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Quartz solubility in the H2O-NaCl system: A framework for understanding vein formation in porphyry copper deposits

Porphyry copper deposits consist of low-grade stockwork and disseminated sulfide zones that contain characteristic vein generations formed during the evolution of the magmatic-hydrothermal systems. The present contribution proposes an interpretive framework for the formation of porphyry veins that is based on quartz solubility calculations in the H 2 O-NaCl system at temperatures of 100° to 1,000°C and pressures of 1 to 2,000 bar. The model predicts that high-temperature (≳500°C) quartz in A veins of deep (≳4 km) porphyry deposits forms as a result of the cooling of ascending intermediate-density fluids at lithostatic conditions. In deposits of intermediate depths (~1.5–4 km), A vein quartz is mostly formed through cooling of ascending hydrothermal fluids under closed-system conditions or quasi-isobaric cooling under open-system conditions within the two-phase field of the H 2 O-NaCl system. In shallow (≲1.5 km) porphyry deposits, rapid decompression can also result in quartz precipitation, forming so-called banded veins. The high-temperature quartz in A veins is associated with potassic alteration. During continued cooling of the magmatic-hydrothermal system, quartz is formed at intermediate temperatures (≳375°–500°C). This quartz overprints earlier A veins and forms B veins. The fluid inclusion inventory of this quartz generation suggests formation at fluctuating pressure conditions, marking the lithostatic to hydrostatic transition, and the change of wall-rock behavior from ductile to brittle conditions. The quartz is precipitated because of cooling and decompression of the magmatic-hydrothermal fluids under K-feldspar-stable conditions. Textural evidence from many porphyry veins suggests that hypogene sulfide minerals present in A and B veins postdate the quartz, as contacts between quartz and sulfide minerals commonly show dissolution textures. Hypogene sulfide minerals in C veins form at conditions of retrograde quartz solubility, explaining why these veins contain little to no quartz. The quartz solubility calculations suggest that C vein formation occurs at temperatures of ~375° to 450°C from low-salinity, single-phase fluids escaping from the lithostatic to the hydrostatic environment. At the upper end of this temperature range, C veins are biotite stable. However, these veins are associated with chlorite, chlorite-K-feldspar, or chlorite-sericite alteration in most deposits. Late quartz is formed during continued cooling of the hydrothermal fluids at ≲375°C within the single-phase field of the H 2 O-NaCl system as quartz solubility under these conditions decreases with temperature. This process is responsible for the formation of quartz in D veins and later base metal-bearing E veins, which are associated with phyllic, advanced argillic, or argillic alteration.

Economic Geology↗

Organic-carbon sequestration in soil/sediment of the Mississippi River deltaic plain — Data; landscape distribution, storage, and inventory; accumulation rates; and recent loss, including a post-Katrina preliminary analysis

Soil/sediment of the Mississippi River deltaic plain (MRDP) in southeastern Louisiana is rich in organic carbon (OC). The MRDP contains about 2 percent of all OC in the surface meter of soil/sediment in the Mississippi River Basin (MRB). Environments within the MRDP differ in soil/sediment organic carbon (SOC) accumulation rate, storage, and inventory. The focus of this study was twofold: (1) develop a database for OC and bulk density for MRDP soil/sediment; and (2) estimate SOC storage, inventory, and accumulation rates for the dominant environments (brackish, intermediate, and fresh marsh; natural levee; distributary; backswamp; and swamp) in the MRDP. Comparative studies were conducted to determine which field and laboratory methods result in the most accurate and reproducible bulk-density values for each marsh environment. Sampling methods included push-core, vibracore, peat borer, and Hargis1 sampler. Bulk-density data for cores taken by the "short push-core method" proved to be more internally consistent than data for samples collected by other methods. Laboratory methods to estimate OC concentration and inorganic-constituent concentration included mass spectrometry, coulometry, and loss-on-ignition. For the sampled MRDP environments, these methods were comparable. SOC storage was calculated for each core with adequate OC and bulk-density data. SOC inventory was calculated using core-specific data from this study and available published and unpublished pedon data linked to SSURGO2 map units. Sample age was estimated using isotopic cesium ( 37 Cs), lead ( 210 Pb), and carbon ( 14 C), elemental Pb, palynomorphs, other stratigraphic markers, and written history. SOC accumulation rates were estimated for each core with adequate age data. Cesium-137 profiles for marsh soil/sediment are the least ambiguous. Levee and distributary 137 Cs profiles show the effects of intermittent allochthonous input and/or sediment resuspension. Cesium-137 and 210 Pb data gave the most consistent and interpretable information for age estimations of soil/sediment deposited during the 1900s. For several cores, isotopic 14 C and 137 Cs data allowed the 1963-64 nuclear weapons testing (NWT) peak-activity datum to be placed within a few-centimeter depth interval. In some cores, a too old 14 C age (when compared to 137 Cs and microstratigraphic-marker data) is the probable result of old carbon bound to clay minerals incorporated into the organic soil/sediment. Elemental Pb coupled with Pb source-function data allowed age estimation for soil/sediment that accumulated during the late 1920s through the 1980s. Exotic pollen (for example, Vigna unguiculata and Alternanthera philoxeroides ) and other microstratigraphic indicators (for example, carbon spherules) allowed age estimations for marsh soil/sediment deposited during the settlement of New Orleans (1717-20) through the early 1900s. For this study, MRDP distributary and swamp environments were each represented by only one core, backswamp environment by two cores, all other environments by three or more cores. MRDP core data for the surface meter soil/sediment indicate that (1) coastal marshes, abandoned distributaries, and swamps have regional SOC-storage values >16 kg m -2 ; (2) swamps and abandoned distributaries have the highest SOC storage values (swamp, 44.8 kg m -2 ; abandoned distributary, 50.9 kg m -2 ); (3) fresh-to-brackish marsh environments have the second highest site-specific SOC-storage values; and (4) site-specific marsh SOC storage values decrease as the salinity of the environment increases (fresh-marsh, 36.2 kg m -2 ; intermediate marsh, 26.2 kg m -2 ; brackish marsh, 21.5 kg m -2 ). This inverse relation between salinity and SOC storage is opposite the regional systematic increase in SOC storage with increasing salinity that is evident when SOC storage is mapped by linking pedon data to SSURGO map units (fresh marsh, 47 kg m -2 ; intermediate marsh, 67 kg m -2 ; brackish marsh, 75 kg m -2 ; and salt marsh, 80 kg m -2 ). MRDP core data for this study also indicate that levees and backswamp have regional SOC-storage values <16 kg m -2 . Group-mean SOC storage for cores from these environments are natural levee (17.0 kg m -2 ) and backswamp (14.1 kg m -2 ). An estimate for the SOC inventory in the surface meter of soil/sediment in the MRDP can be made using the SSURGO mapped portion of the coastal-marsh vegetative-type map (13,236 km 2 , land-only area) published by the Louisiana Department of Wildlife and Fisheries and U.S. Geological Survey (1997). This area has a SOC inventory (surface meter) of 677 Tg (slightly more than 2 percent of the 30,289 Tg SOC inventory for the MRB). The MRDP (6,180 km2, land-only area) has an estimated SOC inventory of 397 Tg. Most of the MRDP is located within the SSURGO mapped coastal marshlands. The entire MRDP, including water, has an area of about 10,800 km 2 . Using the ratio of total MRDP area to SSURGO mapped MRDP area as an adjustment, the MRDP SOC inventory is estimated at 694 Tg. This larger estimate of 694 Tg for the SOC inventory is probably more realistic, because it is reasonable to assume that the marsh sediments overlain by shallow water have comparable SOC storage to that of the adjacent land areas. MRDP core data for this study indicate that there is some variability in long-term SOC mass-accumulation rates for centuries and millennia and that this variability may indicate important geologic changes or changes in land use. However, the consistency of the range in rates of SOC accumulation through time suggests a remarkable degree of marsh sustainability throughout the Holocene, including the recent period of significant marsh modification/channelization for human use. One example of marsh sustainability is its present ability to function as a SOC sink even with Louisiana's large-scale coastal land loss during the last several decades. With coastal-marsh restoration efforts, this sink potential will increase. Looking to the future, a total of 1,101 g m -2 yr -1 SOC is projected to be lost from all of coastal Louisiana (U.S. Army Corps of Engineers, Louisiana Coastal Area (LCA) subprovinces 1-4; not just the MRDP) through coastal erosion from year 2000 to 2050. This translates to a projected SOC-loss rate of about 0.20 percent per year. The recent Hurricanes Katrina and Rita, which devastated the Louisiana coast during late August and late September 2005, transformed about 259 km 2 (100 mi 2 ) of marsh to open water (U.S. Geological Survey, 2005). To the extent that some or all of this land loss is permanent, this result equates to a SOC loss of about 15 Tg. This estimate is based on the year-2000 15,153-km 2 land area for the LCA study area that includes LCA subprovince 4. Using the year-2000 land area, the LCA study area had an estimated SOC inventory of 858 Tg. The estimated 15 Tg SOC loss attributable to Hurricanes Katrina and Rita is 1.7 percent of the year-2000 LCA inventory and 2.3 percent of the year-2000 MRDP inventory. If this SOC loss is included in the projection for the year 2050, then the MRDP would either remain a source with a net SOC loss of 3 Tg or become a weak sink with a net SOC gain of 4 Tg. These estimates are lower bounds for potential SOC flux because they are only for the surface meter of landmass.

Louisiana↗

Isotopic composition of pyrite: Relationship to organic matter type and iron availability in some North American cretaceous shales

The S isotope composition of pyrite in Cretaceous shales from the Western Interior of North America is related to organic C abundance, kerogen type and Fe availability. Both calcareous and noncalcareous rocks show a correlation between S and C, but noncalcareous rocks are relatively enriched in S with a higher S/C ratio. This higher ratio probably shows that pyrite formation was Fe limited in the calcareous rocks. Organic-carbon-rich noncalcareous shales accumulated slowly beneath anoxic bottom waters. The anoxic bottom waters allowed hydrogen-rich organic matter to be preserved. Such shales have a narrow range of 34 S-depleted sulfide and have Fe/S ratios like stoichiometric pyrite, suggesting that pyrite formation in organic-rich shales was also limited by Fe availability. Conversely, organic-poor shales commonly accumulated at comparatively high rates, contain hydrogen-poor and refractory organic matter, and have a wide range of pyrite-S isotopic compositions. These organic-poor shales contain post-sulfidic authigenic minerals such as siderite and have excess reactive Fe rather than pyrite stoichiometry. Evidently Fe played a large role in early diagenesis and determined the course of post-sulfidic diagenesis. Fe availability was, however, mainly controlled by provenance, by the rates of sediment accumulation, and by the oxygen content of the depositional environment.

Chemical Geology: Isotope Geoscience Section↗

Fluid inclusion gas chemistry as a potential minerals exploration tool: Case studies from Creede, CO, Jerritt Canyon, NV, Coeur d'Alene district, ID and MT, southern Alaska mesothermal veins, and mid-continent MVT's

Recent advances in instrumentation now permit quantitative analysis of gas species from individual fluid inclusions. Fluid inclusion gas data can be applied to minerals exploration empirically to establish chemical (gas composition) signatures of the ore fluids, and conceptually through the development of genetic models of ore formation from a framework of integrated geologic, geochemical, and isotopic investigations. Case studies of fluid inclusion gas chemistry from ore deposits representing a spectrum of ore-forming processes and environments are presented to illustrate both the empirical and conceptual approaches. We consider epithermal silver-gold deposits of Creede, Colorado, Carlin-type sediment-hosted disseminated gold deposits of Jerritt Canyon, Nevada, metamorphic silver-base-metal veins of the Coeur d'Alene district, Idaho and Montana, gold-quartz veins in accreted terranes of southern Alaska, and the mid-continent base-metal sulfide deposits of Mississippi Valley-Type (MVT's). Variations in gas chemistry determine the redox state of the ore fluids, provide compositional input for gas geothermometers, characterize ore fluid chemistry (e.g., CH 4 CO 2 , H 2 SSO 2 , CO 2 /H 2 S, organic-rich fluids, gas-rich and gas-poor fluids), identify magmatic, meteoric, metamorphic, shallow and deep basin fluids in ore systems, locate upwelling plumes of magmatic-derived volatiles, zones of boiling and volatile separation, interfaces between contrasting fluids, and important zones of fluid mixing. Present techniques are immediately applicable to exploration programsas empirical studies that monitor fluid inclusion gas threshold concentration levels, presence or absence of certain gases, or changes in gas ratios. We suggest that the greater contribution of fluid inclusion gas analysis is in the integrated and comprehensive chemical dimension that gas data impart to genetic models, and in the exploration concepts based on processes and environments of ore formation derived from these genetic models.

Journal of Geochemical Exploration↗

Petrogenesis of the Superstition-Superior volcanic area as inferred from strontium- and oxygen-isotope studies

Apparent initial Sr 87 /Sr 86 ratios of five ash-flow tuffs (0.7063 to 0.7139) and several mafic to silicic lavas (0.7055 to 0.7131) indicate that the magmas were derived below the base of the Precambrian granitic crust (0.7231 to 1.0906). Liquidus compositions in the system Q-Or-Ab-H 2 O and oxygen-isotope geother-mometry suggest that the silicic magmas started to crystallize quartz, magnetite, and two feldspars in a water-undersaturated environment of high pressure (∼10 kb) and moderate temperature of at least 830°C. During or after ascent into the crust, the magmas underwent varying degrees of crystal-melt re-equilibration. Measured plagioclase-biotite O 18 fractionations (0.5 to 0.7) imply a temperature that is too high for the observed mineral assemblage, and the inference is that the two minerals did not crystallize in equilibrium. Prior to eruption, the upper part of the magma column assimilated crustal Sr such that the base of each ash flow is now enriched in Sr 87 . In some cases, this assimilation was too rapid to allow crystal-melt equilibration of Sr isotopes. δO 18 values for the magmas are within the range typical of similar magma types, indicating that no significant interaction took place between the melts and meteoric water; however, some rocks have exchanged oxygen isotopes with meteoric water at low temperatures after eruption. Some of the magma appears to have had a long residence in the crust at lower pressure (1 kb) and temperature (750°C), because two of the ash-flow tuffs and one lava are greatly enriched in Sr 87 and have largely re-equilibrated under the P-T conditions of a shallow magma chamber. Even these, however, have retained evidence for a multistage genesis.

Geological Society of America Bulletin↗

Insights into glendonite formation from the upper Oligocene Sagavanirktok Formation, North Slope, Alaska

The type locality for the upper Oligocene Nuwok Member of the Sagavanirktok Formation (Carter Creek, North Slope, Alaska, USA) contains abundant occurrence of glendonite, a pseudomorph after the calcium carbonate mineral ikaite, which typically forms in the shallow subsurface of cold marine sediments. The region during the time of Nuwok Member deposition was located at a high latitude, similar to today, and the study site is characterized by sands and silty muds interpreted here to have been deposited in coastal and shelfal marine environments. Isotopic (Sr) and biostratigraphic (foraminifera) evidence presented here refine the depositional age of the outcrop to approximately 24 Ma. Glendonites occur in two basic forms: radial clusters, commonly centered around a single larger primary crystal ( approx. 10 cm; Type A) and larger single blades generally without accessory crystals (approx. 15–25 cm; Type B). Microscopic examination revealed a sequence of multiple types of replacive calcite that formed as a direct result of ikaite transformation: Type 1 rhombohedral crystals characterized by microporous and inclusion-rich cores and concentric zones, Type 2A, composed of clear calcite that overgrew and augmented Type 1 crystals, and inclusion-rich, microcrystalline Type 2B, which formed a matrix surrounding the rhombs and commonly dominates the outer rims of glendonite specimens. Type 3 calcite precipitated as fibrous, botryoidal epitaxial cement atop previous phases and is not ikaite-derived. These phases are distributed in similar ways in all examined specimens and are consistent with several previously described glendonite occurrences around the world, despite differing diagenetic and geologic histories. Stable isotope evidence (δ13C and δ18O) suggests sourcing of glendonite carbon from both organic and methanogenic sources. Glendonites of the Nuwok Member can therefore assist in the determination of a more comprehensive ikaite transformation model, improving our understanding of glendonite formation and the sedimentological and environmental context of their occurrence. Oligocene glendonites are uncommon globally; the well-preserved occurrence described here can allow future studies to better reconstruct Arctic environmental conditions and paleoclimates during this time.

Alaska↗

Alteration and vein mineralization, Ladwig uranium mine, Jefferson County, Colorado

Uranium ore at the Ladwig mine, Jefferson County, Colo., occurs in steeply dipping, northwest-striking faults and related fractures with a carbonate-adularia assemblage that forms in altered wallrocks and fills veins. The faults occur between large intrusive pegmatites and garnetiferous gneisses of Precambrian age, and were reactivated as the result of the early Paleocene uplift of the Front Range foothills. Mineralization in the deposit includes both wallrock alteration and vein filling. Alteration was intense but local, and chiefly involved the carbonatization of mafic minerals in the wallrocks. Felsic minerals in the wallrocks are relatively unaltered. The veins are filled with an adularia-pitchblende-carbonate assemblage with minor related sulfides and coffinite. Many of the iron-bearing carbonates in both the alteration and vein assemblages have been altered to hematite. The mineralization and alteration are believed to have formed in response to initially high amounts of CO2 and the subsequent release of dissolved CO2 by boiling or effervescence. Uranium, carried in a dicarbonate complex, was precipitated directly as pitchblende when the CO2 was released. The expulsion of H+ during boiling created a net oxidizing environment which oxidized the iron-bearing carbonates. Late stage calcite and sulfides were deposited in existing voids in the veins.

Open-File Report↗

Seamount mineral deposits: A source of rare metals for high technology industries

The near exponential growth in Earth’s population and the global economy puts increasing constraints on our planet’s finite supply of natural metal resources, and, consequently, there is an increasing need for new sources to supply high-tech industries. To date, effectively all of our raw-metal resources are produced at land-based sites. Except for nearshore placer deposits, the marine environment has been largely excluded from metal mining due to technological difficulties, even though it covers more than 70% of the planet. The case can be made that deep-water seabed mining is inevitable in the future, owing to the critical and strategic metal needs for human society. In this paper, we evaluate the case that seamounts offer significant potential for mining.

Oceanography↗

Mars orbiter for resources, ices, and environments (MORIE)

The MORIE mission concept study examined the science and technical trade space to address high priority questions related to ice reservoirs and environmental transitions. The study team converged on a medium-class SEP-enabled orbiter with seven instruments to unlock the extent and volume of subsurface ice and geologic sequence stratigraphy through time. Observations would include the first radar imaging from orbit, the first radar sounding directly over the poles, and surface mineral mapping at unprecedented spatial scales.

Planetary Science Decadal Survey, Planetary Missio↗

Strontium isotopic signatures of the streams and lakes of Taylor Valley, Southern Victoria Land, Antarctica: Chemical weathering in a polar climate

We have collected and analyzed a series of water samples from three closed-basin lakes (Lakes Bonney, Fryxell, and Hoare) in Taylor Valley, Antarctica, and the streams that flow into them. In all three lakes, the hypolimnetic waters have different 87Sr/86Sr ratios than the surface waters, with the deep water of Lakes Fryxell and Hoare being less radiogenic than the surface waters. The opposite occurs in Lake Bonney. The Lake Fryxell isotopic ratios are lower than modern-day ocean water and most of the whole-rock ratios of the surrounding geologic materials. A conceivable source of Sr to the system could be either the Cenozoic volcanic rocks that make up a small portion of the till deposited in the valley during the Last Glacial Maximum or from marble derived from the local basement rocks. The more radiogenic ratios from Lake Bonney originate from ancient salt deposits that flow into the lake from Taylor Glacier and the weathering of minerals with more radiogenic Sr isotopic ratios within the tills. The Sr isotopic data from the streams and lakes of Taylor Valley strongly support the notion documented by previous investigators that chemical weathering has been, and is currently, a major process in determining the overall aquatic chemistry of these lakes in this polar desert environment.

Aquatic Geochemistry↗

A synthesis of Martian aqueous mineralogy after 1 Mars year of observations from the Mars Reconnaissance Orbiter

Martian aqueous mineral deposits have been examined and characterized using data acquired during Mars Reconnaissance Orbiter's (MRO) primary science phase, including Compact Reconnaissance Imaging Spectrometer for Mars hyperspectral images covering the 0.4-3.9 ??m wavelength range, coordinated with higher-spatial resolution HiRISE and Context Imager images. MRO's new high-resolution measurements, combined with earlier data from Thermal Emission Spectrometer; Thermal Emission Imaging System; and Observatoire pour la Min??ralogie, L'Eau, les Glaces et l'Activiti?? on Mars Express, indicate that aqueous minerals are both diverse and widespread on the Martian surface. The aqueous minerals occur in 9-10 classes of deposits characterized by distinct mineral assemblages, morphologies, and geologic settings. Phyllosilicates occur in several settings: in compositionally layered blankets hundreds of meters thick, superposed on eroded Noachian terrains; in lower layers of intracrater depositional fans; in layers with potential chlorides in sediments on intercrater plains; and as thousands of deep exposures in craters and escarpments. Carbonate-bearing rocks form a thin unit surrounding the Isidis basin. Hydrated silica occurs with hydrated sulfates in thin stratified deposits surrounding Valles Marineris. Hydrated sulfates also occur together with crystalline ferric minerals in thick, layered deposits in Terra Meridiani and in Valles Marineris and together with kaolinite in deposits that partially infill some highland craters. In this paper we describe each of the classes of deposits, review hypotheses for their origins, identify new questions posed by existing measurements, and consider their implications for ancient habitable environments. On the basis of current data, two to five classes of Noachian-aged deposits containing phyllosilicates and carbonates may have formed in aqueous environments with pH and water activities suitable for life. Copyright 2009 by the American Geophysical Union.

Journal of Geophysical Research E: Planets↗

Sediment parameters for a fine-grained sediment deposit on the southeastern New England continental shelf

An area of fine-grained sediments south of Martha's Vineyard, Massachusetts, has been interpreted as a contemporary deposit. Textural analysis of cores from this area indicates that the deposit consists of sandy to clayey silts overlying a well sorted relict sand. The maximum thickness of the fine sediments is about 6 meters as determined from a core near the center of this deposit. The mineralogy of the <2 um size fraction is similar in both the fine sediments of the contemporary deposit and the underlying coarse sands. The assemblage consists of about 60% illite, 20% chlorite, and 10% kaolinite with minor amounts of mixed-layered clay and smectites. Heavy mineral analysis from a core near the center of the deposit reveals that opaque minerals, framboidal pyrite, muscovite, hornblende, garnet, and tourmaline constitute over 65% of the total downcore assemblage. Pyrite concentrations vary widely at some intervals and may reflect areas of micro-reducing conditions within the core or changes in source area with time. A persistent mica content indicates the presence of a low-energy environment throughout the depositional history of these fine sediments. Downcore organic carbon concentrations are generally uniform in the fine sediments and average about 1.5 percent. Surficial concentration from a core near the center of this feature is about 10 times greater than concentrations for coarse-grained sands on the surrounding shelf.

New England continental shelf↗

Conceptual models in exploration geochemistry-The Basin and Range Province of the Western United States and Northern Mexico

This summary of geochemical exploration in the Basin and Range Province is another in the series of reviews of geochemical-exploration applications covering a large region; this series began in 1975 with a summary for the Canadian Cordillera and Canadian Shield, and was followed in 1976 by a similar summary for Scandinavia (Norden). Rather than adhering strictly to the type of conceptual models applied in those papers, we have made use of generalized landscape geochemistry models related to the nature of concealment of ore deposits. This study is part of a continuing effort to examine and evaluate geochemical-exploration practices in different areas of the world. Twenty case histories of the application of geochemical exploration in both district and regional settings illustrate recent developments in techniques and approaches. Along with other published reports these case histories, exemplifying generalized models of concealed deposits, provide data used to evaluate geochemical-exploration programs and specific sample media. Because blind deposits are increasingly sought in the Basin and Range Province, the use of new sample media or anomaly-enhancement techniques is a necessity. Analysis of vapors or gases emanating from blind deposits is a promising new technique. Certain fractions of stream sediments show anomalies that are weak or not detected in conventional minus 80-mesh fractions. Multi-element analysis of mineralized bedrock may show zoning patterns that indicate depth or direction of ore. Examples of the application of these and other, more conventional methods are indicated in the case histories. The final section of this paper contains a brief evaluation of the applications of all types of sample media to geochemical exploration in the arid environment of the Basin and Range Province. ?? 1978.

Journal of Geochemical Exploration↗

Sulfur isotope geochemistry of ore and gangue minerals from the Silesian-Cracow Mississippi Valley-type ore district, Poland

Studies of the sulfur isotopic composition of ore and gangue minerals from the Silesian-Cracow Zn-Pb district were conducted to gain insights into processes that controlled the location and distribution of the ore deposits. Results of this study show that minerals from the Silesian-Cracow ore district have the largest range of sulfur isotope compositions in sulfides observed from any Mississippi Valley-type ore district in the world. The ??34S values for sulfide minerals range from +38 to -32 per mil for the entire paragenetic sequence but individual stages exhibit smaller ranges. There is a well developed correlation between the sulfur isotope composition and paragenetic stage of ore deposition. The first important ore stage contains mostly positive ??34S values, around 5 per mil. The second stage of ore formation are lower, with a median value of around -5 to -15 per mil, and with some values as low as -32 per mil. Late stage barite contains isotopically heavy sulfur around +32 per mil. The range in sulfur isotope compositions can be explained by contributions of sulfur from a variety of source rocks together with sulfur isotope fractionations produced by the reaction paths for sulfate reduction. Much of the variation in sulfur isotope compositions can be explained by bacterial reduction of sedimentary sulfate and disequilibrium reactions by intermediate-valency sulfur species, especially in the late-stage pyrite and sphalerite. Organic reduction of sulfate and thermal release of sulfur from coals in the Upper Silesian Coal Basin may have been important contributors to sulfur in the ore minerals. The sulfur isotopic data, ore mineral textures, and fluid inclusion data, are consistent with the hypothesis that fluid mixing was the dominant ore forming mechanism. The rather distinct lowering of ?? 34S values in sulfides from stage 2 to stage 3 is believed to reflect some fundamental change in the source of reduced sulfur and/or hydrology of the ore-forming environment. A change in the hydrology of the ore forming environment could be accomplished by extensional faulting that was coeval with ore formation. Late stage barite contains high values of ??34S which may reflect the final collapse of the hydrothermal system.

Prace - Panstwowego Instytutu Geologicznego↗

Barite-forming environments along a rifted continental margin, Southern California Borderland

The Southern California Continental Borderland (SCCB) is part of the broad San Andreas transform-fault plate boundary that consists of a series of fault-bounded, petroleum-generating basins. The SCCB has high heat flow and geothermal gradients produced by thinned continental crust and Neogene volcanism. Barite deposits in the SCCB occur along faults. Barite samples from two sea-cliff sites and four offshore sites in the SCCB were analyzed for mineralogy, chemical (54 elements) and isotopic (S, Sr) compositions, and petrography. Barite from Palos Verdes (PV) Peninsula sea-cliff outcrops is hosted by the Miocene Monterey Formation and underlying basalt; carbonate rocks from those outcrops were analyzed for C, O, and Sr isotopes and the basalt for S isotopes. Cold-seep barite from Monterey Bay, California was analyzed for comparison. SCCB offshore samples occur at water depths from about 500 to 1800 m. Those barites vary significantly in texture and occurrence, from friable, highly porous actively growing seafloor mounds to dense, brecciated, vein barite. This latter type of barite contrasts with cold-seep barite in being much more coarse grained, forms thick veins in places, and completely replaced rock clasts in breccia. The barite samples range from 94 to 99 wt% BaSO4, with low trace-element contents, except for high Sr, Zr, Br, U, and Hg concentrations compared to their crustal abundances. δ34S for SCCB offshore barites range from 21.6‰ to 67.4‰, and for PV barite from 62‰ to 70‰. Pyrite from PV sea-cliff basalt and sedimentary rocks that host the barites averages 7.8‰ and 2.2‰, respectively. Two offshore barite samples have δ34S values (21.6‰, 22.1‰) close to that of modern seawater sulfate, whereas all other samples are enriched to strongly enriched in 34S. 87Sr/86Sr ratios for the barites vary over a narrow range of 0.70830–0.70856 and are much lower than that of modern seawater and also lower than the middle Miocene seawater ratio, the time of deposition of the host rocks for the PV samples. This indicates that the mineralizing fluids were not unaltered seawater. We develop a model in which the barites precipitated both below the sediment–water interface and at the seafloor from low-temperature fluids that circulated along faults. The isotopic, chemical, and textural data indicate that the barites formed by several processes. Mesozoic and Cenozoic basement rocks (crystalline and overlying sedimentary rocks), Quaternary basin fill, turbidite fans, and seawater provided various elements for the barites in different environments. The fluids had a deep-seated source and were hydrothermal in the deeper parts of the system for all the barite types, including the seafloor cold-seep deposit, based on Sr isotopes and regional geothermal gradients. These deep-seated fluids mixed with other fluids as they ascended, including seawater at and near the seafloor. The high δ34S values may have resulted from extreme Rayleigh fractionation during bacterially mediated (semi)closed-system sulfate reduction, probably driven by the flux of methane- and hydrocarbon-bearing fluids through basement rocks and basin sediments. Early diagenetic dolomite and pyrite in the host Monterey Formation in the PV Headland also formed in a zone of sulfate reduction, but within sediment buried only centimeters to a few meters and with a predominantly seawater source for the sulfur. Dolomite occurring with vein barite in the PV Headland formed at temperatures in the range of 40–90 °C. The cold-seep barites have δ34S values near that of modern seawater, although still somewhat fractionated. The barites that precipitated below the sediment–water interface have higher δ34S values, suggesting that the fluids were relatively reduced with molar dissolved barium in excess of dissolved sulfate. Those samples were exposed at the seafloor by uplift along faults and are composed predominantly of massive, brecciated, and vein barite.

California↗

Plant biomass and rates of carbon dioxide uptake are enhanced by successful restoration of tidal connectivity in salt marshes

Salt marshes, due to their capability to bury soil carbon (C), are potentially important regional C sinks. Efforts to restore tidal flow to former salt marshes have increased in recent decades in New England (USA), as well as in some other parts of the world. In this study, we investigated plant biomass and carbon dioxide (CO 2 ) fluxes at four sites where restoration of tidal flow occurred five to ten years prior to the study. Site elevation, aboveground biomass, CO 2 flux, and porewater chemistry were measured in 2015 and 2016 in both restored marshes and adjacent marshes where tidal flow had never been restricted. We found that the elevation in restored marsh sites was 2–16 cm lower than their natural references. Restored marshes where porewater chemistry was similar to the natural reference had greater plant aboveground biomass, gross ecosystem production, ecosystem respiration, as well as net ecosystem CO 2 exchange (NEE) than the natural reference, even though they had the same plant species. We also compared respiration rates in aboveground biomass (AR) and soil (BR) during July 2016, and found that restored marshes had higher AR and BR fluxes than natural references. Our findings indicated that well-restored salt marshes can result in greater plant biomass and NEP, which has the potential to enhance rates of C sequestration at 10-yrs post restoration. Those differences were likely due to lower elevation and greater flooding frequency in the recently restored marshes than the natural marsh. The inverse relationship between elevation and productivity further suggests that, where sea-level rise rate does not surpass the threshold of plant survival, the restoration of these salt marshes may lead to enhanced organic and mineral sedimentation, extending marsh survival under increased sea level, and recouping carbon stocks that were lost during decades of tidal restriction.

Massachusetts↗

Geologic framework and hydrogeologic characteristics of the Edwards aquifer, Uvalde County, Texas

The Edwards aquifer in Uvalde County is composed of Lower Cretaceous carbonate (mostly dolomitic limestone) strata of the Devils River Formation in the Devils River trend and of the West Nueces, McKnight, and Salmon Peak Formations in the Maverick basin. Rocks in the Devils River trend are divided at the bottom of the Devils River Formation into the (informal) basal nodular unit. Maverick basin rocks are divided (informally) into the basal nodular unit of the West Nueces Formation; into lower, middle, and upper units of the McKnight Formation; and into lower and upper units of the Salmon Peak Formation. The Edwards aquifer overlies the (Lower Cretaceous) Glen Rose Limestone, which composes the lower confining unit of the Edwards aquifer. The Edwards aquifer is overlain by the (Upper Cretaceous) Del Rio Clay, the basal formation of the upper confining unit. Upper Cretaceous and (or) Lower Tertiary igneous rocks intrude all stratigraphic units that compose the Edwards aquifer, particularly in the southern part of the study area. The Balcones fault zone and the Uvalde salient are the principal structural features in the study area. The fault zone comprises mostly en echelon, high-angle, and down-to-the-southeast normal faults that trend mostly from southwest to northeast. The Uvalde salient—resulting apparently from a combination of crustal uplift, diverse faulting, and igneous activity—elevates the Edwards aquifer to the surface across the central part of Uvalde County. Downfaulted blocks associated with six primary faults—Cooks, Black Mountain, Blue Mountain, Uvalde, Agape, and Connor—juxtapose the Salmon Peak Formation (Lower Cretaceous) in central parts of the study area against Upper Cretaceous strata in the southeastern part. The carbonate rocks of the Devils River trend and the Maverick basin are products of assorted tectonic and depositional conditions that affected the depth and circulation of the Cretaceous seas. The Devils River Formation formed in a fringing carbonate bank—the Devils River trend— in mostly open shallow marine environments of relatively high wave and current energy. The West Nueces, McKnight, and Salmon Peak Formations resulted mostly from partly restricted to open marine, tidal-flat, and restricted deep-basinal environments in the Maverick basin. The porosity of the Edwards aquifer results from depositional and diagenetic effects along specific lithostratigraphic horizons (fabric selective) and from structural and solutional features that can occur in any lithostratigraphic horizon (non-fabric selective). In addition to porosity depending upon the effects of fracturing and the dissolution of chemically unstable (soluble) minerals and fossils, the resultant permeability depends on the size, shape, and distribution of the porosity as well as the interconnection among the pores. Upper parts of the Devils River Formation and the upper unit of the Salmon Peak Formation compose some of the most porous and permeable rocks in Uvalde County.

Texas↗

Magmatic-vapor expansion and the formation of high-sulfidation gold deposits: Chemical controls on alteration and mineralization

Large bulk-tonnage high-sulfidation gold deposits, such as Yanacocha, Peru, are the surface expression of structurally-controlled lode gold deposits, such as El Indio, Chile. Both formed in active andesite–dacite volcanic terranes. Fluid inclusion, stable isotope and geologic data show that lode deposits formed within 1500 m of the paleo-surface as a consequence of the expansion of low-salinity, low-density magmatic vapor with very limited, if any, groundwater mixing. They are characterized by an initial ‘Sulfate’ Stage of advanced argillic wallrock alteration ± alunite commonly with intense silicification followed by a ‘Sulfide’ Stage — a succession of discrete sulfide–sulfosalt veins that may be ore grade in gold and silver. Fluid inclusions in quartz formed during wallrock alteration have homogenization temperatures between 100 and over 500 °C and preserve a record of a vapor-rich environment. Recent data for El Indio and similar deposits show that at the commencement of the Sulfide Stage, ‘condensation’ of Cu–As–S sulfosalt melts with trace concentrations of Sb, Te, Bi, Ag and Au occurred at > 600 °C following pyrite deposition. Euhedral quartz crystals were simultaneously deposited from the vapor phase during crystallization of the vapor-saturated melt occurs to Fe-tennantite with progressive non-equilibrium fractionation of heavy metals between melt-vapor and solid. Vugs containing a range of sulfides, sulfosalts and gold record the changing composition of the vapor. Published fluid inclusion and mineralogical data are reviewed in the context of geological relationships to establish boundary conditions through which to trace the expansion of magmatic vapor from source to surface and consequent alteration and mineralization. Initially heat loss from the vapor is high resulting in the formation of acid condensate permeating through the wallrock. This Sulfate Stage alteration effectively isolates the expansion of magmatic vapor in subsurface fracture arrays from any external contemporary hydrothermal activity. Subsequent fracturing is localized by the embrittled wallrock to provide high-permeability fracture arrays that constrain vapor expansion with minimization of heat loss. The Sulfide Stage vein sequence is then a consequence of destabilization of metal-vapor species in response to depressurization and decrease in vapor density. The geology, mineralogy, fluid inclusion and stable isotope data and geothermometry for high-sulfidation, bulk-tonnage and lode deposits are quite different from those for epithermal gold–silver deposits such as McLaughlin, California that formed near-surface in groundwater-dominated hydrothermal systems where magmatic fluid has been diluted to less than about 30%. High sulfidation gold deposits are better termed ‘Solfataric Gold Deposits’ to emphasize this distinction. The magmatic-vapor expansion hypothesis also applies to the phenomenology of acidic geothermal systems in active volcanic systems and equivalent magmatic-vapor discharges on the flanks of submarine volcanoes.

Ore Geology Reviews↗