Identification of phase II in vivo metabolites of alkyl-anthracenes in rainbow trout (Oncorhynchus mykiss)

Metabolism of xenobiotics is a two-step process that increases the polarity of compounds to facilitate their excretion. In previous work, the major in vitro phase I metabolites of alkyl-anthracenes by rainbow trout (Oncorhynchus mykiss) CYP enzymes were shown to be predominantly ring hydroxylated metabolites. Here, we present the first report on the identification of in vivo phase II metabolites of alkyl-anthracenes in juvenile rainbow trout. Bile was collected from trout injected with individual alkyl-anthracenes with, in some cases, a co-injection of β-naphthoflavone (BNF). Some samples were digested with the β-glucuronidase enzyme to confirm the presence of glucuronide conjugates. The metabolites were separated using a water-acetonitrile gradient on a HPLC system equipped with a C₁₈ column and a UV-diode array detector. Trout with endogenous and BNF-induced enzymes produced the same metabolites, but higher concentrations of metabolites were detected after enzyme induction. Alkyl-anthracenes were metabolized predominantly on the rings as evidenced by the UV spectral analysis. Likewise, mass spectrometry and UV spectral analysis confirmed a predominance of glucuronide conjugates for all systems investigated.     

Quantitative analysis of remedial approaches,costs, and time required to remediate dry cleaner sites

This article presents an analysis of remedial approaches, costs, and time required to remediate dry cleaner sites in the United States based on data compiled by the State Coalition for the Remediation of Dry Cleaners (SCRD). Trends in soil and groundwater remedy selection are identified and discussed. Median costs and the time required to remediate dry cleaner sites are presented. In addition, median costs and the duration of soil and groundwater remediation for the most widely used remedial approaches are reported. The analysis is intended to serve the needs of stakeholders, including responsible parties, consultants, regulators, and litigants, as well as real estate developers, banks, and other holders of portfolios of impacted dry cleaner sites by providing quantitative results useful for planning and transactional analysis. © 2011 Wiley Periodicals, Inc.     

Concurrent and Complete Anaerobic Reduction and Microaerophilic Degradation of Mono‐, Di‐, and Trichlorobenzenes

Bio‐Trap^®–based in situ microcosm studies were conducted to evaluate EHC‐M^® stimulated degradation of mono‐, di‐, and trichlorobenzenes in anaerobic groundwater at a site in Michigan. The data show that the EHC‐M^® amendment stimulated an overall increase in microbial activity and a shift in the microbial community structure, indicating more reduced conditions. Stable isotope probing with ¹³C₆‐chlorobenzene demonstrated attenuation of chlorobenzene and subsequent separation and characterization of the ¹²C‐ and ¹³C‐deoxyribonucleic acid (DNA) fractions were used to identify the attenuating microbes. These data clearly show the participation of an obligate aerobe in the chlorobenzene biodegradation process. Decreases in concentrations of trichlorobenzenes were also observed in comparison to a control. Due to the thermodynamically favorable reducing conditions stimulated by EHC‐M^®, the mechanism of degradation of the trichlorobenzenes is presumed to be reductive dehalogenation. However, on the strength of the DNA‐based analysis of microbial community structure, concurrent microaerophilic degradation of chlorobenzene or its metabolites was definitively demonstrated and cannot be ruled out for the other chlorobenzenes. © 2013 Wiley Periodicals, Inc.     

Improvements to TCE Microcosm Protocols for Biostimulation in Bedrock Aquifers

In this study, a factorial‐designed experiment of biostimulated trichloroethene (TCE) dechlorination in fractured bedrock aquifers using microcosms evaluated several potential biostimulants (i.e., nutrients, vitamins, and sterile groundwater). Substantial cost savings and resource efficiency can be provided by this approach because: factorial designs require relatively few microcosms per factor; the interpretation of the observations can proceed largely by common sense, simple arithmetic, and computer graphics; the observations can indicate promising directions for further experimentation and causative relationships; and designs can be suitably augmented when a more in‐depth exploration is needed. TCE degradation was evaluated using three methods of data analysis: (1) analysis of covariance (ANCOVA) between biotic and abiotic treatment trend‐line slopes; (2) calculation of biodegradation half‐life; and (3) effects screening by model fitting. Microcosm preparation with crushed rock in groundwater was found to more closely match the previously observed field rates than the preparation with only groundwater. Injection of nutrient and vitamin mixtures was made into microcosms that were previously aged to obtain consistent conditions, and the TCE concentration measured after incubating for 45 days. Comparison of results indicated that the nutrient mixture slows or inhibits the degradation of TCE compared to the sterile groundwater; however, the vitamin mixture offsets and nearly compensates for the inhibitory effect of the nutrient mixture. It is recommended that this factorial experiment be augmented with additional studies of individual or groups of compounds from the vitamin mixture using this methodology to isolate and identify the specific factor or interaction responsible for the inhibitory compensation. © 2013 Wiley Periodicals, Inc.     

Trimethylphenylammonium-Smectite as an Effective Adsorbent of Water Soluble Aromatic Hydrocarbons

Homoionic trimethylphenylammonium (TMPA)- and tetramethylammonium (TMA)-clays were prepared by Ion-exchange reactions using two smectite clays that differed in their cation exchange capacities and surface charge densities. These clays are referred to as a low-charge (SAC) and high-charge (SWa)-smectite. The organo-clays were evaluated as adsorbents of water soluble aromatic hydrocarbons including benzene, toluene, ethylbenzene, p-xylene, butylbenzene, and naphthalene. All of the aromatic hydrocarbons tested were effectively removed from water by the low-charge TMPA-smectite. The low-charge TMA-smectite was an effective adsorbent for benzene but was ineffective in the removal of the alkylbenzenes and naphthalene from water. The effect of surface charge on the adsorption properties of TMPA-smectite was pronounced. The uptake of benzene and toluene by the high-charge TMPA-smectite was greatly reduced as compared to the low-charge TMPAsmectite. These results suggest the utility of TMPA-smectite as a liner material for petroleum storage containers and waste disposal reservoirs. The use of TMPA-smectite in conjunction with Na-smectite would provide a barrier with the ability to impede the flow of water and to effectively adsorb dissolved organic contaminants.     

Use of n-Fold Cross-Validation to Evaluate Three Methods to Calculate Heavy Truck Annual Average Daily Traffic and Vehicle Miles Traveled

Abstract

Reliable estimates of heavy-truck volumes in the United States are important in a number of transportation applications including pavement design and management, traffic safety, and traffic operations. Additionally, because heavy vehicles emit pollutants at much higher rates than passenger vehicles, reliable volume estimates are critical to computing accurate inventories of on-road emissions. Accurate baseline inventories are also necessary to forecast future scenarios. The research presented in this paper evaluated three different methods commonly used by transportation agencies to estimate annual average daily traffic (AADT), which is used to determine vehicle miles traveled (VMT). Traffic data from continuous count stations provided by the Iowa Department of Transportation were used to estimate AADT for single-unit and multiunit trucks for rural freeways and rural primary highways using the three methods. The first method developed general expansion factors, which apply to all vehicles. AADT, representing all vehicles, was estimated for short-term counts and was multiplied by statewide average truck volumes for the corresponding roadway type to obtain AADT for each truck category. The second method also developed general expansion factors and AADT estimates. Truck AADT for the second method was calculated by multiplying the general AADT by truck volumes from the short-term counts. The third method developed expansion factors specific to each truck group. AADT estimates for each truck group were estimated from short-term counts using corresponding expansion factors. Accuracy of the three methods was determined by comparing actual AADT from count station data to estimates from the three methods. Accuracy of the three methods was compared using n-fold cross-validation. Mean squared error of prediction was used to estimate the difference between estimated and actual AADT. Prediction error was lowest for the method that developed separate expansion factors for trucks. Implications for emissions estimation using the different methods are also discussed.     

Understanding the Effectiveness of Precursor Reductions in Lowering 8-Hr Ozone Concentrations—Part II. The Eastern United States

Abstract

Analyses of ozone (O₃) measurements in conjunction with photochemical modeling were used to assess the feasibility of attaining the federal 8-hr O₃ standard in the eastern United States. Various combinations of volatile organic compound (VOC) and oxides of nitrogen (NO_x) emission reductions were effective in lowering modeled peak 1-hr O₃ concentrations. VOC emissions reductions alone had only a modest impact on modeled peak 8-hr O₃ concentrations. Anthropogenic NO_x emissions reductions of 46–86% of 1996 base case values were needed to reach the level of the 8-hr standard in some areas. As NO_x emissions are reduced, O₃ production efficiency increases, which accounts for the less than proportional response of calculated 8-hr O₃ levels. Such increases in O₃ production efficiency also were noted in previous modeling work for central California. O₃ production in some urban core areas, such as New York City and Chicago, IL, was found to be VOC-limited. In these areas, moderate NO_x emissions reductions may be accompanied by increases in peak 8-hr O₃ levels. The findings help to explain differences in historical trends in 1- and 8-hr O₃ levels and have serious implications for the feasibility of attaining the 8-hr O₃ standard in several areas of the eastern United States.     

Enhanced Desorption of Atmospheric Samples from Activated Carbon

It has been previously shown that the desorption of either a chemisorbed or a physically adsorbed gas can be enhanced by the subsequent introduction of a foreign gas. Under conditions in which desorption recovery of butane from activated, carbon was 50 to 65%, subsequent adsorption of CCl₄ enhanced the recovery of butane to 100%. Recovery of CCl₂F₂, originally 79%, was enhanced to 99% by the same method. The method of enhanced desorption was applied to the recovery of samples from activated carbons exposed to atmospheres in Chicago, New Orleans, Philadelphia, Washington, D. C, and Cincinnati. Three different types of carbons, characterized by different distributions of pore diameters, were used simultaneously in the Cincinnati sampling. In general, the enhanced desorption technique was advantageous in providing analytical information on adsorbed samples recovered from carbon media. The enhancement effect is especially marked with hydrocarbon material. The effects of these structural attributes of the carbon media are evaluated by detailed consideration of infrared absorptions.     

Combustion as the Principal Source of Carbonaceous Aerosol in the Ohio River Valley

Organic and elemental carbon and a number of carboxylic acids and n-alkanes were measured in aerosol samples collected at three sites in the Ohio River Valley between October 1980 and August 1981. Approximately 100 filters were analyzed for organic and elemental carbon for each site. For the 11-month period organic and elemental carbon comprised about 19 percent of the total aerosol mass with about two-thirds of the carbon as organic. Regression analysis showed that the principal source of organic carbon was combustion. The measurements of the specific organic compounds indicated a weak biogenic component to the organic aerosol.