High-volume hydraulic fracturing (HVHF) has revolutionized the oil and gas industry worldwide but has been accompanied by highly controversial incidents of reported water contamination. For example, groundwater contamination by stray natural gas and spillage of brine and other gas drilling-related fluids is known to occur. However, contamination of shallow potable aquifers by HVHF at depth has never been fully documented. We investigated a case where Marcellus Shale gas wells in Pennsylvania caused inundation of natural gas and foam in initially potable groundwater used by several households. With comprehensive 2D gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS), an unresolved complex mixture of organic compounds was identified in the aquifer. Similar signatures were also observed in flowback from Marcellus Shale gas wells. A compound identified in flowback, 2-n-Butoxyethanol, was also positively identified in one of the foaming drinking water wells at nanogram-per-liter concentrations. The most likely explanation of the incident is that stray natural gas and drilling or HF compounds were driven ∼1–3 km along shallow to intermediate depth fractures to the aquifer used as a potable water source. Part of the problem may have been wastewaters from a pit leak reported at the nearest gas well pad—the only nearby pad where wells were hydraulically fractured before the contamination incident. If samples of drilling, pit, and HVHF fluids had been available, GCxGC-TOFMS might have fingerprinted the contamination source. Such evaluations would contribute significantly to better management practices as the shale gas industry expands worldwide.

The design, fabrication, and performance of gas chromatography columns etched in silicon substrates are described. Deep reactive-ion etching formed the 3-m-long, 150-microm-wide, 240-microm-deep rectangular cross section channels. A glass cover plate was anodically bonded to the remaining surface of the substrate forming the gastight channel. For some of the columns, the silicon channels were oxidized before the channels were sealed with the glass plates. Fused-silica capillary connecting tubes were sealed into ports on the edge of the 3.2-cm x 3.2-cm substrate chips. Dynamic coating was used to deposit a film of nonpolar dimethyl polysiloxane or moderately polar trifluoropropylmethyl polysiloxane stationary phase. The columns were evaluated in a conventional benchtop GC instrument with split injection and flame ionization detection. Column efficiency was evaluated by the use of plots of height equivalent to a theoretical plate versus average carrier gas velocity using both hydrogen and air as carrier gases. The number of theoretical plates measured at the average carrier gas velocity giving the minimum plate height ranged from 4600 to 8200 plates for the dimethyl polysiloxane columns and from 3500 to 5500 plates for the trifluoropropylmethyl polysiloxane columns. Minimum plate height was significantly smaller with air as carrier gas. For the nonpolar phase, the nonoxidized surface gave approximately 1500 plates more than the oxidized surface for both carrier gases. For the polar phase, the oxidized surface gave approximately 200 plates more than the nonoxidized surface. Isothermal chromatograms of a 20-component multifunctional mixture and temperature-programmed chromatograms of a normal alkane mixture are presented.

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