Investigating the Effect of Bioirrigation on In Situ Porewater Concentrations and Fluxes of Polychlorinated Biphenyls Using Passive Samplers.

Polychlorinated biphenyl (PCB) fluxes from contaminated sediments can be caused by mechanisms including diffusion, bioirrigation, and resuspension, but it is often unclear which mechanisms are important. In the Lower Duwamish Waterway (Seattle, Washington), the presence of abundant benthic macrofauna suggests that porewater bioirrigation may be an important mechanism for PCB transport from the bed into the overlying water column. In this field study, the fluxes of PCBs due to bioirrigation were quantified by using (a) polyethylene (PE) samplers to quantify in situ and ex situ (i.e., equilibrium) PCB porewater concentration profiles and (b) measurements of the geochemical tracer 222Rn to quantify the rate of porewater exchange with overlying water. The results showed that bioirrigation caused sorptive disequilibrium with the surrounding sediment, which led to lower in situ porewater concentrations than expected from sediment concentrations. The combined fluxes of seven PCB congeners (Σ7PCBs) were 1.6-26 ng/m2/day for the three field sites, similar in magnitude to the upper limit estimates of diffusive fluxes calculated assuming water-side boundary layer control (Σ7PCBs = 1.3-47 ng/m2/day). Moreover, the depleted in situ porewater concentrations imply lower diffusive flux estimates than if the ex situ porewater concentrations had been used to estimate fluxes (Σ7PCBs = 89-670 ng/m2/day). These results suggest that nondiffusive PCB fluxes from the sediment bed are occurring and that quantifying in situ porewater concentrations is crucial for accurately quantifying both diffusive and nondiffusive PCB fluxes.

Advancing the Use of Passive Sampling in Risk Assessment and Management of Sediments Contaminated with Hydrophobic Organic Chemicals: Results of an International Ex Situ Passive Sampling Interlaboratory Comparison.

This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (

Adsorption of Organic Compounds to Diesel Soot: Frontal Analysis and Polyparameter Linear Free-Energy Relationship.

Black carbons (BCs) dominate the sorption of many hydrophobic organic compounds (HOCs) in soils and sediments, thereby reducing the HOCs' mobilities and bioavailabilities. However, we do not have data for diverse HOCs' sorption to BC because it is time-consuming and labor-intensive to obtain isotherms on soot and other BCs. In this study, we developed a frontal analysis chromatographic method to investigate the adsorption of 21 organic compounds with diverse functional groups to NIST diesel soot. This method was precise and time-efficient, typically taking only a few hours to obtain an isotherm. Based on 102 soot-carbon normalized sorption coefficients (KsootC) acquired at different sorbate concentrations, a sorbate-activity-dependent polyparameter linear free-energy relationship was established: logKsootC = (3.74 ± 0.11)V + ((-0.35 ± 0.02)log ai)E + (-0.62 ± 0.10)A + (-3.35 ± 0.11)B + (-1.45 ± 0.09); (N = 102, R(2) = 0.96, SE = 0.18), where V, E, A, and B are the sorbate's McGowan's characteristic volume, excess molar refraction, and hydrogen acidity and basicity, respectively; and ai is the sorbate's aqueous activity reflecting the system's approach to saturation. The difference in dispersive interactions with the soot versus with the water was the dominant factor encouraging adsorption, and H-bonding interactions discouraged this process. Using this relationship, soot-water and sediment-water or soil-water adsorption coefficients of HOCs of interest (PAHs and PCBs) were estimated and compared with the results reported in the literature.

Validating the use of performance reference compounds in passive samplers to assess porewater concentrations in sediment beds.

Hydrophobic organic compounds (HOCs) like polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) tend to accumulate in sediment beds when they are released into aquatic environments. Due to this buildup of HOCs in the sediment, the highest water concentrations are often in the pore water. Passive samplers can be used in the field (i.e., in situ) to measure freely dissolved porewater concentrations if target contaminants diffusing through the sediment and into the sampler exhibit the same diffusive retardation factors as performance reference compounds (PRCs) that are diffusing out of the sampler and into the sediment. To test this assumption, polyethylene (PE) passive samplers were placed in an organic- and black- carbon-rich sediment bed in the laboratory with samplers removed every 30 days for 4 months. The concentrations of target contaminants in the PE at each time point, corrected using measures of the losses of PRCs, were in good agreement with separately measured equilibrium concentrations in a well-mixed system. Concentrations in the PE passive samplers, normalized by their polyethylene-water partition coefficients, were also in good agreement with directly measured porewater concentrations. Finally, PE-deduced porewater concentrations were compared with the traditional equilibrium partitioning models and showed that considering sorption to only organic carbon substantially overestimated porewater concentrations. However, predictions improved greatly if sorption to black carbon was also considered.

Measuring free, conjugated, and halogenated estrogens in secondary treated wastewater effluent.

Steroidal estrogens are potent endocrine-disrupting chemicals that enter natural waters through the discharge of treated and raw sewage. Because estrogens are detrimental to aquatic organisms at sub-nanogram per liter concentrations, many studies have measured so-called "free" estrogen concentrations in wastewater effluents, rivers, and lakes. Other forms of estrogens are also of potential concern because conjugated estrogens can be easily converted to potent free estrogens by bacteria in wastewater treatment plants and receiving waters and halogenated estrogens are likely produced during wastewater disinfection. However, to the best of our knowledge, no studies have concurrently characterized free, conjugated, and halogenated estrogens. We have developed a method that is capable of simultaneously quantifying free, conjugated, and halogenated estrogens in treated wastewater effluent, in which detection limits were 0.13-1.3 ng L(-1) (free), 0.11-1.0 ng L(-1) (conjugated), and 0.18-18 ng L(-1) (halogenated). An aqueous phase additive, ammonium fluoride, was used to increase the electrospray (negative mode) ionization efficiency of free and halogenated estrogens by factors of 20 and 2.6, respectively. The method was validated using treated effluent from the greater Boston metropolitan area, where conjugated and halogenated estrogens made up 60-70% of the steroidal estrogen load on a molar basis.

Carbon isotopic (13C and 14C) composition of synthetic estrogens and progestogens.

RATIONALE: Steroids are potent hormones that are found in many environments. Yet, contributions from synthetic and endogenous sources are largely uncharacterized. The goal of this study was to evaluate whether carbon isotopes could be used to distinguish between synthetic and endogenous steroids in wastewater and other environmental matrices. METHODS: Estrogens and progestogens were isolated from oral contraceptive pills using semi-preparative liquid chromatography/diode array detection (LC/DAD). Compound purity was confirmed by gas chromatography/flame ionization detection (GC/FID), gas chromatography/time-of-flight mass spectrometry (GC/TOF-MS) and liquid chromatography/mass spectrometry using negative electrospray ionization (LC/ESI-MS). The (13)C content was determined by gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and (14)C was measured by accelerator mass spectrometry (AMS). RESULTS: Synthetic estrogens and progestogens are (13)C-depleted (δ(13)C(estrogen) = -30.0 ± 0.9 ‰; δ(13)C(progestogen) = -30.3 ± 2.6 ‰) compared with endogenous hormones (δ(13)C ~ -16 to -26 ‰). The (14)C content of the majority of synthetic hormones is consistent with synthesis from C(3) plant-based precursors, amended with 'fossil' carbon in the case of EE(2) and norethindrone acetate. Exceptions are progestogens that contain an ethyl group at carbon position 13 and have entirely 'fossil' (14)C signatures. CONCLUSIONS: Carbon isotope measurements have the potential to distinguish between synthetic and endogenous hormones in the environment. Our results suggest that (13)C could be used to discriminate endogenous from synthetic estrogens in animal waste, wastewater effluent, and natural waters. In contrast, (13)C and (14)C together may prove useful for tracking synthetic progestogens.

Thermogravimetry-mass spectrometry for carbon nanotube detection in complex mixtures.

In spite of the growth of the carbon nanotube (CNT) industry, there are no established analytical methods with which to detect or quantify CNTs in environmental matrices. Given that CNTs have relatively high thermal stabilities, we investigated the use of thermal techniques to isolate and quantify single wall carbon nanotubes (SWCNTs). Test materials included ten types of commercial SWCNTs, representative biological macromolecules (bovine serum albumin and methylcellulose), soot, natural coastal sediments, and SWCNT-amended sediments. Different SWCNTs exhibited widely diverse degradation temperatures, and thermal analytical methods may require SWCNT-type specific parameters. To improve quantification capabilities, evolved gases were monitored by mass spectrometry. SWCNTs produced diagnostic ion ratios reflective of their high carbon and low hydrogen and oxygen contents. Current detection limits are roughly 4 µg(SWCNT) per sample (e.g., 100 µg(SWCNT) g(-1)(sediment) and 40 mg sample), controlled by interfering ions associated with the instrument's non-airtight design. Although future modifications could improve this limitation, the current method is sufficient for quantifying SWCNTs in laboratories and industrial sites where SWCNTs are handled. Furthermore, the method shows promise to distinguish between incidental (e.g., soot) and engineered (e.g., SWCNTs) nanoparticles, which is not possible with current state-of-the-art techniques.

Estimating phospholipid membrane-water partition coefficients using comprehensive two-dimensional gas chromatography.

Recent studies have shown that membrane-water partition coefficients of organic chemicals can be used to predict bioaccumulation and type I narcosis toxicity more accurately than the traditional K(OW)-based approach. In this paper, we demonstrate how comprehensive two-dimensional gas chromatography (GC × GC) can be used to estimate such membrane-water partition coefficients (K(PLW)s), focusing in particular on phosphatidyl choline based lipids. This method performed well for a set of 38 compounds, including polycyclic aromatic hydrocarbons, polychlorinated benzenes and biphenyls, and substituted benzenes including some phenols and anilines. The average difference between the estimated and the measured log K(PLW) values of 0.47 log units is smaller than in the case of a log K(OW) correlation approach but larger than seen using a polyparameter linear free energy relationship based approach. However, the GC × GC based method presents the advantage that it can be applied to mixtures of chemicals that are not completely identified, such as petroleum hydrocarbon mixtures. At the same time, our application of the GC × GC method suffered larger errors when applied to certain hydrogen bonding compounds due to the inability of the GC × GC capillary columns phases that we used to interact with analytes via hydrogen bond donation/electron acceptance.

Interlaboratory Study of Polyethylene and Polydimethylsiloxane Polymeric Samplers for Ex Situ Measurement of Freely Dissolved Hydrophobic Organic Compounds in Sediment Porewater.

We evaluated the precision and accuracy of multilaboratory measurements for determining freely dissolved concentrations (Cfree ) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in sediment porewater using polydimethylsiloxane (PDMS) and low-density polyethylene (LDPE) polymeric samplers. Four laboratories exposed performance reference compound (PRC) preloaded polymers to actively mixed and static ex situ sediment for approximately 1 month; two laboratories had longer exposures (2 and 3 months). For Cfree results, intralaboratory precision was high for single compounds (coefficient of variation 50% or less), and for most PAHs and PCBs interlaboratory variability was low (magnitude of difference was a factor of 2 or less) across polymers and exposure methods. Variability was higher for the most hydrophobic PAHs and PCBs, which were present at low concentrations and required larger PRC-based corrections, and also for naphthalene, likely due to differential volatilization losses between laboratories. Overall, intra- and interlaboratory variability between methods (PDMS vs. LDPE, actively mixed vs. static exposures) was low. The results that showed Cfree polymer equilibrium was achieved in approximately 1 month during active exposures, suggesting that the use of PRCs may be avoided for ex situ analysis using comparable active exposure; however, such ex situ testing may not reflect field conditions. Polymer-derived Cfree concentrations for most PCBs and PAHs were on average within a factor of 2 compared with concentrations in isolated porewater, which were directly measured by one laboratory; difference factors of up to 6 were observed for naphthalene and the most hydrophobic PAHs and PCBs. The Cfree results were similar for academic and private sector laboratories. The accuracy and precision that we demonstrate for determination of Cfree using polymer sampling are anticipated to increase regulatory acceptance and confidence in use of the method. Environ Toxicol Chem 2022;41:1885-1902. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Influence of low oxygen tensions and sorption to sediment black carbon on biodegradation of pyrene.

Sorption to sediment black carbon (BC) may limit the aerobic biodegradation of polycyclic aromatic hydrocarbons (PAHs) in resuspension events and intact sediment beds. We examined this hypothesis experimentally under conditions that were realistic in terms of oxygen concentrations and BC content. A new method, based on synchronous fluorescence observations of (14)C-pyrene, was developed for continuously measuring the uptake of dissolved pyrene by Mycobacterium gilvum VM552, a representative degrader of PAHs. The effect of oxygen and pyrene concentrations on pyrene uptake followed Michaelis-Menten kinetics, resulting in a dissolved oxygen half-saturation constant (K(om)) of 14.1 microM and a dissolved pyrene half-saturation constant (K(pm)) of 6 nM. The fluorescence of (14)C-pyrene in air-saturated suspensions of sediments and induced cells followed time courses that reflected simultaneous desorption and biodegradation of pyrene, ultimately causing a quasi-steady-state concentration of dissolved pyrene balancing desorptive inputs and biodegradation removals. The increasing concentrations of (14)CO(2) in these suspensions, as determined with liquid scintillation, evidenced the strong impact of sorption to BC-rich sediments on the biodegradation rate. Using the best-fit parameter values, we integrated oxygen and sorption effects and showed that oxygen tensions far below saturation levels in water are sufficient to enable significant decreases in the steady-state concentrations of aqueous-phase pyrene. These findings may be relevant for bioaccumulation scenarios that consider the effect of sediment resuspension events on exposure to water column and sediment pore water, as well as the direct uptake of PAHs from sediments.

Ex situ determination of freely dissolved concentrations of hydrophobic organic chemicals in sediments and soils: basis for interpreting toxicity and assessing bioavailability, risks and remediation necessity.

The freely dissolved concentration (Cfree) of hydrophobic organic chemicals in sediments and soils is considered the driver behind chemical bioavailability and, ultimately, toxic effects in benthic organisms. Therefore, quantifying Cfree, although challenging, is critical when assessing risks of contamination in field and spiked sediments and soils (e.g., when judging remediation necessity or interpreting results of toxicity assays performed for chemical safety assessments). Here, we provide a state-of-the-art passive sampling protocol for determining Cfree in sediment and soil samples. It represents an international consensus procedure, developed during a recent interlaboratory comparison study. The protocol describes the selection and preconditioning of the passive sampling polymer, critical incubation system component dimensions, equilibration and equilibrium condition confirmation, quantitative sampler extraction, quality assurance/control issues and final calculations of Cfree. The full procedure requires several weeks (depending on the sampler used) because of prolonged equilibration times. However, hands-on time, excluding chemical analysis, is approximately 3 d for a set of about 15 replicated samples.

Passive sampling of DDT, DDE and DDD in sediments: accounting for degradation processes with reaction-diffusion modeling.

Passive sampling is becoming a widely used tool for assessing freely dissolved concentrations of hydrophobic organic contaminants in environmental media. For certain media and target analytes, the time to reach equilibrium exceeds the deployment time, and in such cases, the loss of performance reference compounds (PRCs), loaded in the sampler before deployment, is one of the common ways used to assess the fractional equilibration of target analytes. The key assumption behind the use of PRCs is that their release is solely diffusion driven. But in this work, we show that PRC transformations in the sediment can have a measurable impact on the PRC releases and even allow estimation of that compound's transformation rate in the environment of interest. We found that in both field and lab incubations, the loss of the 13C 2,4'-DDT PRC from a polyethylene (PE) passive sampler deployed at the sediment-water interface was accelerated compared to the loss of other PRCs (13C-labeled PCBs, 13C-labeled DDE and DDD). The DDT PRC loss was also accompanied by accumulation in the PE of its degradation product, 13C 2,4'-DDD. Using a 1D reaction-diffusion model, we deduced the in situ degradation rates of DDT from the measured PRC loss. The in situ degradation rates increased with depth into the sediment bed (0.14 d-1 at 0-10 cm and 1.4 d-1 at 30-40 cm) and although they could not be independently validated, these rates compared favorably with literature values. This work shows that passive sampling users should be cautious when choosing PRCs, as degradation processes can affect some PRC's releases from the passive sampler. More importantly, this work opens up the opportunity for novel applications of passive samplers, particularly with regard to investigating in situ degradation rates, pathways, and products for both legacy and emerging contaminants. However, further work is needed to confirm that the rates deduced from model fitting of PRC loss are a true reflection of DDT transformation rates in sediments.

Performance of passive sampling with low-density polyethylene membranes for the estimation of freely dissolved DDx concentrations in lake environments.

Laboratory and field studies were used to evaluate the performance of low-density polyethylene (PE) passive samplers for assessing the freely dissolved concentrations of DDT and its degradates (DDD and DDE, together referred to as DDx) in an Italian lake environment. We tested commercially available 25 µm thick PE sheets as well as specially synthesized, 10 µm thick PE films which equilibrated with their surroundings more quickly. We measured PE-water partitioning coefficients (Kpew) of the 10 µm thick PE films, finding good correspondence with previously reported values for thicker PE. Use of the 10 µm PE for ex situ sampling of a lake sediment containing DDx in laboratory tumbling experiments showed repeatability of ±15% (= standard deviation/mean). Next, we deployed replicate 10 µm and 25 µm PE samplers (N = 4 for 10 d and for 30 d) in the water and sediment of a lake located in northern Italy; the results showed dissolved DDx concentrations in the picogram/L range in porewater and the bottom water. Values deduced from 10 µm thick PE films compared well (95% of all comparison pairs matched within a factor of 5) with those obtained using PE films of 25 µm thickness when dissolved DDx concentrations were estimated using performance reference compound (PRC) corrections, whether left at the bed-water interface for 10 or 30 days. These results demonstrated the potential of this sampling method to provide estimation of the truly dissolved DDx concentrations, and thereby the mobile and bio-available fractions in both surface waters and sediment beds.

Ferrous iron oxidation rates in the pycnocline of a permanently stratified lake.

Ferrous iron was found year round at 2-4 mM in the anoxic hypolimnion of the Halls Brook Holding Area (HBHA), a small lake in eastern Massachusetts. Oxygenated epilimnion waters always had total iron concentrations of <80 nanomolar, implying nearly complete oxidation of ferrous iron as it mixed upward across the lake's pycnocline. Assuming conductivity was a conservative parameter, and using data on the lake's water balance, upward advection rates (0.02-0.05 m d(-1)) and vertical eddy diffusion coefficients (0.007-0.05 m2 d(-1)) were determined for the lake's pycnocline on five dates. Using the same advection and diffusion parameters, corresponding pseudo first-order rate coefficients for ferrous iron oxidation, k(ox) (s(-1)), on those dates were calculated (0.0004-0.007 s(-1)). The values of k(ox) (s(-1)) were always too large to reflect only homogeneous solution reactions; and on at least four dates they appeared too fast to be due to heterogeneous catalysis on iron oxyhydroxides. This suggested that ferrous iron oxidation in this lake's pycnocline was primarily due to catalysis by microorganisms, and this was supported by comparison of azide-poisoned vs. untreated batch tests. As a result of their continuous production, iron oxyhydroxide precipitates and any associated sorbates/coprecipitates are most likely continuously settling back into the lake's deep water and bed sediments, except when episodic storm events flush these solids out of the pycnocline and downstream via the Aberjona River.

The atmosphere as a source/sink of polychlorinated biphenyls to/from the Lower Duwamish Waterway Superfund site.

Waterbodies polluted with polychlorinated biphenyls (PCBs) may cause the air in the surrounding area to become PCB-contaminated. Conversely, when a waterbody is located in or near an urban area, the deposition of atmospheric PCBs may act as a low-level, ongoing source of PCB contamination to that water. Distinguishing these situations is necessary to be protective of human populations and to guide efforts seeking to cleanup such aquatic ecosystems. To assess the situation at the Lower Duwamish Waterway (LDW) Superfund site, low-density polyethylene passive samplers were deployed in the summer of 2015 to quantify freely dissolved water and gaseous air concentrations of PCBs thereby enabling estimates of the direction and magnitude of air-water exchange of PCB congeners. For the sum of the 27 PCB congeners, average concentrations were 220 pg/m3 (95% C.I.: 80-610) in the air and 320 pg/L (95% C.I.: 110-960) in the water. The sum of air-water exchange fluxes of these PCB congeners was estimated to be 68 ng/m2/day (95% C.I.: 30-148) into the lower atmosphere, contrasting with the reported wet and dry depositional flux of only 5.5 ng/m2/day (95% C.I.: 1-38) from the air into the water. Therefore, the atmosphere was ultimately a sink of PCBs from the LDW Superfund site, at least under 2015 summertime conditions. However, we conclude that air-water exchange of PCBs is likely only a minor sink of PCBs from the LDW and only a minor source of contamination to the region's local atmosphere.

In situ passive sampling of sediments in the Lower Duwamish Waterway Superfund site: Replicability, comparison with ex situ measurements, and use of data.

Superfund sites with sediments contaminated by hydrophobic organic compounds (HOCs) can be difficult to characterize because of the complex nature of sorption to sediments. Porewater concentrations, which are often used to model transport of HOCs from the sediment bed into overlying water, benthic organisms, and the larger food web, are traditionally estimated using sediment concentrations and sorption coefficients estimated using equilibrium partitioning (EqP) theory. However, researchers have begun using polymeric samplers to determine porewater concentrations since this method does not require knowledge of the sediment's sorption properties. In this work, polyethylene passive samplers were deployed into sediments in the field (in situ passive sampling) and mixed with sediments in the laboratory (ex situ active sampling) that were contaminated with polychlorinated biphenyls (PCBs). The results show that porewater concentrations based on in situ and ex situ sampling generally agreed within a factor of two, but in situ concentrations were consistently lower than ex situ porewater concentrations. Imprecision arising from in situ passive sampling procedures does not explain this bias suggesting that field processes like bioirrigation may cause the differences observed between in situ and ex situ polymeric samplers.

Understanding the rates of nonpolar organic chemical accumulation into passive samplers deployed in the environment: Guidance for passive sampler deployments.

Polymeric passive samplers have become a common method for estimating freely dissolved concentrations in environmental media. However, this approach has not yet been adopted by investigators conducting remedial investigations of contaminated environmental sites. Successful adoption of this sampling methodology relies on an understanding of how passive samplers accumulate chemical mass as well as developing guidance for the design and deployment of passive samplers. Herein, we outline the development of a simple mathematical relationship of the environmental, polymer, and chemical properties that control the uptake rate. This relationship, called a timescale, is then used to illustrate how each property controls the rate of equilibration in samplers deployed in the water or in the sediment. Guidance is also given on how to use the timescales to select an appropriate polymer, deployment time, and suite of performance reference compounds. Integr Environ Assess Manag 2016;12:486-492. © 2015 SETAC.

Steroidal estrogen sources in a sewage-impacted coastal ocean.

Estrogens are known to be potent endocrine disrupting chemicals that are commonly found in wastewater effluents at ng L(-1) levels. Yet, we know very little about the distribution and fate of estrogens in coastal oceans that receive wastewater inputs. This study measured a wide range of steroidal estrogens in sewage-impacted seawater using ultra high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS) together with the method of standard addition. In Massachusetts Bay, we find conjugated, free, and halogenated estrogens at concentrations that are consistent with dilution at sites close to the sewage source. At a site 6 miles down current of the sewage source, we observe estrone (E1) concentrations (520 ± 180 pg L(-1)) that are nearly double the nearfield concentrations (320 ± 60 pg L(-1)) despite 9-fold dilution of carbamazepine, which was used as a conservative sewage tracer. Our results suggest that background E1 concentrations in Massachusetts Bay (∼270 ± 50 pg L(-1)) are derived largely from sources unrelated to wastewater effluent such as marine vertebrates.

The electrostatic origin of Abraham's solute polarity parameter.

A computational method was developed which relates the empirical linear solvation energy relationship (LSER) solute polarity parameter, S (formerly denoted ), to two more fundamental quantities: a polarizability term and a computed solvent-accessible-surface electrostatic term. Electrostatics computations were conducted explicitly or with dielectric field polarizable continuum models (PCM, SCIPCM, IPCM), employing a density functional theory (B3LYP/6-311G(2df,2p)) or efficient Hartree-Fock (HF/MIDI!) method for 90 polar and nonpolar organic solutes. Electrostatic parameters calculated at electron isodensity solute surfaces were found to produce significantly better correlations with empirical S values than the same electrostatic parameters deduced from a fixed Bondi atomic radii based surface. The best-fit expression was found employing SCIPCM/IPCM at the 0.0004 e(-)/bohr(3) solvent-accessible-surface: S(fit)() = 0.46E - 0.091SigmaV(s)()(2), with squared correlation coefficient = 0.96 and standard deviation = 0.10, where E is a measured solute excess polarizability scale and SigmaV(s)()(2) is a quantum-calculated solute electrostatic descriptor in kcal A/mol. The resulting model is more accurate than previously developed estimation approaches and relies on only two fitted coefficients; it has the potential advantage of applicability to any solute composed of C, H, N, O, S, F, Cl, and Br. Finally, this investigation offers quantitative insight into the relative contributions of solute polarity and solute polarizability to the empirical LSER polarity parameter, S.

A physical-chemical screening model for anticipating widespread contamination of community water supply wells by gasoline constituents.

Continuing modifications of fuels like gasoline should include evaluations of the proposed constituents for their potential to damage environmental resources such as subsurface water supplies. Consequently, we developed a screening model to estimate well water concentrations and transport times for gasoline components migrating from underground fuel tank (UFT) releases to typical at-risk community water supply wells. Representative fuel release volumes and hydrogeologic characteristics were used to parameterize the transport calculation. Subsurface degradation processes were neglected in the model in order to make risk-conservative assessments. The model was tailored to individual compounds based on their abundances in gasoline, gasoline-water partition coefficients (Kgw), and organic matter-water partition coefficients (Kom). Transport calculations were conducted for 20 polar and 4 nonpolar compounds found in gasoline, including methyl tert-butyl ether (MTBE) and other ether oxygenates, ethanol, methanol, and some aromatic hydrocarbons. With no calibration, the screening model successfully captured the reported magnitude of MTBE contamination of at-risk community supply wells. Such screening indicates that other oxygenates would cause similar widespread problems unless they were biodegradable. Stochastic analysis of field parameter variability concluded that community supply well contamination estimates had order-of-magnitude reliability. This indicated that such pre-manufacturing analyses may reasonably anticipate widespread environmental problems and/or inspire focused investigations into chemical properties (e.g., biodegradability) before industrial adoption of new fuel formulations.