Sorption, mobility, and transformation of estrogenic hormones in natural soil

Potent estrogenic hormones are consistently detected in the environment at low concentration, yet these chemicals are strongly sorbed to soil and are labile. The objective of this research was to improve the understanding of the processes of sorption, mobility, and transformation for estrogens in natural soils, and their interaction. Equilibrium and kinetic batch sorption experiments, and a long-term column study were used to study the fate and transport of 17beta-estradiol and its primary metabolite, estrone, in natural soil. Kinetic and equilibrium batch experiments were done using radiolabeled 17beta-estradiol and estrone. At the concentrations used, it appeared that equilibrium sorption for both estrogens was achieved between 5 and 24 h, and that the equilibrium sorption isotherms were linear. The log K(oc) values for 17beta-estradiol (2.94) and estrone (2.99) were consistent with previously reported values. Additionally, it was found that there was rate-limited sorption for both 17beta-estradiol (0.178 h(-1)) and estrone (0.210 h(-1)). An approximately 42 h long, steady-flow, saturated column experiment was used to study the transport of radiolabeled 17beta-estradiol, which was applied in a 5.00 mg L(-1) solution pulse for 44 pore volumes. 17beta-estradiol and estrone were the predominant compounds detected in the effluent. The effluent breakthrough curves were asymmetric and the transport modeling indicated that sorption was rate-limited. Sorption rates and distributions of the estrogens were in agreement between column and batch experiments. This research can provide a better link between the laboratory results and observations in the natural environment.     

Do lab-derived distribution coefficient values of pesticides match distribution coefficient values determined from column and field-scale experiments? A critical analysis of relevant literature

In this study, we analyzed sorption parameters for pesticides that were derived from batch and column or batch and field experiments. The batch experiments analyzed in this study were run with the same pesticide and soil as in the column and field experiments. We analyzed the relationship between the pore water velocity of the column and field experiments, solute residence times, and sorption parameters, such as the organic carbon normalized distribution coefficient ( ) and the mass exchange coefficient in kinetic models, as well as the predictability of sorption parameters from basic soil properties. The batch/column analysis included 38 studies with a total of 139 observations. The batch/field analysis included five studies, resulting in a dataset of 24 observations. For the batch/column data, power law relationships between pore water velocity, residence time, and sorption constants were derived. The unexplained variability in these equations was reduced, taking into account the saturation status and the packing status (disturbed-undisturbed) of the soil sample. A new regression equation was derived that allows estimating the values derived from column experiments using organic matter and bulk density with an value of 0.56. Regression analysis of the batch/column data showed that the relationship between batch- and column-derived values depends on the saturation status and packing of the soil column. Analysis of the batch/field data showed that as the batch-derived value becomes larger, field-derived values tend to be lower than the corresponding batch-derived values, and vice versa. The present dataset also showed that the variability in the ratio of batch- to column-derived value increases with increasing pore water velocity, with a maximum value approaching 3.5.     

Effects of dissolved organic carbon on sorption and mobility of imidacloprid in soil

To evaluate the effects of dissolved organic carbon on sorption and mobility of the insecticide imidacloprid [1-(6-chloro-3-pyridinyl) methyl-N-nitro-2-imidazolidinimine] in soils, adsorption and column experiments were performed by using a typical calcareous soil from southeastern Spain and two different types of dissolved organic carbon, that is, dissolved organic carbon extracts from a commercial peat (DOC-PE) and high-purity tannic acid (DOC-TA). The experiments were carried out from a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results obtained from the sorption experiments show that the presence of both DOC-PE and DOC-TA, over a concentration range of 15 to 100 mg L(-1), produces in all cases a decreasing amount of imidacloprid adsorbed in the soil studied. From the column experiments the retardation coefficients (RC) were calculated for imidacloprid by using either 0.01 M CaCl2 aqueous solution (RC = 2.10), 0.01 M CaCl2 DOC-PE solution (RC = 1.65), or 0.01 M CaCl2 DOC-TA solution (RC = 1.87). The results indicate that mobility of imidacloprid is increased 21.4 and 11.0% in the presence of DOC-PE and DOC-TA solutions, respectively. Dissolved organic carbon reduces imidacloprid sorption by competing with the pesticide molecules for sorption sites on the soil surface, allowing enhanced leaching of imidacloprid and potentially increasing ground water contamination.     

Calibrating a model to 30 years of data to capture the accumulation of chloride from winter deicers in a shallow aquifer

Winter deicers are a major source of chloride contamination to shallow aquifers in northern latitudes. In the greater Chicago area of northeast Illinois, chloride has been accumulating for decades and in many places now exceeds the United States Environmental Protection Agency secondary standard of 250 mg/L. MODFLOW-NWT and MT3D-USGS were used to simulate the accumulation of chloride with 30 years of data in the shallow aquifer of Will County in northeast Illinois. This aquifer is composed of unconsolidated sediments, largely from glacial deposits, overlying a fractured dolomite bedrock. To calibrate to observed heads and chloride, the model needed refined geologic features, higher chloride concentrations on cells representing commercial or industrial lands, lower chloride concentrations on cells representing roads, and point source areas to speed chloride's emergence in the aquifer. These point sources are locally significant and could represent different anthropogenic or geologic features, such as municipal stormwater infrastructure. Future simulations indicate that chloride is not at steady state in the shallow aquifer and wells are at risk of exceeding the secondary standard if winter deicing applications are not reduced. It may take decades for the full impacts of reduced deicing rates to be observed in wells, owing to the long residence time of water in the aquifer. This transient model calibration was possible because of the 30-year dataset collected by communities and government agencies.     

Nonlinear and competitive sorption of apolar compounds in black carbon-free natural organic materials

Numerous studies have reported a spectrum of sorption phenomena in soils, sediments, and organic matter isolates of those materials that are inconsistent with a partition model proposed in the late 1970s and early 1980s, a model predicated on a hypothesis that sorption is linear and noncompetitive. To explain these nonideal phenomena, prior studies have proposed a hard-soft (glassy-rubbery) model for SOM (soil and sediment organic matter), while others have attributed them singularly to BC (black carbon: soot and charcoal) particles present in topsoils and sediments. In this study, we demonstrated nonideal sorption behavior (isotherm nonlinearity, competitive effects) for a group of apolar compounds in a large set of natural and model organic materials, including a commercial lignin and humic acids from different sources. Complete oxidation of samples by an acidic dichromate method was taken to signify the absence of BC. (However, polymethylene units are stable even if functionalized on both ends, making the technique unreliable for quantifying BC.) Other samples were inferred free of BC by their source and method of preparation. Characterization by thermalanalytical methods indicated the glassy character of the organic materials. The origin of the nonideal behaviors appears to be the glassy character of these materials. Sorption nonlinearity increased or decreased by changing temperature, cosolvent content, or degree of cross-linking by metal ions as predicted for organic solids in a glassy state. We conclude that macromolecular humic substances in the environment may exhibit nonideal sorption behavior in soils and sediments, quite apart from any such behaviors attributable to BC.     

Enhanced radionuclide immobilization and flow path modifications by dissolution and secondary precipitates

Caustic radioactive wastes that have leaked at Hanford Site (Richland, WA) induce mineral dissolution and subsequent secondary precipitation that influence the fate and transport of contaminants present in the waste solutions. The effects of secondary mineral precipitates, formed after contacting solids with simulated caustic wastes, on the flow path changes and radionuclide immobilization were investigated by reacting quartz, a mixture of quartz and biotite, and a Hanford sediment (Warden soil: coarse-silty, mixed, superactive, mesic Xeric Haplocambids) with simulated caustic tank waste solution. Continuous Si dissolution and concomitant secondary mineral precipitation were the principal reactions observed in both batch and flow-through tests. Nitrate-cancrinite was the dominant secondary precipitate on mineral surfaces after 3- to 10-d reaction times in batch experiments. X-ray microtomography images of a reacted quartz column revealed that secondary precipitates cemented quartz grains together and modified pore geometry in the center of the column. Along the circumference of the packed column, however, quartz dissolution continuously occurred, suggesting that wastes that leaked from buried tanks in the past likely did not migrate vertically as modeled in risk assessments but rather the pathways likely changed to be dominantly horizontal on precipitation of secondary precipitate phases in the Hanford vadose zone. Based on batch equilibrium sorption results on the reacted sediments, the dominant secondary precipitates (cancrinites) on the mineral surfaces enhanced the sorption capacity of typical Hanford sediment for radionuclides 129I(-I), 79Se(VI), 99Tc(VII), and 90Sr(II), all of which are of major concern at the Hanford Site.     

The role of condensed organic matter in the nonlinear sorption of hydrophobic organic contaminants by a peat and sediments

This study examines the effect of soil organic matter heterogeneity on equilibrium sorption and desorption of phenanthrene, naphthalene, 1,3,5-trichlorobenzene (1,3,5-TCB), and 1,2-dichlorobenzene (1,2-DCB) by soils and sediments. Two estuary sediments, a Pahokee peat (PP; Euic, hyperthermic Lithic Haplosaprist), and two subsamples (base- and acid-treated peat [TP] and acid-treated peat [FP]) of the peat were used as the sorbents. The contents of black carbon particles were quantified with a chemical extraction method. Petrographical examinations revealed the presence of the condensed soil and sediment organic matter (SOM) in Pahokee peat. The Freundlich isotherm model in two different forms was used to fit both sorption and desorption data. The results show that the sorption and desorption isotherms are generally nonlinear and that the apparent sorption-desorption hysteresis is present for phenanthrene and TCB. Detailed analysis of sorption data for the tested sorbent-sorbate systems indicates that black carbon is probably responsible for sorption isotherm nonlinearity for the two sediments, whereas the humic substances and kerogen may play the dominant role in nonlinear sorption by the peat. This investigation suggests that the microporosity of SOM is important for the hydrophobic organic contaminant (HOC) sorption capacity on the peat.     

RHODAMINE WT DYE LOSSES IN A MOUNTAIN STREAM ENVIRONMENT1

ABSTRACT: A significant fraction of rhodamine WT dye was lost during a short term multitracer injection experiment in a mountain stream environment. The conservative anion chloride and the sorbing cation lithium were concurrently injected. In-stream rhodamine WT concentrations were as low as 45 percent of that expected, based on chloride data. Concentration data were available from shallow‘wells’dug near the stream course and from a seep of suspected return flow. Both rhodamine WT dye and lithium were nonconservative with respect to the conservative chloride, with rhodamine WT dye closely following the behavior of the sorbing lithium. Nonsorption and sorption mechanisms for rhodamine WT loss in a mountain stream were evaluated in laboratory experiments. Experiments evaluating nonsorption losses indicated minimal losses by such mechanisms. Laboratory experiments using sand and gravel size streambed sediments show an appreciable capacity for rhodamine WT sorption. The detection of tracers in the shallow wells and seep indicates interaction between the stream and the flow in the surrounding subsurface, intergravel water, system. The injected tracers had ample opportunity for intimate contact with materials shown in the laboratory experiments to be potentially sorptive. It is suggested that in the study stream system, interaction with streambed gravel was a significant mechanism for the attenuation of rhodamine WT dye (relative to chloride).     

Analysis of soils to demonstrate sustained organic carbon removal during soil aquifer treatment

Soil samples from column studies using five soil types and from a field site were analyzed to assess the ability of soil aquifer treatment to sustain removal of organic carbon. The soil types used in the column studies were chosen to represent a wide range of soil properties that might be used for soil aquifer treatment. Soil samples were analyzed for total organic matter, and a subset of samples was sequentially extracted to determine the effects of soil aquifer treatment. For both column studies and the field site, no accumulation of organic matter was observed below a depth of 8 cm. Near the surface, biological activity at the soil-water interface resulted in an accumulation of biomass and associated organic matter. For the column studies, the accumulation of organic matter in the top 8 cm of soil was <20% of the total organic matter applied to the columns. Soils at depths greater than 8 cm had total organic matter levels less than the original soils before soil aquifer treatment. Significant changes in extractable iron and manganese oxides were observed at the field site, which had been in operation for >10 yr with extended periods of low redox conditions. However, these changes had no apparent effect on the removal of organic carbon in the system. This study provides evidence that soil aquifer treatment can remove organic carbon without accumulation from adsorption that might eventually lead to breakthrough.     

Sorption and desorption of cadmium by different fractions of biosolids-amended soils

To evaluate the importance of both the inorganic and organic fractions in biosolids on Cd chemistry, a series of Cd sorption and desorption batch experiments (at pH 5.5) were conducted on different fractions of soils from a long-term field experimental site. The slope of the Cd sorption isotherm increased with rate of biosolids and was different for the different biosolids. Removal of organic carbon (OC) reduced the slope of the Cd sorption isotherm but did not account for the observed differences between biosolids-amended soils and a control soil, indicating that the increased adsorption associated with biosolids application was not limited to the increased OC from the addition of biosolids. Removal of both OC and Fe/Mn further reduced the slopes of Cd sorption isotherms and the sorption isotherm of the biosolids-amended soil was the same as that of the control, indicating both OC and Fe/Mn fractions added by the biosolids were important to the increased sorption observed for the biosolids-amended soil samples. Desorption experiments failed to remove from 60 to 90% of the sorbed Cd. This "apparent hysteresis" was higher for biosolids-amended soil than the control soil. Removal of both OC and Fe/Mn fractions was more effective in removing the observed differences between the biosolids-amended soil and the control than either alone. Results show that Cd added to biosolids-amended soil behaves differently than Cd added to soils without biosolids and support the hypothesis that the addition of Fe and Mn in the biosolids increased the retention of Cd in biosolids-amended soils.     

Microbial reduction of hexavalent chromium under vadose zone conditions

Hexavalent chromium [Cr(VI)] is a common contaminant associated with nuclear reactors and fuel processing. Improper disposal at facilities in and and semiarid regions has contaminated underlying vadose zones and aquifers. The objectives of this study were to assess the potential for immobilizing Cr(VI) using a native microbial community to reduce soluble Cr(VI) to insoluble Cr(III) under conditions similar to those in the vadose zone, and to evaluate the potential for enhancing biological Cr(VI) reduction through nutrient addition. Batch microcosm and unsaturated flow column experiments were performed. Native microbial communities in subsurface sediments with no prior Cr(VI) exposure were shown to be capable of Cr(VI) reduction. In both the batch and column experiments, Cr(VI) reduction and loss from the aqueous phase were enhanced by adding high levels of both nitrate (NO3-) and organic C (molasses). Nutrient amendments resulted in up to 87% reduction of the initial 67 mg L(-1) Cr(VI) in an unsaturated batch experiment. Molasses and nitrate additions to 15 cm long unsaturated flow columns receiving 65 mg L(-1) Cr(VI) resulted in microbially mediated reduction and immobilization of 10% of the Cr during a 45-d experiment. All of the immobilized Cr was in the form of Cr(III), as shown by XANES analysis. This suggests that biostimulation of microbial Cr(VI) reduction in vadose zones by nutrient amendment is a promising strategy, and that immobilization of close to 100% of Cr contamination could be achieved in a thick vadose zone with longer flow paths and longer contact times than in this experiment.     

The influence of nitrate on selenium in irrigated agricultural groundwater systems

Selenium (Se) contamination of groundwater is an environmental concern especially in areas where aquifer systems are underlain by Se-bearing geologic formations such as marine shale. This study examined the influence of nitrate (NO?) on Se species in irrigated soil and groundwater systems and presents results from field and laboratory studies that further clarify this influence. Inhibition of selenate (SeO?) reduction in the presence of NO? and the oxidation of reduced Se from shale by autotrophic denitrification were investigated. Groundwater sampling from piezometers near an alluvium-shale interface suggests that SeO? present in the groundwater was due in part to autotrophic denitrification. Laboratory shale oxidation batch studies indicate that autotrophic denitrification is a major driver in the release of SeO? and sulfate. Similar findings occurred for a shale oxidation flow-through column study, with 70 and 31% more reduced Se and S mass, respectively, removed from the shale material in the presence of NO? than in its absence. A final laboratory flow-through column test was performed with shallow soil samples to assess the inhibition of SeO? reduction in the presence of NO?, with results suggesting that a concentration of NO? of approximately 5 mg L or greater will diminish the reduction of SeO?. The inclusion of the fate and transport of NO? and dissolved oxygen is imperative when studying or simulating the fate and transport of Se species in soil and groundwater systems.     

Phosphorus adsorption and desorption potential of stream sediments and field soils in agricultural watersheds

Phosphorus release from stream sediments into water could increase P loads leaving agricultural watersheds and contribute to lag-time between implementation of best management practices and improvement in water quality. Improved understanding of P release from stream sediments can assist in setting water quality goals and designing stream monitoring programs. The objective of this study was to estimate the relative potential of sediments and soils to release P to stream water in two agricultural watersheds. Stream sediments were collected from banks, pools, riffles, and depositional features. Soils were sampled from wheat, row crop, pasture, and manure-amended fields. Sediments and soils were analyzed for equilibrium P concentration at zero net P sorption (EPC0), maximum P adsorption capacity (P(max)), anion exchange extractable P (P(lab)), and degree of P saturation. Dissolved reactive P (DRP) of stream water was monitored. Stream sediment EPC0 was similar to or less than EPC0 from field soils; however, P(lab) of stream sediments was three times less than field soils. Sediments were sandy and had low P(max) due to low oxalate-extractable Fe and Al, which could be explained by stream geomorphology. Manure-amended fields had the highest EPC0 and P(lab) due to continued inputs of manure-based P; however, conventionally fertilized fields also represented an important P source due to their vast extent. Stream water DRP was similar to EPC0 of sediments during base flow and similar to EPC0 of field soils during storm flow. These results indicate that sediments in these streams are a relatively minor P source.     

PHOSPHORUS ASSIMILATION IN A STREAM SYSTEM OF THE LAKE OKEECHOBEE BASIN1

ABSTRACT: The ability to predict how streams and wetlands retain phosphorus (P) is critical to the management of watersheds that contribute nutrients to adjacent aquatic systems such as lakes. Field and laboratory experiments were conducted to determine the P assimilatory capacity of a stream (Otter Creek) in the Taylor Creek/Nubbin Slough Basin located north of Lake Okeechobee, Florida. Dominant soils in this basin are sandy Spodosols; landuse is primarily dairy farms and beef cattle pastures. Estimates of P assimilation show that sediments assimilate approximately 5 percent of the P load. Phosphorus assimilation rates in the stream were estimated using first-order relationships based on the total P concentration of the water column as a function of distance from the primary source. This method assumes minimal lateral inputs. Stream lengths required for one turnover in P assimilation were estimated to be in the range of 3–16 km. Laboratory studies using intact sediment cores indicated a P assimilation rate of 0.025 m day^?1, and equilibrium P concentration of 0.16 ± 0.03 mg L^?1 in the water column. Dissolved P concentration gradients in the sediments showed upward flux of P at water column P concentration of <0.16 mg L^?1. Approximately 56–77 percent of the P assimilated in the above-ground vegetation during active growth was released or translocated within six months of senesence, suggesting short-term storage in above-ground vegetation. Bottom sediments and recalcitrant detrital plant tissue provide for long-term P assimilation in the creek. Although stream sediments have the potential to adsorb P, high flow rate and low contact period between water and sediment limits this process.     

Dredging of drainage ditches increases short-term transport of soluble phosphorus

Managed drainage ditches are common in the midwestern United States. These ditches are designed to remove water from fields as quickly as possible, and sediment buildup necessitates dredging, to ensure adequate water removal. This laboratory study was conducted to determine the impact of ditch dredging on soluble phosphorus (P) transport. Ditch sediments were collected from a drainage ditch in northeastern Indiana immediately before and after dredging. The sediments were placed in a stream simulator, and stream water was loaded with 0.55 mM P for 5 d (adsorption experiment). Water was then removed, and "clean" water (no P added) was used for a desorption experiment, lasting 1 d. During the adsorption experiment, pre-dredged sediments were able to remove P from the water column quicker, and P concentrations 120 h after introduction of high P water were lower for the pre-dredged sediments (0.075 mM P) than the dredged sediments (0.111 mM P). During the desorption experiment, P was released to the water column slower in the pre-dredged treatment than the dredged treatment (instantaneous flux at t = 0 was 0.205 microM P h(-1) for pre-dredged and 0.488 microM P h(-1) for dredged). This occurred despite higher Mehlich 3-extractable P in the pre-dredged sediments than the dredged sediments. Equilibrium phosphorus concentrations (EPCo) were lower in the pre-dredged sediments during both adsorption and desorption experiments. Transport of soluble P immediately after dredging will likely increase in drainage ditches; however, dredging is a necessary management tool to ensure adequate discharge of water from surrounding fields.     

PARAMETER ESTIMATION FOR AQUIFER EVALUATION1

ABSTRACT A discussion of the various tools and techniques available for evaluation of aquifers is presented. Data for evaluation studies can be obtained from laboratory experiments, geological maps, well logs and field studies. Such data can be used in analytic or electric analog models to determine the sustained yield of the aquifer under various operating conditions.     

Dissolution and transport of TNT, RDX, and composition B in saturated soil columns

Low-order detonations and blow-in-place procedures on military training ranges can result in residual solid explosive formulations to serve as distributed point sources for ground water contamination. This study was conducted to determine if distribution coefficients from batch studies and transport parameters of pure compounds in solution adequately describe explosive transport where compounds are present as solid particles in formulations. Saturated column transport experiments were conducted with 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and the explosive formulation, Composition B (Comp B) (59.5 +/- 2.0% RDX, 39.5 +/- 2.3% TNT, and 1% wax) in solid and dissolved forms. The two soils used were Plymouth loamy sand (mesic, coated Typic Quartzipsamments) from Camp Edwards, MA and Adler silt loam (coarse-silty, mixed, superactive, thermic Fluvaquentic Eutrudepts) from Vicksburg, MS. Interrupted flow experiments were used to determine if explosives were at equilibrium distribution between soil and solution phases. The HYDRUS-1D code was used to determine fate and transport parameters. Results indicated that sorption of high explosives was rate limited. The behavior of dissolved Comp B was similar to the behavior of pure TNT and RDX. Behavior of solid Comp B was controlled by dissolution that depended on physical properties of the Comp B sample. Adsorption coefficients determined by HYDRUS-1D were different from those determined in batch tests for the same soils. Use of parameters specific to formulations will improve fate and transport predictions.     

Using nonequilibrium thin-disc and batch equilibrium techniques to evaluate herbicide sorption

Nonequilibrium disc-flow techniques may better reproduce dynamic soil-pesticide interactions than traditional batch sorption studies. Batch kinetic and equilibrium experiments and dual-label thin-disc flow experiments were conducted with atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazine-2,4-diamine) and imazaquin [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid] using a Demopolis silt loam (loamy-skeletal, carbonatic, thermic, shallow Typic Udorthent; 8% clay, 62 g kg(-1) organic matter, 7.6 pH). Batch kinetic studies with both herbicides revealed an almost instantaneous rapid phase and a much slower gradual phase. The rapid phase was complete after 5 min and equilibrium was reached at 24 h. The rapid phase accounted for 74% and 12 to 30% of the total amounts adsorbed for atrazine and imazaquin, respectively. The sorption of both the rapid and 24-h isotherms for each herbicide best fit the Freundlich equation. The rapid and 24-h K(f) values of atrazine were 1.38 and 2.41, respectively, and the N value of both phases was approximately 0.93. For imazaquin, the rapid and 24-h K(f) values were 0.056 and 035, respectively, and the N value for the rapid phase of imazaquin was 0.71, compared with 0.86 for the 24-h isotherm. In the dual-label thin-disc flow experiments, the average partition coefficient for atrazine at the peak soil concentration point was 1.54. This value closely agreed with the observed rapid-phase K(f) value of 1.38. In contrast, the thin-disc flow experiments failed to detect any imazaquin retention. The thin-disc flow method can allow for a greater resolution of rapid sorption kinetics, which is impractical with batch studies. Along with dynamic partitioning data, the thin-disc flow method may provide kinetics data that may better complement environmental models than coefficients generated with batch techniques.     

Prediction of radionuclide aging in soils from the Chernobyl and Mediterranean areas

The aging of soil-pollutant interaction, which may lead to an increase in pollutant fixation, is the main driving force in the natural attenuation of contaminated soils. Here a test was evaluated to predict the aging of radiostrontium and radiocesium in soils from the Chernobyl and Mediterranean areas. After contamination, soils were maintained at various temperatures for up to 12 mo, with or without drying-wetting (DW) cycles. Changes in the quantity of radionuclide reversibly sorbed over time were monitored using an extraction test (1 mol L(-1) NH(4)Cl; 10 mL g(-1); 16 h). The fixed fraction could not be predicted from soil properties controlling the sorption step. Aging was not as relevant for Sr as for Cs. The time elapsed since contamination was the main factor responsible for the slight (up to 1.3-fold) decreases in Sr extraction yields. The additional effect of DW cycles was negligible. Instead, all factors accelerated Cs aging due to the enhancement of Cs trapping by clay interlayer collapse, with up to 20-fold increases in Cs fixation. The DW cycles also caused secondary effects on the Cs-specific sorption pool, which were beneficial or detrimental depending on the soil type. Extraction yields from laboratory aged samples agreed with those from field samples taken a few years after the Chernobyl accident. These results confirm the prediction capacity of the laboratory test and its usefulness in risk assessment exercises and in the design of intervention actions, particularly because neither fixation nor aging were related to the soil properties, such as clay content.     

A thermodynamically based method to quantify true sorption hysteresis

Sorption of organic chemicals to soils and sediments often shows true hysteresis (i.e., nonsingularity of the sorption-desorption isotherm not attributable to known experimental artifacts). Since true sorption hysteresis is fundamentally important to contaminant fate, a way to quantify it is desirable. Previously proposed indices of hysteresis are empirical and usually depend on the isotherm model. True sorption hysteresis to synthetic and natural organic solids has been attributed to irreversible alteration of the solid during the sorption-desorption cycle. Given this mechanism, we propose the Thermodynamic Index of Irreversibility (TII) for quantifying hysteresis in soils where natural organic matter dominates the sorption process. The TII is based on the difference in free energy between the real desorption state and the hypothetical fully reversible state. The index is 0 for completely reversible systems and approaches 1 as the process tends toward complete irreversibility. It does not require any assumptions about the physical properties or molecular composition of the solid, and it does not depend on a specific equilibrium model. A sensitivity analysis of measurement errors provides general recommendations for the setup of sorption-desorption experiments. The TII was applied to sorption of 1,4-dichlorobenzene (DCB) to two high-organic soils, Pahokee peat (PP) and Amherst soil (AS), and a low-rank coal reference material, Beulah-Zap lignite (BZL). Common artificial causes of hysteresis were eliminated. Hysteresis was significant in the peat and the coal. The TII was clearly concentration dependent for both solids; it decreased with concentration for the peat, but increased with concentration for the coal. The TII allows quantification of hysteresis as a function of sorbate-sorbent combination, concentration, time, and other variables.