Why Should We Care About Mercury Deposition?

1. Why Should We Care About Mercury Deposition? David Gay Illinois State Water Survey University of Illinois Champaign, IL dgay@uiuc.edu (217) 244.0462 http://nadp.sws.uiuc.edu

2. Goal of this Presentation…. • Describe the issues surrounding the mercury problem, and • Introduce you to how we operate and measure wet deposition (& dry deposition).

3. Why Monitor for Mercury in Precipitation?Issues Surrounding Mercury

4. NWQMN’s “Relevant Questions” 2. Which water quality-related coastal resource management issues would be addressed by the Network? Examples • Excessive algal growth, loss of aquatic vegetation • Toxic chemicals in food chains, and fish consumption advisories • Protracted, recurring or episodic hypoxic (or anoxic) conditions • Habitat loss or impairment affecting propagation of fish and wildlife resources • Harmful algal blooms that pose human health risks • Beach and shellfish bed closures • Impacts of extreme natural events and climate change • Quantity and trends in freshwater delivery, groundwater contamination, and atmospheric deposition of contaminants.

5. Problems NWQMN is Designed to Address • …. improving the water quality of our streams, estuaries and coastal waters… • …. 22,000 waterbodies are not attaining their designated uses … • Transport of contaminants from non-point sources: • Atmospheric Deposition – rapid and long-range transport of certain pollutants • Groundwater flow – wide range of residence time • Seepage from on-site waste treatment -- septic systems • Agricultural drainage -- fertilizer and manure applications • Runoff from coastal watersheds • Riverine transport from upland watersheds –gathering pollutants from multiple sources • others….

6. Dry Deposition Wet Deposition Bacterial action (water and sediment) predatory fish The mercury problem?Bioaccumulation Through Fall (wet+dry) Geologic Sources (soil, rock, base flow etc.) Litter Fall Water Body Hg Hg Hg Me-Mercury Concentration Methylation Small fish Zooplankton

7. Why monitor for Mercury in Precipitation? • Atmospheric transport and deposition is the dominant pathway to most aquatic ecosystems. • Between 40 and 75% of the mercury input to lakes and streams is by wet deposition • most falls into water; • <20% of catchment deposition reaches lake • probably less in the West. (Sorensen et al., 1997; Scherbatskoy et al., 1997; Lamborg et al., 2005; Mason et al., 1997) • “New” mercury is more likely converted to organic form than “old” mercury (preliminary, METAALICUS)

8. How Mercury is Wet Deposited Hgp RGM RGM Hgo Hgo Hgp rainout Hgp RGM washout

9. How Mercury is Wet Deposited RGM Oxidation Hgo Oxidation RGM

10. 1.4-1.8 ng/m3 Typical Atm. Mercury Species Abundance Atmospheric Mercury Species Abundance Hg0 – Elemental Mercury (lifetime up to 1 year) RGM – Reactive Gaseous Mercury (lifetime hours to days) Hgp – Particulate Bound Mercury (lifetime hours to days)

11. Many Mercury Sources • Volcanoes (St. Helens) • Enriched ores/soils • Tectonic (plate) boundaries • Cinnabar (HgS), taconite, others • Soil surfaces (0.5 ppm in crust) • Fresh water and oceans • Forests (surfaces and stomates) • Forest fires • (wood fire places?) • Tree bark, volatilization from rocks? • Coal combustion (Power 50t/yr) • Incineration • Industrial emissions • chlor-alkali • cement production (lime) • Hg use in mining and mining of Hg • Automobile Recycling • Mercury in Landfills • fluorescent lamps • dental amalgams (also in sewers) • thermometers, batteries • electrical switches • Taconite mining

13. Map of Fish Consumption Warnings (EPA)

14. Conclusion • It is important to measure the major source of mercury input to your water bodies • Fits the purpose of your network • Important contribution to your water bodies • Definitely a water concern • fish • wildlife • humans

15. How Should You Monitor? here is how we operate and measure mercury…..

16. The Mercury Deposition Network? • A 93 site sub-network of the NADP • Measuring wet deposition of mercury • Our Charge: • to determine if trends exist in wet deposition of mercury over time

17. How Do We Measure Wet? ETI or Ott_Pluvio

18. Where We Measure Mercury (Active Sites, May 2006)

19. Analysis Methods • Cold Vapor Atomic Florescence Spectroscopy (CVAFS) • Contract Lab is Frontier Geosciences, Inc. • EPA Method 1631 • reporting Limit – 0.2 ng/L • detection appr. 0.05 ng/L • report concentration (ng/L) • Two precipitation depth measurements • rain gage • bottle catch • report deposition (ng/m2 week)

20. Problems, Things to Remember • Very low concentrations (ng/L), so contamination is always a concern, • Mercury is volatile, so loss is possible, • Cleaning Glassware • No Teflon • Keeping lab clean • Gloves on site • Strict protocols

21. Problems, Things to Remember • Sampling difficulties • Hard to measure low concentrations • Rain bounce • Cold always a problem • Light rain events • very difficult but have the high concentrations • Good Operators are essential, • Need lots of sites • Concentration change over space • Precipitation is highly variable

22. MDN is being integrated into NWQMN • M. Brigham/USGS • Locating MDN sites on the side of water bodies of concern • Michigan (MI31), north east of Detroit • South Carolina (SC05), coastal • New Jersey (NJ30), Rutgers area • Provides him with input values, wet deposition

23. MDN integration……… • M. Risch/USGS • Has five MDN sites in Indiana • Along Ohio River (IN21) • Side of Lake Michigan (IN34) • Also measuring atmospheric concentrations and calculatingdry deposition • Reporting total mercury deposition

24. Other Things We Measure • Methyl mercury in rainfall • methyl comes down in rain also • Trace metals in rainfall

25. QA Summary, Docs and the like • Quality Management Plan • Quality Assurance Plan • Program and lab • Blanks, Lab Blanks • Blind Tests run by USGS

26. Mercury Concentrations in Precipitation 2004

27. Mercury Wet Deposition2004

28. Total Deposition(we need to estimate dry deposition)

29. Measurements of Dry Deposition • ? • Very few measurements • Very few calculations of dry deposition • BUT YOU WANT TOTAL DEPOSTION • (wet + dry)

30. Modeling Dry Deposition DRY DEPOSITION Seigneur and others, ES&T, 2004, V38, 555-569

31. Plans for Dry Deposition Manually Operated Mercury Species Sampling Monitoring station for manually-operated sampling system EPA Method IO-5 Gold-Trap Method for Hg0 i Sampling box for manual system

32. Methods are: -Lab Tested -Widely used -QA challenged -EPA Accepted Automated Hg Speciation PHg RGM Hg0

33. Future Directions for MDN • Monitoring Network Design Document • Where future sites should be located • Environmental Response Committee • Dry Deposition Initiative

34. Why Should We Care About Mercury Deposition? David Gay Illinois State Water Survey University of Illinois Champaign, IL dgay@uiuc.edu (217) 244.0462 http://nadp.sws.uiuc.edu