Controls on the Barium and Strontium Isotopic Records of Water Chemistry Preserved in Freshwater Bivalve Shells.

Biogenic carbonates, including bivalve shells, record past environmental conditions, but their interpretation requires understanding environmental and biological factors that affect trace metal uptake. We examined stable barium (δ138Ba) and radiogenic strontium (87Sr/86Sr) isotope ratios in the aragonite shells of four native freshwater mussel species and two invasive species in five streams and assessed the effects of species identity, growth rate, and river water chemistry on shell isotopic composition. Shells were robust proxies for Sr, accurately reflecting 87Sr/86Sr ratios of river water, regardless of species or growth rate. In contrast, shell δ138Ba values, apart from invasive Corbicula fluminea, departed widely from those of river water and varied according to species and growth rate. Apparent fractionation between river water and the shell (Δ138Bashell-water) reached -0.86‰, the greatest offset observed for carbonate minerals. The shell deposited during slow growth periods was more enriched in lighter Ba isotopes than the rapidly deposited shell; thus, this phenomenon cannot be explained by aragonite precipitation kinetics. Instead, biological ion transport processes linked to growth rate may be largely responsible for Ba isotope variation. Our results provide information necessary to interpret water chemistry records preserved in shells and provide insights into biomineralization processes and bivalve biochemistry.

Barium Isotopes Track the Source of Dissolved Solids in Produced Water from the Unconventional Marcellus Shale Gas Play.

Waters coproduced with hydrocarbons from unconventional oil and gas reservoirs such as the hydraulically fractured Middle Devonian Marcellus Shale in the Appalachian Basin, USA, contain high levels of total dissolved solids (TDS), including Ba, which has been variously ascribed to drilling mud dissolution, interaction with pore fluids or shale exchangeable sites, or fluid migration through fractures. Here, we show that Marcellus Shale produced waters contain some of the heaviest Ba (high 138Ba/134Ba) measured to date (δ138Ba = +0.36‰ to +1.49‰ ± 0.06‰) and are distinct from overlying Upper Devonian/Lower Mississippian reservoirs (δ138Ba = -0.83‰ to -0.52‰). Marcellus Shale produced water values do not overlap with drilling mud barite (δ138Ba ≈ 0.0‰) and are significantly offset from Ba reservoirs within the producing portion of the Marcellus Shale, including exchangeable sites and carbonate cement. Precipitation, desorption, and diffusion processes are insufficient or in the wrong direction to produce the observed enrichments in heavy Ba. We hypothesize that the produced water is derived primarily from brines adjacent to and most likely below the Marcellus Shale, although such deep brines have not yet been obtained for Ba isotope analysis. Barium isotopes show promise for tracking formation waters and for understanding water-rock interaction under downhole conditions.

Strontium isotopes test long-term zonal isolation of injected and Marcellus formation water after hydraulic fracturing.

One concern regarding unconventional hydrocarbon production from organic-rich shale is that hydraulic fracture stimulation could create pathways that allow injected fluids and deep brines from the target formation or adjacent units to migrate upward into shallow drinking water aquifers. This study presents Sr isotope and geochemical data from a well-constrained site in Greene County, Pennsylvania, in which samples were collected before and after hydraulic fracturing of the Middle Devonian Marcellus Shale. Results spanning a 15-month period indicated no significant migration of Marcellus-derived fluids into Upper Devonian/Lower Mississippian units located 900-1200 m above the lateral Marcellus boreholes or into groundwater sampled at a spring near the site. Monitoring the Sr isotope ratio of water from legacy oil and gas wells or drinking water wells can provide a sensitive early warning of upward brine migration for many years after well stimulation.

Utica/Point Pleasant brine isotopic compositions (δ7Li, δ11B, δ138Ba) elucidate mechanisms of lithium enrichment in the Appalachian Basin.

Global Li production will require a ∼500 % increase to meet 2050 projected energy storage demands. One potential source is oil and gas wastewater (i.e., produced water or brine), which naturally has high total dissolved solids (TDS) concentrations, that can also be enriched in Li (>100 mg/L). Understanding the sources and mechanisms responsible for high naturally-occurring Li concentrations can aid in efficient targeting of these brines. The isotopic composition (δ7Li, δ11B, δ138Ba) of produced water and core samples from the Utica Shale and Point Pleasant Formation (UPP) in the Appalachian Basin, USA indicates that depth-dependent thermal maturity and water-rock interaction, including diagenetic clay mineral transformations, likely control Li concentrations. A survey of Li content in produced waters throughout the USA indicates that Appalachian Basin brines from the Marcellus Shale to the UPP have the potential for economic resource recovery.

Geochemical and strontium isotope characterization of produced waters from Marcellus Shale natural gas extraction.

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ~375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (ε(Sr)(SW) = +13.8 to +41.6, where ε(Sr) (SW) is the deviation of the (87)Sr/(86)Sr ratio from that of seawater in parts per 10(4)); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

Strontium isotope study of coal utilization by-products interacting with environmental waters.

Sequential leaching experiments on coal utilization by-products (CUB) were coupled with chemical and strontium (Sr) isotopic analyses to better understand the influence of coal type and combustion processes on CUB properties and the release of elements during interaction with environmental waters during disposal. Class C fly ash tended to release the highest quantity of minor and trace elements-including alkaline earth elements, sodium, chromium, copper, manganese, lead, titanium, and zinc-during sequential extraction, with bottom ash yielding the lowest. Strontium isotope ratios ((87)Sr/(86)Sr) in bulk-CUB samples (total dissolution of CUB) are generally higher in class F ash than in class C ash. Bulk-CUB ratios appear to be controlled by the geologic source of the mineral matter in the feed coal, and by Sr added during desulfurization treatments. Leachates of the CUB generally have Sr isotope ratios that are different than the bulk value, demonstrating that Sr was not isotopically homogenized during combustion. Variations in the Sr isotopic composition of CUB leachates were correlated with mobility of several major and trace elements; the data suggest that arsenic and lead are held in phases that contain the more radiogenic (high-(87)Sr/(86)Sr) component. A changing Sr isotope ratio of CUB-interacting waters in a disposal environment could forecast the release of certain strongly bound elements of environmental concern. This study lays the groundwork for the application of Sr isotopes as an environmental tracer for CUB-water interaction.

A method for generating uniform size-segregated pyrite particle fractions.

BACKGROUND: Standardized sample preparation techniques allow comparison of pyrite dissolution experiments under diverse conditions. Our objective was to assess dry and wet sieving preparation methodologies, and to develop a reproducible technique that yields uniformly size-distributed material within a limited size range of interest. RESULTS: Here, we describe a wet sieving preparation method that successfully concentrates pyrite particles within a 44-75 microm diameter range. In addition, this technique does not require a post-processing cleanup step to remove adhering particles, as those particles are removed during the procedure. We show that sample preparation methods not only affect the pyrite size distribution, but also apparent dissolution rates. CONCLUSION: The presented methodology is non-destructive to the sample, uses readily available chemical equipment within the laboratory, and could be applied to minerals other than pyrite.