Diel Cycling of Trace Metals in Streams

PROBLEM:

Historically, scientists have assumed that a properly collected water sample will provide an accurate assessment of constituent concentrations in a water body on a given day assuming constant hydrologic conditions. However, an increasing body of evidence indicates that the concentration of many potentially toxic trace elements (such as As, Cd, Cu, Mn, Zn) in streams can vary over a large range (up to 500 percent) during a 24-hour period irrespective of changes in streamflow. These diel concentration cycles have been shown to be robust and reproducible, having been documented in many streams separated by large distances, in different geologic environments, and over a large range of metal concentrations (Nimick and others, 2003). Diel cycles in trace-metal concentrations are controlled primarily by chemical and biological processes that respond to the daily cycle of sunlight and darkness.  These processes transfer metals between solution and solid phases in the water column or streambed, thus causing diel metal cycles.  This new information on diel metal cycles may have an important bearing on our understanding of the mobility of trace metals in watersheds. Awareness of diel cycles could affect the collection and interpretation of water-quality data, determination of the effects of metals on aquatic organisms, and establishment of total-maximum daily loads (TMDLs). Increasing the understanding of mechanisms responsible for the observed diel cycling of metals requires a multi-disciplinary approach using innovative techniques.

OBJECTIVE:

The objective of this project is to examine the biogeochemical processes responsible for diel cycling of trace metals using a combination of detailed field studies, laboratory experiments, and theoretical modeling. This research will be used to further the understanding of trace-metal mobility and diel metal cycles.

APPROACH:

Research scientists from the USGS, Montana State University, Montana Tech of the University of Montana, University of Wyoming, and Montana Fish, Wildlife and Parks have worked collaboratively for the last several years to improve the understanding of diel metal cycling. Hypothesized causes of these diel metal cycles include streamflow variation, ground-water exchange, temperature- and pH-dependent sorption, precipitation and dissolution of solid phases, redox cycling, and biotic uptake. While recent work has begun to document the extent and magnitude of diel cycling and to measure variables likely related to diel cycling, the relative effect of each of the plausible processes has not been ascertained. Current (2007) research plans are directed at determining the relative importance of these processes and providing guidance on appropriate strategies for sampling streams with diel cycles of metal concentrations.

STATUS:

Six diel data sets were collected in 1990-93 for the Madison and Missouri Rivers in Montana to document diel variation in arsenic concentrations. Eighteen diel data sets were collected during 1995-2002 for 14 sites on 12 streams in Montana and Idaho to demonstrate the widespread occurrence of diel cycling of arsenic, cadmium, nickel, manganese, and zinc in neutral to alkaline streams during low flow. During 2000-03, seven data sets were collected for Prickly Pear Creek to demonstrate the persistence of diel metal cycles throughout the year and during different streamflow conditions.  During 2002-03, diel cycling of trace metals and rare earth elements was studied in a stream where pH changed from acidic to neutral over a short distance.  During 2003-04, data sets were collected to determine whether mercury concentrations exhibit diel cycles. During 2004-05, field data were collected to determine the relative differences in acute toxicity to aquatic organisms from exposure to constant metal concentrations compared to exposure to varying metal concentrations that follow the diel cycle observed in streams. During 2006, field data were collected from the Rio Tinto and Rio Odiel in southwestern Spain to examine diel cycling of ferrous and ferric iron and how iron photoreduction supplies energy to the microbial population in these rivers. In addition, field study of diel metal cycling in the Animas River and its major tributaries (Mineral and Cement Creeks) in southwestern Colorado was initiated in 2006. During 2007, field data were collected from two streams near the historical Mike Horse mine in the headwaters of the Blackfoot River in western Montana.

PUBLICATIONS:

Gammons, C.H., Nimick, D.A., Parker, S.R., Snyder, D.M., McCleskey, R.B., Amils, R., and Poulson, S.R., in press, Photoreduction fuels biogeochemical cycling of iron in Spain’s acid rivers: Chemical Geology.

Borrok, D.M., Nimick, D.A., Wanty, R.B., and Ridley, W.I., 2008, Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining: Geochimica Cosmochimica Acta, v. 72, p. 329-344.

Nimick, D.A., Harper, D.D., Farag, A.M., Cleasby, T.E., MacConnell, E., and Skaar, D., 2007, Influence of in-stream diel concentration cycles of dissolved trace metals on acute toxicity to one-year-old cutthroat trout (Oncorhynchus clarki lewisi): Environmental Toxicology and Chemistry, v. 26, p. 2667-2678.

Chapin, T.P., Nimick, D.A., Gammons, C.H., and Wanty, R.B., 2007, Diel cycling of zinc in a stream impacted by acid rock drainage: Initial results from a new in situ Zn analyzer: Environmental Monitoring and Assessment, v. 133, p. 161-167.

Gammons, C.H., Grant, T.M., Nimick, D.A., Parker, S.R., and DeGrandpre, M.D., 2007, Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system: Science of the Total Environment, v. 384, p. 433-451.

Gammons, C.H., Milodragovich, Lica, and Belanger-Woods, Jodi, 2007, Influence of diurnal cycles on metal concentrations and loads in streams draining abandoned mine lands: an example from High Ore Creek, Montana: Environmental Geology, v. 53, p. 611-622.

Parker, S.R., Gammons, C.H., Poulson, S.R., and DeGrandpre, M.D., 2007, Diel variations in stream chemistry and isotopic composition of dissolved inorganic carbon, upper Clark Fork River, Montana, USA: Applied Geochemistry, v. 22, p. 1329-1343.

Parker, S.R., Gammons, C.H., Jones, C.A., and Nimick, D.A., 2007, Role of hydrous iron oxide formation in attenuation and diel cycling of dissolved trace metals in a stream affected by acid rock drainage: Water, Air, and Soil Pollution, v. 181, p. 247-263.

Nimick, D.A., McCleskey, R.B., and Gammons, C.H., 2007, Diel mercury-concentration variations in streams affected by mining and geothermal discharge: Science of the Total Environment, v. 373, p. 344-355.

Morris, J.M., and Meyer, J.S., 2007, Photosynthetically mediated Zn removal from the water column in High Ore Creek, Montana: Water, Air, and Soil Pollution, v. 179, p. 391-395.

Morris, J.M., Farag, A.M., Nimick, D.A., and Meyer, J.S., 2006, Light-mediated Zn uptake in photosynthetic biofilm: Hydrobiologia, v. 571, p. 361-371.

Morris, J.M., and Meyer, J.S., 2006, Extracellular and intracellular uptake of zinc in a photosynthetic biofilm matrix: Bulletin of Environmental Contamination and Toxicology, v. 77, p. 30–35.

Shope, C.L., Xie, Ying, and Gammons, C.H., 2006, The influence of hydrous Mn-Zn oxides on diel cycling of Zn in an alkaline stream draining abandoned mine lands: Applied Geochemistry, v. 21, p. 476-491.

Morris, J.M., Nimick, D.A., Farag, A.M, and Meyer, J.S., 2005, Does biofilm contribute to diel cycling of Zn in High Ore Creek, Montana?: Biogeochemistry, v. 76, p. 233-259.

Parker, S.R., Poulson, S.R., and Gammons, C.H., and DeGrandpre, M.D., 2005, Biogeochemical controls on diel cycling of stable isotopes of dissolved O2 and dissolved inorganic carbon in the Big Hole River, Montana: Environmental Science and Technology, v. 39, p. 7134-7140.

Chapin, T.P., and Wanty, R.B., 2005, Development of a solenoid pumped in situ zinc analyzer for environmental monitoring: Analytica Chimica Acta, v. 543, p. 199-208.

Gammons, C.H., Shope, C.L., and Duaime, T.E., 2005, A 24 h investigation of the hydrogeochemistry of baseflow and stormwater in an urban area impacted by mining: Butte, Montana: Hydrological Processes, v. 19, p. 2737-2753.

Gammons, C.H., S.A. Woods, and D.A. Nimick, 2005, Diel behavior of rare earth elements in a mountain stream with acidic to neutral pH: Geochimica Cosmochimica Acta, v. 69, p. 3747-3758.

Gammons, C.H., D.A. Nimick, S.R. Parker, T.E. Cleasby, and R.B. McCleskey, 2005, Diel behavior of iron and other trace metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA: Geochimica Cosmochimica Acta, v. 69, p. 2505-2516.

Nimick, D.A., T.E. Cleasby, and R.B. McCleskey, 2005, Seasonality of diel cycles of dissolved metal concentrations in a Rocky Mountain stream: Environmental Geology, v. 47, no. 5, p. 603-614.

Lambing, J.H., Nimick, D.A., and Cleasby, T.E., 2004, Short-term variation of trace-element concentrations during base flow and rainfall runoff in small basins, August 1999, chap. D7 in Nimick, D.A., Church, S.E., and Finger, S.E., eds., Integrated investigation of environmental effects of historical mining in the Basin and Boulder mining districts, Boulder River watershed, Jefferson County, Montana:  U.S. Geological Survey Professional Paper 1652, p. 263-278. http://pubs.usgs.gov/pp/2004/1652/pdf/chapd7.pdf

Jones, C.A., Nimick, D.A., and McCleskey, R.B., 2004, Relative effect of temperature and pH on diel cycling of dissolved Zn and As in Prickly Pear Creek, Montana: Water, Air, and Soil Pollution, v. 153, p. 95-113.

Nimick, D.A., Gammons, C.H., Cleasby, T.E, Madison, J.P., Skaar, Don, and Brick, C.M., 2003, Diel cycles in dissolved metal concentrations in streams-Occurrence and possible causes: Water Resources Research, v. 39, no. 9, citation number 1247, doi:10.1029/WR001571.

Nimick, D.A., 2003, Diurnal variation in trace-metal concentrations in streams: U.S. Geological Survey Fact Sheet FS-086-03, 4 p.

Nimick, D.A., Moore, J.N., Dalby, C.E., and Savka, M.W., 1998, The fate of geothermal arsenic in the Madison and Missouri Rivers, Montana and Wyoming: Water Resources Research, v. 34, p. 3051-3067.

PROJECT CHIEF: David Nimick