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H A Z A R D O U S M A T E R I A L S C O O P E R A T I V E R E S E A R C H P R O G R A M HMCRP REPORT 13 Test Procedures and Classification Criteria for Release of Toxic Gases from Water-Reactive Materials Gregory M. Smith ScienceSmith conSulting, inc. Englishtown, NJ Jonathan Chun Anatoly Nemzer AlliAnce technologieS, llc Monmouth Junction, NJ Bob Richard lAbelmASter ServiceS, inc. Chicago, IL Subscriber Categories Marine Transportation ⢠Railroads ⢠Safety and Human Factors TRANSPORTAT ION RESEARCH BOARD WASHINGTON, D.C. 2014 www.TRB.org Research sponsored by the Pipeline and Hazardous Materials Safety Administration
HAZARDOUS MATERIALS COOPERATIVE RESEARCH PROGRAM The safety, security, and environmental concerns associated with transportation of hazardous materials are growing in number and complexity. Hazardous materials are substances that are flammable, explosive, or toxic or that, if released, produce effects that would threaten human safety, health, the environment, or property. Hazardous materials are moved throughout the country by all modes of freight transportation, including ships, trucks, trains, airplanes, and pipelines. The private sector and a diverse mix of government agencies at all levels are responsible for controlling the transport of hazardous materials and for ensuring that hazardous cargoes move without incident. This shared goal has spurred the creation of several venues for organizations with related interests to work together in preventing and responding to hazardous materials incidents. The freight transportation and chemical industries; government regulatory and enforcement agencies at the federal and state levels; and local emergency planners and responders routinely share information, resources, and expertise. Nevertheless, there has been a long- standing gap in the system for conducting hazardous materials safety and security research. Industry organizations and government agencies have their own research programs to support their mission needs. Collaborative research to address shared problems takes place occasionally, but mostly occurs on an ad hoc basis. Acknowledging this gap in 2004, the U.S. DOT Office of Hazardous Materials Safety, the Federal Motor Carrier Safety Administration, the Federal Railroad Administration, and the U.S. Coast Guard pooled their resources for a study. Under the auspices of the Transportation Research Board (TRB), the National Research Council of the National Academies appointed a committee to examine the feasibility of creating a cooperative research program for hazardous materials transportation, similar in concept to the National Cooperative Highway Research Program (NCHRP) and the Transit Cooperative Research Program (TCRP). The committee concluded, in TRB Special Report 283: Cooperative Research for Hazardous Materials Transportation: Defining the Need, Converging on Solutions, that the need for cooperative research in this field is significant and growing, and the committee recommended establishing an ongoing program of cooperative research. In 2005, based in part on the findings of that report, the Safe, Accountable, Flexible, Efficient Transportation Equity Act: A Legacy for Users (SAFETEA-LU) authorized the Pipeline and Hazardous Materials Safety Administration (PHMSA) to contract with the National Academy of Sciences to conduct the Hazardous Materials Cooperative Research Program (HMCRP). The HMCRP is intended to complement other U.S. DOT research programs as a stakeholder-driven, problem-solving program, researching real-world, day-to-day operational issues with near- to mid- term time frames. Published reports of the HAZARDOUS MATERIALS COOPERATIVE RESEARCH PROGRAM are available from: Transportation Research Board Business Office 500 Fifth Street, NW Washington, DC 20001 and can be ordered through the Internet at: http://www.national-academies.org/trb/bookstore Printed in the United States of America HMCRP REPORT 13 Project HM-14 ISSN 2150-4849 ISBN: 978-0-309-30799-4 Library of Congress Control Number 2014948976 © 2014 National Academy of Sciences. All rights reserved. COPYRIGHT INFORMATION Authors herein are responsible for the authenticity of their materials and for obtaining written permissions from publishers or persons who own the copyright to any previously published or copyrighted material used herein. Cooperative Research Programs (CRP) grants permission to reproduce material in this publication for classroom and not-for-profit purposes. Permission is given with the understanding that none of the material will be used to imply TRB, AASHTO, FAA, FHWA, FMCSA, FTA, Office of the Assistant Secretary for Research and Technology, or PHMSA endorsement of a particular product, method, or practice. It is expected that those reproduc- ing the material in this document for educational and not-for-profit uses will give appropriate acknowledgment of the source of any reprinted or reproduced material. For other uses of the material, request permission from CRP. NOTICE The project that is the subject of this report was a part of the Hazardous Materials Cooperative Research Program, conducted by the Transportation Research Board with the approval of the Governing Board of the National Research Council. The members of the technical panel selected to monitor this project and to review this report were chosen for their special competencies and with regard for appropriate balance. The report was reviewed by the technical panel and accepted for publication according to procedures established and overseen by the Transportation Research Board and approved by the Governing Board of the National Research Council. The opinions and conclusions expressed or implied in this report are those of the researchers who performed the research and are not necessarily those of the Transportation Research Board, the National Research Council, or the program sponsors. The Transportation Research Board of the National Academies, the National Research Council, and the sponsors of the Hazardous Materials Cooperative Research Program do not endorse products or manufacturers. Trade or manufacturersâ names appear herein solely because they are considered essential to the object of the report.
The National Academy of Sciences is a private, nonprofit, self-perpetuating society of distinguished scholars engaged in scientific and engineering research, dedicated to the furtherance of science and technology and to their use for the general welfare. Upon the authority of the charter granted to it by the Congress in 1863, the Academy has a mandate that requires it to advise the federal government on scientific and technical matters. Dr. Ralph J. Cicerone is president of the National Academy of Sciences. The National Academy of Engineering was established in 1964, under the charter of the National Academy of Sciences, as a parallel organization of outstanding engineers. It is autonomous in its administration and in the selection of its members, sharing with the National Academy of Sciences the responsibility for advising the federal government. The National Academy of Engineering also sponsors engineering programs aimed at meeting national needs, encourages education and research, and recognizes the superior achievements of engineers. Dr. C. D. Mote, Jr., is president of the National Academy of Engineering. The Institute of Medicine was established in 1970 by the National Academy of Sciences to secure the services of eminent members of appropriate professions in the examination of policy matters pertaining to the health of the public. The Institute acts under the responsibility given to the National Academy of Sciences by its congressional charter to be an adviser to the federal government and, upon its own initiative, to identify issues of medical care, research, and education. Dr. Victor J. Dzau is president of the Institute of Medicine. The National Research Council was organized by the National Academy of Sciences in 1916 to associate the broad community of science and technology with the Academyâs purposes of furthering knowledge and advising the federal government. Functioning in accordance with general policies determined by the Academy, the Council has become the principal operating agency of both the National Academy of Sciences and the National Academy of Engineering in providing services to the government, the public, and the scientific and engineering communities. The Council is administered jointly by both Academies and the Institute of Medicine. Dr. Ralph J. Cicerone and Dr. C. D. Mote, Jr., are chair and vice chair, respectively, of the National Research Council. The Transportation Research Board is one of six major divisions of the National Research Council. The mission of the Transporta- tion Research Board is to provide leadership in transportation innovation and progress through research and information exchange, conducted within a setting that is objective, interdisciplinary, and multimodal. The Boardâs varied activities annually engage about 7,000 engineers, scientists, and other transportation researchers and practitioners from the public and private sectors and academia, all of whom contribute their expertise in the public interest. The program is supported by state transportation departments, federal agencies including the component administrations of the U.S. Department of Transportation, and other organizations and individu- als interested in the development of transportation. www.TRB.org www.national-academies.org
C O O P E R A T I V E R E S E A R C H P R O G R A M S AUTHOR ACKNOWLEDGMENTS The research reported herein was performed under HMCRP Project HM-14 via a collaboration between ScienceSmith Consulting, Inc., Alliance Technologies, LLC, and Labelmaster Services, Inc. Gregory M. Smith, PhD, Managing Principal at ScienceSmith Consulting, Inc., served as principal investigator and project lead. The other authors of this report are Jonathan Chun, PhD, Director of Tech- nology, and Anatoly Nemzer, Director of Operations, both of Alliance Technologies, LLC, and Bob Rich- ard, Vice President, Regulatory Affairs, Labelmaster Services, Inc. Most of the experimental work reported in this research report was carried out by William Poinsett of Alliance Technologies, LLC. CRP STAFF FOR HMCRP REPORT 13 Christopher W. Jenks, Director, Cooperative Research Programs Edward T. Harrigan, Senior Program Officer Anthony P. Avery, Senior Program Assistant Eileen P. Delaney, Director of Publications Ellen M. Chafee, Editor HMCRP PROJECT 14 PANEL Robert D. Waters, Sandia National Laboratories, Albuquerque, NM (Chair) Geoffrey J. Davies, National Cargo Bureau, Inc., New York, NY Anne Ellis, Arizona DOT, Phoenix, AZ Robert E. Fronczak, Association of American Railroads, Washington, DC Michael C. Strong, Wacker Chemical Corporation, Adrian, MI David Willauer, IEM, Inc., Arlington, VA Richard C. Bornhorst, FAA Liaison Roxane A. Drayton-Greene, FMCSA Liaison Joseph Nicklous, PHMSA Liaison George R. Famini, US Department of Homeland Security Liaison
F O R E W O R D By Edward T. Harrigan Staff Officer Transportation Research Board This report presents a proposed improved procedure for measuring the rate of gas pro- duction when a water-reactive material evolving either a flammable gas or a toxic gas is combined with water. Water-reactive materials, which are defined in international regulations as substances that, in contact with water, release flammable gases, are assigned to USDOT Hazard Class 4.3. The gases released may also be toxic. For instance, silicon tetrachloride, when in contact with water, releases hydrogen chloride. However, the present test procedures and classifica- tion criteria for Hazard Class 4.3 do not take into account (1) water reactions that may lead to the release of toxic gases, (2) the quantity of water-reactive substances being shipped, or (3) the potential effect of water salinity on release of toxic gases. The objective of HMCRP Project HM-14 was to develop a test procedure and classifica- tion criteria for water-reactive materials that take account of the potential release of toxic gases during transport. The research was performed by ScienceSmith Consulting, Inc., Eng- lishtown, New Jersey, with support from Alliance Technologies, LLC, Monmouth Junction, New Jersey, and Labelmaster Services, Inc., Chicago, Illinois. The initial phase of the research was a critical review of the worldwide literature on water-reactive materials test procedures, test results for various water-reactive materials, and potential flammable and toxic reaction products. Then testing variables that should be specified as part of the testing procedures and shortcomings in present procedures were identified. Based on these results, a laboratory program was carried out to develop and vali- date a precise, reliable test procedure and classification criteria. The procedure presented in the report is capable of determining the rate at which flammable gas or toxic gas is produced when a substance is combined with water, under laboratory conditions, in a closed vessel, by monitoring the change in pressure as a function of time after the substance and water are mixed. This report fully documents the research and includes the following Appendixes: ⢠Appendix A: Full Technical Test Description ⢠Appendix B: Proposed Classification System ⢠Appendix C: ASTM Format Test Procedure
C O N T E N T S Note: Many of the photographs, figures, and tables in this report have been converted from color to grayscale for printing. The electronic version of the report (posted on the Web at www.trb.org) retains the color versions. 1 Summary 3 Chapter 1 Background 4 Chapter 2 Research Approach 6 Chapter 3 Findings and Applications 8 Chapter 4 Conclusions and Suggested Research 9 References 10 Abbreviations, Acronyms, and Initialisms 11 Appendix A Full Technical Test Description 46 Appendix B Proposed Classification System 48 Appendix C ASTM Format Test Procedure
