoal. Larger relative amount of Am, compared to Pu, in the form of low-molecular-weight nonspecific compounds is responsible for higher migration mobility of Am, compared to Pu, in the environment. The sorption of organic complexes of Pu and Am on carbon nanotubes was studied. The degree of Pu sorption only slightly depends on the nature of the organic substance, except solutions of humic acids from which the Pu sorption is appreciably higher. The degree of Am sorption regularly increases with a decrease in the molecular weight of the organic substances.     

An investigation on magnetic susceptibility of hazardous saline-alkaline soils from the contaminated Hai River Basin, China

Magnetic susceptibility can provide rich environmental information, especially for hazardous heavy metals and saline-alkaline in the contaminated soils. Magnetic susceptibility in four vertical profiles from saline-alkaline soils in lower Hai River basin was investigated. Soil sites were extended from alluvial fan to coastal plain areas. They are aligned along a latitudinal strip. Magnetic parameters including low/high frequency susceptibility, frequency-dependent susceptibility was measured. Moreover, some standard pedological parameters such as pH value and organic matter content were also determined. The results showed that low frequency magnetic susceptibility values is very high at the surface and decreases with the profile to a low value. In all profiles from alluvial fan frequency-dependent susceptibility greater than 3% may suggest the presence of relatively more super-paramagnetic particles. Magnetic susceptibility showed obvious vertical distribution in alluvial fan higher than coastal plain. No significant correlations between organic matter, pH and low frequency magnetic susceptibility were found, while there is a negative correlation between organic matter and frequency-dependent susceptibility. A positive correlation between pH and frequency-dependent susceptibility was found in the study areas.     

Effect of aggregate structure on VOC gas adsorption onto volcanic ash soil

The understanding of the gaseous adsorption process and the parameters of volatile organic compounds such as organic solvents or fuels onto soils is very important in the analysis of the transport or fate of these chemicals in soils. Batch adsorption experiments with six different treatments were conducted to determine the adsorption of isohexane, a gaseous aliphatic, onto volcanic ash soil (Tachikawa loam). The measured gas adsorption coefficient for samples of Tachikawa loam used in the first three treatments, Control, AD (aggregate destroyed), and AD-OMR (aggregate destroyed and organic matter removed), implied that the aggregate structure of volcanic ash soil as well as organic matter strongly enhanced gas adsorption under the dry condition, whereas under the wet condition, the aggregate structure played an important role in gas adsorption regardless of the insolubility of isohexane. In the gas adsorption experiments for the last three treatments, soils were sieved in different sizes of mesh and were separated into three different aggregate or particle size fractions (2.0–1.0 mm, 1.0–0.5 mm, and less than 0.5 mm). Tachikawa loam with a larger size fraction showed higher gas adsorption coefficient, suggesting the higher contributions of macroaggregates to isohexane gas adsorption under dry and wet conditions.     

Influence of clay mineral structure and surfactant nature on the adsorption capacity of surfactants by clays

Adsorption of three surfactants of different nature, Triton X-100 (TX100) (non-ionic), sodium dodecylsulphate (SDS) (anionic) and octadecyltrimethylammonium bromide (ODTMA) (cationic) by four layered (montmorillonite, illite, muscovite and kaolinite) and two non-layered (sepiolite and palygorskite) clay minerals was studied. The objective was to improve the understanding of surfactant behaviour in soils for the possible use of these compounds in remediation technologies of contaminated soils by toxic organic compounds. Adsorption isotherms were obtained using surfactant concentrations higher and lower than the critical micelle concentration (cmc). These isotherms showed different adsorption stages of the surfactants by the clay minerals, and were classified in different subgroups of the L-, S- or H-types. An increase in the adsorption of SDS and ODTMA by all clay minerals is observed up to the cmc of the surfactant in the equilibrium solution is reached. However, there was further TX100 adsorption when the equilibrium concentration was well above the cmc. Adsorption constants from Langmuir and Freundlich equations (TX100 and ODTMA) or Freundlich equation (SDS) were used to compare adsorption of different surfactants by clay minerals studied. These constants indicated the surfactant adsorption by clay minerals followed this order ODTMA>TX100>SDS. The adsorption of TX100 and ODTMA was higher by montmorillonite and illite, and the adsorption of SDS was found to be higher by kaolinite and sepiolite. Results obtained show the influence of clay mineral structure and surfactant nature on the adsorption capacity of surfactants by clays, and they indicate the interest to consider the soil mineralogical composition when one surfactant have to be selected in order to establish more efficient strategies for the remediation of soils and water contaminated by toxic organic pollutants.     

Investigation on the solubilization of polycyclic aromatic hydrocarbons in the presence of single and mixed Gemini surfactants

Water solubility enhancements of naphthalene (Naph), phenanthrene (Phen) and pyrene (Py) by a series of single cationic Gemini surfactants (CG(s), s=4, 8, 12 and 16) as well as their equimolar binary combinations (CG(12-m), m=4, 8 and 16) have been investigated. The relationships between their surface properties and solubilizing capacities toward three polycyclic aromatic hydrocarbons (PAHs) have been quantified and discussed. The selected single Gemini surfactants observably enhance the water solubility of PAHs following the order of Phen>Py>Naph except for CG(8) which has a superior solubilizing ability for Py. For the same organic compound, the solubilizing abilities of single Gemini surfactants are in tune with the order of variation tendencies of CMC values. However, the different mixed Gemini surfactant systems have shown selective solubilization on various PAHs which is not simply related to their mixed molar properties. Particularly, the CG(12-16) surfactant has relatively comparable solubilization on Py and inferior solubilization on Phen compared to all other investigated solubilizing systems. It is presumably attributed to the relationships between the structure of surfactants and the chemical nature of both solutes and surfactants. The analysis studied herein has provided valuable information for the selection of mixed Gemini surfactants for solubilizing water-insoluble compounds.     

Effects of soil properties on surfactant adsorption

Abstract

The effects of surface area, soil organic matter (SOM) content, and cation exchange capacity (CEC) of natural soils and clays on the adsorption capacity of cationic, anionic, and nonionic surfactants in water‐solid systems were investigated based on the adsorption isotherm analysis. The sorption capacity for a cationic surfactant was proportional to the CEC of the solids. For both anionic and nonionic surfactants, the sorption capacity was related to the soil mineral fraction. However, other soil properties probably affect the practical sorption. The investigated soil properties were treated case by case.     

Application of multiphase transport models to field remediation by air sparging and soil vapor extraction

The design and operation of air sparging and soil vapor extraction (AS/SVE) remediation systems remains in large an art due to the absence of reliable physically based models that can utilize the limited available field data. In this paper, a numerical model developed for the design and operation of air sparging and soil vapor extractions systems was used to simulate two field case studies. The first-order mass transfer kinetics were incorporated into the model to account for contaminant mass transfer between the water and air (stripping), NAPL and water (dissolution), NAPL and air (volatilization), and water and soil (sorption/desorption), the model also accounted for soil heterogeneity. Benzene, toluene, ethyl benzene and xylenes (BTEX) were the contaminants of concern in both case studies. In the second case study, the model was used to evaluate the effect of pulsed sparging on the removal rate of BTEX compounds. The pulsed sparging operation was approximated assuming uniform contaminant redistribution at the beginning of the shut-off period. The close comparison between the observed and simulated contaminant concentration in the aqueous phase showed that the approximation of the pulsed sparging operation yielded reasonable prediction of the removal process. Field heterogeneity was simulated using Monte Carlo analysis. The model predicted about 80-85% of the contaminant mass was removed by air-water mass transfer, which was similar to the average removal obtained by Monte Carlo analysis. The analysis of the removal/rebound cycles demonstrated that removal rate was controlled by the organic-aqueous distribution coefficient K(oc). Due to the lack of site-specific data, the aerobic first-order biodegradation coefficients (k(bio)) were obtained from a literature survey, therefore, uncertainty analysis of the k(bio) was conducted to evaluate the contribution of the aerobic biodegradation to total contaminant removal. Results of both case studies showed that biodegradation played a major role in the remediation of the contaminated sites.     

Electric arc furnace filter dust: Influence of organic material on the bulk density and flowability

In this study, the influence of condensed organic matter on the flowability and the bulk density of electric arc furnace (EAF) dust was investigated. The properties of the original dust samples containing some organic matter were compared with the properties of these samples after the removal of the condensed organic compounds by a deoiling procedure. The particle size distribution and the density of the three investigated dust samples were quite similar but the content of organic matter (TOC) was different. The values for the bulk density were lower for the original dust compared to the deoiled dust samples. The higher the TOC content, the higher the difference in the bulk density. Thus, the storage capacity of the dust silo was reduced by 9–17%. The flowability of all deoiled dust samples was very similar, whereas the flowability of the original dust was worse. The higher the TOC content, the worse the flowability. The average reduction of ff_c in comparison to the deoiled dust samples was 48, 38, and 17% for EAF dust samples with 0.65, 0.46, and 0.26% TOC, respectively. Evidently, the condensed organic matter on the dust particles reduces the flowability of the material. Therefore, the bulk density for dust with a higher TOC content is also lower.     

A photoinduced electron-transfer reagent for peroxyacetic acid, 4-ethylthioacetylamino-7-phenylsulfonyl-2,1,3-benzoxadiazole,based on the method for predicting the fluorescence quantum yields

To develop new photoinduced electron-transfer (PET) reagents, we established a method for predicting the fluorescence quantum yields (phi) of the benzofurazan compounds bearing an aliphatic substituent group having an n-electron. The PET process occurred sufficiently to reduce the phi values in the benzofurazan compounds bearing an aliphatic moiety, which had a high quenching ability. The quenching ability was estimated by the molecular orbital calculation and Stern-Volmer plotting. The phi values of the benzofurazan compounds could be controlled by changing the quenching ability of a substituent group. We succeeded in designing a PET reagent for peroxyacetic acid (PAA), 4-ethylthioacetylamino-7-phenylsulfonyl-2,1,3-benzoxadiazole (EPB), using the established method for predicting the phi values. EPB and its oxidized derivative were separated by reversed-phase HPLC and fluorometrically detected at 479 nm with excitation at 362 nm. The attained detection limit for PAA was 105 fmol (S/N = 3) and the cross-reactivity toward hydrogen peroxide was very low, indicating EPB is a highly sensitive and selective reagent for PAA.     

Dependence of the migration ability of plutonium and americium in soils on additions of natural and modified organic compounds

The nature and content of modified humic acid derivatives influence the intensity of the recovery of Pu, Am, and C_org from soddy podzolic soil with distilled water. Under the dynamic conditions, these radionuclides are recovered more intensely in the presence of carboxylated humic acids, compared to the hydroxymethylated derivatives. When soils with the introduced modified humic acid derivatives are subjected to prolonged washing with distilled water, the radionuclides undergo redistribution within the columns, suggesting their migration. Under the action of dissolved organic substances isolated from soils (low-molecular-weight nonspecific organic compounds and fulvic acids), the radionuclide migration in soils occurs still more intensely. In the course of soil column washing with an aqueous phase containing the dissolved organic matter, Pu and Am pass into the mobile state to a greater extent than in washing the soils with distilled water.     

Impact of exotic and inherent dissolved organic matter on sorption of phenanthrene by soils

The impacts of exotic and inherent dissolved organic matter (DOM) on phenanthrene sorption by six zonal soils of China, chosen so as to have different soil organic carbon (SOC) contents, were investigated using a batch technique. The exotic DOM was extracted from straw waste. In all cases, the sorption of phenanthrene by soils could be well described by the linear equation. The presence of inherent DOM in soils was found to impede phenanthrene sorption, since the apparent distribution coefficients (K(d)(*)) for phenanthrene sorption by deionized water-eluted soils were 3.13-21.5% larger than the distribution coefficients (K(d)) by control soils. Moreover, the enhanced sorption of phenanthrene by eluted versus control soils was in positive correlation with SOC contents. On the other hand, it was observed that the influence of exotic DOM on phenanthrene sorption was related to DOM concentrations. The K(d)(*) values for sorption of phenanthrene in the presence of exotic DOM increased first and decreased thereafter with increasing the added DOM concentrations (0-106mgDOC/L). The K(d)(*) values at a low exotic DOM concentration (< or =28mgDOC/L) were 14.7-48.4% larger than their control K(d) values. In contrast, higher concentrations (> or =52mgDOC/L) of added exotic DOM clearly impeded the distribution of phenanthrene between soil and water. The effects of exotic and inherent DOM on phenanthrene sorption by soils may primarily be described as 'cumulative sorption', association of phenanthene with DOM in solution, and modified surface nature of soil solids due to DOM binding.     

Attenuating toluene mobility in loess soil modified with anion-cation surfactants

Soils, subsoils, and aquifer materials can be modified with hydrophobic cationic surfactants to increase their sorption capabilities for organic contaminants. The objective of this study was to examine in detail the sorptive characteristics of the natural loess soil and the resultant organo-modified soils for aqueous-phase neutral organic compounds (NOCs) in an attempt to define the operative sorptive mechanisms. Under the laboratory conditions, a series of modified loess soils in this study were prepared by replacing the cations of loess soil with both cationic surfactant hexadecyltrimethylammonium bromide (HDTMA-Br) and anionic surfactant sodium dodethylbenzene sulfonate (SDBS). Toluene was selected as an indicator to study the sorption behavior of the NOCs in loess soils. The sorption isotherms of toluene in soil samples obtained using the batch equilibration method. The results indicated that natural loess had a poor sorption capability for NOCs, and sorption isotherms of toluene appeared likely nonlinear and fit the Freundlich equation very well. When the soils were coated with large alkyl surfactants such as HDTMA-Br, sorption isotherms correspondingly became linear and the sorptive capability was prominently dependent on the quantity of hexadecyltrimethylammonium (HDTMA) and SDBS added into the soils. The study could provide an essential basis on attenuation of organic contaminants in the subsurface environment.     

An analysis of synergistic and antagonistic behavior during BTEX removal in batch system using response surface methodology

The removal of benzene, toluene, ethylbenzene and xylene (BTEX) as quaternary mixtures were studied in batch systems using a well-defined mixed microbial culture. The synergistic and antagonistic effects of total BTEX removal (BTEXT-RE) due to the presence of mixed substrate was evaluated through experiments designed by response surface methodology (RSM). The low and high concentrations of individual BTEX were 15 and 75 mg l(-1), respectively. The results showed that, increasing the concentration of xylene increased the cumulative BTEX removal (BTEXT-RE), however the reverse occurred when benzene concentrations were increased from low to high levels. A mixed response of increasing and decreasing trend in the BTEXT-RE value was observed when either of toluene or ethylbenzene concentration was increased. When the concentrations of individual BTEX compounds were 30 mg l(-1), the BTEXT-RE was about 58%. Complete BTEXT-RE was achieved at optimal BTEX concentrations of 48.1, 45.6, 49.3 and 56.6 mg l(-1). The RSM approach was found efficient in explaining the main, squared and interaction effects among individual BTEX concentrations on the BTEXT-RE in a more statistically meaningful way.