1 TEDX The Endocrine Disruption Exchange

P.O. Box 1407, Paonia, CO 81428 970-527-4082 www.endocrinedisruption.org tedx@tds.net



### INTRODUCTION The following summary is based on an analysis of the poten tial health effects of pr oducts and chemicals used during natural gas operations. The names and possible heal th effects of the products and chemicals summarized below are available in an Excel spreadsheet for easy sorti ng and searching.* Note that th is is not a complete list of products and chemicals used in natural gas operations.



### METHODS: What we did Data sources Acquiring information about the produc ts and chemicals used in natura l gas operations continues to be extremely difficult. TEDX has spent se veral years collecting data from a variety of sources including state Emergency Planning and Community Right-to-Know Act (EPCRA) Tier II reports, Environmental Impact Statement and Environmental Assessment Statement disc losures, rule-making documents, accident and spill reports, the U.S. Bureau of Land Management, the U.S. Forest Service, state agen cies, non-profit organizations, and the natural gas industry.

For nearly every product identified, Ma terial Safety Data Sheets (MSDSs) were acquired, with the exception of a few that came from state Tier II Reports. MSDSs are designed to inform those who handle, ship, and use products that contain toxic ch emicals about their physical and chemical ch aracteristics, and th eir direct and/or immediate health effects, in order to prevent injury while working w ith the products. The sheets are also designed to inform emergency response crews in case of accidents or spills. Many MSDSs do not address the outcome of long term, intermittent or chronic exposures, or adverse health effects that may not be expressed until years after the exposure. The Occupational Safety and Health Administration (OSHA) requires product manufacturers to include certain elements in MSDSs, but they are not required to submit them to OSHA for approval before attaching them to their products. T hus, accuracy and completeness are entirely up to the company that produces the MSDS.

MSDSs can be lacking in information in many ways. The majority of MSDSs do not disclose 100% of the product composition. They also list non-specific ingredients, such as “surfactant” or “biocide” that describe the function of the ingredient but do not specify the ingredient name. Other vague words that are used include: proprietary, mixture, unspecified, vari ous, unregulated, or no hazardous ingredients. The most specific way to identify chemical ingredients is by using CAS numbers. The American Chemical Society developed the CAS (Chemical Abstract Service) number system using unique number sequences to identify chemical elements, compounds, isomers of chemicals, polymers, biological sequences, or mixtures. CAS numbers provide a universal identity to substances th at can be known by different names.


### Health Effects Only chemicals with CAS numbers could be accurately in vestigated for their health effects. Information about the potential health effects of each chemical with a CAS number wa s obtained from these sources:

• Material Safety Data Sheets

• Publicly available government databases:

o TOXNET

o Hazardous Substances Database

• Published scientific stud ies (located through PubMed and Web of Science)2 Information was often limited because of the lack of published research on many products, including industry laboratory studies submitted to EPA for registration but classified as confiden tial business information.

Health effect data were organized in to 14 health categories, focusing on the main organs and systems that are identified on MSDSs, government t oxicological reports, and in the medical literature. The categories encompass all seven priority health conditions identified by the Agency for Toxic Subs tances and Disease Registry. For our summary analysis we subsumed developmental and reprodu ctive health effects under th e category for endocrine disruption, resulting in 12 categories. The 12 health effect categories are: ski n, eye and sensory organ; respiratory; gastrointestin al and liver; brain and ne rvous system; immune; kidney; cardiovascular and blood; cancer; mutagenic; endocrine disrupti on; other; and eco logical effects.


### Data Analysis The products, the chemicals they contai n, and their health effect s were entered into an Excel spreadsheet. We also entered data indicating what pe rcentage of each product was disclose d in the MSDS. Then, using only the chemicals that had a CAS number, we produced a prof ile based on how many chemicals showed evidence of potential health effects in each of the 12 categories. We also created separate profiles for the water soluble chemicals and volatile chemicals.



### RESULTS: What we learned Product composition disclosure Products may contain more than one chemical, and a give n chemical may occur in more than one product. Our spreadsheet currently contains 980 products. For 421 of the 980 products ( 43%), less than 1% of the total composition of the product was reported on the MSDS (Figure 1). Less than 50% of the composition was reported for 136 products (14%), and between 51% and 95% of the composition was reported for 291 (30%) of the products. Only 133 products (14%) had informa tion on more than 95% of their full composition.

For each product, we totaled the number of health effect s of the chemicals in that product. Figure 2 shows that 10% of the products had no health effects, while 90% had at least one potential health effect. Nearly half of the products (47%) contained one or more chemicals consider ed to be endocrine disruptors, which are chemicals that interfere with the e ndocrine system, including development and reproduction.3 

### Chemical summary In the 980 products identified above, th ere were a total of 649 chemicals. Specific chemical names and CAS numbers could not be determined for 286 (44%) of the chem icals, therefore, the health effects summary is based on the remaining 362 chemicals with CA S numbers. Figure 3 shows percentage s of the 362 chemicals that were found to be associated with effects in each of the 12 h ealth effect categories. Note that many chemicals have health effects in more than one categ ory. Over 78% of the chemicals are a ssociated with skin, eye or sensory organ effects, respiratory effects and gastrointestinal or liver effects. The brain and nervous system can be harmed by 55% of the chemicals. These four health effect categories (on the left side of the figure) are likely to appear immediately or soon after exposure. They include symptoms su ch as burning eyes, rashes, coughs, sore throats, asthma-like effects, nausea, vomiting, headaches , dizziness, tremors, and convulsions. Other effects, including cancer, organ damage, and harm to the endocrine system, may not appear for months or years later. Between 22% and 47% of the chemicals were associated with these possibly longer-term health effects. Fortyeight percent of the chemicals have health effects in th e category labeled ‘Other’. Th e ‘Other’ category includes such effects as changes in weight, or effects on teeth or bones, for example, but the most often cited effect in this category is the ability of the chemical to cause death.4 Figure 4 breaks out the health effect s by pathway of exposure. A total of 210 chemicals (58%) are water soluble while 131 chemicals (36%) are volatile; in other words, they can become airborne. Of these volatile chemicals over 93% can harm the eyes, skin, sensory organs, respirat ory tract, gastrointestinal tract or liver. Compared with the soluble chemicals, far more of these chemical s (86%) can cause harm to th e brain and nervous system. Seventy-two percent of the volatile chemicals can harm the cardiovasc ular system and blood, and 66% can harm the kidneys. Overall, the volatile chemicals produce a different profile with hi gher percentages than the water soluble chemicals. Because they can be inhaled, swallowed, and also reach th e skin, the potential for exposure to volatile chemicals is greater.

Appendix A provides a list of the ch emicals with CAS numbers found in th e highest number of products and their associated number of health effects, to assi st in prioritizing the chem icals to be monitored.


### DISCUSSION: What we have to say about it Clearly, many of the products and chemicals used by the natural gas industry are not benign. As the industry continues to expand and tap into additional natural gas formations, the list of pr oducts will grow. New products and chemicals continue to be introduced into the market as a result of increasing competition among those who manufacture and sell products; a nd product specialization to address the geology and varying geochemical conditions of natural gas formations.

Without full knowledge of what products and chemicals ar e being used, it is extrem ely difficult to know what air and water quality tests to conduct. Appendix A displays the chemicals th at appear in the highest number of products, along with the number of hea lth effects of each chemical. Although th is does not necessarily equate to the most frequently used chemicals at any given time or location, it can provide some guidance in developing air and water quality monitoring protocols. Regular ai r and water quality monitori ng in and around natural gas development should become standard procedure that includes baseline mo nitoring prior to new wells being developed. For those living near natural gas development, measurable changes in air quality will take place well before changes in drinking water qual ity. In addition to the chemicals intr oduced during drilling and fracturing, air quality monitoring should targ et the numerous volatile, naturally occurring, toxic chemicals found underground that may also be released during the process.

Of note is that 47% of the products have the potential to affect the endocrine system, including human and wildlife development and reproduction. The endocrine system is the exquisitel y balanced system of glands and hormones that regulates such vital functions as body growth, response to stress, sexual development and5 behavior, production and use of insulin, rate of metabo lism, intelligence and beha vior, and the ability to reproduce. The endocrine system operates at very low conc entrations of hormones, of ten in parts-per-billion or less, making it susceptible to very lo w levels of exposure, which can im pact organisms and their offspring, including humans. Prenatal exposure should especially be avoided. Endocrine disrupting effects include reduced sperm production, infertility, hormone imbalances, effects on the thyroid, adrenals, p ituitary, and more. Effects like these might not be seen for months or years and w ould be difficult to trace back to exposure to gas industry chemicals.

For over seven years, environmental and public health advocates have ca lled for full product disclosure of drilling and fracking chemicals. After a nurse became critically ill while attending a laborer involved in a fracking accident, and the attending physic ians could not find out what she wa s exposed to, the real urgency for full disclosure became apparent. In 2008 Colorado passed a rule (the first of its ki nd) that upon request through the Colorado Oil and Gas Conservation Commission, operators must disclose product ingredients to victims or their physicians in case of an accident. Unfortunately, th e response to such a request could take several days, long after it could be of any assist ance for emergency diagnosis and trea tment. In 2010, Wyoming became the first state to require publicly availa ble disclosure of chemicals in frack ing products, including the volumes or quantity of chemicals used. Already Wyoming is receivi ng requests for proprietary status which would prevent public disclosure of a number of fracking products.

These efforts are a good start, but there is much more in formation that needs to be disclosed fully and publicly. Each drilling and fracturing event is custom-designed depending on the ge ology, depth and resources available. The chemicals and products used and the amounts or volumes used can differ from well to well. Complete records for each well must be kept for an accurate account ing of what is being introduced into watersheds, air, and soil. This information should include the exact loca tion of the well; the complete composition of the fluids injected underground, including the comp lete formulation, weight and volume of every product and chemical used; the depths and pressures at which material/mix tures were injected; the amount and composition of the recovered liquids; and their di sposal method and location.

However, while the drilling and fracking contractors can be required to tell everything they know about a product, they largely rely on MSDSs from the product ma nufacturers. As our analys is indicates, many MSDSs provide information on only a fraction of the full product ingredients. There will not be true full disclosure until the product manufacturers divulge 100% of the chemical ingredient s in their products. It is time for those charged with protecting public health and the environment to demand full disc losure directly from the natural gas products industry. Additionally, responsible drilling and fracking companies should be insisting on safer products from their suppliers to pr otect the health of their employees and reduce their liability. Most importantly, the industry needs to assure its drilling a nd fracking fluids and toxic byproducts are retained in closed-loop production systems that prev ent the release of any toxic chemi cals into the ambient environment.

For a more in-depth discussion of these issues, read our manuscript “Natural Gas Operations from a Public Health Perspective” accepted for publication in the International Journal of Human and Ecological Risk Assessment

. *To download the database of products, chemicals and hea lth effects in an Excel spreadsheet; a PDF of this Summary Statement; and our manuscript “Natural Gas Op erations from a Public Health Perspective” go to http://www.endocrinedisruption. com/chemicals.multistate.php

.6 Appendix A. Chemicals found in the highest number of products

Chemical CAS # Number of Products Number of Health effects

Crystalline silica, quartz 14808-60-7 124 7

Methanol 67-56-1 76 11 Isopropanol (Propan-2-OL) 67-63-0 50 10 Petroleum distillate hydrotr eated light 64742-47-8 24 6 (2-BE) Ethylene glycol monobutyl ether 111-76-2 23 11

Bentonite 1302-78-9 20 6

Diesel 2 68476-34-6 20 10 Naphthalene 91-20-3 19 12 Ethylene glycol 107-21-1 18 10

Aluminum oxide 1344-28-1 17 3 Sodium hydroxide 1310-73-2 17 5
Barite (BaSO4) 7727-43-7 15 5 Heavy aromatic petroleum naphtha (aromatic solvent) 64742-94-5 15 5

Sodium chloride 7647-14-5 15 9 Crystalline silica, cris tobalite 14464-46-1 14 5

Mica 12001-26-2 14 3 Crystalline silica, tridymite 15468-32-3 13 3 Hydrochloric acid (HCl) 7647-01-0 13 7 Xylene 1330-20-7 12 10 Glutaraldehyde 111-30-8 11 11 Guar gum 9000-30-0 10 3
Iron oxide (Fe203, Diiron trioxide) 1309-37-1 10 4

Potassium chloride 7447-40-7 10 8 Potassium hydroxide 1310-58-3 10 7 Xanthan gum 11138-66-2 10 4

Fuel oil #2 68476-30-2 9 11 Hydrotreated heavy petroleum naphtha 64742-48-9 9 8 Limestone (Calcium carbonate) 1317-65-3 9 3 Sodium carboxymethylcellulose ( Polyanionic cellulose) 9004-32-4 9 5 Butanol (N-butyl alcohol, Buta n-1-OL, 1-Butanol) 71-36-3 8 8 Calcium hydroxide 1305-62-0 8 8 Crystalline silica (silicon dioxide) 7631-86-9 8 4 Ethanol (Acetylenic alcohol) 64-17-5 8 12

Formic acid 64-18-6 8 11 Graphite 7782-42-5 8 4 2-Ethylhexanol 104-76-7 7 11

Acetic acid 64-19-7 7 9

Ammonium bisulfate 10192-30-0 7 6 Asphaltite (Gilsonite, Hydrocarbon black solid) 12002-43-6 7 4

Calcium chloride 10043-52-4 7 8 Ethylbenzene 100-41-4 7 11 Ethoxylated nonylphenol 9016-45-9 7 6 Petroleum distillate naphtha 8002-05-9 7 12

Polyacrylamide/polyacrylate copol ymer (Copolyer of acrylamide & sodium acrylate, partially hydr olyzed polyacrylalmide) 25085-02-3 7 3 Propargyl alcohol (Prop-2-YN-1-OL) 107-19-7 7 9 Tetramethylammonium chloride 75-57-0 7 8