Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

Comparison of vehicle activity and emission inventory between Beijing and Shanghai

Vehicle emission inventory is a critical element for air quality study. This study created systemic methods to establish a vehicle emission inventory in Chinese cities. The methods were used to obtain credible results of vehicle activity in Beijing and Shanghai. On the basis of the vehicle activity data, the International Vehicle Emission model is used to establish vehicle emission inventories. The emissions analysis indicates that 3 t of particulate matter (PM), 199 t of nitrogen oxides (NO(x)), 192 t of volatile organic compounds (VOCs), and 2403 t of carbon monoxide (CO) are emitted from on-road vehicles each day in Beijing, whereas 4 t of PM, 189 t of NO(x), 113 t of VOCs, and 1009 t of CO are emitted in Shanghai. Although common features were found in these two cities (many new passenger cars and a high taxi proportion in the fleet), the emission results are dissimilar because of the different local policy regarding vehicles. The method to quantify vehicle emission on an urban scale can be applied to other Chinese cities. Also, knowing how different policies can lead to diverse emissions is beneficial knowledge for other city governments.     

Matrix based fertilizers reduce nitrogen and phosphorus leaching in three soils

We compared the efficacy of matrix based fertilizers (MBFs) formulated to reduce NO3-, NH4+, and total phosphorus (TP) leaching, with Osmocoate 14-14-14, a conventional commercial slow release fertilizer (SRF) and an unamended control in three different soil textures in a greenhouse column study. The MBFs covered a range of inorganic N and P in compounds that are relatively loosely bound (MBF 1) to more moderately bound (MBF 2) and more tightly bound compounds (MBF 3) mixed with Al(SO4)3H2O and/or Fe2(SO4)3 and with high ionic exchange compounds starch, chitosan and lignin. When N and P are released, the chemicals containing these nutrients in the MBF bind N and P to a Al(SO4)3H2O and/or Fe2(SO4)3 starch-chitosan-lignin matrix. One milligram (8000 spores) of Glomus intradices was added to all formulations to enhance nutrient uptake. In all three soil textures the SRF leachate contained a higher amount of NH4+, NO3- and TP than leachate from all other fertilizers. In all three soils there were no consistent differences in the amount of NH4+, NO3- and TP in the MBF leachates compared to the control leachate. Plants growing in soils receiving SRF had greater shoot, root and total biomass than all MBFs regardless of Al(SO4)3H2O or Fe2(SO4)3 additions. Arbuscular mycorrhizal infection in plant roots did not consistently differ among plants growing in soil receiving SRF, MBFs and control treatments. Although the MBFs resulted in less plant growth in this experiment they may be applied to soils growing plants in areas that are at high risk for nutrient leaching to surface waters.     

Modeling the Effects of Potential Salinity Shifts on the Recovery of Striped Bass in the Savannah River Estuary,Georgia–South Carolina,United States

Increased salinity in spawning and nursery grounds in the Savannah River estuary was cited as the primary cause of a 97% decrease in adult striped bass (Morone saxatilis) and a concomitant 96% decrease in striped bass egg production. Restoration efforts focused on environmental remediation and stock enhancement have resulted in restored salinity patterns and increased egg and adult abundances. However, future water needs or harbor development may preclude further recovery by reducing freshwater inflow or increasing salinity intrusion. To assess the effect of potential changes in the salinity regime, we developed models relating discharge, tidal phase, and salinity to striped bass egg and early larval survival and re-cast these in a quantitative Bayesian belief network. The model indicated that a small upstream shift (≤1.67 km) in the salinity regime would have the least impact on striped bass early life history survival, whereas shifts >1.67 km would have progressively larger impacts, with a 8.33-km shift potentially reducing our estimated survival probability by >28%. Such an impact could have cumulative and long-term detrimental effects on the recovery of the Savannah River striped bass population. The available salinity data were collected during average and low flows, so our model represents some typical and some extreme conditions during a striped bass spawning season. Our model is a relatively simplistic, “first-order” attempt at evaluating potential effects of changes in the Savannah River estuarine salinity regime and points to areas of concern and potential future research.     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

Physicochemical parameters aid microbial community? A case study from marine recreational beaches,Southern India

A total of 176 (water and sediment) samples from 22 stations belonging to four different (urban, semi-urban, rural, and holy places) human habitations of Tamil Nadu beaches were collected and analyzed for physiochemical and microbial parameters during 2008–2009. Bacterial counts were two- to tenfold higher in sediments than in water due to strong bacterial aggregations by dynamic flocculation and rich organic content. The elevated bacterial communities during the monsoon explain rainfalls and several other wastes from inlands. Coliform counts drastically increased at holy and urban places due to pilgrimage and other ritual activities. Higher values of the pollution index (PI) ratio (>1) reveals, human fecal pollutions affect the water quality. The averaged PI ratio shows a substantial higher microbial contamination in holy places than in urban areas and the order of decreasing PI ratios observed were: holy places?>?urban areas?>?semi-urban areas?>?rural areas. Correlation and factor analysis proves microbial communities were not related to physicochemical parameters. Principal component analysis indicates 55.32 % of the total variance resulted from human/animal fecal matters and sewage contaminants whereas 19.95 % were related to organic contents and waste materials from the rivers. More than 80 % of the samples showed a higher fecal coliform and Streptococci by crossing the World Health Organization's permissible limits.     

Toxicodynamic modeling of 137Cs to estimate white-tailed deer background levels for the Department of Energy's Savannah River Site

The U.S. Department of Energy's (USDOE) Savannah River Site (SRS) is a former nuclear weapon material production and current research facility adjacent to the Savannah River in South Carolina, USA. The purpose of this study was to determine the background radiocesium (¹³⁷Cs) body burden (e.g., from global fallout) for white-tailed deer (Odocoileus virginianus) inhabiting the SRS. To differentiate what the background burden is for the SRS versus ¹³⁷Cs obtained from SRS nuclear activities, data were analyzed spatially, temporally and compared to other off-site hunting areas near the SRS. The specific objectives of this study were: to compare SRS and offsite deer herds based on time and space; to interpret comparisons based on how data were collected as well as the effect of environmental and anthropogenic influences; to determine what the ecological half-life/decay rate is for ¹³⁷Cs in the SRS deer herd; and to give a recommendation to what should be considered the background ¹³⁷Cs level in the SRS deer herd. Based on the available information and analyses, it is recommended that the determination of what is considered background for the SRS deer herd be derived from data collected from the SRS deer herd itself and not offsite collections for a variety of reasons. Offsite data show extreme variability most likely due to environmental factors such as soil type and land-use patterns (e.g., forest, agriculture, residential activities). This can be seen from results where samples from offsite military bases (Fort Jackson and Fort Stewart) without anthropogenic ¹³⁷Cs sources were much higher than both the SRS and a nearby (Sandhills) study site. Moreover, deer from private hunting grounds have the potential to be baited with corn, thus artificially lowering their ¹³⁷Cs body burdens compared to other free-ranging deer. Additionally, sample size for offsite collections were not robust enough to calculate a temporal decay curve with an upper confidence level to determine if the herds are following predicted radioactive decay rates like the SRS or if the variability is due to those points described above. Using mean yearly values, the ecological half-life for ¹³⁷Cs body burdens for SRS white-tailed deer was determined to be 28.79 years—very close to the 30.2 years physical half-life.     

Automated riverine landscape characterization: GIS-based tools for watershed-scale research, assessment, and management

River systems consist of hydrogeomorphic patches (HPs) that emerge at multiple spatiotemporal scales. Functional process zones (FPZs) are HPs that exist at the river valley scale and are important strata for framing whole-watershed research questions and management plans. Hierarchical classification procedures aid in HP identification by grouping sections of river based on their hydrogeomorphic character; however, collecting data required for such procedures with field-based methods is often impractical. We developed a set of GIS-based tools that facilitate rapid, low cost riverine landscape characterization and FPZ classification. Our tools, termed RESonate, consist of a custom toolbox designed for ESRI ArcGIS®. RESonate automatically extracts 13 hydrogeomorphic variables from readily available geospatial datasets and datasets derived from modeling procedures. An advanced 2D flood model, FLDPLN, designed for MATLAB® is used to determine valley morphology by systematically flooding river networks. When used in conjunction with other modeling procedures, RESonate and FLDPLN can assess the character of large river networks quickly and at very low costs. Here we describe tool and model functions in addition to their benefits, limitations, and applications.     

Occupational and environmental aerosol exposure assessment: a scientific journey from the past, through the present and into the future

This paper reviews how aerosol exposure assessment, for people in both working and living environments, has evolved over the years. It charts the main scientific developments that led to progressively improved ways of thinking and methods to assess exposure to airborne particulate matter in a manner more relevant to human health. It has been a long scientific journey as one generation of pioneering contributors has handed off to the next. In the process a consistent rationale has emerged, producing aerosol sampling criteria--and in turn exposure standards--which have been increasingly relevant to actual human exposures. The journey continues as a new generation of scientists steps up to deal with the new challenges that are emerging. An appreciation of the history of what went before is essential to charting the most effective path looking forward.