Ammonia and ammonium measurements from the southeastern United States

Twenty-four-hour integrated gaseous ${\mathrm{NH}}_3$ and fine particulate $({\mathrm{PM}}_{2.5}){\mathrm{NH}}_4^{+}$ were measured during 2004 at eight sites in the southeastern U.S. Mean ${\mathrm{NH}}_3$ concentrations for 2004 ranged from 2.44 ppbv at an urban-industrial site in North Birmingham, AL, to 0.23 ppbv at a rural-forested site near Centreville, AL. ${\mathrm{NH}}_3$ mixing ratios were found to be higher at urban sites than at nearby rural (or suburban sites) except for sites which were directly influenced by local sources. Only weak correlations with temperature were observed for ${\mathrm{NH}}_3$ at the sites; slightly greater correlations were observed for total ammonia $({\mathrm{NH}}_x={\mathrm{NH}}_3+{\mathrm{NH}}_4^{+})$ vs. temperature. A weak seasonal variation was observed for ${\mathrm{NH}}_3$ mixing ratios at all sites, with all but one site exhibiting biannual maxima in spring and late summer/fall. Mean ${\mathrm{PM}}_{2.5}$ ${\mathrm{NH}}_4^{+}$ concentrations ranged from $1.78\mathrm{\mu }\mathrm{g}{\mathrm{m}}^{-3}$ in Atlanta, GA, to $1.02\mathrm{\mu }\mathrm{g}{\mathrm{m}}^{-3}$ at Oak Grove, MS, and were more uniform across the network than ${\mathrm{NH}}_3$ mixing ratios, with only slightly larger values at urban sites as compared to nearby rural (or suburban) sites. All sites exhibited highest ${\mathrm{NH}}_x$ between July and September and lowest ${\mathrm{NH}}_x$ in November and December. The gaseous ${\mathrm{NH}}_3$ fraction $({\mathrm{NH}}_3/({\mathrm{NH}}_3+{\mathrm{NH}}_4^{+}))$ was observed to decrease with increasing values of ${\mathrm{PM}}_{2.5}$ ${\mathrm{SO}}_4^{2-}$ at all sites. At two rural-forested sites and two sites near the Gulf of Mexico, the ${\mathrm{NH}}_3$ gaseous fraction approached a relatively constant value of 5–10% as ${\mathrm{PM}}_{2.5}{\mathrm{SO}}_4^{2-}$ increased beyond 5–$7\mathrm{\mu }\mathrm{g}{\mathrm{m}}^{-3}$, suggesting that ${\mathrm{NH}}_3$ availability at these locations limits aerosol neutralization.     

Quantifying Asian and biomass burning sources of mercury using the Hg/CO ratio in pollution plumes observed at the Mount Bachelor observatory

Total airborne mercury (TAM) and carbon monoxide (CO) were measured in 22 pollution transport “events” at Mt. Bachelor Observatory (MBO), USA (2.8 km asl) between March 2004 and September 2005. Submicron particulate scattering (${\sigma }_{\mathrm{sp}})$, ozone (${\mathrm{O}}_3)$, and nitrogen oxides (${\mathrm{NO}}_y)$ were also measured and enhancement ratios for each chemical and aerosol species with CO were calculated. Events were categorized based on their source regions, which were determined by a combination of back trajectories, satellite fire detections, chemical and aerosol enhancement ratios, and meteorology. The mean $\mathrm{\Delta }\mathrm{TAM}/\mathrm{\Delta }\mathrm{CO}$ values for each source region are: East Asian industrial ($0.0046\pm 0.0013\mathrm{ng}{\mathrm{m}}^{-3}{\mathrm{ppbv}}^{-1}$, $n=10$ events, 236 h), Pacific Northwest U.S. (PNW) biomass burning ($0.0013\pm 0.008\mathrm{ng}{\mathrm{m}}^{-3}{\mathrm{ppbv}}^{-1}$, $n=7$ events, 173 h), and Alaska biomass burning ($0.0014\pm 0.0006\mathrm{ng}{\mathrm{m}}^{-3}{\mathrm{ppbv}}^{-1}$, $n=3$ events, 96 h). The $\mathrm{\Delta }\mathrm{TAM}/\mathrm{\Delta }\mathrm{CO}$ means from Asian long-range transport (ALRT) and biomass burning events are combined with previous estimates of CO emissions from Chinese anthropogenic, global biomass burning, and global boreal biomass sources in order to estimate the emissions of gaseous elemental mercury (GEM) from these sources. The GEM emissions that we calculate here are: Chinese anthropogenic ($620\pm 180\mathrm{t}{\mathrm{y}}^{-1}$), global biomass burning $(670\pm 330\mathrm{t}{\mathrm{y}}^{-1})$, and global boreal biomass burning $(168\pm 75\mathrm{t}{\mathrm{y}}^{-1})$, with errors estimated from propagating the uncertainty in the mean enhancement ratios and CO emissions. A comparison of our results with published mercury (Hg) emissions inventories reveals that the Chinese GEM emissions from this study are higher by about a factor of two, while our estimate for global biomass burning is consistent with previous studies.     

Coarse particulate matter concentrations from residential outdoor sites associated with the North Carolina Asthma and Children's Environment Studies (NC-ACES)

Coarse particulate matter (PM${}_{10\text{-}2.5})$ concentration data from residential outdoor sites were collected using portable samplers as part of an exposure assessment for the North Carolina Asthma and Children's Environment Studies (NC-ACES). PM${}_{10\text{-}2.5}$ values were estimated using the differential between independent PM${}_{10}$ and PM${}_{2.5}$ collocated MiniVol measurements. Repeated daily 24-h integrated PM${}_{10}$ and PM${}_{2.5}$ residential outdoor monitoring was performed at a total of 26 homes during September 2003–June 2004 in the Research Triangle Park, NC area. This effort resulted in the collection of 73 total daily measurements. This assessment was conducted to provide data needed to investigate the association of exposures to coarse particle PM mass concentrations with observed human health effects. Potential instrument bias between the differential MiniVol methodology and a dichotomous sampler were investigated. Results indicated that minimal bias of PM${}_{10\text{-}2.5}$ mass concentration estimates (slope $=$ 0.8, intercept $=0.36\mathrm{\mu }$g m${}^{-3})$ existed between the dichotomous and differential MiniVol procedures. Residential outdoor PM${}_{10\text{-}2.5}$ mass concentrations were observed to be highly variable across measurement days and ranged from 1.1 to $12.6\mathrm{\mu }$g m${}^{-3}$ (mean of $5.4\mathrm{\mu }$g m${}^{-3})$. An average correlation coefficient of $r=0.75$ existed between residential outdoor PM${}_{10\text{-}2.5}$ mass concentrations and those obtained from the central ambient monitoring site. Temporal and spatial variability of PM${}_{10\text{-}2.5}$ mass concentrations during the study were observed and are described in this report.     

Precipitation chloride at West Point,NY: Seasonal patterns and possible contributions from non-seawater sources

Chloride derived from the atmosphere can be a valuable tracer in ecosystem and watershed processes. For these purposes and other environmental studies, it is important to establish temporal patterns and sources for ${\mathrm{Cl}}^{-}$ in wet deposition. Weekly composite precipitation samples have been analyzed by the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) at West Point, NY during 1981–2003, although systematic contamination of precipitation ${\mathrm{Na}}^{+}$ significantly perturbed data for ${\mathrm{Na}}^{+}$ prior to 1998. Chloride and sodium ion seasonal wet deposition were highest in winter and lowest in summer through most of the record, probably as a result of more frequent marine-trajectory storms in winter. During 1998–2003, the period of highest quality ${\mathrm{Na}}^{+}$ data, the ratio of $[{\mathrm{Cl}}^{-}]/[{\mathrm{Na}}^{+}]$ was significantly higher than average in summer and lower in winter. Higher summer $[{\mathrm{Cl}}^{-}]/[{\mathrm{Na}}^{+}]$ occurred consistently throughout the record, often reaching values four times the seawater ratio. Based on the ratio of $[{\mathrm{Cl}}^{-}]/[{\mathrm{Na}}^{+}]$ in seawater $(1.16)\sim 16\%$ of annual wet deposition of ${\mathrm{Cl}}^{-}$ during 1998–2003 was in excess of that for surface seawater. Additionally, a minor terrestrial dust ${\mathrm{Na}}^{+}$ component was approximated, which had the net effect of increasing annual excess ${\mathrm{Cl}}^{-}$ wet deposition to $\sim 22\%$ ($2.56\mathrm{mEq}{\mathrm{m}}^{-2}$ or $0.90\mathrm{kg}{\mathrm{ha}}^{-1}$) of the mean annual ${\mathrm{Cl}}^{-}$ wet deposition at West Point ($11.9\mathrm{mEq}{\mathrm{m}}^{-2}$ or $4.2\mathrm{kg}{\mathrm{ha}}^{-1}$). Consistent with plausible sources of non-seawater ${\mathrm{Cl}}^{-}$, we attribute excess ${\mathrm{Cl}}^{-}$ wet deposition to HCl emission from coal fired generating stations, HCl emissions from domestic and industrial waste incineration and to HCl formation in the regional atmosphere from reactions of sea-salt aerosols with S and N acidic gases.     

Characterization of aging wood chip combustion aerosol in an environmental chamber

Aging of aerosol from wood chip combustion in a stoker burner was monitored in an outdoor environmental chamber for 19–27 h in order to study the size, volatility and organic carbon (OC) content of the combustion aerosol particles during aging. A scanning mobility particle sizer, a volatility tandem differential mobility analyzer (VTDMA), and a thermal–optical carbon analyzer were utilized. The VTDMA and carbon analyses were performed at the beginning, after 17–24 h of aging and at one intermediate point. The size decrease of freshly emitted particles was 6–10% when heated to $360{}^{\circ }\mathrm{C}$, and was found to depend on the experiment start time. For particles aged for 24 h, a 74–86% decrease in particle size at $360{}^{\circ }\mathrm{C}$ was observed. The more volatile OC fraction and the total OC fraction in the particles increased and the less volatile OC fraction decreased with aging. This suggests that during aging more volatile compounds condense on or heavier compounds photodegrade into lighter ones in the particles. Occasionally, new particle formation and growth were observed in the following day. The new particles were found to be composed mainly of volatile material.     

Observations of hydroxyl and the sum of peroxy radicals at Summit,Greenland during summer 2003

The first measurements of peroxy (HO₂+RO₂) and hydroxyl (OH) radicals above the arctic snowpack were collected during the summer 2003 campaign at Summit, Greenland. The median measured number densities for peroxy and hydroxyl radicals were 2.2×10⁸ mol cm⁻³ and 6.4×10⁶ mol cm⁻³, respectively. The observed peroxy radical values are in excellent agreement ($R^2=0.83$, $\mathrm{M}/\mathrm{O}=1.06$) with highly constrained model predictions. However, calculated hydroxyl number densities are consistently more than a factor of 2 lower than the observed values. These results indicate that our current understanding of radical sources and sinks is in accord with our observations in this environment but that there may be a mechanism that is perturbing the (HO₂+RO₂)/OH ratio. This observed ratio was also found to depend on meteorological conditions especially during periods of high winds accompanied by blowing snow. Backward transport model simulations indicate that these periods of high winds were characterized by rapid transport (1–2 days) of marine boundary layer air to Summit. These data suggest that the boundary layer photochemistry at Summit may be periodically impacted by halogens.     

A field comparison of ethylene vinyl acetate and low-density polyethylene thin films for equilibrium phase passive air sampling of polycyclic aromatic hydrocarbons

Ethylene vinyl acetate (EVA) and low-density polyethylene (LDPE) were compared as thin film polymer passive air samplers for polycyclic aromatic hydrocarbons (PAHs). These samplers were co-deployed for periods of up to 27 days at an urban field site in Brisbane. Despite demonstrated air side resistance to mass transfer, sampling rate ratios indicate rapid accumulation kinetics for EVA compared with LDPE. Confirming theoretically predicted values, sampler-air partition coefficients were greater for EVA as compared with LDPE. The relatively high capacity of EVA films may be an advantage in terms of sensitivity, when film thickness and hence amounts accumulated at equilibrium, are low.Predictions of times to effective equilibrium $(t_{\mathrm{eq}(95\%)})$ were made for a nominal film thickness of 1 μm. These predictions indicate that both types of films would be effective equilibrium phase samplers for predominantly vapour phase PAHs with log octanol-air partition coefficients $(\log K_{\mathrm{OA}})$ values of ⩽8.7 (pyrene). Despite comparatively rapid linear stage kinetics for EVA, the predicted times to effective equilibrium for PAHs are less for LDPE. This arises due to the relative magnitude of their respective K_SA values. The predicted times to equilibrium (25 °C) for pyrene for example are approximately 94 and 34 days for EVA and LDPE, respectively.