Organic sulfur fingerprint indicates continued injection fluid signature 10 months after hydraulic fracturing

Hydraulic fracturing requires the injection of large volumes of fluid to extract oil and gas from low permeability unconventional resources (e.g., shale, coalbed methane), resulting in the production of large volumes of highly complex and variable waste fluids. Shale gas fluid samples were collected from two hydraulically fractured wells in Morgantown, WV, USA at the Marcellus Shale Energy and Environment Laboratory (MSEEL) and analyzed using ultrahigh resolution mass spectrometry to investigate the dissolved organic sulfur (DOS) pool. Using a non-targeted approach, ions assigned DOS formulas were analyzed to identify dominant DOS classes, describe their temporal trends and their implications, and describe the molecular characteristics of the larger DOS pool. The average molecular weight of organic sulfur compounds in flowback decreased and was lowest in produced waters. The dominant DOS classes were putatively assigned to alcohol sulfate and alcohol ethoxysulfate surfactants, likely injected as fracturing fluid additives, on the basis of exact mass and homolog distribution matching. This DOS signature was identifiable 10 months after the initial injection of hydraulic fracturing fluid, and an absence of genes that code for alcohol ethoxysulfate degrading proteins (e.g., sulfatases) in the shale well genomes and metagenomes support that these additives are not readily degraded biologically and may continue to act as a chemical signature of the injected fluid. Understanding the diversity, lability, and fate of organic sulfur compounds in shale wells is important for engineering productive wells and preventing gas souring as well as understanding the consequences of unintended fluid release to the environment. The diversity of DOS, particularly more polar compounds, needs further investigation to determine if the identified characteristics and temporal patterns are unique to the analyzed wells or represent broader patterns found in other formations and under other operating conditions.