Applied Geochemistry (v.16, #15)

Geochemistry of suspended particles in a mine-affected mountain stream by Annett B Sullivan; James I Drever (1663-1676).
The particles in a mine drainage and the creek into which it drains were examined using microbeam and filtration methods. The composition of the particles in the drainage and creek were distinctly different, though both carried a chemical signal from the mine. High concentrations of particles made up of Fe and S were seen in the drainage, especially during low flow. The molar Fe:S ratio of these suspended particles was 3.5:1. The influx of the mine drainage into the creek increased the relative number of aggregates and particles with associated Fe. However, few discrete Fe–S particles were seen in the creek, where solid-phase Fe and S were consistently associated with aluminosilicate minerals. Instream precipitation is predicted and appears to be an important additional source of Fe and Al oxyhydroxides to the particles. Some of the Fe and Al associated with particles in the creek was acid-soluble, but most of the acid-soluble Zn, Mn, Cu, Ca, Mg and Si were transported in the <0.45 μm fraction at a site downstream of the mine drainage. One third of the suspended particles had associated P. These suspended particles take part in the complex geochemistry of this system, and represent an important pool as a potential sink and source of metals and other elements.

Mercury (Hg) and methylmercury (CH3Hg+) concentrations in streambed sediment and water were determined at 27 locations throughout the Sacramento River Basin, CA. Mercury in sediment was elevated at locations downstream of either Hg mining or Au mining activities where Hg was used in the recovery of Au. Methylmercury in sediment was highest (2.84 ng/g) at a location with the greatest wetland land cover, in spite of lower total Hg at that site relative to other river sites. Mercury in unfiltered water was measured at 4 locations on the Sacramento River and at tributaries draining the mining regions, as well as agricultural regions. The highest levels of Hg in unfiltered water (2248 ng/l) were measured at a site downstream of a historic Hg mining area, and the highest levels at all sites were measured in samples collected during high streamflow when the levels of suspended sediment were also elevated. Mercury in unfiltered water exceeded the current federal and state recommended criterion for protection of aquatic life (50 ng/l as total Hg in unfiltered water) only during high streamflow conditions. The highest loading of Hg to the San Francisco Bay system was attributed to sources within the Cache Creek watershed, which are downstream of historic Hg mines, and to an unknown source or sources to the mainstem of the Sacramento River upstream of historic Au mining regions. That unknown source is possibly associated with a volcanic deposit. Methylmercury concentrations also were dependent on season and hydrologic conditions. The highest levels (1.98 ng/l) in the Sacramento River, during the period of study, were measured during a major flood event. The reactivity of Hg in unfiltered water was assessed by measuring the amount available for reaction by a strong reducing agent. Although most Hg was found to be nonreactive, the highest reactivity (7.8% of the total Hg in water) was measured in the sample collected from the same site with high CH3Hg+ in sediment, and during the time of year when that site was under continual flooded conditions. Although Hg concentrations in water downstream of the Hg mining operations were measured as high as 2248 ng/l during stormwater runoff events, the transported Hg was found to have a low potential for geochemical transformations, as indicated by the low reactivity to the reducing agent (0.0001% of the total), probably because most of the Hg in the unfiltered water sample was in the mercury sulfide form.

Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii) bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, particularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indicates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in the carbonate fraction (CaCO3), while the exchangeable and residual phases are the main fractions for Ca at the smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.

The depth-related content of polycyclic aromatic hydrocarbons (PAH) and heavy metals was determined for two soil profiles (i.e. one Fluvisol and one Gleyic Cambisol) which developed in sediments from floodplains located at an old meander of the Rhine river. The meander had been cut off from the main river in 1829. The separation of the meander from the main river caused a change in sediment deposition (i.e. from sand to silt) which is clearly visible in the soil-profiles. Since that time, approximately 100 cm of sediments have accumulated due to temporary flooding of the area. Each soil profile was separated into 18 samples. The samples were analysed for their content of PAH after solvent extraction. Additionally, several trace elements (Co, Ni, Cd, Pb, Zn, Cr and Cu) were determined in the same sample set, and depth-related concentration profiles for both PAH and trace elements were developed. The distribution patterns of PAH with more than 3 condensed rings did not provide any evidence for PAH biodegradation or vertical transport after deposition of the sediments. Thus, in the case of PAH, the historical record can be derived not only from subhydric sediments but also from floodplain sediments. It was not possible to distinguish between atmospheric and fluvial input of PAH into the sediments from the observed distribution patterns due to the same origin of PAH from pyrolytic processes. A source determination of the PAH was not possible except for perylene, for which biogenic formation can be assumed. A comparison of the results shows that the depth-related PAH and trace element concentrations display similar trends over most of the total profiles. In the uppermost section of the profiles, the concentration of most trace elements declines whereas the PAH concentration remains high. This indicates the presence of different sources for PAH and trace elements in the last decades.