Potential concerns related to using octadecyltrichlorosilane (OTS) in rendering soils and porous ceramics hydrophobic

The treatment of hydrophilic porous ceramics to render them hydrophobic and wetting to non-aqueous phase liquids (NAPLs) is frequently needed in multiphase flow experiments to control the flow or to measure the pressure of the NAPL. In addition, research dealing with soil wettability implies a need for hydrophobic or NAPL-wet soils. The traditional procedure, which has been widely used in literature, to render hydrophilic porous ceramics and soils hydrophobic is achieved by placing the hydrophilic solid in a 5% (by volume) octadecyltrichlorosilane (OTS) solution in ethanol followed by rinsing in ethanol. This research assesses the use of this procedure as it was found that this treatment procedure resulted in excess OTS on the surface of treated hydrophobic solids which can dissolve in an organic phase and in turn alter the wettability condition of adjacent hydrophilic soils. A modified procedure, which results in hydrophobic solids free of excess OTS, is presented.     

Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

Effect of soil texture on surfactant-based remediation of hydrophobic organic-contaminated soil

Surfactants may be used in remediation of subsoil and aquifer contaminated with hydrophobic compounds. The objectives of this study were to examine the effect of soil texture on hydrophobic organic contaminant (HOC; toluene, or 1,2,4-trichlorobenzene [TCB]) removal from six soils and to evaluate the optimal composition of soil texture for maximum HOC removal using aqueous surfactant solution. Selected surfactants were 4% (vol/vol) sodium diphenyl oxide disulfonate (DOSL) and 4% (wt/vol) sodium lauryl sulfate (LS). Toluene and TCB were selected as the lighter-than-water nonaqueous phase liquid (LNAPL) and denser-than-water nonaqueous phase liquid (DNAPL) model substances, respectively. Soil types used for this study were Ottawa sand and five Iowa soils (Fruitfield, Keomah, Crippin, Webster, and Galvar). The greatest recovery of toluene and TCB in batch tests was 73% and 84%, respectively, which was obtained with DOSL surfactant in Ottawa sand. The toluene removal of 95% in column tests has been achieved in the Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 3750 ml (about 32 pore volume) passed. TCB removal of 98% in column tests has been achieved in Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 2500 ml (about 21 pore volume) passed. These results were related with soil texture (clay content 30%), clay mineralogy (kaolinite and smectite), as a function of transported pore volume.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

Enhancement of association of organic molecules on silica gel by surface water: surface photoreaction of stilbene

Here, we show that association of stilbene molecules is facilitated by water on silica gel because of hydrophobic interaction and photodimerization becomes the main photochemical process. Irradiation of trans-stilbene (t-1) on silica gel gives cis-stilbene (c-1), phenanthrene (2), benzaldehyde (3), and dimers r-ctt-4 and r-tct-4. The yields of the dimers increase and those of 2 and 3 decrease with an increase in the amount of t-1 loaded on silica gel. Atmospheric oxygen is responsible for the formation of 2 and 3. The yields of the dimers also increase with an increase in the water on a silica-gel surface and change drastically at the point where the percentage of water to silica gel is around 25 wt%. All active sites on a silica-gel surface would be covered completely with 25 wt% of water.     

Effect of housing geometry on the performance of Chemcatcher passive sampler for the monitoring of hydrophobic organic pollutants in water

Passive sampling of pollutants in water has been gaining acceptance for environmental monitoring. Previously, an integrative passive sampler (the Chemcatcher) was developed and calibrated for the measurement of time weighted average concentrations of hydrophobic pollutants in water. Effects of physicochemical properties and environmental variables (water temperature and turbulence) on kinetic and thermodynamic parameters characterising the exchange of analytes between the sampler and water have been published. In this study, the effect of modification in sampler housing geometry on these calibration parameters was studied. The results obtained for polycyclic aromatic hydrocarbons show that reducing the depth of the cavity in the sampler body geometry increased the exchange kinetics by approximately twofold, whilst having no effect on the correlation between the uptake and offload kinetics of analytes. The use of performance reference compounds thus avoids the need for extensive re-calibration when the sampler body geometry is modified.     

Dioxins,chlorophenols and other chlorinated organic pollutants in colloidal and water fractions of groundwater from a contaminated sawmill site

BACKGROUND, AIM, AND SCOPE: The distribution of chlorinated organic contaminants in groundwater and the importance of colloids were studied in groundwater from a sawmill site contaminated by chlorophenol preservatives. MATERIALS AND METHODS: The groundwater was fractionated into three different size ranges: (1) >0.7 mum, (2) 0.4-0.7 mum and (3) 0.2-0.4 mum and the filtered water phase. The concentrations of chlorophenols (CP), chlorinated phenoxy phenols (PCPP), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD) were determined in each fraction. The colloids were characterised regarding the chemical composition using X-ray photoelectron spectroscopy (XPS). RESULTS: Chlorophenols were mostly found in the water fraction and PCDD/Fs were found almost exclusively in the particulate fractions. For example, the filtered water phase contained 2,100 mug l(-1) and 0.72 ng l(-1) for CPs and PCDD/Fs, respectively, and the particulate fractions contained 27 mug l(-1) and 32 ng l(-1) for CPs and PCDD/Fs, respectively. XPS evaluation of the particulate phases showed no correlation between the surface chemistry of the particle properties and the distribution of chlorinated compounds. DISCUSSION: The results suggest that groundwater transport of CPs, PCPPs, PCDEs and PCDD/Fs may occur from contaminated sawmill sites and that the colloid-facilitated transport, especially of PCDD/Fs, is substantial. The results correlated well with previous studies of compounds sorbed to dissolved organic carbon, which indicate that dissolved and colloidal organic carbon facilitated the transport of PCDEs, PCDFs and PCDDs particularly. CONCLUSIONS: Several classes of chlorinated compounds were readily detected in the groundwater samples. Due to the differences in their physicochemical properties, CPs, PCPPs, PCDEs and PCDD/Fs vary in their partitioning between colloidal fractions and the filtered groundwater. The proportion of the bound fraction increased with an increasing hydrophobicity of the chlorinated compounds. The groundwater transport of colloid-associated pollutants from the site may be significant. RECOMMENDATIONS AND PERSPECTIVES: The results imply that colloidal particles <0.7 mum are freely mobile in groundwater from this site. The groundwater transport of colloid-associated pollutants may be significant. However, the extent of the problem is not yet known and, thus, further research is needed to evaluate the impact of colloidal transport of hydrophobic organic contaminants. In Sweden alone, 400 to 500 sawmill sites are estimated to be contaminated with PCDD/Fs as a result of the former use of CP-based wood preservatives. The widespread use of CP mixtures for a variety of applications, including wood preservation, indicates that potential colloidal transport will be an issue of concern in many countries.     

Sulfamethoxazole sorption by sediment fractions in comparison to pyrene and bisphenol A

The environmental behavior of antibiotics has attracted great research attention. However, their sorption mechanisms in soils/sediments are still unknown. Comparison of the sorption properties between the widely-studied hydrophobic organic contaminants (HOCs) and antibiotics may provide valuable insight to antibiotic sorption mechanisms. Thus, in this study batch experiments for pyrene (PYR), bisphenol A (BPA), and sulfamethoxazole (SMX) sorption were conducted on a sediment sample and its separated fractions. Our results showed the high sorption of PYR on black carbon and organic matter. Although high sorption of SMX was observed for both separated organic fractions (humic acids) and inorganic mineral particles, the original sediment particles showed relatively low sorption. Competitive sorption between SMX and dissolved humic acid on mineral particles was observed in this study. This competitive interaction is a unique process for antibiotic sorption in soils/sediments compared with apolar HOCs and may be one of the important factors controlling the antibiotic sorption.     

Sorption and desorption hysteresis of organic contaminants by kerogen in a sandy aquifer material

Sorption and desorption hysteresis of 1,2-dichlorobenzene, 1,3,5-trichlorobenzene, naphthalene, and phenanthrene were investigated for the Borden aquifer material with total organic carbon of 0.021% and the isolated natural organic matter (NOM). The isolated NOM is a kerogen type of organic matter with relatively low maturation degree and contained many different types of organic matters including vitrinite particles. The modified Freundlich sorption capacities (logK^′_f and logK^′_foc) are very close for the sorption of the four solutes by the isolated NOM and the original sand, respectively. Isotherm non-linearity (n value) and hysteric behaviors are related to solute molecular properties (e.g. K_ow and molecular size). Kerogen encapsulated by inorganic matrices in the original aquifer may not be accessed fully by solutes. The larger the hydrophobic organic chemical (HOC) (hydrophobic organic contaminant) molecule is, the lower accessibility of the HOC to kerogen. This study disputes widely held hypothesis that sorption to mineral surfaces may play a major role in the overall sorption by low TOC (e.g. 0.1% by mass) geomaterials such as Borden sand. It also demonstrates the importance of the condensed NOM domain, even at very low contents, in the sorption and desorption hysteresis of HOCs in groundwater systems.     

Relationship between metabolic enzyme activities and bioaccumulation kinetics of PAHs in zebrafish (Danio rerio)

Many studies have investigated bioaccumulation and metabolism of polycyclic aromatic hydrocarbons (PAHs) in aquatic organisms. However, lack of studies investigated both processes simultaneously, and the interaction between these two processes is less understood so far. This study investigated the bioaccumulation kinetics of PAHs and metabolic enzyme activities, including total cytochrome P450 (CYPs) and total superoxide dismutase (T-SOD), in zebrafish. Mature zebrafish was exposed to the mixture of phenanthrene and anthracene under constant concentration maintained by passive dosing systems for 16 days. The results showed that PAH concentrations in zebrafish experienced a peak value after exposure for 1.5 days, and then decreased gradually. The bioaccumulation equilibrium was achieved after exposure for 12 days. Both of the uptake rate constants (k_u) and the elimination rate constants (k_e) decreased after the peak value. The variation of PAH concentrations and metabolic enzyme activities in zebrafish had an interactive relationship. CYPs and T-SOD activities increased initially with the increase of PAH concentrations, but decreased to the lowest state when PAH concentrations reached the peak value. When the bioaccumulation equilibrium of PAHs was achieved, CYPs and T-SOD activities also reached the steady state. In general, CYPs and T-SOD activities were activated after exposure to PAHs. The decrease of PAH concentrations in zebrafish after the peak value may be attributed to the great drop of k_u and the variation of CYPs activities. This study suggests that an interactive relationship exists between bioaccumulation kinetics of PAHs and metabolic enzyme activities in aquatic organisms.