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Kinga Revesz

Publications and source records attributed to Kinga Revesz.

17 recordsLinked to original sources

Geochemical investigation of the hydrothermal system on Akutan Island, Alaska, July 2012

We have studied the geochemistry of the hot springs on Akutan Island in detail for the first time since the early 1980s. Springs in four discrete groups (A-D) along Hot Springs Creek showed generally higher temperatures and substantially higher Na, Ca, and Cl concentrations than previously reported, and total hot-spring discharge has also increased markedly. The springs now account for a heat output of ~29 MW, about an order of magnitude more than in 1981. Gas samples from the hot springs and from a fumarolic area on the flank of Akutan Volcano show high 3 He/ 4 He ratios (>6.4 RA) after correction for air contamination and reveal a common magmatic heat source. Hot-spring gases are unusually rich in N 2 , Ar, and CH 4 , suggesting that the water has boiled and lost CO 2 during upflow beneath the flank fumarole field. Gas geothermometry calculations applied to the flank fumarole field implies temperatures of 200–240 °C for the reservoir, and Na-K-Ca geothermometry implies temperatures near 180 °C for the outflow waters that feed the hot springs. The results of our study confirm the existence of a substantial geothermal resource on the island.

Alaska

Determination of the δ 13 C of dissolved inorganic carbon in water; RSIL lab code 1710

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1710 is to present a method to determine the δ 13 C of dissolved inorganic carbon (DIC) of water. The DIC of water is precipitated using ammoniacal strontium chloride (SrCl 2 ) solution to form strontium carbonate (SrCO 3 ). The δ 13 C is analyzed by reacting SrCO 3 with 100-percent phosphoric acid (H 3 PO 4 ) to liberate carbon quantitatively as carbon dioxide (CO 2 ), which is collected, purified by vacuum sublimation, and analyzed by dual inlet isotope-ratio mass spectrometry (DI-IRMS). The DI-IRMS is a DuPont double-focusing mass spectrometer. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other measurable ion beams are collected in the front collector. By changing the ion-accelerating voltage under computer control, the instrument is capable of measuring mass/charge ( m/z ) 45 or 46 in the rear collector and m/z 44 and 46 or 44 and 45, respectively, in the front collector. The ion beams from these m/z values are as follows: m/z 44 = CO 2 = 12 C 16 O 16 O, m/z 45 = CO 2 = 13 C 16 O 16 O primarily, and m/z 46 = CO 2 = 12 C 16 O 18 O primarily. The data acquisition and control software calculates δ 13 C values.

Techniques and Methods

Determination of the delta(2H/1H)of Water: RSIL Lab Code 1574

Reston Stable Isotope Laboratory (RSIL) lab code 1574 describes a method used to determine the relative hydrogen isotope-ratio delta(2H,1H), abbreviated hereafter as d2H of water. The d2H measurement of water also is a component of the National Water Quality Laboratory (NWQL) schedules 1142 and 1172. The water is collected unfiltered in a 60-mL glass bottle and capped with a Polyseal cap. In the laboratory, the water sample is equilibrated with gaseous hydrogen using a platinum catalyst (Horita, 1988; Horita and others, 1989; Coplen and others, 1991). The reaction for the exchange of one hydrogen atom is shown in equation 1.

Techniques and Methods

Determination of the delta(18O/16O)of Water: RSIL Lab Code 489

The purpose of the technique described by the Reston Stable Isotope Laboratory (RSIL) lab code 489 is to present a method to determine the delta(180/160), abbreviated as delta-180, of water. This delta-18O measurement of water also is a component of National Water Quality Laboratory (NWQL in USGS) schedules 1142 and 1172. Water samples are loaded into glass sample containers on a vacuum manifold to equilibrate gaseous CO2 at constant temperature (25 deg C) with water samples. After loading water samples on the vacuum manifold, air is evacuated through capillary to avoid evaporation, and CO2 is added. The samples are shaken to increase the equilibration rate of water and CO2. When isotopic equilibrium has been attained, an aliquot of CO2 is extracted sequentially from each sample container, separated from water vapor by means of a dry ice trap, and introduced into a dual-inlet isotope-ratio mass spectrometer (DI-IRMS) for determination of the delta-18O value. There is oxygen isotopic fractionation between water and CO2, but it is constant at constant temperature. The DI-IRMS is a DuPont double-focusing mass spectrometer. It has a double collector. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other ion beams are collected in the front collector. The instrument is capable of measuring mass/charge (m/z) 44 and 45 or 44 and 46 by changing the ion-accelerating voltage under computer control. The ion beams from these m/z values are as follows: m/z 44=CO2=12C16O16O, m/z 45=CO2=13C16O16O primarily, and m/z 46 = CO2=12C16O18O primarily. The data acquisition and control software calculates delta-18O values.

Techniques and Methods

Natural gases in ground water near Tioga Junction, Tioga County, north-central Pennsylvania: Occurrence and use of isotopes to determine origins, 2005

In January 2001, State oil and gas inspectors noted bubbles of natural gas in well water during a complaint investigation near Tioga Junction, Tioga County, north-central Pa. By 2004, the gas occurrence in ground water and accumulation in homes was a safety concern; inspectors were taking action to plug abandoned gas wells and collect gas samples. The origins of the natural-gas problems in ground water were investigated by the U.S. Geological Survey, in cooperation with the Pennsylvania Department of Environmental Protection, in wells throughout an area of about 50 mi2, using compositional and isotopic characteristics of methane and ethane in gas and water wells. This report presents the results for gas-well and water-well samples collected from October 2004 to September 2005. Ground water for rural-domestic supply and other uses near Tioga Junction is from two aquifer systems in and adjacent to the Tioga River valley. An unconsolidated aquifer of outwash sand and gravel of Quaternary age underlies the main river valley and extends into the valleys of tributaries. Fine-grained lacustrine sediments separate shallow and deep water-bearing zones of the outwash. Outwash-aquifer wells are seldom deeper than 100 ft. The river-valley sediments and uplands adjacent to the valley are underlain by a fractured-bedrock aquifer in siliciclastic rocks of Paleozoic age. Most bedrock-aquifer wells produce water from the Lock Haven Formation at depths of 250 ft or less. A review of previous geologic investigations was used to establish the structural framework and identify four plausible origins for natural gas. The Sabinsville Anticline, trending southwest to northeast, is the major structural feature in the Devonian bedrock. The anticline, a structural trap for a reservoir of deep native gas in the Oriskany Sandstone (Devonian) (origin 1) at depths of about 3,900 ft, was explored and tapped by numerous wells from 1930-60. The gas reservoir in the vicinity of Tioga Junction, depleted of native gas, was converted to the Tioga gas-storage field for injection and withdrawal of non-native gases (origin 2). Devonian shale gas (shallow native gas) also has been reported in the area (origin 3). Gas might also originate from microbial degradation of buried organic material in the outwash deposits (origin 4). An inventory of combustible-gas concentrations in headspaces of water samples from 91 wells showed 49 wells had water containing combustible gases at volume fractions of 0.1 percent or more. Well depth was a factor in the observed occurrence of combustible gas for the 62 bedrock wells inventoried. As well-depth range increased from less than 50 ft to 51-150 ft to greater than 151 ft, the percentage of bedrock-aquifer wells with combustible gas increased. Wells with high concentrations of combustible gas occurred in clusters; the largest cluster was near the eastern boundary of the gas-storage field. A subsequent detailed gas-sampling effort focused on 39 water wells with the highest concentrations of combustible gas (12 representing the outwash aquifer and 27 from the bedrock aquifer) and 8 selected gas wells. Three wells producing native gas from the Oriskany Sandstone and five wells (two observation wells and three injection/withdrawal wells) with non-native gas from the gas-storage field were sampled twice. Chemical composition, stable carbon and hydrogen isotopes of methane (13CCH4 and DCH4), and stable carbon isotopes of ethane (13CC2H6) were analyzed. No samples could be collected to document the composition of microbial gas originating in the outwash deposits (outwash or 'drift' gas) or of native natural gas originating solely in Devonian shale at depths shallower than the Oriskany Sandstone, although two of the storage-field observation wells sampled reportedly yielded some Devonian shale gas. Literature values for outwash or 'drift' gas and Devonian shale gases were used to supplement the data collection. Non-native gases fr

Pennsylvania

Determination of the δ 15 N of nitrate in solids; RSIL lab code 2894

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2894 is to determine the δ 15 N of nitrate (NO 3 - ) in solids. The nitrate fraction of the nitrogen species is dissolved by water (called leaching) and can be analyzed by the bacterial method covered in RSIL lab code 2899. After leaching, the δ 15 N of the dissolved NO 3 - is analyzed by conversion of the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods

Determination of the δ 15 N and δ 18 O of nitrate in solids; RSIL lab code 2897

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2897 is to determine the δ 15 N and δ 18 O of nitrate (NO 3 - ) in solids. The NO 3 - fraction of the nitrogen species is dissolved by water (called leaching) and can be analyzed by the bacterial method covered in RSIL lab code 2900. After leaching, the δ 15 N and δ 18 O of the dissolved NO 3 - is analyzed by conversion of the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods

Determination of the δ 15 N of nitrate in water; RSIL lab code 2899

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2899 is to determine the δ 15 N of nitrate (NO 3 - ) in water. The δ 15 N of the dissolved NO 3 - is analyzed by conversion of the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of the NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods

Determination of the δ 15 N and δ 18 O of nitrate in water; RSIL lab code 2900

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2900 is to determine the δ 15 N and δ 18 O of nitrate (NO 3 - ) in water. The δ 15 N and δ 18 O of the dissolved NO 3 - are analyzed by converting the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of the NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods

Determination of the δ 34 S of sulfate in water; RSIL lab code 1951

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1951 is to determine the δ( 34 S/ 32 S), abbreviated as δ 34 S, of dissolved sulfate. Dissolved sulfate is collected in the field and precipitated with BaCl 2 at pH 3 to 4 as BaSO 4 in the laboratory. However, the dissolved organic sulfur (DOS) is oxidized to SO 2 , and the carbonate is acidified to CO 2 . Both are degassed from the water sample before the sulfate is precipitated. The precipitated BaSO 4 is filtered and dried before introduction into an elemental analyzer (EA) Carlo Erba NC 2500. The EA is used to convert sulfur in a BaSO 4 solid sample into SO 2 gas, and the EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines the differences in the isotope-amount ratios of stable sulfur isotopes ( 34 S/ 32 S) of the product SO 2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in a tin capsule and loaded into the Costech Zero Blank Autosampler of the EA. Under computer control, samples are dropped into a heated tube reaction tube that combines the oxidation and reduction reactions. The combustion takes place in a helium atmosphere containing an excess of oxygen gas at the oxidation zone at the top of the reaction tube. Combustion products are transported by a helium carrier through the reduction zone at the bottom of the reaction tube to remove excess oxygen and through a separate drying tube to remove any water. The gas-phase products, mainly CO 2 , N 2 , and SO 2 , are separated by a gas chromatograph. The gas is then introduced into the isotope-ratio mass spectrometer (IRMS) through a Finnigan MAT (now Thermo Scientific) ConFlo II interface, which also is used to inject SO 2 reference gas and helium for sample dilution. The IRMS is a Thermo Scientific Delta V Plus CF-IRMS. It has a universal triple collector with two wide cups and a narrow cup in the middle. It is capable of measuring mass/charge ( m/z ) 64 and 66 simultaneously. The ion beams from SO 2 are as follows: m/z 64 = SO 2 = 32 S 16 O 16 O; m/z 66 = SO 2 = 34 S 16 O 16 O primarily.

Techniques and Methods

Determination of the δ 15 N of total nitrogen in solids; RSIL lab code 2893

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2893 is to determine the δ( 15 N/ 14 N), abbreviated as δ 15 N , of total nitrogen in solid samples. A Carlo Erba NC 2500 elemental analyzer (EA) is used to convert total nitrogen in a solid sample into N 2 gas. The EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines relative difference in the isotope-amount ratios of stable nitrogen isotopes ( 15 N/ 14 N)of the product N 2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in a tin capsule and loaded into the Costech Zero Blank Autosampler of the EA. Under computer control, samples are dropped into a heated reaction tube that contains an oxidant, where the combustion takes place in a helium atmosphere containing an excess of oxygen gas. Combustion products are transported by a helium carrier through a reduction tube to remove excess oxygen and convert all nitrous oxides into N 2 and through a drying tube to remove water. The gas-phase products, mainly CO 2 and N 2 , are separated by a gas chromatograph. The gas is then introduced into the isotope-ratio mass spectrometer (IRMS) through a Finnigan MAT (now Thermo Scientific) ConFlo II interface, which also is used to inject N 2 reference gas and helium for sample dilution. The IRMS is a Thermo Scientific Delta V Plus CF-IRMS. It has a universal triple collector, two wide cups with a narrow cup in the middle, capable of measuring mass/charge ( m/z ) 28, 29, 30, simultaneously. The ion beams from N 2 are as follows: m/z 28 = N 2 = 14 N 14 N; m/z 29 = N 2 = 14 N 15 N primarily; m/z 30 = NO = 14 N 16 O primarily, which is a sign of contamination or incomplete reduction.

Techniques and Methods

Determination of the δ 34 S of Total Sulfur in Solids: RSIL Lab Code 1800

The purpose of Reston Stable Isotope Laboratory Lab (RSIL) Code 1800 is to determine the δ( 34 S/ 32 S), abbreviated as δ 34 S, of total sulfur in a solid sample. A Carlo Erba NC 2500 elemental analyzer (EA) is used to convert total sulfur in a solid sample into SO 2 gas. The EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines the relative difference in stable sulfur isotope-amount ratio ( 34 S/ 32 S) of the product SO 2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in tin capsules and loaded into a Costech Zero-Blank Autosampler on the EA. Under computer control, samples are dropped into a heated tube reaction tube that combines both the oxidation and the reduction reactions. The combustion takes place in a He atmosphere that contains an excess of oxygen gas at the oxidation zone at the top of the reaction tube. Combustion products are transported by a He carrier through the reduction zone at the bottom of the reaction tube to remove excess oxygen and through a separate drying tube to remove any water. The gas-phase products, mainly CO 2 , N 2 , and SO 2 , are separated by a gas chromatograph (GC). The gas is then introduced into the isotope-ratio mass spectrometer (IRMS) through a Thermo-Finnigan ConFlo II interface, which also is used to inject SO 2 reference gas and He for sample dilution. The IRMS is a Thermo-Finnigan DeltaPlus CF-IRMS. It has a universal triple collector with two wide cups and a narrow cup in the middle. It is capable of measuring mass/charge ( m/z ) 64 and 66 simultaneously. The ion beams from SO 2 are as follows: m/z 64 = SO 2 = 32 S 16 O 16 O; and m/z 66 = SO 2 = 34 S 16 O 16 O primarily.

Techniques and Methods

Determination of the δ 15 N and δ 13 C of total nitrogen and carbon in solids; RSIL lab code 1832

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1832 is to determine the δ( 15 N/ 14 N), abbreviated as δ 15 N, and the δ( 13 C/ 12 C), abbreviated as δ 13 C, of total nitrogen and carbon in a solid sample. A Carlo Erba NC 2500 elemental analyzer (EA) is used to convert total nitrogen and carbon in a solid sample into N 2 and CO 2 gas. The EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines the relative difference in stable nitrogen isotope-amount ratio ( 15 N/ 14 N) of the product N 2 gas and the relative difference in stable carbon isotope-amount ratio ( 13 C/ 12 C) of the product CO 2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in tin capsules and loaded into a Costech Zero Blank Autosampler on the EA. Under computer control, samples then are dropped into a heated reaction tube that contains an oxidant, where combustion takes place in a helium atmosphere containing an excess of oxygen gas. Combustion products are transported by a helium carrier through a reduction furnace to remove excess oxygen and to convert all nitrous oxides into N 2 and through a drying tube to remove water. The gas-phase products, mainly CO 2 and N 2 , are separated by a gas chromatograph. The gas is then introduced into the IRMS through a Finnigan MAT (now Thermo Scientific) ConFlo II interface. The Finnigan MAT ConFlo II interface is used for introducing not only sample into the IRMS but also N 2 and CO 2 reference gases and helium for sample dilution. The flash combustion is quantitative; no isotopic fractionation is involved. The IRMS is a Thermo Scientific Delta V CF-IRMS. It has a universal triple collector, two wide cups with a narrow cup in the middle; it is capable of measuring mass/charge ( m/z ) 28, 29, 30 or with a magnet current change 44, 45, 46, simultaneously. The ion beams from these m/z values are as follows: m/z 28 = N 2 = 14 N/ 14 N; m/z 29 = N 2 = 14 N/ 15 N primarily; m/z 30 = NO = 14 N/ 16 O primarily, which is a sign of contamination or incomplete reduction; m/z 44 = CO 2 = 12 C 16 O 16 O; m/z 45 = CO 2 = 13 C 16 O 16 O primarily; and m/z 46 = CO 2 = 12 C 16 O 18 O primarily.

Techniques and Methods

Determination of the δ 34 S of low-concentration sulfate in water; RSIL lab code 1949

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1949 is to determine the δ( 34 S/ 32 S), abbreviated as δ 34 S, of dissolved sulfate having a concentration less than 20 milligrams per liter. Dissolved sulfate is collected on an anion-exchange resin in the field, eluted in the laboratory with 3 M KCl, and precipitated with BaCl 2 at pH 3 to 4 as BaSO 4 . The precipitated BaSO 4 is filtered and dried before introduction into an elemental analyzer (EA) Carlo Erba NC 2500. The EA is used to convert sulfur in a BaSO 4 solid sample into SO 2 gas, and the EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines differences in the isotope-amount ratios of stable sulfur isotopes ( 34 S/ 32 S) of the product SO 2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in a tin capsule and loaded into the Costech Zero Blank Autosampler of the EA. Under computer control, samples are dropped into a heated reaction tube that combines the oxidation and reduction reactions. The combustion takes place in a helium atmosphere containing an excess of oxygen gas at the oxidation zone at the top of the reaction tube. Combustion products are transported by a helium carrier through the reduction zone at the bottom of the reaction tube to remove excess oxygen and through a separate drying tube to remove any water. The gas-phase products, mainly CO 2 , N 2 , and SO 2 , are separated by a gas chromatograph. The gas is then introduced into the isotope-ratio mass spectrometer (IRMS) through a Finnigan MAT (now Thermo Scientific) ConFlo II interface, which is also used to inject SO 2 reference gas and helium for sample dilution. The IRMS is a Thermo Scientific Delta V Plus CF-IRMS. It has a universal triple collector with two wide cups and a narrow cup in the middle. It is capable of measuring mass/charge ( m/z ) 64 and 66 simultaneously. The ion beams from SO 2 are as follows: m/z 64 = SO 2 = 32 S 16 O 16 O; m/z 66 = SO 2 = 34 S 16 O 16 O primarily.

Techniques and Methods

Methane production and consumption monitored by stable H and C isotope ratios at a crude oil spill site, Bemidji, Minnesota

Stable isotopic ratios of C and H in dissolved CH 4 and C in dissolved inorganic C in the ground water of a crude-oil spill near Bemidji, Minnesota, support the concept of CH 4 production by acetate fermentation with a contemporaneous increase in HCO 3 − concentration. Methane concentrations in the saturated zone decrease from 20.6 mg L −1 to less than 0.001 mg L −1 along the investigated flow path. Dissolved N 2 and Ar concentrations in the ground water below the oil plume are 25 times lower than background; this suggests that gas exsolution is removing dissolved CH 4 (along with other dissolved gases) from the ground water. Oxidation of dissolved CH 4 along the flow path seems to be minimal because no measurable change in isotopic composition of CH 4 occurs with distance from the oil body. However, CH 4 is partly oxidized to CO 2 as it diffuses upward from the ground water through a 5- to 7-m thick unsaturated zone; the δ 13 C of the remaining CH 4 increases, the δ 13 C of the CO 2 decreases, and the partial pressure of CO 2 increases. Calculations of C fluxes in the saturated and unsaturated zones originating from the degradation of the oil plume lead to a minimum estimated life expectancy of 110 years. This is a minimum estimate because the degradation of the oil body should slow down with time as its more volatile and reactive components are leached out and preferentially oxidized. The calculated life expectancy is an order of magnitude estimate because of the uncertainty in the average linear ground-water velocities and because of the factor of 2 uncertainty in the calculation of the effective CO 2 diffusion coefficient.

Minnesota