Influence of arsenate adsorption to ferrihydrite, goethite, and boehmite on the kinetics of arsenate reduction by Shewanella putrefaciens strain CN-32

The kinetics of As(V) reduction by Shewanella putrefaciens strain CN-32 was investigated in suspensions of 0.2, 2, or 20 g L(-1) ferrihydrite, goethite, or boehmite at low As (10 μM) and lactate (25 μM) concentrations. Experimental data were compared with model predictions based on independently determined sorption isotherms and rates of As(V) desorption, As(III) adsorption, and microbial reduction of dissolved As(V), respectively. The low lactate concentration was chosen to prevent significant Fe(III) reduction, but still allowing complete As(V) reduction. Reduction of dissolved As(V) followed first-order kinetics with a 3 h half-life of As(V). Addition of mineral sorbents resulted in pronounced decreases in reduction rates (32-1540 h As(V) half-life). The magnitude of this effect increased with increasing sorbent concentration and sorption capacity (goethite < boehmite < ferrihydrite). The model consistently underestimated the concentrations of dissolved As(V) and the rates of microbial As(V) reduction after addition of S. putrefaciens (～5 × 10(9) cells mL(-1)), suggesting that attachment of S. putrefaciens cells to oxide mineral surfaces promoted As(V) desorption and thereby facilitated As(V) reduction. The interplay between As(V) sorption to mineral surfaces and bacterially induced desorption may thus be critical in controlling the kinetics of As reduction and release in reducing soils and sediments.     

Critical evaluation of desorption phenomena of heavy metals from natural sediments

In natural sediments, the majority of heavy metal ions are generally associated with the solid phase. To become bioavailable, the metal ions must desorb from the solid. Numerous studies of heavy metals in sediments have suggested that sorption and desorption exhibit hysteresis (i.e., the two processes are not reversible), while other studies have suggested that desorption hysteresis does not exist. In this study, sorption/desorption hysteresis of lead (Pb) and cadmium (Cd) was evaluated over the following range of conditions: (i) desorption induced by replacing the supernatant liquid with contaminant-free electrolyte solution; (ii) desorption induced by lowering the solution pH with mineral acid; and (iii) desorption induced by sequestration with EDTA. Given the importance of dissolved organic and inorganic ligands in regulating heavy metal behavior in nature sediments, sorption/desorption experiments were conducted on both untreated and prewashed sediments. Prewashing treatment increases the sorption potential of Cd but not Pb. Desorption hysteresis is observed in both the untreated and the prewashed sediments using the replaced supernatant method, and the desorption hysteresis appears to increase with aging time. Hysteresis is not observed when desorption is initiated by lowering the solution pH. A large fraction of the sorbed heavy metal ions can be easily desorbed by EDTA; between 0.04 and 1.2 mmol/kg Cd and Pb ions are resistant to desorption.     

Metal ion sorption and desorption on zeolitized tuffs from the Nevada Test Site

Because of the hundreds of nuclear weapon tests conducted on the Nevada Test Site (NTS) during the Cold War, the migration of radionuclides and contaminants is a potential concern. The mobility of these compounds and our ability to remediate contaminated sites are controlled by sorption and desorption processes, which depend frequently on the nature of the contaminant, the mineralogy of the site, and the geochemical conditions. The sorption and desorption behavior of strontium (Sr) and lead (Pb), two metal cations with different chemistries, commonly found on nuclear test sites were studied. Strontium showed pH-independent and ionic-strength-dependent sorption, consistent with ion exchange processes at permanent charge sorption sites. The sorption uptake of Sr increased with decreasing ionic strength of background solution. Strontium desorption from the adsorbents was enhanced by increased background electrolyte concentration and was a function of background electrolyte composition. The fractional uptake of Pb was higher, compared to that of Sr, and was only pH dependent at the highest ionic strength used (1.0 M). This pH-dependent sorption behavior, consistent with formation of surface complexes at amphoteric surface hydroxyl sites or formation of surface precipitates, could explain the decreased Pb desorption, compared to that of Sr, especially at increased background electrolyte concentrations. Under conditions typical for the groundwater at the NTS (I = 0.003 M, pH = 8.0), both Pb and Sr are expected to bind strongly on tuffs with composition similar to the zeolitized tuffs used in this study. Any increase in the dissolved ion concentration of the groundwater, however, may result in, at least partial, release of Sr and enhanced Sr mobility.     

Influence of dissolved sodium and cesium on uranyl oxide hydrate solubility

The solubility of uranium-containing minerals can control the mobility of uranium in contaminated soil and groundwater. The identity and solubility of these minerals are strongly influenced by solution composition. The influence of dissolved sodium and cesium on the solubility of uranyl oxide hydrates has been investigated in a series of batch experiments conducted with synthetic metaschoepite ((UO2)8O2(OH)12 x 10H2O). During reaction of metaschoepite in NaNO3, CsNO3, and NaF solutions, an initial increase in the dissolved uranium concentration was followed by a decrease as uranium was incorporated into a secondary solid phase. Given sufficient reaction time, metaschoepite was completely transformed to a clarkeite-like sodium uranyl oxide hydrate or a cesium uranyl oxide hydrate that has not previously been described. These secondary solid phases exhibited X-ray diffraction patterns and Raman spectra that were distinct from those of the original metaschoepite. Dissolved uranium concentrations in equilibrium with the sodium and cesium uranyl oxide hydrates can be more than 2 orders of magnitude lower than those in equilibrium with metaschoepite. Initial changes in metaschoepite solubility may also result from particle growth induced by sodium and cesium incorporation into the solid phase.     

Effect of temperature on Cs+ sorption and desorption in subsurface sediments at the Hanford Site,U.S.A

The effects of temperature on Cs+ sorption and desorption were investigated in subsurface sediments from the U.S. Department of Energy Hanford Site. The site has been contaminated at several locations by the accidental leakage of high-level nuclear waste (HLW) containing 137Cs+. The high temperature of the self-boiling, leaked HLW fluid and the continuous decay of various radionuclides carried by the waste supernatant have resulted in elevated vadose temperatures (currently up to 72 degrees C) below the Hanford S-SX tank farm that have dissipated slowly from the time of leakage (1970). The effect of temperature on Cs+ sorption was evaluated through batch binary Cs(+)-Na+ exchange experiments on pristine sediments, while Cs+ desorption was studied in column experiments using 137Cs(+)-contaminated sediments. Cs+ adsorption generally decreased with increasing temperature, with a more apparent decrease at low aqueous Cs+ concentration (10(-10)-10(-6) mol/L). Cs+ desorption from the contaminated sediments increased with increasing temperature. The results indicated that the free energy of Na(+)-Cs+ exchange on the Hanford sediment had a significant enthalpy component that was estimated to be -17.87 (+/- 2.01) and -4.82 (+/- 0.44) kJ/mol (at 298 degrees C) for the high- and low-affinity exchange sites, respectively. Both Cs+ adsorption and desorption at elevated temperature could be well simulated by a two-site ion exchange model, with the conditional exchange constants corrected by the exchange enthalpy effect. The effect of temperature on Cs+ desorption kinetics was also evaluated using a stop-flow technique. The kinetics of desorption of the exchangeable pool (which was less than the total adsorbed concentration) were found to be rapid under the conditions studied.     

Pesticide sorption and desorption by lignin described by an intraparticle diffusion model

Lignin was used as a model compound for soil organic matter to gain insight into the mechanisms that control the kinetics of pesticide sorption and desorption. Hydrolytic lignin was immobilized in a matrix of alginate gel, and sorption-desorption experiments were undertaken with isoproturon. Sorption increased with time and was close to equilibrium after 14 days. Desorption was measured after sorption for different time intervals and for a number of successive desorption steps of different lengths. The results showed strong differences between the sorption and desorption isotherms. The ratio of sorbed to dissolved pesticide approached and even exceeded the equilibrium ratio, depending on the number of desorption steps and the length of each equilibration period. A numerical diffusion model was developed to describe radial diffusion into the lignin particles in combination with Freundlich sorption inside the particles. Key model parameters were adjusted to fit the sorption data, and the same parameters were then used to predict stepwise desorption. Desorption was well described by the model, which suggests that sorption and desorption were driven by the same mechanism and occurred at the same rate. The observed difference between the sorption and desorption isotherms could be fully explained by the nonattainment of equilibrium due to slow diffusion into and out of the lignin particles.     

Herbicide runoff along highways. 2. Sorption control

Controversy remains about the importance of nonlinear sorption isotherms, desorption rate limitations, and aging effects, collectively referred to as nonideal sorption processes, in controlling the fate and transport of organic contaminants. Herbicide runoff from highway soils represents a good test case for assessing the relative importance of nonideal sorption because runoff flow rates are often high, soil-water contacttimes are short, and significant time is available for contaminant aging after application. This study examines the sorption and desorption of five herbicides with a wide range of properties (isoxaben, oryzalin, diuron, clopyralid, and glyphosate) on soil samples from two roadsides in northern California and uses the results to examine field runoff data from multiple rainy seasons. Nonideal sorption processes do not appear to be significant in determining herbicide runoff at the field sites because (i) sorption isotherms were linear or slightly nonlinear for all compounds but glyphosate, (ii) field runoff concentration ratios between isoxaben and oryzalin were consistent with linear partitioning predictions, (iii) runoff leaving the site appeared to be in equilibrium with local soil concentrations, and (iv) desorption distribution coefficients for aged herbicides on soil samples collected from the field site did not differ substantially from those obtained in short-term laboratory adsorption experiments. Collectively, these findings indicate that linear equilibrium models are adequate for predicting the concentration of herbicides in runoff in these field settings and that more complicated nonideal models do not need to be invoked. Vegetated slopes effectively reduced the herbicide loads, with average removals of 35-80% occurring as runoff traversed a 3-m segment 1 m from the edge of the spray zone.     

Effect of grain size on uranium(VI) surface complexation kinetics and adsorption additivity

The contribution of variable grain sizes to uranium adsorption/desorption was studied using a sediment from the US DOE Hanford site. The sediment was wet sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.053-0.2 mm), and clay/silt fraction (<0.053 mm). For each size fraction and their composite (sediment), batch and flow-cell experiments were performed to determine uranium adsorption isotherms and kinetic uranium adsorption and subsequent desorption. The results showed that uranium adsorption isotherms and adsorption/desorption kinetics were size specific, reflecting the effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. One important implication of this study is that grain-size distribution may be used to estimate uranium adsorption site and adsorption/desorption kinetic rates in heterogeneous sediments from a common location.     

Desorption kinetics of phenanthrene in aquifer material lacks hysteresis

Desorption experiments were carried out in flow through columns following long-term sorption batch experiments (up to 1010 days at 20 degrees C; Rügner, H.; Kleineidam, S.; Grathwohl, P. Long-term sorption kinetics of phenanthrene in aquifer materials. Environ. Sci. Technol. 1999, 33, 1645-1651) to elucidate sorption/desorption hysteresis phenomena of phenanthrene in aquifer materials. Most of the sorbents employed in this study (homogeneous lithocomponents separated from aquifer sediments or fresh rock fragments) showed highly nonlinear sorption isotherms because of coal particles embedded inside the grains. Because sorption capacities were high, sorption equilibrium was not reached in most of the sorbents during the initial sorptive uptake experiments lasting up to 1010 days. Desorption was studied up to 90 days at 20 degrees C. The temperature was raised after that stepwise from originally 20 to 30, 40, 50, and finally to 70 degrees C for selected samples to estimate activation energies of desorption. A numerical intraparticle pore diffusion model was used to fit sorptive uptake data and subsequently for pure forward prediction of the release rates in the desorption column experiments. Desorption was initially fast followed by extended tailing which in other studies is fitted by using multirate first-order models. Our results demonstrate that the retarded intraparticle pore diffusion model can predict the desorption rates with a single diffusion rate constant obtained independently from the long-term batch sorption experiment. No evidence for hysteresis was found, suggesting that many hysteresis phenomena reported earlier are experimental artifacts resulting from nonequilibrium effects and "nonphysical" models. The different temperature steps allowed one to additionally calculate activation energies of desorption (45-59 kJ mol(-1)), which were in reasonably good agreement with results from earlier studies for a retarded pore diffusion process. In addition, equilibrium sorption isotherms were determined at 20 and 40 degrees C to compare sorption and desorption enthalpies. Both were in good agreement, confirming that desorption was not significantly different from sorption.     

Influence of pH on plutonium desorption/solubilization from sediment

Aqueous Pu concentrations and oxidation state transformations as a function of pH were quantified and compared between sorption/desorption studies and literature solubility values. When Pu(V) was added to a red subsurface sandy-clay-loam sediment collected near Aiken, South Carolina, 99% of the Pu sorbed to the sediment within 48 h. Throughout the study, > or = 94% of the Puaq remained as Pu(V), whereas < or = 6% was Pu(VI) and < or = 1% was Pu(IV). This is in stark contrast to the sorbed Pu which was almost exclusively in the +4 oxidation state. The fraction of aqueous Pu (Puaq/Pusolid) decreased by >2 orders-of-magnitude when the contact time was increased from 1- to 33-days, presumably the result of Pu(V) reduction to Pu(IV). The desorption studies were conducted with a sediment that had been in contact with Pu (originally as PuIV(NO3)4) for 24 years. At near neutral pH, a decrease of 1-pH unit resulted in almost an order-of-magnitude increase in the concentration of Puaq (7.5 x 10(-10) M at pH 7 and 3.6 x 10(-9) M at pH 6). Similar to the sorption experiment, > or = 96% of the Puaq was Pu(V/VI). The Puaq concentrations from the desorption experiment were similar to those of the Pu(V) amended sorption studies that were permitted to equilibrate for 33 days, suggesting that the latter had reached steady state. The Puaq concentrations as a function of pH followed near identical trends with literature solubility values for PuO2(am), except that the desorption values were lower by a fixed amount, suggesting either Pu sorption was occurring in this sediment system or that a more crystalline, less soluble form of Pu existed in the sediment than in the literature water-PuO2(am) system. Based on Pu sorption experiments and measured sediment surface charge properties as a function of pH, the latter explanation appears more likely. pH had a more pronounced effect on solubility and Puaq concentrations than on sediment charge density (or Puaq oxidation state distribution). Slight changes in system pH can have a large impact on Pu solubility and the tendency of Pu to sorb to sediment, thereby influencing Pu subsurface mobility.     

Dissolved organic carbon enhances the mass transfer of hydrophobic organic compounds from nonaqueous phase liquids (NAPLs) into the aqueous phase

The hypothesis that dissolved organic carbon (DOC) enhances the mass transfer of hydrophobic organic compounds from nonaqueous phase liquids (NAPLs) into the aqueous phase above that attributable to dissolved molecular diffusion alone was tested. In controlled experiments, mass transfer rates of five NAPL-phase PAHs (log K(OW) 4.15-5.39) into the aqueous phase containing different concentrations of DOC were measured. Mass transfer rates were increased by up to a factor of 4 in the presence of DOC, with the greatest enhancement being observed for more hydrophobic compounds and highest DOC concentrations. These increases could not be explained by dissolved molecular diffusion alone, and point to a parallel DOC-mediated diffusive pathway. The nature of the DOC-mediated diffusion pathway as a function of the DOC concentration and PAH sorption behavior to the DOC was investigated using diffusion-based models. The DOC-enhanced mass transfer of NAPL-phase hydrophobic compounds into the aqueous phase has important implications for their bioremediation as well as bioconcentration and toxicity.     

Modeling kinetics of Cu and Zn release from soils

Kinetics of Cu and Zn release from soil particles was studied using two surface soils with a stirred-flow method. Different solution pH, dissolved organic matter (DOM) concentrations, and flow rates were tested in this study. A model for kinetics controlled sorption/desorption reactions between soils and solutions was globally fit to all experimental data simultaneously. Results were compared to a model that assumes local instantaneous equilibrium. We obtained one unique set of model parameters applicable to different pH, dissolved organic carbon (DOC), and flow conditions. We included DOM complexation of copper ions, which decreased their sorption. The effect of pH was included by assuming proton competition with metal ions for binding sites on soil particles. These results provide the basis for developing predictive models for metal release from soil particles to surface waters and soil solution.     

Effect of two organic amendments on norflurazon retention and release by soils of different characteristics

The influence of two organic amendments on norflurazon sorption-desorption processes in four soils with very different physicochemical characteristics was studied in laboratory experiments to evaluate the potential leaching of this pesticide through organic fertilized soils. Sorption-desorption experiments were performed on original soils and on a mixture of these soils with urban waste compost (SUW) and a commercial amendment from olive-mill wastes (OW), at a rate of 6.25% (w/w). These mixtures were used immediately after preparation and after aging for 2 months. Norflurazon was analyzed by using a HPLC method. Norflurazon retention in original soils was related not only to the organic matter (OM) content but also to mineral surfaces present in soils. Norflurazon sorption increases largely after amendment in soils with low OM content, but the addition of exogenous OM to soils with medium OM content and/or other available adsorptive surfaces did not significantly affect norflurazon sorption. Even in some cases pesticide sorption decreases, due to the blocking of the mineral and organic soil surfaces with the amendment added. Transformation of exogenous OM during incubation depends both on the amendment added and on the type of soil and can affect sorption-desorption behavior of the soils surfaces in different manner, due to the modification of their hydrophobic-hydrophilic characteristics. Norflurazon desorption from original soils showed hysteresis in all cases, but it was not affected or even decreased in amended soils. It was a nonexpected behavior, especially in sandy soil, since it is generally assumed that a higher sorption always implies a lower mobility in soils. Norflurazon sorption must be taking place on very low affinity sites on exogenous OM through weak bindings, from which the pesticide can be easily desorbed. The application to soils of the organic amendments used in the present study could not be accepted to reduce norflurazon losses due to leaching processes.     

An isotope exchange technique to assess mechanisms of sorption hysteresis applied to naphthalene in kerogenous organic matter

The sorption of organic compounds to natural sorbents is often found to show hysteresis. The objective of this study was to develop an experimental technique based on the use of 14C isotopes to distinguish hysteresis due to experimental artifacts from true hysteresis due to thermodynamically irreversible processes. The study was also designed to investigate causation of true hysteresis (irreversible sorption). The technique determines the rates and the degree of isotope exchange (IE) on equilibrated sorption and desorption points at different constant bulk chemical concentrations. The technique was applied to the sorption of naphthalene (NAPH) on Beulah-Zap lignite, a low rank reference coal composed mainly of kerogen. Sorption of bulk was found to be reversible below 10(-5) g L(-1), but irreversible above 10(-4) g L(-1). Complete isotope exchange on sorption and desorption points that defined an irreversible cycle demonstrated that hysteresis was true. A comparison of normalized uptake and release kinetics of labeled and bulk NAPH at different concentrations revealed slow structural deformation processes of the sorbent during bulk sorption and desorption. This is taken as corroborating evidence for the pore deformation hypothesis of hysteresis in which incoming sorbate molecules induce quasi-reversible changes in the organic matter that lead to different pathways for sorption and desorption. Although unable to rule it out completely, the data demonstrate that physical entrapment of sorbate molecules plays a minor, if any, role to the observed hysteresis in this system.     

Solution speciation controls mercury isotope fractionation of Hg(II) sorption to goethite

The application of Hg isotope signatures as tracers for environmental Hg cycling requires the determination of isotope fractionation factors and mechanisms for individual processes. Here, we investigated Hg isotope fractionation of Hg(II) sorption to goethite in batch systems under different experimental conditions. We observed a mass-dependent enrichment of light Hg isotopes on the goethite surface relative to dissolved Hg (ε(202)Hg of -0.30‰ to -0.44‰) which was independent of the pH, chloride and sulfate concentration, type of surface complex, and equilibration time. Based on previous theoretical equilibrium fractionation factors, we propose that Hg isotope fractionation of Hg(II) sorption to goethite is controlled by an equilibrium isotope effect between Hg(II) solution species, expressed on the mineral surface by the adsorption of the cationic solution species. In contrast, the formation of outer-sphere complexes and subsequent conformation changes to different inner-sphere complexes appeared to have insignificant effects on the observed isotope fractionation. Our findings emphasize the importance of solution speciation in metal isotope sorption studies and suggest that the dissolved Hg(II) pool in soils and sediments, which is the most mobile and bioavailable, should be isotopically heavy, as light Hg isotopes are preferentially sequestered during binding to both mineral phases and natural organic matter.     

Sorption-induced effects of humic substances on mass transfer of organic pollutants through aqueous diffusion boundary layers: the example of water/air exchange

This study examines the effect of dissolved humic substances (DHS) on the rate of water-gas exchange of organic compounds under conditions where diffusion through the aqueous boundary layer is rate-determining. A synthetic surfactant was applied for comparison. Mass-transfer coefficients were determined from the rate of depletion of the model compounds by means of an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution. In addition, experiments with continuous passive dosing of analytes into the water phase were conducted to simulate a system where thermodynamic activity of the chemical in the aqueous phase is identical in the presence and absence of DHS. The experimental results show that DHS and surfactants can affect water-gas exchange rates by the superposition of two mechanisms: (1) hydrodynamic effects due to surface film formation ("surface smoothing"), and (2) sorption-induced effects. Whether sorption accelerates or retards mass transfer depends on its effect on the thermodynamic activity of the pollutant in the aqueous phase. Mass transfer will be retarded if the activity (or freely dissolved concentration) of the pollutant is decreased due to sorption. If it remains unchanged (e.g., due to fast equilibration with a sediment acting as a large source phase), then DHS and surfactant micelles can act as an additional shuttle for the pollutants, enhancing the flux through the boundary layer.     

Sonochemical desorption and destruction of 4-chlorobiphenyl from synthetic sediments

The application of ultrasound for the treatment of polychlorinated biphenyl (PCB) contaminated sediments was explored in this study with a model system of 4-chlorobiphenyl (4-CB) and synthetic sediments. In the presence of an ultrasonic probe, operating at 20 kHz with a power density of 460 W L(-1), more than 90% of 4-CB in aqueous homogeneous solution was destroyed after 20 min, with an apparent first-order rate constant, k, of 0.120 min(-1). In addition, experiments investigating the destruction of dissolved 4-CB in the presence of bare silica or alumina particles or dissolved humic acid (HA) had lower degradation rates than in aqueous homogeneous solutions. Increasing the bare particle concentration or dissolved HA concentration further lowered the degradation rate. However, in investigating the desorption and destruction of sorbed 4-CB from humic acid laden alumina particles, the effect of particles and released dissolved HA on the degradation rate are simply additive, and desorption of 4-CB does not appear to further complicate the system. A kinetic analysis of the system revealed that desorption of 4-CB from particles was not a limiting factor in this system.     

Lead phosphate minerals: solubility and dissolution by model and natural ligands

Due to their relatively low solubility, lead-phosphate minerals may control Pb solution levels at a low value in natural environments. We reportthe solubility of Pb from two lead-orthophosphate mineral suspensions (beta-Pb9(PO4)6 and PbHPO4) after aging for 3 years. Lead (Pb2+) activity in the aged suspensions was compared to the activity calculated using the Ksp values of various Pb-PO4 minerals reported in the literature. We also determine the time-dependent dissolution of the aged lead-phosphate minerals by organic and inorganic ligands containing S-functional groups (cysteine, methionine, and thiosulfate) and by a soil extracted humic acid. We find the activity of Pb2+ in the aged lead-phosphate suspensions to be 1-2 orders of magnitude higher than predicted by the Ksp values reported in the literature. Disagreement between measured and Ksp-calculated activities has been reported in other investigations of Pb-PO4 minerals; we compiled some of the data and present them together with our results. Furthermore, the time-dependent dissolution experiments indicate that, in most cases, lead phosphates are partly dissolved in the presence of soluble ligands, i.e., model sulfides and humic acid. The soil-extracted humic acid enhanced the dissolution of Pb from the high pH (7.2) lead-phosphate (beta-Pb9(PO4)6) mineral while suppressing Pb dissolution from the low pH (3.8) lead-phosphate (PbHPO4) mineral. While the low molecularweight sulfur-containing ligands enhanced Pb dissolution, their effect was less pronounced. We conclude that (i) nonequilibrium conditions prevail in the mineral suspensions even after 3 years of aging; and (ii) soluble ligands present in soils, sediments, and natural waters can potentially dissolve Pb from lead-phosphate minerals; such ligands, then, may enhance the biological availability and mobility of Pb in the environment.     

Sorption/desorption reversibility of phenanthrene in soils and carbonaceous materials

Sorption/desorption of phenanthrene in two soil samples and carbonaceous materials was found to yield co-incident equilibrium isotherms and no significant hysteresis was observed. Additionally, release of native phenanthrene was investigated. Equilibrium sorption and desorption isotherms were determined using pulverized samples of Pahokee peat, lignite, and high-volatile bituminous coal, a mineral soil, and an anthropogenic soil. Instead of the conventional decant-and-refill batch method, sorption/desorption was driven by temperature changes using consistent samples. Sorption started at 77 degrees C and was increased by reducing the temperature stepwise to 46, 20, and finally 4 degrees C. For desorption the temperature was increased stepwise again until 77 degrees C was reached. Besides the co-incident sorption and desorption isotherms at each temperature step, the solubility-normalized sorption/desorption isotherms of all different temperatures collapseto unique overall isotherms. Leaching of native phenanthrene occurred at much lower concentrations but was well predicted by extrapolation of the spiked sorption isotherms indicating that the release of native phenanthrene involves the same sorption/desorption mechanisms as those for newly added phenanthrene.     

Comparative sorption and desorption of benzo[a]pyrene and 3,4,3',4'-tetrachlorobiphenyl in natural lake water containing dissolved organic matter

The sorption and desorption of two model compounds, benzo[a]pyrene (BaP) and 3,4,3',4'-tetrachlorobiphenyl (TCBP), were studied in natural lake water with high dissolved organic matter (DOM) content using the equilibrium dialysis and Tenax extraction methods. The sorption of TCBP was lower and reached steady value more slowly than did BaP. Tenax extraction revealed at least two differently desorbing fractions for both model compounds, which also supported the conclusion that DOM-HOC associations may involve several mechanisms. The rapidly desorbing fraction may be attributed to freely dissolved and loosely sorbed compound, whereas the more strongly sorbed fraction may indicate the presence of specific binding sites. The data indicated that the association between hydrophobic organic contaminants (HOC) and DOM is not simply absorption that is solely driven by the lipophilicity of the sorbates. Although contact time had a rather negligible effect on the sorption of BaP, the proportion of desorption resistant fraction increased with time, whereas the desorption of TCBP was less affected by contact time. Steric factors may be the cause of the lower sorption and smaller desorption resistant fraction of TCBP. The results indicate potential differences in the behavior of PAHs and PCBs in the aquatic environment.