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Saturated linear aliphatic lactones are widespread aroma compounds in wine, linked to stone fruit, dried red fruit, and coconut descriptors. Despite their ubiquity, bioproduction pathways associated with these compounds in wine are unclear, but higher concentrations have been linked to many common vitivinicultural practices, including grape variety, microbiological influence, oak- and bottle-aging, and wine styles such as late harvest, noble rot, and icewine. Development of analytical techniques has enabled increasingly accurate quantification of lactones in wine, shedding more light on their potential origins. This review provides an in-depth summary of the research into linear aliphatic lactones over the past 50 years and provides direction for possible future research to elucidate the biogenesis of these compounds and better estimate their impact on wine aroma.

Two series of high molecular weight disulfonated poly(arylene ether sulfone) random copolymers were synthesized as proton exchange membranes for high-temperature water electrolyzers. These copolymers differ based on the position of the ether bonds on the aromatic rings. One series is comprised of fully para-substituted hydroquinone comonomer, and the other series incorporated 25 mol % of a meta-substituted comonomer resorcinol and 75 mol % hydroquinone. The influence of the substitution position on water uptake and electrochemical properties of the membranes were investigated and compared to that of the state-of-the-art membrane Nafion. The mechanical properties of the membranes were measured for the first time in fully hydrated conditions at ambient and elevated temperatures. Submerged in water, these hydrocarbon-based copolymers had moduli an order of magnitude higher than Nafion. Selected copolymers of each series showed dramatically increased proton conductivities at elevated temperature in fully hydrated conditions, while their H 2 gas permeabilities were well controlled over a wide range of temperatures. These improved properties were attributed to the high glass transition temperatures of the disulfonated poly(arylene ether sulfone)s.

The soil fumigant metam-sodium (CH3NHCS2Na) produces the bioactive respiratory irritant methyl isothiocyanate (MITC). Recent laboratory gas-phase oxidative studies indicate that MITC rapidly transforms to the more toxic methyl isocyanate (MIC) in the lower atmosphere. Inhalation exposure risks from MITC plus MIC may therefore be an occupational worker and/or bystander health concern. To address this concern, MIC was monitored, along with MITC, in outdoor residential air in Washington state during the peak fall metam fumigation season. XAD-7 cartridges, coated with 1-(2-pyridyl)piperazine, were developed to retain MIC as its stable substituted urea derivative. Of the 68 residential air measurements of MIC, 15 (22%) were observed to be above the California Environmental Protection Agency's chronic inhalation reference level of 1 μg/m(3), with an observed maximum MIC air concentration of 4.4 μg/m(3). This study indicates MIC air concentrations can be anticipated along with MITC in residential air where seasonal metam soil fumigant applications occur.

Gaseous methyl isothiocyanate (MITC), the principal breakdown product of the soil fumigant metam sodium (sodium N-methyldithiocarbamate), is an inhalation exposure concern to persons living near treated areas. Inhalation exposure also involves gaseous methyl isocyanate (MIC), a highly reactive and toxic transformation product of MITC. In this work, gas-phase hydroxyl (OH) radical reaction rate constants of MITC and MIC have been determined using a static relative rate technique under controlled laboratory conditions. The rate constants obtained are 15.36 × 10(-12) cm(3) molecule(-1) s(-1) for MITC and 3.62 × 10(-12) cm(3) molecule(-1) s(-1) for MIC. The average half-lives of MITC and MIC in the atmosphere are estimated to be 15.7 and 66.5 h, respectively. The molar conversion of MITC to MIC for OH radical reactions is 67% ± 8%, which indicates that MIC is the primary product of the MITC-OH reaction in the gas phase.

The emission rates [ER (μg m⁻² s⁻¹)] for subsurface injections and surface chemigations for 15 fumigant applications were combined with the physicochemical properties of the fumigants [vapor pressure, VP (Pa); water solubility, S(w) (mg L⁻¹); soil adsorption coefficient, K(oc) (mL g⁻¹)] and with application conditions [application rate, AR (kg ha⁻¹); depth of application, d (cm)]. This resulted in the regression Ln ER = 3.598 + 0.9400 Ln R [R = (VP × AR)/(S(w) × K(oc) × d)], which can be used to estimate emissions for new applications. Emission rates derived from the linear correlation were used as input to an atmospheric dispersion model to estimate concentrations of fumigants in air at various downwind distances, and the results were compared with concentration values measured in the field near sources. The fumigant correlation along with an atmospheric dispersion model can be used as a rapid screening method by regulatory and enforcement agencies for exposure and risk assessment.

Linear anionic polyacrylamide (PAM) has been used in irrigation practices as a flocculating agent to minimize water losses through seepage in earthen canals. The stability of PAM is of concern because of the possibility of acrylamide (AMD) monomer release during environmental weathering. Aqueous solutions of commercial PAM mixed with ferric sulfate, subjected to simulated and natural sunlight irradiation, showed polymer chain scission and release of the AMD monomer. At acid/neutral pH, the amount of AMD released was directly related to the concentration of ferric ion and the irradiation time. At alkaline pH (approximately 8), PAM/Fe(3+) mixtures were stable under irradiation. PAM chain scission involved the hydroxyl radical, but specific AMD release appeared to require PAM-bound iron. Low iron concentrations and alkaline pH of irrigation water would limit AMD release. Residual monomer in PAM can contribute AMD to irrigation water, but concentrations would remain below the U.S. EPA drinking water standard of 0.5 ppb.

Growing demands for potable water have strained water resources and increased interest in wastewater reclamation for potable reuse. This interest has brought increased attention to endocrine-disrupting chemicals (EDCs) as emerging water contaminants. The effect of EDCs, and in particular natural steroid hormones, on humans is of heightened interest in the study of wastewater reuse in advanced life support systems (e.g., space missions) because they are excreted in urine and have high endocrine-disrupting potencies. Direct contact membrane distillation (DCMD) and forward osmosis (FO) are being investigated for wastewater treatment in space. Retention of two natural steroid hormones, estrone and 17beta-estradiol, by these two processes was evaluated in the current investigation. DCMD provided greater than 99.5% hormone rejection; DCMD also provided constant flux, greater than 99.9% urea and ammonia rejection, and high water recovery. FO provided from 77 to 99% hormone rejection depending on experiment duration and feed solution chemistry.

Methods were developed to determine OH reaction rates for medium-weight organophosphorus pesticides in the gas phase. A 57-L chamber was constructed that utilized xenon arc irradiation (>290 nm) to photolyze the OH precursor, methyl nitrite. Experiments were performed at elevated temperatures ranging from 60 to 80 degrees C to minimize wall sorption. Solid-phase microextraction (SPME) sampling of the gas phase was employed to assess the simultaneous rate of loss of the pesticides in relation to the rate of loss of two reference substances with known OH rate constants. An internal gas-phase standard (hexachlorobenzene), relatively stable to hydroxyl radicals, was used to assess other processes, which included dilution and wall sorption. The relative reaction rates of the organophosphorus insecticides, diazinon and chlorpyrifos, when compared to reference compounds, were unaffected by various air temperatures between 60 and 80 degrees C. Although both insecticides were expected to react at similar rates on the basis of structural activity model predictions, diazinon reacted 3 times more rapidly than chlorpyrifos and gave estimated environmental OH half-lives of 0.5 and 1.4 h, respectively. The degree of sorption onto the chamber walls was minimal and similar for each of the compounds examined. Experimental gas-phase determinations at elevated temperatures may provide important information that can be used when in the assessment of the potential of airborne pesticide risks to nontarget and ecologically sensitive areas.

New methods were developed to determine photolysis rates of medium-weight pesticides in the gas phase using elevated air temperatures and solid-phase microextraction (SPME). A 57-L glass chamber was constructed that utilized collimated xenon arc irradiation that could heat chamber air to increase the amount of pesticide in the gas phase. Gas-phase photolysis rates were determined at various air temperatures by comparing the rate of loss of each of the tested pesticides to a photochemically stable tracer, hexachlorobenzene. Interval sampling of gas-phase constituents was performed using SPME immediately followed by GC-ECD or GC-MSD analysis. The two pesticides under examination were the dinitroaniline herbicide trifluralin and the organophosphorus insecticide chlorpyrifos. The gas-phase photolysis for trifluralin was found to be rapid with half-lives of 22-24 min corrected for sunlight. These results were comparable to photochemical lifetime estimates from other investigators under sunlight conditions. Elevating temperatures from 60 to 80 degrees C did not affect photolysis rates, and these rates could be extrapolated to environmental temperatures. From 60 to 80 degrees C, gas-phase chlorpyrifos photolysis lifetimes were observed to range from 1.4 to 2.2 h corrected for sunlight and will thus be important together with hydroxyl radical reactions for removing this substance from the atmosphere. At these elevated temperatures, pesticides and tracer compounds were found to be substantially in the gas phase, and possible effects on reaction rates from wall interactions were minimized.

The increase in deep pit mining in western North America raises concerns about the environmental impact of mine closure.