Calibration, optimization, and deployment of PTR-MS instruments during the AIRMAP project

Proton Transfer Reaction Mass Spectrometry (PTR-MS) is an increasingly popular technique for monitoring volatile organic compounds with high sensitivity and time resolution. This dissertation encompasses three different projects, sharing the common theme of expanding the knowledge and utility of the technique. The first project focuses on elucidating the ion chemistry that occurs within the PTR-MS drift tube reaction chamber. The PTR-MS uses a differentially pumped skimmer to prevent excess water from the ion source from entering the drift tube reaction chamber. By placing a metering valve in between the skimmer region and the pump, it was possible to control the amount of water entering the drift tube. The valve made it possible to parameterize the impact of the pumping speed of the skimmer on ion source performance, cluster formation, and sensitivity. These results are compared with a kinetics model that simulates the protonated cluster distributions in the drift tube. The second part of this dissertation describes the process for calibrating and deploying the instrument to measure acetic acid. Generating calibrations and measurements of ambient levels acetic acid are challenging because it adsorbs on instrument surfaces and transfer lines. To overcome the challenge of calibrating, a special permeation oven was used to generate a stable flow of acetic acid in the range of 7.0 to 26.5 ppbv, yielding calibration factors of 7.0 +/- 0.3 ncps·ppbv-1 to 10.9 +/- 0.7 ncps·ppbv-1 at 132 Td. At 88 Td, the calibration factor was found to be 30.8 +/- 2.6 ncps·ppbv-1. Measurements made on Appledore Island during ICARTT show that the PTR-MS measurements correlate well with those from the MC/IC technique, with a correlation coefficient of 0.78. The final project uses the high time resolution of PTR-MS measurements to quantify the impact of storm systems on monoterpene mixing ratios in rural New Hampshire. Analysis of five years of monoterpene measurements at Thompson Farm (in Durham, NH) show storm events with intense precipitation correlate with brief periods of enhanced monoterpene mixing ratios. These events are classified based on duration and intensity, finding that storms can temporarily increase emissions by as much as 4260 g·km-2·hr -1

Coastal water source of short‐lived halocarbons in New England

Short‐lived halocarbon tracers were used to investigate marine influences on air quality in a coastal region of New England. Atmospheric measurements made at the University of New Hampshire\u27s Observing Station at Thompson Farm (TF) in Durham, New Hampshire, indicate that relatively large amounts of halocarbons are emitted from local estuarine and coastal oceanic regions. Bromine‐containing halocarbons of interest in this work include bromoform (CHBr3) and dibromomethane (CH2Br2). The mean mixing ratios of CHBr3 and CH2Br2 from 11 January to 5 March 2002 were 2.6 pptv and 1.6 pptv, and from 1 June to 31 August 2002 mean mixing ratios were 5.9 pptv and 1.4 pptv, respectively. The mean mixing ratio of CHBr3 was not only highest during summer, but both CHBr3 and CH2Br2 exhibited large variability in their atmospheric mixing ratios during this season. We attribute the greater variability to increased production combined with faster atmospheric removal rates. Other seasonal characteristics of CHBr3 and CH2Br2 in the atmosphere, as well as the impact of local meteorology on their distributions at this coastal site, are discussed. Tetrachloroethene (C2Cl4) and trichloroethene (C2HCl3) were used to identify time periods influenced by urban emissions. Additionally, measurements of CHBr3, CH2Br2, C2Cl4, methyl iodide (CH3I), and ethyl iodide (C2H5I) were made at TF and five sites throughout the nearby Great Bay estuarine area between 18 and 19 August 2003. These measurements were used to elucidate the effect of the tidal cycle on the distributions of these gases. The mean mixing ratios of CHBr3, CH2Br2, CH3I, and C2H5I were ∼82%, 46%, 14%, and 17% higher, respectively, near the coast compared to inland sites, providing evidence for a marine source of short‐lived halocarbons at TF. Correlation between the tidal cycle and atmospheric concentrations of marine tracers on the night of 18 August 2003 showed that the highest values for the brominated species occurred ∼2–3 hours after high tide. Emission fluxes of CHBr3, CH2Br2, CH3I, and C2H5I on this night were estimated to be 26 ± 57, 4.7 ± 5.4, 5.9 ± 4.6, and 0.065 ± 0.20 nmol m−2 h−1, respectively. Finally, the anthropogenic source strength of CHBr3 was calculated to determine its impact on atmospheric levels observed in this region. Although our results indicate that anthropogenic contributions could potentially range from 15 to 60% of the total dissolved CHBr3 in the Great Bay, based on the observed ratio of CH2Br2/CHBr3 and surface seawater measurements in the Gulf of Maine, it appears unlikely that anthropogenic activities are a significant source of CHBr3 in the region

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

Changing concentrations of CO, CH₄, C₅H₈, CH₃Br, CH₃I, and dimethyl sulfide during the Southern Ocean Iron Enrichment Experiments

Oceanic iron (Fe) fertilization experiments have advanced the understanding of how Fe regulates biological productivity and air–sea carbon dioxide (CO₂) exchange. However, little is known about the production and consumption of halocarbons and other gases as a result of Fe addition. Besides metabolizing inorganic carbon, marine microorganisms produce and consume many other trace gases. Several of these gases, which individually impact global climate, stratospheric ozone concentration, or local photochemistry, have not been previously quantified during an Fe-enrichment experiment. We describe results for selected dissolved trace gases including methane (CH₄), isoprene (C₅H₈), methyl bromide (CH₃Br), dimethyl sulfide, and oxygen (O₂), which increased subsequent to Fe fertilization, and the associated decreases in concentrations of carbon monoxide (CO), methyl iodide (CH₃I), and CO₂ observed during the Southern Ocean Iron Enrichment Experiments

Unexpected consequences of increasing CO2 and ocean acidity on marine production of DMS and CH2ClI: Potential climate impacts

Increasing atmospheric mixing ratios of CO2 have already lowered surface ocean pH by 0.1 units compared to preindustrial values and pH is expected to decrease an additional 0.3 units by the end of this century. Pronounced physiological changes in some phytoplankton have been observed during previous CO2 perturbation experiments. Marine microorganisms are known to consume and produce climate-relevant organic gases. Concentrations of (CH3)2S (DMS) and CH2ClI were quantified during the Third Pelagic Ecosystem CO2 Enrichment Study. Positive feedbacks were observed between control mesocosms and those simulating future CO2. Dimethyl sulfide was 26% (±10%) greater than the controls in the 2x ambient CO2 treatments, and 18% (±10%) higher in the 3xCO2 mesocosms. For CH2ClI the 2xCO2 treatments were 46% (±4%) greater than the controls and the 3xCO2 mesocosms were 131% (±11%) higher. These processes may help contribute to the homeostasis of the planet

Integrating solutions to adapt cities for climate change

Record climate extremes are reducing urban liveability, compounding inequality, and threatening infrastructure. Adaptation measures that integrate technological, nature-based, and social solutions can provide multiple co-benefits to address complex socioecological issues in cities while increasing resilience to potential impacts. However, there remain many challenges to developing and implementing integrated solutions. In this Viewpoint, we consider the value of integrating across the three solution sets, the challenges and potential enablers for integrating solution sets, and present examples of challenges and adopted solutions in three cities with different urban contexts and climates (Freiburg, Germany; Durban, South Africa; and Singapore). We conclude with a discussion of research directions and provide a road map to identify the actions that enable successful implementation of integrated climate solutions. We highlight the need for more systematic research that targets enabling environments for integration; achieving integrated solutions in different contexts to avoid maladaptation; simultaneously improving liveability, sustainability, and equality; and replicating via transfer and scale-up of local solutions. Cities in systematically disadvantaged countries (sometimes referred to as the Global South) are central to future urban development and must be prioritised. Helping decision makers and communities understand the potential opportunities associated with integrated solutions for climate change will encourage urgent and deliberate strides towards adapting cities to the dynamic climate reality.Peer reviewe

Plant Diversity Surpasses Plant Functional Groups and Plant Productivity as Driver of Soil Biota in the Long Term

One of the most significant consequences of contemporary global change is the rapid decline of biodiversity in many ecosystems. Knowledge of the consequences of biodiversity loss in terrestrial ecosystems is largely restricted to single ecosystem functions. Impacts of key plant functional groups on soil biota are considered to be more important than those of plant diversity; however, current knowledge mainly relies on short-term experiments.We studied changes in the impacts of plant diversity and presence of key functional groups on soil biota by investigating the performance of soil microorganisms and soil fauna two, four and six years after the establishment of model grasslands. The results indicate that temporal changes of plant community effects depend on the trophic affiliation of soil animals: plant diversity effects on decomposers only occurred after six years, changed little in herbivores, but occurred in predators after two years. The results suggest that plant diversity, in terms of species and functional group richness, is the most important plant community property affecting soil biota, exceeding the relevance of plant above- and belowground productivity and the presence of key plant functional groups, i.e. grasses and legumes, with the relevance of the latter decreasing in time.Plant diversity effects on biota are not only due to the presence of key plant functional groups or plant productivity highlighting the importance of diverse and high-quality plant derived resources, and supporting the validity of the singular hypothesis for soil biota. Our results demonstrate that in the long term plant diversity essentially drives the performance of soil biota questioning the paradigm that belowground communities are not affected by plant diversity and reinforcing the importance of biodiversity for ecosystem functioning