TOXICOLOGICAL & CHEMICAL REVIEW
EXPLORATION AND EXPLOITATION OF SHALE GAS AND SHALE OIL (PARENT-ROCK HYDROCARBON) BY FRACKING (New Edition, september 2012)
André Picot
Toxico-chimist Honorary Research Director C.N.R.S. (C.N.R.S : French National Scientific Search Center) Honorary French expert from the European Union Specialist of Chemicals products in Workplace Président of Toxicology-Chemistry Association (Paris) Honor Member of No Fracking France Association Paris, October 2011 Collaboration with Joelle and Pierre DAVID and Jerome TSAKIRIS(ATC)
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EXPLOITATION OF SHALE GAS AND SHALE OIL (PARENT ROCK HYDROCARBON) AND RISKS SUMMARY
INTRODUCTION I
: THE UNCONVENTIONAL GAS EXTRACTION
II : FRACKING FLUIDS III : MINERAL CHEMICAL COMPOUNDS CHARACTERIZED IN FRACKING FLUIDS IV : ORGANIC CHEMICAL COMPOUNDS CHARACTERIZED IN FRACKING FLUIDS V : FRACKING FLUIDS, A REACTIONAL ENVIRONMENT VI : ROUTES OF EXPOSURE TO CHEMICALS IN FRACKING FLUIDS AND RISKS VII : MAJOR TOXIC PRODUCTS FOR HUMANS IN FRACKING FLUIDS VIII : A CONCLUSION THAT REMAINS STILL TENTATIVE In french edition : - LETTER TO FRENCH MINISTERS AND PARLEMENT, PERSONAL DELIVERY WITH THE FIRST VERSION OF TOXICOLOGICAL AND CHEMICAL END RESULT. - APPENDICES.
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... " We are living a historic moment. Future prospects are such that, if we lose Earth, it is humanity that we will lose. To avoid such an outcome, which will ruin the future of our children and ours perhaps we have to make choices today that will lead to monumental implications. "... ... "This book is a call for a revolution. The earth is in danger. She can not cope with everything we demand it. She loses her balance and humanity that is the cause. "... ... "This book reminds us that we must find our links with our past to better control our future. "... ... "The system that sustains life on our planet begins to go haywire and our very survival is in question. What our children and grandchildren will wonder, this is not what we said, but what we did, remember-in. Therefore propose an answer, an answer we can be proud. "
Excerpts from "HARMONY, A new way of looking at the world" by the Prince of Wales. Editions Odile Jacob, Paris (October 2010)
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INTRODUCTION As the reserves of conventional natural gas (methane ...) falling inexorably and could be exhausted in about sixty years, the extraction of oil and gas (non conventional) trapped in shale or parent-rock hydrocarbons (sedimentary rocks) where coal appears to be an attractive alternative for several countries (USA,Canada, Europe and now in the future Russia, China, ...). Recently, American economists & analysts have stated that gaz and oil companies overestimate productivity and size of reserves of shale gas in the U.S.A (The New York Times, June 25, 2011). Table 1 lists the world's resources (in trillion cubic meters of three different types of gas).
Type of gas
World Resources In trillion m³
Cost estimate thousands of extraction dollars
Shale gas
666
140 to $ 210
Coal gas
256
$ 35 at 100
185
-
Conventional gas
Table 1 : WORLD RESOURCES OF DIFFERENT HYDROCARBON GAS (Source: Investors Chronicle, April 2010) Unconventional gas account for more than four times the conventional gas resources. If you could well use these unconventional gas, it would change significantly global energy policy, but what are the environmental and health consequencies ? Techniques of extraction currently in place seem polluting and also not as profitable than touted !
I : THE UNCONVENTIONAL GAS EXTRACTION
-
If the layers of conventional gas (methane) are located in pockets in most cases airtight against by the unconventional gas fields are distributed diffusely in different geological layers. Conventionally, these unconventional gas fall into three categories: The parent-rock gas (shale gas) locked in different geological formations clay. The coal gas trapped in coal beds (coal) and cause of sunburns firedamp, which hit several countries still frequently coal (3,000 deaths / year in China). Other sources of gas, confined in reservoirs with low permeability (Tight gas). The extraction of natural gas or shale bedrock by hydraulic fracturing (fracking) is a recent technology, which began in the United States across industry in 2005, first in the United States and locally in Europe (Germany, Great Britain ...) Currently the gas extracted by this technology is about 15% of total production gas in the United States. 4
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Classically, two drilling techniques are used: The vertical drilling, directed from the ground surface. The horizontal drilling, from a vertical shaft and to operate on large distances (1-3 miles). These technologies increasingly sophisticated, achieve geological deep (up to 4000 meters deep). At these depths, as the permeability of shale is very low and can not allow the extraction of gas included, it is mandatory to fracture the rock by chemical techniques very powerful (water, special fluids, pressure). Said hydraulic fracturing is by injection of water (2000 to 20,000 m³ per cycle of fracturing) under high pressure (over 76MPa) with fine sand and chemicals prevent the fractures from closing, as shown in Figures 1 and 2, below:
Figure 1: DRILLING METHOD CONVENTIONNALY USEDFOR REMOVING THE SHALE GAS AND SHALE OIL
(Source: ifpenergiesnouvelles.fr)
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Figure 2: CIRCULATION OF FRACKING FLUIDS IN SHALE GAS & SHALE OIL EXTRACTION (Source: lecercle.lesechos.fr) Apart from water, fracking fluids may be mud or a synthetic fluid viscosity controlled, hard-enriched agents (sieved sand, ceramic beads ...). Historically, the first fracking test on a vertical well was tested to United States in 1947 by the company "HALLIBURTON". As to the first horizontal drilling it was successful in June 1980 by Elf-Aquitaine in Lacq.
Pits of shale gas (Source: en.wikipedia.org) ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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II : FRACKING FLUIDS Fracking fluids (fracturing fluid) are fluids injected under high pressure in a geological formation in order to grinding hard rocks with low permeability, in order to release the hydrocarbons (gas, oil) witch are trapped. The fracturing fluid has three main functions: a-Transporting chemicals, which will help to desorb from the rock to extract the gas. Until recently, the composition of fracturing fluids was kept secret by the operators, under the trade secret. b-Open and expand a network of fractures. c-Transporting proppants which are solid particles in suspension in a fluid and this, along fractures. Before the Concern increasing people surrounding Agency Protection U.S. Environmental (U.S. EPA) requested in March 2010 in nine companies, which in United States, exploiting oil and shale gas, to provide the list of chemicals, used in their various processes. In fact, it seems pretty folk! (2500 products, more or less identified). A preliminary report, 2 February 2011, concerning the impact of fracturing fluids on resources water, provides interesting information, for chemicals characterized in effluent water extraction. Logically, the chemical composition of fracturing fluids should vary with the nature of rocks to fragment, the well depth and certainly compared to many other criteria not published, the trade secret of being put into this activity. According to the website of the U.S. oil firm HALLIBURTON3, the fracturing fluid by the company used contain on average 99.5% of a mixture of water and sand (silica crystal), this sand can be film-coated resins or be replaced by ceramic beads. In addition to water and proppants (sand, ceramic beads ...), the fluid fracturing may contain various chemicals and this in varying concentrations, depending on firms and mining sites. According to oil companies, chemical additives in the composition varies considerably. Some companies claim to use less than 10 products, neglecting even to biocides. If the latter information is accurate, there is concern a microbiological contamination aquatic ecosystems and soil during the ascent of the fracturing fluid.
2
3
EPA/600/D-II/001/February 2011/www.epa.gov/research http://www.halliburton.com/public/projects/pubsdata/hydraulic_fracturing/fracturing.101html ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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In Table 2, using published data on the fluids used so-called fragmentation in the extraction of oil and shale gas in the United States, summarizes the main types of agents chemical and their average concentration.
MAIN COMPOUND CHEMICAL
TYPE OF ADDITIVE A
Water
2
Proppants
Crystalline silica, ceramic balls
9.51
3
Strong acids, metals dissolving
Hydrochloric acid
0.123
4
Friction reducing agents
Polyacrylamide, mineral oils
0.088
5
Surfactants (agents that lower blood superficial)
6
Clay stabilizers
Potassium chloride Tetramethylammonium chloride
0.06
7
Gelling agents
Bentonite, guar gum, Hydroxyethylcellulose
0.056
Inhibitors of ofeposits in the pipes
Ethylene glycol, propylene glycol
9
PH control agents
Sodium carbonate, Potassium carbonate, Ammonium chloride
0.011
10
Officers holding gels
Hemicellulase, ammonium persulfate, Quebracho
0.01
11
Agents maintenance of fluidity in the case Sodium perborate, borates, increase in temperature Acetic anhydride
0.007
12
Agents control the rate of iron
Citric acid, EDTA *
0.004
13
Corrosion inhibitors
Quinoline derivatives, Dimethylformamide (DMF), Propargyl alcohol
0.002
14
Biocides (antiseptics)
Dibromoacetonitrile, Glutaraldehyde, DBNPA **
0.001
8
COMPOSITION % VOLUME 90
2-Butoxyethanol, Isopropanol, Octylphenolethoxyled
0.085
0.043
Table 2 :
ADDITIVES CATEGORIES AND THEIR PERCENTAGE IN A FRAGMENTATION LIQUID OF SHALE GAS EXTRACTION IN USA. (Source: Ground water protection and consulting all 2009) http://www.netl.doe.gov/technologies/oil-gas/publications * EDTA: ethylenediaminetetraacetic acid ** DBNPA: 2,2-dibromo-3-nitropropionamide ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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From the available lists, the chemical compounds most often cited, can be classified into two main groups: Mineral compounds, which include all the chemical elements listed in periodic Table (proposed by the Russian chemist Mendelievv), with the exception of carbon compounds organic. Organic compounds, which as defined by IUPAC (International Union of Pure and Applied Chemistry) correspond to the compounds of the carbon linked to itself (forming the family carbides) or, essentially, hydrogen, constituting the large family of hydrocarbons. Basic skeleton of all organic compounds, hydrocarbons are the highly predominant constituent of conventional gas (methane) or those unconventional but also oils. Figure 3 summarizes the classification of chemicals that can be learned to separate the main chemical compounds described in the fracturing fluids, because it allows separation of chemicals minerals are most abundant in concentration as in fracturing fluids (water, hydrochloric acid, alkali salts ...), chemicals organics, which are the most numerous.
CHEMICALS
Constituents of matter
Inert Material
Living material
Elements Minerals (Some of which compounds carbon)
Carbon compounds related to itself and / or hydrogen C ─ C and / or C ─ H
Mineral Products Metals and Non-metals (metalloids) C─C Carbides
C─H Hydrocarbons
Organic Products Figure 3 CLASSIFICATION OF CHEMICALS Table 3, below, contains the main inorganic chemical compounds, identified in the U.S. in fluids billing. These products are identified by their CAS (Chemical Abstract Service of the American Chemical Society) and their possible toxicity in the short, medium or long term reported (only indicative). ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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III, MINERAL CHEMICAL COMPOUNDS CHARACTERIZED IN FRACKING FLUIDS Table 3
MAIN FAMILIES WITH MINERAL COMPOUNDS CHEMICALS
MINERAL DATING IN THE MOST FEATURES FRACTURING FLUIDS MINERAL CHEMICAL FAMILY
MAIN MINERAL CHEMICAL COMPOUND IN FRACTURING FLUIDS 1
2
Nitrogen
3
4 5
Dinitrogen (Nitrogen) N2 Nitrites NO2Nitrates NO3-
TOXICITY CASE Nbr
Acute and Subacute
7727-37-9
Anoxia
In the long term
Méthémoglobinisant Méthémoglobinisant
Ammonia NH3 Ammonium salts X− NH4+
7664-41-7
Asphyxia
Respiratory irritant
-
compounds
6
Urea NH2 O
7
Compounds brominated
8
9
10
Chlorinated
11
12
13
compounds
14
57-13-6
C
NH2 Sodium bromide NaBr
Sodium bromate Na O3Br Chlorine (Chlorine) Cl2 Chlorine dioxide ClO2 Chloride hydrogen, HCl (Acid hydrochloric) Chlorides Cl-‐ Sodium hypochlorite (from Water bleach) NaOCl Sodium chlorite Na O2Cl
7647-15-6
Hypnotic
7789-38-0
Méthémoglobinisant
Reprotoxic
7782-50-5
Corrosive
Irritant
10049-04-4
Irritant
Bronchial
7647-01-0
Corrosive
Irritant
Hypertension 7681-52-9
Irritant
7647-14-5
Irritant
10
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MINERAL CHEMICAL
LY
MAJOR MINERALS CHEMICAL COMPOUNDS IN FRACTURING FLUIDS
7429-90-5
26
Carbon Black
7440-44-0
27
Graphite
7782-42-5
28
Chromium (Metal) ° Cr Trivalent chromium acetate (Chromic acetate) Cr (CH3COO)3
7440-47-3
Copper (metal) Cu ° Cupric chloride, dihydrate CuCl2, 2H2O Cupric sulfate CuSO4 Iron (metal) Fe ° Ferric chloride FeCl3 Ferrous sulfate heptahydrate Fe SO4, 7H2O Ferric oxide Fe2O3
7440-50-8
16
Aluminium
17
18 19
20
Compounds Calcium
21
22
23 24
25
Compounds Inorganic carbon
Compounds Chromium
29
30
Copper compounds
CASE Nbr
Aluminum Al ° Alumina (Aluminium oxide) Al2O3 Aluminum trichloride AlCl3 Aluminum silicate Al2SiO5 Barium sulphate BaSO4 Calcium oxide (Lime) CaO Calcium hydroxide (Slaked) Ca (OH) 2 Calcium chloride CaCl2 Calcium carbonate CaCO3 Calcium hypochlorite Ca (OCl) 2 Carbon dioxide (Carbon Dioxide supercritical) CO2
15
Compounds of
Compounds Barium
TOXICITY
31
32 33 34
Compounds of Iron 35
36
Acute Subacute
or
In the long term
1344-28-1 Irritant
Neurotoxic central
1305-78-8
Corrosive
Irritant
1305-62-0
Irritant
7446-70-0 1241-46-7 7727-43-7
10043-52-4 471-34-1 7778-54-3 124-38-9
1066-30-4
Anoxia, Frostbite
Allergenic
7447-39-4
Irritant
7758-98-7
Irritant
7439-89-6 7705-08-0 7782-63-0
Irritant Irritant
1309-37-1
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CHEMICAL MINERAL Family
COMPOUNDS IN MEETINGS FRACTURING FLUIDS 37
Compounds Magnesium
38
39
Compounds Nickel Compounds Potassium
40
41
42
43
Compounds Silicon
Compounds Sodium
TOXICITY
MAJOR MINERALS CHEMICAL
44
45
Magnesium chloride MgCl2 Magnesium nitrate Mg (NO3)2 Magnesium aluminosilicate Nickel sulphate NiSO4 Potassium hydroxide (Potash) KOH Potassium chloride KCl Crystalline silica (Cristobalite, Quartz, Tridymite) (SiO2)n Talc (Magnesium silicate, anhydrous) Mg3 (SiO3)2 Attapulgite (Polygorcite)
CASE Nbr
7786-81-4 1310-58-3
14464-46-1
48
Diatomaceous earth
49
Sodium hydroxide (Caustic Soda) NaOH
NaNO2
53
Sodium nitrate NaNO3
54
Sodium sulphite Na2SO3 Sodium sulfate Na2SO4
55
Irritant
Fibrosis (silicosis), Carcinogen in form of particles (IARC Group 1)
12174-11-7
12001-26-2
52
Irritant
14807-96-6
Mica
Sodium nitrite
Corrosive
15468-32-3
47
Sodium carbonate Na2CO3
Allergenic
7447-40-7
1302-78-9
51
In the long term
10377-60-3
Bentonite
Sodium hydrogeno carbonate NaHCO3
or
7786-30-3
46
50
Acute Subacute
Lung irritant Lung irritant
1310-73-2
If the presence of quartz fibrosis If the presence of quartz fibrosis
Corrosive
Irritant
Irritant
Irritant
144-55-8
497-19-8 7632-00-0
Méthémoglobinisant
7631-99-4
Méthémoglobinisant
7757-83-7
Irritant
Méthémoglobinisant, Carcinogen (Group 2A IARC) Méthémoglobinisant, Carcinogen (Group 2A IARC)
7757-82-6
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MINERAL CHEMICAL
Family
COMPOUNDS IN MEETINGS FRACTURING FLUIDS
56
Compounds 57
Sulfur 58 59
60
61
Compounds Titanium
Sulfuric acid
CASE Nbr
7664-93-9
Corrosive
Sulfamic acid (Amino sulfonic acid) HOSO2NH2 Ammonium sulfate (NH4)2 SO4 Ammonium thiocyanate (NH4)2 SO3 Ammonium persulfate (Ammonium peroxydisulfate) (NH4)2 S2O8
5329-14-6
Skin irritant, mucous
Titanium (metal) Ti °
7727-54-0
Zinc (metal) Zn ° Zinc carbonate ZnCO3 Zirconium nitrate Zr (NO3)4 Zirconium sulfate Zr (SO4)2 Zirconium oxychloride (Zirconyl chloride) ZrOCI2 Boric acid H3BO3 Borates BO3 3Sodium metaborate, octahydrate Na BO2, 8 H2O Boric oxide B2 O3 Sodium perborate, tetrahydrate Na BO4 , 4 H2O
7440-66-6
66 67
68 69
Compounds 70
Boron 71
72
Eye irritant, skin, respiratory
Allergenic
7440-32-6
63
Compounds
Irritating, Carcinogen form Aerosols (Group 1 IARC)
1762-95-4
13463-67-7
65
In the long term
7783-20-2
Titanium dioxide TiO2
64
Acute or Subacute
H2SO4
62
Zinc compounds
Zirconium
TOXICITY
MAJOR MINERALS CHEMICAL
Carcinogen possible (Group 2B IARC)
3486-35-9 13746-89-9 14644-61-2 7699-43-6
Corrosive
Irritant
10043-35-3
Skin irritant
Reprotoxic (Repro2)
Irritant
Reprotoxic
7775-19-1
Irritant
1303-86-2
Skin irritant, ocular
Reprotoxic
10486-00-7
Eye irritant
Reprotoxic (Repro2/Repro3)
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MINERAL CHEMICAL
TOXICITY
MAJOR MINERALS CHEMICAL COMPOUNDSIN MEETINGS FRACTURING FLUIDS
FAMILY
7664-39-3
Corrosive
Irritant
74
Ammonium bifluoride F2 (NH4)2
1341-49-7
Corrosive
Irritant
Hydrogen peroxide
7722-84-1
Irritating, skin, ocular
Promoter carcinogenesis
75
(Hydrogen peroxide)
oxygenated
phosphorus
A long term
Hydrogen fluoride (Hydrofluoric acid)
compounds
Compounds
Acute or Subacute
73
Fluorinated
Compounds
CASE Nbr
76
77
HF
H 2O 2
Dipotassium phosphate K2H (PO4)
7758-11-4
Trisodium phosphate Na3 (PO4)
7601-54-9
(Source: swarthmore.edu)
(Source: Unknown) Evolution of the landscape of pits of Marcellus shale gas in shale (USA) ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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IV, ORGANIC CHEMICALS CHARACTERIZED IN FRACTURING FLUIDS If mineral products can be grouped around the chemical elements themselves, by cons organic products will be classified by chemical family. All the organic compounds are carbon-based, most often linked to hydrogen, constituting and their hydrocarbon backbone and on which will generally be added one or more functions responsible for chemical reactivity of these molecules. Table 4 contains the main organic compounds, classified by family and which were collected by Environmental Protection Agency (EPA), in fracturing fluids. On this table, each compound is identified by CASE number and for information purposes only, is reported when described, acute or subacute, and the long-term toxicity. Table 4 : MAJOR ORGANIC COMPOUNDS, HIGHLIGHTED IN FLUIDS FRACTURING ORGANIC CHEMICAL FAMILIES
N°
MAIN ORGANIC
CASE Nbr
CHEMICAL COMPOUNDS
HUMAN TOXICITY
Acute or subacute
78
Methane CH4
79
Ethane CH3-CH3
Hydrocarbons Saturated Alkanes
80
Propane CH3-CH2-CH3
81
82
Butane CH3-CH2-CH2-CH3
Pentane CH3-(CH2)3-CH3
83
Hexane CH3-(CH2)4-CH3
84
85
Heptane CH3-(CH2)5-CH3
Propylene H2C═ CH-CH3
Hydrocarbons unsaturated ethylene: Alkenes
74-82-8
Asphyxiant
74-84-0
Asphyxiant
74-98-6
Asphyxiant
106-97-8
Asphyxiant
109-66-0
Narcotic
110-54-3
Narcotic
142-82-5
Narcotic
115-07-1
Asphyxiant
86
1 - Eicosene C20 H40
3452-07-1
87
1-Hexadecene C17 H34
629-73-2
1-Octadecene
112-88-9
88
C18 H36
In the long term
Neurotoxic peripheral (Polyneuritis)
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MAIN ORGANIC CHEMICAL FAMILIES
N°
CHEMICAL COMPOUNDS
1-Tetradecene C14 H30 d-Limonene
89
Hydrocarbons unsaturated ethylene: Alkenes
HUMAN TOXICITY
MAIN ORGANIC
CASE Nbr
Acute subacute
or
A long term
1120-36-1
5989-54-8
90
Irritating, Allergenic cutaneous
Irritating, Allergic skin
Styrene Neurotoxic, 100-42-5
91
Irritant
Benzene 71-43-2
92
Neurotoxic central
Toluene 108-88-3
93
Irritating, Neurotoxic central
Carcinogen possible (group 2B IARC) Haematological, Carcinogen (Leukemia) (Group 1 IARC) Neurotoxic central Ototoxic, Reprotoxic (Repro3)
Xylene (three isomers) 1330-20-7
94
1,2
1,3
Irritating, Neurotoxic central
central
1,4
Ethylbenzene 100-41-4
95
Hydrocarbons
Irritating, Neurotoxic moderate central
Cumene (Isopropylbenzene)
Aromatic (Arena)
Neurotoxic
98-82-8
96
Eye irritant
Skin irritant, Neurotoxic central moderate Carcinogen possible (group 2B IARC) Carcinogen possible (group 2B IARC, 2012)
Pseudocumene (1 ,2,4-Trimethylbenzene)
97
95-63-6
Irritating, Neurotoxic moderate central
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ORGANIC CHEMICAL FAMILIES
N°
HUMAN TOXICITY
MAIN ORGANIC CHEMICAL COMPOUNDS
CASE Nbr
Acute subacute
25340-17-4
Irritant
or
A long term
Diethylbenzene (Mixture of 3 isomers) 98
1,2
1,3
1,4
Dodecylbenzene 123-01-3
99
Naphthalene Irritant
Hydrocarbons
91-20-3
100
gastrointestinal Hepatotoxic Haematotoxic
Haematotoxic (Anemia hemolytic) Cataract, Carcinogen possible (Group 2 B IARC)
1-Methylnaphthalene
Aromatic (Arena)
101
90-12-0
Mutagenic
91-57-6
Mutagenic
86-73-7
Mutagenic
2-Methylnaphthalene 102
9H-Fluorene 103
Phenanthrene
85-01-8
104
Photo-
Mutagenic
sensitizing
105
Isoparaffin hydrocarbons oil
106
Paraffin oil, light
Mixtures Hydrocarbons
107
Terpenes, lemon extract
94266-47-4
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Allergenic
17
ORGANIC CHEMICAL FAMILIES
HUMAN TOXICITY
MAIN ORGANIC
N°
108
CHEMICAL COMPOUNDS
110
Acute subacute Allergy
Turpentine
8002-09-3
(Pine oil)
109
CASE Nbr
toluene, xylene, ethylbenzene)
Poly aromatic hydrocarbons
Irritant
(PAHs)
Mixtures 111
Hydrocarbons
112 113 114
Refined petroleum
Diesel
116
Heavy naphtha
117
Kerosene
Irritant 8006-20-6
Irritant
68334-30-5
Irritant
64741-68-0 64742-94-5
Irritant
8008-20-6
Irritant
8052-42-4
Irritant
Asphalt 118
119
Vinylidene chloride (1,1-dichloroethylene)
Cl
Eye irritant, 75-35-4
Cl
Compounds
Tetrachloroethylene (Perchloroethylene) 120
Organochlorine
Cl
Cl
Cl
Cl
Benzene is Carcinogen (Group 1 IARC) Several PAHs Carcinogens are in humans [Benzo (a) pyrene ...]
Irritant
Naphthalene heavy, hydrogenated
115
Allergic skin
Irritant
Light oil, hydrogenated
Motor gasoline (Gasoline)
A long term
(by origin) Irritant
Aromatic solvents (benzene,
or
skin, respiratory
Eye irritant, 127-18-4
Carcinogen possible (group 2B IARC) Carcinogen (Group 1, IARC) Carcinogen IARC) possible
May contain products carcinogenic Hepatotoxic Nephrotoxic, Carcinogen possible Hepatotoxic
skin, respiratory
Carcinogen probable (group 2A IARC)
Eye irritant,
Mutagenic,
skin, respiratory
Carcinogen (Group 2A IARC)
Benzyl chloride 121
Cl
100-44-7 l
Alcohols
122
Methanol CH3-OH
67-56-1
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Eye irritant cutaneous
Neurotoxic peripheral (Optic nerve) Acidosis
18
ORGANIC CHEMICAL FAMILIES
N°
HUMAN TOXICITY
MAIN ORGANIC CHEMICAL COMPOUNDS
CASE Nbr
Acute or subacute
Ethanol 123
64-17-5
CH3-CH2-OH
Eye irritant, cutaneous
Propanol 71-23-8
124
CH3-CH2-CH2-OH Isopropanol CH3 H C OH CH
125
67-63-0
3 3
126
Butanol CH3-CH2-CH2-CH2-OH
71-36-3
In the long term Toxic ingestion, Hepatotoxic Carcinogen (Group 1 IARC), Reprotoxic
Eye irritant, cutaneous Eye irritant, cutaneous Eye irritant, Cutaneous, narcotic
Isobutanol
Alcohols
CH3
127
CH3 128
CH3
Eye irritant, cutaneous
Isooctanol CH
CH3
78-83-1
CH CH2 OH
(CH2)4 CH2
OH
26952-21-6
Eye irritant, cutaneous
129
130
2-Ethyl hexanol CH3 (CH2)3 CH CH2 OH CH2
104-76-7
Eye irritant
107-19-7
Irritant
112-42-5
Skin irritant
Reprotoxic
CH3 131 132
Propargyl alcohol H-C ≡ C-CH2-OH Undecanol CH3 (CH2)9 CH2 OH Ethylene glycol
133
CH2 OH
107-21-1
Neurotoxic, Nephrotoxic
CH2 OH 134
Glycerol HOCH2-CHOH-CH2OH
56-81-5
Eye irritant, cutaneous
135
Sorbitol HOCH2-(CH2) 4-CH2OH
50-70-4
Intestinal irritant
136
Polyvinyl alcohol
9002-89-5
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19
MAIN ORGANIC CHEMICAL FAMILIES
N°
Amino Alcohols
137
MAIN ORGANIC CHEMICAL COMPOUNDS Ethanolamine H2N-CH2-CH2-OH
HUMAN TOXICITY CASE Nbr
141-43-5
Acute or subacute Irritant
Diethanolamine 138
H N
CH2 CH2 OH
111-42-2
CH2 CH2 OH
Eye irritant, skin, respiratory
Ethylene oxide 75-21-8
139
140
2-Methoxyethanol (Methyl ether of ethylene glycol) O O H
109-86-4
Méthoxyéthylacetate (methyl ether of ethylene glycol acetate) 141
O
O
Eye irritant, cutaneous
O
O
110-49-6
A Long-term
Allergenic Possibility of formation of Nnitrosodiéthanola -mine, carcinogenic Mutagenic, Carcinogen (Group 1 IARC)
Eye irritant,
Reprotoxic
cutaneous
(Repro-2)
Eye irritant,
Reprotoxic
bronchial
(Repro-2)
Eye irritant,
Reprotoxic
cutaneous
(Repro-2)
Eye irritant,
Reprotoxic
cutaneous
(Repro-2)
Eye irritant, cutaneous
Nephrotoxic
Ether-oxides 142
(Epoxides Glycol ethers, Ether-oxides Polymers)
143
2-Ethoxyethanol (ethyl ether of ethylene glycol)
O
O H
2 Ethoxyéthylacétate (Ethyl ether ofethylene glycol acetate) O O O
Diethylene glycol 144
O H
O
H O
110-80-5
111-15-9
111-46-6
1,4-Dioxane
O
145
123-91-1
Eye irritant, cutaneous
O 1,2-Dimethoxyethane
O
O
146
110-71-4
Irritant
Reprotoxic (Repro-2)
629-14-1
Eye irritant
Reprotoxic (Repro-2/3)
1,2-Diethoxyethane
O
O
147
Dipropylene glycol 148
H O
O
O H
Carcinogen possible (Category 2B IARC)
25265-71-8
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MAIN ORGANIC CHEMICAL FAMILIES
N°
HUMAN TOXICITY
MAIN ORGANIC CHEMICAL COMPOUNDS
CASE Nbr
Acute or subacute
2-Butoxyethanol (Butyl ether of ethylene glycol)
O H
O
149
111-76-2
Skin irritant
111-77-3
Eye irritant
In the long term Toxic blood Disruptive endocrine (Ovaries, adrenal)
2 - (2-Methoxyethoxy) ethanol. Methyl ether of diethylene glycol
O H
O
O
150
Ether-oxides
(Epoxides Glycol ethers, Ether-oxides Polymers)
151
2 - (2-Ethoxyethoxy) ethanol Ethyl ether of diethylene glycol O H O O
111-90-0
Eye irritant, cutaneous
2 - (2-Butoxyethoxy) ethanol Butyl ether of diethylene glycol 152
O H
O
O
112-34-5
Eye irritant
10213-77-1
Eye irritant
93-18-5
Skin irritant
104780-82-7
Irritant
2 - (2-Methoxypropoxy) propoxy propanol Methyl ether of tripropylene glycol 153
O
154
155
156
Polymers
O
O
2-ethoxynaphthalene O
Ethyl alcohol ethoxylate (Polyethoxy ethanol) (C2H4O) n, C2H5O
O
H
Lauryl alcohol ethoxylated (C2H4O)n, C12H26O
Irritant
157
Ethoxylated octyl phenol (C2H4O)n, C14H22O
9036-19-5
Eye irritant
158
Ethoxylated nonylphenol (C2H4O) n, C15H24O
9016-45-6
Irritant
Aether-oxides
159
160
Polyethoxylated alkanols (C2H4O)n, CnHn'O Polyethylene glycol (C2H4O) n, H2O
Irritant 25322-68-3
Eye irritant, cutaneous
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21
MAIN ORGANIC CHEMICAL FAMILIES
Aldehydes
N°
MAIN ORGANIC CHEMICAL COMPOUNDS Formaldehyde H C O H
161
HUMAN TOXICITY CASE Nbr
50-00-0
Eye irritant, skin, respiratory
111-30-8
Irritant eye skin, respiratory
67-64-1
Eye irritant, skin, Neurotoxic
108-10-1
Eye irritant, skin, respiratory Neurotoxic
Glutaraldehyde 162
H
H O
O
Acetone
O
163
CH3 C CH3
Ketones
Methyl isobutyl ketone 164
CH3 CH
CH2
O C CH3
CH3 Formic acid 165
H
O C
64-18-6
OH
Acetic acid O
166
64-19-7
CH3 C OH
Acute or subacute
Corrosive (Eyes, skin, mucous membranes ...)
In the long term Allergenic Carcinogen (Group 1 IARC) Allergenic
Irritant
Eye irritant, cutaneous
Fumaric acid O
HO C
167
C H C H
Acids
168
Carboxylic
HO
cutaneous
OH
O
(CH2)4
Glycolic acid 169
Eye irritant,
O
Adipic acid O
HO C
C
110-17-8
C OH
124-04-9
O
CH2 C OH
79-14-1
Eye irritant
Eye irritant, skin, respiratory
Citric acid O 170
HO
CH2
C OH O
C
C
CH2
C
77-92-9
OH OH
O
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MAIN ORGANIC CHEMICAL FAMILIES
N°
MAIN ORGANIC CHEMICAL COMPOUNDS
CASE Nbr
HUMAN TOXICITY
Acute subacute
or
A Long-term
Thioglycolic acid (Mercaptoacetic acid)
Acids Carboxylic
O
171
68-11-1
CH2 C O H
HS
Eye irritant, skin, respiratory
Acetic anhydride
Anhydride acid carboxylic
O 172
CH3 C CH3 C
108-24-7
O
Eye irritant, cutaneous
O 173
174
Esters carboxylic
175
Sorbitan monooleate C24H44O6
1388-43-8
Polyethylene glycol oleate O C17H33 C O
CH2-CH2-O
n
Fatty acid esters O
917-44-20-6
R1 C O R2 176
Castor oil, ethoxylated
61791-12-6
Ethyllactate
O
177
97-64-3
HO O Triethanolamine glycolate
Acid salts
178
carboxylic
O N+
HO
OH OH
H
OH O OH Tributylphosphate (TBP) O
Esters phosphoric (Phosphates organic)
179
180
- +
O
O P O O
Tributyltétradécyl phosphonium chloride
126-73-8
Irritant
80741-28-8
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23
MAIN ORGANIC CHEMICAL FAMILIES
N°
181
Amines
HUMAN TOXICITY
MAIN ORGANIC CHEMICAL COMPOUNDS
CASE Nbr
Aminoethylethanediamine (Diethylenetriamine) H
111-40-0
N-Oxides Amine
183
184
Allergenic
NH2
1,6-hexanediamine 182
Eye irritant,
A long term
cutaneous
N
H2N
Acute or subacute
H2N
124-09-4
NH2
Trimethylamine N-oxide + N O
Eye irritant, skin, respiratory
1184-78-7 Irritant
Tetramethyl- ammonium chloride + Cl N
75-57-0
Dimethyldiallylammonium chloride
Salts
+
185
Ammonium quaternary 186
Irritant
Cl
N
Dimethyl didecylammonium chloride +
N
7173-515-5
Skin irritant
593-81-7
Irritant
75-12-7
Eye irritant
Cl
Trimethylammonium chloride
+
187
Cl
N
H N-benzyl alkylpyridinium chloride
Salts of immonium Bases Heterocyclic nitrogenous unsaturated
188
Cl
N+
R
1 (-Phenylmethyl) quinolinium chloride 189
N+ H
Amides
190
Cl
Formamide O
H C NH2
Reprotoxic (Repro 2)
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MAIN ORGANIC CHEMICAL FAMILIES
N°
MAIN ORGANIC CHEMICAL COMPOUNDS
HUMAN TOXICITY CASE Nbr
Dimethylformamide (DMF)
O CH3
191
68-12-12
H C N CH3
192
2,2-Dibromo-3-nitropropionamide (DBNPA) NO2 Br
10222-01-2
NH2
Br
Acute or subacute Eye irritant, skin, respiratory
In the long term
Dermatosis, Hepatotoxic Reprotoxic (Repro 2)
Eye irritant, skin, respiratory
O
Amides
2-Bromo-3-nitrilopropionamide (MBNPA) 193
Irritant 1113-55-9
H
N
Br
NH2
O 2,2-Dibromomalonamide
Irritant eye skin, respiratory
O
194
Br
NH2 NH2
Br
O BrAcrylamide O NH
Irritant
2
79-06-1
195
O
Dibromoacetonitrile 196
Br
N
Br
Nitriles
3252-43-5
2-Bromo-3-nitrilopropanol
H Br
1,2-Benzoisothiazolinine-2-one S 198
eye skin, respiratory
Neurotoxic peripheral (Polyneuropathy) Carcinogen probable (Group IARC 2A)
Irritant eye skin, respiratory Irritant eye skin, respiratory
N OH
197
eye skin, respiratory
2634-39-5
O N H
Heterocycles
4-Méthylisothiazolidine S 199
N H
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MAIN ORGANIC CHEMICAL FAMILIES
HUMAN TOXICITY
MAIN ORGANIC CHEMICAL COMPOUNDS
N°
CASE Nbr
Acute or subacute
A long term
2-Quinaldine chloride
Heterocycles
91-63-4-20
200
Eye irritant, cutaneous
N+ CH3 H Cl Diisopropylnaphthalene sulphonic acids SO3H
201
Sodium octanesulphonate SO3 Na +
202
Ammonium cumene sulfonates
Compounds
SO3
203
-
+ NH4
Isopropylamine dodecylbenzenesulfonate
sulphonated 204
+ H2N
-
SO3
Sodium alcénylsulfonate 205 CH
R
CH
SO3
*
-
+ Na
n
Sodium ligninsulfonate
206
Sodium alkylaryl sulfonates 207 R
CH
CH
SO3
*
-
+ Na
n
Polyvinyl alcohol
Polymers
208
CH2 CH OH
209
9003-89-5 9002-89-5 n
Anionic polyacrylamide
9003-03-8
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26
MAIN ORGANIC CHEMICAL FAMILIES
HUMAN TOXICITY
N°
210 211 212
MAIN ORGANIC CHEMICAL COMPOUNDS
Copolymers of acrylamide Oleic ester of polyethylene glycol
CASE Nbr
Acute or subacute
A long term
38-192-60-1
9004-57-3
Irritant cutaneous
Polyhexamethyleneadipamide Polymers of acrylic acid
Polymers
213
OH O
n
Polymers of thiourea 68527-49-1 214
215
216
217
Carbohydrates
218
219
and
S C
NH2 NH2
n
Guar resin (Natural polymer saccharide) Hemicellulase (Enzyme) Cellulose (C6H10O5)n
9000-30-0 9025-56-3 9004-34-6
Ethylcellulose
9003-05-8
Sucrose (Sucrose) C12H22O11
57-50-1
Ethylenediaminetetraacetic acid
derivatives
Chelating
Various
60-00-4
220
Compounds simple
NTA Nitrilotriacetic acid (NTA) O
N HO O
Chelating
OH
139-13-9
221
Irritant eye skin, respiratory
O OH
Irritant eye skin, respiratory
Nephrotoxic, Chelating Ca+ 2 and Zn+ 2
Nephrotoxic, Chelating Ca+ 2 and Zn+ 2 Carcinogen possible to Rights (group 2B IARC)
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27
V, fracturing fluids: A REACTIONAL ENVIRONMENT Of the 392 products or mixtures, listed in the EPA document of February 21, 2011 (EPA / 60/D-11) and was used to create the tables 3 and 4, only 221 were selected, the others have could be identified from their chemical name, which is not obvious. Note several repetitions, such as hydrochloric acid which is also known muriatic acid, a very old name. Among the products identified by the EPA in water recovery, it is surprising to find the numerous halogenated hydrocarbons (methyl chloride, methyl bromide, 1,4-dichlorobutane, 2 - fluorobiphenyl...) Which may have formed in the fracturing environment from initial hydrocarbon, in the presence of halogenating reagents, themselves initially present in the fracturing environment. Everything seems as if the fracking zone, which is located at great depths (1000 3000 m or more), subjected to high pressures and temperatures high enough, is included as a chemical reactor in which several hundred products, including some are powerful catalysts (metal salts ...), interacted and formed into final new compounds, results of one or more chemical reactions. One that may seem, the most amazing results is 4-nitroquinoline-N-oxide (4-NQO), that found in the output water of fracturing, according to documents of the NYSDEC, the State of New York at concentrations that can approach 15 mg/L-1. Where can come from this compound, which may seem very unusual in water fracturing, whereas it is only used by specialists in experimental carcinogenesis selectively trigger in rodents (rats, mice) of cancers of the oral cavity and tongue, but also by microbiologists as an effective control mutagenesis substance, for example with Escherichia coli (SOS-chromotest). For the sake of profitability, oil inject some fracturing fluids, cuts crude oil, which correspond to very complex mixtures and that have also not been taken into account in Table 4. Among them is injected routinely mixtures of nitrogenous bases easily removable for crude oils by treatment in acidic medium, among which are mixtures of the quinoline and its derivatives (for example, the compound No. 200). The quinoline is a unsaturated nitrogen heterocyclic base, whose structure can be likened to the naphthalene (mothballs, moth products) in which a carbon atom is replaced by a nitrogen atom.
One can imagine that initially is injected a mixture of nitrogen bases containing quinoline and a reactive nitrating such as metal nitrate while the acid (HCl ...). At the area fracturing, the quinoline will easily is selectively nitrated, So only on the top para to the nitrogen atom, the 4-nitroquinoline thus formed can be easily oxidized, at of the heterocyclic nitrogen atom by a peroxidizing agent such as hydrogen peroxide and in final 4-nitroquinoline-N-oxide, as shown in Figure 4. If, in the fracturing fluid, EPA has identified several derivatives of quinoline, is a single found in substantial quantities in water output. This is the N-oxide of 4 - nitroquinoline, known as a model animal to trigger specifically in rodents, cancers of the oral cavity selective and language.
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28
The formation of N-oxide can be envisaged as shown in Figure 4, from the 4 - Nitroquinoline, by oxidation in the presence of oxidizing chemical reagents present in the liquid as the fragmentation hydrogen peroxide (Hydrogen peroxide, No. 75), the perborate sodium (No. 72) or the ammonium peroxydisulfate (No. 60).
NO3 H
N
NO2
NO2
-
H2O2
+
N 4-Nitroquinoleine
Quinoléine
N+ O N-Oxyde de 4-nitroquinoleine
Figure 4 : Formation of 4-nitroquinoline-N-oxide by oxidation of 4-nitroquinoline, after the selective nitration of quinoline. Similarly, it appears in the output water fracturing, of hexavalent chromium compounds :(chromates...) While in the initial liquid the EPA has only identified one trivalent chromium salt, chromic acetate (No. 29). In an oxidizing medium, it is easily transformed into compound hexavalent, as shown in Figure 5 O
Cr (CH3COO)3 Acétate chromique
CrO4
2-
Chromate
Figure 5: Oxidation of Chromic acetate chromate dianion. Moreover, it seems surprising that we find in the water output, as reactive compounds that ethylene oxide (No. 139), Just waiting to hydrolyze into ethylene glycol (No. 133) such as Figure 6 shows
CH2 CH2 O
H2 O H
Oxyde d'éthylène
+
H O CH2 CH2 O H Ethylène-Glycol
Figure 6 Hydrolysis of Ethylene oxide to Ethylene glycol.
VI, ROUTES OF EXPOSURE TO CHEMICALS IN FRACKING FLUIDS AND RISKS Regarding the effects of chemical compounds produced during the various processes during extraction of gas or oil from shale or parentrock, it is necessary to distinguish several exposure steps : 1) During initial step, must take into account the handling of all products departure which is mixed to obtain the final product which will be injected. During these manipulations, the priority channel will be inhalation exposure products, including the volatility be highly variable ... from methane at naphtha ! Many petroleum fractions can be implemented rich volatile organic compounds (VOCs) such as benzene (No. 92), a potent human carcinogen. As the majority of hydrocarbons are very soluble in fat, penetration through the skin should not be neglected because it can contribute to the toxic process. In fact, the pollution levels higherwill be located near sites of mining activity. ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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Note that the co-existence among air pollutants of volatile hydrocarbons and of nitrogen oxides (NO)x may, at ground level result in formation of ozone (O3), pollutant often found on sites operating. Further more, we observe in the mining areas of shale or bedrock, an increase non-negligible particles, especially the many fine nanoscale. These preferably from the last combustion of diesel (n°115, carcinogen in human, Group2A IARC)), the fuel of choice of transport units extremely numerous on the extraction sites (truck transport tank of water, gas ...).
Fire pits on a U.S. (Source: frackcheckwv.net)
Explosion at a construction site extraction. Marcellus shale (Source: rue89.com)
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30
It must be remembered that major accidents may threaten the workers health, but also surrounding populations, Are explosions (see photo page 30), fire (See photo page 30) the rest ... often linked to leakage and to Pipeline ruptures or accidental spills, indeed criminals, dangerous substances. Without official statistics, seems difficult to assess the frequency of this type of incident or accident, but the United States, it may not be negligible! Of course, people whose exposure to various air pollutants (hydrocarbons,NOx, SOx, O3 particles varied....) Is likely to increase in an area of operation of the gas or shale bedrock, are those whose homes and related activities are located near production sites. Nevertheless, the problem is to correctly estimate the real level of the contamination, both mixtures can be complex and variable concentration. In addition, synergies between compounds can greatly increase their aggressiveness.
Marcellus Shale. Pits (Source: powderriverbasin.org) 2) The actual extraction of gas will begin with a vertical borehole in which the thewater mixed with sand, or barium sulfate (BaSO4) (No. 19) and various other additives chemical, Is injected from the drill bit head. This mixture comes to the surface under a sludge (100 to 125 m³ per well), the latter will the storage object in specialized centers or landfill. In a second step, the hydraulic fracturing itself will require the use of very large amounts of water, of the order of 2 million liters of water per fracturing step.
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As a vertical shaft allows for 6 to 10 steps of fracturing horizontal, volume of water needed at all stages of operation can be estimated at nearly 12 to 20 million liters of water per well (Data from the National Public Health Institute of Quebec, November 2010). United States, in Pennsylvania, where there are 71 000 is an active well drilling for 1.6 km2, the use of instead of water in underground 2008, resulted in the drying several groundwater! One can only wonder about ecological future of these regions! Excavation with holding tank Marcellus Shale (Source: Unknown)
At the operating phase of a well, rising to the surface of the gas is sometimes accompanied a large amount ofbrackish water. This water rich in salt (sodium chloride) from of ancient seas, whose water remains trapped in the shale or bedrock. In general if a part of the reclaimed water can be reused for new fractures, the majority of the water worn very high salt, Is stored in a lagoon where it will desalinate slowly. Then Use routing this water is eithered in a treatment center, is injected into deep geological formations, resulting in significant risk of pollution, such as water can remain contaminated by many chemicals pollutants. Business Survey in the United States, showed that waste and the debris or drilling wastes can show a significant radioactivity. According to the EPA, in Pennsylvania, wastewater presented a levels of radioactivity 100 to 300 times higher than the standards applied in the U.S.. Among the radionuclides are mainly characterized radium-226 (1600 year half-life), but also radon 222, or thorium-232 and uranium 235. These radioactive elements, in particular the radon 222, radium-226 and the thorium-232 are formidable lung carcinogen in humans (IARC, Group 1), the latter having been detected in drinking water, distributed to local populations (NYSDEC. 2009). Still, according to EPA (2009), "The exploitation of shale or bedrock, is not coherent with a supply of drinking water unfiltered "This is only confirm the great distrust of the U.S. environmental agency for all matters relating exploitation of gas and oil shale or bedrock, which resulted in so many ecological disasters North America and that will in fact lead to desertification of vast areas formerly prosperous.
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32
Very generally, among environmental impacts related to the operation or gas oilsor shale bedrock, the most important is, in fact, Water whose management must scrupulously three general principles :
•
a) The amount of water necessary drilling and fracturing, must be evaluated as soon departure, taking into account the essential water resources in local. This may seem obvious, yet this vital data has been completely ignored in some regions of the United States, dedicated no doubt in future close to desertification. As previously reported, the amount of water required for drilling and fracking ranges from 10 000 to 15 000 m³ drilling Or much more!
•
b) It is extremely important evaluate ways to implement for recycling and above the treatment of water out of the fracturing. In general, 20 to 70% of the injected water is recovered but sometimes much least depending on local geology ! This water is either treated on site, is routed to a processing center. Having circulated under high pressure in the various sedimentary strata, this Water will load in salt, and different chemical elements minerals encountered on its way sooner or later. These elements vary in nature, can be released by the action of various constituents of the liquid fracturing (acid ...) even microorganisms.
Colonies Desulfovibrio desulfuricans (Source: sustainableotsego.org) Regarding the latter case, various rocks especially rich hematite (Fe2 O3), host colonies anaerobic bacteria almost, sulfate-reducing such as Desulfovibrio desulfuricans that feeding metal sulphides (pyrites...). Release of dihydrogen sulfide (H2S) gas is very toxic met from time to time in the gas recovered in the fracturing. It remember that this smelly gas (The rotten egg smell), kills faster that the carbon monoxide (CO) and is also endowed with an effect powerful anesthetic on the nerve olfactory. This may explain some deaths in the animal population living near farms, but also events like the "rain bird" found in the U.S States as has been said by the local press.
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33
As noted on page 65 the information report of the National Assembly on the "Mission information on gas and oil shale "of 8 June 2011, he can indeed" be at the very Unless of hazardous circumstances "because similar phenomena occurred in other parts of the world, including Sweden. We fully support this extremely careful reading of our report « écotoxicochimique ». We have also reported these doubts to the journalist Audrey Chauvet (article in the May 11, 2011 the daily 20 minutes). This does not diminish the effectiveness "lethal" H2S, which may for example killing a horse in a few seconds (beach of Saint-Michel en Greve in France, July 28, 2009)!
Rain Bird in Beebe, Arkansas late 2010 (Source: AP / WarrenWatkins)
Note that in wastewater discharged appear at the fracturing many salts water-soluble, Driven at the leaching through during different geological layers the recovery of fluids. Many of these are toxic to humans, including some very toxic (As, Ba, Cd, Pb, Tl ...). The chemical species detected for these different elements are grouped in Table 5. CHEMICAL ELEMENTS
Antimony
Sb3+, Sb5+
Beryllium
As3-‐, As3+, As5+ Ba2+ Be2+
Cadmium
Cd2+
Arsenic Barium
Chromium
Cr3+,Cr6+
Cobalt
Co2+, Co3+
Copper
Cu+, Cu2+
Nickel
Ni2+
Lead
Table 5 :
CHEMICAL SPECIES DETECTED
Pb2+, Pb4+
Thallium
TI+, TI3+
Thorium Uranium
Th4+ U4+, U6+
Vanadium
V5+
Yttrium
Y2+
CHEMICAL ELEMENTS OF NATURAL AND SPECIES DETECTED WATERS OUT OF FRACTURE (Ratio EPA / 600 / D - February 11, 2011. Page 98) ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
34
It is obvious that these natural elements that enrich outlet water wells fracturing are many pollutants, which will disrupt treatment plants classically saturated in these extraction areas. Height of difficulty, these discharges, can also focus radioactive elements such as radium (Ra226), it is virtually impossible to eliminate. Generally, many metals (Iron, Copper, Manganese, Silver, Mercury, Lead, Cadmium, ...) and non-metal (Arsenic, Antimony, Selenium...), in rocks in the state of sulphides, may be released in a soluble ionized form. Various chemical reagents added to start in Water fracturing can facilitate this release. And from their sulphide, mercury, lead, cadmium and the thallium but also non-metals as arsenic and antimony will release their water-soluble cations, which are extremely toxic.Therefore, it is not surprising to find all these toxic elements in wastewater, as shown in Table 6. TYPE OF CONTAMINANTS
EXAMPLES
Gas
Hydrocarbons (Methane, Ethane) Carbon dioxide (CO2) Dihydrogen sulfide (H2 S) Dinitrogen (N2) Helium (He)
Toxic Trace Elements
Radionuclides
Organic Compounds
Mercury (Hg) Lead (Pb) Arsenic (As) Radium (Ra 226) Radon (Rn 222) Thorium (Th 232) Uranium (U 235) Carboxylic acids Polycyclic Aromatic Hydrocarbons (PAHs) Volatile Organic Compounds (VOCs)
Table 6 : MAJOR CHEMICAL COMPOUNDS IN TRAINING MEETINGS GEOLOGICAL CROSSINGS DURING EXTRACTION OF OIL AND GAS NO CONVENTIONAL (EPA / 600 D - II, February 2011)
From a quantitative point of view, if one is confined to the EPA document (EPA / 600 D - II, February 2011), injected fluid in the hydraulic fracturing is conventionally formed of a mixture of water (90% by volume) and sand (8 to 9.5% based firms), with various chemical additives. The concentration of these additives does not appear to exceed 2% and is located in average around 1%. According to geological structures encountered, chemical additives, whose primary role is to strengthen the hydraulic fracturing and to avoid bacterial contamination, will have compositions vary. This explains, in addition to the products listed by the EPA, whose main representatives are given in Tables 3 and 4, numerous other compounds are reported by many organizations. The variety is impressive ranging ... amino acid essential (lysine, arginine..) to the alkyl glycosides... In fact, all the chemistry seems to have concentrated in the fracturing fluids ... all chemical reactions in power! In fact, is the real obstacle to obtain information on the actual concentration of the products in this chemical soup, which one can only wonder about the need to contain both constituents! 35 ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
Historically, exploitation of shale or bedrock, spreads in the U.S. about a decade but worryingly, the number of producing wells is growing, with its attendant of environmental damage. But what we see, it is the scarcity of operating areas, which are monitored regular quality water this does not suggest the absence of risk contamination and gives free rein to the optimism displayed by oil tankers! In most cases, a monitoring takes place following an incident or accident but it is never routine. Thus, 5 May 2004, in Pennsylvania, an explosion occurred in a dwelling in which the owner, by opening a water tap in the presence of a flame, resulting in the destruction of his home and the deaths of three residents. It is astonishing to learn that the concentration of methane in drinking water is sometimes of the order of 1 mg/L-1, which is a factor of explosion and fire very important this has forced him to set up locally prevention (Degassing of the water, bottled water distribution ...). A recent study by Robert Jackson et al (8) showed that in Pennsylvania, in the area drilling activity, the methane concentration of the water outlet is located in the fracturing between 10 and 28 mg/L-1. A maximum concentration of 66 was observed mg/L-1, Which corresponds to a explosive atmosphere very important. In the documentary film Gasland (January 2011) John FOX very effectively alerted the consciences on the real dangers of oil and gas operations in the U.S., ecological disasters and social which indeed can reproduce throughout the world. Following this film, widely distributed, a controversy has developed, with U.S. oil on the real origin of methane responsible for the contamination of drinking water. Indeed, the methane perhaps of biogenic origin, mainly due to the decomposition by fermentation of contents organic (biogenic methane) is derived from the the thermal decomposition of buried organic matter (thermogenic methane) and which is released during fracturing of rocks impregnated shale gas. The differentiation of the origin of methane, is based on analysis isotope 14C. HOW TO CONSOLIDATE THE CHEMICAL ADDITIVES? The chemical additives added to the water fracturing (Table 3 and 4) can be grouped into three broad categories : a) Products • that promote the penetration of sand or ceramic beads in fractures. Among them, hydrochloric acid (No. 11) is the most abundant (Table 2 and 3). b) products that increase productivity wells, Including the gelling agents (Gelling agent) increase the viscosity of the drilling mud. Then you need break the gel with ammonium persulfate (No. 60) • allergenic), who left the sand in the well, can be traced back phase liquid. (product For maintain the fluidity of gel, when the temperature of the well increases, it is necessary add liaison officers (Cross linker) based oxygenated derivatives of boron as boric acid (No. 68) and borates (No. 69), some of which are classified reprotoxic (Repro2) by the European Union. c) Biocidal products that reduce bacterial growth in the fluid fracturing, but also in the wells themselves. These antiseptic products, a classical usage (medical) are present in fracturing fluids at very low concentrations of the order of 0.001% (Table 2) and do not seem endowed with a significant long-term toxicity. However, a process of substitution of these biocides, was proposed by the company • HALLIBURTON uses for disinfecting the ultraviolet which do not forget it, are classified by IARC, probably carcinogenic in humans (Group 2A). 36 ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
3) Consideration of assessing the degree of contamination of aquifers drinking water, is of particular importance. If the United States, thousands of wells drilling using horizontal hydraulic fracturing are in operation and under development accelerated, by cons we have only very few descriptions of contamination of water tables, the surface water and drinking water. Considering the increase in suspected cases and for overcome this deadlock constant information by oil companies, US-EPA has been mandated by the U.S. government to conduct a comprehensive study to determine the health and environmental impacts of hydraulic fracturing activities on sources of drinking water. The initial results should be available late 2011, but until this essential data, a very caution must be exercised. Ultimately, the wide variety of chemicals used in fracturing fluids and uncertainty regarding the concentrations used, do not facilitate an objective analysis of actual impacts on the health of workers and surrounding populations, but also the environment itself (wildlife). ∗
Regarding the latter, as noted the Quebec Association of Wrestling Against Air Pollution (AQLPA ) one wonders the real impact Environmental intensive exploitation of shale gas and this generally on the economy green. The answer seems to have been issued by Fatih Birol of the International Energy Agency (IEA) which is convinced that the shale gas boom has already resulted in a decrease of 50% investments in renewable energy, such as the United States, the solar and the wind. It seems unnecessary to comment on the official position! As was defined in 1996, the World Health (WHO), health is not merely the absence of disease, but also a state that allows the full development of individuals and communities. The major energy industries such as oil and gas extraction from shale or hydrocarbon source rock, lead on human communities an effect called across the Atlantic: "boom town". This effect "boom town" combines the benefits (economic development) and the effects negative population (National Institute of Public Health of Quebec, November 2010). In the U.S., in this context, the long-term effects on quality of life, health psychological and social communities living on the diamond fields of gas or oil Oil shale or bedrock, as few studies are available globally negative ... which is certainly not encouraging for the future country operators
∗
http://www.aqlpa.com/catalogue-de-documents/doc_download/60-lexploration-et-lexploitation-des-gaz-de-schiste-dans-la-vallee-du-saint-laurent.html ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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VII, MAJOR TOXIC PRODUCTS FOR HUMANS IN FRACKING FLUIDS Most recently, the United States, the Comission of the Energy and Commerce House of Representatives represented by H.A.WAXMAN, E. J. MARKEY and D. DEGETTE, published on 16 April 2011, a list of various 2500 products (Pure or mixtures), corresponding to 750 well-defined chemical compounds. This document contains data from 14 companies services, working for the American oil industry gas, which are spread between 2005 and 2009 (Chemicals Used in hydraulic fracturing, United States House of Representatives commitee on energy Minority staff and Trade, April 2011). In this impressive list, one finds proven carcinogens for Human such as Benzene (No. 92, leucemiant agent), as well as everyday products such as instant coffee, apparently he low toxicity and for which one can ask about its real usefulness in fluids fracturing! In concluding this report, it is reported that the chemical mixtures in 2500, over 650 contain potentially harmful products. Among the latter, 22 are classified as carcinogens and are subject to U.S. laws on clean drinking water and clean air. It is likely that oil companies who want to extract in France, oil and gas shale, will not use the "cocktail delusional" of 2500 products listed in the U.S.. But from there, to think, that as some proclaim (pétroliers. relayed by official experts) that to barely a around six chemicals would be sufficient for the extraction, is a "Dream oil" very optimistic! Especially since these tankers do not forget that shale oil (CASE 68308 - 34 - 9) is classified by IARC (Thus theWHO) and this since 1987 (IARC vol 35, suppl 7) carcinogenic in humans (Group 1!) Without deciding whether the real figure of the minimum number of chemicals, necessary for a profitable exploitation of shale gas, one can nevertheless comment on the list of products considered dangerous by U.S. health authoritiesBut, of course in privileging our own assessment criteria! Indeed, if one relies on list prepared by the International Agency for Research on Cancer (IARC, Lyon, January 2011), an offshoot of the World Health (WHO), we arrive as shown in Table 7, accounted for 10 human carcinogens (groups 1 and 2A), plus nine compounds carcinogenic in animals and suspected to be carcinogenic in humans (Group 2B) but whose involvement in human cancer is not currently established with certainty. Obviously, this classification developed by panels of international experts, is only provisional classification of the WHO and is therefore constantly changing, depending on the progress of scientific knowledge.
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CHEMICAL COMPOUNDS
CLASSIFICATION IARC (January 2011) Carcinogenic in humans Group 1
Group 2A
Acetaldehyde NTA
X
Sulfuric acid concentrate (aerosols) Acrylamide
X
Benzene
X
X
Benzyl chloride
X
Inorganic compounds Lead 1,4 - Dioxane
X X
Titanium dioxide
X
Epichlorohydrin
X
Ethylbenzene Formaldehyde
X X
Naphthalene
X
Nitrates and nitrites Ethylene oxide
X X
Propylene oxide Crystalline silica (Inhaled in the form of Quartz or Cristobalite) Styrene
Suspected carcinogenic Group 2B X
X X
X
Antimony trioxide
X
Table 7 : CHEMICALS CLASSIFIED BY IARC FOR THEIR POWER Human carcinogen. Compared to the original list of EPA, reported in Tables 3 and 4, some products additional to add, because that can cause health problems. Therefore, we must add among the mineral products, inorganic lead compounds (Classified by IARC in 2006, probable carcinogen in humans, and more well known as neurotoxic and reprotoxic especially in young children in developing) and the antimony (listed as carcinogens by IARC 2B). From organic compounds, one must add the epichlorhydrin (Classified by IARC in Group 2A), and hexamethylene tretramine (Known in France under the name of Uroformine, a bactericidal for urinay tract), not classified by IARC, but nevertheless a potential source in slightly acidic medium, of formaldehyde (IARC Group 1) (No. 161). ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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From the tables together in the U.S. investigation report that lists the number of times chemicals are detected in the various drilling selected, it is possible to measure frequency of use of the most commonly encountered, As shown in Table 8. CHEMICAL COMPOUNDS
NUMBER OF TIMES Found in DRILLING
Methanol (No. 122)
392
Isopropanol (125)
279
Crystalline silica (Quartz) (No. 43)
207
2 - Butoxyethanol (No. 149)
126
Ethylene glycol (No. 133)
119
Light oil fractions hydrogenated
89
Soda (sodium hydroxide) (No. 49)
80
* BTEX compounds (92, 93, 95, 94)
60
* BTEX: Benzene, Toluene, Ethylbenzene, Xylene.
Table 8 EXAMPLE OF CHEMICALS IN MOST CASES DETECTED IN UILISES FRACTURING FLUIDS IN THE UNITED STATES BETWEEN 2005 AND 2009. As guise of trade secret, the U.S. drilling companies themselves still refuse to provide quantitative data. This is a major handicap for assess the real risks toxic chemicals used. It remains the data provided by ecological associations or by official agencies such as the Office of regulating oil and shale gas in the State of New York, whose preliminary report NYSDEC in 2009 (804 pages) gives some values interesting, given in table 9. CHEMICAL COMPOUNDS N-oxide 4 - nitroquinoline Divalent cation Barium (Ba+ 2) Toluene (No. 93) Xylene (mixed of 3 isomers) (No. 94) Benzene (No. 92)
NUMBER OF DETECTION
AVERAGE in mg / L-1
24/24
13908
34/34
662
15/29
833
14/22
487
14/29
280
Table 9 : CONCENTRATION OF SOME PRODUCTS IN WATERS FRACTURE OF DRILLING OUT, IN THE UNITED STATES (NYSDEC, 2009) ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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Attendance at such rates of all these compounds is of particular concern. The benzene (Leucemiant powerful agent in humans) and 4-nitroquinoline-N-oxide (Cancer mouth, very active in rodents), are very dangerous carcinogens, to banish imperative. The divalent cation barium (Ba2+) is an aqueous medium highly toxic, especially at the digestive tract. The benzene (No. 92), toluene (No. 93), ethylbenzene (No. 95) and xylene (No. 94), grouped in the family BTEX, are mono-aromatic hydrocarbons, excellent Volatile Organic Compounds (VOCs) and recognized as important neurotoxic and for toluene, reprotoxic (3 for European Union). The benzene (No. 92), which is certainly provided by external petroleum products (Fuel, light petroleum fractions ...) constitutes a real public health problem as powerful toxic to bone marrow (Instead of the synthesis of all blood cells) promoting, among other, the appearance of acute myeloblastic leukemia and to this doses which may be extremely low (Of the order of a few parts per million). The young children are a population particularly sensitive. These effects on bone marrow, can be increased by other constituents reported in fracturing fluids, such as ethylene oxide (Table 4) (No. 139) and the formaldehyde (Table 4) (No. 161). Apparently benzene continues to recover as contaminating rivers and streams through the extraction sites or shale bedrock. So recently, EPA has obviously, the aqueous waste discharged into the river "Allegheny" in Pennsylvania, contain benzene, at a concentration 28 times greater than the force in U.S. standard (EPA, April 2010). Recent media reports tell of the leakage light aromatic hydrocarbons, which upon rise by Plastic Pipe, of liquid outlet, disseminate these compounds suggest volatile, which once on the surface, evaporate into the atmosphere, resulting in significant pollution of ecosystems : Thus the United States but also Germany, of residents of drilling platforms shale gas frequently complain of headaches and gastrointestinal disorders, certainly related to inhalation of these hydrocarbon compounds. For proof, lower Saxony (Northern Germany) in the territory of Sohlingen or EXXON-MOBIL produces gas drilling, a local resident who complained of headaches had in his blood, a rate of 0.7 µg / L-1 of benzene, a sign of impregnation substantial as normally benzene is not present in the blood ! To assess the real risks of some chemicals found in common fluids fracturing, it is necessary in a first approach classify the compounds according to their degree of dangerous, both for workers in this sector gazo-oil, for local people and more generally environment.
(Source: thermojetstove.com)
(Source: explorepahistory.com)
"Allegheny River" in Pennsylvania
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1) What products are essential to eliminate as responsible irreversible effects ? • The enemy number one is the benzene (No. 92), the aromatic hydrocarbon most simple, but also the more dangerous to health, toxic selective marrow bone in Man. By acting on stem cells, The benzene will disturbthe synthesis of red cells, Hence the appearance anemia more or less irreversible. Its action on platelets will cause disorders coagulation, but especially its impact on white blood cells may lead to their uncontrolled reproduction, Hence the appearance of leukemia. It is important toindicate that there is a clear dose-effect relationship between the importance of exposure in ppm / month and the incidence of leukemia4. Other products often present in the fracturing fluids should be absolutely prohibited, as • formaldehyde (No. 161), ethylene oxide (No. 139), acrylamide (No. 195) and the crystalline silica (No. 43). a) The formaldéhyde (No. 161), and more powerful irritant properties and allergenic in humans is a carcinogenic oro-laryngeal and is involved in causing leukemia. b) Ethylene oxide (No. 139), which is poorly understood in the presence of fluids fracturing, is also a strong leucemiant agent. c) With respect to the acrylamide (No. 195), in addition to being a neurotoxic peripheral (Polyneuritis), it is also a carcinogenic in humans, which is not the case of polyacrylamide gels, commonly used in liquid fracturing. d) As for the crystalline silica (SiO2)n (No. 43), which exists in different forms (Quartz, Cristobalite), it is a and fibrotic lung irritant powerful (Silicosis ...), but also a bronchial carcinogen, which occurs essentially to the form of dust and its use as wet sand (Table 2), does not correspond to a situation in which the crystalline silica, should present a activity genotoxic. e) Sulfuric acid (No. 56) concentrated is a carcinogenic bronchial Man, but only in the form of aerosols, such as at ist synthesis in the "lead chambers." It would be surprising to intervene and in fracturing fluids, but we must remain cautious, because it is very corrosive ! In general, when selecting a product for its impact health, it would be wise to consider its real conditions exposure, which would avoid real controversy.
2) What are the products of health concern and should replaced by less toxic compounds ? • In this category, you must put products endowed with selective toxicity as the reprotoxic or neurotoxic, not to mention haematotoxic, hepatotoxic, nephrotoxic, immunotoxic, and disruptive endocrine. a) Among the compounds known reproductive toxins in humans (Classification European) and glycol ethers, are a group ethers of well represented in the fracturing liquid. In particular, should be only be replaced the methyl and ethyl ethers of ethylene glycol and their acetates and by this 1-propylene glycol ethers which are not reprotoxic.
4
Benzene, MSDS No. 49, 2004 INRS ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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O
O H
2-Methoxyethanol (No. 140)
O
O
O
O
Acetate 2 Methoxyethanol (No. 141)
O
O H
2-Ethoxyethanol (No. 142)
H O
O
O
Acetate 2 Ethoxyethanol No. 143)
O R
Ether of 1Propylene glycol
b) The compounds of boron, Most reprotoxic as boric acid (No. 68) could be replaced by the sodium metaborate (No. 70), not reproductive toxicant. O H B O H O H Boric acid (No. 68)
O B O
+
Na , 8 H2O
Sodium metaborate, Octahydrate (No. 70)
c) As for formamide (formamide and dimethylformamide), and N-methyl pyrrolidone all classified reprotoxic 2 by the European Union. They could be substitutioned by the dimethylsulfoxide (DMSO) not reprotoxic. O CH3
O H C NH2
H C N CH3
N
O
O
+
S
CH3 CH3
CH3
Formamide (No. 190)
Dimethylformamide (DMF)
(No. 191)
N-Methyl Pyrrolidone (NMP) (No. 192)
Dimethylsulfoxide (DMSO) (No. 139))
d) Among the haematotoxic , In addition to the benzene and ethylene oxide already taken into account as proven carcinogens in humans must be added the 2-butoxyethanol (2-BE), a glycol ether, which burst blood cells red causing anemia and neprhotoxicity. In animals, the 2-butoxyethanol would be responsible for adrenal tumors, but nothing is proven in humans. It is obvious that the 2-butoxyethanol, is like other glycol ethers, a product that essentially penetrates through the skin and which should be particularly wary. Used as a surfactant in fracturing fluids (Table 2, page 6) the 2-butoxyethanol should be easily replaced by a compound very low toxicity, as isopropanol.
O
O H
CH3 C CH3
2-Butoxyethanol (No. 149)
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H OH
Isopropanol (No. 125)
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e) Although of other products should be avoided in fracturing fluids and can be reported: some are of neurotoxic powerful (the group of BTEX, methanol, acrylamide, ...).
f) Other compounds are hepatotoxic such as organochlorine derivatives : trichloroethylene, perchloroethylene (No. 120), benzyl chloride (No. 121), (in animal experimentation) Cl
Cl
Cl
Cl
Cl
H
Cl
Cl
Trichloroethylene
Cl
Tetrachloroethylene (No. 120)
Benzyl chloride (No. 121)
It should be noted that some organochlorines are also nephrotoxic and probable carcinogen in humans (Group 2A IARC). g) Among the toxic renal powerful, we must warn against the ethylene glycol (No. 133) and the diethylene glycol (No. 144) which should be excluded fracturing fluids and also easily replaced by the propylene glycol, non-nephrotoxic.
CH2 OH
CH2 O
CH2 OH
CH2 OH CH2
Ethylene glycol (No. 133)
CH3
CH2
CH
OH
OH
CH2 OH
Diethylene glycol (No. 144)
Propylene glycol
h) Some compounds found in fracturing fluids are products allergenic powerful among which are compounds organics such as formaldehyde (No. 161) and glutaraldehyde (No. 162), and inorganic compounds, such as nickel sulphate (No. 40) and chromic acetate (No. 29). H H
C O
Formaldehyde (No. 161)
H
H O
O
Glutaraldehyde (No. 162))
O
O S
Ni
++
O
O
CH3 COO CH3 COO CH3 COO
Nickel sulphate (No. 40)
-
Cr + + +
-
Chromic acetate (No. 29)
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Documents prepared by the United States (EPA, Committee on Energy and Commerce, NYSDEC) where Quebec (INSP) show some heterogeneity in the data Toxicological information on the products characterized in the fracturing fluids, this is due to different approaches. For example, a compound with low current, 4-nitroquinoline-N- oxide, as used corrosion inhibitor is found in the document INSP Quebec and the NYSDEC (2009) State of New York, at an average concentration of 13,908 in 24 mg/L-1 samples of 24, with a maximum concentration of 48,336 mg/L-1. This is a rate considerable for a compound, mainly used in laboratories as carcinogenic model of the oral cavity and the tongue, in rodents (Rats, Mice). At a time identical (2005, 2009) the Commission document of the Energy and Commerce of U.S. House of Representatives, makes no mention of this product and report only the presence of nitrogenous bases extracted tar (Tar bases, quinoline derivates, ...). No trace of the N-oxide of 4-nitroquinoline! If we do not yet have enough experience to properly evaluate the effects of the cocktail chemicals used in the United States in 2005-2009, by cons, media Local recounted several fatal acute poisoning in animals alongside sites drilling.
(Source: durangotexas.blogspot.com)
(Source: huntervalleyprotectionalliance.com)
Website of Chesapeake Energy, poisoning of 19 cattle that had ingested water fracturing Also in 2009, it is reported in a local newspaper in Louisiana, "The Shreveport Times" of April 29 2010, only 19 cows died after being in contact with a fracturing fluid of the company "Chesapeake Energy". If acute intoxication is no doubt, the newspaper reported that animals died had the foam in the mouth, and their language was bloody ... The same target that biological Rats and Mice, intoxicated by the long-term N-oxide of 4 - nitroquinoline ! A very strange coincidence, that would certainly require that American scientists seriously interested in this compound, known for its highly carcinogenic powerful and selectivity amazing ... even if the oils are no longer used quinoline United States! If cows have survived the poisoning, it would also be wise to follow over the long term, which could hold some surprises. Only by this, it is imperative that vigilance implementation is increased among populations in these mining areas gazo-oil… Otherwise epidemiology can be daunting ...
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Head of a cow having died from the ingestion of water outlets on the site of fracture Chesapeake Energy Louisiana, 2010. (Source: Unknown)
VIII, A CONCLUSION THAT REMAINS STILL TENTATIVE. For ten years, the exploitation of gas and oil shale or rock-oil mother, called unconventional, have boomed in the U.S., resulting in also an environmental deterioration which it is still difficult to measure all long-term consequences. Will he the same for the Europe ? The Poland, which would have the largest reserves in Europe (5,3 billion m3 according the U.S. Information Agency Energy, EIA) dream to break free from his tutelage energy toward its Russian supplier. As regards the France (Whose riches would come right after those of the Poland) its non-conventional hydrocarbon reserves are estimated at 100 million cubic meters, technically exploitable in the Paris Basin (Mostly as of shale oil). According to the report 5 of 8 June 2011 and CGIET6 CGEDD7, resources exploitable in the south would be about 500 billion m3 but these figures correspond to a mere suspicion of the existence of such reserves and this in the absence of any reliable assessment. Other European countries are currently at the exploration stage, as the Britain on the site of Blackpool, the Germany in Lower Saxony, but also the Switzerland. Strangely, while North American companies in the United States now report the Chemical composition (sometimes folk) of these fracturing fluids companies in Europe have no exceptions, so far disclosed the nature of the compounds they implement ... probably just an oversight! In France, the national debate on oil and shale gas, focused on the one hand considerable amounts of water implementation (From 10 000 to 20 000 m3 per cycle fracturing) and on the other hand on the nature and quantities of chemical additives addedThis is actually tens of tons of products. As noted by Francois-Michel GONNOT and Philippe MARTIN, the two rapporteurs document on gas and oil shale of 8 June 2011 (page 50) " the communication from the composition of fracturing fluids, is a precondition to opening a debate on the desirability of the exploitation of gas and oil shale ". A list of products allowed, for example established by the National Agency for Sanitary Security of Food, Environment and Labour (ANSES) would according to these authors, a guarantee acceptable by public opinion.
5
Report No. 3517 of the National Assembly on finding mission on shale gas June 8, 2011. CGIET: General Council of Industry and Technology 7 CGEDD: General Council of the Environment and Sustainable Development 6
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That acceptance will certainly conditioned the composition of the Committee of Experts. In the same report (page 50) gas and oil companies have said "working at the job always less harmful additives "such as the compounds used in the food and products everyday consumer. Hopefully it's not instant coffee in U.S. oil (page 34 of our document). It is obvious thatin France, we can not do without a national debate on our energy strategies, as it is hoped that it precedes a more open debate on the future of our energy policy and the operation of our basement. The position of the U.S. Agency of Environment (US-EPA) is in this sense particularly instructive. Indeed, for EPA, which invests several million dollars to accurately assess the environmental and health impacts related to the exploitation of shale gas, it seems well established that environmental hazards are much greater than the benefits economic, it seems you very profitable for the oil and secondarily for populations local. In the U.S., the example of Pennsylvania is particularly telling. If 71,000 wells are currently operates (there were 36,000 in 2000), entire regions of this state very green are now almost desert, the groundwater being drained and the sub-totally polluted soil, plus a water surface partially radioactive. But in fact, nothing impedes the gold rush of the XXI century ... 3000 new licenses were granted in 2010 and it is not the explosion of a well on April 20 that will begin this leap before the operation "Marcellus" ... To each his future! If gas or shale bedrock has recently become the second largest source of U.S. energy, it is unacceptable that France should follow this example, Both the disaster is convincing overseas. To us, to learn that ... the rest seem to Quebec and Africa South, the New York area and the Swiss canton of Fribourg, which all have a moratorium. Particularly important, especially in South-Eastern France, is the seismic risk, following fracturing operations. Indeed the basement of the southern gas-rich shale is abundantly crossed by faults and fractures. Gold geological study of deep underground is almost nonexistent and yet it is at this level that is the deep aquifer, Which represent in our future water supply. Hence the absolute necessity of taking no active petroleum gas deep in such regions, before they have a real knowledge of the subsoil. By example, it was noted, as in Arkansas, at Blackpool in Britain, that areas shale gas exploration, can be more vulnerable to natural earthquakes. As for example, 700 earthquakes were recorded in six months in Arkansas! Relying mainly on the EPA report to February 2011 (EPA / 600 D / - 11/001) supplemented by that of NYSDEC (2009) State of New York and Monograph the National Public Health Institute of Quebec (November 2010) it was possible to draw a list (Sadly temporary!) the main products used most frequently to United States in the extraction of oil or gas or oil shale bedrock (Tables 3 and 4). From these lists, we grouped the chemicals according to their type of toxicity, in a summary table (Table 10)
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TYPE OF TOXICITY
NUMBER OF PRODUCTS MADE ACCOUNT
Neurotoxicity
7
Hematotoxicity
3
Hepatotoxicity
1
Nephrotoxicity
3
Reproductive toxicity (Repro 2 and 3) Carcinogenic in humans (Groups 1 and 2A of the IARC)
6 8+1 *
1 * 4-nitroquinoline-N-oxide (cancers of the mouth and tongue in rodents), was not still considered by IARC. Table 10: MAJOR TOXIC IN HUMANS IN LISTED TABLES 3 AND 4 It must be remembered that many of these products as sand, hydrochloric acid, various corrosion inhibitors and biocides, are commonly used in oil and gas industries conventional. If we put aside, from tables 3 and 4), corrosive (10) essentially minerals (HCl, HF, NaOH, KOH, CaO) and some allergenic products (sulfate nickel, chromic acetate, formaldehyde, glutaraldehyde...), can be grouped in Table 10, thirty products that must be considered toxic to humans, including some highly toxic, such as carcinogens or toxic for reproduction, it is imperative to banish. As Table 5 lists, wastewater, discharged after fracturing are enriched after the crossing of different geological layers, with various water-soluble compounds inorganic. Among these compounds, metal compounds correspond either to toxic trace elements very bioaccumulative such as lead, cadmium, mercury and thallium, or to metals transition, less toxic and less bioaccumulative, as cobalt, nickel, copper... Other metals, under soluble form are dangerous toxic such as beryllium and barium. Among the mixed elements, arsenic and antimony are also powerful toxic. Of course depending on the type of geological traverses, the nature and concentration of elements minerals can be very variable. All these toxic hazards in the longer term, should not overshadow the potential risk Explosion and fire, Related to presence in the water output, gas in particular methane extremely volatile and highly flammable. In this context the influence of environmental harm, fracturing techniques and oils gas or oil shale bedrock, we were very sensitive to the recent study of Professor Robert HOWARTH8 Cornell University, who believes that the impact of exploration shale gas on global warming could exceed 20% that of coal! This to be the leakage methane during the fracturing cemented along the pipes, methane being on average 22 times more effective than CO2 As greenhouse gas emissions!
8
Howarth R and Col. 2011.Methers and the greenhouse-gas footprint of natural gas from shale formations. Climatic change in press ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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In the end, a ecological balance inefficient ! The gas and oil companies, Who have invested in Europe in the operation of gas oils and shale and develop this for the extraction, would do well to banish from the outset in the composition of their fracturing fluids, chemical additives, unless they familiar with other techniques fractures (compressed air, liquid propane ...) less polluting. These chemical additives, widely used in the United States, especially early in gas exploitation unconventional and which one is gradually irreversible ecological damage can be summarized in Table 11.
N°
1
2 3
COMPOUNDS CHEMICAL AND MIXTURE
Boric acid and Sodium perborate Hydrofluoric acid Nitrilotriacetic acid (NTA)
LONG-TERM TOXICITY ACUTE (+ Corrosive, Irritant)
CANCEROGENIC
OTHER
EFFECTS ADVERSE on The ENVIRONMENT
PRODUCT SUBSTITUTE
_
_
Repro 2
_
_
Corrosive
_
Fluorosis Osteoporosis
_
_
_
_
Nephrotoxic
2A
Neurotoxic device, Allergenic
EDTA Dangerous for fish
4
Acrylamide
Irritant
5
Benzene
Neurotoxic central
A
Haematotoxic (Anemia)
6
2-Butoxyethanol
_
_
Haematotoxic (Hemolysis)
Irritant
2A
(Basic fractions oil)
Irritant
?
9
1.2 Diethoxyethane
Irritant
Repro 2
Propylene glycol mono 1-methyl ether
10
1.2 Dimethoxyethane (Glyme)
Irritant
Repro 2
Propylene glycol mono 1-methyl ether
11
Dimethylformamide (DMF)
Irritant
Repro 2
Dimethylsulfoxide (DMSO)
12
Epichlorohydrin
Irritant
13
2-Ethoxyethanol
_
Repro 2
Propylene glycol mono 1-methyl ether
7
8
Benzyl chloride Derivatives of Quinoline
Ethylene glycol Diethylene glycol
Cumene Isopropanol
?
2A
(+ Acetate) 14
Very toxic for life aquatic
Bis-acrylamide
Nephrotoxic
Propylene glycol
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15
Formaldehyde
Irritant
16
Hexane
Neurotoxic
17
Methanol
Acidosis
18
Methoxyethanol
_
A
20
Heavy naphtha
21
Ethylene oxide
22
Aluminum salts
23
24
25
Barium salts (Soluble) Tetrachloroethylene
Toluene
Irritant Neurotoxic central
Propylene glycol mono 1-methyl ether
Toxic to wildlife aquatic 2A
Irritant
Heptane Cyclohexane Ethanol Isopropanol
Repro 2
Irritant
Nitrate / Nitrite
Glutaraldehyde
Neurotoxic peripheral Neurotoxic ocular
(+ Acetate) 19
Allergenic
Haematotoxic (Methemoglobin izers)
Fractions non-oil genotoxic
Proliferation algae
A
2A
Neurotoxic, Ostéotoxiques Toxic intestinal Neurotoxic, Hepatotoxic Nephrotoxic Repro 3 Ototoxic
Toxic to wildlife aquatic Toxic to wildlife aquatic
Dichloromethane
Cumene
Table 11 : THE 25 CHEMICALS AND THEIR MIXTURES, CONSIDERED AS VERY TOXIC AND (OR) DANGEROUS FOR THE ENVIRONMENT AND IN BANNING FRACTURING FLUIDS.
A bill to ban exploration and exploitation of gas and oil shale or appointed since the last report and CGIET CGEDD " hydrocarbon source rock ", was discussed on 10 and 12 May 2011. The bill relating to the exploration and mining of oil not conventional liquid (Shale oil) or gaseous (Methane) was adopted by June 21 National Assembly and the Senate, June 30, 2011. This law prohibits drilling vertical, horizontal hydraulic fracturing followed the schistose rocks, rich in hydrocarbons, was enacted on July 13, and gazetted 14 July 2011 (11). The France, joins the Suede which was the first prohibits the exploration of gas and oil shale in his basement. Unquestionably, this is a first advanced but remains to rehabilitate the mining code French (The basement is the property of the state) in social issues in current economic y including the requirement to consult the surrounding population from one site to explore. Hope that this will happen in the future?
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The principal author of the analysis that we offer, being originally a chemist Group Roussel-Uclaf (Romainville) and the CNRS (Gif-sur-Yvette), our approach to dangerousness Chemicals, the EPA detected in the fluid output of fracturing, may seem somewhat remote from what is described elsewhere. In fact our own approach is to consider that events that occur at the middle of fracturing, can be treated a "chemical reactor "wherein, to temperatures higher or lower and under various pressures, hundreds of molecules interact with each other and thus, the mixture final output, maybe not different initial products injected. And nothing should prohibit oxidants to modify the structure of reducing molecules. This is for example what should happen with Trivalent chromium salts (As acetate chromic) easily oxidizable in compounds hexavalent chromiumSuch as chromates (Figure 2). Nothing prohibits a given molecule can undergo a series of reactions, As can be imagine from the quinoline, An aromatic nitrogen heterocyclic base, which is found in basic fractions oil, which are added in some fracturing fluids. In the presence of a source of nitrating agent (nitrates...) quinoline is preferentially nitrated on the top 4 in the pyridine ring. The 4-nitroquinoline, thus formed, can then selectively oxidize on its nitrogen atom heterocyclic and led in the final N-oxide of 4-nitroquinoline, found in the fluid output (Figure 4) The majority of chemicals detected in the hydraulic fracturing fluids exploration and exploitation of oil and gas or oil shale bedrock, are essentially xenobiotics (substances foreign to the body), many of which are very and highly toxic environmental pollutants. It is therefore essential to consider that only fracturing techniques that respect the human health and the environment, would be to study the prospect of a political energy, acceptable to all. Hopefully in future reports that are sure to appear, this dimension multidisciplinary is not omitted. THE CHEMISTRY THAT'S LIFE! DO NOT FORGET IT, EVEN IF MANY MODELS DO ECONOMIC-POLITICALNOT SEEM to care. HOPE THIS MESSAGE WILL BE HEARD! Paris, October 2011 André Picot, Association president Toxicology and Chemistry (ATC-Paris) Joelle and Pierre DAVID, ATC members, Paris Jerome TSAKIRIS, ATC member, Paris NOTES: - The updating of this document and a number of product sheets discussed herein, including that of N-oxide 4-nitroquinoline and a brief bibliography can be found on the site Association Toxicology and Chemistry : atctoxicologie.free.fr If inaccuracies scientists have yet slipped into this summary, please accept our apologies and thank you inform us ... We will gain in credibility ... Our primary motivation! - ATC would like to thank all our colleagues and friend (s) who have reported some inaccuracies in the first edition. Contact :
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Summary bibliography
1 - NYSDEC (2009) Supplemental Generic Environmental Impact Statement On The Oil, Gas and Solution Mining Regulatory Program. Document of 804 pages. Bureau of Oil & Gas Regulation New York State, Albany, ftp://ftp.dec.state.ny.us/dmn/download/OGdSGEISFull.pdf 2 - Colborn T. 2010 Natural Gas operation from a Public Health Perspective. Inter day.The of Human and Ecological Risk Assessment, Current Release. http://www.bctwa.org/Frk-NatGa&Health-Sept4-2010.pdf 3 - National Institute of Public Health. November 2010 State of knowledge on the relationship between activities related to shale gas and public health. National Public Health Institute of Quebec, 73 pages. http://www.inspq.qc.ca/pdf/publications/1177_RelGazSchisteSantePubRapPreliminaire.pdf 4 - Bishop R. Juanary 2011 Chemical and Biological Risk Assessment for Natural Gas Extraction in New York. Chemistry & Biochemistry Department State University of New York College at Oneonta. http://ge.tt/2VfEsZw/Risk%% 20Natural% 20Assessment 20Gas% 20Extraction.pdf? type = download 5-EPA. February 2011 Draft plan to study the potential. impacts of hydraulic fracturing on drinking water ressouces EPA/600 / D-11/001 Office of Research and Development. http://water.epa.gov/type/groundwater/uic/class2/hydraulicfracturing/upload/HFStudyPlanDraft_SAB_0 20711.pdf 6-Leteurtrois JP Pillet D Durville JL Gazeau and JC. April 2011. The hydrocarbon source rock in France. Interim Report CGIET No. 2011-04-G CGEDD No. 007318-01. Paris http://www.economie.gouv.fr/services/rap11/110421rap-hydrocarbures-roche-mere.pdf 7 - H Waxman, Markey E, DeGette D. April 2011. Chemicals Used in Hydraulic Fracturing. UNITED STATES HOUSE OF ENERGY AND ON REPRESENTATIVESCOMMITTEE MINORITY BUSINESS STAFF. http://lenouvelordre.com/util/dl/Liste_des_produit_chimiques_du_fraking.pdf 8 - SG Osborn, Vengosh A, NR Warner, RB Jackson. 9 May 2011. Methane contamination of drinking water Accompanying gas well drilling and hydraulic fracturing PNAS , 108, 20, 8172-8176. http://www.pnas.org/content/108/20/8172.full.pdf+html ASSOCIATION TOXICOLOGY-CHEMISTRY MDA 10, 206 Quai de Valmy, 75010 PARIS http://atctoxicologie.free.fr
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9 - Gonnot F.M, Ph. Martin June 8, 2011. Mission of information on gas and oil shale. Information Report No. 3517 National Assembly, 2011, Paris http://www.assemblee-nationale.fr/13/rap-info/i3517.asp 10 - Mr. Marino in June 2011. Hydrocarbon source rock: Towards a new Gasland? Investigations Health # 7 June-July 201, p 30-39 http://www.enquetesdesante.com/revue/index.html 11 - ACT No. 2011-835 of 13 July 2011 to ban exploration and mining hydrocarbon liquids and gases by hydraulic fracturing and to repeal the exclusive licenses Research involving projects using this technique. Official Gazette No 0162 of 14 July 2011, pp. 12 217, text 2. http://www.legifrance.gouv.fr/ 12 - Shale Gas Production SEAB Subcommittee - 90-Day Report. August 2011. The Shale Gas Production Subcommittee of the Secretary of Energy Advisory Board (SEAB.
http://www.shalegas.energy.gov/resources/081111_90_day_report.pdf
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