Mercury deposition in southern New Hampshire, 2006–2009

The atmospheric deposition of mercury (Hg) occurs via several mechanisms including wet, dry, and occult processes. In an effort to understand the atmospheric cycling and seasonal depositional characteristics of Hg, event-based wet deposition samples and reactive gaseous Hg (RGM) measurements were collected for approximately 3 years at Thompson Farm (TF), a near-coastal rural site in Durham, NH, part of the University of New Hampshire AIRMAP Observing Network. Total aqueous mercury exhibited seasonal patterns in Hg wet deposition at TF. The lowest Hg wet deposition was measured in the winter with an average total seasonal deposition of 1.56 μg m−2compared to the summer average of 4.71 μg m−2. Inter-annual differences in total wet deposition are generally linked with precipitation volume, with the greatest deposition occurring in the wettest year. Relationships between surface level RGM and Hg wet deposition were also investigated based on continuous RGM measurements at TF from November 2006 to September 2009. No correlations were observed between RGM mixing ratios and Hg wet deposition, however the ineffective scavenging of RGM during winter precipitation events was evidenced by the less frequent depletion of RGM below the detection level. Seasonal dry deposition of reactive gaseous Hg (RGM) was estimated using an order-of-magnitude approach. RGM mixing ratios and dry deposition estimates were greatest during the winter and spring. The seasonal ratios of Hg wet deposition to RGM dry deposition vary by up to a factor of 80

Carbonyl sulfide exchange in a temperate loblolly pine forest grown under ambient and elevated CO2

Vegetation, soil and ecosystem level carbonyl sulfide (COS) exchange was observed at Duke Forest, a temperate loblolly pine forest, grown under ambient (Ring 1, R1) and elevated (Ring 2, R2) CO2. During calm meteorological conditions, ambient COS mixing ratios at the top of the forest canopy followed a distinct diurnal pattern in both CO2 growth regimes, with maximum COS mixing ratios during the day (R1=380±4 pptv and R2=373±3 pptv, daytime mean ± standard error) and minimums at night (R1=340±6 pptv and R2=346±5 pptv, nighttime mean ± standard error) reflecting a significant nighttime sink. Nocturnal vegetative uptake (−11 to −21 pmol m−2s−1, negative values indicate uptake from the atmosphere) dominated nighttime net ecosystem COS flux estimates (−10 to −30 pmol m−2s−1) in both CO2 regimes. In comparison, soil uptake (−0.8 to −1.7 pmol m−2 s−1) was a minor component of net ecosystem COS flux. In both CO2 regimes, loblolly pine trees exhibited substantial COS consumption overnight (50% of daytime rates) that was independent of CO2 assimilation. This suggests current estimates of the global vegetative COS sink, which assume that COS and CO2 are consumed simultaneously, may need to be reevaluated. Ambient COS mixing ratios, species specific diurnal patterns of stomatal conductance, temperature and canopy position were the major factors influencing the vegetative COS flux at the branch level. While variability in branch level vegetative COS consumption measurements in ambient and enhanced CO2 environments could not be attributed to CO2 enrichment effects, estimates of net ecosystem COS flux based on ambient canopy mixing ratio measurements suggest less nighttime uptake of COS in R2, the CO2 enriched environment

Controls on atmospheric chloroiodomethane (CH2ClI) in marine environments

Mixing ratios of chloroiodomethane (CH2ClI) in ambient air were quantified in the coastal North Atlantic region (Thompson Farm, Durham, New Hampshire, and Appledore Island, Maine) and two remote Pacific areas (Christmas Island, Kiribati, and Oahu, Hawaii). Average mixing ratios were 0.15 ± 0.18 and 0.68 ± 0.66 parts per trillion by volume (pptv) at Thompson Farm and Appledore Island, respectively, compared to 0.10 ± 0.05 pptv at Christmas Island and 0.04 ± 0.02 pptv in Hawaii. Photolysis constrained the daytime mixing ratios of CH2ClI at all locations with the minimum occurring at 1600 local time. Daily average fluxes to the atmosphere were estimated from mixing ratios and loss due to photolysis at Appledore Island, Christmas Island and Hawaii, and were 58 ± 9, 19 ± 3, and 5.8 ± 1.0 nmol CH2ClI m−2 d−1, respectively. The measured sea‐to‐air flux from seawater equilibrator samples obtained near Appledore Island was 6.4 ± 2.9 nmol CH2ClI m−2 d−1. Mixing ratios of CH2ClI at Appledore Island increased with increasing wind speed. The maximum mixing ratios observed at Thompson Farm (1.6 pptv) and Appledore Island (3.4 pptv) are the highest reported values to date, and coincided with high winds associated with the passage of Tropical Storm Bonnie. We estimate that high winds during the 2004 hurricane season increased the flux of CH2ClI from the North Atlantic Ocean by 8 ± 2%

Cross-cultural validation of the Health Care Provider HIV/AIDS Stigma Scale (HPASS) in China

The study aimed to validate the Health Care Provider HIV/AIDS Stigma Scale among medical staff in China. The validation was conducted in four steps from March to December 2017: translation and back-translation; content validity test with six experts; test–retest reliability testing with 63 medical staff with 2 weeks interval; and structural validation with 349 medical staff from 52 hospitals with a convenience sample,using exploratory factor analysis,including principal component analysis and varimax rotation. The scale content validity index average was 0.88, while for test–retest reliability, the ICC was 0.87. Three factors of “discrimination”, “prejudice” and “stereotype” with 16 items were extracted and explained 59.61% variance. The Cronbach’s alpha value for the total scale was of 0.88, and for the three factors, the values were 0.89, 0.86 and 0.74, respectively. The discrimination factor showed identical means between Canadian medical students and Chinese medical staff, while the prejudice and stereotype factors had higher mean scores in the Chinese sample. The three-factor structure of Health Care Provider HIV/AIDS Stigma Scale was confirmed in Chinese medical staff with a simpler solution. This could provide a basis for trans-cultural application and comparison

Characterization of aerosol associated with enhanced small particle number concentrations in a suburban forested environment

Two elevated particle number/mass growth events associated with Aitken‐mode particles were observed during a sampling campaign (13–29 September 2004) at the Duke University Free‐Air CO2 Enrichment facility, a forested field site located in suburban central North Carolina. Aerosol growth rates between 1.2 and 4.9 nm hr−1 were observed, resulting in net increases in geometric mean diameter of 21 and 37 nm during events. Growth was dominated by addition of oxidized organic compounds. Campaign‐average aerosol mass concentrations measured by an Aerodyne quadrupole aerosol mass spectrometer (Q‐AMS) were 1.9 ± 1.6 (σ), 1.6 ± 1.9, 0.1 ± 0.1, and 0.4 ± 0.4 μg m−3 for organic mass (OM), sulfate, nitrate, and ammonium, respectively. These values represent 47%, 40%, 3%, and 10%, respectively, of the measured submicron aerosol mass. Based on Q‐AMS spectra, OM was apportioned to hydrocarbon‐like organic aerosol (HOA, likely representing primary organic aerosol) and two types of oxidized organic aerosol (OOA‐1 and OOA‐2), which constituted on average 6%, 58%, and 36%, respectively, of the apportioned OM. OOA‐1 probably represents aged, regional secondary organic aerosol (SOA), while OOA‐2 likely reflects less aged SOA. Organic aerosol characteristics associated with the events are compared to the campaign averages. Particularly in one event, the contribution of OOA‐2 to overall OM levels was enhanced, indicating the likelihood of less aged SOA formation. Statistical analyses investigate the relationships between HOA, OOA‐1, OOA‐2, other aerosol components, gas‐phase species, and meteorological data during the campaign and individual events. No single variable clearly controls the occurrence of a particle growth event

Bromoform and dibromomethane measurements in the seacoast region of New Hampshire, 2002–2004

Atmospheric measurements of bromoform (CHBr3) and dibromomethane (CH2Br2) were conducted at two sites, Thompson Farm (TF) in Durham, New Hampshire (summer 2002–2004), and Appledore Island (AI), Maine (summer 2004). Elevated mixing ratios of CHBr3 were frequently observed at both sites, with maxima of 37.9 parts per trillion by volume (pptv) and 47.4 pptv for TF and AI, respectively. Average mixing ratios of CHBr3 and CH2Br2 at TF for all three summers ranged from 5.3–6.3 and 1.3–2.3 pptv, respectively. The average mixing ratios of both gases were higher at AI during 2004, consistent with AI\u27s proximity to sources of these bromocarbons. Strong negative vertical gradients in the atmosphere corroborated local sources of these gases at the surface. At AI, CHBr3 and CH2Br2 mixing ratios increased with wind speed via sea‐to‐air transfer from supersaturated coastal waters. Large enhancements of CHBr3 and CH2Br2 were observed at both sites from 10 to 14 August 2004, coinciding with the passage of Tropical Storm Bonnie. During this period, fluxes of CHBr3 and CH2Br2 were 52.4 ± 21.0 and 9.1 ± 3.1 nmol m−2 h−1, respectively. The average fluxes of CHBr3 and CH2Br2 during nonevent periods were 18.9 ± 12.3 and 2.6 ± 1.9 nmol m−2 h−1, respectively. Additionally, CHBr3 and CH2Br2 were used as marine tracers in case studies to (1) evaluate the impact of tropical storms on emissions and distributions of marine‐derived gases in the coastal region and (2) characterize the transport of air masses during pollution episodes in the northeastern United States

Are biogenic emissions a significant source of summertime atmospheric toluene in the rural Northeastern United States?

Summertime atmospheric toluene enhancements at Thompson Farm in the rural northeastern United States were unexpected and resulted in a toluene/benzene seasonal pattern that was distinctly different from that of other anthropogenic volatile organic compounds. Consequently, three hydrocarbon sources were investigated for potential contributions to the enhancements during 2004–2006. These included: (1) increased warm season fuel evaporation coupled with changes in reformulated gasoline (RFG) content to meet US EPA summertime volatility standards, (2) local industrial emissions and (3) local vegetative emissions. The contribution of fuel evaporation emission to summer toluene mixing ratios was estimated to range from 16 to 30 pptv d−1, and did not fully account for the observed enhancements (20–50 pptv) in 2004–2006. Static chamber measurements of alfalfa, a crop at Thompson Farm, and dynamic branch enclosure measurements of loblolly pine trees in North Carolina suggested vegetative emissions of 5 and 12 pptv d−1 for crops and coniferous trees, respectively. Toluene emission rates from alfalfa are potentially much larger as these plants were only sampled at the end of the growing season. Measured biogenic fluxes were on the same order of magnitude as the influence from gasoline evaporation and industrial sources (regional industrial emissions estimated at 7 pptv d−1 and indicated that local vegetative emissions make a significant contribution to summertime toluene enhancements. Additional studies are needed to characterize the variability and factors controlling toluene emissions from alfalfa and other vegetation types throughout the growing season

Volatile organic compounds in northern New England marine and continental environments during the ICARTT 2004 campaign

Volatile organic compound (VOC) measurements were made during the summer 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) at Thompson Farm (TF), a continental site 25 km from the New Hampshire coast, and Appledore Island (AI), a marine site 10 km off the Maine coast. The 24 h mean total hydroxyl radical (OH) reactivity (±1σ) for the suite of VOCs was 4.15 (±2.64) s−1 at TF and 2.57 (±1.10) s−1 at AI. The larger range of reactivity at TF was dominated by isoprene and the monoterpenes (mean combined reactivity = 2.01 (±2.57) s−1). The impact of local anthropogenic hydrocarbon sources such as liquefied petroleum gas (LPG) leakage and fossil fuel evaporation was evident at both sites. During the campaign, a propane flux of 9 (±2) × 109 molecules cm−2 s−1 was calculated from the linear regression of the mean 0100–0400 local time mixing ratios at TF. This is consistent with fluxes observed in 2003 at sites spread throughout the coastal area of New Hampshire indicating that LPG tank leakage is a major hydrocarbon source throughout the region. Net monoterpene fluxes during ICARTT at TF were 6 (±2), 1.8 (±0.4), 1.2 (±0.6), and 0.4 (±0.5) × 109 molecules cm−2 s−1 for α‐pinene, β‐pinene, camphene, and limonene, respectively. Comparison to estimated NO3 and O3 loss rates indicate that gross monoterpene emission rates were approximately double the observed net fluxes at TF and comparable to current monoterpene nighttime emission inventory estimates for the northeast

Carbonyl sulfide exchange in a temperate loblolly pine forest grown under ambient and elevated CO<sub>2</sub>

Vegetation, soil and ecosystem level carbonyl sulfide (COS) exchange was observed at Duke Forest, a temperate loblolly pine forest, grown under ambient (Ring 1, R1) and elevated (Ring 2, R2) CO2. During calm meteorological conditions, ambient COS mixing ratios at the top of the forest canopy followed a distinct diurnal pattern in both CO2 growth regimes, with maximum COS mixing ratios during the day (R1=380±4 pptv and R2=373±3 pptv, daytime mean ± standard error) and minimums at night (R1=340±6 pptv and R2=346±5 pptv, nighttime mean ± standard error) reflecting a significant nighttime sink. Nocturnal vegetative uptake (−11 to −21 pmol m−2s−1, negative values indicate uptake from the atmosphere) dominated nighttime net ecosystem COS flux estimates (−10 to −30 pmol m−2s−1) in both CO2 regimes. In comparison, soil uptake (−0.8 to −1.7 pmol m−2 s−1) was a minor component of net ecosystem COS flux. In both CO2 regimes, loblolly pine trees exhibited substantial COS consumption overnight (50% of daytime rates) that was independent of CO2 assimilation. This suggests current estimates of the global vegetative COS sink, which assume that COS and CO2 are consumed simultaneously, may need to be reevaluated. Ambient COS mixing ratios, species specific diurnal patterns of stomatal conductance, temperature and canopy position were the major factors influencing the vegetative COS flux at the branch level. While variability in branch level vegetative COS consumption measurements in ambient and enhanced CO2 environments could not be attributed to CO2 enrichment effects, estimates of net ecosystem COS flux based on ambient canopy mixing ratio measurements suggest less nighttime uptake of COS in R2, the CO2 enriched environment