Sources and deposition of reactive gaseous mercury in the marine atmosphere

Observations of reactive gaseous mercury (RGM) in marine air show a consistent diurnal cycle with minimum at night, rapid increase at sunrise, maximum at midday, and rapid decline in afternoon. We use a box model for the marine boundary layer (MBL) to interpret these observations in terms of RGM sources and sinks. The morning rise and midday maximum are consistent with oxidation of elemental mercury (Hg⁰) by Br atoms, requiring <2 ppt BrO in most conditions. Oxidation of Hg⁰ by Br accounts for 35–60% of the RGM source in our model MBL, with most of the remainder contributed by oxidation of Hg⁰ by ozone (5–20%) and entrainment of RGM-rich air from the free troposphere (25–40%). Oxidation of Hg⁰ by Cl is minor (3–7%), and oxidation by OH cannot reproduce the observed RGM diurnal cycle, suggesting that it is unimportant. Fitting the RGM observations could be achieved in the model without oxidation of Hg⁰ by ozone (leaving Br as the only significant oxidant) by increasing the entrainment flux from the free troposphere. The large relative diurnal amplitude of RGM concentrations implies rapid loss with a lifetime of only a few hours. We show that this can be quantitatively explained by rapid, mass-transfer-limited uptake of RGM into sea-salt aerosols as HgCl₃^? and HgCl₄^2?. Our results suggest that 80–95% of Hg^II in the MBL should be present in sea-salt aerosol rather than gas-phase, and that deposition of sea-salt aerosols is the major pathway delivering Hg^II to the ocean.     

The effect of a woodstove changeout on ambient levels of PM2.5 and chemical tracers for woodsmoke in Libby,Montana

Residential woodstoves are the single largest source of PM_2.5 in Libby, MT, resulting in the community being designated as a nonattainment area for PM_2.5. Beginning in 2005, a community-wide woodstove changeout program was implemented that replaced nearly 1200 old stoves with EPA-certified units. In an effort to track the reduction of woodsmoke particles throughout the program, ambient PM_2.5 samples were collected before, during, and after the changeout. These samples were analyzed for seven selected woodsmoke tracers, including vanillin, acetovanillone, guaiacol, 4-ethylguaiacol (methoxyphenols), levoglucosan (sugar anhydride), abietic acid, and dehydroabietic acid (resin acids). Results of the changeout showed that PM_2.5 levels decreased by 20% during the changeout period, while levels of the seven chosen tracer compounds gave variable responses. Levoglucosan levels decreased by 50% while both resin acids increased after the changeout, suggesting a change in the chemistry of the particles. No trend was observed in the levels of methoxyphenols as a group over the changeout period. The results suggest that the concentrations of woodsmoke related PM_2.5 in the Libby airshed have decreased; however, the chemistry of the emitted particles also changed when old woodstoves were replaced with new EPA-certified stoves.     

Woody biomass phytoremediation of contaminated brownfield land

Economic and environmental regeneration of post-industrial landscapes frequently involves some element of re-afforestation or tree planting. We report field trials that evaluate whether woody biomass production is compatible with managing residual trace element contamination in brownfield soils. Large-scale mapping of contamination showed a heterogenous dispersion of metals and arsenic, and highly localised within-site hotspots. Yields of Salix, Populus and Alnus were economically viable, showing that short-rotation coppice has a potentially valuable role in community forestry. Mass balance modelling demonstrated that phytoextraction potentially could reduce contamination hotspots of more mobile elements (Cd and Zn) within a 25-30-year life cycle of the crops. Cd and Zn in stems and foliage of Salix were 4-13 times higher than EDTA-extractable soil concentrations. Lability of other trace elements (As, Pb, Cu, Ni) was not increased 3 years after planting the coppice; woody biomass may provide an effective reduction of exposure (phyto-stabilization) to these less mobile contaminants.     

Nanoscale zero-valent iron (nZVI): aspects of the core-shell structure and reactions with inorganic species in water

Aspects of the core-shell model of nanoscale zero-valent iron (nZVI) and their environmental implications were examined in this work. The structure and elemental distribution of nZVI were characterized by X-ray energy-dispersive spectroscopy (XEDS) with nanometer-scale spatial resolution in an aberration-corrected scanning transmission electron microscope (STEM). The analysis provides unequivocal evidence of a layered structure of nZVI consisting of a metallic iron core encapsulated by a thin amorphous oxide shell. Three aqueous environmental contaminants, namely Hg(II), Zn(II) and hydrogen sulfide, were studied to probe the reactive properties and the surface chemistry of nZVI. High-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis of the reacted particles indicated that Hg(II) was sequestrated via chemical reduction to elemental mercury. On the other hand, Zn(II) removal was achieved via sorption to the iron oxide shell followed by zinc hydroxide precipitation. Hydrogen sulfide was immobilized on the nZVI surface as disulfide (S(2)(2-)) and monosulfide (S(2-)) species. Their relative abundance in the final products suggests that the retention of hydrogen sulfide occurs via reactions with the oxide shell to form iron sulfide (FeS) and subsequent conversion to iron disulfide (FeS(2)). The results presented herein highlight the multiple reactive pathways permissible with nZVI owing to its two functional constituents. The core-shell structure imparts nZVI with manifold functional properties previously unexamined and grants the material with potentially new applications.     

A Screening-Level Assessment of Lead, Cadmium, and Zinc in Fish and Crayfish from Northeastern Oklahoma, USA

The objective of this study was to evaluate potential human and ecological risks associated with metals in fish and crayfish from mining in the Tri-States Mining District (TSMD). Crayfish (Orconectes spp.) and fish of six frequently consumed species (common carp, Cyprinus carpio; channel catfish, Ictalurus punctatus; flathead catfish, Pylodictis olivaris; largemouth bass, Micropterus salmoides; spotted bass, M. punctulatus; and white crappie, Pomoxis annularis) were collected in 2001--2002 from the Oklahoma waters of the Spring River (SR) and Neosho River (NR), which drain the TSMD. Samples from a mining-contaminated site in eastern Missouri and from reference sites were also analyzed. Individual fish were prepared for human consumption in the manner used locally by Native Americans (headed, eviscerated, and scaled) and analyzed for lead, cadmium, and zinc. Whole crayfish were analyzed as composite samples of 5--60 animals. Metals concentrations were typically higher in samples from sites most heavily affected by mining and lowest in reference samples. Within the TSMD, most metals concentrations were higher at sites on the SR than on the NR and were typically highest in common carp and crayfish than in other taxa. Higher concentrations and greater risk were associated with fish and crayfish from heavily contaminated SR tributaries than the SR or NR mainstems. Based on the results of this and previous studies, the human consumption of carp and crayfish could be restricted based on current criteria for lead, cadmium, and zinc, and the consumption of channel catfish could be restricted due to lead. Metals concentrations were uniformly low in Micropterus spp. and crappie and would not warrant restriction, however. Some risk to carnivorous avian wildlife from lead and zinc in TSMD fish and invertebrates was also indicated, as was risk to the fish themselves. Overall, the wildlife assessment is consistent with previously reported biological effects attributed to metals from the TSMD. The results demonstrate the potential for adverse effects in fish, wildlife, and humans and indicate that further investigation of human health and ecological risks, to include additional exposure pathways and endpoints, is warranted.This study was conducted by the Columbia Environmental Research Center (CERC) of the U.S. Geological Survey (USGS) and cooperating organizations and government agencies. All field and laboratory procedures conformed to the “Guidelines for the use of fishes in research” of the American Fisheries Society (AFS), Institute of Fishery Research Biologists (AIFRB), and American Society of Ichthyologists and Herpetologists (ASIH) Use of Fishes in Research Committee (AFS, AIFRB, and ASIH 2004), and with all USGS and CERC guidelines for the humane treatment of test organisms during culture and experimentation. Use of trade names does not constitute USGS or U.S. government endorsement.     

Equity trade‐offs in conservation decision making

Conservation decisions increasingly involve multiple environmental and social objectives, which result in complex decision contexts with high potential for trade‐offs. Improving social equity is one such objective that is often considered an enabler of successful outcomes and a virtuous ideal in itself. Despite its idealized importance in conservation policy, social equity is often highly simplified or ill‐defined and is applied uncritically. What constitutes equitable outcomes and processes is highly normative and subject to ethical deliberation. Different ethical frameworks may lead to different conceptions of equity through alternative perspectives of what is good or right. This can lead to different and potentially conflicting equity objectives in practice. We promote a more transparent, nuanced, and pluralistic conceptualization of equity in conservation decision making that particularly recognizes where multidimensional equity objectives may conflict. To help identify and mitigate ethical conflicts and avoid cases of good intentions producing bad outcomes, we encourage a more analytical incorporation of equity into conservation decision making particularly during mechanistic integration of equity objectives. We recommend that in conservation planning motivations and objectives for equity be made explicit within the problem context, methods used to incorporate equity objectives be applied with respect to stated objectives, and, should objectives dictate, evaluation of equity outcomes and adaptation of strategies be employed during policy implementation.     

Alternatives to biodiversity offsets for mitigating the effects of urbanization on stream ecosystems

Globally, offset schemes have emerged in many statutory frameworks relating to development activities, with the aim of balancing biodiversity conservation and development. Although the theory and use of biodiversity offsets in terrestrial environments is broadly documented, little attention has been paid to offsets in stream ecosystems. Here we examine the application of offset schemes to stream ecosystems and explore whether they suffer similar shortcomings to those of offset schemes focused on terrestrial biodiversity. To challenge the applicability of offsets further, we discuss typical trajectories of urban expansion and their cascading physical, chemical and biological impacts on stream ecosystems. We argue that the highly connected nature of stream ecosystems and urban drainage networks can transfer impacts of urbanization across wide areas, complicating the notion of like‐for‐like exchange and the prospect of effectively mitigating biodiversity loss. Instead, we identify in‐catchment options for stormwater control, which can avoid or minimize the impacts of development on downstream ecosystems, while presenting additional public and private benefits. We describe the underlying principles of these alternatives, some of the challenges associated with their uptake, and policy initiatives being trialed to facilitate adoption. In conclusion, we argue that stronger policies to avoid and minimize the impacts of urbanization provide better prospects for protecting downstream ecosystems, and can additionally, stimulate economic opportunities and improve urban liveability.     

Ensemble ecosystem modeling for predicting ecosystem response to predator reintroduction

Introducing a new or extirpated species to an ecosystem is risky, and managers need quantitative methods that can predict the consequences for the recipient ecosystem. Proponents of keystone predator reintroductions commonly argue that the presence of the predator will restore ecosystem function, but this has not always been the case, and mathematical modeling has an important role to play in predicting how reintroductions will likely play out. We devised an ensemble modeling method that integrates species interaction networks and dynamic community simulations and used it to describe the range of plausible consequences of 2 keystone‐predator reintroductions: wolves (Canis lupus) to Yellowstone National Park and dingoes (Canis dingo) to a national park in Australia. Although previous methods for predicting ecosystem responses to such interventions focused on predicting changes around a given equilibrium, we used Lotka–Volterra equations to predict changing abundances through time. We applied our method to interaction networks for wolves in Yellowstone National Park and for dingoes in Australia. Our model replicated the observed dynamics in Yellowstone National Park and produced a larger range of potential outcomes for the dingo network. However, we also found that changes in small vertebrates or invertebrates gave a good indication about the potential future state of the system. Our method allowed us to predict when the systems were far from equilibrium. Our results showed that the method can also be used to predict which species may increase or decrease following a reintroduction and can identify species that are important to monitor (i.e., species whose changes in abundance give extra insight into broad changes in the system). Ensemble ecosystem modeling can also be applied to assess the ecosystem‐wide implications of other types of interventions including assisted migration, biocontrol, and invasive species eradication.     

A habitat‐based approach to predict impacts of marine protected areas on fishers

Although marine protected areas can simultaneously contribute to biodiversity conservation and fisheries management, the global network is biased toward particular ecosystem types because they have been established primarily in an ad hoc fashion. The optimization of trade‐offs between biodiversity benefits and socioeconomic values increases success of protected areas and minimizes enforcement costs in the long run, but it is often neglected in marine spatial planning (MSP). Although the acquisition of spatially explicit socioeconomic data is perceived as a costly or secondary step in MSP, it is critical to account for lost opportunities by people whose activities will be restricted, especially fishers. We developed an easily reproduced habitat‐based approach to estimate the spatial distribution of opportunity cost to fishers in data‐poor regions. We assumed the most accessible areas have higher economic and conservation values than less accessible areas and their designation as no‐take zones represents a loss of fishing opportunities. We estimated potential distribution of fishing resources from bathymetric ranges and benthic habitat distribution and the relative importance of the different resources for each port of total catches, revenues, and stakeholder perception. In our model, we combined different cost layers to produce a comprehensive cost layer so that we could evaluate of trade‐offs. Our approach directly supports conservation planning, can be applied generally, and is expected to facilitate stakeholder input and community acceptance of conservation.     

Evolutionary algorithm for vehicle driving cycle generation

Modeling transit bus emissions and fuel economy requires a large amount of experimental data over wide ranges of operational conditions. Chassis dynamometer tests are typically performed using representative driving cycles defined based on vehicle instantaneous speed as sequences of "microtrips", which are intervals between consecutive vehicle stops. Overall significant parameters of the driving cycle, such as average speed, stops per mile, kinetic intensity, and others, are used as independent variables in the modeling process. Performing tests at all the necessary combinations of parameters is expensive and time consuming. In this paper, a methodology is proposed for building driving cycles at prescribed independent variable values using experimental data through the concatenation of "microtrips" isolated from a limited number of standard chassis dynamometer test cycles. The selection of the adequate "microtrips" is achieved through a customized evolutionary algorithm. The genetic representation uses microtrip definitions as genes. Specific mutation, crossover, and karyotype alteration operators have been defined. The Roulette-Wheel selection technique with elitist strategy drives the optimization process, which consists of minimizing the errors to desired overall cycle parameters. This utility is part of the Integrated Bus Information System developed at West Virginia University.