ARL Mercury Measurements in the mid-Atlantic and Gulf of Mexico Regions: Status and Update Winston Luke, Paul Kelley, Mark Cohen NOAA/Air Resources Laboratory NOAA/Air Resources Laboratory Prepared for EPA/NOAA Meeting Silver Spring, June 24, 2009

Measurement Elemental mercury * 2 (NOAA/EPA) Fine particulate mercury *2 Reactive gaseous mercury *2 Sulfur dioxide (EPA/MACTEC) Ozone Carbon Monoxide Nitrogen Oxides (NO, NOy) Wind speed Wind Direction Relative Humidity Temperature Precipitation SO 4 2-, NO 3 -, NH 4 +, HNO 3, SO 2 (Weekly) Total mercury in precip (weekly) (MD DNR/UMD) Major ions in precip(weekly) Measurements at Beltsville, MD CASTNet Site

coal incinerator metals manuf/other Symbol color indicates type of mercury source – – 1000 > 1000 Symbol size and shape indicates 1999 mercury emissions, kg/yr rural AQS NADP/MDN CASTNet IMPROVE Monitoring sites other AQS Hg site Beltsville, MD CASTNet Site 100 miles from DC Bremo Beltsville monitoring site Morgantown Chalk Point Dickerson Possum Point Eddystone Arlington - Pentagon MSW Incin Brandon Shores and H.A. Wagner Montgomery County MSW Incin Harford County MSW Incin

Site is impacted by a variety of local- regional sources with unique emissions characteristics. Coupled chemical- meteorological analysis will yield important insights into mercury emissions, transport, transformation, and removal at the site.

As at Grand Bay, higher RGM is typically associated with high O 3 concentrations and chemically aged air masses, suggesting that reactive gaseous mercury concentrations at the site reflect the influence of regional continental emissions.

Multi-Day RGM Event, April 16-19, 2008

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions All back trajectories run at 12 km resolution

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

The next day…

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

The next day…

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

The next day…

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

The next day…

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Large Point Sources of Reactive Gaseous Mercury (RGM) Emissions Based on the 2002 U.S EPA National Emissions Inventory (NEI) size/shape of symbol denotes amount of mercury emitted (kg/yr) – color of symbol denotes type of mercury source coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other Back-trajectories starting at the indicated fraction of the mixed layer height. Circles on the trajectories mark the hourly positions

Recent measurements

Issues/Updates/Challenges at Beltsville The more polluted environment at Beltsville leads to significant trap bias The more polluted environment at Beltsville leads to significant trap bias in Tekran Cleaning gold traps, even in Aqua Regia, provides only temporary improvement. Traps must really be replaced every 6 months ($1400/pair per instrument). We will explore the option of making our own gold traps to save considerable expense. We will explore the option of making our own gold traps to save considerable expense. EPA-purchased 2537B detector has been plagued by more persistent problems than any of the 2537A’s fielded by NOAA at Grand Bay or Beltsville. Problems are mostly transient and so far have defied diagnosis at Tekran. It may be necessary to return the instrument for a thorough analysis and repair. EPA-purchased 2537B detector has been plagued by more persistent problems than any of the 2537A’s fielded by NOAA at Grand Bay or Beltsville. Problems are mostly transient and so far have defied diagnosis at Tekran. It may be necessary to return the instrument for a thorough analysis and repair. Power stability at Beltsville, for the most part acceptable, deteriorated in Summer We will monitor stability closely this Summer. Power stability at Beltsville, for the most part acceptable, deteriorated in Summer We will monitor stability closely this Summer. We are collaborating with Mark Engle and Allan Kolker, USGS-Reston, to collect MOUDI and Hi-Vol aerosol samples periodically at the site. We are collaborating with Mark Engle and Allan Kolker, USGS-Reston, to collect MOUDI and Hi-Vol aerosol samples periodically at the site.

Measurements at Grand Bay NERR, MS Measurement Elemental mercury * 2 Fine particulate mercury *2 Reactive gaseous mercury *2 Sulfur dioxide Ozone Carbon Monoxide Nitrogen Oxides (NO, NOy) Wind speed Wind Direction Relative Humidity Temperature Precipitation

View from top of 10 m tower looking at the southerly (prevailing wind) sampling sector over the U.S. Fish and Wildlife Service Pavilion at Grand Bay NERR

Spring 2008 Spring 2007 As in 2007, most pronounced correlation was between ozone and RGM, especially during the Spring (March-May). Similar concentrations of RGM and O 3 were observed in Springtime 2007 and Higher RGM in Summer ’08 than Summer ‘07

Across all seasons, higher RGM levels were associated with drier air parcels containing aged emissions. Together with the RGM/O 3 correlation, this suggests that aged continental emissions, not extremely local sources, are responsible for enhanced RGM at the site. Downward mixing from the middle and upper trop may be involved as well. Lack of increase of FPM at high RH suggests no phase partitioning of RGM to small particles at high RH, but sea salt aerosols may take up RGM.

Two systems were configured identically (pink), then System 2 was fitted with a 10-micron cut point elutriator (blue) over the course of several days. Results suggest that there may be as much mercury in the coarse (sea salt) aerosol fraction as in the fine fraction. Studies will be repeated periodically at the site.

Upgrades to the Site Under the auspices of the Mississippi Department of Environmental Quality, precipitation collectors will be added at the Grand Bay NERR for the measurement of: Under the auspices of the Mississippi Department of Environmental Quality, precipitation collectors will be added at the Grand Bay NERR for the measurement of: Rainfall amounts Ott Pluvio gauge Major ions in precipitation (NTN) Aerochem collector, upgrade to NCON when approved Total mercury and trace metals in precipitation (MDN) Aerochem collector, upgrade to NCON when approved Siting criteria have been reviewed and approved, and purchase requisitions have been prepared for site improvement and instrument procurement. Siting criteria have been reviewed and approved, and purchase requisitions have been prepared for site improvement and instrument procurement.

Planned Intensive, Spring-Summer 2010 Collaborative research involving NOAA, GA Tech, Florida State University, and others Collaborative research involving NOAA, GA Tech, Florida State University, and others Focus is on the role of halogen species in the MBL and their oxidation of Focus is on the role of halogen species in the MBL and their oxidation of Hg(0) to RGM species, at the surface and aloft. Components include ongoing speciated mercury and ancillary trace gas measurements at the NERR. A 3-wavelength nephelometer will be added, as will radiosonde/ozonesonde launches from the NERR to determine thermal and chemical structure of the troposphere. Components include ongoing speciated mercury and ancillary trace gas measurements at the NERR. A 3-wavelength nephelometer will be added, as will radiosonde/ozonesonde launches from the NERR to determine thermal and chemical structure of the troposphere. Greg Huey (GA Tech) will measure Br 2, BrO, BrCl, and HOBr at the surface via Chemical Ionization Mass Spectrometry. Greg Huey (GA Tech) will measure Br 2, BrO, BrCl, and HOBr at the surface via Chemical Ionization Mass Spectrometry. Tony Hynes (U. Miami) will attempt to measure total and speciated RGM at the surface and aloft using coated and uncoated denuders using the technique of programmable thermal desorption. Tony Hynes (U. Miami) will attempt to measure total and speciated RGM at the surface and aloft using coated and uncoated denuders using the technique of programmable thermal desorption. Other measurements and participants to be added as work progresses. Other measurements and participants to be added as work progresses.

Data Reduction Scheme at ARL/HQ A batch file is executed that first concatenates all the five-minute data files A batch file is executed that first concatenates all the five-minute data files During review of the raw data, three files (.bGEM,.bRGM,.bFPM) are produced by-hand that contain the JDD start and end times of any period of bad data. The program then reads these files and flags the data During review of the raw data, three files (.bGEM,.bRGM,.bFPM) are produced by-hand that contain the JDD start and end times of any period of bad data. The program then reads these files and flags the data A FORTRAN program is then run in batch mode A FORTRAN program is then run in batch mode All automatic calibrations are parsed out and written to a separate file GEM trap bias is calculated for each hour. If it exceeds 10% then each five-minute period in the GEM cycle and each period in the desorb cycle is adjusted to increase the low-trap result up to the proper ratio. GEM for the hour is just the average of the 12 five-minute results. FPM for the hour is the sum of the three FPM desorbs minus three times the pyrolyzer value.

Data Reduction Scheme at ARL/HQ (cont’d) RGM for the hour is the sum of the three RGM desorbs minus three times the second flush value. If flush values exceed 1.0 ngm/m3 then there is a leak in the system and the GEM, RGM & FPM are all flagged with If there has been more than 2.1 hours since the previous desorb and greater than 1.1 hours since the last automatic calibration, then the RGM & FPM are flagged with If average GEM for the hour is less than 0.8ngm/m3 then GEM, RGM & FPM are flagged with Hours where results are missing or there is an unexpected number of GEM / RGM / FPM cycles are flagged Each row in the results file (.prHg) is assigned a JDD & decimal year timestamp for the midpoint of the hour, as well as the MM/DD/YY HH/MM/SS values. Start and end times of each desorb are also reported, along with trap bias ratio.

Data Reduction Scheme at ARL/HQ (cont’d) A “.stHg” file is generated that contains statistics on the processed data. This includes the JDD start & end times used to flag data, any warnings such as high or low GEM readings, high or low flow volumes, low baseline voltages, multiple peaks or over-ranges, and any periods that data is automatically rejected. Calibration times and intervals between calibrations are listed. Time of power resets are also listed. At the end of this file is a listing of overall statistics such as: number of A low bias hours, number of B low bias hours, number of leaky hours, number of hours where the time between desorbs was outside limits, number of hours where the proper timing sequence was not found, number of hours that had negative desorb results for RGM or FPM, and total number of valid processed hours.