July 2005 System Assessment and Validation for Emergency Responders (SAVER)

Summary

Guide for the Selection of Chemical Agent and Toxic Industrial Material Detection Equipment for

The U.S. Department of Homeland Emergency First Responders, Guide Security (DHS) established the System 100­04, Volume I and II Assessment and Validation for Emergency Responders (SAVER) Program to assist emergency responders This document focuses specifically on chemical agent (CA) and toxic making procurement decisions. industrial material (TIM) detection equipment and was developed to Located within the Science and assist the emergency responder community in the evaluation and Technology Directorate (S&T) of DHS, purchase of detection equipment. The information contained in the the SAVER Program conducts objective guide was obtained through literature searches and market surveys. operational tests on commercial Vendors were contacted multiple times during the preparation of the equipment and systems and provides those results along with other relevant guide to ensure data accuracy, and information is supplemented with equipment information to the emergency test data from other sources (e.g., Department of Defense) if response community in an operationally available. The guide is an update of the Guide for the Selection of useful form. SAVER provides Chemical Agent and Toxic Industrial Material Detection Equipment information on equipment that falls for Emergency First Responders, NIJ Guide 100­04, published in within the categories listed in the DHS Authorized Equipment List (AEL). June 2000.

The SAVER Program is supported by a network of technical agents who perform Background assessment and validation activities. Further, SAVER focuses primarily on The Office of Law Enforcement Standards (OLES) at the National two main questions for the emergency Institute of Standards and Technology (NIST), supported by the responder community: “What equipment is available?” and “How does it Department of Homeland Security (DHS), the Technical Support perform?” Working Group (TSWG), the U.S. Army Edgewood Chemical and To contact the SAVER Program Biological Center (ECBC), and the Interagency Board for Equipment Support Office Standardization and Interoperability (IAB), has developed chemical Telephone: 877­336­2752 and biological defense equipment guides. The guides focus on E­mail: [email protected] chemical and biological equipment in areas of detection, personal Visit the SAVER Web site: protection, decontamination, and communication. https://www.rkb.us/saver

Reference herein to any specific commercial The primary purpose of the Guide for the Selection of Chemical products, processes, or services by trade Agent and Toxic Industrial Material Detection Equipment for name, trademark, manufacturer, or otherwise Emergency First Responders is to provide emergency responders does not constitute or imply its endorsement, recommendation, or favoring by the United with information to aid them in the selection and utilization of CA States Government. Neither the United States and TIM detection equipment. The guide is intended to be more Government nor any of its employees make practical than technical and provides information on a variety of any warranty, express or implied, including but not limited to the warranties of merchantability and fitness for a particular purpose for any specific commercial product, process, or service referenced herein.

The nerve agents considered in the guide factors that should be considered when are described below. The term volatility purchasing and using detection equipment, refers to a substance’s ability to become a including sensitivity, detection states, and vapor at relatively low temperatures. A portability to name a few. Due to the large highly volatile (nonpersistent) substance number of chemical detection equipment poses a greater respiratory hazard than a less items identified in the guide, the guide is volatile (persistent) substance. separated into two volumes. Volume I

represents the actual guide and Volume II serves as a supplement to Volume I since it • GA: A low volatility persistent CA that contains the detection equipment data sheets is taken up through skin contact and only. inhalation of the substance as a gas or aerosol. Chemical Agents • GB: A volatile nonpersistent CA that is Chemical agents are chemical substances that mainly taken up through inhalation. are intended for use in warfare or terrorist • GD: A moderately volatile CA that can activities to kill, seriously injure, or seriously be taken up by inhalation or skin incapacitate people through their physiological contact. effects. A CA attacks the organs of the human body in such a way that it prevents those organs • GF: A low volatility persistent CA that from functioning normally. The results are is taken up through skin contact and usually disabling or even fatal. Chemical inhalation of the substance either as a agents, when referred to in the guide, refer to gas or aerosol. nerve and blister agents only. The most VX common CAs are the nerve agents, GA • : A low volatility persistent CA that (Tabun), GB (Sarin), GD (Soman), GF, and can remain on material, equipment, and VX; the blister agents, HD (sulfur mustard) and terrain for long periods. Uptake is HN (nitrogen mustard); and the arsenical mainly through the skin but also through vesicants, L (Lewisite). inhalation of the substance as a gas or aerosol. Nerve Agents Nerve agents, either as a gas, aerosol, or liquid, enter the body through inhalation or All nerve agents belong to the chemical group through the skin. Poisoning may also occur of organo­phosphorus compounds; many through consumption of liquids or foods common herbicides and pesticides also belong contaminated with nerve agents. The route to this chemical group. Nerve agents are stable, of entry also influences the symptoms easily dispersed, highly toxic, and have rapid developed and, to some extent, the sequence effects when absorbed both through the skin of the different symptoms. Generally, the and the respiratory system. Nerve agents can be poisoning works fastest when the agent is manufactured by means of fairly simple absorbed through the respiratory system chemical techniques. The raw materials are rather than other routes because the lungs inexpensive but some are subject to the controls contain numerous blood vessels and the of the Chemical Weapons Convention and the inhaled nerve agent can rapidly diffuse into Australia Group Agreement. the

2

the blood circulation and thus reach the target in most organic solvents but has negligible organs. If a person is exposed to a high solubility in water. In aqueous solutions, concentration of nerve agent, death may occur mustard agent decomposes into nonpoisonous within a couple of minutes. products by means of hydrolysis but, since only dissolved mustard agent reacts, the The poisoning works slower when the agent is decomposition proceeds very slowly. Oxidants absorbed through the skin. Because nerve such as chloramine, however, react violently agents are somewhat fat­soluble, they can with mustard agent, forming nonpoisonous easily penetrate the outer layers of the skin, but oxidation products. Consequently, these it takes longer for the poison to reach the substances are used for the decontamination of deeper blood vessels. Consequently, the first mustard agent. symptoms do not occur until 20 minutes to 30 minutes after the initial exposure but Arsenical vesicants are not as common or as subsequently, the poisoning process may be stable as the sulfur or nitrogen mustards. All rapid if the total dose of nerve agent is high. arsenical vesicants are colorless to brown liquids. They are more volatile than mustard Blister Agents and have fruity to geranium­like odors. These types of vesicants are much more dangerous as There are two major families of blister agents liquids than as vapors. Absorption of either (vesicants): sulfur mustard (HD) and nitrogen vapor or liquid through the skin in adequate mustard (HN), and the arsenical vesicants (L). dosage may lead to systemic intoxication or All blister agents are persistent and may be death. employed in the form of colorless gases and liquids. They burn and blister the skin or any Most blister agents are relatively persistent other part of the body they contact. Blister and are readily absorbed by all parts of the agents are likely to be used to produce body. Poisoning may also occur through casualties rather than to kill, although exposure consumption of liquids or foods contaminated to such agents can be fatal. with blister agents. These agents cause inflammation, blisters, and general destruction In its pure state, mustard agent is colorless and of tissues. almost odorless. It earned its name as a result of an early production method that resulted in In the form of gas or liquid, mustard agent an impure product with a mustard­like smell. attacks the skin, eyes, lungs, and Mustard agent is also claimed to have a gastrointestinal tract. Internal organs, mainly characteristic odor similar to rotten onions. blood­generating organs, may also be injured However, the sense of smell is dulled after as a result of mustard agent being taken up only a few breaths so after initial exposure the through the skin or lungs and transported into odor can no longer be distinguished. In the body. Since mustard agent gives no addition, mustard agent can cause injury to the immediate symptoms upon contact, a delay of respiratory system in concentrations that are so between 2 hours and 24 hours may occur low that the human sense of smell cannot before pain is felt and the victim becomes distinguish them. aware of what has happened. By then, cell damage has already occurred. The delayed At room temperature, mustard agent is a liquid effect is a characteristic of mustard agent. with low volatility and is very stable during storage. Mustard agent can easily be dissolved 3

Toxic Industrial Materials TIM that has high toxicity and is easily vaporized. Medium Hazard indicates a TIM Toxic industrial materials are chemicals that may rank high in some categories but other than chemical warfare agents that have lower in others such as number of producers, harmful effects on humans. Toxic industrial physical state, or toxicity. Low Hazard materials, often referred to as toxic industrial indicates that this TIM is not likely to be a chemicals (TICs) are used in a variety of hazard unless specific operational factors settings such as manufacturing facilities, indicate otherwise. Table 1 lists TIMs by maintenance areas, and general storage areas. hazard index (see Page 5). While exposure to some of these chemicals may not be immediately dangerous to life Overview of Chemical Agent and and health, these compounds may have TIM Detection Technologies extremely serious effects on an individual’s health after multiple low­level exposures. The applicability of CA and TIM detection equipment to potential user groups will be Although they are not as lethal as the highly dependent upon the characteristics of the toxic nerve agents, TIMs’ ability to make a detection equipment, as well as the type of significant impact on the populace is CA or TIM detected and the objective of the assumed to be more related to the amount of emergency responder unit. Numerous chemical a terrorist can employ on the technologies are available for the detection of target(s) and less related to their lethality. CA and TIM vapors; some technologies are None of these compounds are as highly toxic available for detection and identification of as the nerve agents, but they are produced in liquid droplets of CAs on surfaces; and many very large quantities (multi­ton) and are laboratory­based technologies exist for readily available; therefore, they pose a far detection of TIMs in water. The quality of greater threat than CAs. analytical results from the various analyzers is dependent upon the ability to effectively For instance, sulfuric acid is not as lethal as sample the environment and get the sample to the nerve agents, but it is easier to the analyzer. disseminate large quantities of sulfuric acid because of the large amounts that are Equipment designed for vapor detection will manufactured and transported every day. It is not be readily applicable for detection of low assumed that a balance is struck between the volatility liquid contamination on surfaces or lethality of a material and the amount of contamination in water. In addition, vapor materials produced worldwide. Other toxic detection equipment could have difficulty in chemicals such as hydrogen cyanide identifying a small amount of CA or TIM in a (characterized as a chemical blood agent by high background of nonhazardous the military) or phosgene (characterized as a environmental chemicals. For example, a choking agent) are included as TIMs. chemical vapor detector may readily detect trace levels of CAs or TIMs in a rural setting TIMs are ranked into one of three such as a forest or an open field, but the same categories—high, medium, low—that detector may not be capable of detecting the indicate their relative importance and assist same level of CA or TIM in an urban setting in hazard assessment. High Hazard indicates such as a crowded subway station or busy city a widely produced, stored, or transported street. More urban (continued on page 6)

4

High Medium Low Ammonia Acetone cyanohydrin Ally isothiocyanate Arsine Acrolein Arsenic trichloride Borontrichloride Acrylonitrile Bromine Boron trifluoride Allyl alcohol Bromine chloride Carbon disulfide Allylamine Bromine pentafluoride Chlorine Allyl chlorocarbonate Bromine trifluoride Diborane Boron tribromide Carbonyl fluoride Ethylene oxide Carbon monoxide Chlorine pentafluoride Fluorine Carbonyl sulfide Chlorine trifluoride Formaldehyde Chloroacetone Chloroacetaldehyde Hydrogen bromide Chloroacetonitrile Chloroacetyl chloride Hydrogen chloride Chlorosulfonic acid Crotonaldehyde Hydrogen cyanide Diketene Cyanogen chloride Hydrogen fluoride 1,2­Dimethylhydrazine Dimethyl sulfate Hydrogen sulfide Ethylene dibromide Diphenylmethane­4,4'­diisocyanate Nitric acid, fuming Hydrogen selenide Ethyl chloroformate Phosgene Methanesulfonyl chloride Ethyl chlorothioformate Phosphorus trichloride Methyl bromide Ethyl phosphonothioic dichloride Sulfur dioxide Methyl chloroformate Ethyl phosphonic dichloride Sulfer acid Methyl chlorosilane Ethyleneimine Tungsten hexafluoride Methyl hydrazine Hexachlorocyclopentadiene Methyl isocyanate Hydrogen iodide Methyl mercaptan Iron pentacarbonyl Nitrogen dioxide Isobutyl chloroformate Phosphine Isopropyl chloroformate Phosphorus oxychloride Isopropyl isocyanate Phosphorus pentafluoride n­Butyl chloroformate Selenium hexafluoride n­Butyl isocyanate Silicon tetrafluoride Nitric oxide Stibine n­Propyl chloroformate Sulfur trioxide Parathion Sulfuryl chloride Perchloromethyl mercaptan Sulfuryl fluoride sec­Butyl chloroformate Tellurium hexafluoride tert­Butyl isocyanate n­Octyl mercaptan Tetraethyl lead Titanium tetrachloride Tetraethyl pyroposphate Trichloroacetyl chloride Tetramethyl lead Trifluoroacetyl chloride Toluene 2,4­diisocyanate Toluene 2,6­diisocyanate Table 1. Toxic industrial materials listed by hazard index 5

environments typically contain many life threatening, point detectors may not chemicals produced by everyday human provide sufficient time to take protective activities (driving an automobile, deodorant/ measures. perfumes use, insecticide/herbicide application, etc.) that look like a CA or TIM Another use of a point detector would be to to the detection equipment and may affect the monitor the vapor contamination originating reliability (number of false readings) of the from a decontamination site. Point detectors instrument as well as its sensitivity. However, can also be used during post­release triage to by testing the equipment prior to an determine the contamination level of each emergency use, the operator can become person (i.e., highly contaminated personnel, familiar with the idiosyncrasies of the lightly contaminated personnel, and detection equipment when exposed to various uncontaminated personnel) with the idea that environmental chemicals expected in all contaminated people need rapid operational areas. As technological advances decontamination while noncontaminated continue to be made, more effective and people do not need to be decontaminated. accurate methods of detection that are less This allows for conservation of affected by environmental chemicals in decontamination resources and prevents operational areas will become commercially wasted effort on noncontaminated personnel. available at lower costs. The following point detection techniques were identified in the guide: Chemical agents can be detected by several means that incorporate various technologies. The technologies discussed in this guide are • Ionization/Ion Mobility Spectrometry (18 grouped into three major categories: point items identified) detection, standoff detection, and analytical • Flame Photometry (7 items identified) instruments. The technology needed for CA and TIM detection will be dependent on the • Infrared Spectroscopy (5 items identified) CA agent or TIM used and the objective of • Electrochemistry (63 items identified) the emergency responder unit. • Colorimetric (24 items identified) Point Detection Technologies • Surface Acoustic Wave (4 items Point detection technology is applicable in identified) determining the presence of CA or TIM and • Photoionization Detection (8 items can be used to map out contaminated areas if identified) enough time is available. Point detectors can be used as warning devices to alert personnel • Thermal and Electrical Conductivity (2 to the presence of a toxic vapor cloud. In this items identified) scenario, the detector is placed up­wind of the first responder location. When the toxic • Flame Ionization (1 item identified) chemical is carried towards this location, it • Polymer Composite Detection Materials first encounters the detector, thus sounding an (1 item identified) alarm and allowing the emergency responders to don the necessary protective clothing. It should be noted that if the concentration of CA or TIM is high enough to be immediately 6

Standoff Detectors developed for field applications. The following analytical techniques were Standoff detectors are used to give advance identified in the guide: warning of a CA cloud. Standoff detectors typically use optimal spectroscopy and can • Mass Spectrometry (15 items identified) detect CAs at distances as great as 5 km. • Gas Chromatography (14 items Agent­free spectra are used as a baseline to identified) compare with freshly measured spectra that may contain CA. Standoff detectors are • High Performance Liquid generally difficult to operate and usually Chromatography (4 items identified) require the operator to have some knowledge of spectroscopy in order to interpret results. • Ion Chromatography (1 item identified) Passive standoff detectors collect infrared • Capillary Zone Electrophoresis (1 item radiation emitted and/or measure infrared identified) radiation absorbed from the background to detect CA and TIM vapor clouds. The Detection Equipment Selection following standoff techniques were identified Factors in the guide: The guide recommends the emergency • Fourier Transform Infrared and Forward responder community consider 16 selection Looking Infrared (6 items identified) factors when selecting and purchasing CA and TIM detection equipment. The selection • Ultraviolet Spectroscopy (1 item identified) factors were compiled by a panel of scientists and engineers with multiple years of experience and relevant expertise in the areas Analytical Instruments of CA and TIM detection, identification and analysis, domestic preparedness, and Analytical instruments can be used to analyze identification of emergency responder needs. samples as small as a few microliters or The factors have also been shared with the milligrams. They are designed to differentiate emergency responder community in order to between and accurately measure the unique obtain their thoughts and comments. The chemical properties of different molecules. following analytical techniques were Accuracy and reliability requires that only very identified in the guide: pure reagents be used, very rigid protocol and operating procedures be followed, and careful • Mass Spectrometry (15 items identified) handling be employed to prevent • Gas Chromatography (14 items contamination and malfunction. Since the identified) instruments do not display the measured data in a straightforward manner, interpretation of • High Performance Liquid the measured data generally requires a Chromatography (4 items identified) technical background and extensive formal • Ion Chromatography (1 item identified) training. This typically precludes their use outside of a laboratory environment, which is • Capillary Zone Electrophoresis (1 item staffed by technically trained people. However, identified) some analytical instruments have been

7

Detection Equipment Selection Equipment Evaluation Factors The market survey conducted for CA and The guide recommends the emergency TIM detection equipment identified 186 responder community consider 16 selection different pieces of detection equipment. The factors when selecting and purchasing CA and details of the market survey to include data TIM detection equipment. The selection on each piece of equipment are provided in factors were compiled by a panel of scientists Volume II of the guide. Each equipment item and engineers with multiple years of was evaluated against the 16 selection factors experience and relevant expertise in the areas and the results are presented in Volume I. of CA and TIM detection, identification and In order to display the evaluation results in a analysis, domestic preparedness, and meaningful format, the detection equipment identification of emergency responder needs. was grouped into seven categories based on The factors have also been shared with the the prospective manner of usage by the emergency responder community in order to emergency responder community. These obtain their thoughts and comments. The usage categories included the following: factors are as follows: • Handheld­portable detection equipment • Chemical agents detected (92 equipment items identified) • Toxic industrial materials detected • Handheld­stationary detection equipment • Sensitivity (31 equipment items identified) • Resistance to interferents • Vehicle­mounted detection equipment (5 equipment items identified) • Response time • Fixed­site detection systems equipment • Start­up time (16 items identified) • Detection states • Fixed­site analytical laboratory systems (13 equipment items identified) • Alarm capability • Standoff detection systems items (4 • Portability equipment identified) • Battery needs • Detection systems with limited data (25 • Power capabilities equipment items identified). • Operational environment Along with the evaluation results of the 186 pieces of detection equipment, a series of • Durability questions are offered that should assist • Unit cost officials in selecting products from the large number in the present day marketplace. • Operator skill level For more information, or for reports on • Training requirements. other technologies, visit the SAVER Web site (https://www.rkb.us/saver).

8