Influence of hydrogeochemical processes on zero-valent iron reactive barrier performance: a field investigation

Geochemical and mineralogical changes were evaluated at a field Fe0-PRB at the Oak Ridge Y-12 site concerning operation performance during the treatment of U in high NO3- groundwater. In the 5-year study period, the Fe0 remained reactive as shown in pore-water monitoring data, where increases in pH and the removal of certain ionic species persisted. However, coring revealed varying degrees of cementation. After 3.8-year treatment, porosity reduction of up to 41.7% was obtained from mineralogical analysis on core samples collected at the upgradient gravel-Fe0 interface. Elsewhere, Fe0 filings were loose with some cementation. Fe0 corrosion and pore volume reduction at this site are more severe due to the presence of NO3- at a high level. Tracer tests indicate that hydraulic performance deteriorated: the flow distribution was heterogeneous and under the influence of interfacial cementation a large portion of water was diverted around the Fe0 and transported outside the PRB. Based on the equilibrium reductions of NO3- and SO4(2-) by Fe0 and mineral precipitation, geochemical modeling predicted a maximum of 49% porosity loss for 5 years of operation. Additionally, modeling showed a spatial distribution of mineral precipitate volumes, with the maximum advancing from the interface toward downgradient with time. This study suggests that water quality monitoring, coupled with hydraulic monitoring and geochemical modeling, can provide a low-cost method for assessing PRB performance.     

Influence of hydrogeochemical processes on zero-valent iron reactive barrier performance: a field investigation

Geochemical and mineralogical changes were evaluated at a field Fe0-PRB at the Oak Ridge Y-12 site concerning operation performance during the treatment of U in high NO3- groundwater. In the 5-yr study period, the Fe0 remained reactive as shown in pore water monitoring data, where increases in pH and the removal of certain ionic species persisted. However, coring revealed varying degrees of cementation. After 3.8-yr treatment, porosity reduction of up to 41.7% was obtained from mineralogical analysis on core samples collected at the upgradient gravel-Fe0 interface. Elsewhere, Fe0 filings were loose with some cementation. Fe0 corrosion and pore volume reduction at this site are more severe due to the presence of NO3- at a high level. Tracer tests indicate that hydraulic performance deteriorated: the flow distribution was heterogeneous and under the influence of interfacial cementation a large portion of water was diverted around the Fe0 and transported outside the PRB. Based on the equilibrium reductions of NO3- and SO4(2-) by Fe0 and mineral precipitation, geochemical modeling predicted a maximum of 49% porosity loss for 5 yr of operation. Additionally, modeling showed a spatial distribution of mineral precipitate volumes, with the maximum advancing from the interface toward downgradient with time. This study suggests that water quality monitoring, coupled with hydraulic monitoring and geochemical modeling, can provide a low-cost method for assessing PRB performance.     

Does the Harvard/U.S. Environmental Protection Agency Ambient Particle Concentrator change the toxic potential of particles?

Inhalation exposure to urban air particles is known to increase morbidity in humans and animals. Our group utilizes the Harvard/U.S. Environmental Protection Agency Ambient Particle Concentrator (HAPC) to generate concentrated aerosols of outdoor air particles for experimental exposures. We have reported increased pathologic responses to inhalation of concentrated urban air particles and identified silicon (as silicate) as an element associated with many of these responses. Using silicate-rich Mt. St. Helen's volcanic ash (MSHA), we exposed three groups of Sprague-Dawley rats by inhalation for 6 hr to filtered air, MSHA, or MSHA passed though the HAPC. Twenty-four hours following exposure, bronchoalveolar lavage was performed to assess total cell count, differential cell count, protein, lactate dehydrogenase, and n-beta-glucosaminidase levels. Peripheral blood was examined for packed cell volume, total protein, total white cells, and differential cell count. Morphologic studies localized particles in the lung and assessed pulmonary vasculature. No significant differences were observed among any of the groups in any parameter measured including morphometric analysis of pulmonary vasoconstriction. Scanning electron microscopy and X-ray analysis identified particles as silicates typical of MSHA throughout the lung. These findings suggest that particles passing through the HAPC have no change in their toxic potential in an exposure setting where particle deposition in the lung has occurred.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: characterization of microbial community structure

A polyphasic approach based on cultivation and direct recovery of 16S rRNA gene sequences was utilized for microbial characterization of an aquifer contaminated with chlorinated ethenes. This work was conducted in order to support the evaluation of natural attenuation of chlorinated ethenes in groundwater at Area 6 at Dover Air Force Base (Dover, DE). Results from these studies demonstrated the aquifer contained relatively low biomass (e.g. direct microscopic counts of < 10(7) bacteria/g of sediment) comprised of a physiologically diverse group of microorganisms including iron reducers, acetogens, sulfate reducers, denitrifiers, aerobic and anaerobic heterotrophs. Laboratory microcosms prepared with authentic sediment and groundwater provided direct microbiological evidence that the mineralization of vinyl chloride and cis-dichloroethene as well as each step in the complete reductive dechlorination of tetracloroethene to ethene can occur in the Area 6 aquifer. Enrichment cultures capable of the oxidative degradation of cis-1,2-dichloroethene (cis-DCE) and vinyl chloride (VC) were obtained from groundwater across the aquifer demonstrating the possible importance of direct, non-cometabolic oxidation of cis-DCE and VC in natural attenuation. Culture-independent analyses based upon recovery of 16S rRNA gene sequences revealed the presence of anaerobic organisms distributed primarily between two major bacterial divisions: the delta subdivision of the Proteobacteria and low-G + C gram positive. Recovery of sequences affiliated with phylogenetic groups containing known anaerobic-halorespiring organisms such as Desulfitobacterium, Dehalobacter, and certain groups of iron reducers provided qualitative support for a role of reductive dechlorination processes in the aquifer. This molecular data is suggestive of a functional linkage between the microbiology of the site and the apparent natural attenuation process. The presence and distribution of microorganisms were found to be consistent with a microbially driven attenuation of chlorinated ethenes within the aquifer and in accord with a conceptual model of aquifer geochemistry which suggest that both reductive and oxidative mechanisms are involved in heterogeneous, spatially distributed processes across the aquifer.     

Photodechlorination of polychlorinated biphenyls in the presence of hydroquinone in aqueous alcoholic media

On exposure to sunlight or photolysis at λ >300nm, the dechlorination of a polychlorinated biphenyl mixture (Aroclor 1254) in the H donor alcohol 2-propanol under neutral conditions is enhanced by the presence of the photosensitizer hydroquinone. Dechlorination is strongly promoted by an increasingly aqueous solvent (1:1 water:alcohol) and by maintaining neutral conditions (pH 7.0 buffer) both in the presence and absence of sensitizer. Atmospheric oxygen (continuous aeration) retards the hydroquinone induced dechlorination less than the direct photolysis process.     

Driving self-regulation and ride service utilization in a multicommunity,multistate sample of U.S. older adults

Objectives: This study examined a multicommunity alternative transportation program available 24 hours a day, 7 days a week, for any purpose, offering door-through-door service in private automobiles to members who either do not drive or are transitioning away from driving. Specific aims were to describe the characteristics of members by driving status and ride service usage of these members.

Methods: Data came from administrative records maintained by a nonprofit ride service program and include 2,661 individuals aged 65+ residing in 14 states who joined the program between April 1, 2010, and November 8, 2013. Latent class analysis was used to group current drivers into 3 classes of driving status of low, medium, and high self-regulation, based on their self-reported avoidance of certain driving situations and weekly driving frequency. Demographics and ride service use rate for rides taken through March 31, 2014, by type of ride (e.g., medical, social, etc.) were calculated for nondrivers and drivers in each driving status class.

Results: The majority of ride service users were female (77%) and aged 65–74 years (82%). The primary method of getting around when enrolling for the transportation service was by riding with a friend or family member (60%). Among the 67,883 rides given, nondrivers took the majority (69%) of rides. Medical rides were the most common, accounting for 40% of all rides.

Conclusions: Reported ride usage suggests that older adults are willing to use such ride services for a variety of trips when these services are not limited to specific types (e.g., medical). Further research can help tailor strategies to encourage both nondrivers and drivers to make better use of alternative transportation that meets the special needs of older people.     

Modeling Flow,Nutrient, and Sediment Delivery from a Large International Watershed Using a Field‐Scale SWAT Model

A large international watershed, the St. Clair‐Detroit River System, containing both extensive urban and agricultural areas, was modeled using the Soil and Water Assessment Tool (SWAT) model. The watershed, located in southeastern Michigan, United States, and southwestern Ontario, Canada, encompasses the St. Clair, Clinton, Detroit (DT), Sydenham (SY), Upper, and Lower Thames subwatersheds. The SWAT input data and model resolution (i.e., hydrologic response units, HRUs), were established to mimic farm boundaries, the first time this has been done for a watershed of this size. The model was calibrated (2007–2015) and validated (2001–2006) with a mix of manual and automatic methods at six locations for flow and water quality at various time scales. The model was evaluated using Nash–Sutcliffe efficiency and percent bias and was used to explore major water quality issues. We showed the importance of allowing key parameters to vary among subwatersheds to improve goodness of fit, and the resulting parameters were consistent with subwatershed characteristics. Agricultural sources in the Thames and SY subwatersheds and point sources from DT subwatershed were major contributors of phosphorus. Spatial distribution of phosphorus yields at HRU and subbasin levels identified locations for potential management targeting for both point and nonpoint sources and revealed that in some subwatersheds nonpoint sources are dominated by urban sources.     

Remediation of PCB‐Contaminated Soil Using Extraction and Destruction: Bench‐Scale Test

Polychlorinated biphenyls (PCBs) are a persistent environmental issue worldwide. This study summarizes the results obtained from a bench‐scale test of remediating PCB‐impacted soil. The research aimed to evaluate the effectiveness of extracting the PCB Aroclor 1260 from soil, transferring it to a liquid matrix, and then treating the PCB‐containing liquid using an Activated Metal Treatment System, a technology developed by NASA based on zero valent magnesium (ZVMg). The soil was from a former electrical plant area impacted by PCBs. The initial concentration of untreated soil contained an average of 4.7 ± 0.15 mg/kg of Aroclor 1260. The results showed that the mass transfer phenomena is possible using ethanol as a liquid matrix, reaching transfer results up to 93 percent. The ZVMg enabled the destruction of the Aroclor 1260, which reached 20 percent without any buildup of undesirable by‐products, such as less chlorinated PCBs.  ©2016 Wiley Periodicals, Inc.     

Characterizing In Situ Methane‐Enhanced Biostimulation Potential for 1,4‐Dioxane Biodegradation in Groundwater

This study characterizes the 1,4‐dioxane biodegradation potential for an in situ methane‐enhanced biostimulation field pilot study conducted at Air Force Plant 44, located south of the Tucson International Airport in Arizona. In this study, the use of methane as the primary substrate in aerobic cometabolic biodegradation of 1,4‐dioxane is evaluated using environmental molecular diagnostic tools. The findings are compared to an adjacent pilot study, wherein methane was generated via enhanced reductive dechlorination and where methane monooxygenase and methane‐oxidizing bacteria were also found to be abundant. This article also presents the use of ¹³C and ²H isotopic ratio enrichment, a more recent tool, to support the understanding of 1,4‐dioxane biodegradation in situ. This study is the first of its kind, although alkane gas‐enhanced biodegradation of 1,4‐dioxane has been evaluated extensively in microcosm studies and propane‐enhanced biodegradation of 1,4‐dioxane has been previously studied in the field. ©2016 Wiley Periodicals, Inc.     

The undermining effect revisited: The salience of everyday verbal rewards and self‐determined motivation

Self‐determination theory suggests that some rewards can undermine autonomous motivation and related positive outcomes. Key to this undermining is the extent to which rewards are perceived as salient in a given situation; when this is the case, individuals tend to attribute their behavior to the incentive, and the intrinsic value of the task is undermined. The role of salience has yet to be explicitly tested with respect to work motivation; we know little about whether undermining occurs in relation to verbal rewards, which characterize everyday work. We examine this in a field‐based quantitative diary study of 58 employees reporting 287 critical incidents of motivated behavior. When considering simple direct effects, the undermining effect was not supported; highly salient verbal rewards associated positively with introjected and external motivation, but at no cost to autonomous motivation. However, moderator analysis found support for the undermining effect for complex tasks; highly salient verbal rewards associated positively with external motivation while associating negatively with intrinsic and identified motivation. The findings suggest that verbal reward salience is an important characteristic of verbal reward perceptions and that salient verbal rewards are not advisable for more complex tasks but can have a valuable motivational impact for simple tasks. Copyright © 2015 John Wiley & Sons, Ltd.