Michele L.W. Tuttle

The 1986 Lake Nyos gas disaster in Cameroon, West Africa

The sudden, catastrophic release of gas from Lake Nyos on 21 August 1986 caused the deaths of at least 1700 people in the northwest area of Cameroon, West Africa. Chemical, isotopic, geologic, and medical evidence support the hypotheses that (i) the bulk of gas released was carbon dioxide that had been stored in the lakes hypolimnion, (ii) the victims exposed to the gas cloud died of carbon dioxide asphyxiation, (iii) the carbon dioxide was derived from magmatic sources, and (iv) there was no significant, direct volcanic activity involved. The limnological nature of the gas release suggests that hazardous lakes may be identified and monitored and that the danger of future incidents can be reduced.

The analysis of forms of sulfur in ancient sediments and sedimentary rocks: comments and cautions

Assumptions commonly made during analysis of the amount of monosulfides [acid-volatile sulfides (AVS)] and disulfides in modern sediments, may not be valid for ancient sedimentary rocks. It is known that ferric iron can oxidize H2S during AVS analysis unless a reducing agent such as stannous chloride is added to the treatment. In addition, some monosulfides such as greigite and pyrrhotite require heat during the AVS analysis in order to dissolve completely. However, the use of heat and/or stannous chloride in the AVS treatment may partially dissolve disulfides and it is generally recommended that stannous chloride not be used in the AVS treatment for modern sediments. Most of the monosulfides are assumed to be recovered as AVS without the addition of stannous chloride. This study investigates the recovery of monosulfides during sulfur speciation analysis with application to ancient sedimentary rocks. Sulfur in samples containing naturally occurring greigite and mackinawite or pyrite was measured using variations of a common sulfur-speciation scheme. The sulfur-speciation scheme analyzes for monosulfide sulfur, disulfide sulfur, elemental sulfur, inorganic sulfate and organically bound sulfur. The effects of heat, stannous chloride and ferric iron on the amounts of acid-volatile sulfide and disulfide recovered during treatment for AVS were investigated. Isotopic compositions of the recovered sulfur species along with yields from an extended sulfur-speciation scheme were used to quantify the effects. Hot 6 N HCl AVS treatment recovers > 60% of the monosulfides as AVS in samples containing pure greigite and mackinawite. The remaining monosulfide sulfur is recovered in a subsequent elemental sulfur extraction. Hot 6 N HCl plus stannous chloride recovers 100% of the monosulfides as AVS. The addition of ferric iron to pure greigite and mackinawite samples during AVS treatment without stannous chloride decreased the amount of monosulfides recovered as AVS and, if present in great enough concentration, oxidized some of the AVS to a form not recovered in later treatments. The hot stannous chloride AVS treatments dissolve <5% of well-crystallized pyrite in this study. The amount of pyrite dissolved depends on grain size and crystallinity. Greigite in ancient sedimentary rocks was quantitatively recovered as AVS only with hot 6 N HCl plus stannous chloride. Hot 6 N HCl AVS treatment of these rocks did not detect any monosulfides in most samples. A subsequent elemental sulfur extraction did not completely recover the oxidized monosulfides. Therefore, the use of stannous chloride plus heat is recommended in the AVS treatment of ancient sedimentary rocks if monosulfides are present and of interest. All assumptions about the amount of monosulfides and disulfides recovered with the sulfur-speciation scheme used should be verified by extended sulfur-speciation and/or isotopic analysis of the species recovered.

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 CO2 and CH4 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 CO2 profile constructed from the 1990 data to one obtained in May 1987 shows that CO2 concentrations have increased at depths to below 150 m. Based on these profiles, the average rate of CO2 input to bottom waters was 2.6 × 108 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 CO2, heat, and major ions into the hypolimnion suggest that a low-temperature reservoir of free CO2 exists a short distance below lake bottom and that convective cycling of lake water through the sediments is involved in transporting the CO2 into the lake from the underlying diatreme. Increased CH4 concentrations at all depths below the oxycline and a high14C content (41% modern) in the CH4 4 m above lake bottom show that much of the CH4 is biologically produced within the lake. The CH4 production rate may vary with time, but if the CO2 recharge rate remains constant, CO2 saturation of the entire hypolimnion below 50 m depth would require ∼140a, given present-day concentrations.

The evolution of thermal structure and water chemistry in Lake Nyos

Abstract We collected a time series of physical and chemical data to gain a better understanding of the dynamics of Lake Nyos. Measurements of water and gas chemistry, and temperature made during January, March, and May 1987 are compared to data taken in September 1986 just after the initial CO 2 gas release. There is no pattern of change in overall heat content of the lake, although heat input to bottom waters (185–208 m) has occurred at a rate of 1600 mW m −2 . This increase in heat content translates to a change from 23.38 to 24.12°C at 200 m and can be explained by geothermal heat flow and addition of thermal spring water. Concentrations of Ca 2+ , Mg 2+ , Na + , K + , Fe 2+ and alkalinity have increased only in bottom waters. In situ lake processes such as sulfate and iron reduction are unable to account for the changes in alkalinity. Observed chemical changes are consistent with a scenario where slightly thermal soda water is being input to the bottom of the lake. Measurements of p CO 2 at depth ranged from 18 to 28% of saturation and exhibited horizontal variability. Overall recharge of CO 2 in bottom waters is negligible. Mainly because of increasing ion concentrations in bottom water, total stability of the water column increased 33% from 48,800 J m −2 in September 1986 to 64,700 J m −2 in May 1987. As long as CO 2 concentrations remain the same, this level of stability is higher than could be disrupted by common limnologic or meteorologic processes. There is thermal and chemical evidence that a buildup of dissolved iron and CO 2 in bottom waters must have preceded the August 1986 gas release. In addition, a survey of all crater lakes in Cameroon indicates that only Lakes Nyos and Monoun contain high concentrations of dissolved iron and CO 2 . Thus there is a low probability of any other Cameroonian lake releasing a substantial volume of CO 2 .

Biogeochemical Evolution of a Landfill Leachate Plume, Norman, Oklahoma

Leachate from municipal landfills can create groundwater contaminant plumes that may last for decades to centuries. The fate of reactive contaminants in leachate-affected aquifers depends on the sustainability of biogeochemical processes affecting contaminant transport. Temporal variations in the configuration of redox zones downgradient from the Norman Landfill were studied for more than a decade. The leachate plume contained elevated concentrations of nonvolatile dissolved organic carbon (NVDOC) (up to 300 mg/L), methane (16 mg/L), ammonium (650 mg/L as N), iron (23 mg/L), chloride (1030 mg/L), and bicarbonate (4270 mg/L). Chemical and isotopic investigations along a 2D plume transect revealed consumption of solid and aqueous electron acceptors in the aquifer, depleting the natural attenuation capacity. Despite the relative recalcitrance of NVDOC to biodegradation, the center of the plume was depleted in sulfate, which reduces the long-term oxidation capacity of the leachate-affected aquifer. Ammonium and methane were attenuated in the aquifer relative to chloride by different processes: ammonium transport was retarded mainly by physical interaction with aquifer solids, whereas the methane plume was truncated largely by oxidation. Studies near plume boundaries revealed temporal variability in constituent concentrations related in part to hydrologic changes at various time scales. The upper boundary of the plume was a particularly active location where redox reactions responded to recharge events and seasonal water-table fluctuations. Accurately describing the biogeochemical processes that affect the transport of contaminants in this landfill-leachate-affected aquifer required understanding the aquifers geologic and hydrodynamic framework.

Greigite (Fe3S4) as an indicator of drought – The 1912–1994 sediment magnetic record from White Rock Lake, Dallas, Texas, USA

Combined magnetic and geochemical studies were conducted on sediments from White Rock Lake, a reservoir in suburban Dallas (USA), to investigate how land use has affected sediment and water quality since the reservoir was filled in 1912. The chronology of a 167-cm-long core is constrained by the recognition of the pre-reservoir surface and by 137Cs results. In the reservoir sediments, magnetic susceptibility (MS) and isothermal remanent magnetization (IRM) are largely carried by detrital titanomagnetite that originally formed in igneous rocks. Titanomagnetite and associated hematite are the dominant iron oxides in a sample from the surficial deposit in the watershed but are absent in the underlying Austin Chalk. Therefore, these minerals were transported by wind into the watershed.After about 1960, systematic decreases in Ti, Fe, and Al suggest diminished input of detrital Fe-Ti oxides from the surficial deposits. MS and IRM remain constant over this interval, however, implying compensation by an increase in strongly magnetic material derived from human activity. Anthropogenic magnetite in rust and ferrite spherules (from fly ash?) are more common in sediment deposited after about 1970 than before and may account for the constant magnetization despite the implied decrease in detrital Fe-Ti oxides.An unexpected finding is the presence of authigenic greigite (Fe3S4), the abundance of which is at least partly controlled by climate. Greigite is common in sediments that predate about 1975, with zones of concentration indicated by relatively high IRM/MS. High greigite contents in sediment deposited during the early to mid-1950s and during the mid-1930s correspond to several-year periods of below-average precipitation and drought from historical records. Relatively long water-residence times in the reservoir during these periods may have led to elevated levels of sulfate available for bacterial sulfate reduction. The sulfate was probably derived via the oxidation of pyrite that is common in the underlying Austin Chalk. These results provide a basis for the paleoenvironmental interpretation of greigite occurrence in older lake sediments. The results also indicate that greigite formed rapidly and imply that it can be preserved in the amounts produced over a short time span (in this lake, only a few years). This finding thus suggests that, in some lacustrine settings, greigite is capable of recording paleomagnetic secular variation.

Results of chemical and isotopic analyses of sediment and water from alluvium of the Canadian River near a closed municipal landfill, Norman, Oklahoma

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Sedimentology and petroleum occurrence, Schoolhouse Member, Maroon Formation (Lower Permian), northwestern Colorado

The Lower Permian Schoolhouse Member of the Maroon Formation (formerly considered the Schoolhouse Tongue of the Weber Sandstone) forms a partly exhumed petroleum reservoir in the Eagle basin of northwestern Colorado. The Schoolhouse consists mainly of yellowish gray to gray, low-angle to parallel bedded, very fine to fine-grained sandstone of eolian sand-sheet origin; interbedded fluvial deposits are present in most sections. The sand-sheet deposits of the Schoolhouse Member are sedimentologically and petrologically similar to those in the underlying red beds of the main body of the Maroon Formation, and the Schoolhouse is considered the uppermost sand sheet in the Maroon depositional sequence. The bleached and oil-stained Schoolhouse Member is distinguished from the unde lying Maroon red beds on the basis of its diagenetic history, which is related to regional hydrocarbon migration and development of secondary porosity. Geological and geochemical data suggest that Schoolhouse Member oils have upper Paleozoic sources, including the intrabasinal Belden Formation. Late Paleozoic faults have served as local conduits for vertical petroleum migration. Large-scale (>200 km) lateral migration from sources in the Permian Phosphoria Formation is also possible but less likely. Belden oil was generated and migrated before about 75 Ma. Subsequently, the Schoolhouse Member reservoir was uplifted, then partly exhumed on the monoclinal flank of the Laramide (latest Cretaceous-Paleogene) White River uplift. Based on this study, exploration models for Maroon Formation and Weber Sandstone reservoirs in northwestern Colorado should be expanded to more fully consider Belden source rocks and the controls of late Paleoz ic structures on hydrocarbon migration and trapping. Stratigraphic units of diagenetic origin comparable to the Schoolhouse Member are likely in other basin provinces, and their proper interpretation is critical for reconstructing the histories of associated petroleum systems.

Ancient Microbial Gas in the Upper Cretaceous Milk River Formation, Alberta and Saskatchewan: A Large Continuous Accumulation in Fine-grained Rocks

The Upper Cretaceous Milk River Formation in southeastern Alberta and southwestern Saskatchewan has produced more than 2 tcf of dry (99% methane) microbial gas (65 to 71) that was internally sourced. Production is from underpressured fine-grained sandstone and siltstone reservoirs, whereas the gas was generated in interbedded organic-bearing mudstones with low organic carbon contents (0.5–1.50%). The formation experienced a shallow burial history (maximum burial, 1.3 km [0.8 mi]) and cool formation temperatures (50C [122F]). Petrologic and isotopic studies suggest that methanogenesis began shortly after deposition and continued for at least 20 to 25 m.y. Mercury injection capillary pressure data from the Milk River Formation and the overlying Upper Cretaceous Pakowki Formation, which contains numerous regionally extensive bentonitic claystones, reveal a strong lithologic control on pore apertures and calculated permeabilities. Pore apertures and calculated permeabilities in Milk River mudstones range from 0.0255 to 0.169 m and less than 0.002 to 0.414 md, respectively, and claystones from the overlying Pakowki Formation have pore apertures from 0.011 to 0.0338 m and calculated permeabilities of 0.0017 to 0.0065 md. The small pore apertures and low permeabilities indicate that claystones and mudstones served as seals for microbial Milk River gas, thereby permitting gas to accumulate in economic quantities and be preserved for millions of years. Based on the timing of gas generation, the gas system of the Milk River Formation can be considered an ancient microbial gas system, which is one of several ways it differs from that of the Devonian Antrim Shale, Michigan Basin, where microbial gas generation is a geologically young (Pleistocene and younger) phenomenon. The difference in timing of gas generation between the Milk River and Antrim systems implies that gases in the two formations represent end members of a spectrum of microbial gas accumulations in fine-grained rocks, with the Milk River Formation being an excellent example on which to base a paradigm for an ancient microbial gas system.

U.S. Geological Survey Science for the Wyoming Landscape Conservation Initiative - 2008 Annual Report

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