Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay

A combination of CTD casts, discrete bottle sampling and in situ voltammetric microelectrode profiling was used to examine changing redox conditions in the water column at a single station south of the Bay Bridge in the upper Chesapeake Bay in late July/early August, 2002–2005. Short-term (2–4 h) fluctuations in the oxic/suboxic/anoxic interface were documented using in situ voltammetric solid-state electrodes. Profiles of dissolved oxygen and sulfide revealed tidally-driven vertical fluctuations of several meters in the depth and thickness of the suboxic zone. Bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ also varied over the tidal cycle by approximately an order of magnitude. These data indicate that redox species concentrations at this site varied more due to physical processes than biogeochemical processes. Based on analysis of ADCP data, tidal currents at this station were strongly polarized, with the principal axis of tidal currents aligned with the mainstem channel. Together with the chemical data, the ADCP analysis suggests tidal flushing of anoxic bottom waters with suboxic water from north of the site. The present study is thus unique because while most previous studies have focused on processes across relatively stable redox interfaces, our data clearly demonstrate the influence of rapidly changing physical mixing processes on water column redox chemistry.Also noted during the study were interannual differences in maximum bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺. In 2003, for example, heavy spring rains resulted in severe hypoxia/anoxia in June and early July. While reported storm-induced mixing in late July/early August 2003 partially alleviated the low-oxygen conditions, bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ were still much higher than in the previous year. The latter implies that the response time of the microbial community inhabiting the suboxic/anoxic bottom waters to changing redox conditions is slow compared to the time scale of episodic mixing events. Bottom water concentrations of the redox-sensitive chemical species should thus be useful as a tracer to infer prior hypoxic/anoxic conditions not apparent from ambient oxygen levels at the time of sampling.     

Upper Cretaceous carbonate hosted zinc–lead–barite deposits in Northern Thrust Zone, northern Iraq: petrography and geochemistry

Zinc–lead–barite deposits located in Lefan and Lower Banik localities of about 25 km northeast of Zakho City, Northern Iraq consist of a group of strata-bound sulfides hosted in Upper Cretaceous (Upper Campanian–Maastrichtian) dolomitic limestone. Carbonate-hosted ores contain 3.77% Zn, 2% Pb, and 5% Fe, while in lower Banik, they contain 1.5% Zn, 0.37% Pb, and 1.4% Fe. Diagenetic processes, such as dolomitization and recrystalization in addition to the type of microfacies, provided appropriate physical and chemical conditions that permitted the passage of ore-bearing fluids and participated in precipitation and ore localization. These deposits are precipitated in a platform and developed within the Foreland Thrust Belt. Ore precipitated as infill of intergranular dolomite porosity with replaced dolomite and rudist shells forming disseminated crystals that occupy intergranular pore spaces around dolomite and calcite and as infill of dissolution spaces and fractures.     

Sulfide oxidation—an environmental problem within colliery spoil dumps

Because of the high degree of automation in the coal mining industry in the Ruhr area, Germany, about 1 metric ton of crushed rock/colliery spoil is brought to the surface for every metric ton of coal. Most of the colliery spoil disposed of must be dumped. These colliery spoil dumps are anthropogenic geological sediment bodies, which have a characteristic facies resulting from geological, technical, and economical factors connected with the formation of the dumps. The relation between the facies of the dumps and these factors, for example, is examplified with the pyrite content within the colliery spoil. Pyrite content within the dumps is dependent both on the conditions during sedimentation and (early) diagenesis and the techniques used for mining and processing. Thus, this geologic-technical facies of the dumps controls the weathering processes on and in dumps. These humaninduced processes are mainly responsible for the environmental impact on soil and groundwater. Oxidation of pyrite as well as alteration of pyrite under anoxic conditions yields dissolution of carbonates, accompanied by gypsum formation, by acid attack and strong acidification takes place.     

Magma evolution and the formation of porphyry Cu–Au ore fluids: evidence from silicate and sulfide melt inclusions

Silicate and sulfide melt inclusions from the andesitic Farallón Negro Volcanic Complex in NW Argentina were analyzed by laser ablation ICPMS to track the behavior of Cu and Au during magma evolution, and to identify the processes in the source of fluids responsible for porphyry-Cu-Au mineralization at the 600 Mt Bajo de la Alumbrera deposit. The combination of silicate and sulfide melt inclusion data with previously published geological and geochemical information indicates that the source of ore metals and water was a mantle-derived mafic magma that contained approximately 6 wt.% H₂O and 200 ppm Cu. This magma and a rhyodacitic magma mixed in an upper-crustal magma chamber, feeding the volcanic systems and associated subvolcanic intrusions over 2.6 million years. Generation of the ore fluid from this magma occurred towards the end of this protracted evolution and probably involved six important steps: (1) Generation of a sulfide melt upon magma mixing in some parts of the magma chamber. (2) Partitioning of Cu and Au into the sulfide melt (enrichment factor of 10,000 for Cu) leading to Cu and Au concentrations of several wt.% or ppm, respectively. (3) A change in the tectonic regime from local extension to compression at the end of protracted volcanism. (4) Intrusion of a dacitic magma stock from the upper part of the layered magma chamber. (5) Volatile exsolution and resorption of the sulfide melt from the lower and more mafic parts of the magma chamber, generating a fluid with a Cu/Au ratio equal to that of the precursor sulfide. (6) Focused fluid transport and precipitation of the two metals in the porphyry, yielding an ore body containing Au and Cu in the proportions dictated by the magmatic fluid source. The Cu/S ratio in the sulfide melt inclusions requires that approximately 4,000 ppm sulfur is extracted from the andesitic magma upon mixing. This exceeds the solubility of sulfide or sulfate in either of the silicate melts and implies an additional source for S. The extra sulfur could be added in the form of anhydrite phenocrysts present in the rhyodacitic magma. It appears, thus, that unusually sulfur-rich, not Cu-rich magmas are the key to the formation of porphyry-type ore deposits. Our observations imply that dacitic intrusions hosting the porphyry–Cu–Au mineralization are not representative of the magma from which the ore-fluid exsolved. The source of the ore fluid is the underlying more mafic magma, and unaltered andesitic dikes emplaced immediately after ore formation are more likely to represent the magma from which the fluids were generated. At Alumbrera, these andesitic dikes carry relicts of the sulfide melt as inclusions in amphibole. Sulfide inclusions in similar dykes of other, less explored magmatic complexes may be used to predict the Au/Cu ratio of potential ore-forming fluids and the expected metal ratio in any undiscovered porphyry deposit.Editorial handling: B. Lehmann     

Sulfide evolution in high-temperature to ultrahigh-temperature metamorphic rocks from Lützow–Holm Complex, East Antarctica

The high-temperature (HT) to ultrahigh-temperature (UHT) metamorphic rocks from Lützow–Holm Complex, East Antarctica show a systematic difference between sulfide assemblages in the rock matrix and those found as inclusions in the silicates stable in high-temperatures. Matrix sulfides are commonly pyrite with or without pentlandite and chalcopyrite. On the other hand, inclusion sulfides are pyrrhotite with or without pentlandite and chalcopyrite lamellae. When recalculated into integrated single-phase sulfide compositions, inclusion sulfides from the UHT region showed a wider range of solid–solution composition than the inclusion sulfides from the HT region. The host minerals of the sulfides with extreme solid–solution compositions are those stable at the peak of metamorphism such as orthopyroxene and garnet. One of the most extreme ones is included in orthopyroxene coexisting with sillimanite ± quartz, which is the diagnostic mineral assemblage of UHT metamorphism. These observations suggest that sulfide inclusions preserve their peak metamorphic compositions. Pyrrhotite did not revert to pyrite because of the closed system behavior of sulfur in inclusion sulfides. On the other hand, in the rock matrix where the open system behavior of sulfur is permitted, original sulfides were partly to completely altered by the later fluid activity.     

Water-rock-tailings interactions and sources of sulfur and metals in the subtropical mining region of Taxco,Guerrero (southern Mexico): A multi-isotopic approach

Multi-isotope (H, O, S, Sr, Pb) systems coupled with conventional (major and trace element) hydrogeochemical analysis were applied to determine the origin of water, to model water-rock-tailings interactions and for source apportionment of sulfur and associated toxic metals in the mining region of Taxco, Guerrero in southern Mexico. Oxygen and H isotopes indicate that meteoric water in the zone is rainwater undergoing varying degrees of isotopic fractionation by atmospheric evaporation whereas Sr isotopes trace the interaction of pristine water from volcanics of the regional recharge zone and subsequently flowing through sandstone and shale to spring points. Leachates form from two distinctive sources (spring water and surface water) having differential interactions with bedrocks prior to entering the tailings. Compared to pristine water, leachates are enriched in sulfate, metals (e.g. Fe, Mn, Pb and Zn) and metalloids (e.g. As). The sulfur isotopic composition of ore-sulfides, leachates, secondary precipitates, regional surface water and hypogenic sulfates is described in terms of a two-component mixing model with shale of Mexcala and limestone of Morelos formations representing the light and heavy end-members, respectively, whereas Sr isotopic composition is bracketed combining three lithogenic (Mexcala/Morelos, Tilzapotla and Taxco Schist) sources. Finally, leachates have a mixture of lead from ore-sulfides and Taxco Schist Formation (Family I) or from ore-sulfides alone (Family II). The application of multiple environmental isotopic techniques is an outstanding tool for elucidating complex interactions of water with bedrocks and tailings and for determining the source of sulfur and toxic metal from mining and other metal polluted environments.     

Methylmercury production in sediments of Chesapeake Bay and the mid-Atlantic continental margin

Methylmercury (MeHg) concentration and production rates were studied in bottom sediments along the mainstem of Chesapeake Bay and on the adjoining continental shelf and slope. Our objectives were to 1) observe spatial and temporal changes in total mercury (HgT) and MeHg concentrations in the mid-Atlantic coastal region, 2) investigate biogeochemical factors that affect MeHg production, and 3) examine the potential of these sediments as sources of MeHg to coastal and open waters. Estuarine, shelf and slope sediments contained on average 0.5 to 1.5% Hg as MeHg (% MeHg), which increased significantly with salinity across our study site, with weak seasonal trends. Methylation rate constants (k_meth), estimated using enriched stable mercury isotope spikes to intact cores, showed a similar, but weaker, salinity trend, but strong seasonality, and was highly correlated with % MeHg. Together, these patterns suggest that some fraction of MeHg is preserved thru seasons, as found by others [Orihel, D.M., Paterson, M.J., Blanchfield, P.J., Bodaly, R.A., Gilmour, C.C., Hintelmann, H., 2008. Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem. Environmental Pollution 154, 77] Similar to other ecosystems, methylation was most favored in sediment depth horizons where sulfate was available, but sulfide concentrations were low (between 0.1 and 10 μM). MeHg production was maximal at the sediment surface in the organic sediments of the upper and mid Bay where oxygen penetration was small, but was found at increasingly deeper depths, and across a wider vertical range, as salinity increased, where oxygen penetration was deeper. Vertical trends in MeHg production mirrored the deeper, vertically expanded redox boundary layers in these offshore sediments. The organic content of the sediments had a strong impact on the sediment:water partitioning of Hg, and therefore, on methylation rates. However, the HgT distribution coefficient (K_D) normalized to organic matter varied by more than an order of magnitude across the study area, suggesting an important role of organic matter quality in Hg sequestration. We hypothesize that the lower sulfur content organic matter of shelf and slope sediments has a lower binding capacity for Hg resulting in higher MeHg production, relative to sediments in the estuary. Substantially higher MeHg concentrations in pore water relative to the water column indicate all sites are sources of MeHg to the water column throughout the seasons studied. Calculated diffusional fluxes for MeHg averaged  1 pmol m^− 2 day^− 1. It is likely that the total MeHg flux in sediments of the lower Bay and continental margin are significantly higher than their estimated diffusive fluxes due to enhanced MeHg mobilization by biological and/or physical processes. Our flux estimates across the full salinity gradient of Chesapeake Bay and its adjacent slope and shelf strongly suggest that the flux from coastal sediments is of the same order as other sources and contributes substantially to the coastal MeHg budget.     

A comparative mineralogical and geochemical study of sulfide mine tailings at two sites in New Mexico, USA

A comparative study of sulfide mine tailings from two sites near Silver City in southwest New Mexico has shown the need for environmental monitoring in a geological context. The Cyprus-Piños Altos and Cleveland deposits consist of Cu and Zn skarn mineralization in the Piños Altos Mountains of New Mexico. Primary ore minerals in both deposits include chalcopyrite, sphalerite, and galena. The Cyprus-Piños Altos Mine ceased operation in 1995 and the Cleveland Mill closed in 1950. The deposits have similar mineralogical characteristics; however, the tailings are different in terms of age, degree of oxidation and method of disposal. The Cyprus-Piños Altos tailings (CPAT) are stored in a lined, bermed impoundment. They are dominantly water-saturated and exhibit no secondary-phase formation. The grains are not cemented and show no evidence of primary-mineral dissolution. The geochemical data show a predominantly primary signature. The tailings pond water is neutral to slightly alkaline (pH?from 7 to 8.3), partly as a result of processing methods. The Cleveland mill tailings (CMT) were deposited in a valley at the headwaters of an ephemeral stream. They are highly oxidized and differentially cemented. They have undergone numerous wet/dry cycles resulting in extensive oxidation. Secondary minerals predominate, and consist mainly of jarosite, goethite, hematite, and Fe-oxyhydroxides and -oxyhydroxysulfates. The pH of the stream draining the CMT is as high as 2.15. Maximum metal contents in the stream immediately downstream from the tailings are 5305?ppm Zn, 454?ppm Cu, 1.16?ppm Pb, 17.5?ppm Cd, 1.4?ppm As, and 0.01?ppm Hg.     

云南巧家仓房沟铅锌矿矿床成矿模式

铅锌矿赋存于灯影组硅质条带白云岩中,局部产于筇竹寺组,脉状、透镜状,与峨眉山玄武岩喷发关系密切,属岩浆晚期热液成因。     

吉林延边红太平铜多金属矿床脉型矿化的成矿时代与构造背景

吉林延边红太平铜多金属矿床位于兴蒙造山带东段,区内发育产于晚古生代火山沉积岩系中的层状铜多金属矿体和受岩体及构造控制的脉状铅锌矿体。为了确定脉型铅锌矿化的成矿时代与构造背景,本文对与脉状铅锌矿体相关的英安岩开展了LA-ICP-MS锆石U-Pb定年及岩石地球化学研究,并对脉状铅锌矿体中金属硫化物开展了Rb-Sr同位素定年。结果表明,英安岩中28个锆石测点的~(206)Pb/~(238)U加权平均年龄为204.1±2.0Ma(MSWD=0.24),脉状铅锌矿石中4件金属硫化物的Rb-Sr等时线年龄为206.8±9.0Ma(MSWD=2.0),二者在误差范围内基本一致,表明红太平矿床脉型铅锌矿化的成矿时代为晚三叠世末期。英安岩的稀土元素配分模式呈明显的轻稀土元素(LREEs)富集,轻重稀土分馏明显[(La/Yb)N=7.59～8.28],存在弱的Eu异常(δEu=0.65～0.68);微量元素以富集大离子亲石元素(LILEs:Rb、Ba和K)和不相容元素(U、Th),亏损高场强元素(HFSEs:Nb、Ta、P和Ti)为特征,表明原始岩浆应为壳-幔混源;脉状铅锌矿体中4件金属硫化物初始Sr同位素比值(87Sr/86Sr)i为0.705954～0.707101(均值0.706390),表明脉型铅锌矿化与壳-幔混源的岩浆作用密切相关。根据Rb-(Yb+Ta)及La/Yb-Th/Yb图解判别结果,结合区域构造演化分析,认为红太平矿区英安岩及相关的脉型铅锌矿化形成于活动大陆边缘的构造环境,与晚三叠世-早侏罗世(T_3-J_1)古太平洋板块向欧亚板块的俯冲作用密切相关。