Nonideal transport of contaminants in heterogeneous porous media: 10. Impact of co-solutes on sorption by porous media with low organic-carbon contents

The impact of co-solutes on sorption of tetrachloroethene (PCE) by two porous media with low organic-carbon contents was examined by conducting batch experiments. The two media (Borden and Eustis) have similar physical properties, but significantly different organic-carbon (OC) contents. Sorption of PCE was nonlinear for both media, and well-described by the Freundlich equation. For the Borden aquifer material (OC = 0.03%), the isotherms measured with a suite of co-solutes present (1,2-dichlorobenzene, bromoform, carbon tetrachloride, and hexachloroethane) were identical to the isotherms measured for PCE alone. These results indicate that there was no measurable impact of the co-solutes on PCE sorption for this system. In contrast to the Borden results, there was a measurable reduction in sorption of PCE by the Eustis soil (OC = 0.38%) in the presence of the co-solutes. The organic-carbon fractions of both media contain hard-carbon components, which have been associated with the manifestation of nonideal sorption phenomena. The disparity in results observed for the two media may relate to relative differences in the magnitude and geochemical nature of these hard-carbon components.     

Occurrence and fate of pesticides in four contrasting agricultural settings in the United States

Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.     

A framework for valuing the health benefits of improved bathing water quality in the River Irvine catchment

A simple model predicting bathing water concentrations of Escherichia coli from livestock in the Irvine catchment in SW Scotland has been adapted for intestinal enterococci (IE). This has been used to predict risk of bather illness by extrapolation of published data on bather IE exposure vs incidence of gastro-enteritis. Simulated reduction in the risk of illness by reduced faecal loading was multiplied by a willingness to pay for risk reduction to estimate the annual benefits of mitigation. Health benefits of reducing loading by 75% at Irvine Beach were estimated by a willingness to pay method to be about pound 276k pa. Estimated annualised costs of diffuse pollution mitigation measures across the catchment were higher (> pound 1m), and it is very unlikely that 75% mitigation is achievable with current stocking rates. Further work should explore the influence of uncertainty of model parameters, and use emerging epidemiological information on specific zoonotic pathogens such as E. coli O157 and Cryptosporidium. Other components of the value of clean water should also be included to obtain a complete estimate of the cost:benefit of mitigation.     

Efficient and Practical Approaches to Ground‐Water Right Transfers Under the Prior Appropriation Doctrine and the Snake River Example1

Abstract: Water right transfers are one of the basic means of implementing changes in water use in the highly appropriated water resource systems of the western United States. Many of these systems are governed by the Prior Appropriation Doctrine, which was not originally intended for application to ground‐water pumping and the conjunctive management of ground water and surface water, and thus creates an administrative challenge. That challenge results from the fact that ground‐water pumping can affect all interconnected surface‐water bodies and the effects may be immeasurably small relative to surface water discharge and greatly attenuated in time. Although we may have the ability to calculate the effects of ground‐water pumping and transfers of pumping location on surface‐water bodies, mitigating for all the impacts of each individual transfer is sufficiently inefficient that it impedes the transfer process, frustrates water users, and consequently inhibits economic development. A more holistic approach to ground‐water right transfers, such as a ground‐water accounting or banking scheme, may adequately control transfer third‐party effects while reducing mitigation requirements on individual transfers. Acceptance of an accounting scheme can accelerate the transfer process, and possibly reduce the administrative burden.     

Effects of Riparian Vegetation and Watershed Urbanization on Fishes in Streams of the Mid‐Atlantic Piedmont (USA)1

Abstract: The joint influences of riparian vegetation and urbanization on fish assemblages were analyzed by depletion sampling in paired forested and nonforested reaches of 25 small streams along an urbanization gradient. Nonforested reaches were narrower than their forested counterparts, so densities based on surface area differ from linear densities (based on reach length). Linear densities (based on number or biomass of fish) of American eel, white sucker and tesselated darter, and the proportion of biomass of benthic invertivores were significantly higher in nonforested reaches, while linear densities of margined madtom and the number of pool species were significantly higher in forested reaches. Observed riparian effects may reflect differences in habitat and algal productivity between forested and nonforested reaches. These results suggest that relatively small‐scale riparian restoration projects can affect local geomorphology and the abundance of fish. Dense vegetative cover in riparian zones and similar or analogous habitats in both forested and nonforested reaches, the relatively small scale of the nonforested reaches, and the low statistical power to detect differences in abundance of rare species may have limited the observed differences between forested and nonforested reaches. There was a strong urbanization gradient, with reductions of intolerant species and increases of tolerant species and omnivores with increasing urbanization. Interactions between riparian vegetation type and urbanization were found for blacknose dace, creek chub, tesselated darter, and the proportion of biomass of lithophilic spawners. The study did not provide consistent support for the hypotheses that responses of fish to riparian vegetation would be overwhelmed by urban degradation or insignificant at low urbanization.     

Electrolytic debromination of PBDEs in DE-83 technical decabromodiphenyl ether

Electrochemical debromination of the commercial decabromodiphenyl ether flame retardant DE-83 in partly aqueous tetrahydrofuran (THF) solution gave lower brominated congeners by sequential loss of bromine atoms. Hydrodebromination was most facile for the most heavily brominated congeners. It involves initial electron transfer and proton transfer from water, rather than hydrogen atom abstraction from THF, as shown by experiments with deuterated water. The product distribution from electrolysis involves preferential loss of bromine meta- and para- to the ether linkage, comparable with the products of metabolism of BDE-209 in various organisms. Significantly, the environmentally relevant congeners BDE-47, BDE-99, and BDE-154 were not major products of debromination of BDE-209 by the electron transfer mechanism.     

Aldehyde and Monocyclic Aromatic Hydrocarbon Mixing Ratios at an Urban Site in Las Vegas,Nevada

ABSTRACT

Linhong Jing completed a master's degree in chemistry at UNLV and is currently enrolled in the Ph.D. program at Purdue University. Her address is Department of Chemistry, Purdue University, West Lafayette, IN 47907. Dr. Spencer Steinberg is an associate professor of chemistry at UNLV. His address is UNLV Department of Chemistry, P.O. Box 454003, Las Vegas, NV 89154-4003. Dr. Brian Johnson is an associate professor of chemistry at UNLV. His address is UNLV Department of Chemistry, P.O. Box 454003, Las Vegas, NV 89154-4003.

Oxidation of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air, of significance due to, for example, the potential for O₃ formation, is believed to be initiated by OH attack on the ring (addition) or on the alkyl side chain (H abstraction). A series of ring-breaking reactions follows, with major products predicted to be a-dicarbonyls, simple aldehydes, and organic acids. To test this prediction, ambient air mixing ratios of aldehydes (formaldehyde, ac-etaldehyde, benzaldehyde, glyoxal, and pyruvaldehyde), along with some supporting BTEX data, were measured at an urban site in Las Vegas, NV. Samples were collected on sorbents and determined by chromatographic methods; mixing ratios were compared to ambient levels of CO, O₃, and NO_x. A meteorological analysis (temperature, wind speed, and wind direction) was also included. Statistically significant relationships were noted among the BTEX hydrocarbons (HCs) and among the photochemi-cally derived species (e.g., O₃, NO₂, and some of the aldehydes), although there was seasonal variation. The observations are consistent with a common primary source (i.e., vehicular exhaust or fuel evaporation) for the BTEX compounds and a common secondary source (e.g., OH attack) for glyoxal and pyruvaldehyde.     

Natural emissions for regional modeling of background ozone and particulate matter and impacts on emissions control strategies

Natural emissions adopted in current regional air quality modeling are updated to better describe natural background ozone and PM concentrations for North America. The revised natural emissions include organosulfur from the ocean, NO from lightning, sea salt, biogenic secondary organic aerosol (SOA) precursors, and pre-industrial levels of background methane. The model algorithm for SOA formation was also revised. Natural background ozone concentrations increase by up to 4 ppb in annual average over the southeastern US and Gulf of Mexico due to added NO from lightning while the revised biogenic emissions produced less ozone in the central and western US. Natural PM_2.5 concentrations generally increased with the revised natural emissions. Future year (2018) simulations were conducted for several anthropogenic emission reduction scenarios to assess the impact of the revised natural emissions on anthropogenic emission control strategies. Overall, the revised natural emissions did not significantly alter the ozone responses to the emissions reductions in 2018. With revised natural emissions, ozone concentrations were slightly less sensitive to reducing NOx in the southeastern US than with the current natural emissions due to higher NO from lightning. The revised natural emissions have little impact on modeled PM_2.5 responses to anthropogenic emission reductions. However, there are substantial uncertainties in current representations of natural sources in air quality models and we recommend that further study is needed to refine these representations.