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Physical properties and rock physics models of sediment containing natural and laboratory-formed methane gas hydrate

This paper presents results of shear strength and acoustic velocity (p-wave) measurements performed on: (1) samples containing natural gas hydrate from the Mallik 2L-38 well, Mackenzie Delta, Northwest Territories; (2) reconstituted Ottawa sand samples containing methane gas hydrate formed in the laboratory; and (3) ice-bearing sands. These measurements show that hydrate increases shear strength and p-wave velocity in natural and reconstituted samples. The proportion of this increase depends on (1) the amount and distribution of hydrate present, (2) differences, in sediment properties, and (3) differences in test conditions. Stress-strain curves from the Mallik samples suggest that natural gas hydrate does not cement sediment grains. However, stress-strain curves from the Ottawa sand (containing laboratory-formed gas hydrate) do imply cementation is present. Acoustically, rock physics modeling shows that gas hydrate does not cement grains of natural Mackenzie Delta sediment. Natural gas hydrates are best modeled as part of the sediment frame. This finding is in contrast with direct observations and results of Ottawa sand containing laboratory-formed hydrate, which was found to cement grains (Waite et al. 2004). It therefore appears that the microscopic distribution of gas hydrates in sediment, and hence the effect of gas hydrate on sediment physical properties, differs between natural deposits and laboratory-formed samples. This difference may possibly be caused by the location of water molecules that are available to form hydrate. Models that use laboratory-derived properties to predict behavior of natural gas hydrate must account for these differences.

American Mineralogist

A methodology to estimate CO2 and energy gas storage resources in depleted conventional gas reservoirs

Depleted hydrocarbon reservoirs are subsurface geological structures capable of sequestering vast quantities of carbon dioxide (CO 2 ) as well as storing other energy gases for later usage, such as natural gas, and potentially hydrogen (H 2 ). Here we outline a methodology to quantify multi-gas storage resources in depleted conventional gas reservoirs for usage in assessments by the United States Geological Survey (USGS) at the scale of sedimentary basins. The methodology consists first of quantifying accessible pore volume in a depleted reservoir for natural gas storage using up to three equations. Input data are derived from commonly reported or estimated reservoir parameters and natural gas production volumes, and equations may be combined in linear models to improve pore volume estimates. Storage estimates from these equations are tested and validated for 31 reservoirs in the Michigan Basin Province, USA that were previously converted to underground gas storage facilities and have known (federally reported) natural gas storage capacities. Secondly, natural gas storage capacities can be transformed via fluid substitution calculations to estimate the storage resources for non-native fluids, applied here for, CO 2 , H 2 , and methane-H 2 blends, accounting for molecule-specific deviations from ideal gas behavior at reservoir pressures and temperatures as well as differing storage efficiencies. Importantly, the storage of non-native fluids may not be appropriate in all depleted gas reservoir settings due to potential risks like leakage, in particular in the case of H 2 storage, requiring additional knowledge of caprock sealing capacity. Given this caveat, we demonstrate the fluid substitution method for natural gas reservoirs of the Northern Niagaran Reef and Southern Niagaran Reef USGS plays in the Michigan Basin Province, as these trends of Silurian pinnacle reefs are capped with tight-sealing evaporite facies. The deterministic equations outlined from this methodology can be incorporated into future probabilistic USGS gas storage assessments for CO 2 , H 2 , and natural gas resources in the United States.

Michigan

Molecular and isotopic compositions of hydrocarbons at Site 533, Deep Sea Drilling Project Leg 76

In an investigation of gas hydrates in deep ocean sediments, gas samples from Deep Sea Drilling Project Site 533 on the Blake Outer Ridge in the northwest Atlantic were obtained for molecular and isotopic analyses. Gas samples were collected from the first successful deployment of a pressure core barrel (PCB) in a hydrate region. The pressure decline curves from two of the four PCB retrievals at in situ pressures suggested the presence of small amounts of gas hydrates. Compositional and isotopic measurements of gases from several points along the pressure decline curve indicated that (1) biogenic methane (δ13C = -68‰; CJ/CJ = 5000) was the dominant gas (>90%); (2) little fractionation in the C,/ C2 ratio or the C carbon isotopic composition occurred as gas hydrates decomposed during pressure decline experi ments; (3) the percent of C3 , i-C4 , and CO2 degassed increased as the pressure declined, indicating that these molecules may help stabilize the hydrate structure; (4) excess nitrogen was present during initial degassing; and (5) Cj/Q ratios and isotopic ratios of C gases were similar to those obtained from conventional core sampling. The PCB gas also con tained trace amounts of saturated, acyclic, cyclic, and aromatic C5 -C14 hydrocarbons, as well as alkenes and tetrahydrothiophenes. Gas from a decomposed specimen of gas hydrate had similar molecular and isotopic ratios to the PCB gas (δ13C of -68% for methane and a q/ Q ratio of -6000). Regular trends in the δ 13C of methane ( 95 60%) and C{ /C2 ratios (-25000 — 2000) were observed with depth. Capillary gas chromatography (GC) and total scanning fluorescence measurements of extracted organic material were characteristic of hydrocarbons dominated by a marine source, though significant amounts of perylene were also present.

Initial Reports of the D.S.D.P.

Heavy oil and natural bitumen resources in geological basins of the world

Heavy oil and natural bitumen are oils set apart by their high viscosity (resistance to flow) and high density (low API gravity). These attributes reflect the invariable presence of up to 50 weight percent asphaltenes, very high molecular weight hydrocarbon molecules incorporating many heteroatoms in their lattices. Almost all heavy oil and natural bitumen are alteration products of conventional oil. Total resources of heavy oil in known accumulations are 3,396 billion barrels of original oil in place, of which 30 billion barrels are included as prospective additional oil. The total natural bitumen resource in known accumulations amounts to 5,505 billion barrels of oil originally in place, which includes 993 billion barrels as prospective additional oil. This resource is distributed in 192 basins containing heavy oil and 89 basins with natural bitumen. Of the nine basic Klemme basin types, some with subdivisions, the most prolific by far for known heavy oil and natural bitumen volumes are continental multicyclic basins, either basins on the craton margin or closed basins along convergent plate margins. The former includes 47 percent of the natural bitumen, the latter 47 percent of the heavy oil and 46 percent of the natural bitumen. Little if any heavy oil occurs in fore-arc basins, and natural bitumen does not occur in either fore-arc or delta basins.

Open-File Report

Geochemical analysis of potash mine seep oils, collapsed breccia pipe oil shows and selected crude oils, Eddy County, New Mexico

Oil shows, in the form of oil stains and bleeding oil, in core samples from two breccia pipes, Hills A and C, Eddy County, New Mexico, and seepage oils in a potash mine near Hill C breccia pipe are geochemically similar. The geochemical similarities strongly suggest that they belong to the same family of oils and were derived from similar sources. The oils are relatively high in sulfur (0.89 to 1.23 percent), rich in hydrocarbons (average 82 percent), relatively high in saturated hydrocarbon/aromatic hydrocarbon ratios (average 2.9), and based on analysis of seep oils alone, have a low API gravity (average 19.4?). The oils are for the most part severely biodegraded as attested by the loss of n-paraffin molecules. Geochemical comparison of seven crude oils collected in the vicinity of the breccia pipes indicates that the Yates oils are the likely source of the above family of oils. Six barrels of crude oil that were dumped into a potash exploration borehole near Hill C breccia pipe, to release stuck casing, are considered an unlikely source of the breccia pipe and mine seep oils. Volumetric and hydrodynamic constraints make it highly improbable that such a small volume of 'dumped' oil could migrate over distances ranging from about 600 feet to 2.5 miles to the sites of the oil shows.

Open-File Report

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of organochlorine pesticides and polychlorinated biphenyls in bottom sediment by dual capillary-column gas chromatography with electron-capture detection

A method for the determination of 30 individual organochlorine pesticides, total toxaphene, and total polychlorinated biphenyls (PCBs) in bottom sediment is described. The method isolates the pesticides and PCBs by solvent extraction with dichlorobenzene, removes inorganic sulfur, large naturally occurring molecules, and other unwanted interferences by gel permeation chromatography, and further cleans up and class fractionates the extract using adsorption chromatography. The com- pounds then are instrumentally determined using dual capillary-column gas chromatography with electron-capture detection. Reporting limits range from 1 to 5 micrograms per kilogram for 30 individual pesticides, 50 micrograms per kilogram for total PCBs, and 200 micrograms per kilogram for total toxaphene. The method also is designed to allow the simultaneous isolation of 79 other semivolatile organic compounds from the sediment, which are separately quantified using gas chromatography with mass spectrometric detection. The method was developed in support of the U.S. Geological Survey's National Water-Quality Assessment program.

Open-File Report

Evaluation of conceptual models of natural organic matter (humus) from a consideration of the chemical and biochemical processes of humification

Natural organic matter (NOM) has been studied for more than 200 years because of its importance in enhancing soil fertility, soil structure, and water-holding capacity and as a carbon sink in the global carbon cycle. Two different types of models have been proposed for NOM: (1) the humic polymer models and (2) the molecular aggregate models. In the humic polymer models, NOM molecules are depicted as large (humic) polymers that have unique chemical structures that are different from those of the precursor plant degradation products. In the molecular aggregate models, NOM is depicted as being composed of molecular aggregates (supramolecular aggregates) of plant degradation products held together by non-covalent bonds. The preponderance of evidence favors the supramolecular aggregate models. These models were developed by studying the properties of NOM extracted from soils and natural waters, and as such, they provide only a very generalized picture of the structure of NOM aggregates in soils and natural waters prior to extraction. A compartmental model, in which the structure of the NOM in each of the compartments is treated separately, should provide a more accurate representation of NOM in soil and sediment systems. The proposed NOM compartments are: (1) partially degraded plant tissue, (2) biomass from microorganisms, (3) organic coatings on mineral grains, (4) pyrolytic carbon, (5) organic precipitates, and (6) dissolved organic matter (DOM) in interstitial water. Within each of these compartments there are NOM supramolecular aggregates that will be dissolved by the solvent systems that are used by researchers for extraction of NOM from soils and sediments. In natural water systems DOM may be considered as existing in two subcompartments: (1) truly dissolved DOM and (2) colloidal DOM.

Scientific Investigations Report

Concentrations, loads, and sources of polychlorinated biphenyls, Neponset River and Neponset River Estuary, eastern Massachusetts

Polychlorinated biphenyls (PCBs) are known to contaminate the Neponset River, which flows through parts of Boston, Massachusetts, and empties into the Neponset River Estuary, an important fish-spawning area. The river is dammed and impassable to fish. The U.S. Geological Survey, in cooperation with the Massachusetts Department of Fish and Game, Division of Ecological Restoration, Riverways Program, collected, analyzed, and interpreted PCB data from bottom-sediment, water, and (or) fish-tissue samples in 2002, 2004-2006. Samples from the Neponset River and Neponset River Estuary were analyzed for 209 PCB congeners, PCB homologs, and Aroclors. In order to better assess the overall health quality of river-bottom sediments, sediment samples were also tested for concentrations of 31 elements. PCB concentrations measured in the top layers of bottom sediment ranged from 28 nanograms per gram (ng/g) just upstream of the Mother Brook confluence to 24,900 ng/g measured in Mother Brook. Concentrations of elements in bottom sediment were generally higher than background concentrations and higher than levels considered toxic to benthic organisms according to freshwater sediment-quality guidelines defined by the U.S. Environmental Protection Agency. Concentrations of dissolved PCBs in water samples collected from the Neponset River (May 13, 2005 to April 28, 2006) averaged about 9.2 nanograms per liter (ng/L) (annual average of monthly values); however, during the months of August (about 16.5 ng/L) and September (about 15.6 ng/L), dissolved PCB concentrations were greater than 14 ng/L, the U.S. Environmental Protection Agency's freshwater continuous chronic criterion for aquatic organisms. Concentrations of PCBs in white sucker (fillets and whole fish) were all greater than 2,000 ng/g wet wt, the U.S. Environmental Protection Agency's guideline for safe consumption of fish: PCB concentrations measured in fish-tissue samples collected from the Tileston and Hollingsworth and Walter Baker Impoundments were 3,490 and 2,450 ng/g wet wt (filleted) and 6,890 and 4,080 ng/g wet wt (whole fish). Total PCB-congener concentrations measured in the whole bodies of estuarine bait fish (common mummichog) averaged 708 ng/g wet wt. PCBs that pass from the Neponset River to the Neponset River Estuary are either dissolved or associated with particulate matter (including living and nonliving material) suspended in the water column. A small proportion of PCBs may also be transported as part of the body burden of fish and wildlife. During the period May 13, 2005 to April 28, 2006, about 5,100 g (3.8 L or 1 gal) of PCBs were transported from the Neponset River to the Neponset River Estuary. Generally, about one-half of these PCBs were dissolved in the water column and the other half were associated with particulate matter; however, the proportion that was either dissolved or particulate varied seasonally. Most PCBs transported from the river to the estuary are composed of four or fewer chlorine atoms per biphenyl molecule. The data suggest that widespread PCB contamination of the lower Neponset River originated from Mother Brook, a Neponset River tributary, starting sometime around the early 1950s or earlier. In 1955, catastrophic dam failure caused by flooding likely released PCB-contaminated sediment downstream and into the Neponset River Estuary. PCBs from this source area likely continued to be released after the flood and during subsequent rebuilding of downstream dams. Today (2007), PCBs are mostly trapped behind these dams; however, some PCBs either diffuse or are entrained back into the water column and are transported downstream by river water into the estuary or volatilize into the atmosphere. In addition to the continuing release of PCBs from historically contaminated bottom sediment, PCBs are still (2007) originating from source areas along Mother and Meadow Brook as well as other sources along the river and Boston Harbor. PCBs from the river (transported by river water) and from the harbor (transported by tidal action) appear to have contaminated parts of the Neponset River Estuary.

Massachusetts

Brookian sequence well log correlation sections and occurrence of gas hydrates, north-central North Slope, Alaska

Gas hydrates are naturally occurring crystalline, ice-like substances that consist of natural gas molecules trapped in a solid-water lattice. Because of the compact nature of their structure, hydrates can effectively store large volumes of gas and, consequently, have been identified as a potential unconventional energy source. First recognized to exist geologically in the 1960s, significant accumulations of gas hydrate have been found throughout the world. Gas hydrate occurrence is limited to environments such as permafrost regions and subsea sediments because of the pressure and temperature conditions required for their formation and stability. Permafrost-associated gas hydrate accumulations have been discovered in many regions of the Arctic, including Russia, Canada, and the North Slope of Alaska. Gas hydrate research has a long history in northern Alaska. This research includes the drilling, coring, and well log evaluation of two gas hydrate stratigraphic test wells and two resource assessments of gas hydrates on the Alaska North Slope. Building upon these previous investigations, this report provides a summary of the pertinent well log, gas hydrate, and stratigraphic data for key wells related to gas hydrate occurrence in the north-central North Slope. The data are presented in nine well log correlation sections with 122 selected wells to provide a regional context for gas hydrate accumulations and the relation of the accumulations to key stratigraphic horizons and to the base of the ice-bearing permafrost. Also included is a well log database that lists the location, available well logs, depths, and other pertinent information for each of the wells on the correlation section.

Alaska

Baseline water-quality sampling to infer nutrient and contaminant sources at Kaloko-Honokōhau National Historical Park, Island of Hawai‘i, 2009

Baseline water-quality sampling was conducted for dissolved nutrients and for chemical and isotopic tracers at Kaloko-Honokōhau National Historical Park on the Island of Hawai'i. Existing and future urbanization in the surrounding areas have the potential to affect water quality in the Park, and so the National Park Service and the U.S. Geological Survey designed a water-sampling strategy to document baseline conditions against which future changes can be compared. Sites in and near the Park were sampled twice, in July and December 2009, and included four anchialine pools, two large fishponds, five monitoring wells, an upland production well, tap water, and a holding pond for golf-course irrigation water. Water samples within the coastal park were brackish, ranging in salinity from 15 to 67 percent seawater. Samples were analyzed for dissolved inorganic nutrients (nitrogen and phosphorus), stable isotopes (nitrogen and oxygen in dissolved nitrate; hydrogen and oxygen in the water molecule), pharmaceuticals, wastewater compounds, and volatile organic compounds. A case of acute, but temporary, fertilizer contamination was evident along the Park's north boundary during the turf grow-in period of a newly constructed golf course. A maximum nitrogen concentration 280 percent above background level was measured in monitoring well MW401 in July, later falling to 109 percent above background by December. Two nearby sites (MW400 and AP 144) had nitrogen concentrations that were elevated compared to remaining sites but less severely than at MW401. Aside from this localized fertilizer influence, other water samples had lower nutrient enrichments: 40 percent or less above background for nitrogen and 57 percent or less above background for phosphorus. Background was defined in this study by a graphical mixing line between saltwater from a deep well in the Park and freshwater at a reference well in the mountainous uplands (Honokōhau production well, at 1,675 ft altitude). Potential nutrient sources between the uplands and coastal lowlands that could contribute to enrichment include rock weathering, natural vegetation, fertilizers, septic leachate, and atmospheric deposition – including motor-vehicle exhaust. Some fraction of septic leachate is expected in groundwater because there are unsewered suburban and commercial developments upslope from the Park that rely on cesspools and septic systems. However, stable isotopes of nitrate did not implicate septic-waste nitrogen (heavy δ 15 N values on the order of +10 per mil or greater). Instead, the heaviest δ 15 N values of +6 to +8 per mil were associated with the large fishponds, likely as a result of biotic cycling. Water samples with δ 15 N values of +3 to +5 per mil were still isotopically heavier than the upland groundwater value of +2 per mil and likely reflect addition of heavier nitrogen, possibly from septic sources, nitrogen-fixing vegetation, or vehicular exhaust. Pharmaceuticals, wastewater compounds, and volatile organic compounds indicated that if contamination is present, it appears to be at low, barely detectable, levels--at least as reflected by the results of this study. The most diagnostic indication of septic contamination was at monitoring well KAHO 2, closest to Kaloko Light Industrial Park, where three pharmaceuticals (carbamazepine, sulfamethoxazole, and thiobendazole) were detected at trace-level parts-per-trillion concentrations. A screening-level test for laundry fabric brighteners indicated positive detection at most sites; however, readings were quite low and if laundry graywater is present, it appears to be a small, dilute fraction. Because the weather was persistently dry throughout the study period, the USGS team was unable to conduct a wet-weather “storm” sampling. Wet-weather results are expected to differ from those reported here, though by how much remains unknown.

Hawai‘i

Tritium deposition in precipitation in the United States, 1953–2012

Tritium is a radioactive isotope of hydrogen (half-life is equal to 12.32 years). Since it is part of the water molecule, tritium can be used to track and date groundwater and surface water when the history of tritium in precipitation and recharge is known. To facilitate that effort, tritium concentrations in precipitation were reconstructed from measurements and correlations for 10 precipitation stations in the continental United States. Using these data, and other data sets and correlations, estimates of tritium concentrations in precipitation from 1953 through 2012 and total tritium deposition from 1953 through 1983 were derived for 2 degrees latitude by 5 degrees longitude quadrangles of the continental United States. For August 1953 through December 1987 correlations were derived from the data of the Ottawa, Canada, station; for estimates after 1987, the Vienna, Austria, station was used. For quadrangles where no precipitation station records are available from measurements or correlations, concentrations were interpolated. The International Atomic Energy Agency has proposed that a correlation with the Vienna, Austria, station, which has been in operation since 1960, be used instead of the Ottawa, Canada, station for the period after 1987. Linear correlations calculated for all stations with the Vienna data are reported. Correlations also have been calculated for each latitude-longitude quadrangle using the estimated concentrations and the measured Vienna data for 1960–87. Because the Vienna, Austria, station is on a different continent, and not subject to the same seasonal weather patterns that affect North American stations, a correlation was obtained for each month individually. This reflects the fact that the North American stations were strongly affected by the input of low-tritium moisture from the south during the summer. The correlated station values were then used with measured Vienna data to obtain estimates of tritium concentrations in precipitation for the period 1988–2012 at each precipitation station and latitude-longitude quadrangles. This approach has two major advantages: (1) it blends the Ottawa correlation with the Vienna correlation to cover the period 1953 to present, and (2) it yields correlation coefficients for each quadrangle that can be used in future years when more data become available from the Vienna, Austria, station. The data, the estimated tritium concentrations derived from the correlations, and the correlation coefficients are provided as spreadsheets and associated comma delimited files in a data release that accompanies this report.

Scientific Investigations Report

Nutrient chemistry in the Elizabeth Lake subwatershed—Effects of onsite wastewater treatment systems on groundwater and lake water quality, Los Angeles County, California

Nutrient (nitrogen [N] and phosphorus [P] chemistry) downgradient from onsite wastewater treatment system (OWTS) was evaluated with a groundwater study in the area surrounding Elizabeth Lake, the largest of three sag lakes within the Santa Clara River watershed of Los Angeles County, California. Elizabeth Lake is listed on the “303 (d) Impaired Waters List” for excess nutrients and is downgradient from more than 600 OWTS. The primary objective of this study was to develop a conceptual hydrogeological model to determine if discharge from OWTS is transported into shallow groundwater within the Elizabeth Lake subwatershed and contributes nutrients to Elizabeth Lake in excess of the total maximum daily load limit. An analysis of historical data and data collected for this study provided estimates of aquifer properties, such as hydraulic gradients and other parameters necessary to estimate boundary conditions. Electrical resistivity tomography (ERT) surveys were done to determine the best monitoring well locations and to estimate depth to groundwater. During 4 separate sampling events, 11 wells, 2 imported water tanks, 1 spring (sampled on March 17, 2019), and Elizabeth Lake were sampled, which occurred during February–September 2020. ERT transects and borehole geophysical measurements indicated that there were low to high resistivity materials in the subsurface and potential perched fresh water. Most of the aquifer material was characterized as sandy silt, occasionally with mixed clays and medium gravels, and was estimated to have a hydraulic conductivity from 3.28x10 −3 to 16.4 feet per day, a porosity from 0.34 to 0.42, and a hydraulic gradient from 0.01 to 0.03. Although bedrock was not obvious in ERT transects, all well depths were terminated at depths of an impassible confining layer observed to be a highly consolidated blue-gray clay. Depths to granitic bedrock, based on road outcrops and lithologic driller logs, varied throughout the study area. Depth to the bedrock was estimated to be shallow on the north side of Elizabeth Lake at approximately 30 feet below land surface (ft bls). Depth to bedrock is at 50 ft bls toward the east of the Elizabeth Lake subwatershed, which is at topographic ground surface to the north and south of the residential development. Groundwater levels ranged from approximately 0 to 12 ft bls during this study. Historical water levels ranged from 8 to 16 ft bls in the lower elevation of the study area and increased to depths of as much as 80 ft bls at higher elevations on the north and south boundaries of the Elizabeth Lake subwatershed. Water-quality samples were analyzed for major ions, nutrients, dissolved organic carbon, stable isotopes, and age-dating tracers. A principal component analysis was completed to determine organic matter sources. The proportion of recharge from imported waters, used for domestic consumption, was calculated using stable water isotopes, deuterium (δD) and oxygen (δ 18 O). Recharge from imported waters accounted for approximately 15–71 percent of the total recharge to groundwater within the study area. Total nitrogen concentrations ranged from 0.17 to 30.9 milligrams per liter (mg/L) as N, and phosphorus, measured in the soluble form as orthophosphate, ranged from 0.03 to 0.35 mg/L as P. Nitrate concentrations in groundwater samples ranged from less than the detection limit (0.01 mg/L as N) to approximately 24 mg/L as N. Nitrate was not detected in 3 of the 12 sites sampled during the study (2 wells and Elizabeth Lake). Dissolved organic carbon concentrations ranged from 0.4 to 27 mg/L in groundwater and from 9.9 to 100 mg/L in Elizabeth Lake. Ammonium and orthophosphate concentrations generally were low in groundwater. However, elevated concentrations of ammonium in Elizabeth Lake were assumed to be due to avian waste products or biological nitrogen fixation. Groundwater ages were mostly modern (recharged since 1952), with a median recharge temperature of 13 degrees Celsius. Redox conditions in groundwater indicated the likely occurrence of nitrate attenuation by denitrification downgradient from the wells to the south of Elizabeth Lake before groundwater discharges to the lake. Undetectable nitrate in Elizabeth Lake at the time of sampling was likely due to algal uptake. Most wells contained stable isotopes of nitrogen and oxygen in nitrate (δ 15 N-NO 3 and δ 18 O-NO 3 ) molecules with values consistent with denitrification. However, one monitoring well on the north of Elizabeth Lake (ELLA-8) had no evidence of denitrification, based on elevated concentrations of nitrate and a sufficient amount of dissolved oxygen such that the water was oxic and not favorable for the denitrification reaction. Consequently, this nitrate could be delivered to Elizabeth Lake through groundwater discharge if nitrate is not removed from the system by denitrifying bacteria downgradient from the well before the groundwater discharges into Elizabeth Lake. The principal component analysis demonstrated that dissolved organic matter optical properties track different sources of dissolved organic matter from decayed plants, animals, and animal-derived wastes. Two wells contained strong indicators of OWTS water presence, although geochemical evidence indicated other wells may also be affected by OWTS discharge.

California

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 glyphosate, its degradation product aminomethylphosphonic acid, and glufosinate, in water by isotope dilution and online solid-phase extraction and liquid chromatography/tandem mass spectrometry

The U.S. Geological Survey method (0-2141-09) presented is approved for the determination of glyphosate, its degradation product aminomethylphosphonic acid (AMPA), and glufosinate in water. It was was validated to demonstrate the method detection levels (MDL), compare isotope dilution to standard addition, and evaluate method and compound stability. The original method USGS analytical method 0-2136-01 was developed using liquid chromatography/mass spectrometry and quantitation by standard addition. Lower method detection levels and increased specificity were achieved in the modified method, 0-2141-09, by using liquid chromatography/tandem mass spectrometry (LC/MS/MS). The use of isotope dilution for glyphosate and AMPA and pseudo isotope dilution of glufosinate in place of standard addition was evaluated. Stable-isotope labeled AMPA and glyphosate were used as the isotope dilution standards. In addition, the stability of glyphosate and AMPA was studied in raw filtered and derivatized water samples. The stable-isotope labeled glyphosate and AMPA standards were added to each water sample and the samples then derivatized with 9-fluorenylmethylchloroformate. After derivatization, samples were concentrated using automated online solid-phase extraction (SPE) followed by elution in-line with the LC mobile phase; the compounds separated and then were analyzed by LC/MS/MS using electrospray ionization in negative-ion mode with multiple-reaction monitoring. The deprotonated derivatized parent molecule and two daughter-ion transition pairs were identified and optimized for glyphosate, AMPA, glufosinate, and the glyphosate and AMPA stable-isotope labeled internal standards. Quantitative comparison between standard addition and isotope dilution was conducted using 473 samples analyzed between April 2004 and June 2006. The mean percent difference and relative standard deviation between the two quantitation methods was 7.6 plus or minus 6.30 (n = 179), AMPA 9.6 plus or minus 8.35 (n = 206), and glufosinate 9.3 plus or minus 9.16 (n = 16). The analytical variation of the method, comparison of quantitation by isotope dilution and multipoint linear regressed standard curves, and method detection levels were evaluated by analyzing six sets of distilled-water, groundwater, and surface-water samples spiked in duplicate at 0.0, 0.05, 0.10 and 0.50 microgram per liter and analyzed on 6 different days during 1 month. The grand means of the normalized concentration percentage recovery for glyphosate, AMPA, and glufosinate among all three matrices and spiked concentrations ranged from 99 to 114 plus or minus 2 to 7 percent of the expected spiked concentration. The grand mean of the percentage difference between concentrations calculated by standard addition and linear regressed multipoint standard curves ranged from 8 to 15 plus or minus 2 to 9 percent for the three compounds. The method reporting levels calculated from all the 0.05- microgram per liter spiked samples were 0.02 microgram per liter for all three compounds. Compound stability experiments were conducted on 10 samples derivatized four times for periods between 136 to 269 days. The glyphosate and AMPA concentrations remained relatively constant in samples held up to 136 days before derivatization. The half life of glyphosate varied from 169 to 223 days in the underivatized samples. Derivatized samples were analyzed the day after derivitization, and again 54 and 64 days after derivatization. The derivatized samples analyzed at days 52 and 64 were within 20 percent of the concentrations of the derivatized samples analyzed the day after derivatization.

Techniques and Methods

Hydrogeologic setting and potential for denitrification in ground water, Coastal Plain of southern Maryland

The types and distribution of Coastal Plain sediments in the Patuxent River Basin may contribute to relatively low concentrations of nitrate (typically less than 1 milligram per liter) in stream base flow because of the chemical reduction of dissolved nitrate (denitrification) in ground water. Water chemistry data from synoptic stream base-flow surveys in the Patuxent River Basin show higher dissolved nitrate concentrations in the Piedmont than in the Coastal Plain section of the watershed. Stream base flow reflects closely the chemistry of ground water discharging from the surficial (unconfined) aquifer to the stream. Because land use in the sampled subbasins is virtually the same in each section, differences in the physical and geochemical characteristics of the surficial aquifer may explain the observed differences in water chemistry. One possible cause of lower nitrate concentrations in the Coastal Plain is denitrification within marine sediments that contain chemically reduced compounds. During denitrification, the oxygen atoms on the nitrate (N0 3 -) molecule are transferred to a reduced compound and N gas is produced. Organic carbon and ferrous iron (Fe 2+ ), derived from the dissolution of minerals such as pyrite (FeS 2 ) and glauconite (an iron aluminosilicate clay), can act as reducing substrates; these reduced chemical species are common in the marine and estuarine deposits in Southern Maryland. The spatial distribution of geologic units and their lithology (sediment type) has been used to create a map of the potential for denitrification of ground water in the surficial aquifer of the Coastal Plain in Southern Maryland.

Maryland