Heterogeneous uptake of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) onto mineral dust aerosol under variable RH conditions

We have carried out kinetic studies to characterize the heterogeneous decay of octamethylcyclotetrasiloxane (D₄) and decamethylcyclopentasiloxane (D₅) in the presence of representative mineral dust aerosol in order to obtain a better understanding of the atmospheric fate of these siloxanes. The heterogeneous chemistry of D₄ and D₅ with various mineral dusts was studied in an environmental aerosol reaction chamber using FTIR absorption spectroscopy to monitor the reaction. The apparent heterogeneous uptake coefficient, γ_app, for D₄ and D₅ with various mineral dusts was measured under dry conditions and as a function of relative humidity (RH). In addition, the effect of initial D₄ and D₅ concentration on the rate and yield of the reaction was examined. The uptake coefficient, γ_app, for D₄ and D₅ was similar for the most reactive aerosols tested, with kaolinite ≈hematite > silica. Limited uptake onto carbon black and calcite surfaces was observed for either siloxane. Reaction with hematite and kaolinite resulted in multilayer coverages, suggesting extensive polymerization of D₄ and D₅ on the aerosol surface.     

Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry

The high-molecular weight water-soluble organic compounds present in atmospheric aerosols underwent functional-group characterization using liquid chromatography tandem mass spectrometry (LC-MS/MS), with a focus on understanding the chemical structure and origins of humic-like substances (HULIS) in the atmosphere. Aerosol samples were obtained from several locations in North America at times when primary sources contributing to organic aerosol were well-characterized: Riverside, CA, Fresno, CA, urban and peripheral Mexico City, Atlanta, GA, and Bondville, IL. Chemical analysis targeted identification and quantification of functional groups, such as aliphatic, aromatic, and bulk carboxylic acids, organosulfates, and carbohydrate-like substances that comprise species with molecular weights (MW) 200–600 amu. Measured high-MW functional groups were compared to modeled primary sources with the purpose of identifying associations between aerosol sources, high-MW aerosol species, and HULIS. Mobile source emissions were linked to high-molecular weight carboxylic acids, especially aromatic acids, biomass burning was associated with carboxylic acids and carbohydrate-like substances, and secondary organic aerosol (SOA) correlated well with the total amount of HULIS measured, whereas organosulfates showed no correlation with aerosol sources and exhibited unique spatial trends. These results suggested the importance of motor vehicles, biomass burning, and SOA as important sources of precursors to HULIS. Structural characteristics of atmospheric HULIS were compared to terrestrial humic and fulvic acids and revealed striking similarities in chemical structure, with the exception of organosulfates which were unique to atmospheric HULIS.     

A computational study of particulate emissions from an open pit quarry under neutral atmospheric conditions

The extraction of minerals from surface mines and quarries can produce significant fugitive dust emissions as a result of site activities such as blasting, road haulage, loading, crushing and stockpiling. If uncontrolled, these emissions can present serious environmental, health, safety and operational issues impacting both site personnel and the wider community.The dispersion of pollutant emissions within the atmosphere is principally determined by the background wind systems characterized by the atmospheric boundary layer (ABL). This paper presents an overview of the construction and solution of a computational fluid dynamics (CFD) model to replicate the development of the internal ventilation regime within a surface quarry excavation due to the presence of a neutral ABL above this excavation. This model was then used to study the dispersion and deposition of fugitive mineral dust particles generated during rock blasting operations. The paths of the mineral particles were modelled using Lagrangian particle tracking. Particles of four size fractions were released from five blast locations for eight different wind directions.The study concluded that dependent on the location of the bench blast within the quarry and the direction of the wind, a mass fraction of between 0.3 and 0.6 of the emitted mineral particles was retained within the quarry. The retention was largest when the distance from the blast location to the downwind pit boundary was greatest.     

Influence of organic waste type and soil structure on the bacterial filtration rates in unsaturated intact soil columns

Organic wastes are considered to be a source for the potentially pathogenic microorganisms found in surface and sub-surface water resources. Following their release from the organic waste matrix, bacteria often infiltrate into soil and may be transported to significant depths contaminating aquifers. We investigated the influence of soil texture and structure and most importantly the organic waste properties on the transport and filtration coefficients of Escherichia coli and total bacteria in undisturbed soil columns. Intact soil columns (diameter 16 cm and height 25 cm) were collected from two soils: sandy clay loam (SCL) and loamy sand (LS) in Hamadan, western Iran. The cores were amended with cow manure, poultry manure and sewage sludge at a rate of 10 Mg ha(-1) (dry basis). The amended soil cores were leached at a steady-state flux of 4.8 cm h(-1) (i.e. 0.12 of saturated hydraulic conductivity of the SCL) to a total volume of up to 4 times the pore volume of the columns. The influent (C(0)) and effluent (C) were sampled at similar time intervals during the experiments and bacterial concentrations were measured by the plate count method. Cumulative numbers of the leached bacteria, filtration coefficient (lambda(f)), and relative adsorption index (S(R)) were calculated. The preferential pathways and stable structure of the SCL facilitated the rapid transport and early appearance of the bacteria in the effluent. The LS filtered more bacteria when compared with the SCL. The effluent contamination of poultry manure-treated columns was greater than the cow manure- and sewage sludge-treated ones. The difference between cow manure and sewage sludge was negligible. The lambda(f) and S(R) values for E. coli and total bacteria were greater in the LS than in the SCL. This indicates a predominant role for the physical pore-obstruction filtration mechanisms as present in the poorly structured LS vs. the retention at adsorptive sites (chemical filtration) more likely in the better structured SCL. While the results confirmed the significant role of soil structure and preferential (macroporous) pathways, manure type was proven to have a major role in determining the maximum penetration risk of bacteria by governing filtration of bacteria. Thus while the numbers of bacteria in waste may be of significance for shallow aquifers, the type of waste may determine the risk for microbial contamination of deep aquifers.     

Evaluation of the aggressive potential of marine chloride and sulfate salts on mortars applied as renders in the Metropolitan Region of Salvador--Bahia, Brazil

In recent years, growing interest has focused on determining the performance of materials and evaluating the service life of structures exposed to various environmental forces. In this context, the determination of the aggressive potential of marine salts on mortars used as external renders is critical. The present study aimed to evaluate the spatial distribution of marine salts relative to distance from the sea. This was done by monitoring the deposition rate of chlorides and sulfates in wet candle sensors, located at nine stations scattered around the Metropolitan Region of Salvador, state of Bahia, Brazil. The study also determined the effectiveness of water-soluble salts at penetrating three different types of mortars of varying cement content via deposition and diffusion. The methodology employed enabled an evaluation of the efficiency of the monitoring sensors' measurement of the aggressiveness potential of local marine aerosol, and determination of the comparative performance of the three mortars tested, from the standpoint of resistance to salt penetration. The type and amount of salts captured both in solution and in powder samples extracted from the mortars were determined by ion chromatography. The analysis of the various types of mortars tested indicated which types are more resistant to the aggressive potential of the region's marine aerosol and the distance from the shore where local buildings are liable to be most strongly affected.     

Conceptual issues in designing a policy to phase out metal-based antifouling paints on recreational boats in San Diego Bay

In marine areas throughout the world where recreational boats are densely located, concentrations of copper in the water are being found to be in excess of government standards, due to the hull coatings used on these boats. Copper-based hull coatings are intended to be antifouling in that they retard the growth of algae, barnacles and tubeworms; but alternatives exist that can eliminate the harm that copper contamination does to marine organisms. A variety of policy options are available to mandate or provide economic incentives to switch to these less harmful alternatives. This paper puts forth a conceptual framework for thinking about how to design and evaluate alternative policies to transition to nontoxic boat hulls, drawing from the authors' experience designing a policy for use in San Diego Bay. Many of the issues raised are broadly applicable to environmental problems where the solution involves a large-scale replacement of durable consumer goods.     

Increasing exfiltration from pervious concrete and temperature monitoring

Pervious concrete typically has an infiltration rate far exceeding any expectation of precipitation rate. The limiting factor of a retention based pervious concrete system is often defined by how quickly the underlying soil subgrade will infiltrate the water temporarily stored within the concrete and/or aggregate base. This issue is of particular importance when placing a pervious concrete system on compacted fine textured soils. This research describes the exfiltration from twelve pervious concrete plots constructed on a compacted clay soil in eastern Tennessee, USA. Several types of treatments were applied to the clay soil prior to placement of the stone aggregate base and pervious concrete in an attempt to increase the exfiltration rate, including: 1) control – no treatment; 2) trenched – soil trenched and backfilled with stone aggregate; 3) ripped – soil ripped with a subsoiler; and 4) boreholes – placement of shallow boreholes backfilled with sand. The average exfiltration rates were 0.8 cm d⁻¹ (control), 4.6 cm d⁻¹ (borehole), 10.0 cm d⁻¹ (ripped), and 25.8 cm d⁻¹ (trenched). The trenched treatment exfiltrated fastest, followed by the ripped and then the borehole treatments, although the ripped and borehole treatments were not different from one another at the 5% level of significance. The internal temperature of the pervious concrete and aggregate base was monitored throughout the winter of 2006–2007. Although the temperature of the pervious concrete dropped below freezing 24 times, freezing concrete temperatures never coincided with free water being present in the large pervious concrete pores. The coldest recorded air temperature was −9.9 °C, and the corresponding coldest recorded pervious concrete temperature was −7.1 °C. The temperature of the pervious concrete lagged diurnal air temperature changes and was generally buffered in amplitude, particularly when free water was present since the addition of water increases the thermal capacity of the pervious concrete greatly. The temperature of the aggregate base was further buffered to diurnal changes, and no freezing temperatures were recorded.     

Vulnerability of Rehabilitated Agricultural Production Systems to Invasion by Nontarget Plant Species

Vast areas of arable land have been retired from crop production and “rehabilitated” to improved system states through landowner incentive programs in the United States (e.g., Conservation and Wetland Reserve Programs), as well as Europe (i.e., Agri-Environment Schemes). Our review of studies conducted on invasion of rehabilitated agricultural production systems by nontarget species elucidates several factors that may increase the vulnerability of these systems to invasion. These systems often exist in highly fragmented and agriculturally dominated landscapes, where propagule sources of target species for colonization may be limited, and are established under conditions where legacies of past disturbance persist and prevent target species from persisting. Furthermore, rehabilitation approaches often do not include or successfully attain all target species or historical ecological processes (e.g., hydrology, grazing, and/or fire cycles) key to resisting invasion. Uncertainty surrounds ways in which nontarget species may compromise long term goals of improving biodiversity and ecosystem services through rehabilitation efforts on former agricultural production lands. This review demonstrates that more studies are needed on the extent and ecological impacts of nontarget species as related to the goals of rehabilitation efforts to secure current and future environmental benefits arising from this widespread conservation practice.     

Lessons from Integrating Fishers of Arapaima in Small-Scale Fisheries Management at the Mamirauá Reserve,Amazon

Fishers and small-scale fisheries worldwide have been marginalized historically. Now it is clear that integrating fishers in management processes is key to resource conservation, but it is less clear how to do it. Here, based on a literature review and new information, we present and analyze a case in which the participation of fishers in the management process was crucial in recovering an overexploited small-scale fishery for the pirarucu (Arapaima spp.) in the Amazon Basin, Brazil. In 8 years of experimental management, from 1999 to 2006, the population of pirarucu increased 9-fold (from about 2200 to 20,650 individuals), harvest quotas increased 10-fold (from 120 to 1249 individuals), and fishers’ participation in the management process increased and they benefited from increased monetary returns. Additionally, the number of communities conducting the management scheme increased from 4 in 1999 to 108 in 2006, following the demands of fishers and regional government agencies. Based on our analysis, we suggest that the participation of fishers in the management of other small-scale fisheries in the world can be improved by focusing on (1) applying the knowledge and skills of fishers in resource monitoring and management, (2) bridging knowledge systems among all involved stakeholders, (3) collaborating with fishers that are interested in, and capable of conducting, resource conservation schemes, and (4) conducting management under conditions of uncertainty.     

Arctic Lake Physical Processes and Regimes with Implications for Winter Water Availability and Management in the National Petroleum Reserve Alaska

Lakes are dominant landforms in the National Petroleum Reserve Alaska (NPRA) as well as important social and ecological resources. Of recent importance is the management of these freshwater ecosystems because lakes deeper than maximum ice thickness provide an important and often sole source of liquid water for aquatic biota, villages, and industry during winter. To better understand seasonal and annual hydrodynamics in the context of lake morphometry, we analyzed lakes in two adjacent areas where winter water use is expected to increase in the near future because of industrial expansion. Landsat Thematic Mapper and Enhanced Thematic Mapper Plus imagery acquired between 1985 and 2007 were analyzed and compared with climate data to understand interannual variability. Measured changes in lake area extent varied by 0.6% and were significantly correlated to total precipitation in the preceding 12 months (p < 0.05). Using this relation, the modeled lake area extent from 1985 to 2007 showed no long-term trends. In addition, high-resolution aerial photography, bathymetric surveys, water-level monitoring, and lake-ice thickness measurements and growth models were used to better understand seasonal hydrodynamics, surface area-to-volume relations, winter water availability, and more permanent changes related to geomorphic change. Together, these results describe how lakes vary seasonally and annually in two critical areas of the NPRA and provide simple models to help better predict variation in lake-water supply. Our findings suggest that both overestimation and underestimation of actual available winter water volume may occur regularly, and this understanding may help better inform management strategies as future resource use expands in the NPRA.