Volatile organic compounds in the unsaturated zone from radioactive wastes

Volatile organic compounds (VOCs) are often comingled with low-level radioactive wastes (LLRW), but little is known about subsurface VOC emanations from LLRW landfills. The current study systematically quantified VOCs associated with LLRW over an 11-yr period at the USGS Amargosa Desert Research Site (ADRS) in southwestern Nevada. Unsaturated-zone gas samples of VOCs were collected by adsorption on resin cartridges and analyzed by thermal desorption and GC/MS. Sixty of 87 VOC method analytes were detected in the 110-m-thick unsaturated zone surrounding a LLRW disposal facility. Chlorofluorocarbons (CFCs) were detected in 100% of samples collected. Chlorofluorocarbons are powerful greenhouse gases, deplete stratospheric ozone, and are likely released from LLRW facilities worldwide. Soil-gas samples collected from a depth of 24 m and a horizontal distance 100 m south of the nearest waste-disposal trench contained >60,000 ppbv total VOCs, including >37,000 ppbv CFCs. Extensive sampling in the shallow unsaturated zone (0-2 m deep) identified areas where total VOC concentrations exceeded 5000 ppbv at the 1.5-m depth. Volatile organic compound concentrations exceeded background levels up to 300 m from the facility. Maximum vertical diffusive fluxes of total VOCs were estimated to be 1 g m yr. Volatile organic compound distributions were similar but not identical to those previously determined for tritium and elemental mercury. To our knowledge, this study is the first to characterize the unsaturated zone distribution of VOCs emanating from a LLRW landfill. Our results may help explain anomalous transport of radionuclides at the ADRS and elsewhere.     

Effects of economic growth on biodiversity in the United States

For many citizens and policymakers, the empirical relationship between economic growth and biodiversity conservation has not been sufficiently established for purposes of identifying the types of economic policies amenable to biodiversity conservation. Some think economic growth conflicts with biodiversity conservation; others think economic growth conduces biodiversity conservation. With panel data from 1997‐2011, encompassing US continental states, we developed a series of statistical models to investigate the relationships among species endangerment, human population, and economic growth as indicated by GDP and per capita GDP. Species endangerment is highly correlated with population and GDP, and per capita GDP is a significant regressor of species endangerment. Across US continental states, competitive exclusion of non‐human species occurs via human economic growth and population growth.     

Nitrogen leaching from Douglas-fir forests after urea fertilization

Leaching of nitrogen (N) after forest fertilization has the potential to pollute ground and surface water. The purpose of this study was to quantify N leaching through the primary rooting zone of N-limited Douglas-fir [Pseudotsuga menziesii (Mirb.) Franco] forests the year after fertilization (224 kg N ha(-1) as urea) and to calculate changes in the N pools of the overstory trees, understory vegetation, and soil. At six sites on production forests in the Hood Canal watershed, Washington, tension lysimeters and estimates of the soil water flux were used to quantify the mobilization and leaching of NO(3)-N, NH(4)-N, and dissolved organic nitrogen below the observed rooting depth. Soil and vegetation samples were collected before fertilization and 1 and 6 mo after fertilization. In the year after fertilization, the total leaching beyond the primary rooting zone in excess of control plots was 4.2 kg N ha(-1) (p = 0.03), which was equal to 2% of the total N applied. The peak NO(3)-N concentration that leached beyond the rooting zone of fertilized plots was 0.2 mg NO(3)-N L(-1). Six months after fertilization, 26% of the applied N was accounted for in the overstory, and 27% was accounted for in the O+A horizon of the soil. The results of this study indicate that forest fertilization can lead to small N leaching fluxes out of the primary rooting zone during the first year after urea application.     

Nutrient dynamics and tree growth of silvopastoral systems: impact of poultry litter

Fertilizing pastures with poultry litter has led to an increased incidence of nutrient-saturated soils, particularly on highly fertilized, well drained soils. Applying litter to silvopastures, in which loblolly pine (Pinus taeda L.) and bahiagrass (Paspalum notatum) production are integrated, may be an ecologically desirable alternative for upland soils of the southeastern USA. Integrating subterranean clover (Trifolium subterraneum) into silvopastures may enhance nutrient retention potential. This study evaluated soil nutrient dynamics, loblolly pine nutrient composition, and loblolly pine growth of an annually fertilized silvopasture on a well drained soil in response to fertilizer type, litter application rate, and subterranean clover. Three fertilizer treatments were applied annually for 4 yr: (i) 5 Mg litter ha(-1) (5LIT), (ii) 10 Mg litter ha(-1) (10LIT), and (iii) an inorganic N, P, K pasture blend (INO). Litter stimulated loblolly pine growth, and neither litter treatment produced soil test P concentrations above runoff potential threshold ranges. However, both litter treatments led to accumulation of several nutrients (notably P) in upper soil horizons relative to INO and unfertilized control treatments. The 10LIT treatment may have increased N and P leaching potential. Subterranean clover kept more P sequestered in the upper soil horizon and conferred some growth benefits to loblolly pine. Thus, although these silvopasture systems had a relatively high capacity for nutrient use and retention at this site, litter should be applied less frequently than in this study to reduce environmental risks.     

Some issues relating to the use of perfluorooctanesulfonate (PFOS) samples as reference standards

Samples of potassium perfluorooctanesulfonate (PFOSK) from three suppliers were analyzed by LC-ESI-MS/MS for purity and by LC-ESI-MS for the percentage of linear isomer present. Our data indicated that the purity ranged from 80% to 98% and the percentages of linear isomer from 67% to 79%. The proportion of branched isomers present in the samples was also estimated using (19)F NMR. These results agreed quite closely with those found by LC-ESI-MS indicating that there is essentially no difference in overall SIM response factor for the branched isomers vs. that of the linear isomer. Several further observations relevant to the use of standards when analyzing for PFOS were encountered during this study. It appears unlikely that matrix effects attributable to the cation (sodium or potassium) present in PFOSNa or PFOSK internal standards is an issue. In seeking potential matrix effects, it was found that the chromatography was improved substantially when the standard was injected as a solution in 80:20 methanol/water rather than 100% methanol. Notably, in concert with the improvement in chromatography, an increase of about 10% in response was observed. In some closely related studies, when (18)O(2) mass-labeled perfluorohexanesulfonate was used as an internal standard, the actual and theoretical concentration ratios matched closely those for related native sulfonates as long as they did not co-elute. However, when they did co-elute, the peak intensities of the native species were enhanced by about 5%, while those of the labeled compound were suppressed by a similar amount. If this effect were not taken into account, the concentration of the native would be inflated by 10%.     

Contaminant-induced irreversible changes in properties of the soil-vadose-aquifer zone: an overview

Most studies on contaminant interactions with the subsurface environment focus on contaminant transport, retention and persistence, and on potential remediation of polluted soils, vadose zones and aquifers. Changes in the soil-vadose-aquifer zone (SVAZ) matrix and properties, caused by human activities, are thus usually considered to be deviations from a normal geochemical environment, which will disappear by natural processes or by specific remediation procedures. However, contaminants may also cause, under specific conditions, irreversible changes in SVAZ properties. In this critical overview, we discuss a different aspect of contaminant-SVAZ interactions: irreversible changes in natural SVAZ properties as a result of anthropogenically-induced chemical contamination. We survey selected research results that illustrate various aspects of such phenomena, in soils, aquifers and the vadose zone. Grouping contaminants according to major and trace elements, we observe that major elements can irreversibly affect water transmission and other physical and chemical properties of the SVAZ, mainly in the liquid phase, while trace elements affect mostly the solid phase matrix.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Making a life in the physical sciences

As a practicing physical chemist, I argue that the challenges faced by the physical sciences have more parallels with organization science than it might first appear. While the physical sciences do represent a strong paradigm endeavor, many of the same issues that were raised in the article “Making a life in the field of organizational science” arise in physical sciences. An essential difference between the physical sciences and organization science is the essentially capital intensive nature of our research. Ironically, the constant pursuit of the requisite research dollars leads to substantial similarity between the fields. The state of academic physical sciences is analyzed in this context informed by the current state of research funding in the United States. Copyright © 2008 John Wiley & Sons, Ltd.