James J. Rytuba

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides: I. Effects of pH☆

The study of mercury sorption products in model systems using appropriate in situ molecular-scale probes can provide detailed information on the modes of sorption at mineral/water interfaces. Such studies are essential for assessing the influence of sorption processes on the transport of Hg in contaminated natural systems. Macroscopic uptake of Hg(II) on goethite (alpha-FeOOH), gamma-alumina (gamma-Al(2)O(3)), and bayerite (beta-Al(OH)(3)) as a function of pH has been combined with Hg L(III)-edge EXAFS spectroscopy, FTIR spectroscopy, and bond valence analysis of possible sorption products to provide this type of information. Macroscopic uptake measurements show that Hg(II) sorbs strongly to fine-grained powders of synthetic goethite (Hg sorption density Gamma=0.39-0.42 micromol/m(2)) and bayerite (Gamma=0.39-0.44 micromol/m(2)), while sorbing more weakly to gamma-alumina (Gamma=0.04-0.13 micromol/m(2)). EXAFS spectroscopy on the sorption samples shows that the dominant mode of Hg sorption on these phases is as monodentate and bidentate inner-sphere complexes. The mode of Hg(II) sorption to goethite was similar over the pH range 4.3-7.4, as were those of Hg(II) sorption to bayerite over the pH range 5.1-7.9. Conversion of the gamma-Al(2)O(3) sorbent to a bayerite-like phase in addition to the apparent reduction of Hg(II) to Hg(I), possibly by photoreduction during EXAFS data collection, resulted in enhanced Hg uptake from pH 5.2-7.8 and changes in the modes of sorption that correlate with the formation of the bayerite-like phase. Bond valence calculations are consistent with the sorption modes proposed from EXAFS analysis. EXAFS analysis of Hg(II) sorption products on a natural Fe oxyhydroxide precipitate and Al/Si-bearing flocculent material showed sorption products and modes of surface attachment similar to those for the model substrates, indicating that the model substrates are useful surrogates for the natural sediments.

Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg(-1) (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of +/-25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis, is beneficial in the prioritization and remediation of mercury-contaminated mine sites.

Mercury mine drainage and processes that control its environmental impact

Mine drainage from mercury mines in the California Coast Range mercury mineral belt is an environmental concern because of its acidity and high sulfate, mercury, and methylmercury concentrations. Two types of mercury deposits are present in the mineral belt, silica-carbonate and hot-spring type. Mine drainage is associated with both deposit types but more commonly with the silica-carbonate type because of the extensive underground workings present at these mines. Mercury ores consisting primarily of cinnabar were processed in rotary furnaces and retorts and elemental mercury recovered from condensing systems. During the roasting process mercury phases more soluble than cinnabar are formed and concentrated in the mine tailings, commonly termed calcines. Differences in mineralogy and trace metal geochemistry between the two deposit types are reflected in mine drainage composition. Silica-carbonate type deposits have higher iron sulfide content than hot-spring type deposits and mine drainage from these deposits may have extreme acidity and very high concentrations of iron and sulfate. Mercury and methylmercury concentrations in mine drainage are relatively low at the point of discharge from mine workings. The concentration of both mercury species increases significantly in mine drainage that flows through and reacts with calcines. The soluble mercury phases in the calcines are dissolved and sulfate is added such that methylation of mercury by sulfate reducing bacteria is enhanced in calcines that are saturated with mine drainage. Where mercury mine drainage enters and first mixes with stream water, the addition of high concentrations of mercury and sulfate generates a favorable environment for methylation of mercury. Mixing of oxygenated stream water with mine drainage causes oxidation of dissolved iron(II) and precipitation of iron oxyhydroxide that accumulates in the streambed. Both mercury and methylmercury are strongly adsorbed onto iron oxyhydroxide over the pH range of 3.2-7.1 in streams impacted by mine drainage. The dissolved fraction of both mercury species is depleted and concentrated in iron oxyhydroxide such that the amount of iron oxyhydroxide in the water column reflects the concentration of mercury species. In streams impacted by mine drainage, mercury and methylmercury are transported and adsorbed onto particulate phases. During periods of low stream flow, fine-grained iron hydroxide sediment accumulates in the bed load of the stream and adsorbs mercury and methylmercury such that both forms of mercury become highly enriched in the iron oxyhydroxide sediment. During high-flow events, mercury- and methylmercury-enriched iron hydroxide sediment is transported into larger aquatic systems producing a high flux of bioavailable mercury.

Mineralized and unmineralized calderas in Spain; Part II, evolution of the Rodalquilar caldera complex and associated gold-alunite deposits

The Rodalquilar caldera complex is located in the western part of the Cabo de Gata volcanic field in southeastern Spain and is the first documented example of epithermal gold-alunite mineralization within a caldera in Europe. The Rodalquilar caldera is an oval collapse structure having a maximum diameter of 8 km and formed at 11 Ma from eruption of the Cinto ash-flow tuff. The oval Lomilla caldera, with a diameter of 2 km, is nested within the central resurgent dome of the older Rodalquilar caldera. The Lomilla caldera resulted from the eruption of the Lazaras ash-flow tuff which was ponded within the moat of the Rodalquilar caldera. The last phase of volcanic activity in the caldera complex was the emplacement of hornblende andesite flows and intrusions. This magmatic event resulted in structural doming of the caldera, opening of fractures and faults, and provided the heat source for the large hydrothermal systems which deposited quartz-alunite type gold deposits and base metal vein systems. The gold-alunite deposits are enclosed in areas of intense acid sulfate alteration and localized in ring and radial faults and fractures present in the east wall of the Lomilla caldera. Like other acid-sulfate type deposits, the Rodalquilar gold-alunite deposits are closely related in time and space to porphyritic, intermediate composition magma emplaced along caldera structures but unrelated to the caldera forming magmatic system.

New Technique for Quantification of Elemental Hg in Mine Wastes and Its Implications for Mercury Evasion into the Atmosphere

Mercury in the environment is of prime concern to both ecosystem and human health. Determination of the molecular-level speciation of Hg in soils and mine wastes is important for understanding its sequestration, mobility, and availability for methylation. Extended X-ray absorption fine structure (EXAFS) spectroscopy carried out under ambient P-T conditions has been used in a number of past studies to determine Hg speciation in complex mine wastes and associated soils. However, this approach cannot detect elemental (liquid) mercury in Hg-polluted soils and sediments due to the significant structural disorder of liquid Hg at ambient-temperature. A new sample preparation protocol involving slow cooling through the crystallization temperature of Hg(0) (234 K) results in its transformation to crystalline α-Hg(0). The presence and proportion of Hg(0), relative to other crystalline Hg-bearing phases, in samples prepared in this way can be quantified by low-temperature (77 K) EXAFS spectroscopy. Using this approach, we have determined the relative concentrations of liquid Hg(0) in Hg mine wastes from several sites in the California Coast Range and have found that they correlate well with measured fluxes of gaseous Hg released during light and dark exposure of the same samples, with higher evasion ratios from samples containing higher concentrations of liquid Hg(0). Two different linear relationships are observed in plots of the ratio of Hg emission under light and dark conditions vs % Hg(0), corresponding to silica-carbonate- and hot springs-type Hg deposits, with the hot springs-type samples exhibiting higher evasion fluxes than silica-carbonate type samples at similar Hg(0) concentrations. Our findings help explain significant differences in Hg evasion data for different mine sites in the California Coast Range.

Mineralized and unmineralized calderas in Spain; Part I, evolution of the Los Frailes Caldera

The Cabo de Gata volcanic field of southeastern Spain contains several recently-recognized calderas. Some of the calderas are mineralized with epithermal gold, alunite, and base metal deposits, and others are barren, and yet they formed under generally similar conditions. Comparison of the magmatic, geochemical, and physical evolution of the Los Frailes, Rodalquilar, and Lomilla calderas provides insight into the processes of caldera evolution that led to precious-metal mineralization. The Los Frailes caldera formed at 14.4 Ma and is the oldest caldera. It formed in response to multiple eruptions of hornblende dacite magma. Following each eruption, the area collapsed and the caldera was invaded by the sea. Dacite domes fill the lower part of the caldera. Pyroxene andesites were erupted through the solidified core of the caldera and were probably initially responsible for magma generation. The Los Frailes caldera did not evolve to rhyolites nor was it subjected to the amount of structural development that the younger, mineralized Rodalquilar and Lomilla calderas were.

Micro)spectroscopic Analyses of Particle Size Dependence on Arsenic Distribution and Speciation in Mine Wastes

The chemical speciation and distribution of potentially toxic metal(loid)s in mine wastes is critical to assessing the risks posed by these wastes and predicting the potential bioavailability of the metal(loid)s present. Of additional potential importance is the role of particle size in the fate, transport, and toxicity of contaminated mining materials. Spectroscopic analyses of size-separated mine tailings and adjacent background samples from the Randsburg Historic Mining District, California were conducted to quantify the speciation and distribution of arsenic (As) as a function of particle size. Micro-X-ray fluorescence (μXRF) mapping of separate size fractions was used to identify multiple populations of particles with different As:Fe ratios, indicating a variety of distinct arsenic-bearing species. Bulk extended X-ray absorption fine structure (EXAFS) spectroscopy identified phases including arseniosiderite, Ca2Fe3(3+)(AsO4)3O3·3H2O, and As(V) sorbed to iron hydroxides (ferrihydrite, goethite), confirming a strong statistical correlation between arsenic and iron observed in both μXRF studies and bulk chemical analyses. Differences in As speciation between the mine tailings and background samples also suggest that weathering of crystalline As-bearing phases in tailings leads to sorption of dissolved arsenic to iron hydroxides in nontailings background material.

Microbially enhanced dissolution of HgS in an acid mine drainage system in the California Coast Range

Mercury sulfides (cinnabar and metacinnabar) are the main ores of Hg and are relatively stable under oxic conditions (Ksp = 10⁻⁵⁴ and 10⁻⁵² , respectively). However, until now their stability in the presence of micro-organisms inhabiting acid mine drainage (AMD) systems was unknown. We tested the effects of the AMD microbial community from the inoperative Hg mine at New Idria, CA, present in sediments of an AMD settling pond adjacent to the main waste pile and in a microbial biofilm on the surface of this pond, on the solubility of crystalline HgS. A 16S rRNA gene clone library revealed that the AMD microbial community was dominated by Fe-oxidizing (orders Ferritrophicales and Gallionellas) and S-oxidizing bacteria (Thiomonas sp.), with smaller amounts (≤ 6%) being comprised of the orders Xanthomondales and Rhodospirillales. Though the order Ferritrophicales dominate the 16S rRNA clones (>60%), qPCR results of the microbial community indicate that the Thiomonas sp. represents ~55% of the total micro-organisms in the top 1 cm of the AMD microbial community. Although supersaturated with respect to cinnabar and metacinnabar, microcosms inoculated with the AMD microbial community were capable of releasing significantly more Hg into solution compared to inactivated or abiotic controls. Four different Hg-containing materials were tested for bacterially enhanced HgS dissolution: pure cinnabar, pure metacinnabar, mine tailings, and calcine material (processed ore). In the microcosm with metacinnabar, the presence of the AMD microbial community resulted in an increase of dissolved Hg concentrations up to 500 μg L ⁻¹during the first 30 days of incubation. In abiotic control microcosms, dissolved Hg concentrations did not increase above 100 ng L⁻¹ . When Hg concentrations were below 50 μg L⁻¹ , the Fe-oxidizing bacteria in the AMD microbial community were still capable of oxidizing Fe(II) to Fe(III) in the AMD solution, whereas concentrations above 50 μg L⁻¹ resulted in inhibition of microbial iron oxidation. Our experiments show that the AMD microbial community contributes to the dissolution of mercury sulfide minerals. These findings have major implications for risk assessment and future management of inoperative Hg mines worldwide.

Geology and geochemistry of epithermal precious metal vein systems in the intra-oceanic arcs of Palau and Yap, western Pacific

Abstract The Palau and Yap arcs are part of an intra-oceanic island-arc-trench system which separates the Pacific and Philippine plates in the western Pacific Ocean. The 350-km-long Palau arc consists of over 200 islands while the 400-km-long Yap arc located to the north has only four major islands exposed. Four of the largest islands in Palau are composed primarily of early Eocene to mid-Miocene volcanic rocks and the four islands comprising Yap contain only Miocene volcanic rocks. Basalt and basaltic andesites of the Babelthuap Formation are the oldest volcanic rocks in Palau and are characterized by high MgO, Ni and Cr and low TiO2 and have a boninitic affinity. They form the central and southeastern parts of Babelthuap Island. Oligocene arc tholeiite flows having an age of 34–35.5 Ma comprise most of the three smaller volcanic islands in Palau and the western part of Babelthuap. The youngest volcanic rocks are dacitic intrusions having an age of 22.7–23.2 Ma. The Yap arc is unusual in that metamorphic rocks up to amphibolite grade form most of the islands. These are underlain by a melange composed of igneous and volcanic clasts as well as clasts from a dismembered copper-gold skarn deposit. Miocene volcanic rocks consisting of flows and volcaniclastic deposits overlie the melange and metamorphic complex. An epithermal precious-metal vein system hosted by flows and flow breccias of the Babelthuap Formation occurs in an area 1.5 km by 1 km on the southeast side of Babelthuap Island. Over 50 veins and mineralized breccias ranging up to 2 m in width and having a strike length up to 500 m contain from trace to 13.0 ppm gold. The veins consist of quartz with varying amounts of sulfides and iron oxides after sulfides and the mineralized breccias consist of brecciated country rock cemented by quartz and iron oxides after sulfides. The veins and mineralized breccias generally dip within 15° of vertical and have two preferred orientations, north-northwest and north-northeast. Hydrothermal alteration of the host rocks consists of a widespread weak to moderately strong propylitic alteration and a more restricted sericitic alteration adjacent to the veins and shear zones. Sulfide minerals in the veins consist primarily of pyrite accompanied by lesser amounts of sphalerite, chalcopyrite, galena, acanthite, native silver, cerargyrite, and iodyrite in partly oxidized parts of the vein system. Gold is typically fine-grained, 1–20 microns, and occurs as native gold, electrum and gold-silver-telluride. Elements correlated with high gold concentrations include molybdenum, tellurium, bismuth, lead, silver, copper, zinc and arsenic. In Yap a similar vein system to that present in Palau is hosted by the Miocene Tomil Volcanics on the islands of Maap and Gagil Tamil. The quartz veins and quartz-cemented breccias contain up to 3.7 ppm gold and trace elements associated with the gold include tellurium, copper, silver and vanadium. Within the mineralized area an unusually iron-rich (3–20%), 4-m-thick, hot-spring deposit contains up to 1.04 ppm gold and high concentrations of tellurium, copper and vanadium. Hydrothermal eruption breccia beds are present within the deposit. The presence of the hot-spring deposit and banded and comb textures of the vein quartz suggest that the vein system presently exposed formed at a shallow level. The vein systems in Palau and Yap have similar textures, geochemical suites and alteration assemblages. Both vein systems formed late in the volcanic evolution of the intra-oceanic arc. Media tested for their effectiveness in geochemical exploration in the tropical, deeply weathered environment of Palau and Yap included stream sediments, heavy-mineral concentrates from stream sediments, and sediment from the mangrove coastal environment which is well developed around most of the islands of Yap and Palau. Geochemical surveys in both Yap and Palau of mangrove sediment show that adjacent to areas of gold mineralization, gold and tellurium contents are anomalous, ranging from 10 to 100 ppb gold and from 100 to 2100 ppb tellurium. Away from areas of mineralization gold contents are less that 6 ppb and tellurium less then 40 ppb. Mangrove coastal environments are common throughout the western Pacific and geochemical sampling of mangrove sediment can provide an effective method to quickly evaluate the potential of land adjacent to the coast as a first step in exploration.

Lithium in the McDermitt caldera, Nevada and Oregon

Anomalously high concentrations of lithium in fluviatile-lacustrine sediments near McDermitt, Nevada, may constitute a potential resource. These sediments are associated with a caldera about 45 km in diameter that is a result of volcanic activity, subsidence and sedimentation chiefly of Miocene age. The sediments originally were vitroclastic and now consist chiefly of authigenic zeolites, clay minerals, feldspar and quartz. Calcite occurs as thin beds, nodules and cement Gypsum is presnt but sparse.