The sorption of polycyclic aromatic hydrocarbons in Zegrzyńskie Lake

The sorption of polycyclic aromatic hydrocarbons in aquatic sediments from Zegrzyńskie Lake was examined. Batch experiment was performed in order to determine sorption efficiency in different kinds of sediments from Zegrzyńskie Lake. Five polycyclic aromatic hydrocarbons (phenanthrene, fluoranthene, pyrene, chrysene benzo[a]pyrene) were chosen to this experiment and sorption process was examined on seven sediments of different properties. Chosen hydrocarbons are of different structure of molecule and different chemical and physical properties. Concentrations of polycyclic aromatic hydrocarbons in aquatic sediments and in water phase were measured in the following order: extraction with dichloromethane, concentration on rotary evaporator, silica gel clean up, n-hexane elution, concentration on rotary evaporator and in vials, GC/MS analysis. Chemical composition of aquatic sediments were examined using methods for sewage sludge and soils analysis. In every sediment concentrations of PAHs, organic matter and organic: carbon, phosphorus, nitrogen and sulphur were measured. Also fractional analysis of sediments was made. Isotherms of sorption were measured for these sediments and compounds. Equations of these isotherms were performed and were used in order to find relationships between sorption efficiency and sediments composition. Depending on sediment properties and composition different concentrations of polycyclic aromatic hydrocarbons were found in solid phase. Sediments of high quantities of organic matter and small particles were the best sorbents for PAHs. Fluoranthene, pyrene and chrysene were efficiently sorbed in sediments of high concentration of organic matter. And efficiency of phenanhrene and benzo[a]pyrene sorption were better in sediments with high quantity of organic sulphur.     

Atrazine and metribuzin sorption in soils of the Argentinean humid pampas

Laboratory studies were conducted to determine the influence of surface and subsurface properties of three representative soils of the humid pampas of Argentina on atrazine and metribuzin sorption. Atrazine and metribuzin sorption isotherms were constructed for each soil at four depths. Sorption affinity of herbicides was approximated by the Freundlich constant (K(f)), distribution coefficient (Kd), and the normalized Kd based on organic carbon content (K(oc)). Multiple regression of the sorption constants against selected soil properties indicated that organic carbon content (OC) and silt were related positively and negatively, respectively, to atrazine K(f) coefficient (r2 = 0.93), while Kd coefficient of atrazine was related positively to organic carbon content and negatively to both silt and cation exchange capacity (CEC) (r2 = 0.96). For metribuzin, only organic matter content was related positively to Kr coefficient (r2 = 0.51). Lower K(f) values for atrazine were obtained for all soils with increasing depth, indicating lesser sorption at greater depths. Metribuzin sorption was quite similar across all depths. Sorption constant K(f) of atrazine ranged from 2.06 to 7.82, while metribuzin K(f) values ranged from 1.8 to 3.52 and were lower than atrazine for all soils and depths, indicating a greater leaching potential across the soil profile.     

Sorption of acetochlor, S-metolachlor, and atrazine in surface and subsurface soil horizons of Argentina

Understanding herbicide sorption within soil profiles is the first step to predicting their behavior and leaching potential. Laboratory studies were conducted to determine the influence of surface and subsurface soil properties on acetochlor, atrazine, and S-metolachlor sorption. Soil samples were taken from horizons A, B, and C of two loamy soils of the humid pampas of Argentina under no-till management; horizon A was divided into two layers, A(0) (0-5 cm) and A(1) (5 cm to the full thickness of an A horizon). Sorption isotherms were determined from each sampled horizon using the batch equilibrium method and seven concentrations (0, 0.1, 0.5, 2.0, 5.0, 10.0, and 20.0 mg?L(-1)). Sorption affinity of herbicides was approximated by the Freundlich equation. The sorption strength K(f) (mg(1 - 1/n) kg(-1) L(1/n) ) over the soils and horizons studied followed the order S-metolachlor (16.51-29.19)?>?atrazine (4.85-12.34) ≥ acetochlor (5.17-11.97), which was closely related to the hydrophobicity of herbicides expressed as octanol-water partition coefficient (K(OW) ). The K(f) values of the three herbicides were positively correlated with soil organic carbon, with a significance of p < 0.01. Values of K(f) for the three herbicides decreased with depth in the two soils, indicating greater sorption onto surficial soil horizons and possibly a delayed transport toward subsurface soils and subsequent pollution of groundwater.     

Degradation and persistence of metolachlor in soil: effects of concentration,soil moisture,soil depth,and sterilization

The present study evaluated the influence of soil depth, soil moisture, and concentration on the persistence and degradation of metolachlor in soil. Greater percentages of metolachlor persisted in subsurface soils than in surface soil regardless of the soil moisture or initial herbicide concentration. Larger quantities of bound residues and extractable degradation products were found in the surface soils as a result of the increased soil sorption and biodegradation of metolachlor associated with the surface soil, which had more organic matter. Saturated soil favored the dissipation of metolachlor and the formation of soil-bound residues. Significantly greater quantities of a dechlorinated metabolite were measured in the saturated surface soil compared to the unsaturated soil. Mineralization of metolachlor to CO2 and volatilization of metolachlor or metolachlor degradates was minimal in surface and subsurface soils at both soil moistures and herbicide concentrations. Increased metolachlor concentrations did not inhibit microbial activity; however, the greater rate of application did result in the reduced percentage of applied [14C]metolachlor that was bound to surface or subsurface soil. A significant reduction in the quantity of extractable metolachlor degradates and unextractable soil-bound residues in sterile soil revealed the significance of biodegradation to the dissipation of metolachlor in soil.     

Modeling biphasic sorption and desorption of hydrophobic organic contaminants in sediments

A model was developed to predict biphasic sorption and desorption of hydrophobic organic compounds in contaminated sediments. The model was based on relatively rapid porous diffusion in amorphous organic carbon and slow solid-phase diffusion in condensed-phase organic carbon. The model was used to simulate measured solid-fluid phase desorption (rates and pore-water concentrations) for four polycyclic aromatic hydrocarbons exhibiting a range of hydrophobicities (phenanthrene, anthracene, pyrene, and benzo[a]pyrene) in two field-contaminated sediments from Utica Harbor (Utica, NY, USA) and Rouge River (Detroit, MI, USA). Pore-water concentrations have been related to bioavailability, indicating the potential usefulness of the model to predict bioavailability. Key model parameters included the fraction of condensed-phase carbon (estimated by combustion at 375 degrees C), partition coefficient to the condensed-phase carbon (estimated by desorption measurements on coal-like particles physically separated from Utica Harbor sediments), and diffusivity and ratio of volume to surface area of the condensed-phase organic matter (fitted to measured desorption data on both sediments and for the measured polycyclic aromatic hydrocarbons). Best fit for the diffusion coefficient in the condensed-phase organic matter was 8.5 x 10(-20) m2/s, and ratio of volume to surface area was 2 microm. These parameters estimated measured pore-water concentrations of all polycyclic aromatic hydrocarbons in both sediments with an average error of 46% and a correlation coefficient of 0.76 and the fast-desorbing fractions (as measured by the fraction removed with a nonpolar polymeric sorbent XAD-2) with an average error of approximately 30% and a correlation coefficient of 0.54 (14% and 0.76, respectively, for all but benzo[a]pyrene). Modeling results were relatively insensitive to the two fitted parameters, with changes of an order of magnitude or more being required to affect the correlation between the model and observations significantly.     

Sorption of chlorophenolates in soils and aquifer and marine sediments

This article describes the sorption behavior of 3 hydrophobic ionizable chlorophenols-2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, and pentachlorophenol-in different types of natural sorbents. A series of experiments was carried out with 11 topsoil samples, 9 aquifer sediments, and 12 marine sediments differing in pH, organic-matter content, and mineral composition and presumably also in type of organic matter due to their differing origins. Ionized forms of chlorophenols dominated in almost all sorption experiments. Freundlich isotherm coefficients K(f) and 1/n, as well as organic-matter sorption coefficient (log K(om)) and free-energy change (DeltaG(o)), were calculated for all 3 compounds in all sorbents. The sorption intensity of predominantly ionized chlorophenols increased linearly with the increase of sorbent organic-matter content and decreased with the increasing sorbent pH. Different sorption behavior of all 3 compounds in marine sediments with respect to topsoils and aquifer sediments was indicated by significant differences in K(f) and 1/n coefficients as well as in log K(om) and DeltaG(o) values. The highest K(f) and log K(om) values were obtained for sorption of chlorophenolic compounds in topsoils and the lowest in marine sediments, although both groups of sorbents had similar organic-matter content. The 1/n coefficient, reflecting the isotherm nonlinearity, was considerably lower than unity for all compounds in almost all sorbents. The most significant deviation of sorption isotherms from linearity was observed in marine sediments. Only marine sediments showed a linear increase in sorption intensity of all 3 compounds with the increase in sorbent-specific surface area. These results pointed to a different mechanism of sorption in marine and terrestrial sorbents and confirmed that the capacity of sorption was related to amount as well as type and origin of organic matter.     

Pyrethroid sorption to Sacramento River suspended solids and bed sediments

Sorption of pyrethroid insecticides to solid materials will typically dominate the fate and transport of these hydrophobic compounds in aquatic environments. Batch reactor isotherm experiments were performed with bifenthrin and λ-cyhalothrin with suspended material and bed sediment collected from the Sacramento River, California, USA. These batch reactor experiments were performed with low spiking concentrations and a long equilibration time (28?d) to be more relevant to environmental conditions. Sorption to suspended material and bed sediment was compared to examine the role of differential sorption between these phases in the environmental transport of pyrethroids. The equilibrium sorption data were fit to the Freundlich isotherm model and fit with r(2) >?0.87 for all experiments. Freundlich exponents ranged from 0.72?±?0.19 to 1.07?±?0.050, indicating sorption nonlinearity for some of the experimental conditions and linearity for others over the concentration range tested. The Freundlich capacity factors were larger for the suspended solids than for the bed sediments, and the suspended material had a higher specific surface area and higher organic carbon content compared to the bed sediment. Calculated organic carbon-normalized distribution coefficients were larger than those previously reported in the literature, by approximately an order of magnitude, and ranged from 10(6.16) to 10(6.68) at an equilibrium aqueous concentration of 0.1?μg/L. Higher than expected sorption of pyrethroids to the tested materials may be explained by sorption to black carbon and/or mineral surfaces.     

Sorption of phenanthrene and atrazine by plant cuticular fractions

Several studies have shown selective preservation of plant cuticular materials in soils. However, very little is known about their function as sorbents for the hydrophobic organic contaminants (HOCs) in the soil. In this study, we investigated the sorption and desorption of phenanthrene and atrazine by cuticular fractions of pepper (bulk, dewaxed, nonsaponifiable, and nonhydrolyzable) to better understand the sorptive activity of cuticular matter in soils. The bulk and dewaxed cuticles exhibited carbon-normalized distribution coefficients (Koc) for phenanthrene and atrazine in the range of that reported for soil humic substances, although both samples were rich in aliphatic structures. No hysteresis was observed in the desorption isotherms of either solute. The nonhydrolyzable residue exhibited a very high Koc value for atrazine, whereas the nonsaponifiable sample be exhibited the lowest Koc value for both sorbates. Based on solubility parameter data, it is suggested that the nonsponifiable sample be considered an intermediate between the physical and chemical mixture of pectin and cutan/lignin-like fractions, whereas the dewaxed cuticle is a chemical blending of cutin and pectin. The n-hexane-normalized sorption data suggest that the pepper cuticle can interact specifically with atrazine. This study leads to the conclusion that the contribution of aliphatic-rich plant biopolymers to the sorption of HOCs can be significant because of their preservation and accumulation in soils.     

Differential roles of humic acid and particulate organic matter in the equilibrium sorption of atrazine by soils

Recent studies have indicated that soil organic matter (SOM) may consist of physically and chemically different fractions, including particulate organic matter (POM), such as black carbon and unburned coal materials. The present study examined the differential roles of three different SOM fractions isolated from a peat and a topsoil in the equilibrium sorption of the herbicide atrazine (ATZ). The SOM fractions isolated from the two samples included humic acids (HAs), base-extracted humin (HM), and POM after demineralization of HM. A batch technique was employed to measure both the nonequilibrium ATZ sorption on the original and HA samples and the equilibrium ATZ sorption and desorption. The results showed that the phase-distribution relationships measured under nonequilibrium conditions were more linear and had lower sorption-capacity parameters compared with their respective isotherms measured under equilibrium conditions. The sorption isotherms were variously nonlinear, with POM exhibiting the greatest organic carbon-normalized sorption capacity. There existed apparent sorption-desorption hysteresis for each sorbent-sorbate system. It appeared that the extracted HAs could facilitate hydrolysis of ATZ when the reaction time extended to 4 d or longer. The equilibrium sorptive behavior of the HAs therefore was not examined. The present study indicated that both original samples showed lower organic carbon-normalized sorption distribution coefficients compared with their respective SOM fractions, suggesting that a fraction of sorption sites in soil aggregates were not accessed by ATZ.     

Assessing the biological relevance of exposing freshwater organisms to atrazine and molinate in environmentally realistic exposure test systems

Assessing the toxicity of chemicals in treated laboratory water may not accurately represent the toxicity of chemicals in natural aquatic systems. In natural water, dissolved organic matter, suspended particulate matter, and sediment play key roles in the sorption of contaminants from the water. Our previously published series of papers illustrated that the presence of sediment in aquatic toxicity testing systems significantly (p < 0.05) reduced the bioavailability of the herbicides atrazine and molinate to five Australian freshwater organisms. It is not clear whether the reduced bioavailability means that the trigger values (TVs) in the current Australian and New Zealand water quality guidelines, which are calculated using toxicity data from water-only toxicity tests, provide appropriate environmental protection. Several new sets of TVs were derived in the present study and were compared to each other and to the current Australian and New Zealand TVs for atrazine and molinate. The current Australian and New Zealand TVs for atrazine and molinate provided appropriate protection to Australian freshwater species. Australian freshwater species have a sensitivity distribution similar to those of overseas species to atrazine and molinate.     

Shake-flask test for determination of biodegradation rates of (14)C-labeled chemicals at low concentrations in surface water systems

A simple shake-flask surface water biodegradability die away test with (14)C-labeled chemicals added to microgram per liter concentrations (usually 1-100 microg/L) is described and evaluated. The aim was to provide information on biodegradation behavior and kinetic rates at environmental (low) concentrations in surface water systems. The basic principle of measurement was to determine evolved CO(2) indirectly from measurements of total organic activity in subsamples after stripping off their content of CO(2). Used with surface water alone the test simulates a pelagic environment and amended with sediments (0.1-1 dry weight/L) the test is intended to simulate a water environment with suspended solids (e.g., resuspended sediments). A protocol of the test used with the (14)C technique or with specific chemical analysis was recently developed by the International Organization for Standardization. Practical experience with the method is presented for a set of reference substances. These substances could be ranked in five groups of decreasing biodegradability: aniline>p-nitrophenol, 2, 4-dichlorophenoxyacetic acid>4-chloroaniline>maleic hydrazide, pentachlorophenol>atrazine. It was found that degradation rates and lag periods varied considerably among sampling sites and sometimes also among samples from the same site. No significant correlation could be established between degradation rates and microbial biomass estimates. Even small portions of added sediments greatly enhanced biodegradation of the absorbable compound pentachlorophenol, probably by providing sites for microbial attachment. Repeated tests indicated consistent degradation behavior for the readily degradable substances, whereas degradation sometimes stopped or failed with the more recalcitrant substances. A preadaptation step involving regular reinoculation with freshly collected surface water could, however, overcome the problems of false-negative results.     

Partitioning and matrix-specific toxicity of bifenthrin among sediments and leaf-sourced organic matter

Synthetic pyrethroids readily partition from the aqueous to the solid phase in aquatic systems. Previous work has focused on pyrethroid partitioning to sediment matrices. Within many aquatic systems, however, other carbon-containing materials are present and can be critically important to certain invertebrate species and ecosystem functioning. For example, some invertebrates readily process leaf material, and these processes may represent an additional route of contaminant exposure. To our knowledge, estimates for partitioning of pyrethroids to these nondissolved organic matter matrices and associated toxicity have not been examined. The objectives of the present study were to examine variation in organic carbon (OC)-based partition coefficient (K(OC)) among three size fractions of particulate organic matter from sugar maple (Acer saccharum) leaf litter and sediments for the pyrethroid insecticide bifenthrin and to examine variation in toxicity to Hyalella azteca among bifenthrin-bound organic matter matrices and sediment. Log K(OC) of [(14)C]bifenthrin was greatest within sediment (6.63+/-0.23; mean +/- standard deviation throughout) and lowest in coarse particulate leaf material (4.86+/-0.03). The H. azteca median lethal concentration was 0.07, 0.11, and 0.15 microg/g OC for leaf material, sediment, and a 50% mix of leaf and sediment, respectively. Nonoverlapping 95% confidence intervals occurred between the leaf treatment and the leaf-sediment treatment. This pattern was supported in an additional experiment, and at 0.22 microg/g OC, H. azteca survival was greater in the leaf-sediment mixture than in sediment or in leaf material alone (F=29.5, p<0.0001). In systems that contain sediment and leaf material, both greater partitioning of bifenthrin to the sediment fraction and preferential use of leaf substrates may drive H. azteca survival.     

Development of a coupled metal speciation-fate model for surface aquatic systems

A coupled metal transport and speciation model (TRANSPEC) has been developed for surface aquatic systems that explicitly considers the influence of metal speciation on fate. The TRANSPEC, which is general to most metal and surface aquatic systems, is constructed by sequentially coupling the speciation/complexation module (in this application MINEQL+) with the fugacity/aquivalence approach for the fate calculations. This model formulation increases the mechanistic detail, predictive power, and fidelity to reality of current fugacity-aquivalence fate models for metals by estimating aqueous speciation and complexation, rather than relying on empirically derived partition coefficients. A pseudo-steady state version of TRANSPEC was used to simulate Zn dynamics in Ross Lake (Flin Flon, MB, Canada) that received elevated metal and organic matter inputs for over 50 years. Field studies revealed that ZnS forms soluble ZnL, Zn2+, and ZnSO4(0) increasing pore water concentrations when surficial sediments turn oxic during fall. The model results for three seasonal scenarios suggest that Zn remobilization is driven by resuspension of insoluble ZnS and the contribution of diffusion is negligible, even during fall when ZnS dissolves to increase the concentration of soluble species under oxic conditions in the sediments. The low diffusive flux is due to the binding of Zn to colloidal dissolved organic matter (DOM) for which sediment-water diffusion is relatively slow, a result that was obtained as a result of considering metal speciation in the fate calculations.     

Effect of sediment on the fate of metolachlor and atrazine in surface water

In aquatic environments, pesticides can partition between the dissolved phase and particulate phase depending on the type of suspended sediment present and the physical and chemical properties of the pesticides and water. Particulate matter and sediment can alter the bioavailability of contaminants to organisms and therefore influence their toxicity and availability for microbial degradation. Experiments were conducted to determine the degradation of atrazine (6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2.4-diamine) and metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(methooxyprop-2-yl)acetamide) in surface water, and to evaluate the contribution of sediment to their dissipation. Sediment significantly reduced concentrations of atrazine and metolachlor in the surface water as a result of greater degradation, evident by increased quantities of degradates in the surface water, and the partitioning of the herbicide or herbicide degradates in the sediment. First-order 50% dissipation time (DT50) values for atrazine and metolachlor were 42 and 8 d in the surface water-sediment incubation systems, which were almost four times less than the DT50s calculated for the sediment-free systems. The results of this research illustrate the importance of sediment in the fate of pesticides in surface water. Greater comprehension of the role of sediment to sequester or influence degradation of agrichemicals in aquatic systems will provide a better understanding of the bioavailability and potential toxicity of these contaminants to aquatic organisms.     

Sorption of Chlorophenolates in Soils and Aquifer and Marine Sediments

This article describes the sorption behavior of 3 hydrophobic ionizable chlorophenols—2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, and pentachlorophenol—in different types of natural sorbents. A series of experiments was carried out with 11 topsoil samples, 9 aquifer sediments, and 12 marine sediments differing in pH, organic-matter content, and mineral composition and presumably also in type of organic matter due to their differing origins. Ionized forms of chlorophenols dominated in almost all sorption experiments. Freundlich isotherm coefficients K_f and 1/n, as well as organic-matter sorption coefficient (log K_om) and free-energy change (G^o), were calculated for all 3 compounds in all sorbents. The sorption intensity of predominantly ionized chlorophenols increased linearly with the increase of sorbent organic-matter content and decreased with the increasing sorbent pH. Different sorption behavior of all 3 compounds in marine sediments with respect to topsoils and aquifer sediments was indicated by significant differences in K_f and 1/n coefficients as well as in log K_om and G^o values. The highest K_f and log K_om values were obtained for sorption of chlorophenolic compounds in topsoils and the lowest in marine sediments, although both groups of sorbents had similar organic-matter content. The 1/n coefficient, reflecting the isotherm nonlinearity, was considerably lower than unity for all compounds in almost all sorbents. The most significant deviation of sorption isotherms from linearity was observed in marine sediments. Only marine sediments showed a linear increase in sorption intensity of all 3 compounds with the increase in sorbent-specific surface area. These results pointed to a different mechanism of sorption in marine and terrestrial sorbents and confirmed that the capacity of sorption was related to amount as well as type and origin of organic matter.     

Shake-Flask Test for Determination of Biodegradation Rates of C-Labeled Chemicals at Low Concentrations in Surface Water Systems

A simple shake-flask surface water biodegradability die away test with ¹⁴C-labeled chemicals added to microgram per liter concentrations (usually 1–100 μg/L) is described and evaluated. The aim was to provide information on biodegradation behavior and kinetic rates at environmental (low) concentrations in surface water systems. The basic principle of measurement was to determine evolved CO₂ indirectly from measurements of total organic activity in subsamples after stripping off their content of CO₂. Used with surface water alone the test simulates a pelagic environment and amended with sediments (0.1–1 dry weight/L) the test is intended to simulate a water environment with suspended solids (e.g., resuspended sediments). A protocol of the test used with the ¹⁴C technique or with specific chemical analysis was recently developed by the International Organization for Standardization. Practical experience with the method is presented for a set of reference substances. These substances could be ranked in five groups of decreasing biodegradability: aniline>p-nitrophenol, 2,4-dichlorophenoxyacetic acid>4-chloroaniline>maleic hydrazide, pentachlorophenol>atrazine. It was found that degradation rates and lag periods varied considerably among sampling sites and sometimes also among samples from the same site. No significant correlation could be established between degradation rates and microbial biomass estimates. Even small portions of added sediments greatly enhanced biodegradation of the absorbable compound pentachlorophenol, probably by providing sites for microbial attachment. Repeated tests indicated consistent degradation behavior for the readily degradable substances, whereas degradation sometimes stopped or failed with the more recalcitrant substances. A preadaptation step involving regular reinoculation with freshly collected surface water could, however, overcome the problems of false-negative results.     

Biochemical ripening of dredged sediments. Part 2. Degradation of polycyclic aromatic hydrocarbons and total petroleum hydrocarbons in slurried and consolidated sediments

Ripening of polycyclic aromatic hydrocarbons (PAH) and total petroleum hydrocarbons (TPH) polluted dredged sediment can be considered as a bioremediation technique. Aerobic biodegradation of PAH and TPH was studied in five previously anaerobic-slurried sediments during a 350-d laboratory incubation experiment. In addition, oxygen penetration and degradation of PAH and TPH were studied in three consolidated (physically ripened) sediments. All experiments were conducted in the laboratory at 30 degrees C. A double exponential decay model could adequately describe PAH and TPH degradation kinetics in the slurried sediments. First-order degradation rate constants for the rapidly degradable fractions (12-58%) were approximately 0.13 and 0.058 d(-1) for PAH and TPH, respectively, whereas the rate constants for the slowly degradable fractions were approximately 0.36 x 10(-3) (PAH) and 0.66 x 10(-3) d(-1) (TPH). Rate constants for the rapidly and slowly degrading fractions have the same order of magnitude as the mineralization rate constants of the rapidly and slowly mineralizing organic matter (OM) fractions in the sediments. Oxygen uptake by degradation of PAH and TPH was negligible compared to the oxygen uptake by sulfur oxidation and OM mineralization. In consolidated sediments, PAH and TPH degradation was limited to the oxygenated part. Amounts of PAH and TPH that degraded in the oxygenated parts of the consolidated sediments during 21 d of incubation were similar to the amounts that degraded during 21 d in the slurried sediments.     

Degradation and sorption of selected organophosphate and carbamate insecticides in urban stream sediments

Monitoring studies show that urban surface streams in the United States are commonly contaminated with pesticides, and contamination by organophosphates and carbamates is of particular concern because of their aquatic toxicity. The degradation and sorption of four common organophosphate and carbamate insecticides were studied in urban creek sediments from southern California, USA. In sediment, malathion was quickly degraded under either aerobic or anaerobic conditions, with a half-life (t(1/2)) <3 d. Diazinon and chlorpyrifos were moderately persistent under aerobic conditions (t(1/2) = 14-24 d). However, persistence of chlorpyrifos increased significantly under anaerobic conditions, and t(1/2) was prolonged to 58 to 223 d. The greatest effect of redox potential was found with carbaryl. Although rapid dissipation occurred under aerobic conditions (t(1/2) = 1.8-4.9 d), carbaryl became virtually nondegradable under anaerobic conditions (t(1/2) = 125-746 d). The sorption coefficient consistently increased with time for all pesticides, and chlorpyrifos displayed greater sorption potential than the other pesticides. This study indicates that pesticides in sediment may become less available with time because of increased sorption, and pesticide persistence in sediment may vary greatly among compounds and with redox conditions. Under anaerobic conditions, long persistence may occur even for nonpersistent compounds.     

Electron paramagnetic resonance analysis of the distribution of a hydrophobic spin probe in suspensions of humic acids, hectorite, and aluminum hydroxide-humate-hectorite complexes

Until recently, there were no techniques capable of direct observation of the microscale locations where nonpolar organic compounds accumulate when associated with natural geosorbents. The ability of electron paramagnetic resonance (EPR) spectroscopy to monitor and elucidate directly the different molecular-scale environments of paramagnetic spin probes has been demonstrated lately in model soils, yet it remains untested in complex systems. In this general context, the present investigation was aimed at assessing the extent to which EPR could be used to monitor the sorption of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy benzoate (TEMPO benzoate), a hydrophobic spin probe, on a smectite (hectorite), two humic acids, and their complexes in the presence or absence of aluminum hydroxide. Results demonstrate that EPR is able to monitor easily adsorption on these sorbents in batch-style experiments. Distribution coefficient (Kd) values of 455.4 and 483.1 ml/g were found for the adsorption of TEMPO benzoate on hectorite-humic acids complexes, compared to respective Kd values of 46 and 147 ml/g predicted solely on the basis of the mass of humic acids present in the complexes. These observations confirm the significant role of hectorite for the sorption of hydrophobic compounds, together with humic acids, contrary to common belief that emphasizes the almost exclusive sorptive role of organic matter. In addition, for the first time, EPR is able to provide evidence that hydrophobic molecules in the presence of geosorbents can segregate in multimolecular clusters that are in equilibrium with aqueous probe concentrations below the probe's solubility threshold. Possible consequences of this clustering process in terms of the fate and transport of hydrophobic compounds in subsurface environments are discussed.     

Distinctive sorption mechanisms of soil organic matter and mineral components as elucidated by organic vapor uptake kinetics

Sorption kinetics and capacities of volatile organic compounds (VOCs) affect the remediation and fate of these pollutants in soils. The soil organic-mineral compositional heterogeneity complicates the transport and fate of VOCs in soils. The sorption kinetics of toluene vapor with two common soil components, kaolinite and humic acid, shows two distinct sorption patterns. Results with kaolinite are characteristic of surface adsorption, whereas results with humic acid are characteristic of solvation and partition effects. On soils, the kinetics of toluene vapor sorption show a two-stage sorption phenomenon. The first stage is reflective of surface adsorption (1-4 h to completion) and the second stage of much slower partitioning into soil organic matter, which was preceded by a lag phase (approximately 4 h) and took as long as 15 h for completion. The relative contributions of these two stages to soil uptake are quantifiable by two independent parameters, the soil organic fraction and the surface area. A better understanding of the effect of soil compositional heterogeneity on sorption kinetics and capacities facilitates our understanding of the prediction for the fate of organic contaminants in the environment.