第2章 1-4-4-3. 河川の富栄養化に伴う河川の各種窒素プールの窒素同位体比の変動

Spearman correlation among all nutrients. (DOC 32 kb

Age Dating Oil and Gas Wastewater Spills Using Radium Isotopes and Their Decay Products in Impacted Soil and Sediment

Spills from oil and gas operations can contaminate water resources, sediment, and soil, but in many cases, information about spill sources and environmental impacts is not available. Here we present age dating methods to estimate the time since the accumulation of radium in impacted soils and sediments from oil and gas wastewater spills. The retention of unsupported ²²⁶Ra and ²²⁸Ra from spill water to soil and sediment and the ingrowth of Ra progeny result in three independent age dating methods using the ²²⁸Th/²²⁸Ra, ²¹⁰Pb/²²⁶Ra, and ²²⁸Ra/²²⁶Ra activity ratios. We tested the ²²⁸Th/²²⁸Ra method on spill sites in North Dakota and West Virginia, where the dates of the spills are known. The ²²⁸Th/²²⁸Ra method yields ages similar to the documented spill ages and can reveal the initial ²²⁸Ra/²²⁶Ra ratios of the spill waters, validating the notion that Ra isotopes and their decay products in contaminated soils and sediments can reveal the ages and origins of spills

Water Footprint of Hydraulic Fracturing

We evaluated the overall water footprint of hydraulic fracturing of unconventional shale gas and oil throughout the United States based on integrated data from multiple database sources. We show that between 2005 and 2014, unconventional shale gas and oil extraction used 708 billion liters and 232 billion liters of water, respectively. From 2012 to 2014, the annual water use rates were 116 billion liters per year for shale gas and 66 billion liters per year for unconventional oil. Integrated data from 6 to 10 years of operation yielded 803 billion liters of combined flowback and produced water from unconventional shale gas and oil formations. While the hydraulic fracturing revolution has increased water use and wastewater production in the United States, its water use and produced water intensity is lower than other energy extraction methods and represents only a fraction of total industrial water use nationwide

Evidence for Coal Ash Ponds Leaking in the Southeastern United States

Coal combustion residuals (CCRs), the largest industrial waste in the United States, are mainly stored in surface impoundments and landfills. Here, we examine the geochemistry of seeps and surface water from seven sites and shallow groundwater from 15 sites in five states (Tennessee, Kentucky, Georgia, Virginia, and North Carolina) to evaluate possible leaking from coal ash ponds. The assessment for groundwater impacts at the 14 sites in North Carolina was based on state-archived monitoring well data. Boron and strontium exceeded background values of 100 and 150 μg/L, respectively, at all sites, and the high concentrations were associated with low δ¹¹B (−9‰ to +8‰) and radiogenic ⁸⁷Sr/⁸⁶Sr (0.7070 to 0.7120) isotopic fingerprints that are characteristic of coal ash at all but one site. Concentrations of CCR contaminants, including SO₄, Ca, Mn, Fe, Se, As, Mo, and V above background levels, were also identified at all sites, but contamination levels above drinking water and ecological standards were observed in 10 out of 24 samples of impacted surface water. Out of 165 monitoring wells, 65 were impacted with high B levels and 49 had high CCR-contaminant levels. Distinct isotope fingerprints, combined with elevated levels of CCR tracers, provide strong evidence for the leaking of coal ash ponds to adjacent surface water and shallow groundwater. Given the large number of coal ash impoundments throughout the United States, the systematic evidence for leaking of coal ash ponds shown in this study highlights potential environmental risks from unlined coal ash ponds

Naturally Occurring Radioactive Materials in Uranium-Rich Coals and Associated Coal Combustion Residues from China

Most coals in China have uranium concentrations up to 3 ppm, yet several coal deposits are known to be enriched in uranium. Naturally occurring radioactive materials (NORM) in these U-rich coals and associated coal combustion residues (CCRs) have not been well characterized. Here we measure NORM (Th, U, ²²⁸Ra, ²²⁶Ra, and ²¹⁰Pb) in coals from eight U-rich coal deposits in China and the associated CCRs from one of these deposits. We compared NORM in these U-rich coals and associated CCRs to CCRs collected from the Beijing area and natural loess sediments from northeastern China. We found elevated U concentrations (up to 476 ppm) that correspond to low ²³²Th/²³⁸U and ²²⁸Ra/²²⁶Ra activity ratios (≪1) in the coal samples. ²²⁶Ra and ²²⁸Ra activities correlate with ²³⁸U and ²³²Th activities, respectively, and ²²⁶Ra activities correlate well with ²¹⁰Pb activities across all coal samples. We used measured NORM activities and ash yields in coals to model the activities of CCRs from all U-rich coals analyzed in this study. The activities of measured and modeled CCRs derived from U-rich coals exceed the standards for radiation in building materials, particularly for CCRs originating from coals with U > 10 ppm. Since beneficial use of high-U Chinese CCRs in building materials is not a suitable option, careful consideration needs to be taken to limit potential air and water contamination upon disposal of U- and Ra-rich CCRs

Sources of Radium Accumulation in Stream Sediments near Disposal Sites in Pennsylvania: Implications for Disposal of Conventional Oil and Gas Wastewater

In Pennsylvania, Appalachian oil and gas wastewaters (OGW) are permitted for release to surface waters after some treatment by centralized waste treatment (CWT) facilities. While this practice was largely discontinued in 2011 for unconventional Marcellus OGW at facilities permitted to release high salinity effluents, it continues for conventional OGW. This study aimed to evaluate the environmental implications of the policy allowing the disposal of conventional OGW. We collected stream sediments from three disposal sites receiving treated OGW between 2014 and 2017 and measured ²²⁸Ra, ²²⁶Ra, and their decay products, ²²⁸Th and ²¹⁰Pb, respectively. We consistently found elevated activities of ²²⁸Ra and ²²⁶Ra in stream sediments in the vicinity of the outfall (total Ra = 90–25,000 Bq/kg) compared to upstream sediments (20–80 Bq/kg). In 2015 and 2017, ²²⁸Th/²²⁸Ra activity ratios in sediments from two disposal sites were relatively low (0.2–0.7), indicating that a portion of the Ra has accumulated in the sediments in recent (<3) years, when no unconventional Marcellus OGW was reportedly discharged. ²²⁸Ra/²²⁶Ra activity ratios were also higher than what would be expected solely from disposal of low ²²⁸Ra/²²⁶Ra Marcellus OGW. Based on these variations, we concluded that recent disposal of treated conventional OGW is the source of high Ra in stream sediments at CWT facility disposal sites. Consequently, policies pertaining to the disposal of only unconventional fluids are not adequate in preventing radioactive contamination in sediments at disposal sites, and the permission to release treated Ra-rich conventional OGW through CWT facilities should be reconsidered

Radium and Barium Removal through Blending Hydraulic Fracturing Fluids with Acid Mine Drainage

Wastewaters generated during hydraulic fracturing of the Marcellus Shale typically contain high concentrations of salts, naturally occurring radioactive material (NORM), and metals, such as barium, that pose environmental and public health risks upon inadequate treatment and disposal. In addition, fresh water scarcity in dry regions or during periods of drought could limit shale gas development. This paper explores the possibility of using alternative water sources and their impact on NORM levels through blending acid mine drainage (AMD) effluent with recycled hydraulic fracturing flowback fluids (HFFFs). We conducted a series of laboratory experiments in which the chemistry and NORM of different mix proportions of AMD and HFFF were examined after reacting for 48 h. The experimental data combined with geochemical modeling and X-ray diffraction analysis suggest that several ions, including sulfate, iron, barium, strontium, and a large portion of radium (60–100%), precipitated into newly formed solids composed mainly of Sr barite within the first ∼10 h of mixing. The results imply that blending AMD and HFFF could be an effective management practice for both remediation of the high NORM in the Marcellus HFFF wastewater and beneficial utilization of AMD that is currently contaminating waterways in northeastern U.S.A

Impacts of Shale Gas Wastewater Disposal on Water Quality in Western Pennsylvania

The safe disposal of liquid wastes associated with oil and gas production in the United States is a major challenge given their large volumes and typically high levels of contaminants. In Pennsylvania, oil and gas wastewater is sometimes treated at brine treatment facilities and discharged to local streams. This study examined the water quality and isotopic compositions of discharged effluents, surface waters, and stream sediments associated with a treatment facility site in western Pennsylvania. The elevated levels of chloride and bromide, combined with the strontium, radium, oxygen, and hydrogen isotopic compositions of the effluents reflect the composition of Marcellus Shale produced waters. The discharge of the effluent from the treatment facility increased downstream concentrations of chloride and bromide above background levels. Barium and radium were substantially (>90%) reduced in the treated effluents compared to concentrations in Marcellus Shale produced waters. Nonetheless, ²²⁶Ra levels in stream sediments (544–8759 Bq/kg) at the point of discharge were ∼200 times greater than upstream and background sediments (22–44 Bq/kg) and above radioactive waste disposal threshold regulations, posing potential environmental risks of radium bioaccumulation in localized areas of shale gas wastewater disposal

A Critical Review of the Risks to Water Resources from Unconventional Shale Gas Development and Hydraulic Fracturing in the United States

The rapid rise of shale gas development through horizontal drilling and high volume hydraulic fracturing has expanded the extraction of hydrocarbon resources in the U.S. The rise of shale gas development has triggered an intense public debate regarding the potential environmental and human health effects from hydraulic fracturing. This paper provides a critical review of the potential risks that shale gas operations pose to water resources, with an emphasis on case studies mostly from the U.S. Four potential risks for water resources are identified: (1) the contamination of shallow aquifers with fugitive hydrocarbon gases (i.e., stray gas contamination), which can also potentially lead to the salinization of shallow groundwater through leaking natural gas wells and subsurface flow; (2) the contamination of surface water and shallow groundwater from spills, leaks, and/or the disposal of inadequately treated shale gas wastewater; (3) the accumulation of toxic and radioactive elements in soil or stream sediments near disposal or spill sites; and (4) the overextraction of water resources for high-volume hydraulic fracturing that could induce water shortages or conflicts with other water users, particularly in water-scarce areas. Analysis of published data (through January 2014) reveals evidence for stray gas contamination, surface water impacts in areas of intensive shale gas development, and the accumulation of radium isotopes in some disposal and spill sites. The direct contamination of shallow groundwater from hydraulic fracturing fluids and deep formation waters by hydraulic fracturing itself, however, remains controversial

Enhanced Formation of Disinfection Byproducts in Shale Gas Wastewater-Impacted Drinking Water Supplies

The disposal and leaks of hydraulic fracturing wastewater (HFW) to the environment pose human health risks. Since HFW is typically characterized by elevated salinity, concerns have been raised whether the high bromide and iodide in HFW may promote the formation of disinfection byproducts (DBPs) and alter their speciation to more toxic brominated and iodinated analogues. This study evaluated the minimum volume percentage of two Marcellus Shale and one Fayetteville Shale HFWs diluted by fresh water collected from the Ohio and Allegheny Rivers that would generate and/or alter the formation and speciation of DBPs following chlorination, chloramination, and ozonation treatments of the blended solutions. During chlorination, dilutions as low as 0.01% HFW altered the speciation toward formation of brominated and iodinated trihalomethanes (THMs) and brominated haloacetonitriles (HANs), and dilutions as low as 0.03% increased the overall formation of both compound classes. The increase in bromide concentration associated with 0.01–0.03% contribution of Marcellus HFW (a range of 70–200 μg/L for HFW with bromide = 600 mg/L) mimics the increased bromide levels observed in western Pennsylvanian surface waters following the Marcellus Shale gas production boom. Chloramination reduced HAN and regulated THM formation; however, iodinated trihalomethane formation was observed at lower pH. For municipal wastewater-impacted river water, the presence of 0.1% HFW increased the formation of <i>N</i>-nitrosodimethylamine (NDMA) during chloramination, particularly for the high iodide (54 ppm) Fayetteville Shale HFW. Finally, ozonation of 0.01–0.03% HFW-impacted river water resulted in significant increases in bromate formation. The results suggest that total elimination of HFW discharge and/or installation of halide-specific removal techniques in centralized brine treatment facilities may be a better strategy to mitigate impacts on downstream drinking water treatment plants than altering disinfection strategies. The potential formation of multiple DBPs in drinking water utilities in areas of shale gas development requires comprehensive monitoring plans beyond the common regulated DBPs