Heterogeneous mercury reaction chemistry on activated carbon

Experimental and theory-based investigations have been carried out on the oxidation and adsorption mechanism of mercury (Hg) on brominated activated carbon (AC). Air containing parts per billion concentrations of Hg was passed over a packed-bed reactor with varying sorbent materials at 140 and 30 degrees C. Through X-ray photoelectron spectroscopy surface characterization studies it was found that Hg adsorption is primarily associated with bromine (Br) on the surface, but that it may be possible for surface-bound oxygen (O) to play a role in determining the stability of adsorbed Hg. In addition to surface characterization experiments, the interaction of Hg with brominated AC was studied using plane-wave density functional theory. Various configurations of hydrogen, O, Br, and Hg on the zigzag edge sites of graphene were investigated, and although Hg-Br complexes were found to be stable on the surface, the most stable configurations found were those with Hg adjacent to O. The Hg-carbon (C) bond length ranged from 2.26 to 2.34 A and is approximately 0.1 A shorter when O is a nearest-neighbor atom rather than a next-nearest neighbor, resulting in increased stability of the given configuration and overall tighter Hg-C binding. Through a density of states analysis, Hg was found to gain electron density in the six p-states after adsorption and was found to donate electron density from the five s-states, thereby leading to an oxidized surface-bound Hg complex.     

In situ chemical oxidation: Lessons learned at multiple sites

This paper compiles a detailed set of in situ chemical oxidation (ISCO) lessons learned pertaining to design, execution, and safety based on global experiences over the last 20 years. While the benefits of a “correct” application are known (e.g., cost effectiveness, speed, permanence of treatment), history also provides examples of a variety of “incorrect” applications. These provide an opportunity to highlight recurring themes that resulted in failures. ISCO is, and will continue to provide, an important remedial tool for site remediation, particularly as a component of a multifaceted approach for addressing large and complex sites. Future success, however, requires an objective understanding of both the benefits and the limitations of the technology. The ability to learn from the mistakes of the past provides an opportunity to eliminate, or at least minimize, them in the future. Over the last 25 years of ISCO application, process understanding and knowledge have improved and evolved. This paper combines a thorough discussion of lessons learned through decades of ISCO implementation throughout all aspects of ISCO projects with an analysis of changes to the ISCO remediation market. By discussing the interplay of these two themes and providing recommendations from collective lessons learned, we hope to improve the future of safe, cost‐effective, and successful applications of ISCO.     

Flow‐Biology Relationships Based on Fish Habitat Guilds in North Carolina

The health of freshwater biota is dependent on streamflow, yet identification of the flow regimes required to maintain ecological integrity remains challenging to states in the United States seeking to establish ecological flows. We tested the relationship between decreases in streamflow and Shannon‐Weaver diversity index of fish species for four flow‐based habitat guilds: riffle, riffle‐run, pool‐run, and pool in North Carolina. We found species that prefer shallow habitats, such as riffles and riffle‐runs were the most sensitive to decreases in streamflow; whereas no significant relationships were found for pool or pool‐run species. The sensitivity to decreases in streamflow was greatest during summer and fall, when streams are naturally lower. When all fish habitat guilds were included in the assessment of flow‐biology relationships, there were no significant relationships to decreases in streamflow. As the sensitivity of fish to reductions in streamflow is not constant across habitat guilds, combining all fish species together for flow‐biology analyses may greatly underestimate the response of fish species to decreases in flow and should be acknowledged when establishing ecological flows.     

Community gardening: cultivating subjectivities,space, and justice

Community gardens have been lauded for being inherently resistant to neoliberalism and criticised for underwriting it. To move beyond this either/or debate, we need to employ more focused lenses and specify both the processes of neoliberalisation at play and the outcomes they can produce. This paper explores the ways in which neoliberal processes of privatisation, state entrepreneurialism, and devolution intersect with community gardens, and the subjectivities that may be cultivated, the spaces that may be created and the types of justice that may be advanced as a result. It argues that certain characteristics and orientations of gardens are more conducive to resisting neoliberalism. These include the cultivation of producer, citizen, and activist subjectivities (over those of consumer, entrepreneur, and volunteer); the elevation of the use value of shared lived space (over a site’s potential exchange value) and the advancement of spatial justice through community access to non-privatised space; and food justice, through non-commodified means of obtaining food. Holding these ends in mind can help ensure that proponents of community gardening sow the seeds of the fruits they most wish to reap.     

Hydraulic fracturing as an interpretive policy problem: lessons on energy controversies in Europe and the U.S.A.

This special issue addresses hydraulic fracturing for shale gas extraction as an interpretive policy problem. Bringing together empirical cases from the U.S.A., the Netherlands, the U.K., Poland, and Germany, we identify three approaches to the interpretation of hydraulic fracturing in the article: understanding its meaning, contextual explanation of the institutionalization of its meaning, and policy design as intervention to alter its meaning. By exploring differences and similarities across these cases, we identified two central tensions in the meaning of shale gas in all cases: (1) economic opportunity or environmental threat and (2) transition toward a more carbon-free energy future or perpetuation of a fossil fuel system. We found that when actors shift the meaning of hydraulic fracturing to consider it predominantly an issue of threat, this explains the dominance of risk governance as an approach to managing the controversy. Alternately, when the meaning of fracking shifts from consideration as an economic opportunity or a bridge fuel to consideration of it as a barrier to an energy transition, this explains the decision to ban fracking. Therefore, a comparative assessment of the papers demonstrates the ways interpretive dimensions of politics can influence the governance of public policy.     

Framing Dynamics and Political Gridlock: The Curious Case of Hydraulic Fracturing in New York

‘Fracking’ was on New York's agenda since 2008, yet no decision was made about it until late 2014. The gridlock is an intriguing puzzle given that the Marcellus shale is considered a ‘world class’ energy supply, and development has been aggressive in other US states. While policy scholars typically conceptualize gridlock as policy stability, this paper examines it as a dynamic process by which competing discourse coalitions engage in interactive framing processes that (re)structure the discussion. This suggests that the interaction between contending coalitions influences gridlock. Yet, we lack knowledge about interactive framing between competing coalitions during policy controversies. Our main finding is that a central mechanism of gridlock is the production of conflict through interactive framing dynamics that deny a shared discursive space capable of ushering in a consensus, or reasoned agreement. In New York, this contest evolved from a policy consensus about the economic benefits of fracking to policy negotiation that incorporated environmental threats, and to prolonged policy controversy in which competing discourse coalitions contested notions of fracking in relation to energy production, environmental protection, public health, economic development, and governance. While a ban has been instituted, the failure to bridge discourse coalitions suggests that controversy will persist unless meaning disputes are resolved.     

Optimization and validation of enhanced biological reduction of 1,2,3‐trichloropropane in groundwater

Laboratory and field demonstration studies were conducted to assess the efficacy of enhanced biological reduction of 1,2,3‐trichloropropane (TCP) in groundwater. Laboratory studies evaluated the effects of pH and initial TCP concentrations on TCP reduction and the activity of a microbial inoculum containing Dehalogenimonas (Dhg). Laboratory results showed successful reduction at a pH of 5 to 9 with optimal reduction at 7 to 9 and at initial TCP concentrations ranging from 10 to over 10,000 micrograms per liter (μg/L). Based on findings from the laboratory study, the effects of TCP concentration, geochemical conditions, and amendment concentration on bioremediation efficacy were investigated during a field demonstration at a site with relatively low initial concentrations of TCP (< 2 μg/L). The field demonstration included injection of emulsified vegetable oil (EVO) and lactate as a carbon substrate for biostimulation, followed by bioaugmentation using the microbial inoculum containing Dhg. Post‐injection performance monitoring demonstrated reduction of TCP to below laboratory detection limits (< 0.005 μg/L) after an initial lag period of approximately six months following injections. TCP reduction was accompanied by generation of the degradation byproduct propene. A marginal increase in TCP concentrations, potentially due to an influx of upgradient aerobic groundwater containing TCP, was observed eight months after injections thereby demonstrating the sensitivity of this bioaugmentation application to changes in geochemical parameters. Despite this marginal increase, performance monitoring results indicate continued TCP biodegradation 15 months after implementation of the injection program. This demonstration suggests that enhanced biodegradation of TCP by combining biostimulation and bioaugmentation may be a promising solution to the challenges associated with remediation of TCP, even when present at low part per billion concentrations in groundwater.     

Source-pathway-receptor investigation of the fate of trace elements derived from shotgun pellets discharged in terrestrial ecosystems managed for game shooting

Spent shotgun pellets may contaminate terrestrial ecosystems. We examined the fate of elements originating from shotgun pellets in pasture and woodland ecosystems. Two source-receptor pathways: i) soil-soil pore water-plant and ii) whole earthworm/worm gut contents - washed and unwashed small mammal hair were investigated. Concentrations of Pb and associated contaminants were higher in soils from shot areas than controls. Arsenic and lead concentrations were positively correlated in soils, soil pore water and associated biota. Element concentrations in biota were below statutory levels in all locations. Bioavailability of lead to small mammals, based on concentrations in washed body hair was low. Lead movement from soil water to higher trophic levels was minor compared to lead adsorbed onto body surfaces. Lead was concentrated in earthworm gut and some plants. Results indicate that managed game shooting presents minimal risk in terms of element transfer to soils and their associated biota.