Repeated Aqueous Film-Forming Foams Applications: Impacts on Polyfluoroalkyl Substances Retention in Saturated Soil.

Historical practices at firefighter-training areas involved repeated aqueous film-forming foams (AFFFs) applications, resulting in source zones characterized by high concentrations of perfluoroalkyl and polyfluoroalkyl substances (PFAS). Repeated applications of AFFF composed of 14 anionic and 23 zwitterionic perfluoroalkyl substances (PFAS) were conducted on a single one-dimensional saturated soil column to quantify PFAS retention. An electrofluorination-based (3M) Milspec AFFF, which was above the mixture's critical micelle concentration (CMC), was at application strength (3%, v/v). Retention and retardation of PFAS mass increased with each successive AFFF addition, although the PFAS concentration profiles for subsequent applications differed from the initial. Greater degree of mass retention and retardation correlated with longer PFAS carbon-fluorine chain length and charged-headgroup type and as a function of AFFF application number. Anionic PFAS were increasingly retained with each subsequent AFFF application, while zwitterionic PFAS exhibited an alternating pattern of sorption and desorption. Surfactant-surfactant adsorption and competition during repeat AFFF applications that are at concentrations above the CMC resulted in adsorbed PFAS from the first application, changing the nature of the soil surface with preferential sorption of anionic PFAS and release of zwitterionic PFAS due to competitive elution. Applying a polyparameter quantitative structure-property relationship developed to describe sorption of AFFF-derived PFAS to uncontaminated, saturated soil was attempted for our experimental conditions. The model had been derived for data where AFFF is below the apparent CMC and our experimental conditions that included the presence of mixed micelles (aggregates consisting of different kinds of surfactants that exhibit characteristics properties different from micelles composed of a single surfactant) resulted in overall PFAS mass retained by an average of 27.3% ± 2.7% (standard error) above the predicted values. The correlation was significantly improved by adding a "micelle parameter" to account for cases where the applied AFFF was above the apparent CMC. Our results highlight the importance of interactions between the AFFF components that can only be investigated by employing complex PFAS mixtures at concentrations present in actual AFFF at application strength, which are above their apparent CMC. In firefighter-training areas (AFFF source zones), competitive desorption of PFAS may result in downgradient PFAS retention when desorbed PFAS become resorbed to uncontaminated soil.

Evaluating Neutral PFAS for Potential Dermal Absorption from the Gas Phase.

Exposures to per- and polyfluoroalkyl substances (PFAS) are of increasing concern. Assessments typically focus only on ingestion and inhalation exposure due to a lack of generally accepted approaches for estimating dermal absorption. Prior work indicates limited dermal absorption of ionic PFAS, but absorption of neutral PFAS has not been examined from the liquid vehicle or from vapor. Partitioning of semivolatile organic compounds from the gas phase to the skin surface (i.e., stratum corneum) is well known, but the potential for partitioning of neutral PFAS from the gas phase to the stratum corneum has yet to be estimated. The SPARC-estimated physicochemical properties were used to calculate transdermal permeability coefficients (kp_g) and dermal-to-inhalation (D/I) exposure ratios for two groups of neutral PFAS, including those on a U.S. Environmental Protection Agency PFAS list. 11 neutral PFAS gave calculated D/I ratios >5, indicating that direct transdermal absorption may be an important exposure pathway compared to inhalation. Data on consumer products or indoor air is needed for the 11 neutral PFAS, followed by possible biomonitoring to experimentally verify dermal absorption from air. Additional PFAS should be estimated by the protocol used here as they are identified in commercial products.

Investigation into reversed-phase chromatography peptide separation systems part V: Establishment of a screening strategy for development of methods for assessment of pharmaceutical peptides' purity.

The paper describes a simple and rapid reversed-phase UHPLC method development screening strategy for the purity determination of peptide-based pharmaceuticals. The protocol utilises five disparate column and six volatile or non-volatile mobile phases (i.e., 30 combinations). The method development strategy has been demonstrated to be highly effective in identifying conditions which generate complementary selectivity and good peak shape. Columns with varying degrees of charge (positive and negative), in addition to their differing hydrophobic character, were used in combination with mobile phases within the pH range of 2.3 to 5.1. The novel ion-pair / chaotropic reagent ammonium hexafluorophosphate at pH 2.3 was shown to be an extremely useful mobile phase additive in that it produced excellent complementary separation and good peak shape. Methanesulfonic acid was demonstrated to be a good alternative to the ubiquitously employed trifluoroacetic acid which failed to generate optimum separation for the peptides investigated highlighting the importance of screening disparate mobile phase additives. Both ammonium hexafluorophosphate and methanesulfonic acid were shown not to adversely affect the stability of C18 columns or demonstrated any irreversible adsorption / memory effects. No pH hysteresis effects were demonstrated with any of the stationary phases on mobile phase pH cycling. No major problems have been observed with the novel mobile phase additives ammonium hexafluorophosphate and methanesulfonic acid, however, it is recommended that they be used with caution until long-term routine use has been established.

Investigation into reversed-phase chromatography peptide separation systems Part IV: Characterisation of mobile phase selectivity differences.

The differentiation of mobile phase compositions between sub-classes which exhibit distinct chromatographic selectivity (i.e. termed characterisation) towards a range of peptide probes with diverse functionality and hence the possibility for multi-modal retention mechanisms has been undertaken. Due to the complexity of peptide retention mechanisms in given mobile phase conditions, no attempt has been made to explain these, instead mobile phases have simply been classified into distinct groups with an aim of identifying those yielding differing selectivities for use in strategic method development roadmaps for the analysis of peptide mixtures. The selectivity differences between nine synthetic peptides (fragments of [Ile27]-Bovine GLP-2) were used to assess how fifty-one RPC mobile phase compositions of differing pH (range 1.8 - 7.8), salt types, ionic strengths, ion-pair reagents and chaotropic / kosmotropic additives affected chromatographic selectivity on a new generation C18 stationary phase (Ascentis Express C18). The mobile phase compositions consisted of commonly used and novel UV or MS compatible additives. The chemometric tool of Principal Component Analysis (PCA) was used to visualise the differences in selectivity generated between the various mobile phases evaluated. The results highlight the importance of screening numerous mobile phases of differing pH, ion-pair reagents and ionic strength in order to maximise the probability of achieving separation of all the peptides of interest within a complex mixture. PCA permitted a ranking of the relative importance of the various mobile phase parameters evaluated. The concept of using this approach was proven in the analysis of a sample of Bovine GLP-2 (1-15) containing synthesis related impurities. Mobile phases with high ionic strength were demonstrated to be crucial for the generation of symmetrical peaks. The observations made on the C18 phase were compared on three additional stationary phases (i.e. alkyl amide, fluorophenyl and biphenyl), which had previously been shown to possess large selectivity differences towards these peptides, on a limited sub-set of mobile phases. With the exception of the ion-pair reagent, similar trends were obtained for the C18, fluorophenyl and biphenyl phases intimating the applicability of these findings to the vast majority of RPC columns (i.e. neutral or weakly polar in character) which are suitable for the analysis of peptides. The conclusions were not relevant for columns with a more disparate nature (i.e. containing a high degree of positive charge).

The Interactive Effects of Crude Oil and Corexit 9500 on Their Biodegradation in Arctic Seawater.

The risk of petroleum spills coupled with the potential application of chemical dispersants as a spill response strategy necessitates further understanding of the fate of oil and dispersants and their interactive effects during biodegradation. Using Arctic seawater mesocosms amended with either crude oil, Corexit 9500, or both together, we quantified the chemical losses of crude oil and Corexit 9500 and identified microbial taxa implicated in their biodegradation based on shifts in the microbial community structure over a 30-day time course. Chemical analyses included total petroleum hydrocarbons (TPH), n-alkanes, branched alkanes, and polycyclic aromatic hydrocarbons (PAHs) for oil loss and the surfactant components dioctyl sodium sulfosuccinate (DOSS), Span 80, Tween 80, Tween 85, and the DOSS metabolite ethylhexyl sulfosuccinate (EHSS) for Corexit loss. Changes to the microbial communities and identification of key taxa were determined by 16S rRNA gene amplicon sequencing. The nonionic surfactants of Corexit 9500 (Span 80 and Tweens 80 and 85) biodegraded rapidly, dropping to below the limits of detection within 5 days and prior to any detectable initiation of oil biodegradation. This resulted in no observable suppression of petroleum biodegradation in the presence of Corexit compared to that of oil alone. In contrast, biodegradation of DOSS was delayed in the presence of oil, based on the prolonged presence of DOSS and accumulation of the degradation intermediate EHSS that did not occur in the absence of oil. Microbial analyses revealed that oil and Corexit enriched different overall microbial communities, with the presence of both resulting in a community composition that shifted from one more similar to that of Corexit only to one reflecting the oil-only community over time, in parallel with the degradation of predominantly Corexit and then oil components. Some microbial taxa (Oleispira, Pseudofulvibacter, and Roseobacter) responded to either oil or Corexit, suggesting that some organisms may be capable of utilizing both substrates. Together, these findings reveal interactive effects of crude oil and Corexit 9500 on chemical losses and microbial communities as they biodegrade, providing further insight into their fate when copresent in the environment.IMPORTANCE Chemical dispersants such as Corexit 9500 are commonly used in oil spill response and are currently under consideration for use in the Arctic, where their fate and effects have not been well studied. This research was performed to determine the interactive effects of the copresence of crude oil and Corexit 9500 on the degradation of components from each mixture and the associated microbial community structure over time in Arctic seawater. These findings will help yield a better understanding of the biodegradability of dispersant components applied to an oil spill, the temporal microbial community response to dispersed oil, and the fundamental microbial ecology of organic contaminant biodegradation processes in the Arctic marine environment.

Investigation into reversed phase chromatography peptide separation systems part III: Establishing a column characterisation database.

The Peptide RPC Column Characterisation Protocol was applied to 38 stationary phases, varying in ligand chemistry, base silica, end capping and pore size, which are suitable for the analysis of peptides. The protocol at low and intermediate pH is based on measuring retention time differences between peptides of different functionality to calculate selectivity delta values. The characterisation was designed to explore increases / decreases in positive or negative charge (deamidation), steric effect (i.e. racemisation / switch in amino acid order), oxidation and addition / removal of aromatic moieties. The necessity of developing a characterisation protocol specifically for peptide analysis was highlighted by the fact that the small molecule databases (Snyder's Hydrophobic Subtraction Model and the extended Tanaka protocol) failed to correlate with the Peptide RPC Column Characterisation Protocol. Principal Component Analysis was used to demonstrate that the protocol could be used to identify columns with similar or dissimilar chromatographic selectivity for the purpose of selectivity back-up or method development columns respectively. This was validated using peptide fragments derived from the tryptic digest of bovine insulin and carbonic anhydrase. It was also demonstrated that the presence of positively charged functional groups on the stationary phase was advantageous as it yielded very different chromatographic selectivity and improved peak shape.

Investigation into reversed phase chromatography peptide separation systems part I: Development of a protocol for column characterisation.

A protocol was defined which utilised peptides as probes for the characterisation of reversed phase chromatography peptide separation systems. These peptide probes successfully distinguished between differing stationary phases through the probe's hydrophobic, electrostatic, hydrogen bonding and aromatic interactions with the stationary phase, in addition, to more subtle interactions such as the phase's ability to separate racemic or isomeric probes. The dominating forces responsible for the chromatographic selectivity of peptides appear to be hydrophobic as well as electrostatic and polar in nature. This highlights the need for other types of stationary phase ligands with possibly mixed mode functionalities / electrostatic / polar interactions for peptide separations rather than the hydrophobic ligands which dominate small molecule separations. Selectivity differences are observed between phases, but it appears that it is the accessibility differences between these phases which play a crucial role in peptide separations i.e. accessibility to silanols, the hydrophobic acetonitrile / ligand layer or a thin adsorbed water layer on the silica surface.

Investigation into reversed phase chromatography peptide separation systems part II: An evaluation of the robustness of a protocol for column characterisation.

The robustness of the Peptide Reversed Phase Chromatography (RPC) Column Characterisation Protocol was evaluated using reduced factorial design, to ascertain the degree of control required for parameters including temperature, flow rate, dwell volume, a systematic shift in the gradient, amount of formic acid in the aqueous and organic, pH of the ammonium formate and amount of acetonitrile (%MeCN) in the strong solvent, where a loss of MeCN resulted in an unacceptable variation. Mitigations have been introduced to ensure the integrity of the data to allow RPC columns to be characterised using peptides as probes, with the definitive protocol described. In addition, the instrument and column batch to batch variability were assessed with good reproducibility.

Assessment of local tissue water in the arms and trunk of breast cancer survivors with and without upper extremity lymphoedema.

Given the paucity of information on local tissue water (LTW) in the upper extremity and trunk of women after breast cancer surgery, the purpose of this study was to compare tissue dielectric constant (TDC) values between the affected and unaffected sides of breast cancer survivors with and without upper extremity lymphoedema (LE). Differences in LTW were assessed using the TDC method for three sites in the upper limbs, three sites in the lateral thorax and two sites on the back. Additional measures included demographic and clinical characteristics, arm circumference and bioimpedance analysis. For the 112 survivors without LE, no differences in TDC values were found between the affected and unaffected sides for the first dorsal web space, ventral forearm and upper arm, and upper and lower back. Compared to the unaffected side, TDC values were significantly higher on the affected side for the upper, mid and lower lateral thorax. For the 78 survivors with LE, compared to the unaffected side, TDC was significantly higher on the affected side for all of the sites evaluated except the hand web space. Our findings support the use of the TDC method to detect differences in upper extremity and truncal oedema in survivors with LE following breast cancer treatment. Measurement of LTW may provide a useful method to determine truncal as well as extremity LE. The ability to detect early signs of truncal oedema may lead to pre-emptive interventions in breast cancer survivors.

In-Vial Extraction Large Volume Gas Chromatography Mass Spectrometry for Analysis of Volatile PFASs on Papers and Textiles.

Volatile per- and polyfluorinated alkyl substances (PFASs) are found in consumer goods that contribute to human exposure to PFASs. Volatile PFAS precursors transform to perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs) in both humans and the environment. Established methods for volatile PFASs in consumer goods exist, but higher sample throughput and greener sample preparation methods are needed to minimize analyte loss, while maintaining sensitivity. New analytical methodology was developed where a 1.5 × 1.5 cm piece of paper or textile is placed into an autosampler vial with solvent and mass-labeled internal standards, sonicated for 30 min, and directly injected without removal of material from the autosampler vial. Large volume injection (20 µL) gas chromatography mass spectrometry was applied for the quantification for 21 individual PFASs from five classes: fluorotelomer alcohols (FTOHs), fluorinated sulfonamides (N-MeFASA, N-EtFASA), and fluorinated sulfonamidoethanols (N-MeFASE, N-EtFASE). Nontargeted analysis revealed additional C2-C7 homologues of N-MeFASE and N-EtFASE, which accounted for 14-18% of the total volatile PFASs on three textiles. Overlooking short-chain (≤C7) N-MeFASE, N-EtFASE, and long-chained (10:2-14:2) FTOHs on older textiles from the 1980s leads to an underestimation of human and environmental exposure to volatile PFAS.

RELIABILITY AND VALIDITY OF THE HALO DIGITAL GONIOMETER FOR SHOULDER RANGE OF MOTION IN HEALTHY SUBJECTS.

BACKGROUND: Range of motion (ROM) of the shoulder is an integral component of assessment of musculoskeletal shoulder impairments. ROM is typically measured using a universal goniometer (UG). The UG has demonstrated good intra and inter-rater reliability for measuring shoulder ROM, although limitations exist. In recent years, alternative measurement devices such as smartphone applications and digital goniometers have been introduced, potentially addressing some of the shortcomings of the UG. Limited research is available on the validity and reliability of these alternative devices, including the laser-guided digital goniometer, in measuring shoulder ROM.Purpose: The purpose of this study was to investigate the intra- and inter-rater reliability and concurrent validity of a laser-guided digital goniometer (HALO) for measuring active shoulder ROM. METHODS: A convenience sample of healthy volunteers was recruited. To be eligible, participants were required to be between 18 and 75 years of age and able to actively move at least one shoulder into 90 ° of glenohumeral abduction. Self-report of previous significant shoulder injury; previous shoulder surgery; current bilateral shoulder pain; current neck or upper back pain; or referred pain into the upper extremity were exclusion criteria. Active shoulder flexion, abduction, internal rotation, and external rotation were measured for each shoulder. Two evaluators measured each motion twice with each device (HALO and the UG) per shoulder. The intra-class correlation coefficient (ICC) for reliability and validity/agreement between devices was calculated using a two-way mixed model with a 95% confidence interval. RESULTS: Data were analyzed for 75 shoulders from 41 participants (seven participants had only one shoulder evaluated). Intra-rater reliability ICCs are between 0.82 and 0.91 for the HALO, and 0.83 to 0.95 for the UG. Inter-rater reliability for the HALO was 0.89 to 0.98 and for the UG was 0.90 to 0.98. The ICCs for agreement, comparing the HALO digital goniometer to the UG ranged from 0.79 to 0.99. CONCLUSION: This study provides evidence that the HALO digital goniometer can be a reliable and valid tool for measuring shoulder ROM in individuals with healthy shoulders. However, the two devices should not be used interchangeably to evaluate a single individual's change over time for any motion. LEVEL OF EVIDENCE: Diagnostic Study (clinical measurement), Level 2b.

Biodegradation of Crude Oil and Corexit 9500 in Arctic Seawater.

The need to understand the biodegradation of oil and chemical dispersants in Arctic marine environments is increasing alongside growth in oil exploration and transport in the region. We chemically quantified biodegradation and abiotic losses of crude oil and Corexit 9500, when present separately, in incubations of Arctic seawater and identified microorganisms potentially involved in biodegradation of these substrates based on shifts in bacterial community structure (16S rRNA genes) and abundance of biodegradation genes (GeoChip 5.0 microarray). Incubations were performed over 28-day time courses using surface seawater collected from near-shore and offshore locations in the Chukchi Sea. Within 28 days, the indigenous microbial community biodegraded 36% (k = 0.010 day-1) and 41% (k = 0.014 day-1) of oil and biodegraded 77% and 33% (k = 0.015 day-1) of the Corexit 9500 component dioctyl sodium sulfosuccinate (DOSS) in respective near-shore and offshore incubations. Non-ionic surfactants (Span 80, Tween 80, and Tween 85) present in Corexit 9500 were non-detectable by 28 days due to a combination of abiotic losses and biodegradation. Microorganisms utilized oil and Corexit 9500 as growth substrates during the incubation, with the Corexit 9500 stimulating more extensive growth than oil within 28 days. Taxa known to include oil-degrading bacteria (e.g., Oleispira, Polaribacter, and Colwellia) and some oil biodegradation genes (e.g., alkB, nagG, and pchCF) increased in relative abundance in response to both oil and Corexit 9500. These results increase our understanding of oil and dispersant biodegradation in the Arctic and suggest that some bacteria may be capable of biodegrading both oil and Corexit 9500.

Sorption of Fluorotelomer Sulfonates, Fluorotelomer Sulfonamido Betaines, and a Fluorotelomer Sulfonamido Amine in National Foam Aqueous Film-Forming Foam to Soil.

During fire-fighter training, equipment testing, and emergency responses with aqueous film-forming foams (AFFFs), milligrams per liter concentrations of anionic, zwitterionic, and cationic per- and polyfluoroalkyl substances (PFASs) enter the environment. Because the behavior of zwitterionic and cationic PFASs in the subsurface is unknown, batch sorption experiments were conducted using National Foam AFFF, which contains anionic fluorotelomer sulfonates (FtSs), zwitterionic fluorotelomer sulfonamido betaines (FtSaBs), and cationic 6:2 fluorotelomer sulfonamido amine (FtSaAm). Sorption of the FtSs, FtSaBs, and 6:2 FtSaAm to six soils with varying organic carbon, effective cation-exchange capacity, and anion-exchange capacity was evaluated to determine sorption mechanisms. Due to the poor recovery of the FtSaBs and 6:2 FtSaAm with published PFAS soil extraction methods, a new soil extraction method was developed to achieve good (90-100%) recoveries. The 6:2 FtSaAm was depleted from the aqueous phase in all but one soil, which is attributed to electrostatic and hydrophobic interactions. Sorption of the FtSs was driven by hydrophobic interactions, while the FtSaBs behave more like cations that strongly associate with the solid phase relative to groundwater. Thus, the sorption mechanisms of the FtSs, FtSaBs, and 6:2 FtSaAm are more complex than expected and cannot be predicted by bulk soil properties.

Trace Analysis of Surfactants in Corexit Oil Dispersant Formulations and Seawater.

After the April 2010 explosion on the Deepwater Horizon oil rig, and subsequent release of millions of barrels of oil, two Corexit oil dispersant formulations were used in unprecedented quantities both on the surface and sub-surface of the Gulf of Mexico. Although the dispersant formulations contain four classes of surfactants, current studies to date focus on the anionic surfactant, bis-(2-ethylhexyl) sulfosuccinate (DOSS). Factors affecting the integrity of environmental and laboratory samples for Corexit analysis have not been systematically investigated. For this reason, a quantitative analytical method was developed for the detection of all four classes of surfactants, as well as the hydrolysis products of DOSS, the enantiomeric mixture of α- and ß-ethylhexyl sulfosuccinate (α-/ß-EHSS). The analytical method was then used to evaluate which practices for sample collection, storage, and analysis resulted in high quality data. Large volume, direct injection of seawater followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) minimized analytical artifacts, analysis time, and both chemical and solid waste. Concentrations of DOSS in the seawater samples ranged from 71 - 13,000 ng/L, while the nonionic surfactants including Span 80, Tween 80, Tween 85 were detected infrequently (26% of samples) at concentrations from 840 - 9100 ng/L. The enantiomers α-/ß-EHSS were detected in seawater, at concentrations from 200 - 1,900 ng/L, and in both Corexit dispersant formulations, indicating α-/ß-EHSS were applied to the oil spill and may be not unambiguous indicator of DOSS degradation. Best practices are provided to ensure sample integrity and data quality for environmental monitoring studies and laboratory that require the detection and quantification of Corexit-based surfactants in seawater.

Combined Experimental and Molecular Simulation Investigation of the Individual Effects of Corexit Surfactants on the Aerosolization of Oil Spill Matter.

We report laboratory aerosolization experiments and classical molecular dynamics (MD) simulations, with the objective of investigating the individual effects of the two Corexit surfactants Span 80 (nonionic) and dioctyl sodium sulfosuccinate (DOSS, ionic), on the aerosolization of oil spill matter to the atmosphere. Our simulation results show that Span 80, DOSS, and the oil alkanes n-pentadecane (C15) and n-triacontane (C30) exhibit deep free energy minima at the air/seawater interface. C15 and C30 exhibit deeper free energy minima at the interface when Span 80 is present, as compared to the situation when DOSS or no surfactants are at the interface. These results suggest that Span 80 makes these oil hydrocarbons more likely to be adsorbed at the surface of seawater droplets and carried out to the atmosphere, relative to DOSS or to the situation where no surfactants are present. These simulation trends are in qualitative agreement with our experimental observations in a bubble-column setup, where larger amounts of oil hydrocarbons are ejected when Span 80 is mixed with oil and injected into the column, as compared to when DOSS is used. Our simulations also indicate that Span 80 has a larger thermodynamic incentive than DOSS to move from the seawater phase and into the air/seawater interface. This observation is also in qualitative agreement with our experimental measurements, which indicate that Span 80 is ejected in larger quantities than DOSS. Our simulations also suggest that DOSS predominantly adopts a perpendicular orientation with respect to the air/seawater interface at a dispersant to oil ratio (DOR) of 1:20, but has a slight preference to lie parallel to the interfaces at a DOR = 1:5; in both cases, DOSS molecules have their tails wide open and stretched. In contrast, Span 80 has a slight preference to align parallel to the interfaces with a coiled conformation at both DOR values.

Chemical dispersants can suppress the activity of natural oil-degrading microorganisms.

During the Deepwater Horizon oil well blowout in the Gulf of Mexico, the application of 7 million liters of chemical dispersants aimed to stimulate microbial crude oil degradation by increasing the bioavailability of oil compounds. However, the effects of dispersants on oil biodegradation rates are debated. In laboratory experiments, we simulated environmental conditions comparable to the hydrocarbon-rich, 1,100 m deep plume that formed during the Deepwater Horizon discharge. The presence of dispersant significantly altered the microbial community composition through selection for potential dispersant-degrading Colwellia, which also bloomed in situ in Gulf deep waters during the discharge. In contrast, oil addition to deepwater samples in the absence of dispersant stimulated growth of natural hydrocarbon-degrading Marinobacter. In these deepwater microcosm experiments, dispersants did not enhance heterotrophic microbial activity or hydrocarbon oxidation rates. An experiment with surface seawater from an anthropogenically derived oil slick corroborated the deepwater microcosm results as inhibition of hydrocarbon turnover was observed in the presence of dispersants, suggesting that the microcosm findings are broadly applicable across marine habitats. Extrapolating this comprehensive dataset to real world scenarios questions whether dispersants stimulate microbial oil degradation in deep ocean waters and instead highlights that dispersants can exert a negative effect on microbial hydrocarbon degradation rates.

Quantitative determination of 1,4-dioxane and tetrahydrofuran in groundwater by solid phase extraction GC/MS/MS.

Groundwater contamination by cyclic ethers, 1,4-dioxane (dioxane), a probable human carcinogen, and tetrahydrofuran (THF), a co-contaminant at many chlorinated solvent release sites, are a growing concern. Cyclic ethers are readily transported in groundwater, yet little is known about their fate in environmental systems. High water solubility coupled with low Henry's law constants and octanol-water partition coefficients make their removal from groundwater problematic for both remedial and analytical purposes. A solid-phase extraction (SPE) method based on activated carbon disks was developed for the quantitative determination of dioxane and THF. The method requires 80 mL samples and a total of 1.2 mL of solvent (acetone). The number of steps is minimized due to the "in-vial" elution of the disks. Average recoveries for dioxane and THF were 98% and 95%, respectively, with precision, as indicated by the relative standard deviation of <2% to 6%. The method quantitation limits are 0.31 microg/L for dioxane and 3.1 microg/L for THF. The method was demonstrated by analyzing groundwater samples for dioxane and THF collected during a single sampling campaign at a TCA-impacted site. Dioxane concentrations and areal extent of dioxane in groundwater were greater than those of either TCA or THF.