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AMERICAN COAL ASH ASSOCIATION FGD GYPSUM SAFETY DATA SHEET GUIDANCE DOCUMENT by Haley & Aldrich, Inc. Burlington, MA for ACAA Farmington Hills, MI File No. 129672-002 August 2018
www.haleyaldrich.com
August 2018 Table of Contents
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ii
List of Tables iv
1. Introduction/Purpose 1
2. Introduction to GHS 3
3. Flue Gas Desulfurization (FGD) Systems 4
3.1 WET FGD SYSTEMS 4 3.1.1 Forced Oxidation 4 3.1.2 Inhibited Oxidation 4 3.1.3 Natural Oxidation 5 3.1.4 Additives 5
3.2 DRY FGD SYSTEMS 6 3.3 OTHER FGD SYSTEMS 6 3.4 FGD SOLIDS 6
4. FGD Gypsum Composition 7
4.1 GYPSUM IDENTIFICATION 7 4.1.1 Typical FGD Gypsum Composition 7
4.2 ANALYTICAL METHODOLOGY 9 4.3 COMMON PITFALLS IN COMPOSITION DETERMINATION 9
5. OSHA HCS 2012 FGD Gypsum Hazard Classification 12
5.1 DATA SUPPORTING THE HAZARD CLASSIFICATION OF FGD GYPSUM 12 5.1.1 EU REACH Dossiers 12 5.1.2 Other Supporting Data 15 5.1.3 Conclusion 16
5.2 SILICA 17 5.2.1 Amorphous Silica and Aluminosilicates 17 5.2.2 Crystalline Silica 17
5.3 CALCIUM CARBONATE 24 5.4 MAGNESIUM CARBONATE 24 5.5 FLY ASH 24
5.5.1 RCS 24 5.5.2 Calcium Oxide 24 5.5.3 Bromide Substances 25
5.6 FINAL FGD HAZARD CLASSIFICATION 25
August 2018 Table of Contents
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6. SDS Development 27
6.1 GENERAL COMMENTS 27 6.2 SDS SECTION-BY-SECTION COMMENTS 28
References 53
Tables Appendix A – FGD Gypsum Safety Data Sheet (SDS) Development Checklist Appendix B – FGD Gypsum Safety Data Sheet (SDS) Template Appendix C – FGD Gypsum Compositions Summary Workbook Appendix D – FGD Gypsum Analytical Methodologies
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List of Tables Table No. Title 1 Substances Present In Typical FGD Gypsum 2 Substances That May Be Identified in Raw Analytical Data That Should Not Be
Considered As A Unique Component Of FGD Gypsum 3 Residual Fly Ash Components That May Be Identified In Laboratory Analyses
That Do Not Require Disclosure On The SDS 4 Toxicological Data On Calcium Sulfate 5 Physical Hazard Classification Of Calcium Sulfate 6 Hazard Classifications Associated With FGD Gypsum Compositions A FGD Gypsum And Associated Impurities That May Require Disclosure B Occupational Exposure Limits for FGD Gypsum And Typical Impurities C FGD Gypsum Physical Properties D Toxicological Data For FGD Gypsum Composition 1 E Toxicological Data For FGD Gypsum Composition 2 F FGD Gypsum Or Its Impurities Present On The State Right-to-Know Lists
August 2018 List of Acronyms
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ACA American Coatings Association ACAA American Coal Ash Association ACGIH American Conference of Governmental Industrial Hygienists ANSI American National Standards Institute ASTM American Society for Testing and Materials BCF Bioconcentration Factor C Celsius CA California CAA Clean Air Act CAS Chemical Abstract Service CCP Coal Combustion Product CFB Circulating Fluidized Bed CFR Code Of Federal Regulation COPD Chronic Obstructive Pulmonary Disease CWA Clean Water Act EC European Community ECHA European Chemicals Agency EC50 Effective Concentration that results in 50% immobility or reduction in growth EPA Environmental Protection Agency EPRI Electric Power Research Institute EU European Union FGD Flue Gas Desulfurization FSS Fixated Scrubber Sludge GHS United Nations Globally Harmonized System Of Classification And Labelling H Hours HCS Hazard Communication Standard HMIS Hazard Materials Information System IARC International Agency For Research On Cancer IMA Industrial Minerals Association ITS Integrated Laboratory Systems, Inc. Kow Octanol-Water Partition Coefficient LC50 Lethal Concentration that results in a mortality in 50% of an animal
population LEL Lower Explosive Limit MA MMAD
Massachusetts Mass Median Aerodynamic Diameter
mg/kg Milligrams Per Kilogram mg/L Milligrams Per Liter mg/m3 Milligrams Per Cubic Meter MSHA Mine Safety And Health Administration NIOSH National Institute For Occupational Safety And Health NJ New Jersey NOAEL No Observed Adverse Effect Level NTP National Toxicology Program OECD Organization for Economic Cooperation and Development
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OEHHA Office of Environmental Health Hazard Assessment OEL Occupational Exposure Limit OSHA Occupational Safety And Health Administration Pa Pascal PA Pennsylvania PBT Persistent, Bioaccumulative and Toxic PEL Permissible Exposure Limit PNOR Particulates Not Otherwise Regulated PPE Personal Protective Equipment REACH Registration, Evaluation, Authorisation and Restriction of Chemicals
Regulation REL Recommended Exposure Limit RCS Respirable Crystalline Silica RI Rhode Island RTK Right-To-Know SARA Superfund Amendments And Reauthorization Act SCBA Self-Contained Breathing Apparatus SDS Safety Data Sheet SEM Scanning Electron Microscopy SIAR SIDS Initial Assessment Report SIDS Screening Information Data Set 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 TLV Threshold Limit Value TSCA Toxic Substances Control Act TWA Time-Weighted Average UNEP United Nations Economic Programme UEL Upper Explosive Limit µm Micron UN United Nations US United States U.S. DOT United States Department Of Transportation U.S. EPA United States Environmental Protection Agency UVCB Unknown Or Variable Composition/Biological VOC Volatile Organic Compound vPvB Very Persistent and Very Bioaccumulative
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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 (US OSHA HCS, 2012a,b) 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. SDSs in the US must follow the requirements set forth in HCS 2012. This document represents an update to the American Coal Ash Association Flue Gas Desulfurized (FGD) Gypsum Safety Data Sheet Guidance Document, dated November 2015. Its primary purpose is to assist ACAA member companies in developing SDSs for FGD Gypsum. The update was required to incorporate new information/rulings associated with crystalline silica and beryllium promulgated since 2015. During the development of the document, other regulatory updates/guidance that may affect the development of FGD gypsum SDSs were also incorporated. The primary purpose of this document and associated appendices is to assist ACAA member companies in developing SDSs for FGD gypsum. A similar guidance document for other CCPs including fly ash, bottom ash, circulating fluidized bed (CFB) fly ash, and CFB bed ash was previously prepared and recently updated (Haley & Aldrich, 2018). The current FGD SDS guidance document (Guidance), the associated checklist (Appendix A) and a generic FGD gypsum SDS template (Template) (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 FGD gypsum. This Guidance represents the combined knowledge and information available at the time of development; the Guidance and associated Appendices were based on composition data compiled in Appendix C (Composition Summary Data). Only FGD gypsum produced as by-product of the wet-scrubber process whose compositions are inclusive of the substances identified at or below the levels specified in that Appendix and Table 1 are covered in this Guidance. Under OSHA 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 OSHA HCS 2012. OSHA HCS 2012 specifies that the chemical/product manufacturer is responsible for the development of the SDS (in this case, the FGD gypsum 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
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to accurately assess the potential hazards associated with FGD gypsum so that the SDSs developed by each member company are consistent and accurately reflect the potential hazards of the FGD gypsum during normal shipping and handling from initial development through the supply chain. The FGD Gypsum SDS template (Appendix B) has been developed per OSHA HCS 2012 specifications using the OSHA recognized American National Standards Institute (ANSI) Standard Z400.1: American National Standard for Hazardous 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 were used to support the development of this Guidance 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. Following OSHA HCS 2012 specifications, impurities classified as sensitizers, carcinogens, reproductive toxicants or a Category 1 mutagens at or above 0.1% must be disclosed on the SDS and considered in the final product classification. Impurities associated with other defined OSHA HCS 2012 hazards (i.e., acute toxicity, flammability, etc.) at or above 1% must be disclosed on the SDS and considered in the final product classification. Non-hazardous substances, based on the OSHA HCS 2012 classification scheme do not require disclosure on the SDS, but may be disclosed at the discretion of the SDS author. This Guidance 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 OSHA HCS 2012 compliant SDSs from understanding the products covered in the guidance document and templates through the development of the representative SDS. The primary sections include: Introduction – This section provides an overview of the goals of the document.
Introduction to GHS/HCS 2012 - This section provides information on how hazards are evaluated and communicated under HCS 2012.
FGD Process Systems - This section provides an overview of the processes used in the coal combustion industry to remove the sulfur from flue gases.
FGD Gypsum Composition – This section provides a detailed review of the FGD gypsum composition.
OSHA HCS 2012 FGD Gypsum Hazard Classification – This section provides available test data on FGD gypsum in support of the hazard classification(s). The hazard classification(s) of the FGD gypsum and identified impurities that may impact the overall hazard classifications per OSHA HCS 2012 are presented.
SDS Development – This section provides guidance on the development of an SDS for FGD gypsum.
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2. Introduction to GHS With the adoption of OSHA 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 OSHA HCS 2012, it is now the responsibility of the chemical manufacturer/importer to assess the hazards of products distributed in the U.S. marketplace and communicate those hazards through the use of SDSs. OSHA HCS 2012 implements UN GHS Guideline, Revision 3 (GHS Guideline) as the basis for this classification/hazard determination process which also prescribes specific labeling, pictograms, and SDS format. HCS 2012 also includes additional hazard classes not derived from the GHS Guideline; these include: combustible dust, pyrophoric gases and simple asphyxiant classifications.1 The standard requires an evaluation of physical/chemical, human health, and environmental hazards of products. This can be done through product testing, read-across to data from similar products or using a calculation process provided in the UN GHS Guideline for taking into consideration the individual components of the product. The GHS Guideline has been implemented, or is in the process of being implemented in over 72 countries throughout the world. One of the earliest regions to adopt the GHS Guideline was the European Union (EU). The EU instituted the system with the adoption of 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 large database of information developed for REACH registration purposes, publicly available publically from the European Chemicals Agency (ECHA), was used in the classification assessment of FGD gypsum evaluated in this Guidance. Conversely, Canada is one of the most recent to implement GHS. The promulgation of the Canadian Workplace Hazardous Materials Information System, 2015 (WHMIS, 2015) translates GHS, revision 5. The initial transition phase for SDSs distributed in Canada is currently underway.
1 The pyrophoric gases and simple asphyxiant classifications do not apply to FGD gypsum based on its physical form. However, the combustible dust classification cannot be ruled out based on the product form.
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3. Flue Gas Desulfurization (FGD) Systems FGD systems produce solids through a chemical reaction in the scrubbers that remove sulfur from the flue gases of coal fired power plants. The primary purpose of FGD systems is for pollution control, specifically the removal of SO2, from the exhaust gas stream of coal fired power plants. The systems are generally categorized as wet or dry scrubbers. Wet systems are further delineated by the type of oxidation. A brief summary of the primary desulfurization systems and their respective outputs are described below. 3.1 WET FGD SYSTEMS In wet FGD systems, flue gas is ducted to a spray tower where an aqueous slurry of a reagent material (typically limestone; CaCO3) is injected into the flue gas. The SO2 in the flue gas reacts with the calcium in the sorbent reagent solution and precipitates as calcium sulfate or calcium sulfite to form what is known as FGD solids. The FGD solids contain other compounds that are removed from the flue gas stream or directly introduced by the sorbent reagent with calcium from the limestone to create FGD gypsum. Various forms of oxidation systems are incorporated into the wet FGD system. These oxidation systems define the FGD gypsum produced, as discussed below. 3.1.1 Forced Oxidation Forced oxidation systems pump air into the absorber tanks to achieve essentially 100% sulfite oxidation forming gypsum (calcium sulfate dihydrate: CaSO4•2H2O), also known as FGD gypsum or synthetic gypsum with a purity of greater than 85% percent, based on data from industry information. Forced oxidation systems are typically located downstream from the electrostatic precipitators or baghouses used for capturing fly ash; therefore, the gypsum produced has a typical fly ash content of 1-2%. The forced oxidation process generally includes processing by dewatering equipment such as rotary drums, belt filters, centrifuges, etc. to result in a moist but easy-to-handle solid. Further, FGD processes that were not designed specifically to create an FGD gypsum may result in the creation of a product that may be sluiced into a retention pond without dewatering. This product may later be excavated (reclaimed) for beneficial use. 3.1.2 Inhibited Oxidation Inhibited oxidation systems add sodium thiosulfate or elemental sulfur to react with calcium sulfite to form thiosulfate; the thiosulfate ion then further acts as a sulfite inhibitor. The solid produced in this system is primarily calcium sulfite hemihydrate in a slurry with a 5% solids content. Calcium sulfite hemihydrate is difficult to dewater and handle as a solid so it is often mixed with fly ash and lime to create a more stable material referred to as fixated scrubber sludge (FSS). FSS has limited uses and is often landfilled, but can be used as structural fill or for mine reclamation. This Guidance document does not cover the SDS development of fixated scrubber sludge.
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3.1.3 Natural Oxidation Some high-sulfur FGD systems naturally operate at a low sulfite oxidation levels. These systems produce a mixture of calcium sulfite hemihydrate (CaSO3•½H2O) and gypsum (CaSO4•2H2O) that varies in percentage by power plant. 3.1.4 Additives Additives may be used to increase the performance of the FGD system, mitigate the presence of foam in the process, or for mercury control. Data reviewed for the development of this document, which included the 1995 Electric Power Research Institute (EPRI) report, publically available literature, and submitted ACAA member company SDSs, did not identify additives at levels that would require disclosure or consideration in the FGD gypsum hazard classification. For completeness, information associated with those additives is summarized here. 3.1.4.1 Performance Additives Performance additives, used to enhance the level of alkalinity of the sorbent material may be used to supplement the oxidation process and thus increase wet FGD system performance. Although only used in a small number of facilities, the most common additives include adipic acid, dibasic acid and formate. Residual levels of these substances may be present in landfilled or stacked gypsum but based on their water solubility, they are readily washed from FGD filter cakes. Even if present in landfilled/stacked gypsum, based on their initial use level the substances, the additives are not likely be present at or above 0.1% in the FGD solid and therefore, would not require consideration in the hazard classification of the FGD gypsum, nor in any OSHA HCS 2012 communication requirements. Chlorides may be similarly used in wet FGD systems employing forced oxidation. Based on a use level of 5000 ppm, it is possible that the chloride (in the form of chloride salts, i.e., potassium chloride, sodium chloride or magnesium chloride) could be present in landfilled/stacked gypsum at levels up to 0.5%; the level in filter cakes would as with other soluble substances likely be lower in FGD filter cakes (Ladwig, 2015). As these inorganic chloride compounds would not contribute to the FGD gypsum classification until their level was minimally 1%, their presence does not need to be considered for hazard classification or SDS communication purposes. In an EPRI report on the effects of FGD system additives, these additives were not shown to significantly impact the FGD gypsum particle size distribution; further, these impurities would not be present at levels requiring the impurities to be considered in the FGD gypsum classification process or disclosured on the SDS. (EPRI, 1995) 3.1.4.2 Anti-foaming Agents Various anti-foaming agents were identified as being used in FGD systems. These anti-foaming agents include, but are not inclusive of Foamtrol AF3561, Nalco FM-37 and Foamcontrol 2290. Anti-foaming agents are typically used intermittently with a typical use level of 0.03g/L. As these anti-foaming agents are soluble, the process would result in most of the anti-foaming agent to be washed from the FGD gypsum. However, if the entire foam control agent became an impurity in the FGD gypsum, the maximum final concentration would be 0.02%. This level is below the threshold requiring consideration
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for classification or SDS communication obligations; therefore, anti-foaming agents need not be considered in the SDS development of FGD gypsum. If the use level of these anti-foaming agents is increased such that the agent could become ≥0.1% of the FGD gypsum, the hazards associated with the specific additive would need to be evaluated to assess any hazard classification or communication obligations. 3.1.4.3 Mercury Control Additives An activated carbon polish may also be added to the FGD process to mitigate mercury emissions from the flue gases. Based on the low use level in the process (<1%), the carbon residual in the finished product would not affect the final classification for the FGD product or require disclosure on the SDS. 3.2 DRY FGD SYSTEMS Dry FGD systems use a spray drying process that produces a dry FGD solid composed of a mixture of calcium sulfite hemihydrate, gypsum, calcium carbonate and ash that does not require dewatering. These systems do not produce FGD gypsum and are not further discussed in this document. 3.3 OTHER FGD SYSTEMS Other technologies for producing FGD solids include, but are not limited to, Lime Dual Alkali Process, Magnesium Promoted Lime, Seawater Process, Sodium Scrubbing Process, and Ammonia Scrubbing Process. As these technologies do not produce FGD gypsum, they will not be further evaluated here. 3.4 FGD SOLIDS Based on the prevalence of these FGD systems and the potential for beneficial use of each of the products, this guidance document focuses solely on FGD gypsum produced by wet FGD systems using limestone as the reagent material and incorporating forced oxidation. FGD solids produced using other systems identified herein are outside the scope of this guidance.
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4. FGD Gypsum Composition FGD gypsum is used primarily as a direct replacement for mined gypsum in manufactured products (e.g., wallboard), as an additive to cement and concrete or for agricultural applications. It is generally produced by wet FGD systems using limestone as the reagent and incorporating forced oxidization (Section 3.1.1). 4.1 GYPSUM IDENTIFICATION The FGD gypsum produced from the wet forced oxidation process is calcium sulfate dihydrate, (CaSO4•2H2O); Chemical Abstract Service (CAS) # 10101-41-4; calcium sulfate or calcium sulfate dihydrate are typically identified as the chemical name for gypsum. Calcium sulfate dihydrate (CaSO4•2H2O) has a CAS# of 10101-41-4 (EC# 600-148-1), with a
chemical name of sulfuric acid, calcium salt (1:1), dihydrate. Although the dihydrate is not directly listed as an existing substance on the Toxic Substances Control Act (TSCA) inventory, TSCA considers hydrates the same as the parent compound for listing purposes.2 The ECHA under the REACH Regulation (EC/1907/2006) evaluates hydrated substances similarly.
Calcium sulfate, anhydrous has a CAS # of 7778-18-9 (EC# 231-900-3) with a chemical identity under the TSCA of sulfuric acid, calcium salt (1:1); the substance is also present on the EU’s Chemical Inventory.
ChemIDplus (2015) also identifies gypsum as phosphogypsum with a CAS# 13397-24-5. This CAS number should not be used to represent gypsum produced using the FGD process as phosphogypsum is formed as a by-product of the production of fertilizer from phosphate rock.
Phosphogypsum has a propensity to be radioactive due to the presence of naturally occurring uranium and radium. The United States Environmental Protection Agency (U.S. EPA) has banned most applications of phosphogypsum with a radium-226 concentration of greater than 10 picocurie/grams. This level restricts its use in agricultural and construction purposes and as a result, phosphogypsum is most often stockpiled by the manufacturers as a waste byproduct (NTP, 2006).
For the purposes of this Guidance, the classifications and other communication requirements associated with gypsum under OSHA HCS 2012 were assessed using toxicological data on both calcium sulfate, anhydrous (CAS # 7778-18-9 and EC# 231-900-3) and calcium sulfate dihydrate (CAS# 10101-41-4 and EC# 600-148-1).3 4.1.1 Typical FGD Gypsum Composition FGD gypsum has a higher purity (85-99%) than most natural gypsum (80%) (Eurogypsum, 2007). Potential impurities in FGD gypsum include substances scrubbed from the flue gas or substances 2 The TSCA inventory represents substances present in U.S. 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 U.S. without Environmental Protection Agency (EPA) approval. Hydrates are considered to be listed if their parent compound is listed.
3 Based on the method of manufacture and the potential for phosphogypsum to be radioactive, neither phosphogypsum nor its CAS# 13397-24-5 were further evaluated to assess the classification or communication requirements associated with FGD gypsum.
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introduced from the reagent material (limestone) or additives. Analytical data available from ACAA member companies, EPRI, and other publically available data show the presence of trace elements below the minimum percentage required for disclosure on the SDS (0.1%).4 The level of each impurity was evaluated to assess the obligations associated with its potential presence in FGD gypsum. Using composition information provided by ACAA member companies, EPRI, and other publically available sources, the levels of calcium sulfate, calcium sulfate dihydrate and impurities that met the OSHA HCS 2012 thresholds were evaluated to generate the composition of a typical FGD gypsum in the context of this Guidance. The typical FGD gypsum composition is listed in Table 1. Calcium sulfate in FGD gypsum ( CaSO4•2H2O) contains chemically bound water hence the “dihydrate” identification. Should the analytical test results report calcium sulfate, as anhydrous, a molecular weight conversion factor should be used to determine and report calcium sulfate as dihydrate in the FGD gypsum. The substances listed in Table 1 do not represent a single FGD gypsum formulation nor should they be used to represent an individual ACAA member FGD gypsum composition without testing. The substance list is not meant to be exhaustive, nor does it restrict the levels of these substances or other substances at the identified levels. It is presented to provide information on the substances and their concentrations in a typical FGD gypsum. If an individual company’s FGD gypsum varies in either composition or component level, the hazard classifications assigned to a typical FGD gypsum, listed in Section 5.6, should be reevaluated as the classification(s) may not apply. Table 1: Substances Present In Typical FGD Gypsum1
Substance Percent Range in a Typical FGD Gypsum
Calcium sulfate, dihydrate 85-99% Calcium carbonate ≤ 8% Magnesium carbonate < 5% Crystalline silica2 ≤ 3% Respirable crystalline silica (RCS)2 < 2.5% Fly Ash3 ≤ 2%
Notes: 1 This composition assumes that the limestone used as a reagent in the FGD process is 95% CaCO3. If the purity of the limestone is below this level, the presence of additional insoluble substances in the FGD gypsum that may require disclosure must be evaluated. 2 The crystalline silica and RCS concentrations represent the total level that may be contributed by limestone or fly ash. For purposes of this evaluation, the various forms of crystalline silica (crystalline silica, cristobalite and quartz) were considered the same substance (silicon dioxide). For purposes of this document, silica may be noted as silica or silicon dioxide. 3 Fly ash is a UVCB (unknown or variable composition or biological) substance. It is defined by the U.S. 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.” Information from industry indicates that other elemental oxides, low levels of chlorides and ammonium salts may also be present based on analytical data and the use of pollution control additives. Low levels (<1%) of multiple elemental substances and oxides were identified in various analytical data on FGD gypsum. These substances are likely present from residual fly ash in the product.
4 Some substances may not require disclosure or consideration when developing the classification of the FGD gypsum until they meet or exceed 1% of the overall composition; 0.1% is noted as a conservative level. Each contaminant over 0.1% was reviewed individually to assess any obligations that may have been associated with that substance.
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4.1.1.1 FGD Gypsum Impurities Trace inorganic substances above 0.1% may be present in the FGD gypsum due to residual fly ash in the flue gases or from the limestone (CaCO3) used to generate the FGD gypsum. Examples of these substances include: aluminum, calcium, iron, potassium, magnesium and sodium (EPRI, 2011). Other substances that may be present at less than 0.1% were not considered for SDS disclosure or for their impact on the FGD gypsum hazard classification, consistent with OSHA HCS 2012 specifications. Most of the impurities identified during laboratory analyses are those previously identified as components of fly ash during the development of the ACAA CCP SDS Guidance Document (Haley and Aldrich, 2018). As fly ash is likely present in the FGD gypsum based on the production method (either unintentionally or as an additive), these trace inorganic substances are likely present as components of the residual fly ash. Hazardous substances that may be of concern in relation to air emissions or environmental exposures, such as arsenic or mercury, were not observed in any FGD gypsum samples at levels that would trigger hazard classification(s) or communication obligations as specified in OSHA HCS 2012 (EPRI, 2011). 4.1.1.2 Impurities Due to Additive Use Based on data from EPRI and ACAA member companies, none of the additives noted in Section 3.1.4, at their recommended use levels, would trigger additional hazard classifications or communication obligations per OSHA HCS 2012. 4.2 ANALYTICAL METHODOLOGY Although Section 4.1 provides general information on the composition of typical FGD gypsum, the composition of an individual manufacturer’s product must be assessed prior to determination of the hazard classification and subsequent SDS development for that product. Therefore, chemical analysis is required to determine a FGD gypsum’s composition. Analytical methodology that may be used to determine the chemical composition of FGD gypsum is provided in Appendix D (FGD Gypsum Analytical Methodologies). The methods provided therein are based on industry use and American Society for Testing and Materials (ASTM) 471M; they may be used to assess the composition, but are not required nor recommended by the ACAA. Upon obtaining the results of the FGD gypsum analysis, the composition should then be evaluated against the typical FGD gypsum composition presented in Table 1. If the composition includes only substances listed in Table 1 at or below the specified percentages, one of the OSHA HCS 2012 hazard classification(s) presented in Section 5.6, Table 6 will apply. If the analysis identifies additional impurities above 0.1% or identified impurities at or above the levels specified in Table 1, it is necessary to determine if the hazards associated with that FGD gypsum varies from those presented in this Guidance. 4.3 COMMON PITFALLS IN COMPOSITION DETERMINATION In assessing the FGD gypsum composition, it is important to correctly interpret the results of the chemical analyses performed. The material characteristics and the test method must be considered when interpreting the raw analytical data in order to provide proper context for the results
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Examples of substances that would not be present in the FGD gypsum, but may be reported based on the analytical methods performed include sulfur trioxide (gas) or sodium (elemental form is explosive in contact with air). Common substances that may be reported by the laboratory, but determined not to be present in the FGD composition based on their physical form or reactivity are listed in Table 2. It is therefore recommended that a chemist or material scientist familiar with the wet FGD process and the composition of FGD solids be consulted to evaluate analytical data and determine the appropriate FGD gypsum composition, including impurities, as the results may be reported in terms of substances that are not actually present in the product. For example, some methods do not distinguish between various sulfur compounds and simply report all detected sulfur as sulfur trioxide, which is a gas not found in solid CCPs. This and other examples of potentially misleading reporting conventions are presented in Table 2. These substances should not be directly used to determine the overall FGD gypsum hazard classification, but rather should be evaluated by a chemist or materials scientist familiar to assess the actual substances that may be present in the CCP. Table 2: Substances That May Be Identified In Raw Analytical Data That Should Not Be Considered As A Unique Component Of FGD Gypsum1
Substance Rationale
Calcium Based on the methodologies used to analyze gypsum, this substance may be identified as its elemental form. The substance; however, would be present as a component of CaSO4, 2H2O.
Calcium oxide Based on the methodologies used to analyze gypsum, this substance may be identified; however, it would react with sulfur trioxide to form CaSO4.2
Sulfur Based on the methodologies used to analyze gypsum, this substance may be identified as its elemental form. The substance; however, would be present as a component of CaSO4, 2H2O.
Sulfur trioxide Based on the methodologies used to analyze gypsum, this substance may be identified; however, it would react with calcium oxide to form CaSO4.
Chlorine This substance is a gas at standard temperature and pressure. If chlorine is present, it would be present as an ionic component of a salt.
Carbon dioxide This substance is a gas at standard temperature and pressure.
Silica
Based on the methodologies used to analyze gypsum, this substance may be identified as its elemental form; however; it is likely present as silicon dioxide (crystalline or amorphous). This substance may originate from the fly ash or limestone.3
Notes: 1 This list is not exhaustive. Using similar exclusion rationale, other substances, with similar properties should not be considered as present in the composition (e.g., gases would not be present as a component of the FGD gypsum). 2 Calcium oxide reacts with sulfur trioxide in the FGD system to create CaS04. Therefore, this substance should not be considered as present in the FGD gypsum. It should also not be disclosed separately on the SDS, nor should hazards associated with calcium oxide be considered in the FGD gypsum hazard classification.
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3 Common laboratory analyses may identify elemental silica or silicon dioxide. The silica would likely be present as silicon dioxide. As silicon dioxide in respirable crystalline form may result in additional hazard classifications of the FGD gypsum, it is listed in Table 1 requiring disclosure and further discussed in Section 5.2.
Other non-hazardous substances that may be identified during the compositional analyses of FGD gypsum due to residual fly ash are presented in Table 3. Based on the lack of hazards associated with these substances they do not require disclosure, nor consideration in evaluating the hazards associated with FGD gypsum. Table 3: Residual Fly Ash Components That May Be Identified In Laboratory Analyses That Do Not Require Disclosure On The SDS1
Substance Rationale
Aluminum oxide Common laboratory analyses may identify the elemental substance, or aluminum oxide. Likely present as an aluminosilicate, a component of fly ash.
Iron oxide Common laboratory analyses may identify the elemental substance or iron oxide. Likely present as iron oxide, a component of fly ash.
Sodium oxide Common laboratory analyses may identify the elemental substance or sodium oxide. Likely present as sodium oxide, a component of fly ash.
Potassium oxide Common laboratory analyses may identify the elemental substance or potassium oxide. Likely present as potassium oxide, a component of fly ash.
Magnesium oxide
Common laboratory analyses may identify the elemental substance or magnesium oxide. Likely present as magnesium oxide, a component of fly ash or dolomite, a component of limestone.
Note: 1 This list is not exhaustive. Using similar exclusion rationale, other substances that may be found in fly ash should not be considered as present in the composition.
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5. OSHA HCS 2012 FGD Gypsum Hazard Classification OSHA HCS 2012 aligns with the methodology set forth in the UN GHS Guideline, Revision 3 for the classification of physical and human health hazard categories of substances and mixtures (U.S. OSHA, 2012a,b).5 Hazard classes evaluated include: 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. It also includes additional hazard classes not derived from the GHS Guideline; these include: combustible dust, pyrophoric gases and simple asphyxiant classifications.6 Within each hazard class, a set of criteria has been established to classify the substance or mixtures into a specific hazard category (U.S. OSHA HCS, 2012b, Appendix A and B). Signal words, hazard statements, precautionary statements and pictograms are then assigned to the substance or mixture as required by OSHA HCS 2012 based on the assigned hazard categories. To assign a hazard classification per OSHA HCS 2012, data on the actual product (in this case the FGD gypsum) is first considered. The hazard classifications presented in this document are primarily based on data present on the ECHA Dissemination Portal for gypsum provided in the record for calcium sulfate.7 In addition, where applicable, the classifications of individual impurities were evaluated to assess if the presence of a particular impurity would alter the overall hazard classification. This section details the OSHA HCS 2012 hazard classification(s) for a typical FGD gypsum, as well as the hazard classifications that may apply to specific impurities which could alter the final FGD gypsum classification, if present. 5.1 DATA SUPPORTING THE HAZARD CLASSIFICATION OF FGD GYPSUM 5.1.1 EU REACH Dossiers The hazard classification(s) assigned to FGD gypsum followed OSHA HCS 2012 guidelines primarily using data provided by registrants of “calcium sulfate” under the EU’s REACH regulation as compiled in dossiers made available through the ECHA Dissemination Portal (ECHA, 2010a; ECHA, 2010b). Consideration was given to the reliability of that data. As hydrates are considered the same as parent compounds in terms of toxicity, information on both the anhydrous and hydrated form of calcium sulfate were used. Table 4 provides a summary of the human health data used to determine the FGD gypsum hazard classification(s), while Table 5 lists physical hazard classifications specified by registrants of calcium sulfate under the EU’s REACH regulation as compiled in dossiers and made available through the ECHA Dissemination Portal.
5 Environmental/ecological GHS classifications are not mandatory under OSHA HCS 2012 and do not need to be included in the SDS. Therefore, this guidance document does not include a review and classification of FGD gypsum with respect to environmental/ecological endpoints. 6 The pyrophoric gases and simple asphyxiant classifications do not apply to FGD based on its physical form. However, the combustible dust classification cannot be ruled out based on the product form. 7 The ECHA Dissemination Portal record for calcium sulfate includes test data for both calcium sulfate, anhydrous and calcium sulfate, dihydrate.
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Table 4: Toxicological Data/Hazard Classification for Calcium Sulfate a,b,c,d
Hazard Endpoint Calcium Sulfate, Dihydrate CAS# 10101-41-4
Calcium Sulfate, Anhydrous
CAS# 7778-18-9 Acute Oral Toxicity Acute oral LD50: > 2000 mg/kg.
Not classified No data
Acute Dermal Toxicity No data. Not classified
No data
Acute Inhalation Toxicity
Acute inhalation LC50: > 3.26 mg/L (Mass Median Aerodynamic Diameter (MMAD) for the product of 2.92 microns after a 4-hour, nose-only exposure to rats). Not classified
No data
Skin Corrosion / Irritation
No data Not irritating or corrosive to skin based on 4-hour, semi-occlusive exposure to rabbits. The average of the erythema and edema assessments for the 3 animals after 24, 48 and 72 hours was 0.2, 0.0 and 0.0, respectively. Not classified
Eye Damage / Irritation No data No positive responses in rabbits based upon 24, 48, and 72 hour mean scores for corneal opacity, iritis, or conjunctival redness/edema. Irritation cleared in 2/3 rabbits by 72 hours with 1/3 rabbits with minor conjunctival hyperemia remaining at 72 hours. Not classified
Skin Sensitization Not a dermal sensitizer. Not classified
No data
Germ Cell Mutagenicity Several in vitro and in vivo mutagenicity assays determined that calcium sulfate, dihydrate was non-mutagenic both with and without metabolic activation. Not classified
No data
Carcinogenicity Carcinogenic studies were not conducted with calcium sulfate on the basis of the non-neoplastic effects noted in the oral repeated dose study as well as the negative mutagenicity assays. Not classified
No data
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Hazard Endpoint Calcium Sulfate, Dihydrate CAS# 10101-41-4
Calcium Sulfate, Anhydrous
CAS# 7778-18-9
Reproductive Toxicity No statistically significant or dose-response effects in the parental animals or their litters based on a reproduction / developmental toxicity screening test. The NOAEL (No Observed Adverse Effect Level) for reproduction and development was 1000 mg/kg body weight (highest dose tested). Not classified
A developmental toxicity study conducted in mice, rats and rabbits with calcium sulfate, anhydrous, did not report maternal or fetal effects up to highest dose tested (1600 mg/kg bodyweight). Not classified
Specific Target Organ Toxicity: Single Exposure (STOT-SE)
Acute toxicity testing did not result in direct organ toxicity after a single exposure. Not classified
No data
Specific Target Organ Toxicity: Repeated Exposure (STOT-RE)
A repeat dose oral toxicity study (35-45 days) with calcium sulfate, dihydrate conducted using rats reported a NOAEL for males of 100 mg/kg/day on the basis of decreased total protein, albumin, blood urea nitrogen, and creatinine levels observed at the 300 and 1,000 mg/kg/day dose groups. No effects were observed in females. Not classified
No data
Aspiration Hazard Not applicable Not applicable
Combustible Dust No data No data
Hazard Classification for Calcium sulfate and calcium sulfate dihydrate
NOT CLASSIFIED NOT CLASSIFIED
Notes: a This table evaluates hazards associated with calcium sulfate and calcium sulfate, dihydrate. These classifications do not take into considerations of impurities that may impart a hazard to the final FGD gypsum. The final hazards and classifications associated with a typical FGD gypsum (as defined in Table 1) are presented in Table 6. b A non-classification under OSHA HCS 2012 is applied when: 1) the available data does not result in a classification, 2) the classification does not apply based on identified properties of the substance, or 3) if there is insufficient data to apply the classification. c Data for all endpoints listed in Table 4 except for Combustible dust was sourced from the ECHA REACH Registration Dossier for calcium sulfate. http://apps.echa.europa.eu/registered/data/dossiers/DISS-9ebe5c1d-2d61-3cd3-e044-00144f67d031/DISS-9ebe5c1d-2d61-3cd3-e044-00144f67d031_DISS-9ebe5c1d-2d61-3cd3-e044-00144f67d031.html. d Neither the exact composition, nor the level of respirable crystalline silica in the tested products was provided. It was further not possible to determine if the registrants considered that information.
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Table 5: Physical Hazard Classification Of Calcium Sulfatea,b
GHS Endpoint/Classification Calcium Sulfate, Dihydrate CAS# 10101-41-4
Calcium Sulfate, Anhydrous
CAS# 7778-18-9
Explosivity Not classified Not classified
Flammable Solids Not classified Not classified
Oxidizing Solids Not classified Not classified
Self-Reactive Chemicals Not classified Not classified
Self-Heating Chemicals Not classified Not classified
Pyrophoric Solids Not classified Not classified
Chemicals Which in Contact with Water, Emit Flammable Gases Not classified Not classified
Organic Peroxides Not classified Not classified
Corrosive to Metals Not classified Not classified
Notes: a A non-classification under OSHA HCS 2012 is applied when: 1) the available data does not result in a classification, 2) the classification does not apply based on identified properties of the substance, or 3) if there is insufficient data to apply the classification. b Information in Table 5 can be found in the ECHA REACH Registration Dossier for calcium sulfate. http://apps.echa.europa.eu/registered/data/dossiers/DISS-9ebe5c1d-2d61-3cd3-e044-00144f67d031/DISS-9ebe5c1d-2d61-3cd3-e044-00144f67d031_DISS-9ebe5c1d-2d61-3cd3-e044-00144f67d031.html.
5.1.2 Other Supporting Data 5.1.2.1 National Toxicology Program Review Additional information on the short-term and chronic health effects of exposures to synthetic and naturally mined gypsum in humans and animals was evaluated in a chemical and toxicological information review document prepared for the National Toxicology Program (NTP, 2006). Although epidemiological studies of FGD gypsum were not identified, due to the product similarities between natural and FGD gypsum, studies of gypsum miners were reviewed. In the studies, chronic exposure to gypsum did not correlate with pneumoconiosis. In a study of underground male workers employed in gypsum mines, observed lung shadows were associated with the higher quartz content in dust rather than to gypsum as the small round opacities noted in the lungs are more characteristic of respirable crystalline silica exposures. Short-term and subchronic inhalation studies with male rats exposed to calcium sulfate fiber aerosols for six hours per day, five days per week for three weeks found non-pathological local effects due to physical factors related to the shape of the gypsum fibers and not to calcium sulfate itself. In a chronic inhalation study in guinea pigs, only minor effects in the lungs were observed with no significant gross signs of pulmonary disease or nodular or diffuse pneumoconiosis when treated with calcined gypsum.
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In carcinogenicity studies, various forms of gypsum were weakly tumorigenic. Rats given intraperitoneal injections of natural anhydrite dusts induced abdominal cavity tumors, carcinomas of the heart and kidney were observed in hamsters after intratracheal doses of calcium sulfate fibers and inhalation of gypsum for 24 months produced no lung tumors in guinea pigs. However, NTP concluded that none of these long term studies were considered adequate since the test methodologies, species, and exposure routes utilized did not represent current standards and protocols for the conduct of chronic / carcinogenicity studies. Based on the gypsum worker exposure studies demonstrating that lung effects were more related to respirable crystalline silica exposures than gypsum and the limited applicability of other chronic exposure studies in animals, the focus of long-term effects of gypsum in this Guidance will be on the presence of crystalline silica and its respirable form as a result of the FGD gypsum processes and reagents as further detailed in Section 5.2. 5.1.2.2 United Nations Economic Programme (UNEP) Screening Information Data Set (SIDS) Initial
Assessment Report: Calcium sulfate, dihydrate SIDS Initial Assessment Reports (SIAR) are completed as a voluntary cooperative international testing program under the Organization for Economic Cooperation and Development (OECD). SIARs provide a review and summary of available toxicological studies to support human health and environmental assessments with recommendations on additional work or studies that might be useful to further evaluate a substance’s toxicological profile. A SIAR on calcium sulfate, dihydrate that included a comprehensive summary of toxicological studies on acute and long-term effects to human health after exposure to calcium sulfate, dihydrate was identified (UNEP, 2003). Most of the studies evaluated in the SIAR are identical to those identified in Table 4. One additional study on primary skin irritation was included. This study showed no irritation to the skin of rabbits at 1, 24, 48 and 72 hours after a 4-hour exposure to calcium sulfate, dihydrate. The SIAR presents similar results as those reported from the ECHA Dissemination Portal for calcium sulfate and calcium sulfate, dihydrate (Table 4); specifically, calcium sulfate, dihydrate was not orally toxic, not irritating to skin, and not a dermal sensitizer. The NOAEL in an oral repeated dose study was found to be 100 mg/kg/day in male rats based on some effects on the kidney; no effects in females were observed at the highest dose tested in the same study. No developmental or reproductive effects were noted at the highest dose tested in a reproduction/developmental toxicity screening test in rats. Calcium sulfate, dihydrate was not mutagenic in in vitro and in vivo mutagenicity studies. Like both the REACH registration data included and information identified in the review by the NTP, the SIAR also indicates that calcium sulfate, dihydrate is not expected to be carcinogenic based on negative mutagenicity data and limited data indicating the potential for any tumorigenic or carcinogenic effects from long-term exposures. The SIAR concluded that any further work required for calcium sulfate, dihydrate is of low priority due to its low hazard profile (UNEP, 2003). 5.1.3 Conclusion Taking into consideration the test data on calcium sulfate, anhydrous and calcium sulfate, dihydrate and considering that FGD gypsum may exist as a dust, especially during processing and handling, a
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mechanical irritation of the respiratory tract may occur. Therefore, a conservative hazard classification for gypsum (CaSO4, 2H2O) for Specific Toxic Organ Toxicity-Single Exposure (STOT-SE), Category 3 (respiratory irritation) is applied as there is a potential for the generation of airborne particulates during handling and use. Prior to assigning a final hazard classification to the typical FGD gypsum composition identified in Table 1, Section 4.1.3, the hazards of identified impurities listed in that table were also considered. The final FGD gypsum classification is therefore based on the test data presented in Section 5.1.1, Tables 3 and 4, and Section 5.1.2 as well as the hazard classifications of the identified impurities. The impact of impurities on the overall FGD gypsum hazard classification is discussed further in the following sections with the FINAL OSHA HCS 2012 FGD gypsum hazard classifications provided in Section 5.6. 5.2 SILICA FGD gypsum may contain both amorphous and crystalline forms of silica. The term “crystalline” refers to the ordered arrangement of silicon and oxygen atoms in the silicon dioxide (SiO2) molecules in a fixed pattern, compared to the disordered and random molecular arrangement defined as amorphous silica. 5.2.1 Amorphous Silica and Aluminosilicates Amorphous silica and the aluminosilicates have not been linked to significant health effects. No specific hazard classifications associated with the chemical nature of these substances is attributable to the FGD. It is recognized however that the presence of these substances in a FGD dust may contribute to a transient respiratory irritation classification of FGD assigned herein as a Single Exposure – Specific Target Organ Toxicity, Category 3 (Respiratory Irritation). 5.2.2 Crystalline Silica This section serves to provide information related to: (1) the presence of crystalline silica and respirable crystalline silica (RCS) in FGD, (2) health effects data, both epidemiological and animal associated with exposure to RCS, (3) recent regulatory rulings as they affect the data interpretation and (4) the implications for the hazard classification of FGD containing RCS, per OSHA HCS 2012. 5.2.2.1 Presence of Crystalline Silica and RCS in FGD
Crystalline silica may be present in the limestone, which serves as a primary reactant in the development of FGD gypsum, and in the fly ash added during the flue gas desulfurization process. The amount of free crystalline silica available from the fly ash is dependent 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, 2006). The National Institute for Occupational Safety and Health (NIOSH) defines 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)
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The theoretical maximum concentration of RCS in the FGD gypsum is 2.1% based on the levels of RCS that may be present in both the limestone and fly ash components, in conjunction with available particulate size data. 5.2.2.2 Limestone Component Based on available data from industry, limestone may contain up to 2% crystalline silica (total). As insufficient data is available on the respirable percent of the crystalline silica in the limestone, the crystalline silica in the FGD gypsum from the limestone was conservatively estimated to be composed entirely of RCS. Therefore, as much as 2% of the FGD gypsum may consist of RCS contributed by the limestone. 5.2.2.3 Fly Ash Component Fly ash may be present in the FGD gypsum at levels up to 2% based on available data. Using data from the ACAA SDS Guidance for CCPs, crystalline silica may be present at up to 36% in fly ash (Haley & Aldrich, 2018). Therefore, up to 0.72% crystalline silica may be present in the FGD Gypsum from the fly ash. This same document also states that no more than 10% of the crystalline silica in fly ash would be respirable. Therefore, the maximum level of RCS that would be contributed to the FGD gypsum from the fly ash would be 0.1%. 5.2.2.4 Particle Size The size of the FGD gypsum particulates, specifically respirable particles, may affect the hazard classification of the FGD gypsum. A review of publically available data on FGD particulate size provides the following information: An U.S. Gypsum Corporation guideline notes that the minimum median particle size for FGD
gypsum for use in their applications is 20 µm (microns) (U.S. Gypsum, undated). Further, in an EPRI study evaluating the effects of various additives on FGD gypsum, both the mean particle size as well as minimal particle size was reported. Mean particle sizes ranged from 8.7 µm - 35 µm (n=14), with all but one sample having a mean value of >10 µm. The minimum particle size; however, across these same samples was 1.5 µm – 12 µm, with all but one minimum value being in the respirable range (EPRI, 1995).
As no characterization of the respirable particulates was conducted using Scanning Electron Microscopy (SEM) or other techniques, it is not possible to discern the level of RCS in the respirable particulates.
5.2.2.5 Health Effects The health effects associated with crystalline silica have been linked to the fraction of free airborne crystalline silica that when inhaled can penetrate the nose and upper respiratory tract and deposit into the deep tissues of the lung. These effects have been studied extensively for over twenty years in both in vitro and in vivo animal models as well as in epidemiological occupational studies on 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.
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Recent reviews sponsored by the Industrial Minerals Association (IMA)-Europe (Morfeld, 2010), EPRI (EPRI, 2006a), the American Chemistry Council (ACC, 2014), and the new OSHA Final Rule for RCS (OSHA, 2016) were used as the primary sources for assessing the health effects of RCS that may be present in FGD. These reviews contain the most up to date information and utilize current risk assessment methodologies. It is noted; however, that OSHA’s assessment of the toxicological effects of RCS did not result in the same conclusions of the IMA (Morfeld, 2010), the ACC (ACC, 2014) or EPRI (EPRI, 2006a) even though the same (or similar) data was reviewed. 5.2.2.5.1. Silicosis For many years, the prolonged inhalation of fine dust containing RCS has been recognized as a causative agent of silicosis (IMA, 2014a). Silicosis is defined by fibrotic changes (scarring) that affect the ability of the lung to exchange gases (MSHA, 2008). In terms of OSHA HCS 2012, substances or mixtures resulting in silicosis would be classified for Repeat Dose Toxicity – Specific Target Organ Toxicity (Lungs) when the level of RCS exceeds the threshold for this classification of 1%. Silicosis has primarily been observed in workers from industries where significant exposure to RCS occurs 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 have been noted to be insufficient to cause this disease. Silicosis is therefore considered to be an occupational disease. Epidemiological and animal studies have shown clear a positive dose-response relationship between occupational 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. Researchers have concluded that no other non-malignant health effect is as specific and so clearly linked to RCS as silicosis (Morfeld, 2010). It is important to note; however, that the United States has shown a decline of more than 90% in the overall silicosis mortality rate from 1968-2010 resulting with death rates decreasing from 1,065 in 1968 to 101 in 2010 (ACC, 2014). CDC has suggested that many of the deaths attributed to RCS in the early years occurred prior to the implementation of the first permissible exposure limits for RCS established by OSHA in the early 1970s (ACC, 2014).8 This indicates that low levels of RCS do not result in silicosis and the current worker exposure levels are protective (ACC, 2014). Furthermore, silicosis typically appears only among workers exposed to levels of RCS above the current OSHA Permissible Exposure Limit (PEL) for RCS of 100 ug/m3 for extended periods of time. In its 2014 review, the ACC provided summaries of data that show crystalline silica exposures in excess of OSHA’s existing PEL are averaging around 30% or more each year (ACC, 2014). This led Dr. Peter Morfeld to conclude that these significant overexposures are likely, “the driving cause of cases of silicosis, lung cancer, and other silica-related diseases reported in registries, screening programs and epidemiological studies and presumably is the reason why silicosis has not yet been eliminated from American workplace (ACC, 2014).” EPRI cites the American Conference of Governmental Industrial Hygienists
8 The original OSHA PELs for crystalline silica were established based on the form of the crystalline silica, with the TWA for total quartz of 30 ÷ (%SiO2+2) mg/m3, and a PEL for RCS of 10 ÷ (%SiO2+2) ) mg/m3.
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(ACGIH) 2004 report on crystalline silica in which the ACGIH acknowledges that workers protected at the 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).9 5.2.2.5.2. Carcinogenicity The most controversial endpoint related to RCS exposure is the potential cancer risk due to airborne exposures. In 1997, the International Agency for Research on Cancer (IARC) classified RCS dust in the form of quartz or cristobalite as a Group 1 Human Carcinogen (carcinogenic to humans). The expert Working Group 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)." (IARC, 1997; EPRI 2006a) Following the IARC classification, the U.S. National Toxicology Program (NTP) also classified RCS as known to be a human carcinogen in the Ninth Report on Carcinogens in 2000 citing “sufficient evidence of carcinogenicity from studies in humans indicating a causal relationship between exposure to RCS and increased lung cancer rates in workers exposed to crystalline silica.” (NTP, 2016). The ACGIH listed RCS silica as a suspected human carcinogen in 2000, lowering the prior TLV to 50 ug/m3. In 2006, ACGIH further lowered the TLV for total crystalline silica to 25 ug/m3 (OSHA, 2016). EPRI (2006a) generated a summary of mechanistic studies evaluated after the IARC 1997 classification of RCS that observed that crystalline silica is not directly genotoxic. 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). Evidence for this mode of action is supported by the negative mutagenicity studies included in the REACH registration dossiers on gypsum (Table 4) and fly ash (that may have contained RCS)(Haley & Aldrich, 2018). Epidemiological data further indicate that the carcinogenic effects associated with occupational RCS exposures are limited to the lung with no evidence of significant causality of other cancers. It is also important to note that the only animal species to produce lung tumors in response to RCS was the rat; no carcinogenic effects were seen in mice, hamsters or guinea pigs, which has led some researchers to conclude that the response in the rat is specific to that species (EPRI, 2006a). After the IARC and NTP carcinogencity classification, several additional studies of lung cancer in RCS workers have been published, with additional reviews of existing animal toxicology and epidemiology data in human workers exposed to RCS conducted by various researchers and organizations. These more recent studies reflect updates from supplementary follow-up, data from nested case-control studies of previously assessed cohorts, or new results based on refined exposure assessments or adjustment for confounders. The conclusions from these more recent studies have called into question the validity of the carcinogenic risk of RCS from occupational exposures (EPRI, 2006a; ACC, 2014).
9 A recent OSHA ruling lowered the PEL for crystalline silica to 0.05 mg/m3 (OSHA 2017). ACGIH recently reduced their TLV for RCS to 0.025 mg/m3.
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In 2009, IARC established a new Working Group of 27 scientists from eight countries to conduct an additional review of the available scientific literature; this group reaffirmed the original classification of RCS dust as a Group 1 Human Carcinogen (IARC, 2012). This reassessment focused on quantitative exposure data from occupational exposures as well as a summary of findings from eight published meta-analyses reports of lung cancer. A member of the 2009 Working Group further analyzed the IARC database as well as additional studies on RCS (Gamble, 2011). Gamble found that the association between RCS and carcinogenicity was consistently weak in the majority of studies and showed a lack of exposure response trends. He concluded that the “weight of evidence from occupational epidemiology does not support a causal association of lung cancer and silica exposure, which is contrary to the IARC conclusion using essentially the same data (Gamble, 2014). The ACC provided a review and summary of the epidemiological studies associated with crystalline silica with input from various experts and concluded that: “the hypothesis that crystalline silica exposure is causally associated with increased risk of lung cancer was – and has remained – controversial and unsettled. Epidemiological studies have been negative as often as they have been positive; exposure response trends have generally been absent even in the studies that appeared to be positive; and the effects of confounding factors such as smoking or other occupational exposures and/or the necessity of a mediating silicotic response cannot be ruled out where increased risks have been found.” (ACC, 2014) Environment Canada and Health Canada concluded the following in a recent assessment of potential health risks associated with exposure to quartz and cristobalite, “At this time, within the epidemiology literature there is debate on whether human workplace exposure to silica which does not cause silicosis can be associated with lung cancer… Thus, the question of whether silica exposure, in the absence of silicotic response, results in lung tumours remains unanswered.” (Environment Canada, 2013). Morfelds’ review identified lifestyle factors (especially smoking) and socioeconomic status as confounding factors in the excessive lung cancer risk and mortality patterns associated with worker exposure studies of RCS (Morfeld, 2010). He also recognized that lung cancer risks were observed only under high occupational exposure conditions. These observations, based on studies published in recent years, led EPRI to 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) 5.2.2.5.3. Relationship between Silicosis and Lung Cancer The relationship between silicosis and lung cancer is complex, as most studies have depended on cohorts of compensated workers with silicosis (silicotics) leading to a positive bias in results and conclusions. Recent literature provides evidence supporting this 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 the primary effect resulting from significant exposure to RCS and that it is a consequence of inflammation in the lung. Although excess cancer risks are observed in silicotics, the mechanistic role of silicosis in the development of lung cancer is not clear; additional data is necessary for an exact determination. ACC indicates in their review that studies, “supporting an association between silicosis and increased lung cancer risk (while not conclusive) are far more compelling than the mixed and inconclusive results of studies evaluating the association of silica
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exposure and lung cancer risk in the absence of silicosis or where silicosis status was unknown.” (ACC, 2014) Independently, Morfeld concluded that minimizing the risk of silicosis will also mitigate the lung cancer risk due to RCS (Morfeld, 2010). 5.2.2.6 Recent OSHA Ruling on RCS For purposes of this document, it is imperative to look not only to scientific documentation and technical interpretations of the available data, but to regulatory rule making and the associated requirements. The recent OSHA Final Silica Rule must be considered in the assignment of hazards to FGD gypsum and information provided in the associated SDS and labels per OSHA HCS 2012. OSHA promulgated the Final Rule for Occupational Exposure to Respirable Crystalline Silica (RCS) (Final Rule) on March 25, 2016 (Federal Register Volume 81, No. 58, Pages 16285-16890). The Final Rule was based on OSHA’s review and risk assessment of the health effects associated with exposure to RCS that determined that employees exposed to RCS at the previous PEL are at increased risk of developing silicosis and lung cancer. As a result, the Final Rule establishes a new PEL of 50 micrograms of RCS per cubic meter of air (50 ug/m3) as an 8-hour time-weighted average. In addition, the Final Rule includes other provisions to protect employees such as requirements for exposure assessment, methods for controlling exposure, respiratory protection, medical surveillance, hazard communication, and recordkeeping (OSHA, 2016). To support this change, OSHA conducted an extensive search and review of the peer-revised scientific literature on the health effects of inhalation exposure to crystalline silica. OSHA also assessed exposure-response data from epidemiological studies to estimate quantitative risks for lung cancer and silicosis mortality. A draft document outlining OSHA’s findings on the health effects and the resulting quantititative risk assessment was submitted to a panel of scientific experts for independent peer review and subsequently opened for public comment. OSHA concluded in its Draft Rule for Occupational Exposure to Respirable Crystalline Silica (Draft Rule) that exposure to RCS causes silicosis and is the only known cause of silicosis. For the lung cancer endpoint, OSHA reviewed 60 epidemiological studies covering more than 30 occupational groups and concluded that the data provided evidence that exposure to RCS increases the risk of lung cancer among workers, consistent with the IARC Group 1 Human Carcinogen classification (OSHA, 2016). OSHA concluded that RCS is an independent risk for lung cancer mortality and that silicosis is not a necessary precursor to lung cancer (OSHA, 2016). OSHA received both supportive and critical comments and testimony regarding their findings and the proposed draft rule. In its evaluation of submitted comments, OSHA indicated that the peer reviewers found that OSHA was reasonable in its interpretation of the studies and the health effects conclusions were generally well founded (OSHA, 2016). OSHA “believes that the external, independent peer-review process supports and lends legitimacy to its risk assessment methods and findings.” Stakeholders such as the American Public Health Association (APHA) and the National Consumers League (NCL) commented, “OSHA has thoroughly reviewed and evaluated the peer-reviewed literature on the health effects associated with exposure to respirable crystalline silica. OSHA’s quantitative risk assessment is sound.” Dr. Mirer, one of OSHA’s expert peer reviewers who served on several National Academy of Sciences committees setting risk assessment guidelines, further concluded that OSHA’s risk analysis is “scientifically correct, and consistent with the latest thinking on risk assessment.” (OSHA, 2016).
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Other stakeholders such as the American Chemistry Council (ACC) provided extensive comments and criticisms regarding the epidemiological studies used to support the risks and causality associated with RCS, lung cancer, and silicosis. In addition, ACC asserted that the methodology used to determine the risk assessment numbers were invalid as the uncertainty and confounding factors applied to the study results were not appropriately accounted for. The OSHA Final Rule incorporates responses and comments to the Draft Rule, OSHA’s final conclusion on the health effects of RCS and updated PELs. After its review of stakeholder comments, OSHA indicated that it “…did not find them adequate to alter OSHA’s overall conclusions of health risk…OSHA believes that the external, independent peer-review process supports and lends legitimacy to its risk assessment methods and findings.” (OSHA, 2016) In the Final Rule OSHA states that, “Multiple organizations with great expertise in this area, including the American Cancer Society, submitted comments supporting the thorough and authoritative nature of IARC’s findings regarding silica’s carcinogenicity (e.g., Document ID 1171; 1878). OSHA places great weight on the IARC and NTP classifications and, based on their findings, concludes that the carcinogenic nature of crystalline silica dust has been well established.” Relative to the updated PELs, OSHA concludes “...that long-term exposure at and above the previous PELs would pose a significant risk to workers’ health, and that adoption of the new PEL and other provisions of the final rule will substantially reduce this risk.” (OSHA, 2016) 5.2.2.7 RCS Carcinogenicity Classification: Implications on FGD Hazard Classification The reviews and hazard assessments of the health effects of RCS as summarized in section 5.2.2.5 indicate that researchers and regulators agree that RCS may causes systemic target organ toxicity after repeated exposures (STOT-RE) in humans in the form of silicosis and that it should be classified as a STOT-RE Category 1 (Lungs) based on the potential silocotic effects. The identification of RCS as a carcinogen; however, varies from not classified to the most severe classification, Carcinogen Category 1A per OSHA HCS 2012 criteria (Gradient, 2015a). As the levels of RCS in the FGD gypsum evaluated in support of European Union REACH registration and summarized in Section 5.1 were not disclosed, RCS may have been present in the test samples at levels below 0.1%. As a result, this data cannot be used to negate the required carcinogenicity classification of the FGD gypsum based on the potential presence RCS (a Carcinogen Category 1A) as an impurity. On the basis of OSHA’s classification, and the lack of information on the levels of RCS present in the FGD gypsum test data, FGD gypsum that contains RCS at or above 0.1%, must be classified as a Carcinogen category 1A per 29 CFR 1910.1200. Therefore, the STOT RE and Carcinogenicity classification of FGD gypsum under HCS 2012 is driven by the level of RCS present10 as follows:
Not classified, when the RCS concentrations is below 0.1%;
10 It has 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
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Carcinogen Category 1A, when the RCS concentrations is greater than or equal to 0.1 and less than 1%; or
Carcinogen Category 1A and STOT RE Category 1, when the RCS concentration is greater than or equal to 1%.
5.3 CALCIUM CARBONATE Calcium carbonate is not considered hazardous under OSHA HCS 2012. Therefore, it does not require consideration in the FGD gypsum hazard classification. 5.4 MAGNESIUM CARBONATE Magnesium carbonate is not considered hazardous under OSHA HCS 2012. Therefore, it does not require consideration in the FGD gypsum hazard classification. 5.5 FLY ASH Fly ash may be included as an impurity in the FGD gypsum. It is defined as a Substance of Unknown or Variable Composition or Biological (UVCB). The ACAA CCP SDS Guidance Document assigned multiple potential classifications to fly ash, with all fly ash formulations deemed to be a STOT-SE, Category 3 (Respiratory Irritant) primarily based on its form as a dust (Haley & Aldrich, 2018).11 5.5.1 RCS RCS present in a mixture is subject to a hazard classification of STOT-RE, Category 1 and Carcinogen Category 1A. Further details on hazards associated with RCS can be found in Section 5.2. 5.5.2 Calcium Oxide Toxicological data on calcium oxide support its classification under OSHA HCS 2012 as a Skin Irritant, Category 2 and an Eye Irritant, Category 1. The threshold for disclosure and consideration for these classifications is 1%. As the maximum level of fly ash in the typical FGD gypsum is 2% and the maximum level of calcium oxide in a typical fly ash was shown to be ≤41%, the level of calcium oxide in the FGD gypsum would be ≤0.8%. Therefore, calcium oxide would not impact the FGD gypsum SDS or hazard classification when a typical fly ash is added at or below 2%. If however, fly ash is added at levels of 2.5% or greater, or if the level of CaO in the fly ash included is >41%, the calcium oxide level in the FGD gypsum will need to be determined. If the level of CaO exceeds 1%, it would need to be disclosed on the SDS and the final FGD gypsum hazard classification will require reevaluation.
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. 11 Other fly ash hazard classifications may have been assigned to fly ash in the ACAA CCP SDS Guidance document; however, these were based on individual component levels in the ash. Any classifications resulting from unique fly ash components and their potential impact on the overall FGD gypsum classification are detailed in section 5.51, 5.52, and 5.53.
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5.5.3 Bromide Substances Bromide salts may be used as an additive in the coal combustion process and be present in fly ash at up to 2%.Various bromide salts have been classified as Reproductive Toxicants, Category 1. The threshold for disclosure and consideration for this classification is 0.1%. As the maximum level of fly ash in the typical FGD gypsum is 2% and the maximum level of bromide substances in a typical fly ash was shown to be < 2.1%, the level of bromide substances in the FGD gypsum would be no more than 0.04%. Since this level is below the identified threshold for consideration in determining the final FGD gypsum classification, the presence of bromide substances was deemed not relevant.12 5.6 FINAL FGD HAZARD CLASSIFICATION Following the classification process specified in OSHA HCS, 2012, multiple hazard classifications for the typical FGD gypsum (Table 1) were identified as potentially applicable, based on the level of the various impurities. The various classifications that may be applicable are detailed below along with the rationale for applying those classifications: Specific Target Organ Toxicity – Single Exposure (STOT-SE), Category 3 (Respiratory Irritation)
Due to the potential for FGD gypsum to form a dust and become airborne during handling and use, it is recommended that FGD gypsum be classified as a STOT-SE, Category 3 (Respiratory Irritation).
Specific Target Organ Toxicity – Repeat Exposure (STOT-RE), Category 1
This classification is applied when the level of respirable crystalline silica has not been determined or when the respirable crystalline silica is present at levels greater than or equal to 1%.
Carcinogen – Category 1A
This classification is applied when the level of respirable crystalline silica has not been determined or when the respirable crystalline silica is present at levels greater than or equal to 0.1%.
Table 6 summarizes the different hazard classifications that may be applicable to a typical FGD gypsum based on test data on calcium sulfate and calcium sulfate, dihydrate and the level of respirable crystalline silica that may be present. Table 6: Hazard Classifications Associated With FGD Gypsum Compositions1
FGD Gypsum Classifications Compositional Specifications
Composition 1 STOT-SE Category 3 (Respiratory Irritation) STOT-RE Category 1
(Lungs) Carcinogen Category 1A
FGD gypsum with: Respirable crystalline silica: undetermined or ≥1%2
12 Should chemical analyses of the FGD gypsum identify bromide substances at >0.1%, these substances should be disclosed on the SDS and the final FGD gypsum hazard classification(s) be reevaluated.
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FGD Gypsum Classifications Compositional Specifications
Composition 2 STOT-SE Category 3 (Respiratory Irritation)
FGD gypsum with: Respirable crystalline silica: <0.1%
Composition 3 STOT-SE Category 3 (Respiratory Irritation) Carcinogen Category 1A
FGD gypsum with: Respirable crystalline silica: ≥0.1 to <1%2
Notes: 1 These classifications only apply to FGD Gypsum formulations that meet the composition specifications summarized in Table 1. Should an individual company’s composition have additional substances present, or have substance(s) above the maximum percentage identified in Table 1, an evaluation of those differences should be assessed to determine if the noted classification(s) would still apply. 2 The maximum level of RCS identified as potentially present in the FGD gypsum was 3% (see Table 1).
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6. SDS Development The information prescribed by OSHA to develop and generate a SDS for the FGD gypsum was based on OSHA HCS 2012 (29CFR 1910.1200) and associated guidance from OSHA (OSHA 2012a, OSHA 2012b, OSHA 2012c, OSHA 2012d, OSHA 2012e, OSHA 2012f, OSHA undated a, and OSHA undated b). The data included is applicable to the development of SDSs for FGD gypsum compositions that conform to the typical composition as summarized in Section 4.1.1, Table 1. The hazard classifications associated with variations from the typical composition are summarized in Section 5.6 Table 6. Recommendations presented here may not be applicable to FGD gypsum with a lower purity (<85%) or with impurities that differ in impurities or identified impurity levels. 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 OSHA HCS 2012. ANSI Standard Z400.1 provides recommendations on SDS format that can be used to meet the requirements of OSHA HCS 2012. The ANSI standard recommendations are used throughout this Guidance to generate the FGD gypsum 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; and
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.
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6.2 SDS SECTION-BY-SECTION COMMENTS This portion of the Guidance is partitioned into individual sections required for inclusion in a OSHA HCS 2012 compliant SDS. Under each section (and some subsections) the following information is provided: The purpose of the section;
Required/recommended text; and
Example text. The information recommended or required for inclusion in the SDS, based on the OSHA HCS 2012 hazard classification and other properties of the FGD gypsum, as well as OSHA guidance 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
• 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 the substance, all names should be listed.
Note: Per OSHA HCS 2012, the identifier used on the SDS should be the same as that on the product label.
• Example text: Product Name(s): Apex Gypsum Product Code(s): 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 FGD gypsum, 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”.
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• Example text: Relevant/identified uses: Component of building products such as drywall, cement additives and plaster, as a set retardant and grinding aid in cement, or as an agricultural additive. Uses advised against: None known
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 Gypsum 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: 1-800-555-5555 (SDS Emergency Response Support) Hours Available: 24 hours a day, 7 days per week Note: The emergency phone number and availability indicated here should not be copied directly into the SDS. This information should be based on individual company practice and contractual relationships.
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 are specified in 29 CFR 1910.1200, Appendices A and B. Arrange this section with following subheadings:
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2.1 Classification of the substance (or mixture) Purpose: Section 2.1 lists the product classification per 29 CFR 1910.1200, Appendices A and B.
• Recommended/required text/information Include the appropriate hazard classification(s) for each health and physical hazard based on available data on the substance or its impurities, following specifications of Appendices A & B of HCS 2012 .
• Example text:
Hazard classification(s) according to 29 CFR 1910.1200) may include: - STOT-SE Category 3 (Respiratory Irritation);
STOT-RE Category 1 (Lungs); and Carcinogen Category 1A or
- STOT-SE Category 3 (Respiratory Irritation); and Carcinogen Category 1A or
- STOT-SE Category 3 (Respiratory Irritation)
Note: These hazard classifications are those associated with the typical FGD Gypsum as identified in the SDS Guidance. Insert the classification applicable to your specific product based on the product composition using Table 1 in Section 4.1.1 and Table 6 in Section 5.6.
2.2 Label elements
• Recommended/required text The appropriate hazard pictograms, signal word, hazard statements, and precautionary statements should be provided as specified in 29 CFR 1910.1200(f) and defined in 29 CFR 1910.1200, Appendix C.
• Example text:
Include information appropriate for the FGD gypsum being evaluated, based on its composition. For FGD Gypsum Composition 1:
• STOT-SE Category 3 (Respiratory irritation) • STOT-RE Category 1 (Lungs) • Carcinogen Category 1A
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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. Causes damage to lungs after repeated/prolonged exposure via inhalation. May cause cancer of the lung.
Precautionary Statement(s):
Obtain special instructions before use. Do not handle until all safety precautions have been read and understood. Do not breathe dust. Wear protective gloves/protective clothing/eye protection/face protection. Do not eat, drink or smoke when using this product. Use outdoors or in a well ventilated area. Get medical advice/attention if you feel unwell. If exposed or concerned: Get medical advice/attention. Store in a secure area. Dispose of product in accordance with local/national regulations.
For FGD Gypsum Composition 2:
• STOT-SE Category 3 (Respiratory Irritation)
Labelling according to 29 CFR 1910.1200 Appendices A, B and C
Hazard Pictogram(s):
Signal Word: Warning
Hazard Statement(s): May cause respiratory irritation.
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.
For FGD Gypsum Composition 3:
• STOT-SE Category 3 (Respiratory irritation) • Carcinogen Category 1A
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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 cancer of the lung.
Precautionary Statement(s):
Obtain special instructions before use. Do not handle until all safety precautions have been read and understood. Wear protective gloves/protective clothing/eye protection/face protection. Do not breathe dust. Use outdoors or in a well ventilated area. Get medical advice/attention if you feel unwell. Store in a secure area. Dispose of product in accordance with local/national regulations.
2.3 Other hazards
Listed Carcinogens:
• 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 FGD Gypsum Composition 1 and 3 only. This composition includes RCS in the final product at or above 0.1% or the level of RCS has not been determined. No carcinogen listings are required for FGD Gypsum Composition 2.
• Example text:
o For FGD Gypsum Composition 1: Listed Carcinogens: Respirable Crystalline Silica IARC: yes NTP: yes OSHA: yes Other (specify, i.e., ACGIH): yes
o For FGD Gypsum Composition 2:
Listed Carcinogens: None Known
o For FGD Gypsum Composition 3:
Listed Carcinogens: Respirable Crystalline Silica
IARC: yes NTP: yes OSHA: yes Other (specify, i.e., ACGIH): yes
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Section 3: Composition/information on Ingredients Purpose: Section 3 identifies the components of the final product. All components of the product that would be assessed as hazardous must be listed above the appropriate reporting thresholds. This includes the primary substance (FGD gypsum) and any hazardous impurities that meet or exceed the thresholds for disclosure. 3.1 Substances
• Recommended/required text Disclosure of OSHA hazardous substances above reportable thresholds is required (>0.1% for carcinogens, reproductive hazards, sensitizers and Category 1 mutagens; >1% for other hazards).
Disclose hazardous substances. The typical FGD composition is detailed in Section 4.1.1 Table 1, with the hazards of those components specified in Section 5. Substance Disclosure Requirements/Recommendations:
a) Chemical name/identity b) Chemical Abstract Services Number c) Percentage in final product d) Impurities (above disclosure thresholds), especially if these impurities result in the classification of
the final product. Populate this section of the SDS with information on the substance and impurities identified as hazardous per OSHA HCS 2012 present at or above the respective threshold limits. Non-hazardous substances may be disclosed in the SDS; however, this is not required.
• Example text Table A: FGD Gypsum and associated impurities that may require disclosurea,b
Substance CAS No. Concentration Hazard Classification Disclosure required?
Calcium sulfate, dihydrate
(FGD gypsum) 10101-41-4 85-99%
Specific Target Organ Toxicity – Single Exposure
(respiratory effects)-Category 3
Yes
Crystalline silica c 14808-60-7 <3%
Specific Target Organ Toxicity – Repeated Exposure
(lung)-Category 1 Carcinogen Category 1A
Yes, if RCS level is undetermined and level
is ≥0.1%
Respirable crystalline silica
(RCS)d 14808-60-7 Report level
present if ≥0.1%
Specific Target Organ Toxicity – Repeated Exposure
(lung)-Category 1 Carcinogen Category 1A
Yes if ≥0.1%
Fly Ash e 68131-74-8 <2%
Specific Target Organ Toxicity – Single Exposure
(respiratory effects)-Category 3
Yes if ≥1%
a Should hazardous components/impurities other than those listed in Section 4.11, Table 1 be present above their respective reporting thresholds, those should be disclosed as well.
b Information in columns 1-3 should be disclosed for all hazardous substances and may be disclosed for non-hazardous substances.
cWhere RCS has not been determined, delete the row for RCS and report out the crystalline silica value with a footnote indicating, “Respirable fraction has not been determined.”
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d 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 FGD Gypsum has not been determined, and delete this row.
eOther hazard classifications associated with fly ash, identified in the ACAA CCP SDS Guidance Document (Haley & Aldrich 2018) are attributable to individual substances that would not meet disclosure thresholds.
3.2 Mixtures FGD gypsum is considered to be a pure substance (with impurities); as such this section is not applicable and should not be included in the SDS. 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
• Recommended/required text
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 of the SDS 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).
• 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 may be provided, based on professional judgment:
o remove exposed individual from area (to fresh air);
o remove material from individual;
o remove and launder contaminated clothing and shoes;
o seek medical advice or assistance.
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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: 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.
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 FGD Gypsum Composition 1 Acute Effects Direct exposure may cause respiratory irritation, eye irritation and skin irritation. Acute exposure to FGD gypsum dust can dry and irritate the skin and cause dermatitis or eye irritation through mechanical abrasion. Chronic Effects Chronic exposure to FGD gypsum may cause lung damage from repeated exposure. Prolonged inhalation of respirable crystalline silica above certain concentrations may cause lung disease (silicosis), and lung cancer. For FGD Gypsum Composition 2 Acute Effects Direct exposure may cause respiratory irritation, eye irritation and skin irritation. Acute exposure to FGD gypsum dust can dry and irritate the skin and cause dermatitis or eye irritation through mechanical abrasion. Chronic Effects None known
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For FGD Gypsum Composition 3 Acute Effects Direct exposure may cause respiratory irritation, eye irritation and skin irritation. Acute exposure to FGD gypsum dust can dry and irritate the skin and cause dermatitis or eye irritation through mechanical abrasion. Chronic Effects Chronic exposure to FGD gypsum may cause lung damage from repeated exposure. Prolonged inhalation of respirable crystalline silica above certain concentrations may cause lung cancer.
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:
Seek first aid or call a doctor or Poison Control Center if contact with eyes occurs and irritation remains after rinsing. Get medical advice if inhalation of dust occurs and respiratory symptoms persist.
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. Arrange this section with following subheadings: 5.1 Extinguishing media
• Recommended/required text Indicate the appropriate extinguishing media to be used in the event of a fire. Extinguishing media to be avoided (unsuitable) should also be provided.
• Example text: 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.
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• Example text: Hazardous Combustion Products: Above 1450oC (~2600oF), gypsum decomposes to calcium oxide and sulfur dioxide.
5.3 Advice for firefighters
• Recommended/required text Provide instructions for firefighters to allow them to protect themselves while controlling/containing a fire.
• Example text: 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. Arrange this section with following subheadings:
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:
Personal precautions/Protective equipment: See Section 8.3 Individual Protective Measures. For airborne 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
• Recommended/required text
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.
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• Example text: 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:
Do not use brooms or compressed air to clean surfaces. Use dust collection vacuum and extraction systems. Avoid creating airborne dust during clean-up. 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 for additional information on exposure controls.
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
• 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: Practice good housekeeping. Avoid creating airborne dust. 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.
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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: 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. Arrange this section with following subheadings: 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 for disclosure in Section 3 should be listed. As 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 U.S. 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). If the product is manufactured or marketed in California, CA-OSHA PELs should also be included. • Example Text
Insert information from Table B for hazardous substances disclosed in the SDS in Sections 2 or 3. Table B: Occupational Exposure Limits For FGD Gypsum And Typical Impurities
OCCUPATIONAL EXPOSURE LIMITS1
SUBSTANCE OSHA PEL TWA (mg/m3)
NIOSH REL TWA (mg/m3)
ACGIH TLV TWA (mg/m3)
CA - OSHA PEL (mg/m3)
Particulates Not Otherwise Regulated
Total Dust 15 15 - 10
Respirable 5 5 - 5
Crystalline Silica Total Respirable 0.05 0.05 0.025 0.05
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OCCUPATIONAL EXPOSURE LIMITS1
SUBSTANCE OSHA PEL TWA (mg/m3)
NIOSH REL TWA (mg/m3)
ACGIH TLV TWA (mg/m3)
CA - OSHA PEL (mg/m3)
Calcium Sulfate, anhydrous (CAS# 7778-18-9)
Total Dust * 10 102 *
Respirable * 5 - * 1 OELs are also available for phosphogypsum: CAS# 13397-24-5. This substance is associated with this
gypsum generated as a by-product of the production of fertilizer from phosphate rock. It is not applicable to FGD gypsum.
2 The value is for particulate matter containing no asbestos and <1% crystalline silica. * In the absence of a defined CA-PEL, the value for Particulates Not Otherwise Regulated (PNOR) is applied for
this substance.
Exposure controls
• Recommended/required text:
Present the information on appropriate exposure controls in the applicable subsection.
8.2.1 Engineering controls
• Recommended/required text: Provide information on appropriate engineering controls (e.g., use local exhaust ventilation, or use only in an enclosed system).
• Example Text: Provide ventilation to maintain the ambient workplace atmosphere below 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: 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. For excessive dust both OSHA and NIOSH recommend the use of goggles. Glasses are recommended as a minimum level of protection.
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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. Arrange this section with following subheadings:
9.1 Information on basic physical and chemical properties
• Recommended/required text
List information associated with the following required physical/chemical properties. If information on a particular property is not available, the property should still be listed on the SDS with a notation indicating that the information has not been determined or is 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.
• Example Text:
Table C below is based on a consensus from the SDSs submitted for the development of this Guidance Document, as well as publically identified information on FGD gypsum. Data applicable to a typical FGD gypsum composition (as defined in Section 4.1.1 Table 1) was included. Where the data was deemed highly variable, input from the ACAA companies on the specific product is required when populating an individual SDS for fields noted as “to be populated” in the following table. Upon completion, insert the following table directly into Section 9.1 of the SDS.
Table C: FGD Gypsum Physical Properties
Property: Value Property: Value
Appearance: White/gray cake-like material Upper Explosive Limit (UEL): Not applicable
Odor: Odorless Lower Explosive Limit (LEL): Not applicable
Odor Threshold: Not applicable Vapor Pressure (Pa): Not applicable
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Property: Value Property: Value
pH (25 °C) (in water) : 6-8 Vapor Density: Not applicable
Melting/freezing Point (°C): 128 Relative Density/Specific Gravity: 2.0 – 2.9
Initial Boiling Point (°C): >163 Water Solubility: 0.1 – 0.3%
Boiling Range (°C): >163 Partition Coefficient: n-octanol/water: No data
Flash Point (°C): None Autoignition Temperature (°C): Not applicable
Evaporation Rate: Not applicable Decomposition Temperature (°C): 1450
Flammability: Non-flammable, non-combustible
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 FGD gypsum would be particle size and particle size distribution.
• Example text: Particle size: MMAD = 20 µm
Section 10: Stability and Reactivity Purpose: Provide the physical hazards associated with the stability of the product, as well as related conditions and consequences associated with hazardous chemical reactions in the applicable subsections. Arrange this section with following subheadings: 10.1 Reactivity
• Recommended/required text Describe any reactivity hazard, provide specific data where available.
• Example text:
Avoid contact with strong acids or oxidizers and diazomethane.
10.2 Chemical stability
• Recommended/required text Indicate the chemical stability of the product under normal ambient temperature and conditions.
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• Example text:
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.
• Example text: The material is a relatively stable, inert material; polymerization will not occur.
10.4 Conditions to avoid
• Recommended/required text
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).
• Example text: 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:
Acids, ammonium salts, diazomethane, phosphorus and aluminum metal.
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: None known.
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Section 11: Toxicological Information Purpose: Section 11 identifies toxicological and health effects information on the substance, or its components, or should indicate that such data are not available. Where no data is available on the product, information on components/impurities may be provided. Arrange Section 11 data according to the defined GHS Human Health Endpoints. 11.1 Information on toxicological effects Purpose: Section 11 identifies toxicological and health effects information on the substance, or indicates that such data are not available. Information on impurities may also be provided, especially if it the data results in a final product classification. 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 component/impurity is listed by the National Toxicology Program (NTP) ,the International Agency for Research on Cancer (IARC), by OSHA or other scientific/regulatory entities, when present at ≥0.1%.
• Example text:
Toxicological data for the three typical FGD gypsum compositions are presented in Tables D and E. Transpose the appropriate table (based on the FGD composition/classification) into the SDS. Table D: Toxicological Data For FGD Gypsum Composition 1 and 3 (as defined in Section 5.6, Table 6)
Endpoint Data Acute oral toxicity Oral LD50: > 2,000 mg/kg Acute dermal toxicity No data. Acute inhalation toxicity Inhalation LC50: > 3.26 mg/L Skin corrosion/irritation Not irritating or corrosive to skin based on 4-hour, semi-occlusive
exposure to rabbits. Eye damage/irritation No positive responses in rabbits based upon 24, 48, and 72 hour mean
scores for corneal opacity, iritis, or conjunctival redness/edema. Respiratory/skin sensitization Not a sensitizer. Germ cell mutagenicity Several in vitro and in vivo mutagenicity assays determined that
calcium sulfate, dihydrate was non-mutagenic, with and without metabolic activation.
Carcinogenicity No data on calcium sulfate, dihydrate. Carcinogenic studies were not conducted based on the non-neoplastic effects noted in the oral and inhalation repeated dose studies as well as the negative mutagenicity assays. Respirable crystalline silica has been identified as a carcinogen by NTP, IARC and OSHA.
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Endpoint Data Reproductive toxicity No significant developmental or reproductive toxicity were identified
in rabbits after exposure to either calcium sulfate, dihydrate or calcium sulfate, dihydrate.
Specific Target Organ Toxicity–Single Exposure
Acute toxicity testing did not result in direct organ toxicity after a single exposure to calcium sulfate, dihydrate. However, as the form of material tested was not indicated, FGD gypsum dust may result in mechanical irritation.
Specific Target Organ Toxicity–Repeated Exposure
A repeat dose oral toxicity study (35-45 days) with calcium sulfate, dihydrate conducted using rats reported a NOAEL for males of 100 mg/kg/day on the basis of decreased total protein, albumin, blood urea nitrogen, and creatinine levels observed at the 300 and 1,000 mg/kg/day dose groups. No effects were observed in females. Repeated inhalation exposures to high levels of respirable crystalline silica may result in lung damage (i.e., silicosis).
Aspiration Hazard Not applicable.
Table E: Toxicological Data For FGD Gypsum Composition 2 (as defined in Section 5.6, Table 6)
Endpoint Data Acute oral toxicity Oral LD50: > 2,000 mg/kg Acute dermal toxicity No data. Acute inhalation toxicity Inhalation LC50: > 3.26 mg/L Skin corrosion/irritation Not irritating or corrosive to skin based on 4-hour, semi-occlusive
exposure to rabbits. Eye damage/irritation No positive responses in rabbits based upon 24, 48, and 72 hour mean
scores for corneal opacity, iritis, or conjunctival redness/edema. Respiratory/skin sensitization Not a sensitizer. Germ cell mutagenicity Several in vitro and in vivo mutagenicity assays determined that
calcium sulfate, dihydrate was non-mutagenic, with and without metabolic activation.
Carcinogenicity No data on calcium sulfate, dihydrate. Carcinogenic studies were not conducted based on the non-neoplastic effects noted in the oral and inhalation repeated dose studies as well as the negative mutagenicity assays.
Reproductive toxicity No significant developmental or reproductive toxicity were identified in rabbits after exposure to either calcium sulfate, dihydrate or calcium sulfate, dihydrate.
Specific Target Organ Toxicity–Single Exposure
Acute toxicity testing did not result in direct organ toxicity after a single exposure to calcium sulfate, dihydrate. However, as the form of material tested was not indicated, FGD gypsum dust may result in mechanical irritation.
Specific Target Organ Toxicity–Repeated Exposure
A repeat dose oral toxicity study (35-45 days) with calcium sulfate, dihydrate conducted using rats reported a NOAEL for males of 100 mg/kg/day on the basis of decreased total protein, albumin, blood urea nitrogen, and creatinine levels observed at the 300 and 1,000 mg/kg/day dose groups. No effects were observed in females.
Aspiration Hazard Not applicable.
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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, should contain ecotoxicological and environmental fate information to assist in the evaluation of the environmental impact of the product if released. Data on the environmental hazards or environmental interactions of the product or its components may be provided, but it is not required.
• Recommended/required text Indicate: “No data available” or if desired, provide available information as noted in each subsection on FGD gypsum.
If provided, arrange available data into the following subsections:
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:
Indicate: No data available or if desired, insert data into similar tables as those detailed below.
Calcium sulfate, dihydrate1
Toxicity to fish LC50: >100 mg/L, 96H (Oryzia latipes)
Toxicity to invertebrates EC50: >100 mg/L, 48H (Daphnia magna)
Toxicity to algae and plants EC50: >100 mg/L, 72H (Selenastrum carpicornatum) 1 Data taken from SIDS Initial Assessment Report: Calcium Sulfate, dihydrate
12.2 Persistence and degradability
• Recommended/required text This property is not applicable to FGD gypsum as the substance is an inorganic material.
• Example text:
Not relevant for inorganic materials.
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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).
• Example text:
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.
• Example text:
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.
• Example text:
No data available.
12.6 Other adverse effects
• Recommended/required text Indicate: None known or if desired, provide information available.
• Example text:
None known.
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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.
• Recommended text
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:
Dispose of in accordance with local and national regulations. Local regulations may be more stringent than regional or national requirements.
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., U.S. Department of Transportation; DOT).
• Recommended text Provide information associated with U.S. DOT shipping regulations, such as: Shipping Name, Hazard Class, ID Number and Packing Group.
• Example text:
Regulatory entity: U.S. 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. If provided, arrange available data into the following subsections.
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15.1 Safety, health and environmental regulations/legislation specific for the substance Provide information regarding relevant regulatory status of FGD gypsum (and associated impurities), 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:
• Recommended text 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: Calcium sulfate and the identified impurities from the various sources reviewed for this document were present on the TSCA Inventory. Should additional impurities not listed in Section 4.1.1 Table 1 of the Guidance Document be present, the presence of those substances on the TSCA Inventory will need to be confirmed. The public inventory can be found at: http://www.epa.gov/oppt/existingchemicals/pubs/tscainventory/ (TSCA, 2017).
For typical FGD gypsum compositions, provide the following statement: FGD gypsum as well as listed impurities are on the TSCA Inventory.
o California Proposition 65
For typical FGD gypsum compositions, list the following text and substances as specified by the California Office of Environmental Health Hazard Assessment (CA OEHHA, 2017). Disclose the following if present (at any level): The following substances are known to the State of California to be carcinogens and/or reproductive toxicants:
Respirable crystalline silica (RCS)
o State Right-to-Know (RTK) status
Disclose identified impurities present at ≥1% if the product is manufactured or distributed in that State. Non-applicable substances and jurisdictions should be omitted from the list. Impurities present on the State RTK lists in Massachusetts (MA), New Jersey (NJ), Pennsylvania (PA), and Rhode Island (RI) are provided in Table D. Note: References to each State Right to Know list are included as footnotes to the Table and in the Reference section.
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The following substances are present on various State Right-to-Know Lists. Table F: FGD Gypsum Or Its Impurities Present On The State Right-to-Know Lists
Component CAS MA1,2 NJ3,4 PA5 RI6
Gypsum; calcium sulfate; calcium sulfate, dihydrate
7778-18-9 OR 10101-41-4
Yes Yes Yes No
Calcium carbonate 1317-65-3 Yes Yes Yes No Silica-crystalline (SiO2), quartz 14808-60-7 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 calcium sulfate or impurities present on other environmental listings such as SARA 311/312, SARA 313 TRI, CWA or CAA may also be included. 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 that supports the understanding of Sections 1-15 of the SDS should be provided. At the end of the SDS provide an appropriate legal disclaimer associated with use of the SDS and information it contains. Arrange data into the following subsections: 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 typical FGD gypsum compositions where an SDS was not previously released. Initial SDS prepared on (insert date)
• Example text for typical FGD gypsum compositions where an SDS was previously released. SDS Revision date (insert date), Revision X (insert Revision number)
16.2 Acronyms and Abreviations
• Recommended/required text Include a key to abbreviations and acronyms used throughout the SDS.
• Example text:
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Acronym/Abbreviation list:
• 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 • CFR: Code of Federal Regulations • CWA: Clean Water Act • EC50: Effective Concentration that elicits an identified effect. • FGD: Flue Gas Desulfurization • 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 • MMAD: Mass Median Aerodynamic Diameter • 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 - HMIS Classification
• Recommended/required text Provide a table detailing the Hazardous Material Information System (HMIS) rating for the FGD gypsum. The system was developed by the American Coatings Association. The incorporation of PPE information is not recommended for inclusion in the SDS. Further information on assigning specific rating is available from the American Coatings Association. (ACA, 2014) As the HMIS rating will vary based on the OSHA HCS 2012 hazard assigned to the FGD gypsum, apply the HMIS applicable to the final product.
• Example text:
Apply the HMIS ratings table applicable to the final product classification FGD Gypsum Composition 1:
Hazardous Materials Identification System (HMIS) Degree of hazard (0= low, 4 = extreme) Health: 1* Flammability: 0 Physical
Hazards: 0 Personal
protection:
* Chronic Health Effects FGD Gypsum Composition 2:
Hazardous Materials Identification System (HMIS) Degree of hazard (0= low, 4 = extreme) Health: 1 Flammability: 0 Physical
Hazards: 0 Personal
protection:
FGD Gypsum Composition 3:
Hazardous Materials Identification System (HMIS) Degree of hazard (0= low, 4 = extreme) Health: 1* Flammability: 0 Physical
Hazards: 0 Personal
protection:
* Chronic Health Effects
• Recommended/required text
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.
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References 1. American Chemistry Council (ACC). 2014. Comments of the American Chemistry Council
Crystalline Silica Panel. Docket No. OSHA-2010-0034. February 11. Available at: https://www.americanchemistry.com/ProductsTechnology/Crystalline-Silica/ACC-Comments-on-Crystalline-Silica-Feb-14-2014.pdf
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. 2014. Standard C 471M-14: Standard Test Methods for Chemical Analysis of Gypsum and Gypsum Products [Metric].
5. California Office of Environmental Health Hazard Assessment (CA OEHHA). 2017. Chemicals known to the State to cause cancer or reproductive toxicity. https://oehha.ca.gov/media/downloads/crnr/p65single07072017.pdf. Accessed October 16, 2017.
6. ChemIDplus. 2015. [search for “gypsum”] Available at: http://chem.sis.nlm.nih.gov/chemidplus/ProxyServlet?QV1=gypsum&objectHandle=Search&actionHandle=searchChemIdLite&responseHandle=JSP&QF1=Name&nextPage=jsp%2Fchemidheavy%2FChemidDataview.jsp&submit.x=0&submit.y=0. Accessed September 1, 2015.
7. Electric Power Research Institute (EPRI). 1995. The Effects of Flue Gas Desulfurization (FGD) System Additives on Solid By-Products. Technical Report No. 102367. December.
8. Environment Canada and Health Canada. 2013. Screening Assessment for the Challenge: Quartz and Cristobalite. June 2013. Available at: https://www.ec.gc.ca/ese-ees/default.asp?lang=En&n=1EB4F4EF-1
9. EPRI. 2006. Potential Health Effects of Crystalline Silica Exposures from Coal Fly Ash: A Literature Review. Report No. 1012821. March.
10. EPRI. 2011. Composition and Leaching of FGD Gypsum and Mined Gypsum. Technical Report No. 1022146. November.
11. European Chemicals Agency (ECHA). 2010. REACH Registration Dossier for calcium sulfate. http://apps.echa.europa.eu/registered/data/dossiers/DISS-9ebe5c1d-2d61-3cd3-e044-00144f67d031/DISS-9ebe5c1d-2d61-3cd3-e044-00144f67d031_DISS-9ebe5c1d-2d61-3cd3-e044-00144f67d031.html. Accessed August 23, 2015
12. Gradient. 2015a. Tuit, C and A. Lewis. Between a Rock and a Hard Place: Classifying CS. Gradient Trends Risk Science & Application. Issue 62. Winter.
13. Gradient. 2015b. Long, C. OSHA’s Proposed Silica Rule. Gradient Trends Risk Science & Application. Issue 62. Winter.
14. Haley & Aldrich, Inc. 2018. American Coal Ash Association Safety Data Sheet Guidance Document (for CCPs). Prepared for American Coal Ash Association (ACAA). Version 5.0. January, 2018.
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15. Health Canada. 2015. National Workplace Hazardous Information System (as amended by Hazardous Product Regulation. SOR 2015-17). February 11, 2015.
16. Henkels PJ. Undated. Characterizing Synthetic Gypsum for Wallboard Manufacture. US Gypsum Corporation Research Center. https://web.anl.gov/PCS/acsfuel/preprint%20archive/Files/41_2_NEW%20ORLEANS_03-96_0568.pdf. Accessed August 31, 2015.
17. Interactive Learning Paradigms Incorporated (ILPI). 2015. The SDS HyperGlossary: HMIS. http://www.ilpi.com/msds/ref/hmis.html. Accessed April 26, 2015.
18. 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.
19. IARC. 2012. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. Arsenic, Metals, Fibres, and Dusts. Volume 100 C-A Review of Human Carcinogens. IARC, Lyons, France. Available at: http://monographs.iarc.fr/ENG/Monographs/vol100C/mono100C.pdf
20. 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.
21. 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.
22. Ladwig, K. 2015. Personal Communication to M. Sanders titled RE: FGD System Additives. September 11, 2015.
23. Marinkovic SR, Pulek AK, and Logar V. 2005. Recycling of Waste FGD Gypsum. ResearchGate. May 2005.
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 August 27, 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.
26. Miller EC. No date. Flue gas desulfurization (FGD) gypsum production, processing and disposal. Tennessee Valley Authority.
27. 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.
28. 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.
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http://www.crystallinesilica.eu/sites/crystallinesilica.eu/files/documents/Summary%20Morfeld%20Classification%20CLP_GHS_RCS.pdf. Accessed March 30, 2015.
29. 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.
30. 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.
31. National Toxicology Program (NTP). 2006. Chemical Information Review Document for Synthetic and Naturally Mined Gypsum (Calcium Sulfate Dihydrate). Prepared by Integrated Laboratory Systems, Inc. Research Triangle Park, NC. Contract No. N01-ES-35515. January.
32. National Toxicology Program (NTP). 2016. Department of Health and Human Services. Report on Carcinogens. Silica, Crystalline (Respirable Size). Fourteenth Edition. Available at: https://ntp.niehs.nih.gov/pubhealth/roc/index-1.html#C
33. 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.
34. New Jersey Department of Health. 2010b. Right to Know Hazardous Substance List. http://web.doh.state.nj.us/rtkhsfs/rtkhsl.aspx. Accessed August 27, 2015.
35. Pennsylvania Code. 1986. Chapter 323: Hazardous Substances List. http://www.pacode.com/secure/data/034/chapter323/chap323toc.html. Accessed August 27, 2015.
36. Rhode Island Department of Labor and Training (DLT). No date. DLT Right to Know Hazardous Substances List. https://www.ri.gov/DLT/righttoknow/. Accessed August 27, 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. United Nations Environment Programme (UNEP). 2003. Calcium sulfate, dihydrate CAS No: 10101-41-4, Screening Information Data Set Initial Assessment Report. http://www.chem.unep.ch/irptc/sids/OECDSIDS/10101414.pdf. Accessed September 2, 2015.
39. United States Environmental Protection Agency (EPA). 2017. Toxic Substance Chemical Inventory. http://www.epa.gov/oppt/existingchemicals/pubs/tscainventory/. Accessed October 16, 2017.
40. US Occupational Safety and Health Administration (US OSHA). 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 OSHA. 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 OSHA. 2012b. Hazard Communication. 29 CFR 1910. Federal Register Vol.77, No. 58. March 26, 2012. https://www.osha.gov/FedReg_osha_pdf/FED20120326.pdf
August 2018
56
43. US OSHA. 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 OSHA. 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.
45. US OSHA. 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 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 OSHA. Undated (a). OSHA Brief Hazard Communication Standard: Safety Data Sheets. https://www.osha.gov/Publications/OSHA3514.pdf. Accessed April 8, 2015.
48. US OSHA. Undated (b). OSHA Brief Hazard Communication Standard: Labels and Pictograms. https://www.osha.gov/Publications/OSHA3636.pdf. Accessed April 15, 2015.
49. U.S. Occupational Safety and Health Administration. 2016. Final Rule-Occupational Exposure to Respirable Crystalline Silica. Federal Register Vol. 81, No. 58. Docket No. OSHA-2010-0034. March 25, 2016. https://www.federalregister.gov/documents/2016/03/25/2016-04800/occupational-exposure-to-respirable-crystalline-silica
August 2018
APPENDIX A
FGD Gypsum Safety Data Sheet (SDS) Development Checklist
Appendix A FGD Gypsum Safety Data Sheet (SDS) Development Checklist
FGD Gypsum SDS Checklist Page 1 of 6 Preparation Date: 2015‐11‐25
This SDS Checklist was developed to provide ACAA member companies the information necessary to develop a Safety Data Sheet (SDS) for FGD Gypsum. When used in concert with the SDS Guidance Document and the SDS Template for FGD Gypsum, the checklist can be used by ACAA Member Companies to develop the SDSs required based on Company and specific FGD gypsum composition. Prior to developing an SDS using this Guidance Document and associated Appendices, confirm that the FGD gypsum formulation meets the composition specifications detailed in Appendix C (Composition Summary). Should the FGD gypsum evaluated have additional impurities present, or have impurities above the maximum percentage identified, the Guidance should not be used until an assessment of compositional variations is evaluated to confirm that those differences do not result in additional GHS classifications of the FGD gypsum. This checklist specifies the information required/recommended for inclusion in the SDS for FGD gypsum per 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. A 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 or the Appendix B: FGD Gypsum SDS Template 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
FGD Gypsum SDS Checklist Page 2 of 6 Preparation Date: 2015‐11‐25
SECTION 2. HAZARDS IDENTIFICATION Provide the following information in the SDS. See the SDS Guidance Document or Appendix B: FGD Gypsum SDS Template to select the data applicable to the product composition. 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 or Appendix B: FGD Gypsum SDS Template 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 impurities in the FGD gypsum. A range may be provided.
SECTION 4. FIRST AID MEASURES See the SDS Guidance Document or Appendix B: FGD Gypsum SDS Template 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
FGD Gypsum SDS Checklist Page 3 of 6 Preparation Date: 2015‐11‐25
SECTION 5. FIREFIGHTING MEASURES See the SDS Guidance Document or the Appendix B: FGD Gypsum SDS Template 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 or Appendix B: FGD Gypsum SDS Template 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 or Appendix B: FGD Gypsum SDS Template 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 or Appendix B: FGD Gypsum SDS Template for the list of OEL’s identified based on identified FGD components or impurities. 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
FGD Gypsum SDS Checklist Page 4 of 6 Preparation Date: 2015‐11‐25
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 or Appendix B: FGD Gypsum SDS Template 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 or Appendix B: FGD Gypsum SDS Template 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 human health hazard classification categories should be provided. Where data is not available or not known, that should be indicated. See the SDS Guidance Document or Appendix B: FGD Gypsum SDS Template, for the appropriate toxicological information to populate the section based on the FGD composition and corresponding toxicity information on the human health hazards.
FGD Gypsum SDS Checklist Page 5 of 6 Preparation Date: 2015‐11‐25
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 final product and component substances following the format indicated in the SDS Guidance Document or Appendix B: FGD Gypsum SDS Template. 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 or Appendix B: FGD Gypsum SDS Template 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
FGD Gypsum SDS Checklist Page 6 of 6 Preparation Date: 2015‐11‐25
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 or Appendix B: FGD Gypsum SDS Template. 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 or Appendix B: FGD Gypsum SDS Template. 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 or Appendix B: FGD Gypsum SDS Template 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
August 2018
APPENDIX B
FGD Gypsum Safety Data Sheet (SDS) Template
FGD Gypsum SDS Template Preparation Date: 2018‐08
Appendix B
FGD Gypsum Safety Data Sheet (SDS) Template
This Appendix provides a generic template that can be used to develop an OSHA compliant SDS for Flue Gas Desulfurization (FGD) gypsum. For ease of use, a Word (.docx) file of this template is provided as a companion to this Guidance Document.
Comments have been included within the template to assist American Coal Ash Association (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. Other required information for populating the template may originate from the manufacturer/distributer or the FGD gypsum. The SDS Guidance Document can be used as a source of required information if it is not available here.
Note: 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 14
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 building products such as drywall, cement additives and plaster, as a set retardant and grinding aid in cement, or as an agricultural additive.
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
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 2 of 14
Section 2
Hazards Identification
2.1 Classification of the Substance GHS Classification(s) according to OSHA Hazard Communication Standard (29 CFR 1910.1200):
Insert applicable classifications. For FGD Gypsum Composition 1:
STOT‐SE Category 3 (Respiratory Irritation)
STOT‐RE Category 1 (Lungs)
Carcinogen Category 1A
For FGD Gypsum Composition 2:
STOT‐SE Category 3 (Respiratory Irritation)
For FGD Gypsum Composition 3:
STOT‐SE Category 3 (Respiratory Irritation)
STOT‐RE Category 1 (Lungs)
2.2 Label Elements
For FGD Gypsum Composition 1:
STOT‐SE Category 3 (Respiratory Irritation)
STOT‐RE Category 1 (Lungs)
Carcinogen Category 1A
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. Causes damage to lungs after repeated/prolonged exposure via inhalation. May cause cancer of the lungs.
Precautionary Statement(s):
Obtain special instructions before use. Do not handle until all safety precautions have been read and understood. Do not breathe dust. Wear protective gloves/protective clothing/eye protection/face protection. Do not eat drink or smoke when using this product. 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.
Commented [A1]: These hazard classifications are those associated with the typical FGD Gypsum as identified in the SDS Guidance. Insert the classification and table applicable to your specific product based on the product composition using Table 1 in Section 4.1.1 and Table 7 in Section 5.6. Note: The FGD 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 at a levels of 0.1% or greater, the classification of the FGD gypsum may need to be re‐evaluated.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 3 of 14
For FGD Gypsum Composition 2:
STOT‐SE Category 3 (Respiratory Irritation)
Labelling according to 29 CFR 1910.1200 Appendices A, B and C*
Hazard Pictogram(s):
Signal Word: Warning
Hazard Statement(s):
May cause respiratory irritation.
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.
For FGD Gypsum Composition 3:
STOT‐SE Category 3 (Respiratory Irritation)
Carcinogen Category 1A
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 cancer of the lungs.
Precautionary Statement(s):
Obtain special instructions before use. Do not handle until all safety precautions have been read and understood. Wear protective gloves/protective clothing/eye protection/face protection. 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.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 4 of 14
2.3 Other Hazards Listed Carcinogens:
For FGD Gypsum Composition 1
Respirable Crystalline Silica
IARC: Yes NTP: Yes OSHA: Yes Other (ACGIH): Yes
For FGD Gypsum Composition 2:
None Known
For FGD Gypsum Composition 3 Respirable Crystalline Silica
IARC: Yes NTP: Yes OSHA: Yes Other (ACGIH): Yes
Section 3
Composition/Information on Ingredients/Impurities
Substance CAS No. Percentage (%) GHS Classification
Calcium sulfate, dihydrate 10104‐14‐1 Include %
Specific Target Organ Toxicity –
Single Exposure Category 3
(Respiratory Irritation)
Crystalline silica 14808‐60‐7 See Note 1
Specific Target Organ Toxicity –
Repeated Exposure ‐ Category 1
(Lung)
Carcinogen Category 1A
Respirable crystalline silica
(RCS) 14808‐60‐7 ≥0.1%; See Note 2
Specific Target Organ Toxicity –
Repeated Exposure Category 1
(Lungs)
Fly Ash 68131‐74‐8 If >1%
Specific Target Organ Toxicity –
Single Exposure Category 3
(Respiratory Irritation)
1. Report the level of crystalline silica in the product if the level of RCS has not been determined, or is present at or above 0.1%. If the level of RCS has been determined this information is not required; delete the crystalline silica row.
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 FGD gypsum has not been determined; delete the RCS row.
Section 4
First Aid Measures
Commented [A2]: Insert the concentrations of hazardous substances (based on GHS criteria) present if present at or above identified percentage thresholds. If a substance is present below the listed threshold, that substance does not require disclosure and the row may be deleted. Non‐hazardous substances present in Table 1 of the FGD gypsum SDS Guidance may be disclosed at the SDS preparer’s discretion. NOTE: This disclosure list assumes that all components/impurities are present in the identified substance/impurities defined in Section 4.1.1 Table 1 of the FGD Gypsum SDS Guidance Document. If additional substances are identified at levels of 0.1% or greater, additional disclosure may be required.
Commented [A3]: Insert the following footnote if the level of respiratory crystalline silica was not determined. Footnote: The percentage of respirable crystalline silia has not been determined.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 5 of 14
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.
4.2 Most Important Health Effects, Both Acute and Delayed
For FGD Gypsum Composition 1 and 3:
Acute effects: Exposure to FGD gypsum dust may cause respiratory irritation. Acute exposure can dry and irritate the skin
and cause dermatitis or eye irritation through mechanical abrasion.
Chronic effects: Chronic exposure to FGD gypsum may cause lung damage from repeated exposure. Prolonged inhalation
of dusts containing respirable crystalline silica above certain concentrations may cause lung disease (silicosis) and lung
cancer.
For FGD Gypsum Composition 2:
Acute Effects
Direct exposure may cause respiratory irritation, eye irritation and skin irritation. Acute exposure to FGD gypsum dust can
dry and irritate the skin and cause dermatitis or eye irritation through mechanical abrasion.
Chronic Effects
None known
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. Get
medical advice if inhalation of dust occurs and respiratory symptoms persist.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 6 of 14
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: Above 1450oC (~2600oF), gypsum decomposes to calcium oxide and sulfur dioxide.
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.
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. Avoid creating airborne dust during clean‐up.
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 for additional information on exposure controls.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 7 of 14
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, 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.
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 TWA (mg/m3)
Particulates Not Otherwise Regulated
Total 15 15 ‐ 10
Respirable 5 5 ‐ 5
Crystalline Silica Total
Respirable 0.05 0.05 0.025 0.05
Calcium Sulfate, anhydrous (CAS# 7778‐18‐9)
Total Dust * 10 10 *
Respirable * 5 ‐ *
* In the absence of a CA‐PEL, the value for Particulates Not Otherwise Regulated (PNOR) is applied.
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.
Commented [A4]: OELs are also available for Gypsum: CAS# 13397-24-5. The substance associated with this CAS# is not produced in a FGD system as it correlates to phosphogypsum which is a by-product of the production of fertilizer from phosphate rock. The OELs for this gypsum CAS# therefore should not be included as this substance is not associated with FGD gypsum.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 8 of 14
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 (SCBA) 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.): White/gray
cake‐like material
Upper/lower flammability or explosive limits: Not
applicable
Odor: Odorless Vapor Pressure (Pa): Not applicable
Odor threshold: Not applicable Vapor Density: Not applicable
pH (25 °C)(in water): 6‐8 Specific gravity or relative density: 2.0 – 2.9
Melting point/freezing point (°C): 128 Water Solubility: 0.1‐0.3%
Initial boiling point and boiling range (°C): >163 Partition coefficient: n‐octane/water: No data
Flash point (°C): None Auto ignition temperature (°C): Not applicable
Evaporation rate: Not applicable Decomposition temperature (°C): 1450
Flammability (solid, gas): Non‐flammable, non‐
combustible Viscosity: Not applicable
9.2 Other Information
Commented [A5]: Do not delete any rows or individual properties. These data are a compilation of the reviewed SDSs as per the Guidance Document.
Commented [A6]: If available, list other properties that might be applicable to evaluate the hazards of the product. One such example would be particle size determination. If none are available, delete this section.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 9 of 14
Section 10
Stability and Reactivity
10.1 Reactivity: Avoid contact with strong acids or oxidizers and diazomethane.
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.
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: Acids, ammonium salts, diazomethane, phosphorus and aluminum metal.
10. 6 Hazardous decomposition products:
None known.
Section 11
Toxicological Information
11.1 Information on Toxicological Effects
Insert the Table that is applicable to the FGD composition. Delete the other table.
Toxicological data for FGD Gypsum Composition 1 and 3
Endpoint Data
Acute oral toxicity Oral LD50: > 2000 mg/kg
Acute dermal toxicity No data
Acute inhalation toxicity Inhalation LC50: > 3.26 mg/L
Skin corrosion/irritation Not irritating or corrosive to skin based on 4‐hour, semi‐occlusive exposure to rabbits.
Eye damage/irritation No positive responses in rabbits based upon 24‐, 48‐, and 72‐hour mean scores for corneal opacity, iritis, conjunctival redness/edema.
Respiratory/skin sensitization Not a sensitizer.
Germ cell mutagenicity Several in vitro and in vivo mutagenicity assays determined that calcium sulfate, dihydrate was non‐mutagenic, with and without metabolic activation.
Carcinogenicity
No data on calcium sulfate, dihydrate. Carcinogenic studies were not conducted based on the non‐neoplastic effects noted in the oral and inhalation repeated dose studies as well as the negative mutagenicity assays. Respirable crystalline silica has been identified as a carcinogen by NTP, IARC and OSHA.
Reproductive toxicity No significant developmental or reproductive toxicity were identified
Commented [A7]: Insert the appropriate table based on the FGD Gypsum classification determined in Section 2.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 10 of 14
Endpoint Data
in rabbits after exposure to either calcium sulfate, dihydrate or calcium sulfate, dihydrate.
Specific Target Organ Toxicity–Single Exposure
Acute toxicity testing did not result in direct organ toxicity after a single exposure to calcium sulfate, dihydrate. However, as the form tested was not indicated, FGD gypsum dust may result in mechanical respiratory irritation.
Specific Target Organ Toxicity–Repeated Exposure
A repeat dose oral toxicity study (35‐45 days) with calcium sulfate, dihydrate conducted using rats reported a NOAEL for males of 100 mg/kg/day on the basis of decreased total protein, albumin, blood urea nitrogen, and creatinine levels observed at the 300 and 1,000 mg/kg/day dose groups. No effects were observed in females. Repeated inhalation exposures to high levels of respirable crystalline silica may result in lung damage (silicosis) and lung cancer.
Aspiration Hazard Not applicable
Toxicological data for FGD Gypsum Composition 2
Endpoint Data
Acute oral toxicity Oral LD50: > 2000 mg/kg
Acute dermal toxicity No data
Acute inhalation toxicity Inhalation LC50: > 3.26 mg/L
Skin corrosion/irritation Not irritating or corrosive to skin based on 4‐hour, semi‐occlusive exposure to rabbits.
Eye damage/irritation No positive responses in rabbits based upon 24‐, 48‐, and 72‐hour mean scores for corneal opacity, iritis, conjunctival redness/edema.
Respiratory/skin sensitization Not a sensitizer.
Germ cell mutagenicity Several in vitro and in vivo mutagenicity assays determined that calcium sulfate, dihydrate was non‐mutagenic, with and without metabolic activation.
Carcinogenicity
No data on calcium sulfate, dihydrate. Carcinogenic studies were not conducted based on the non‐neoplastic effects noted in the oral and inhalation repeated dose studies as well as the negative mutagenicity assays.
Reproductive toxicity No significant developmental or reproductive toxicity were identified in rabbits after exposure to either calcium sulfate, dehydrate or calcium sulfate, dihydrate.
Specific Target Organ Toxicity–Single Exposure
Acute toxicity testing did not result in direct organ toxicity after a single exposure to calcium sulfate, dihydrate. However, as the form tested was not indicated, FGD gypsum dust may result in mechanical irritation.
Specific Target Organ Toxicity–Repeated Exposure
A repeat dose oral toxicity study (35‐45 days) with calcium sulfate, dihydrate conducted using rats reported a NOAEL for males of 100 mg/kg/day on the basis of decreased total protein, albumin, blood urea nitrogen, and creatinine levels observed at the 300 and 1,000 mg/kg/day dose groups. No effects were observed in females.
Aspiration Hazard Not applicable
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 11 of 14
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 for safe handling and use, including appropriate hygienic practices.
Dispose of in accordance with local and national regulations. Local regulations may be more stringent than regional or
national requirements.
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
Commented [A8]: The identification and inclusion of data into this section is non‐mandatory per 29CFR 1910.1200. If desired, the data table for SDS section 12, as apresented in section 6 of the SDS Guidance Document can be included but is not required.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 12 of 14
Section 15
Regulatory Information
15.1 Safety, Health and Environmental Regulations/Legislation Specific for the Mixture
TSCA Inventory Status
FGD gypsum as well as listed impurities are on the TSCA Inventory.
California Proposition 65
The following substance(s) are known to the State of California to be carcinogens and/or reproductive toxicants: Respirable crystalline silica
State Right‐to‐Know (RTK)
The following substances are present on various State Right‐to‐Know Lists.
Component CAS MA1,2 NJ3,4 PA5 RI6
Gypsum; calcium sulfate; calcium sulfate, dihydrate
7778‐18‐9 OR 10101‐41‐4
Yes Yes Yes No
Calcium carbonate 1317‐65‐3 Yes Yes Yes No
Silica‐crystalline (SiO2), quartz 14808‐60‐7 Yes Yes Yes No 1 Massachusetts 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
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
Revision number:
16.2 Abbreviations and Acronyms
ACAA American Coal Ash Association
ACGIH: American Conference of Industrial Hygienists
ANSI: American National Standards Institute
Commented [A9]: Disclose the following if present (at any level).
Commented [A10]: Disclose identified components/impurities present at ≥1% if the product is manufactured or distributed in that State. Non‐applicable substances/jurisdictions should be deleted.
Commented [A11]: 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.
Commented [A12]: Insert the SDS development/revision date. Also designate a revision number (i.e.V2, or new).
Commented [A13]: Include abbreviations that were used in the SDS development. Add or remove other acronyms as applicable.
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 13 of 14
CA: California
CAA: Clean Air Act
CAS: Chemical Abstract Services
CFR: Code of Federal Regulations
EPA: Environmental Protection Agency
FGD Flue Gas Desulfurization
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
MA: Massachusetts
NA: Not Applicable
NIOSH: National Institute of Occupational Safety and Health
NJ: New Jersey
NOEC: No observed effect concentration
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
PNOR Particulates Not Otherwise Regulated
PPE: Personal Protective Equipment
RCS: Respirable Crystalline Silica
REL: Recommended exposure limit
RI: Rhode Island
RTK: Right‐to‐Know
SARA: Superfund Amendments and Reauthorization Act
SCBA: Self‐contained breathing apparatus
SDS: Safety Data Sheet
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
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
INSERT LOGO INSERT PRODUCT NAME
SDS Number: 0.0 Revision Date: N/A
Preparation Date: INSERT Page 14 of 14
16.3 Other Hazards
FGD Gypsum Classification 1 and 3:
Hazardous Materials Identification System (HMIS)
Degree of hazard (0= low, 4 = extreme)
Health: 1* Flammability: 0 Physical
Hazards:
0 Personal
protection:
* Chronic Health Effects
FGD Gypsum Classification 2:
Hazardous Materials Identification System (HMIS)
Degree of hazard (0= low, 4 = extreme)
Health: 1 Flammability: 0 Physical
Hazards:
0 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.
Commented [A14]: Apply the HMIS ratings table that is applicable for the product. Delete the classification references and the HMIS table that does not apply.
Commented [A15]: Include a disclaimer at the end of your SDS. Prior to using the disclaimer provided, it should be reviewed by legal counsel.
August 2018
APPENDIX C
FGD Gypsum Compositions Summary Workbook
TABLE C‐1
COMPOSITION SUMMARY
FGD GYPSUM COMPOSITIONS SUMMARY WORKBOOK
FGD GYPSUM ACAA SDS GUIDANCE DOCUMENT
Page 1 of 8
FGD Gypsum
Composition 11FGD Gypsum Composition
21FGD Gypsum Composition
31
STOT‐SE Category 3
(Respiratory Irritation)
STOT‐RE Category 1 (lungs)
Carcinogen Category 1A
STOT‐SE Category 3
(Respiratory Irritation)
STOT‐SE Category 3
(Respiratory Irritation)
Carcinogen Category 1A
Calcium sulfate, dihydrate 85 ‐ 99% 85‐ 99% 85‐ 99% Yes
Calcium carbonate ≤8% ≤8% ≤8% Not required
Magnesium carbonate <5% <5% <5% Not required
Crystalline silicon dioxide (SiO2)2 ≤3% ≤3% ≤3%
If respirable fraction has NOT
been determined
Silica, crystalline (respirable) (RCS)3 undetermined or ≥1% <1% ≥0.1 to <1% If known and ≥0.1%
Fly Ash4 ≤2% ≤2% ≤2% If >1%
NOTES:
Substance/Classification
1 The classification specified applies to FGD gypsum compositions that include only these substances at the levels indicated.
2 Includes crystalline silica, cristobalite or quartz.3 Includes crystalline silica, cristobalite or quartz below 10 um in diameter.
4 Fly ash is a UVCB substances (substance of unknown or variable composition or biological). It is defined by the U.S. 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.” Information from industry indicates that other elemental oxides, low
levels of chlorides and ammonium salts may also be present based on analytical data and the use of pollution control additives.
SDS Section 2
Disclosure
2018_0112_FGD Gypsum Appendix C_updated_DF.xlsx JANUARY 2018
TABLE C‐2
CHEMICAL COMPOSITION DATA
FGD GYPSUM COMPOSITIONS SUMMARY WORKBOOK
FGD GYPSUM ACAA SDS GUIDANCE DOCUMENT
Page 2 of 8
FGD Gypsum Chemical Composition Data (Percent)1
Source
CAS#
ASTM C22/C 22M‐00‐
Standard Specification
for Gypsum (2005)
United States Gypsum
Company (USGC)
Guidelines
Italy Specifications for
FGD Gypsum for
Reutilization
(Marinkovic et al. 2005)
Germany Specifications
for FGD Gypsum for
Reutilizaton
(Marinkovic et al. 2005)
German Gypsum
Association Guidelines
Calcium sulfate dihydrate 10101‐41‐4 > 70 95 ≥ 95 ≥ 95 95 90‐99 66‐98
Calcium Sulfite 10257‐55‐3 1 0.25
Calcium carbonate 1317‐65‐3 < 1.5
Magnesium carbonate 39409‐82‐0
Crystalline silica (Quartz, SiO2) 14808‐60‐7 1
Fly Ash3 68131‐74‐8 1
NOTES:
Standards/References EPRI Reports
1 This list contains the concentration ranges for calcium sulfate, dihydrate and associated impurities that may be present at >0.1% (minimum threshold for SDS disclosure/consideration per OSHA HCS 2012) in the FGD gypsum. Other substances may be present at <0.1% in the FGD gypsum, but
they not delineated in this spreadsheet.2 Multiple gypsum samples were analyzed according to method SW‐846 3051a, a microwave assisted aqua regia digestion method. Digests were analyzed using a combination of ICP‐AES and ICP‐MS. It encompasses 32 samples from 29 power plants, with 20 washed samples and 5 unwashed
samples. These elemental analyses were evaluated based on the substance, their most likely form and their respective concentrations. The impact of sorbents/additives was also analyzed for the 20 washed samples. 5 were from plants injecting lime‐based sorbents (Lime, ammonia), 6 were
from plants injecting sodium‐based sorbents (Trona, Sodium sulfite, Sodium carbonate) and 6 were from plants that did not inject any sorbent (and 3 were unknown). For both sorbent types, concentrations of most constituents were within the range of values for the 6 without SO3 controls and
only minor differences between the groups. The identified elements were determined to be components from residual fly ash that may be present in the gypsum and as such were not delineated here.3 Fly ash is a UVCB substance (substance of unknown or variable composition or biological). It is defined by the U.S. 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.” Information from industry indicates that other elemental oxides, low levels of chlorides and ammonium salts may also be present based on analytical data and the use of pollution control additives.4 Calcium sulfate, dihydrate levels were calculated by adding sulfur trioxide and calcium oxide levels resulting based on analytical method used. 5 Limestone is parent compound for FGD gypsum and consists of calcium carbonate and crystalline silica as represented by SDS.
6 The SDS listed the chemical name of calcium sulfate, anhydrous with the CAS# for calcium sulfate, dihydrate. Based on the highest percent purity range listed the substance was assumed to be the dihydrate form.
Composition and Leaching of FGD Gypsum and
Mined Gypsum (2011)2
FGD Gypsum Mined Gypsum
Chemical Composition
2018_0112_FGD Gypsum Appendix C_updated_DF.xlsx JANUARY 2018
TABLE C‐2
CHEMICAL COMPOSITION DATA
FGD GYPSUM COMPOSITIONS SUMMARY WORKBOOK
FGD GYPSUM ACAA SDS GUIDANCE DOCUMENT
Page 3 of 8
FGD Gypsum Chemical Composition Data (Percent)1
Source
CAS#
Calcium sulfate dihydrate 10101‐41‐4
Calcium Sulfite 10257‐55‐3
Calcium carbonate 1317‐65‐3
Magnesium carbonate 39409‐82‐0
Crystalline silica (Quartz, SiO2) 14808‐60‐7
Fly Ash3 68131‐74‐8
Chemical Composition
Parent Limestone5
FGD Gypsum from
Bohemian Power Plant
(Marinkovic et al. 2005)
FGD Gypsum from
W.H. Zimmer Station in
Moscow,
OH‐Cinergy Corp. 4
(Spectrum Analytic)
Member Company DataSynthetic Gypsum
SDS
Synthetic
Gypsum SDS
Synthetic Gypsum
SDS Limestone SDS
If declared
Minimum %
If declared
Maximum %
78.524 97.444 94‐99 85‐986 92‐99 85 99
0‐2 2‐8 < 2.5 >95 0 8
0‐5 0 5
0.63 1.31 0‐1 < 2.5 <2 0.63 2.5
0‐2 0 2
FGD SDSs SummaryTest Data
2018_0112_FGD Gypsum Appendix C_updated_DF.xlsx JANUARY 2018
TABLE C‐3
RAW ANALYTICAL DATA
FGD GYPSUM COMPOSITIONS SUMMARY WORKBOOK
FGD GYPSUM ACAA SDS GUIDANCE DOCUMENT
Page 4 of 8
FGD Gypsum Analytical/Compositional Data (Percent)
Parent Limestone/
Calcium Carbonate
ASTM C22/C 22M‐
00‐Standard
Specification for
Gypsum (2005)
United States
Gypsum Company
(USGC) Guidelines
Italy Specifications
for FGD Gypsum
for Reutilization
(Marinkovic et al.
2005)
Germany
Specifications for
FGD Gypsum for
Reutilization
(Marinkovic et al.
2005)
German Gypsum
Association
Guidelines
FGD Gypsum from
Bohemian Power Plant
(Marinkovic et al. 2005)
FGD Gypsum from W.H.
Zimmer Station in
Moscow, OH‐Cinergy
Corp. 4
(Spectrum Analytic)
Member Company Data Synthetic Gypsum SDS Synthetic Gypsum SDS Synthetic Gypsum SDS Limestone SDS
If declared
Minimum %
If declared
Maximum %
Calcium 19.9‐26.8 23.0 19.9 26.8
Sulfur 15.6‐20.8 18.7 15.6 20.8
Sulfur dioxide < 0.25 < 0.25
Sulfur trioxide 7446‐11‐9 45.725 56.045 45.72 56.04
Gypsum (calcium
sulfate)
(CAS# seems to
represent
phosphogypsum
which is
radioactive, does
not appear to be
correct?)
13397‐24‐5 92‐99
Calcium hydroxide8 1305‐62‐0
This substance is only present when
hydrated lime is used to react with
the SO3 in the flue gases to form
CaSO4. The ACAA SDS Guidance does
not cover FGD gypsums made with
hydrated lime.
0‐20 2
Calcium oxide7 1305‐78‐8
This substance may be present as a
component of the gypsum (CaSO4 ‐ in
reaction with SO3), or it may be
present as a component of the fly ash
impurity.
If fly ash is present at >2% then the
potential for CaO to be present at >1%
must be evaluated to assess the
proper hazard classification and for
the disclosure of CaO on the SDS.
32.85 41.445 0‐2 32.8 41.44
Magnesium oxide 1309‐48‐4 < 0.01 < 0.1 2.18 0‐2 0 2.18
Aluminum oxide 0.14 0.63 0.14 0.63
Iron oxide 0.38 0.55 0.38 0.55
Potassium oxide 0.01 0.01 0.01
Sodium oxide 1313‐59‐3 < 0.06 < 0.06 0 0.06
Carbon dioxide
This substance would not be present
in gypsum under normal
temperatures/pressures as it is a gas. 1.16 1.16 1.16
Summary
SourceCAS#Chemical
Composition6Composition and Leaching of FGD Gypsum and
Mined Gypsum (2011)1, 2, 3
FGD Gypsum Mined Gypsum
Standards/References EPRI Reports Test Data FGD SDSs
The level of these substances may be
reported by the laboratory, however
they are not present in this form, but
rather react in the FGD process to
form FGD gypsum (CaSO4, dihydrate)
These substances are all components
of fly ash. The presence of these
substances is likely due to residual fly
ash that may be present at up to 2%
in FGD gypsum. The hazard
classification associated with fly ash,
as determined in the ACAA CCP SDS
Guidance Document, are incorporated
in the FGD gypsum summary tab.
Should additional information on the
fly ash composition be required, and
individual substance classifications,
please see that document.
2018_0112_FGD Gypsum Appendix C_updated_DF.xlsx
JANUARY 2018
TABLE C‐3
RAW ANALYTICAL DATA
FGD GYPSUM COMPOSITIONS SUMMARY WORKBOOK
FGD GYPSUM ACAA SDS GUIDANCE DOCUMENT
Page 5 of 8
FGD Gypsum Analytical/Compositional Data (Percent)
Parent Limestone/
Calcium Carbonate
ASTM C22/C 22M‐
00‐Standard
Specification for
Gypsum (2005)
United States
Gypsum Company
(USGC) Guidelines
Italy Specifications
for FGD Gypsum
for Reutilization
(Marinkovic et al.
2005)
Germany
Specifications for
FGD Gypsum for
Reutilization
(Marinkovic et al.
2005)
German Gypsum
Association
Guidelines
FGD Gypsum from
Bohemian Power Plant
(Marinkovic et al. 2005)
FGD Gypsum from W.H.
Zimmer Station in
Moscow, OH‐Cinergy
Corp. 4
(Spectrum Analytic)
Member Company Data Synthetic Gypsum SDS Synthetic Gypsum SDS Synthetic Gypsum SDS Limestone SDS
If declared
Minimum %
If declared
Maximum %
Summary
SourceCAS#Chemical
Composition6Composition and Leaching of FGD Gypsum and
Mined Gypsum (2011)1, 2, 3
FGD Gypsum Mined Gypsum
Standards/References EPRI Reports Test Data FGD SDSs
Magnesium 0.005‐0.6 0.03 0.03 0.03
Silica 0.007‐0.11 0.007 0.11
Aluminum 0.006‐0.16 0.006 0.16
Iron 0.0130‐0.18 0.013 0.18
Potassium 0.0029‐0.074 0.0029 0.074
Sodium
NOTES:
Note: Member has stated that
company internal standard is
that gypsum will be no less than
97% pure calcium sulfate
dihydrate.
Note on SDS: Synthetic
Gypsum is formed from the
reaction between limestone
and gaseous sulfur dioxide
that is generated during the
combustion of coal. Trace
amounts of components of
fly ash and other compounds
may be detected during
chemical analysis. Trace
components of synthetic
gypsum is variable depending
on the coal source, the coal
vein, and the limestone vein.
Synthetic gypsum contains
particles in the inhalable and
respirable range.
Note on SDS: Synthetic
Gypsum is formed from the
reaction between limestone
and gaseous sulfur dioxide,
formed from the combustion
of coal. Trace amounts of
components of fly ash and
other chemicals may be
detected during chemical
analysis. Depending on the
composition of coal and
limestone used, synthetic
gypsum may contain trace
amounts of magnesium
sulfate, sulfur compounds,
and other trace compounds.
1Total composition analysis for all elements was performed on the gypsum according to method SW‐846 3051a, a microwave assisted aqua regia digestion method. Digests were analyzed using a combination of ICP‐AES and ICP‐MS. Thirty two samples from 29 power plants were taken with 20 samples washed and
5 samples unwashed. Most concentrations of unwashed samples generally fall within the upper half of the range of concentrations for the washed samples. The ranges in this summary include both unwashed and washed samples.
2The concentrations for the following elements were below 500 mg/kg or 0.05% and were not considered further since they would not meet SDS disclosure requirements or have an impact on GHS classification of final material: As, B, Ba, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sr, Tl, V, Zn. Only elements
with concentrations greater than 0.05% were considered further for impact on SDS disclosure and GHS classification of final material.
3The impact of sorbents/additives injected for SO3 control was also analyzed for the 20 washed samples. 5 were from plants injecting lime‐based sorbents (Lime, ammonia), 6 were from plants injecting sodium‐based sorbents (Trona, Sodium sulfite, Sodium carbonate) and 6 were from plants that did not inject any
sorbent (and 3 were unknown). For both sorbent types, concentrations of most constituents were within the range of values for the six without SO3 controls and only minor differences between the groups. Concentrations of Be, Mg, Sr, Tl, and Zn were statistically higher in the lime‐based samples compared to no
control but still within the max range concentrations of all samples, while Ca, S, Se, and Si were lower. Only Na had a statistically significant higher concentration in the sodium‐based sorbent samples compared to no‐control, while Ca, K, S, Se, and Si concentrations were lower.
4Boron, iron, manganese, and phosphorus were also detected using EPA Method 3050 but were all under 300 ppm which is less than the 0.1% (1000 ppm) required for SDS disclosure or classification considerations. Trace metal content was also evaluated according to method EPA Part 503 for As, Cd, Cr, Co, Cu, Pb,
Hg, Mo, Ni, Se, and Zn with concentrations below 10 ppm which are again significantly below the 0.1% or 1000 ppm requiring SDS disclosure or consideration for classifications.
5Calcium sulfate, dihydrate levels were calculated by adding sulfur trioxide and calcium oxide levels resulting based on analytical method used. Based on analytical method used for FGD Gypsum, calcium oxide and sulfur trioxide may be reported; however, based on discussions with ACAA members, these two
substances would not exist individually but would combine to form calcium sulfate as part of the FGD process. Sulfur trioxide exists at room temperature either as a gas or a volatile liquid. Therefore, calcium oxide and sulfur trioxide is not anticipated to affect the final product classification or to be present in the
final formulation at levels requiring disclosure on the SDS.
6 Should any of these substances be identified in the laboratory report, they should be evaluated by a chemist familiar with the FGD process and FGD gypsum creation process. The substances are likely components of the calcium sulfate, dihydrate or fly ash added as part of the FGD process and should not be
reported on the SDS or considered in the calculation of the finished product hazard classification.
7 Calcium oxide will not exist or form in FGD gypsum due to the use of limestone as a reagent under acid conditions.
8 Calcium hydroxide will not form when limestone is used as reagent in the FGD gypsum process, it will only form when hydrated lime is used. For purposes of these analyses and the FGD gypsum SDS Guidance Document, FGD processes that use hydrated lime are excluded from consideration and subsequently
calcium hydroxide will not be considered further.
These substances would not appear in
their elemental form, but rather as
oxides, sulfates or chlorides.
None of these substances at the levels
identified would require disclosure on
the SDS or consideration in the FGD
gypsum classification.
2018_0112_FGD Gypsum Appendix C_updated_DF.xlsx
JANUARY 2018
TABLE C‐4
P‐CHEM PROPERTIES
FGD GYPSUM COMPOSITIONS SUMMARY WORKBOOK
FGD GYPSUM ACAA SDS GUIDANCE DOCUMENT
Page 6 of 8
EPRI Reports
PropertyUnited States Gypsum
Company (USGC)
Guidelines
Italy Specifications for FGD
Gypsum for Reutilization
(Marinkovic et al 2005)
Germany Specifications for
FGD Gypsum for Reutilization
(Marinkovic et al 2005)
German Gypsum
Association Guidelines
The Effects of Flue Gas
Desulfurization System Additives
on Solid By‐Products (1995)
(n=14)
FGD Gypsum from Bohemian
Power Plant
(Marinkovic et al 2005)
FGD Gypsum from W.H. Zimmer
Station in Moscow, OH‐Cinergy Corp.
(Spectrum Analytic)
pH 6‐8 5‐8 5‐8 5‐9 7.5
Particle size
Common Median: 35‐45 um
Minimum Acceptable
Median: 20 um
NAAverage Mean: 20.1 um*
Average Minimum: 2.7 um**120 microns
NOTES:
* 10 of the 14 samples had mean particle sizes between 17.5 and 22 um. Two samples had mean particle sizes of 31 and 35 um. Two samples had mean particle sizes of 8.7 and 14 um.
** 13 of 14 samples had a minimum particle size of between 1 and 2.5 um. A single sample had a minimum particle size of 12 um.
FGD Gypsum P‐Chem Properties
Test Data
2018_0112_FGD Gypsum Appendix C_updated_DF.xlsx JANUARY 2018
TABLE C‐5
POLLUTION CONTROL ADDITIVES
FGD GYPSUM COMPOSITIONS SUMMARY WORKBOOK
FGD GYPSUM ACAA SDS GUIDANCE DOCUMENT
Page 7 of 8
AdditiveSubstance in Final
ProductComments
Adipic acid <0.1%No disclosure required
No impact on gypsum classification
Dibasic acid <0.1%No disclosure required
No impact on gypsum classification
Formate <0.1%No disclosure required
No impact on gypsum classification
Sulfur <0.1%No disclosure required
No impact on gypsum classification
Chlorides <0.1%No disclosure required
No impact on gypsum classification
Activated Carbon <1%No disclosure required
No impact on gypsum classification
Potential FGD System Additives
2018_0112_FGD Gypsum Appendix C_updated_DF.xlsx JANUARY 2018
TABLE C‐6
REFERENCES
FGD GYPSUM COMPOSITIONS SUMMARY WORKBOOK
FGD GYPSUM ACAA SDS GUIDANCE DOCUMENT
Page 8 of 8
Source Notes
EPRI, 2008. Impact of Air Emissions Controls on Coal Combustion Products. Additive information.
EPRI, 2011. Composition and Leaching of FGD Gypsum and Mined Gypsum. 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%.
Marinkovic SR, Pulek AK, and Logar V. 2005. Recycling of Waste FGD Gypsum. ResearchGate. May
2005.
Contains standards for FGD Gypsum in Germany and Italy; Sample analyses from Bohemian power plant.
Spectrum Analytic. No date. Gypsum‐Benefits and Misconceptions. Available at:
http://www.spectrumanalytic.com/suppoort/library/rf/Gypsum.htm
Samples from W.H. Zimmer Station in Moscow, OH owned by Cinergy Corp.
Henkels, PR and Gaynor, JC. Characterizing Synthetic Gypsum for Wallboard Manufacture. United
States Gypsum Corporation (USGC).
German Gypsum Associate guidelines and USGC guidelines.
SDS from various ACAA member companies. Confidential formulary information.
ASTM International. 2012. Composition data.
European Chemicals Agency (ECHA). 2010a. REACH Registration Dossier for Calcium Sulfate.
http://apps.echa.europa.eu/registered/data/dossiers/DISS‐9ebe5c1d‐2d61‐3cd3‐e044‐
00144f67d031/DISS‐9ebe5c1d‐2d61‐3cd3‐e044‐00144f67d031_DISS‐9ebe5c1d‐2d61‐3cd3‐e044‐
00144f67d031.html. Accessed July, 2015.
Composition data.
U.S. Bureau of Mines. Crystalline Silica Primer.
http://minerals.usgs.gov/minerals/pubs/commodity/silica/780292.pdf. Accessed August 25, 2015.
Composition data.
EPRI, 1995. The Effects of Flue Gas Desulfurization (FGD) System Additives on Solid By‐Products. Additive information.
2018_0112_FGD Gypsum Appendix C_updated_DF.xlsx JANUARY 2018
August 2018
APPENDIX D
FGD Gypsum Analytical Methodologies
Appendix D FGD Gypsum Analytical Methodologies
It is the responsibility of each manufacturer, processer and distributer to assess the composition of their FGD gypsum, including impurities to accurately communicate the hazards of the product they are marketing to workers and downstream users through the Safety Data Sheet (SDS). This Appendix is provided as a guide to methodologies that may be useful in the determination of the FGD gypsum composition (including impurities). Interpretation of the results of these analyses requires a basic understanding of the chemistry of the coal combustion process and the flue gas desulfurization processes as well as the SDS requirements per OSHA HCS 2012. Results obtained using these methods must be taken in context of the material being sampled. Analytical Methods for Assessing the FGD Gypsum Purity and Impurities1 Table 1 of this Appendix specifies a list of analytical techniques that may be employed to assess the FGD gypsum purity and impurities. The included methods will identify the level of calcium sulfate, dihydrate (CaSO4, 2H2O) as well as potentially hazardous impurities that may be present in a typical FGD gypsum as defined in Table 1 of the ACAA FGD Gypsum SDS Guidance Document. Identified substances may require disclosure on the SDS and/or be considered in the determination of the hazard classification(s) of the FGD gypsum. The methodologies were derived from industry knowledge, the EPRI FGD Chemistry and Analytical Methods (Volume 1 and 2) and ASTM C 471M‐14: Standard Test Methods for Chemical Analysis of Gypsum and Gypsum Products [Metric] (EPRI, 2007; ASTM, 2014). None of the listed test methods are recommended by Haley & Aldrich, ACAA or any ACAA member companies. Additional analytical methods may be required to determine other impurities anticipated in a particular FGD gypsum but not identified as present in the typical FGD composition. If based on process knowledge or prior test results, other impurities/substances not listed in Table 1 of the FGD Gypsum SDS Guidance are identified above 0.1%, they should be evaluated to determine if they are present. If additional substances are identified, their hazard classification should be determined to assess SDS disclosure obligations and determine if their presence will affect the final FGD gypsum hazard classification. It is recommended that a person versed in OSHA HCS 2012 hazard classification methodology as well as SDS development perform this evaluation. Further, as oxides of aluminum, iron, potassium, sodium, magnesium and manganese (among others), are likely present as components of fly ash which may either be added or present as an impurity in the gypsum, these substances should not be listed individually but rather are considered to be present as a component of fly ash.
1 The methods included in this Appendix will identify substances that may affect the FGD gypsum hazard classification and SDS communication requirements based on the typical FGD composition presented in the ACAA FGD Gypsum SDS Guidance Document; they may not identify impurities that trigger other regulatory obligations (i.e., mercury levels).
Appendix D FGD Gypsum Analytical Methodologies Page 2 of 3
Table 1: Analytical Methods that may be used to Determine FGD Gypsum Purity and Impurity Levels 1
Analytical Technique Compound(s) Identified
Thermogravimetric Analysis Determination of Solid Concentration and Gypsum (CaSO4) Purity
Particle Size Methods – Wet Screening Slurry Particle Size
Atomic Absorption Spectroscopy Calcium, magnesium, sodium, potassium, iron, manganese and aluminum
Ion Chromatography Fluoride, chloride, sulfite, sulfate, thiosulfate and total sulfur
EDTA Titration Calcium and magnesium in scrubber solids
Iodine‐thiosulfate Titration Sulfite determination
Acid‐Base Titration Carbonates, oxides and hydroxides
Coulometric Determination Carbonates
Mercuric Nitrate Titration, Chloride Ion Specific Electrode Chlorides
1 The test methods defined will identify compounds present in a typical FGD gypsum composition (as determined in the ACAA FGD Gypsum SDS Guidance Document). Should additional hazardous substances be identified above 0.1% using these or other test methodologies, they should be considered in the FGD gypsum hazard classification and SDS communication obligations.
Appendix D FGD Gypsum Analytical Methodologies Page 3 of 3
Potential Analytical Laboratories Although some ACAA member companies analyze their gypsums in‐house, the laboratories listed in Table 2 have been used by ACAA member companies to perform some or all testing required to determine the purity and impurities of their gypsum. Inclusion on this list does not imply an endorsement of a specific laboratory, nor does exclusion from this list imply that a laboratory is not capable or qualified to provide the data necessary to determine the composition of a given FGD gypsum. Additional laboratories may be added to the list below as they become known.
Table 2: Analytical Testing Laboratories
SGS North America Inc. / Minerals Services Division http://www.sgsgroup.us.com
4665 Paris Street, Suite B‐200 Denver, CO 80239
Wyoming Analytical 1511 Washington Avenue Golden, CO 80401 (303) 278‐2446
RJ Lee Group, Inc. (Headquarters) http://www.rjlg.com/
350 Hochberg Road Monroeville, PA 15146 (724) 325‐1776 Fax: (724) 733‐1799
Xenco Laboratories http://www.xenco.com/
Energy Laboratories www.energylab.com
Helena, MT (877) 472‐0711 Billings, MT (800) 735‐4489 Casper, WY (888) 235‐0515 Gilletts, WY (866) 686‐7175 Rapid City, SD (888) 872‐1225 College Station, TX (888) 690‐2218
TestAmerica http://testamericainc.com/
Innogyps www.innogyps.com
122‐7 Innovation Drive Flamborough, Ontario Canada (905) 690‐6161 [email protected]
RESPIRABLE SILICA – this lab says they can get to 0.1% detection limit DCM Science Laboratory https://www.dcmsciencelab.com/ 12421 W. 49th Avenue, Unit #6 Wheat Ridge, CO 80033 Office: 303.463.8270 800.852.7340 ‐ Toll‐Free 303.463.8267 ‐ Fax