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E.C. Spiker

Publications and source records attributed to E.C. Spiker.

16 recordsLinked to original sources

Tracing sources of sulfur in the Florida Everglades

We examined concentrations and sulfur isotopic ratios ( 34 S/ 32 S, expressed as δ 34 S in parts per thousand [‰] units) of sulfate in surface water, ground water, and rain water from sites throughout the northern Everglades to establish the sources of sulfur to the ecosystem. The geochemistry of sulfur is of particular interest in the Everglades because of its link, through processes mediated by sulfate-reducing bacteria, to the production of toxic methylmercury in this wetland ecosystem. Methylmercury, a neurotoxin that is bioaccumulated, has been found in high concentrations in freshwater fish from the Everglades, and poses a potential threat to fish-eating wildlife and to human health through fish consumption. Results show that surface water in large portions of the Everglades is heavily contaminated with sulfate, with the highest concentrations observed in canals and marsh areas receiving canal discharge. Spatial patterns in the range of concentrations and δ 34 S values of sulfate in surface water indicate that the major source of sulfate in sulfur-contaminated marshes is water from canals draining the Everglades Agricultural Area. Shallow ground water underlying the Everglades and rain water samples had much lower sulfate concentrations and δ 34 S values distinct from those found in surface water. The δ 34 S results implicate agricultural fertilizer as a major contributor to the sulfate contaminating the Everglades, but ground water under the Everglades Agricultural Area (EAA) may also be a contributing source. The contamination of the northern Everglades with sulfate from canal discharge may be a key factor in controlling the distribution and extent of methylmercury production in the Everglades.

Florida

Geochemistry of sulfur in the Florida Everglades: 1994 through 1999

In this report, we present data on the geochemistry of sulfur in sediments and in surface water, groundwater, and rainwater in the Everglades region in south Florida. The results presented here are part of a larger study intended to determine the roles played by the cycling of carbon, nitrogen, phosphorus, and sulfur in the ecology of the south Florida wetlands. The geochemistry of sulfur in the region is particularly important because of its link to the production of toxic methylmercury through processes mediated by sulfate reducing bacteria. Sediment cores were collected from the Everglades Agricultural Area (EAA), Water Conservation Areas (WCAs) 1A and 2A, from Lake Okeechobee, and from Taylor Slough in the southern Everglades. Water collection was more widespread and includes surface water from WCAs 1A, 2A, 3A, 2B, the EAA, Taylor Slough, Lake Okeechobee, and the Kissimmee River. Groundwater was collected from The Everglades Nutrient Removal Area (ENR) and from WCA 2A. Rainwater was collected at two month intervals over a period of one year from the ENR and from WCA 2A. Water was analyzed for sulfate concentration and sulfate sulfur stable isotopic ratio (34S/32S). Sediment cores were analyzed for total sulfur concentration and/or for concentrations of sulfur species (sulfate, organic sulfur, disulfides, and acid volatile sulfides (AVS)) and for their stable sulfur isotopic ratio. Results show a decrease in total sulfur content (1.57 to 0.61 percent dry weight) with depth in two sediment cores collected in WCA 2A, indicating that there has been an increase in total sulfur content in recent times. A sediment core from the center of Lake Okeechobee shows a decrease in total sulfur content with depth (0.28 to 0.08 percent dry weight). A core from the periphery of the lake (South Bay) likewise shows a decrease in total sulfur content with depth (1.00 to 0.69 percent dry weight), however, the overall sulfur content is greater than that near the center at all depths. This suggests input of sulfur in recent times, especially near the lake margins. Sediments show a general decrease in sulfur concentration with depth, probably because of increases in sulfur input to the marshes in recent times. Regional differences in the concentrations and stable isotopic ratios of sulfate sulfur in surface water show that sulfur contamination to the northern Everglades likely originates from canals draining the EAA.

Florida

Speciation and isotopic composition of sedimentary sulfur in the Everglades, Florida, USA

We have studied the sulfur speciation and isotopic composition of two peat cores from Water Conservation Area 2A (WCA 2A) in the Florida Everglades. Core site E1 is affected by agricultural runoff from the Hillsboro Canal which drains the Everglades Agricultural Area; Core site U3 is distant from the canal and relatively unaffected by agricultural runoff. Depth profiles of the total sulfur content of both cores show fairly constant levels (??0.7 wt.%) below about 25-30 cm depth in Core E1 and below 40-45 cm in Core U3. Above these depths, total sulfur increases to as much as 1.52 wt.% in Core E1 and 1.74 wt.% in Core U3, suggesting that more sulfur has entered the sediments and/or that more sulfur is being retained in recent times at both sampling sites. These changes in total sulfur content with depth in Core E1 correlate with changes in total phosphorus that have been observed in other studies at core sites near the Hillsboro Canal. This correlation of total sulfur with phosphorus with depth is not seen in Core U3 located away from the canal, possibly because phosphorus is more effectively retained than sulfur in the organic sediment near the canal. Organic-sulfur (OS) concentrations are at least twice as high as the dusulfide-sulfur (DS) concentrations in the upper parts of both cores suggesting that iron is presently limiting the amount of dusulfide minerals formed in these sediments. The degree of pyritization (DOP) in the upper parts of the cores suggest that sulfide mineralization is limited by the availability of highly reactive iron during the earliest stages of diagenesis. Positive ??34S values for reduced sulfur forms in both cores indicate a relatively restricted sulfate reservoir, consistent with nearly complete reduction of the sulfate available in the sediment at any given time. Differences between the two core appear in the ??34S values for the near-surface sediments. The DS ??34S values in the upper 10.0 cm of sediment are more posotive at site E1, with a mean ??34S value of +12.9???, than at site U3, with a mean ??34S value of +2.9???. These reuslts may indicate that increased rates of organic deposition due to nutrient loading near the canal have increased the rate of sulfate reduction at the E1 site in recent times. Acid-volatile-sulfide (AVS) concentrations are lower than DS and OS concentrations by at least a factor of 10. Increasing ??34S values for AVS with increasing depth in both cores suggests ongoing reduction of a limited porewater sulfate reservoir after deposition. The disulfide and organic-sulfur ??34S values diverge from the ??34S values for AVS with depth, suggesting that most of the transformation of AVS into disulfide minerals or incorporation of sulfur into orgnaic matter occurs in the near-surface sediments. A comparison of organic-sulfur ??34S values in the dominant flora at the U3 site (sawgrass leaves and periphyton) with organic-sulfur ??34S values at the top of the U3 core indicates that there was early incorporation of an isotopically light sulfide species into the orgnaic matter.

Chemical Geology

Air pollutant intrusion into the Wieliczka Salt Mine

The Wieliczka Salt Mine World Cultural Heritage Site contains many rock salt sculptures that are threatened by water vapor condensation from the mine ventilation air. Gaseous and particulate air pollutant concentrations have been measured both outdoors and within the Wieliczka Salt Mine, along with pollutant deposition fluxes to surfaces within the mine. One purpose of these measurements was to determine whether or not low deliquescence point ionic materials (e.g., NH4NO3) are accumulating on surfaces to an extent that would exacerbate the water vapor condensation problems in the mine. It was found that pollutant gases including SO2 and HNO3 present in outdoor air are removed rapidly and almost completely from the air within the mine by deposition to surfaces. Sulfur isotope analyses confirm the accumulation of air pollutant-derived sulfur in liquid dripping from surfaces within the mine. Particle deposition onto interior surfaces in the mine is apparent, with resulting soiling of some of those sculptures that have been carved from translucent rock salt. Water accumulation by salt sculpture surfaces was studied both experimentally and by approximate thermodynamic calculations. Both approaches suggest that the pollutant deposits on the sculpture surfaces lower the relative humidity (RH) at which a substantial amount of liquid water will accumulate by 1% to several percent. The extraordinarily low SO2 concentrations within the mine may explain the apparent success of a respiratory sanatorium located deep within the mine.

Environmental Science & Technology

Laboratory study of SO2 dry deposition on limestone and marble: Effects of humidity and surface variables

The dry deposition of gaseous air pollutants on stone and other materials is influenced by atmospheric processes and the chemical characteristics of the deposited gas species and of the specific receptor material. Previous studies have shown that relative humidity, surface moisture, and acid buffering capability of the receptor surface are very important factors. To better quantify this behavior, a special recirculating wind tunnel/environmental chamber was constructed, in which wind speed, turbulence, air temperature, relative humidity, and concentrations of several pollutants (SO2, O3, nitrogen oxides) can be held constant. An airfoil sample holder holds up to eight stone samples (3.8 cm in diameter and 1 cm thick) in nearly identical exposure conditions. SO2 deposition on limestone was found to increase exponentially with increasing relative humidity (RH). Marble behaves similarly, but with a much lower deposition rate. Trends indicate there is little deposition below 20% RH on clean limestone and below 60% RH on clean marble. This large difference is due to the limestone's greater porosity, surface roughness, and effective surface area. These results indicate surface variables generally limit SO2 deposition below about 70% RH on limestone and below at least 95% RH on marble. Aerodynamic variables generally limit deposition at higher relative humidity or when the surface is wet.The dry deposition of gaseous air pollutants on stone and other materials is influenced by atmospheric processes and the chemical characteristics of the deposited gas species and of the specific receptor material. Previous studies have shown that relative humidity, surface moisture, and acid buffering capability of the receptor surface are very important factors. To better quantify this behavior, a special recirculating wind tunnel/environmental chamber was constructed, in which wind speed, turbulence, air temperature, relative humidity, and concentrations of several pollutants (SO2, O3, nitrogen oxides) can be held constant. An airfoil sample holder holds up to eight stone samples (3.8 cm in diameter and 1 cm thick) in nearly identical exposure conditions. SO2 deposition on limestone was found to increase exponentially with increasing relative humidity (RH). Marble behaves similarly, but with a much lower deposition rate. Trends indicate there is little deposition below 20% RH on clean limestone and below 60% RH on clean marble. This large difference is due to the limestone's greater porosity, surface roughness, and effective surface area. These results indicate surface variables generally limit SO2 deposition below about 70% RH on limestone and below at least 95% RH on marble. Aerodynamic variables generally limit deposition at higher relative humidity or when the surface is wet.

Conference Paper

Isotopic evidence for the source of sulfur in the Upper Freeport coal bed (west-central Pennsylvania, U.S.A.)

Sulfur isotopic variations were used to determine the sources of sulfur in a medium-sulfur coal (???2 wt%S) that lacked marine influence, which is often cited as a major source of sulfur in coal. Variations in the amount and isotopic composition of the organic and pyritic sulfur among the coal-bed facies of the Upper Freeport coal bed (Middle Pennsylvanian) are attributed to differential incorporation of syngenetic and epigenetic sulfur. These variations reflect varying environmental conditions during paleopeat formation, porosity and permeability, and the availability of sulfate and iron. A large increase in the abundance and sulfur isotopic value of pyritic sulfur in the upper facies of the coal bed, in proximity to the overlying lacustrine shale, corresponds to an increase in massive and irregular forms of pyrite. This relationship is attributed to at least two stages of epigenetic pyrite incorporation. An early stage of epigenetic pyrite, moderately enriched in 34S, apparently formed during the fluvial-lacustrine period immediately following peat accumulation. A late stage of epigenetic pyrite, highly enriched in 34S, formed after compaction of the original peat as cleat- and fracture-filling pyrite; this sulfur was probably derived from bacterial reduction of dissolved sulfate in groundwater. Isotopic mass-balance calculations indicate that this late-stage epigenetic pyrite may account for up to ???50% of the pyritic sulfur in some upper facies of the coal bed. These results suggest that most of the pyritic sulfur in the Upper Freeport coal bed may be epigenetic, incorporated either soon after peat accumulation or later during coalification. ?? 1994.

Chemical Geology

Speciation and isotopic composition of sulfur in sediments from Jellyfish Lake, Palau

Jellyfish Lake, Palau, is a meromictic marine lake with high organic productivity, low reactive Fe content, and anoxic bottom waters. Sediment samples from Jellyfish Lake were examined for the distribution of sulfur species and their isotopic signatures in order to gain a better understanding of sedimentary sulfur incorporation in Fe-poor environments. Surface samples were taken along a transect from a near-shore site to the center of the lake, and include a sample below oxic water, a sample below the chemocline layer, and samples below anoxic waters. Three additional samples were taken from a core, 2 m long, collected near the lake center. Sulfur to organic carbon weight ratios in all samples were lower than the expected value of 0.36 for normal marine sediment, probably because the lake water is deficient in reactive Fe to form iron sulfides. Total sulfur contents in the surface sediments indicated no changes with distance from shore; however, the sulfur content of the surface sample at the chemocline layer may be slightly higher. Total sulfur content increased with depth in the core and is inversely related to organic carbon content. Organic sulfur is the major sulfur species in the samples, followed in descending order by sulfate, disulfides and monosulfides. Sulfate sulfur isotope ??34S-values are positive (from +20.56 to +12.04???), reflecting the marine source of sulfate in Jellyfish Lake. Disulfide and monosulfide ??34S-values are negative (from -25.07 to -7.60???), because of fractionation during bacterial reduction of sulfate. Monosulfide ??34S-values are somewhat higher than those of disulfides, and they are close to the ??34S-values of organic sulfur. These results indicate that most of the organic sulfur is formed by reaction of bacteriogenic monosulfides, or possibly monosulfide-derived polysulfides, with organic matter in the sediment. ?? 1993.

Chemical Geology

Chemical changes and carbon isotope variations in a cross-section of a large Miocene gymnospermous log

The cross-sectional radius of a 3-m (diam.) brown coal gymnospermous log of Miocene age, previously analyzed for carbohydrate and lignin methoxyl content by solid-state 13 C nuclear magnetic resonance spectroscopy, was examined using stable carbon isotopic ratios in order to determine if the isotopic composition could be related to chemical changes or to radial position. This study found a possible relationship between δ 13 C-values and radial position; however, these changes cannot be linked to carbohydrate content and are probably attributable to changing growth conditions during the lifetime of the tree. An apparent linear relationship between the changes in carbohydrate content after sodium para-periodate treatment and corresponding changes in the δ 13 C-values indicates constant isotopic fractionation between lignin and carbohydrates along the cross-sectional radius. This result indicates that diagenesis has not produced any significant change in the lignin-carbohydrate carbon isotopic fractionation or, alternatively, that diagenesis has erased any fractionation pattern that once existed. A sample of fresh wood from another gymnospermous species was analyzed by the same methods and found to have lignin-carbohydrate carbon isotopic fractionation significantly different from that of the Miocene log section samples, suggesting that differences may be species-related or that the complex mixture of carbohydrates in the fresh wood was isotopically different from that of the degraded wood, and the whole Miocene log was uniformly altered.

Chemical Geology

Isotopic evidence for organic matter oxidation by manganese reduction in the formation of stratiform manganese carbonate ore

Unlike other marine-sedimentary manganese ore deposits, which are largely composed of manganese oxides, the primary ore at Molango (Hidalgo State, Mexico) is exclusively manganese carbonate (rhodochrosite, Mn-calcite, kutnahorite). Stable isotope studies of the carbonates from Molango provide critical new information relevant to the controversy over syngenetic and diagenetic models of stratiform manganese deposit formation. Negative δ 13 C values for carbonates from mineralized zones at Molango are strongly correlated with manganese content both on a whole rock scale and by mineral species. Whole rock δ 13 C data fall into three groups: high-grade ore = −16.4 to −11.5%.; manganese-rich, sub-ore-grade = −5.2 to 0%.; and unmineralized carbonates = 0 to +2.5%. (PDB). δ 18 O data show considerable overlap in values among the three groups: +4.8 to −2.8, −5.4 to −0.3%., and −7.4 to +6.2 (PDB), respectively. Isotopic data for individual co-existing minerals suggest a similar separation of δ 13 C values: δ 13 C values from calcite range from −1.1 to +0.7%. (PDB), whereas values from rhodochrosite are very negative, −12.9 to −5.5%., and values from kutnahorite or Mn-calcite are intermediate between calcite and rhodochrosite. 13 C data are interpreted to indicate that calcite ( i.e . unmineralized carbonate) formed from a normal marine carbon reservoir. However, 13 C data for the manganese-bearing carbonates suggest a mixed seawater and organic source of carbon. The presence of only trace amounts of pyrite suggests sulfate reduction may have played a minor part in oxidizing organic matter. It is possible that manganese reduction was the predominant reaction that oxidized organic matter and that it released organic-derived CO 2 to produce negative δ 13 C values and manganese carbonate mineralization.

Geochimica et Cosmochimica Acta

A ground-water mixing model for the origin of the Imini manganese deposit (Cretaceous) of Morocco

Three beds of manganese oxide ore in a 10 m-thick dolomite unit are associated with diagenetic features, and, are accordingly also diagenetic in their present aspect. Whether primary or introduced, the Mn mineralogy is attributed to reactions between fresh and saline ground-waters as the zone of mixing passed through the dolomite unit during a period of falling sea-level. The succession of diagenetic changes is: 1) precursor carbonates, 2) dolomite-janggunite, 3) hollandite-pyrolusite-chert-calcite.-G.J.N.

Economic Geology

Contrasting magma types and steady-state, volume-predictable, basaltic volcanism along the Great Rift, Idaho

The Great Rift is an 85-km-long, 2- to 8-km-wide volcanic rift zone in the Snake River Plain, Idaho. Three latest Pleistocene to Holocene basaltic lava fields, Craters of the Moon, Kings Bowl, and Wapi, are located along the Great Rift. The Craters of the Moon lava field is a composite of more than 60 lava flows, 25 cinder cones, and at least 8 eruptive fissure systems. It covers 1,600 km 2 and contains ∼30 km 3 of lava flows and associated pyroclastic deposits. Field, radiocarbon, and paleomagnetic data show that the Craters of the Moon lava field formed in eight eruptive periods, each of which was typically several hundred years or less in duration and was separated from others before and after by intervals of several hundred to several thousand years. The first eruptive period began ∼15,000 yr B.P., and the latest eruptive period ended ∼2100 yr B.P. The small Kings Bowl lava field (3.3 km 2 , 0.01 km 3 ) and the larger Wapi lava field (330 km 2 , 6 km 3 ) both formed ∼2250 yr B.P. Three magma types have fed flows along the Great Rift. The types are (1) a contaminated type that has a SiO 2 range of ∼49%–64% and commonly shows petrographic evidence of contamination, (2) a fractionated type that has a SiO 2 range of ∼44%–54% and shows no evidence of contamination and whose chemical and mineralogical variation can be accounted for mainly by crystal fractionation, and (3) a Snake River Plain type that has a SiO 2 range of ∼45%–48%, shows little evidence of fractionation, and is represented by Kings Bowl–Wapi flows and olivine basalts of the Snake River Plain. The contaminated and fractionated magma types were erupted at the Craters of the Moon lava field, and the Snake River Plain magma type was erupted at the Kings Bowl and Wapi lava fields. These relations imply that the magma reservoirs are spatially isolated. The magma output rate for the Craters of the Moon segment of the Great Rift was constant at ∼1.5 km 3 /1,000 yr for the period from 15,000 to 7000 yr B.P. The rate increased to ∼2.8 km 3 /1,000 yr from 7000 to 2000 yr B.P., mainly as a result of the addition of contaminated magma to the nearly constant output rate of fractionated magma. The Craters of the Moon segment of the Great Rift has experienced quasi-steady-state, volume-predictable volcanism for the last 15,000 yr. The recurrence interval of eruptive activity for the Craters of the Moon lava field ranges from several hundred to ∼3,000 yr. Because the present interval has lasted ∼2,100 yr, another eruptive period seems likely to occur within the next 1,000 yr. The steady-state, volume-predictable relationship suggests that 5–6 km 3 of lava will be erupted in the next eruptive period.

Idaho

Selective preservation and origin of petroleum-forming aquatic kerogen

Studies of a marine algal sapropel from Mangrove Lake, Bermuda, by 13C NMR and stable carbon isotopic methods show that precursors of aquatic kerogen (insoluble, macromolecular, paraffinic humic substances) are primary components of algae and possibly associated bacteria and that these substances survive microbial decomposition and are selectively preserved during early diagenesis. ?? 1983 Nature Publishing Group.

Nature

Stratigraphy, structure, absolute age, and paleontology of the upper Pleistocene deposits at Sankaty Head, Nantucket Island, Massachusetts

The Sankaty Head cliff exposes drift of at least two glaciations and interglacial marine deposits. Radiocarbon, amino-acid- racemization, and uranium-thorium analyses were used to determine the absolute ages of the beds. The results indicate that 1) the Sankaty Sand correlates with oxygen-isotope stage 5 (Sangamonian), 2) the underlying drift is older than stage 5 (Illinoian or older) , and 3) the overlying drift is Wisconsinan in age. -from Authors

Massachusetts

Geochemical evidence for modern sediment accumulation on the continental shelf off southern New England

An area of fine-grained sediment approximately 170 km x 74 km in size, located in water depths between 60 m and 150 m, south of Martha's Vineyard, Mass., is a site of modern sediment deposition. The 14 C ages systematically increase with sediment depth from about 1,300 years B.P. at the surface to 8,000-10,000 years B.P. at the depth of maximum core penetration. The old age for the surface sediments probably results from a combination of deposition of old carbon and faunal mixing. In the finest sediments, the sedimentation rates were approximately 130 cm/1,000 yrs when deposition began and have decreased to about 25 cm/1,000 yrs. The decreasing sedimentation rate reflects a diminishing source of fine sediments, which presumably came from the Georges Bank and Nantucket Shoals area. Inventories of excess 210 Pb in undisturbed cores average 70 dpm/cm 2 (disintegrations per minute per square centimeter), more than two times higher than the flux of 210 Pb from the atmosphere and from 226 Ra decay in the overlying water. This additional influx of 210 Pb either must be with new fine-grained sediment material or from solutions that are stripped of their 210 Pb by particulates in the bottom nepheloid layer. Stable Pb concentrations in surface sediments are about 28 ppm, as much as two times higher than concentrations at depth. The high accumulation rates, 210 Pb inventories, and trace-metal profiles imply that this area is a modern sink for fine-grained sediments and for pollutants associated with particulate matter in the water column. To our knowledge, this is the only site of present-day natural deposition on the Continental Shelf off the eastern United States, exclusive of the Gulf of Maine. Because the net currents on the outer half of this Continental Shelf flow from northeast to southwest, this fine-grained deposit may receive its sediments and possible contaminants from the Nantucket Shoals and Georges Bank regions.

Massachusetts

Texture, clay mineralogy, trace metals, and age of cored sediments from the North Atlantic Outer Continental Shelf

The concentration of 9 trace metals in sediment cores collected from the Continental Shelf off the northeastern United States are generally uniform with sediment depth and are low compared to average crustal abundances. No evidence for the accumulation of anthropogenic metals was found in these samples. The sediment texture on Georges Bank is predominantly sand at essentially all sediment depths and at all locations. A larger concentration of silts and clays was found at some locations west of Great South Channel. The major clay mineral group in these sediments is illite with moderate amounts of chlorite and small amounts of kaolinite. 14 C ages on total organic matter in sediments have given the first evidence that the area of fine—grained sediment south of Martha's Vineyard is a modern deposit. This area may be the only sink for fine sediments and sediment—related contaminants on the Continental Shelf exclusive of the Gulf of Maine. 14 C ages on total organic matter in glacial till recovered south of Nantucket Island tentatively suggest the presence of Late Wisconsin ice at this location. Confirmation requires analysis of detrital coal in these samples.

North Atlantic Outer Continental Shelf