Sources and sinks of selected trace gases in the tropospheric boundary layer of the eastern United States

This dissertation describes three major research projects with the common goal of characterizing sources and sinks of trace gases of strong relevance to regional air quality and global climate issues. In the first study, volatile organic compound (VOC) measurements collected at a marine and continental site in northern New England were compared and examined for evidence of regional VOC sources. Biogenic VOCs, including isoprene, monoterpenes, and oxygenated VOCs, were significant components of the total reactivity at both locations. However, very different VOC distributions were observed for each site. The impact of local anthropogenic hydrocarbon sources such as liquefied petroleum gas (LPG) leakage was also evident at both sites. During the campaign, a propane flux of 9 (+/-2) x 109 molecules cm-2 s-1 was calculated for the continental site. In the second study, three hydrocarbon sources were investigated for their potential contributions to the summertime atmospheric toluene enhancements observed at a rural location in southern New Hampshire. These sources included: (1) warm season fuel evaporation emissions, (2) local industrial emissions, and (3) local vegetative emissions. The estimated contribution of fuel evaporation emissions (16-30 pptv d-1) could not fully account for observed summertime toluene enhancements (20-50 pptv d-1). Vegetation enclosure measurements suggested biogenic toluene emissions (5 and 12 pptv d-1 for alfalfa and pine trees) made significant contributions to summertime enhancements. Industrial toluene emissions, estimated at 7 pptv d-1, most likely occurred year round rather than seasonally. Finally, controls over carbonyl sulfide (COS) uptake in a temperate loblolly pine forest grown under ambient and elevated CO2 were examined in the third study. Vegetative consumption dominated net ecosystem COS uptake (10 to 40 pmol m-2 s-1) under both CO2 regimes. Environmental controls over vegetation stomatal conductance and photosynthetic capacity were the major factors influencing COS uptake rates. The loblolly pines 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

Controls on the seasonal exchange of CH3Br in temperate peatlands

Measurements of CH3Br exchange at two New Hampshire peatlands (Sallie\u27s Fen and Angie\u27s Bog) indicate that net flux from these ecosystems is the sum of competing production and consumption processes. Net CH3Br fluxes were highly variable and ranged from net emission to net uptake between locations within a single peatland. At Sallie\u27s Fen, net CH3Br flux exhibited positive correlations with peat temperature and air temperature during all seasons sampled, but these relationships were not observed at Angie\u27s Bog where flux varied according to microtopography. The major CH3Br production process at Sallie\u27s Fen appeared dependent on aerobic conditions within the peat, while CH3Br production at Angie\u27s Bog was favored by anaerobic conditions. There was evidence of aerobic microbial consumption of CH3Br within the peat at both sites. In a vegetation removal experiment conducted at Sallie\u27s Fen with dynamic chambers, all collars exhibited net consumption of CH3Br. Net CH3Br flux had a negative correlation with surface temperature and a positive correlation with water level in collars with all vegetation clipped consistent with aerobic microbial consumption. Vegetated collars showed positive correlations between net CH3Br flux and air temperature. A positive correlation between net CH3Br flux and surface temperature was also observed in collars in which all vegetation except Sphagnum spp. were clipped. These correlations are consistent with seasonal relationships observed in 1998, 1999, and 2000 and suggest that plants and/or fungi are possible sources of CH3Br in peatlands. Estimates of production and consumption made on two occasions at Sallie\u27s Fen suggest that peatlands have lower rates of CH3Br consumption compared to upland ecosystems, but a close balance between production and consumption rates may allow these wetlands to act as either a net source or sink for this gas

Production of methyl bromide in a temperate forest soil

Field enclosure measurements of a temperate forest soil show net uptake of ambient methyl bromide (CH3Br), an important trace gas in both tropospheric and stratospheric ozone cycling. The net flux for 1999 was estimated to be −168 ± 72 μg CH3Br m−2 (negative indicates loss from the atmosphere). Individual enclosure flux measurements ranged from −4.0 to +3.3 μg CH3Br m−2 d−1. Soil consumption of CH3Br was estimated from laboratory soil incubations. Production of CH3Br was calculated as the difference between net flux and predicted consumption. Fungi could be responsible for the production of CH3Br in this temperate forest soil

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

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

Genetic determinants of telomere length from 109,122 ancestrally diverse whole-genome sequences in TOPMed

Genetic studies on telomere length are important for understanding age-related diseases. Prior GWAS for leukocyte TL have been limited to European and Asian populations. Here, we report the first sequencing-based association study for TL across ancestrally-diverse individuals (European, African, Asian and Hispanic/Latino) from the NHLBI Trans-Omics for Precision Medicine (TOPMed) program. We used whole genome sequencing (WGS) of whole blood for variant genotype calling and the bioinformatic estimation of telomere length in n=109,122 individuals. We identified 59 sentinel variants (p-value OBFC1indicated the independent signals colocalized with cell-type specific eQTLs for OBFC1 (STN1). Using a multi-variant gene-based approach, we identified two genes newly implicated in telomere length, DCLRE1B (SNM1B) and PARN. In PheWAS, we demonstrated our TL polygenic trait scores (PTS) were associated with increased risk of cancer-related phenotypes

Genetic diversity fuels gene discovery for tobacco and alcohol use

Tobacco and alcohol use are heritable behaviours associated with 15% and 5.3% of worldwide deaths, respectively, due largely to broad increased risk for disease and injury(1-4). These substances are used across the globe, yet genome-wide association studies have focused largely on individuals of European ancestries(5). Here we leveraged global genetic diversity across 3.4 million individuals from four major clines of global ancestry (approximately 21% non-European) to power the discovery and fine-mapping of genomic loci associated with tobacco and alcohol use, to inform function of these loci via ancestry-aware transcriptome-wide association studies, and to evaluate the genetic architecture and predictive power of polygenic risk within and across populations. We found that increases in sample size and genetic diversity improved locus identification and fine-mapping resolution, and that a large majority of the 3,823 associated variants (from 2,143 loci) showed consistent effect sizes across ancestry dimensions. However, polygenic risk scores developed in one ancestry performed poorly in others, highlighting the continued need to increase sample sizes of diverse ancestries to realize any potential benefit of polygenic prediction.Peer reviewe

Psychology and aggression

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/68264/2/10.1177_002200275900300301.pd