Using Large Databases of Groundwater Chemistry in the Northern Midwest USA: The Effects of Geologic and Anthropogenic Factors

Regional geochemical databases for the northern Midwest USA are being compiled to examine the various geogenic and anthropogenic factors that control the chemistry of groundwater. At the regional scale, variations are seen that are attributable to agricultural and urban effects, or to geologic factors. Examples of the former include enrichments of nitrate in groundwater, while examples of the latter mainly highlight geochemical differences between carbonate rocks and all other rock types in the region. This paper examines a few of these regional effects and the spatial scales at which they can be observe

A 20-year record of water chemistry in an alpine setting, Mount Emmons, Colorado, USA

From 1997 to the present, the U.S. Geological Survey and other agencies have been collecting water samples for chemical analyses on Mount Emmons in central Colorado, USA. The geology of Mount Emmons is dominated by Upper Cretaceous to Paleogene sediments of marine to continental origin, with felsic intrusive rocks interrupting the sedimentary block. Extensive sulphide-rich alteration accompanied the intrusive events and forms an alteration halo in the sediments. Weathering of these sulphide minerals has led to numerous springs and seeps with a naturally low pH and high concentrations of metals, especially Fe and Zn. Superimposed on the natural geochemical signature are acid, metal-rich drainages from several mines and drill holes. Thus, streams on Mt. Emmons have a mix of natural and anthropogenic metal sources. Nearly 450 samples compose the database, with numerous sample locations replicated from the late 1990s to the present. Although there does not appear to be any temporal pattern in the data, consistent spatial variations are observed that allow us to characterize the natural and anthropogenic water sources

Zinc isotope and transition-element dynamics accompanying hydrozincite biomineralization in the Rio Naracauli, Sardinia, Italy

The Rio Naracauli in SW Sardinia drains part of the Ingurtosu Zn-Pb mining district, and contains extreme concentrations of dissolved Zn at near-neutral pH. In the upper reaches of the stream, pH, alkalinity and Zn concentrations are such that hydrozincite [Zn5(CO3)2(OH)6] precipitates in a biologically mediated process facilitated by a microalga (Chlorella sp.) and a cyanobacterium (Scytonema sp.). Values of d66Zn in water and solid samples ranged from -0.35 ‰ to +0.5 ‰ relative to the JMC 3-0749- Lyon standard, and closely follow a mass-dependent fractionation line. Two composite samples of sphalerite, the primary ore mineral in the Ingurtosu deposits, had an average d66Zn of +0.15 ‰, similar to sphalerite measured elsewhere in hydrothermal mineral deposits. Zinc isotope measurements of the stream water and the hydrozincite forming in the stream show a consistent preference for the heavy isotope, 66Zn, in the hydrozincite relative to 64Zn. Synthetic hydrozincites produced without added bacteria have d66Zn identical to the dissolved Zn, thus suggesting a biologically mediated mineralization process in Rio Naracauli. The average fractionation, Dhdz-water, is 0.35 ‰, the magnitude of which is consistent with other studies, and suggests an extracellular mechanism of the biomineralization process. Zinc concentration and dissolved d66Zn steadily decrease in the reach of the stream where the biomineralization occurs. The biomineralization process also leads to the sequestration of Pb, Cu and Ni in the hydrozincite lattice, and the coeval precipitation of an amorphous CdCO3 solid, prompting the suggestion that if optimized, the biomineralization process might represent a feasible passive remediation strategy for streams with high Zn and other metals, and with near-neutral pH

Formation of a low-crystalline Zn-silicate in a stream in SW Sardinia, Italy

In southwestern Sardinia, Italy, the Rio Naracauli drains a catchment that includes several abandoned mines. The drainage from the mines and associated waste rocks has led to extreme concentrations of dissolved Zn, but because of the near-neutral pH, concentrations of other metals re main low. In the reach from approximately 2300 to 3000 m downstream from the headwaters area, an amorphous Zn-silicate precipitates from the water. In this reach, concentrations of both Zn and silica remain nearly constant, but the loads (measured in mass/time) of both increase, suggesting that new Zn and silica are supplied to the stream, likely from emerging groundwater. Zinc isotope signatures of the solid are heavier than the dissolved Zn by about 0.5 permil in 66/64 Zn, suggesting that an extracellular biologically mediated adsorption process may be involved in the formation of the Zn-silica

Historical mine pollution and environmental resilience: Biomineralization processes and biogeochemical barriers

Three streams in SW Sardinia were studied to evaluate the transport of metals in the environment, and to characterize the natural processes that lead to decreased metal loads. Here we focus on Zn. Although the metal load varies by 2-3 orders of magnitude, we have observed natural biologically mediated attenuation processes, including uptake by vegetation and biomineralization. In this paper, we review the chemical and physical processes that lead to natural Zn attenuation, and discuss the merits of mimicking those processes when designing remediation schemes