The reactive transport of trichloroethene is influenced by residence time and microbial numbers

The dechlorination rate in a flow-through porous matrix can be described by the species specific dechlorination rate observed in a liquid batch unless mass transport limitations prevail. This hypothesis was examined by comparing dechlorination rates in liquid batch with that in column experiments at various flow rates (3-9-12 cm day(-1)). Columns were loaded with an inoculated sand and eluted with a medium containing 1mM trichloroethene (TCE) for 247 days. Dechlorination in the column treatments increased with decreasing flow rate, illustrating the effect of the longer residence time. Zeroth order TCE or cis-DCE degradation rates were 4-7 folds larger in columns than in corresponding batch systems which could be explained by the higher measured Geobacter and Dehalococcoides numbers per unit pore volume in the columns. The microbial numbers also explained the variability in dechlorination rate among flow rate treatments marked by a large elution of the dechlorinating species' yield as flow increased. Stop flow events did not reveal mass transport limitations for dechlorination. We conclude that flow rate effects on reactive transport of TCE in this coarse sand are explained by residence time and by microbial transport and that mass transport limitations in this porous matrix are limited.     

Plant communities in relation to flooding and soil contamination in a lowland Rhine River floodplain

Using canonical correspondence analysis (CCA), relationships were investigated between plant species composition and flooding characteristics, heavy metal contamination and soil properties in a lowland floodplain of the Rhine River. Floodplain elevation and yearly average flooding duration turned out to be more important for explaining variation in plant species composition than soil heavy metal contamination. Nevertheless, plant species richness and diversity showed a significant decrease with the level of contamination. As single heavy metal concentrations seemed mostly too low for causing phytotoxic effects in plants, this trend is possibly explained by additive effects of multiple contaminants or by the concomitant influences of contamination and non-chemical stressors like flooding. These results suggest that impacts of soil contamination on plants in floodplains could be larger than expected from mere soil concentrations. In general, these findings emphasize the relevance of analyzing effects of toxic substances in concert with the effects of other relevant stressors.     

Volatile nanoparticle formation and growth within a diluting diesel car exhaust

A major source of particle number emissions is road traffic. However, scientific knowledge concerning secondary particle formation and growth of ultrafine particles within vehicle exhaust plumes is still very limited. Volatile nanoparticle formation and subsequent growth conditions were analyzed here to gain a better understanding of "real-world" dilution conditions. Coupled computational fluid dynamics and aerosol microphysics models together with measured size distributions within the exhaust plume of a diesel car were used. The impact of soot particles on nucleation, acting as a condensational sink, and the possible role of low-volatile organic components in growth were assessed. A prescribed reduction of soot particle emissions by 2 orders of magnitude (to capture the effect of a diesel particle filter) resulted in concentrations of nucleation-mode particles within the exhaust plume that were approximately 1 order of magnitude larger. Simulations for simplified sulfuric acid-water vapor gas-oil containing nucleation-mode particles show that the largest particle growth is located in a recirculation zone in the wake of the car. Growth of particles within the vehicle exhaust plume up to detectable size depends crucially on the relationship between the mass rate of gaseous precursor emissions and rapid dilution. Chassis dynamometer measurements indicate that emissions of possible hydrocarbon precursors are significantly enhanced under high engine load conditions and high engine speed. On the basis of results obtained for a diesel passenger car, the contributions from light diesel vehicles to the observed abundance of measured nucleation-mode particles near busy roads might be attributable to the impact of two different time scales: (1) a short one within the plume, marked by sufficient precursor emissions and rapid dilution; and (2) a second and comparatively long time scale resulting from the mix of different precursor sources and the impact of atmospheric chemistry.     

Total fuel-cycle analysis of heavy-duty vehicles using biofuels and natural gas-based alternative fuels

Heavy-duty vehicles (HDVs) present a growing energy and environmental concern worldwide. These vehicles rely almost entirely on diesel fuel for propulsion and create problems associated with local pollution, climate change, and energy security. Given these problems and the expected global expansion of HDVs in transportation sectors, industry and governments are pursuing biofuels and natural gas as potential alternative fuels for HDVs. Using recent lifecycle datasets, this paper evaluates the energy and emissions impacts of these fuels in the HDV sector by conducting a total fuel-cycle (TFC) analysis for Class 8 HDVs for six fuel pathways: (1) petroleum to ultra low sulfur diesel; (2) petroleum and soyoil to biodiesel (methyl soy ester); (3) petroleum, ethanol, and oxygenate to e-diesel; (4) petroleum and natural gas to Fischer-Tropsch diesel; (5) natural gas to compressed natural gas; and (6) natural gas to liquefied natural gas. TFC emissions are evaluated for three greenhouse gases (GHGs) (carbon dioxide, nitrous oxide, and methane) and five other pollutants (volatile organic compounds, carbon monoxide, nitrogen oxides, particulate matter, and sulfur oxides), along with estimates of total energy and petroleum consumption associated with each of the six fuel pathways. Results show definite advantages with biodiesel and compressed natural gas for most pollutants, negligible benefits for e-diesel, and increased GHG emissions for liquefied natural gas and Fischer-Tropsch diesel (from natural gas).     

Issues with ozone attainment methodology for Houston, TX

To comply with the federal 8-hr ozone standard, the state of Texas is creating a plan for Houston that strictly follows the U.S. Environmental Protection Agency's (EPA) guidance for demonstrating attainment. EPA's attainment guidance methodology has several key assumptions that are demonstrated to not be completely appropriate for the unique observed ozone conditions found in Houston. Houston's ozone violations at monitoring sites are realized as gradual hour-to-hour increases in ozone concentrations, or by large hourly ozone increases that exceed up to 100 parts per billion/hr. Given the time profiles at the violating monitors and those of nearby monitors, these large increases appear to be associated with small parcels of spatially limited plumes of high ozone in a lower background of urban ozone. Some of these high ozone parcels and plumes have been linked to a combination of unique wind conditions and episodic hydrocarbon emission events from the Houston Ship Channel. However, the regulatory air quality model (AQM) does not predict these sharp ozone gradients. Instead, the AQM predicts gradual hourly increases with broad regions of high ozone covering the entire Houston urban core. The AQM model performance can be partly attributed to EPA attainment guidance that prescribes the removal in the baseline model simulation of any episodic hydrocarbon emissions, thereby potentially removing any nontypical causes of ozone exceedances. This paper shows that attainment of all monitors is achieved when days with observed large hourly variability in ozone concentrations are filtered from attainment metrics. Thus, the modeling and observational data support a second unique cause for how ozone is formed in Houston, and the current EPA methodology addresses only one of these two causes.     

Experimental investigation of outdoor and indoor mean concentrations and concentration fluctuations of pollutants

Tracer gas was released upwind of a two-compartment complex shaped building under unstable atmospheric conditions. The mean wind direction was normal to or at 45° to the long face of the building. The general patterns of concentration distribution on the building external walls and inside the building were analysed and the influence of natural and mechanical ventilation on indoor concentration distributions was discussed. Mean concentration levels, as well as the concentration fluctuation intensity, were higher on the windward walls of the building, although concentration levels varied along each wall. Concentration fluctuations measured inside the building were lower than those measured outside. Inside the two compartments of the building, the time series of concentrations had a similar general behaviour; however, gas concentrations took approximately 1.5 times longer to reach the mean maximum concentration value at the downwind compartment 02 while they also decreased more rapidly in the upwind compartment 01 after the source was turned off. The highest indoor concentration and concentration fluctuation values were observed at the detectors located close to the windward walls, especially when the building windows were open. Experiments with and without natural ventilation suggested that infiltration and exfiltration of contaminants is much faster when the building windows are open, resulting to higher indoor concentration levels. Furthermore, mechanical ventilation tends to homogenize concentrations and suppress concentration fluctuations, leading to lower maximum concentration values.     

Variability of dust iron solubility in atmospheric waters: Investigation of the role of oxalate organic complexation

Atmospheric dust deposition is a major external iron source for remote surface ocean waters. Organic complexation is known to play a role in the dissolution of iron-containing minerals. In this paper, we present our study on the effect of oxalate on dust iron solubility in simulated rainwater. Our results reveal that the solubility of iron carried by analogs of different African dusts varies with the dust source. Our experiments indicate a positive linear correlation between iron solubility and oxalate concentration. Soluble iron (SFe) increases from 0.0025(±0.0005)% to 0.26(±0.01)% of total iron, considering all dust sources and with oxalate concentrations ranging from 0 to 8 μM. These results show that the observed variability of iron solubility in aerosols collected over the Atlantic Ocean is, at least partly, due to an increase in dust iron solubility, with the presence of oxalate complexation, rather than to the presence of more soluble anthropogenic iron. Considering the mineralogical composition of those particles, experiments with pure minerals (hematite, goethite and illite) were performed to study the dissolution process. We found that oxalate promotes the solubility of iron contained in clay and hence confirmed that more than 95% of SFe from soil dust is provided by clay (illite). This experimental work enables us to establish a parameterization of iron solubility in dust as a function of oxalate concentration and based on the individual iron solubility of pure iron-bearing minerals usually present in dust particles. Finally, our results emphasize that oxalate contributes to iron solubility on the same order of magnitude as the acid processes. Organic complexation appears to be a process that increases iron solubility and likely enhances the bioavailability of iron from dust.     

Limits and dynamics of methane oxidation in landfill cover soils

In order to understand the limits and dynamics of methane (CH₄) oxidation in landfill cover soils, we investigated CH₄ oxidation in daily, intermediate, and final cover soils from two California landfills as a function of temperature, soil moisture and CO₂ concentration. The results indicate a significant difference between the observed soil CH₄ oxidation at field sampled conditions compared to optimum conditions achieved through pre-incubation (60 days) in the presence of CH₄ (50 ml l⁻¹) and soil moisture optimization. This pre-incubation period normalized CH₄ oxidation rates to within the same order of magnitude (112-644 μg CH₄ g⁻¹ day⁻¹) for all the cover soils samples examined, as opposed to the four orders of magnitude variation in the soil CH₄ oxidation rates without this pre-incubation (0.9-277 μg CH₄ g⁻¹ day⁻¹).Using pre-incubated soils, a minimum soil moisture potential threshold for CH₄ oxidation activity was estimated at 1500 kPa, which is the soil wilting point. From the laboratory incubations, 50% of the oxidation capacity was inhibited at soil moisture potential drier than 700 kPa and optimum oxidation activity was typical observed at 50 kPa, which is just slightly drier than field capacity (33 kPa). At the extreme temperatures for CH₄ oxidation activity, this minimum moisture potential threshold decreased (300 kPa for temperatures <5 °C and 50 kPa for temperatures >40 °C), indicating the requirement for more easily available soil water. However, oxidation rates at these extreme temperatures were less than 10% of the rate observed at more optimum temperatures (∼30 °C). For temperatures from 5 to 40 °C, the rate of CH₄ oxidation was not limited by moisture potentials between 0 (saturated) and 50 kPa. The use of soil moisture potential normalizes soil variability (e.g. soil texture and organic matter content) with respect to the effect of soil moisture on methanotroph activity. The results of this study indicate that the wilting point is the lower moisture threshold for CH₄ oxidation activity and optimum moisture potential is close to field capacity.No inhibitory effects of elevated CO₂ soil gas concentrations were observed on CH₄ oxidation rates. However, significant differences were observed for diurnal temperature fluctuations compared to thermally equivalent daily isothermal incubations.     

Editor's perspective‐‐‐Shale gas development: Environmental issues and opportunities

Many professionals in the environmental industry have questioned whether the rapid expansion in shale gas development, particularly in the Marcellus Shale Play, is providing business opportunities. While gas production is a routine practice, the development of shale gas requires a process (fracturing, or, more commonly, “fracing'') that uses chemicals and is far more intrusive to the subsurface environment than traditional gas production. In this Editor's Perspective, we evaluate the environmental issues surrounding shale gas development, with a specific focus on the Marcellus Shale Play because it is currently the most active play in the United States, from both the drilling and political perspectives. In addition, we examine where the business opportunities are likely to be for environmental professionals relative to shale gas development. © 2011 Wiley Periodicals, Inc.     

Framework for integrating sustainability into remediation projects

The US Sustainable Remediation Forum (SURF) created this Framework to enable sustainability parameters to be integrated and balanced throughout the remediation project life cycle, while ensuring long‐term protection of human health and the environment and achieving public and regulatory acceptance. Parameters are considerations, impacts, or stressors of environmental, social, and economic importance. Because remediation project phases are not stand‐alone entities but interconnected components of the wider remediation system, the Framework provides a systematic, process‐based approach in which sustainability is integrated holistically and iteratively within the wider remediation system. By focusing stakeholders on the preferred end use or future use of a site at the beginning of a remediation project, the Framework helps stakeholders form a disciplined planning strategy. Specifically, the Framework is designed to help remediation practitioners (1) perform a tiered sustainability evaluation, (2) update the conceptual site model based on the results of the sustainability evaluation, (3) identify and implement sustainability impact measures, and (4) balance sustainability and other considerations during the remediation decision‐making process. The result is a process that encourages communication among different stakeholders and allows remediation practitioners to achieve regulatory goals and maximize the integration of sustainability parameters during the remediation process. © 2011 Wiley Periodicals, Inc.