Introduction: Memorial volume to Honor Ivan Barnes (1931-1989)
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Applied Geochemistry↗
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Sources and fractionation processes influencing the isotopic distribution of H, O and C in the Long Valley hydrothermal system, California, U.S.A.
The isotopic ratios of H, O and C in water within the Long Valley caldera, California reflect input from sources external to the hydrothermal reservoir. A decrease in δD in precipitation of 0.5‰ km −1 , from west to east across Long Valley, is caused by the introduction of less fractionated marine moisture through a low elevation embayment in the Sierra Nevada Mountain Range. Relative to seasonal fluctuations in precipitation (−158 to −35‰.), δD ranges in hot and cold surface and groundwaters are much less variable (−135 to −105‰.). Only winter and spring moisture, reflecting higher precipitation rates with lighter isotopic signatures, recharge the hydrological system. The hydrothermal fluids are mixtures of isotopically heavy recharge (δD = − 115‰, δ 18 O = − 15‰) derived from the Mammoth embayment, and isotopically lighter cold water (δD = −135‰, δ 18 O = −18‰). This cold water is not representative of current local recharge. The δ 13 C values for dissolved carbon in hot water are significantly heavier (− 7 to − 3‰) than in cold water (−18 to −10‰) denoting a separate hydrothermal origin. These δ 13 C values overlie the range generally attributed to magmatic degassing of CO 2 . However, δ 13 C values of metamorphosed Paleozoic basement carbonates surrounding Long Valley fall in a similar range, indicating that hydrothermal decarbonization reactions are a probable source of CO 2 . The δ 13 C and δ 18 O values of secondary travertime and vein calcite indicate respective fractionation with CO 2 and H 2 O at temperatures approximating current hydrothermal conditions.
California↗
Oxygen isotope map of the giant metamorphic-hydrothermal system around the northern part of the Idaho batholith, U.S.A.
Determinations of δ 18 O values from 100 outcrops of Belt Supergroup (Wallace Fm.) metasedimentary rocks in the Idaho panhandle reveal a regular regional pattern that was produced by pervasive fluid infiltration and isotopic exchange. Low grade argillites at large distances (60 km) from the Idaho batholith have high δ 18 O values +15, compatible with their probable primary values. Pelitic rocks with anomalously low δ 18 O values of + 8.7 to + 12.7‰ occur in the following zones: (1) in a 5000 km 2 zone of schist and gneiss peripheral to the Idaho batholith, generally coincident with high-grade (sillimanite-bearing) assemblages; (2) in high-grade metasedimentary roof pendants within the Idaho batholith; (3) peripheral to small Cretaceous stocks; and (4) within and near the scapolite-bearing zone south-west of St. Regis. On δ 18 O−δ 18 O plots, data from coexisting minerals define trends with unit slopes, indicating that the reductions in 18 O occurred under high-grade metamorphic conditions. This metamorphism culminated in the emplacement of the Idaho batholith, probably as a consequence of profound crustal thickening associated with the Cretaceous accretion of the Wallowa-Seven Devils arc terranes with North America. The huge low- 18 O region is bounded by a “steep” δ 18 O gradient (0.1–0.5‰/km) that occurs in low-grade rocks along and near the Lewis and Clark Line, well below the biotite isograd. This boundary zone may be analogous to, but is not nearly as sharp as, those of meteoric-hydrothermal systems in many regions. The important ore deposits of the Coeur d'Alene district are located in this peripheral zone, suggesting that the metamorphic-hydrothermal system may have been intimately involved in their formation. In addition, the metamorphic-hydrotermal system in Idaho is larger, deeper and higher in temperature than typical meteoric-hydrothermal systems, and it involved fluids with much higher δ 18 O values that were probably dominantly derived from formation waters. Accordingly, this system produced rocks with δ 18 O values similar to those of the Idaho batholith, and mineral assemblages that approach isotopic equilibrium under high temperature conditions.
Idaho↗
Geochemical evidence for Se mobilization by the weathering of pyritic shale, San Joaquin Valley, California, U.S.A.
Acidic (pH 4) seeps issue from the weathered Upper Cretaceous-Paleocene marine sedimentary shales of the Moreno Formation in the semi-arid Coast Ranges of California. The chemistry of the acidic solutions is believed to be evidence of current reactions ultimately yielding hydrous sodium and magnesium sulfate salts, e.g. mirabilite and bloedite, from the oxidation of primary pyrite. The selenate form of Se is concentrated in these soluble salts, which act as temporary geological sinks. Theoretically, the open lattice structures of these hydrous minerals could incorporate the selenate (SeO 4 −2 ) anion in the sulfate (SO 4 −2 ) space. When coupled with a semi-arid to arid climate, fractional crystallization and evaporative concentration can occur creating a sodium-sulfate fluid that exceeds the U.S. Environmental Protection Agency limit of 1000 μg l −1 for a toxic Se waste. The oxidative alkaline conditions necessary to ensure the concentration of soluble selenate are provided in the accompanying marine sandstones of the Panoche and Lodo Formations and the eugeosynclinal Franciscan assemblage. Runoff and extensive mass wasting in the area reflect these processes and provide the mechanisms which transport Se to the farmlands of the west-central San Joaquin Valley. Subsurface drainage from these soils consequently transports Se to refuge areas in amounts elevated to cause a threat to wildlife.
California↗
Radon-222 and its parent radionuclides in groundwater from two study areas in New Jersey and Maryland, U.S.A.
A study of groundwater chemistry and radionuclide mobility in New Jersey and Maryland was conducted to investigate natural processes that control the mobility of radionuclides in the water-rock system. Groundwater was sampled from two geological units in New Jersey and from six in Maryland. The water sampled was from aquifiers in fractured metamorphic rocks of varying composition and metamorphic grade. In both areas, groundwater chemistry was affected most by aquifier mineralogy and lithology; concentrations of total dissolved U, 226Ra and 222Rn were similarly affected. In evey sample for which measurements were made, dissolved Utotal and 226Ra were present in much lower concentrations than 222Rn when expressed in terms of their radioactivity. On the other hand, the total amount of 222Rn that could be produced in these rocks, given their U contents, is much higher than the concentrations observed in groundwater. Thus, the emanating efficiencies of the aquifer rocks studied must be near 10% or less. Such low emanating efficiencies require that a fraction of the 226Ra in the rock be located close to the water-rock interface so that 222Rn, when produced, can be rapidly and efficiently transferred to the aqueous phase. This condition is established when a similar fraction of the U is in a readily leachable position. No known U or Ra solids were supersaturated in any of the samples. Thus, adsorption processes probably play a role in limiting mobilities of Utotal and 226Ra. Concentrations of Utotal and 226Ra found in the water samples are comparable to those found in experimental studies of adsorption onto mineral surfaces. ?? 1991.
Maryland, New Jersey↗
Selectivity and effectiveness of extractants used to release metals associated with organic matter
Partial extraction procedures can be used to release metals associated with organic matter in natural materials. Reagents commonly employed for this purpose include hydrogen peroxide, Na hypochlorite and Na pyrophosphate. This study tested the selectivity of these reagents by comparing the amount of Fe, Mn, Zn and Cu they released from sulfide and oxide minerals and determined the ability of these reagents to release the same metals from peat. Sodium hypochlorite and Na pyrophosphate released between 0.2 and 8.7% of the total metal content of the Fe, Cu and Zn minerals. In contrast, three commonly used hydrogen peroxide reagents released significantly more metals from the oxides and sulfides. Percentages of Zn and Mn released from the peat samples were comparable for all extractions tested. Per cent Cu released from peat by Na pyrophosphate was very low compared to that released by hydrogen peroxide/HNO 3 or na hypochlorite. A smaller fraction of Fe was released from peat by Na hypochlorite than by the other reagents. Iron release by Na hypochlorite correlates with the organic carbon content of the peat samples. A universal extractant for metals associated with organic matter in all types of samples has not been identified. Sodium hypochlorite and Na pyrophosphate are better than hydrogen peroxide in selectively releasing metals bound to organic matter because they do not release significant amounts of metals from oxide and sulfide minerals.
Applied Geochemistry↗
Seasonal and geothermal production variations in concentrations of He and CO2 in soil gases, Roosevelt Hot Springs Known Geothermal Resource Area, Utah, U.S.A.
To increase understanding of natural variations in soil gas concentrations, CO 2 , He, O 2 and N 2 were measured in soil gases collected regularly for several months from four sites at the Roosevelt Hot Springs Known Geothermal Resource Area, Utah. Soil temperature, air temperature, per cent relative humidity, barometric pressure and amounts of rain and snowfall were also monitored to determine the effect of meteorological parameters on concentrations of the measured gases. Considerable seasonal variation existed in concentrations of CO 2 and He. The parameters that most affected the soil-gas concentrations were soil and air temperatures. Moisture from rain and snow probably affected the soil-gas concentrations also. However, annual variations in meteorological parameters did not appear to affect measurements of anomalous concentrations in samples collected within a time period of a few days. Production from some of the geothermal wells probably affected the soil-gas concentrations.
Utah↗
Large-scale distribution of metal contamination in the fine-grained sediments of the Clark Fork River, Montana, U.S.A.
Historic discharges from the mining and smelting complex at the head-waters of the Clark Fork River have resulted in elevated Ag, Cd, Cu, Pb and Zn concentrations in the <60 μm fraction of both bed and flood-plain sediments of the river. Processes affecting the trends in longitudinal distributions of these metals were investigated by repeated sampling over a 380 km river reach between August 1986 and July 1989. At the most upstream site, bed-sediment metal concentrations were enriched 18–115 times above least enriched tributaries, depending on the metal. All metals decreased exponentially with distance downstream away from mining. The exponential model predicts that elevated metal concentrations should occur over 550 km downstream, in Lake Pend Oreille. Longitudinal trends, obvious on a scale of hundreds of kilometers, were obscured by small-scale spatial variability when shorter stretches of the river were considered. Longitudinal dispersion appeared to be controlled largely by physical dilution with less-contaminated sediments. Evidence suggests that erosion of contaminated flood-plains contributes to metal contamination in the bed sediments. Tributary input appeared to have little influence on the large-scale, downstream distribution of metals; however, it did contribute to local variability in bed-sediment metal concentrations. Association of metals with specific mineral grains, as well as variability in total organic C and Fe concentration, appeared also to contribute to variability. Some year-to-year variability in bed-sediment metal concentrations was observed, however, trends in longitudinal dispersion were not significantly different between at least two of the years sampled.
Montana↗
Petrogenesis and geological history of a uranium source rock: a case study in northeastern Washington, U.S.A.
A small (4 km 2 ) drainage basin in northeastern Washington contains highly uraniferous groundwater and highly uraniferous peaty sediments of Holocene age. The U is derived from granitic bedrock that underlies the entire drainage basin and that contains 9–16 ppm U. This local bedrock was studied by petrographic, chemical and isotopic methods to determine conditions of its petrogenesis and post-emplacement history that may have contributed to its present high U content and source-rock capability. The original magma was derived by anatexis of Precambrian continental crust of probable mixed metaigneous and metasedimentary character. Mineral-melt partitioning controlled the enrichment of U in chemically evolved phases of the crystallizing melt. Following emplacement in the upper crust at ∼100Ma, the pluton interacted with meteoric-hydrothermal water at ambient temperatures 300°C. Locally intense fracturing promoted alteration, and fracturing and alteration probably continued during later regional uplift in the Eocene. Regional uplift was followed by low-temperature alteration and weathering in the middle to late Tertiary. The combined result of hydrothermal alteration and low-temperature alteration and weathering was the redistribution of U from primary mineral hosts such as allanite to new sites on fracture surfaces and in secondary minerals such as hematite. Zones of highly fractured and altered rock show the most obvious evidence of this process. A model is proposed in which high-angle fractures beneath the drainage basin were the sites of Tertiary supergene enrichments of U. Recent glacio-isostatic uplift has elevated these older enriched zones to shallow levels where they are now being leached by oxidizing groundwater. The chemistry, mineralogy, texture and geological history of this U source-rock suggest criteria for locating other granitic terrane that may contain uraniferous waters and associated young surficial U deposits. The details of U distribution and mobility at this site also apply to the general topic of U mobility in granitic rocks.
Washington↗
Release of 226Ra from uranium mill tailings by microbial Fe(III) reduction
Uranium mill tailings were anaerobically incubated in the presence of H 2 with Alteromonas putrefaciens , a bacterium known to couple the oxidation of H 2 and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved 226 Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of 226 Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved 226 Ra from uranium mill tailings.
Applied Geochemistry↗
Host-rock controlled epigenetic, hydrothermal metasomatic origin of the Bayan Obo REEFe-Nb ore deposit, Inner Mongolia, P.R.C.
Bayan Obo, a complex rare earth element (REE) Fe Nb ore deposit, located in Inner Mongolia, P.R.C. is the world's largest known REE deposit. The deposit is chiefly in a marble unit (H8), but extends into an overlying unit of black shale, slate and schist unit (H9), both of which are in the upper part of the Middle Proterozoic Bayan Obo Group. Based on sedimentary structures, the presence of detrital quartz and algal fossil remains, and the 16-km long geographic extent, the H8 marble is a sedimentary deposit, and not a carbonatite of magmatic origin, as proposed by some previous investigators. The unit was weakly regionally metamorphosed (most probably the lower part of the green schist facies) into marble and quartzite prior to mineralization. Tectonically, the deposit is located on the northern flank of the Sino-Korean craton. Many hypotheses have been proposed for the origin of the Bayan Obo deposit; the studies reported here support an epigenetic, hydrothermal, metasomatic origin. Such an origin is supported by field and laboratory textural evidence; 232 Th/ 208 Pb internal isochron mineral ages of selected monazite and bastnaesite samples; 40 Ar/ 39 Ar incremental heating minimum mineral ages of selected alkali amphiboles; chemical compositions of different generations of both REE ore minerals and alkali amphiboles; and evidence of host-rock influence on the various types of Bayan Obo ores. The internal isochron ages of the REE minerals indicate Caledonian ages for various episodes of REE and Fe mineralization. No evidence was found to indicate a genetic relation between the extensive biotite granitic rocks of Hercynian age in the mine region and the Bayan Obo are deposit, as suggested by previous workers.
Applied Geochemistry↗
Geochemical effects of deep-well injection of the Paradox Valley brine into Paleozoic carbonate rocks, Colorado, U.S.A.
Brine seepage into the Dolores River from ground water in Paradox Valley, Colorado constitutes a major source of salt to the Colorado River. Plants are enderway to remove this source of salt by drawing down the Paradox Valley brine (PVB) and forcibly injecting it into a deep disposal well (4.8 km). Experiments were conducted to determine the effects of deep-well injection of PVB. The results show that PVB is near saturation with anhydrite at 25°C, and that heating results in anhydrite precipitation. The amount and the rate at which anhydrite forms is temperature, pressure, and substrate dependent. Paradox Valley brine heated in the presence of Precambrian rocks from the drill core produces the same amount of anhydrite as PVB heated alone, but at a greatly accelerated rate. A 30% dilution of PVB with Dolores River water completely eliminates anhydrite precipitation when the fluid is heated with the Precambrian rocks. Interaction of PVB and Leadville Limestone is characterized by dolomitization of calcite by brine Mg which releases Ca to solution. This added Ca reacts with SO 4 to form increased amounts of anhydrite. A 20% dilution of PVB by Dolores River water has no effect on dolomitization and reduces the amount of anhydrite only slightly. A 65% dilution of PVB by Dolores River water still does not prevent dolomitization but does suppress anhydrite formation. Computer modeling of PVB by programs utilizing the Pitzer ion-interaction parameters is in general agreement with the experimental results. Ion-activity products calculated by both SOLMINEQ and PHRQPITZ are close to equilibrium with both anhydrite and dolomite whenever these phases are present experimentally, although the calculations over-estimate by a factor of 2 the degree of saturation. Some discrepancies in the calculated results between the two programs are due largely to differences in mineral solubility data.
Colorado↗
Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization
Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206 Pb/ 204 Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206 Pb/ 204 Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb-rich base-metal veins, and sedimentary country rocks. Stream-sediment anomalies detected using oxalic acid leaches can be evaluated using Pb isotope analysesof selected geochemical anomalies. Such an evaluation procedure, given regional target Pb isotope signatures for concealed mineralization, can greatly reduce the cost of exploration for undiscovered ore deposits concealed beneath barren overburden. Lead isotope measurements on aliquots of the same solutions showed that ICP-MS determinations are of low precision and vary non-systematically when compared with the Pb isotope values of the higher precision thermal ionization method. These variations and lower precision of the ICP-MS measurements are attributed to matrix effects.
Colorado↗
Generation of aliphatic acid anions and carbon dioxide by hydrous pyrolysis of crude oils
Two crude oils with relatively high (0.60 wt%) and low (0.18 wt%) oxygen contents were heated in the presence of water in gold-plated reactors at 300??C for 2348 h. The high-oxygen oil was also heated at 200??C for 5711 h. The compositions of aqueous organic acid anions of the oils and of the headspace gases were monitored inn order to investigate the distribution of organic acids that can be generated from liquid petroleum. The oil with higher oxygen content generated about five times as much organic anions as the other oil. The dominant organic anions produced were acetate, propionate and butyrate. Small amounts of formate, succinate, methyl succinate and oxalate were also produced. The dominant oxygen-containing product was CO2, as has been observed in similar studies on the hydrous pyrolysis of kerogen. These results indicate that a significant portion (10-30%) of organic acid anions reported i be generated by thermal alteration of oils in reservoir rocks. The bulk of organic acid anions present in formation waters, however, is most likely generated by thermal alteration of kerogen in source rocks. Kerogen is more abundant than oil in sedimentary basins and the relative yields of organic acid anions reported from the hydrous pyrolysis of kerogen are much higher than the yields obtained for the two oils. ?? 1993.
Applied Geochemistry↗
Crude oil in a shallow sand and gravel aquifer-III. Biogeochemical reactions and mass balance modeling in anoxic groundwater
Crude oil floating on the water table in a sand and gravel aquifer provides a constant source of hydrocarbons to the groundwater at a site near Bemidji, Minnesota. The degradation of hydrocarbons affects the concentrations of oxidized and reduced aqueous species in the anoxic part of the contaminant plume that developed downgradient from the oil body. The concentrations of Fe 2+ , Mn 2+ and CH 4 , Eh measurements, and the δ 13 C ratios of the total inorganic C indicate that the plume became more reducing ver a 5-a period. However, the size of the contaminant plume remained stable during this time. Field data coupled with laboratory microcosm experiments indicate that benzene and the alkylbenzenes are degraded in an anoxic environment. In anaerobic microcosm experiments conducted under field conditions, almost complete degradation (98%) was observed for benzene in 125 d and for toluene in 45 d. Concentrations of aqueous Fe 2+ and Mn 2+ increased in these experiments, indicating that the primary reactions were hydrocarbon degradation coupled with Fe and Mn reduction. Mass transfer calculations on a 40-m flowpath in the anoxic zone, downgradient from the oil body, indicated that the primary reactions in the anoxic zone are oxidation of organic compounds, precipitation of siderite and a ferroan calcite, dissolution of iron oxide and outgassing of CH 4 and CO 2 . The major difference in the two models presented is the ratio of CO 2 and CH 4 that outgasses. Both models indicate quantitatively that large amounts of Fe are dissolved and reprecipitated as ferrous iron in the anoxic zone of the contaminant plume.
Minnesota↗
Selenium source identification and biogeochemical processes controlling selenium in surface water and biota, Kendrick Reclamation Project, Wyoming, U.S.A.
The major tributaries draining the Kendrick Reclamation Project (KRP) account for an average of 52% of the total Se load measured in the North Platte River downstream from Casper, Wyoming. The Casper Creek drainage basin contributed the largest Se load of the five tributary sites to the North Platte River. The 4-d average Se concentration in water samples from one site in the part of the North Platte River that receives irrigation return flows exceeded the 5 μg/l U.S. Environmental Protection Agency's aquatic life criterion five time during a 50-d monitoring period in 1989. In agreement with the water-quality data, muscle and liver tissue rom rainbow trout collected from the same part of the North Platte River had Se concentrations exceeding levels known to cause reproductive failure and chronic Se poisoning. On the basis of Se: Cl, 18 O/ 16 O and D/H ratios in water from Goose and Rasmus Lee Lakes (closed-basin systems), the large Se concentrations in those lakes were derived by natural evaporation of irrigation water without leaching of soluble forms of Se from soil or rocks. Water samples from Thirtythree Mile Reservoir and Illco Pond (flow-through systems) showed considerable enrichment in Se over evaporative concentration, presumably due to leaching and desorption of Se from soil and rock. The Se: Cl ratios of irrigation drain water collected from the KRP indicate that leaching and desorption of soluble forms of Se from soils and rocks are the dominant processes in drain water. Results of a Wilcoxon matched-pairs test for 43 paired drain-water samples collected during June and August 1988, indicated there is a statistically larger concentration of Se (0.01 significance level) during the June sampling period. The larger concentrations of Se and other chemical constitutents during the early part of the irrigation season probably were due to dissolution of seleniferous salts that have accumulated in soils within the KRP since the last irrigation season. The large Se concentrations in water samples from wetland sites in the KRP were reflected in the aquatic-bird food chain. Most waterfowl and shorebirds nesting at the KRP showed Se concentrations in livers and eggs greater than levels suspected of causing adverse reproductive effects.
Wyoming↗
Gas buildup in Lake Nyos, Cameroon: The recharge process and its consequences
The gases dissolved in Lake Nyos, Cameroon, were quantified recently (December 1989 and September 1990) by two independent techniques: in-situ measurements using a newly designed probe and laboratory analyses of samples collected in pre-evacuated stainless steel cylinders. The highest concentrations of CO 2 and CH 4 were 0.30 mol/kg and 1.7 mmol/kg, respectively, measured in cylinders collected 1 m above lake bottom. Probe measurements of in-situ gas pressure at three different stations showed that horizontal variations in total dissolved gas were negligible. Total dissolved-gas pressure near the lake bottom is 1.06 MPa (10.5 atm), 50% as high as the hydrostatic pressure of 2.1 MPa (21 atm). Comparing the CO 2 profile constructed from the 1990 data to one obtained in May 1987 shows that CO 2 concentrations have increased at depths to below 150 m. Based on these profiles, the average rate of CO 2 input to bottom waters was 2.6 × 10 8 mol/a. Increased deep-water temperatures require an average heat flow of 0.32 MW into the hypolimnion over the same time period. The transport rates of CO 2 , heat, and major ions into the hypolimnion suggest that a low-temperature reservoir of free CO 2 exists a short distance below lake bottom and that convective cycling of lake water through the sediments is involved in transporting the CO 2 into the lake from the underlying diatreme. Increased CH 4 concentrations at all depths below the oxycline and a high 14 C content (41% modern) in the CH 4 4 m above lake bottom show that much of the CH 4 is biologically produced within the lake. The CH 4 production rate may vary with time, but if the CO 2 recharge rate remains constant, CO 2 saturation of the entire hypolimnion below 50 m depth would require ∼140a, given present-day concentrations.
Lake Nyos↗
Manganese minerals and associated fine particulates in the streambed of Pinal Creek, Arizona, U.S.A.: a mining-related acid drainage problem
The Pinal creek drainage basin in Arizona is a good example of the principal non-coal source of mining-related acid drainage in the U.S.A., namely copper mining. Infiltration of drainage waters from mining and ore refining has created an acid groundwater plume that has reacted with calcite during passage through the alluvium, thereby becoming less acid. Where O 2 is present and the water is partially neutralized, iron oxides have precipitated and, farther downstream where the pH of the stream water is near neutral, high-Mn crusts have developed. Trace metal composition of several phases in the Pinal Creek drainage basin illustrates the changes caused by mining activities and the significant control Mn-crusts and iron oxide deposits exert on the distribution and concentration of trace metals. The phases and locales considered are the dissolved phase of Webster Lake, a former acid waste disposal pond; selected sections of cores drilled in the alluvium within the intermittent reach of Pinal Creek; and the dissolved phase, suspended sediments, and streambed deposits at specified locales along the perennial reach of Pinal creek. In the perennial reach of Pinal Creek, manganese oxides precipitate from the streamflow as non-cemented particulates and coatings of streambed material and as cemented black crusts. Chemical and X-ray diffraction analyses indicate that the non-cemented manganese oxides precipitate in the reaction sequence observed in previous laboratory experiments using simpler solution composition, Mn 3 O 4 to MnOOH to an oxide of higher oxidation number usually <4.0, i.e. Na-birnessite, and that the black cemented crusts contain (Ca,Mn,Mg)CO 3 and a 7-Åphyllomanganate mixture of rancieite ((Ca,Mn)Mn 4 O 9 · (3H 2 O)) and takanelite ((Mn,Ca)Mn 4 O 9 · (3H 2 O)). In the laboratory, aerating and increasing the pH of Pinal Creek water to 9.00 precipitated (Ca,Mn,Mg)CO 3 from an anoxic groundwater that contained CO 2 HCO 3 , and precipitated Mn 3 O 4 and subsequently MnOOH from an oxic surface water from which most of the dissolved CO 2 had been removed. It is suggested that the black cemented crusts form by precipitation of Fe on the Mn-enriched carbonates, creating a site for the Mn Fe oxidation cycle and thus encouraging the conversion of the carbonates to 7-Åphysllomanganates. The non-magnetic <63-μm size-fractions of the black cemented crusts consisted mostly of the manganese-calcium oxides but also contained about 20% (Ca,Mn,Mg)CO 3 , 5% Fe (calculated as FeOOH), 2–4% exchangeable cations, and trace amounts of several silicates.
Applied Geochemistry↗