Fracking and hydrocarbon baseline monitoring of methane in wells by GC-FID

The United States has what some estimate to be the largest known shale gas reserves in the world. The process for releasing the natural gas combines a new form of horizontal drilling with hydraulic fracturing more commonly known as fracking. Fracturing is the fracturing of rock by a pressurized liquid. The Fracking boom started in 2005 after the Energy Policy Act exempted companies from compliance with the Safe Drinking Water Act, the Clean Air and the Clean Water Act. Fracking sites are also exempted from CERCLA. Regulation is now controlled by the states and about 18 states allow fracking. Many of the states are involved in running baseline measurements of methane (CH4). One of the concerns with fracking is that contamination may migrate into wells and pollute the drinking water. The USGS has done a number of background studies of CH4 in well water and soil around the country (1, 2 ). The USGS uses gas chromatography (GC) with a flame ionization detector (FID) to detect CH4 after collecting a soil or water headspace sample. PID Analyzers, LLC of Sandwich, MA has developed a portable GC with an FID that can be used to monitor methane and other hydrocarbons in air or water. A photo of the GC 312 is shown below on Fig. 1. This GC has an embedded PC with easy-to-use PeakWorks for Windows software, a touch screen, capability to run two detectors simultaneously, and an 8 GB memory stick to save data (including chromatograms). The GC312 has a 30L tank for carrier gas or an optional 70L hydride cylinder for H2. It

also has a pump with a charcoal scrubber to provide air for the FID. The battery will last for 7-8 hours and can be recharged from line or 12 VDC from a car 12 VDC.

The sensitivity of the GC312 for methane is in the ppb range can be seen in the chromatogram of methane in ambient air in Fig. 2 below:

Water samples are collected in a VOA vial, a headspace is created, the sample is

Applications Note: 7/13

Fracking and hydrocarbon baseline monitoring of methane in wells by GC-FID

equilibrated, now, according to Henrys law, the concentration in the liquid phase is proportional to the concentration in the liquid phase and the gas sample is injected into the GC. Henrys law can be stated (at constant temperature) as : P = Kh C where: P= the partial pressure of the solute in the gas above the solution, C=the concentration of the solute, and Kh=a constant with the dimensions of pressure divided by concentration. The constant, known as the Henrys law constant, depends on the solvent, the solute, and the temperature. The packed column will resolve the C2 HC on the same column below: The GC FID has sufficient sensitivity to detect ppb levels of methane in water so it will be very useful to determine background levels of hydrocarbons in water in the field. The specifications of the GC 312 are given below: GC 312 Specifications GC Detectors available: PID, FID, COD, FPD, FUV, & TCD Measurement mode: Manual or Continuous Battery life- NiMH 6-8 hours Temperature range- 30-100 C on battery; 30125C on line or 12 VDC Zero drift- Automatic zero Span drift- less than 1%every month with calibration Wide range of response- from ppb to 100 %PC: 500 MHz Pentium Readout- 7 Color VGA Monitor with touch screen (640 x 480resolution) Storage device: 2 Gbyte smartcard; 8 GB USB memory stick Operating System: Windows XP Standard outputs:1 RS232; USB ports, 1 010VDC analog output Enclosure: Heavy duty plastic Dimensions: 18.75" L x 13.75"Wx7.5"H Weight: 27.5 pounds Power requirements- 90-240 VAC-1 amp; 12 VDC

If higher molecular weight HC are needed, a capillary column can be used to separate the peaks as shown in the chromatogram below:

Applications Note: 7/13

Fracking and hydrocarbon baseline monitoring of methane in wells by GC-FID