Gschwend
Philip M.
Gschwend
Philip M.
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ThesisVolatile organic compounds in seawater(Woods Hole Oceanographic Institution, 1979-01) Gschwend, Philip M.Vapor phase stripping and solid adsorbent trapping were applied to seawater and related samples to concentrate volatile organic compounds. The concentrates were subsequently analyzed by glass capillary gas chromatography and combined gas chromatography-mass spectrometry. The compound identities and the spatial and temporal distributions of their concentrations were used to determine some sources, transformations, and transport mechanisms of organic matter in the sea. Volatile organic compounds were determined in seawater samples from the Sargasso Sea, the western Equatorial Atlantic, and the upwelling region off Peru. Pentadecane was present in all three areas in surface samples at 10-40ng/kg and decreased to 1-2 ng/kg in the deep water. A source related to the transformation of the algal fatty acid, hexadecaugic acid, by zooplankton is proposed since anthropogenic and direct phytoplankton sources are unlikely. C2-alkylated benzenes were found in the upwelled water off Peru at about 4 ng/kg in the surface (5 and 20m), 3 ng/kg below the thermocline (100m), and 2 ng/kg or less in deeper water. A surface or atmospheric source is required to produce this distribution. C6-C10 aldehydes were also found in seawater from off Peru. The direct correlation of their concentrations with chlorophyll a and with oxygen indicated that they are derived from chemical oxidation of algal metabolites, for example, unsaturated fatty acids. Total volatiles in the oligotrophic Sargasso Sea were about 10-30 ng/kg while the biologically productive upwelling region off Peru contained up to 100 ng/kg. The temporal variations of volatile organic compound concentrations were investigated in coastal seawater from Vineyard Sound, Massachusetts. Pentadecane and heptadecane showed large summertime concentration increases which were ascribed to benthic algal sources. Laboratory incubations of benthic algal samples supported this conclusion. The saturated hydrocarbons, from C13-C17, and alkylated benzenes and naphthalenes were all abundant after an oil spill several miles from the sampling site. C2- and C3- benzenes were the most persistently abundant volatile compounds and their concentrations were observed to be 2-10 times higher than average immediately after summer weekends, peak periods of tourist and recreational activities on Cape Cod. Naphthalene and its homologues were more abundant in the winter than in the summer. C6-C10 aldehydes were observed year-round, but showed a concentration maximum at the time of the late-winter phytoplankton bloom. C12-C15 aldehydes were also found in abundance at that time. Oxidation of algal matter by zooplankton or photochemically-produced oxidizing agents may produce the aldehydes, since laboratory cultures of phytoplankton did not produce these oxygenated volatiles. An alkene, structurally similar to the known benthic algal gamone, fucoserraten, was also found in Vineyard Sound seawater and in the upwelling region off Peru. Its appearance in Vineyard Sound samples coincided with the period of expected algal reproductive activity in February and March. Dimethyl polysulfides were found in coastal seawater. They may be produced within the water from precursors such as methyl mercaptan or other known polysulfide metabolites. Total volatile concentrations in Vineyard Sound seawater varied between 2OO and 500 ng/kg for the period from January to June. Maximum concentrations occurred during the late-winter phytoplankton bloom and again in the spring from anthropogenic inputs of hydrocarbons. The highest concentrations of C2- and C3-benzenes found in Vineyard Sound seawater coincided with motorboat use in the immediate vicinity of the sampling station. The average year-round isomer distribution most closely resembled distributions from gasoline and auto exhaust dissolved in seawater, consistent with an inboard or inboard/outboard motorboat source. Atmospheric and runoff delivery of C2- and C3-benzenes to Vineyard Sound seawater during the period from spring through fall was concluded to be of lesser importance. The atmosphere may serve as a buffer for seawater concentrations of the aromatic compounds, supporting low concentrations in the winter and limiting high concentrations in the summer.
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PreprintCarbon isotopic (13C and 14C) composition of synthetic estrogens and progestogens( 2012-06) Griffith, David R. ; Wacker, Lukas ; Gschwend, Philip M. ; Eglinton, Timothy I.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. 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). 13C content was determined by gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and 14C was measured by accelerator mass spectrometry (AMS). Synthetic estrogens and progestogens are 13C depleted (δ13Cestrogen = -30.0 ± 0.9 ‰; δ13Cprogestogen = -30.3 ± 2.6 ‰) compared to endogenous hormones (δ13C ~ -16 ‰ to -26 ‰). The 14C content of the majority of synthetic hormones is consistent with synthesis from C3 plant-based precursors, amended with “fossil” carbon in the case of EE2 and norethindrone acetate. Exceptions are progestogens that contain an ethyl group at carbon position 13 and have entirely “fossil” 14C signatures. Carbon isotope measurements have the potential to distinguish between synthetic and endogenous hormones in the environment. Our results suggest that 13C could be used to discriminate endogenous from synthetic estrogens in animal waste, wastewater effluent, and natural waters. In contrast, 13C and 14C together may prove useful for tracking synthetic progestogens.
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PreprintPolyparameter linear free energy relationship for wood char–water sorption coefficients of organic sorbates( 2015-01) Plata, Desiree L. ; Hemingway, Jordon D. ; Gschwend, Philip M.Black carbons (BCs), including soots, chars, activated carbons, and engineered nanocarbons, have different surface properties, but we do not know to what extent these affect their sorbent properties. To evaluate this for an environmentally ubiquitous form of BC, biomass char, we probed the surface of a well-studied wood char using 14 sorbates exhibiting diverse functional groups and then fit the data with a polyparameter linear free energy relationship (ppLFER) to assess the importance of the various possible sorbate-char surface interactions. Sorption from water to water-wet char evolved with the sorbate's degree of surface saturation and depended on only a few sorbate parameters: log Kd(L/kg) = [(4.03 ± 0.14) + (-0.15 ± 0.04) log ai)] V + [(-0.28 ± 0.04) log ai)] S + (-5.20 ± 0.21) B where ai is the aqueous saturation of the sorbate i, V is McGowan’s characteristic volume, S reflects polarity, and B represents the electron-donation basicity. As generally observed for activated carbon, the sorbate’s size encouraged sorption from water to the char, while its electron donation/proton acceptance discouraged sorption from water. However, the magnitude and saturation dependence differed significantly from what has been seen for activated carbons, presumably reflecting the unique surface chemistries of these two BC materials and suggesting BC-specific sorption coefficients will yield more accurate assessments of contaminant mobility and bioavailability and evaluation of a site's response to remediation.