Investigation of Atmospheric Mercury Concentrations and Dry Deposition Rates Using Established and Novel Methods

This work presents new methods for and measurements of concentrations and dry deposition of atmospheric mercury. Chapter 2 reports on measurements of gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and mercury bound to particles (PBM), mercury soil flux, and mercury in precipitation at two locations in northern Nevada, U.S.A. Concentrations of GEM were influenced by both local substrate emission and transport from regional source areas. Concentrations of GOM and PBM were within ranges reported for other rural sites, and mercury wet deposition rates were similar to other sites in the arid West. In Chapter 3, multiple methods were used simultaneously at the same sites to estimate dry deposition of atmospheric mercury. The ratio of dry to wet deposition was between 10 and 90%, and varied with season and with the methods used for dry deposition approximations. Chapter 4 reports on two years of measurements of atmospheric mercury fractions in Reno, Nevada. Concentrations of GEM and PBM were influenced by emission from local sources and meteorological conditions. Concentrations of GOM were higher during periods with higher temperature and lower dew point, confirming the findings of others that warm, dry air from the free troposphere is a source of GOM to the surface. Chapter 5 details work focused on development of a surrogate surface for estimating GOM dry deposition. Deposition of mercury to surfaces was well correlated with GOM concentrations (r2 = 0.84, p < 0.01, n = 326) and was not significantly influenced by temperature, humidity, or ozone concentrations. The surrogate surface is not able to mimic natural surface variability, but it is useful to measure the maximum potential for and spatial and temporal trends of GOM dry deposition. Chapter 6 reports on the development of a passive sampler for characterizing GOM concentrations. Uptake of Hg by the passive sampler was correlated with measured air GOM concentration (r2 = 0.89, p < 0.01, n = 22), and did not appear to be significantly affected by changes in temperature, humidity, or ozone concentration, but sampler performance did appear to be slightly dependent on wind speed. The detection limit for a 14 day sample was ~5 pg m-3

Aerial and Ground-Based Optical Gas Imaging Survey of Uinta Basin Oil and Gas Wells

We deployed a helicopter with an infrared optical gas imaging camera to detect hydrocarbon emissions from 3,428 oil and gas facilities (including 3,225 producing oil and gas well pads) in Utah’s Uinta Basin during winter and spring 2018. We also surveyed 419 of the same well pads from the ground. Winter conditions led to poor contrast between emission plumes and the ground, leading to a detection limit for the aerial survey that was between two and six times worse than a previous summertime survey. Because the ground survey was able to use the camera’s high-sensitivity mode, the rate of detected emission plumes was much higher in the ground survey (31% of all surveyed well pads) relative to the aerial survey (0.5%), but colder air temperatures appeared to impair plume detection in the ground survey as well. The aerial survey cost less per facility visited, but the ground survey cost less per emission plume detected. Well pads with detected emissions during the ground and aerial surveys had higher oil and gas production, were younger, were more likely to be oil well pads, and had more liquid storage tanks per pad relative to the entire surveyed population. The majority of observed emission plumes were from liquid storage tanks (75.9% of all observed plumes), including emissions from pressure relief valves and thief hatches on the tank or from piping that connects to the tank. Well pads with control devices to reduce emissions from tanks (combustors or vapor recovery units) were more likely to have detected emissions. This finding does not imply that the control devices themselves were not functioning properly. Instead, gas was escaping into the atmosphere before it reached control devices. Pads with control devices tended to be newer and have higher oil and gas production, which probably explains their higher rate of detected emissions

An Updated Review of Atmospheric Mercury

The atmosphere is a key component of the biogeochemical cycle of mercury, acting as a reservoir, transport mechanism, and facilitator of chemical reactions. The chemical and physical behavior of atmospheric mercury determines how, when, and where emitted mercury pollution impacts ecosystems. In this review, we provide current information about what is known and what remains uncertain regarding mercury in the atmosphere. We discuss new ambient, laboratory, and theoretical information about the chemistry of mercury in various atmospheric media. We review what is known about mercury in and on solid- and liquid-phase aerosols. We present recent findings related to wet and dry deposition and spatial and temporal trends in atmospheric mercury concentrations. We also review atmospheric measurement methods that are in wide use and those that are currently under development

Development of an Understanding of Reactive Mercury in Ambient Air: A Review

This review focuses on providing the history of measurement efforts to quantify and characterize the compounds of reactive mercury (RM), and the current status of measurement methods and knowledge. RM collectively represents gaseous oxidized mercury (GOM) and that bound to particles. The presence of RM was first recognized through measurement of coal-fired power plant emissions. Once discovered, researchers focused on developing methods for measuring RM in ambient air. First, tubular KCl-coated denuders were used for stack gas measurements, followed by mist chambers and annular denuders for ambient air measurements. For ~15 years, thermal desorption of an annular KCl denuder in the Tekran® speciation system was thought to be the gold standard for ambient GOM measurements. Research over the past ~10 years has shown that the KCl denuder does not collect GOM compounds with equal efficiency, and there are interferences with collection. Using a membrane-based system and an automated system—the Detector for Oxidized mercury System (DOHGS)—concentrations measured with the KCl denuder in the Tekran speciation system underestimate GOM concentrations by 1.3 to 13 times. Using nylon membranes it has been demonstrated that GOM/RM chemistry varies across space and time, and that this depends on the oxidant chemistry of the air. Future work should focus on development of better surfaces for collecting GOM/RM compounds, analytical methods to characterize GOM/RM chemistry, and high-resolution, calibrated measurement systems

Emissions of organic compounds from produced water ponds I: Characteristics and speciation

We measured fluxes of methane, a suite of non-methane hydrocarbons (C2–C11), light alcohols, and carbon dioxide from oil and gas produced water storage and disposal ponds in Utah (Uinta Basin) and Wyoming (Upper Green River Basin) United States during 2013–2016. In this paper, we discuss the characteristics of produced water composition and air-water fluxes, with a focus on flux chamber measurements. In companion papers, we will (1) report on inverse modeling methods used to estimate emissions from produced water ponds, including comparisons with flux chamber measurements, and (2) discuss the development of mass transfer coefficients to estimate emissions and place emissions from produced water ponds in the context of all regional oil and gas-related emissions. Alcohols (made up mostly of methanol) were the most abundant organic compound group in produced water (91% of total volatile organic concentration, with upper and lower 95% confidence levels of 89 and 93%) but accounted for only 34% (28 to 41%) of total organic compound fluxes from produced water ponds. Non-methane hydrocarbons, which are much less water-soluble than methanol and less abundant in produced water, accounted for the majority of emitted organics. C6–C9 alkanes and aromatics dominated hydrocarbon fluxes, perhaps because lighter hydrocarbons had already volatilized from produced water prior to its arrival in storage or disposal ponds, while heavier hydrocarbons are less water soluble and less volatile. Fluxes of formaldehyde and other carbonyls were low (1% (1 to 2%) of total organic compound flux). The speciation and magnitude of fluxes varied strongly across the facilities measured and with the amount of time water had been exposed to the atmosphere. The presence or absence of ice also impacted fluxes

Evaluation of the Community Multiscale Air Quality Model for Simulating Winter Ozone Formation in the Uinta Basin

The Weather Research and Forecasting (WRF) and Community Multiscale Air Quality (CMAQ) models were used to simulate a 10 day high-ozone episode observed during the 2013 Uinta Basin Winter Ozone Study (UBWOS). The baseline model had a large negative bias when compared to ozone (O3) and volatile organic compound (VOC) measurements across the basin. Contrary to other wintertime Uinta Basin studies, predicted nitrogen oxides (NOx) were typically low compared to measurements. Increases to oil and gas VOC emissions resulted in O3 predictions closer to observations, and nighttime O3 improved when reducing the deposition velocity for all chemical species. Vertical structures of these pollutants were similar to observations on multiple days. However, the predicted surface layer VOC mixing ratios were generally found to be underestimated during the day and overestimated at night. While temperature profiles compared well to observations, WRF was found to have a warm temperature bias and too low nighttime mixing heights. Analyses of more realistic snow heat capacity in WRF to account for the warm bias and vertical mixing resulted in improved temperature profiles, although the improved temperature profiles seldom resulted in improved O3 profiles. While additional work is needed to investigate meteorological impacts, results suggest that the uncertainty in the oil and gas emissions contributes more to the underestimation of O3. Further, model adjustments based on a single site may not be suitable across all sites within the basin

State of the climate in 2018

In 2018, the dominant greenhouse gases released into Earth’s atmosphere—carbon dioxide, methane, and nitrous oxide—continued their increase. The annual global average carbon dioxide concentration at Earth’s surface was 407.4 ± 0.1 ppm, the highest in the modern instrumental record and in ice core records dating back 800 000 years. Combined, greenhouse gases and several halogenated gases contribute just over 3 W m−2 to radiative forcing and represent a nearly 43% increase since 1990. Carbon dioxide is responsible for about 65% of this radiative forcing. With a weak La Niña in early 2018 transitioning to a weak El Niño by the year’s end, the global surface (land and ocean) temperature was the fourth highest on record, with only 2015 through 2017 being warmer. Several European countries reported record high annual temperatures. There were also more high, and fewer low, temperature extremes than in nearly all of the 68-year extremes record. Madagascar recorded a record daily temperature of 40.5°C in Morondava in March, while South Korea set its record high of 41.0°C in August in Hongcheon. Nawabshah, Pakistan, recorded its highest temperature of 50.2°C, which may be a new daily world record for April. Globally, the annual lower troposphere temperature was third to seventh highest, depending on the dataset analyzed. The lower stratospheric temperature was approximately fifth lowest. The 2018 Arctic land surface temperature was 1.2°C above the 1981–2010 average, tying for third highest in the 118-year record, following 2016 and 2017. June’s Arctic snow cover extent was almost half of what it was 35 years ago. Across Greenland, however, regional summer temperatures were generally below or near average. Additionally, a satellite survey of 47 glaciers in Greenland indicated a net increase in area for the first time since records began in 1999. Increasing permafrost temperatures were reported at most observation sites in the Arctic, with the overall increase of 0.1°–0.2°C between 2017 and 2018 being comparable to the highest rate of warming ever observed in the region. On 17 March, Arctic sea ice extent marked the second smallest annual maximum in the 38-year record, larger than only 2017. The minimum extent in 2018 was reached on 19 September and again on 23 September, tying 2008 and 2010 for the sixth lowest extent on record. The 23 September date tied 1997 as the latest sea ice minimum date on record. First-year ice now dominates the ice cover, comprising 77% of the March 2018 ice pack compared to 55% during the 1980s. Because thinner, younger ice is more vulnerable to melting out in summer, this shift in sea ice age has contributed to the decreasing trend in minimum ice extent. Regionally, Bering Sea ice extent was at record lows for almost the entire 2017/18 ice season. For the Antarctic continent as a whole, 2018 was warmer than average. On the highest points of the Antarctic Plateau, the automatic weather station Relay (74°S) broke or tied six monthly temperature records throughout the year, with August breaking its record by nearly 8°C. However, cool conditions in the western Bellingshausen Sea and Amundsen Sea sector contributed to a low melt season overall for 2017/18. High SSTs contributed to low summer sea ice extent in the Ross and Weddell Seas in 2018, underpinning the second lowest Antarctic summer minimum sea ice extent on record. Despite conducive conditions for its formation, the ozone hole at its maximum extent in September was near the 2000–18 mean, likely due to an ongoing slow decline in stratospheric chlorine monoxide concentration. Across the oceans, globally averaged SST decreased slightly since the record El Niño year of 2016 but was still far above the climatological mean. On average, SST is increasing at a rate of 0.10° ± 0.01°C decade−1 since 1950. The warming appeared largest in the tropical Indian Ocean and smallest in the North Pacific. The deeper ocean continues to warm year after year. For the seventh consecutive year, global annual mean sea level became the highest in the 26-year record, rising to 81 mm above the 1993 average. As anticipated in a warming climate, the hydrological cycle over the ocean is accelerating: dry regions are becoming drier and wet regions rainier. Closer to the equator, 95 named tropical storms were observed during 2018, well above the 1981–2010 average of 82. Eleven tropical cyclones reached Saffir–Simpson scale Category 5 intensity. North Atlantic Major Hurricane Michael’s landfall intensity of 140 kt was the fourth strongest for any continental U.S. hurricane landfall in the 168-year record. Michael caused more than 30 fatalities and $25 billion (U.S. dollars) in damages. In the western North Pacific, Super Typhoon Mangkhut led to 160 fatalities and$6 billion (U.S. dollars) in damages across the Philippines, Hong Kong, Macau, mainland China, Guam, and the Northern Mariana Islands. Tropical Storm Son-Tinh was responsible for 170 fatalities in Vietnam and Laos. Nearly all the islands of Micronesia experienced at least moderate impacts from various tropical cyclones. Across land, many areas around the globe received copious precipitation, notable at different time scales. Rodrigues and Réunion Island near southern Africa each reported their third wettest year on record. In Hawaii, 1262 mm precipitation at Waipā Gardens (Kauai) on 14–15 April set a new U.S. record for 24-h precipitation. In Brazil, the city of Belo Horizonte received nearly 75 mm of rain in just 20 minutes, nearly half its monthly average. Globally, fire activity during 2018 was the lowest since the start of the record in 1997, with a combined burned area of about 500 million hectares. This reinforced the long-term downward trend in fire emissions driven by changes in land use in frequently burning savannas. However, wildfires burned 3.5 million hectares across the United States, well above the 2000–10 average of 2.7 million hectares. Combined, U.S. wildfire damages for the 2017 and 2018 wildfire seasons exceeded $40 billion (U.S. dollars)

High Ethylene and Propylene in an Area Dominated by Oil Production

We measured the spatial distribution and composition of ozone-forming hydrocarbons, alcohols, and carbonyls in Utah&rsquo;s Uinta Basin during the winter months of 2019 and 2020. The Uinta Basin contains about 10,000 producing oil and gas wells. Snow cover and the region&rsquo;s unique topography (i.e., a large basin entirely surrounded by mountains) promote strong, multi-day temperature inversion episodes that concentrate pollution and lead to wintertime ozone production. Indeed, organic compound concentrations were about eight times higher during inversion episodes than during snow-free springtime conditions. We examined spatial associations between wintertime concentrations of organics and oil and gas sources in the region, and we found that concentrations of highly reactive alkenes were higher in areas with dense oil production than in areas with dense gas production. Total alkene+acetylene concentrations were 267 (42, 1146; lower and upper 95% confidence limits) &micro;g m&minus;3 at locations with 340 or more producing oil wells within 10 km (i.e., 75th percentile) versus 12 (9, 23) &micro;g m&minus;3 at locations with 15 or fewer oil wells (i.e., 25th percentile). Twenty-eight percent of the potential for organic compounds to produce ozone was due to alkenes in areas with dense oil production. Spatial correlations and organic compound ratios indicated that the most likely source of excess alkenes in oil-producing areas was natural gas-fueled engines, especially lean-burning (i.e., high air:fuel ratio) artificial lift engines

Winter Ozone Pollution in Utah’s Uinta Basin is Attenuating

High concentrations of ground-level ozone have been observed during wintertime in the Uinta Basin of western Utah, USA, beginning in 2010. We analyze existing ozone and ozone precursor concentration data from 38 sites over 11 winter seasons and conclude that there has been a statistically significant (p &lt; 0.02) decline in ozone concentration over the previous decade. Daily exceedances of the National Ambient Air Quality Standard for ozone (70 ppb) have been trending downward at the rate of nearly four per year. Ozone and NOx concentrations have been trending downward at the rates of about 3 and 0.3 ppb per year, respectively. Concentrations of organics in 2018 were at about 30% of their values in 2012 or 2013. Several markers, annual ozone exceedance counts and median ozone and NOx concentrations, were at their largest values in the period 2010 to 2013 and have never recovered since then. We attribute the decline to (1) weakening global demand for oil and natural gas and (2) more stringent pollution regulations and controls, both of which have occurred over the previous decade. We also see evidence of ozone titration when snow cover is absent

Atmospheric mercury concentrations and speciation measured from 2004 to 2007 in Reno, Nevada, USA

Atmospheric elemental, reactive and particulate mercury (Hg) concentrations were measured north of downtown Reno, Nevada, USA from November 2004 to November 2007. Three-year mean and median concentrations for gaseous elemental Hg (Hg0) were 1.6 and 1.5 ng m−3 (respectively), similar to global mean Hg0 concentrations. The three-year mean reactive gaseous Hg (RGM) concentration (26 pg m−3) was higher than values reported for rural sites across the western United States. Well defined seasonal and daily patterns in Hg0 and RGM concentrations were observed, with the highest Hg0 concentrations measured in winter and early morning, and RGM concentrations being greatest in the summer and mid-afternoon. Elevated Hg0 concentrations in winter were associated with periods of cold, stagnant air; while a regularly observed early morning increase in concentration was due to local source and surface emissions. The observed afternoon increase and high summer values of RGM can be explained by in situ oxidation of gaseous Hg0 or mixing of RGM derived from the free troposphere to the surface. Because both of these processes are correlated with the same environmental conditions it is difficult to assess their overall contribution to the observed trends