Kathleen S. Smith

Selectivity and effectiveness of extractants used to release metals associated with organic matter

Partial extraction procedures can be used to release metals associated with organic matter in natural materials. Reagents commonly employed for this purpose include hydrogen peroxide, Na hypochlorite and Na pyrophosphate. This study tested the selectivity of these reagents by comparing the amount of Fe, Mn, Zn and Cu they released from sulfide and oxide minerals and determined the ability of these reagents to release the same metals from peat. Sodium hypochlorite and Na pyrophosphate released between 0.2 and 8.7% of the total metal content of the Fe, Cu and Zn minerals. In contrast, three commonly used hydrogen peroxide reagents released significantly more metals from the oxides and sulfides. Percentages of Zn and Mn released from the peat samples were comparable for all extractions tested. Per cent Cu released from peat by Na pyrophosphate was very low compared to that released by hydrogen peroxide/HNO3 or na hypochlorite. A smaller fraction of Fe was released from peat by Na hypochlorite than by the other reagents. Iron release by Na hypochlorite correlates with the organic carbon content of the peat samples. A universal extractant for metals associated with organic matter in all types of samples has not been identified. Sodium hypochlorite and Na pyrophosphate are better than hydrogen peroxide in selectively releasing metals bound to organic matter because they do not release significant amounts of metals from oxide and sulfide minerals.

Chapter 24 – Predictive Double-Layer Modeling of Metal Sorption in Mine-Drainage Systems

Previous comparison of predictive double-layer modeling and empirically derived metal-partitioning data has validated the use of the double-layer model to predict metal sorption reactions in iron-rich mine-drainage systems. The double-layer model subsequently has been used to model data collected from several mine-drainage sites in Colorado with diverse geochemistry and geology. This work demonstrates that metal partitioning between dissolved and sediment phases can be predictively modeled simply by knowing the water chemistry and the amount of suspended iron-rich particulates present in the system. Sorption on such iron-rich suspended sediments appears to control metal and arsenic partitioning between dissolved and sediment phases, with sorption on bed sediment playing a limited role. At pH > 5, Pb and As are largely sorbed by iron-rich suspended sediments and Cu is partially sorbed; Zn, Cd, and Ni usually remain dissolved throughout the pH range of 3 to 8.

Exposure of insects and insectivorous birds to metals and other elements from abandoned mine tailings in three Summit County drainages, Colorado

Concentrations of 31 metals, metalloids, and other elements were measured in insects and insectivorous bird tissues from three drainages with different geochemistry and mining histories in Summit Co., Colorado, in 2003, 2004, and 2005. In insect samples, all 25 elements that were analyzed in all years increased in both Snake and Deer Creeks in the mining impacted areas compared to areas above and below the mining impacted areas. This distribution of elements was predicted from known or expected sediment contamination resulting from abandoned mine tailings in those drainages. Element concentrations in avian liver tissues were in concordance with levels in insects, that is with concentrations higher in mid-drainage areas where mine tailings were present compared to both upstream and downstream locations; these differences were not always statistically different, however. The lack of statistically significant differences in liver tissues, except for a few elements, was due to relatively small sample sizes and because many of these elements are essential and therefore well regulated by the bird’s homeostatic processes. Most elements were at background concentrations in avian liver tissue except for Pb which was elevated at mid-drainage sites to levels where δ-aminolevulinic acid dehydratase activity was inhibited at other mining sites in Colorado. Lead exposure, however, was not at toxic levels. Fecal samples were not a good indication of what elements birds ingested and were potentially exposed to.

An enriched stable-isotope approach to determine the gill-zinc binding properties of juvenile rainbow trout (Oncorhynchus mykiss) during acute zinc exposures in hard and soft waters†

The objective of the present study was to employ an enriched stable-isotope approach to characterize Zn uptake in the gills of rainbow trout (Oncorhynchus mykiss) during acute Zn exposures in hard water (approximately 140 mg/L as CaCO3) and soft water (approximately 30 mg/L as CaCO3). Juvenile rainbow trout were acclimated to the test hardnesses and then exposed for up to 72 h in static exposures to a range of Zn concentrations in hard water (0-1000 microg/L) and soft water (0-250 microg/L). To facilitate detection of new gill Zn from endogenous gill Zn, the exposure media was significantly enriched with 67Zn stable isotope (89.60% vs. 4.1% natural abundance). Additionally, acute Zn toxicity thresholds (96-h median lethal concentration [LC50]) were determined experimentally through traditional, flow-through toxicity tests in hard water (580 microg/L) and soft water (110 microg/L). Following short-term (< or =3 h) exposures, significant differences in gill accumulation of Zn between hard and soft water treatments were observed at the three common concentrations (75, 150, and 250 microg/L), with soft water gills accumulating more Zn than hard water gills. Short-term gill Zn accumulation at hard and soft water LCS0s (45-min median lethal accumulation) was similar (0.27 and 0.20 microg/g wet wt, respectively). Finally, comparison of experimental gill Zn accumulation, with accumulation predicted by the biotic ligand model, demonstrated that model output reflected short-term (<1 h) experimental gill Zn accumulation and predicted observed differences in accumulation between hard and soft water rainbow trout gills. Our results indicate that measurable differences exist in short-term gill Zn accumulation following acclimation and exposure in different water hardnesses and that short-term Zn accumulation appears to be predictive of Zn acute toxicity thresholds (96-h LC50s).

Fractionation of fulvic acid by iron and aluminum oxides--influence on copper toxicity to Ceriodaphnia dubia.

This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC50 13 ± 0.6 μg Cu/L) than were the unfractionated dissolved FAs (EC50 39 ± 0.4 and 41 ± 1.2 μg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA254), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.

Measurement of total Zn and Zn isotope ratios by quadrupole ICP-MS for evaluation of Zn uptake in gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss).

This study evaluates the potential use of stable zinc isotopes in toxicity studies measuring zinc uptake by the gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss). The use of stable isotopes in such studies has several advantages over the use of radioisotopes, including cost, ease of handling, elimination of permit requirements, and waste disposal. A pilot study using brown trout was performed to evaluate sample preparation methods and the ability of a quadrupole inductively coupled plasma mass spectrometer (ICP-MS) system to successfully measure changes in the (67)Zn/(66)Zn ratios for planned exposure levels and duration. After completion of the pilot study, a full-scale zinc exposure study using rainbow trout was performed. The results of these studies indicate that there are several factors that affect the precision of the measured (67)Zn/(66)Zn ratios in the sample digests, including variations in sample size, endogenous zinc levels, and zinc uptake rates by individual fish. However, since these factors were incorporated in the calculation of the total zinc accumulated by the gills during the exposures, the data obtained were adequate for their intended use in calculating zinc binding and evaluating the influences of differences in water quality parameters.

What's weathering? Mineralogy and field leach studies in mine waste, Leadville and Montezuma mining districts, Colorado

Weathering is important in the development of rock fabrics that control porosity in mine-waste materials, and in turn, porosity affects metal transport through and from mine-waste piles into watersheds. Mine-waste piles are dynamic physical and chemical systems as evidenced by remnant Fe-oxide boxwork structures after sulfide minerals, development of alteration rinds and etch pits on grains, and precipitation of secondary minerals under low temperature conditions. These microscale changes in the mine-waste materials are the result of partial to total dissolution of sulfide and other minerals. Mine-waste materials from the Dinero, Lower Chatauqua, and Saints John sites, Leadville and Montezuma mining districts, Colorado, exhibit rock fabrics that indicate that weathering products, e.g., Fe oxyhydroxides, jarosite, and clays, have been transported in suspension through the waste piles and deposited in voids and as coatings on rock fragments. Microscale characterization of weathered, partially dissolved minerals lends insight into the source of leachable metals in these mine-waste sites. Mineralogic studies show that galena in the Lower Chatauqua waste is enriched in Ag. Qualitative and semiquantitative microanalysis of weathered, altered galena grains from all three sites show that the Ag-bearing galena is more susceptible to dissolution. It is not surprising, then, that solutions experimentally leached from Lower Chatauqua waste are higher in Pb (2310 ppb) compared to leachates from the Dinero (31 ppb) and Saints John (1360 ppb) wastes. The mobility of metals is increased at acidic pH. Using the USGS Field Leach Test protocol, leachate derived from the Dinero waste has a pH of 3 and high concentrations of Al (443 ppb), Fe (441 ppb), and Zn (7970 ppb). Leachate from Sts. John tailings has a pH about 4 and high concentrations of Mn (1520 ppb), Zn (2240 ppb), and Pb (1360 ppb). Leachate from the Lower Chatauqua waste has an intermediate pH of 5, but in addition to the high Pb level already mentioned, it contains high levels of K (1.9 ppm), Mn (6720 ppb), and Zn (1550 ppb). The high concentration of metals, despite the intermediate pH of the leachate, may be explained by acidic microenvironments that exist at the surfaces of sulfide minerals, where sulfurand iron-oxidizing microbes may flourish. It is at the reactive mineral-oxygen-water interface where metals are released and low-pH sulfate precipitates such as jarosite-beudantite form. Additional

The use of synthetic jarosite as an analog for natural jarosite

The presence of jarosite in soil or mining waste is an indicator of acidic sulfate-rich conditions. Physical and chemical properties of synthetic jarosites are commonly used as analogs in laboratory studies to determine solubility and acid-generation of naturally occurring jarosites. In our work we have mineralogically and chemically characterized both natural and synthetic jarosites. Analysis of 32 natural hydrothermal and supergene K- and Na-jarosites indicates no (< 5 mole %) solid solution between K and Na end members. Instead, our detailed study of cell dimensions and composition reveals discrete mixtures of K and Na end members. Hydronium-bearing jarosite was detected in only one natural sample, and it appears that hydronium-bearing jarosites are metastable. Although the presence of hydronium in jarosite cannot be directly measured, we found that when synthetic hydronium-bearing jarosites are heated at 120°C for 78 days or 240°C for 24 hours, Fe(OH)SO4 is formed. The Fe(OH)SO4 is easily detected by X-ray diffraction and, hence, can be used as a post-mortem indicator of the presence of hydronium jarosite. Results from our synthetic jarosite studies indicate that natural metastable hydronium-bearing jarosite or iron-deficient forms of natural jarosite likely play an important role in acid generation in some mining wastes, but are not accurately represented by synthetic jarosite prepared by commonly used methods. The widespread practice of heating to at least 110°C after jarosite synthesis appears to drive off structural waters from protonated hydroxyl sites, which changes the properties of the jarosite. Therefore, synthetic jarosite should not be heated above 95 o C if it is to be used as an analog

Predicting toxic effects of copper on aquatic biota in mineralized areas by using the Biotic Ligand Model

The chemical speciation of metals influences their biological effects. The Biotic Ligand Model (BLM) is a computational approach to predict chemical speciation and acute toxicological effects of metals on aquatic biota. Recently, the U.S. Environmental Protection Agency incorporated the BLM into their regulatory waterquality criteria for copper. Results from three different laboratory copper toxicity tests were compared with BLM predictions for simulated test-waters. This was done to evaluate the ability of the BLM to accurately predict the effects of hardness and concentrations of dissolved organic carbon (DOC) and iron on aquatic toxicity. In addition, we evaluated whether the BLM and the three toxicity tests provide consistent results. Comparison of BLM predictions with two types of Ceriodaphnia dubia toxicity tests shows that there is fairly good agreement between predicted LC50 values computed by the BLM and LC50 values determined from the two toxicity tests. Specifically, the effect of increasing calcium concentration (and hardness) on copper toxicity appears to be minimal. Also, there is fairly good agreement between the BLM and the two toxicity tests for test solutions containing elevated DOC, for which the LC50 is 3-to-5 times greater (less toxic) than the LC50 for the lower-DOC test water. This illustrates the protective effects of DOC on copper toxicity and demonstrates the ability of the BLM to predict these protective effects. In contrast, for test solutions with added iron there is a decrease in LC50 values (increase in toxicity) in results from the two C. dubia toxicity tests, and the agreement between BLM LC50 predictions and results from these toxicity tests is poor. The inability of the BLM to account for competitive iron binding to DOC or DOC fractionation may be a significant shortcoming of the BLM for predicting site-specific water-quality criteria in streams affected by iron-rich acidic drainage in mined and mineralized areas. Additional

A Simple Scheme to Determine Potential Aquatic Metal Toxicity from Mining Wastes

A decision tree (mining waste decision tree) that uses simple physical and chemical tests has been developed to determine whether effluent from mine waste material poses a potential toxicity threat to the aquatic environment. For the chemical portion of the tree, leaching tests developed by the United States Geological Survey, the Colorado Division of Minerals and Geology (Denver, CO), and a modified 1311 toxicity characteristic leaching procedure (TCLP) test of the United States Environmental Protection Agency have been extensively used as a surrogate for readily available metals that can be released into the environment from mining wastes. To assist in the assessment, element concentration pattern graphs (ECPG) are produced that compare concentrations of selected groups of elements from the three leachates and any water associated with the mining waste. The MWDT makes a distinction between leachates or waters with pH less than or greater than 5. Generally, when the pH values are below 5, the ECPG of the solutions are quite similar, and potential aquatic toxicity from cationic metals, such as Pb, Cu, Zn, Cd, and Al, is assumed. Below pH 5, these metals are mostly dissolved, generally are not complexed with organic or inorganic ligands, and hence are more bioavailable. Furthermore, there is virtually no carbonate alkalinity at pH less than 5. All of these factors promote metal toxicity to aquatic organisms. On the other hand, when the pH value of the water or the leachates is above 5, the ECPG from the solutions are variable, and inferred aquatic toxicity depends on factors in addition to the metals released from the leaching tests. Hence, leachates and waters with pH above 5 warrant further examination of their chemical composition. Physical ranking criteria provide additional information, particularly in areas where waste piles exhibit similar chemical rankings. Rankings from physical and chemical criteria generally are not correlated. Examples of how this decision tree has been applied in assessing mine sites are discussed.