Hanadi S. Rifai

Natural Attenuation of Fuels and Chlorinated Solvents in the Subsurface: Wiedemeier/Natural Attenuation of Fuels and Chlorinated Solvents in the Subsurface

Overview of Natural Attenuation. Attenuation of Source Zones and Formation of Plumes. Abiotic Processes of Natural Attenuation. Overview of Intrinsic Bioremediation. Intrinsic Bioremediation of Petroleum Hydrocarbons. Intrinsic Bioremediation of Chlorinated Solvents. Evaluating Natural Attenuation. Modeling Natural Attenuation. Case Studies: Fuel Hydrocarbons. Case Studies: Chlorinated Solvents. Design of Long-Term Monitoring Programs. Appendices. Index.

Biodegradation Rates for Fuel Hydrocarbons and Chlorinated Solvents in Groundwater

Numerous studies presented in the general literature have shown that the key mechanism affecting the rate and extent of migration of a contaminant plume is biodegradation since it removes contaminant mass and reduces average plume concentrations. This paper attempts to address the importance of biodegradation for fuel and chlorinated solvent plumes and to present a comprehensive review of rates of biodegradation obtained from field and laboratory studies. Data from approximately 280 studies are statistically analyzed to determine ranges of biodegradation rates for various contaminants under different redox conditions. A review of 133 studies for fuel hydrocarbons has yielded first-order biodegradation coefficients up to 0.445 day−1 under aerobic conditions and up to 0.522−1 under anaerobic conditions in 90% of the cases. A median rate constant for benzene of 0.3% day−1 was estimated from all studies, while those for toluene, ethylbenzene, and xylenes were estimated to be 4, 0.3, and 0.4% day−1, respective...

A Comprehensive Analysis of Groundwater Quality in The Barnett Shale Region

The exploration of unconventional shale energy reserves and the extensive use of hydraulic fracturing during well stimulation have raised concerns about the potential effects of unconventional oil and gas extraction (UOG) on the environment. Most accounts of groundwater contamination have focused primarily on the compositional analysis of dissolved gases to address whether UOG activities have had deleterious effects on overlying aquifers. Here, we present an analysis of 550 groundwater samples collected from private and public supply water wells drawing from aquifers overlying the Barnett shale formation of Texas. We detected multiple volatile organic carbon compounds throughout the region, including various alcohols, the BTEX family of compounds, and several chlorinated compounds. These data do not necessarily identify UOG activities as the source of contamination; however, they do provide a strong impetus for further monitoring and analysis of groundwater quality in this region as many of the compounds we detected are known to be associated with UOG techniques.

Spatial and temporal variation of polychlorinated biphenyls in the Houston Ship Channel

An on-going study in the Houston Ship Channel (HSC) characterized polychlorinated biphenyl (PCB) levels in sediment, water, and tissue in 2002-2003 and 2008. The observed PCB concentration ranges in all media were higher than those measured in other PCB-impacted water bodies in the world, with the highest concentrations occurring within the industrialized segments. Contrary to polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) observations, the PCB concentrations in the dissolved phase were greater than the suspended phase. Possible explanations include passage of colloids, competition for adsorption sites from other hydrophobic contaminants, and continuing current sources. The PCB homologue distributions were similar for suspended water, sediment and tissue with the profile normalized around penta-chlorobiphenyls, while the dissolved phase profile normalized around tri-chlorobiphenyls. PCB-209 was detected in the suspended water phase and in sediment (10%) prompting interest into its sources to the HSC since PCB-209 was present only in rare commercial mixtures and is a byproduct in very few manufacturing processes. Inter-media analyses showed a significant correlation and transfer of PCBs. Dioxin-like PCBs contributed significant toxicity to total equivalent in tissue (33%), while they were insignificant in water (<10%) and sediment (<5%). The PCB concentrations over time showed a significant decrease in suspended water, sediment and tissue, while dissolved water concentrations showed insignificant change. The homolog distribution, however, showed a significant change in dissolved water and fish, a minor change in sediment and insignificant change in suspended water. Furthermore, an analysis for six representative congeners showed that they were accurate in predicting the total PCB concentrations and could be thus used as indicator PCBs.

Comparative distribution, sourcing, and chemical behavior of PCDD/Fs and PCBs in an estuary environment.

PCDD/F and PCB field data (1041 samples) in five media (dissolved, suspended sediment, bed sediment, catfish, and blue crab) were studied to explore dual contaminant patterns in the Houston Ship Channel, Texas, USA. PCDD/Fs showed greater concentration than PCBs in suspended sediments while PCBs were higher in apparent dissolved (truly dissolved+DOC-associated), fish, and crab. PCDD/Fs at nearly all locations contributed more strongly to dioxin-like toxicity. The fraction of PCB TEQ was, however, enriched in biotic over abiotic media due in large part to the presence of PCB 126, which was mostly undetected in water and sediment and yet exhibited a BAF three times greater than 2,3,7,8-TCDD. Dissolved-suspended sediment and suspended-bed sediment relationships showed that (1) observed apparent dissolved concentration differences (as fraction of total water were mean 10% PCDD/Fs and 63% PCBs) can reasonably be explained by a four-phase partition model (truly dissolved, DOC-associated, suspended OC, and suspended BC) for PCBs but not for PCDD/Fs and (2) the contaminants behaved similarly in bed to suspended sediment concentration ratios (C(bed)/C(susp)) upstream of a major confluence but not downstream. PCA-cluster analysis pointed to the possibility that suspended sediment PCB contamination originates from resuspended bed sediment while PCDD/Fs in suspended sediment originates more probably from other sediment sources such as upstream wash load or air deposition. Finally, examinations of a congener marker ratio (PCB 209/206) seemed to indicate that a source of pure PCB 209 may exist in bed sediment near Patrick Bayou though the source was not completely localized.

Efficacy of carbonaceous materials for sorbing polychlorinated biphenyls from aqueous solution.

Interest in incorporating nanomaterials into water treatment technologies is steadily growing, driving the necessity to understand the interaction of these new materials with specific water contaminants. In the present study, five different carbonaceous materials: activated carbon (AC), charcoal (BC), carbon nanotubes (CNT), graphene (GE), and graphene oxide (GO) were investigated as sorbent materials for 11 polychlorinated biphenyl (PCB) congeners in aqueous concentrations in the pg-μg/L range. Sorbent-water distribution coefficients (Ks) calculated in aqueous concentrations of ng/L show that AC is superior to GE, GO, CNT, and BC for the 11 PCB congeners investigated by an average of 1.1, 1.1, 1.3, and 2.5 orders of magnitude, respectively. Additionally, maximum capacity and sorption affinity parameters from the Langmuir, Freundlich, and Polanyi-Dubinin-Manes (PDM) models show a similar result. Interestingly, however, the effect of molecular planarity has greater impact on PCB sorption to the nanomaterials, such that the planar congeners form stronger bonds with CNT, GE, and GO compared to AC and BC. This work demonstrated superior PCB sorption by AC as compared with the nanomaterials examined such that substantial post production modifications would be necessary for the nanomaterials to out-perform AC.

Elucidating hydraulic fracturing impacts on groundwater quality using a regional geospatial statistical modeling approach

Hydraulic fracturing operations have been viewed as the cause of certain environmental issues including groundwater contamination. The potential for hydraulic fracturing to induce contaminant pathways in groundwater is not well understood since gas wells are completed while isolating the water table and the gas-bearing reservoirs lay thousands of feet below the water table. Recent studies have attributed ground water contamination to poor well construction and leaks in the wellbore annulus due to ruptured wellbore casings. In this paper, a geospatial model of the Barnett Shale region was created using ArcGIS. The model was used for spatial analysis of groundwater quality data in order to determine if regional variations in groundwater quality, as indicated by various groundwater constituent concentrations, may be associated with the presence of hydraulically fractured gas wells in the region. The Barnett Shale reservoir pressure, completions data, and fracture treatment data were evaluated as predictors of groundwater quality change. Results indicated that elevated concentrations of certain groundwater constituents are likely related to natural gas production in the study area and that beryllium, in this formation, could be used as an indicator variable for evaluating fracturing impacts on regional groundwater quality. Results also indicated that gas well density and formation pressures correlate to change in regional water quality whereas proximity to gas wells, by itself, does not. The results also provided indirect evidence supporting the possibility that micro annular fissures serve as a pathway transporting fluids and chemicals from the fractured wellbore to the overlying groundwater aquifers.

Polychlorinated biphenyls (PCBs) in industrial and municipal effluents: Concentrations, congener profiles, and partitioning onto particulates and organic carbon

Wastewater effluent samples were collected in the summer of 2009 from 16 different locations which included municipal and industrial wastewater treatment plants and petrochemical industrial outfalls in the Houston area. The effluent samples were analyzed for all 209 polychlorinated biphenyls (PCBs) congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) using the USEPA method 1668A. The total PCBs (∑209) concentration in the dissolved medium ranged from 1.01 to 8.12 ng/L and ranged from 2.03 to 31.2 ng/L in the suspended medium. Lighter PCB congeners exhibited highest concentrations in the dissolved phase whereas, in the suspended phase, heavier PCBs exhibited the highest concentrations. The PCB homolog concentrations were dominated by monochlorobiphenyls through hexachlorobiphenyls, with dichlorobiphenyls exhibiting the highest concentration amongst them at most of the effluent outfalls, in the suspended phase. Both total suspended solids (TSS) and various organic carbon fractions played an important role in the distribution of the suspended fractions of PCBs in the effluents. The log Koc values determined in the effluents suggest that effluent PCB loads might have more risk and impact than what standard partitioning models predict.

Childhood Obesity Research Demonstration Project: Cross-Site Evaluation Methods

INTRODUCTION The Childhood Obesity Research Demonstration (CORD) project links public health and primary care interventions in three projects described in detail in accompanying articles in this issue of Childhood Obesity. This article describes a comprehensive evaluation plan to determine the extent to which the CORD model is associated with changes in behavior, body weight, BMI, quality of life, and healthcare satisfaction in children 2-12 years of age. DESIGN/METHODS The CORD Evaluation Center (EC-CORD) will analyze the pooled data from three independent demonstration projects that each integrate public health and primary care childhood obesity interventions. An extensive set of common measures at the family, facility, and community levels were defined by consensus among the CORD projects and EC-CORD. Process evaluation will assess reach, dose delivered, and fidelity of intervention components. Impact evaluation will use a mixed linear models approach to account for heterogeneity among project-site populations and interventions. Sustainability evaluation will assess the potential for replicability, continuation of benefits beyond the funding period, institutionalization of the intervention activities, and community capacity to support ongoing program delivery. Finally, cost analyses will assess how much benefit can potentially be gained per dollar invested in programs based on the CORD model. CONCLUSIONS The keys to combining and analyzing data across multiple projects include the CORD model framework and common measures for the behavioral and health outcomes along with important covariates at the individual, setting, and community levels. The overall objective of the comprehensive evaluation will develop evidence-based recommendations for replicating and disseminating community-wide, integrated public health and primary care programs based on the CORD model.

Bioaccumulation of Polychlorinated Dibenzodioxins and Dibenzofurans in Catfish and Crabs Along an Estuarine Salinity and Contamination Gradient

Elevated but variable levels of polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/Fs) were observed in hardhead sea catfish (HH) and blue crabs (BCs), as well as in water and sediment, of the Houston Ship Channel system, Texas, USA. It is hypothesized that the variation was caused by the spatial variability of PCDD/F contamination, together with the natural mobility of organisms in satisfying prey, temperature, salinity, and reproductive requirements. Structural equation modeling was applied to explore the congener-specific relationships between PCDD/F levels in HH and BC tissues and independent predictors such as PCDD/F contamination levels, environmental factors such as salinity and temperature, temporal-spatial factors such as site depth and season, and biological factors such as length, weight, and lipid content. Contamination levels in both sediment and water were statistically significant predictors of the levels of less chlorinated congeners in both HH and BCs, with the standardized regression weight for sediment concentration roughly twice that for the water concentration. This implies that sediments are the dominant route for PCDDIF exposure and remediation efforts should focus on legacy sediment ontamination. Tissue lipid content was a significant predictor of tissue concentrations in HH but only to a lesser extent in BCs, perhaps due to their low lipid content. Site depth and seasonal factors also were significant predictors of tissue concentrations. For the highly chlorinated congeners, only a small fraction of the variance in tissue concentrations was explained by the independent predictors, possibly indicating that uptake and elimination kinetics, biotransformation processes, or both may be more important factors controlling the bioaccumulation of those congeners.