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Harry E. Lerch

Publications and source records attributed to Harry E. Lerch.

11 recordsLinked to original sources

Organic substances in produced and formation water from unconventional natural gas extraction in coal and shale

Organic substances in produced and formation water from coalbed methane (CBM) and gas shale plays from across the USA were examined in this study. Disposal of produced waters from gas extraction in coal and shale is an important environmental issue because of the large volumes of water involved and the variable quality of this water. Organic substances in produced water may be environmentally relevant as pollutants, but have been little studied. Results from five CBM plays and two gas shale plays (including the Marcellus Shale) show a myriad of organic chemicals present in the produced and formation water. Organic compound classes present in produced and formation water in CBM plays include: polycyclic aromatic hydrocarbons (PAHs), heterocyclic compounds, alkyl phenols, aromatic amines, alkyl aromatics (alkyl benzenes, alkyl biphenyls), long-chain fatty acids, and aliphatic hydrocarbons. Concentrations of individual compounds range from < 1 to 100 μg/L, but total PAHs (the dominant compound class for most CBM samples) range from 50 to 100 μg/L. Total dissolved organic carbon (TOC) in CBM produced water is generally in the 1–4 mg/L range. Excursions from this general pattern in produced waters from individual wells arise from contaminants introduced by production activities (oils, grease, adhesives, etc.). Organic substances in produced and formation water from gas shale unimpacted by production chemicals have a similar range of compound classes as CBM produced water, and TOC levels of about 8 mg/L. However, produced water from the Marcellus Shale using hydraulic fracturing has TOC levels as high as 5500 mg/L and a range of added organic chemicals including, solvents, biocides, scale inhibitors, and other organic chemicals at levels of 1000 s of μg/L for individual compounds. Levels of these hydraulic fracturing chemicals and TOC decrease rapidly over the first 20 days of water recovery and some level of residual organic contaminants remain up to 250 days after hydraulic fracturing. Although the environmental impacts of the organics in produced water are not well defined, results suggest that care should be exercised in the disposal and release of produced waters containing these organic substances into the environment because of the potential toxicity of many of these substances.

International Journal of Coal Geology

Organic intermediates in the anaerobic biodegradation of coal to methane under laboratory conditions

Organic intermediates in coal fluids produced by anaerobic biodegradation of geopolymers in coal play a key role in the production of methane in natural gas reservoirs. Laboratory biodegradation experiments on sub-bituminous coal from Texas, USA, were conducted using bioreactors to examine the organic intermediates relevant to methane production. Production of methane in the bioreactors was linked to acetate accumulation in bioreactor fluid. Long chain fatty acids, alkanes (C 19 –C 36 ) and various low molecular weight aromatics, including phenols, also accumulated in the bioreactor fluid and appear to be the primary intermediates in the biodegradation pathway from coal-derived geopolymers to acetate and methane.

Texas

Preliminary use of uric acid as a biomarker for wading birds on Everglades Tree Islands, Florida, United States

Concentrations of organic biomarkers and concentrations of phosphorus in soil cores can potentially be used as proxies for historic population densities of wading birds on tree islands in the Florida Everglades. This report focuses on establishing a link between the organic biomarker uric acid found in wading bird guano and the high phosphorus concentrations in tree island soils in the Florida Everglades. Uric acid was determined in soil core sections, in surface samples, and in bird guano by using a method of high-performance liquid chromatography-mass spectrometry (HPLC-MS) developed for this purpose. Preliminary results show an overall correlation between uric acid and total phosphorus in three soil cores, with a general trend of decreasing concentrations of both uric acid and phosphorus with depth. However, we have also found no uric acid in a soil core having high concentrations of phosphorus. We believe that this result may be explained by different geochemical circumstances at that site.

Florida

Organic geochemistry of sediments in nearshore areas of the Mississippi and Atchafalaya Rivers: I. General organic characterization

This report presents results on the general organic characteristics of sediment cores collected from the coastal zone of the Mississippi River system, including distributions of the important nutrient elements (C, N, P, and S). This was part of a larger study conducted from 2001-2005 to examine the delivery of sediment-associated contaminants to the Gulf of Mexico by the Mississippi River system, funded by the USGS Coastal and Marine Geology Program. Companion reports emphasize organic contaminants (Rosenbauer and others, 2006), and metals (Swarzenski and others, 2006). The level of contamination within the deltaic system of the Mississippi River system was determined through the collection of sediment cores from interdistributary bays, and offshore in the Gulf of Mexico, including the zone of hypoxia. Results provide the basis for reconstructing contaminant inventories from which to develop historic perspectives on nutrient loading and hypoxia, and to better understand how sediment-hosted contaminants either directly or indirectly move through biota and ultimately affect ecosystem health. Concentrations of C, N, P, and S in sediments varied by a factor of 10 between sites, and in down core profiles. Nearshore cores collected in 2001 proved to have erratic downcore C, N, P, and S profiles and sediment deposition rates, suggesting a high energy regime controlled more by variability in river flow rather than by geochemical processes and reactions within the system. These results focused further coring activities further offshore. Atomic C/N ratios suggest that organic matter deposited at all sites is a mix of microbial (algal) and terrestrial (vascular plant) remains, but with algal material dominant. Concentrations of total sulfur in sediments from cores in the zone of hypoxia were often higher than those in nearby zones with oxic water columns. Corresponding atomic C/S ratios were typically lower in sediments from sites in the zone of hypoxia compared to nearby sites with oxic water columns, and thus atomic C/S values may be useful as a proxy for identifying sites impacted by hypoxic conditions in the water column and for examining historical trends in hypoxia. At one site examined in this study, maximum hypoxic conditions were observed in the mid 1960's. The organic elemental composition (C, N, P, and S) of sediments was also used to guide sample selection for contaminant analysis, and to normalize the contaminant data to organic C content of the sediments. Dissolved hydrocarbon gases in sediments showed a dominance of methane, but identifiable concentrations of ethane and hexane, and trace concentrations of propane, butane, and pentane were also detected. All dissolved gases except hexane were dominated by 'bound' gas, gas released only after agitation of the sediment in a blender. Hexane, in contrast was observed mostly as free gas, determined by headspace analysis.

Louisiana

Assessment of groundwater input and water quality changes impacting natural vegetation in the Loxahatchee River and floodplain ecosystem, Florida

The Loxahatchee River and Estuary are small, shallow, water bodies located in southeastern Florida. Historically, the Northwest Branch (Fork) of the Loxahatchee River was primarily a freshwater system. In 1947, the river inlet at Jupiter was dredged for navigation and has remained permanently open since that time. Drainage patterns within the basin have also been altered significantly due to land development, road construction (e.g., Florida Turnpike), and construction of the C-18 and other canals. These anthropogenic activities along with sea level rise have resulted in significant adverse impacts on the ecosystem over the last several decades, including increased saltwater encroachment and undesired vegetation changes in the floodplain. The problem of saltwater intrusion and vegetation degradation in the Loxahatchee River may be partly induced by diminished freshwater input, from both surface water and ground water into the River system. The overall objective of this project was to assess the seasonal surface water and groundwater interaction and the influence of the biogeochemical characteristics of shallow groundwater and porewater on vegetation health in the Loxahatchee floodplain. The hypothesis tested are: (1) groundwater influx constitutes a significant component of the overall flow of water into the Loxahatchee River; (2) salinity and other chemical constituents in shallow groundwater and porewater of the river floodplain may affect the distribution and health of the floodplain vegetation.

Florida

Preliminary geochemical, microbiological, and epidemiological investigations into possible linkages between lignite aquifers, pathogenic microbes, and kidney disease in northwestern Louisiana

In May 2002, 15 wells and four surface water sites were sampled, and in September 2002, those same wells and sites plus four additional surface sites were sampled in five parishes of northwestern Louisiana. A geographic information system (GIS) was used to select residential water wells for sampling. Well water samples were analyzed for pH, conductivity, organic compounds, and nutrient and anion concentrations. All samples were further tested for presence of fungi (maintained for up to 28 days and colonies counted and identified microscopically), and metal and trace element concentration by inductively-coupled plasma mass spectrometry and atomic emission spectrometry. Surface water samples were tested for dissolved oxygen and evidence of leptospiral bacterial presence. A polymerase chain reaction protocol was optimized for detection of pathogenic leptospires, and the sensitivity of the assay was determined. The Spearman correlation method was used to assess the association between the endpoints for these field/laboratory analyses and the incidence of cancer of the renal pelvis obtained from the Louisiana Tumor Registry. Significant associations were revealed between the cancer rate and the overall number of organic compounds, the fungi Zygomycetes, the nutrients PO4 and NH3, and thirteen chemical elements (As, B, Br, Cl, Cr, F, Li, Na, P, Rb, Se, Sr, W) from the well water as compared to the controls. Among the species of fungi from the total of 136 isolates were 12 Penicillium spp., at least two Aspergillus spp., a number of other genera (Alternaria sp., Eupenicillium lapidosum, Cladosporium sp., Epicoccum sp., Trichoderma sp., Paecilomyces sp., Chrysosporium sp., Chloridium sp.), and Zygomycetes, and Coelmycetes -- some of which are known mycotoxin producers. The two control wells yielded a mean of 6.5 (SD = 3.5355) individual isolates, while the mean number of isolates from all other sites was 7.6 (SD = 4.4866). Presence of human pathogenic leptospires was detected in 4/8 (50 percent) of the surface water sites sampled. These initial results suggest that additional investigation into these relationships is warranted.

Open-File Report

Geochemistry of surface and pore water at USGS coring sites in wetlands of South Florida, 1994 and 1995

In this report, we present preliminary data on surface and pore water geochemistry from 22 sites in south Florida sampled during 1994 and 1995. These results are part of a larger study designed to evaluate the role of biogeochemical processes in sediments in the cycling of carbon, nitrogen, phosphorus, and sulfur in the south Florida ecosystem. The data are briefly discussed in regard to regional trends in the concentrations of chemical species, and general diagenetic processes in sediments. These results are part of a larger study designed to evaluate the role of biogeochemical processes in sediments in the cycling of carbon, nitrogen, phosphorus, and sulfur in the south Florida ecosystem. These elements play a crucial role in regulating organic sedimentation, nutrient dynamics, redox conditions, and the biogeochemistry of mercury in the threatened wetlands of south Florida. Pore water samples for chemical analyis were obtained using a piston corer/squeezer designed to avoid compression of the sediment and avoid oxidation and contamination of the pore water samples. Results show distinct regional trends in both surface water and pore water geochemistry. Most chemical species in surface and pore water show peak concentrations in Water Conservation Area 2A, with diminishing concentrations to the south and west into Water Conservation Area 3A, and Everglades National Park. The largest differences observed were for phosphate and sulfide, with concentrations in pore waters in Water Conservation Area 2A up to 500x higher than concentrations observed in freshwater marsh areas of Water Conservation Area 3A and Everglades National Park. Sites near the Hillsboro Canal in Water Conservation Area 2A are heavily contaminated with both phosphorus and sulfur. Pore water profiles for dissolved reactive phosphate suggest that recycling of phosphorus at these contaminated sites occurs primarily in the upper 20 cm of sediment. High levels of sulfide in pore water in Water Conservation Area 2A may inhibit mercury methylation here. At sites in Water Conservation Area 3A south of Alligator Alley, sulfide levels are much lower and sulfate reduction in the sediments here may be conducive to methyl mercury formation. Concentration versus depth profiles of biogeochemically important chemical species in pore water at most sites are smoth curves amenable to modelling using standard diagenetic equations. This should allow prediction of rates of biogeochemical processes in these sediments for incorporation in ecosystem models.

Florida

Studies of a peatified angiosperm log cross section from Indonesia by nuclear magnetic resonance spectroscopy and analytical pyrolysis

Samples from a 10 cm cross-sectional radius of a peatified angiosperm log from Sumatra, Indonesia, were examined by 13 C nuclear magnetic resonance and pyrolysis-gas chromatography in order to understand chemical changes due to the peatification process. NMR results show degradation by selective loss of carbohydrates in all parts of the log section compared with fresh wood; however, the degree of degradation is less near the center of the log section. The degree of ring substitution of aromatic lignin monomeric units, as measured by dipolar dephasing NMR methods, appears to be less at the center of the log section than at the periphery. The methoxyl carbon content of lignin in the log is lower than in unaltered angiospermous lignin but does not appear to change as a function of either radial position or the degree of aromatic ring substitution. Pyrolysis-gas chromatography indicates higher yields of catechols in the outer areas relative to the heartwood. Other than the variations in catechol contents and in the yields of carbohydrate-derived pyrolysis products (e.g. levoglucosan, angelicalactones), the pyrolysis results do not show significant changes related to radial position, indicating that the lignin is not significantly altered across the log section.

Organic Geochemistry

Solid-state 13C nuclear magnetic resonance studies of coalified gymnosperm xylem tissue from Australian brown coals

We report here on the use of solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy to contrast the average chemical composition of modern degraded gymnosperm woods with fossil gymnosperm woods from Australian brown coals (Miocene). We first established the quantitative nature of the NMR techniques for these samples so that the conventional solid-state 13 C NMR spectra and the dipolar dephasing NMR spectra could be used with a high degree of reliability to depict average chemical compositions. The NMR results provide some valuable insights about the early coalification of xylem tissue from gymnosperms. Though the cellulosic components of wood are degraded to varying degrees during peatification and ensuing coalification, it is unlikely that they play a major role in the formation of aromatic structures in coalified woods. The NMR data show that gynmosperm lignin, the primary aromatic contribution to the coal, is altered in part by demethylation of guaiacyl-units to catechol-like structures. The dipolar dephasing NMR data indicate that the lignin also becomes more cross-linked or condensed.

Organic Geochemistry

PYROLYSIS/GAS CHROMATOGRAPHY/MASS SPECTROMETRY OF A SERIES OF BURIED WOODS AND COALIFIED LOGS THAT INCREASE IN RANK FROM PEAT TO SUBBITUMINOUS COAL.

To better understand the coalification process, we have conducted numerous studies of the chemical structural composition of xylem tissue from gymosperm wood and related woods that has been coalified to varying degrees. The studies presented here, examine the chemical nature of buried and coalified xylem tissue at the molecular level. To achieve this, we employed pyrolysis/gas chromatography (py/gc) and pyrolysis/gas chromotography/mass spectrometry (py/gc/ms). Pyrolysis techniques have been used to examine peat, coal, coalified wood, and related substances. However, the technique has not been previously applied to a systematic and histologically-related series of coalified woods. It is particularly useful to compare the results from pyrolytic studies with the data obtained from solid-state **1**3C NMR.

Conference Paper