The use of hard- and soft-modelling to predict radiostrontium solid-liquid distribution coefficients in soils

The solid-liquid distribution coefficient (K_d) is the parameter that governs the incorporation of contaminants in soils. Its estimation allows the prediction of the fate of contaminants in the short- and long-term after a contamination event. Here, the K_d of radiostrontium (K_d(Sr)), a radionuclide of significant environmental interest, was predicted by hard models, which are based on knowledge of the mechanisms governing its sorption, and by soft models based on Partial Least Squares (PLS), using a large data set with the main soil parameters. The two approaches were tested and compared for 30 soils in Spain. Correlations between the predicted and experimental values of K_d(Sr) obtained using hard- and soft-modelling showed slopes close to 1 and regression coefficients higher than 0.95, which confirms that both approaches are able to obtain satisfactory estimates for K_d(Sr) from soil parameters.     

The kinetic stability of colloid-associated plutonium: settling characteristics and species transformation

The colloid-associated plutonium-239, as the dominant species of Pu in natural environment, was formed through sorption of Pu onto in situ colloids. In case of chemical perturbations present in pore water, the fate and transport of Pu would be therefore impacted by changes in sorption affinity of Pu for the colloid surfaces. The present study reveals that colloidal ²³⁹Pu exhibited the kinetic stability in two respects. First, in situ colloids isolated from the vadose zone sediments at Lop Nor, when in contact with solutions of high ion concentrations or low pH, were significantly aggregated and then exhibited fast settling. Kinetics settling characteristics were described by the parameters, including settling index and characteristic time. Second, Pu dissociation from colloid surfaces occurred immediately after the introduction of Na⁺. However, the dissolved species was still unstable and had the potential for re-association with the fraction of colloids that had not settled out from the suspensions due to small size and then remained in suspension. This implies that Pu sorption sites on initial colloids were changed to the sites of suspended colloids.     

2,4-二氯苯酚在土壤中的吸附及其批实验与柱实验的分配系数比较

为了研究2,4-二氯苯酚在土壤中的吸附及比较其批实验与柱实验的分配系数Kd,开展了2,4-二氯苯酚的批实验（不同液固比条件下）和柱实验。通过分析结果可知,在批实验中,不同液固比条件下2,4-二氯苯酚达到平衡的时间类似,都在60～70 h,吸附动力学曲线符合伪二级动力学方程,吸附规律是：液固比越大,平衡吸附量增大,反应速率常数K2减小,初始吸附速率常数减小;Kd随液固比增大而降低,范围在2.91～2.12 L/kg。柱实验结果表明,2,4-二氯苯酚的贯穿曲线可以很好地用化学非平衡模型来拟合,通过模型拟合得到的Kd值要低于批实验的结果。该研究对表征2,4-二氯苯酚在环境中的行为、预测其对土壤和地下水的污染及其治理提供了依据。     

Uptake rate constants and partition coefficients for vapor phase organic chemicals using semipermeable membrane devices (SPMDs)

To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants (k_ua) and no SPMD air partitioning coefficient (K_sa) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining k_ua and K_sa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The k_uas were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07 m³ g^?1 d^?1. In cases where uptake was approaching equilibrium, K_sas were approximated. K_sa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean k_ua values (n = 3) of anthracene and p,p′-DDE at 0.96 and 1.57 m³ g^?1 d^?1 with relative standard deviations of 8.4% and 8.6% respectively.     

Effects of black carbon on bioturbation-induced benthic fluxes of polychlorinated biphenyls

It is unknown whether carbonaceous geosorbents, such as black carbon (BC) affect bioturbation by benthic invertebrates, thereby possibly affecting sediment-water exchange of sediment-bound contaminants. Here, we assess the effects of oil soot on polychlorinated biphenyl (PCB) mass transfer from sediment to overlying water, for sediments with and without tubificid oligochaeta as bioturbators. PCB levels were so low that toxicity to the oligochaeta played no role, whereas soot levels and binding affinity of PCBs to soot were so low that pore water PCB concentrations were not significantly affected by binding of PCBs to soot. This setup left direct effects of BC on bioturbation activity as the only explanation for any observed effects on mass transfer. Mass transfer coefficients (K_L) for benthic boundary layer transport were measured by a novel flux method using Empore™ disks as a sink for PCBs in the overlying water. For the PCBs studied (logK_ow 5.2-8.2), K_L values ranged from 0.2 to 2 cm × d⁻¹ in systems without tubificids. Systems with tubificids showed K_L values that were a factor of 10-25 higher. However, in the presence of oil soot, tubificids did not cause an increase in mass transfer coefficients. This suggests that at BC levels as encountered under field conditions, the mechanism for reduction of sediment-water transfer of contaminants may be twofold: (a) reduced mass transfer due to strong binding of the contaminants to BC, and (b) reduced mass transfer of contaminants due to a decrease in bioturbation activity.     

The residues, distribution, and partition of organochlorine pesticides in the water, suspended solids, and sediments from a large Chinese lake (Lake Chaohu) during the high water level period

The levels of organochlorine pesticides (OCPs) in the water, suspended solids, and sediments from Lake Chaohu during the high water level period were measured by a solid-phase extraction gas chromatograph–electron capture detector. The spatial distributions of the three phases and the water/suspended solids and sediment/water partition coefficients were analyzed. The results showed the following: (1) The mean contents of OCPs in the water, suspended solids, and sediments were 132.4?±?432.1 ng/L, 188.1?±?286.7 ng/g dry weight (dw), and 13.7?±?9.8 ng/g dw, respectively. The dominant OCP components were isodrin (85.1 %) for the water, DDTs (64.4 %) for the suspended solids, and both isodrin (48.5 %) and DDTs (31.8 %) for the sediments. (2) β-HCH was the primary isomer of HCHs in the water and sediments, and the proportions were 61.7 and 41.3 %; γ-HCH was the primary isomer in the suspended solids, accounting for 49.3 %; p,p′-DDT was the dominant content of DDTs in the water and suspended solids, whereas p,p′-DDD was the main metabolite of DDTs in the sediments. (3) The concentrations of contaminants in the water from the western lake were greater than those from the eastern lake, but the concentrations in the suspended solids from the western lake were less than those from the eastern lake. (4) There was no significant correlation between the water–suspended solids partition coefficient K _d and the n-octanol–water partition coefficient K _ow, and between the sediment–water organic-C weighted sorption coefficients K _oc and K _ow.     

Sorption of chlorinated solvents and degradation products on natural clayey tills

The sorption of chlorinated solvents and degradation products on seven natural clayey till samples from three contaminated sites was investigated by laboratory batch experiments in order to obtain reliable sorption coefficients (K_d values). The sorption isotherms for all compounds were nearly linear, but fitted by Freundlich isotherms slightly better over the entire concentration range. For chloroethylenes, tetrachloroethylene (PCE) was most strongly sorbed to the clayey till samples (K_d = 0.84-2.45 L kg⁻¹), followed by trichloroethylene (TCE, K_d = 0.62-0.96 L kg⁻¹), cis-dichloroethylene (cis-DCE, K_d = 0.17-0.82 L kg⁻¹) and vinyl chloride (VC, K_d = 0.12-0.36 L kg⁻¹). For chloroethanes, 1,1,1-trichloroethane (1,1,1-TCA) was most strongly sorbed (K_d = 0.2-0.45 L kg⁻¹), followed by 1,1-dichloroethane (1,1-DCA, K_d = 0.16-0.24 L kg⁻¹) and chloroethane (CA, K_d = 0.12-0.18 L kg⁻¹). This is consistent with the order of hydrophobicity of the compounds. The octanol-water coefficient (log K_ow) correlated slightly better with log K_d values than log K_oc values indicating that the K_d values may be independent of the actual organic carbon content (f_oc). The estimated log K_oc or log K_d for chlorinated solvents and degradation products determined by regression of data in this study were significantly higher than values determined by previously published empirical relationships. The site specific K_d values as well as the new empirical relationship compared well with calculations on water and soil core concentration for cis-DCE and VC from the Rugårdsvej site. In conclusion, this study with a wide range of chlorinated ethenes and ethanes - in line with previous studies on PCE and TCE - suggest that sorption in clayey tills could be higher than typically expected.     

Influence of contaminant burial depth on the bioaccumulation of PCBs and PBDEs by two benthic invertebrates (Monoporeia affinis and Marenzelleria spp.)

The bioaccumulation of buried polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) added to specific depths in sediment (2.0-2.5, 5.0-5.5 and 10.0-10.5 cm) was studied in two infaunal species with similar feeding habits (surface deposit-feeders) but different bioturbation modes. The deep-burrowing polychaetes Marenzelleria spp. (Mz) displayed up to 36 times higher tissue concentrations of buried (spiked) contaminants than the surface-dwelling biodiffusing amphipod Monoporeia affinis. The differences in bioaccumulation were most pronounced for less hydrophobic contaminants due to the bioirrigating activity of Mz. Contaminants buried at shallow depths displayed higher accumulation than more deeply buried contaminants. In contrast, the bioaccumulation of unspiked (native) contaminants with a uniform vertical distribution in the sediment was similar between the species. For Mz, the BSAFs increased with increased K_OW for the uniformly distributed contaminants, but decreased for the buried contaminants, which indicates that the dominant uptake routes of the buried contaminants can differ from the uniformly distributed contaminants. The surface sediment concentration of buried contaminants increased in Mz treatments, showing that Mz bioturbation can remobilize historically buried contaminants to the biologically active surface layer and increase the exposure for surface-dwelling species.     

Inferences About Radionuclide Mobility in Soils Based on the Solid/Liquid Partition Coefficients and Soil Properties

To assist transport modeling in assessments of the radiological impact of a geological repository for radioactive wastes, the mobility of various elements was studied in arable and wetland soils in the Forsmark region, Sweden. Pore water and total element contents were determined for five types of unconsolidated deposits (regolith), spanning a wide range of soil properties with respect to pH and organic matter content. Two soil depths were sampled to capture element mobility in regolith layers affected and unaffected by soil-forming processes. The solid/liquid partition coefficients (K _d values) for most elements varied significantly among regolith types. For most elements, the observed variations in K _d values could be explained by variations in soil properties. For many elements, mobility increased with decreasing soil pH. The results provide a significant addition of data on radionuclide retention in soils, taking account of soil properties and processes.     

Removal mechanisms and fate of insecticides in constructed wetlands

Constructed wetlands (CWs), along with other vegetative systems, are increasingly being promoted as a mitigation practice to treat non-point source runoff to reduce contaminants such as pesticides. However, studies so far have mostly focused on demonstrating contaminant removal efficiency. In this study, using two operational CWs located in the Central Valley of California, we explored the mechanisms underlying the removal of pyrethroids and chlorpyrifos from agricultural runoff water, and further evaluated the likelihood for the retained pesticides to accumulate within the CWs over time.In the runoff water passing through the CWs, pyrethroids were associated overwhelmingly with suspended solids >0.7 μm, and the sorbed fraction accounted for 38-100% of the total concentrations. The derived K_d values for the suspended solids were in the order of 10⁴-10⁵, substantially greater than those reported for bulk soils and sediments. Distribution of pyrethroids in the wetland sediments was found to mimic organic carbon distribution, and was enriched in large particles that were partially decomposed plant materials, and clay-size particles (<2 μm). Retention of suspended particles, especially the very large particles (>250 μm) and the very fine particles, is thus essential in removing pyrethroids and chlorpyrifos in CWs. Under flooded and anaerobic conditions, most pyrethroids and chlorpyrifos showed moderate persistence, with DT₅₀ values between 106-353 d. However, the retained pyrethroids were very stable in dry and aerobic sediments between irrigation seasons, suggesting a possibility for accumulation over time. Therefore, the long-term ecological risks of CWs should be further understood before their wide adoption.     

Sorption comparison between phenanthrene and its degradation intermediates, 9,10-phenanthrenequinone and 9-phenanthrol in soils/sediments

The degradation intermediates of phenanthrene (PHE) may have increased health risks to organisms than PHE. Therefore, environmental fate and risk assessment studies should take into considerations of PHE degradation products. This study compared the sorption properties of PHE and its degradation intermediates, 9,10-phenanthrenequinone (PQN) and 9-phenanthrol (PTR) in soils, sediments and soil components. A relationship between organic carbon content (f_OC) and single-point sorption coefficient (log K_d) was observed for all three chemicals in 10 soils/sediments. The large intercept in the log f_OC − log K_d regression for PTR indicated that inorganic fractions control PTR sorption in soils/sediments. No relationship between specific surface area and K_d was observed. This result indicated that determination of surface area based on gas sorption could not identify surface properties for PHE, PQN, and PTR sorption and thus provide limit information on sorption mechanisms. The high sorption and strong nonlinearity (low n values) of PTR in comparison to PHE suggested that the mobility of PTR could be lower than PHE. Increased mobility of PQN compared with PHE may be expected in soils/sediments because of PQN lower sorption. The varied sorption properties of the three chemicals suggested that their environmental risks should be assessed differently.     

Sorption of 1,2,4-trichlorobenzene and tetrachloroethene within an authigenic soil profile: Changes in Koc with soil depth

The sorption of 1,2,4-trichlorobenzene and tetrachloroethene was investigated in a series of well-controlled batch experiments, using authigenic soil materials from a profile extending to 2.5 m below ground surface. Batch experiment techniques were verified by study with both pulverized and unpulverized soil at different times of equilibration, using two widely different soil:water ratios, and at a wide range of aqueous concentration. Sorption isotherms were approximately linear, with sorption distribution coefficients (K_d) found to decrease roughly 100-fold down the soil profile. K_d decreased with depth to an extent greater than could be predicted on the basis of the only 10-fold decrease in natural solid organic matter (SOM) content and despite significantly higher specific surface area in the lower horizons. All base-extractable SOM in these deeper soil horizons was operationally defined as fulvic acid (FA), although there was also a significant fraction that was not extracted by the standard base technique. The lower K_d of the deeper soil horizons is believed to reflect a complex combination of (1) lower SOM content; (2) a more hydrophilic form of SOM; and (3) a more intimate association of the SOM with the mineral fraction, affecting its accessibility, sorptivity, or both. For the deeper horizons, an increase in overall K_d by more than 4-fold was observed on solids treated by either base extraction or H₂O₂ treatment, demonstrating that sorption to remaining soil components could be dramatically increased by fractional SOM removal and/or chemical alteration of the soil. A simple regression model that divides SOM into only two types (shallow and deep SOM) provides a reasonably good explanation of sorption in all seven horizons and suggests an order-of-magnitude variability in K_oc among surface soil and deeper horizons.     

Uptake and translocation of organophosphates and other emerging contaminants in food and forage crops

Emerging contaminants in wastewater and sewage sludge spread on agricultural soil can be transferred to the human food web directly by uptake into food crops or indirectly following uptake into forage crops. This study determined uptake and translocation of the organophosphates tris(1-chloro-2-propyl) phosphate (TCPP) (log K _ow 2.59), triethyl-chloro-phosphate (TCEP) (log K _ow 1.44), tributyl phosphate (TBP) (log K _ow 4.0), the insect repellent N,N-diethyl toluamide (DEET) (log K _ow 2.18) and the plasticiser N-butyl benzenesulfonamide (NBBS) (log K _ow 2.31) in barley, wheat, oilseed rape, meadow fescue and four cultivars of carrot. All species were grown in pots of agricultural soil, freshly amended contaminants in the range of 0.6–1.0 mg/kg dry weight, in the greenhouse. The bioconcentration factors for root (RCF), leaf (LCF) and seed (SCF) were calculated as plant concentration in root, leaf or seed over measured initial soil concentration, both in dry weight. The chlorinated flame retardants (TCEP and TCPP) displayed the highest bioconcentration factors for leaf and seed but did not show the same pattern for all crop species tested. For TCEP, which has been phased out due to toxicity but is still found in sewage sludge and wastewater, LCF was 3.9 in meadow fescue and 42.3 in carrot. For TCPP, which has replaced TCEP in many products and also occurs in higher residual levels in sewage sludge and wastewater, LCF was high for meadow fescue and carrot (25.9 and 17.5, respectively). For the four cultivars of carrot tested, the RCF range for TCPP and TCEP was 10–20 and 1.7–4.6, respectively. TCPP was detected in all three types of seeds tested (SCF, 0.015–0.110). Despite that DEET and NBBS have log K _ow in same range as TCPP and TCEP, generally lower bioconcentration factors were measured. Based on the high translocation of TCPP and TCEP to leaves, especially TCPP, into meadow fescue (a forage crop for livestock animals), ongoing risk assessments should be conducted to investigate the potential effects of these compounds in the food web.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Transport of reactive colloids and contaminants in groundwater: effect of nonlinear kinetic interactions

Transport of reactive colloids in groundwater may enhance the transport of contaminants in groundwater. Often, the interpretation of results of transport experiments is not a simple task as both reactions of colloids with the solid matrix and reactions of contaminants with the solid matrix and mobile and immobile colloids may be time dependent and nonlinear. Further colloid transport properties may differ from solute transport properties. In this paper, a one-dimensional model for coupled and contaminant in a porous medium (COLTRAP) is presented together with simulation results. Calculated breakthrough curves (BTC's) during contamination and decontamination show systematically the effect of nonlinear and kinetic interactions on contaminant transport in the presence of reactive colloids, and the effect of colloid transport properties that differ from solute transport properties. It is shown that in case of linear kinetic reactions, the rate of exchange of mobile and immobile colloids have a large impact on the shape of BTC's even if the solid matrix is saturated with respect to colloids. BTC's during the contamination and decontamination phase have identical shapes in this case. Moreover, the slow reactions of contaminants and colloids may lead to unretarded breakthrough of contaminants. Independent of reaction rates, nonlinear reactions lead to BTC's that are steeper during contamination than in the linear case. A characteristic aspect of nonlinear sorption is that shapes of BTC's differ during the contamination and decontamination phase. It has been observed that shapes of some of the simulated adsorption and desorption curves are similar as shapes found in experiments reported in literature. This stresses the importance of incorporating both kinetics and nonlinearity in models for coupled colloid and contaminant transport and the capability of COLTRAP to interpret experimental results. Finally, to figure out whether nonlinear processes play a role, it is very important to consider both contamination and decontamination in transport experiments.     

Tylosin Sorption to Silty Clay Loam Soils,Swine Manure,and Sand

The objectives of this study were to assess sorption and desorption of tylosin, a macrolide antimicrobial chemical used in swine, cattle, and poultry production, in three silty clay loam soils of South Dakota and compare soil sorption to sand and manure sorption. The silty clay loam soils, from a toposequence in eastern South Dakota, standardized sand samples, and swine manure were used in 24-h batch sorption studies with tylosin concentrations ranging from 25 to 232 μ mole/L. Desorption from soil was conducted over a four-day period. Partition coefficients, based on the Freundlich isotherm (K _f ) or K _d values, were calculated. K _f values for the silty clay loams were similar, not influenced by landscape position, and averaged 1350 with isotherm slopes ranging from 0.85 to 0.93. K _f values for sand were dependent on solution/sand ratios and pH, ranging from 1.4 to 25.1. K _d values of manure were dependent on the solution type and ranged from 840 L/kg with urine to about 175 L/kg when sorbed from water. Desorption of tylosin from each soil over the four-day period was < 0.2% of the amount added. The soils' high K _f values and low desorption amounts suggest that once tylosin is in these soils, leaching to lower depths may not occur. However, this does not preclude runoff with soil eroded particles. If tylosin reaches a sand aquifer, through bypass flow or other mechanism(s), movement in the aquifer most likely would occur.     

Sorption of 17α-ethinyl estradiol, bisphenol A and phenanthrene to different size fractions of soil and sediment

The potential for negative effects caused by endocrine disrupting chemicals (EDCs) release into the environment is a prominent concern and numerous research projects have investigated possible environmental fate and toxicity. However, their sorption behavior by size fractions of soil and sediment has not been systematically represented. The sorption of bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and phenanthrene (Phen) by different size fractions of soil and sediment were investigated. Sorption isotherms of EE2, BPA, and Phen by size fractions of soil (SL) and sediment (ST) were well fitted to the Freundlich model. The positive correlation between EE2, BPA and Phen sorption capacity (log K_d) of size fractions and their organic carbon (OC) content suggests that OC of size fractions in SL and ST should regulate sorption, while the surface area (SA) of size fractions may not account for sorption of EE2, BPA and Phen. Each size fraction of ST had higher sorption capacity (K_d or K_OC) of EE2 and BPA than that of SL due to their difference in the polarity of organic matter (OM) between terrestrial and aquatic sources. Sorption capacity logK_d for size fractions of SL and ST did not follow the order: clay > silt > sand due to the difference in OM abundance and composition between the size fractions. Large particle fractions of ST contributed about 80% to the overall sorption for any EE2, BPA, and Phen. This study was significant to evaluate size fractions of soil and sediment as well as their associated OM affecting EE2 and BPA sorption processes.     

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.