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.     

Distribution of polycyclic aromatic hydrocarbons in soil-water system containing a nonionic surfactant

The effect of a nonionic surfactant, Triton X-100 (TX100), on the distribution of four representative polycyclic aromatic hydrocarbons (PAHs), phenanthrene, fluorene, acenaphthene and naphthalene, in soil-water system was studied on a natural soil. The apparent soil-water distribution coefficient with surfactant (Kd*) for these compounds increased when TX100 equilibrium concentration from zero to around the critical micelle concentration (CMC), followed by a decrease in Kd* at TX100 equilibrium concentration greater than CMC. This is a direct result of surfactant sorption onto soil followed by PAHs partitioning to the sorbed surfactant. The values of carbon-normalized solute distribution coefficient (Kss) with the sorbed TX100 are greater than the corresponding partition coefficients with soil organic matter (Koc), which indicates the soil-sorbed nonionic surfactant is more effective per unit mass as a partitioning medium than the native soil organic matter for PAHs. When Kd* = Kd the corresponding initial concentration of surfactant was defined as critical washing concentration (CWC). Depending on the surfactant initial concentration below or above the CWC, the addition of nonionic surfactant can enhance the retardation of soil for PAHs or promote the removal of PAHs from soil, respectively. The values of Kd* and CWC can be predicted by a model, which correlates them with the compounds' octanol-water partition coefficients (Kow), soil property and the amount of soil-sorbed surfactant.     

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.     

Solubilization of nitrotoluenes in micellar nonionic surfactant solutions

A key factor in selecting surfactants to enhance chemical or biological transformation or physical removal of an organic pollutant from contaminated soil is knowledge of the pollutant's solubility behavior in the surfactant solution. This study investigated the influence of nonionic surfactant structure on the solubility of 4-nitrotoluene (NT), 2,3-dinitrotoluene, 2,4-dinitrotoluene, 2,6-dinitrotoluene, and 2,4,6-trinitrotoluene (TNT) at room temperature. For a series of alkyl phenol ethoxylates (Tergitol NP-8 to NP-40), decreasing the ethoxylate chain length increased the solubility of these nitrotoluenes by a factor of two or less in 10 g l(-1) surfactant solutions, but did not significantly change their molar solubilization ratios (MSR, e.g. 0.02 for TNT) or their micelle-water partition coefficients (K(m), e.g. 3.4 for TNT). For Tergitol NP-8 solutions ranging from 1.0 to 12.4 g l(-1), no enhancement in NT solubility was found, suggesting that the cloud point was reached. The MSRs for Tween 80 were higher than those of Tween 20 and the MSRs of Brij-58 were higher than those for Brij-35. When comparing solutes, NT had the highest solubility and MSR (0.28-0.41), while TNT had the lowest solubility and MSR (0.02-0.03). A linear relationship between K(m) values and octanol-water partition coefficients based on Triton X-100 predicted the logK(m) values within 0.5 of their measured values. A linear solvation free energy correlation for K(m) suggested the importance of solute volume and effective hydrogen bond basicity in the partitioning process while implying that the nitrotoluenes are solubilized in a polar portion of the micelle.     

Solubilization of DNAPLs by mixed surfactant: reduction in partitioning losses of nonionic surfactant

Efforts to remediate the dense nonaqueous phase liquids (DNAPLs) by mobilizing them face with risks of driving the contaminants deeper into aquifer zones. This spurs research for modifying the approach for in situ remediation. In this paper, a novel solubilization of DNAPLs by mixed nonionic and anionic surfactant, Triton X-100 (TX100) and sodium dodecylbenzene sulfonate (SDBS), was presented and compared with those by single ones. Given 1:40 phase ratio of DNAPL:water (v/v) and the total surfactant concentration from 0.2 to 10gl(-1), mixed TX100-SDBS at the total mass ratios of 3:1, 1:1 and 1:3 exhibited significant solubilization for the DNAPLs, trichloroethene (TCE), chlorobenzene (CB) and 1,2-dichlorobenzene (1,2-DCB). The solubilization extent by mixed TX100-SDBS was much larger than by single TX100 and even larger than by single SDBS at the ratios of 1:1 and 1:3, respectively. TX100 partitioning into the organic phase dictated the solubilization extent. The TX100 losses into TCE, CB and 1,2-DCB phases were more than 99%, 97% and 97% when single TX100 was used. With SDBS alone, no SDBS partitioned into DNAPLs was observed and in mixed systems, SDBS decreased greatly the partition loss of TX100 into DNAPLs. The extent of TX100 partition decreased with increasing the amount of SDBS. The mechanism for reduction of TX100 partition was discussed. TX100 and SDBS formed mixed micelles in the solution phase. The inability of SDBS to partition into DNAPLs and the mutual affinity of SDBS and TX100 in the mixed micelle controlled the partitioning of TX100 into DNAPL phase. The work presented here demonstrates that mixed nonionic-anionic surfactants would be preferred over single surfactants for solubilization remediation of DNAPLs, which could avoid risks of driving the contaminants deeper into aquifers and decrease the surfactant loss and remediation cost.     

Combined effect of nonionic surfactant Tween 80 and DOM on the behaviors of PAHs in soil--water system

Batch experiments were performed to examine the desorption behavior of phenanthrene and pyrene in soil–water system in the presence of nonionic surfactant Tween 80 and dissolved organic matter (DOM) derived from pig manure or pig manure compost. Addition of 150 mg l⁻¹ Tween 80 desorbed 5.8% and 2.1% of phenanthrene and pyrene from soil into aqueous phase, respectively, while the addition of both Tween 80 and DOM derived from pig manure compost and pig manure could further enhance the desorption of phenanthrene to 15.8% and 16.2%, respectively, and 6.4% and 10.9%, respectively, for pyrene. In addition, our finding also suggested that subsequent addition of Tween 80 into the soil–water system could further enhance PAHs desorption. The enhancement effect of the co-existence of Tween 80 and DOM was more than the additive effect of the Tween 80 and DOM individually. It is likely that the formation of DOM–surfactant complex in the soil–water system may be a possible reason to explain such desorption enhancement phenomenon. Therefore, it is anticipated that the coexistence of both Tween 80 and DOM derived from pig manure or pig manure compost in soil environment will enhance the bioavailability of PAHs as well as other hydrophobic organic contaminants (HOCs) by enhancing the desorption during remediation process.     

Use and validation of novel snow samplers for hydrophobic, semi-volatile organic compounds (SVOCs)

Two novel gas-tight snow samplers (snow-can and snow-tube) are presented and the performance of the snow-can in a field trial was assessed. The methodology for the sampling, extraction and analysis of persistent organic pollutants (POPs) are detailed. These samplers allow the various components of a snow sample to be analysed separately; these included the meltwater (MW), particulate matter (GFF) and vapour in the headspace (HS). Snow samples collected on the Punta Indren glacier in the Italian Alps revealed the occurrence of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OC). Replicate samples of the same snow type were undertaken as a test of sampling precision. Relative standard deviations (RSDs) for SigmaPCBs and SigmaPAHs were approximately 30% and approximately 35% respectively. The lowest precision was found for the particle-laden snow, notably for the heavier PCB homologues. For the chlorinated compounds, the pesticides lindane and endosulfan-I had the highest levels in snow, with mean concentrations of 402 and 103 pgl(-1) (snow meltwater) respectively. The vapour present in the headspace (HS) comprised a minor component of a collected sample for all compounds, but HS concentrations for three lighter PAHs gave good agreement with those calculated based on their dimensionless Henry's law constants. This suggests that volatilisation during melting of aged snow-can be reasonably predicted with knowledge of the temperature-dependent Henry's law constant.     

Air sampling and analysis of volatile organic compounds with solid phase microextraction

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.     

Environmental properties and effects of nonionic surfactant adjuvants in pesticides: a review

Little is known about the environmental fate of adjuvants after application on the agricultural land. Adjuvants constitute a broad range of substances, of which solvents and surfactants are the major types. Nonionic surfactants such as alcohol ethoxylates (AEOs) and alkylamine ethoxylates (ANEOs) are typically examples of pesticide adjuvants. In view of their chemical structure this paper outlines present knowledge on occurrence, fate and effect on the aquatic and terrestrial environment of the two adjuvants: AEOs and ANEOs.Both AEOs and ANEOs are used as technical mixtures. This implies that they are not one single compound but a whole range of compounds present in different ratios. Structurally both groups of substances have a mutual core with side chains of varying lengths. Each of these compounds besides having the overall ability to distribute between different phases also possesses some single compound behaviour. This is reflected in the parameters describing the fate e.g. distribution coefficient, leaching, run-off, adsorption to soil, degradation and effects of these substances. The adsorption behaviour of ANEOs in contrast to AEOs is particularly variable and matrix dependent due to the ability of the compound to ionise at environmentally relevant pH. Probably because the compounds exceeds high soil adsorption and are easily degradable which is reflected in the low environmental concentrations generally found in monitoring studies. The compounds generally possess low potency to both terrestrial and aquatic organisms. The major environmental problem related to these compounds is the ability to enhance the mobility of other pollutants in the soil column.     

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.     

Adsorption of anionic and nonionic surfactant mixtures from synthetic detergents on soils

Adsorption of anionic surfactant (sodium dodecylbenzenesulfonate, SDBS) and nonionic surfactant (an alcohol ethoxylates with 12 carbons and 9 oxyethyl groups, A12E9) mixtures, widely used as the major constituents of synthetic detergents in China and become the most common pollutants in the environment, on soils was conducted to investigate the behavior of mixed surfactants in soils. The effects of addition order and mixing ratios of two surfactants, associated with pH and ion strength in solutions, on adsorptions were considered. The results show that saturated adsorption amount of SDBS and A12E9 on soils decreased respectively when A12E9 was added into soils firstly compared with that secondly, possibly resulting from the screening of A12E9 to part adsorption sites on soils and the hydrocarbon chain-chain interactions between SDBS and A12E9. The adsorption of SDBS and A12E9 on soils was enhanced each other at pre-plateau region of isotherms. At plateau region of isotherms, the adsorption of SDBS on soils decreased with the increase of molar fraction of A12E9 in mixed surfactant solutions, while that of A12E9 increased except the molar ratio of SDBS to A12E9 0.0:1.0. With the increase of pH in mixed surfactant solutions, adsorption amount of SDBS and A12E9 on soils decreased, respectively. The reduction of ion strength in soils resulted in the decrease of adsorption amount of SDBS and A12E9 on soils, respectively.     

Dynamic air sampling of volatile organic compounds using solid phase microextraction

A new dynamic air sampling system was devised and evaluated in conjunction with solid phase microextraction (SPME) fiber materials for extracting odor-causing volatile organic compounds (VOCs) present in swine building environments. Utilizing a standard solution consisting of 11 compounds (i.e., volatile fatty acids, indoles, and phenol), sampling times, volumes, and flow rates were adjusted to establish optimal extraction conditions. Results indicated that the sampling system was effective with the Carboxen/Polydimethylsiloxane (CAR/PDMS) fiber in extracting all 11 standard compounds. The best sampling conditions for the extraction were a 100-mL sampling vial subjected to a continuous flow of 100 mL/min for 60 min. The gas chromatographic analysis showed that the reproducibility was within acceptable ranges for all compounds (RSD=4.24-17.26% by peak areas). In addition, field tests revealed that the sampling system was capable of detecting over 60 VOCs in a swine house whose major components were identified by gas chromatography-mass spectrometry (GC-MS) and by their retention times as volatile fatty acids, phenols, indole, and skatole. The field tests also showed that considerably different levels of VOCs were present in various parts of the swine building.     

Surfactant solubilization of hydrophobic compounds in soil and water

The soil/water partition coefficient (K_d) of hexachlorobenzene (HCB) ranged from 220 1/kg to 1800 1/kg for eight soils having a wide range of physico-chemical properties. K_d normalised to soil organic carbon (K_oc) was found to be 28000 ± 4800 1/kg. Anionic surfactant dodecylsulphate (DS) present at concentrations above the critical micellar concentration (CMC) caused reductions in the apparent soil/water partition coefficient (K_d ^*) in the range of 3–26 times for most soils and up to 36–91 times for sandy soils. Below CMC, at environmentally relevant surfactant concentrations, K_d ^* was reduced by a factor of 1–13. For clay and calcareous soils significant adsorption/complexation/precipitation of DS occurred. At the lowest DS concentration this produced a two-fold increase in K_d ^*. At increasing DS concentrations this effect was shielded by the solubihzing effect from DS. Monomer (K_mn) and micellar (K_mc) surfactant/water partition coefficients for HCB were determined to be, 980 ± 190 1/kg and 21000 ± 1600 1/kg, respectively.     

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.     

Prediction of hydroxyl radical reaction rates with organic compounds in the gas phase

Room temperature rate constants for the gas phase reaction of OH radicals with organic substrates can be estimated by means of a statistically significant correlation with the corresponding rate constants in liquid water.     

Investigation of partitioning mechanism for volatile organic compounds in a multiphase system

Laboratory experiments were performed to investigate the partitioning behavior of a set of diverse volatile organic compounds (VOCs). After equilibration at a temperature of 25 °C, the VOC concentrations were measured by headspace method in combination with gas chromatography/mass spectrometry (GC/MS). The obtained data were used to determine the partition coefficients (K_P) of VOCs in a gas-liguid-solid system. The results have shown that the presence and nature of solid materials in the working solution control the air-water partitioning of dissolved VOCs. The air/solution partitioning of BTEX and C₉-C₁₀ aldehydes was most affected in the presence of diesel soot. K_P values decreased by a factor ranging from 1.5 for toluene to 3.0 for ethylbenzene. The addition of mineral dust in the working solution exhibited greater influence on the partitioning of short aldehydes. K_P values decreased by a factor of 1.8. The experimental partition coefficients were used to develop a predictive model for partitioning of BTEX and n-aldehydes between air, water and solid phases.