1. Physical and chemical factors controlling mercury and methylmercury concentrations in stream water Mark E. Brigham and Dennis A. Wentz 5 th National Monitoring Conference San José, California May 7-11, 2006 U.S. Department of the Interior U.S. Geological Survey

2. Willamette Basin Georgia-Florida Coastal Plain Western Lake Michigan Drainages Reference stream Urban stream USGS NAWQA mercury study areas

3. Aqueous methylmercury (MeHg) is a major control on mercury bioaccumulation. Mean Hg in forage fish (μg/g wet wt.) N ≈ 24 at each site (2 species x 12 individuals) Mean aqueous MeHg (ng/L) N ≈ 35 at each site

4. What controls aqueous MeHg (and THg) concentrations in streams? Weight-of-evidence approach to assess: –Atmospheric inputs –Watershed processes (methylation and subsequent delivery to stream) –Methylation in channel sediments

5. Simplified mass balance Watershed soils: storage / runoff methylation demethylation fluvial transport Wet deposition Channel sediments: storage / resuspension methylation demethylation Evasion (Hg°) Dry deposition resuspension

6. Wet Hg & MeHg deposition: Mercury Deposition Network (MDN) sites Load: ∑ (weekly [Hg] x precip volume), expressed as μg/m 2 /yr

7. Hg in precipitation Popple River, WI site (WI09—Mercury Deposition Network) Oct ‘02 Jan ’03 Jan ’04 Jan ’05

8. Methylmercury (MeHg) and total mercury (THg) in stream water ~35 samples per site from 2003-05 Key measure of food- web exposure Key component of mass balance

9. Mercury in stream water: sample processing 0.7 μm QFF Whole water MeHg THg Particulate PMeHg PTHg Filtered FMeHg FTHg ====== ++++++

10. Fluvial mercury loads & yields Fluvial load: Regress load vs. flow for sampled dates. Predict to unsampled dates using daily flows Reference: Runkel et al., 2004, USGS Techniques & Methods, Book 4, Ch. A5; LOADEST S-Plus program by D. Lorenz, USGS Yield = load / watershed area, μg/m 2 /yr Examine yield as % of wet depositional loads to ecosystem…

11. MeHg deposition unrelated to MeHg yield 0 100 200 300 400 500 600 700 800 900 1000 OR-Urb OR-Ref-L WI-Ref-H WI-Ref-L WI-Urb FL-Ref-H FL-Ref-L FL-Urb Fluvial yield as % of wet dep load 2003-04 * THg yield: 4.4–48% of wet deposition MeHg yield: 22–926 % of wet deposition (excludes site where MeHg < MDL*) *

12. Florida Wisconsin Oregon THg yield vs precip Hg deposition, 2003-2004 1:10 line Fluvial THg yield, μg/m 2 /yr Wet THg deposition, μg/m 2 /yr, 2003-04 Urban Reference

13. Summary of partial mass balance Wet MeHg deposition could account for MeHg in most streams –low [MeHg] streams. Caveat—Missing key components of mass balance –watershed retention –demethylation –dry deposition Must invoke watershed methylation to explain high [MeHg] streams.

14. Aqueous total Hg and methylmercury correlate strongly to dissolved organic carbon (DOC): among all sites (shown here) within a site (most sites) Log 10 [FMeHg] (ng/L) Log 10 [FTHg] (ng/L) Log 10 [DOC] (mg/L)

15. Runoff-mobilized Hg-DOC complexes controls: -- THg in most streams -- MeHg in half the study streams. Evidence for watershed inputs of MeHg Evidence against in-channel methylation as dominant source Santa Fe River, Florida Log 10 [Q] (cfs) Log 10 [FTHg] (ng/L)Log 10 [FMeHg] (ng/L)

16. Negative relation between MeHg and flow? Evidence for in- channel methylation? Or, high [MeHg] in wetlands during low-flow periods? St Mary’s River, Florida Log 10 [Q] (cfs) Log 10 [FTHg] (ng/L)Log 10 [FMeHg] (ng/L)

17. Aqueous methylmercury strongly linked to wetland density (mean methylmercury; all study sites)

18. Log 10 THg concentration (ng/L) DOC and Suspended Sediment—a potential screening tool for total mercury… R 2 =0.62 Log 10 DOC (mg/L) Log 10 Susp Sed (mg/L)

19. …and methylmercury. Log 10 MeHg concentration (ng/L) Log 10 DOC (mg/L) Log 10 Susp Sed (mg/L)

20. What have we learned about THg and MeHg in streams?

21. Summary Precipitation and watershed influences Precipitation inputs –main source of THg to ecosystem –Could account for all MeHg in some streams Watershed inputs –major vector for MeHg and THg delivery to streams, particularly in wetland-rich basins

22. Summary Concentration relationships DOC and suspended sediment –Control THg & MeHg in streams (MeHg picture is noisier) –key explanatory variables –perhaps a useful screening tool –Erosion control—useful to reduce particulate Hg, and hence THg

23. Summary Role of channel sediments MeHg source? –At most, a minor source of MeHg to stream water –Low MeHg at low flow (evidence against substantial inputs from sediments)… –…except at one site (either sediment methylation or seasonally high MeHg from wetlands) MeHg sink? –Fast demethylation rates in sand, a dominant substrate in some streams

24. Implications for monitoring THg & MeHg in streams Sample size (N)—depends on objectives… –BAF’s: Perhaps as few as N ≈ 6, well spaced seasonally (see: Paller and others, 2004, Archives of Environ. Contam. & Toxicology) –Concentration relationships & fluvial loads: N ≥ 35, well spaced seasonally and hydrologically

25. Acknowledgements USGS: Dennis Wentz, Barb Scudder, Lia Chasar, Amanda Bell, Michelle Lutz, Dave Krabbenhoft, Mark Marvin- DiPasquale, George Aiken, Robin Stewart, Carol Kendall, Bill Orem, Rod DeWeese, Jeff Isely, and many others … USGS: NAWQA and several other USGS programs MDN site support: USGS, Wisconsin DNR, Oregen DEQ, Forest Service, US Fish & Wildlife Service, St. John’s River Water Management District (FL) Menomonie Indian Tribe of Wisconsin