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AMERICAN COAL ASH ASSOCIATION SAFETY DATA SHEET GUIDANCE DOCUMENT

by Haley & Aldrich, Inc. Burlington, MA for ACAA Farmington Hills, MI File No. 42002‐000 May 2015

www.haleyaldrich.com

Table of Contents Page

i

List of Tables iii

List of Acronyms iv

1. Introduction/Purpose 1

2. Introduction to GHS 3

3. Coal Combustion Products 4

3.1 FLY ASH 4 3.2 BOTTOM ASH 4 3.3 CFB ASH (FLUE AND BED) 5 3.4 SYNTHETIC GYPSUM 5

4. CCP Composition 6

4.1 COMPOSITION EVALUATION DETERMINATION 6 4.2 CCP ANALYTICAL METHODOLOGY 8 4.3 COMMON PITFALLS IN COMPOSITION DETERMINATION/DISCLOSURE 10

5. GHS Classification 11

5.1 DATA SUPPORTING GHS CLASSIFICATION OF CCPS 11 5.2 CRYSTALLINE SILICA 16

5.2.1 Particle Size 17 5.2.2 Health Effects 18 5.2.3 Implications for GHS Classifications 20 5.2.4 OSHA Proposed Silica Rule 21

5.3 OTHER CONSIDERATIONS THAT MAY IMPACT CCP GHS CLASSIFICATIONS 21 5.3.1 Irritation/Corrosivity 21 5.3.2 Acute Toxicants 23 5.3.3 Substances Defined as Toxic to Reproduction 24 5.3.4 Single Exposure – Specific Toxic Organ Toxicity 24

5.4 FINAL CCP GHS CLASSIFICATION 24

6. SDS Development 27

6.1 GENERAL COMMENTS 27 6.2 SDS SECTION‐BY‐SECTION COMMENTS 27

References 52

Table of Contents (cont’d)

ii

Appendix A – SDS Development Checklist Appendix B – CCP SDS Template Appendix C – Compositions Summary Workbook Appendix D – SDS Section 2 Data Appendix E – SDS Section 11 Data

iii

List of Tables

Table No. Title

1 Substances Identified as Present in CCPs

2 Examples of substances that would not be applicable for listing as a component of CCPs

3 Toxicological Data on CCP

4 Physical Hazard Data/GHS Classification on CCPs

5

6

Example GHS Skin/Eye Irritants or Corrosive Substances that MAY be present in

CCPs

Example GHS Acutely Toxic Substances that MAY be present in CCPs

7 CCP Composition Classification

A CCP components that may require disclosure

B Available Occupational Exposure Limits for Identified CCP components

C Physical Properties

D CCP components present on the State Right to Know Lists

iv

List of Acronyms

ACA ACAA

American Coatings Association American Coal Ash Association

ACGIH American Conference Of Governmental Industrial Hygienists ANSI American National Standards Institute As Arsenic ASTM American Society for Testing and Materials Ba Barium BCF Bioconcentration Factor Be Beryllium Bi Bismuth C Celsius Ca Cadmium CA California CAS Chemical Abstract Service CCP Coal Combustion Product CCSEM Computer‐Controlled Scanning Electron Microscopy CFB Circulating Fluidized Bed CFBC Circulating Fluidized Bed Combustion CFR Code Of Federal Regulation COPD Chronic Obstructive Pulmonary Disease Cr Chromium Cs Cesium Cu Copper CWA Clean Water Act EC European Classification ECHA European Chemicals Agency EHS Environmental Health And Safety EPA Environmental Protection Agency EPRI Electric Power Research Institute EU European Union FBA Furnace Bottom Ash FBC Fluidized Bed Combustion FGD Flue Gas Desulfurization Ga Gallium Ge Germanium GHS Globally Harmonized System Of Classification And Labelling HCS Hazard Communication Standard Hg Mercury HMIS Hazard Materials Information System HSDB Hazardous Substances Database IARC International Agency For Research On Cancer IMA Industrial Minerals Association Kow Octanol‐Water Partition Coefficient LC Lethal Concentration LD Lethal Dose LEL Lower Explosive Limit

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List of Acronyms (cont’d) Li Lithium MA MMAD

Massachusetts Mass Median Aerodynamic Diameter

mg/kg Milligrams Per Kilogram mg/L Milligrams Per Liter mg/m3 Milligrams Per Cubic Meter Mn Manganese Mo Molybdenum MSHA Mine Safety And Health Administration Nb Neobium Ni Nickel NIOSH National Institute For Occupational Safety And Health NJ NOAEC

New Jersey No Observed Adverse Effect Concentration

NOAEL No Observed Adverse Effect Level NTP National Toxicology Program OEL Occupational Exposure Level OEHHA OSHA

Office of Environmental Health Hazard Assessment Occupational Safety And Health Administration

Pa Pascal Pb Lead PA Pennsylvania PBT Persistent, Bioaccumulative and Toxic PEL Permissible Exposure Limit PMN Premanufacture Notice PPE Personal Protective Equipment Rb Rubidium REACH Registration, Evaluation, Authorisation And Restriction Of Chemicals REL Recommended Exposure Limit RCS Respirable Crystalline Silica RI RTK

Rhode Island Right‐To‐Know

SARA Superfund Amendments And Reauthorization Act Sb Antimony Sc Scandium SCBA Self‐Contained Breathing Apparatus SDS Safety Data Sheet Se Selenium Sr Strontium STEL Short‐Term Exposure Limit STOT Systemic Target Organ Toxicity STOT‐RE Systemic Target Organ Toxicity, Repeat Exposure STOT‐SE Systemic Target Organ Toxicity, Single Exposure Th Thorium Tl Thallium TLV Threshold Limit Value

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List of Acronyms (cont’d) TSCA Toxic Substances Control Act TWA Time‐Weighted Average U Uranium UEL Upper Explosive Limit µg/m3 Micrograms Per Cubic Meter µm Micron UN United Nations US United States US DOT United States Department Of Transportation USEPA United States Environmental Protection Agency UPL Upper Prediction Limits UVCB Unknown Or Variable Composition/Biological V Vanadium VOC Volatile Organic Compound vPvB Very Persistent And Very Bioaccumulative XRD X‐Ray Diffraction Analysis XRF X‐Ray Fluorescence Analysis Y Yttrium Zn Zinc

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1. Introduction/Purpose This document has been prepared for the American Coal Ash Association (ACAA), whose mission is to advance the management and use of coal combustion products (CCPs) in ways that are environmentally responsible, technically sound, commercially competitive, and supportive of a sustainable global community. ACAA is a nonprofit trade association devoted to the beneficial use of materials created when coal is burned to generate electricity. While ACAA is not a producer of CCPs, its members include CCP generators, marketers, and associated industries. Recent updates to the United States (US) Occupational Safety and Health Administration (OSHA) Hazard Communication Standard (HCS) Code of Federal Regulation (CFR) Part 29, Section 1910.1200, 2012 (HCS, 2012) have brought the prior version of the US HCS into alignment with the United Nations (UN) Globally Harmonized System of Classification and Labelling System (GHS) ‐ Revision 3; the update provides a common and coherent approach to classifying chemicals and communicating hazard information via Safety Data Sheets (SDSs) and labels distributed not only across North America, but globally (OSHA 2012b, UNECE,2009).The revised standard was established to improve the quality and consistency of hazard information in the workplace, making it safer for workers by providing easily understandable information on the appropriate handling and safe use of chemicals. The deadline in the US for the development of SDSs compliant to HCS 2012 is June 1, 2015. The primary purpose of this document and its associated appendices is to assist ACAA member companies in developing SDSs for their CCPs. For purposes of this guidance document, CCPs include fly ash, bottom ash, circulating fluidized bed (CFB) fly ash, and CFB bed ash flue gas desulfurization (FGD) gypsum, also a CCP, is not considered in this version of the document. The primary purpose of the document and its associated appendices is to assist ACAA member companies in developing a SDS for the various CCPs, however where possible and appropriate, the use of this guidance document with other CCPs was considered. This guidance document, the associated checklist (Appendix A) and a generic Fly Ash SDS Template (Template, in Appendix B) were developed to provide ACAA member companies a guide for the creation of US OSHA compliant SDSs that accurately reflect the hazards associated with CCPs. This guidance document represents the combined knowledge and information available at the time of development. As the guidance and associated appendices were based on composition data compiled in Appendix C (Composition Summary Data) only CCPs whose composition are inclusive of the substances identified at or below the levels specified are covered. Under the updated HCS 2012, it is the responsibility of the producer/distributor of a substance or mixture to provide a SDS if that product is considered hazardous per the GHS, Revision 3. HCS 2012 specifies that the chemical/product manufacturer is responsible for the development of the SDS (in this case the CCP generator); it is also however, the responsibility of each workplace to ensure the safety of its workers and downstream users where their products are distributed. Therefore, it is in the best interest of the ACAA members, including generators, marketers, handlers, repackagers and distributors to accurately assess the potential hazards associated with fly ash and other CCPs so that the SDSs developed by each member company are consistent and accurately reflect the potential hazards of the CCPs during normal shipping and handling from initial development through the supply chain. The SDS template has been developed per HCS 2012 specifications using the OSHA recognized American National Standards Institute (ANSI) Standard Z400.1: American National Standard for Hazardous

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Workplace Chemicals – Hazard Evaluation and Safety Data Sheet and Precautionary Labeling Preparation, as a guide. Publically available information as well as data received directly from ACAA member companies was used to support the development of this document including composition determinations. This information was also used to identify potential formulation variations that could result in other hazards that would require incorporation into individual company SDSs. Further, other CCPs (i.e., bottom ash) were also evaluated for composition similarities and subsequent classification to assess if the documents being developed for fly ash (i.e., Guidance Document, Checklist and Template SDS) could also be applied to the other CCPs. This report has been organized to assist the reader by providing a natural flow of information. The defined sections allow for the evaluation of the information required to develop US OSHA compliant SDSs from understanding the products covered in the guidance document and templates through the development of the representative SDSs. The primary sections include: Introduction – This section provides an overview of how product hazards are evaluated under

the new HCS 2012 vs. the old Rule.

Introduction to GHS

Coal Combustion Products – This section is a general information overview of the CCPs.

CCP Composition – This section provides a more detailed view on the composition of the various CCPs and how they are defined in both the US and Europe.

GHS Classification – This section provides available test data on CCPs, the GHS Classifications of CCP components that may impact the overall CCP classifications and the overall GHS classifications for CCPs determined as applicable.

SDS Development – This section provides guidance on the specific development of an SDS for CCPs.

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2. Introduction to GHS With the adoption of HCS 2012, there was a major shift in the determination of the hazards of substances and mixtures. Previously, OSHA had specifically defined the substances determined to be hazardous through a listing in the 29 CFR 1910, Subpart Z. Under HCS 2012, it is still the responsibility of the chemical manufacturer/importer to assess the hazards of products distributed in the marketplace and communicate those hazards through the use of SDSs; however, HCS 2012 implements UN GHS Standard, Revision 3 as the basis for this classification/hazard determination process which also prescribes specific labeling, pictograms, and SDS format. The standard requires an evaluation of physical/chemical, human health, and environmental hazards of products. This can be done by product testing, read‐across to data from similar products or using a calculation process provided in the UN GHS Standard for taking into consideration the individual components of the product. The GHS Classification system has been implemented, or is in the process of being implemented in over 65 countries throughout the world. One of the earliest regions to adopt the GHS system was the European Union (EU). The EU instituted the system with the Classification Labelling and Packaging Regulation (EC/1272/2008). This regulation in concert with the EU Registration, Evaluation and Authorisation (REACH) Regulation (EC/1907/2006), led to the review of available information and the development of new information on the physical /chemical, human health and environmental characteristics of substances and mixtures. The data developed for REACH registration purposes is available as public information from the European Chemicals Agency (ECHA) and was used to assist in the classification of the CCPs evaluated and summarized in this guidance document.

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3. Coal Combustion Products 3.1 FLY ASH

Fly ash is a fine, powdery material composed of inorganic material with a small proportion of carbon particles resulting from the incomplete combustion of the parent fuel, coal. Electrostatic precipitators or fabric filters remove the dust‐like particles from the flue gasses of furnaces fueled by pulverized coal with or without co‐combustion procedures. The combustion occurs at temperatures between 1300 – 1500 °Celsius (C). About 80 % of the ash is entrained in the flue gas and is termed fly ash. Fly ash particles are predominantly spherical in shape, and may include a small percentage of thin‐walled hollow particles called cenospheres. In addition, there may also be crystalline particles present that either pass through the combustion zone unchanged or are formed at high temperatures. The particles typically range in size from 1 to 100 microns in diameter, with median particle diameter of 20 to 25 microns. Fly ash is normally light gray or tan to dark gray in color and without odor. Fly ash has been further defined as: The finely divided residue that results from the combustion of ground or powdered coal that is

transported by flue gasses (ASTM Standard C618‐12a; ASTM International, 2012).

Note: This definition of fly ash does not include, among other things, the residue resulting from: (1) the burning of municipal garbage or any other refuse with coal; (2) the injection of lime directly into the boiler for sulfur removal; or (3) the burning of industrial or municipal garbage in incinerators commonly known as “incinerator ash.”

A fine powder mainly of spherical glassy particles, derived from the burning of pulverized coal, with or without co‐combustion materials, which has pozzolanic properties and consists primarily of silica dioxide (SiO2) and aluminum oxide (Al2O3) (Caddas‐Vieira F. et al, 2013; EN‐450 Standard).

3.2 BOTTOM ASH

Bottom ash is agglomerated ash particles, created in a combustion furnace of a coal‐fired power station, that are too large/heavy to be carried in the flue gases, and therefore fall through open grates to an ash hopper at the bottom of the furnace. Bottom ash is generally extracted by a hydraulic process from the base of the furnace. It is a semi‐vitrified granular material with a size similar to sand or gravely sand ranging in color from tan or light gray to dark grey with virtually no odor. It is composed principally of aluminosilicates, and iron oxides, with smaller percentages of calcium, magnesium, oxides, sulfates, and other compounds, with the composition of the particles being controlled primarily by the source of the coal. Bottom ash derived from lignite or sub‐bituminous coals have a higher percentage of calcium than the bottom ash from anthracite or bituminous coals. Sulfate levels are generally low. About 10 to 20% of the residue from the burning of pulverized coal is recovered as bottom ash. In the United Kingdom, bottom ash is also known as Furnace Bottom Ash (FBA).

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3.3 CFB ASH (FLUE AND BED)

CCPs are also generated from Circulating Fluidized Bed Combustion (CFBC) facilities. In a CFBC boiler, fuel particles are suspended in a hot, bubbling fluidized bed of ash and other particulate materials (sand, limestone, etc.) through which jets of air are blown to provide the oxygen required for combustion. Ash generated from this process is termed CFB Fly or Bed Ash. CFB ash is similar to pulverized coal ash products with the exception that it will generally have higher levels of non‐glassy aluminosilicates (mullite), calcium sulfate (anhydrite gypsum) and calcium oxide (due to the use of limestone in the CFB process which reacts with SOx emissions to produce anhydrite gypsum). 3.4 SYNTHETIC GYPSUM

Synthetic gypsum, also called flue‐gas‐desulfurization (FGD) gypsum is produced through a chemical reaction in the scrubbers that remove sulfur from the flue gases of coal‐fired power plants. The scrubbers remove sulfur dioxide (SO2) from power plant emissions by passing the flue gases through a slurry of limestone (calcium carbonate: CaCO3). The sulfur dioxide in the flue gases reacts with the calcium carbonate to produce calcium sulfite (CaSO3); calcium sulfite is then converted into gypsum (CaSO4 ∙ 2H2O) by oxidizing it with air. Gypsum has a Chemical Abstract Services Number (CAS #) of 7778‐18‐9 with a chemical identity under Toxic Substances Control Act (TSCA) of sulfuric acid, calcium salt (1:1). Approximately half of all gypsum beneficially re‐used in the United States is FGD gypsum. Due to compositional differences from fly ash and bottom ash, synthetic gypsum is not evaluated as one of the CCPs in this guidance document. Future versions of this guidance document may incorporate this evaluation.

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4. CCP Composition 4.1 COMPOSITION EVALUATION DETERMINATION Two distinct types of processes that generate CCPs were evaluated: (1) pulverized coal combustion and (2) fluidized bed combustion. Ashes (residues) as well as the following alternate names for Ash(es); Ashes; Ash; Ash residues;

Ashes, residues, bottom; Bottom ash; Bottom ash residues; Waste solids, ashes are identified by the Chemical Abstract Services (CAS), a division of the American Chemistry Society, as CAS number 68131‐74‐8 and by the European Union with the European Classification (EC) number of 931‐322‐8 (no CAS number specified). The European Union and the US TSCA Inventory recognize these CCPs as a singular substance of Unknown or Variable Composition/Biological (UVCB).

– The US TSCA further defines the ashes as: “A residuum from the burning of a combination of carbonaceous materials. The following elements may be present as oxides: aluminum, calcium, iron, magnesium, nickel, phosphorus, potassium, silicon, sulfur, titanium, and vanadium.”

Note: These metals and metal oxides are generally present as inclusions in the aluminosilicate matrix.

– The definition applied by the ECHA to this EC number is the same found on the US TSCA Inventory.1

Fluidized Bed Combustion (FBC) Ash is categorized by the ECHA using the same CAS # (68131‐74‐8) as well; however it is assigned a distinct EC number (931‐257‐5). The name associated with the EC number is Fluidized Bed Combustion (FBC) Ash (residues of coal combustion in fluidized bed combustion boilers).

Regardless of the process, it is clear that the composition of the different ashes is similar although component percentages may be different. Both types of ash, those produced by pulverized coal‐fired furnaces as well as fluidized bed combustion ashes, are acknowledged by US and EU regulatory agencies as UVCB substances with a CAS# of 68131‐74‐8. It is important to note that due to the variable composition, the GHS classification (and subsequent SDS requirements) of each type of ash (i.e., fly ash, bottom ash and fluidized combustion bed ash) as well as ash formed by the same process but arising from different coal sources may vary. In order to assess the proper classification, a compositional analysis of each ash must be performed. Therefore, for the purposes of this project and obligations associated with the new HCS 2012 (29 CFR 1910.1200), fly ash, bottom ash, CFB fly ash, and CFB bed ash are defined as a singular substance of unknown or variable composition (UVCB substance) with a CAS # of 68131‐74‐8. Compositional variants that may result in different/unique GHS classifications have been explored using data from ACAA member companies as well as other publically available sources such as regulatory

1 The TSCA Inventory represents substances present in US Commerce. It does not identify nor delineate substances based on hazard. If a substance is not on the TSCA Inventory, it may not be placed into commerce in the US without Environmental Protection Agency (EPA) approval.

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entities, the Electric Power Research Institute (EPRI), various standards organizations, and the United Kingdom Quality Ash Association. Note: Two additional CAS#s were also identified and considered prior to the determination of the above. They are: (1) CAS# 69012‐84‐6 which appears to have been merged with CAS# 68131‐74‐8 and (2) CAS# 71243‐67‐9 which is associated with pozzolans, coal ash on the TSCA Inventory. The TSCA Inventory further defines it as a “pulverulent substance derived from by‐product coal ash which reacts with slaked lime in the presence of water to form a cementitious compound. The following elements may be present as oxides: aluminum, calcium, iron, magnesium, potassium, silicon, sodium, sulfur, and titanium.” In addition, potential impurities that may be present in the ash were evaluated for their ability to require disclosure on the SDS and for any impacts on the GHS classification of the finished product. The impurities may be trace elements present from the coal and/or pollution control additives.

Trace Elements: The trace elements with potential human health and/or environmental

concerns including arsenic, beryllium, boron, cadmium, chromium, cobalt, lead, mercury, manganese, and nickel were evaluated. Based on an analysis of elemental composition of coal fly ash and bottom ash using the 90th percentile concentrations, these identified trace elements were found to be present at less than 1000 mg/kg or 0.1% (EPRI, 2010). Therefore, these trace elements would typically be below the threshold level for SDS disclosure and will not have an impact on the final product GHS classification. No further review of the trace elements is provided in this document however, if an individual CCP analysis shows that any of the trace elements may exceed 0.1%, the GHS classification and SDS disclosure will need to be re‐evaluated.

Additives: Based on identified level of the additives, most would not meet the reporting threshold for disclosure on the SDS and would not alter the overall classification of the final product. Further information on the impact of these additives can be found in Section 5, GHS Classification.

Using information provided by ACAA member companies (SDSs), ASTM Standard 618c, EPRI, the United Kingdom Quality Ash Association, the European Chemicals Agency, as well as CCP compositional data found in peer reviewed published literature, the CCP compositions considered for evaluation in the scope of the project contain the substances listed in Table 1. Table 1 provides information on the substances and concentrations present in the CCP compositions evaluated for this SDS Guidance. It is understood that the substances listed in Table 1 do not represent a single CCP formulation nor should they be used to represent an individual ACAA member CCP composition. The substance list is not meant to be exhaustive, nor does it restrict the levels of these substances in CCPs to the identified levels. If the composition of a CCP varies in either composition or level, the CCP classifications assigned in Section 5.4 Table 7 may not apply and that CCP classification may need to be reevaluated.

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Table 1: Substances Identified as Present in CCPs

Substance Range Identified in CCP

Compositions Reviewed1, 2

Aluminosilicates 3 ≤ 95%

Calcium oxide (CaO) ≤ 41%

Silicon dioxide (SiO2); Silica, crystalline, cristobalite; Silica, crystalline, quartz4

≤ 36%

Iron minerals (Fe2O3, Fe3O4)5 1‐35%

Calcium carbonate ≤ 10%

Calcium sulfate6 < 6% 7

Carbon ≤ 6% 8

Magnesium oxide (MgO) ≤ 6 %

Titanium dioxide (TiO2) 1 ‐ 5%

Potassium oxide (K2O) ≤ 5%

Silica, crystalline respirable (RCS) < 4%

Bromide Salts (various) (including NaBr) ≤ 2%

Chloride salts (various) ≤ 2%

Magnesium sulfate ≤ 2%

Sodium sulfate ≤ 2%

Sodium oxide (Na2O) < 2%

Phosphorus pentoxide (P2O5) ≤ 1%

Halide salt (not further specified) < 1%

Barium oxide (BaO) < 1%

Manganese dioxide (MnO2) < 0.2%

Ammonium bisulfate < 0.01%

Ammonium sulfate < 0.01% 1 The substances listed and the maximum levels noted represent the information available on CCP compositions at the time of document development. It is understood that this substance list may not be exhaustive, nor does it restrict the maximum levels of these substances in CCPs. It is presented to provide information on the substances and the concentrations evaluated for this SDS Guidance. Some constituent concentrations may exceed those presented as a result of sorbent injection in flue gas. 2 If the composition of a CCP varies from the above table in either composition or percentage, the CCP classifications assigned in Section 5.4 Table 7 may not apply. 3 Represents a combination of Amorphous silica and Aluminum oxide. Aluminosilicates may be in the form of mullite (CAS#1302‐93‐8); pozzolans, coal ash (CAS#71243‐67‐9); or aluminosilicates (CAS# 1327‐36‐2). The form is dependent on the source of the coal and/ or the process used to create the CCP. Pulverized coal combustion would be more likely to create high levels of pozzolans, coal ash (particularly bottom ash) due to the high heat of combustion while the CFB process would be less likely to generate this glassy aluminosilicate. 4 For purposes of this evaluation the various forms of crystalline silica were considered the same substance. 5 Includes Iron oxide. 6 For purposes of this exercise, calcium sulfate, calcium sulfate dihydrate and calcium sulfate (gypsum) were considered the same substance. 7 Although the maximum level of calcium sulfate in any of the ash formulations evaluated was ~6%, it was found that calcium sulfate may be present in a CCP formulation up to a level of 12 % due to the use of various inorganic calcium compounds that may be used as pollution control additives. 8 The ASTM 618 limit for the level of carbon in ash to be used in concrete is 6%. Unburned carbon can be found at higher levels; it can be as high as 20% in ash from cyclone boilers.

4.2 CCP ANALYTICAL METHODOLOGY Although Section 4.1 provides general information on the composition of the various forms of CCPs and information on the composition of the CCPs considered in the development of this SDS Guidance, it is

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important that each CCP is analyzed to determine its specific composition and concentrations in order to generate a SDS that accurately reflects the composition of a that CCP. The results of that individual CCP’s compositional analysis should then be compared to the GHS classifications for CCPs present in Section 5.4 Table 7. The analytical methodology, as presented in ASTM Standards as well as those used in a US Geological Survey (USGS) reports can be used to determine the composition of CCPs.2 3 A brief description of these methodologies are presented below. Using inductively coupled plasma mass spectroscopy (ICPMS) and by inductively coupled plasma atomic emission spectroscopy (ICPAES), the USGS determined the concentrations of the following elements in fly ash, As, Be, Bi, Cd, Co, Cr, Cs, Cu, Ga, Ge, Li, Mn, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Th, Tl, U, V, Y, and Zr and SiO2, Al2O3, CaO, MgO, Na2O, K2O, Fe2O3, TiO2, P2O5, SO3, Ba, and Sr, respectively (Affolter, 2011). X‐ray fluorescence (XRF) spectroscopy has also been used to assess the elemental composition of the coal ash with the results reported as the oxides of the particular elements (Swanson, 1976). ASTM D4326‐04: Standard Test Method for Major and Minor Elements in Coal and Coke Ash by x‐ray fluorecence provides a specific XRF analytical methodology for determining CCP composition (ASTM, 2004). Commercial instrumentation that utilizes XRF for the compositional analysis of CCPs was also identified (Thermo‐Fisher Scientific, 2012). As ICPMS, ICPAES and XRF are not able to specifically evaluate the presence of some substances that may contribute to the classification of the CCP, other methods may be required. Crystalline silica may be measured through the use of X‐ray diffraction (XRD). The typical

detection limit of XRD is generally between 1–3 weight percent (Affolter, 2011). EPRI has used computer‐controlled scanning electron microscopy (CCSEM) and x‐ray diffraction (XRD) to assess not only the level of crystalline silica, but also the level of the respirable portion of the crystalline silica which is the compositional fraction that may have an impact on the overall CCP hazard classification.

Calcium oxide and free calcium oxide may be measured using methodology presented in ASTM D4326‐04. The level of CaO and more specifically free CaO, may impact the irritation classification of the CCP.

Bromide compounds if present at or above 0.1% could also result in classification of the final CCP. If present, this substance would be identified using XRF or ICPMS.

Other substances deemed significant for evaluation by the USGS were also evaluated for using compound specific methods. Those compounds with associated methods include: mercury (direct mercury analyzer), selenium (hydride generation atomic absorption), chlorine (total chlorine analyzer) and sulfur (LECO SC 632) (Affolter, 2011).

2 The ASTM Standards reviewed include: C618‐12a: Standard Specification for Coal Fly Ash and Raw or Calcined Natural Pozzolan for Use in Concrete, D4326‐13: Standard Test Method for Major and Minor Elements in Coal and Coke Ash by X‐ray fluorescence, D311/311M‐13: Standard Test Methods for Sampling and Testing Fly Ash or Natural Pozzolans for Use in Portland‐Cement Concrete and D114‐15: Standard Test Methods for Chemical Analysis of Hydraulic Cement. 3 The references and methods specified are not required to determine the composition of the CCP. They are presented to provide ACAA member companies information on how the required data may be generated.

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4.3 COMMON PITFALLS IN COMPOSITION DETERMINATION/DISCLOSURE In assessing the composition of a given CCP it is important to correctly interpret the results of any chemical analyses performed. Composition of the CCP can be determined using varying methods such as X‐Ray Fluorescence analysis (XRF), X‐Ray Diffraction analysis (XRD), Inductively Coupled Ion Plasma analysis (ICAP) or other methodologies. These methodologies may result in the reporting of elemental substances (such as sodium or phosphorus); as these substances are not stable in their elemental form, they would be present in the final CCP as a compound, likely sodium oxide or phosphorus pentoxide. Further, other substances that would be in a gaseous form under normal atmospheric conditions, such as carbon dioxide or sulfur trioxide should not be reported as a component of the CCP. A list of some substances identified that were deemed to be inappropriate for inclusion in CCP composition based on reviewed compositional data and with input from ACAA members is presented in Table 2. Table 2: Examples of substances that would not be applicable for listing as a component of CCPs1 Substance Rationale

Sodium This substance is not stable in its elemental form and would likely be present as an oxide in CCPs.

Phosphorus This substance is not stable in its elemental form and would likely be present as an oxide in CCPs.

Sulfur trioxide This substance is a gas at standard temperature and pressure.

Chlorine This substance is a gas at standard temperature and pressure.

Carbon dioxide This substance is a gas at standard temperature and pressure.

Ammonia This substance is a gas at standard temperature and pressure. It may be present in the ash as ammonium sulfate or bisulfate.

1 This list reflects substances that may be identified in raw CCP analytical data that should not be identified as a component of a CCP composition based on the rationale provided. Other substances, not listed here, should not be considered in the GHS classification of CCPs based on similar exclusion rationale (e.g., gases should not be considered as a component of the ash) .

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5. GHS Classification

The US OSHA HCS 2012 aligns with the methodology set forth in the UN GHS, Revision 3 to assign appropriate physical and human health hazard categories to substances and mixtures (HCS, 2012). Hazard classes included in GHS are: explosives; flammable gases/aerosols; gases under pressure; flammable liquids/solids; self‐reactive substances/mixtures; pyrophoric liquids/solids; self‐heating substances/mixtures; oxidizing liquids/solids/gases; organic peroxides; metal corrosivity; acute oral, dermal and inhalation toxicity; aspiration hazard; skin and eye corrosion/irritation; respiratory or dermal sensitization; mutagenicity; carcinogenicity; reproductive toxicity; specific target organ toxicity‐single exposure; and specific target organ toxicity‐repeated exposure. Within each hazard class, a set of criteria has been established by GHS to classify the substance or mixtures into a specific hazard category (HCS, 2012, Appendix A and B). Signal words, hazard statements, precautionary statements and pictograms are then assigned to the substance or mixture as required by GHS and HCS 2012 based on the assigned hazard categories. To assign a GHS Classification per HCS 2012, data on the actual product (in this case the final CCP) is first considered. If data on the CCP is inadequate to assess the hazard or is unavailable, information on similar materials (defined as read‐across) or individual component data are used to assess a classification to the CCP. The GHS Classifications presented in this document are based on data present on the ECHA Dissemination Portal for both fly ash and a CFB ash, and where applicable, specific components such as silica dioxide (and its form and size), and identified skin and eye irritants that may be present were evaluated to assess if or when their presence would alter the overall CCP classification. This section details the GHS classification for typical CCPs, as well as the GHS classifications that may apply to specific components which could alter the final substance classification if present.4 As specified in the HCS 2012 and the GHS Guidance document, the CCP GHS classifications were assessed first based on primary data on fly ash and CFB fly ash as well as individual component classifications. Note: Environmental/ecological GHS classifications are not mandatory under HCS 2012 and do not need to be included in Section 12 of the SDS. Therefore, this guidance document does not include a review and classification for fly ash with respect to environmental/ecological endpoints.

5.1 DATA SUPPORTING GHS CLASSIFICATION OF CCPS

GHS classifications for the CCPs were based on data provided by registrants of “ashes (residue), coal” (including fly ash) and fluidized bed combustion (FBC) ash under the European Union’s (EU’s) Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) regulation as compiled in dossiers made available through the (ECHA) Dissemination Portal (ECHA, 2010a; ECHA, 2010b). Table 3 provides a summary of the human health endpoints evaluated under GHS for the final CCPs where available.

4Ash residues of the coal combustion process are considered to be a UVCB substance not a mixture of other substances; however, the composition variability may result in different classifications.

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Table 3. Toxicological Data on CCP GHS Endpoint Fly Asha

No CAS# listed EC# 931‐322‐8

FBC Fly Ash #1b

CAS# 68131‐74‐8 EC# 931‐257‐5

FBC Fly Ash #2c

CAS# 68131‐74‐8 EC# 931‐257‐5

Acute Oral Toxicity The acute oral LD50 was determined to be greater than 2000 mg/kg. Based on the GHS criteria, no classification with respect to acute oral toxicity is required.

The acute oral LD50 was determined to be greater than 2000 mg/kg. Based on the GHS criteria, no classification with respect to acute oral toxicity is required.

The acute oral LD50 was determined to be greater than 2000 mg/kg. Based on the GHS criteria, no classification with respect to acute oral toxicity is required.

Acute Dermal Toxicity

The acute dermal LD50 was determined to be greater than 2000 mg/kg. Based on the GHS criteria, no classification with respect to acute dermal toxicity is required.

Not available. Not available.

Acute Inhalation Toxicity

An acute inhalation toxicity LC50 was determined to be greater than 1.4 mg/L. Since the exposure to 1.4 mg/L of respirable coal fly ash particles on three consecutive days for 4 hours/day did not result in mortality and the respirable fraction of ashes (residue) typically does not exceed 20% of the total mass, the registrant determined that the LC50 is expected to exceed 5 mg/L. Based on the GHS criteria, no classification with respect to acute inhalation toxicity is required.

An acute inhalation toxicity LC50 was determined to be greater than 5.38 mg/L with a Mass Median Aerodynamic Diameter (MMAD) for the product of 2.33 microns after 4‐hour exposure to rats. Based on the GHS criteria, no classification with respect to acute inhalation toxicity is required.

An acute inhalation toxicity LC50 was determined to be greater than 5.38 mg/L with a MMAD for the product of 3.71 microns after 4‐hour exposure to rats. Based on the GHS criteria, no classification with respect to acute inhalation toxicity is required.

Skin Corrosion / Irritation

Not irritating or corrosive to skin based on in vitro and in vivo assays. Based on the GHS criteria, no classification with respect to skin corrosion/irritation is required.



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GHS Endpoint Fly Asha


FBC Fly Ash #1b

CAS# 68131‐74‐8 EC# 931‐257‐5

FBC Fly Ash #2c

CAS# 68131‐74‐8 EC# 931‐257‐5

Eye Damage / Irritation

Slight, reversible irritation based on in vitro and in vivo assays. Based on the GHS criteria, no classification with respect to eye damage/irritation is required.

Positive irritation scores for conjunctivae and chemosis in 2/3 rabbits. Moderate irritation observed in in vitro assay. Based on the GHS criteria, the classification is determined to be Eye Damage/Irritation Category 2A.

Animals with some scores for chemosis or conjunctivae but none resulting in a positive score; Irritation cleared within 21 days. An in vitro eye irritation assay did note moderate eye irritation. Based on the GHS criteria, no classification with respect to eye damage/irritation is required.

Skin Sensitization Not a dermal sensitizer. Based on the GHS criteria, no classification with respect to skin sensitization is required.

Not a dermal sensitizer. Based on the GHS criteria, no classification with respect to skin sensitization is required.

Not a dermal sensitizer. Based on the GHS criteria, no classification with respect to skin sensitization is required.

Germ Cell Mutagenicity

Several in vitro and in vivomutagenicity assays determined that fly ash was non‐mutagenic both with and without metabolic activation. Based on the GHS criteria, no classification with respect to mutagenicity is required.

Various in vitro mutagenicity assays determined that the test substance was non‐mutagenic both with and without metabolic activation. Based on the GHS criteria, no classification with respect to mutagenicity is required.

Various in vitro mutagenicity assays determined that the test substance was non‐mutagenic both with and without metabolic activation. Based on the GHS criteria, no classification with respect to mutagenicity is required.

Carcinogenicity Carcinogenic studies were not conducted with fly ash on the basis of the non‐neoplastic effects noted in the oral and inhalation repeated dose studies as well as the negative mutagenicity assays. Based on the GHS criteria, no classification with respect to carcinogenicity is required.

Carcinogenic studies were not conducted with FBC fly ash on the basis of the non‐neoplastic effects noted in the oral repeated dose studies as well as the negative mutagenicity assays. Based on the GHS criteria, no classification with respect to carcinogenicity is required.

Carcinogenic studies were not conducted with FBC fly ash on the basis of the non‐neoplastic effects noted in the oral repeated dose studies as well as the negative mutagenicity assays. Based on the GHS criteria, no classification with respect to carcinogenicity is required.

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FBC Fly Ash #1b

CAS# 68131‐74‐8 EC# 931‐257‐5

FBC Fly Ash #2c

CAS# 68131‐74‐8 EC# 931‐257‐5

Reproductive Toxicity

No statistically significant or dose‐response effects in the parental animals or their litters based on a reproduction / developmental toxicity screening test. Based on the GHS criteria, no classification with respect to reproductive toxicity is required.

The test substance did not have effect on reproduction in parental males and females and development in pups. The NOAEL (No Observed Adverse Effect Level) for reproduction and development was 800 mg/kg body weight/day. Based on the GHS criteria, no classification with respect to reproductive toxicity is required.

The NOAEL (No Observed Adverse Effect Level) for reproduction effects on parental animals was 50 mg/kg body weight/day. Various histopathological changes in males (testes and sperm motility) and in female reproductive parameters were observed across all dose groups, however, the data was deemed insufficient for classification. The NOAEL (No Observed Adverse Effect Level) for development was 800 mg/kg body weight/day. Based on the GHS criteria, no classification with respect to reproductive toxicity is required.

Specific Target Organ Toxicity: Single Exposure (STOT‐SE)

The acute toxicity data summarized above did not result in direct organ toxicity after a single exposure.

The acute toxicity data summarized above did not result in direct organ toxicity after single exposures.

The acute toxicity data summarized above did not result in direct organ toxicity after single exposures.

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FBC Fly Ash #1b

CAS# 68131‐74‐8 EC# 931‐257‐5

FBC Fly Ash #2c

CAS# 68131‐74‐8 EC# 931‐257‐5

Specific Target Organ Toxicity: Repeated Exposure (STOT‐RE)

A long term repeat inhalation exposure study (180 days) with fly ash dust conducted using rats did not result in significant adverse effects at the highest dose tested (NOAEC = 4.2 mg/m3) after the 180 day exposure period. Responses in the lungs were considered an adaptive response to inhaled particles and not unique to fly ash. As no effects were observed at the highest dose tested, it is not possible to assess the level at which toxicologically significant effects may occur in the rat. Therefore, a STOT‐RE classification based on available test data is not possible based on inconclusive evidence. Based on GHS criteria, no classification with respect to STOT‐RE is required.

A long term repeat oral exposure study (90 days) with 50, 200, and 800 mg/kg/day FBC fly ash conducted using rats reported a NOAEL for males of 200 mg/kg/day. The value was established on the basis of biochemical and histopathological examination. The target organ is the liver. The NOAEL for females was the highest dose tested, 800 mg/kg/day. Based on GHS criteria, no classification with respect to STOT‐RE is required.

A long term repeated oral exposure (90 days) with 50, 200, and 800 mg/kg/day FBC fly ash conducted using rats reported a NOAEL for males and females of 200 mg/kg/day. The value was established on the basis of biochemical and histopathological examination. The target organ is the liver. Based on GHS criteria, no classification with respect to STOT‐RE is required.

Aspiration Hazard Not applicable. Not applicable. Not applicable.

GHS Classification based on data in the ECHA Dissemination Portalf

NOT CLASSIFIEDd Eye Damage/Irritation Category 2A e

NOT CLASSIFIEDd

aDefined on the ECHA Portal as Ashes (residue), coal. The exact composition not provided but consists of silicon dioxide, aluminosilicates, oxides and other standard fly ash components bDefined on the ECHA Portal as FBC Ash (residues of coal combustion in fluidized bed boilers(Formulation 1). The composition was (FBC/230309/T2): SiO2 ‐ 27.78%, Fe2O3 – 5.98%, CaO (total) – 35.65%, Na2O – 0.25%, P2O5 – 0.38%, CO2 ‐ 0.5%, CaO (free) – 19.91%, Al2O3 – 11.16%, TiO2 – 2.65%, MgO – 0.44%, K2O – 0.42%, SO3 (sulphate) – 2.84%; Impurities: Metals: As, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Tl, V, Zn ‐ sum < 0.1% cDefined on the ECHA Portal as FBC Ash (residues of coal combustion in fluidized bed boilers(Formulation 2). The composition was (FBC/230309/T1): SiO2 – 35.59%, Fe2O3 – 7.69%, CaO (total) – 19.46%, Na2O – 0.53%, P2O5 ‐ 0.4%, CO2 – 1.11%, CaO (free) – 8.41%, Al2O3 – 20.88%, TiO2 – 4.93%, MgO – 0.41%, K2O – 0.43%, SO3 (sulphate) – 6.89%; Impurities: Metals: As, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Tl, V, Zn ‐ sum < 0.1% dNeither the exact composition, nor the level of respirable crystalline silica in the ashes were provided. It was further not possible to determine if the registrants considered that information. eAlthough not classified for this endpoint by the REACH registrants, a review and evaluation of the data provided in the ECHA portal determined that the eye irritation study data would result in a GHS classification of Eye Damage/Irritation Category 2.

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fData from Table 3 is sourced from the following: European Chemicals Agency (ECHA). REACH Registration Dossier for Ashes (residues), coal. http://apps.echa.europa.eu/registered/data/dossiers/DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031/DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031_DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031.html and ECHA REACH Registration Dossier for FBC Ash (residues of coal combustion in fluidized bed boilers. http://apps.echa.europa.eu/registered/data/dossiers/DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031/DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031_DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031.html.

Table 4. Physical Hazard Data/GHS Classification on CCPsa

GHS Endpoint/Classificatione Fly Ashb


FBC Fly Ash #1c

CAS# 68131‐74‐8 EC# 931‐257‐5

FBC Fly Ash #2d

CAS# 68131‐74‐8 EC# 931‐257‐5

Explosivity Not Classified Not Classified Not Classified

Flammable Solids Not Classified Not Classified Not Classified

Oxidizing Solids Not Classified Not Classified Not Classified

Self‐Reactive Chemicals Not Classified Not Classified Not Classified

Self‐Heating Chemicals Not Classified Not Classified Not Classified

Pyrophoric Solids Not Classified Not Classified Not Classified

Chemicals Which in Contact with Water, Emit Flammable Gases

Not Classified Not Classified Not Classified

Organic Peroxides Not Classified Not Classified Not Classified

Corrosive to Metals Not Classified Not Classified Not Classified aA non‐classification under the GHS is applied when the available data does not result in a classification; the classification does not apply based on identified properties of the substance or if there is insufficient data to apply the classification. bExact composition not provided but consists of silicon dioxide, aluminosilicates, oxides and other typical fly ash components cComposition tested (FBC/230309/T2): SiO2 ‐ 27.78%, Fe2O3 – 5.98%, CaO (total) – 35.65%, Na2O – 0.25%, P2O5 – 0.38%, CO2 ‐ 0.5%, CaO (free) – 19.91%, Al2O3 – 11.16%, TiO2 – 2.65%, MgO – 0.44%, K2O – 0.42%, SO3 (sulphate) – 2.84%; Impurities: Metals: As, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Tl, V, Zn ‐ sum < 0.1% dComposition tested (FBC/230309/T1): SiO2 – 35.59%, Fe2O3 – 7.69%, CaO (total) – 19.46%, Na2O – 0.53%, P2O5 ‐ 0.4%, CO2 – 1.11%, CaO (free) – 8.41%, Al2O3 – 20.88%, TiO2 – 4.93%, MgO – 0.41%, K2O – 0.43%, SO3 (sulphate) – 6.89%; Impurities: Metals: As, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Tl, V, Zn ‐ sum < 0.1% eInformation in Table 4 can be found in the European Chemicals Agency (ECHA). REACH Registration Dossier for Ashes (residues), coal. http://apps.echa.europa.eu/registered/data/dossiers/DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031/DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031_DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031.html and ECHA REACH Registration Dossier for FBC Ash (residues of coal combustion in fluidized bed boilers. http://apps.echa.europa.eu/registered/data/dossiers/DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031/DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031_DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031.html.

5.2 CRYSTALLINE SILICA

The term “crystalline” refers to the ordered arrangement of silicon dioxide (SiO2) molecules in a fixed pattern compared to the disordered and random molecular arrangement defined as amorphous silica. The most common forms of crystalline silica are quartz, cristobalite, and tridymite. CCPs may contain both amorphous and crystalline forms of silica. Pulverized coal fly ash consists mainly of amorphous aluminosilicates since the temperature within the boiler during the coal combustion process exceeds the melting point of the inorganic fraction of the coal. Rapid cooling of the fly ash as it exits the boiler in the flue‐gas stream resulting in vitrification of the non‐carbon material and transformation to glassy

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aluminosilicates. The aluminosilicates are typically a combination of the amorphous silica and aluminum oxide. Amorphous silica and the aluminosilicates have not been linked to significant health effects. CCP particles may contain some crystalline silica that either pass through the combustion process unchanged, partially vitrifies, or reforms from high temperatures. The amount of free crystalline silica available depends on various factors such as (1) the amount of crystalline silica in the pre‐combustion coal; (2) the temperature of combustion, and (3) the pollution control technologies utilized (EPRI, 2006a). It has also been concluded that “…there is no evidence that the health effects associated with respirable crystalline silica exposures are caused by other dust fractions, by other occurrences of crystalline silica, or by other routes of exposure to crystalline silica” (Morfeld, 2010). Therefore, only the respirable fraction of crystalline silica was considered in development of the GHS classifications of the CCPs and subsequent SDS development.

5.2.1 Particle Size

To evaluate the human health hazards associated with crystalline silica, it is important to consider not only the form, but also the particle size that may be present. Significant health effects associated with silica have not been linked to amorphous silica or crystalline silica embedded in other materials but rather the airborne crystalline silica dust that when inhaled by humans can penetrate through the nose and upper respiratory tract and deposit into the deep tissues of the lung. The National Institute for Occupational Safety and Health (NIOSH) defines Respirable Crystalline Silica (RCS) as “that portion of airborne crystalline silica that is capable of entering the gas‐exchange regions of the lungs if inhaled; by convention, a particle‐size‐selective fraction of the total airborne dust; includes particles with aerodynamic diameters less than approximately 10 microns (µm) and has a 50% deposition efficiency for particles with an aerodynamic diameter of approximately 4 µm.” (NIOSH, 2002) Recognizing that accurate determination of the particle size of the crystalline silica is important in understanding potential health effects that may result from exposure to CCPs, EPRI developed and investigated the use of a new computer‐controlled scanning electron microscopy (CCSEM) methodology as compared to the standard methodology using x‐ray diffraction (XRD) to quantify and qualitatively evaluate RCS size and particle shape in bulk fly ash samples as well as air/breathing zone samples from workers exposed to fly ash (EPRI, 2006b; 2008). In bulk ash samples (EPRI, 2006b), using CCSEM, the amount of RCS ranged from 0.1 to 3.2 volume % in contrast to the XRD measurements indicating 7.0 to 16.0 weight % of quartz. It was therefore concluded that the traditional XRD methodology based on weight percent of total quartz may overestimate the actual concentration of RCS. The CCSEM analysis also compared the number % particle size distribution (PSD) of the silica particles to a volume‐based PSD. Looking strictly at the number % PSD, most of the particles fall into the respirable range as defined in this study as 4 microns. Number PSD gives each particle equal weighting which may not be representative of the contributions of the size and volume of the particles. From the volume PSD, this study observed that most of the volume contained in the silica particles is actually larger than 6 microns in size with only a small fraction (less than 1%) less than 4 microns. The amount of RCS was determined by CCSEM for various airborne dust samples from plant maintenance activities and ranged from 0.6 to 3.1% (EPRI, 2008). In this study, the CCSEM volume % RCS levels and XRD weight % of quartz results were in reasonably good agreement for most airborne samples.

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In a NIOSH investigation of the potential exposures to crystalline silica as a constituent of the fly ash used in the cement manufacturing process, the personal air samples collected from workers found that the levels of respirable dust and quartz (crystalline silica) did not exceed applicable exposure criteria even when the levels of total dust were found to exceed acceptable levels (NIOSH, 2001). Therefore, even under dusty conditions in the workplace, the use of fly ash by workers in the cement plant did not result in significant exposure to RCS. For purposes of the GHS classification and SDS development for CCPs, the CCSEM results for RCS will be considered representative of the free respirable crystalline silica available in the CCPs rather than the use of total crystalline silica/quartz weight percent levels based on XRD or an assumption that all silicon dioxide in fly ash is respirable. Therefore, the hazard classification for coal fly ash will consider RCS in the ranges of 0.1 to 10%.

5.2.2 Health Effects

The health effects of RCS have been studied extensively for over twenty years in both in vitro and in vivo animal models as well as epidemiological occupational studies with workers exposed to RCS. As a result of the findings from these studies and overall risk assessments by various scientific and technical bodies, the two most common effects associated with exposures to RCS include silicosis and carcinogenicity. Recent reviews sponsored by the Industrial Minerals Association (IMA)‐Europe (Morfeld, 2010) and EPRI (EPRI, 2006a) were used as the primary sources for this guidance document as these reviews contained the most up to date information and utilize current risk assessment methodologies. A summary of the information with respect to potential RCS effects is provided below. 5.2.2.1 Silicosis

For many years, the prolonged inhalation of fine dust containing RCS was identified as causing silicosis (IMA, 2014a). As a result of deposition of RCS into the lungs, silicosis is defined by fibrotic changes (similar to scars) that affect the ability of the lung to exchange gases (MSHA, 2008). This disease has primarily been observed in workers from industries where significant exposure to RCS occurred over long periods of time, typically over several to many years.. Exposures to RCS in the natural environment are much lower than those found in the workplace and are insufficient to cause this occupational specific disease. Epidemiological and animal studies have shown clear positive dose‐response relationships between occupation exposure to RCS and silicosis. Inhalation studies with rats show a definite fibrogenic pulmonary response after repeated RCS exposure. Based on a review of epidemiological morbidity studies, the prevalence of silicosis is the most pronounced dose‐response effect identified in workers exposed to RCS as compared to other endpoints such as chronic obstructive pulmonary disease (COPD), autoimmune diseases or lung cancer. Therefore, researchers have concluded that no other non‐malignant health effect due to RCS is as specific and so clearly linked to RCS as silicosis (Morfeld, 2010). However, it is important to note that the silicosis typically appears only among workers exposed to high levels of RCS for extended periods of time. EPRI cites the American Conference of Governmental Industrial Hygienists (ACGIH) 2004 report on crystalline silica in which the ACGIH acknowledges that workers protected at the current Threshold Limit Value (TLV) of 0.05 mg/m3…”have not shown changes in life expectancy or lung function, although a small percentage may develop radiographic changes consist with pneumoconiosis (i.e., accumulation of dust in the lungs)” (EPRI, 2006a). This suggests that low levels of RCS will not result in silicosis and the current worker exposure levels are protective.

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With respect to CCPs, fly ash has been tested in long‐term inhalation exposures in rats and was found to result in minor adaptive effects in the lungs more generally associated with particulate dusts and tissue damage consistent with a fibrosis such as silicosis, but “the relative dose required to produce these effects was very high, and likely not representative of workplace exposures even under extreme conditions” (EPRI, 2006a). Therefore, the levels of RCS present in the CCPs are not anticipated to result in silicosis if the workers follow the current exposure limits provided by OSHA and ACGIH for RCS and crystalline silica.

5.2.2.2 Carcinogenicity

The most controversial endpoint to be considered is the potential cancer risk due to RCS dust exposure. Based on reviews of epidemiological data it has been determined that carcinogenic effects associated with occupation RCS exposures are limited to the lung with no evidence of significant causality of other cancers. In 1997, the International Agency for Research on Cancer (IARC) updated its evaluation of crystalline silica to Human Carcinogen (Group 1). The experts; however, expressed difficulty in coming to this decision as indicated in this explanatory note preceding the conclusion: "In making the overall evaluation, the Working Group noted that carcinogenicity in humans was not detected in all industrial circumstances studied. Carcinogenicity may be dependent on inherent characteristics of the crystalline silica or on external factors affecting its biological activity or distribution of its polymorphs. Crystalline silica inhaled in the form of quartz or cristobalite from occupational sources is carcinogenic to humans (Group 1). Amorphous silica is not classifiable as to its carcinogenicity to humans (Group 3)" (IARC, 1997; EPRI 2006a) Interestingly, the same working group of experts determined that coal dust, which may contain up to 15% crystalline silica, as an IARC Group 3 carcinogen (IMA, 2014a).5 Following the revised IARC classification, the US National Toxicology Program (NTP) also re‐classified RCS as known to be a human carcinogen in the Ninth Report on Carcinogens in 2000citing sufficient evidence of carcinogenicity from studies in experimental animals. As a result of these classifications, additional reviews of animal toxicology data and epidemiology data in human workers exposed to RCS have been conducted by different researchers and organizations. In addition, several studies of lung cancer in RCS workers have been published since the IARC and NTP evaluations. The conclusions from these more recent studies have called into question the validity of the carcinogenic risk of RCS from occupational exposures. EPRI (2006a) provides a summary of mechanistic studies evaluated after the IARC 1997 classification that observed that crystalline silica is not directly genotoxic. These results were confirmed in mutagenicity studies conducted with fly ash and FBC fly ash that may contain RCS. The suggested mode of action for how RCS causes lung cancer has instead been established as an indirect or secondary effect of the silicosis (Morfeld, 2010). Moreover, the only animal species to produce lung tumors in response to RCS was the rat; no effects were seen in mice, hamsters or guinea pigs, which has led some researchers to conclude that the carcinogenic response in the rat is specific to that species (EPRI, 2006a). With respect to a review of the worker exposure studies, lifestyle factors (especially smoking) as well as socioeconomic status may have been confounding factors in the excessive lung cancer risk and mortality patterns associated with RCS exposures. The review provided by Morfeld also took into account studies that show that lung cancer risks were observed only under high occupational exposure conditions (Morfeld, 2010). These observations based on studies published in recent years led EPRI to

5Substance which cannot be classified as to its carcinogenicity due to inadequate evidence in humans and animals.

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conclude that “given the lack of a direct association between crystalline silica and lung cancer among workers exposed to crystalline silica, there should be no concern regarding the potential carcinogenicity of crystalline silica in coal fly ash.” (EPRI, 2006a)

5.2.2.3 Relationship between Silicosis and Lung Cancer

Evaluation of the relationship between silicosis and lung cancer is complicated as most studies depended on cohorts of compensated workers with silicosis (silicotics) leading to a bias in study results and conclusions. The recent literature does not provide evidence supporting the relationship between silicosis and lung cancer (EPRI, 2006a). In a meta‐analysis study of workers exposed to RCS, there was no evidence that non‐silicotics suffered from higher lung cancer risks especially after smoking habits were considered (Morfeld, 2010). IMA Europe has concluded that silicosis is a primary effect of significant exposure to RCS and that silicosis is a result of inflammation in the lung. Although excess cancer risks are observed in silicotics, it is not clear as to the actual mechanistic role of silicosis in the development of lung cancer and additional data is necessary for an exact determination. Based on a review of these data, it has been established that minimizing silicosis risk will also minimize lung cancer risk due to RCS (Morfeld, 2010). 5.2.3 Implications for GHS Classifications

Although there is a general understanding that significant exposures to RCS may result in adverse health effects, there is not a scientific consensus on the appropriate classification for RCS. Most researchers and regulators agree that RCS causes systemic target organ toxicity (STOT) in humans in the form of silicosis and classify as such, but the carcinogenicity classifications vary from Not Classified to the most severe, Carcinogen Category 1A (Gradient, 2015a). Based on the review and hazard assessment of the health effects of RCS, rationale and conclusions summarized above, a recent position paper from IMA‐Europe supports a classification for RCS as STOT‐RE Category 1 based on the silicosis effects (IMA, 2014b). The position paper concluded that no carcinogen classification for RCS is required if silicosis is defined as the endpoint for classification (Morfeld, 2010). Using the STOT classification, substances and mixtures containing RCS in the form of an identified impurity, additive or individual constituent will be classified under GHS as:

STOT RE 1, if the RCS concentration is equal to or greater than 10%;

STOT RE 2, if the RCS concentration is between 1 and 10%;

Not Classified, if the RCS concentration is below 1%. Although levels of RCS in the fly ash and FBC fly ash studies performed in support of REACH registration and summarized above were not disclosed, some level of RCS will likely be found in the CCPs. As a result, the toxicology testing with these CCPs as described above appear to confirm the IMA Europe classification approach based on the negative mutagenicity studies and minimal effects observed in repeated inhalation studies in animals. The EPRI analysis also suggests that there is not a concern for carcinogenic effects from exposures to coal fly ash based on the studies with RCS (EPRI, 2006a). Therefore, for purposes of this guidance document, RCS will be classified as a Repeat Dose STOT with the CCP classification following the IMA‐Europe approach being used.

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5.2.4 OSHA Proposed Silica Rule It is important to note that OSHA has issued a proposed silica rule that includes a stricter workplace permissible exposure limit (PEL) for RCS supported by a new hazard and risk assessment (OSHA, 2013). A single uniform PEL of 50 ug/m3 for all forms of RCS in the proposed rule represents a 50 to 80% reduction in the PEL from the current PELs for industries including general industry and construction (Gradient, 2015b). The rule also includes provisions with respect to exposure assessment, methods for controlling exposure, respiratory protection, medical surveillance, hazard communication, and record keeping. Researchers and industry had hoped that OSHA would give consideration to the data supporting a threshold effect of RCS based on the development of silicosis; however, OSHA has not yet conducted a thorough analyses and evaluation as part of the proposed rule. At the time of the development of this guidance document, OSHA has not finalized the rule and is still evaluating the many comments submitted.

Once the rule becomes final and the implications of the OSHA scientific underpinnings behind the reduction in the PELs becomes clear, it will be important to re‐evaluate the rationale for the GHS classifications for RCS and their implications on the overall classification of CCPs as presented in this document to ensure continued compliance with OSHA requirements under both the HCS 2012 and the final OSHA Silica Rule. 5.3 OTHER CONSIDERATIONS THAT MAY IMPACT CCP GHS CLASSIFICATIONS

5.3.1 Irritation/Corrosivity Multiple substances classified either as skin/eye irritants may be present in the CCPs naturally or as a result of the use of various pollution control additives. The level of these substances was evaluated against data available on the fly ash and FBC ash formulations evaluated for REACH registration purposes to determine if these substances 1) were included in the formulations tested at similar levels; 2) may be present at different concentrations than those tested; or 3) are unique to the information gathered during the course of this project on CCPs. If these individual components were present at higher concentrations or were not noted in the tested products, the potential contribution to the hazards of the formula and the need for additional hazard classifications for the ashes was assessed. The individual components (natural and additive based) classified as either skin or eye irritants or skin corrosive substances are presented in Table 5. The Table also specifies the classification of the individual substances as found in the ECHA portal as well as the maximum level present in the CCPs based on a review of the formulation data from ACAA member companies and various publicly available sources by the industry’s technical experts.

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Table 5: Example GHS Skin/Eye Irritants or Corrosive Substances that MAY be present in CCPs1

Substance Source Classification

Natural Additive

Calcium oxide2 X X Skin Irritation ‐ Category 2Eye Irritation ‐ Category 1

Phosphorous pentoxide X Skin Corrosivity – Category 1A

Potassium oxide X Skin Irritation ‐ Category 2Eye Irritation ‐ Category 2

1 This table represents irritating or corrosive substances at the maximum level that MAY be present in CCPs based on compositional information submitted by ACAA member companies or identified in technical publications. 2 When the Calcium Oxide levels are determined by XRF analysis, the presence of calcium aluminosilicate, and other calcium species in the form of sulfate, carbonate, chloride, etc. may falsely elevate the level of CaO reported.

As mentioned previously, classification per the GHS Guideline follows a hierarchy with the classifications based first on finished product testing, and in the absence of those data, based on read‐across to similar products or individual components of the final product. Although data on both a representative fly ash and FBC ash is available for skin and eye irritation, there are distinct differences in the results from the various studies. A review of the formulations indicate that this is likely due to different levels of some of the ash components. A comparison of the compositional and toxicology data between these two materials demonstrate that: The fly ash tested was not irritating or corrosive to skin or eyes; however, the exact level of

calcium oxide in the sample tested was not provided to be able to determine if it is representative of the ACAA member formulations.

Two FBC fly ash compositions tested under the REACH registration showed variable results.

– The FBC fly ash composition with a total calcium oxide level of 35.65% (free calcium oxide level of 19.91%) was determined to be:

An eye irritant, Category 2A; but

Non‐irritating to skin.

– The FBC fly ash composition with a total calcium oxide level of 19.46% (free calcium oxide level of 8.41%) was determined to be:

Non‐irritating to skin; and

Non‐irritating to eyes.

Note 1: See information in Section 5.1, Table 3 for additional information. Note 2: The level of total calcium oxide may be falsely elevated based on the presence of other compounds in the ash such as calcium aluminosilicate, and other calcium species in the form of sulfate, carbonate, chloride.

In order to assess the hazards associated with a particular CCP formulation, it is necessary to assess the components of the CCPs and the likelihood of those components to impact the hazards of the CCP.

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Based on this evaluation, the results from the final product testing and the percentages of these component irritants in the CCPs, the level of calcium oxide was determined to be the primary driver for the skin/eye GHS classifications and the following conclusions can be made: CCPs with levels of total calcium oxide at or below 20% or, if determined free (reactive) calcium

oxide at or below 8%, would NOT be classified for either skin or eye irritation.

CCPs with levels of total calcium oxide above 20% or, if determined free (reactive) calcium oxide above 8%,would be classified as an Eye Irritant Category 2A.

Note: If the CaO levels are only determined by XRF analysis, the 20% threshold specified as resulting in classification of the CCP as an Eye Irritant, Category 2 would apply. If data on free CaO is available, this level (and the lower threshold value of 8%) should be used to assess the classification of the CCP as an Eye Irritant, Category 2A.

5.3.2 Acute Toxicants Multiple substances classified as acutely toxic may be present in the CCPs naturally or as a result of the use of various pollution control additives. The level of the acutely toxic substances was evaluated in consideration of the GHS Guideline classification criteria and the lack of classification from the testing of a fly ash and two FBC ashes (REACH registration purposes) to determine if the presence of these substances could result in additional hazards to the CCP if they are present. The individual components (natural and additive based) classified as acutely toxic (and the route of exposure: oral, inhalation or dermal) are presented in Table 6. The Table provides the classification of each substance from the ECHA portal along with the maximum level present in the CCPs based on a review of the formulation data from ACAA member companies and various publicly available sources by the industry’s technical experts.

Table 6: Example GHS Acutely Toxic Substances that MAY be present in CCPs1

Substance Source Classification Natural Additive

Calcium oxide X X Acute Oral Toxicity – Category 4

Magnesium sulfate X

Acute Oral Toxicity – Category 4 Acute Inhalation Toxicity – Category 4 Acute Dermal Toxicity – Category 4

Manganese dioxide X Acute Oral Toxicity – Category 4 Acute Inhalation Toxicity – Category 4

1 This table represents acutely toxic substances at the maximum level that MAY be present in CCPs based on compositional information submitted by ACAA member companies or otherwise identified in technical publications.

Using the data available in the ECHA portal for the final fly ash and FBC fly ash products as well as the GHS defined method for assigning a classification of a mixture based on its components, the presence of these substances at the levels identified would not result in a classification of the final CCP (UN, 2009).

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5.3.3 Substances Defined as Toxic to Reproduction

Bromide salts may be present in the final CCP based on the introduction of sodium or calcium bromide as pollution control additives at levels up to 2% based on typical additive levels provided by ACAA members. A review of reproductive toxicity data on sodium bromide (as a representative inorganic bromide salt, specifically sodium bromide) indicates that the substance may result in reproductive toxicity as well as developmental effects (HSDB, 2015; CA EPA 2001). Based on these data, a Toxic to Reproduction, Category 2 classification is appropriate. As inorganic bromide salts were not noted as present in the fly ash or FBC ashes tested for REACH registration by the ECHA, the presence of this substance must be considered for the CCP classifications if inorganic bromide compounds are introduced as a pollution control additive. Although, HCS 2012 does not require disclosure of reproductive toxicants below 1%, when these substances are present at levels greater than or equal to 0.1%, a GHS Toxic to Reproduction classification would be applied to the CCP. Therefore, it is recommended that the presence of inorganic bromide salts be disclosed on the CCPs SDSs when present at levels greater than or equal to 0.1% and the reproductive toxicity effects be considered in the classification of the CCPs. 5.3.4 Single Exposure – Specific Toxic Organ Toxicity

A large part of the identified CCPs compositions consist of substances present in a dust matrix. As the CCP dust itself may result in mechanical irritation of the respiratory tract, the CCPs would be classified as a Specific Toxic Organ Toxicity‐Single Exposure (STOT‐SE), Category 3 (respiratory irritation). 5.4 FINAL CCP GHS CLASSIFICATION

When the information on the GHS classification testing of fly ash, CFB fly ash, and an evaluation of the classifications associated with individual components of the CCPs are considered, multiple classifications of the CCPs are possible. The various classifications that are or may be applicable to a CCP based on component compositions are detailed below along with the rationale for applying those classifications. Specific Target Organ Toxicity (STOT) – Single Exposure (SE), Category 3 (Respiratory Irritation)

Due to the overall level of aluminosilicates, calcium oxide, and the form of the CCP as a dust, it is recommended that all CCPs be classified as a STOT‐SE (Respiratory Irritation).

Specific Target Organ Toxicity (STOT) – Repeat Exposure (RE), Category 2 This classification is applied to CCPs with either an undetermined level of respiratory crystalline silica or where the respiratory crystalline silica is present at levels above 1%. This classification is based on a review of information from the IMA as described above.

Eye Irritation, Category 2

Multiple eye irritants were identified in a typical CCP formulation. When the presence of these substances was critically evaluated, it was clear that the level of calcium oxide was the primary driver of these hazards. Using data available on the percentage of calcium oxide (and other irritants) in the two FBC ashes tested for REACH registration purposes, it was determined that CCPs with greater than 20% total calcium oxide and greater than 8% free calcium oxide should be classified under GHS as an Eye Irritant, Category 2.

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Toxic to Reproduction, Category 2

CCPs may require a Toxic to Reproduction, Category 2 classification if sodium bromide or other pollution control additives containing inorganic bromide salts are incorporated into the CCP process and result in a final concentration of greater than or equal to 0.1%. A review of toxicity data on sodium bromide (assessed as the representative inorganic bromide salt) indicates that a Toxic to ReproductionCategory 2 classifications for these substances is appropriate based on some evidence of reproductive toxicity in animals. Per HCS 2012 Appendix A, when a reproductive toxicant is included at a level of greater than or equal to 0.1%, the final product should also be classified.

Table 7 summarizes the different CCP Classifications that may be applicable including the variations in component levels that result in the identified classifications. As noted, the classifications are derived from the overall CCP composition as well as specified individual component variations.

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Table 7: CCP Composition Classifications1, 2 CCP Classifications Compositional Specifications

CCP 1 Composition

STOT‐SE Category 3 (Respiratory Irritation)

STOT‐RE Category 2

Ashes with:

Undetermined or ≥1 to < 10% respirable crystalline silica;

Total calcium oxide levels less than or equal to 20%;or if determined, free calcium oxide levels less than or equal to 8%; and

Inorganic bromide salts less than 0.1%.

CCP 2 Composition


Eye Irritant Category 2A STOT‐RE Category 2

Ashes with:

Undetermined or ≥1 and < 10% respirable crystalline silica;

Total calcium oxide levels greater than 20%; or if determined, free calcium oxide levels greater than 8%; and


CCP 3 Composition


Ashes with:

<1% respirable crystalline silica; Total calcium oxide levels less than or equal to 20%; or if determined, free calcium oxide levels less than or equal to 8%; and


CCP 4 Composition

1. STOT‐SE Category 3 (Respiratory Irritation)

Eye Irritant Category 2A

Ashes with:

<1% respirable crystalline silica; Total calcium oxide greater than 20%; or if determined, free calcium oxide levels less than or equal to 8%; and


CCP 5 Composition


STOT‐RE Category 2 Toxic to Reproduction Category 2

Ashes with:


Total calcium oxide levels less than or equal to 20%;or if determined, free calcium oxide levels less than or equal to 8%; and

Inorganic bromide salts ≥ 0.1%.

CCP 6 Composition


Toxic to Reproduction Category 2

Ashes with:

<1% respirable crystalline silica; Total calcium oxide levels less than or equal to 20%;or if determined, free calcium oxide levels less than or equal to 8%; and


CCP 7 Composition


Eye Irritant Category 2A STOT‐RE Category 2 Toxic to Reproduction Category 2

Ashes with:


Total calcium oxide levels greater than 20%; or if determined, free calcium oxide levels less than or equal to 8%; and


CCP 8 Composition


Eye Irritant Category 2A Toxic to Reproduction Category 2

Ashes with:

<1% respirable crystalline silica; Total calcium oxide greater than 20%; or if determined, free calcium oxide levels less than or equal to 8%; and

Inorganic bromide salts ≥ 0.1%. 1 These classifications only apply to CCP formulations that meet the composition specifications detailed in Appendix C. Should a CCP have additional substances present, or have substance(s) above the maximum percentage identified in Appendix C, an evaluation of those differences should be assessed to confirm that one of the classifications defined would still apply.

2 When the Calcium Oxide levels are determined by XRF analysis on pulverized coal ash, the presence of calcium aluminosilicate and other non‐CaO calcium species may falsely elevate the level of CaO reported. If the CaO levels are only determined by XRF analysis, the 20% threshold resulting in classification of the CCP as an Eye Irritant, Category 2 would apply. If data on free CaO is available, this level (and the lower threshold value of 8%) should be used to assess the classification of the CCP as an Eye Irritant, Category 2A.

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6. SDS Development The information prescribed by OSHA to develop and generate a SDS for the CCPs was based on HCS 2012 and associated guidance from OSHA (OSHA 2012a, OSHA 2012b, OSHA 2012c, OSHA 2012d, OSHA 2012e, OSHA 2012f, OSHA undated a, and OSHA undated b).

6.1 GENERAL COMMENTS

The American National Standard for Hazardous Workplace Chemicals: Hazard Evaluation and Safety Data Sheet and Precautionary Labeling Preparation (ANSI Z400.1, 2010) is referenced in the HCS 2012. ANSI Standard Z400.1 provides recommendations on SDS format that can be used to meet the requirements of HCS 2012. The ANSI standard recommendations are used throughout this guidance document to generate the fly ash SDS template. These recommendations provide guidance to improve the readability and comprehensibility of the generated SDS including: Use of a vertical (portrait) format on a standard paper size (8‐1/2 x 11 inch).

Use of 10 to 14 point simple fonts, with the use of multiple fonts being avoided.

Avoid long strings of text typed in upper‐case letters.

Use only common abbreviations and acronyms. Provide full definitions in the legend in Section 16.

Choose commonly used words, but avoid colloquialisms and slang.

Include ample margins so that copying and binding do not cut off information.

Use left justification of text, consistent line spacing and spaces to separate fields and sections.

Avoid footnotes on the SDS. Pertinent information may be placed in parentheses or as a “note” directly following information requiring clarification.

Use Arabic numbers (e.g., 1, 2, 3), where required. It is further noted that the audiences required to acknowledge and understand the information provided in the SDS vary widely and can range from an untrained person requiring general information to highly technical staff. The information conveyed must be sufficiently complete for the technical specialist yet understandable for general use. 6.2 SDS SECTION‐BY‐SECTION COMMENTS This portion of the Guidance document is partitioned into individual sections required for inclusion in a HCS 2012 compliant SDS. Under each section (and some subsections) the following information is provided: The purpose of the section;

Required/recommended text; and The information recommended or required for inclusion is presented as italicized text for ease of viewing.

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Example text The information recommended for inclusion in the applicable CCP SDS, based on the HCS 2012 GHS classification and other properties of the CCP are presented as italicized text for ease of viewing.

Section 1: Identification of the Substance and of the Company/Undertaking Purpose: Section 1 provides the material name/product codes to link the SDS to the label and shipping documents. It also identifies the manufacturer and provides an address and contact information (i.e., phone number). Arrange this section with following subheadings: 1.1 Product identifier 1.2 Relevant identified uses of the substance and uses advised against 1.3 Details of the supplier of the safety data sheet 1.4 Emergency telephone number 1.1 Product identifier

Recommended/required text The product identifier should consist of the trade name or the designation of the substance or mixture as found on the product label. Other names or synonyms by which the product is labeled or commonly known as, such as alternative names, numbers, company product codes, or other unique identifiers may also be provided. If one generic SDS is used to cover several variants of a substance or mixture, all names and variants should be listed.

Note: Per HCS 2012, the identifier used on the SDS should be the same as that on the product label.

Example text: Product Name: Apex Fly Ash Product Code: C12345 (if available). If no code is used indicate “Not applicable” Formula: Substance (Indicate if the product is considered a substance or a mixture; in the case of fly ash, it is considered a substance)

1.2 Relevant identified uses of the substance and uses advised against

Recommended/required text Specify the relevant uses for the product.

Specify the uses advised against: If no uses are advised against enter: “None known” or “Any other uses other than those recommended”.

Example text: Relevant/identified uses: Component of wallboard, concrete, roofing material, bricks (EPA, 2014) Uses advised against: None known

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1.3. Details of the supplier of the product/safety data sheet

Recommended/required text Specify the company name, address, and business phone number based on the site of manufacture.

Provide an e‐mail address for a competent person responsible for the safety data sheet. (i.e., EHS manager)

Example text: Manufacturer/Supplier: Apex Ash Street Address: 123 Main Street City, State and Zip Code: Any town, MI 48210 Telephone number for responsible person: 555‐555‐5555 (Optional: Email address of Responsible Person: [email protected])

1.4. Emergency telephone number

Recommended/required text Include an emergency telephone number and name of outside company providing the service if applicable. Indicate restrictions, such as hours of operation (e.g., Monday – Friday, 8:00 a.m. – 6:00 p.m. Eastern Time zone or 24 hours). The emergency number for each national jurisdiction in which the product is sold or the use of an international service number should be included. Be aware that domestic toll‐free numbers may not operate from an outside country.

Example text: Emergency Phone Number: 1‐800‐555‐1212 (Chemtrec) Hours Available: 24 hours a day, 7 days per week

Section 2: Hazards Identification Purpose: Section 2 describes the hazard(s) associated with the product and the appropriate warning information (pictogram, signal word and hazard and precautionary statements). This data on the inherent hazards of the product per 29CFR 1910.1200 and the GHS Guideline, Revision 3. Arrange this section with following subheadings: 2.1 Classification of the substance 2.2 Label elements 2.3 Other hazards 2.1. Classification of the substance (or mixture) Purpose: Section 2.1 lists the product classification per 29CFR 1910.1200 and the GHS Guideline, Revision 3.

Recommended/required text/information Include the appropriate GHS hazard class & category for each health and physical hazard using available data on the finished product or its components, following specifications of Appendices A & B of the HCS Standard and the GHS Guideline, Revision 3.

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Example text:

GHS Classification(s) for this product according to OSHA Hazard Communication Standard (29 CFR 1910.1200) include: ‐ STOT‐SE Category 3 (Respiratory Irritation) ‐ STOT‐RE Category 2

Note: The level of respiratory crystalline silica (RCS) present in this product has not been determined; however, a

conservative classification for STOT‐RE, Category 2 has been assigned.

Note: These GHS Classifications are those associated with CCP 1. Insert the classification applicable to the CCP being evaluated as provided in Table 7 from Section 5.4.

2.2 Label elements

Recommended/required text The appropriate hazard pictograms, signal word, hazard statements, and precautionary statements should be provided as specified in 29CFR 1910.1200(f) and defined in29 CFR 1910.1200, Appendix C and the GHS Guideline, Appendix 1

Example text: Include information appropriate to your CCP, based on its composition. The information to be provided for CCP 1 is presented here. Appendix D provides the hazard pictograms, signal word, hazard statements, and precautionary statements associated with each identified CCP. The information within each table can be transposed into the SDS. The footnote to the table provided herein is also recommended to detail the nature of the CCP.

Labelling according to 29 CFR 1910.1200 Appendices A,B and C

Hazard Pictogram(s):

Signal word: Danger

Hazard Statement(s):

May cause respiratory irritation.May cause damage to lungs after repeated/prolonged exposure via inhalation.

Precautionary Statement(s)

Do not breathe dust.Use outdoors or in a well ventilated area. If inhaled: Remove to fresh air and keep comfortable for breathing. Get medical advice/attention if you feel unwell. Store in a secure area. Dispose of product in accordance with local/national regulations.

* Fly ash and other CCPs are UVCB substances (substance of unknown or variable composition or biological). Fly ash is defined by the US EPA as: “The residuum from the burning of a combination of carbonaceous materials. The following elements may be present as oxides: aluminum, calcium, iron, magnesium, nickel, phosphorus, potassium, silicon, sulfur, titanium, and vanadium.” The exact composition of the fly ash is dependent on the fuel source and flue

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additives composed of a large number of constituents. The classification of the final substance is dependent on the presence of specific identified oxides as well as other trace elements.

2.3 Other hazards

Recommended/required text

Specify the presence of OSHA, IARC, NTP or ACGIH Carcinogens that may be present in the product. The information noted here below is recommended for inclusion if the level of respirable crystalline silica in the final product is above 0.1% or has not been determined.

Example text:

Listed Carcinogens: o Respirable Crystalline Silica

IARC: yes NTP: yes OSHA: no Other (specify, i.e., European Union): no

Section 3: Composition/information on Ingredients Purpose: Section 3 identifies the components of the final product. UVCB substances, such as fly ash, may be listed as a single component; however, if a cited hazard is attributed to one or more components of the UVCB (i.e. crystalline silica), then it is advisable to indicate its presence. 3.1 Substances

Recommended/required text Disclosure of OSHA hazardous substance above reportable thresholds is required (>0.1% for carcinogens, >1% for other hazardous materials). Disclosure of hazardous substance below the threshold is also required if that substance/concentration results in the classification of the final product. Disclosure of substances defined as non‐hazardous per GHS criteria may be disclosed; however this is not required per HCS 2012 (e.g., iron oxide)

Substance Disclosure Requirements/Recommendations:

a) Chemical name/identity b) Percentage in final product (range is appropriate) c) Chemical Abstract Services Number (or other Number of Identity, i.e., PMN number) d) GHS Classification of the hazardous components greater that the HCS 2012 defined threshold. e) Impurities, especially if these impurities result in the classification of the final product.

The substances that may require disclosure, with their threshold for disclosure are noted in Table A.

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TABLE A: CCP components that may require disclosure

Substance CAS No. Disclose ? GHS Classification

Crystalline Silica 14808‐60‐7 See note 1 Repeat Dose STOT, Category 2

Silica, crystalline respirable (RCS)

14808‐60‐7 ≥0.1% 2 Repeat Dose STOT, Category 2

Aluminosilicates Various 3 Yes Specific Target Organ Toxicity – Single Exposure

Calcium oxide (CaO) 1305‐78‐8 ≥1% Skin Irritant Category 2 Eye irritant Category 2B

Manganese dioxide (MnO2) 1313‐13‐9 ≥1% Skin Irritant Category 2 Eye irritant Category 2B

Phosphorus pentoxide (P2O5)

1314‐56‐3 ≥1% Skin Irritant Category 2 Eye irritant Category 2B

Potassium oxide (K2O) 12136‐45‐7 ≥1% Skin Irritant Category 2 Eye irritant Category 2B

Magnesium sulfate 7487‐88‐9 ≥1% Skin Irritant Category 2 Eye irritant Category 2B

1 Report the level of crystalline silica found in the product if the level of Respirable Crystalline Silica has not been determined. 2 Report the level of RCS if known. If the RCS level has not been determined, footnote the crystalline silica value to indicate that the respirable portion of the substance in the CCP has not been determined. 3 Aluminosilicates may be in the form of mullite (CAS#1302‐93‐8); pozzolans, coal ash (CAS#71243‐67‐9); or aluminosilicates (CAS# 1327‐36‐2). The form is dependent on the source of the coal and or the process used to create the CCP. Pulverized coal combustion would be more likely to create high levels of pozzolans, coal ash (particularly bottom ash) due to the high heat of combustion while the CFB process would be less likely to generate this glassy aluminosilicate.

Example text for All CCP Compositions (1‐8)

Populate this section of the SDS with the components identified as hazardous (per GHS) defined above that are present in the product at or above the identified exposure limits for disclosure as noted in Table A(above) . Information on components of CCPs that are above the HCS 2012 thresholds or results in CCP classification should be disclosed. Disclose either the exact percentage of the necessary substances or provide a percent range. The recommended composition ranges are:

– Less than 1 percent;



– 5 to 10 percent;





– 40 to 70 percent; and

– 60 to 100 percent. 3.2 Mixtures

This section is not applicable to the various CCPs evaluated in this Guidance Document and should not be included in the SDS.

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Section 4: First Aid Measures Purpose: Section 4 is intended to provide appropriate emergency and first aid information. Instructions for each applicable route, in plain language, should be provided when the results of exposure require immediate treatment (first aid) and when simple measures may be taken before professional medical assistance is available. First aid procedures should be brief and easily understood. Arrange this Section with the following subheadings: 4.1 Description of first aid measures 4.2 Most important symptoms and effects, both acute and delayed 4.3 Indication of any immediate medical attention and special treatment needed 4.1 Description of first aid measures


Provide instructions based on route of exposure. Use subheadings to indicate the procedure for each route (e.g., inhalation, skin, eye and ingestion). Instructions may reflect precautionary statements found in Section 2 or may reflect actions required based on non‐classifiable effects (i.e., a product that has irritant effects but those effects do not result in an irritant classification, or a substance where nuisance dust may be generated).

Include simple remedial measures (i.e., wash affected area, remove clothing, remove the exposed individual from the area) if the action will lessen exposure.

Indicate whether immediate medical attention is required and if delayed effects can be expected after exposure.

When no specific information is available, the following types of information should be provided, based on sound professional judgment:

o remove exposed individual from area (to fresh air);

o removal of material from individual;

o advice on removal and handling of contaminated clothing and shoes;

o advice on obtaining medical assistance.

If no adverse health effects are identified, indicate that first aid measures are not necessary. A statement regarding normal hygiene practices can still be included.

Example Text for all CCPs compositions (1‐8) Inhalation If product is inhaled and irritation of the nose or coughing occurs, remove person to fresh air. Get medical advice/attention if respiratory symptoms persist. Skin contact If skin exposure occurs, wash with soap and water.

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Eye Contact If product gets into the eye, rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Seek medical attention/advice if irritation occurs or persists. Ingestion No specific first aid measures are required.

4.2 Most important symptoms and effects, both acute and delayed

Recommended/required text Provide information on the symptoms/effects that may occur based on the type of exposure (acute or chronic). Use subheadings to indicate both types of exposure.

Example text for CCP compositions 1 through 4 Acute Effects Direct exposure may cause respiratory irritation, eye irritation and skin irritation. The product dust can dry and irritate the skin and cause dermatitis and can irritate eyes and skin through mechanical abrasion. Chronic Effects Chronic exposure may cause lung damage from repeated exposure. Chronic inhalation of dusts containing respirable crystalline silica may result in silicosis.

Example text for CCP compositions 5 through 8 Acute Effects Direct exposure may cause respiratory irritation, eye irritation and skin irritation. The product dust can dry and irritate the skin and cause dermatitis and can irritate eyes and skin through mechanical abrasion. Chronic Effects Chronic exposure may cause lung damage from repeated exposure. Chronic inhalation of dusts containing respirable crystalline silica may result in silicosis. Repeated exposure to dusts containing inorganic bromide salts may effect fertility and/or result in effects to the unborn child.

4.3 Indication of any immediate medical attention and special treatment needed

Recommended/required text Provide additional information on specific conditions requiring treatment and/or diagnostic procedures outside of customary first aid treatment for use by healthcare professionals.

Example text for all CCP Compositions (1‐8)

Seek first aid or call a doctor or Poison Control Center if contact with eyes occurs and irritation remains after rinsing.

Section 5: Firefighting Measures Purpose: Section 5 provides information describing specific hazards arising from the fire and explosive properties of the material, the appropriate extinguishing media for the fire and special protective equipment and precautions for fire‐fighting.

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Arrange this section with following subheadings: 5.1 Extinguishing media 5.2 Special hazards arising from the substance 5.3 Advice for firefighters 5.1 Extinguishing media

Recommended/required text Indicate the appropriate extinguishing media to be used in the event of a fire. Extinguishing media that should be avoided (unsuitable) should also be provided. If applicable, provide guidance on media application of suitable media.

Example text for all CCP formulations (1‐8)

Suitable extinguishing media: Product is not flammable. Use extinguishing media appropriate for surrounding fire. Unsuitable extinguishing media: Not applicable, the product is not flammable.

5.2 Special hazards arising from the substance

Recommended/required text Provide information as it relates to additional physical, chemical or thermal hazards that may occur while fighting a fire containing the product that may result in a health hazard.

Example text for all CCP formulations (1‐8) Hazardous Combustion Products: None known.

5.3 Advice for firefighters

Recommended/required text Provide instructions for firefighters to allow them to protect themselves while controlling and containing a fire.

Example text for all CCP formulations (1‐8) Special protective equipment and precautions for firefighters: As with any fire, wear self‐contained breathing apparatus (NIOSH approved, or equivalent) and full protective gear.

Section 6: Accidental Release Measures Purpose: Section 6 contains information for responding to spills, leaks or releases to prevent or minimize adverse effects on persons, property and the environment. Methods for handling spills or leaks, in the absence of fire, should be included.

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Arrange this section with following subheadings: 6.1 Personal precautions, protective equipment and emergency procedures 6.2 Environmental precautions 6.3 Methods and material for containment and clean up 6.4 Reference to other sections

6.1 Personal precautions, protective equipment and emergency procedures

Recommended/required text Provide information on appropriate protective clothing and personal protective equipment (PPE) as well as precautions relating to spills and releases of the material. Emergency procedures including information such as warnings to stay upwind, securing the area and evacuation procedures should be included where applicable.

Example text for all CCP compositions (1‐8) See Section 8.3 Individual Protective Measures. For concentrations exceeding Occupational Exposure Levels (OELs), use a self‐contained breathing apparatus (SCBA). Use scooping, water spraying/flushing/misting or ventilated vacuum cleaning systems to clean up spills. Do not use pressurized air.

6.2 Environmental precautions


Provide information on methods and materials used for containment of spills or leaks. Include techniques and equipment to contain (e.g., diking or capping) or prevent further spread of spilled material or leaking containers. Where appropriate, distinguish between responses for large and small spills.

Example text for all CCP compositions (1‐8) Prevent contamination of drains or waterways and dispose according to local and national regulations.

6.3 Methods and material for containment and cleaning up

Recommended/required text Provide information on appropriate techniques (e.g., absorption, scooping, vacuuming) and equipment to clean‐up spilled or leaked material and decontaminate the site. Where appropriate, distinguish between responses for large and small quantities of material. Also provide information on personal protection equipment including respiratory protection and protective clothing necessary to avoid injury or death.

Example text for all CCP compositions (1‐8) Do not use brooms or compressed air to clean surfaces. Use dust collection vacuum and extraction systems. Large spills of dry product should be removed by a vacuum system. Dampened material should be removed by mechanical means and recycled or disposed of according to local and national regulations.

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See Sections 8 and 13 for additional information on exposure controls and disposal. Section 7: Handling and Storage Purpose: Section 7 provides guidance on safe handling and conditions for safe storage. Arrange this section with following subheadings: 7.1 Precautions for safe handling 7.2 Conditions for safe storage, including any incompatibilities 7.1 Precautions for safe handling

Recommended/required text Include general warnings on what practices to avoid or perform. List handling practices that minimize: contact between the worker and the material, fire risks from flammable and combustible materials (including combustible dust and static accumulating liquids), and dangerous reactions with incompatible materials.

Example text for all CCP compositions (1‐8) Practice good housekeeping. Use adequate exhaust ventilation, dust collection and/or water mist to maintain airborne dust concentrations below permissible exposure limits (note: respirable crystalline silica dust may be in the air without a visible dust cloud). Do not permit dust to collect on walls, floors, sills, ledges, machinery, or equipment. Maintain and test ventilation and dust collection equipment. In cases of insufficient ventilation, wear a NIOSH approved respirator for silica dust when handling or disposing dust from this product. Avoid contact with skin and eyes. Wash or vacuum clothing that has become dusty. Avoid eating, smoking, or drinking while handling the material.

7.2 Conditions for safe storage, including any incompatibilities

Recommended/required text Provide information on conditions necessary to maintain the integrity of the product as it applies to the safe storage and the quality/functionality of the product.

Example text for all CCP compositions (1‐8) Minimize dust produced during loading and unloading.

Section 8: Exposure Controls/Personal Protection Purpose: Section 8 provides information on the applicable exposure limits, engineering controls, and personal protective measures that can be used to minimize worker exposure.

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Arrange this section with following subheadings: 8.1 Control parameters 8.2 Exposure controls 8.1 Exposure controls

Recommended/required text Provide available Occupational Exposure Limits (OELs) for the product and/or its components in the jurisdictions where the product is manufactured and or marketed. OELs for hazardous components, above applicable thresholds, disclosed in Sections 2/3 should be listed. If the product is a particulate, include the OEL for Particulates Not Otherwise Regulated. The applicable OELs to be considered for marketing a product in the US are: OSHA Permissible Exposure Limits (PELs), National Institute for Occupational Safety and Health (NIOSH) Recommended Exposure Limits (RELs), the American Conference of Governmental Industrial Hygienist (ACGIH) Threshold Limit Values (TLVs). Also if the product is manufactured or marketed in California, CA‐OSHA PELs should also be included. Table B: Available Occupational Exposure Limits for Identified CCP Components

OCCUPATIONAL EXPOSURE LIMITS

SUBSTANCE OSHA PEL

TWA (mg/m3) NIOSH REL

TWA (mg/m3) ACGIH TLV

TWA (mg/m3) CA ‐ OSHA PEL (mg/m3)

Calcium oxide 5 2 2 2

Particulates Not Otherwise Regulated

Total 15 15 ‐ 10

Respirable 5 5 ‐ 5

Crystalline Silica

Total Quartz 30 ÷ (%SiO2+2) (Total Quartz)

‐ ‐ 0.3

Respirable Crystalline Silica

10 ÷ (%SiO2+2) 0.05 0.025 (α‐quartz

& cristobalite) 0.1

Cristobalite ‐ 0.05

0.025

(α‐quartz &

cristobalite)

0.05 (respirable)

Manganese dioxide (as manganese compounds)

Total 5 (ceiling) 1

STEL ‐ 3 0.1 0.2

Respirable ‐ ‐ 0.02 ‐

Example Text

Insert information from Table B above for all hazardous components disclosed in the SDS in Sections 2 or 3.

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8.2 Exposure controls


Present the information on the different exposure controls in the appropriate subsection (i.e., Engineering controls and Personal Protective Equipment (PPE)). See Section 8.2.1 and 8.2.2 for applicable text.

8.2.1 Engineering controls

Recommended/required text Provide information on applicable engineering controls (e.g., use local exhaust ventilation, or use only in an enclosed system).

Example Text for all CCP compositions (1‐8) Provide ventilation to maintain the ambient workplace atmosphere below the occupational exposure limit(s). Use general and local exhaust ventilation and dust collection systems as necessary to minimize exposure.

8.2.2 Personal Protective Equipment

Recommended/required text Provide PPE recommendations based on route of exposure. Include any special requirements (e.g., type of glove material).

Example Text for all CCP compositions (1‐8) Respiratory Protection: Wear a NIOSH approved particulate respirator if exposure to airborne particulates is unavoidable and where occupational exposure limits may be exceeded. If airborne exposures are anticipated to exceed applicable PELs or TLVs, a self‐contained breathing apparatus or airline respirator is recommended. Eye and Face Protection: If eye contact is possible, wear protective glasses with side shields. Avoid contact lenses. Hand and Skin Protection: Wear gloves and protective clothing. Wash hands with soap and water after contact with material.

Section 9: Physical and Chemical Properties Purpose: Section 9 provides information on the physical and chemical properties of the material for characterization. Arrange this section with following subheadings: 9.1 Information on basic physical and chemical properties 9.2 Other information

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9.1 Information on basic physical and chemical properties


List the following minimum required physical/chemical properties to be evaluated and provided. If information is not available, the property should still be listed on the SDS with a notation indicating that the information is not determined or not applicable.

Appearance (physical state, color, etc.)

Odor;

Odor threshold;

pH;

Melting point/freezing point;

Initial boiling point and boiling range;

Flash point;

Evaporation rate;

Flammability;

Upper/lower flammability or explosive limits;

Vapor pressure;

Vapor density;

Relative density;

Solubility(ies);

Partition coefficient: n‐octanol/water;

Auto‐ignition temperature;

Decomposition temperature; and

Viscosity

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Example text for all CCP formulations (1‐8) The table below is based on a consensus of the SDSs submitted for the development of this Guidance Document as well as publically identified information on the CCPs. Data that was identified as applicable for the CCPs were included. Where the data was deemed highly variable, input from the ACAA companies on the specific product is required for fields noted as “to be populated” in the following table. Upon completion, insert the following table directly into Section 9.1. Table C: Physical Properties

Property: Value Property: Value

Appearance: Fine Gray Particulate Upper Explosive Limit (UEL): Not applicable

Odor: Odorless 1 Lower Explosive Limit (LEL): Not applicable

Odor Threshold: Not applicable Vapor Pressure (Pa): Not applicable

pH (25 °C) (in water) :to be populated Vapor Density: Not applicable

Melting/freezing Point (°C): Not applicable Relative Density/Specific Gravity: to be populated

Initial Boiling Point (°C): Not applicable Water Solubility: Slight

Boiling Range (°C): Not applicable Partition Coefficient: n‐octanol/water: Not determined

Flash Point (°C): Not determined Autoignition Temperature (°C): Not applicable

Evaporation Rate: Not applicable Decomposition Temperature (°C): Not available

Flammability: Not combustible Viscosity: Not applicable 1 The use of urea or aqueous ammonia injected into the flue gas to reduce NOx emissions may result in the presence of ammonium sulfate or ammonium bisulfate in the ash at less than 0.1%. When ash containing these substances becomes wet under high pH (>9), free ammonia gas may be released resulting in objectionable/nuisance ammonia odor and potential exposure to ammonia gas especially in confined spaces.

9.2 Other information

Recommended/required text While not required, additional properties may be reported if they would assist in the determination of proper handling. Examples of properties that may be applicable to CCPs would be particle size and particle size distribution.

Section 10: Stability and Reactivity Purpose: Provide the physical hazards associated with the product in the specified subsections. The stability of the product and related conditions and consequences associated with hazardous chemical reactions.

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Arrange this section with following subheadings: 10.1 Reactivity 10.2 Chemical stability 10.3 Possibility of hazardous reactions 10.4 Conditions to avoid 10.5 Incompatible materials 10.6. Hazardous decomposition products 10.1 Reactivity

Recommended/required text Describe any reactivity hazard, provide specific data where available.


The material is an inert, inorganic material primarily composed of elemental oxides. 10.2 Chemical stability

Recommended/required text Indicate the chemical stability of the product under normal ambient temperature and conditions.


The material is stable under normal use conditions. 10.3 Possibility of hazardous reactions

Recommended/required text Indicate possible hazardous reactions, including a statement whether the product will react or polymerize. Polymerization has been shown to release excess pressure or heat, or create other hazardous conditions. Describe conditions under which hazardous reactions may occur.


The material is a relatively stable, inert material; however, when ash containing ammonia becomes wet under high pH (>9), free ammonia gas may be released resulting in an objectionable/nuisance ammonia odor and potential exposure to ammonia gas especially in confined spaces. Polymerization will not occur.

10.4 Conditions to avoid


List conditions to avoid (e.g., heat, wind, shock) that can result in a hazardous situation (e.g., explosion, release of toxic or flammable materials).


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Product can become airborne in moderate winds. Dry material should be stored in silos. Materials stored out of doors should be covered or maintained in a damp condition.

10.5 Incompatible materials

Recommended/required text Indicate the possibility of hazardous reactions. List the classes of incompatible materials (e.g., oxidizers, acids) that could react with the product to produce a hazardous situation.

Example text for all CCP formulations (1‐8) None Known. Or Due to the presence of ammonium sulfate or ammonium bisulfate in the ash at less than 0.1%, when the ash becomes wet under high pH (>9), free ammonia gas may be released resulting in an objectionable / nuisance ammonia odor and potential exposure to ammonia gas especially in confined spaces.

10.6 Hazardous decomposition products

Recommended/required text List anticipated hazardous decomposition products that may be produced during use, storage, or heating. Note: Hazardous combustion products should also be included in Section 5: Fire‐Fighting Measures

Example text for all CCP formulations (1‐8) None known.

Section 11: Toxicological Information Purpose: Section 11 identifies toxicological and health effects information on the substance, mixture, and/or its components, or indicates that such data are not available. Where no data is available on the product, information on components may be provided. Arrange Section 11 data according to the defined GHS Human Health Endpoints. 11.1 Information on toxicological effects

Recommended/required text For each individual endpoint, provide scientific data that supports a classification of the product; where data is available on the finished product that data should be summarized and provided. If data is available on a similar product or components of the product, that information MAY also be provided. Declare whether the product or any of its components are listed in the National Toxicology Program (NTP) Report on Carcinogens (latest edition) or has been found to be a carcinogen in the International Agency for Research on Cancer (IARC) Monographs (latest edition), or as a carcinogen by OSHA.

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Example Text

Data to be provided for CCP 1 (STOT‐SE Category 3; STOT‐RE Category 2) are presented here. Appendix E provides the toxicological data associated with each identified CCP. Transpose the information from the appropriate table (based on the composition) into the SDS.

Endpoint Data

Acute oral toxicity LD50 > 2000 mg/kg

Acute dermal toxicity LD50 > 2000 mg/kg

Acute inhalation toxicity LC50 > 5.0 mg/L

Skin corrosion/irritation Not irritating to skin.

Eye damage/irritation Slight but reversible eye irritation.

Respiratory/skin sensitization Not a respiratory or dermal sensitizer.

Germ cell mutagenicity Not mutagenic in in vitro and in vivo assays with or without metabolic activation.

Carcinogenicity Not available. Respirable crystalline silica has been classified as a carcinogen.

Reproductive toxicity An animal study with a CCP has indicated some effects on male and female reproductive organs and parameters without a clear dose response while studies with other CCPs have not shown reproductive effects. Therefore, there is not enough evidence available to classify according to reproductive toxicity. No developmental toxicity has been observed in available animal studies.

Specific Target Organ Toxicity–Single Exposure

No specific target organ toxicity after a single exposure to the substance is expected; however, presence as a nuisance dust may result in respiratory irritation.

Section 12 Ecological Information The identification and inclusion of data into this section is non‐mandatory per 29 CFR 1910.1200 and any information provided in this section is not evaluated by OSHA. Purpose: Section 12, if populated, it should contain ecotoxicological and environmental fate information to assist in the evaluation of the environmental impact of the product if released to the environment. Data on the environmental hazards or environmental interactions of the product or its components may be provided, but it is not required. If provided, arrange available data into the following subsections: 12.1 Toxicity 12.2 Persistence and degradability 12.3 Bioaccumulative potential 12.4 Mobility in soil 12.5 Results of PBT and vPvB assessment 12.6 Other adverse effects

Recommended/required text Indicate: No data available or if desired, provide available information as noted in each subsection.

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12.1 Toxicity

Recommended/required text If desired, provide available ecotoxicity data on fish invertebrates and or algae/plants for the ash or its components.

Example Text for all CCP formulations (1‐8)

Indicate: No data available or if desired, insert data into similar tables as those detailed below.

Fly Ash CAS# 68131‐74‐8

Toxicity to fish LC50 >100 mg/L

Toxicity to invertebrates Data indicates that the test substance is not toxic to Daphnia magna (EC50 undetermined)

Toxicity to algae and plants EC50 = 10 mg/L

Calcium oxide CAS# 1305‐78‐8

Toxicity to fish LC50 = 50.6 mg/LThe findings were closely related to the pH of the test solutions; therefore pH is considered to be the main reason for the effects.

Toxicity to invertebrates

EC50 = 49.1 mg/L

The findings were closely related to the pH of the test solutions; therefore pH is considered to be the main reason for the effects.

Toxicity to algae and plants

NOEC =48 mg/L @ 72 hours based on Ca(OH)2

The initial pH of the test medium was not directly related to the biologically relevant effects. The formation of precipitates is likely the result of the reaction between CO2 dissolved in the medium.

12.2 Persistence and degradability

Recommended/required text This property is not applicable to CCPs. Indicate: Not relevant for inorganic materials.


Not relevant for inorganic materials. 12.3 Bioaccumulative potential

Recommended/required text Indicate: No data is available or if desired, provide information related to the bioaccumulation potential of the material, making reference to the octanol‐water partition coefficient (Kow) and the bioconcentration factor (BCF).

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Example Text for all CCP formulations (1‐8) No data available.

12.4 Mobility in soil

Recommended/required text Indicate: No data is available or if desired, provide information regarding the potential for the product to move from the soil to the groundwater, based on data from adsorption studies or leaching studies.


No data available. 12.5 Results of PBT and vPvB assessment

Recommended/required text Indicate: No data is available or if desired, provide information available.


No data available. 12.6 Other adverse effects

Recommended/required text Indicate: None known or if desired, provide information available.


None known. Section 13: Disposal Considerations The identification and inclusion of data into this section is non‐mandatory per 29 CFR 1910.1200 and any information provided in this section is not evaluated by OSHA. Purpose: Section 13 is not mandatory, however guidance on proper disposal practices, and recycling or reclamation may be provided.


Provide information on proper disposal, recycling or reclamation may be provided. As applicable, refer to Section 8 (Exposure Controls/Personal Protection) of the SDS for methods to minimize exposures.

Example text for all CCP compositions (1‐8)

Dispose of in accordance with local and national regulations. Local regulations may be more stringent than regional or national requirements.

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Section 14: Transport Information The identification and inclusion of data into this section is non‐mandatory per 29 CFR 1910.1200 and any information provided in this section is not evaluated by OSHA. Purpose: Section 14 is not mandatory for OSHA; however, it is recommended to include information related to US transportation (e.g., US Department of Transportation; DOT).

Recommended/required text Provide information associated with US DOT shipping regulations, such as: Shipping Name, Hazard Class, ID Number and Packing Group.


Regulatory entity: US DOT

Shipping Name Not Regulated

Hazard Class Not Regulated

ID Number Not Regulated

Packing Group Not Regulated

Note: This data should be reviewed and confirmed by each manufacturer/distributor as it is ultimately the responsibility of the individual shipping the product to verify the proper shipping classification.

Section 15: Regulatory Information The identification and inclusion of data into this section is non‐mandatory per 29 CFR 1910.1200 and any information provided in this section is not evaluated by OSHA. Purpose: Although Section 15 is not mandatory, it is recommended that the following information be provided. 15.1 Safety, health and environmental regulations/legislation specific for the substance Provide information regarding relevant regulatory status information related to the substance, including advice regarding action that should be taken by the recipient as a result of these provisions. The regulations include but are not inclusive of:


Provide information associated with the compositional analysis of the final product and their presence on any of the following lists. o TSCA Inventory Status

Note: All components in the various sources reviewed for this document were present on the TSCA Inventory. Should a specific CCP include other substances, regardless of classification under the new HCS 2012, those substances will need to be reviewed to confirm their inclusion on the TSCA Inventory. The public inventory can be found at http://www.epa.gov/oppt/existingchemicals/pubs/tscainventory/ (TSCA, 2015).

For all CCPs compositions (1‐8), provide the following statement:

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The CCP and all components are listed on the TSCA Inventory.

o California Proposition 65

For all CCPs compositions (1‐8), list the following text and substances as specified by the California Office of Environmental Health Hazard Assessment (CA OEHHA, 2015): Disclose the following if present in the CCP (at any level). The following substances are known to the State of California to be carcinogens and/or reproductive toxicants:

Respirable crystalline silica (RCS) Titanium dioxide (airborne particles)

o State Right‐to‐Know (RTK) status

For all CCP compositions (1‐8), the CCP components present on the State RTK lists in Massachusetts (MA), New Jersey (NJ), Pennsylvania (PA), and Rhode Island (RI) are provided in Table D. Disclose identified CCP components present at ≥ 1% if the CCP is manufactured or distributed in that State. Non‐applicable substances and jurisdictions should be omitted from the list. Note: References for each State Right to Know list are included as footnotes to the Table. Table D: CCP components present on the State Right to Know Lists

Component CAS MA1,2 NJ3,4 PA5 RI6

Ammonium bisulfate 7803‐63‐6 No Yes No No

Ammonium sulfate 7783‐20‐2 Yes No Yes No

Barium oxide‐as Barium compounds 1304‐28‐5; Various No Yes Yes Yes

Calcium carbonate 1317‐65‐3 Yes Yes Yes No

Calcium oxide 1305‐78‐8 Yes Yes Yes No

Calcium sulfate 7778‐18‐9 Yes Yes Yes No

Iron oxide 1309‐37‐1 Yes Yes Yes No

Magnesium oxide 1309‐48‐4 No Yes No No

Manganese oxide‐as manganese compounds

1313‐13‐9; Various No No Yes Yes

Phosphorus pentoxide (or phosphorus oxide)

1314‐56‐3 Yes Yes Yes No

Potassium oxide 12136‐45‐7 No Yes No No

Silica‐crystalline (SiO2), quartz 14808‐60‐7 Yes Yes Yes No

Sodium oxide 1313‐59‐3 No Yes No No

Sodium sulfate 7757‐82‐6 Yes No Yes No

Titanium dioxide 13463‐67‐7 Yes Yes Yes No 1Massachusetts Department of Public Health, no date 2 189th General Court of The Commonwealth of Massachusetts, no date

3 New Jersey Department of Health and Senior Services, 2010a 4 New Jersey Department of Health, 2010b 5 Pennsylvania Code, 1986 6 Rhode Island Department of Labor and Training, no date

Note: Other information related to the presence of component substance on other environmental listings such as SARA 311/312, SARA 313 TRI, CWA or CAA may also be included.

49

Section 16: Other Information Purpose: Section 16 provides information relevant to the compilation of the safety data sheet. Incorporate other information required to communicate product hazards that may not be present in Sections 1 to 15. Information to support the understanding of Sections 1‐15 should be provided. Arrange data into the following subsections: 16.1 Revision Information 16.2 Acronyms and Abbreviations 16.3 HMIS Information At the end of the SDS provide an appropriate legal disclaimer associated with use of the SDS and information it contains. 16.1 Revision Information

Recommended/required text Include the SDS Revision status (date of SDS development/revision and a revision number, if appropriate.

Example text for all CCP compositions (1‐8) where an SDS was not previously released. Initial SDS prepared on (insert date)

Example text for all CCP compositions (1‐8) where an SDS was previously released. SDS Revision date (insert date), Revision X (insert Revision number)

16.2 Acronyms and Revisions

Recommended/required text Include a key to abbreviations and acronyms used throughout the SDS. Acronyms used in the development of this template are included below; if additional acronyms are used they should be added as well.


50

Abbreviations that may be appropriate to include on the SDS include the following. Prior to finalization of the SDS review the following list against the SDS to include appropriate acronyms/abbreviations:

ACA: American Coatings Association

ACGIH: American Conference of Industrial Hygienists

ANSI: American National Standards Institute

CA California

CAA: Clean Air Act

CAS: Chemical Abstract Services

CCP: Coal Combustion Product

CFR: Code of Federal Regulations

CWA: Clean Water Act

EC50: Effective Concentration that elicits an identified effect.

GHS: Globally Harmonized System of Classification and Labelling

HCS 2012 Hazard Communication Standard, 2012

HMIS: Hazardous Materials Identification System

IARC: International Agency for Research on Cancer

LC50: Concentration resulting in the mortality of 50 % of an animal population

LD50: Dose resulting in the mortality of 50 % of an animal population

LEL: Lower explosive limit

MA: Massachusetts

NA: Not Applicable

NJ: New Jersey

NOEC: No observed effect concentration

NIOSH: National Institute of Occupational Safety and Health

NTP: US National Toxicology Program

OEL: Occupational Exposure Limit

OSHA: Occupational Safety and Health Administration

Pa: Pascal

PA: Pennsylvania

PBT: Persistent, Toxic and Bioaccumulative

PEL: Permissible exposure limit

PPE: Personal Protective Equipment

REL: Recommended exposure limit

RI: Rhode Island

SARA: Superfund Amendments and Reauthorization Act

SWCBA: Self‐contained breathing apparatus

SDS: Safety data sheet

STEL: Short‐term exposure limit

STOT‐RE: Specific target organ toxicity‐repeated exposure

STOT‐SE: Specific target organ toxicity‐single exposure

TLV: Threshold limit value

TSCA: Toxic Substances Control Act

TWA: Time‐weighted average

UEL: Upper explosive limit

UVCB: Unknown or Variable Composition/Biological

US: United States

US DOT: United States of Department of Transportation

VOC: Volatile organic compound

vPvB: very persistent and very bioaccumulative

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16.3 Other Hazards

Recommended/required text Provide a table detailing the HMIS rating for the product. Include a rating for the hazards associated with the final Health, Flammability, Reactivity associated with product usage, as prescribed by the ACA. The ACA recommends that the incorporation of PPE information not be included on the SDS. Further information on assigning specific rating is available from the American Coatings Association (ACA, 2014) The HMIS rating will vary based on the GHS Hazard assigned to the CCP.

Example text

Apply the HMIS ratings table that is applicable to the CCP Classification For CCP 1 and CCP 2 Hazardous Materials Identification System (HMIS) Degree of hazard (0= low, 4 = extreme) Health: 1* Flammability: 1 Reactivity: 1 Personal protection:

* Chronic Health Effects For CCP 3 and CCP 4 Hazardous Materials Identification System (HMIS) Degree of hazard (0= low, 4 = extreme) Health: 1 Flammability: 1 Reactivity: 1 Personal protection:

For CCP 5 and CCP 6 Hazardous Materials Identification System (HMIS) Degree of hazard (0= low, 4 = extreme) Health: 3* Flammability: 1 Reactivity: 1 Personal protection:

* Chronic Health Effects For CCP 7 and CCP 8 Hazardous Materials Identification System (HMIS) Degree of hazard (0= low, 4 = extreme) Health: 3 Flammability: 1 Reactivity: 1 Personal protection:


Include an appropriate legal disclaimer associated with use of the SDS and information it contains. The example Disclaimer noted below may be use; however, legal counsel review is recommended.

Example text Include the Legal Disclaimer below or one developed by your legal department.

Recommended Disclaimer: This SDS has been prepared in accordance with the Hazard Communication Standard 29 CFR 1910.1200. Information herein is based on data considered to be accurate as of date prepared. No warranty or representation, express or implied, is made as to the accuracy or completeness of this data and safety information. No responsibility can be assumed for any damage or injury resulting from abnormal use, failure to adhere to recommended practices, or from any hazards inherent in the nature of the product.

52

References 1. Affolter, R.H., Groves, Steve, Betterton, W.J., Benzel, William, Conrad, K.L., Swanson, S.M.,

Ruppert L.F., Clough J.G., Belkin, H.E., Kolker, Allan, and Hower, J.C. 2011. Geochemical database of feed coal and coal combustion products (CCPs) from five power plants in the United States: U.S. Geological Survey Data Series 635, pamphlet.

2. American Coatings Association. 2014. HMIS Sample Training Presentation. December 2014.

3. American National Standard Institute (ANSI). 2010. ANSI for Workplace Chemicals‐Hazard

Evaluation and Safety Data Sheet and Precautionary Labeling Preparation. American Chemistry Council. Z400.1/Z129.1‐2010. May 28.

4. ASTM International. 2011. Standard D311/311M‐13: Standard Test Methods for Sampling and Testing Fly Ash or Natural Pozzolans for Use in Portland‐Cement Concrete. December 1, 2011.

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Calcined Natural Pozzolan for Use in Concrete. February 12, 2012.

6. ASTM International. 2013. Standard D4326‐13: Standard Test Method for Major and Minor Elements in Coal and Coke Ash by X‐ray fluorescence. January 9, 2013.

7. ASTM International. 2015. Standard D114‐15: Standard Test Methods for Chemical Analysis of Hydraulic Cement. April 15, 2015.

8. Caddas‐Vieira F, Feuerborn H, Saraber A. 2013. European Product Standards (EN) – Update on

status and changes with relevance to CCPs. http://www.flyash.info/2013/135‐Feuerborn‐2013.pdf. Accessed April 5, 2015.

9. California Environmental Protection Agency (CA EPA). 2001. Summary of Toxicology Data: Sodium bromide. http://www.cdpr.ca.gov/docs/risk/toxsums/pdfs/1103.pdf. Accessed April 24, 2015.

10. California Office of Environmental Health Hazard Assessment (CA OEHHA). 2015. Chemicals known to the State to cause cancer or reproductive toxicity. http://oehha.ca.gov/prop65/prop65_list/files/P65single03272015.pdf. Accessed April 25, 2015.

11. Electric Power Research Institute (EPRI). 2006a. Potential Health Effects of Crystalline Silica Exposures from Coal Fly Ash: A Literature Review. Report No. 1012821. March.

12. EPRI. 2006b. Development of a Method to Identify Respirable Crystalline Silica (Quartz) in Coal Fly Ash: An Application of Computer Controlled Scanning Electron Microscopy. Report No. 1012571. November.

13. EPRI. 2008. Computer‐Controlled Scanning Electron Microscopy (CCSEM) Investigation of Respirable Quartz in Air Samples Collected During Power Plant Maintenance Activities. Report No. 1015632. December.

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14. EPRI. 2010. Comparison of Coal Combustion Products to Other Common Materials. Report No. 1020556. September.

15. European Chemicals Agency (ECHA). 2010a. REACH Registration Dossier for Ashes (residues), coal. http://apps.echa.europa.eu/registered/data/dossiers/DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031/DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031_DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031.html. Accessed April 17, 2015.

16. European Chemicals Agency (ECHA). 2010b. REACH Registration Dossier for FBC Ash (residues of coal combustion in fluidized bed boilers. http://apps.echa.europa.eu/registered/data/dossiers/DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031/DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031_DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031.html. Accessed April 25, 2015.

17. Gradient 2015a Tuit, C and A. Lewis. Between a Rock and a Hard Place: Classifying CS. Gradient Trends Risk Science & Application. Issue 62. Winter.

18. Gradient 2015b. Long, C. OSHA’s Proposed Silica Rule. Gradient Trends Risk Science & Application. Issue 62. Winter.

19. Hazardous Substances Database (HSDB). Sodium Bromide, CAS #7647‐15‐6. http://toxnet.nlm.nih.gov/cgi‐bin/sis/search2/f?./temp/~fhKzXW:1. Accessed April 25, 2015.

20. Interactive Learning Paradigms Incorporated (ILPI). 2015. The SDS HyperGlossary: HMIS. http://www.ilpi.com/msds/ref/hmis.html. Accessed April 26, 2015.

21. International Agency for Research on Cancer (IARC). 1997. Monograph of the Evaluation of the Carcinogenic Risk of Chemicals to Humans: Silica, Some Silicates, Coal Dust and Para‐aramid Fibrils. Volume 68. IARC Press, Geneva.

22. Industrial Minerals Association (IMA) Europe. 2014a. Position Paper: Classification and labeling of crystalline silica (fine fraction). http://www.crystallinesilica.eu/sites/crystallinesilica.eu/files/documents/Position%20Paper%20Classification%20of%20RCS%20%28January%202014%29.pdf. Accessed March 30, 2015.

23. IMA Europe. 2014b. Position Paper: Classification and labeling of crystalline silica (fine fraction). http://www.crystallinesilica.eu/sites/crystallinesilica.eu/files/documents/Position%20Paper%20Classification%20of%20RCS%20%28January%202014%29.pdf. Accessed March 30, 2015.

24. Massachusetts Department of Public Health. No date. 105 CMR 6700.000: Right to Know. http://www.mass.gov/courts/docs/lawlib/104‐105cmr/105cmr670.pdf. Accessed April 25, 2015.

25. 189th General Court of The Commonwealth of Massachusetts. No date. Hazardous Substances

Disclosure by employers. https://malegislature.gov/Laws/GeneralLaws/PartI/TitleXVI/Chapter111F. Accessed April 25, 2015.

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26. Mine Safety and Health Administration (MSHA) and Industrial Minerals Association‐North America. 2008. A Practical Guide to an Occupational Health Program for Respirable Crystalline Silica. MSHA Alliance Program. Instruction Guide Series IG 103. 2008. Available at: http://www.msha.gov/alliances/formed/IG103.pdf.

27. Morfeld, P. 2010. Respirable Crystalline Silica: Rationale For Classification According to the CLP Regulation and within the Framework of the Globally Harmonised System (GHS) of Classification and Labelling of Chemicals. Institute for Occupational Epidemiology and Risk Assessment of Evonik Industries. Germany. http://www.crystallinesilica.eu/sites/crystallinesilica.eu/files/documents/Summary%20Morfeld%20Classification%20CLP_GHS_RCS.pdf. Accessed March 30, 2015.

28. National Institute for Occupational Safety and Health (NIOSH). 2001. Health Hazard Evaluation Report 2000‐0309‐2857‐Lehigh Portland Cement Company. Ronald M. Hall and Kristin K. Gwin. Hazard Evaluations and Technical Assistance Branch (HETAB), Division of Surveillance, Hazard Evaluations, and Field Studies (DSHEFS). August.

29. NIOSH. 2002. NIOSH Hazard Review: Health Effects of Occupational Exposure to Respirable

Crystalline Silica. Department of Health and Human Services. Centers for Disease Control and Prevention. DHHS (NIOSH) Publication No. 2002‐129. April.

30. National Toxicology Program (NTP). Department of Health and Human Services. Report on Carcinogens. Silica, Crystalline (Respirable Size). Thirteenth Edition. Available at: http://ntp.niehs.nih.gov/ntp/roc/content/profiles/silica.pdf.

31. New Jersey Department of Health and Senior Services. 2010a. Worker and Community Right to

Know Act. http://nj.gov/health/eoh/rtkweb/documents/rtkregs.pdf. Access April 25, 2015. 32. New Jersey Department of Health. 2010b. Right to Know Hazardous Substance List.

http://web.doh.state.nj.us/rtkhsfs/rtkhsl.aspx. and http://web.doh.state.nj.us/rtkhsfs/rtkhsl.aspx. Accessed April 25, 2015.

33. Pennsylvania Code. 1986. Chapter 323: Hazardous Substances List.

http://www.pacode.com/secure/data/034/chapter323/chap323toc.html. Accessed April 25, 2015.

34. Rhode Island Department of Labor and Training (DLT). No date. DLT Right to Know Hazardous Substances List. https://www.ri.gov/DLT/righttoknow/. Accessed April 25, 2015.

35. Swanson V, Huffman C Jr. 1976. Guidelines for Sample Collecting and Analytical Methods used in the U.S. Geological Survey for determining the Chemical Composition of Coal. Geological Survey Circular 735. http://energy.er.usgs.gov/products/databases/CoalQual/Docs/c735.pdf. Accessed May 13, 2015.

55


36. Thermo‐Fisher Scientific. 2012. Application Note: 41661 ‐ Analysis of Coal Fly Ash: Thermo Scientific ARL PERFORM’X Series Advanced X‐Ray Fluorescence Spectrometers. http://www.thermoscientific.com/content/dam/tfs/ATG/CAD/CAD%20Documents/Application%20&%20Technical%20Notes/Elemental%20Analysis/XRF/XR‐AN41661‐ARL%20PERFORMX‐Coal%20fly%20ash‐0312.pdf. Accessed May 13, 2015.

37. United Nations Economic Commission for Europe. 2009. Globally Harmonized System of Classification and Labelling of Chemicals (GHS), Revision 3. 2009. http://www.unece.org/trans/danger/publi/ghs/ghs_rev03/03files_e.html. Accessed April 15, 2015.

38. US Environmental Protection Agency (EPA). 2014. Coal Ash Reuse. http://www2.epa.gov/coalash/coal‐ash‐reuse. Accessed April 15, 2015.

39. US EPA. 2015. Toxic Substance Chemical Inventory. http://www.epa.gov/oppt/existingchemicals/pubs/tscainventory/. Accessed April 20, 2015.

40. US Occupational Safety and Health Administration. 1996. Report of the Hazard Communication Workshop to the National Advisory Committee on Occupational Safety and Health (NACOSH). https://www.osha.gov/dsg/hazcom/wgfinal.html. Accessed April 8, 2015.

41. US Occupational Safety and Health Administration. 2012a. Comparison of Hazard Communication Requirements: OSHA Hazard Communication Standard 29 CFR 1910.1200(HCS) and Globally Harmonized System (GHS). https://www.osha.gov/dsg/hazcom/ghoshacomparison.html. Accessed April 16, 2015.

42. US Occupational Safety and Health Administration. 2012b. Hazard Communication. 29 CFR 1910. Federal Register Vol.77, No. 58. March 26, 2012. https://www.osha.gov/FedReg_osha_pdf/FED20120326.pdf

43. US Occupational Safety and Health Administration. 2012c. Occupational Safety and Health Standards. Subpart Z: Toxic and Hazardous Substances. Standard Number 1910.1200. Hazard Communication. https://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=STANDARDS&p_id=10099. Accessed April 8, 2015.

44. US Occupational Safety and Health Administration. 2012d. Occupational Safety and Health Standards. Subpart Z: Toxic and Hazardous Substances. Standard Number 1910.1200. Appendix D, Safety Data Sheets (mandatory). https://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=STANDARDS&p_id=10103. Accessed April 8, 2015.

56


45. US Occupational Safety and Health Administration. 2012e. Occupational Safety and Health Standards. Subpart Z: Toxic and Hazardous Substances. Standard Number 1910.1200. Table Z‐1, Limits for Air Contaminants. https://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=STANDARDS&p_id=9992. Accessed April 8, 2015.

46. US Occupational Safety and Health Administration (OSHA). 2013. Occupational Exposure to Respirable Crystalline Silica‐Review of Health Effects Literature and Preliminary Quantitative Risk Assessment. Docket No. OSHA‐2010‐0034.

47. US Occupational Safety and Health Administration. Undated (a). OSHA Brief Hazard Communication Standard: Safety Data Sheets. https://www.osha.gov/Publications/OSHA3514.pdf. Accessed April 8, 2015.

48. US Occupational Safety and Health Administration. Undated (b). OSHA Brief Hazard Communication Standard: Labels and Pictograms. https://www.osha.gov/Publications/OSHA3636.pdf. Accessed April 15, 2015.

https://hank.haleyaldrich.com/sites/communities/ProductStewardship/Shared Documents/Client Folders/ACAA/42002/000/Working Folder/05152015 SDS Guidance Document‐F.docx

APPENDIX A

SDS Development Checklist

SDS Checklist Page 1 of 7 Preparation Date: 2015‐05‐15

Safety Data Sheet (SDS) Checklist This SDS Checklist was developed to provide ACAA member companies the information necessary to develop a Safety Data Sheet (SDS) for Coal Combustion Products. When used in concert with the SDS Guidance Document and the SDS Template for Coal Combustion Products (CCPs), the checklist can be used by ACAA Member Companies to develop the SDSs required based on Company and product specific information on their CCPs. Prior to developing an SDS using the SDS Guidance Document and associated Appendices, confirm that the CCP formulation meets the composition specifications detailed in Appendix C (Composition Summary Workbook). Should the CCP being evaluated have additional substances present, or have substances above the maximum percentage identified, the SDS Guidance Document should not be used until an assessment of the compositional differences is evaluated to confirm that the compositional differences do not result in additional GHS classifications of the CCP. This checklist specifies the information required/recommended for inclusion in the SDS per the OSHA HazCom 2012 Rule as specified in 29 CFR 1910.1200, the OSHA recognized ANSI Z400.1 Standard (Hazard Evaluation and Safety Data Sheet and Precautionary Labeling Preparation Standard), or recommendations based on expert judgement. An SDS Template that can be used to communicate the necessary information detailed on a Section by Section basis is available as Appendix B to the SDS Guidance Document. Additional information and further guidance on how to populate the SDS, including appropriate information to be provided can be found in the SDS Guidance Document.

General SDS Development Information

Although specifically required in Section 16, it is recommended that the date of SDS development/update and the SDS Version (i.e., New or Revision number) be included in the SDS Header

Paginate the SDS Include a Legal Disclaimer at the end of the SDS Section 16 (last section)

SECTION 1. IDENTIFICATION Provide the following information in the SDS. See the SDS Guidance Document for additional detail on the required information. Product identifier (name used on label), common names/synonyms Name, address, email and telephone number of the manufacturer, packager or supplier Emergency telephone number and any restrictions to the availability Recommended uses Any restricted uses


SECTION 2. HAZARDS IDENTIFICATION Provide the following information in the SDS for the CCP. See the SDS Guidance Document and Appendix D: SDS Section 2 Data, to select the data applicable to the CCP composition. Individual data tables in Appendix D provide the information listed below for each CCP Classification. Hazard classification Signal word Hazard statements Pictograms Precautionary statements Hazards not otherwise classified

SECTION 3. COMPOSITION / INFORMATION ON INGREDIENTS Provide the following information on the composition of the product. See the SDS Guidance Document to select appropriate substances and related information from the list of identified hazardous constituents. Disclose substances that:

o Are present above their threshold limits or; o Result in a classification of the final product regardless of their respective threshold

limits Provide the following information on those substances:

o Substance name o Chemical Abstracts Service (CAS) number o Percentage of the ingredient in the CCP. A range may be provided.

SECTION 4. FIRST AID MEASURES See the SDS Guidance Document for the appropriate information to populate the section. Describe the first aid measures organized by relevant route of exposure (inhalation, skin and eye

contact, ingestion) Provide information on the most important health effects and symptoms (both acute and

delayed) Indicate information related to the need for immediate medical attention and special treatment

needed, when necessary

SECTION 5. FIREFIGHTING MEASURES See the SDS Guidance Document for the appropriate information to populate the section. Provide information on suitable and unsuitable extinguishing media Identify special hazards arising from the substance or mixture, including hazardous combustion

products Provide any special advice for firefighters


SECTION 6. ACCIDENTAL RELEASE MEASURES

See the SDS Guidance Document for the appropriate information to populate the section.

Specify any personal precautions, protective equipment and emergency procedures Indicate any environmental precautions Provide information on the methods and materials necessary for containment and cleanup

procedures

SECTION 7. HANDLING AND STORAGE

See the SDS Guidance Document for the appropriate information to populate the section.

Provide precautions for safe handling (e.g., protective measures, measures to prevent fire, aerosol and dust generation, measures to protect the environment, and advice on general occupational hygiene)

Indicate proper storage conditions including any incompatibilities and specific storage requirements or ventilation requirements

SECTION 8. EXPOSURE CONTROLS / PERSONAL PROTECTION Provide information on the Occupation Exposure Limits (OELs) associated with substances disclosed in Section 2 of the SDS. See the SDS Guidance Document for the list of OEL’s identified based on identified CCP constituents, as determined in Appendix C. Provide appropriate occupational exposure limits for particulates not otherwise regulated

(PNOR) and substances disclosed in Section 3 based on manufacture/market jurisdiction. OELs to be provided, where available include OSHA permissible exposure limits (PEL), American Conference of Governmental Industrial Hygienists (ACGIH), Threshold Limit Values (TLV), California EPA PEL

Detail appropriate exposure controls, including engineering controls, personal protective equipment, and environmental exposure controls


SECTION 9. PHYSICAL AND CHEMICAL PROPERTIES Provide information on the following physical and chemical properties. If no information is available or if the data is not applicable, do not delete the parameter; rather, note that data is “Not available” or that the parameter is “Not applicable”. See the SDS Guidance Document for more information. Odor Odor threshold pH Melting point/freezing point Initial boiling point and boiling range Flash point Evaporation rate Flammability Upper/lower flammability or explosive limits Vapor pressure Vapor density Relative density Solubility(ies) Partition coefficient: n‐octanol/water Auto‐ignition temperature Decomposition temperature Viscosity

Additional information such as particle size, etc. may also be provided.

SECTION 10. STABILITY AND REACTIVITY See the SDS Guidance Document for the appropriate information to provide in the section. Reactivity Chemical stability Possibility of hazardous reactions Conditions to avoid Incompatible materials Hazardous decomposition products


SECTION 11. TOXICOLOGICAL INFORMATION Available information on the recognized GHS Human Health Classification Categories should be provided. Where data is not available or not known, that should be indicated. See the SDS Guidance Document and Appendix E: SDS Section 11 Data, for the appropriate toxicological information to populate the section based on the CCP composition and corresponding toxicity information on the Human Health Hazards. The following categories should be included:

Acute Toxicity [include information on the route of exposure (inhalation, ingestion, skin and eye contact)]

Skin Corrosion/Irritation Eye Damage/Irritation Skin or Respiratory Sensitization Germ Cell Mutagenicity Carcinogenicity Reproductive Toxicity STOT ‐ Single Exposure STOT – Repeated Exposure Aspiration Hazard

Note: Additional data on component substances may also be provided, but is not required; however, under carcinogenicity, it is required to declare any components (such as respirable crystalline silica) listed on the U.S. National Toxicology Program (NTP) Report on Carcinogens (latest edition) or has been found to be a carcinogen in the International Agency for Research on Cancer (IARC) Monographs (latest edition), or as a carcinogen by OSHA.

SECTION 12. ECOLOGICAL INFORMATION This section is non‐mandatory. Enter “No data available” or if desired, provide available data for component substances following the format indicated in the SDS Guidance Document. Ecotoxicity data (aquatic and terrestrial, where available) Persistence and degradability Bioaccumulative potential Mobility in soil Other adverse effects


SECTION 13. DISPOSAL CONSIDERATIONS This section is non‐mandatory; however, it is recommended that information on proper disposal, recycling or reclamation of the product be included. Refer to the SDS Guidance Document and information related to Section 8 (Exposure Controls/Personal Protection) for appropriate information. Reference Section 8 for safe handling precautions Describe appropriate disposal containers to use Recommend appropriate disposal methods Describe any physical and chemical properties that may affect disposal activities Include language discouraging sewage disposal

SECTION 14. TRANSPORT INFORMATION This section is non‐mandatory however, it is recommended to include information related to U.S. transportation (e.g., U.S. DOT) as detailed in the SDS Guidance Document. UN Number (4 figure identification number) Proper UN shipping name Transport hazard class(es) Packing group number, if applicable

SECTION 15. REGULATORY INFORMATION This section is not mandatory; however, it is recommended to include the following information related to the presence of the finished product and components above identified thresholds on relevant safety, health and environmental regulatory lists. Information on the recommended lists is present in the SDS Guidance. TSCA InventoryCalifornia Proposition 65 Listing Applicable State Right‐to‐Know Lists (Massachusetts, New Jersey, Pennsylvania and Rhode

Island). Appropriate lists include those where the product is manufactured, packaged or distributed

Note: Additional information related to the presence of component substances on other environmental listings such as SARA 311/312, SARA 313 TRI, CWA or CAA may also be included.


SECTION 16. OTHER INFORMATION Populate this section with the following information to assist the user in understanding the information provided in the SDS. See the SDS Guidance Document for information that may be required to populate this section. Date of preparation/last revision The abbreviations and acronyms used in the SDS Other hazards including information related to the HMIS Hazard Rating System Legal disclaimer

APPENDIX B

CCP SDS Template

CCP SDS Template Preparation Date: 2015‐05‐15

Coal Combustion Product (CCP) Safety Data Sheet (SDS) Template

This Appendix provides a generic template that can be used to develop an OSHA compliant SDS for Coal Combustion Products (CCPs). Unless specifically noted, the text included in the SDS template may be applied to all eight CCP classifications identified in the SDS Guidance Document. Comments have been included within the SDS to assist ACAA members in populating the SDS appropriately. In general, items highlighted in yellow will require additional input from the SDS developer to identify/include the appropriate information. The necessary information for populating the template may be related to the manufacturer/distributer or the CCP composition. The SDS Guidance Document, as well as Appendices C, D, and E to that document can be used as a source of required information if it is not available here. Delete highlights and comments upon generation of an SDS using the template. Adjust Page Breaks as necessary to keep section, subsection or tabular information together.

INSERT LOGO INSERT PRODUCT NAME

SDS Number: 0.0 Revision Date: N/A

Preparation Date: INSERT Page 1 of 12

Safety Data Sheet

Section 1

Identification of the Substance and of the Supplier

1.1 Product Identifier

Product Name/Identification: INSERT

Synonyms: LIST HERE, Delete row if not applicable

Product Code: INSERT or enter Not Applicable

Formula: UVCB Substance

1.2 Relevant Identified Uses of the Substance or Mixture and Uses Advices Against

Relevant Identified Uses: Component of wallboard, concrete, roofing material, bricks

Uses Advised Against: None known

1.3 Details of the Supplier of the SDS

Manufacturer/Supplier: INSERT

Street Address: INSERT

City, State and Zip Code: INSERT

Customer Service Telephone: INSERT

E-mail Address: OPTIONAL, Insert if desired, otherwise delete row

1.4 Emergency Telephone Number

Emergency Phone Number: INSERT

Hours Available: INSERT

Page 2 of 12

Preparation Date: INSERT



Section 2

Hazards Identification

2.1 Classification of the Substance

GHS Classification(s) according to OSHA Hazard Communication Standard (29 CFR 1910.1200):

Insert Classifications applicable to the CCP formulation. Include “note” if applicable.

2.2 Label Elements

Labelling according to 29 CFR 1910.1200 Appendices A, B and C*


Signal word:


Precautionary Statement(s):

* Fly ash and other coal combustion products (CCPs) are UVCB substances (substance of unknown or variable composition or biological. Various CCPs, noted as Ashes; Ash; Ash residues; Ashes, residues, bottom; Bottom ash; Bottom ash residues; Waste solids, ashes under TSCA are defined by the US EPA as: “The residuum from the burning of a combination of carbonaceous materials. The following elements may be present as oxides: aluminum, calcium, iron, magnesium, nickel, phosphorus, potassium, silicon, sulfur, titanium, and vanadium.” Ashes including fly ash and fluidized bed combustion ash are identified by CAS number 68131-74-8. The exact composition of the ash is dependent on the fuel source and flue additives composed of a large number of constituents. The classification of the final substance is dependent on the presence of specific identified oxides as well as other trace elements.

2.3 Other Hazards Listed Carcinogens: -Respirable Crystalline Silica

IARC: [Yes] NTP: [Yes] OSHA: [No] Other: [No]

Comment [A1]: 1. Insert the appropriate GHS Classification(s) applicable to the CCP based on its formulation. Present in Section 5.4 of the Guidance Document.

2. If the level of respirable crystalline silica has not been determined insert the following note directly below the classification(s).

Note: The level of respirable crystalline silica (RCS) present in this product has not been determined; however, a conservative classification for STOT‐RE, Category 2 has been assigned.

Comment [A2]: Insert the information from the appropriate Table in Appendix D that corresponds with the CCP GHS classification selected above. Note: The various CCP classifications determined in the course of this project assume that only the list of substances present in Table 7 in section 5.4 of the Guidance document are present at or below the levels noted. If additional substances are present in the CCP composition at levels of 0.1% or greater, the classification of the CCP may need to be re‐evaluated.

Page 3 of 12




Section 3

Composition/Information on Ingredients

Substance CAS No. Percentage (%) GHS Classification

Aluminosilicates Various: See note 1 Include % Single Exposure STOT, Category 3

Crystalline Silica 14808‐60‐7 See note 2 Repeat Dose STOT, Category 2

Silica, crystalline respirable

(RCS) 14808‐60‐7 ≥0.1% ; See note 3 Repeat Dose STOT, Category 2

Calcium oxide (CaO) 1305‐78‐8 If ≥1%; See note 4 Skin Irritant Category 2

Eye irritant Category 2B

Manganese dioxide (MnO2) 1313‐13‐9 If ≥1% Skin Irritant Category 2


Phosphorus pentoxide

(P2O5) 1314‐56‐3 If ≥1%

Skin Irritant Category 2


Potassium oxide (K2O) 12136‐45‐7 ≥1% Skin Irritant Category 2


Magnesium sulfate 7487‐88‐9 ≥1% Skin Irritant Category 2


1. Aluminosilicates may be in the form of mullite (CAS#1302‐93‐8); pozzolans, coal ash (CAS#71243‐67‐9); or aluminosilicates (CAS# 1327‐36‐2). The form is dependent on the source of the coal and or the process used to create the CCP. Pulverized coal combustion would be more likely to create high levels of pozzolans, coal ash (particularly bottom ash) due to the high heat of combustion while the circulating fluidized bed (CFB) process would be less likely to generate this glassy aluminosilicate.

2. Report the level of crystalline silica in the product if the level of Respirable Crystalline Silica has not been determined. 3. Report the level of RCS if known. If the RCS level has not been determined, footnote the crystalline silica value to indicate that the

respirable portion of the substance in the CCP has not been determined. 4. This percentage includes either total calcium oxide or free calcium oxide, if available. Please specify type of calcium oxide that the

percentage represents or report both if available.

Section 4

First Aid Measures

4.1 Description of First Aid Measures

Inhalation:

If product is inhaled and irritation of the nose or coughing occurs, remove person to fresh air. Get medical advice/attention if respiratory symptoms persist.

Skin Contact: If skin exposure occurs, wash with soap and water.

Eye Contact:

If product gets into the eye, rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Seek medical attention/advice if irritation occurs or persists.

Ingestion: No specific first aid measures are required.

Comment [A3]: Insert the concentrations of hazardous substances (based on GHS criteria) present in the CCP if present at or above identified percentage thresholds. Insert the appropriate Aluminosilicate CAS# based on the type of CCP. If a substance is present in the CCP composition below the listed threshold, that substance does not require disclosure and the row may be deleted. Disclosure of non‐hazardous substances present in the CCP composition may be disclosed at the SDS preparer’s discretion. NOTE: This disclosure list assumes that all components of the CCP were included in the evaluation of CCP compositions for this project as defined in Section 5.4 of the SDS Guidance Document. If additional substances are identified at levels of 0.1% or greater, additional disclosure may be required.

Comment [A4]: Insert the following footnote if the level of respiratory crystalline was not determined. Footnote: The percentage of respirable crystalline silia has not been determined.

Comment [A5]: Delete footnotes after composition information is populated

Page 4 of 12




4.2 Most Important Health Effects, Both Acute and Delayed For CCP compositions 1 through 4

Acute effects: Direct exposure may cause respiratory irritation, eye irritation and skin irritation. The product dust can dry and irritate the skin and cause dermatitis and can irritate eyes and skin through mechanical abrasion. Chronic effects: Chronic exposure may cause lung damage from repeated exposure. Chronic inhalation of dusts containing respirable crystalline silica may result in silicosis. For CCP compositions 5 through 8

Acute Effects: Direct exposure may cause respiratory irritation, eye irritation and skin irritation. The product dust can dry and irritate the skin and cause dermatitis and can irritate eyes and skin through mechanical abrasion.

Chronic Effects: Chronic exposure may cause lung damage from repeated exposure. Chronic inhalation of dusts containing respirable crystalline silica may result in silicosis. Repeated exposure to dusts containing inorganic bromide salts may affect fertility and/or result in effects to the unborn child.

4.3 Indication of Any Immediate Medical Attention and Special Treatment Needed Seek first aid or call a doctor or Poison Control Center if contact with eyes occurs and irritation remains after rinsing.

Section 5

Firefighting Measures

5.1 Extinguishing Media

Suitable Extinguishing Media: Product is not flammable. Use extinguishing media appropriate for surrounding fire.

Unsuitable Extinguishing Media: Not applicable, the product is not flammable.

5.2 Special Hazards Arising From the Substance or Mixture

Hazardous Combustion Products:

None known.

5.3 Advice for Firefighters

Special Protective Equipment and Precautions for Firefighters:

As with any fire, wear self-contained breathing apparatus (NIOSH approved or equivalent) and full protective gear.

Comment [A6]: : Select the appropriate text based on the CCP composition. Delete text associated with the other CCP compositions.

Page 5 of 12




Section 6

Accidental Release Measures

6.1 Personal Precautions, Protective Equipment and Emergency Procedures

Personal precautions/Protective Equipment:

See Section 8.3 Individual Protective Measures. For concentrations exceeding Occupational Exposure Levels (OELs), use a self-contained breathing apparatus (SCBA).

Emergency procedures: Use scooping, water spraying/flushing/misting or ventilated vacuum cleaning systems to clean up spills. Do not use pressurized air.

6.2 Environmental precautions

Environmental precautions: Prevent contamination of drains or waterways and dispose according to local and national regulations.

6.3 Methods and Material for Containment and Cleaning Up

Methods and materials for containment and cleaning up:

Do not use brooms or compressed air to clean surfaces. Use dust collection vacuum and extraction systems.

Large spills of dry product should be removed by a vacuum system. Dampened material should be removed by mechanical means and recycled or disposed of according to local and national regulations.

See Sections 8 and 13 for additional information on exposure controls and disposal.

Section 7

Handling and Storage

7.1 Precautions for Safe Handling

Practice good housekeeping. Use adequate exhaust ventilation, dust collection and/or water mist to maintain airborne dust concentrations below permissible exposure limits (note: respirable crystalline silica dust may be in the air without a visible dust cloud).

Do not permit dust to collect on walls, floors, sills, ledges, machinery, or equipment. Maintain and test ventilation and dust collection equipment. In cases of insufficient ventilation, wear a NIOSH approved respirator for silica dust when handling or disposing dust from this product. Avoid contact with skin and eyes. Wash or vacuum clothing that has become dusty. Avoid eating, smoking, or drinking while handling the material.

7.2 Conditions for safe storage, including any incompatibilities

Minimize dust produced during loading and unloading.

Page 6 of 12




Section 8

Exposure Controls/Personal Protection

8.1 Control Parameters OCCUPATIONAL EXPOSURE LIMITS

SUBSTANCE OSHA PEL

TWA (mg/m3)

NIOSH REL

TWA (mg/m3)

ACGIH TLV

TWA (mg/m3)

CA - OSHA PEL

(mg/m3)

Calcium oxide 5 2 2 2

Particulates Not Otherwise Regulated

Total 15 15 - 10

Respirable 5 5 - 5

Crystalline

Silica

Total Quartz

30 ÷ (%SiO2+2) (Total Quartz)

- - 0.3

Respirable Crystalline Silica

10 ÷ (%SiO2+2) 0.05

0.025

(α-quartz &

cristobalite)

0.1

Cristobalite - 0.05

0.025

(α-quartz &

cristobalite)

0.05 (respirable)

Manganese dioxide

(as manganese compounds)

Total 5 (Ceiling) 1

3 (STEL) 0.1 0.2

Respirable - - 0.02 -

8.2 Exposure Controls

8.2.1 Engineering Controls Provide ventilation to maintain the ambient workplace atmosphere below the occupational exposure limit(s). Use general and local exhaust ventilation and dust collection systems as necessary to minimize exposure.

Comment [A7]: Include substances disclosed in Section 3. Delete rows for non‐applicable substances.

Page 7 of 12




8.2.2 Personal Protective Equipment (PPE)

Respiratory protection:

Wear a NIOSH approved particulate respirator if exposure to airborne particulates is unavoidable and where occupational exposure limits may be exceeded. If airborne exposures are anticipated to exceed applicable PELs or TLVs, a self-contained breathing apparatus or airline respirator is recommended.

Eye and face protection: If eye contact is possible, wear protective glasses with side shields. Avoid contact lenses.

Hand and skin protection: Wear gloves and protective clothing. Wash hands with soap and water after contact with material.

Section 9

Physical and Chemical Properties

9.1 Information on Basic Physical and Chemical Properties

Property: Value Property: Value

Appearance (physical state, color, etc.): Fine tan/ gray particulate

Upper/lower flammability or explosive limits: Not applicable

Odor: Odorless1 Vapor Pressure (Pa): Not applicable

Odor threshold: Not applicable Vapor Density: Not applicable

pH (25 °C): INSERT Specific gravity or relative density: INSERT

Melting point/freezing point (°C): Not applicable Water Solubility: Slight

Initial boiling point and boiling range (°C): Not applicable

Partition coefficient: n-octane/water: Not determined

Flash point (°C): Not determined Auto ignition temperature (°C): Not applicable

Evaporation rate: Not applicable Decomposition temperature (°C): Not determined

Flammability (solid, gas): Not combustible Viscosity: Not applicable 1 The use of urea or aqueous ammonia injected into the flue gas to reduce nitrogen oxides (NOx) emissions may result in the presence of ammonium sulfate or ammonium bisulfate in the ash at less than 0.1%. When ash containing these substances becomes wet under high pH (>9), free ammonia gas may be released resulting in objectionable/nuisance ammonia odor and potential exposure to ammonia gas especially in confined spaces.

9.2 Other Information

Comment [A8]: Do not delete any rows or individual properties. If data is not available insert – Not Determined or Not Applicable.

Comment [A9]: If urea or ammonia are injected into the flue gas as a pollution control agent, include a notation next to the odor value and the footnote provided. If urea or ammonia are not used, delete the footnote.

Comment [A10]: If available, list other properties that might be applicable to evaluate the hazards of the CCP. One such example would be particle size determination. If none are available, delete this section.

Page 8 of 12




Section 10

Stability and Reactivity

10.1 Reactivity: The material is an inert, inorganic material primarily composed of elemental oxides.

10.2 Chemical stability: The material is stable under normal use conditions.

10.3 Possibility of hazardous reactions:

The material is a relatively stable, inert material; polymerization will not occur.

or

The material is a relatively stable, inert material; however, when ash containing ammonia becomes wet under high pH (>9), free ammonia gas may be released resulting in an objectionable/nuisance ammonia odor and potential exposure to ammonia gas especially in confined spaces. Polymerization will not occur.

10.4 Conditions to avoid: Product can become airborne in moderate winds. Dry material should be stored in silos. Materials stored out of doors should be covered or maintained in a damp condition.

10.5 Incompatible materials: None known.

10. 6 Hazardous decomposition products:

None known.

Section 11

Toxicological Information

11.1 Information on Toxicological Effects

Endpoint Data

Acute oral toxicity

Acute dermal toxicity

Acute inhalation toxicity

Skin corrosion/irritation

Eye damage/irritation

Respiratory/skin sensitization

Germ cell mutagenicity

Comment [A11]: Choose the appropriate statement. Choose Statement 1 if ammonia or urea are NOT incorporated as pollution control additives. Choose Statement 2 if urea or ammonia ARE used as a pollution control agent.

Comment [A12]: Insert the data that is applicable to the CCP as presented in Appendix E.

Page 9 of 12




Endpoint Data

Carcinogenicity

Reproductive toxicity

STOT-SE

STOT-RE

Section 12

Ecological Information

12.1 Toxicity

No data available on final product.

12.2 Persistence and Degradability

Not relevant for inorganic materials.

12.3 Bioaccumulative Potential

No data available.

12.4 Mobility in Soil

No data available.

12.5 Results of PBT and vPvB Assessment

No data available.

12.6 Other Adverse Effects

None known.

Section 13

Disposal Considerations

See Sections 7 and 8 above for safe handling and use, including appropriate hygienic practices.

Dispose of all waste product and containers in accordance with federal, state and local regulations.

Comment [A13]: The identification and inclusion of data into this section is non‐mandatory per 29CFR 1910.1200. If desired, tables as presented in the SDS Guidance Document can be included but is not required.

Page 10 of 12




Section 14

Transport Information

Regulatory entity: U.S. DOT

Shipping Name: Not Regulated

Hazard Class: Not Regulated

ID Number: Not Regulated

Packing Group: Not Regulated

Section 15

Regulatory Information

15.1 Safety, Health and Environmental Regulations/Legislation Specific for the Mixture

o TSCA Inventory Status All components are listed on the TSCA Inventory.

o California Proposition 65

The following substances are known to the State of California to be carcinogens and/or reproductive toxicants:

Respirable crystalline silica Titanium dioxide (airborne particles)

o State Right-to-Know (RTK)

Component CAS MA1,2 NJ3,4 PA5 RI6

Ammonium bisulfate 7803-63-6 No Yes No No Ammonium sulfate 7783-20-2 Yes No Yes No Barium oxide-as Barium compounds

1304-28-5; Various

No Yes Yes Yes

Calcium carbonate 1317-65-3 Yes Yes Yes No Calcium oxide 1305-78-8 Yes Yes Yes No Calcium sulfate 7778-18-9 Yes Yes Yes No Iron oxide 1309-37-1 Yes Yes Yes No Magnesium oxide 1309-48-4 No Yes No No Manganese oxide-as manganese compounds

1313-13-9; Various

No No Yes Yes

Phosphorus pentoxide (or phosphorus oxide)

1314-56-3 Yes Yes Yes No

Potassium oxide 12136-45-7 No Yes No NoSilica-crystalline (SiO2), quartz 14808-60-7 Yes Yes Yes No Sodium oxide 1313-59-3 No Yes No No Sodium sulfate 7757-82-6 Yes No Yes No Titanium dioxide 13463-67-7 Yes Yes Yes No

1 Massachusetts Department of Public Health, no date

Comment [A14]: Disclose the following if present in the CCP (at any level).

Comment [A15]: Disclose identified components of the CCP present at ≥1% if the CCP is manufactured or distributed in that State. Non‐applicable substances/jurisdictions should be deleted.

Page 11 of 12




2 189th General Court of The Commonwealth of Massachusetts, no date 3 New Jersey Department of Health and Senior Services, 2010a 4 New Jersey Department of Health, 2010b 5 Pennsylvania Code, 1986 6 Rhode Island Department of Labor and Training, no date

o Other Environmental Listings

Section 16

Other Information, Including Date of Preparation or Last Revision

16.1 Indication of Changes Date of preparation or last revision: INSERT

16.2 Abbreviations and Acronyms

ACGIH: American Conference of Industrial Hygienists ANSI: American National Standards Institute CA: California CAA: Clean Air Act CAS: Chemical Abstract Services CCP: Coal Combustion Product CFB: Circulating Fluidized Bed CFR: Code of Federal Regulations CWA: Clean Water Act EPA: Environmental Protection Agency GHS: Globally Harmonized System of Classification and Labelling HMIS: Hazardous Materials Identification System IARC: International Agency for Research on Cancer LC50: Concentration resulting in the mortality of 50 % of an animal population LD50: Dose resulting in the mortality of 50 % of an animal population LEL: Lower explosive limit MA: Massachusetts NA: Not Applicable NJ: New Jersey NOEC: No observed effect concentration NIOSH: National Institute of Occupational Safety and Health NOx: Nitrogen oxides NTP: US National Toxicology Program OEL: Occupational Exposure Limit OSHA: Occupational Safety and Health Administration PA: Pennsylvania Pa: Paschal PBT: Persistent, Toxic and Bioaccumulative PEL: Permissible exposure limit PPE: Personal Protective Equipment REL: Recommended exposure limit RI: Rhode Island RCS: Respirable Crystalline Silica RTK: Right-to-Know

Comment [A16]: Other information related to the presence of component substance on other environmental listings such as SARA 311/312, SARA 313 TRI, CWA or CAA may also be included, but is not required.. If none are added delete the bullet

Comment [A17]: Insert the SDS development/revision date. Also designate a revision number (or new).

Comment [A18]: Include abbreviations that were used in the SDS development. Add or remove other acronyms as applicable.

Page 12 of 12




SARA: Superfund Amendments and Reauthorization Act SCBA: Self-contained breathing apparatus SDS: Safety Data Sheet STEL: Short-term exposure limit STOT-RE: Specific target organ toxicity-repeated exposure STOT-SE: Specific target organ toxicity-single exposure TLV: Threshold limit value TSCA: Toxic Substances Control Act TWA: Time-weighted average UEL: Upper explosive limit UVCB: Unknown or Variable Composition/Biological U.S.: United States U.S. DOT: United States of Department of Transportation vPvB: Very Persistent and Very Bioaccumulative

16.3 Other Hazards

Table 1: CCP 1 and CCP 2 Hazardous Materials Identification System (HMIS)Degree of hazard (0= low, 4 = extreme) Health: 1* Flammability: 1 Reactivity: 1 Personal protection:

* Chronic Health Effects

Table 2: CCP 3 and CCP 4 Hazardous Materials Identification System (HMIS)Degree of hazard (0= low, 4 = extreme) Health: 1 Flammability: 1 Reactivity: 1 Personal protection:

Table 3: CCP 5 and CCP 6 Hazardous Materials Identification System (HMIS)Degree of hazard (0= low, 4 = extreme) Health: 3* Flammability: 1 Reactivity: 1 Personal protection:

* Chronic Health Effects

Table 4: CCP 7 and CCP 8 Hazardous Materials Identification System (HMIS)Degree of hazard (0= low, 4 = extreme) Health: 3 Flammability: 1 Reactivity: 1 Personal protection:

DISCLAIMER: This SDS has been prepared in accordance with the Hazard Communication Rule 29 CFR 1910.1200. Information herein is based on data considered to be accurate as of date prepared. No warranty or representation, express or implied, is made as to the accuracy or completeness of this data and safety information. No responsibility can be assumed for any damage or injury resulting from abnormal use, failure to adhere to recommended practices, or from any hazards inherent in the nature of the product.

Comment [A19]: Apply the HMIS ratings table that is applicable to the CCP classification as noted. Delete the other HMIS tables and the “table” reference.

Comment [A20]: Include a disclaimer at the end of your SDS. Prior to using the disclaimer provided, it should be reviewed by legal counsel.

APPENDIX C

Compositions Summary Workbook

TABLE C‐1

CCP CLASSIFICATIONS

CCP COMPOSITION SUMMARY

ACAA SDS GUIDANCE DOCUMENT

Page 1 of 1

CCP 1

Composition*

CCP 2

Composition

CCP 3

Composition*

CCP 4

Composition*

CCP 5

Composition*

CCP 6

Composition*

CCP 7

Composition*

CCP 8

Composition*

1. STOT‐SE Category 3

(Respiratory Irritation)

2. STOT‐RE Category 2



2. Eye Irritant Category 2A


STOT‐SE Category 3








3.Toxic to Reproduction,

Category 2



2. Toxic to Reproduction,

Category 2





5.Toxic to Reproduction,

Category 2




3. Toxic to Reproduction,

Category 2

Yes No

Silicon dioxide (SiO2); Silica, crystalline, cristobalite;

Silica, crystalline, quartz (SiO2)2≤17% ≤17% ≤17% ≤17% ≤17% ≤17% ≤17% ≤17%

If respirable fraction has NOT

been determined

If respirable fraction HAS

been determined

Silica, crystalline, respirableundetermined or

≥0.1 < 10%

undetermined or

≥1 < 10%<1% <1%

undetermined or

≥0.1 < 10%<1%

undetermined or

≥1 < 10%<1% If known and ≥ 0.1% If below 0.1%

Aluminosilicates

(Sum of reported Amorphous silicon dioxide and

Aluminum oxide)

≤95% ≤95% ≤95% ≤95% ≤95% ≤95% ≤95% ≤95% Yes

Barium oxide (BaO) <5% <5% <5% <5% <5% <5% <5% <5% If ≥1% If <1%

Calcium carbonate <10% <10% <10% <10% <10% <10% <10% <10% Not required

Calcium oxide (CaO) (total/free) ≤20%/≤8% >20%/>8% ≤20%/≤8% >20%/>8% ≤20%/≤8% ≤20%/≤8% >20%/>8% >20%/>8% If ≥1% If <1%

Calcium Sulfate <10% <10% <10% <10% <10% <10% <10% <10% Not required

Carbon <6% <6% <6% <6% <6% <6% <6% <6% Not required

Iron oxide ≤35% ≤35% ≤35% ≤35% ≤35% ≤35% ≤35% ≤35% Not required

Magnesium oxide (MgO) ≤5.87% ≤5.87% ≤5.87% ≤5.87% ≤5.87% ≤5.87% ≤5.87% ≤5.87% Not required

Manganese dioxide (MnO2) <1% <1% <1% <1% <1% <1% <1% <1% If ≥1% If <1%

Phosphorus pentoxide (P2O5) ≤1% ≤1% ≤1% ≤1% ≤1% ≤1% ≤1% ≤1% If ≥1% If <1%

Potassium oxide (K2O) <5% <5% <5% <5% <5% <5% <5% <5% If ≥1% If <1%

Sodium oxide (Na2O) ≤1.82% ≤1.82% ≤1.82% ≤1.82% ≤1.82% ≤1.82% ≤1.82% ≤1.82% Not required

Titanium dioxide (TiO2) ≤2.5% ≤2.5% ≤2.5% ≤2.5% ≤2.5% ≤2.5% ≤2.5% ≤2.5% Not required

Ammonium bisulfate ≤0.01% ≤0.01% ≤0.01% ≤0.01% ≤0.01% ≤0.01% ≤0.01% ≤0.01% Not required

Ammonium sulfate ≤0.01% ≤0.01% ≤0.01% ≤0.01% ≤0.01% ≤0.01% ≤0.01% ≤0.01% Not required

Bromide Salts (various) (including NaBr) <0.1% <0.1% <0.1% <0.1% ≥0.1% ≥0.1% ≥0.1% ≥0.1% If ≥0.1% If <0.1%

Chloride salts (various) ≤2% ≤2% ≤2% ≤2% ≤2% ≤2% ≤2% ≤2% Not required

Halide salt (not further specified) ‐ Arising from As‐ Hgx (Novinda)

≤0.2% ≤0.2% ≤0.2% ≤0.2% ≤0.2% ≤0.2% ≤0.2% ≤0.2% Not required

Magnesium sulfate ≤2% ≤2% ≤2% ≤2% ≤2% ≤2% ≤2% ≤2% If ≥1% If <1%

Sodium sulfate ≤2% ≤2% ≤2% ≤2% ≤2% ≤2% ≤2% ≤2% Not required

* CCPs whose composition includes only these substances at or below the levels indicated would be considered to fall within this classification.

SDS Section 2

Disclosure

Substance/Classification

HALEY & ALDRICH, INC.

Copy of CCP Composition Summary_Appendix C_04292015.xlsx MAY 2015

TABLE C‐2

SUMMARY



Page 1 of 4

Compositional

Summary

Data

Additives Disclose on SDS Consider for GHS ClassificationGHS Classification

(ECHA Portal)

Chemical Composition Minimum % Maximum % Minimum % Maximum % Minimum % Maximum % Anticipated levels %

Silicon dioxide (SiO2); Silica,

crystalline, cristobalite; Silica,

crystalline, quartz (SiO2)12 17 0 15* 27.78 35.59

Disclose if respirable fraction

has not been determined

Yes, if no respiratory fraction has been determined it is

recommended that a classification of STOT‐RE

Category 2 be assigned based on the potential

presence of the respiratory fraction

I think a max of a Cat 2 because the EPRI report

indicates that the respirable crystalline silica max was

3.2%.

Quartz (SiO2) CAS# 14808‐60‐7

‐ No Harmonized Classification

‐ Majority of notifiers note this as Not Classified

‐ Some notifiers site a STOT‐RE Category 1 or STOT‐RE Category 2 classification7

Crystalline silica CAS# 1317‐95‐9

‐ No harmonized classification

‐ Many notifiers classified as STOT RE‐27

Cristobalite CAS# 14464‐46‐1

‐ No harmonized classification

‐ Many notifiers classified as STOT‐RE 1 or as a Carc 1A or Carc 2 or STOT‐RE 27

Silica, crystalline respirable (RCS) <4 <4Disclose if ≥0.1% Yes, if available

No Harmonized Classification

Based on IMA‐Europe

‐ Less than 1% is Not Classified

‐ Between 1‐10% is STOT‐RE 2

‐ Greater than 10% is STOT‐RE 1

ALthough presence of respirable crystalline silica at >10% would result in a STOT RE CAtegory

1, data from EPRI indicates that theis level does not exceed 3.2%. If this ERI data is

considered representative of the fly ash generated in the US, the worst case Repeat Dose

STOT classification would be STOT‐RE Category 2.

Although diosclosure for non‐carcinogens is technically not required until 1%. IF known it is

recommended that levels be disclosed at ≥0.1%

Aluminosilicate glass (mullite ‐

Mullite (Al6O5(SiO4)2)

1302‐93‐8)

(Combination of Amorphous silica

and Aluminum oxide)

<35 95 65 95 25 70 <0.55Disclose

Fly Ash ‐ No

Other CCP's ‐ Yes

Toxicological testing on fly ash indicates that it does

not require classification for these endpoints, however

for other CCPs the irritation classification will need to

be assessed based on the level of all irritants in the

final composition.


Classified as skin/eye 2

Amorphous Silica with CAS# 112945‐52‐5

‐ 791 notifiers classified as Skin Irrit‐Category 2, Eye Irrit Category 2 and STOT SE‐3

(respiratory irritation)

‐ 687 notifiers indicated Not Classified

Mullite

‐ Most notified indicated Not Classified

Barium oxide (BaO) 0.08 < 1.0 Not required No


‐ Most notifiers indicated an Acute Tox 4 Classification‐ oral/inhalation

‐ A search of data related to the toxicity of barium oxide did not identify any Acute toxicity

data. This substance would not require disclosure.

Note: If all acute toxicants in the product were present at their maximum level, no

classification would be prescribed to the final product

CFBC AshFly Ash Bottom Ash


C:\Users\met\Desktop\MaryAnn\Copy of CCP Composition Summary_Appendix C_04292015.xlsx MAY 2015

TABLE C‐2

SUMMARY



Page 2 of 4

Compositional

Summary

Data


(ECHA Portal)



Calcium carbonate 0 10 Not required NoNo Harmonized Classification

Not classified

Calcium oxide (CaO) 1 30 0 20 0 41.19 <12

Disclose

Fly Ash ‐ No

Other CCP's ‐ Yes



for other CCPs the irritation classification will be

assessed using read across to final ash products with

similar levels of components classified as skin/eye

irritants/corrosive agents.


‐ 500 notifiers classified as Skin Irrit‐2, Eye Damage 1 and STOT‐SE 3 (respiratory irritation)

‐ 355 classified as Acute Tox 4‐Oral, Skin Corr 1C and Eye Damage 1

Note: If all acute toxicants in the product were present at their maximum leve, no


Calcium sulfate2 0.62 5.87 1.31 1.51 1‐2 Not required NoNo Harmonized Classification

‐ Most Notifiers indicated Not Classified

Carbon <2 <6 0.06‐2 NA No Not applicable

Iron minerals (Fe2O3, Fe3O4)3 3.57 35 2 35 1.19 7.69 Not required No


‐ Most notifiers of Iron Oxide (CAS# 1309‐37‐1) indicated Not Classified

‐ Most notifiers of oxides listed under CAS# 1317‐61‐9, CAS# 1345‐25‐1, and CAS# 1332‐37‐2

indicated Not Classified

Magnesium oxide (MgO) 0.62 5.87 1 4 0.41 1.51 1‐2 Not required NoNo Harmonized Classification


Manganese dioxide (MnO2) < 1.0 Disclose if present at ≥1% No

Harmonized Classification = Acute tox 4 Oral/Inhal

Note: If all acute toxicants in the product were present at their maximum leve, no


Phosphorus pentoxide (P2O5) 0.45 1 Disclose if present at ≥1%

Fly Ash ‐ No

Other CCP's ‐ Yes







Harmonized Classification = Skin Corr 1A

Potassium oxide (K2O) 0.56 5 1 5 0.42 0.7 Disclose if present at ≥1%

Fly Ash ‐ No

Other CCP's ‐ Yes








‐ Most notifiers indicated some degree of skin/eye irritation or corrosion

‐ Approximately 1/3 of notifers (131) indicated Not Classified.



TABLE C‐2

SUMMARY



Page 3 of 4

Compositional

Summary

Data


(ECHA Portal)



Sodium oxide (Na2O) 0.26 1.82 0.8 1.7 0.29 0.53 Not required NoNo Harmonized Classification


Strontium oxide (SrO)8 < 1.0 Not required NoNo Harmonized Classification

‐ Most notifiers classified as a Skin Corr 1B

Titanium dioxide (TiO2) 0.8 2.5 0.8 2.5 2.65 4.93 0.02 Not required NoNo Harmonized Classification


Sulfur trioxide (SO3)4 0.09 1.7 0.3 1.3 4.21 10.13 Not required No Not considered present in final product. See footnote 4

Chlorine5 0.05 0.15 Not required No Not considered present in final product. See footnote 5

Ammonium bisulfate <0.01 Not required No

From additives


‐ Approximately 60% of notifiers indicated Not Classified

‐ Approximately 40% indicate some degree of Skin/eye irritation/corrosion

Based on low level of addtive usage no disclosure is recommended.

Ammonum sulfate <0.01 Not required No

From additives



Based on low level of addtive usage no disclosure is recommended.

Bromide Salts (various)

(including NaBr)1‐2.1 Disclose at ≥0.1% Yes if >0.1%

From additives


‐ Sodium bromide

‐ Most Notifiers classified as Repro 1B

See 29 CFR 1910.1200 Appendix A, A.0.4.2 ‐ Reprotoxic agents present at 0.1% or greater as

referenced in A.6 will result in the classification of a finished product. So althought per the

OSHA fact sheet, reprotoxic agents do not require disclosure until 1%, however, it is

recommended that this substance be disclosed and considered for classification at levels

above 0.1%

Chloride salts (various) 1‐2 Not required No

From additives

No Harmonized Classifications for Inorganic chloride salts were identified.

‐ Based on read across to NaCL wihich notifers indicated as Not Classified, no classification of

chloride salts is assigned.

Halide salt (not further specified) 0.04‐0.2 Not required No

From additives

‐ Specific halide salt not defined on supplier SDS

‐ SDS does not indicate the tpye of halide salt

‐ Based on lack of disclosure/classification of halide salts on supplier SDS, further

consideration is not required.



TABLE C‐2

SUMMARY



Page 4 of 4

Compositional

Summary

Data


(ECHA Portal)



Magnesium sulfate 1‐2 Disclose if present at ≥1% No

From additives


‐ 747 notifiers classified as Acute Tox 4‐oral/inhalation/dermal

‐ 618 notifiers classified as Not Classified

Note: If all acute toxicants in the product were present at their maximum level, no


Sodium sulfate 1‐2 Not required No

From additives



Notes:

ASTM C 618 ‐ ASTM C618‐12a, Standard Specification for Coal Fly Ash and Raw or Calcined Natural Pozzolan for Use in Concrete, ASTM International, West Conshohocken, PA, 2012, www.astm.org.

CAS ‐ Chemical Abstracts Service.

CFB ‐ Circulating Fluidized Bed.

NA ‐ Not Applicable/Not Available.

1 For purposes of this evaluation the various forms of crystalline silica were considered the same substance2 For purposes of this evaluation Calcium sulfate, Calcium sulfate dihydrate and calcium sulfate gypsum were considered the same substance3 Includes iron oxide as well4 As Sulfur trioxide exists at room temperature either as a gas or a volatile liquid it is not anticipated to affect the final product classification or to be present in the final formulation at levels requiring disclosure on the SDS.5 Chlorine does not exist free in nature and therefore it is not being further considered in this project. 6 This level would be for FBC only7 The percentage of respirable free silica was not indicated. Ths classification is likely applicable to the respirable content of the crystalline silica8 Based on disucssions with ACAA members, Strontium oxide would not be present in the finished product and is not considered further.



TABLE C‐3

FLY ASH



Page 1 of 2

Fly Ash Chemical Composition

Data (Percent)Source

Single Component

Data

Chemical Composition CAS#Class C Fly

Ash

ASTM C 618

Class F Fly

Ash

ASTM C 618

Pulverised Fuel

Ash/Fly Ash and

Furnace Bottom Ash

(FBA) report, UKQA

Crystalline Silica

Analysis

Fly Ash ‐ Western

Subbituminous

Fly Ash ‐

Eastern

Bituminous

Fly Ash ‐ Low

S (<0.4%)

Western

Bituminous

Fly Ash ‐ NIST

Measured

Fly Ash ‐ NIST

Certified

Aluminosilicates

(Sum of reported Amorphous silicon

dioxide and Aluminum oxide) ≥50* ≥70* 72‐83 89.22 85.49 85.77 78.47 77.76

Iron oxide (Fe2O3) 1309‐37‐1 7‐11 3.57 5.54 4.53 11.14 11.11

Silicon dioxide (SiO2); Silica, crystalline,

cristobalite; Silica, crystalline, quartz

(SiO2)2

14464‐46‐1

14808‐60‐7 1.82‐16.8

Silica, crystalline, respirable 0.97‐3.52

Calcium oxide (CaO) (also known as free

lime) 1305‐78‐8 1‐5 2.87 1.23 3.79 2.01 2.11

Carbon 7440‐44‐0

Magnesium oxide (MgO) 1309‐48‐4 1‐4 0.62 1.04 1.08 0.77 0.8

Potassium oxide (K2O) 12136‐45‐7 1‐5 0.71 2.81 1.13 2.28 2.35

Titanium dioxide (TiO2) 13463‐67‐7 0.8‐1.1 0.86 1.52 1.15 1.28 1.32

Sodium oxide (Na2O) 1313‐59‐3 0.8‐1.7 1.1 0.26 1.5 0.24 0.27

Phosphorus pentoxide (P2O5) 1314‐56‐3 0.37 0.56 0.45 1.08 0.53

Barium oxide (BaO) 1304‐28‐5 0.15 0.15 0.24 0.08 0.08

Manganese dioxide (MnO2) 1313‐13‐9

Strontium oxide (SrO) 1314‐11‐0

Sulfur trioxide (SO3)** 7446‐11‐9 ≤ 5 ≤ 5 0.3‐1.3

Chlorine*** 7782‐50‐5 0.05‐0.15

Standards/References EPRI Reports



TABLE C‐3

FLY ASH



Page 2 of 2

Fly Ash Chemical Composition

Data (Percent)Source

Chemical Composition CAS#

Aluminosilicates

(Sum of reported Amorphous silicon

dioxide and Aluminum oxide)

Iron oxide (Fe2O3) 1309‐37‐1

Silicon dioxide (SiO2); Silica, crystalline,

cristobalite; Silica, crystalline, quartz

(SiO2)2

14464‐46‐1

14808‐60‐7

Silica, crystalline, respirable

Calcium oxide (CaO) (also known as free

lime) 1305‐78‐8

Carbon 7440‐44‐0

Magnesium oxide (MgO) 1309‐48‐4

Potassium oxide (K2O) 12136‐45‐7

Titanium dioxide (TiO2) 13463‐67‐7

Sodium oxide (Na2O) 1313‐59‐3

Phosphorus pentoxide (P2O5) 1314‐56‐3

Barium oxide (BaO) 1304‐28‐5

Manganese dioxide (MnO2) 1313‐13‐9

Strontium oxide (SrO) 1314‐11‐0

Sulfur trioxide (SO3)** 7446‐11‐9

Chlorine*** 7782‐50‐5

Fly Ash SDS Fly Ash SDS Fly Ash SDS Fly Ash SDSFly Ash/ASTM

Class C SDS

Class C Fly

Ash SDS

Fly Ash C/F

SDS

Fly Ash/ASTM

Class F

SDS

Class F Fly Ash

SDS

If declared

Minimum %

If declared

Maximum %

Number of Sources

(out of 14)

>65 75‐90 59.7 60.53‐90.10* 50‐90 <35‐51 50‐95 85‐95 <55‐74 <35 95 14

15‐35 4‐7 5.8 5.27‐13.57 <5 4‐7 <1‐5 <5 5‐9 3.57 35 14

2‐10 5‐10 <17 5‐10 <10 <17 2 17 6

<4 <4 <4 <4 2

2‐12 3‐6 22.9 1.15‐25.82 <30 25‐30 <1‐30 1‐14 1 30 13

<2 <6 <2 <6 1

4.9 0.62‐5.87 0.62 5.87 6

< 1.0 0.56‐2.58 0.56 5 6

≤ 2.5 1.4 0.8 2.5 6

1.8 0.30‐1.82 0.26 1.82 6

1 0.45 1 5

< 1.0 0.08 < 1.0 5

< 1.0 < 1.0 1

< 1.0 < 1.0 1

< 1.0 0.09‐1.70 0.09 1.70 2

Notes:


1 For purposes of this evaluation amorphous silica and silica fumes amorphous are considered the same substance2 For purposes of this evaluation the various forms of crystalline silica were considered the same substance3 For purposes of this evaluation Calcium sulfate, Calcium sulfate dihydrate and calcium sulfate gypsum were considered the same substance

* includes iron oxide as well

***Chlorine does not exist free in nature and therefore it is not being further considered in this project.

** as Sulfur trioxide exists at room temperature either as a gas or a volatile liquid it is not anticipated to affect the final product classification or to be present

in the final formulation at levels requiring disclosure on the SDS.

Fly Ash SDSs Summary

ASTM C 618 ‐ ASTM C618‐12a, Standard Specification for Coal Fly Ash and Raw or Calcined Natural Pozzolan for Use in Concrete, ASTM International,

West Conshohocken, PA, 2012, www.astm.org.



TABLE C‐4

BOTTOM ASH



Page 1 of 1

Fly Ash Chemical Composition Data

(Percent)Source

Pulverised Fuel

Ash/Fly Ash and

Furnace Bottom

Ash (FBA), UKQA

Bottom Ash SDSBottom Ash

SDS Minimum % Maximum %

Count

(out of 3)

Silicon dioxide (SiO2)

Silica, crystalline, cristobalite

Silica, crystalline, quartz (SiO2)214464‐46‐1

14808‐60‐7 45‐51 0‐15 2‐12 0 15* 3

Iron oxide (Fe2O3) 1309‐37‐1 7‐11 2‐12 15‐35 2 35 3

Aluminosilicate glass

(Sum of reported Amorphous silicon dioxide

and Aluminum oxide) 70‐95 65‐100 65 100 2

Calcium oxide (CaO) 1305‐78‐8 1‐5 0‐20 2‐12 0 20 3

Magnesium oxide (MgO) 1309‐48‐4 1‐4 1 4 1

Potassium oxide (K2O) 12136‐45‐7 1‐5 1 5 1

Sodium oxide (Na2O) 1313‐59‐3 0.8‐1.7 0.8 1.7 1

Titanium dioxide (TiO2) 13463‐67‐7 0.8‐1.1 ≤ 2.5 0.8 2.5 2

Sulfur trioxide (SO3)* 7446‐11‐9 0.3‐1.3 0.3 1.3 1

Chlorine** 7782‐50‐5 0.05‐0.15 0.05 0.15 1

Notes:



* Values from the UK evaluation were not considered when assigning a maximum level as this does not appear to be representative of bottom ash generated in the US

** as Sulfur trioxide exists at room temperature either as a gas or a volatile liquid it is not anticipated to affect the final product classification or to be present in the final formulation at levels requiring disclosure on the SDS.

** Chlorine does not exist free in nature and therefore it is not being further considered in this project.



TABLE C‐5

CFB ASH



Page 1 of 1

Chemical Composition CAS: Type:

CFBC fly ash (co‐firing coal

and high‐sulphur petroleum

coke with limestone as SO2

sorbent)

Sheng et al, 2007

Fluidized Bed Fly Ash CFB Boiler Bed Ash

Fluidized Bed

Combustion Fly Ash 1

(230390/T2)

ECHA

Fluidized Bed

Combustion Fly Ash 1

(230390/T1)

ECHA

Minimum % Maximum % Count

(out of 5)

Silicon dioxide (SiO2); Silica, crystalline, cristobalite;

Silica, crystalline, quartz (SiO2)214464‐46‐1

14808‐60‐7Not Determined Not Determined 27.78 35.59 27.78 35.59 2

Silica, crystalline, respirable Not Determined Not Determined NA NA

Aluminosilicates (clays, dehydroxylated) 27.38 ‐ 47.24 60‐70 25‐35 25 70 3

Aluminum Oxide (Al2O3) 11.16 20.88 11.16 20.88 2

Calcium carbonate 1317‐65‐3 0‐10 Not listed 0 10 1

Calcium oxide (CaO) 1305‐78‐8 22‐41.19 0‐10 15‐35 35.65 19.46 0 41.19 5

Calcium Oxide (CaO)‐Free 19.91 8.41 8.41 19.91 2***

Iron minerals, Iron mineral dusts (Fe2O3, Fe3O4) 1.19‐2.32 2‐5 2‐5 5.98 7.69 1.19 7.69 5

Titanium dioxide (TiO2) 2.65 4.93 2.65 4.93 2

Magnesium oxide (MgO) 1309‐48‐4 1.13‐1.51 0.44 0.41 0.41 1.51 3

Potassium oxide (K2O) 12136‐45‐7 0.45‐0.70 0.42 0.43 0.42 0.7 3

Sodium oxide (Na2O) 1313‐59‐3 0.29‐0.39 0.25 0.53 0.25 0.53 3

Phosphorus pentoxide (P2O5) 1314‐56‐3 0.38 0.4 0.38 0.4 2

Carbon dioxide (CO2) 0.5 1.11 0.5 1.11 2

Sulfur trioxide (SO3)** 7446‐11‐9 4.21‐10.13 2.84 6.89 0 0 3

Notes:



CFB ‐ Circulating Fluidized Bed.

*** not disclosed on available SDS or in Sheng publication

1Composition tested (FBC/230309/T2): SiO2 ‐ 27,78%, Fe2O3 ‐ 5,98%, CaO (total) ‐ 35,65%, Na2O ‐ 0,25%, P2O5 ‐ 0,38%, CO2 ‐ 0,5%, CaO (free) ‐ 19,91%, Al2O3 ‐ 11,16%, TiO2 ‐ 2,65%, MgO ‐ 0,44%, K2O ‐ 0,42%, SO3 (sulphate) ‐ 2,84%2Composition tested (FBC/230309/T1): SiO2 ‐ 35,59%, Fe2O3 ‐ 7,69%, CaO (total) ‐ 19,46%, Na2O ‐ 0,53%, P2O5 ‐ 0,4%, CO2 ‐ 1,11%, CaO (free) ‐ 8,41%, Al2O3 ‐ 20,88%, TiO2 ‐ 4,93%, MgO ‐ 0,41%, K2O ‐ 0,43%, SO3 (sulphate) ‐ 6,89%

** as information regarding the presence of SO2 in the final product came from an EU source and that it exists at room temperature either as a gas or a volatile liquid it is not anticipated to be present in the final

formulation at levels requiring disclosure on the SDS or to affect the final product classification.



TABLE C‐6

POLLUTION CONTROL ADDITIVES



Page 1 of 2

AdditiveComponent level

(if appropriate)Use Level

Substance in Final

Product

Additive Value for Final

CompositionComments

Ammonium sulfate <0.01%

Ammonium bisulfate <0.01%

Calcium bromide 7789‐41‐3 1‐2%Various Bromide

salts1‐2% total bromide salts

At or below this use level, no significant impact on final Ash classification will

occur, nor is disclosure on the SDS required.

Calcium oxide <10%

Calcium sulfate <10%

Calcium chloride 1‐2%Various Chloride

salts1‐2% total chloride salts



Calcium hydroxide 1305‐62‐0 1‐2% 1‐2%

Calcium oxide 1305‐78‐8 1‐2% 1‐2%

calcium sulfate 13397‐24‐5 1‐2% 1‐2%At or below this use level, no significant impact on final Ash classification will


Calcium sulfite 10257‐55‐3 1‐2% 1‐2%At or below this use level, no significant impact on final Ash classification will


0.06‐2% Carbon carbon 0.06‐2%

0.04‐0.2% Halide salt halide salt 0.04‐0.2%

Magnesium carbonate 1‐2% 1‐2%

Magnesium hydroxide 1309‐42‐8 1‐2%

Magnesium oxide 1309‐48‐4 1‐2%

Magnesium sulfate 1‐2% Magnesium sulfate 1‐2%Expensive so not injected directly, is also found as a contaminant in natural lime



Potential Additives/resulting product ‐ potential levels

Activated carbon (halogenated or non‐

halogenated)

Trade names)‐ PowerPAC Premium®,

PowerPAC Premium Plus™, FastPAC

Premium™, FastPAC Premium ‐80™



1‐2%

Overall presence of CaO will need to be evaluated for final product classification

and disclosure on SDS

This represents both halogenated and unhalogenated powdered carbon sorbents .

The actual halide salt was not provided.



Ammonia 7664‐41‐7 600 ppm

Calcium carbonate 10%

Specific to FBC only

Overall presence of CaO will need to be evaluated for final product classification

and disclosure on SDS

1‐2%

Expensive substances so they are generally not injected directly, is also found as a

contaminant in natural lime.



Calcium oxide

calcium sulfate

Magnesium oxide



TABLE C‐6

POLLUTION CONTROL ADDITIVES



Page 2 of 2

AdditiveComponent level

(if appropriate)Use Level

Substance in Final

Product

Additive Value for Final

CompositionComments

Potential Additives/resulting product ‐ potential levels

Sodium bicarbonate 144‐55‐8 (In mineral

form: Trona)1‐2% 1‐2%

Sodium carbonate 497‐19‐8 (In mineral form:

Trona)1‐2% 1‐2%

0.03‐0.05% trade

secret)Unknown 0.03‐0.05%

<0.05% silica Amorphous silica <0.05%

50% Kaolin Aluminosilicates 0.50%

1‐2% TiO2 TiO2 0.02%

2‐10 % NaBr Bromide Salts 0.10%

5‐40% Carbon Carbon 0.40%

Notes:

Source: EPRI, 2008. Impact of Air Emissions Controls on Coal Combus on Products and ACAA member companies

X (SO3 control) below this use level, no significant impact on final Ash classification

will occur, nor is disclosure on the SDS required.





Mercury Sorbent HX600 series (BASF)

1%

1%

Sodium sulfate

Amended clay

Trade name: As‐Hgx (Novinda)



TABLE C‐7

REFERENCES



Page 1 of 1

Source NotesEPRI, 1993. Fly Ash Exposure in Coal‐Fired Power Plants No composition data found, mostly air data

EPRI, 2008. Computer‐Controlled Scanning Electron Microscopy (CCSEM) Investigation of Respirable Quartz in Air

Samples Collected During Power Plant Maintenance ActivitiesTable 4‐1 has some CCSEM method weight and volume data for quarts and SI‐Rich glass

EPRI, 2010. Comparison of Coal Combustion Products to Other Common Materials

Primarily elemental analysis ‐ Page 3‐1‐ Fly ash and bottom ash are most similar in bulk chemical composition to siliceous

rocks, and the greatest similarity is observed between fly ash and bottom ash and rocks such as volcanic ash and shale

(Figure 3‐1). The overall chemical composition of coal ash resembles that of siliceous rocks from which it was derived,

particularly shale. Oxides of silicon, aluminum, iron, and calcium make up more than 90% of most siliceous rocks, soils, fly

ash, and bottom ash. Other major and minor elements (sulfur, sodium, potassium, magnesium, titanium) make up an

additional 8%, while trace constituents account for less than 1%.

EPRI, 2011. Composition and Leaching of FGD Gypsum and Mined Gypsum

I think this is elemental analysis. This has some % taken from the median concentrations ‐ "The 32 samples analyzed were all

greater than 90% calcium sulfate dihydrate. Median Ca and S concentrations in the FGD gypsum were 23.7% and 18.8%,

respectively. Median concentrations for all other constituents were less than 0.1%.

EPRI, 2006. Potential Health Effects of Crystalline Silica Exposures from

Coal Fly Ash: A Literature ReviewNo composition data found

United Kingdom Quality Ash Association. 2011. Technical Datasheet 9.0. COSHH – Safety Data Sheet for PFA/Fly Ash and

FBA (including CenospheresComposition data

Sheng G, Zhai J, Li Q, Li F. 2007. Utilization of fly ash coming from a CFBC boiler co‐firing coal and petroleum coke in

Portland Cement. FUEL 86 (2007) 2625‐2631Composition data

SDS from various ACAA member companies Confidential formulary information

ASTM International. 2012. Standard 618‐12a: Standard Specification for Coal Fly Ash and Raw or Calcined Natural

Pozzolan for Use in Concrete. February 12, 2012.Composition data

European Chemicals Agency (ECHA). 2010a. REACH Registration Dossier for Ashes (residues), coal.

http://apps.echa.europa.eu/registered/data/dossiers/DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031/DISS‐a000ebe7‐

e6d4‐0933‐e044‐00144f67d031_DISS‐a000ebe7‐e6d4‐0933‐e044‐00144f67d031.html. Accessed April 17, 2015

Composition data

European Chemicals Agency (ECHA). 2010b. REACH Registration Dossier for FBC Ash (residues of coal combustion in

fluidized bed boilers. http://apps.echa.europa.eu/registered/data/dossiers/DISS‐97d85c15‐4762‐3e07‐e044‐

00144f67d031/DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031_DISS‐97d85c15‐4762‐3e07‐e044‐00144f67d031.html.

Accessed April 25, 2015.

Composition data



APPENDIX D

SDS Section 2 Data

SDS Section 2 Data Page 1 of 7 Preparation Date: 2015‐05‐15

SDS Section 2 Data This Appendix details the information to be populated into Section 2 of the SDS for each CCP Classification as defined in the Guidance document. Section 2 lists the final product hazard classification per 29CFR 1910.1200 and the GHS Guideline, Revision 3. As the information to be populated in this section is dependent on the classification, unique data tables that includes the GHS hazard class and category for each applicable hazard using available data on the finished product or its components, following the specifications of Appendices A & B of the OSHA HazCom Standard (29 CFR 1910.1200) and the GHS Guideline, Revision 3 are provided here. Note: As these GHS Classifications were based on CCP compositional data compiled in Appendix C: CCP Composition Summary, the classifications assigned are only applicable to CCPs whose compositions are inclusive of the substances listed in Section 4.1 Table 1 of the SDS Guidance Document, at or below the maximum level identified.

1. Data to be provided for CCP 1 Classifications:





Signal Word: Danger

Hazard Statement(s): May cause respiratory irritation.May cause damage to lungs after repeated/prolonged exposure via inhalation.


Do not breathe dust. Use outdoors or in a well ventilated area. If inhaled: Remove to fresh air and keep comfortable for breathing. Get medical advice/attention if you feel unwell. Store in a secure area. Dispose of product in accordance with local/national regulations.








Signal Word: Danger


Causes serious eye irritation. May cause respiratory irritation. May cause damage to lungs after repeated/prolonged exposure via inhalation.


Do not breathe dust. Wash thoroughly after handling. Wear eye protection. Use outdoors or in a well ventilated area. If inhaled: Remove to fresh air and keep comfortable for breathing. Get medical advice/attention if you feel unwell. If in eyes: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. If eye irritation persists, get medical advice/attention. Store in a secure area. Dispose of product in accordance with local/national regulations.

3. Data to be provided for CCP 3

Classification:




Signal Word: Warning


May cause respiratory irritation.


Avoid breathing dust. Use outdoors or in a well ventilated area. If inhaled: Remove to fresh air and keep comfortable for breathing. Get medical advice/attention if you feel unwell. Store in a secure area. Dispose of product in accordance with local/national regulations.









May cause respiratory irritation. Causes serious eye irritation.


Avoid breathing dust. Wash thoroughly after handling. Wear eye protection. Use outdoors or in a well ventilated area. If inhaled: Remove to fresh air and keep comfortable for breathing. Get medical advice/attention if you feel unwell. If in eyes: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. If eye irritation persists, get medical advice/attention. Store in a secure area. Dispose of product in accordance with local/national regulations.








Signal Word: Danger


May cause respiratory irritation. May cause damage to lungs after repeated/prolonged exposure via inhalation. Suspected of damaging fertility or the unborn child.


Do not breathe dust. Obtain special instructions before use. Do not handle until all safety precautions have been read and understood. Wear protective gloves, protective clothing, eye protection and face protection. Use outdoors or in a well ventilated area. If inhaled: Remove to fresh air and keep comfortable for breathing. If exposed or concerned: Get medical attention if you feel unwell. Store in a secure area. Dispose of product in accordance with local/national regulations









May cause respiratory irritation. Suspected of damaging fertility or the unborn child.


Avoid breathing dust. Obtain special instructions before use. Do not handle until all safety precautions have been read and understood. Wear protective gloves, protective clothing, eye protection and face protection. Use outdoors or in a well ventilated area. If inhaled: Remove to fresh air and keep comfortable for breathing. If exposed or concerned: Get medical advice/attention. Store in a secure area. Dispose of product in accordance with local/national regulations.









Signal Word: Danger


May cause respiratory irritation. May cause damage to lungs after repeated/prolonged exposure via inhalation. Causes serious eye irritation. Suspected of damaging fertility or the unborn child.


Do not breathe dust. Obtain special instructions before use. Do not handle until all safety precautions have been read and understood. Wear protective gloves, protective clothing, eye protection and face protection. Wash thoroughly after handling. Use outdoors or in a well ventilated area. If inhaled: Remove to fresh air and keep comfortable for breathing. If exposed or concerned: Get medical advice/attention. If in eyes: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. If eye irritation persists, get medical advice/attention. Store in a secure area. Dispose of product in accordance with local/national regulations.






Labelling according to 29 CFR 1910.1200 Appendices A,B and C*




May cause respiratory irritation. Causes serious eye irritation. Suspected of damaging fertility or the unborn child.


Avoid breathing dust. Obtain special instructions before use. Do not handle until all safety precautions have been read and understood. Wear protective gloves, protective clothing, eye protection and face protection. Wash thoroughly after handling. Use outdoors or in a well ventilated area. If inhaled: Remove to fresh air and keep comfortable for breathing. If in eyes: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. If eye irritation persists, get medical advice/attention. Store in a secure area. Dispose of product in accordance with local/national regulations.

APPENDIX E

SDS Section 11 Data


SDS Section 11 Data This Appendix details the information to be populated into Section 11 of the SDS for each CCP Classification as defined in the SDS Guidance Document. Section 11 identifies the toxicological and health effects information available on the CCP and or its components (as required for disclosure). Where information is not available on the product (CCP), it is appropriate to indicate that data is not available. Where no data is available on the product, information on components may be provided. As the GHS Classifications associated with the various CCPs are different, the information required to be disclosed also varies. Note: As the GHS Classifications were based on CCP compositional data compiled in Appendix C: CCP Composition Summary, the classification assigned and the associated toxicological data supplied here, are only applicable to CCPs whose compositions are inclusive of the substances listed in Appendix C ‐ Tab 1: CCP Classifications, at or below the maximum level identified.


1. Data to be provided for CCP 1 (STOT‐SE Category 3, STOT‐RE Category 2)

Endpoint Data







Not a respiratory or dermal sensitizer.


Carcinogenicity Not available. Respirable crystalline silica has been identified as a carcinogen by NTP and IARC.




Specific Target Organ Toxicity–Repeated Exposure

NOAEC = 4.2 mg/m3 fly ash dust; as no effects were observed at the highest dose tested during the 180 day inhalation study, it is not possible to assess the level at which toxicologically significant effects may occur. Repeated inhalation exposures to high levels of respirable crystalline silica may result in lung damage (i.e., silicosis).

Aspiration hazard Not applicable based on product form.


2. Data to be provided for CCP 2 (Eye Irritant Category 2A, STOT‐SE Category 3, STOT‐RE Category 2)

Endpoint Data





Eye damage/irritation Positive scores for conjunctiva irritation and chemosis in 2/3 animals based on average of 24, 48 and 72 hour scores with irritation clearing within 21 days; No corneal or iritis effects observed.












3. Data to be provided for CCP 3 (STOT‐SE Category 3)

Endpoint Data














NOAEC = 4.2 mg/m3 fly ash dust; as no effects were observed at the highest dose tested, it is not possible to assess the level at which toxicologically significant effects may occur.



4. Data to be provided for CCP 4 (Eye Irritant Category 2A, STOT‐SE Category 3)

Endpoint Data














NOAEC = 4.2 mg/m3 fly ash dust; as no effects were observed at the highest dose tested during the 180 day inhalation study, it is not possible to assess the level at which toxicologically significant effects may occur.



5. Data to be provided for CCP 5 (STOT‐SE Category 3, STOT‐RE Category 2A, Toxic to Reproduction Category 2)

Endpoint Data










Reproductive toxicity An animal study with a CCP has indicated some effects on male and female reproductive organs and parameters without a clear dose response while studies with other CCPs have not shown reproductive effects. Therefore, there is not enough evidence available to classify according to reproductive toxicity. No developmental toxicity has been observed in available animal studies. Inorganic bromide salts have been shown to have adverse effects on reproductive parameters in some animal studies.







6. Data to be provided for CCP 6 (STOT‐SE Category 3, Toxic to Reproduction Category 2)

Endpoint Data

















7. Data to be provided for CCP 7 (STOT‐SE Category 3, STOT‐RE Category 2, Eye Irritant Category 2; Toxic to Reproduction Category 2)

Endpoint Data

















8. Data to be provided for CCP 8 (STOT‐SE Category 3, Eye Irritant Category 2, Toxic to Reproduction Category 2)

Endpoint Data














