Partitioning and desorption behavior of polycyclic aromatic hydrocarbons from disparate sources

Contaminated sediments pose a unique challenge for risk assessment or remediation because the overlying water column may transport contaminants offsite or to ecological receptors. This research compares the behavior of polycyclic aromatic hydrocarbons (PAHs) on marine sediments from two sites. The first site was affected by shipping activities and the second was impacted by a creosote seep. Organic carbon:water partitioning coefficients (Koc values) were measured with three solutions. Desorption was measured using Tenax beads. PAHs from the ship channel had lower Koc values than those from the creosote facility. For example, the average logKoc value of ship channel pyrene was significantly lower than that of creosote facility pyrene (4.39 +/- 0.35 and 5.29 +/- 0.09, respectively, when tested in 5 mM calcium chloride). These results were consistent with the greater desorption of pyrene, phenanthrene and benzo(a)pyrene from the ship channel than from the creosote facility sediments. Organic compound desorption from sediments can be considered to be a two-stage process, with a labile fraction that desorbs quickly and a refractory fraction that desorbs much more slowly. In both sediments, more than 75% of the benzo(a)pyrene was found to have partitioned into the refractory phase. The amounts of phenanthrene and pyrene that partitioned into the refractory phase were lower. Linear correlations of logKoc with log(CR/CL) (where CR and CL are the fractions of the compound in the refractory and labile phases, respectively, at time zero) showed that partitioning measurements made with the US EPA's Toxicity Characteristic Leaching Procedure fluid (US EPA, 1996) most closely matched predictions of desorption behavior. The data imply that with a larger data set, it may be possible to relate simple partitioning measurements to desorption behavior. Partitioning measurements were used to predict water concentrations. Despite having higher concentrations of carcinogenic PAHs [cPAHs, the seven PAHs categorized by the US EPA (2004) as class B2 carcinogens], creosote facility sediments were predicted to produce lower aqueous concentrations of cPAHs. These results indicate that both sediment and contaminant characteristics will impact contaminant release from sediments.     

Study of pyrene biodegradation capacity in two types of solid media

Removal of pyrene, a representative PAH, was studied using laboratory tests in two different types of solid media: an organic matter collected on the surface of a vertical flow constructed wetland (VFCW) and a formulated clay silicate sand (inorganic matter). The aim of this study was to evaluate the capacity of pyrene biodegradation in these media in order to use them for treating run-off water. The sorption process, the kinetics of pyrene biodegradation and the influence of selected bacteria were also investigated. The sorption process was evaluated by adsorption isotherms and desorption kinetics using a batch equilibration method. The adsorption coefficient values of 28.8 and 2.1 for the organic and the inorganic matter respectively, confirmed the relationship of adsorption with organic carbon content. A small proportion of the sorbed pyrene was available for desorption (8% and 15% for the organic and the inorganic matter, respectively), indicating that sorption was partially irreversible, with the presence of hysteresis. For the formulated clay silicate sand inoculated with a specific bacteria (Mycobacterium sp.6PY1), selected for its ability to degrade PAHs, pyrene removal was complete in 32 days. With the organic matter, these values ranged from 40% to 95% for the different experiments, following a lag time of 3 weeks before observation of a significant degradation. Indigenous bacterial species in the organic medium had the metabolic capacity to degrade pyrene, and microbial populations pre-exposed to the PAH degraded pyrene faster than similar unexposed populations. Three metabolites of pyrene degradation by Mycobacterium were found. They accumulated in both organic and inorganic matter, indicating that the enzymes catalyzing them have slow kinetics.     

Modeling the sorption kinetics of divalent metal ions to hematite

The sorption kinetics of the divalent metals Zn, Co, Ni, and Cd to hematite were studied in single sorbate systems with high sorbate/sorbent ratios (from 1.67 to 3.33mol sorbate/mol sorption sites) in 10mM Na-piperazine N,N'-bis 2-ethane sulfonic acid (Na-PIPES) solution at pH 6.8. The experimental data showed a rapid initial sorption (half-time about 1min) followed by slower sorption that continued for 1-5 days. The sequence of fast to slow sorption kinetics was modeled by slow inner-sphere (IS) complexation in equilibrium with outer-sphere (OS) complexes. Although the OS reaction was fast and considered to be in equilibrium, the extent of OS complexation changed over time due to increased surface potential from the IS complexes. For example, the model showed that the dimensionless OS complexation function, K(os), decreased from 0.014 initially to 0.0016 at steady state due to sorption of 4x10(-5)M Zn(II) to 2gL(-1) hematite. Sorption rate constants, k(ads), for the various divalent metals ranged from 6.1 to 82.5M(-1)s(-1). Desorption rate constants, k(des), ranged from 5.2x10(-7) to 6.7x10(-5)s(-1). This study suggests that the conversion from OS to IS complex was the rate-determining step for the sorption of divalent metals on crystalline adsorbents.     

Partitioning of hydrophobic organic chemicals (HOC) into anionic and cationic surfactant-modified sorbents

Surfactant-modified sorbents have been proposed for the removal of organic compounds from aqueous solution. In the present study, one cationic (HDTMA) and three anionic (DOWFAX-8390, STEOL-CS330, and Aerosol-OT) surfactants were tested for their sorptive behavior onto different sorbents (alumina, zeolite, and Canadian River Alluvium). These surfactant-modified materials were then used to sorb a range of hydrophobic organic chemicals (HOCs) of varying properties (benzene, toluene, ethylbenzene, 1,2-dichlorobenzene, naphthalene, and phenanthrene), and their sorption capacity and affinity (organic-carbon-normalized sorption coefficient, K(oc)) were quantified. The HDTMA-zeolite system proved to be the most stable surfactant-modified sorbent studied because of the limited surfactant desorption. Both anionic and cationic surfactants resulted in modified sorbents with higher sorption capacity and affinity than the unmodified Canadian River Alluvium containing only natural organic matter. The affinities of the surfactant-modified sorbents (K(oc)) for most HOCs are lower than octanol/water partition coefficient (K(ow)) normalized to the organic carbon content (f(oc)) and the density of octanol (K(oc) octanol); naphthalene and phenanthrene are the exceptions to this rule.     

Adsorption, desorption and isotopic exchange of cadmium on illite: evidence for complete reversibility

Adsorption, desorption and isotopic exchange of Cd on illite clay have been studied at low Cd concentrations and low ionic strength. The results indicate that under the conditions of the experiments Cd sorption on illite is completely reversible. Long equilibration times (7–8 weeks) were shown to be essential because of slow desorption kinetics.     

Exploratory Analysis of the Effects of Particulate Characteristics on the Variation in Partitioning of Nonpolar Organic Contaminants to Marine Sediments

The partitioning of nonpolar organic contaminants to marine sediments is considered to be controlled by the amount of organic carbon present. However, several studies propose that other characteristics of sediments may affect the partitioning of contaminants. For this exploratory analysis, we measured 19 sediment characteristics from five marine sediments and 11 characteristics of humic acids extracted from the sediments. These characteristics included elemental composition, grain size, soot carbon, polarity indices and molar ratios. Each individual characteristic and combinations of these characteristics were then used to normalize partition coefficients (K_p) generated for three organic contaminants: lindane, fluoranthene and a tetrachlorinated biphenyl (PCB). A coefficient of variation (CV) was then calculated for each contaminant to determine which normalization characteristic (individually or in combination) resulted in the lowest variability in partitioning between study sediments. For lindane and the PCB, normalization by the amount of sediment organic carbon resulted in the lowest variability in partition coefficients with CVs of 16.2% and 37.7%, respectively. However, normalization of fluoranthene by silt content resulted in lower CVs than those generated by organic carbon normalization: 31.0% vs. 37.6%. Normalization of contaminants K_p's by combined values of sediment characteristics resulted in lower CVs but only by a few percent. Using humic acid characteristics, humic organic carbon reduced variability between sediments most effectively. But only the normalized fluoranthene values had a CV (i.e., 25.4%) lower than the one based on normalization by sediment characteristics. When combined, humic acid characteristics resulted in lower CVs than normalization by individual or combinations of sediment characteristics for fluoranthene and the PCB with CVs of 19.3% and 28.7%, respectively. This analysis indicates variability associated with the partitioning of some organic contaminants to marine sediments can be further reduced when normalization by sediment characteristics other than organic carbon are utilized.     

Sorbed atrazine shifts into non-desorbable sites of soil organic matter during aging

Soil-chemical contact time (aging) is an important determinant of the sorption and desorption characteristics of the organic contaminants and pesticides in the environment. The effects of aging on mechanism-specific sorption and desorption of atrazine were studied in soil and clay slurries. Sorption isotherm and desorption kinetic experiments were performed, and soil-water distribution coefficients and desorption rate parameters were evaluated using linear and non-linear sorption equations and a three-site desorption model, respectively. Aging time for sorption of atrazine in sterilized soil and clay slurries ranged from 2 days to 8 months. Atrazine sorption isotherms were nearly linear (r(2)>0.97) and sorption coefficients were strongly correlated to soil organic carbon content. Sorption distribution coefficients (K(d)) increased with increase in age in all five soils studied, but not for K-montmorillonite. Sorption non-linearity did not increase with increase in age except for the Houghton muck soil. Desorption profiles were well described by the three-site desorption model. The equilibrium site fraction (f(eq)) decreased and the non-desorbable site fraction (f(nd)) increased as a function of aging time in all soils. For K-montmorillonite, f(nd) approximately 0 regardless of aging, showing that aging phenomena are sorbent/mechanism specific. In all soils, it was found that when normalized to soil organic matter content, the concentration of atrazine in desorbable sites was relatively constant, whereas that in non-desorbable site increased. This, and the lack of aging effects on desorption from montmorillonite, suggests that sorption into non-desorbable sites of soil organic matter is primary source of increased atrazine sorption in soils during aging.     

Influence of algal and bacterial particulate organic matter on benzo[a]pyrene bioaccumulation in Daphnia magna

In order to better asses the influence of organic matter on the bioavailability of hydrophobic organic contaminants, the effect of algae and POM of bacterial origin on the bioaccumulation of benzo[a]pyrene in Daphnia magna was evaluated. The bioaccumulation was monitored with increasing concentrations of particulate organic matter (POM) and dissolved organic matter (DOM). In all experiments, the presence of POM greatly reduced the bioaccumulation of benzo[a]pyrene. The reduction was more pronounced in the presence of algae, for which we observed a 99%-reduction effect in the presence of 6 x10 (5) cell/mL (equivalent to 5.3 mg C/L). The bioaccumulation of benzo[a]pyrene was decreased by 49% by organic matter of bacterial origin at 4.7 mg C/L. Assuming that benzo[a]pyrene was partitioned between water, DOM and POM and supposing that D. magna accumulated free benzo[a]pyrene via respiration and POM-bond benzo[a]pyrene via ingestion, bioaccumulation data allowed to estimate the dietary uptake rate of benzo[a]pyrene as well as partitioning coefficients K(POC) and K(DOC). Despite the ingestion of contaminated particles, we could not observe any dietary uptake of benzo[a]pyrene in daphnids. We verified, as usually supposed, that the bioaccumulation of benzo[a]pyrene to D. magna occurs mainly via direct contact. Very high partitioning coefficients (log K(POC) between 5.2 and 6.2) were estimated. This study pointed out the great influence of biogenic organic matter on the fate and the bioavailability of benzo[a]pyrene in aquatic ecosystems.     

Decision support model for hazardous waste application rates at land treatment systems‡

A mathematical model is described which provides a rational approach for obtaining, organizing and evaluating the specific information needed for the determination of hazardous waste application on land treatment systems. The model is divided into five modules. These modules represent the principal mechanisms which are assumed to govern the fate of an organic hazardous material in the vadose zone. They are the following: loading conditions, degradation, advective transport, dispersive transport and sorption/desorption. The numerical algorithm for advective transport is described in some detail using a soil-water system as an example. The model is demonstrated for selected aro-matics found in a refinery waste sludge. Application of the model provides a methodology for predicting the behavior of hazardous constituents in soil systems and ranking chemicals according to their need to be controlled.     

Sorption and desorption behaviours of 2,4‐D and glyphosate in calcareous soil from Antalya,Turkey

2,4‐Dichlorophenoxyl acetic acid (2,4‐D) and glyphosate are used extensively as a herbicide in vicinity of Antalya, Turkey. Laboratory batch experiments were conducted to investigate the sorption isotherm and sorption‐desorption characteristics of 2,4‐D and glyphosate. Results indicated that degree of sorption of glyphosate was approximately 50 times higher than 2,4‐D (K_d= 34.43 vs. 0.66 L/Kg). The sorption of 2,4‐D and glyphosate was described by linear and rate‐limited processes for soil. Organic carbon content was most likely responsible for sorption behaviour of 2,4‐D and glyphosate. The rapid desorption can be attributed to soft carbon fraction (humic/fluvic acid and lipids) whereas slower desorption can be responsible by hard carbon fraction (black carbon, kerogen) of soils that led to chemically nonideal behaviour (hysteresis). Sorption of 2,4‐D was low due to most likely deactivation of organic carbon surfaces by excess carbonate fraction, whereas strong binding of glyphosate onto organic carbon causing high sorption behaviour.     

Prognose der Sorptionskinetik organischer Schadstoffe in heterogenem Aquifermaterial

A model for the simulation of kinetic sorption processes in heterogeneous aquifer material is presented. Sorption kinetics is responsible for the long persistence of many organic contaminants in the subsurface. Therefore, reliable model predictions of these processes are of major importance concerning, for instance, the design of efficient remediation strategies. The modeling approach presented here recognizes sorption kinetics as retarded diffusion within the intra-particle pore space and, in particular, takes into account the sedimentological and petrographical composition of the aquifer material. This is in accordance with results from laboratory experiments quantifying sorption/desorption processes. For solving the model equations a finite-difference scheme is applied which incorporates several features proven to be relevant in practical model applications (mass balance, flexible choice of boundary conditions, easy handling). The simulation results shown here focus on the impact of aquifer heterogeneity (lithological composition, grain size distribution) on sorption and desorption kinetics of organic contaminants. Furthermore, this approach can be straightforwardly coupled to existing software for simulating multi-dimensional solute transport.     

Retention of organophosphorous insecticides on a calcareous soil modified by organic amendments and a surfactant

Pesticides may affect soil quality since they are applied either directly to the soil or transported from the treated crops. Although the soil is able to partially retain environmental contaminants, the use of organic amendments, such as sewage sludge, peat or surfactants, may increase the retention in the upper soil layers, where the contaminants can be degraded and thus diminish their environmental fate. The effect of adding sewage sludge, peat and humic acids, together with a cationic surfactant to the soil, on the adsorption and desorption of organophosphorous insecticides has been studied. The results indicate that humic acids induce an adsorption increment of the pesticides, while peat and sewage sludge do not significantly affect pesticide adsorption at the dosage applied. The use of a cationic surfactant considerably enhances the insecticide retention. The increase was highest for the combined application of the surfactant and the humic acids. Desorption isotherms are inversely related to the adsorption behaviour, being higher for only soil, lower for soil added with carbon-rich amendments, and drastically reduced when the cationic surfactant is present. Concerning the insecticides, adsorption and desorption are related to their physicochemical properties.     

Geographically distributed classification of surface water chemical parameters influencing fate and behavior of nanoparticles and colloid facilitated contaminant transport

The current production and use of nanomaterials in consumer products have increased the concern about the possibility that these enter the rivers during their entire life cycle. Further, many aquatic contaminants undergo partitioning to the ubiquitous aquatic colloids. Here is presented the development of a set of European water types for environmental risk assessment of chemicals transported as nanovectors as is the case of environmental fate of manufactured nanoparticles and colloid-bound contaminants.     

Sorption of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) to synthetic resins

Methyl tert-butyl ether (MTBE) is a widely used gasoline oxygenate. Contamination of MTBE and its major degradation product tert-butyl alcohol (TBA) in groundwater and surface water has received great attention. However, sorption affinity and sorption mechanisms of MTBE and TBA to synthetic resins, which can be potentially used in removal of these contaminants from water, in passive sampling, or in enrichment of bacteria, have not been studied systemically. In this study, kinetic and equilibrium sorption experiments (single solute and binary mixtures) on four synthetic resins were conducted. The sorption affinity of the investigated sorbents for MTBE and TBA decreases in the order Ambersorb 563>Optipore L493>Amberlite XAD4>Amberlite XAD7, and all show higher sorption affinity for MTBE than for TBA. Binary experiments with o-xylene, a major compound of gasoline as co-contaminant, imply that all resins preferentially sorb o-xylene over MTBE or TBA, i.e., there is sorption competition. In the equilibrium aqueous concentration (Ceq) range (0.1-139.0 mg/L for MTBE, and 0.01-48.4 mg/L for TBA), experimental and modeling results as well as sorbent characteristics indicate that micropore filling and/or some other type of adsorption process (e.g., adsorption to specific sites of high sorption potential at low concentrations) rather than partitioning were the dominant sorption mechanisms. Optipore L493 has favourable sorption and desorption characteristics, and is a suitable sorbent, e.g., in bacteria enrichment or passive sampling for moderately polar compounds. However, for highly polar compounds such as TBA, Ambersorb 563 might be a better choice, especially in water treatment.     

A multi-component statistic analysis for the influence of sediment/soil composition on the sorption of a nonionic surfactant (Triton X-100) onto natural sediments/soils

The contents of soil/sediment organic carbon and clay minerals (i.e. montmorillonite, kaolinite, illite, gibbsite and 1.4 nm minerals) for 21 natural soil/sediment samples and the sorption of Triton X-100 on these samples were determined. A multi-component statistic analysis was employed to investigate the importance of soil/sediment organic matters and clay minerals on their sorption of Triton X-100. The sorption power of soil/sediment composition for Triton X-100 conforms to an order of montmorillonite>organic carbon>illite>1.4 nm minerals (vermiculite+chlorite+1.4 nm intergrade mineral)>kaolinite. The sorption of Triton X-100 on a montmorillonite, a kaolinite and a humic acid were also investigated and consistent with the result of multi-component statistic analysis. It is clear that the sorption of Triton X-100 on soils or sediments is the combined contribution of soil/sediment organic matters and clay minerals, which depended on both the contents of soil/sediment organic matters and the types and contents of clay minerals. The important influence of illite on the sorption of nonionic surfactants onto soils/sediments is suggested and demonstrated in this paper. Surfactants for aquifer remediation application may be more efficient for the contaminated soils/sediments that contain little clay minerals with 2:1 structure because of the less sorption of nonionic surfactants on these soils/sediments.     

pH dependence of steroid hormone--organic matter interactions at environmental concentrations

The interaction of estradiol, estrone, progesterone and testosterone with environmentally relevant concentrations of Aldrich humic acid, alginic acid and tannic acid was studied using solid-phase microextraction (SPME). Since bulk organic matter and certain hormones such as estradiol and estrone contain dissociable functional groups, the effect of pH on sorption was investigated as this will influence their fate and bioavailability. For humic acid and tannic acid, sorption was strongest at acidic pH when the bulk organic matter was in a non-dissociated form and decreased when they became partially negatively charged. At acidic and neutral pH the strength of partitioning was influenced by hormone functional groups content, with the strongest sorption observed for progesterone and estrone. At alkaline pH conditions, when the bulk organics were dissociated, sorption decreased considerably (up to a factor of 14), although the non-dissociated hormones testosterone and progesterone indicated greater sorption to humic acid at pH 10 compared to the partially deprotonated estradiol and estrone. This study demonstrates that SPME can be used to assess organic matter sorption behaviour of a selected range of micropollutants and at environmentally relevant organic matter concentrations.     

Comparison of the equilibrium sorption of five organic compounds to HDPE, PP, and PVC geomembranes

This experimental investigation quantified the sorption uptake of five commonly encountered organic groundwater contaminants, methyl tertiary-butyl-ether (MTBE), benzene, trichloroethylene (TCE), 1,2-dichorobenzene (1,2-DCB), and trinitrotoluene (TNT), to geomembranes made from high density polyethylene (HDPE), polypropylene (PP), and polyvinylchloride (PVC). The organic compounds were chosen to span a range of aqueous solubilities and chemical properties. The geomembranes tested in this study exhibited sorption capacities that were of similar magnitude for each of the contaminants tested, with the exception of 1,2-DCB to HDPE, which exhibited strong uptake in comparison to the other solute/sorbent combinations. In general, the PVC geomembrane demonstrated the highest sorption capacities, while the HDPE geomembrane demonstrated the lowest sorption capacities. Measured partitioning coefficients for the contaminant/geomembrane combinations ranged from S_gf<1 to 160, but most commonly had values between 10 and 75.     

Contaminant interactions with geosorbent organic matter: insights drawn from polymer sciences

This is a state-of-science review of interrelationships between the sorption/desorption behaviors and chemical structures of natural organic matter (NOM) matrices associated with soils, sediments and aquifer materials. It identifies similarities between these behavior-property interrelationships for natural geosorbents and those for synthetic organic polymers. It then invokes, with appropriate restrictions and modifications, several structure-function relationships that have been developed for synthetic polymers to explain the behavior of NOM matrices with respect to the sorption and desorption of hydrophobic organic contaminants (HOCs). Previous research regarding HOC sorption and desorption by different types of NOM and by synthetic polymers is summarized, and research requirements for further refinement of the NOM-polymer analogy are examined. The discussion focuses on structural and compositional heterogeneities that exist at the particle and aggregate scale, a scale at which homogeneity is commonly, and often improperly, assumed in the development of contaminant fate and transport models.     

Adsorption and desorption of polydimethylsiloxane, PCBs, cadmium nitrate, copper sulfate, nickel sulfate and zinc nitrate by river surface sediments

An investigation into the adsorption and desorption of polydimethylsiloxane, PCBs, cadmium nitrate, copper sulfate, nickel nitrate and zinc nitrate by river sediments was carried out using either a flow-through system or a semi-static system. The material balance in the sediment compartment could be explained by the equation, dCs/dT= K1Cw-K2Cs. The adsorption rate constants (K1), desorption rate constants (K2) and concentration factors (K1/K2) were calculated. For hydrophobic chemicals, the K1's were independent of water solubility, but the K2's were relatively related to water solubility. For both hydrophobic chemicals and heavy metals, the concentration factors per fraction organic carbon were similar to the soil sorption coefficients (Koc), expressed on a organic carbon basis.     

Development of a kinetic basis for bioavailability of sorbed naphthalene in soil slurries

The degradation of naphthalene in soil-slurry systems was studied using four different organisms and two soils. Organisms with zero-order, first-order, and Michaelis-Menten rates were selected. The soils had substantially different sorption distribution coefficients. Sorption and desorption was evaluated in abiotic soil-slurry systems. The desorption process was described by a model that accounts for equilibrium, rate-limited and non-desorbing sites. Biodegradation parameters were measured in soil-extract solutions. Bioavailability assays, inoculated soil slurries, were conducted and both liquid- and sorbed-phase naphthalene concentrations were measured over time. For the less sorptive soil, the results could be explained by sequential desorption and degradation processes. For the other soil, enhanced degradation was clearly observed for the organisms with first-order and Michaelis-Menten rates. Several explanations are explored for these observations including direct sorbed-phase degradation and the development of elevated substrate concentrations at the organism/sorbent interface. No enhancement was found for the organism with zero-order kinetics.