Summary Thermosets play a key role in the modern plastics and rubber industries, comprising ~20% of polymeric materials with a worldwide annual production of ~65 million tons. 1 , 2 The high density of crosslinks that gives thermosets their useful properties ( e.g ., chemical/thermal resistance, and tensile strength) comes at the expense of degradability and recyclability. Here, using the industrial thermoset polydicyclopentadiene (pDCPD) as a model system, we show that when a small number of cleavable bonds are selectively installed within the strands of thermoset plastics, the resulting materials can display the same mechanical properties as the native material, yet they are able to undergo triggered degradation to yield soluble, recyclable products of controlled size and functionality. In contrast, installation of cleavable crosslinks, even at comparably high loadings, does not produce degradable materials. These findings reveal cleavable bond location as a design principle for controlled thermoset degradation. Moreover, a new class of recyclable thermosets poised for rapid deployment is introduced.

High molecular weight (10 6-3 × 10 7 Da) polyacrylamide (PAM) is commonly used as a flocculant in water and wastewater treatment, as a soil conditioner, and as a viscosity modifier and friction reducer in both enhanced oil recovery and high volume hydraulic fracturing. These applications of PAM can result in significant environmental challenges, both in water management and in contamination of local water supplies after accidental spills. This paper provides a short review of current applications of high molecular weight PAM, including the potential for PAM degradation by chemical, mechanical, thermal, photolytic, and biological processes. Methods for treating wastewater containing partially degraded PAM are then discussed along with issues related to the potential toxicity and mobility of PAM in the environment after disposal or accidental release.

Polyacrylamide (PAM) based friction reducers are a primary ingredient of slickwater hydraulic fracturing fluids. Little is known regarding the fate of these polymers under downhole conditions, which could have important environmental impacts including decisions on strategies for reuse or treatment of flowback water. The objective of this study was to evaluate the chemical degradation of high molecular weight PAM, including the effects of shale, oxygen, temperature, pressure, and salinity. Data were obtained with a slickwater fracturing fluid exposed to both a shale sample collected from a Marcellus outcrop and to Marcellus core samples at high pressures/temperatures (HPT) simulating downhole conditions. Based on size exclusion chromatography analyses, the peak molecular weight of the PAM was reduced by 2 orders of magnitude, from roughly 10 MDa to 200 kDa under typical HPT fracturing conditions. The rate of degradation was independent of pressure and salinity but increased significantly at high temperatures and in the presence of oxygen dissolved in fracturing fluids. Results were consistent with a free radical chain scission mechanism, supported by measurements of sub-μM hydroxyl radical concentrations. The shale sample adsorbed some PAM (∼30%), but importantly it catalyzed the chemical degradation of PAM, likely due to dissolution of Fe at low pH. These results provide the first evidence of radical-induced degradation of PAM under HPT hydraulic fracturing conditions without additional oxidative breaker.

The rapid expansion of unconventional oil and gas development (UD), made possible by horizontal drilling and hydraulic fracturing, has triggered concerns over groundwater contamination and public health risks. To improve our understanding of the risks posed by UD, we develop a physically based, spatially explicit framework for evaluating groundwater well vulnerability to aqueous phase contaminants released from surface spills and leaks at UD well pad locations. The proposed framework utilizes the concept of capture probability and incorporates decision-relevant planning horizons and acceptable risks to support goal-oriented modeling for groundwater protection. We illustrate the approach in northeastern Pennsylvania, where a high intensity of UD activity overlaps with local dependence on domestic groundwater wells. Using two alternative models of the bedrock aquifer and a precautionary paradigm to integrate their results, we found that most domestic wells in the domain had low vulnerability as the extent of their modeled probabilistic capture zones were smaller than distances to the nearest existing UD well pad. We also found that simulated capture probability and vulnerability were most sensitive to the model parameters of matrix hydraulic conductivity, porosity, pumping rate, and the ratio of fracture to matrix conductivity. Our analysis demonstrated the potential inadequacy of current state-mandated setback distances that allow UD within the boundaries of delineated capture zones. The proposed framework, while limited to aqueous phase contamination, emphasizes the need to incorporate information on flow paths and transport timescales into policies aiming to protect groundwater from contamination by UD.