Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the Southeast United States and co-benefit of SO2 emission controls.

Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the Southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the Southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58% of isoprene SOA) from the low-NOx pathway and glyoxal (28%) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US EPA projects 2013-2025 decreases in anthropogenic emissions of 34% for NOx (leading to 7% increase in isoprene SOA) and 48% for SO2 (35% decrease in isoprene SOA). Reducing SO2 emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM2.5 from SO2 emission controls.

Characterizing ammonia emissions from swine farms in eastern North Carolina: part 1--conventional lagoon and spray technology for waste treatment.

Ammonia (NH3) fluxes from waste treatment lagoons and barns at two conventional swine farms in eastern North Carolina were measured. The waste treatment lagoon data were analyzed to elucidate the temporal (seasonal and diurnal) variability and to derive regression relationships between NH3 flux and lagoon temperature, pH and ammonium content of the lagoon, and the most relevant meteorological parameters. NH3 fluxes were measured at various sampling locations on the lagoons by a flowthrough dynamic chamber system interfaced to an environmentally controlled mobile laboratory. Two sets of open-path Fourier transform infrared (FTIR) spectrometers were also used to measure NH3 concentrations for estimating NH3 emissions from the animal housing units (barns) at the lagoon and spray technology (LST) sites. Two different types of ventilation systems were used at the two farms. Moore farm used fan ventilation, and Stokes farm used natural ventilation. The early fall and winter season intensive measurement campaigns were conducted during September 9 to October 11, 2002 (lagoon temperature ranged from 21.2 to 33.6 degrees C) and January 6 to February 2, 2003 (lagoon temperature ranged from 1.7 to 12 degrees C), respectively. Significant differences in seasonal NH3 fluxes from the waste treatment lagoons were found at both farms. Typical diurnal variation of NH3 flux with its maximum value in the afternoon was observed during both experimental periods. Exponentially increasing flux with increasing surface lagoon temperature was observed, and a linear regression relationship between logarithm of NH3 flux and lagoon surface temperature (T1) was obtained. Correlations between lagoon NH3 flux and chemical parameters, such as pH, total Kjeldahl nitrogen (TKN), and total ammoniacal nitrogen (TAN) were found to be statistically insignificant or weak. In addition to lagoon surface temperature, the difference (D) between air temperature and the lagoon surface temperature was also found to influence the NH3 flux, especially when D > 0 (i.e., air hotter than lagoon). This hot-air effect is included in the statistical-observational model obtained in this study, which was used further in the companion study (Part II), to compare the emissions from potential environmental superior technologies to evaluate the effectiveness of each technology.

Characterizing ammonia emissions from swine farms in eastern North Carolina: part 2--potential environmentally superior technologies for waste treatment.

The need for developing environmentally superior and sustainable solutions for managing the animal waste at commercial swine farms in eastern North Carolina has been recognized in recent years. Program OPEN (Odor, Pathogens, and Emissions of Nitrogen), funded by the North Carolina State University Animal and Poultry Waste Management Center (APWMC), was initiated and charged with the evaluation of potential environmentally superior technologies (ESTs) that have been developed and implemented at selected swine farms or facilities. The OPEN program has demonstrated the effectiveness of a new paradigm for policy-relevant environmental research related to North Carolina's animal waste management programs. This new paradigm is based on a commitment to improve scientific understanding associated with a wide array of environmental issues (i.e., issues related to the movement of N from animal waste into air, water, and soil media; the transmission of odor and odorants; disease-transmitting vectors; and airborne pathogens). The primary focus of this paper is on emissions of ammonia (NH3) from some potential ESTs that were being evaluated at full-scale swine facilities. During 2-week-long periods in two different seasons (warm and cold), NH3 fluxes from water-holding structures and NH3 emissions from animal houses or barns were measured at six potential EST sites: (1) Barham farm--in-ground ambient temperature anaerobic digester/energy recovery/greenhouse vegetable production system; (2) BOC #93 farm--upflow biofiltration system--EKOKAN; (3) Carrolls farm--aerobic blanket system--ISSUES-ABS; (4) Corbett #1 farm--solids separation/ gasification for energy and ash recovery centralized system--BEST; (5) Corbett #2 farm--solid separation/ reciprocating water technology--ReCip; and (6) Vestal farm--Recycling of Nutrient, Energy and Water System--ISSUES-RENEW. The ESTs were compared with similar measurements made at two conventional lagoon and spray technology (LST) farms (Moore farm and Stokes farm). A flow-through dynamic chamber system and two sets of open-path Fourier transform infrared (OP-FTIR) spectrometers measured NH3 fluxes continuously from water-holding structures and emissions from housing units at the EST and conventional LST sites. A statistical-observational model for lagoon NH3 flux was developed using a multiple linear regression analysis of 15-min averaged NH3 flux data against the relevant environmental parameters measured at the two conventional farms during two different seasons of the year. This was used to compare the water-holding structures at ESTs with those from lagoons at conventional sites under similar environmental conditions. Percentage reductions in NH3 emissions from different components of each potential EST, as well as the whole farm on which the EST was located were evaluated from the estimated emissions from water-holding structures, barns, etc., all normalized by the appropriate nitrogen excretion rate at the potential EST farm, as well as from the appropriate conventional farm. This study showed that ammonia emissions were reduced by all but one potential EST for both experimental periods. However, on the basis of our evaluation results and analysis and available information in the scientific literature, the evaluated alternative technologies may require additional technical modifications to be qualified as unconditional ESTs relative to NH3 emissions reductions.