002233.0696.SGTG 2233.0696.SGTG-B3494 Quality Assurance Project Plan for the Haynesville Shale Prospective Case Study United States Environmental Pr Protection Agency Hydraulic Fracturing Study December 2011 Prepared for: United States Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Robert S. Kerr Environmental Research Center Ada, Oklahoma Prepared by: ECOLOGY AND ENVIRONM ENVIRONMENT, INC. 368 Pleasant View Drive Lancaster, New York 14086 Table of Contents T able of Contents Section 1 Page Project Management ................................................................ 1-1 1.1 1.2 1.3 1.4 1.5 1.6 2 Project/Task Organization ................................................................................ 1-1 Problem Definition/Background ...................................................................... 1-2 Project/Task Description ............................................................................. 1-81-7 Project Quality Objectives and Criteria .................................................... 1-101-8 Special Training/Certification ................................................................... 1-101-9 Documents and Records .......................................................................... 1-111-10 Data Generation and Acquisition ............................................ 2-1 2.1 2.2 2.3 2.4 2.5 Sampling Process Design (Experimental Design) ........................................... 2-1 2.1.1 Background Geologic and Hydrological Information .......................... 2-2 2.1.2 Ground-Water Monitoring ................................................................... 2-4 2.1.3 Surface Water Sampling....................................................................... 2-6 2.1.4 Soil Sampling .............................................................................. 2-122-11 Sampling Methods ................................................................................... 2-132-12 2.2.1 Installation of Temporary Piezometers ....................................... 2-132-12 2.2.2 Installation of Monitoring Wells ................................................. 2-162-15 2.2.2.1 Geophysical Logging .................................................... 2-162-15 2.2.2.2 Approach ....................................................................... 2-162-15 2.2.2.3 Monitoring Well construction ....................................... 2-182-17 2.2.3 Monitoring Well Sampling.......................................................... 2-192-18 2.2.4 Domestic Wells, Water Supply Wells, and Municipal Supply Well Sampling ............................................................................. 2-322-30 2.2.5 Surface Water Sampling.............................................................. 2-342-32 2.2.6 Soil Sampling .............................................................................. 2-342-32 2.2.6.1 Soil Sampling Procedures. ............................................ 2-352-32 2.2.7 Mechanical Well Integrity Testing .............................................. 2-362-34 2.2.8 Flow Back Sampling ................................................................... 2-382-36 Sample Handling and Custody ................................................................ 2-382-36 2.3.1 Sampling Labeling ...................................................................... 2-382-36 2.3.2 Sample Packing and Shipping ..................................................... 2-382-36 Analytical Methods ................................................................................. 2-392-37 Quality Control ........................................................................................ 2-522-49 2.5.1 Quality Metrics for Aqueous Analysis ........................................ 2-522-49 2.5.2 Measured and Calculated Solute Concentration Data Evaluation2-592-56 2.5.3 Detection Limits .......................................................................... 2-592-56 iii 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/1308/06/1301/06/1201/06/1201/06/1212/20/11 Table of Contents (cont.) Section Page 2.6 2.7 2.8 2.9 2.10 3 Assessment and Oversight ..................................................... 3-1 3.1 3.2 4 Assessments and Response Actions ................................................................. 3-1 3.1.1 Assessments ......................................................................................... 3-2 3.1.2 Assessment Results .............................................................................. 3-2 Reports to Management ................................................................................... 3-3 Data Validation and Usability .................................................. 4-1 4.1 4.2 4.3 5 2.5.4 QA/QC Calculations ................................................................... 2-592-56 Instrument/Equipment Testing, Inspection, and Maintenance ................ 2-602-57 Instrument/Equipment Calibration and Frequency ................................. 2-602-57 Inspection/Acceptance of Supplies and Consumables ............................ 2-612-58 Non-direct Measurements ....................................................................... 2-622-59 Data Management ................................................................................... 2-622-59 2.10.1 Data Analysis, Interpretation, and Management ......................... 2-632-60 2.10.2 Data Recording ............................................................................ 2-632-60 2.10.3 Data Storage ................................................................................ 2-632-60 2.10.4 Analysis of Data .......................................................................... 2-632-60 Data Review, Verification, and Validation ...................................................... 4-1 Verification and Validation Methods ............................................................... 4-1 Reconciliation with User Requirements ........................................................... 4-3 References ................................................................................ 5-1 Appendix A Standard Operating Procedures ............................................ A-1 B Field Forms .............................................................................. B-1 iv 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/1308/06/1301/06/1201/06/1201/06/1212/20/11 List of Tables L ist of Tables Table Page 1 Critical analytes .................................................................................................... 1-91-8 2 Water Quality of the Carizzo-Wilcox Aquifer. Data from LDEQ 2009................... 2-4 3 The Physical Characteristics of the Monitoring Wells Near the Proposed Well Pad.............................................................................................................................. 2-5 4 Field Parameter Stabilization Criteria and Calibration Standards .................... 2-272-25 5 Groundwater Field Analytical Methods............................................................ 2-292-27 6 Ground and Surface Water Sample Collection ................................................. 2-302-28 7 Field QC Samples for Water Samples .............................................................. 2-322-30 8 Region III Laboratory QA/QC Requirements for Glycols ............................... 2-402-38 9 RSKERC Detection Limits for Various Analytes ............................................ 2-442-41 10 Region VIII Detection and Reporting limits and LCS and MS Control Limits for Semivolatile Organic Compounds (SVOC) using Method 8270 ................ 2-482-45 11 RSKERC Laboratory QA/QC Requirements Summary* from SOPs ............... 2-542-51 12 Region VIII Laboratory QA/QC Requirements for Semivolatiles, GRO, DRO2-572-54 13 Region III Detection and Reporting Limits for Glycols ................................... 2-592-56 14 Supplies or Consumables Needed Not Listed in SOPs*................................... 2-622-59 v 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/1308/06/1301/06/1201/06/1201/06/1212/20/11 List of Figures L ist of Figures Figure Page 1 Organizational Chart for the Hydraulic Fracturing Prospective Case Study ........ 1-41-3 2 EPA HF Prospective Case Study Location Map................................................... 1-61-5 3A Proposed Monitoring Well Location Map ............................................................ 2-82-7 3B Expanded View of Proposed Monitoring Wells in Close Proximity to the Proposed Gas Well.............................................................................................. 2-102-9 4 Proposed Soil, Surface Water and Piezometer Locations ................................. 2-142-13 5 Typical Groundwater Monitoring Well ............................................................ 2-212-19 6 Open Tube Sampling Method ........................................................................... 2-232-21 7 Closed Piston Sampling Method....................................................................... 2-252-23 8 Chain of Custody Form for Submittal of Samples to R.S. Kerr Environmental Research Center ................................................................................................ 2-422-39 vii 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/1308/06/1301/06/1201/06/1201/06/1212/20/11 List of Abbreviations and Acronyms L ist of Abbreviations and Acronyms Start here ix 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/1308/06/1301/06/1201/06/1201/06/1212/20/11 Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1 Project Management 1.1 Project/Task Organization The organizational structure for the Hydraulic Fracturing Prospective Case Study located in the Haynesville Shale, in Desoto Parish Louisiana is shown in Figure 1. The responsibilities of the principal personnel associated with this case study are listed below. Dr. Robert Puls, U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, Robert S. Kerr Environmental Research Center (RSKERC), Ada, OK. Dr. Puls is the overall technical lead on the Hydraulic Fracturing Study. He is the principal investigator of this project and is responsible for preparing and maintaining the Quality Assurance Project Plan (QAPP) and ensuring completion of all aspects of this QAPP, including overall responsibility for QA. He will lead the collection, analysis, and interpretation of groundwater and surface water samples. Mr. Steve Vandegrift, U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, RSKERC, Ada, OK. Mr. Vandegrift is responsible for quality assurance review/approval of the QAPP, conducting audits, and QA review/approval of the final report. His HAZWOPER certification is current. Dr. Randall Ross, U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, RSKERC, Ada, OK. Dr. Ross will assist in the analysis of hydrologic conditions at the Haynesville site and will assist in the development of the site hydrologic conditions. His HAZWOPER certification is current. Mr. Steve Acree, U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, RSKERC, Ada, OK. Mr. Acree will assist in the analysis of hydrologic conditions at the Haynesville site and will assist in the development of the site hydrologic conditions. His HAZWOPER certification is current. 1-1 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [nc1]: Need to replace with current person Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management Mr. Russell Neill, Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, RSKERC, Ada, OK. Mr. Neill is responsible for assisting in ground water sampling. His HAZWOPER certification is current. Dr. Sujith Kumar, Shaw Environmental, Ada, OK. Dr. Kumar is responsible for overseeing the analytical work performed under Ground Water and Ecosystems Restoration Division's (GWERD) on site analytical contract (VOC's, dissolved gases, and metals). Ms. Shauna Bennett, Shaw Environmental, Ada, OK. Dr. Ms. Bennett is the QC Coordinator for Shaw Environmental and will coordinate QC for Shaw Environmental portion of this study. Ms. Cynthia Caporale, USEPA Region 3 Analytical Laboratory, Laboratory Branch Chief/Technical Director. Ms. Caporale will act as a liaison between the Region 3 Lab and RSKERC. Mr. Christopher Hill, Chesapeake Energy, Oklahoma City, OK. Mr. Hill will be the single point of contact for Chesapeake Energy throughout the Haynesville prospective study. Dr. Puls is responsible for initiating contact with appropriate project participants as he deems necessary. Other project participants will keep Dr. Puls informed whenever significant developments or changes occur. Lines of communication among project participants may be conducted via in person conversations, electronic mail, phone conversations, conference calls, and periodic meetings. 1.2 Problem Definition/Background The prospective case study in the Haynesville Shale (see Figure 2) will investigate the construction of a new production well, hydraulic fracturing of said well, management and disposal of wastewater and production of gas from said well for about 1 year following hydraulic fracturing to determine if there is a negative impact to drinking water. The investigation will initially involve sampling ground water, surface water and soil and sediment sampling in the vicinity of the well pad to determine baseline characteristics. This study will be conducted in conjunction with the Louisiana Department of Environmental Quality (LDEQ), Chesapeake Energy, U.S. Environmental Protection Agency, Region 6 (EPA R6); and U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory (NRMRL), Ground Water and Ecosystems Restoration Division (GWERD). GWERD will be the lead organization for this case study. In addition, the EPA will undertake a review of all other potential sources of contamination in the area, and identify those sources before the project proceeds. Potential sources that will be identified include USTs, historical oil and 1-2 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Formatted: Not Highlight Comment [CV2]: All potential sources of contamination should be identified before the project during Tier 1 activities as identified the the Final Study Plan (11/3/2011). A EDR/Phase I data review should be used to identify any potential sources such as USTs, landfills, spills along the railroad easement, salt storage yards, septic tanks, sewer lines, stormwater lines, etc within a 3-mile radius of the site. Comment [nc3]: I thought it was decided to not to do the sediment sampling Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management gas wells/pits/pipelines/storage area, landfills, releases, salt storage yards, septic tanks, sewer lines, stormwater lines, ecttc. within a 2 mile radius of the site. 1-3 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management Insert Figure (color) page 1 of 2 1 Organizational Chart for the Hydraulic Fracturing Prospective Case Study, Desoto Parish, LA 1-4 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management Figure 1 page 2 of 2 1-5 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management Insert Figure (color) page 1 of 2 2 EPA HF Prospective Case Study Location Map 1-6 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management Figure 2 page 2 of 2 1-7 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management The proposed pad location is in De Soto Parish in north western LA and has an estimated population of 26,656 individuals (2010). The area surrounding the proposed site is currently experiencing extensive natural gas exploration using horizontal drilling technology and hydraulic fracturing is being employed to stimulate production in these wells. In addition, this area was part of historical oil and gas field developed in the 1950's and 1960's. Prior to proceeding any sampling and monitor well installation as part of Tier 1 & 2 activities (described in the final Study Plan 11/3/2011), all historical oil/gas infrastructure will be identified, such as tank batteries, pipelines, existing and plugged/abandoned oil/gas wells, and pits. Following identification, the final location of monitoring wells and sample sites will be selected. The objectives of this case study are listed below. ? Primary Objective: Evaluate ground water, surface water and soil characteristics before, during and after key phases of a shale gas well development; well drilling, well completion, and production to identify if there is a significant change in media characteristics. Comment [CV4]: Should also note history of the area, as has experienced extensive oil and gas development in the 1950s-60s. Comment [CV5]: Case study objectives should be the same as objectives listed in the Final Study Plan. Comment [c6]: The SAB specifically requested that the study be limited to hydraulic fracturing. It appears the EPA has expanded the scope of the study to include all development activities. CHK recommends that the EPA focus on hydraulic fracturing. ? Secondary Objective 1: Determine the appropriate baseline characteristics of ground water, surface water, and soil. Comment [c7]: The definition of a significant change needs to be defined. It is equally important to determine the cause of all changes; natural or anthropogenic. ? Secondary Objective 2: Determine characteristics of ground water, surface water, and soil throughout the key phases of the gas well development; postpad construction to approximately one year after initial gas production. Comment [CV8]: Given the current schedule, there does not appear to be enough time to capture seasonal variations in sample characteristics, , however, this is critical to determining if a change is significant. ? Secondary Objective 3: Determine the chemistry, volumes and rates of produced water, specifically flowback, over a period of months from the production well following hydraulic fracturing. ? Secondary Objective 4: Compare data gathered for secondary objectives 1 and 2 to determine if significant changes were observed in the media baseline characterisitics, and if this change could be attributed to the gas well development. ? Secondary Objective 5: Review wastewaters site management and disposal practices during drilling and hydraulic fracturing, and qualitatively identify risks to drinking water sources. 1.3 Project/Task Description In order to accomplish the primary objective of the study, the established monitoring well network, along with any pertinent domestic wells and municipal supply wells will be sampled for the components found in Table 1. In addition, select 1-8 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV9]: It remains CHK's position that the QAPP be as complete as possible prior to study commencement. As such, Secondary Objectives 3-5 should be included if they are in fact objectives of this study. Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management hydraulic fracturing fluid components (such as potassium (K), barium (Ba), alcohols, naphthalene, and boron), potentially mobilized naturally occurring substances (such as arsenic (As), selenium (Se), strontium (Sr), and other trace metals) will also be tested along with changes in background water quality (pH, major anions and cations). In addition, during future samplings soil and stream samples will be taken and the critical analytes for these sample types are the same as listed previously. Comment [nc10]: Potassium has not been found to be a good indicator of hydraulic fracturing fluid components. In order to address secondary objective 1, groundwater sampling, surface water sampling and soil sampling will be necessary. The target parameters listed in the primary objective will be needed to address this objective. At least 3 rounds of baseline sampling should be conducted on monitoring wells, streams, and area water wells following completion of the pad. Comment [c12]: As experience has shown, multiple samplings of surface water and groundwater is needed to define the variability of parameter constituents, which will vary depending on climatic conditions, sampling methodology, sample collection depth, and laboratory variability in sample results. Suggest at least 3 baseline samplings be conducted at a minimum to define the water-quality variability. Secondary objective 2 will entail re-sampling of groundwater, surface water, and soils for the same suite of parameters to see if there was any adverse impact. Comment [nc11]: These elements are not necessarily mobilized but rather are naturally present in the formation waters. Comment [n13]: Will probably only be able to do 2 rounds of baseline given slips in schedule Comment [WU14]: I would agree to 2 based on budget. If CHK wants 3, they can pay for it Comment [c15]: All analytes and methods should be consistent for baseline and non-baseline sampling. The data collected from this case study will be incorporated into the larger Hydraulic Fracturing report to Congress. It is also anticipated that this data will be utilized in EPA reports, conference proceedings and journal articles. Work group members, including Chesapeake, will have an opportunity to review and comment on any and all products, including draft reports, related to this prospective study prior to their public release. In addition, the data collected in this case study may be used by policy and decision makers in EPA and state regulatory agencies. Table 1 Gasoline Range Organics (GRO) Diesel Range Organics (DRO) Volatile Organic Compounds (VOC)* Semivolatile Organic Compounds (SVOC) Metals (As, Se, Sr, Ba, B) Major Cations (Ca, Mg, Na, K) Comment [n17]: Given time constraints we can commit to one and maybe 2 post well construction Comment [c18]: The number of sampling events between key phases of the gas well development should be indentified. Comment [WU19]: E&E please add Ra and U to tables, text Comment [n20]: Can discuss this on down the road, lets get the baseline stuff covered under the QAPP so we can do private well sampling before years end Critical Analytes. Analyte Comment [WU16]: I agree Analysis Method ORGM-506 r1.0, EPA Method 8015D ORGM-508 r1.0, EPA Method 8015D RSKSOP-299v1 ORGM-515 r1.1, EPA Method 8270D RSKSOP-213v4 &-257v2 or -332v0 RSKSOP-213v4 Laboratory Performing the Analysis EPA Region VIII Laboratory EPA Region VIII Laboratory Shaw Environmental EPA Region VIII Laboratory Shaw Environmental Shaw Environmental Comment [WU21]: We will consider this Comment [c22]: Chesapeake would appreciate the opportunity to be included in the production and review of these reports. We request that we discuss our role up front. Comment [n23]: This is assumed but if you (CHK) wish to propose some language here do so Comment [WU24]: CHK would be involved in the review of any report or publication coming from this case study. With respect to the reports to Congress, I will raise it up the line but cannot commit to it now Comment [n25]: Rads will be added on later update of QAPP Comment [c26]: Radon and radium are mentioned in the discussion but no methods are identified for use. Comment [WU27]: Need to add 1-9 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management Major Anions (Cl, carbonate, bicarbonate, Br, NO3-+NO2-, SO42-) RSKSOP-276v3 (NO3-+NO2- RSKERC general parameters by RSKSOP-214v5) lab Comment [CV28]: Add carbonate and bicarbonate and bromide. *Ethanol, isopropyl alcohol, tert-butyl alcohol, naphthalene. Only those SVOC compounds in Table 10 that have DL, RL, and Control Limits listed may be used as critical analytes; all others will be used only as screening data. Both VOC and SVOC have many target analytes and initially all are considered critical (with exception for SVOC noted above). A tiered approach will be used to further refine the identification of specific compounds as critical. Data from the first sampling events will be evaluated by the PI to determine if there are specific compounds that are identified in these samples which would warrant their specific identification as critical to narrow the list. These will be identified in a subsequent QAPP revision. GRO analysis provides data for not only TPH as gasoline, but several other compounds. Only TPH as gasoline will be considered critical from this analysis. 1.4 Project Quality Objectives and Criteria As part of this case study, detailed site history has been collected and is continuing to be collected. This data has been collected from Chesapeake and other sources of public information. The site history will be used to determine the background conditions at the site as well as the potential for other activities in the area to be a potential source of the impact to the local aquifer. Natural sources of contaminants or other human activities need to be considered in all interpretations of the data. The installed monitoring well soil sampling and surface water sampling should yield a representative data set that will be analyzed to determine if significant changes were observed in the media baseline characteristics, and if these changes could be attributed to the gas well development. Data from private wells will also be considered but are not considered to be part of the monitoring network. To date EPA has received limited information on the hydrologic conditions near the proposed well pad. During the initial and subsequent sampling events water level measurements will be taken in order to address the hydrologic setting, flow direction and velocity. Other project quality objectives, such as precision, accuracy, sensitivity, and etc. will be discussed primarily in sections 2, 3, and 4. 1.5 Special Training/Certification A current HAZWOPER certification is required for on-site work. HAZWOPER training and yearly refresher training is provided to GWERD personnel at an appropriate training facility chosen by GWERD SHEMP (Safety, Health, and Environmental Management Program) manager. The HAZWOPER certificate and wallet card is provided to each person completing the training. All EPA contractor personnel will also be required to have HAZWOPER training and up-to-date training certificates. In addition to HAZWOPER training, Chesapeake is requiring that all field personnel undergo hydrogen sulfide training. This training will be provided by Chesapeake. All work performed must comply with professional licensing requirement for the State of Louisiana, and those include laboratory, 1-10 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c29]: The study should be designed to ensure a representative data set is collected. Will EPA be collecting enough samples to statistically say that the samples are representative and changes are significant? Comment [c30]: Geophysical techniques will also be used, correct? Comment [c31]: Consider using water-quality trolls such as Specific Conductivity and water level recording trolls to use in-situ in select wells in an area to provide pre-drill baseline data---continuous water-level and water quality data--this is a cheap way of collecting data. Same on streams in area. Need good baseline data that defines variability in sampling, which can be significant, especially for some metals such as iron and manganese. Comment [WU32]: If CHK wants to buy and deploy they can-you guys are part of the team hereplease write things in as you see fit Comment [CV33]: Should add to this section that the geological field work may require supervision by a Louisiana licensed Professional Geologist (depending on when the work is performed). In addition, the monitoring wells and geoprobe borings must be installed and constructed by a licensed driller in Louisiana. Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management drilling, engineering, and professional geological certifications/registrations. All geologists surpervisingsupervising the monitoring well installation should be registered in the State of Louisiana. The laboratories performing critical analyses in support of this case study must demonstrate their competency in the fields of analyses to be conducted, prior to performing such analyses. Competency may be demonstrated through documentation of certification/accreditation or some other means as determined to be acceptable by project participants. The EPA GP laboratory and the Shaw laboratories, the on-site contractor laboratory at RSKERC, will be used to analyze select critical analytes listed in Table 1. These laboratories have demonstrated competency through the implementation of ORD PPM 13.4, Minimum QA/QC Practices for ORD Laboratories Conducting Research which includes external independent assessments. These laboratories are also routinely subjected to internal laboratory assessments and performance evaluation (PE) samples. The USEPA Region VIII Laboratory will be used to analyze those critical analytes listed in Table 1. This laboratory has been subjected to the National Environmental Laboratory Accreditation Program (NELAP) accreditation process through the state of Texas and is expected to soon be granted approval. The Region III Laboratory will be used to analyze glycols, which is not identified as critical at this time. However, it is accredited under the NELAP through the state of New Jersey as the Accrediting Body. The particular method being used by Region III for these analyses are not accredited, but the laboratory follows all the requirements for an accredited method. However, initial data reported from the glycol analysis will be flagged as "screening" data from a method that is currently being developed. Once the data is validated, it will no longer be flagged as screening" data. 1.6 Documents and Records Data reports will be provided electronically as Excel spreadsheets. Shaw's raw data is kept on-site at the GWERD and will be provided on CD/DVD to Dr. Puls. Raw data for sub-contracted laboratories shall be included with the data reports. Calibration and QC data and results shall be included. Field notebooks will be kept as well as customized data entry forms if needed. Data will be uploaded to a FTP website that Chesapeake has access within two weeks of receipt of data by the EPA. Records and documents expected to be produced include: field data, chain-ofcustody (COC), QA audit reports for field and laboratory activities, data reports, raw data, calibration data, QC data, interim reports, and a final report. 1-11 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c34]: Has this lab been approval for their NELAP accreditation. Comment [c35]: EPA Region III Laboratory needs to provide a detailed comparison of the result of their method and a more accepted method to provide documentation that the analytical method is adequate. CHK requests a copy of all nonpromulgated EPA method. Comment [WU36]: OK Comment [c37]: CHK doesn't believe data from testing prior to method validation should be used for the study. Comment [CV38]: CHK is operating under the assumption that EPA will make all data associate with the Haynesville site available on an FTP website in a timely manner. Comment [c39]: Geophysical, well mechanical integrity data needs to be included in this section. Comment [c40]: Secondary Data Gathering and Evaluations needs to be included in this QAPPs. Comment [nc41]: Need to add acknowledgement that this is a trademark. Section No.: 1 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 1. Project Management All field and laboratory documentation shall provide enough detail to allow for reconstruction of events. Documentation practices shall adhere to ORD PPM 13.2, "Paper Laboratory Records." Since this is a QA Category 1 project, all project records require permanent retention per Agency Records Schedule 501, Applied and Directed Scientific Research They shall be stored in Dr. Puls's office in the GWERD until they are transferred to GWERD's Records Storage Room. At an as yet to be determined time in the future the records will be transferred to a National Archive facility. 1-12 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2 Comment [c42]: In order to ensure direct comparison, parameters analyzed in post activities and flowback should be the same as baseline. Comment [c43]: Secondary Data Gathering and Evaluations needs to be included in this QAPPs. Data Generation and Acquisition 2.1 Sampling Process Design (Experimental Design) First sampling events in 2012 will include base line sampling of groundwater, soils, and surface water. Flowback and produced water will be sampled after hydraulically fracturing the well later in 2012. The following is a summary of the planning sampling events. The QAPP will be revised as appropriate prior to succeeding sampling events. Baseline: 23 Rounds (Domestic Wells) ? January 2012 Domestic Well Sampling ? March 2012 Domestic Well Sampling Baseline: 23 Rounds (Monitoring Wells) ? March 2012 MW Sampling ? April 2012 MW Sampling Post-production Well Drilling: (Monitoring Wells) Assumption: Drilling Spud date April 2012 - 45 days to complete ? Late May/early June 2012 MW Sampling Post-fracing (Monitoring Wells Domestic Wells) Assumption: hydraulic fracturing in September 2012 ? September 2012 MW and Domestic Well Sampling Flowback Sampling Over 90 Day Period ? ? ? ? Immediately following hydraulic fracturing 45 days 90 days 120 days 2-1 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c44]: In reality, flowback sampling and quarterly sampling are equivalent. Flowback is a process and brings to the surface produced water immediately after HF has taken place. Comment [c45]: Should this be removed? Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Quarterly Sampling (Assuming Hydraulic Fracturing Occurs in September 2012) ? ? ? ? December 2012 MW Sampling March 2013 MW and Domestic Well Sampling June 2013 MW Sampling September 2013 MW and Domestic Well Sampling 2.1.1 Background Geologic and Hydrological Information Geology Surface exposures consist of Pleistocene and Holocene sediment. Sandy, gravelly and muddy alluvium from rivers and coastal marsh deposits make up the Holocene while terraces of glacial sand, gravel and mud deposits from the North make up the Pleistocene. Underlying the Pleistocene units are the units of the Eocene and Paleocene. Two formations from these periods that are of note are Claiborne group and the underlying Wilcox group. These groups are composed primarily of sandstones and are an important aquifer in Louisiana and Texas. This aquifer will be discussed in greater detail below. Underlying the Wilcox formation is the Midway formation which is a confining layer composed of clays. Underlying this are Upper Cretaceous formations which contain marl, chalk, limestone and shale and some groups which are known for hydrocarbon production in the area. These units, in order from top down are the Navarro, Taylor, Austin, Eagle Ford, Tuscaloosa and the top of the Washita. The Lower Cretaceous is composed of the limestone, chalk, marl, shales and sandstones of the Washita-Fredericksburg and Trinity Groups. Underlying the Lower Cretaceous is the Upper Jurassic which contains the Cotton Valley Group's shallow marine shales. The Haynesville Formation lies below the Cotton Valley group and is a hydrocarbon producing black shale and the equivalent of the Lower Bossier Formation in Texas. Underlying the Haynesville is the calcareous shelf/reef/lagoon formations of the Smackover limestone which is underlain by the Norphlet mudstone. The Louann Salt and Werner red shale and sandstone formations are located underneath the Norphlet mudstone. The underlying Upper Triassic contains the thick red beds of the Eagle Mills Group which are above the undifferentiated rock of the Paleozoic (LAGS 2008 and AKGS). Desoto Parish Desoto Parish is located in the northwestern region of Louisiana in a geologically significant area called the Sabine Uplift. The Sabine Uplift area was created as a result of the combination of the rifting events which created the Gulf of Mexico and shearing forces resulting from tectonics in North America. These same forces are the cause of multiple salt domes that occur in the county. While the stratigraphic sequence is the same in the county as the rest of the state, the Jurassic age formations of the Haynesville and Bossier shales are of note as both are wellknown as hydrocarbon producers. The Bossier Shale is dark, calcareous, 2-2 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c46]: CHK provided EPA and E&E more site specific reference that should be integrated into the background geology and hydrological information. (e.g., well logs) Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition fossiliferous marine shale in sequence with sandstone that is determined to be the source rock for the gas accumulation in upper formations. The Haynesville Shale is a carbonaceous, ultra-low permeability/high porosity black shale below the Bossier Shale with the thin Gilmer Lime separating the two formations (LAGS 2008 and AKGS). Hydrology The Carrizo-Wilcox is an Eocene and Paleocene age aquifer and is comprised of hydraulically connected, well sorted, fine to medium grained, cross bedded sands and silts from the Wilcox Group and the Carrizo Formation of the Claiborne Group (Ashworth and Hopkins, 1995). The origins of the sands which compose the Carrizo-Wilcox are both fluvial and fluvial-deltaic in origin. The CarrizoWilcox aquifer extends across Texas from the Rio Grande in the southwest to Red River the northeast including Desoto Parish in Louisiana. The aquifer is bounded at its base by the confining clays of the Midway group and is overlain by the confining clays and silty clays of Cane River formation. The aquifer has a down-dip trend to the south which is the primary factor in ground water flow direction. Brackish water found in the aquifer is most likely the result of dissolution of salt domes found in the area and most likely also plays a role in the direction of groundwater flow because density differences. Water also moves between overlying alluvial and terrace aquifers, the Sparta aquifer, and the Carrizo-Wilcox aquifer, according to hydraulic head differences and in some places artesian pressures within the aquifer were originally sufficient to drive water above ground. Water level fluctuations are mostly seasonal, and the hydraulic conductivity varies between 2 and 40ft./day. Primary recharge of the Carrizo-Wilcox aquifer occurs from direct infiltration of rainfall in upland outcrop-subcrop areas. Maximum depths of occurrence of freshwater in the Carrizo-Wilcox range from 200ft. above sea level to 1,100ft. below sea level. Based on literature review, and available well logs, the base of the Carrizo-Wilcox aquifer appears to be between 600 to 800 feet deep near the study location. Drinking water wells in the immediate vicinity of the site are screened from between 181 feet to 360 feet below ground surface. The deepest boring in the area, a USGS well (DS-315) extended to a depth of 570 and was still in the Carizzo-Wilcox aquifer. Shallow groundwater in the study area is anticipated to be less than 40 feet bgs (Page, 1964). Analysis of the quality of the water from the Carrizo-Wilcox aquifer shows it to be soft and of good quality with an average pH of 8.31, total dissolved solids (TDS) of 0.48 g/L, a salinity of 0.36 ppt and chloride content of 66.4 mg/L. Further information about the water quality from the Carrizo-Wilcox can be found in Table 2 (LDEQ 2009). 2-3 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c47]: Addition resources are available regarding the groundwater and surface water quality. This information should be complied and tabulated. Examples include USGS NWIS and NURE sites. Comment [WU48]: I think what we have is sufficient Comment [nc49]: Need to be consistent throughout the document in the use of ft. , ft or feet Comment [c50]: The base of USDW from SONRIS should be sited. I believe it was approximately 780 ft. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Laboratory Field Table 2 Water Quality of the Carizzo-Wilcox Aquifer. Data from LDEQ 2009 FY 1995 FY 1998 FY 2001 FY 2004 FY 2007 Parameter Average Average Average Average Average Temperature (OC) pH (SU) Specific Conductance (mmhos/cm) Salinity (ppt) TDS (g/L) Alkalinity (mg/L) Chloride (mg/L) Color (PCU) Specific Conductance (uumhos/cm) Sulfate (mg/L) TDS (mg/L) TSS (mg/L) Turbidity (NTU) Ammonia, as N (mg/L) Hardness (mg/L) Nitrite - Nitrate, as N (mg/L) TKN (mg/L) Total Phosphorus (mg/L) 21.44 7.53 0.676 21.30 7.65 0.732 21.98 7.87 0.808 21.39 7.75 0.80 21.83 8.31 0.740 0.35 267.2 59.2 25.8 726.4 0.36 251.5 71.6 13.8 772.4 0.40 249.4 69.7 24.1 748.1 0.39 0.520 273.5 66.5 14.8 799.5 0.36 0.480 283.4 66.4 8.2 739 30.1 434.7 <4 2.6 0.42 52.4 0.08 0.78 0.29 30.5 435.7 4.9 5.2 0.64 42.2 0.07 0.96 0.24 28.7 449.6 <4 2.3 0.64 31.3 0.07 0.82 0.26 26.6 481.2 <4 1.6 0.81 41.0 0.07 0.97 0.33 Comment [c51]: Has EPA discussed with LA DEQ how they can collaborate on future data gather exercise that would benefit the state and EPA? Since this work the final report for this work is not expect until the end of 2014, there appears to be time to work with the state on this effort. CHK would appreciate the opportunity to participate in any collaborative effort that could benefit the EPA HF Study and the State of LA. 13.1 429.7 <4 1.9 0.63 33.5 0.10 0.77 0.26 2.1.2 Ground-Water Monitoring Groundwater sampling and analysis will provide data that can be used to identify significant changes in water quality and investigate if these changes have potentially been caused by the introduction of drilling fluids, hydraulic fracturing fluids, and formation fluids and gases to underground sources of drinking water. This sampling will aid in the understanding of the potential chemicals constituents that could contaminate shallow ground water as well as the potential future impacts to shallow groundwater that may occur as the result of the transport of contaminants to the site. The groundwater sampling component of this project is intended to provide a survey of water quality in the area of investigation throughout the key phases of the gas well development; post well construction to approximately one year after hydraulic fracturing activities have been completed. Location, distribution, and number of sampling sites can affect the quality and applicability of the resulting data. Therefore, the following criteria may be used to determine groundwater water sampling locations: study objectives and sampling methods; all available historical information; physical characteristics of the area, such as size and shape, land use, geology, point and nonpoint sources of contamination, hydraulic conditions, climate, water depth, historical oil and gas wells/pipeline/storage areas; chemical characteristics of the area; and the types of equipment that will be needed for sampling (USGS, 2010). GWERD, EPA R6, 2-4 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [nc52]: Need to use consistent units for specific conductance throughout the document Comment [c53]: The study should be focused on hydraulic fracturing. If the EPA chooses against Congresses request and SAB recommendation to expand the scope of the study, it is necessary to ensure differentiation between potential sources of contaminations. Comment [CV54]: The list of analytes should be the chemical constituents that could potentially contaminate ground water. The data will aid in determining IF there has been a contamination. Comment [CV55]: Should also factor in preexisting oil/gas development in the area. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition LADEQ, and Chesapeake will survey the existing data and speak to landowners near the proposed pad to determine if ground water wells in the area could be sampled for the study. The domestic wells will be sampled directly from the well casing (if possible) with the sampling pump just above the well pump. In cases where this is not possible, the sampling pump will be placed as close as possible to well pump. If access to the well is limited or the sampling pump cannot be lowered to the desired depth, the sample will be collected from the tap from at the closest port to the wellhead. It is believed that most domestic wells are screened in the Carizzo-Wilcox aquifer between 100 and 500 ft below ground surface. Similarly, any water supplymonitoring wells will be sampled similar to the domestic wells. It is anticipated that the monitoring wells will be sampled quarterly by EPA until approximately one year after hydraulic fracturing activities. The minimum number of post-baseline sampling events to determine if an impact to the aquifer happened is estimated to be three sampling events. It is estimated that 11 monitoring wells will be installed to monitor groundwater quality near the study location. An initial deep boring will be completed and logged using downhole wireline logging techniques to evaluate actual aquifer thickness, zone of preferential flow, and flow direction (see Section 2.2.2.1). This well will then be converted to a deep monitoring well and included as part of the groundwater monitoring well network. Monitoring wells will be clustered to capture up to three water bearing zones (shallow, intermediate and deep) to monitor the full thickness of the aquifer (see Table 3). Proposed monitoring well locations will include: Comment [c56]: Has LADEQ been consulted regarding this statement? Chesapeake is more than happy to work with EPA on conducting a survey and speaking to land owners, however, this is an EPA an therefore, EPA should have responsibility for this task with support for LADEQ and Chesapeake. Comment [GF57]: Is there an EPA SOP for domestic well sampling? Comment [CV58]: Experience has shown that depending on the use of a domestic water well by the landowner before sampling, the baseline results can vary widely. Heavy use before baseline sampling event affects the sampling results different than samples collected from a well with no prior domestic use before baseline sampling. Information on the landowner pump setting is also very important, along with accurate records on well construction and components between the well and tap. Much of these data will not be available unless a downhole survey is done in each water well. Multiple sampling are required under differing pumping conditions to define the variability in analytical results during baseline sampling. Comment [CV59]: Should emphasize more that this is the minimum number of sampling events. ? A well cluster upgradient of the drilling location; ? A directionally drilled well (from an off-pad location) screened beneath the production well pad, downgradient from the proposed production well. ? Two clusters immediately down gradient of the well pad; and ? One deep well approximately mid-way along the lateral Table 3 The Physical Characteristics of the Monitoring Wells Near the Proposed Well Pad Screen Interval Screen Length Monitoring Well (ft) (ft) Total Depth (ft) MW-1 MW-2 MW-3 MW-4 MW-5 MW-6 MW-7 TBD TBD TBD TBD TBD TBD TBD 2-5 TBD TBD TBD TBD TBD TBD TBD 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 TBD TBD TBD TBD TBD TBD TBD Comment [c60]: Chesapeake request additional information on the design and construction of this well. In addition, we would appreciate addition information on the application of this technology for monitoring wells. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition MW-8 TBD TBD TBD The study area and proposed locations of monitoring wells as well as existing domestic water wells and gas wells is illustrated in Figure 3. Prior to installation of groundwater monitoring wells, approximately 7 temporary piezometers will be installed and surveyed. Depth to groundwater measurements will be collected to calculate shallow groundwater flow direction. Temporary piezometers will be installed using a direct push drilling rig or other suitable technology and will be abandoned by plugging with a cement bentonite grout to ground surface prior to pad construction. Testing of the piezometers may be conducted to determine aquifer properties. 2.1.3 Surface Water Sampling While surface water in the vicinity of the proposed production well location does not appear to serve as a source of drinking water, it could be in contact with the underground source of drinking water. Surface water sampling and analysis will provide data that can be used to identify changes in water quality and investigate if these changes have potentially been caused by the introduction of drilling fluids, hydraulic fracturing fluids, and formation fluids and gases to surface water or surface water sources of drinking water. This sampling will aid in the understanding of the potential chemicals constituents that could contaminate surface water that may occur as the result of the transport of contaminants to the site. There are several ways in which surface water quality could be impacted as the result of hydraulic fracturing. One possible mechanism is the direct contamination caused by the spillage of drilling, hydraulic fracturing, or formation fluids into the surface water body. In addition, runoff and or subsurface transport of drilling, hydraulic fracturing, or formation fluid through the soil could cause impacts to surface water. Each surface water location has a unique set of conditions that needs to be identified and considered in the sample selection process. Therefore, it is important that sample locations accurately represent the intended conditions (such as time of year and flow rate or stage) of the aqueous system being studied with respect to study objectives. In most bodies of flowing or still water, a single sampling site or point is not adequate to describe the physical properties and the distribution and abundance of chemical constituents. Location, distribution, and number of sampling sites can affect the quality and applicability of the resulting data (USGS, 2010). Therefore, the following criteria may be used to determine surface water sampling locations: study objectives and sampling methods; all available historical information, including historical oil/gas operations in the area; physical characteristics of the area, such as size and shape, land use, tributary and runoff characteristics, geology, point and nonpoint sources of contamination, hydraulic conditions, climate, water depth, and fluvial-sediment transport characteristics; chem- 2-6 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV61]: There is discrepancy in the number of wells proposed, one said 8 another says 11. Must clarify. Comment [c62]: Post pad construction? Comment [CV63]: Consider using continuous recording sondes for basic water quality parameters for baseline characterization, and during monitoring. With periodic sampling for more comprehensive analytical list per seasonal or local flow conditions-- high flow vs low flow, consider if base flow occurs in stream and its affect on local gw quality. Comment [c64]: The study should be focused on hydraulic fracturing. Comment [c65]: It is understood from this statement that only drinking water sources will be investigated. Comment [CV66]: The list of analytes should be the chemical constituents that could potentially contaminate ground water. The data will aid in determining IF there has been a contamination. Comment [c67]: A clear definition of hydraulic fracturing should be provided because it is used incorrectly to describe oil and gas development throughout this document. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition ical characteristics of the area; and the types of equipment that will be needed for sampling (USGS, 2010). Comment [c68]: CHK agrees with this paragraph, however, it is not well understood how the study will incorporate these criteria. Sampling locations should be prescribed in the QAPP. Comment [WU69]: We can make some tentative selections of locations subject to change-see below 2-7 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Insert Figure (color) page 1 of 2 3A Proposed Monitoring Well Location Map 2-8 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Figure 3A page 2 of 2 2-9 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Insert Figure (color) page 1 of 2 3B Expanded View of Proposed Monitoring Wells in Close Proximity to the Proposed Gas Well 2-10 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Figure 3B page 2 of 2 2-11 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Surface water bodies are of two basic types: flowing water bodies (intermittent and perennial flow) and still water bodies (e.g., lakes and ponds). Flowing-water sites can refer to streams (fast or slow, intermittent, ephemeral, or perennial), canals, ditches, and flumes of all sizes and shapes, or to any other surface feature in which water moves unidirectionally (USGS, 2010). Still-water sites refer to all sizes and shapes of lakes, reservoirs, ponds, swamps, marshes, riverine backwaters, or any other body of surface water where water generally does not move unidirectionally (USGS, 2010). For flowing water the optimal sampling locations is in straight reaches having uniform flow and stable bottom contours; far enough above and below confluences of streamflow or point sources of contamination to avoid sampling a cross section where flows are poorly mixed or not unidirectional; and in reaches upstream from bridges or other structures, to avoid contamination from the structure or from a road surface (USGS, 2010). Similarly, for still water sampling sites the optimal locations should avoid areas near structures or historical oil/gas operationssuch as harbors, boat ramps, piers, fuel docks, and moored houseboats (to avoid point sources of contamination), unless these structures are part of the study. (USGS, 2010). Baseline surface water quality will be assessed in order to establish a benchmark baseline for water quality changes that have occurred as the result of drilling and hydraulic fracturing process in surface water resources. The baseline surface water quality will be collected based on historical data, if available, or both upstream and downstream of the potentially impacted area. At this site, surface water samples will be collected from the stream located west of the drilling pad. Surface water sampling locations are shown in Figure 4. Surface water samples will be collected as outlined in Appendix A.1 (ENV 3.12). 2.1.4 Soil Sampling Soil sampling will be part of the monitoring utilized in the prospective case study. Soil sampling and analysis will provide data that can be used to identify changes in soil characteristics and investigate if these changes have potentially been caused by the transport and release of contaminants during the development process. Not only can soils potentially act as a sink for the contaminants in the environment but, soils could also serve as a source of contaminants to surface water and shallow groundwater through their gradual release back into surface water and shallow groundwater. Therefore, it is important to investigate if there is an accumulation of contaminants in soil as the result of hydraulic fracturing, understand the potential chemicals constituents that could contaminate drinking water; and provide information to understand the risk (frequency and magnitude) to drinking water impacts resulting from hydraulic fracturing operations. Baseline soil samples will be assessed in order to establish a benchmark for impacts to soil that have occurred as the result of drilling and hydraulic fracturing 2-12 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV70]: None of these are present in the area, so is this necessary? Or can be modified to describe structures that actually may be present in the area? Comment [c71]: Baseline downstream information should be collected as well. Comment [WU72]: OK Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition processes. The baseline soil samples will be collected in and around the pad once pad construction has been completed. NRMRL-Ada and Chesapeake will survey the area and speak to stakeholders in Keatchie to determine the location of sampling points. It is anticipated that the soils will be sampled following pad construction and prior to well construction and again (at the same locations) following the hydraulic fracturing of the well. The latitude and longitude and elevation of the sampling locations will be recorded so that the locations can be consistently sampled throughout the study. Soil samples will consist of surface samples collected from 0 to 6 - inches below ground surface. Sampling locations are shown in Figure 4 and have been selected to provide equal representation of existing soil types surrounding the well pad. Soil types include the Keithville very fine sandy loam and Metcalf silt loam as mapped and described in the Soil Survey of De Soto Parish, LA. A sufficient number of background samples should be collected from each soil type present in order to statistically evaluate data collected from this investigation through background comparison. 2.2 Sampling Methods 2.2.1 Installation of Temporary Piezometers Piezometer installations will be accomplished using a GeoProbe 6610DT direct push rig using 2.25" rods and expendable points. Depth of screen placement will be determined by use of the Soil Electrical Conductivity (EC) Logging system by GeoProbe Systems (see RSKSOP 219 in Appendix A.2) and/or by a few soil cores taken using the GeoProbe Macro-Core System (see RSKSOP 221 in Appendix A.3) to locate the local water table level. For the purposes of purchasing well installation supplies the water table depth has been estimated to be no more than 70' below ground surface. It is anticipated that approximately 7 temporary piezometers will be installed around the site as shown in Figure 4. Installations will begin by driving the 2.25" rods with an expendable point to the desired depth. The well (.75" ID, 1.4" OD pre-packed screen 10' in length with a 4" bottom plug/sump) will then be lowered into the rods. The well will be held in position while the rods are retracted 10.5' to allow natural collapse to contact the pre-packed screen. If natural collapse does not occur, sand will be placed around the pre-packed screen. A 2' sand grout barrier will be installed above the prepacked screen via gravity placement. A minimum 2' bentonite seal of granular bentonite will be installed via gravity placement and allowed to hydrate. A highsolids bentonite slurry will then be installed from the bentonite seal to the ground surface via gravity placement. The well riser will be cut leaving 36" of stickup above ground surface and capped with a vented well cap. A painted steel locking well protector will be installed into the bentonite grout column and secured with a 2-13 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV73]: It is recommended that other potential sources of contamination are identified and tested Comment [c74]: A sub-meter GPS should be used for all sample locations. Comment [c75]: Suggest we do an EM-38 survey of the well pad area first (the pad and a 100 foot buffer surrounding the pad footprint), then use those results in conjunction with the soil types to collect representative baseline samples with depth and soil type/horizon. The baseline EM survey can be repeated adjacent to the pad once completed. The EM-38 is an extremely sensitive tool to changes in the conductivity of soils caused by fluid releases containing salts or brines. Comment [WU76]: OK-CHK willing to fund and do it? Comment [CV77]: No mention of QA/QC samples (splits, duplicates, field blanks, equipment blanks etc.) in any of the sampling sections. Formatted: Not Highlight Formatted: Not Highlight Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition 4" thick concrete slab that has a radius of at least 12" from the well protector. The concrete slab will slope away from the protector for drainage purposes. An "X" will be made in the concrete near the protector and a mark made on the well stickup to serve as a reference point for water elevation surveys and the well ID number will be etched into the slab. A threaded hole with drain plug will be installed into the steel protective casing just above the slab surface to allow drainage of any water that may collect between the well stickup and protective casing. Samples of the filter sand, bentonite pellets, and grout will be collected and analyzed for the list of soil and groundwater analytical parameters. Insert Figure (color) page 1 of 2 4 Proposed Soil, Surface Water and Piezometer Locations 2-14 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Figure 4 page 2 of 2 2-15 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition The hydraulic conductivity of geologic materials near the water table will be estimated using slug tests performed in each of the shallow piezometers. These data will be used in conjunction with measured hydraulic heads to estimate shallow groundwater flow direction and rate. The slug tests will be performed by RSKSOP-260 using solid slugs constructed of either PVC or stainless steel or, alternatively, RSKSOP-256 using pneumatic slug testing techniques (see Appendix A.4 and A.5). Both methods provide equivalent data, if hydraulic conductivity is less than 0.02 cm/s. If the estimated hydraulic conductivity of the shallow aquifer materials is greater than 0.02 cm/s, only RSKSOP-256 will be used. These procedures are based on recommendations derived from Butler (1997). The aquifer response data will be analyzed using the methods of Bouwer and Rice (1976) and, if inertial effects are observed, Springer and Gelhar (1991). 2.2.2 Installation of Monitoring Wells The monitoring well network will consist of clusters with up to three wells (shallow, intermediate and deep) based on data collected from an initial exploratory boring. As mentioned above, the initial exploratory boring will be completed as one of the deep monitoring wells. Downhole geophysical logging will be performed on the exploratory boring as described below in section 2.2.2.1. 2.2.2.1 Geophysical Logging Geophysical logging will be conducted by Tthe USGS at the request of the U.S. Environmental Protection Agency Office of Research and Development (ORD). Borehole geophysical data collection and analysis will be conducted on one deep well to be drilled in northwestern Louisiana study area for the purpose of monitoring groundwater in the vicinity of hydraulic fracturing operations of the Haynesville Shale as mentioned in Section 2.1.2. The planned well will be drilled into the Carrizo-Wilcox aquifer under the direction of ORD or their contractor. The targeted depth is about 600 to 800 feet below land surface which is expected to penetrate the freshwater/salinewater interface near the base of the aquifer. 2.2.2.2 Approach The approach is divided into two phases, one phase with data collected at the conclusion of drilling the open hole (before casing is set) and one phase with data collected after the well has been constructed with PVC casing and screen. Phase 1 The proposed borehole geophysical logging methods include basic and advanced logging techniques (listed below) which will be collected in the uncased open borehole shortly after drilling has concluded. Geophysical logging entails the lowering of geophysical probes on a wireline to the total depth of the borehole and the collection of geophysical measurements either during the lowering of the probe or during retrieval of the probe to surface. Several logging runs will be required to collect the proposed parameters. The collection of these logs will require removal of the drill string and will require the borehole to be stabilized with drill2-16 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c78]: The monitoring well design and construction methods should be better defined in this document. CHK has provided some preliminary comments based on current QAPP content. 2" monitoring well may be not be adequate. May require steel casing (preferably stainless). Suggest putting a 1-2 sediment sump below the screen. Comment [CV79]: During the 10/11/2011 F2F meeting it was discussed that samples of the materials brought on site for completion of the piezometers and monitoring wells (e.g. water, drilling mud, bentonite, cement, etc.) were to be sampled. Comment [WU80]: E&E insert mods here based on discussions by team on 091911 Formatted: Not Highlight Comment [c81]: Should this be a subsection of 2.2.2.1 because it is the geophysical logging approach? Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition ing fluid and free of obstructions. If the borehole becomes unstable and begins to collapse during logging runs, additional circulation or mud conditioning by the drilling crew may be necessary before logging can continue. The optional use of sealed radioactive sources to collect density and neutron logs (depending on hole conditions) has also been included to better assess the porosity of the formations to aid in the placement of screen openings. The following is a list of proposed logs to be collected in the uncased borehole shortly after drilling has concluded and before casing is set. About eight logging runs will be necessary to collect these logs. 1. Caliper; 2. Natural Gamma; 3. Normal Resistivity; 4. Single Point Resistance (SPR); 5. Fluid resistivity and temperature; 6. Spontaneous Potential (SP); 7. Induction Conductivity; 8. Magnetic Susceptibility (MS); 9. Full Wave Sonic with post-processing to compute acoustic velocity; 10. Acoustic Borehole Imager with Vertical Deviation and Azimuth; 11. Neutron (optional); and 12. Gamma-Gamma Density (optional). Phase 2 Additional logs such as nuclear magnetic resonance (NMR) and induction conductivity will be collected after the well has been cased with PVC casing. Nuclear magnetic resonance data is useful to assess permeability and total porosity including percent volume of bound and free fluid in the formation. Induction conductivity will be used to locate the fresh water/saline water interface and assess movement of this interface before and after the hydraulic fracturing operation. One additional trip to the wellsite will be necessary to complete the Phase 2 logging after the nearby hydraulic fracturing is completed. The following is a list of proposed logs to be collected in the PVC-cased borehole shortly after the well has been constructed. 1. 2. 3. 4. Magnetic susceptibility; Nuclear Magnetic Resonance; Induction Conductivity (repeated after hydro-fracturing); and Water Quality Logging - conductivity, temperature, DO, PhpH, EeH, etc. Outputs from this effort will included those listed below. Descriptions of each logging method are included in Appendix A.6. 2-17 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition 1. Geophysical well log montage including natural gamma, caliper, SP, long and short normal resistivity, SPR, induction conductivity, MS, full wave sonic processed to include acoustic velocity, density (if collected), neutron (if collected), an azimuth-oriented acoustic borehole image, with deviation, nuclear magnetic resonance data. 2. A time series plot of induction conductivity logs collected at the time of drilling, after well is constructed before nearby hydraulic fracturing and after nearby hydraulic fracturing. Digital data of logs listed above. 2.2.2.3 Monitoring Well construction Monitoring wells will be constructed using a minimum of 2.5-/ to 3-inch schedule 80 PVC casing and slotted PVC screens for both intermediate and deep monitoring wells. Depending on depth (< 100 feet), shallow monitoring wells may be constructed of 2-inch diameter schedule 40 PVC screen and casing. All casing and screen will utilized threaded connections. Screen intervals will be determined based on data collected from the initial exploratory boring. PVC screen will consist of 0.010 factory slotted screen, Monitoring wells will be drilled using conventional mud rotary techniques (see Geo 4.7 in Appendix A.7) and installed in accordance with all State of Louisiana regulations, by a licensed driller, and under supervision of a Louisiana licensed Professional Geologist, if applicable. Typical Mmonitoring well construction is depicted in Figure 5. In general, monitoring well construction will be as follows described below (see Geo 4.10 in Appendix A.8): . ? 1-foot PVC blank section will be threaded to the bottom of the PVC screen to act as a sump for fines which may collect in the well. ? The annular space between the borehole wall and the well screen/sump will backfilled with 10-20 silica sand, to approximately two feet above the screened interval. ? The annular space above the sand pack will be sealed with a 3 foot bentonite pellet seal, which will be placed by tremie pipe. ? The remaining annular space will be filled with bentonite cement grout to within 3 feet below ground surface. Bentonite cement grout will consist of 6 percent by weight of a pH neutral bentonite (e.g. pure-gold brand). ? All permanent wells will be finished as above ground completions (where possible). The above ground completion will consist of an outer (un-painted) 2-18 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c82]: Cleaning up of the monitoring wells should be included in the QAPP. This topic was discussed at the F2F meetings. Comment [CV83]: Is this available? Are these correct? Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition steel protective casing extending at least 3 feet below ground surface and approximately 3 feet above ground. Each stickup will include a lockable cover and keyed padlock. Protective custody seals will also be utilized at each well location, such that a well cannot be opened without tearing the seal. ? A square concrete pad will be placed around each well. The pad will measure 3 feet square (1.5 feet from the center of the well) and extend a minimum of 3.5 to 4-inches below ground surface. ? The annular space between the well and protective casing will be filled with silica sand to with 6-inches of the well top, and a drain hole will be drilled approximately two inches above the well pad ? A minimum of three protective steel bollards will be placed around the well. Additional well protective measures such as chain between the bollards may also be utilized depending on well location. ? Samples of the filter sand, bentonite pellets, and grout will be collected and analyzed for the list of soil and groundwater analytical parameters. In addition, at different times during the drilling process, samples of the drilling fluids will be collected for comprehensive analyses. The designated measuring point and elevation datum at each monitoring well is defined as the ground surface immediately adjacent to the surficial concrete pad to the north and the top of the inner PVC well casing on the north side. These points will be surveyed in the horizontal position to within 1.0 foot accuracy and to within 0.01 foot vertically. The installed wells will be developed by the water well driller and the EPA contractor (E & E) according to procedures in Appendix A.9 (GEO 4.11).. Comment [c84]: The contractors experience needs to be vetted for drilling deep wells, along with the contractors experience. CHK should be involved in this process. 2.2.3 Monitoring Well Sampling EPA low flow sampling procedures will be used to sample the wells as described below (see Appendix A.10). For all duplicate and split samples, an in-line "T" shall be installed on the sample discharge tubing so that the original sample an duplicate sample bottles can be filled simultaneously. When split samples are collected at locations with duplicate samples, multiple inline "T's" will be utilized so that the original, duplicate, and split sample bottles can all be filled simultaneously: : Comment [CV85]: Methane should be baseline sampled in monitoring wells. If methane is present, isotopic analysis should be performed. 2-19 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition 1. Water level measurements will be taken prior to and during the pumping of the wells. The water level measurements will follow the RSKSOP-326 standard operating procedure (see Appendix A.11). Water levels will be recorded in the field notebook prior to and during sampling. 2-20 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c86]: Consider installing trolls in select wells to monitor water levels long term and in getting a baseline. Comment [WU87]: Up to CHK Comment [GF88]: Need from EPA Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Insert Figure (color) page 1 of 2 5 Typical Groundwater Monitoring Well 2-21 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Figure 5 page 2 of 2 2-22 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Insert Figure (color) page 1 of 2 6 Open Tube Sampling Method 2-23 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Figure 6 page 2 of 2 2-24 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Insert Figure (color) page 1 of 2 7 Closed Piston Sampling Method 2-25 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Figure 7 page 2 of 2 2-26 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition 2. A new piece of tubing will be connected to the sampling port of the well and the dedicated pump will be powered on. It is expected that the pump will yield a maximum initial flow rate of approximately 1 L min-1). This flow will pass through a flow cell equipped with an YSI 5600 multi-parameter probe (or equivalent probes). The rate of pumping will be determined by measuring the water volume collected after approximately 15 seconds into a 4 L graduated cylinder; the desirable pumping rate through the flow cell should be less than 1 L/min. The pumping rate will ideally maintain minimal drawdown. Water levels will be taken throughout sampling to confirm the drawdown caused by pumping. 3. The YSI probe (or equivalent probes and electrodes) will be used to track the stabilization of pH, oxidation-reduction potential (ORP), specific conductance (SC), dissolved oxygen (DO), and temperature. In general, the guidelines in Table 4 will be used to determine when parameters have stabilized. These criteria are initial guidelines; professional judgment in the field will be used to determine on a well-by-well basis when stabilization occurs. Field readings must be recorded at no more than 5 minute intervals, or continuously if continuous recordings are being used, until stabilization occurs. Table 4 Comment [CV89]: What kind of pump? Specify. Certain pumps are not well suited for VOC samples. Comment [c90]: Measurement must be taken during the actual sampling, not just afterwards. A warning, in a stratified environment, low flow purging will not result in representative samples. Comment [CV91]: The frequency of recording should be specified. Field Parameter Stabilization Criteria and Calibration Standards Calibration Parameter Stabilization Criteria Standards pH <=0.02 pH units min-1 Oxidation Reduction Po<= 2mV min-1 tential (ORP) Specific Conductance (SC) <= 1% min-1 pH 4, 7, and 10 buffers Zobells Solution 1413 uS Conductivity Standard 4. Once stabilization occurs, the final values for pH, ORP, specific conductance, dissolved oxygen, and temperature will be recorded. Turbidity will also be recorded immediately prior to sampling, and also just before the collection of the metals and radiological samples. 5. After the values for pH, ORP, SC, DO, and temperature have been recorded, the flow cell will be disconnected. A series of unfiltered samples will be collected as follows: a. Duplicate 40 mL VOA vials (amber glass) will be collected, without headspace, for VOC analysis using RSKSOP-299v1. Tribasic Sodium Phosphate (TSP) will be added to the VOA vial prior to shipping to the field for sampling as a preservative. (Acid will not be used as a preservative due to a concern of acid hydrolysis of some analytes.) The samples will be stored and shipped on ice to Shaw, NRMRL-Ada's on-site contractor for GC-MS analysis. 2-27 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV92]: MDH: This applies to all testing comments in this general section. It does not appear that any of these analyses include notations of split samples/ bottleware exceptions, method references, etc...outside of what the EPA is proposing. Is that to be included in this document or elsewhere? Comment [c93]: Method is equivalent to SW846 method 8260B. While TSP is an acceptable preservative, it should not be used if brominated compounds are of critical interest due to possible degradation in the analytical process. Suggest either both HCL and TSP vials be collected (for brominated compounds) or no preservation and a 7 day holding time Comment [n94]: Our analytical chemists differ on this. We may want to consider this for flowback sampling however Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition b. Duplicate 60 mL serum bottles will be collected, without headspace, for dissolved gas analysis (e.g., hydrogen, carbon dioxide, ethane, methane, butane, propane). The bottles will contain trisodium phosphate as a preservative and will be filled with no head space and sealed with a crimp cap. The samples will be stored and shipped on ice to Shaw, NRMRLAda's on-site contractor for analysis. Samples will be collected in accordance with procedures outlined in Appendix A.12. Comment [CV95]: MDH: Again, we would recommend a different set of bottleware for the methodologies we would recommend. c. Duplicate 1 L amber glass bottles will be collected for semi-volatile organic compounds. These samples will be stored and shipped on ice to EPA Region VIII Laboratory for analysis. d. Duplicate 1L amber glass bottles will be collected for diesel range organic (DRO) analysis. These samples will be preserved with HCl, pH <2, and shipped on ice to EPA Region VIII Laboratory for analysis. e. Duplicate 40 mL amber VOA vials will be collected without headspace for gasoline range organic analysis (GRO). These samples will be preserved with HCl, pH <2, and shipped on ice to EPA Region VIII Laboratory for analysis. f. Duplicate 40 mL amber VOA vials will be collected for glycol analysis. These samples will be stored and shipped on ice to EPA Region III Laboratory for analysis. g. Duplicate 40 mL glass VOA vials will be collected for low molecular weight acids using RSKSOP-112v6. Tribasic Sodium Phosphate (TSP) will be added to the VOA vial prior to shipping to the field for sampling as a preservative. The samples will be stored and shipped on ice to Shaw, NRMRL-Ada's on-site contractor for GC-MS analysis. h. A 1-liter plastic beaker will be filled for selected analyses to be conducted in the field. Field measurements will consist of turbidity, alkalinity, ferrous iron, and dissolved sulfide (Table 5). Turbidity (Standard Method 180.1) will be measured using a HACH 2100Q portable turbidimeter (or equivalent instrument). Alkalinity will be measured by titrating ground water with 1.6N H2SO4 to the bromcresol green-methyl red endpoint using a HACH titrator (HACH method 8203, equivalent to Standard Method 2320B for alkalinity). Ferrous iron will be measured using the 1,10phenanthroline colorimetric method (HACH DR/2010 spectrometer, HACH method 8146, equivalent to Standard Method 3500-Fe B for wastewater). Dissolved sulfide will be measured using the methylene blue colorimetric method (HACH DR/2010 spectrometer; HACH method 8131, equivalent to Standard Method 4500-S2- D for wastewater). 2-28 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV96]: Field tests for alkalinity and dissolved sulfide particularly may be suitable for baseline samples but not for flow back samples. High salt and dissolved solids content and matrix color interferences will make these Hach colorimetric method unsuitable with the more complex matrices. Suggest consistent with all matrices using fixed based lab methods for these analyses. Comment [CV97]: What about the other field parameters, going to use the flow cell values, or collect the actual water from the actual time of sampling for these parameters? Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Table 5 Groundwater Field Analytical Methods Parameter Method Alkalinity Ferrous Fe Dissolved Sulfide Turbidity EPA Standard Method 2320B; HACH method 8203 EPA Standard Method 3500Fe B; HACH Method 8146 EPA Standard Method 4500S2- D; HACH Method 8131 EPA Standard Method 180.1 Equipment HACH Model AL-DT Digital Titrator (or equivalent device) HACH DR890 Portable Colorimeter (or equivalent device) HACH DR890 Portable Colorimeter (or equivalent device) HACH 2100Q Portable Turbidity meter 6. After the unfiltered samples have been collected a high-capacity cartridge ground-water filter (0.45um, Pall Corporation, or equivalent manufacturer) will be placed on the end of the pump tubing and filtered samples will be collected into pre-labeled sample bottles. First, approximately 100 mL of ground water will be filtered and sent to waste and next the following series of samples will be collected: a. 125 mL plastic bottle for metals analysis by ICP-OES for Al, Ag, As, B, Be, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Sb, Se, Sr, Ti, Tl, V, Zn, Si, and S; this sample will also be used for ICP-MS analysis for Cd, Cr, As, Cu, Pb, Ni, Se, Hg, and Tl. This sample will be filtered and preserved by adding 5 drops of concentrated HNO3 (pH test strips will be used to confirm that the sample pH is <2). Test strips for pH will be used on every sample to insure that a proper preservation pH is attained. A small amount of sample will be poured into a separate container to test pH. This is especially important in case high alkalinity samples are encountered during the ground-water sampling. The samples will be stored and shipped on ice to Shaw, NRMRL-Ada's on-site contractor for analysis. Comment [CV98]: Measure turbidity of filtered sample in field and record in log book to ensure and document did not have sediment breakthrough in filters. Comment [CV99]: Add carbonate and bicarbonate; and turbidity, and TSS to insure no sediment was in sample analyzed for dissolved cations and metals. Comment [c100]: Are the pH test strip contaminant free, need to see documentation on this. Comment [n101]: Agree - we should add text to insure no contamination from strips Comment [CV102]: MDH: The proper technique for verifying pH of a bottle would be to use disposable glass capillary tubes and use that tube to disperse the sample aliquot onto the pH paper strip b. One 60 mL clear plastic bottle for CE (capillary electrophoresis) sulfate, chloride, bromide and fluoride. This sample will be filtered, no preservative added. The samples will be stored and shipped on ice to the RSKERC general parameters lab. c. One 60 mL clear plastic bottle for nitrate + nitrite and ammonium. This sample will be filtered, 2 drops of sulfuric acid added as preservative (pH test strips will be used to confirm that the sample pH is <2; see note above regarding use of pH test strips). The samples will be stored and shipped on ice to the RSKERC general parameters lab. d. Duplicate 40 mL glass VOA vial in duplicate for analysis of dissolved inorganic carbon (DIC). This sample will be filtered, no preservative added. 2-29 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV103]: Suggest we also test for organic nitrogen or TKN, useful in evaluating septic impacts. Comment [c104]: It is not understood why and how this parameter will be used in the EPA study. Comment [n105]: This gets to the issue of accurate carbonate/bicarbonate numbers. We do not feel that lab alkalinity is the best way to go-prefer field alkalinity together with other analysis to then arrive at accurate numbers Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition The samples will be stored and shipped on ice to the RSKERC general parameters lab. e. Duplicate 40 mL glass VOA vial in duplicate for analysis of dissolved organic carbon (DOC). This sample will be filtered, phosphoric acid added to pH<2. A duplicate set of 40 mL VOA vials will be collected without preservation in case acid preservation interferes with the analysis or primary instrument is unavailable. VOA vials will indicate if preservative was added. The samples will be stored and shipped on ice to the RSKERC general parameters lab. f. Filter radioactive samples also Comment [c106]: It is not understood why and how this parameter will be used in the EPA study. Comment [n107]: An important parameter in terms of binding of organic compounds Comment [CV108]: Add description for gross alpha, gross beta, Uranium, Thorium, Radium 226/228. Very important to include. See Tables 6 and 7 for numbers of sample bottles needed for each sample type and field QC samples for ground and surface water sampling. Table 6 Ground and Surface Water Sample Collection Sample Type Dissolved gases Metals (filtered) Analysis Method (EPA Method) RSKSOP-194v4 &175v5 (No EPA Method) RSKSOP-213v4 &257v3 or 332v0 (EPA Methods 220.7 and 6020) Metals (unfiltered) RSKSOP179v2; RSKSOP-213v4 &257v3 or 332v0 (EPA Methods 220.7 and 6020) SO4, Cl, F, Br RSKSOP-276v3 (EPA Method 6500) NO3 + NO2, NH4 RSKSOP-214v5 (EPA Method 350.1) DIC RSKSOP-330v0 (EPA Method 9060A) DOC RSKSOP-330v0 (EPA Method 9060A) Volatile organic RSKSOP-299v1 or compounds (VOC) 259v1 (EPA Method 5021A plus 8260C) Low Molecular RSKSOP-112V6 Weight Acids (No EPA Method) O, H stable isoRSKSOP-296v0 topes of water (No EPA Method) Sample Bottles/# of bottles* Preservation/ Storage 60 mL serum bottles/2 No Headspace TSP+, pH>10; refrigerate 6?C++ 125 mL plastic bottle/1 HNO3, pH<2; room temperature Holding Time(s) 14 days 6 months (Hg 28 days) 125 mL plastic bottle/1 HNO3, pH<2; room temperature 6 months (Hg 28 days) 30 mL plastic/1 28 days Refrigerate <6?C 30 mL plastic/1 H2SO4, pH<2; refrigerate <6?C 40 mL clear glass VOA refrigerate <6?C vial/2 40 mL clear glass VOA H3PO4, pH<2; refrigvial/2 erate <6?C 40 mL amber glass No Headspace VOA vial/2 TSP+, pH>10; refrigerate <6?C 40 mL glass VOA viTSP+, pH>10; refrigal/2 erate <6?C 20 mL glass VOA viRefrigerate at <6?C al/1? 2-30 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 28 days 14 days 28 days 14 days 30 days stable Comment [CV109]: Where are the radionuclides, analyses must be done on both filtered and unfiltered samples Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Table 6 Ground and Surface Water Sample Collection Sample Type ?13C of inorganic carbon ?13C and ?2H of methane 87 Sr/86Sr analysis Semi-volatile organic compounds DRO GRO 21Glycols Microbial Analysis Method (EPA Method) Sample Bottles/# of bottles* Isotech: gas stripping and IRMS (No EPA Method) Isotech: gas stripping and IRMS (No EPA Method) Thermal ionization mass spectrometry (No EPA Method) ORGM-515 r1.1, EPA Method 8270D 60 mL plastic bottle/1? Preservation/ Storage Refrigerate <6?C Holding Time(s) No information 1 L plastic bottle/1? Caplet of No inforbenzalkonium chlomation ride; refrigerate <6?C 500 mL plastic bottle/1? Refrigerate <6?C No information 1L Amber glass bottle/2 and for every 10 samples of ground water need 2 more bottles for one selected sample, or if <10 samples collected, collect 2 more bottles for one select sample ORGM-508 r1.0, EPA 1L Amber glass bottle/2 Method 8015D and for every 10 samples of ground water need 2 more bottles for one selected sample, or if <10 samples collected, collect 2 more bottles for one select sample ORGM-506 r1.0, EPA 40 mL amber glass Method 8015D VOA vial/2 and for every 10 samples of ground water need 2 more bottles for one selected sample, or if <10 samples collected, collect 2 more bottles for one select sample Region III method** 40 mL amber glass (No EPA Method) VOA vial/2 NA 1 L plastic amber/2 Autoclaved Refrigerate <6?C 7 days until extraction, 30 days after extraction HCl, pH<2; refrigerate <6?C 7 days until extraction, 40 days after extraction No headspace; HCl, pH<2; refrigerate <6?C 14 days Refrigerate <6?C 14 days Refrigerate <6?C NA + trisodium phosphate above freezing point of water * Spare bottles made available for laboratory QC samples and for replacement of compromised samples (broken bottle, QC failures, etc.). ** under development ++ 2-31 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV109]: Where are the radionuclides, analyses must be done on both filtered and unfiltered samples Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Table 7 Field QC Samples for Water Samples QC Sample Frequency Acceptance Criteria/ Corrective Action* One in each ice chest with VOA and dissolved gas samples. RL, PI will determine if significant relative to sample data. One every two days of sampling. RL, PI will determine if significant relative to sample data. One in every 10 samples, or if <10 samples collected for a water type (ground or surface), collect a duplicate for one sample. Measure tempera- Water sample that One per cooler. ture of samples in is transported in the cooler. cooler to lab. Assess contamina- In the field, reaOne per day of tion introduced gent water is col- sampling. from sample con- lected into sample tainer with appli- containers with cable preservative. preservatives. Report duplicate data; RPD > 30 for results greater than RL. The affected data will be flagged as needed. Purpose Method Trip Blanks Assess contamina- Fill bottles with (VOCs and Distion during trans- reagent water and solved Gases only) portation. preserve, take to field and returned without opening. Equipment Blanks Assess contamina- Apply only to tion from field samples collected equipment, samvia equipment, pling procedures, such as filtered decon procedures, samples: Reagent sample container, water is filtered preservative, and and collected into shipping. bottles and preserved same as filtered samples. Field Duplicates Represent preciOne or more samsion of field sam- ples collected impling, analysis, and mediately after site heterogeneity. original sample. Temperature Blanks Field Blanks** Record temperature; condition noted on COC form*** RL, PI will determine if significant relative to sample data. *Reporting limit or Quantitation Limit ** - Blank samples will not be collected for isotope measurements, including O, H, C, and Sr. *** - The PI should be notified immediately if samples arrive with no ice and/or if the temperature recorded from temperature blanks is greater than or equal to 12 ?C. These samples will be flagged accordingly. 2.2.4 Domestic Wells, Water Supply Wells, and Municipal Supply Well Sampling Domestic wells will be sampled directly from the well or the tap (if necessary), by accessing the well directly using pumps lowered down the well casing to immediately above the existing pump. Drawdown of the water table will be tracked by taking water level measurements during well purging and sampling. The water level measurements will follow the RSKSOP-326 standard operating procedure 2-32 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c110]: Need to define how the intake location will be determined, purging times and volumes, and be aware of any in-home water softeners or other treatment units or filters. It is preferable to collect from before the pressure tank, if possible. Use of the well by the landowner in the proceeding 24 hour period must be identified, and experience has shown that use by homeowner can dramatically affect the results, especially heavy use in a low yielding well. Must document this prior to sampling. Comment [CV111]: Type of pump? Some pumps not well suited for the collection of groundwater samples for VOC analyses. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition (see Appendix A.11). Water levels will be recorded in a field notebook. If the well cannot be accessed directly, the sample will be collected from the closest port to the well, preferably before the pressure tank, any water softeners, treatments systems, and filters. Use of the well by the landowner in the preceding 24 hour will be documented. In addition, the homeowner will be interviewed regarding historical water quality issues (e.g., iron or Mn staining, scale buildup, odors, salty tasting water, turbidity issues, and yield issues). The interview will also include questions about well construction, depth, when drilled, driller, etc. For all duplicate and split samples, an in-line "T" shall be installed on the sample discharge tubing so that the original sample and duplicate sample bottles can be filled simultaneously. When split samples are collected at locations with duplicate samples, multiple inline "T's" will be utilized so that the original, duplicate, and split sample bottles can all be filled simultaneously: 1. At each sampling site, GPS coordinates will be collected with a handheld device. Photos will be taken and stamped with the date. Pertinent information about well will (as described above) be recorded where possible. The groundwater level will next be measured using a Solinst water level indicator (or equivalent) and recorded. In cases where a remote pump can be used, the pump will be hooked up with new polyethylene tubing. Tubing will be changed in between each well and the pump will be rinsed with distilled water. The pump (Proactive Hurricane or equivalent) will be lowered down the well casing to a level selected in the field and powered on. In most cases, well construction details will not be available. The goal in domestic well sampling is generally to purge sufficient water to access native aquifer water prior to sampling. Professional judgment will be used in the field and consider variables such as water volume pumped, water level drawdown, and stabilization of geochemical parameters. In all cases, the water volume pumped will be tracked by recording time and purge rate. It is expected that the pump will yield an initial flow rate of approximately 1-2 L/min. This flow will pass through a flow cell equipped with a YSI 5600 multiparameter probe (or equivalent probes). The rate of pumping will be determined by measuring the water volume collected after approximately 15 seconds into a 4 L graduated cylinder; the desirable pumping rate through the flow cell should be less than 2 L/min. The pumping rate will ideally maintain minimal drawdown. Draw down will be monitored by measuring the water level (where possible) approximately every 10 to 15 minutes. 2. The YSI probe (or equivalent probes and electrodes) will be used to track the stabilization of pH, oxidation-reduction potential (ORP), specific conductance (SC), dissolved oxygen (DO), and temperature. In general, the following guidelines in Table 4 will be used to determine when parameters have stabilized. These criteria are initial guidelines; professional judgment in the field will be used to determine on a well-by-well basis when stabilization occurs. 2-33 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV112]: Sub-meter unit. Comment [CV113]: Is this pump well suited for collecting groundwater samples for VOC analyses? Comment [CV114]: The frequency of recording should be specified. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Field readings must be recorded at no more than 5 minute intervals, or continuously if continuous recordings are being used, until stabilization occurs. 3. Once stabilization occurs, the final values for pH, ORP, specific conductance, dissolved oxygen, and temperature will be recorded. For these well types it will be assumed that once stabilization occurs that the samples collected will be water from the formation and not water entrained in the well bore. 4. After the values for pH, ORP, SC, DO, and temperature have been recorded, the flow cell will be disconnected. A series of unfiltered samples and filtered samples will be collected as in section 2.2.1.1 number 5. Following completion of the field filtration for metals, a small portion will be collected and tested for turbidity to document that sediment pass through did not occur. Comment [CV115]: As previously stated, measure turbidity of filtered sample in field and record in log book to insure and document did not have sediment breakthrough in filters. See Tables 6 and 7 for numbers of sample bottles needed for each sample type and field QC samples for ground and surface water sampling. 2.2.5 Surface Water Sampling Two surface water samples will be collected from the locations depicted on Figure 4 using the direct method typically used for stream sampling. Following completion of hydraulic fracturing activities, two confirmation samples will also be collected from the same locations. Sampling stations will be accessed from the bank or if necessary using waders. Methods will be provided if there is a surface water body present that can serve as a source of drinking water. Sample bottles will be submerged into the surface water just below the surface and filled as grab samples. The locations of the sampling sites will be recorded with a handheld GPS device. The site will be photographed. General observations about the flow and the stream depth will be recorded in a field notebook. The sampling will be performed as to minimize any capture of sediment into the sampling bottles. In cases where clear (turbidity <20 10 NTUs) water cannot be retrieved, water samples for metals, all isotope analyses, anions, nutrients, and inorganic/organic carbon will be filtered using a peristaltic pump and a high-capacity (0.45 micron) capsule filter. Clean tubing will be used prior to any sampling and filtration. The readings from the YSI will be recorded by inserting the probe set with protective cover directly into the surface water body and allowing readings to stabilize. Again the logging function will be utilized and readings will be recorded in a field notebook. Following completion of the field filtration for metals, a small portion will be collected and tested for turbidity to document that sediment pass through did not occur. 2.2.6 Soil Sampling Soil sampling will be accomplished using hand held samplers since all samples will be surface soil samples collected from 0 to 6 - inches in depth. Using sampling procedures outline below and in Appendix A.13 (ENV 3.13) 2-34 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [n116]: See new sentence above regarding gw-sw interactions Comment [CV117]: Submerging sample containers will allow preservatives to escape. Possibly utilize Kemmerer sampler or other applicable methods. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition 2.2.6.1 Soil Sampling Procedures. Composite surface soil samples will be collected from the locations shown on Figure 4. Additionally, discreet samples will be collected from the same locations for volatile organic analysis. Dedicated sampling equipment will be used at each location for sample collection. Soil samples will be collected using the following procedure: 1. Carefully remove the top layer of soil/vegetation to the desired sample depth with a pre-cleaned spade; Comment [CV118]: Why not use Terra-core samplers? Comment [CV119]: MDH: Is a rinse/decon blank performed on any "pre-cleaned" device used in between sampling events? 2. Using a stainless-steel scoop, spoon, trowel, or plastic spoon, remove and discard the thin layer of soil from the area that came into contact with the shovel; 3. Transfer the sample into an appropriate container (stainless steel bowl) using a stainless-steel or plastic lab spoon or equivalent. Composite samples will be placed in a stainless-steel bowl and mixed thoroughly to obtain a homogeneous sample representative of the entire sampling interval. Place the soil samples into labeled containers; 4. VOA samples will be collected directly from the bottom of the hole before mixing the sample to minimize volatilization of contaminants; 5. Check to ensure that the VOA vial Teflon liner is present in the cap, if required. Fill the VOA vial fully to the top to reduce headspace. Secure the cap tightly. The chemical preservation of solids is generally not recommended. Refrigeration is usually the best approach, supplemented by a minimal holding time; 6. Ensure that a sufficient sample size has been collected for the desired analysis; Comment [CV120]: MDH: For soil sampling, EPA Method 5035 should be used for VOC analysis. Filling a 40-mL VOA vial to the top does not allow room for chemical preservative and/or purge water for proper purge and trap analysis. Method 5035 should be strictly followed in these cases 7. Split the homogenized sample into appropriate containers a. Metals; b. General parameters (pH, Eh, electrical conductivity, BOD, total organic carbon, total inorganic carbon); Comment [c121]: Needs to be conducted using the saturated paste method. Comment [c122]: The purpose of soil BOD, TOC, TIC is not understood. c. Chemical Analysis (CEC, amporphous Al, Fe, Mn, acid volatile sulfur); d. VOC and semi-VOC; e. Organic chemical analysis (for example THP, DRO, GRO, PAH, etc.); 2-35 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c123]: ? Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition f. Isotopic analysis Comment [c124]: In bullet f, please define isotopic analyses intended, section h define mineralogical analyses intended g. Particle size analysis Comment [c125]: This needs to be defined. Comment [c126]: This needs to be defined. h. Mineralogical Analysis Comment [c127]: Add moisture content. 8. Fill in the hole and replace grass turf, if necessary. 2.2.7 Mechanical Well Integrity Testing Mechanical Integrity Test Meeting Summary ? The information provided in this summary is general in nature to the Haynesville shale play; however, it should be noted that each well within the play is designed and constructed fit-for-purpose and for the specifics of the location. ? The USDW depths very throughout the Haynesville shale play, however, within the study area the base of the USDW has been identified as 780 ft (http://sonris.com/). ? Conductor Casing - The conductor casing is set at 80 ft and cemented to surface. ? Surface Casing - The surface casing is set at approximately 1,850 ft and cemented to the surface, per LA State regulations greater than 1,800 ft (Title 43 Part XIX ?109). - Cement is allowed to cure. - A pressure test is conducted on the casing at a pressure of 1,500 psi for 30 min. - Shoe is drilled out. - A pressure test (or shoe test) is conducted by sealing the volume between the well head and a packer located just below the surface casing shoe and applying an equivalent mud weight of 12 lb/gal. - Wellbore is drilled to the desired intermediate casing depth (typically 10,500 - 11,500 ft). - A pressure test is conducted on the surface casing by sealing the volume between the well head and a packer located just above the surface casing shoe and a pressure of 1,500 psi for 30 min. ? Intermediate Casing (7 5/8") 2-36 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c128]: A meeting summary CHK provided to the EPA was simply pasted below. EPA needs to determine based on the objectives of the study the exact information need. This has not been clearly communicated to CHK. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition - The intermediate casing is installed and cemented to cover oil and gas bearing zones, which varies by location. - A broader discussion of the isolation of oil and gas bearing zones can be found in API STD 65-2 Isolating Potential Flow Zones During Well Construction (http://www.api.org/policy/exploration/hydraulicfracturing/) - The staging of cement is not typically required for this particular area. - The designed extent of cement above oil and gas bearing zones is typically 500 ft. - After the cement has cured, a pressure test is conducted on the intermediate casing with 16.5 - 17.5 lb/gal equivalent mud weight (typical 15.5 lb/gal with appropriate pressure applied at surface). - The shoe is drilled out approximately 10 ft. - A pressure test (shoe test) is conducted for 30 min with 16.5 - 17.5 lb/gal equivalent mud weight (typical 15.5 lb/gal with appropriate pressure applied at surface). ? Production Casing (5 1/2 ") - Directionally drill production wellbore. Laterals are typically 5,000 ft with 4,500 ft in target zone. (standard sq. mi. sections) - Run casing string and cement. The designed extent of cement above the intermediate shoe is typically a minimum of 500 ft. - Drilling rig demobilization - Clean up lateral and prepare for completion, displacing oil based mud with clear fluid. - Conduct cement bond log (CBL) in production casing o Basic acoustic CBL tool o Run tool as it will run on a wireline. Typically 30o to 60o. o Run under zero pressure to identify top of cement o Re-run with applied pressure if the result of initial run is not definitive. - Pressure test production casing for 30 min at maximum fracture pressure (12,500 psi). - Pressure test production and intermediate casing annulus for 30 min at 2,500 psi. ? Completion - Well is stimulated with multiple fracturing stages utilizing the "plug and perf" method. Frac plugs are set between each stage. - Continuous monitoring of backside pressure. o 2,000 - 2,500 psi applied pressure maintained on the production- intermediate casing annulus. o Pressure monitoring of annulus between production and intermediate casing. - Drill out plugs with coil tubing 2-37 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition - Install packer (with ceramic disk in the bottom of the packer) between top perforation and top of the cement. - Pressure test packer o Apply 4,000 psi above packer (also applied to production casing). o Negative pressure test by bleeding off pressure and creating a differential from formation pressure. - Install 2 3/8" production tubing and tree o Test tree to 10,000 psi o Test tubing to 6,000 - 6,500 psi o Test tubing casing annulus to 2,500 psi - Ceramic disk is removed. ? Operating pressure - Well is ready for production. - Typical shut-in tubing pressure after flowback is 7,000 - 8,000 psi. - Telemetry is used to continuously monitor flows and pressures. o Tubing pressure o Production casing pressure o Tubing and production casing annular pressure. o Production and intermediate casing annular pressure. o Intermediate and surface casing annular pressures. - Annular pressure is managed throughout the life of the well. (API RP-90 Annular Casing Pressure Management) 2.2.8 Flow Back Sampling Quarterly flowback water sampling will be conducted over a period of 120, beginning immediately following the completion of hydraulic fracturing activities. The process for collecting flowback/produced water is described in Appendix A.14. 2.3 Sample Handling and Custody 2.3.1 Sampling Labeling Each well, surface water body and soil sample location will be uniquely labeled. Samples collected from each of these locations will also include the unique label, well # or name of sample location, the date, the initials of the sampler, and designation of the sample type, e.g., "metals" and preservation technique (when applicable). This information will be recorded onto labeling tape, using waterinsoluble ink, affixed to each sample bottle. 2.3.2 Sample Packing and Shipping All samples will placed together in a sealed Ziploc plastic bag. The bags will be placed on wet ice in coolers. Glass bottles will be packed with bubble wrap to prevent breakage. The coolers will be sent via FedEx, overnight, to the appropriate lab with chain of custody forms (see Figure 8) and custody seal. 2-38 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [nc129]: Appears to be misplaced. Comment [CV130]: No mention of QA/QC samples, e.g. duplicates, trip blanks, field blanks, etc. Comment [CV131]: Flowback/Produced water samples. Comment [CV132]: MDH: No information is provided on where to send split samples...is this to be included Comment [CV133]: The flowback/produced water samples may need to be pre-chilled prior to packaging for shipment as the temperature of these samples are often quite warm at the time of collection. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition R.S. Kerr Environmental Research Center 919 Kerr Research Drive Ada, OK 74820 1-580-436-8920 ATTN: Andrew Greenwood (for samples analyzed by both Shaw and EPA General Parameters Laboratory) EPA Region 8 Lab 16194 West 45th Drive Golden, CO 80403 1-303-312-7775 ATTN: Mark Murphy Sample receipt and log-in at the Region 8 laboratory shall be conducted as described in their SOP, Sample Receipt and Control Procedure, #GENLP-808 Rev. 1.0 and the Region 8 Quality Manual, # QSP-001 Rev. 1.0 Comment [nc134]: Need to be consistent on references throughout the document on use of roman numerals or not EPA Region 3 Lab 701 Maples Road Ft. Meade, MD 20755 1-410-305-2835 ATTN: Jennie Gundersen Sample receipt and log-in at the Region 3 laboratory shall be conducted as described in their SOP, Sample Scheduling, Receipt, Log-In, Chain of Custody, and Disposal Procedures, R3-QA061. 2.4 Analytical Methods Ground-water samples will be collected and analyzed using RSKERC standard operating procedures (RSKSOPs) at RSKERC and EPA Methods at the Region VIII laboratory (Table 6). Region III's LC-MS-MS method for glycols is under development with the intent to eventually have a validated, documented method. Aqueous samples are injected directly on the HPLC after tuning MS/MS with authentic standards (2butoxyethanol, di-, tri-, and tetraethylene glycols) and development of the HPLC gradient. HPLC column is Waters (Milford MA) Atlantis dC18 3um, 2.1 x 150mm column (p/n 186001299). HPLC gradient is with H2O and CH3CN with 0.1% formic acid. The 3 glycols are run on a separate gradient than the 2butoxyethanol. All details of instrument conditions will be included in case file. EPA SW-846 Method 8000B and C are used for basic chromatographic procedures. A suitable surrogate has not been identified. Since there is no extraction or concentration step in sample preparation, extraction efficiency calculations using a surrogate are not applicable. If a suitable surrogate is found, it will be used 2-39 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV135]: LC-MS-MS for glycols is a suitable method currently under evaluation but not widely accepted or validated. May be suitable for baseline analyses but potential interferences from high solids and salt content in flowback water and produced water may be an issue with this method. Regardless, all methods used should be validated prior to use. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition to evaluate matrix effects. Custom standard mix from Ultra Scientific, (Kingstown RI) is used for the instrument calibration (IC). The working, linear range varies for each compound but is about 10-100 ug L-1 and may change with further development. Initial Calibration (IC) is performed before each day's sample set, calibration verification is done at the beginning, after every 10 sample injections, and at the end of a sample set. The correlation coefficient (r2) of the calibration curve must be >0.99. An instrument blank is also run after every 10 sample injections. The performance criteria are provided in Table 8. The system is tuned with individual authentic standards (at 1mg L-1 concentration) of each compound according to the manufacturer's directions using the Waters Empower "Intellistart" tune/method development program in the MRM (multiple reaction monitoring) ESI+ (electrospray positive) mode. Tune data is included in the case file. Target masses, transition data and voltages determined in each tune for each compound are compiled into one instrument method. Only one MS tune file (which determines gas flow rates and source temperatures) may be used during a sample set. For these samples, the tetraethylene glycol tune is used as it provides adequate response for all targets. Due to differences in optimal chromatographic separation, the three glycols are analyzed in one run and 2-butoxyethanol is analyzed separately. Exact mass calibration of the instrument is done annually with the preventive maintenance procedure. Mass calibration was successfully performed according to manufacturer's specifications with NaCsI on 6/17/2010 by a certified Waters Corp Service technician. Custom mix supplied by Accustandard (New Haven, CT) is used as a second source verification (SSV). The SSV is run after IC. Matrix spikes and matrix spike duplicates are also performed. Table 8 Region III Laboratory QA/QC Requirements for Glycols QC Type Performance Criteria Frequency Method Blanks Solvent Blanks Initial and Continuing Calibration Checks Second Source Standards Laboratory Control Samples (LCS) Matrix Spikes (MS) MS/MSD 10% of the most abundant ion) should be present in the sample spectrum. ? The relative intensities of the major ions should agree within ? 20%. (Example: For an ion with an abundance of 50 % in the reference spectrum, the corresponding sample ion abundance must be between 30 and 70 %.) Comment [c138]: Not recommend: The analysis of TICs is only at best "estimated" data and CHK would not recommend any study to be performed or replicated on the basis of "estimated data". This will only be suspect data at best and not valid data by a chemist review. This would apply to any GC/MS (i.e. VOC or SVOC analyses) method performed. Comment [CV139]: MDH: We would not recommend TICs be analyzed for or reported since they are at best "estimated values. Is there any specific number of TICs that is being proposed to be evaluated? Comment [n140]: Appropriate qualifiers can be added ? Molecular ions present in the reference spectrum should be present in the sample spectrum. ? Ions present in the sample spectrum but not in the reference spectrum should be reviewed for possible background contamination or presence of co-eluting compounds. Ions present in the reference spectrum but not in the sample spectrum should be reviewed for possible subtraction from the sample spectrum because of background contamination or coeluting peaks. Data system library reduction programs can sometimes create these discrepancies. Table 10 Region VIII Detection and Reporting limits and LCS and MS Control Limits for Semivolatile Organic Compounds (SVOC) using Method 8270 Detection Limits Analyte 1-Chloronaphthalene 1,2-Dibromo-3-chloropropane 1,2-Dichlorobenzene 1,2-Dinitrobenzene 1,2-Diphenylhydrazine 1,2,4-Trichlorobenzene 1,2,4,5-Tetrachlorobenzene 1,3-Dichlorobenzene 1,3-Dinitrobenzene 1,4-Dichlorobenzene 1,4-Dinitrobenzene 2-Chloronaphthalene 2-Chlorophenol 2-Fluorobiphenyl (Surrogate) Control Limits Lower Standard Control Deviation Limit Upper Control Limit DL (ug/L) RL (ug/L) Mean 0.218 0.500 67.3 11.4 33 102 0.208 0.500 84.8 71.7 9.4 11.6 57 37 113 107 0.226 0.500 64.8 10.9 32 98 0.225 0.500 64.8 10.9 32 98 0.167 0.243 0.500 0.500 71.3 79.9 11.4 10.6 37 48 106 112 2-48 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [n141]: Not sure what is meant by 'define'-these are analytes identified in prior studies and standards have been obtained and equipment calibrated. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Table 10 Region VIII Detection and Reporting limits and LCS and MS Control Limits for Semivolatile Organic Compounds (SVOC) using Method 8270 Detection Limits Analyte 2-Fluorophenol (Surrogate) 2-Methylnaphthalene 2-Methylphenol 2-Nitroaniline 2-Nitrophenol 2,3,4,6-Tetrachlorophenol 2,4-Dichlorophenol 2,4-Dimethylphenol 2,4-Dinitrophenol 2,4-Dinitrotoluene 2,4,5-Trichlorophenol 2,4,6-Tribromophenol (Surrogate) 2,4,6-Trichlorophenol 2,6-Dichlorophenol 2,6-Dinitrotoluene 3-Methylphenol 3-Nitroaniline 3,3'-Dichlorobenzidine 4-Bromophenyl phenyl ether 4-Chloroaniline 4-Chloro-3-methylphenol 4-Chlorophenyl phenyl ether 4-Methylphenol 4-Nitroaniline 4-Nitrophenol 4,4'-DDD 4,4'-DDE 4,4'-DDT 4,4'-Methylenebis (2chloroaniline) 4,4'-Methylenebis (N,Ndimethylaniline) 4,6-Dinitro-2-methylphenol Acenaphthene Acenaphthylene Acetophenone Aldrin Aniline Anthracene Control Limits Lower Standard Control Deviation Limit Upper Control Limit DL (ug/L) RL (ug/L) Mean 0.190 0.217 0.118 0.197 0.500 0.500 0.500 0.500 63.7 75.0 73.3 81.8 75.8 14.8 9.5 11.7 11.2 12.4 19 46 38 48 39 108 104 109 115 113 0.185 0.142 2.00 0.086 0.151 0.500 0.500 2.00 0.500 0.500 76.3 68.8 75.8 84.3 79.7 82.9 9.6 13.5 20.6 11.2 10.3 13.6 48 28 14 51 49 42 105 109 138 118 111 124 0.166 0.500 80.7 82.7 10.7 11.3 49 49 113 117 0.091 0.189 0.394 0.500 0.500 0.500 0.108 0.546 0.165 0.120 0.189 0.320 0.085 0.500 1.00 0.500 0500 0.500 0.500 0.500 71.3 72.6 65.2 82.9 62.2 78.6 80.6 71.3 77.2 13 17.7 15.3 10.2 15.6 10.7 10.3 13.0 13.7 32 19 19 52 15 47 50 32 36 110 126 111 113 109 111 111 110 118 0.202 0.147 0.139 0.500 0.500 0.500 84.9 77.6 78.5 15.0 10.1 9.4 40 47 40 130 108 107 0.088 0.500 83.0 9.7 54 112 2-49 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [n141]: Not sure what is meant by 'define'-these are analytes identified in prior studies and standards have been obtained and equipment calibrated. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Table 10 Region VIII Detection and Reporting limits and LCS and MS Control Limits for Semivolatile Organic Compounds (SVOC) using Method 8270 Detection Limits Analyte Azinphos-methyl Azobenzene Benzoic acid Benz(a)anthracene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(g,h,i)perylene Benzo(a)pyrene Benzyl alcohol ?-BHC ?-BHC ?-BHC ?-BHC (Lindane) Bis(2-chloroethoxy)methane Bis(2-chloroethyl) ether Bis(2-chloroisopropyl) ether Bis(2-ethylhexyl) phthalate Butyl benzyl phthalate Carbaryl Carbazole Chlorobenzilate Chrysene Dibenz(a,h)anthracene Dibenzofuran Di-n-butyl phthalate Dichlorovos Dieldrin Diethyl phthalate Dimethyl phthalate Dinoseb Diphenylamine Di-n-butyl phthalate Di-n-octyl phthalate Disulfoton Endosulfan I Endosulfan II Endosulfan sulfate Endrin Endrin aldehyde Endrin ketone Upper Control Limit DL (ug/L) RL (ug/L) 0.102 0.500 0.079 0.081 0.088 0.098 0.083 0.500 0.500 0.500 0.500 0.500 82.7 81.8 84.6 80.5 81.3 71.0 8.9 12.1 13.2 14.1 9.5 13.8 56 45 45 38 53 30 109 118 124 123 110 112 0.183 0.238 0.426 0.500 0.190 0.500 0.500 0.500 1.00 0.500 76.2 73.3 78.2 84.2 81.1 10.2 12.3 17.5 14.0 11.7 46 37 26 42 46 107 110 131 126 116 0.084 0.500 82.5 11.4 48 117 0.079 0.110 0.133 0.153 0.500 0.500 0.500 0.500 82.1 84.7 80.3 8.9 14.1 8.8 55 42 54 109 127 107 0.099 0.107 0.500 0.500 79.2 75.9 12.9 16.9 41 25 118 127 0.188 0.500 84.8 87.4 10.3 16.6 54 37 116 137 2-50 Mean Control Limits Lower Standard Control Deviation Limit 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [n141]: Not sure what is meant by 'define'-these are analytes identified in prior studies and standards have been obtained and equipment calibrated. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Table 10 Region VIII Detection and Reporting limits and LCS and MS Control Limits for Semivolatile Organic Compounds (SVOC) using Method 8270 Detection Limits Analyte Fluoranthene Fluorene Heptachlor Heptachlor epoxide Hexachlorobenzene Hexachlorobutadiene Hexachlorocyclopentadiene Hexachloroethane Indeno(1,2,3-cd)pyrene Isophorone Malathion Methoxychlor Mevinphos Naphthalene Nitrobenzene Nitrobenzene-d5 (Surrogate) N-Nitrosodi-n-butylamine N-Nitrosodiethylamine N-Nitrosodimethylamine N-Nitrosodiphenylamine N-Nitrosodi-n-propylamine N-Nitrosomethylethylamine Parathion Pentachlorobenzene Pentachlorophenol Phenanthrene Phenol Phorate Pronamide Pyrene Pyridine Terbufos Terphenyl-d14 (Surrogate) Trifluralin (R)-(+)-Limonene 1,3-Dimethyl adamantine 2-Butoxyethanol Adamantane Squalene Terpiniol Control Limits Lower Standard Control Deviation Limit Upper Control Limit DL (ug/L) RL (ug/L) Mean 0.094 0.120 0.500 0.500 85.2 80.6 10.4 10.3 54 50 116 112 0.116 0.225 0.202 0.196 0.093 0.167 0.500 0.500 0.500 0.500 0.500 0.500 82.3 65.2 10.0 12.6 52 27 112 103 60.9 84.3 81.0 11.1 13.6 10.5 28 43 50 94 125 112 0.212 0.233 0.500 0.500 70.8 76.8 76.0 10.5 10.8 11.8 39 44 41 102 109 111 0.187 0.500 67.9 79.6 80.9 41.1 10.6 15.7 26 48 34 110 111 128 0.199 0.107 0.246 0.500 0.500 0.500 77.6 84.0 13.3 11.0 38 51 117 117 0.087 0.500 88.6 13.2 49 128 92.7 14.0 51 135 0.054 0.028 0.054 0.033 0.565 0.031 0.100 0.100 0.100 0.100 1.00 0.100 2-51 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [n141]: Not sure what is meant by 'define'-these are analytes identified in prior studies and standards have been obtained and equipment calibrated. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Table 10 Region VIII Detection and Reporting limits and LCS and MS Control Limits for Semivolatile Organic Compounds (SVOC) using Method 8270 Detection Limits Analyte Tri(2-butoxyethyl)phosphate DL (ug/L) RL (ug/L) 0.133 Mean Control Limits Lower Standard Control Deviation Limit Upper Control Limit Comment [n141]: Not sure what is meant by 'define'-these are analytes identified in prior studies and standards have been obtained and equipment calibrated. 0.200 Commercial standards for DRO calibration is locally procured DF #2 (source: Texaco station). Surrogates used in DRO include o-terphenyl at spiking concentrations of 10 ug L-1. Commercial standards for GRO calibration are BTEX, MTBE, naphthalene, and gasoline range hydrocarbons (purchased as certified solutions) and unleaded gasoline from Supelco (product number 47516-U). Surrogates used in GRO include 4- bromofluorobenzene at spiking concentrations of 50 ug L-1. 2.5 Quality Control 2.5.1 Quality Metrics for Aqueous Analysis For analyses done at RSKERC, QA/QC practices (e.g., blanks, calibration checks, duplicates, second source standards, matrix spikes, and surrogates) are described in various in-house Standard Operating Procedures (RSKSOPs) and summarized in Table 11. Matrix spikes sample spiking levels are determined at the discretion of the individual analysts (based on sample concentrations) and are included with the sample results. Corrective actions are outlined in the appropriate SOPs and when corrective actions occur in laboratory analysis it will be documented and the PI will be notified as to the nature of the corrective action and the steps taken to correct the problem. The PI will review this information and judge if the corrective action was appropriate. QC samples identified in this study are defined as: Field Duplicate: Independent samples which are collected as close as possible to the same point in space and time. They are two separate samples taken from the same source, stored in separate containers, and analyzed independently. Equipment Blank: A sample of analyte-free media which has been used to rinse the sampling equipment. It is collected after completion of decontamination and prior to sampling. This blank is useful in documenting adequate decontamination of sampling equipment. Method Blank: An analyte-free matrix to which all reagents are added in the same volumes or proportions as used in sample processing. The method blank should be carried through the complete sample preparation and analytical proce- 2-52 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV142]: Is this the certified standard for Fuel Oil #2? Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition dure. The method blank is used to document contamination resulting from the analytical process. Trip Blank: A sample of analyte-free media taken from a laboratory to the sampling site and returned to the laboratory unopened. A trip blank is used to document contamination attributable to shipping and field handling procedures. Matrix Spike: An aliquot of sample spiked with a known concentration of target analyte(s). The spiking occurs prior to sample preparation and analysis. A matrix spike is used to document the bias of a method in a given sample matrix. Matrix Spike Duplicates: Intralaboratory split samples spike with identical concentrations of target analyte(s). The spiking occurs prior to sample preparation and analysis. They are used to document the precision and bias of a method in a given sample matrix. Split Samples: Aliquots of sample taken from the same container and analyzed independently. These are usually taken after mixing or compositing and are used to document intra- or interlaboratory precision. Laboratory Control Sample: A known matrix spiked with compound(s) representative of the target analytes. This is used to document laboratory performance. Quality Control Sample: A sample introduced into a process to monitor the performance of a system. For analyses done by the Region VIII laboratory, QA/QC requirements are: 1. Samples shall be processed and analyzed within the following holding times (from date sampled): - Semivolatiles: 7 days until extraction, 30 days after extraction - DRO: 14 days until extraction*, 40 days after extraction - GRO: 14 days* - *With acid preservation 2. Data verification shall be performed by the Region VIII laboratory to ensure data meets their SOP requirements. 3. Complete data package shall be provided electronically on disk , including copies of chain-of-custody forms, copy of method or Standard Operating Procedure used, calibration data, raw data (including notebook pages), QC data, data qualifiers, quantitation (reporting) and detection limits, deviations from method, and interpretation of impact on data from deviations from QC or 2-53 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition method requirements. (All documentation needed to be able to re-construct analysis.) 2-54 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 Table 11 RSKERC Laboratory QA/QC Requirements Summary* from SOPs Calibration Blanks Checks Analysis Second Source Measurement Method (Frequency) (Frequency) (Frequency) RSKSOP194v4 &175v5* 10xMDL (Beginning and end of each sample queue, 10-15 samples) 5xQL (Every 15 samples) 90-110% Rec. for 80% of metals w/ no individual exceeding 70-130% (one per sample set, 10-15 samples) RPD<20* for 80% of metals above 5xQL; for results <5x QL, difference of b. Matrix Spike Recovery Matrix spikes sample spiking levels are determined at the discretion of the individual analysts (based on sample concentrations) and are included with the sample results. %Recovery= spiked sample concentration-native sample concentration x100 spiked sample concentration 2.6 Instrument/Equipment Testing, Inspection, and Maintenance RSKERC laboratory instrumentation used for analysis of project analytes are in routine use and are tested for acceptable performance prior to analyzing actual samples through the analysis of standards and QC samples. Field instruments are tested prior to use in the field by calibrating or checking calibration with standards. Routine inspection and maintenance of these instruments is documented in instrument logbooks. RSKSOPs provide details on instrument testing and corrective actions. 2.7 Instrument/Equipment Calibration and Frequency RSKERC calibration and calibration frequency are described in RSKSOPs (RSKERC Standard Operating Procedures). For the sub-contracted laboratory, these requirements are identified in the EPA Methods and the SOW (Statement of Work) included with the purchase requisition (PR) as well as in Table 12 Standards used for GRO and DRO calibration will be acquired from a commercial source. The SOW will be reviewed by the QAM for QA requirements prior to issuing the PR. Field instruments are calibrated or checked for calibration daily prior to use, midday, and at the end of the day after the last sample measurement. Calibration standards shall be traceable to NIST, if available and all dated calibration standards are not beyond their expiration date and will not expire during the field trip. 2-61 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Prior to the sampling event each test meter will be check that it is in good working order. Calibration data will be recorded in a bound waterproof notebook and personnel making entries will adhere to the GWERD Notebook policy. Calibration of instruments will be performed daily prior to initiation of sample collection and will be performed according to manufacturer's instructions and will be recorded in the field notebook. In addition calibration checks will be performed using known standards or buffers before use, mid-day and at the end of the day. With the exception of pH all checks must be exceed ? 10 % of known concentrations and in the case of pH must be within ? 0.2 pH units. These calibration checks will be recorded in the field notebook. If a calibration check fails, this will be recorded in the field notebook and the possible causes of the failure will be investigated. Upon investigation corrective action will be taken and the instrument will be recalibrated. Samples taken between the last good calibration check and the failed calibration check will be flagged to indicate there was a problem. Duplicate field measurements are not applicable to measurements in flow through cell (RSKSOP-211). Hach spectrophotometers and turbidity meters will inspected prior to going to the field and there function verified. Calibration of these instruments are internal and calibration will be checked in the lab prior to going to the field. Standards for redox sensitive species such as sulfide and ferrous iron are difficult to use in the field because once exposed to atmospheric oxygen there concentrations can change. Similarly calibration standards for alkalinity are sensitive to atmospheric carbon dioxide. Duplicates will be performed once a day or on every tenth sample. Duplicates acceptance criteria are ? 15 % RPD. The values obtained for each duplicate sample will be recorded in the field notebook and RPD will be calculated (section 2.5.4) and recorded in the field notebook. If the duplicate samples fail and additional duplicate sample will be taken and reanalyzed. If the additional duplicate samples fail to meet the QC criteria, then the instruments will be checked and corrective action taken. The corrective actions will be recorded in the field notebook. Samples collected between the last valid duplicate sample and the failed duplicate sample will be flagged. 2.8 Inspection/Acceptance of Supplies and Consumables RSKSOPs provide requirements for the supplies and consumables needed for each method. The analyst is responsible for verifying that they meet the RSKSOP requirements. The supplies or consumables not addressed by the RSKSOPs that are critical to this project are listed in Table 14. It should be noted that the vendors listed in Table 14 are suggest vendor and equivalent parts may be available from other vendors or substitute for based on purchasing rules. Dr. Puls is responsible for ensuring these are available and to ensure they are those as listed previously. If subcontractors are responsible for sampling, they will be responsible for providing the PI with information on their sample containers to ensure they meet project requirements. 2-62 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition Table 14 Supplies or Consumables Needed Not Listed in SOPs* Item Vendor Buffer Solution, pH 4 Buffer Solution, pH 7 Buffer Solution, pH 10 Conductivity Standard, 1413umho Zobell Solution Oakton DO Probe Membranes Bromcresol Green-Methyl Red Indicator Sulfuric Acid Cartridges, 0.1600N Sulfuric Acid Cartridges, 1.600N Delivery Tubes for Digital Titrator Iron, Ferrous Reagent Sulfide 1 Reagent Sulfide 2 Reagent POL DO cap Memebrane Kit/ Electrolyte Solution Silicone Tubing, size 24 Silicone Tubing, size 36 Polyethylene Tubing 0.25" ID x 0.375" OD Polyethylene Tubing 0.375" ID x 0.50" OD Part Number Fisher Scientific Fisher Scientific Fisher Scientific Fisher Scientific Fisher Scientific Fisher Scientific HACH SB101-500 SB108-500 SB115-500 15-077-951 15-176-222 15-500-039 94399 HACH HACH HACH 1438801 1438901 1720500 HACH HACH HACH YSI 103769 181632 181732 605307 Fondriest Environmental Fondriest Environmental Fondriest Environmental 77050009 77050011 77050502 Fondriest Environmental 77050503 * Equivalent products from other vendors can be used if needed. 2.9 Non-direct Measurements At this stage of the project, there are no non-direct measurements anticipated. 2.10 Data Management The PI is responsible for maintaining data files, including their security and integrity. All files (both electronic and hard copy) will be labeled such that it is evident that they are for the hydraulic fracturing project in Desoto Parish, LA. Data will be submitted to Dr. Puls as either hard copies (field notes), or electronically (laboratory data) in Excel spreadsheets on CD or DVD or via email. Data in hard copy form will be manually entered into Excel spreadsheets on Dr. Puls's computer or designated GWERD staff computer and will be given to Dr. Puls. Either, Dr. Puls or a technician or student will conduct this task. Data will be spot-checked by Dr. Puls to ensure accuracy. If errors are detected during the 2-63 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [CV146]: Electronic Data delivery should be used. Field notes should be digitized. Section No.: 2 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 2. Data Generation and Acquisition spot-check, the entries will be corrected. Detection of an error will prompt a more extensive inspection of the data, which could lead to a 100% check of the data set being entered at that time if multiple errors are found. Data in electronic form shall be electronically transferred to the spreadsheets. Data will be spot-checked by Dr. Puls to ensure accuracy of the transfer. If errors are detected during the spot-check, the entries will be corrected. Detection of an error will prompt a more extensive inspection of the data, which could lead to a 100% check of the data set being entered at that time if multiple errors are found. 2.10.1 Data Analysis, Interpretation, and Management Data validation will consist of initial and final review of data. Initial review will include continuous oversight during field collection of data by the principal investigator to avoid common transcription errors associated with recording of data. Final review will include evaluation of all collected data for suitability in data interpretation. It will include but is not limited to the following activities: (1) assessment of data completeness, (2) review of log books and forms used for data logging, and (3) review of calibration and standard checks. Comment [c147]: Need an outlier data resolution program that is agreeable to both parties. There will be outliers in the data, or unrealistic results, that likely will be traced to sampling or lab error. Needs to be provided in report. 2.10.2 Data Recording Data collected during the ground-water investigation will be recorded into field notebooks and entered into EXCEL spreadsheets. Water quality data will also be entered into AqQA a program for evaluating ground water quality and for evaluating data validity. Graphs will be produced using EXCEL or Origin to show key data trends. Comment [n149]: All data needs to be reviewed by the PI and any outliers (unusual results) will be reviewed to determine why (lab error, etc.) 2.10.3 Data Storage As this is a Category I project, all data and records associated with this project will be kept permanently and will not be destroyed. All data generated in this investigation will be stored electronically in Microsoft EXCEL and backed up in RSKERC's local area network 'M' drive. All paper-based records will be kept in the PI's offices. If the project records are archived, Dr. Puls will coordinate with GWERD management and GWERD's records liaison and contract support the compiling of all data and records. 2.10.4 Analysis of Data All data collected associated with groundwater and surface water sampling will be summarized in EXCEL spreadsheets. Data in spreadsheets will be spot-checked against original data reports by selecting random data points for comparison to verify accuracy of data transfer. When possible, data sets will be graphically displayed using EXCEL to reveal important trends. 2-64 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Is the data going to be shared with the landowners. A discussion, clarification, and description on this issue is needed. Comment [n148]: Data from private sampling of homeowner wells will be shared with them once quality assured and verified. Comment [c150]: Should also be part of final review and final acceptance of data. Comment [nc151]: Need to be consistent in citing of Excel and need to include trademark identificatioin Comment [CV152]: The handling of produced fluids and samples of hydraulic stimulation fluid are not mentioned in this section Comment [CV153]: If comparisons are made to standards, appropriate standards should be used, e.g. drinking water standards are not appropriate for surface water resources which are not directly consumed as human drinking water. The comparison should focus more on comparison to background levels. EPA does need to identify what actions if any will be taken to notify residents if baseline sampling has parameters which are higher than drinking water standards. A discussion on recommendations to a landowner if say nitrate is exceeded (due to septic impacts. This needs to be spelled out in the document, and would recommend the landowner be notified as soon as the baseline result is available that a MCL or SMCL is exceeded, or an organic compound found in their well at high levels.) Section No.: 3 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 3 Assessment and Oversight 3.1 Assessments and Response Actions Technical Systems Audits (TSAs), Audits of Data Quality (ADQs), and Performance Evaluations will be conducted early in the project to allow for identification and correction of any issues that may affect data quality. TSAs will be conducted on both field and laboratory activities. Detailed checklists, based on the procedures and requirements specified in this QAPP, related SOPs, and SOWs, will be prepared and used during these TSAs. These audits will be conducted with contract support from Neptune and Co., with oversight by Steve Vandegrift, QAM, for those that are done outside of RSKERC. Those at RSKERC will be done by the QAM. See Section 4.2 for additional discussion on ADQs. Laboratory TSAs will focus on the critical target analytes at sub-contract laboratories. A laboratory TSA will be conducted at RSKERC for critical target analytes. ADQs will be conducted on a representative sample of data for the critical target analytes. These will also be performed by the Neptune and Co., with oversight by Steve Vandegrift, QAM. Performance Evaluations will be conducted on critical target analytes for those that are available commercially. The QAM shall acquire and submit the PE samples. These shall be coordinated with the PI for the contract laboratory. See Section 3.2 for how and to whom assessment results are reported. Assessors do not have stop work authority; however, they can advise the PI if a stop work order is needed in situations where data quality may be significantly impacted, or for safety reasons. The PI makes the final determination as to whether or not to issue a stop work order. For assessments that identify deficiencies requiring corrective action, the audited party must provide a written response to each finding and observation to the QA Manager, which shall include a plan for corrective action and a schedule. The PI is responsible for ensuring that audit findings are resolved. The QA Manager will 3-1 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c154]: And project specific QMP? Section No.: 3 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 3. Assessment and Oversight review the written response to determine their appropriateness and provide, if necessary. If the audited party is other than the PI, then the PI shall also review and concur the corrective actions. The QA Manager will track implementation and completion of corrective actions. After all corrective actions have been implemented and confirmed to be completed, the QA Manager shall send documentation to the PI and their supervisor that the audit is closed. Audit reports and responses shall be maintained by the PI in the project file and the QA Manager in the QA files, including QLOG. 3.1.1 Assessments TSAs will be conducted on both field and laboratory activities. Detailed checklists, based on the procedures and requirements specified in this QAPP, SOPs, EPA Methods, and SOW will be prepared and used during these TSAs. One field TSA will be done. The laboratory audit will take place when samples are anticipated to be in the laboratory's possession and being processed. Laboratory TSAs will focus on the critical target analytes (Table 1) and will be conducted on-site at RSKERC (involves both EPA and contractor-operated labs) and at an off-site contract laboratory which will analyze for semi-volatile organic, DRO and GRO analyses. It is anticipated this will take place in the summer of 2011. At this time, EPA Region III Laboratory and EPA Region VIII Laboratory are be the off-site laboratories. ADQs will be conducted on a representative sample of data for the critical target analytes. . These will begin with the first data packages to ensure there are no issues with the data and to allow for appropriate corrective actions on subsequent data sets if needed. Performance Evaluations will be conducted on critical target analytes for those that are available commercially. These are anticipated to be done in the summer of 2011. 3.1.2 Assessment Results At the conclusion of a TSA, a debriefing shall be held between the auditor and the PI or audited party to discuss the assessment results. Assessment results will be documented in reports to the PI, the PIs first-line manager, and the GWERD Division Director. If any serious problems are identified that require immediate action, the QAM will verbally convey these problems at the time of the audit to the PI. The PI is responsible for responding to the reports as well ensuring that corrective actions are implemented, if needed, in a timely manner to ensure that quality impacts to project results are minimal. 3-2 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 3 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 3. Assessment and Oversight 3.2 Reports to Management All final audit reports shall be sent to the GWERD Division Director, and copied to Dr. Puls. Audit reports will be prepared by the QA Manager or the QA support contractor, which will be reviewed and approved prior to release. Specific actions will be identified in the reports. 3-3 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 4 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 4 Data Validation and Usability 4.1 Data Review, Verification, and Validation Criteria that will be used to accept, reject, or qualify data will include specifications presented in this QAPP, including the methods used and the measurement performance criteria presented in Tables 6, 7, and 8. In addition, sample preservation and holding times will be evaluated against requirements Table 6. Data will not be released outside of RSKERC until all study data have been reviewed, verified and validated as described below. The PI is responsible for deciding when project data can be shared with interested stakeholders in conjunction with the GWERDs Director's approval. 4.2 Verification and Validation Methods Data verification will evaluate data at the data set level for completeness, correctness, and conformance with the method. Data verification will be done by those generating the data. This will begin with the analysts in the laboratory and the personnel in the field conducting field measurements, monitoring the results in real-time or near real-time. At RSKERC, Shaw's, verification includes team leaders, the QC coordinator, and the program manager. For the EPA GP Lab at RSKERC, data verification includes peer analysts in the GP lab and the team leader. Shaw's and the EPA GP Lab's process goes beyond the verification level, as they also evaluate the data at the analyte and sample level by evaluating the results of the QC checks against the RSKSOP performance criteria. For the Region VIII laboratory, QA/QC requirements include data verification prior to reporting and detailed description can be found in the QSP-001-10 QA Manual (Burkhardt and Datschelet, 2010). Results are reported to the client electronically, unless requested otherwise. Electronic test results reported to the client include the following: Data release memo from the analysts, LQAO, Laboratory Director (or their Designees) authorizing release of the data from the Laboratory, and a case narrative prepared by the analysts summarizing the samples received, test methods, QC notes with identification of noncompliance issues and their impact on data quality, and an explanation of any data qualifiers applied to the data. 4-1 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 4 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 4. Data Validation and Usability The Region III laboratory data verification and validation procedure is described in detail in their Laboratory Quality Manual (Metzger et al., 2011). Briefly, the procedure is as follows. The actual numeric results of all quality control procedures performed must be included in the case file. The data report and narrative must describe any limitations of the data based on a comprehensive review of all quality control data produced. A written procedure or reference must be available for the method being performed and referenced in the narrative. If the method to be performed is unique, the procedures must be fully documented and a copy included in the case file. Verify that the calibration and instrument performance was checked by analyzing a second source standard (SCV). (The concentration of the second source standard must be in the range of the calibration.) Results must be within the method, procedure, client or in-house limits. At least one blank (BLK), duplicate analysis, and spiked sample must be carried through the entire method or procedure. Peer reviewers complete the On-Demand Data Checklist. The data report must document the accuracy and precision of the reported data by applying qualifier codes, if applicable, and include a summary of the quality control in the case file. For field measurements, Dr. Puls, E & E staff and Chesapeake field staff will verify the field data collected. The laboratories shall contact the PI upon detection of any data quality issues which significantly affect sample data. They shall also report any issues identified in the data report, corrective actions, and their determination of impact on data quality. Data validation is an analyte- and sample-specific process that evaluates the data against the project specifications as presented in the QAPP. Data validation will be performed by a party independent of the data collection activity. Neptune and Company, a QA support contractor, will conduct data validation on a representative sample of the critical analytes with oversight by the QAM. Data packages for the critical analytes that have been accepted by Doug Beak as ready to use or report shall be provided to Steve Vandegrift, QAM, who will coordinate the data validation with Neptune. Neptune shall evaluate data against the QAPP specifications. Neptune will use NRMRL SOP #LSAS-QA-02-0, "Performing Audits of Data Quality" as a guide for conducting the data validation. The outputs from this process will include the validated data and the data validation report. The report will include a summary of any identified deficiencies, a summary statement regarding the adequacy of the data for its intended use, and a discussion on each individual deficiency and any effect on data quality and recommended corrective action. As part of the data validation process, the synthesis of data and conclusions drawn from the data will be reviewed by the RSKERC Case Study Team (minimally will include case study PIs, Technical Research Lead for case studies, and GWERD 4-2 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Comment [c155]: A common problem is data review of field readings in a timely manner. Experience has shown that field reading often contain outliers due to instrument calibration issues, misreading by technicians, or transcription errors. Review of the field results is very important and needs to be conducted immediately after sample collection by both EPA and CHK, jointly. Validation of field screening parameters should not be left to one person. Section No.: 4 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 4. Data Validation and Usability Director) prior to release of this information or data to entities outside of RSKERC. Once reviewed by the RSKERC Case Study Team in coordination with the GWERD Director, the GWERD Director will approve its release. 4.3 Reconciliation with User Requirements The PI, Dr. Puls, shall analyze the data, as presented below. Dr. Puls shall also review the results from the data verification and validation process. Dr. Puls shall make a determination as to whether or not the data quality has met project requirements and thereby the user requirements. If there are data quality issues that impact their use, the impact will be evaluated by the PI. If corrective actions are available that would correct the issue, Dr. Puls will make the determination to implement such actions. For example, the PI may have the option to re-sample or re-analyze the affected samples. If not, then the PI will document the impact in the final report such that it is transparent to the data users how the conclusions from the project are affected. The types of statistical analyses that will be performed include summary statistics (mean, median, standard deviation, minimum, maximum, etc.) if applicable. In addition, the data will be plotted graphically over time and trends in the data will be analyzed, for example increasing or decreasing concentrations of a particular analyte. Data will be presented in both graphical and tabular form. Tabular forms of the data will include Excel spreadsheets for raw data and tables containing the processed data. Graphical representations of the data will not only include time series plots as previously described, but also Durov and Piper Diagrams for major anions and cations. In addition, concentrations of data could be plotted on surface maps of the Killdeer site showing well locations and concentrations of analytes and contours may be developed to show "analyte plumes", if present. 4-3 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 5 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 5 References Arkansas Geological Survey. Petroleum Geology of southern Arkansas and the Gulf Coastal Plain. http://www.geology.ar.gov/fossil_fuels/oil_geol_prodarea.htm Burkhardt, Mark; Datschelet, William. 2010. U.S. EPA Region 8 Environmental Laboratory Quality Assurance Manual. SOP No. QSP-001 rev 1.0. EPA Region 8 Laboratory. Domenico, Patrick A. and Schwartz, Franklin W. 1990. Physical and Chemical Hydrogeology. John Wiley & Sons, Inc. New York. Kiernan, Jesse. 2010. Determination of BTEX, MTBE, Naphthalene and TPH/GRO using EPA Method 8021B and 8015D Modified. SOP No.: ORGM-506 rev. 1.0. EPA Region 8 Laboratory. Kiernan, Jesse. 2010. Determination of Diesel Range Organics Using EPA Method 5015D Modified. SOP No. ORGM-508 rev. 1.0. EPA Region 8 Laboratory. Louisiana Department of Environmental Quality. 2009. Carizzo-Wilcox Aquifer Summary, 2007. Appendix 2 to the Triennial Summary Report, Aquifer Sampling and assessment Program. Louisiana Geological Survey 2008. General Geology of Louisiana, http://www.lgs.lsu.edu/deploy/uploads/gengeotext.pdf Marti, Vicente. 2011. Determination of Semivolatile Organic Compounds Using Method 8270D. SOP No. ORGM-515 rev. 1.1. EPA Region 8 Laboratory. Metzger, Cynthia; Caporale, Cynthia; Bilyeu, Jill. 2011. Laboratory Quality Manual, Version 8. 5-1 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 5 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 5. References U.S. Environmental Protection Agency Region 3, Environmental Science Center Environmental Assessment and Innovation Division, Office of Analytical Services and Quality Assurance. Page, L.V., and Pree', H.L., Jr., 1964, Water resources of De Soto Parish, Louisiana: U.S. Geological Survey Water-Supply Paper 1774 , 152 p. RSKSOP-152v3. Ground-Water Sampling. 5 p. RSKSOP-175v5. Sample Preparation and Calculations for Dissolved Gas Analysis in Water Samples Using a GC Headspace Equilibration Technique. 33 p. RSKSOP-194v4. Gas Analysis by Micro Gas Chromatograph (Agilent Micro 3000). 13 p. RSKSOP-211v3. Field Analytical QA/QC. 4 p. RSKSOP-212v6. Standard Operating Procedure for Quantitative Analysis of Low Molecular Weight Acids in Aqueous Samples by HPLC. 22 p. RSKSOP-213v4. Standard Operating Procedure for Operation of Perkin Elmer Optima 3300 DV ICP-OES. 22 p. RSKSOP-216v2. Sample Receipt and Log-In Procedures for the On-Site Analytical Contractor. 5 p. RSKSOP-257v3. Operation of Thermo Elemental PQ Excell ICP-MS. 16 p. RSKSOP-275v1. Collection of Water Samples from Monitoring Wells. 10 p. RSKSOP-276v3. Determination of Major Anions in Aqueous Samples Using Capillary Ion Electrophoresis with Indirect UV Detection and Empower 2 Software. 11 p. RSKSOP-299v1. Determination of Volatile Organic Compounds (Fuel Oxygenates, Aromatic and Chlorinated Hydrocarbons) in Water Using Automated Headspace Gas Chromatography/Mass Spectrometry (Agilent 6890/5973 Quadrupole GC/MS System). 25 p. RSKSOP-326v0. Manual Measurement of Groundwater Levels for Hydrogeologic Characterization. 4 p. RSKSOP-330v0. Determination of Various Fractions of Carbon in Aqueous Samples Using the Shimadzu TOC-VCPH Analyzer. 15 p. 5-2 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: 5 Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 5. References Tetra Tech. 2003. Literature review and report surface sediment sampling technologies. Report for U.S. Environmental Protection Agency, National Exposure Research Laboratory. GSA Contract No. GS-10F-0076K. 5-3 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: A Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 A Comment [nc156]: Without all the Figures and Appendices to review, it is difficult to totally review this document. Standard Operating Procedures A-1 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011 Section No.: B Revision No.: 00 Date: May October 21, 2013August 6, 2013January 6, 2012January 6, 2012January 6, 2012December 20, 2011 B Field Forms B-1 02:002233_0696_SGTG-B3494 4_attachment_EPA CHK Case Study QAPP working copy 121611 (CEPA CHK Case Study QAPP working copy 121611.doc10/21/20138/6/20131/6/20121/6/20121/6/201212/20/2011