On a 2012 speaking tour in Michigan, citizens asked Ernst what was going to happen to all the toxic waste.
Ernst replied, “We’ll be made to eat and drink it.”
For Immediate Release
April 19, 2017
Chemical regulations that govern hydraulic fracturing do not apply to numerous other uses of the same chemicals on oil- and gas-development fields.
OAKLAND, Calif. – California and more than two dozen other states require oil and gas producers to disclose the chemicals they use during hydraulic fracturing activities, enabling scientific and public scrutiny of the environmental and human health hazards these substances may pose. But all existing disclosure regulations cover chemical use only in hydraulic fracturing, known as fracking, and, in California, two other types of well-stimulation treatments. Many of the same chemicals used in hydraulic fracturing go undisclosed when they are used in numerous routine, unregulated oil- and gas-field activities such as the drilling, cleaning and maintenance of wells, according to a study published in PLOS ONE today (April 19) [PAPER ALSO INCLUDED BELOW]. The study, conducted by scientists at the Lawrence Berkeley National Laboratory, University of the Pacific and the California-based energy science and policy institute PSE Healthy Energy, is the first published research to investigate chemicals used in unregulated routine oil- and gas-field activities, including the overlap between chemicals used in both regulated and unregulated activities.
Analyzing publicly available data of chemical use in oil and gas production operations in the Los Angeles Basin, researchers found that the number of the chemicals used for routine activities is as high or higher than the number used for hydraulic fracturing, and those chemicals are used frequently and in high quantities. Further, the disclosure data showed that the same chemicals used in hydraulic fracturing were also used in more than half of recorded routine activities, which are unregulated. For example, they found common use of biocides, a class of hazardous chemicals that includes formaldehyde, and acidizing agents including hydrofluoric acid, in both regulated well-stimulation activities and unregulated routine activities. These findings have major implications for chemical disclosure policies and risk assessments of oil and gas development in California and across the nation, the researchers concluded.
“Policies that focus exclusively on hydraulic fracturing or well stimulation miss a huge swath of chemical usage that poses environmental and human health hazards,” said Seth B.C. Shonkoff, executive director of PSE and corresponding author on the study.
“Especially as water produced by oil and gas development is increasingly used to replenish aquifers, irrigate agriculture, water livestock and increase stream flow around the country, we need to know, more than ever, what’s in it. Policies that govern chemical use in oil and gas development should apply to all uses — none of these known hazardous substances should be getting a free pass,” he said.
Same chemicals, different rules
Scientists analyzed data from the South Coast Air Quality Management District, which encompasses the densely populated Southern California counties of San Bernardino, Orange, Riverside and Los Angeles — the second most productive oil and gas region in the third largest oil producing state in the United States, according to the study authors. The air district’s unique chemical disclosure rules for the oil and gas sector provided researchers with the only existing source of chemical use in routine activities in the United States; unlike the rest of the state, oil and gas operators in the jurisdiction must publicly disclose chemical-usage information related to most oil and gas activities, not just in fracking and well stimulation.
The analysis found that of the 548 chemical additives reported to the Los Angeles Basin database, 525 of those – about 95 percent – were used in activities that do not require disclosure under statewide policy. The most frequently used chemicals included solvents, petroleum products and salts, which are blended for production uses; carboxylic acids, which are used to control scale and iron; corrosion inhibitors; and hydrochloric and hydrofluoric acid, which were used extensively and in large quantities for well cleaning and routine maintenance.
Biocides, a class of hazardous chemicals that kill bacteria, were used in 63 percent of routine events recorded, compared to 93 percent of hydraulic fracturing treatments. In routine uses, the most commonly used biocides were formaldehyde, a preservative with numerous medical and industrial applications, which was used in 57 percent of events; and glutaraldehyde, a disinfectant with a variety of applications in medical settings, which was found in 23 percent of events.
“A comparison within the statewide database shows a significant overlap between both types and amounts of chemicals used for well-stimulation treatments included under California’s mandatory-disclosure regulations and routine activities that are currently excluded from state regulations,” said study lead author William Stringfellow, director and professor of the Ecological Engineering Research Program at University of the Pacific in Stockton, California, and an environmental staff engineer at Berkeley Lab.
Due to the extent of chemical usage and the overlap with chemicals that are regulated when used during hydraulic fracturing, researchers called for further study and more policies that expand beyond a focus strictly on hydraulic fracturing.
“Given concerns regarding the use and release of hazardous chemicals during oil and gas development around the country, the increasing reuse of produced water and its rising potential for human exposure, it is important to evaluate chemicals put down wells for any purpose, not just those used during the limited phase of hydraulic fracturing,” Shonkoff said.
Increase in Chemical-Exposure Pathways
An increased interest in expanding the reuse of produced water — water generated as a byproduct of oil and gas production — for food-crop irrigation and aquifer recharging, along with oil and gas fields increasing being co-located in areas of high population density like the Los Angeles Basin, increases the potential for chemical exposures. Hazards posed by these chemical additives are in addition to those posed by naturally occurring constituents of produced water, such as salts, heavy metals, volatile organic compounds, hydrocarbons and naturally occurring radioactive materials. The authors also note that they found many chemicals in use that were considered low-risk for human and environmental exposures.
The study was the outgrowth of research published in 2015 to bring California in compliance with the state’s 2013 Senate Bill 4. In addition to requiring disclosure of chemical use in hydraulic fracturing and two other types of well stimulation treatments, the bill mandated an independent scientific study to identify and describe the hazards, risks and impacts of hydraulic fracturing and oil and gas development throughout the state. Shonkoff, who is also a visiting scholar at the University of California, Berkeley, and an affiliate of Berkeley Lab, was the lead author on the public health portion of that report, which was produced on behalf of the California Council on Science and Technology.
“When we evaluated the reported hydraulic-fracturing chemicals, we saw numerous other chemicals that were unaccounted for in the disclosures,” Shonkoff said. “We saw that there’s a lot we don’t know about the chemicals used in non-hydraulic fracturing events in oil and gas fields — that information gap can put the public’s health at risk.”
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PSE (Physicians, Scientists and Engineers) for Healthy Energy is a nonprofit research institute dedicated to supplying evidence-based scientific and technical information on the public health, environmental and climate dimensions of energy production and use. We are the only interdisciplinary collaboration focused specifically on health and sustainability at the intersection of energy science and policy. Visit us at psehealthyenergy.org and follow us on Twitter @PhySciEng.
The potential hazards and risks associated with well-stimulation in unconventional oil and gas development (hydraulic fracturing, acid fracturing, and matrix acidizing) have been investigated and evaluated and federal and state regulations requiring chemical disclosure for well-stimulation have been implemented as part of an overall risk management strategy for unconventional oil and gas development. Similar evaluations for chemicals used in other routine oil and gas development activities, such as maintenance acidizing, gravel packing, and well drilling, have not been previously conducted, in part due to a lack of reliable information concerning on-field chemical-use. In this study, we compare chemical-use between routine activities and the more closely regulated well-stimulation activities using data collected by the South Coast Air Quality Monitoring District (SCAQMD), which mandates the reporting of both unconventional and routine on-field chemical-use for parts of Southern California. Analysis of this data shows that there is significant overlap in chemical-use between so-called unconventional activities and routine activities conducted for well maintenance, well-completion, or rework. A comparison within the SCAQMD shows a significant overlap between both types and amounts of chemicals used for well-stimulation treatments included under State mandatory-disclosure regulations and routine treatments that are not included under State regulations. A comparison between SCAQMD chemical-use for routine treatments and state-wide chemical-use for hydraulic fracturing also showed close similarity in chemical-use between activities covered under chemical disclosure requirements (e.g. hydraulic fracturing) and many other oil and gas field activities. The results of this study indicate regulations and risk assessments focused exclusively on chemicals used in well-stimulation activities may underestimate potential hazard or risk from overall oil field chemical-use.
Received: January 28, 2017; Accepted: March 26, 2017; Published: April 19, 2017
Funding: This material is based upon work supported by the Department of Energy under Award Number DE-IA0000018. This study was supported in part by grants from The Broad Reach Fund and Laboratory Directed Research and Development (LDRD) funding from Berkeley Lab, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-05CH1123.
Competing interests: The authors have declared that no competing interests exist.
Introduction [NOT ALL VISUALS INCLUDED BELOW. CLICK FOR COMPLETE PAPER WITH ALL VISUALS]
Scientific, regulatory, and public debates on the environmental and public health dimensions of oil and gas development have been focused on hazardous chemicals used for hydraulic fracturing and other well-stimulation treatments, such as matrix acidizing, that are classified as “unconventional” oil and gas development methods [1–4]. Consequently, new regulations that govern oil and gas development require disclosure of chemical-use during well stimulation activities, but do not require disclosure of chemicals used for any other oil and gas field activities [1,2,4]. However, potentially hazardous chemicals are used throughout the entire oil and gas development process, not just during well stimulations [5–9], so there is interest in examining overall chemical-use on oil and gas fields and comparing chemical-use between regulated “unconventional” development activities and other oil and gas field activities.
Disclosure of chemical-use during well stimulation is considered an important requirement for the protection of human and environmental health, since knowledge of the types and amounts of chemicals used is fundamental to risk assessment . Recent Federal and State regulations mandate chemical disclosures for well stimulations, including hydraulic fracturing and in some cases matrix acidizing and acid fracturing, but reporting chemical-use for other oil and gas field activities, such as well drilling, well completion, well maintenance, and well re-work is not required, unless pressures above the fracture gradient are used [1,2,4,11].
Given the public and scientific concern regarding the use and release of hazardous chemicals during the current oil and gas development boom  and the reuse of oil and gas field produced water for beneficial purposes in arid regions [13–15], it is important to evaluate the potential environmental and public health impacts of all chemical additives used in oil and gas development.
Chemicals are used routinely in oil and gas development as part of drilling and cementing of the well casing, repair of formation damage, wellbore clean-outs, scale and corrosion control, and for other production activities. Chemical additives are also used in enhanced oil recovery (EOR) to change fluid properties of oil (e.g. viscosity) and to otherwise increase production of oil within the formation . During well construction, hazardous chemicals may be added to drilling fluids, drilling muds, and cements and are also used to remove debris from wellbores prior to cementing of the annular space between the steel casing and geological formations [9,17]. Chemical additives, including strong acids, are also used for well completion and rework to facilitate hydrocarbon production.
While large numbers and masses of chemical additives are used in routine oil and gas development activities, only a few surveys of routine chemical-use by the oil and gas industry have been conducted [5–8,18]. There is widespread use of potential chemicals of concern, including biocides, quaternary ammonium compounds, and corrosion inhibitors both off-shore and on-shore [5–8,18]. In contrast, several studies examined chemical-use during well stimulation activities, including hydraulic fracturing and matrix acidizing [19–24]. It has been established that chemicals used during well stimulation treatments have environmental pathways of exposure which include accidental spills, reuse of treated produced water, improper zonal isolation of fluids in the subsurface infrastructure and geologies, and discharge of wastewaters to aquatic ecosystems [3,21,24]. It is also known that produced water has similar exposure pathways, so it is of interest to determine overall oil and gas field chemical-use when evaluating the potential environmental and health impacts of oil and gas development.
The reuse of produced water for agricultural purposes is permissible in the western US and produced water is being reused for irrigation, watering livestock, aquifer recharge, and other purposes [13–15,24–26]. In California, produced water from oil fields is used for food crop irrigation, livestock watering, groundwater recharge, and for wetlands and other environmental purposes [15,27]. There are concerns that oil field chemicals or their degradation products will occur in produced water and that these chemicals may pose an unrecognized hazard or risk for produced water beneficial reuse, since potential exposure pathways from beneficial reuse include chemical uptake or deposition on food crops, contamination of regional aquifers through recharge, and the direct contact of farmworkers with produced water . The hazard posed by oil and gas field chemicals would be in addition to other hazards associated with naturally occurring constituents of produced water, such as salts, metals, aromatic hydrocarbons, and naturally occurring radioactive material. The increased interest in reusing produced water [13,28] suggests that the hazards associated with oil and gas field chemicals should be evaluated.
The objective of this study is to assess chemical-use during routine oil and gas development and to compare chemical-use in routine production activities with chemical-use during well stimulation. To our knowledge, only one regulatory agency in the US, the South Coast Air Quality Management District (SCAQMD) in Southern California, requires mandatory disclosure of on-field chemical-use for well drilling, well completion, and well rework activities. These data were used by Abdullah et al.  to characterize chemical-use in acidizing. We use these data to compare chemical additive use between well-stimulation (hydraulic fracturing and matrix acidizing treatments) and routine oil field activities to determine similarities and differences in chemical-use. We summarize the chemicals used with respect to frequency of use, masses applied, and toxicity data. Similar data driven approaches have been used previously to evaluate hazards associated with hydraulic fracturing and matrix acidizing [19,21]. The results of our analysis are interpreted in the context of public and scientific concerns about hydraulic fracturing and the beneficial reuse of produced water.
Chemical-use data reported to the South Coast Air Quality Management District (SCAQMD) in southern California was analyzed in this study . Under SCAQMD Rule 1148.2, which went into effect on June 4, 2013, operators and chemical suppliers are required to submit and make publicly available chemical usage data related to routine oil and gas activities (well drilling, well completion, and well rework) and well stimulation (hydraulic fracturing, matrix acidizing) in the California counties of San Bernardino, Orange, Riverside, and Los Angeles, including the City of Los Angeles . These counties represent the second most productive oil and gas region in the third largest oil producing state in the United States. Chemical-use for enhanced oil recovery (EOR) and activities beyond upstream oil and gas development such as refining, transmission, and storage are not included in the SCAQMD datasets and are not included in this analysis.
Data on chemical type, mass injected, and water volumes used in oil and gas operations were downloaded from the SCAQMD database for the period of June 4, 2013 to September 2, 2015 . The dataset used for this study consists of 51,514 entries from 1,207 oil and gas “events” conducted at 302 unique locations (identified by latitude and longitude). Events were categorized by operators as well drilling, completion, or rework activities. For completion, activities were further categorized as acidizing, gravel packing, hydraulic fracturing, maintenance acidizing, matrix acidizing, or acid fracturing. In order to focus on routine oil and gas activities, we separated well stimulation events (hydraulic fracturing, matrix acidizing and acid fracturing) from other routine events in our dataset. Entries were edited to standardize chemical names and to validate the assigned Chemical Abstracts Services Registry Number (CASRN). Changes to names of proprietary chemicals that could not be identified by CASRN were limited to correcting obvious spelling errors (e.g., aicd to acid, kerosine to kerosene), changing capitalization, and altering punctuation (e.g. removing dashes). Proprietary chemicals with singular and plural names that indicate chemical mixtures (e.g., ionic surfactant vs ionic surfactants) were maintained as separate entries. In cases where duplicate event IDs were reported, data were consolidated into one event ID entry. In cases where multiple chemical information documents were reported for the same event ID, data were individually assessed and duplicates, where apparent, were deleted.
For the chemical additives identified by CASRN, toxicological data were collected from online chemical databases [30–41]. Computational models within the U.S. EPA EPI Suite software (e.g., BIOWIN) were used to fill data gaps when experimental data were unavailable. Rat, mouse, and rabbit acute oral toxicity data and rat and mouse inhalation toxicity data were collected to represent and compare mammalian toxicity among the chemical constituents. To assess acute environmental toxicity, data for water flea (Daphnia magna), fathead minnow (Pimephales promelas), rainbow trout (Oncorhynchus mykiss), and green algae were collected. Mammalian median lethal dose (LD50) and median lethal concentration (LC50) were used to assess mammalian hazard. Median effective concentration (EC50) and LC50 data were used to assess aquatic species hazard. Toxicity ratings were assigned using the United Nations Globally Harmonized System (GHS) of Classification and Labelling of Chemicals . In the GHS system, lower numbers indicate higher toxicity, with a designation of “1” indicating the most toxic category. When multiple GHS values were available for a given chemical, the lowest value was used. Chemicals for which the LD50, LC50, or EC50 exceeded the least toxic GHS category were classified as non-toxic.
Chemical were identified for further hazard assessment based on frequency of use, median mass of chemical-use per event, and available toxicity data. Frequency of use was calculated by dividing the number of events that utilized a given chemical by the total routine oil and gas events reported in the SCAQMD database. The median mass of chemical usage per event represents the median mass for all events containing that chemical. Where chemical mixtures were reported, individual chemical masses were calculated by multiplying the total mixture mass by the maximum individual chemical concentration. When multiple entries for a given chemical were reported for a single event, the chemical masses were summed within that event.
We compared the chemical-use in routine oil and gas activities in the SCAQMD dataset to hydraulic fracturing chemicals disclosed in the state of California via the voluntary FracFocus chemical disclosure registry, as summarized by Stringfellow et al. .
This dataset contains records of chemical use for 1,623 individual hydraulic fracturing operations conducted in California between January 30, 2011 and May 19, 2014. Stringfellow et al.  identified 338 unique additives based on name and CASRN combinations, of which 228 were reported with a CASRN and 110 were identified by chemical or common name only or had proprietary designations. The additives included chemicals, mineral proppants and carriers, and base fluids consisting of water, salt, and brine solutions. There were 326 unique additive names identified in the database .
Results and discussion
Chemical-use in the SCAQMD
In total, 548 chemical additives were used in the SCAQMD between June 2013 and September 2015, with 525 of these being used for routine oil and gas development activities. The most frequently used chemicals include solvents (e.g. methanol), petroleum products (e.g. distillates), and salts (e.g. sodium chloride) that are employed in formulating commercial blends of production chemicals (S1 Table). Also on the list of frequently used chemicals are carboxylic acids (e.g. citric acid and erythorbic acid) used for scale and iron control, biocides, and corrosion inhibitors. For routine acidizing (e.g., acid cleaning for well-maintenance), hydrochloric acid (HCl) and hydrofluoric acid (HF) were used extensively and in large quantities (mean masses of 1,791 and 161 kg per event, respectively). These quantities are consistent with the analysis by Abdullah et al. , who reported mean values of 1,908 kg HCl and 175 kg HF per acidizing event (also exclusive of matrix acidizing). Our values may differ due to the different study periods or deletion of duplicate entries by operators. Other additives used in the highest masses include minerals and other chemicals used for gravel packing (e.g. silica), cementing of well casings (e.g. Portland cement and additives), and sealing wells (e.g. bentonite) (S2 Table).
Table 1 is presented as an analysis of chemical use (numbers of chemicals used and masses) by reported activity. There were only a limited number of well-stimulation events in the SCAQMD during this period and no acid fracturing events were reported. Acidizing, maintenance acidizing, well drilling, and gravel packing accounted for the majority of the 1,207 events in the data set (Table 1). Chemical-use for these types of oil and gas field activities is only subject to mandatory reporting in the SCAQMD region.
Examining different types of acidizing within the SCAQMD, the median numbers of chemicals used in routine acidizing (20 for acidizing and 35 for maintenance acidizing) were similar in number to the median value of 20 used in matrix acidizing (Table 1). An analysis of chemicals used for acid treatments shows that there is considerable overlap in the chemicals used for the different applications of acid (Fig 2). The one compound used exclusively for matrix acidizing was identified only as “DDBSA salt,” presumably a dodecylbenzenesulfonic acid salt, but without a corresponding CASRN, this identification is tentative. Maintenance acidizing used a lower median mass of chemicals (2,028 kg) than treatments reported as acidizing (3,459 kg) or matrix acidizing (3,055 kg). These quantities demonstrate that additives usage in other acidizing is not appreciably different than what is used in matrix acidizing (classified as well stimulation).
Concentrations of hydrochloric acid (HCl) and hydrofluoric acid (HF) used in all types of acidizing events were similar, as were the total masses of additives used (Figs 3 and 4). Hydrochloric acid concentrations ranged from approximately 0–15% (Fig 3) while HF concentrations were approximately 0–3% (Fig 4). In California, the distinction between routine acidizing and acid stimulation (matrix acidizing and acid fracturing) is based on calculation of the acid threshold volume that is determined based on wellbore volume and formation porosity . The acid threshold volume cannot be calculated without site-specific information that is not reported to the publically available SCAQMD database. However, it is apparent that large quantities of acid and high concentrations are being used in all types of acidizing events.
Since there is clear overlap in concentrations and amounts of acid used for events reported as matrix acidizing, which are potentially regulated by state law, and routine maintenance acidizing (Figs 3 and 4), these results suggest that regulations focused only on disclosures of chemicals used in well stimulation events may not be sufficiently protective of public or environmental health.
Fig 3. Concentrations of hydrochloric acid (HCl) used in acidizing. Sixteen events where water was not reported were excluded because the concentrations could not be calculated.
Comparison of chemical-use between routine oil and gas development activities in the SCAQMD and hydraulic fracturing throughout California
The number of chemicals used in routine oil and gas development activities in the SCAQMD is as high or higher than the number of chemicals used for hydraulic fracturing throughout the State of California . In Stringfellow et al. , 338 unique chemical additives were identified as used in hydraulic fracturing fluids in California, with 228 of these identified by CASRN. These data were reported voluntarily by industry, but are believed to be representative of hydraulic fracturing as practiced in California [21,24,43,44]. Here, we identified 525 additives used in routine oil and gas production, with 249 identified by CASRN. In Stringfellow et al. , there was a median of 23 components per hydraulic fracturing treatment, inclusive of base fluids and proppants. In the SCAQMD, the number of additives per event varied by activity (Table 1). The median number of chemical additives was as low as three for gravel packing and the median number of chemical additives used in well drilling was much higher (54).
In the SCAQMD, the median mass used per hydraulic fracturing event was high (142,245 kg), but when water and quartz sand proppants were removed, the median mass of chemical additives was 6,725 kg. This is approximately three times higher than the value of 2,057 kg obtained by Stringfellow et al. , who analyzed voluntarily reported data from the whole state of California. This difference may be attributed to differences in regional reservoir geology between the SCAQMD and the rest of California  and corresponding hydraulic fracturing practices: most of the data analyzed by Stringfellow et al.  was reported from Kern County, CA while the data here originated primarily from Orange and Los Angeles Counties.
Of the 249 chemicals identified by CASRN that are used for routine oil and gas development in the SCAQMD (Table 2), 124 (24%) were identified by Stringfellow et al.  as being used for hydraulic fracturing in California, further demonstrating overlap in chemical usage between hydraulic fracturing and routine activities. Further examination of the types of chemicals used in routine oil and gas development activities and in hydraulic fracturing yields both similarities and differences.
As an example, ten biocides were identified in the hydraulic fracturing data set reported by Stringfellow et al.  while only six were identified here as used in routine activities. The biocides were used in 63% of routine activities conducted in the SCAQMD compared to 93% of hydraulic fracturing treatments . In routine use, the most commonly used biocides were formaldehyde, used in 677 (57%) events, and glutaraldehyde, used in 274 (23%) events. In the hydraulic fracturing treatments, isothiazolones were used in 73% of treatments [21,24]. This demonstrates that biocides are used extensively in different types of oil and gas production activities.
Corrosion inhibitors were used more extensively in routine operations than in hydraulic fracturing treatments. Ten corrosion inhibitors were identified in both the current data set and in the hydraulic fracturing data set , although the numbers are likely higher since many chemicals used as corrosion inhibitors also have other functions in oil and gas production (e.g. surfactants). In routine operations in the SCAQMD, corrosion inhibitors were used in 894 events (75% of all events), but they were only used in 6% of the hydraulic fracturing treatments . The prevalent use of corrosion inhibitors in the SCAQMD is not surprising given the common use of strong acids in well maintenance and completion activities.
The substantial overlap between chemicals used in hydraulic fracturing fluids and those used in routine oil and gas development processes clearly demonstrate that the regulatory focus on reporting chemical-use for well-stimulation activities (e.g. hydraulic fracturing) to the exclusion of routine maintenance activities (e.g. wellbore cleaning) does not fully address potential environmental and public health concerns from on field chemical-use, particularly in the context of beneficial reuse of produced water for agriculture . A more complete understanding of chemical usage–including type; toxicity and environmental profile; and mass, timing, frequency used–in routine oil and gas development is needed to support decision making with respect to beneficial reuse of produced water and this study contributes to filling this data gap.
Comparison of chemical-use between routine oil and gas development activities in the SCAQMD and other oil and gas fields throughout the U.S. and World
It is difficult to determine with certainty if chemical use on oil fields in the SCAQMD is representative of chemical-use on oil fields throughout the U.S. or the world, since data on chemical-use is rarely collected by governments or published by industry.
Hudgins analyzed and published chemical-use data provided voluntarily by off-shore operations in the Gulf of Mexico  and the North Sea . Comparison of the Hudgins’ studies with chemicals used in the SCAQMD shows that chemicals are used for common purposes, such as microbial control, scale control, and cleaning, at all locations [7,8]. Hudgins’ studies did not identify chemicals by CASRN, but some chemicals were identified sufficiently by name to allow positive identification of 47 chemicals from the North Sea study  and 25 chemicals from the Gulf of Mexico study . Thirty-five chemicals could be positively identified as being used in both the North Sea and in the SCAQMD and 15 were positively identified as being used in both the Gulf of Mexico and the SCAQMD. Overall, these results, combined with a review of industrial literature, patents, and other sources, suggests that many of the chemicals used on the SCAQMD, or closely related compounds, would be found on oil fields worldwide [5–8,19–22,45].
Analysis of chemical hazards using data science approaches
One of the important requirements of regulations directed at oil and gas development and production is the disclosure of the types and amounts of chemicals used on-field [1,2,4,11,46]. Chemical disclosure is widely recognized as a fundamental prerequisite for the open and transparent analysis of the hazards and risks associated with chemicals [2,4,10,27,45,46].
[How can regulators like the legally immune, fraudulent, law violating, Charter violating, grossly negligent AER operating often in bad faith, “regulate” the oil and gas industry if the regulator staff and workers in the oilfields do not know what chemicals are being used, spilled, spread on foodlands, injected in massive amounts under massive pressure into community drinking water supplies like Rosebud’s, and vented and flared into air breathed by families, communities, visitors, livestock, wildlife, and dumped illegally into surface waters?]
Previous studies have shown that many oil and gas field chemicals are not expected to have negative environmental or health impacts, but that some compounds, including surfactants, biocides, and corrosion inhibitors may be harmful to the environment, and that in many cases there is insufficient information to confidentially evaluate the potential environmental impact of chemicals that are used in significant amounts on oil and gas fields [19–24,47,48].
A preliminary hazard assessment for oil field chemicals being used in the SCAQMD was conducted using data science methods applied against hydraulic fracturing chemicals [20,21]. As shown in Table 2, 52% of the chemicals used in the SCAQMD were reported without a CASRN and could therefore not be evaluated using a data science approach, which requires CASRN to match compounds with corresponding environmental and toxicity information. Of the 53 chemicals used most frequently (top 10%), 18 were reported without a corresponding CASRN. The top 10% of the chemicals used in the highest median masses per event also did not always have associated CASRN (S2 Table). For example, the fourth most commonly used additive is a proprietary chemical identified only as “polyoxyalkylenes,” which could be any one of potentially hundreds of chemicals or chemical formulations. Compounds reported by CASRN mostly had corresponding mass-usage information, important for risk analysis, but 97 did not have toxicity profiles in the public databases used in this study (Table 2; S3 Table). Altogether, 70% of the chemical additives reported in the SCAQMD could not be fully evaluated using data-based hazard analysis approaches [20,21,47], suggesting that current reporting requirements may need to be strengthened, if the regulatory objective includes generating data needed for risk assessments.
Analysis of chemicals by mammalian toxicity revealed that five chemicals were classified as GHS Category 2 contaminants based on acute mammalian oral exposure and 13 were classified as GHS Category 1 or 2 for acute mammalian inhalation toxicity (Table 3). These results are similar to results found by Stringfellow et al.  for hydraulic fracturing operations. Several of the most toxic chemicals identified are biocides: 5-chloro-2-methyl-3(2H)-isothiazolone, DBNPA (2,2-dibromo-3-nitrilopropionamide), formaldehyde, and glutaraldehyde. Corrosion inhibitors are also represented on the list of most toxic chemical additives: propargyl alcohol and thioglycolic acid (Table 3). Mammalian toxicity data were unavailable for 105 (42%) of the 249 chemicals with CASRN.
Table 3. Chemicals used in routine oil and gas development that are classified by the United Nations Globally Harmonized System (GHS) Categories 1 and 2 for acute mammalian toxicitya.
Analysis of ecotoxicity characteristics of the chemicals revealed that 58 chemical additives were classified as GHS Category 1 or 2 (Table 4). Twenty-six of these classifications were determined using computational estimates from the U.S. EPA Ecological Structure Activity Relationships (ECOSAR) software for green algae ecotoxicity, available through EPI Suite. The remainder of the ecotoxicity determinations were made using experimental data. A wide range of chemicals were identified as being toxic to aquatic organisms. The list includes acids, hydrocarbons, biocides, corrosion inhibitors, surfactants, and other industrial chemicals (e.g. tall oil). Experimental ecotoxicity data were unavailable for 146 (59%) of the 249 chemicals with CASRN; when ECOSAR estimates were included, ecotoxicity data were unavailable for 129 (52%) chemicals with CASRN.
Table 4. Chemicals used in routine oil and gas development that are classified by the United Nations Globally Harmonized System (GHS) in Categories 1 and 2 for ecotoxicitya.
Nine of the most toxic chemicals from an aquatic perspective were used in more than 25% of events (Table 4). The most frequently used chemicals on the list were hydrochloric acid, propargyl alcohol, ammonium chloride, and naphthalene, used in 48% of events or more. Propargyl alcohol and naphthalene were used in small quantities (median masses of less than 5 kg per treatment) although hydrochloric acid and ammonium chloride were used in much higher amounts (median masses of 1,311 and 454 kg per treatment). The higher number of chemical additives posing ecotoxicity issues and the frequent use of these chemicals, suggests that the ecosystem risks need to be fully evaluated in produced water reuse projects.
Evaluation of chemical hazards using regulatory lists
To further investigate the potential hazards associated with chemicals used in routine oil and gas development activities, six regulatory lists were referenced (S4 Table). The result of the comparison with these regulatory lists was that twenty-two of the chemicals were on the California Toxic Air Contaminant List , 12 were on the California Proposition 65 List , 10 were on the U.S. EPA Drinking Water Standards and Health Advisories List , six were present on the U.S. EPA Contaminant Candidate List 4 , three were on the European Chemicals Agency Substance of Very High Concern Candidate List , and two were on the OSPAR List of Substances of Possible Concern . These results demonstrate that some of the chemicals used in routine oil and gas development activities are chemicals of concern, as identified by multiple state, federal, and international environmental agencies due to their toxicities. However, the actual risk proposed by these chemicals would need to be determined in the context of their use and potential release into the environment.
It should be noted that comparison with regulatory lists also indicate that many of the chemicals used in the SCAQMD are expected to present little or no human health or ecotoxicity hazard, even if discharged into the environment. Of the chemicals reported with CASRN, 56 are on the OSPAR list of chemicals not expected to pose environmental harm . These chemicals include inert minerals (e.g. silica, graphite, mica, diatomaceous earth), common salts (e.g. calcium carbonate, calcium chloride, sodium carbonate, etc.), chemicals that rapidly degrade in the environment (e.g. acetic acid, ethylene glycol, 1-butanol), and food additives (e.g. xanthan gum, guar gum, sodium erythorbate, starch).
In this study we compared routine oil and gas field chemical use, which is not typically subject to disclosure regulations, with chemical use for hydraulic fracturing and other well stimulation techniques that are subject to regulation mandating chemical disclosure. Our results indicate that there is substantial overlap between the chemicals used in well stimulation and those used in routine oil and gas development activities. Similarities were observed in the numbers of chemicals used, the masses in which they were applied, the frequency of use, and their toxicological profiles. Our analysis shows that hydraulic fracturing is just one of many applications of hazardous chemicals on oil and gas fields and suggests that limiting disclosure requirements for oil and gas field chemical-use to hydraulic fracturing and other well-stimulation events may not be fully protective of human and environmental health, especially in the context of beneficial reuse of produced water for irrigation, wildlife, livestock watering, and groundwater recharge.
S1 Table. Constituents used for routine oil and gas development activities (exclusive of well stimulation) in the SCAQMD, June 4, 2013 to September 2, 2015, sorted by frequency of use.
Total number of events is 1,187.
S2 Table. The top 10% median masses of additives used in routine oil and gas development activities (exclusive of well stimulation) in the SCAQMD, June 4, 2013 to September 2, 2015.
Total number of events is 1,187.
S3 Table. Chemicals reported to the SCAQMD and used in routine oil and gas production for which experimental toxicity information could not be located (N = 97).
S4 Table. Chemicals reported to the SCAQMD and used in routine oil and gas development activities considered chemicals of concern based on six reference lists consulted.
This material is based upon work supported by the Department of Energy under Award Number DE-IA0000018 (CERC-WET). This study was also supported by grants from The Broad Reach Fund and Laboratory Directed Research and Development (LDRD) funding from Berkeley Lab, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-05CH1123.
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[Refer also to:
2017 04 05: Hypocrites! Health Canda wants “expanded powers” to strengthen regulation of natural health products but not toxic frac chemicals – not even to make companies disclose their secret frac brews to families breathing them! Not even to disclose Health Canada’s own frac health hazard report!
2017 04 04: To see how awful the Canadian legal system is (especially Petro State Alberta’s case “management” system ensured to go nowhere but bankrupt harmed citizens plaintiff while protecting the polluters and their enabling “regulators” like Alberta Environment), read the entire letter: Klippenstein’s April 4, 2017 letter to Encana’s lawyer, Maureen Killoran with Osler, on the company still not having filed with Ernst appropriate records for discovery that heed Alberta’s Rules of Court and the agreed-upon Protocol for Electronic Discovery (that cost Ernst significant funds negotiating with Encana to reach agreement on in 2014).
Deadline for Encana’s filing was ordered by Chief Justice Neil Wittmann to be no later than December 19, 2014. From the letter:
I am writing regarding your letter of May 4, 2015 and my letter of March 27, 2015. We have waited nearly two years now and still have not been provided with any of the promised updated .csv format List of Records, or updates of the pdf’s of the records themselves and remain waiting for a satisfactory response to the other concerns raised.
In my letter, I raised serious concerns regarding Encana’s failure to meet its legal obligations regarding the disclosure of records in this action. I understood from your letter that we would shortly expect both an updated .csv format List of Records, and updates of the pdf’s of the records themselves. We have heard nothing further from you.
As stated in the conclusion of my letter of March 27, 2015, given the nature, number and seriousness of these deficiencies, the only solution must be for Encana to redo its disclosure of records in a manner that complies with the Alberta Rules of Court and the agreed-upon Protocol Regarding Electronic Discovery. If we do not receive the complete, cleaned-up and appropriate disclosure of records by May 30, 2017 in a manner that complies with both Encana’s obligations under the Alberta Rules of Court and the protocol agreed upon between the parties, my client will bring an application for a further and better affidavit of records. I note that Encana has already had more than two years to provide an appropriate response to our serious concerns regarding Encana’s affidavit of records, and has to date failed to do so. [Emphasis added]
2016 09: Hazard Assessment of Chemical Additives Used in Oil Fields that Reuse Produced Water for Agricultural Irrigation, Livestock Watering, and Groundwater Recharge in The San Joaquin Valley of California: Preliminary Results
2016 04 26: New peer-reviewed published paper on unconventional natural gas development (excluding CBM/CSG) impacts: “At least 685 papers have been published in peer-reviewed scientific journals that are relevant to assessing the impacts of UNGD. 84% of public health studies contain findings that indicate public health hazards, elevated risks, or adverse health outcomes; 69% of water quality studies contain findings that indicate potential, positive association, or actual incidence of water contamination; and 87% of air quality studies contain findings that indicate elevated air pollutant emissions and/or atmospheric concentrations”
2015 11 23: Prevent Cancer Now calls out AER’s Health Fraud! “The AER has no jurisdiction for human health, and Alberta is famed for a chill against the medical community linking ill health to petrochemicals.”
2015 03 30: British Medical Journal publishes letter by 20 high profile medical and public health experts calling for ban of “inherently risky” frac industry; Medact’s new report concludes: fracking “poses significant risks to public health”
2014 07 24: Harper government enabling the frac harm cover up? Environment Canada criticized for leaving fracking chemicals off pollutant list saying not enough frac chemicals used – 362,000 litres of diesel invert lost underground near Alberta family home
March 11, 2014: Canada’s National Pollutant Release Inventory [NPRI] Oil and Gas Sector Review; Chemicals injected and fugitive or venting emissions (e.g. H2S) by oil and gas industry exempt from reporting
November 29, 2013: Harper government not ready to reduce pollution from oil companies but willing to waste $40 Million of Canadian tax money in one year to lie for billion dollar profit-making multinational polluters
2007: Ernst Testimony to Parliamentary Committee on water contamination and non-disclosure of chemicals used in shallow hydraulic fracturing even when directly into community drinking water supplies
Ms. Jessica Ernst (Environmental Specialist, Ernst Environmental Services) Testimony, May 8, 2007:
Good morning. Bonjour.
I grew up in Montreal. I now live in Alberta. I’m very sorry, but I have forgotten all my French. I live near Rosebud, Alberta. It’s a small, little-theatre cultural town with a lot of beautiful historic resource.
I have worked in the oil patch for 25 years. I have also been banished by the regulator that Mr. David Pryce was so proudly discussing earlier in his presentation. I believe I was banished—this was in writing—by the energy regulator because they were trying to intimidate me.
I have evidence of EnCana Corporation not complying with the noise regulations, and the EUB actually covering up for the non-compliance in writing. I believe that the EUB, the regulator, did this to try to silence me. They copied the RCMP. So I’m very surprised that you, honourable members, here have allowed me to speak, because I do believe this was the first time this had happened in Alberta. I have been informed that the banishment was a violation of the Canadian Charter of Rights.
I grew up proud to be a Canadian. I grew up proud of our water, of our leadership on peace and mediation, and environmental issues globally. I have worked in other parts of the world. I have to admit, I’m ashamed to be Canadian now, and I plead to you all as this committee to listen carefully and review the documents, and carefully consider whether the federal government needs to get involved.
I have never seen such atrocities in my 25-year career of working in the oil patch as I have now seen in the boom: human rights violations, environmental degradation, and disrespect of the legislation and the regulations.
In regard to noise, the other day when I was leaving from the airport, the night before I left, the compressor noise—we’re surrounded by 13 EnCana compressors—drove me to distraction. Occasionally the noise is mitigated, but not always. There’s a straw-bale wall surrounding these compressors.
I have direct experience with the water. This is my water, on fire, from my tap, poured into a pop bottle, a water bottle. There is no sugar in there. A few minutes later I set it on fire. I’ve lived in my place since 1998, 50 acres. CBM came and my water dramatically changed–a chemical burst on my skin and eyes. My dogs not only refused to drink the water, but they would back up. White smoke was coming off the water.
There were whistling taps. I didn’t know what it was. I was really busy. I thought it was my plumbing. I thought, “Oh my goodness, I have to replace the taps.” Little did I know that I was living in an explosive time bomb. It was methane and other hydrocarbons coming out of my taps. Sometimes I couldn’t even close my taps there was so much gas. I couldn’t get suds out of my soap or shampoo anymore; the water changed.
Also, living rurally, you know you get stains on your plumbing and toilets—sorry to speak so intimately. All of a sudden my toilets went pristine, brand new. Something got rid of the stains, I think probably what was burning my skin.
Mr. Pryce mentioned the good regulations. This happened in 2004. These are the two aquifers in my community. This is an EnCana well. It fractured into—into—our aquifers. So the protection and the separation that was discussed is not possible. Perforations, which explode through the casing, and then the fracs, and who knows what solvents went into our aquifers?
In the States, EnCana was found to contaminate groundwater and did not protect health and safety.
This again is another picture of my water, a different picture. I don’t do this in the house anymore because the flame exploded so high it shot up to the ceiling. I’m a blur in the picture—this is me here—because I had to jump; it scared me.
We have one out of 20 resource wells leaking. The landowner in an investigation is usually blamed, instead of comprehensive testing of the resource wells. There are ways to find out which gas wells are leaking. They can be fixed. In this case, EnCana has stated publicly that they do not need to cooperate with this investigation because they don’t believe in the science that can lead to finding out which wells are leaking.
The regulators misinform the public. We have thousands of resource wells leaking.
The new testing that came up only began when a number of concerned citizens went to the legislature and went to the public. The MAC committee was still in deliberation. I believe the testing requirements wouldn’t have happened.
We have now had, finally, a number of years of CBM, but our knowledge on groundwater is behind. The precautionary principle: where is it?
In 2005, industry advised the Alberta Energy and Utilities Board that some of their shallow fracs were damaging oil and gas wells. So they brought in some new rules. These rules should have been brought in before they began the experiments, especially for our drinking water.
This is a water well that exploded last spring. The farmer had dealt for three years with the regulator–the so-called best regulator. What’s wrong with this picture? Three men were seriously injured on sampling day. After contamination, some companies refused to cough up the data that was needed to investigate and remediate.
This is a diagram that the AEUB, the energy board, and Alberta Environment go to the public with. They say it never happens. Oh, no, there is no leaking.
By the way, methane is a much worse greenhouse gas than CO2, and we have thousands of these leaking methane directly into the atmosphere. There is surface casing vent flow, and gas migration through soils. The interesting thing is that the AEUB, in 2007, is even warning that the gas leakage and the gas migration potential is worse in the shallow zones. This is where we’re going to be doing our CBM and where our water is.
In Rosebud water we have 30 milligrams to 66 milligrams of dissolved methane, as well as free gas. CAPP, which is here today on the video, has a report that one milligram puts you at risk of explosion if the water passes through an unventilated place. A light switch, static in my hair, could have blown up my house.
The regulator is still in denial. They have done tests on our water. You have a table. We have benzene, toluene, ethylbenzene, and xylenes in our water. We have ethane, propane, methane, butane, and octanes, and we have kerosene in the community drinking water. In most cases, the landowner is blamed for the contamination by way of bacteria. On the table, you can look at the process we have to go through.
I read your report that came out recently on the chemicals and your Canadian Environmental Protection Act, and I plead with you to please implement this act in Alberta.
We are told that only nitrogen is used, so our water is safe because nitrogen comes from the air. I would like to show you a list. This came from Oilweek. These are a variety of products, hundreds of them, used in different stages of drilling, [f]racking, and servicing. Some of them contain diesel and mineral oil. In Alberta, the regulator does not require industry to disclose any of the chemicals used, not even if they’re toxic, not even if it’s benzene, a known carcinogen, or toluene, which damages the brain, notably in children. Toluene was found in our water.
We need to know what the chemicals are, especially so shallow, and I believe that the federal act is perfect. I noticed in your report this is seldom used and seldom implemented. I would like to ask that you use this and implement it in Alberta and ask the regulators to control the chemicals being used.
I have seen many pallets of chemicals that aren’t even on this list, bags of chemicals that say, “Danger, Unregulated”. Nobody knows what’s inside, driving through playground zones. We don’t know now how to analyze our water. These chemicals could have gone into our water, but we don’t know what to test for.
I also brought with me a pledge to protect our groundwater. You had this translated. I would like to ask every member of Parliament, not just the committee members, to sign this pledge and fax it to Honourable Minister Baird and our Honourable Premier Stelmach.
There are a few things we would like done to protect our groundwater.
CBM can be a fantastic new resource. We can all share in the prosperity. Canada is a fantastic country. I would like to see the Canada I knew as a child come back from corporate rule. I would like to see the people in charge. I would like to see public health and safety protected. There are still people in my community bathing in and drinking water with benzene and toluene. We do not need to harm people to have prosperity.
Coal-bed methane will spread far. The shales are coming. They will spread far. These impacts, violations of the Canadian Charter of Rights and Freedoms, will spread through the country if we continue to allow industry to rule.
The precautionary principle: why are we allowing perforations and fractures into these shallow zones above the base of groundwater protection? Industry still doesn’t know what these shallow perfs and fracs do. They have stated this in writing to the EUB. Why don’t we learn first? We can do an economical mitigation here, slow down, think first, collect some data first. Let’s find out what we’re doing to our groundwater. This is Canada’s water. We all have water on the table here. This water will affect all of us.
The story has been much in the news. I bring one gift for my French friends here today. Quebec journalists are writing three stories on the water situation. In September, I believe, the Rosebud water situation will be published, but they are also writing about climate change. I find it interesting that Quebec is so concerned about what is happening to our water in Alberta that they’re sending journalists out. There is an Alberta Views article. I have copies here for you. They’ve been handed in. Even Canadian Business magazine has published the story about the water. There I am with my water. I can’t live with this water anymore. It’s too dangerous. I have trucked-in water that the Alberta government is supplying and paying for. I’ve lost my independence. I live rurally. I have to rely on trucked-in deliveries. I want my water back. I want to protect water for others.
In conclusion, in my experience, the regulations are not working. The regulators are not working. Instead of dealing with the industry’s non-compliance, they banished an ordinary citizen, considered me a threat to safety and the public. I had just found out when I got this letter from my regulator in Canada, a country that I thought was a democracy, that I was living in danger of explosion from my water. Yes, methane can be natural, but it is normally at very low levels. Nothing like the levels we have after this company, EnCana, fractured directly into our potable water supplies. They have cemented this well off, but we do not know what damage has been done to our aquifers. This is very serious.
Thank you. [Emphasis added]
Mr. David Pryce, Canadian Association of Petroleum Producers: “in terms of the technical requirements around the completion of the wells, is illustrated in the slide that shows the cement and the steel casing that is put in place. It is intended to separate the producing zones from those upper shallow water aquifer zones. So there is engineering applied to this. There is a regulatory environment that requires us to adhere to those practices to ensure that we do provide that measure of protection…. We test the wells in proximity to the coal-bed methane wells we drill, to confirm the condition of that water prior to drilling those wells, to understand whether or not methane is present. If it is present, the presumption is that it’s naturally occurring, and then following up with that, if there’s any change in that water well after the fact, we know we’ve got something to look at.” [Intentionally too late by then?]