Simulated and experimental evaluation of factors affecting the rate and extent of reductive dehalogenation of chloroethenes with glucose

Carbohydrates such as molasses are being added to aquifers to serve as electron donors for reductive dehalogenation of chloroethenes. Glucose, as a model carbohydrate, was studied to better understand the processes involved and to evaluate the effectiveness for dehalogenation of different approaches for carbohydrate addition. A simulation model was developed and calibrated with experimental data for the reductive dehalogenation of tetrachloroethene to ethene via cis-1,2-dichloroethene. The model included fermentors that convert the primary donor (glucose) into butyrate, acetate and hydrogen, methanogens, and two separate dehalogenator groups. The dehalogenation groups use the hydrogen intermediate as an electron donor and the different haloethenes as electron acceptors through competitive inhibition. Model simulations suggest first that the initial relative population size of dehalogenators and H(2)-utilizing methanogens greatly affects the degree of dehalogenation achieved. Second, the growth and decay of biomass from soluble carbohydrate plays a significant role in reductive dehalogenation. Finally, the carbohydrate delivery strategies used (periodic versus batch addition and the time interval between periodic addition) greatly affect the degree of dehalogenation that can be obtained with a given amount of added carbohydrate.     

The potential of diffuse reflectance spectroscopy for the determination of carbon inventories in soils

Investigations have shown that near- and mid-infrared reflectance spectroscopy can accurately determine organic-C in soil. Efforts have also demonstrated that both can differentiate between organic and inorganic-C in soils, but the mid-infrared produces more accurate calibrations. Nevertheless, the greatest benefit would come with in situ determinations where factors such as particle size, sample heterogeneity and moisture can be important. While the variations in large (> 20 mesh) particle size can adversely effect calibration accuracy, efforts have demonstrated that the scanning of larger amounts of sample can overcome this, but the effects of moisture have not been fully explored. While under in situ conditions C distribution and sample heterogeneity are a problem for any analytical method, the rapid analysis possible with spectroscopic techniques will allow many more samples to be analyzed. In conclusion, near- and mid-infrared spectroscopy have great potential for providing the C values needed for C sequestration studies.     

Reduction of hexachloroethane to tetrachloroethylene in groundwater

At the Canadian Forces Base, Borden, hexachloroethane (HCE) that was introduced into an unconfined sand aquifer disappeared rapidly, with a half-life of about 40 days. Laboratory-scale studies, initiated to help assess the fate of HCE, indicated that it is reductively biotransformed to tetrachloroethylene (PCE) both by aerobic cultures of wastewater microflora and by microcosms containing unhomogenized Borden aquifer material. The results also indicate that the agents involved in the aquifer transformation of HCE to PCE are not homogeneously distributed in the aquifer material.     

Remote sensing-based estimates of annual and seasonal emissions from crop residue burning in the contiguous United States

Crop residue burning is an extensive agricultural practice in the contiguous United States (CONUS). This analysis presents the results of a remote sensing-based study of crop residue burning emissions in the CONUS for the time period 2003-2007 for the atmospheric species of carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrogen dioxide (NO2, sulfur dioxide (SO2), PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter), and PM10 (PM < or = 10 microm in aerodynamic diameter). Cropland burned area and associated crop types were derived from Moderate Resolution Imaging Spectroradiometer (MODIS) products. Emission factors, fuel load, and combustion completeness estimates were derived from the scientific literature, governmental reports, and expert knowledge. Emissions were calculated using the bottom-up approach in which emissions are the product of burned area, fuel load, and combustion completeness for each specific crop type. On average, annual crop residue burning in the CONUS emitted 6.1 Tg of CO2, 8.9 Gg of CH4, 232.4 Gg of CO, 10.6 Gg of NO2, 4.4 Gg of SO2, 20.9 Gg of PM2.5, and 28.5 Gg of PM10. These emissions remained fairly consistent, with an average interannual variability of crop residue burning emissions of +/- 10%. The states with the highest emissions were Arkansas, California, Florida, Idaho, Texas, and Washington. Most emissions were clustered in the southeastern United States, the Great Plains, and the Pacific Northwest. Air quality and carbon emissions were concentrated in the spring, summer, and fall, with an exception because of winter harvesting of sugarcane in Florida, Louisiana, and Texas. Sugarcane, wheat, and rice residues accounted for approximately 70% of all crop residue burning and associated emissions. Estimates of CO and CH4 from agricultural waste burning by the U.S. Environmental Protection Agency were 73 and 78% higher than the CO and CH4 emission estimates from this analysis, respectively. This analysis also showed that crop residue burning emissions are a minor source of CH4 emissions (< 1%) compared with the CH4 emissions from other agricultural sources, specifically enteric fermentation, manure management, and rice cultivation.     

Biological aspects of metal waste reclamation with biosolids

Smelter waste deposits pose an environmental threat worldwide. Biosolids are potentialy useful in reclamation of such sites. Biological aspects of revegetation of Zn and Pb smelter wastelands using biosolids are discussed in this report. The goal of the studies was to assess to what extent biosolid treatment would support ecosystem functioning as measured by biological indicators such as enzyme activities of revegetated metal waste or plant growth. Another crucial aspect was related to the assessment of metal transfer to the ecosystem which could affect the health of local fauna and also create a food chain risk. A field experiment was conducted on a smelter waste deposit in Piekary Slaskie, Silesia, Poland, with two separate fields - established on wastes from the Welz and Doerschel smelting processes. The tested methods allowed revegetation of the fields - application of municipal biosolid at the rate 300 dry t ha(-1) combined with the incorporation of commercial lime in a mixed oxide and carbonate form at the rate of 1.5 and 30 t for Welz waste or use of a 30 cm by-product lime cap followed by incorporation of biosolid at a rate of 300 t ha(-1) for the more acidic Doerschel waste. Studies on biological activities demonstrated that the reclamation methods used are an effective way to establish new, fully-functioning ecosystems that support plant growth. They also provided strong evidence that forage crops grown on Zn, Cd and Pb contaminated sites reclaimed using lime and biosolids do not pose identified risk for wildlife and food safety.     

Effects of biomass accumulation on microbially enhanced dissolution of a PCE pool: a numerical simulation

Recent studies have shown that dechlorinating bacteria can accelerate the dissolution rate of dense, nonaqueous phase liquids (DNAPLs) containing tetrachloroethene (PCE). We present an advection-dispersion-reaction model for a two-dimensional domain, with groundwater flowing over a pool of free-product PCE. PCE is converted to cis-1,2-dichloroethene (cDCE) and toxicity due to PCE or cDCE is neglected. We adopt previously published correlations relating biomass concentrations and hydraulic conductivity, accounting for biofilm growth and plug-like growth. The system of coupled equations is solved numerically. The high biotransformation rate of PCE increases the concentration gradient of PCE at the water-DNAPL interface, enhancing dissolution. The higher the electron donor (ED) concentration, the larger the dissolution enhancement. Based on the values of maximum specific rate we used, when the electron donor is unlimited, the active biomass accumulates adjacent to the water-NAPL interface and microbial reactions can significantly enhance the pool dissolution. The resulting steady-state dissolution rate can be approximated by a half-order solution when zero-order kinetics are suitable for representing the microbial reaction. However, bioclogging may significantly reduce local hydraulic conductivity; thus, it decreases the flow near the water-DNAPL interface, decreasing dissolution. When the ED is the limiting factor, active biomass accumulates away from the interface. This creates a no-flow zone between the active biomass and the interface. The enlargement of the no-flow zone, due to the donor limitation, diminishes the concentration gradient and the flushing around the water-DNAPL interface. Such adverse impacts may significantly decrease the enhancement predicted by models that do not consider the effects of bioclogging.     

Development of the crop residue and rangeland burning in the 2014 National Emissions Inventory using information from multiple sources

Biomass burning has been identified as an important contributor to the degradation of air quality because of its impact on ozone and particulate matter. One component of the biomass burning inventory, crop residue burning, has been poorly characterized in the National Emissions Inventory (NEI). In the 2011 NEI, wildland fires, prescribed fires, and crop residue burning collectively were the largest source of PM_2.5. This paper summarizes our 2014 NEI method to estimate crop residue burning emissions and grass/pasture burning emissions using remote sensing data and field information and literature-based, crop-specific emission factors. We focus on both the postharvest and pre-harvest burning that takes place with bluegrass, corn, cotton, rice, soybeans, sugarcane and wheat. Estimates for 2014 indicate that over the continental United States (CONUS), crop residue burning excluding all areas identified as Pasture/Grass, Grassland Herbaceous, and Pasture/Hay occurred over approximately 1.5 million acres of land and produced 19,600 short tons of PM_2.5. For areas identified as Pasture/Grass, Grassland Herbaceous, and Pasture/Hay, biomass burning emissions occurred over approximately 1.6 million acres of land and produced 30,000 short tons of PM_2.5. This estimate compares with the 2011 NEI and 2008 NEI as follows: 2008: 49,650 short tons and 2011: 141,180 short tons. Note that in the previous two NEIs rangeland burning was not well defined and so the comparison is not exact. The remote sensing data also provided verification of our existing diurnal profile for crop residue burning emissions used in chemical transport modeling. In addition, the entire database used to estimate this sector of emissions is available on EPA’s Clearinghouse for Inventories and Emission Factors (CHIEF, http://www3.epa.gov/ttn/chief/index.html).Implications: Estimates of crop residue burning and rangeland burning emissions can be improved by using satellite detections. Local information is helpful in distinguishing crop residue and rangeland burning from all other types of fires.