Unconventional oil and gas residual solid wastes are generally disposed in municipal waste landfills (RCRA Subtitle D), but they contain valuable raw materials such as proppant sands. A novel process for recovering raw materials from hydraulic fracturing residual waste is presented. Specifically, a novel hydroacoustic cavitation system, combined with physical separation devices, can create a distinct stream of highly concentrated sand, and another distinct stream of clay from the residual solid waste by the dispersive energy of cavitation conjoined with ultrasonics, ozone and hydrogen peroxide. This combination cleaned the sand grains, by removing previously aggregated clays and residues from the sand surfaces. When these unit operations were followed by a hydrocyclone and spiral, the solids could be separated by particle size, yielding primarily cleaned sand in one flow stream; clays and fine particles in another; and silts in yet a third stream. Consequently, the separation of particle sizes also affected radium distribution – the sand grains had low radium activities, as lows as 0.207 Bq g −1 (5.6 pCi g −1 ). In contrast, the clays had elevated radium activities, as high as 1.85–3.7 Bq g −1 (50–100 pCi g −1 ) – and much of this radium was affiliated with organics and salts that could be separated from the clays. We propose that the reclaimed sand could be reused as hydraulic fracturing proppant. The separation of sand from silt and clay could reduce the volume and radium masses of wastes that are disposed in landfills. This could represent a significant savings to facilities handling oil and gas waste, as much as $100 000–300 000 per year. Disposing the radium-enriched salts and organics downhole will mitigate radium release to the surface. Additionally, the reclaimed sand could have market value, and this could represent as much as a third of the cost savings. Tests that employed the toxicity characteristic leaching protocol (TCLP) on these separated solids streams determined that this novel treatment diminished the risk of radium mobility for the reclaimed sand, clays or disposed material, rendering them better suited for landfilling.
more »
« less
Radium in hydraulic fracturing wastewater: distribution in suspended solids and implications to its treatment by sulfate co-precipitation
High concentrations of barium (Ba), strontium (Sr) and radium (Ra) are present in both the liquid and suspended solid portions of wastewater produced from hydraulic fracturing. These high concentrations often require special treatment in which the solid and liquid portions are separated and then independently treated prior to disposal. The solids are typically disposed in landfills while the liquids are further treated, recycled for future hydraulic fracturing, or disposed via injection wells. Finding optimal treatment methods of both the solid and the liquid fractions requires a thorough understanding of potential Ra mobility from both the raw suspended solids and mineral precipitates formed during treatment. Using a sequential extraction procedure, we found that, without treatment, more than 50% of Ra-226 in the suspended solids was associated with soluble salts and readily exchangeable fractions. When the liquid portion of the wastewater was treated by mixing with acid mine drainage (AMD), which contained high sulfate concentrations, approximately 80–97% of the total Ra-226 in the mixture solution is found in the insoluble sulfate fraction of the precipitate. The activity of Ra-226 sequestered in the precipitated solid sulfate fractions is positively correlated with the Sr/Ba ratio of the wastewater-AMD solution. We discuss implications of these findings for effective long-term management of elevated radium in both solid and liquid wastes.
more »
« less
- Award ID(s):
- 1640634
- NSF-PAR ID:
- 10093917
- Date Published:
- Journal Name:
- Environmental Science: Processes & Impacts
- Volume:
- 21
- Issue:
- 2
- ISSN:
- 2050-7887
- Page Range / eLocation ID:
- 339 to 351
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
While development of the Utica/Point Pleasant Shale (UPP) is extensive in Ohio (U.S.) and increasing in Pennsylvania and West Virginia, few studies report the chemistry of produced waters from UPP wells. These data have important implications for developing best management practices for handling and waste disposal, or identifying the fluid in the event of accidental spill events. Here, we evaluated the elemental and isotope chemistry of UPP produced waters from 26 wells throughout Ohio, Pennsylvania, and West Virginia to determine any unique fluid chemistries that could be used for forensic studies. Compared to the Marcellus, UPP produced waters contain higher activities of total radium ( 226 Ra + 228 Ra) and higher 228 Ra/ 226 Ra ratios. As with the Marcellus Shale, elemental ratios (Sr/Ca) and isotope ratios ( 87 Sr/ 86 Sr) can distinguish UPP produced waters from many conventional oil and gas formations. Sr/Ca and 87 Sr/ 86 Sr ratios can fingerprint small fractions (∼0.1%) of UPP produced water in freshwater. However, because Marcellus and UPP produced waters display similar major elemental chemistry ( i.e. , Na, Ca, and Cl) and overlapping ratios of Sr/Ca and 87 Sr/ 86 Sr, 228 Ra/ 226 Ra ratios may be the best tracer to distinguish these waters.more » « less
-
more » « less
Abstract Radium‐226(226Ra) and barium (Ba) exhibit similar chemical behaviors and distributions in the marine environment, serving as valuable tracers of water masses, ocean mixing, and productivity. Despite their similar distributions, these elements originate from distinct sources and undergo disparate biogeochemical cycles, which might complicate the use of these tracers. In this study, we investigate these processes by analyzing a full‐depth ocean section of226Ra activities (
T 1/2 = 1,600 years) and barium concentrations obtained from samples collected along the US GEOTRACES GP15 Pacific Meridional Transect during September–November 2018, spanning from Alaska to Tahiti. We find that surface waters possess low levels of226Ra and Ba due to export of sinking particulates, surpassing inputs from the continental margins. In contrast, deep waters have higher226Ra activities and Ba concentrations due to inputs from particle regeneration and sedimentary sources, with226Ra inputs primarily resulting from the decay of230Th in sediments. Further, dissolved226Ra and Ba exhibit a strong correlation along the GP15 section. To elucidate the drivers of the correlation, we used a water mass analysis, enabling us to quantify the influence of water mass mixing relative to non‐conservative processes. While a significant fraction of each element's distribution can be explained by conservative mixing, a considerable fraction cannot. The balance is driven using non‐conservative processes, such as sedimentary, rivers, or hydrothermal inputs, uptake and export by particles, and particle remineralization. Our study demonstrates the utility of226Ra and Ba as valuable biogeochemical tracers for understanding ocean processes, while shedding light on conservative and myriad non‐conservative processes that shape their respective distributions. -
Wastewater-based epidemiology has gained attention throughout the world for detection of SARS-CoV-2 RNA in wastewater to supplement clinical testing. Raw wastewater consists of small particles, or solids, suspended in liquid. Methods have been developed to measure SARS-CoV-2 RNA in the liquid and the solid fraction of wastewater, with some studies reporting higher concentrations in the solid fraction. To investigate this relationship further, six laboratories collaborated to conduct a study across five publicly owned treatment works (POTWs) where both primary settled solids obtained from primary clarifiers and raw wastewater influent samples were collected and quantified for SARS-CoV-2 RNA. Settled solids and influent samples were processed by participating laboratories using their respective methods and retrospectively paired based on date of collection. SARS-CoV-2 RNA concentrations, on a mass equivalent basis, were higher in settled solids than in influent by approximately three orders of magnitude. Concentrations in matched settled solids and influent were positively and significantly correlated at all five POTWs. RNA concentrations in both settled solids and influent were correlated to COVID-19 incidence rates in the sewersheds and thus representative of disease occurrence; the settled solids methods appeared to produce a comparable relationship between SARS-CoV-2 RNA concentration measurements and incidence rates across all POTWs. Settled solids and influent methods showed comparable sensitivity, N gene detection frequency, and calculated empirical incidence rate lower limits. Analysis of settled solids for SARS-CoV-2 RNA has the advantage of using less sample volume to achieve similar sensitivity to influent methods.more » « less
-
more » « less
Abstract Radium isotopes have been used to trace nutrient, carbon, and trace metal fluxes inputs from ocean margins. However, these approaches require a full accounting of radium sources to the coastal ocean including rivers. Here, we aim to quantify river radium inputs into the Arctic Ocean for the first time for226Ra and to refine the estimates for228Ra. Using new and existing data, we find that the estimated combined (dissolved plus desorbed) annual226Ra and228Ra fluxes to the Arctic Ocean are [7.0–9.4] × 1014dpm y−1and [15–18] × 1014dpm y−1, respectively. Of these totals, 44% and 60% of the river226Ra and228Ra, respectively are from suspended sediment desorption, which were estimated from laboratory incubation experiments. Using Ra isotope data from 20 major rivers around the world, we derived global annual226Ra and228Ra fluxes of [7.4–17] × 1015and [15–27] × 1015dpm y−1, respectively. As climate change spurs rapid Arctic warming, hydrological cycles are intensifying and coastal ice cover and permafrost are diminishing. These river radium inputs to the Arctic Ocean will serve as a valuable baseline as we attempt to understand the changes that warming temperatures are having on fluxes of biogeochemically important elements to the Arctic coastal zone.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C8EM00311D
