Date of Award

Fall 9-2017

Embargo Period


Degree Type

Dissertation (CMU Access Only)

Degree Name

Doctor of Philosophy (PhD)


Civil and Environmental Engineering


Athanasios Karamalidis

Second Advisor

Gregory Lowry


In conjunction with horizontal drilling, hydraulic fracturing or fracking has enabled the recovery of natural gas from low permeable shale formations. In addition to water, these fracking fluids employ proppants and up to 38 different chemical additives to improve the efficiency of the process. One important class of additives used in hydraulic fracturing is biocides. When applied appropriately, they limit the growth of harmful microorganisms within the well, saving energy producers 4.5 billion dollars each year. However, biocides or their harmful daughter products may return to the surface in produced water, which must then be appropriately stored, treated and disposed of. Little is known about the effect of mineral-fluid interactions on the fate of the biocides employed in hydraulic fracturing. In this study, we employed laboratory experiments to determine changes in the persistence and products of these biocides under controlled environments. While many minerals are present in shale formations, pyrite, FeS2(s) is particularly interesting because of its prevalence and reactivity. The FeII groups on the face of pyrite may be oxidized to form FeIII phases. Both of these surfaces have been shown to be reactive with organic compounds. Chlorinated compounds undergo redox reactions at the pyrite-fluid interface, and sulfur-containing compounds undergo exceptionally strong sorption to both pristine and oxidized pyrite. This mineral may significantly influence the degradation of biocides in the Marcellus Shale. Thus, the overall goal of this study was to understand the effect of pyrite on biocide reactivity in hydraulic fracturing, focusing on the influence of pyrite on specific functional groups. The first specific objective was to demonstrate the effect of pyrite and pyrite reaction products on the degradation of the bromine-containing biocide, DBNPA. On the addition of pyrite to DBNPA, degradation rates of the doubly brominated compound were found to increase significantly. DBNPA is proposed to undergo redox reactions with the pyrite surface, accepting two-electrons from pyrite, and thus becoming reduced. The primary product is the monobrominated analogue of DBNPA, 2-monobromo-3-nitrilopropionamide (or MBNPA). The surface area-normalized first-order initial degradation rate constant was found to be 5.1 L.m-2day-1. It was also determined that the dissolution and oxidation products of pyrite, FeII, S2O32- and SO42- are unlikely to contribute to the reduction of the biocide. Taken together, the results illustrate that a surface reaction with pyrite has the ability to reduce the persistence of DBNPA, and as a consequence change the distribution of its reaction products. The second objective was to quantify the influence of water chemistry and interactions with pyrite on the degradation of the sulfur-containing biocide. Dazomet readily hydrolyzes in water due to the nucleophilic attack of hydroxide (OH-) anions. Thus the half-life of dazomet during the shut-in phase of hydraulic fracturing will decrease with increasing pH: 8.5 hours at pH 4.1 to 3.4 hours at pH 8.2.Dazomet degradation was rapidly accelerated upon exposure to the oxidized pyrite surface, reacting five times faster than hydrolysis in the absence of pyrite at a similar pH. The products measured were identical to those identified on hydrolysis (methyl isothiocyanate and formaldehyde) and no dissolved iron was detected in solutions. This suggests that the dithiocarbamate group in dazomet was able to chemisorb onto the oxidized pyrite surface, shifting the electron density of the molecule which resulted in accelerated hydrolysis of the biocide. The third objective explored the reactivity of various biocide functional groups due to the addition of pyrite. Several elimination mechanisms were identified, and tied to the reactivity of the specific functional group involved. The addition of pyrite led to accelerated degradation of dibromodicyanobutane. This is because the bromine (-Br) group is easily reduced. For methylene bis(thiocyanate), hydrolysis was a noteworthy elimination mechanism since the thiocyanate (-SCN) functionality is a good leaving group. Benzisothiazolinone and methyl isothiazolinone were stable at low pH due to the stabilizing donor-acceptor interactions between the organic biocides’ carbonyl (–C=O) groups and salts in the solution. This body of work has illustrated that pristine pyrite can undergo redox reactions with brominated biocides used in hydraulic fracturing, reducing their persistence and altering the product distribution. This will change the efficacy and the risks associated with the use of these biocides in shales containing pyrite, particularly at lower pH where organic compounds are more stable to hydrolysis. However, at higher pH hydrolysis becomes more important, and additional studies will need to be conducted to investigate the pyrite contribution under these conditions. Conversely, the FeIII surface groups on oxidized pyrite can catalyze the hydrolysis of dazomet and may do so for other labile, sulfur-containing biocides as well. Overall, this research has shown that the physicochemical properties (such as the acid dissociation constant and the standard reduction potential) that govern the environmental reactivity of a molecule can be used to anticipate its reactivity in hydraulic fracturing.