December 23, 2013

The Fracking/Ozone Mystery

There is an important atmospheric mystery that needs to be understood, quickly.

As many of you know, natural gas fracking has become widespread across the United States and is now a major source of natural gas used in heating, power generation, and other applications.  Such fracking injects chemicals and sand under high pressure to produce cracks in unerlying rock strata, with the sand keeping the pores open to allow the escape of large quantities of natural gas (methane).

And now the mystery part.   In regions where fracking is being done, some quite rural, extraordinarily high ozone values are being observed.   And such ozone values have been particularly elevated over regions of snow.  But why?

 And let's remember that ozone, while wonderful protection from ultraviolet radiation when concentrated in the stratosphere, is NOT your friend near the surface.  Ozone is a powerful lung irritant that contributes to asthma and other breathing disorders.   High ozone values can also lead to heart disease and premature death and can greatly damage plants.

Pretty nasty stuff.

So it is very important to understand why fracking is associated with high ozone values, why snow is important, and what we can do to mitigate such ozone production during fracking operations.

Now the basic chemistry of ozone production provides some clues of why fracking is a big contributor.    Ozone near the surface is generally associated with three contributors:  solar radiation, nitrogen oxides (often produced by combustion), and volatile organics (including methane, isoprenes from plants, and petroleum products).   We are now learning that fracking operations leak a large amount of methane into the atmosphere, so you have the volatile organics.   Many fracking operations are in fairly dry locations (e.g., Utah, Wyoming, Colorado, Oklahoma, Texas) with lots of solar radiation.  And all the cars, trucks, and machinery associated with fracking produce nitrogen oxides (and there are some natural sources as well).

But why is snow a contributor?  One can speculate.  Snow reflects solar radiation, so with snow the lower atmosphere can get a lot more ultraviolet radiation from the sun's rays coming down directly and reflected off the snow (that is why we need sunglasses while skiing on a bright day).  And snow can act as a catalyst, a substance that encourages a chemical reaction, in this case the production of ozone. 

A fellow professor in my department, Dr. Becky Alexander, would like to go into the field next month with graduate student Maria Zatko, to investigate the snow/fracking/ozone connection and she needs your help.

Let me explain.   A scientific field program is now planned from Jan. 13 – Feb. 7 in Utah's Uintah Basin, a major location of fracking operations (see map).

A central question is the source of the nitrogen oxides (we know where the solar radiation and volatile organics are coming from).  By taking air samples and by measuring the amount and type of nitrates in the snow,  Dr. Alexander and Ms. Zatko, hope to unravel the mystery.  The only hitch is lack of funding to secure the samples and analyze them.

But there is a way: crowdfunding.  If you remember, last year I noted that Dr. Dan Jaffe needed funds for a study of the effluent and coal dust coming off of coal trains, and noted the potential for contributing on the Microoryza web site.  Many of you responded and he secured the full $ 20,000 that was needed. The research was undertaken and completed ...research that is now in review for publication (I will report the important results of this work in a future blog).

Dr. Alexander has established a page on the Microoryza web site that outlines her project (go here to see it).  In total, she is trying to raise $12,000.

Please consider donating to this effort.  The problem is a serious one and amount of funding required is very modest considering it societal importance.

And no, western Washington will not have a white Christmas...sorry.


  1. I follow news from Oklahoma (home state.) Earthquakes are up approx 4,000% per the sources I read. 4,000%

    Lots of fracking going on in OK.

    I like gas in my car but I like to eat and breath even more.

  2. While fugitive emissions at pipe joints, etc. are a growing concern and could certainly contribute to the chemical reaction like you stated, I fail to see how it would be any different whether the well is a standard natural gas well or a fracked well. It seems you are using the word "fracking" in this case more because it is a trigger word that brings out the pitchforks than any direct correlation. A secondary correlation may exist in that fracking is encouraging more gas production through improved yields of zones that would otherwise be reducing in gas production, but this post (and the study) seems to be pitching a direct correlation.

    I have been in the rural parts of the Uintah Basin recently. I would suggest that these researchers look into the dust as a source of nitrates. The road soils are all clays which aerate like nothing I've ever seen before. If a high pressure system moves in the dust gets trapped in the middle of the basin in a powerful inversion. The roads will not be dusty when they are there in the winter though, so although they will likely observe the inversion on a sunny day it won't have as much dust as warmer months.

  3. Due to this posting, (and related to my background), i became curious in seeing if there was a chemical equation that more-or-less started with methane and ended up with ozone. This led me to this Figure from Will Wilson of Duke University (who probably got it from somewhere else (after-all, he's a Biologist! ;) ) buried in his references)

    In short, egads, what a witches' brew is our atmosphere.

  4. All the more reason we should get off the fossil fuel teat and get SERIOUS about solar, wind, geothermal, biomass, and nuclear fusion power.

    This is the kind of thing where the government should take the lead. If I had my way, a person would have to have a science degree in order to hold public office.

  5. I totally concur with Jonn-E's comments.

    Hydraulic fracturing techniques per se do not yield ANY methane because the well is dead during the process (after all, the process involves injecting viscosified water and sand though casing perforations _into_ the formation, so it's impossible for gases to escape to the atmosphere). It's only after the frac fluid is removed and the well is allowed to flow that natural gas is brought to the surface. During the flow-back process the produced gas and water are separated and are either burned or routed to a collector pipeline

    The mention of "fracing" in this study is a non sequitur and it being used just to take advantage of the public's ignorance of the process.

    The only truth in this article is that the process requires a lot of horsepower that is produced by diesel-powered pump trucks, which do emit the pollution typical of any diesel engine.

    The study SHOULD be focused on the problem of natural gas (mostly methane) leaks in surface equipment. Operators lose money on these leaks, so they don't want them either.

  6. Peter Pawlak:
    There is an increasingly deep literature documenting the loss of methane and other chemicals from fracking sites, particularly once they go into production. An accessible review of work by a NOAA scientist is found at this NPR site:

    The work is published in JGR. You can find it here:

    JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 117, D04304, doi:10.1029/2011JD016360, 2012


  7. Sigh ... the article you linked may imply a correlation between natural gas production and higher background levels of methane, but establishes zero causal evidence that hydraulic fracturing is the root cause of this elevated level.

    Barring a serious accident such as a well blowout or pipeline rupture, there are two stages where natural gas (mostly methane) can be released:

    1) While the well is being drilled. When a formation containing hydrocarbon is pulverized by the drill bit and brought to surface by the drilling mud, the hydrostatic head is dropped by thousands of psi, which can cause gas to be emitted from the particles. While gas detectors can track changes in these emissions, the amount is very small because the volume of cuttings is very small as well.

    2) Once the well is brought into production (whether from a conventional permeable formation or tight shale that has been hydraulically fractured).

    I don't dispute the data in the article you linked, but I do dispute her analysis and conclusions.

    I do have some experience and knowledge in this area. I graduated with a degree in Chemical Engineering from the Colorado Scholl of Mines in the '70's, and even though I'm no longer in the energy business, I spent the first 11 years of my career as a petroleum engineer doing worldwide oil & gas exploration.

    We were doing hydraulic fracturing back then and it was a mature technology by 1970, so the process is well understood. What is new is combining horizontal drilling and fracturing to make producing gas from tight shale formations cost effective. That said, once gas or oil from those formations is brought to surface, it's the process for getting it from wellhead to market as it was when I worked in the industry.


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