## Evaluation of Potential Impacts of Hydraulic Fracturing

Flowback Fluid Additives on Microbial Processes in Publicly-Owned Treatment Works (Po-rvvs)

Prepared for Halliburton Energy Services, Inc. (HESI)

P.O. Box 42806 Houston, TX 77242-2806

December 31,2009



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### Table of Contents

1 Introduction .............................................................................................................. 1 2 3 Hydraulic Fracturing Flowback Fluid Disposal to a POTW .................................... 2 Assessment of Potential Impacts of Hydraulic Fracturing Flowback Fluid Additives on POTW Biological Processes ............................................................... 3 3.1 Exposure Analysis .............................................................................................................. 3 3.2 Effects Analysis .................................................................................................................. 4 3.3 Risk Characterization .......................................................................................................... 5 

### 4 Conclusion ................................................................................................................ 6 

### References ........................................................................................................................... 7

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### List of Tables

Table 1 Table 2 Table 3 HF Flowback Disposal to a POTW - Operational Assumptions

HF Flowback Disposal - Acute Risks to Microorganisms Based on Model dSGEIS Fluid Concentrations HF Flowback Disposal - Acute Risks to Microorganisms Based on Measured Flowback Fluid Concentrations from PA and WV



### List of Abbreviations
BOD dSGEIS HESI HF 

### I~Q MGD NYSDEC PA POTW QSAR RBC SPDES TSS Biochemical Oxygen Demand

Draft Supplemental Genetic Environmental Impact Statement Halliburton Energy Services, Inc. Hydraulic Fracturing Hazard Quotient Million Gallons Per Day New York State Department of Environmental Conservation Pennsylvania Publicly-owned Treatment Works Quantitative Structure-Activity Relationship Risk-Based Concentration State Pollutant Discharge Elimination System Total Suspended Solids West Virginia

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### 1 Introduction

The New York State Department of Environmental Conservation (NYSDEC) published a Draft Supplemental Generic Environmental Impact Statement (dSGEIS), dated September 2009, which contains generic permit requirements for the development of natural gas production wells in the Marcellus Shale formation using horizontal drilling and high-volume hydraulic fracturing techniques (NYSDEC, 2009). This memorandum evaluates potential risks of upsetting microbial processes in a wastewater treatment plant from exposure to typical additives likely to be present in hydraulic fracturing (HF) flowback fluid. Gradient has prepared this report on behalf of Halliburton Energy Services, Inc. (HESI).

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### 2 Hydraulic Fracturing Flowback Fluid Disposal to a POTW

Several options exist or are being developed for treatment, recycling or reuse of flowback water generated during HF operations.1 One option is treatment of flowback water at publicly-owned treatment works (POTWs), which typically discharge effluent to surface waters, and are regulated in New York State by the State Pollutant Discharge Elimination System, commonly referred to as SPDES. The POTW’s permit defines whether it can accept non-domestic waste and includes specific discharge limitations and monitoring requirements. A POTW must have a State-approved "pretreatment" program in order to accept industrial wastewater (such as HF flowback water). POTWs must also notify NYSDEC of any new industrial waste or of substantial changes in the volume or character of pollutants they plan to receive at their facility. NYSDEC must then determine if the SPDES permit needs to be modified. In addition to an approved pretreatment program, a headworks analysis is required for a POTW to be able to accept HF flowback water. The data required for conducting a headworks analysis are specified in the dSGEIS (pp. 7-58 and 7-59) and include: general chemistry and aquatic toxicity. The POTW will utilize these data to determine whether the volumes and concentrations of chemicals present in the HF flowback water can be accepted by the facility and the changes needed to the facility’s permit. One of the key objectives of a headworks analysis is to determine whether HF additives could adversely affect the POTW’s microorganisms resulting in disruption of the POTW operation and diminished effluent quality. Therefore, this report presents such an analysis to predict the likely impact of HF additives in flowback water, if any, on microorganisms at a POTW.

1 Information summarized in Section 2 of this memo is based upon information presented in the dSGEIS (NYSDEC, 2009). Gradient POTW Report-Final 2 Gradient



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### 3 Assessment of Potential Impacts of Hydraulic Fracturing Flowback

Fluid Additives on POTW Biological Processes Typically, microorganisms are used in the secondary treatment of wastewater to decompose organic matter at a POTW. As such, conditions in this secondary (biological) wastewater treatment step need to be conducive to microorganism survival. Failure to meet such conditions can cause an upset of the wastewater treatment process and can result in effluents that are not sufficiently treated for discharge to surface water. 

### 3.1 Exposure Analysis As discussed in Section 2, POTWs operate under permitting programs to ensure that upset conditions and discharges of inadequately treated wastewater are avoided under typical conditions. To evaluate the risk of flowback fluid from Marcellus Shale hydraulic fracturing operations causing disruption of POTW biological treatment processes, we used typical HF operations described in the dSGEIS, and operational information provided by HESI to Gradient, and assessed the potential impacts on POTW microorganisms for the operating conditions listed in Table 1.
Table 1 HF Flowback Disposal to a POTW - Operational Assumptions POTW Treatment HF Disposal (gal!tmck) 5,000 Transportation Rate (tmcks/day) 10 Disposal Rate (gal/day) 50,000 POTW Flow (gal/day) 2,000,000[a] Flowback Fluid Dilution in POTW 40 (disposal rate/POTW flow) Notes: [4 Median POTW design flow for POTWs listed in Appendix 21 of the dSGEIS. Based on the list of POTWs permitted to accept industrial wastewater listed in the dSGEIS, the median POTW flow capacity among these POTWs is 2 million gallons per day (MGD) (see Appendix 21 dSGEIS). It is anticipated that a typical HF flowback disposal rate could be 50,000 gal/day, resulting in a 40-fold dilution of the HF flowback fluid with other influent water. To calculate exposure concentrations to which microorganisms in a typical wastewater treatment plant would be exposed, the 40-fold dilution factor was applied to:

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### HESI302164Maximumselected representative pollutant concentrations for the model HF fluid listed in Table

6.13 of the dSGEIS (dSGEIS model HF fluid); and Maximummeasured flowback constituent concentrations,2 based on limited data from Pennsylvania and West Virginia listed in Table 6.2, dSGEIS.3 POTW microorganism exposure concentrations for the dSGEIS model HF fluid are presented in Table 2 and exposure concentrations for the flowback fluid based on PA and WV data are presented in Table 3. These exposure concentrations were compared to microbial toxicity effect concentrations to characterize potential risks for disruption of biological treatment processes at a typical POTW. 

### 3.2 Effects Analysis Traditionally, municipal wastes have been mineralized biologically, employing an assortment of microorganisms. These wastes normally contain readily biodegradable organic substances, however with rapid industrialization, certain synthetic organic chemicals have been shown to cause upset conditions and POTW permit violations. Microbial toxicity data for synthetic organic chemicals are limited. Nonetheless, measured toxicity data were found for three (3) out of the 13 chemicals listed in the dSGEIS HF model fluid (Table 2), and all four (4) synthetic organic chemicals measured in flowback fluid from PA and WV (Table 3). The lowest median inhibitory concentration (IC50),4reported in Trevizo and Nirmalakhandan (1999) or Nirmalakhandan et al. (1994), to have an effect on activated sludge, methanogens, nitrobacteria, or two commercial cultures (Polytox and Microtox) was used as the effects concentration [Risk-Based Concentration (RBC)] for POTW microorganisms. With advances in quantitative structure-activity relationships (QSARs) it has become increasingly possible to derive models using available test results that can reliably predict toxicity for chemicals lacking effects data. For example, aqueous solubility was shown to be a reliable predictor of microbial toxicity by Trevizo and Nirmalakhandan (1999). These authors demonstrated statistically significant correlations between experimental toxicity data [(log (IC50)] and experimental water solubility data [log (solubility)]. An overall correlation was found to be:

2 Constituent concentration estimates based on < 3 measurements were not considered sufficiently robust and were not further retained in our analysis. 3 As stated in the dSGEIS, characteristics of flowback fluid from the Marcellus shale in New- York are expected to be similar to flowback from PA and WV, but not identical (NYSDEC, 2009). 4 IC50 (the median inhibitory concentration): This is a measure of the effectiveness of a chemical in inhibiting biological or biochemical function. For instance, in the Microtox assay, it is the concentration of a chemical at which 50% reduction in bioluminescence by marine bacteria occurs. Gradient POTW Report-Final 4 Gradient



### HESI302165log (IC50, mM/l) 0.68 log (Solubility, mM/l) - 0.25

with a correlation coefficient of 0.756 for nearly 200 data points. This correlation was used to predict microbial toxicity values (RBC) for the remaining organic chemicals in the dSGEIS model HF fluid.


### 3.3 Risk Characterization The risk characterization for our analysis is presented as an HQ, or hazard quotient, relating the estimated HF flowback constituent concentrations in a typical POTW to the chemical’s risk-based concentration, or RBC:
POTW Conc HQ= RBC The numerator of this equation (POTW Conc) was calculated using the dSGEIS HF model fluid or measured flowback data (from PA and WV) and applying a dilution factor of 40. The denominator of this equation is the risk-based concentrations that were derived in the previous section. An HQ value of less than 1 indicates that adverse effects on POTW microorganisms are unlikely. Since all predicted HQs are substantially lower than 1 (Table 2), none of the synthetic organic constituents in the dSGEIS model HF fluid are present at concentrations that are expected to adversely impact biological treatment processes at a typical POTW. Similarly, measured concentrations in HF flowback fluid from PA and WV, after dilution at a typical POTW are more than 3 orders of magnitude below microbial effect concentrations and are therefore not expected to upset plant treatment processes (Table 3). There are a number of additional constituents listed in Table 3, such as conventional pollutant parameters [e.g., biochemical oxygen demand (BOD), pH, total suspended solids (TSS), oil & grease, etc. ] and non-conventional parameters (e.g., metals). These additional constituents are commonly treated at POTWs and regulated under the SPDES permitting program to ensure compliance with applicable statutory and regulatory requirements. Therefore, these parameters are not expected to cause microbial toxicity and disrupt biological treatment processes under the conditions specified in a typical POTW facility’s permit.

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### 4 Conclusion

We evaluated potential risks of upsetting microbial processes in a wastewater treatment plant from exposure to typical organic additives likely to be present in Marcellus Shale HF flowback fluid. Our analysis demonstrates that organic additives in the dSGEIS HF model fluid and measured flowback fluid data from PA/WV are not expected to cause microbial toxicity and upset conditions at POTWs that would treat such discharges in New York. Conventional (e.g., BOD, pH, TSS, oil & grease, etc.) and nonconventional pollutants (e.g., metals) present in HF flowback fluid are commonly treated at POTWs and regulated under the SPDES permitting program to ensure compliance with applicable statutory and regulatory requirements using pre-treatment approaches. They are therefore not expected to cause microbial toxicity and disrupt biological treatment processes under the conditions specified in the POTW’s permit. Based on the analysis presented herein, it can be concluded that the organic HF fluid additives listed in the dSGEIS (both in the dSGEIS HF model fluid and in measured flowback data) are present at concentrations substantially below those that might result in disruption of biological treatment processes at typical POTWs treating HF flowback fluids in New York and therefore the possibility that these HF fluid additives might cause an upset condition is de minimis.

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### References

New York State, Dept. of Environmental Conservation (NYSDEC). 2009. "Well Permit Issuance for Horizontal Drilling and High-Volume Hydraulic Fracturing to Develop the Marcellus Shale and other Low-Permeability Gas Reservoirs (Draft)." Division of Mineral Resources, Bureau of Oil & Gas Regulation / Supplemental Generic Environmental Impact Statement on the Oil, Gas and Solution Mining Regulatory Program. September. Nirmalakhandan, N; Arulgnanendran, V; Mohsin, M; Sun, B; Cadena, F. 1994. "Toxicity of mixtures or organic chemicals to microorganisms." Water Research 28(3):543-551. Trevizo, C; Nirmalakhandan, N. 1999. "Prediction of microbial toxicity of industrial organic chemicals." Water Science and Technology 39(10-11):63-69.

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