Fort Worth Natural Gas Air Quality Study . . .

a critical review by Andy Mechling

8.03.2011

Ambient Monitoring Study

An exercise in looking the other way Here once again, some of the most obvious and important findings from a major air quality study in the Barnett Shale are seen to revolve around measured concentrations of carbon disulfide gas; and yet again, the relevant facts need to be pieced together from information buried in the data tables; as this subject is completely ignored in the narrative sections of the final report released to the public.1 Some truly impressive science was brought to bear in this FWNGAQ study. In the ambient monitoring phase especially, highly sensitive monitoring methods were utilized in systematic fashion at carefully chosen locations over a two month period, and a mountain of high quality data was generated. The Eastern Research Group (ERG) team crunched these numbers hard; of course. A variety of statistical screening tools were put to effective use, and as a result; a very interesting picture snapped into focus right away. We gained some valuable information here, to be sure. Unfortunately, only some of this makes it into the report. The ambient monitoring phase looked at 138 chemicals. One of these compounds behaves unlike all the rest, and this information is quickly shaken out through the statistical analyses. Somehow, this fact doesnt get discussed. Even if toxicological concerns are completely ignored, and those 138 compounds are treated anonymously; these numbers for CS2 clearly behave differently than the others; and not just by a little bit. I am not a statistician. I hold no formal scientific credential of any type.2 With all due respect to the scientists involved however, I believe it is clear that the authors failure to include any discussion of the implications presented by their own statistical analysis of the carbon disulfide canister data represents both a glaring omission, and an obvious problem with the FWNGAQS final report. Further, I believe that any serious independent review of the datasets in question will identify this exact same issue.

 Straight to the charts - Always The rubber finally begins to find the road here a little bit in Table 5.2-3.of this report. 3 In this table, measured concentrations of target compounds are compared to TCEQ long-term health effects screening levels.

Program-Average Concentrations and TCEQ Long-Term Screening Levels

Compound Benzene Carbon disulfide Carbon tetrachloride Formaldehyde

Site S-4 S-5 S-1 S-4

Highest study average (ppb) 0.69 0.94 0.12 1.14

Long term
screening level (ppb)

Type AMCV ESL AMCV AMCV

1.4 1 2 8.9

Thetableabovewasassembledbymeandisbaseddirectlyontable5.23onpages241245ofthereport,which includesentriesforall138studytargetcompounds.Thereaderisencouragedtoviewthefulltable

"Key Point: Key Pollutants The key pollutants, based on the ambient monitoring data, were: Acetaldehyde Benzene 1,3-Butadiene Carbon tetrachloride pDichlorobenzene Formaldehyde (and) Tetrachloroethylene4

If a reader were to consider only the data in this table; and disregard the narrative sections or key points presented in this report, he or she might logically conclude that measured levels of carbon disulfide present as much cause for concern as any compound identified in this study. The other three chemicals presented above are all identified as key pollutants during this study. In previous studies, we have seen calculations presented for percentage of screening level. In this study, ERG chooses not to provide these types of figures. It also seems worth noting that if the ERG team had decided to incorporate the same protocols as utilized in the 2010 TITAN report, where individual 24 hour canister measurements were used for comparison to TCEQ long-term standards; the present study would then have included several measurements of CS2 from site 5 over that 1ppb long-term ESL.5

24hr samples represent short-term exposures now? In the TITAN study and others, short-term health screening levels are compared to 1-hour concentration data. Here in the FWNGAQS; those same short-term screening levels are referenced in comparison to 24hour data. I do not feel qualified to comment on the relative merits of either approach. Either way though, whether its TITAN measuring CS2 at 100% of its short-term ESL, or ERG measuring CS2 at 94% of the longterm ESL, (my math) I believe the public would be better served if these facts were discussed, rather than buried, in these reports. More disappointing than the continued failure to acknowledge potentially troubling levels of carbon disulfide gas detected in the neighborhoods is the fact that this compound was monitored only at sites 1-5, and not at any of the other 350+ locations where air monitoring activities were conducted in this study. As the researchers got closer to the natural gas sites, they simply stopped monitoring for CS2 altogether. Carbon disulfide was not included on the list of chemicals to be monitored at the fenceline sites (sites 6 & 7) in the ambient monitoring portion of this study, and was similarly excluded from all lists of target chemicals during the extensive point source evaluation phase. Perhaps most disappointing of all is the fact that no true sulfur gas analysis was performed at any point during this million-dollar air study. Because of this, some highly toxic gases associated with natural gas production, especially hydrogen sulfide and carbonyl sulfide were completely and intentionally overlooked; and important opportunities for method validation were missed. . Study in General My comments above notwithstanding; I regard this as a vitally important air study of the very highest quality. I admit to some positive bias coming in. A decade ago, I had the opportunity to work with consultants from ERG on an EPA grant project involving fenceline monitors at a California oil refinery. On that project, the decision to bring in ERG as consultants for the final phases came from the EPA Region IX offices in San Francisco.

From my perspective; the ERG team on that project more than lived up to its billing as top dogs in this field. I came away thoroughly impressed with both the capabilities and professionalism of this outfit. The FWNGAQS, authored by ERG, actually represents an amalgamation of two separate air studies with distinctly different objectives. The ambient monitoring phase and the subsequent point-source emissions evaluation utilized different (but sometimes overlapping) analytical labs, instruments, field methods, target chemicals, sub-contractors, and so on. Both of these air studies represent scientifically complex and logistically demanding projects in their own right. Along with the two monitoring programs, this report provides other technical guidance; including analysis of regulatory issues, emissions modeling, estimates of gas reserves, and a host of other issues involving natural gas production in the Fort Worth area. As a whole, I find this 320 page final report, along with the interim report that preceded it, to be exceptionally well-written. If there are any factual errors or inconsistencies associated with the narrative sections or tables; I did not find them. Throughout the report, the authors do an excellent job of presenting some highly complex subject matter in direct and easyto-understand language. As air monitoring reports go, this one is also particularly wide-ranging in scope. The authors touch on a number of subjects where I have no expertise whatsoever. I cannot comment, for example, on the adequacy of ERGs estimates of remaining gas reserves in the Barnett Shale, or on how the price of natural gas might factor into estimates of future pollutant concentrations in the region. I have only very limited experience working with dispersion models. I cant offer any opinions as to the relative quality of modeled concentration values in the point-source testing phase of the project; or provide any type of meaningful insight into analysis regarding the adequacy of existing setback distances performed by ERG. My primary interest in this study is focused on the results of sampling from the ambient monitoring phase; specifically, on the results of the VOC sampling from sites 1-5. These were the only samples analyzed at the (ultra-capable) ERG lab in North Carolina; and also represent the only samples analyzed for CS2 at all during the course of this study. Uneven data quality noted and accepted

Ambient canister samples from the two fenceline sites were sent to the Test America/Austin lab for analysis. Carbon disulfide was left off the list of target compounds to be analyzed via GCMS/TO-15 at these sites (6&7). Even though the concentration data is more spotty in nature, and clearly of lower quality by comparison; ERG incorporates the results from sites 6 and 7 with all the data from their own lab, and attaches equal weight to these figures in the various statistical routines employed during this phase of the study. The authors make clear note of the differences in data quality, but then demonstrate that even with the lower quality data from the fenceline sites added into the mix, the project was still able to meet stated Data Quality Objectives (DQOs) across the board.6 For my purposes, I chose to consider results from the two labs separately. In one of the findings from the ambient monitoring phase, the authors express surprise at the low nature of some of the concentration measurements from sites 6 and 7:

Pollutant concentrations at Sites S-6 and S-7 (located in a medium-level activity area) were surprisingly low relative to other sites, especially given their close proximity to active well pad locations. 7

VOCdata:Sites15 At first glance, the concentration data presented in these tables appears visibly different than most; due to a conspicuous lack of non-detect data. Seemingly, most of these chemicals are being detected most of the time. Dozens of the target VOCs analyzed under TO-15 are detected in every sample from every site. Quality assurance figures included with the final report confirm that the accuracy, precision, and sensitivity demonstrated by the ERG lab throughout the ambient monitoring portion of the study are uniformly outstanding.8 9 For the compounds of most interest, including CS2, detection limits are considerably lower than we have seen in previous monitoring studies in the region. Typically, the MDL figures demonstrated by the ERG lab extend into the low parts-per-trillion range. Generally, these figures run between one and two orders of magnitude better than what we have come to expect from other labs. 5

For what it matters, the extensive data set assembled through the ambient monitoring portion of this study is undoubtedly the most impressive set of air canister data I have ever seen. Because this study was so effectively implemented; and because there are actually numbers in those database tables, (as opposed to cells full of non-detect data), this project provides unique opportunities for researchers to identify potentially meaningful trends among the 15,000 data points generated here. Carbon disulfide vs. carbon tetrachloride: Old buddies on opposite sides? Carbon disulfide and carbon tetrachloride are two substances which have plenty in common, and its not all good. Both of these are highly useful industrial solvents of the highly toxic variety, and they share a great deal of interesting history. In the context of this FWNGAQ study, while both of these compounds are detected in every sample; (sites 1-5) these two historic bad actors find themselves at opposite ends of the scale - in terms of how their measured concentration values are dispersed across the monitoring network. As explained in some detail in the Interim Report, one of the statistical screening tools incorporated by ERG included the calculation of a Coefficient of Variation ratio (CV) for each chemical detected in at least 70% of samples. The CV ratio is the standard deviation divided by the mean, and is used to compare the relative dispersion in one set of data with the relative dispersion of another set of data. The lower the CV ratio, the less variability in the data measurements. 10 From my perspective, the overall picture that emerges from ERGs statistical analysis of this data set is as surprising as it is crystal clear. In the case of these two solvents especially, it is the consistent nature of the data, and the clear-cut nature of the trends observed, that I find so completely unexpected and remarkable.

Carbon Tetrachloride: CV ratio 0.14 Carbon tetrachloride, detected in every sample, is one of those chemicals whose levels are seen to vary the least across the entire monitoring network during the course of the study. The CV ratio of 0.14 calculated for carbon tetrachloride is 5th lowest in this study. 6

It is worth noting also that much of the variability that is observed for carbon tetrachloride comes in the form of slightly depressed readings at sites 6 and 7. If the lower quality data11 from these two sites is left out of the calculations, carbon tetrachloride levels appear even more remarkably stable. (I did not attempt to calculate a new CV ratio based only on the data from sites 1-5.)
Study Average Concentrations By Site (ppb)12

Location Carbon Tetrachloride Carbon Disulfide Benzene

Site 1 Site 2 Site 3a Site 3b Site 4 Site 5

0.118 0.117 0.118 0.115 0.113 0.108

0.043 0.034 0.050 0.013 0.119 0.944

0.245 0.300 0.301 0.165 0.686 0.197

The following is included on a list of Key Findings in the ambient monitoring section of the report: 13 ERG found little variability across the sampling network for certain pollutants, such as carbon tetrachloride, chloroform, chloromethane, crotonaldehyde, dichlorodifluoromethane, dichlorotetrafluoroethane, ethylene, 1-hexene, isoprene, propylene, trichlorotrifluoromethane, and trichlorotrifluoroethane. The low variability across the entire network suggests that these pollutants are not affected by localized, anthropogenic sources, but rather exist as background pollutants.

A solid wall makes a solid argument The authors present a very convincing argument here, in my opinion. The levels of all of pollutants on this list are so remarkably stable and uniform at the various locations across town, and under various wind conditions, and over the course of the study that even from a commonsense point of view; it is hard to imagine how the presence of these 7

chemicals could ever be attributed to any specific source - local or otherwise based on these observed trends. The finding above is entirely consistent with findings published in other recent studies. In this case, and for these chemicals, the favorable finding for industry appears to be based on some very solid science. The fact that local NG activities are not seen as major contributors to ambient levels of these pollutants represents valuable information in every sense. This truly is good news. It stands to reason that the ERG team might also have been interested in considering those chemicals which were seen to display high variability across the network, and for which elevated concentrations might be associated with proximity to NG activities. The following appears as a bulleted item on page 18 in a short list under the heading: Data obtained from this ambient air monitoring network can be used to: Characterize exposure to selected air toxics in ambient air at various locations in the city, as related to the proximity to certain natural gas activities (well pads, compressor stations, fracturing operations, etc.).14

It is interesting to see this type of exposure characterization task show up on a list of things that the data might be used for, rather than as a primary program objective, or some sort of project deliverable. In any case, no discussion of source characterization for carbon disulfide is included in either the interim or final version of the FWNGAQS report. The fact that the authors chose not to explore the other side of the coin here is puzzling; and imparts an unfinished feel to a study which otherwise appears to be logically presented.

The other side of the coin. Carbon disulfide appears on the far opposite end of the scale of CV values in this project from carbon tetrachloride. The study CV ratio for CS2 is calculated at 1.61; which ranks second-highest behind only the 1.84 figure calculated for toluene.

Toluene: CV ratio 1.84 While concentration values reported for toluene were somewhat more variable overall than those for CS2, elevated readings for this compound were far more sporadic in nature; and clear patterns are difficult to discern. For example, with toluene, the highest concentrations overall were recorded at site 2 (near the freeways); whereas on most days, the highest level across the network was recorded at site 4 (municipal dumpsite). On the final day of sampling, the highest concentration of toluene was measured at site 1. (away from the well pads)

Carbon Disulfide: CV ratio 1.61 By contrast, the pattern observed with respect to measured concentrations of carbon disulfide is absolutely clear and unambiguous. The numbers, in-and-of themselves, may not be too startling, especially as measurements at-and-around this 1ppb screening level are roughly in line with results from other recent studies performed in the region. The concentration figures from this ambient monitoring phase were finalized and released with the Interim report in February; and the gas industry has already responded by repeatedly downplaying the significance of these numbers. Fortunately, the scientists involved in this study chose to utilize a method which was sensitive enough to detect the full range of CS2 concentrations encountered; and the study was designed thoughtfully enough to allow the researchers to put this sensitivity to effective use.

"Key Point: Measurement Sensitivity The ambient air monitoring program used highly sensitive measurement methods. For all but two pollutants, the methods were capable of detecting air concentrations at levels below TCEQs most protective health-based screening values. Therefore, the air pollution measurements were sensitive enough to support health evaluations.15

For measured concentrations of carbon disulfide, it is the way the numbers are distributed across the sites, even more than the numbers themselves, which becomes so interesting and revealing. Even If they did choose to leave it out of their report; the ERG team clearly deserves credit for producing what is - upon close inspection - a fairly elegant piece of science in this project.

If youre from Fort Worth, and youre trying to find that million dollars; I say its right here. Buried deep. Please consider:

Site 5 is surrounded by NG activity - by study design16 Site 5 recorded the highest level of CS2 on every day sampling occurred there by a convincing margin. Site 4 was also located near a few well pads. Site 4 recorded the second-highest level of CS2 on 18 of 19 sample days. The lowest 24-hr level recorded at site 5 was 0.492ppb on 10/28. The highest level recorded anywhere else during the two-month period was barely half of that. (0.258ppb on 9/10 @ site 1) The average level of CS2 recorded at site 4 (0.119ppb) is more than double that of any other site. (excluding site 5) The average level of CS2 recorded at site 5 (0.944) is more than 7 times greater than the level recorded at site 4. Sites 1, 2, and 3b all recorded at least one 24-hour period with concentrations at or below 0.010ppb. Seven such days are recorded between these 3 sites.17 Of the 138 chemicals sampled during this study, none can be associated with a particular site in anything resembling the manner in which carbon disulfide is associated with site 5. Besides the situation with CS2, air quality at site 5 generally appears to be as good or better than at the background sites. Please notice that site 5 reports the lowest average concentration of benzene of any of the fixed locations during the course of this study.

Variability at each site explored. Besides examining the variability in measurements across the network for those chemicals detected most often, the researchers were also interested in looking at the variability displayed by each chemical at each location over the course of the study. 10

Pollutant CV Ratios at Each Monitoring Site18 (condensed) Compound S-1 S-2 S-3 S-3a S-4 S-5 Benzene 0.51 0.29 0.56 0.17 0.69 0.37 Carbon disulfide 1.29 1.04 1.40 0.33 0.40 0.34 Carbon tet 0.10 0.09 0.08 0.07 0.11 0.21

S-6 0.51 NA 0.16

S-7 0.52 NA 0.15

Individual CV ratios were calculated for all detected chemicals at each site. Some interesting patterns emerge. Please notice:

Benzene levels are somewhat variable at all sites. The highest variability occurs at site 4, (the dump) which is also where the highest concentrations are recorded. This pattern is typical of many chemicals in this study. Carbon disulfide levels are least variable at the sites that record the highest concentrations, and most variable at those sites where lower levels are measured. (and which are farther removed from NG activities) No other chemical is seen to act like this at all. CV ratios remain low for carbon tetrachloride across the network.

Are these concentration figures for CS2 under-reported? The ERG lab detected carbon disulfide in 92 of 92 samples in this study, at concentrations ranging from 0.008 to 1.64ppb. Because these samples were collected using stainless steel Summa canisters, I believe there is some reason to suspect that all of these figures might be significantly under-reported. The tendency for sulfur compounds to react with and degrade inside stainless steel canisters is well documented; and the interested reader should be able to find ample literature on this subject. The following passage appears on the website for Columbia Analytical Services, a leading analytical lab specializing in sulfur gas analysis:
Since many sulfur compounds are not stable in stainless steel canisters, such as Summa canisters, air samples for this analysis should be collected in Tedlar bags. When the odor is intermittent, unpredictable, or at a remote location, Columbia Analytical may recommend the use of a Silco (glass lined) canister. Please contact the lab for more information on sampling media for sulfur compounds.

11


Due to the unstable and reactive nature of many sulfur compounds, full compliance of the method requires analysis of the samples within 24 hours of collection.19

When the California Air Resources Board monitored carbon disulfide emissions at a series of agricultural fumigations in 2006, they chose to utilize Silco canisters in place of Summa canisters.20 The full report, which includes a description of the sampling methodology, is available on-line. Based on my own experiences collecting field samples for sulfur gas analysis; and on the results of recent studies published by TITAN, Kleinfelder, and others; I suspect that the concentration figures for carbon disulfide presented in the FWNGAQ study probably are underreported to some degree. I personally dont view this as an insurmountable problem, or as a major issue with this report. Here is the crux of the matter in my view:

The ERG lab has been able to demonstrate the sensitivity to detect and quantify carbon disulfide in every sample across an extended network - with precision. This type of capability has not been demonstrated in previous air studies conducted in the Barnett Shale.

We know we need better numbers - even if were not sure what they mean. If we get better information in the future, and if these concentration figures are eventually seen as needing adjustment in some direction, then thats terrific, in my view. Better data is always good. In the case of CS2; I think it is fairly clear that different field methods might be expected to yield significantly different results at this point. Hopefully, this will not be used as an excuse to stop monitoring for this chemical. It is important to keep in mind that due to gaps in the knowledge base regarding carbon disulfide, US EPA and ATSDR have been unable to 12

establish a dose-response relationship in humans,21 and that better information is clearly needed in this area as well.

Point-Source Emissions Evaluation

A very different animal Subsequent to the ambient monitoring phase, ERG contracted with Sage Environmental Consulting LP. (SAGE) to perform extensive leak detection and air sampling work at NG facilities throughout the FW area. The point-source evaluation team took to the field equipped with IR imaging gear, hydrocarbon sniffers, and other specialized sampling equipment for the purpose of identifying leaks and characterizing emissions of various types at natural gas production facilities. Objectives for this phase of the project included attempts to calculate TOC, VOC, and HAP emissions rates for each of the 388 sites visited. Air monitoring activities were driven by the leak-detection activities, and sampling protocols were built around efforts to obtain representative air samples from several different types of detected sources. This point-source emissions evaluation was another enormous undertaking; which was also well documented and explained in the report. The actual emissions monitoring that occurred in support of this project was very different in nature to what occurred in the ambient phase, although Summa canisters and the TO-15 analytical method were utilized for some of the samples collected at some of the sites. The list of VOCs included for analysis is this phase was far more limited than in the ambient study, and did not include CS2.22 The innovative study design incorporated by ERG and SAGE included a combination of hi-tech gadgetry, complex math, down-and-dirty monitoring techniques, and a ton of leg work. Every site was scanned end-to-end with infrared imaging equipment; every fitting and every valve was accounted for; and all of this was documented in the report. This point-source study is fascinating for a number of reasons, and seems to reflect some new thinking. The fact that researchers found it necessary to make key modifications to the monitoring plan during the course of the study reflects both the novelty of the study design, and the ambitious nature of the project as a whole. I have some general comments about this phase of the project, and I would like to make a few things clear before I continue: 13

All of my comments are based on my reading of the FWNGAQS. I have not reviewed any of the supporting documentation, lab reports, IR video files, etc. I have no expertise in dispersion modeling or estimating emissions rates. I think this was a cool study. I wish they had included some testing for sulfur compounds

Another Big Step Forward The amazing thing, which seems almost unbelievable really, is that they did this at all. Teams went into the field, scanned everything with IR, sniffed out leaks, counted valves, named names, and then made all of the data available to the public in this report, including IR video clips apparently. Bravo; I say. If some of their data inputs might have left a little to be desired; at least the point source team used consistent methodology throughout the study, and attempted to maintain a level playing field in this way. During the study, the team identified emissions from 252 tank thief hatches, 175 storage tank vents, and 489 leaking pneumatic valve controllers. The point source emissions team made some important findings as to the relative makeup and magnitude of these tank vs. non-tank emissions.23 The researchers also quickly determined that the IR imaging devices were capable of detecting more emissions than they had anticipated; and needed to scale down the monitoring plan accordingly, as the original sampling protocols would have required considerably more canisters than the project had budgeted for. 24

Emissions Rate Estimates Because no sulfur species were included in the monitoring for this phase of the project, and especially because only some types of emissions sources were considered, its hard to know just what to make of some of these estimates of facility emission rates. It seems pretty clear that the methodology employed by the point source emissions evaluation team was better suited to the well pads, of which they visited 375, than to some of the more complex facilities on the list. 14

In the case of the lone gas processing facility that was visited, entire categories of emissions were ignored, including those from vent stacks and flares. This facility, the Crosstex Amine Treatment Center, was estimated to release 80 tons per year (tpy) of VOC emissions, and represents the single largest emissions source identified in this study. For purposes of this study, in most cases, the emissions were calculated from only those sources in which emissions were detected and/or could be measured following the procedures described . . . . . . other sources of emissions, including but not limited to, storage tank breathing and standing losses, glycol dehydrator reboiler vents, wastewater and/or condensate loading, and flaring were not calculated.25

I want to make it clear that I am not challenging any of these emissions estimates. I know very little about emissions estimating. My only personal interest in estimated emissions rates for industrial sources lies in how these figures might be seen to relate to measured concentrations of sulfur species on the ground.

Monitoring vs. modeling My personal bias favoring measured concentration data over estimated concentrations reflects my own background as an air monitoring technician. Please accept my comments on this subject with this admitted bias in mind. The science of estimating emissions rates and modeling downwind impacts is exceptionally complex, and I think the authors do an excellent job of describing exactly how they did what they did in this section of the report. There is little mystery as to how the researchers arrived at their various calculations, as most of this is spelled out in detail. The following excerpt is an example of how the data from just one sample was integrated into the emissions estimates; and is provided here as an example of just how complex some of this can get; and how carefully the authors have explained their methodology. 1. The non-canister total organic compound emission rate was calculated by the nontank correlation equation. For the tee union with a % CFM of 0.39 the TOC emission rate was 11,644.25 lb/yr calculated as: LR 2.3759*e * 0.39 11,644.25lbs / year 9.674501743 1.250318323 = = . Where: LR = TOC Leak Rate. 2.3759 = SBCF 15

9.674502= non-tank correlation equation intercept.26 Downwind impacts modeled Yet another major undertaking of this project involved the characterization of downwind impacts, and estimations of worst-case scenarios for concentration of various pollutants at facility fencelines; and at distances 200 and 600 ft beyond those fencelines. In Table 5.3-1, on page 248 of the report, the authors compare their modeled predictions for some of the chemicals to the maximum levels measured, and discuss possible explanations for some of the rather large discrepancies in both directions. The reader is encouraged to view this table. In the following passage, the authors discuss the estimated concentration figures for benzene and formaldehyde, both which were estimated at levels higher than they were measured.

. . .the measured concentrations were intended to reflect some of the highest siterelated air quality impacts; however, the monitoring generally did not occur at fence line locations, and the point source testing revealed that the ambient air monitoring stations were not close to some of the highest-emitting well pads This discrepancy most likely explains why, for these two pollutants, the modeled concentrations were considerably higher than the measured ones.. The study authors chose not to include a comparison of monitored vs. measured results for carbon disulfide, or to try to account for the large discrepancies between their modeled worst-case scenario estimates and levels of CS2 detected near NG activities in this, and other recent studies.

Table 5.3-3. Modeled Annual Average Concentrations and TCEQ Long-Term Screening Levels27

Pollutant

Highest Estimated Annual Average Concentration at Locations 200 Feet Beyond Fence Lines ppb 0.24 0.00021

Lowest TCEQ Long-Term Health-Based Screening Level

Type

Benzene Carbon disulfide

1.4 1 16

ESL ESL

Carbon tetrachloride Formaldehyde

0.00096 4.34

2 2.7

ESL ESL

. . . and H2S is not a Hazardous Air Pollutant. In the point-source evaluation, emissions estimates are calculated for several categories of pollutants including Total Organic Compounds, (TOC) Volatile Organic Compounds, (VOC) and Hazardous Air Pollutants (HAP). The following definitions are provided: TOC are the sum of non-VOCs and VOCs. VOCs are the sum of non-HAP VOCs and HAPs. Criteria pollutants are VOCs, particulate matter (PM), Oxides of Nitrogen (NOx), Carbon Monoxide (CO), and sulfur dioxide (SO2). 28 I include this because I think this is an area where many people might become confused. For the record: Carbon disulfide and carbonyl sulfide are both VOCs (although one
rarely sees carbonyl sulfide categorized in this way, or included in VOC monitoring)

Carbon disulfide and carbonyl sulfide are both HAPs (in a big way,
but neither are monitored here)

H2S is none of the above.

Hydrogen sulfide is an inorganic compound that is not identified by EPA as a Hazardous Air Pollutant under the Clean Air Acts of 1990, (CAA) although it remains quite deadly.29

Regulatory Analysis
A whole new ballgame now On July 28, only two weeks after the release of the FWNGAQS final report, EPA unveiled its long-awaited proposal for sweeping changes to federal NSPS and NESHAPS30 rules governing oil drilling and the natural gas industry. Because of this; analysis of federal regulations provided by ERG in the FWNGAQS must now be viewed as pertaining only to the existing rules, most of which will now become obsolete. The regulatory analysis provided by ERG is presented as a general overview of potential issues raised by findings of the study, and was

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never intended to represent or include full-blown compliance audits at any of the visited facilities. This was all clearly communicated. Due to the limited scope of the study, the authors were unable to make determinations regarding compliance status for many of the applicable subsections of the state and federal rules.31 This subject is addressed in section 6.4 of the report; Regulatory Assessment Conclusions:

. . . For many of the rules potentially applicable to oil and gas sources in Fort Worth, we were unable to make a definitive determination on whether the source was subject to the rule, and/or whether the source was in compliance with the rule. 32 Oh, Oh, Oh, Oh. In their analysis of existing federal NSPS regulations, ERG explored the applicability of two of the rules subparts: KKK and LLL.33 (Under the newly-proposed NSPS rules; these two subparts will be eliminated and replaced with subpart OOOO, in which EPA asserts broad new regulatory authority under CAA. Many of the rules outlined in subpart OOOO involve previously unregulated NG production activities.) The FWNGAQS authors found that site 159; the Crosstex Amine Treatment Center was potentially subject to Subpart KKKEquipment Leaks of VOC from Onshore Natural Gas Processing Plants This rule requires VOC leak detection and repair at facilities that remove natural gas liquids from field gas. Site PS-159 (the Crosstex Amine Treatment Center) could be subject to this rule. However, status of compliance with the monitoring requirements under this rule cannot be determined using the data obtained at the time of the survey. Our gas is not the sour gas Because natural gas in the Barnett Shale is not considered to be sour natural gas none of the facilities in Fort Worth are identified as being subject to Subpart LLLOnshore Natural Gas Processing: SO2 Emissions Sour natural gas is natural gas with an H2S concentration greater than 0.25 grains per 100 standard cubic feet. The natural gas in the Barnett Shale is not considered to be sour natural gas, so this rule does not appear to apply to any facilities in Fort Worth. The same language is echoed a few pages later in a section addressing 18

the applicability of a TCEQ rule regarding the Control of Air Pollution from Sulfur Compounds. 34 Compliance with the ground-level concentration requirements under this rule cannot be determined using the data obtained at the time of the survey. As mentioned previously, the natural gas in the Barnett Shale is not considered to be sour natural gas, so this rule does not appear to apply to any facilities in Fort Worth. This part has always puzzled me. We are being told that gas sweetening units in Fort Worth are exempt from regulation of sulfur emissions because the gas they are sweetening was never considered to be sour in the first place. The authors do offer a clear definition of sour gas based on H2S content; but do not provide any specifications for H2S in the feed gas entering the processing facility visited in the study, or provide any other explanation as to why any of the very nice gas in the Barnett Shale might ever even have to visit a place with a such a scary name as the Crosstex Amine Treatment Center. Acid Gas Defined On page 408 of the internet version of its proposed new regulations, EPA offers the following definition of the term acid gas. 35 "Acid gas means a gas stream of hydrogen sulfide (H2S) and carbon dioxide (CO2) that has been separated from sour natural gas by a sweetening unit."

This easy-to-digest description of acid gas is consistent with information regarding acid gas removal from natural gas streams published previously by EPA36; but the language here is so over-simplified as to be dangerously misleading in my estimation. Especially considering that this is being proposed as regulatory language; this definition of acid gas - because it excludes the highly toxic gases carbonyl sulfide and carbon disulfide - has the potential to become extremely problematic from a public health perspective. These particular contaminants are known to be associated with these particular waste streams. These are highly toxic substances. These streams are sometimes vented to atmosphere legally. I believe everyones 19

interests will be better served by improved clarity and specificity from EPA on this subject.

Meet the Pipeline Spec In the natural gas industry, carbonyl sulfide and carbon disulfide are sometimes referred to as the sulfur acids, the organo-sulfur compounds, or simply organic sulfur. Effective removal of these compounds from gas streams on a large scale requires specially designed facilities which are extremely expensive both to build and to operate. Efforts to develop more cost-effective treatment solutions for gas streams containing carbonyl sulfide and carbon disulfide have become a major focus for industry in recent years. This is true in natural gas processing; and especially at domestic oil refineries, which increasingly rely on ready supplies of inexpensive, high-sulfur crudes. Literature on this subject is widely available in various trade publications and technical journals. 37.38 The following information, including the table containing Typical Gas Pipeline Specifications is lifted from the website of Q.B. Johnson Manufacturing, Inc. According to information posted on the site, this outfit specializes in the planning, design and construction of gas processing facilities to fit a wide variety of applications for clients in the natural gas industry.
In addition to H2S and CO2, the sulfur acids, carbonyl sulfide (CS2), carbon disulfide (COS) and the mercaptan family (RSH), when present in sufficient quantities, are also candidates for removal with specific amines.

Typical Gas Pipeline Specifications: 39 H2S CO2 CS2, COS, RSH 0.25 grain/100 scf or 4 ppm 2-3 mol% (5% inerts) 20 grains/100 scf

I have not been able to confirm any the information in this table, which was downloaded from http://www.qbjohnson.com. I am still actively seeking information regarding these specifications. For my own purposes, until I am able to locate reliable information to the contrary, I will assume that these figures are legitimate and not some type of hoax. If the information presented in this table is accurate; and if pipeline specifications allow for levels of carbon disulfide which are some 80x 20

greater than those allowed for hydrogen sulfide, then I think this fact might help to explain some of the results of the recent air sampling surveys in the FW area. If this information does help to provide some answers though; at least in my mind, it also raises these two immediate questions:

Why are we only talking about hydrogen sulfide in the sour gas and acid gas streams? and Why, in regards to carbon disulfide, do we just keep looking the other way?

Thank you very much for your attention in this matter. My name is Andy Mechling. I live in rural southwestern Oregon. I have no affiliation of any kind. Opinions expressed have been my own. I can be reached at firemappr@yahoo.com or (541) 660-8964. I look forward to your questions or comments.
1City

of Fort Worth Natural Gas Air Quality Study Final Report: 7.13.2011 Eastern Research Group, Inc., Sage Environmental Consulting, LP.
2

I did pass a course Probability and Statistics as an undergraduate student at Whitman College in 1981. This was a challenging course. I think I got a C. I hold BAs in History and Communications.
3

Table 5.2-3 Program-Average Concentrations and TCEQ Long-Term Screening Levels pp 241-245.
4

2.5.3 Key Pollutants p67. Health Evaluation for Measured 24-Hour Average Concentrations
Comparing 24-hour average measurements to long-term health-based screening values is scientifically inappropriate and is not done in this report. p232.

55.2.2

2.4 Quality Assurance/Quality Control, Table 2.4-1. pp35-36. Data Quality Objectives, Table 5.2-1. discussion pp226-227.
7

2.6 Ambient Air Monitoring Conclusions p90. Measurement Accuracy

Accuracy for the VOC and carbonyl analyses was established through audits that EPA prepared and submitted to ERG as a regular function of the EPA National Air Toxics Monitoring Program, which ERG manages and operates for EPA. p39.

82.4.3

21

Table 2.4-5. VOC and Carbonyl HAP Audit Results p39.

10City

of Fort Worth Natural Gas Air Quality Study : Interim Ambient Air Monitoring Report. 2.11.2011 Eastern Research Group, Inc. 7.1.1 VOCs p35.

11Lower

quality; not low quality. Test America / Austin produces high quality air data in this study; but in this study; their lab was clearly second best. The ERG lab produces higher quality data, as is clearly documented in the report.
12This

table was compiled by me utilizing information provided in Tables 2.5-4 through 2.5-9 regarding Pollutant Study Averages pp50-62.
13Key

findings from the ambient monitoring studyp90.

14 15

2.0 Ambient Air Monitoring p18. 5.2.1 Sensitivity of Monitoring Methods p226. Site S-5 (High-Level Activity Site, Collocated) This sites location has a high level of natural gas activity and is within a mile of dozens of natural gas wells upwind of this station. p26.

162.1.5

17Please

notice that this figure reads ten parts-per-trillion. Here we finally gain access to detailed information regarding ambient background levels of carbon disulfide in the FW area. This is Urban Ambient Air - and thats Trillion with a T.
18

Table 7-4: Pollutant CV Ratios at Each Monitoring Site Interim Report: p53. http://www.caslab.com

19 20

Carbon Disulfide Method Development and Analytical Results for Kern County Air Monitoring Samples Collected in Six-liter Silco Canisters after Application of Sodium Tetrathiocarbonate California Air Resources Board; December 2006.

21Toxicological

Profile for Carbon Disulfide: 1996. Agency for Toxic Substances Disease Registry (ATSDR) EPA, CDC. Themonitoringdataavailableforcarbondisulfidearetoolimitedtoallow adequatecharacterizationofpotentialhumanexposuretothecompound.
The biggest drawback in the existing studies is the lack of the ability to establish a dose relationship between exposure and effect. More precise measurements of exposure, control of exposure to other chemicals, and long-term follow-up of occupational cohorts may lead to a better understanding of the dose-effect of carbon disulfide.

22


22

Table 3.6-16. pp180-187

23Table

3.4-1: Comparison of Emissions Between Tank and Non-Tank Emission Sources p117.
243.3.7

Canister Sampling . . . However, as Phase I testing commenced, it became apparent that the sampling teams were observing an unexpectedly high frequency of cameradetected emission points. Therefore, an alternative canister sampling strategy was needed; neither the project budget nor laboratory resources would be able to keep up with the canister demand. p107.

25 26

3.4 Emissions Calculation Procedures p113. 3.4.4 Applying Canister Results to Non-Canister Emission Points p118.

27Table

5.3-3: Modeled Annual Average Concentrations and TCEQ Long-Term Screening Levels p257.
28

3.5 Point Source Emissions Results p123.

29This

compound did appear on EPAs original list of 190 HAPs, but was de-listed in the very early 1990s by the agency; apparently at the request of then-president George H.W. Bush.
30NSPS

are New Source Performance Standards. NESHAP are National Emissions Standards for Hazardous Air Pollutants.
31

6.1 Federal Air Quality Rules 6.2 p278, Texas Commission on Environmental Quality Air Quality Rules p283.
326.4
33

Regulatory Assessment Conclusions p288.

6.1.3 New Source Performance Standards p279. Control of Air Pollution from Sulfur Compounds p286. PROTECTION AGENCY 40 CFR Parts 60 and 63 RIN 2060-AP76 Standards of Performance for New Stationary Sources: Oil and Natural Gas Production and Natural Gas Transmission and Distribution; National Emission Standards for Hazardous Air Pollutants From Oil and Natural Gas Production Facilities; and National Emission Standards for Hazardous Air Pollutants From Natural Gas Transmission and Storage
Facilities

346.2.5

35ENVIRONMENTAL

60.5430 What definitions apply to this subpart? p408. 23


36Acid

Gas Removal Options for Minimizing Methane Emissions

Lessons Learned from Natural Gas STAR Producers Technology Transfer Workshop Long Beach, California August 21, 2007 epa.gov/gasstar
37

An Ace at RemovalOlafvonMorstein,JohannesMenzel,UhdeGmbH,GermanyandNagaraju Palla,DennisLeppin,GasTechnologyInstitute,USA,discussthefirstcommercialapplicationofanew physicalsolventforacidgasremoval.(onlinearticlereprintedfromHydrocarbonEngineering February2004)

38The

low-temperature hydrolysis of carbonyl sulfide and carbon disulfide: a review

Catalysis Today, Volume 59, Issues 3-4, 25 June 2000, Pages 443-464Colin Rhodes, Stewart A. Riddel, John West, B. Peter Williams, Graham J. Hutchings The impetus to reduce the emission of sulfur-containing compounds into the environment has become increasingly important in recent years. This paper reviews the progress made towards reaching this goal and highlights the significant contributions made towards developing effective catalysts for the removal of carbonyl sulfide and carbon disulfide. Novel promoter materials, new catalyst morphologies, new reactor designs and developments for the future are reviewed and discussed.
39

http://www.qbjohnson.com
Q. B. Johnson Manufacturing, Inc. can engineer, design and manufacture treaters for any application. We have successfully provided treaters for natural gas field installations, refinery off gas sweetening applications, liquified ethane CO2 treating, raw NGL treating and others. If you have an application requiring H2S, CO2 or any of the sulfur acids removal, please contact . . .

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