Ammonia assessment from agriculture: U.S. status and needs

Recent studies suggest that human activities accelerate the production of reactive nitrogen on a global scale. Increased nitrogen emissions may lead to environmental impacts including photochemical air pollution, reduced visibility, changes in biodiversity, and stratospheric ozone depletion. In the last 50 yr, emissions of ammonia (NH3), which is the most abundant form of reduced reactive nitrogen in the atmosphere, have significantly increased as a result of intensive agricultural management and greater livestock production in many developed countries. These agricultural production practices are increasingly subject to governmental regulations intended to protect air resources. It is therefore important that an accurate and robust agricultural emission factors database exist to provide valid scientific support of these regulations. This paper highlights some of the recent work that was presented at the 2006 Workshop on Agricultural Air Quality in Washington, D.C. regarding NH3 emissions estimates and emission factors from agricultural sources in the U.S. and Europe. In addition, several best management practices are explored as the scientific community attempts to maximize the beneficial use of reactive nitrogen while simultaneously minimizing negative environmental impacts.     

Biological Responses to Contrasting Hydrology in Backwaters of Upper Mississippi River Navigation Pool 25

Water level management in Mississippi River Pool 25 differentially influences off-channel habitats in the mid-pool and lower pool. Hydrologic models indicate lower pool off-channel habitats dry with greater frequency and duration compared to similar habitats at mid-pool. We examined the influence of this contrasting hydrology on substrate characteristics, organic matter, macroinvertebrate, and fish communities in off-channel habitats during 2001–2003. Benthic organic matter standing stocks were stable in mid-pool habitats but lower pool values were variable because of annual differences in moist-soil vegetation production. Generally, small-bodied and multivoltine invertebrate taxa had high community biomass and dominated lower pool habitats, whereas longer-lived and large-bodied taxa were more abundant and had higher community biomass in mid-pool habitats having longer hydroperiods. Fish communities were dominated by cyprinids in both habitats, and mid-pool habitats tended to be higher in overall species richness. Unique fish taxa were collected in each pool, with primarily rheophilic forms in mid-pool habitats and limnophilic forms in lower pool habitats. Results indicate that contrasting hydrology associated with a mid-pool control point directly and indirectly influences biological communities in off-channel habitats. Further, management regimes that promote hydrologic diversity in off-channel habitats may enhance biological diversity at larger spatial and temporal scales.     

Microbial community dynamics in a chemolithotrophic denitrification reactor inoculated with methanogenic granular sludge

Denitrification is applied in the tertiary treatment of wastewater to reduce nitrogen pollution. Fluorescence in situ hybridization (FISH), catalyzed reporter deposition (CARD)-FISH, cloning, and scanning electron microscopy (SEM) were applied to follow the evolution of the microbial composition and structure of granular sludge in chemolithotrophic denitrifying bioreactors fed with nitrate and thiosulfate. FISH oligonucleotide probes for the chemolitoautotrophic denitrifiers Thiobacillus denitrificans and Thiomicrospira denitrificans were designed and their utility tested. CARD-FISH and cloning data showed that bacterial diversity in the biofilms changed during the reactor operation. Chemoorganotrophic fermentative Gram-positive strains in the phyla, Actinobacteria and Firmicutes, were dominant in the methanogenic inoculum, both in terms of biodiversity and in number. Other significant phyla were Bacteroidetes and Chloroflexi. After 6 months of operation, Proteobacteria became dominant (83% of the clones). The diversity of Gram-positive bacteria was partially maintained although their abundance decreased notably. After 110 d of operation, the abundance of Tb. denitrificans cells increased considerably, from 1% to 35% of total DAPI-stained cells and from no isolated clones to 15% of the total clones. Tm. denitrificans only represented a minor fraction of the microorganisms in the sludge (1-4% of the DAPI-stained cells). These findings confirm that Tb. denitrificans was the dominant chemolitoautotrophic denitrifying microorganism in the bioreactors. The Archaeal diversity remained almost unchanged and it was represented mostly by Methanosaeta soehngenii. SEM results indicated a considerable loss in the integrity of the sludge granules during the operation, with risk of sludge buoyancy.     

Locally-calibrated light transmission visualization methods to quantify nonaqueous phase liquid mass in porous media

Five locally-calibrated light transmission visualization (LTV) methods were tested to quantify nonaqueous phase liquid (NAPL) mass and mass reduction in porous media. Tetrachloroethylene (PCE) was released into a two-dimensional laboratory flow chamber packed with water-saturated sand which was then flushed with a surfactant solution (2% Tween 80) until all of the PCE had been dissolved. In all the LTV methods employed here, the water phase was dyed, rather than the more common approach of dyeing the NAPL phase, such that the light adsorption characteristics of NAPL did not change as dissolution progressed. Also, none of the methods used here required the use of external calibration chambers. The five visualization approaches evaluated included three methods developed from previously published models, a binary method, and a novel multiple wavelength method that has the advantage of not requiring any assumptions about the intra-pore interface structure between the various phases (sand/water/NAPL). The new multiple wavelength method is also expected to be applicable to any translucent porous media containing two immiscible fluids (e.g., water-air, water-NAPL). Results from the sand-water-PCE system evaluated here showed that the model that assumes wetting media of uniform pore size (Model C of Niemet and Selker, 2001) and the multiple wavelength model with no interface structure assumptions were able to accurately quantify PCE mass reduction during surfactant flushing. The average mass recoveries from these two imaging methods were greater than 95% for domain-average NAPL saturations of approximately 2.6x10(-2), and were approximately 90% during seven cycles of surfactant flushing that sequentially reduced the average NAPL saturation to 7.5x10(-4).     

A classification and regression tree model of controls on dissolved inorganic nitrogen leaching from European forests

Often, there is a non-linear relationship between atmospheric dissolved inorganic nitrogen (DIN) input and DIN leaching that is poorly captured by existing models. We present the first application of the non-parametric classification and regression tree approach to evaluate the key environmental drivers controlling DIN leaching from European forests. DIN leaching was classified as low (<3), medium (3-15) or high (>15 kg N ha⁻¹ year⁻¹) at 215 sites across Europe. The analysis identified throughfall NO₃⁻ deposition, acid deposition, hydrology, soil type, the carbon content of the soil, and the legacy of historic N deposition as the dominant drivers of DIN leaching for these forests. Ninety four percent of sites were successfully classified into the appropriate leaching category. This approach shows promise for understanding complex ecosystem responses to a wide range of anthropogenic stressors as well as an improved method for identifying risk and targeting pollution mitigation strategies in forest ecosystems.     

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1ng L(-1) and MeHg was less than 0.2ng L(-1). THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56)ng L(-1) at Sleepers River, Vermont; 112 (0.75)ng L(-1) at Rio Icacos, Puerto Rico; and 55 (0.80)ng L(-1) at Panola Mt., Georgia. Filtered (<0.7microm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5ng L(-1) at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.     

Cyanide generation during preservation of chlorinated wastewater effluent samples for total cyanide analysis.

Dechlorinating agents and pH adjustment are often used to preserve wastewater samples for cyanide analysis. The effects of four approved preservation protocols on the results of the total cyanide analysis of effluents from four water reclamation plants were examined. The results differed widely, and a clear pattern emerged. Immediate analysis without pH adjustment generally gave total cyanide concentrations below the reporting limit of 5 microg/L, irrespective of the dechlorinating agents used. When the pH was adjusted to > or =12, a slight increase in the measured total cyanide concentration was observed when thiosulfate was used to dechlorinate the samples, and a significant increase (>10 microg/L) was observed when arsenite was used as the dechlorinating agent. These results provide evidence that approved preservation protocols may give rise to cyanide formation in chlorinated wastewater effluent matrices.     

Fine particulate matter source apportionment for the Chemical speciation Trends Network site at Birmingham, Alabama, using Positive Matrix Factorization

The Positive Matrix Factorization (PMF) receptor model version 1.1 was used with data from the fine particulate matter (PM2.5) Chemical Speciation Trends Network (STN) to estimate source contributions to ambient PM2.5 in a highly industrialized urban setting in the southeastern United States. Model results consistently resolved 10 factors that are interpreted as two secondary, five industrial, one motor vehicle, one road dust, and one biomass burning sources. The STN dataset is generally not corrected for field blank levels, which are significant in the case of organic carbon (OC). Estimation of primary OC using the elemental carbon (EC) tracer method applied on a seasonal basis significantly improved the model's performance. Uniform increase of input data uncertainty and exclusion of a few outlier samples (associated with high potassium) further improved the model results. However, it was found that most PMF factors did not cleanly represent single source types and instead are "contaminated" by other sources, a situation that might be improved by controlling rotational ambiguity within the model. Secondary particulate matter formed by atmospheric processes, such as sulfate and secondary OC, contribute the majority of ambient PM2.5 and exhibit strong seasonality (37 +/- 10% winter vs. 55 +/- 16% summer average). Motor vehicle emissions constitute the biggest primary PM2.5 mass contribution with almost 25 +/- 2% long-term average and winter maximum of 29 +/- 11%. PM2.5 contributions from the five identified industrial sources vary little with season and average 14 +/- 1.3%. In summary, this study demonstrates the utility of the EC tracer method to effectively blank-correct the OC concentrations in the STN dataset. In addition, examination of the effect of input uncertainty estimates on model results indicates that the estimated uncertainties currently being provided with the STN data may be somewhat lower than the levels needed for optimum modeling results.     

Emissions from carpet combustion in a pilot-scale rotary kiln: comparison with coal and particle-board combustion

The use of post-consumer carpet as a potential fuel substitute in cement kilns and other high-temperature processes is being considered to address the problem of huge volumes of carpet waste and the opportunity of waste-to-energy recovery. Carpet represents a high volume waste stream, provides high energy value, and contains other recoverable materials for the production of cement. This research studied the emission characteristics of burning 0.46-kg charges of chopped nylon carpet squares, pulverized coal, and particle-board pellets in a pilot-scale natural gas-fired rotary kiln. Carpet was tested with different amounts of water added. Emissions of oxygen, carbon dioxide, nitric oxide (NO), sulfur dioxide (SO2), carbon monoxide (CO), and total hydrocarbons and temperatures were continuously monitored. It was found that carpet burned faster and more completely than coal and particle board, with a rapid volatile release that resulted in large and variable transient emission peaks. NO emissions from carpet combustion ranged from 0.06 to 0.15 g/MJ and were inversely related to CO emissions. Carpet combustion yielded higher NO emissions than coal and particle-board combustion, consistent with its higher nitrogen content. SO2 emissions were highest for coal combustion, consistent with its higher sulfur content than carpet or particle board. Adding water to carpet slowed its burn time and reduced variability in the emission transients, reducing the CO peak but increasing NO emissions. Results of this study indicate that carpet waste can be used as an effective alternative fuel, with the caveats that it might be necessary to wet carpet or chop it finely to avoid excessive transient puff emissions due to its high volatility compared with other solid fuels, and that controlled mixing of combustion air might be used to control NO emissions from nylon carpet.     

Emission projections for the U.S. Environmental Protection Agency Section 812 second prospective Clean Air Act cost/benefit analysis

Section 812 of the Clean Air Act Amendments (CAAA) of 1990 requires the U.S. Environmental Protection Agency (EPA) to perform periodic, comprehensive analyses of the total costs and total benefits of programs implemented pursuant to the CAAA. The first prospective analysis was completed in 1999. The second prospective analysis was initiated during 2005. The first step in the second prospective analysis was the development of base and projection year emission estimates that will be used to generate benefit estimates of CAAA programs. This paper describes the analysis, methods, and results of the recently completed emission projections. There are several unique features of this analysis. One is the use of consistent economic assumptions from the Department of Energy's Annual Energy Outlook 2005 (AEO 2005) projections as the basis for estimating 2010 and 2020 emissions for all sectors. Another is the analysis of the different emissions paths for both with and without CAAA scenarios. Other features of this analysis include being the first EPA analysis that uses the 2002 National Emission Inventory files as the basis for making 48-state emission projections, incorporating control factor files from the Regional Planning Organizations (RPOs) that had completed emission projections at the time the analysis was performed, and modeling the emission benefits of the expected adoption of measures to meet the 8-hr ozone National Ambient Air Quality Standards (NAAQS), the Clean Air Visibility Rule, and the PM2.5 NAAQS. This analysis shows that the 1990 CAAA have produced significant reductions in criteria pollutant emissions since 1990 and that these emission reductions are expected to continue through 2020. CAAA provisions have reduced volatile organic compound (VOC) emissions by approximately 7 million t/yr by 2000, and are estimated to produce associated VOC emission reductions of 16.7 million t by 2020. Total oxides of nitrogen (NO(x)) emission reductions attributable to the CAAA are 5, 12, and 17 million t in 2000, 2010, and 2020, respectively. Sulfur dioxide (SO2) emission benefits during the study period are dominated by electricity-generating unit (EGU) SO2 emission reductions. These EGU emission benefits go from 7.5 million t reduced in 2000 to 15 million t reduced in 2020.