Dissolved metals and associated constituents in abandoned coal-mine discharges,Pennsylvania, USA. Part 1: Constituent quantities and correlations

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s⁻¹, with a median of 18.4 L s⁻¹. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-μm pore-size filter) SO₄ (34–2000), Fe (0.046–512), Mn (0.019–74), and Al (0.007–108) varied widely. Predominant metalloid elements were Si (2.7–31.3 mg L⁻¹), B (<1–260 μg L⁻¹), Ge (<0.01–0.57 μg L⁻¹), and As (<0.03–64 μg L⁻¹). The most abundant trace metals, in order of median concentrations (range in μg/L), were Zn (0.6–10,000), Ni (2.6–3200), Co (0.27–3100), Ti (0.65–28), Cu (0.4–190), Cr (<0.5–72), Pb (<0.05–11) and Cd (<0.01–16). Gold was detected at concentrations greater than 0.0005 μg L⁻¹ in 97% of the samples, with a maximum of 0.0175 μg L⁻¹. No samples had detectable concentrations of Hg, Os or Pt, and less than half of the samples had detectable Pd, Ag, Ru, Ta, Nb, Re or Sn. Predominant rare-earth elements, in order of median concentrations (range in μg/L), were Y (0.11–530), Ce (0.01–370), Sc (1.0–36), Nd (0.006–260), La (0.005–140), Gd (0.005–110), Dy (0.002–99) and Sm (<0.005–79). Although dissolved Fe was not correlated with pH, concentrations of Al, Mn, most trace metals, and rare earths were negatively correlated with pH, consistent with solubility or sorption controls. In contrast, As was positively correlated with pH.     

Mantle Sources and the Highly Variable Role of Continental Lithosphere in Basalt Petrogenesis of the Kerguelen Plateau and Broken Ridge LIP: Results from ODP Leg 183

Ocean Drilling Program (ODP) Leg 183 was designed to investigatethe origin and evolution of the large igneous province composedof the Kerguelen Plateau and Broken Ridge. Of the eight sitesdrilled, basalt was recovered from seven, five on the plateauand two on Broken Ridge. We present results from four of thesesites, 1136, 1138, 1141 and 1142. Although this large igneousprovince is interpreted as being derived from the Kerguelenmantle plume, the geochemical characteristics of basalt fromsome parts of the province indicate a role for continental lithosphere.The 118–119 Ma basalt flows recovered in the SouthernKerguelen Plateau (Site 1136) have a more subtle continentalsignature than shown by basalt at Leg 119 Site 738. A continentalsignature is absent in the 100–101 Ma tholeiitic basaltsat Site 1138 in the Central Kerguelen Plateau (CKP); their age-correctedNd–Sr–Pb isotopic values and incompatible elementratios are similar to those estimated for primitive mantle.These flows may represent a major mantle source in the Kerguelenstarting-plume head. The 20 basalt units identified are a productof magma chamber replenishment, fractional crystallization,and resorption of crystallizing phases. The topmost unit, Unit1, is a dacite that evolved from a basalt magma similar to thoserepresented by Units 3–22; unlike the basalts the dacitemagma was probably influenced by continental material. MiddleCretaceous (     

Deep submarine pyroclastic eruptions: theory and predicted landforms and deposits

Submarine pyroclastic eruptions at depths greater than a few hundred meters are generally considered to be rare or absent because the pressure of the overlying water column is sufficient to suppress juvenile gas exsolution so that magmatic disruption and pyroclastic activity do not occur. Consideration of detailed models of the ascent and eruption of magma in a range of sea floor environments shows, however, that significant pyroclastic activity can occur even at depths in excess of 3000 m. In order to document and illustrate the full range of submarine eruption styles, we model several possible scenarios for the ascent and eruption of magma feeding submarine eruptions: (1) no gas exsolution; (2) gas exsolution but no magma disruption; (3) gas exsolution, magma disruption, and hawaiian-style fountaining; (4) volatile content builds up in the magma reservoir leading to hawaiian eruptions resulting from foam collapse; (5) magma volatile content insufficient to cause fragmentation normally but low rise speed results in strombolian activity; and (6) volatile content builds up in the top of a dike leading to vulcanian eruptions. We also examine the role of bulk-interaction steam explosivity and contact-surface steam explosivity as processes contributing to volcaniclastic formation in these environments. We concur with most earlier workers that for magma compositions typical of spreading centers and their vicinities, the most likely circumstance is the quiet effusion of magma with minor gas exsolution, and the production of somewhat vesicular pillow lavas or sheet flows, depending on effusion rate. The amounts by which magma would overshoot the vent in these types of eruptions would be insufficient to cause any magma disruption. The most likely mechanism of production of pyroclastic deposits in this environment is strombolian activity, due to the localized concentration of volatiles in magma that has a low rise rate; magmatic gas collects by bubble coalescence, and ascends in large isolated bubbles which disrupt the magma surface in the vent, producing localized blocks, bombs, and pyroclastic deposits. Another possible mode of occurrence of pyroclastic deposits results from vulcanian eruptions; these deposits, being characterized by the dominance of angular blocks of country rocks deposited in the vicinity of a crater, should be easily distinguishable from strombolian and hawaiian eruptions. However, we stress that a special case of the hawaiian eruption style is likely to occur in the submarine environment if magmatic gas buildup occurs in a magma reservoir by the upward drift of gas bubbles. In this case, a layer of foam will build up at the top of the reservoir in a sufficient concentration to exceed the volatile content necessary for disruption and hawaiian-style activity; the deposits and landforms are predicted to be somewhat different from those of a typical primary magmatic volatile-induced hawaiian eruption. Specifically, typical pyroclast sizes might be smaller; fountain heights may exceed those expected for the purely magmatic hawaiian case; cooling of descending pyroclasts would be more efficient, leading to different types of proximal deposits; and runout distances for density flows would be greater, potentially leading to submarine pyroclastic deposits surrounding vents out to distances of tens of meters to a kilometer. In addition, flows emerging after the evacuation of the foam layer would tend to be very depleted in volatiles, and thus extremely poor in vesicles relative to typical flows associated with hawaiian-style eruptions in the primary magmatic gas case. We examine several cases of reported submarine volcaniclastic deposits found at depths as great as 3000 m and conclude that submarine hawaiian and strombolian eruptions are much more common than previously suspected at mid-ocean ridges. Furthermore, the latter stages of development of volcanic edifices (seamounts) formed in submarine environments are excellent candidates for a wide range of submarine pyroclastic activity due not just to the effects of decreasing water depth, but also to: (1) the presence of a summit magma reservoir, which favors the buildup of magmatic foams (enhancing hawaiian-style activity) and episodic dike emplacement (which favors strombolian-style eruptions); and (2) the common occurrence of alkalic basalts, the CO₂ contents of which favor submarine explosive eruptions at depths greater than tholeiitic basalts. These models and predictions can be tested with future sampling and analysis programs and we provide a checklist of key observations to help distinguish among the eruption styles.     

Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.     

Serpentinization of abyssal peridotites from the MARK area, Mid-Atlantic Ridge: sulfur geochemistry and reaction modeling

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated δ³⁴S_sulfide (3.7 to 12.7‰). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high δ³⁴S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (∼400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ∼300°C. Serpentinization produces highly reducing conditions and significant amounts of H₂ and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in ¹³C (up to 4.5‰) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 × 10¹² g seawater S yr⁻¹. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.     

Laboratory and field evaluation of a flushable oxic limestone drain for treatment of net-acidic drainage from a flooded anthracite mine, Pennsylvania, USA

This paper demonstrates the use of dissolution-rate data obtained in the laboratory to indicate the potential quality of effluent from a field-scale oxic limestone drain (OLD) treatment system for neutralization of dilute acidic mine drainage (AMD). Effluent from the Reevesdale Mine South Dip Tunnel, a large source of AMD and base flow to the Wabash Creek and Little Schuylkill River in the Southern Anthracite Coalfield of east-central Pennsylvania, is representative of AMD with low concentrations but high loadings of dissolved Fe, Al and other metals because of a high flow rate. In January 2003, rapid neutralization of the AMD from the Reevesdale Mine was achieved in laboratory tests of its reaction rate with crushed limestone in closed, collapsible containers (Cubitainers). The tests showed that net-alkaline effluent could be achieved with retention times greater than 3 h and that effluent alkalinities and associated dissolution rates were equivalent for Fe(OH)₃-coated and uncoated limestone. On the basis of the laboratory results, a flushable OLD containing 1450 metric tons of high-purity calcitic limestone followed by two 0.7-m deep wetlands were constructed at the Reevesdale Mine. During the first year of operation, monthly data at the inflow, outflow and intermediate points within the treatment system were collected (April 2006–2007). The inflow to the treatment system ranged from 6.8 to 27.4 L/s, with median pH of 4.7, net acidity of 9.1 mg/L CaCO₃, and concentrations of dissolved Al, Fe and Mn of 1.0, 1.9 and 0.89 mg/L, respectively. The corresponding effluent from the OLD had computed void-volume retention times of 4.5–18 h, with median pH of 6.6, net acidity of −93.2 mg/L CaCO₃, and concentrations of dissolved Al, Fe and Mn of <0.1, 0.08 and 0.52 mg/L, respectively. The wetlands below the OLD were effective for retaining metal-rich solids flushed at monthly or more frequent intervals from the OLD, but otherwise had little effect on the effluent quality. During the first year of operation, approximately 43 metric tons of limestone were dissolved and 2 metric tons of Al, Fe and Mn were precipitated within the OLD. However, because of the accumulation of these metals within the OLD and possibly other debris from the mine, the effectiveness of the treatment system declined. Despite the installation of a flush-pipe network at the base of the OLD to remove precipitated solids, the limestone bed clogged near the inflow. Consequently, a large fraction of the AMD bypassed the treatment system. To promote flow through the OLD, the flush pipes were open continuously during the last 4 months of the study; however, this effluent was only partially treated because short-circuiting through the pipes decreased contact between the effluent and limestone. A reconfiguration of the flow path through the limestone bed from horizontal to vertical upward could increase the limestone surface area exposed to the metal-laden influent, increase the cross-sectional area perpendicular to flow, decrease the flow path for solids removal, and, consequently, decrease potential for clogging.     

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on δ¹⁸O and δ³⁴S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O₂ as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)_aq as an oxidant with varying δ¹⁸O_H2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ∼2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ∼2.7. The δ³⁴S_SO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (∼−0.7‰) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O₂) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O₂ varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (ε¹⁸O_SO4-H2O) of ∼3.5‰ was determined for the anaerobic (biological and abiotic) experiments. This measured value was then used to estimate the oxygen isotope fractionation effects between sulfate and dissolved oxygen in the aerobic experiments which were −10.0‰, −10.8‰, and −9.8‰ for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between δ¹⁸O_SO4 values in the biological and abiotic experiments, it is suggested that δ¹⁸O_SO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)_aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions.