Document 62m1LGzgp9yon342V4nGj1e1

EPA-600/2-78-055 arch 1978 Environmental Pratectioo Technology Series DEVELOPMENT OF A KIT FOR DETECTM6 HAZARDOUS MATERIAL SPILLS IN WATERWAYS ' 1 ,jr`Vf* *, i' ' h ' ' ' ' U 1`. CCR 000040596*) Industrial Environmental Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Cincinnati, Ohio 45268 RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U S, Environmental Protection Agency, have been grouped into nine series. These nine broad cate gories were established to facilitate further development and application of en vironmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The nine series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies 6. Scientific and Technical Assessment Reports (STAR) 7. Interagency Energy-Environment Research and Development 8. "Special" Reports 9. Miscellaneous Reports This report has been assigned to the ENVIRONMENTAL PROTECTION TECH NOLOGY series. This series describes research performed to develop and dem onstrate instrumentation, equipment, and methodology to repair or prevent en vironmental degradation from point and non-point sources of pollution. This work provides the new or improved technology required for the control and treatment of pollution sources to meet environmental quality standards. f, ,L '11't This document is available to the public through the National Technical Informa tion Service, Springfield, Virginia 22161. EPA-600/2-78-055 March 1978 DEVELOPMENT OF A KIT FOR DETECTING HAZARDOUS MATERIAL SPILLS IN WATERWAYS by A. Silvestri, A. Goodman, L. M. McCormack, M. Razulis, A. R. Jones, Jr., and M. E. P. Davis Chemical Systems Laboratory Aberdeen Proving Ground, Maryland 21010 EPA-IAG-0546 Project Officer Joseph P. Lafornara Oil and Hazardous Material Spills Branch Industrial Environmental Research Laboratory - Cincinnati Edison, New Jersey 08817 INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268 OCR 000040598 DISCLAIMER This report has been reviewed by the Industrial Environmental Research Laboratory-Cincinnati, U.S. Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorse ment or recommendation for use. ii 0000^05" CCR FOREWORD When energy and material resources are extracted, processed, converted, and used, the related pollutlonal impacts on our environment and even on our health often require that new and Increasingly more efficient pollution control methods be used, the Industrial Environmental Research Laboratory - Cincinnati (IERL-Ci) assists in developing and demonstrating new and improved methodologies that will meet these needs both efficiently and economically. This report is a product of the above efforts. It documents the laboratory and field studies conducted in the development of a field kit for detecting spills of hazardous materials in watercourses. The kit, consisting of 15 different chemical tests packaged in a one-man portable configuration is capable of detecting a wide variety of polluting substances in water. This report should be of value to Federal, state and local government personnel as well as to individuals from the chemical process and transportation industries who are involved in responding to accidental releases of hazardous substances. Information on this subject beyond that supplied in the report may be obtained from the Oil and Hazardous Materials Spills Branch (IEKL), Edison, Hew Jersey 08817. David G, Stephan Director Industrial Environmental Research Laboratory Cincinnati ABSTRACT Chemical System* Laboratory, under a program sponsored by the Environmental Protection Agency, Edison, NJ has developed e kit to detect hazardous material spills into waterways. The purpose of the program was to develop a man-portable field kit able to detect (not necessarily identify) as many contaminants in water in as low a concentration as possible. A list of compounds, representative of potential contaminants, was used to evaluate conmerclal, military and specially designed procedures which have applica tion to water testing. Following the original screening, promising methods were further evaluated against samples of natural waters polluted in the laboratory with compounds from the model list. It was concluded that a selection of 15 multiple non-specific detection systems could be organized into a detection concept which would detect a significant portion of potential contaminants. A "paper analysis" projected that about 85Z of potential contaminants would respond to at least one detection parameter. A field kit was designed containing a spectrophotometer, conductivity meter, pH meter and a variety of accessory equipment and reagents. Prototype kits were fabricated and delivered to Environmental Protection Agency along with engineering drawings, parts lists and manuals. CCR 0040601 iv CONTENTS Foreword . . . Abstract . . . Figures . . . . Tables . . . . Acknowledgment 1. Introduction........................................ 2. Conclusions........................................ 3. Recommendations............................... 4. Experimental Studies...................... 5. Formulation of Detection Concept . References........................................................................................................................ List of Manufacturers and Suppliers....................................................................... Appendices A. Probable Responses of Detector Kit to Materials Listed in Federal Register............................................................................................................... iii iv vi vii viii v CCR 000040602 FIGURES Number Page 1 Hazardous Material Detector Kit ................................................................................................ 34 2 Hazardous Materials Detector Kit In Use ............................................................................ 35 vi CCR 000040603 ACKNOWLEDGMENTS Appreciation la given to: Mr. Robert Gamson who helped establish this project and assisted In the preparation of the original proposal. Mr. James Tarbox who prepared the engineering drawings for the specially fabricated detector kit components. Summer students who participated In the program, Ma. Sandy Gordon, and Michelle Hackley In the summer of 1974 and Mr. Tom Kronau In the summer of 1975. Personnel of Chemical Detection and Alarms Branch who typed the report. vm CCR 000040605 SECTION 1 INTRODUCTION Chemical Systems Laboratory, under the sponsorship of the Environmental Protection Agency (EPA), Oil and Hazardous Materials Spills Branch, Industrial Environmental Research Lab, Edison, NJ, developed a field kit to detect (not necessarily identify) hazardous material spills into inland waterways. Development was implemented by surveying reported procedures, making original studies and evaluating Army and industrial equipment which could be used for detection of contaminants in water. Using a model list of contaminants, procedures were then selected to give a total detection concept. Finally, necessary instru ments and equipment to adapt the procedures to field use were chosen and designed into a man-portable kit. Two prototype kits were fabri cated for EPA complete with drawings, manuals and parts lists. BACKGROUND Every year in the United States there are over 3,000 spills of hazardous polluting materials (other than oil) into waterways. These include in-plant and storage spills, as well as spills caused during transportation of materials by barge, tank truck, railway tank car and pipeline. In addition, agricultural use of chemicals and run-off of natural waters deposit large amounts of materials into rivers, streams and lakes. The materials, many of which of which are hazardous to public health and wildlife, include alcohols, pesticides, phosphates, nitrates, sulfates and a variety of other industrial organic and inorganic chemicals. With the number of incidents increasing every year, an urgent need exists for a simple man-portable field kit capable of detecting contaminants in waterways. At the present time EPA is concerned with detection of about 370 hazardous materials published in the Federal Register, Vol. 40, No. 250 of 30 December 1975. A number of specific points were considered during development: 1. In most cases the nature of the spill will be known; it will be necessary to detect its "plume'' down the waterway until countermeasures can be taken or the contamination disanpears. Non-specific detection methods which are generally responsive to multiple contaminants and can be related to concentration are needed. High sensitivity (while desirable) is not always the most important criteria in tracing a "nlume". Lengthy procedures are to be avoided since a large number of repetitive tests at short intervals will be required. 1 CCR 000040606 2. The kit will frequently be used from a small boat rather than shore. Therefore, techniques requiring complex equipment or open heat are unsuitable. 3. Methods requiring little or no makeup reagents are preferred, to reduce the size of the kit and the logistical burden. 4. EPA prefers shelf-available instrumentation, equipment and prepackaged reagents, since they have a limited staff and propose to maintain the kits themselves. APPROACH It was proposed to develop a total detection concept using a selection of non-specific tests with a broad detection response for as many contami nants as possible. It was decided to make the kit as versatile as possible so that it could be modified or added to as requirements change. The large number of materials of concern to EPA made it necessary to develop a model list of contaminants for evaluation studies. It was agreed to use findings from this evaluation for a "paper analysis" (Appendix A) to indicate the probability of detection of other materials from the Federal Register list. A first estimatj gf^d^tection capabilities for the field was made from standard references'^' ' ' . Literature was obtained from water test kit suppliers and a review was made of Army equipment and devices which could be applied to detection of contamination In water. It was Immediately evident that tests for Inorganic components are well established, and In many cases prepackaged reagent systems are available. Tests for organic materials are comparatively few, and often are not simple nor do they lend themselves to repetitive use. This area required the most new development work. To reduce the need for refill and special reagents, enphasis was placed on instrumental methods. These included pH meters, conductivity meters, ultraviolet light methods, colorimeters and ion-selective electrodes. This approach requires a power supply, but the advantages easily outweigh the inconvenience. In reviewing methods or instruments to be used in the kit, a comprehensive survey of all available selections was not made. When possible, several choices were compared, then the most reliable and/or one most easily worked into a detection concept was selected. Thus, on finding a reliable pH meter, phosphate test or detector tube, that search ended and other detection requirements were addressed. 2 CCR 000040607 Because of the low solubility of many of the materials, concentration techniques were also studied. Detection of contaminants In natural waters is complicated by the fact many interfering ions and materials are present as background components. If the contaminant Is a natural component of water (e.g. sulfate ion) it is necessary to detect its presence by a gain over background. This can be done by comparing the contaminated water with a reference sample. A reference sample is taken at a point upstream from the contaminated area, or in the case of a lake or a pond, at an area removed from the spill area. Once a reference is established, the "plume" is traced by the change in water quality. The program used to develop a detector kit for hazardous material spills is outlined below: PROGRAM PHASE 1. A. Select model list of contaminants. B. Evaluate commercial, military and specially designed tests. PHASE II. A. Evaluate selected methods against contaminants in natural waters. B. Survey background level of natural waters with candidate methods. C. Select methods and formulate concept. D. Prepare "paper analysis" of Federal Register listing. PHASE III. A. Fabricate kits, draft manual. B. Conduct fieldability tests. C. Finalize manual, prepare drawings and parts lists. D. Prepare final report. 3 CCR 000040608 SECTION 2 CONCLUSIONS Chemical Systems Laboratory personnel have developed a field kit for detection of hazardous material spills Into Inland waters. Prototypes have been prepared and provided to EPA along with manuals, parts lists and drawings. While the kit Is not a panacea for all spill situations, In the hands of a dedicated Investigator Its Instrumentation and chemistry can provide a variety of valuable data which will help him accomplish many of his tasks. The makeup of the kit Is simple enough so modifications may be made to suit particular needs and applications. In fact, as Information on Its performance Is received from the field, changes may be made to the detection concept Itself. This program Is a start In assessing the overall nature of contamination and the problems associated with Its detection. Areas of detection weaknesses and suggested leads for continued Investigations are noted In Section 3. 4 CCR 000040609 SECTION 3 RECOMMENDATIONS The hazardous materials detector kit concept has excellent potential for detection of contamination in inland waters. The kit is versatile and easily modified for special applications. It is apparent that a number of gaps exist in the detection systems, particularly for many organic compounds. This further reflects the limited capability of commercial kits in dealing with organic contamination in water. The detection gaps found in the "paper analysis" reflect the same shortcomings. Certain areas showing promise but not brought to conclusion within the time frame of this program, are felt to be worthy of continued study. a) Methods using open cell polyurethane cubes impregnated with chromogenic reagents and prepackaged in plastic tubes are promising. One of the processes developed, used urethane cubes loaded with dithlzone to detect heavy metals. Stability problems which were not resolved prevented their inclusion in the detector kit. Use of anti-oxidants such as ascorbic acid may be of value in stabilizing them. Similar devices employing the 4-aminoantipyrene reagent for phenol were prepared. However, time was not available at the end of the program to determine their stability. b) Compounds known as fluorescent probes are promising detectors for high molecular weight organic materials. This system would be especially useful because it is unrelated to other detection methods and would add a new dimension to the detector kit. The problem to be resolved is one of developing simple universal extraction and concentration techniques. c) Methods using silver salts to detect organochlorine materials would be useful since a significant number of these compounds are listed as hazards in the Federal Register. The problem again, is with extraction and concentration techniques. d) It is evident from the above that continued studies in the area of extraction and concentration techniques would be of general overall applica tion to detection of contaminants in water. e) Enzyme systems, similar to that included in the kit may be designed to more specifically respond to Insecticides and other industrial contaminants. 5 CCR 000040610 f) Certain detector tubes were not considered for use in the effervescent process developed for the detector kit because they do not have multiple response capability; this doesn't preclude their evaluation and use for specific contaminants. Finally, the kit is simple and versatile in makeup so that modifications may easily be made. In fact, Anderson Laboratories Corporation, Fort Worth, TX, carries all the 'reagents necessary to perform tests in the 13th-Edition of Standard Methods for the Examination of Water, many of which are poten tially adaptable to the kit. 6 CCR 000040611 SECTION A EXPERIMENTAL STUDIES MODEL LIST OF CONTAMINANTS As indicated, the large number of materials of concern to EPA made it necessary to develop a model list of contaminants for evaluation studies. Included were the most important materials from a hazards standpoint^ and others representative of the complete list. The materials selected are shown in Table 1 . Solutions for evaluation of candidate detection methods were prepared by mixing a one gram sample of the contaminant in one liter of water. When the contaminant is totally soluble, the concentration of the initial solution is 1000 mg/1; for highly insoluble compounds, the concentration of the initial solution is assumed to be that of a saturated solution as reported in the literature. Three additional dilutions of 1:10, 1:100 and 1:1000 were made from the clear supernatant liquid and the concentrations were calculated from the saturation values. Candidate tests were first screened against the highest concentration of contaminant. When a positive response was noted, lower concentrations were further tested until a negative response was obtained or all four concentrations were tested. Detection tests were applied to all solutions, regardless of whether a response was expected. In this manner, many cross interferences were observed which were useful in a multiple response capa bility concept. EVALUATION OF METHODS Methods are grouped by the process used or the chemical or physical measurement made. Sections are cross-referenced where approriate. Preparations and testing of the contaminant solutions have been described in Section A . Reasons for inclusion or rejection of individual tests are discussed. Response of the tests selected for the kit, to the model list of contam inants is shown in Table 2. Information on the selected methods is sum marized in Section 5 > Detailed procedures for each test are given in the Operator's Manual prepared for the kit (Appendix B). CCS 00*06I* Table 1 Model List of Hazardous Materials (Concentration of Initial Solution) Hazardous Substance mg/1 1. Phenol 1000 2. Methanol 1000 3. Acrylonitrile 1000 4. Chlorosulfonic Acid 1000 5. Benzene 1000 6. Ammonium Chloride 1000 7. Phosphorus Pentasulfide 1000 8. Styrene 660 9. Acetone Cyanohydrin 1000 10. Calcium Hypochlorite 1000 11. Nonvlphenol 17 12. Isoprene 100 13. Xylenes 130 14. Nitrophenol 1000 15. Ammonium Mitrate 1000 16. Aluminum Sulfate 1000 17. Aldrin 0 Hazardous Substance mg/1 18. Toxaphene 3 19. DOT 0.005 20. EPN 500 21. Malathion 145 22. Parathion 25 23. Dieldrin 0.25 24. Heptachlor 0.2 25. Sevin 40 26. Chlordane 0.1 27. Fermate 120 28. Lead Arsenate 2.5 29. Disodium Methyl Arsenate 1000 30. Phenyl Mercuric Chloride 6.9 31. 2,4-D (Acid) 900 32. 2,4,5-T (Acid) 280 33. Ammonium Phosphate,Dibasic 1000 8 CCR 000040613 Certain detection approaches recur in this evaluation. For example, quantitative measurements were made using color comparators, the Hach Chemical Company DR Colorimeter and the Hach DR-EL/2 Spectrophotometer. Color comparators require visual matching of developed colors with a series of permanent glass or plastic standards. The process is highly subjective and under some conditions may only be semiquantitative. Since accurate quantitative measurement is necessary for many situations, an instrumental method is preferred. The Hach DR Colorimeter is a portable battery-operated filter colorimeter. The Hach Spectrophotometer, which is also portable and bat tery operated (Appendix S, p. 9) has a simple variable filter calibrated in nanometers which precludes the need to change filters for different analyses. Hach liquid reagents are packaged with calibrated dropping pipettes. Dry reagents are packaged with automatic measuring devices or in individ ually sealed plastic tubes which are opened with clips to obtain the reagent. The tests evaluated in this investigation are summarized below: a. Acidity. Acidity was determined in the conventional manner by titration with 0.02N NaOH to a phenolphthalein endpoint . The ''dropcount" titration method was used to simplify handling for the field. It was found that acidity data parallels data obtained with a pH meter. A pH meter is preferred for simplicity of use, reliability of data and use of fewer chemicals; the acidity test was rejected. b. Alcohol. Chemigal tests for methyl alcohol in water based on cerric ammonium nitrate and vanadium oxinate were investigated but did not respond at the 1000 mg/1 level. Other alcohol tests based on enzymatic methods are described under Enzyme Systems (Section m). Several tests using detector tubes are discussed under detector Tubes (Section 1). An alcohol test as such was not used. c. Alkalinity. Alkalinity was measured by titration with 0.02N H^SO^ to a mixed bromcresol green-methyl red endpoint using the "dropcount" titration method. Feasons for its rejection are the same as for the Acidity test (Section a). d. Ammonia Nitrogen. The Ammonia Nitrogen Tester, Model NI-8, marketed by the Hach Chemical Company was evaluated. The kit uses the Nessler reagent to develop color which is measured by comparison to colored standards. Use of comparators for the kit was considered too subjective for quantitative analysis, particularly under variable light conditions. The same procedure using either a colorimeter or spectro photometer is preferred. See data Table 2 and procedure (Appendix B, p. 21). The test responds to a wide range of organic and inorganic com pounds . 9 CCR 000040614 Other compounds, which responded to the Nessler reagent at 100 mg/1 or less are chloramine-T, dichloroamine-T, dicyclohexylamine, 2,4-dinitrophenylamine, 2-ethylhexylamine, hexamethylenimine, N-raethylglucamine, 2nitrodiphenylamine, uric acid and m-xylenediamine. A positive response with the Nessler reagent is indicated by formation of a yellow color or a precipitate. e. Chloride. Commercial tests for chloride lack sensitivity or require titration making thgm,,unsuitable for the kit. The test adopted is modified from the literature0' and detects, in addition, a wide range of inorganic components such as iodides, bromides, cyanides, sulfides, thiosulfates, and nitrates. Chloride in water is determined by the red complex formed by the addition of ferric ion and mercuric thiocyanate. Use of the procedure with a spectrophotometer is described in Appendix B, p. 21. The reagents are prepared as follows: 1. Mercuric Thiocyanate. Dissolve 0.3 gm in 100 ml methanol. Allow to stand 24 hours, filter. 2. Ferric Ion Solution. Dissolve 5 gm of ferrous ammonium sulfate, 1ijl_20 ml distilled water, add 38 ml cone HNO^; boil to oxidize to Fe and drive off oxides of nitrogen. Make up to 100 ml. Reagents for kit application, stored in polyethylene bottles, were unstable. Stored in glass bottles the reagents were stable; at room temperature they have been stable for over seven months. Data with this procedure are shown in Table 2 . Kitagawa recently introduced a detector tube for chloride in water. In use the ends are snapped off the tube which is made to stand in a shallow depth of water. As water chromatographs up the tube by capillary action, a colored stain separates in the presence of chloride. The item was found insensitive and data too difficult to reproduce for quantitative work. f. Chlorinated Compounds. Many chlorinated pesticides are detected in thin-layer chromatography by spraying them with solutions of silver nitrate or silver acetate. Following irradiation with shorjyayj ultra violet light, the compounds are seen as gray to black spots ' ' In this study 5 ug quantities of a group of contaminants in chloroform were spotted on silica gel plates, the plates sprayed with 12 aqueous silver nitrate, and then irradiated for five minutes with shortwave ultraviolet light. Many compounds are seen as black, gray or yellow spots. 10 CCR 0000V0615 Detection of Chlorinated Compounds With Silver Nitrate Hazardous Materials Response 17. Aldrin 18. Toxaphene 19. DDT 20. EPN 21. Malathion 22. Parathion 23. Dieldrin 24. Heptachlor 25. Sevin 26. Chlordane 32. 2,4-D (Acid) 33. 2,4,5-T (Acid) + + + + + + + + A v of this process uses bromcresol green in the silver salt reagent^-. While variations were noted in the colors developed, there was no substantial improvement in detection capability. Several obstacles prevent use of this method in the kit concept. Many of the relevant materials have an extremely low solubility in water; to obtain enough material for testing, extraction and concentration techniques are required. It was postulated that sufficient material could be recovered from water by shaking a 50 ml sample with 1 ml of chloroform and spotting the chloroform extracts on silica gel plates for testing. However, the poor reproducibility of extraction techniques and the complexity of operations were discouraging. Another obstacle was the high energy requirement for the ultraviolet light. Five minute on-times periods for the ultraviolet light are excessive requirements for a power supply in the proposed field kit. The orocedure was abandoned. g. Chlorine. The Hach Free and Total Chlorine Test Kit, Model CN-66 was evaluated. The test initially appeared to have a multiple detection response. On reexamination, it was found that the readout, made with a comparator, depended on a poorly compensated reagent blank. When the tests were rerun with the colorimeter, only calcium hypochlorite gave a useful detection response. O-Toliver (Hach No. 141), a reagent for total chlorine gave no response to the model list of contaminants and the reagent was dropped. h. Color. Color in water was measured satisfactorily using either the colorimeter or spectrophotometer. See the data in Table 2 and procedure in Appendix B, p. 19. 11 CCR 000040616 i. Conductivity. A battery-operated conductivity meter, Type 70 Meter, marketed by Chemtrix, Inc., was evaluated and found generally satisfactory. The conductivity meter in the Hach DR-FL/2 kit was also tested. Results with the Hach instrument were more reproducible because it was less sensitive to the depth of immersion or motion of the probe. Data with the model list of contaminants is shown in Table 2 and the procedure is given in Appendix B, p. 18. j. Cyanide. Detection of cyanide was studied using the Hach Cyanide Test Kit, Model CYN-3 which uses a comparator. The same reagents can be used to run the test with the colorimeter or spectrophotometer. The pro cedure is undesirable because it requires four individual reagents and has a 26 minute development time. Although, the test is sensitive to less than 0.01 mg/1 cyanide it did not respond to a wide range of contaminants. A recently marketed detector tube for cyanide ion in water (Kitagawa) was tested. In use the ends of the tube are snapped off and the tube made to stand in a shallow depth of water. Hater rising up the tube by capillary action will elute a blue stain in the presence of cyanide. Other contami nants can elute tan to grayish colored stains. See the data in Table II and the procedure in Appendix B, p. 10 and 17. The procedure is sensitive to 5 mg/1 as CN . k. Detector Papers. This section is addressed to papers for detection of liquid chemical agents. (Papers impregnated with chemicals for determining pH or the presence of hardness are covered under appropriate sections). The Army uses papers impregnated with various dyes to detect liquid chemical agents in the field. Fine aerosols of the agents, on impact with the papers, dissolve a portion of the dye leaving a noticeable colored stain. The possi bility of detecting organics immiscible with water using such papers was investigated. Solutions of the model list of contaminants (1000 mg/1) were shaken vigorously and spotted by pipette to M8 paper (a standard detector for liquid agent), and LAD SIN-55 and LAD SIN-26 (two advanced types cf cetecto'papers). Only nonylphenol produced noticeable rec stains with the papers. No response was obtained at the 100 mg/1 level. The application of the papers is too narrow for use in the kit. l. Detector Tubes. Detector tubes are commonly used in industry to detect airborne contamination. Indeed, the Army relies heavily on these items to detect gaseous chemical agents. Detector tubes consist of a narrow glass tube containing an adsorbent, usually silica gel, held in place by porous retainers. When air is drawn through the tubes contaminants are visualized by colored reactions with chemicals impregnated on the silica gel or by drops of added reagents. Since many of the contaminants have significant vapor pressures, an attempt at detection was made by sampling the vapors, from flasks containing 1000 mg/l concentrations of contaminants using a Berdix/Gastec benzene analyzer tube. A discoloration of the silica gel was sometimes observed. 12 CCR 0000A0617 indicative of a positive test. This finding was significant for three reasons: 1) Use of a detector designed to operate in one environment-- air was extended to function in another--water. 2) This procedure detects some normally non-reactive organics in water, an area of signif icant weakness. 3) A large number of detector tubes for organic contami nants are readily available from many suppliers. These would constitute prepackaged detection systems equivalent to those available for inorganic contaminants. The next effort of the investigation was to devise a means of enhancing sensitivity. One method attempted, used detector tubes to sample air which had been bubbled through the water sample to scrub out the contaminant. No significant improvement in sensitivity was found. A convenient and effective approach made use of effervescent materials (such as Alka-Seltzer- tablets) to scrub out the contaminant. In the process devised, a tablet is added to an 80 ml water sample contained in a widemouth jar. The cap, fitted with tygon tubing holding a detector kit in line is auickly screwed onto the jar. Effervescence forces the gases through the detector tube where contamination may be visualized. This procedure gave a ten-fold increase in sensitivity com pared to methods in which the gases were sampled from the mouth of the flask or air was bubbled through the sample. Findings from this study show that two basic tubes were adaptable to this process and in addition had multiple detection capabilities. One is the iodine pentoxide tube, of which, Bendix/Gastec benzene (No. 121) and toluene (No. 122) tubes are examples, and the other is the potassium dichroraate tube, of which, Bendix/Gastec acetone (No. 151), ethyl acetate (No. 141) and cyclohexane (No. 103) tubes are examples. See the data (Table 2 ) and Appendix B, p. 10 and 16 for use of the benzene tube. The tube also responds to toluene, xylene, styrene and other organic materials. The dichromate-type tube picks up some organic compounds not detected by the benzene tube. It would have also been included in the kit concept except that large quantities of water vapor were found to produce an interfering color response. Studies were conducted which showed that if a scrubber tube for moisture is placed in front of the dichromate detector tube, tests are sharper, easier to read and free from the interference caused by water vapor. Scrubber tubes of the same size as the detector tube were fabricated using calcium sulfate with indicator as is commonly used in drying columns and dessicators. Since moisture tends to fill the "openings'' of silica gel, and retard detection responses, the drying tube concept is generally applicable to all detector tubes. However, since the benzene analyzer tube functions adequately without it, for simplicity, drying tubes are not included in the kit. 13 CCR 000040618 The following Bendlx/Gastec detector tubes were tested but rejected because of lack of response or responded similarly to the iodine pentoxide or dichromate tubes: a) acrylonitrile (No. 191), b) vinyl chloride (No. 131L), c) methyl chloroform (No.-135) and d) styrene (No. 124). Kitagawa tubes: a) butadiene (No. 168b), b) ethylene (No. 108b), c) isopropyl alcohol (No. 150) and d) methyl alcohol (No. 119) were rejected for the same reasons. In conjunction with this study. Army detector tubes for chemical agents were also tested for response to chemical pollutants. The mustard, lewisite and hydrogen cyanide tubes each detected high concentrations of phosphorous pentasulfide. In addition, the hydrogen cyanide tube also detected acetone cyanohydrin at the 10 mg/1 level. The phosgene tube did not detect any of the contaminants. The military tubes were rejected because of their limited application. m. Enzyme Systems. Detection systems for certain materials have been designed based on their ability to inhibit the action of an enzyme on a chemical substrate. The action of the enzyme on the substrate may be monitored electrometrically or in the case of colored substrates, may be measured colorimetrically. Such systems can even be designed into simple "go-no-go" spot tests which can be assessed visually. The Army uses a detector ticket of this type with horse serum cholinesterase to detect nerve agents (Appendix B, p. 10 and 15). This device is also sensitive to certain insecticides ( Table 2 ) . Studies were conducted using the Army enzyme test ticket in solution to obtain better color discrimination. This was achieved, but the range of response was diminished and this approach was abandoned. The Army enzyme test uses Tris buffer, 0.05M, pH 8.0. The buffer is also used for detection of heavy metals (see Section q ) and must be specially prepared. Therefore, for use in the EPA kit Army buffer was discarded and buffer described here was used: 1. Dissolve 2.43 gm of tris (hydroxymethyl) aminomethane in 100 ml distilled water. 2. Using 25 ml of the above solution, add 28.75 ml of 0.1N HC1 to obtain a pH of 8.0. Dilute to a final volume of 100 ml. 3. Wash the buffer with alliquots of dithizone (diphenylthiocarbazone) solution (25 mg/1 chloroform) using one part dithizone solution to 25 parts of buffer. When the dithizone layer remains blue, (about three washings) the buffer is ready for use. Ccs oo04061. 14 A number of readily available enzyme/substrate kits for clinical application were obtained and evaluated. They were generally unresponsive and in addition, because they were intended for clinical use posed certain stability and operational limitations for field use. Included were an Ethyl Alcohol Reagent Set (Cat. No. 7919) and Alkaline Phosphatase Reagent Set (Cat. No. 7040 Code APR) from Worthington Biochemical Corporation and an Alkaline Phosphatase Reagent Set (Cat. No. 15987) and a Blood Sugar (Glucose Oxidase) (Cat. No. 15754) from Boehrlnger Mannheim GMBK, Biochem ical Department. n. Fluorescent Probes. A group of compounds known as fluorescent probes were investigated as general detectors for high molecular weight organic compounds^. Fluorescent probes are compounds which are nonfluorescent in the presence of water or other polar material, but highly fluorescent in non-polar media. To test the probes, columns packed with macroreticular resins (Rohm and Haas, XAD-2)1 were used to concentrate contaminants from water. Then a solution of the fluorescent probe was passed through the column so that the extracted substances would fluoresce. However, all the probes examined gave a positive fluorescent test with resin alone (a styrene-divlnylbenzene copolymer) and with no contaminants present. Contaminants were also extracted by shaking 50 ml of water sample with one ml of chloroform. The chloroform extracts were then spotted on glass fiber material, sprayed with benzene solutions of the probes and examined under longwave ultraviolet light. 7-(p-Methoxybenzylamino)-4-nitrobenz-2oxa-1,3-diazole (MBD) at 0.0032 g/1 benzene gave the best results of a number of probes tested. In many cases, a relatively high fluorescent background was noted. Further testing showed if the glass fiber was sprayed with indandione reagent (2-diphenylacetyl-l,3-indandione)^ after application of the probe, the fluorescent background became very dull and the green fluorescent spots were more easily read. As a next step, MED and indandione were combined into a single spray reagent at concentrations of 0.0032 g and 0.03 g respectively per liter of benzene. When the MBDindandione method was tested against contaminants from the model list, some compounds were seen as bright green spots and others because of their ability to absorb light were seen as dull "quench" spots, both of which were considered positive tests. Materials giving either of these responses are styrene, nonylphenol, nitrophenol, EPN, malathion, parathion, sevin, fermate, 2,4-D (acid) and 2,4,5-T (acid). It should be remembered that water prevented fluorsence of the probes. It was difficult to assure that all the water was removed after extraction with chloroform. Residual water on the glass fiber media would retard the reaction or give the effect of a false positive "quench" test. Use of small electric heaters operating off a DC power supply to remove the water became too cumbersome. 15 000040620 CCR Because of false-positive tests, and need for extraction, need for a specially formulated spray reagent and an ultraviolet light, the procedure was abondoned. Elimination of the the fluorescent probe has no significant effect on detection capability since most of the contami nants (model list) are detected by other tests. It is impossible to determine if there is a serious loss in detection with respect to com pounds from the Federal Register since the reaction is unpredictable. o. Fluoride. Fluoride was determined with both the colorimeter and spectrophotometer. Detection is based on the decolorization of sodium 2-(parasulfophenylazo)-1,8-dihydroxy-3,6=naphthalene disulfonate (SPADNS), a standard test for fluoride in water . A significant number of contaminants in the Federal Register listing contain fluoride. Also, the test detects other materials (see Table 2). See Appendix B, p. 22 for procedure. p. Hardness. The Hach Total Hardness Test Kit, Model HA-71A, was used to measure hardness. The kit uses a "drop-count" titration method with ethylenediamine tetraacetate (EDTA). The end point is determined with Eriochrome Black T. It detected both calcium hypochlorite and aluminum sulfate at the 10 mg/1 level, but it was not expected to have a broad detection capability and was dropped. Test papers for hardness (Micro Essential Laboratory) were too subjective for quantitative analysis. q. Heavy Metals. Diphenvlthiocarbazone (dithizone) is a general complexing reagent commonly used for the qualitative and quantitative analysis of metals^- . The blue reagent (chloroform solution or a similar solvent) is shaken with an aqueous solution of the metal ion; colored metal-dithlzone complexes (usually pink but may be other colors) are extracted into the lower solvent layer. Adjustment of pH can make the procedure selective for specific metals. In view of the number of metals present in the Federal Register listing, a reliable heavy metals test was considered prerequisite for the kit. The method was evaluated by shaking one ml of 0.005% dithizone in chloroform with 25 ml of water sample. Extreme variability was noted in the responses obtained. The problem was traced to the high sensitivity of the test; it was uncertain whether the reagent was reacting with pollutant or with contamination in the equipment and/or reagents. Use of individually sealed expendable plastic tubes eliminated contamination in the system. Inexpensive cellulose acetate tubes (available in bulk), were used. These soften somewhat in chloroform but not to the point of leaking. Polystyrene tubes dissolve after standing in chloroform. Hach MercuVerTM2, a dry dithizone-type reagent designed for quantitative measurment of mercury, was evaluated as a general heavy metals test. The method was simplified to a qualitative spot test. It was studied in neutral and slightly alkaline solutions. When buffered 16 CCR 000040621 with Tris buffer, pH 8.0, detection of multiple heavy metals was Increased significantly. See Appendix B, p. 16 for the procedure developed for the kit. Also, note the section on Enzyme Systems (Section m) for the prepa ration and washing of Tris buffer with dithizone for this application. Response to contaminants from the model list ( Table 2) does not show the capability of this reagent to heavy metals. Additional solutions of metal compounds were prepared for further evaluation. Positive tests were obtained with 100 mg/1 or less of the following heavy metals: cadmium, cobalt, copper, gold, lead, mercury, silver, and zinc. A recent report^ described the preparation of open-cell polyurethane cubes impregnated with chromogenic organic reagents. It was conceived that the expendable cellulose acetate tubes could be prepackaged with dithizone impregnated foam cubes. In use the cube filled tubes would require only the addition of water, shaking, and observation for a change in the color of the cube. Polyurethane was washed and prepared according to the reported procedure. Cubes about 1 cm on the side were placed in polyethylene bags and kneaded until uniform in color with solutions of dithizone in various phthalates (3 ml solutions to 1 gm of cubes was used). The most stable preparation was found to be 0.025 gm of dithizone in 50 ml of diisobutyl phthalate. Tests run with dithizone foam cubes showed them to be as sensitive as MercuVer^-2 even without the use of Tris buffer. Unfortunately, most of the preparations showed serious signs of deterioration after several months at room temperature. Although there is some possibility of stabilizing the reagent cubes with ascorbic acid or other antioxidant?, time limitations prevented completion of this study. r. Ion-Selective Electrodes. Several ion-selective electrodes were obtained to assess their feasibility for the detector kit. An ammonia electrode (Chemtrix) was evaluated in conjunction with the Chemtrix Type 40E battery-operated portable pH meter which was then the current choice of meters. Although supposedly compatible, the ammonia electrode never functioned satisfactorily, apparently due to limitations of the meter. A divalent ion-selective electrode (Corning Mo. 476235) with a laboratory type meter was tested against the contaminants (model list). The electrode was prepared as described in the manufacturer's instructions and immersed in each stirred solution along with a calomel reference electrode. After equilibration the potentials were read and recorded. The concentrations of the contaminants was 1000 mg/1 or a saturated solution whichever was less. The divalent electrode behaved much like a conductivity electrode responsive to total ionic strength of the solution. Results were found to follow a definite trend. Distilled water read a potential of -100 mV. The non ionic organics all showed a reading of -110 to -129 mV. Sevin at -135 and 17 000040622 OCR nitrophenol at -140 mV were the only exceptions. The ionic inorganics all gave readings of -60 to -90 mV. The only significant departures were phosphorus pentasulfide and aluminum sulfate at 0 mV and chlorosufonlc acid at +35 mV. A redox electrode which was considered was found unsuitable; the presence of both the oxidized and reduced form of the substance to be detected was required to obtain a signal. This necessitates polarizing the electrode which in turn requires an additional regulated power supply for use and calibration. Also, the platinum surface is not reproducible from day-to-day and would need continued standardization. All-in-all work with electrodes was not promising. They pose a number of calibration problems and do not appear to be sufficiently versatile for non-routine situations encountered in the field. In addition, they show limited capability for organics which is the area of prime concern. Also, electrodes are expensive and require the use of a significantly more expensive meter. s. Methylene Blue Active Substances (MBAS). This method is used to determine alkyl benzene sulfonate (AES) in water. Under the conditions specified in the test procedure, substances which react are referred to as methylene blue active substances2. It measures surfactants in water. The procedure is subject to interferences such as organically bound sulfates, sulfonates, carboxylates, phosphates, phenols, cyanides, thiocyanates and even some inorganic ions like nitrate and chloride^. It was the long list of interferences which led to its consideration as a multiple response detector. The original method is designed for quantitative measurements using a colorimeter. For simplicity and to reduce the volume of reagents, the procedure was evaluated for use in a spot test application. In use, a buffered aqueous solution of methylene blue is mixed with the water sample in a test tube and shaken with 1 ml of chloroform. Materials in the water phase which are active with methylene blue extract into the solvent phase as blue colored products. The procedure did respond to phosphorus oentasulfide, acetone cyanohydrin, xylenes, nitophenol, ammonium nitrate, malathion, parathion, fermate, 2,4-D (acid) and 2,4,5-T (acid). However, because response was obtained only at the highest concentration and the intensity of the color was not very strong the test was considered too unreliable for the kit. t. Nitrate Nitrogen. Hach Nitrate Test Kit, Model NI-11 was evaluated for nitrate in water. The kit which uses prepackaged reagents and a color comparator was rejected in favor of the method used with the colorimeter or spectrophotometer. See Table 2 for results with the contaminants (model list) and Appendix B, p. 19 for the procedure. It is seen that the method is responsive to materials other than nitrate ion. 18 CCR 000040623 u. Odor. Tests were conducted by simply sniffing the mouths of flasks containing the different dilutions of contaminants in distilled water. Odor was easily one of the most sensitive detection means with broadest response capability. The following materials were detectable at the concentrations noted by two or more investigators: Detection Sensitivities of Contaminants by Odor, mg/l Contaminant Detection Limit Phenol Benzene Phosphorus Pentasulfide Styrene Acetone Cyanohydrin Isoprene Xylenes Nitrophenol Aluminum Sulfate Toxaphene EPN Malathion Parathion Heptachlor Chlordane Fermate 1000 1000 1 0.7 100 0.1 1.3 100 1000 3 5 1.5 0.3 0.02 0.1 120 Use of odor as an analytical tool is difficult because it is extremely subjective and impossible to standardize in a practical man ner for use in the field by different operators. Use of odor as a detector is further complicated by the fact that airborne vapors of contaminant would make it impossible to pinpoint its location in the water. Use of odor as a detection method was rejected. v. H. It was decided that pH monitoring would be important in tracing contamination and therefore accuracy and sensitivity were con sidered prerequisite. Impregnated papers and chemical indicators with comparators were too subjective. Several electronic meters were consid ered. A compact battery-operated pH meter. Type 40E marketed by Chemtrix, provided reliable and accurate measurements. A similar meter by Hach, Model 1975 pH meter, appeared to give quicker responses with more reproducible results. The Hach meter, however, was selected only for convenience in design (see Section 5). Combination pE electrodes were studied with both meters and were satisfactory. A sealed combination pH electrode marketed by Chemtrix requiring no servicing was also tested. The unit was convenient in that it was ruggedized, expendable and had a life of two years. However, response with it was sluggish and generally slower than with the con ventional combination electrodes. 19 CCR 000040624 See Table 2 for the pH -data; Appendix B, p. 9 and 18 describes pH measurement in the field. w. Phenolics. Commercial kits for phenol use the 4-aminoantipyrene method which involves a lengthy and awkward extraction procedure. ^ extremely sensitive test for phenol based on the Berthelot reaction^- * ' was studied for use with the Hach DR Colorimeter or Spectrophotometer. The reagents required and the procedure developed is described: 1. Reagents: Bleach/Caustic - Dilute 10 ml commercial bleach (5% NaOCl) + 60 ml 10% aqueous NaOH to 1 liter with distilled water. Ammonia Reagent - Dilute 10 ml cone, ammonium hydroxide to 100 ml with distilled water. Sodium Nitroprusside - Dissolve 6.0 g of sodium nitroprusside in 100 ml distilled water. Dilute 12.5 ml of this solution to 500 ml with . distilled water to make a working solution. 2. Procedure: Place 21 ml water sample in a glass-stoppered 25 ml graduate. Add 2 ml Bleach/Caustic, 1 ml Ammonia Reagent and 1 ml working solution of Sodium Nitroprusside. Run a blank in parallel. Incubate the sample and blank for 5 minutes in a water bath at 56 + 2C. Cool at room temperature for 5 minutes. Read in the DR Colorimeter using the 2408 filter or in the spectrophotometer at a wavelength of 625 nm. Compare with phenol standards prepared in a similar manner (Heating for field application was accomplished using a canned dry heat). Although extraction procedures are avoided, the method is lengthy and it introduced a need for heat and a temperature controlled water hath. The method was found vey useful as a laboratory procedure but unsuitable for field work. A phenol spot test was developed by modifying the quantitative Hach procedure. The developed method sacrifices quantification for simplicity and reduction of reagent volume. See Table 2 for the data and Appendix B, p. 17 for the procedure. Several experiments were conducted to prepare phenol test devices similar to the cellulose acetate devices containing dithizone cubes for heavy metals. A solution was prepared containing 1 g 4-aminoantlpyrene and 1 g tris (hydroxymethyl) aminomethane in 5 ml dimethylphthalateacetone (1:1). This solution was kneaded with 1 g urethane cubes!? in a plastic bag to obtain a uniform yellow color. The cubes sprinkled with 5-10 crystals of potassium ferricyanide are ready for use. The Items were found to give quick and easily discernible tests with solutions containing as little as C.l mg/1 phenol. Sufficient time was not available at the end of the program to determine the stability of the system. 20 x. Phosphate. Hach Total Phosphate Test Kit, Model PO-24, was evaluated for detection of phosphate in water. The kit has prepackaged reagents and a color comparator. Results were more reliable when the same reagents are used with the Hach DR Colorimeter or Hach Spectrophoto meter. See data, Table 2 and procedure. Appendix B, p.20. Additional experiments in support of the "paper analysis" showed that the procedure would also detect concentrations of less than 100 mg/l of arsenates, arsenltes, and bromates. y. Sulfate. Hach Sulfate Test Kit, Model SF-1, was evaluated for detection of sulfate. The kit uses prepackaged reagent which causes a turbidity in the presence of sulfate ion. Concentration is correlated to the ability to observe a heavy "X" marking at the bottom of a graduate through different depths of the water sample with the turbidity. The procedure is extremely insensitive and can only be considered semiquantltative. The same reagent with either the colorimeter or spectrophotometer gives a 10-fold increase in sensitivity with greater reliability. The procedure is highly specific; it was adopted for the kit in spite of this fact due to the large number of sulfate compounds in the Federal Register listing. See Table II for the data; the procedure is given in Appendix B, p. 20. z. Turbidity. Turbidity was measured using both the colorimeter and spectrophotometer. Tests were conducted only to show that turbidity can be measured and could be indicative of insoluble contamination. Because the physical form of contaminants (e.g. fine powders, flakes, granules, emulsions, etc.) cannot be anticipated, nor can the conditions of water environment (e.g. turbulent creek, quiet pond, etc.) no attempt was made to correlate turbidity caused by the contaminants (model list) to contamination. See Appendix R, p. 18 for the procedure adopted for the kit. TESTING WITH NATURAL WATERS The efficacy of the selected procedures was determined with water samples taken from Winter's Run, Big Gunpowder Falls and the Susquehanna River In Harford County, MD. The waters were analyzed as received using the candidate methods. Afterwards the samples were polluted in the laboratory with contaminants from the model list In the manner described previously. The detection limit was determined for the qualitative spot tests; the lowest quantity of contaminant required to produce a signifi cant change over that of the original water was determined for the quan titative tests. Usually, there was some loss In sensitivity when compared to distilled water; however, nothing significant was found to preclude use of these methods in a detector kit. The data is summarized in Tables 3, 4 and 5. 1 21 M to n n 33 O o o o r> Q O' (NJ Ut Table 2 Detection Systems for Hazardous Materials (Concentrations of Hazardous Materials In mg/1 showing a measureable response) Hazardous Materials .1. Phenol___________ 2 Methyl Aleoho1_ HO 4"eH3C JUS,Mts 4p4NP1) CO n >CQ 4PJ Oc0) Xtu 0o) Pid U Ua T3I a--_sOi______ P _____ 4PJ PU Cd hH UV HUoO P r-3t _____ ... ..10, . 4J) XPO-oC P ao iB ^ 3. Acrylonitrile 4. Chlorosulfonlc Acld_ 1000 1000 10 10 5. Benzene 6. Ammonium Chloride .7. Phosphorus Pentasulflde 8 Styrene______________________ 100 6.6 100 100 100 10 660 9. Acetone Cyanohydrin__ .10 Calcium Hypochlorlte_ .11 Honylpheno1__________ .12 Isoprene________________ 100 100 1000 100 ]. 7 17 10 1000 13. Xylenes_ 1.3 14. Hitropheno1_______ 10 100 15. Ammonium Nitrate 1000 100 10 16. Aluminum Sulfate_ 10 1000 10 17. AldrIn______________ 18. Toxaphene__________ 19. DDT__________________ .20 EPN .21 Malathion__ .22 Parsthion__ 500 14.5 2.5 145 50 0.5 50 145 145 2.5 23. Dieldrin___ 0.3 0.03 24. Heptachlor_ 0.2 0.02 25. Sevln 0.04 0.4 0.4 26. Chlordane_ 27. Permste 12 120 12 12f 120 12 28. Lead Arsenate______________ 2.5 0.3 2.5 29. Dieodium Methylarsenate_ 10 1000 2.5 30. Phenylmercuric Chloride 6.9 0.7 31. 2,4-D (Acid)_ 90 90 32. 2,4,5-T (Acid)____ __________ 280 28 280 33. Ammonium Phosphate, Dibasic 1000 10 100 TMOVHJ rJHC u_____ ______ T03) UHOH3Hi 10 1000 10 10 10 660 10 100 1000 1000 500 14.5 25 0.2 12 120 1000 100 NOTE: Instrumental measureable responses are Indicated by a change of 0.5 pH unit, gain in conductivity of SOjunhoa/cm or change of transmittance of 5. Table 3 Detection of Contaminants In Water from Winter's Run (Concentrations of Hazardous Materials In mg/1 showing a measureable response) Hazardous Materials A- 41 xUo xHc sN S PC tW *W1 ax xoe T(C(r3jdti. 4-> 0} Ou 3 to M c M csJ O c 4J T. XP. o H O o 4) UJ cd 4J tO 4-1 i a. a crt o cw H oU o 3 .c i1 ^ iH eC m a. < u 4) 3 H U O 3 iH 1. Phenol 2. Methyl Alcohol_ 3. Acrylonitrile 4. Chiorosulfonic Acid_ 1000 1000 10 10 10 10 1000 5. Benzene ___ 6. Ammonium Chloride _______ 7. Phosphorus Pentasulfide_ 8. Styrene_ 9. Acetone Cyanohydrln_ 10. Calcium Hypochlorite_ 100 6.6 1000 100 100 10 100 10 100 1000 100 10 10 100 1000 10 100 .11. Nonylpheno 1_________ ___ 12 T anprene 1.7 10 10 13. Xylenes_______ ___________ tcoo 14. Nltrophenol_______ 15. Ammonium Nltrate_ 1.3 10 100 100 10 10 1000 1000 16. Aluminum Sulfate 100 1000 10 17. Aldrin 18. Toxaphene 19. DDT_______ ~ 20. KPN 500 500 21. Malathlon 22. Parathlon 14.5 2.5 145 145 145 145 2.5 2.5 23. DieIdrIn 0.03 2ft. Heptachlor_ 0.02 25. Sevln 0.4 40 26. Chlordane_ 27. Fermate 12 120 120 120 120 28. Lead Arsenate______________ 29. Dlsodium Methylarsenate_ 100 1000 2.5 2.5 1000 30. Phenylmercurie Chloride 6.9 6.9 31. 2,4-D (Acid)______________ " 90 900 32. 2,4,5-T (Acid)_____________ 280 280 33. Ammonium Phosphate, Dibasic 1000 10 100 10 NOTE Instrumental measureable responses are indicated by a change of 0.5 pH unit, gain In conductivity of 50 ytmhos/ or change of transmittance of 5X. CCR 0 0 0 0 4 0 6 2 6 -____ Table 4 Detection of Contaminants In Hater from Big Gunpowder Falls rn(Concentrations of Hazardous Materials In mg/1 showing a tneasureable response) Hazardous Materials r-i X-rl NW0c) xO Xa $C JLtL__ e_ .rH O >i UO*B x0C) -S __ __ Ea o rl 8 _Si_ u s fe,, oo3 k ssCM uo 01 <0 (3O o CL, .1. Phenol 2 Methyl Alcohol_ 01 o tJ T0o1l o o3 3. Acrylonitrile_ 4. Chlorosulfonlc Acld_ 1000 1000 10 10 10 10 1000 5. Benzene ___ _____ 6. Ammonium Chloride________ 100 10 7. Phosphorus Pentasulfide_ 8. Styrene______________________ 100 6.6 100 10 100 100 10 10 100 9. Acetone Cyanohydrin .10 Calcium Hypochlorlte_ .11 Nonylpheno1_____________ .12 Isoprene________________ 1000 1.7 10 100 100 100 100 10 1000 10 100 13. Xylenes__________________ N> 14. Nltrophenol_______ 1.3 10 100 1000 15. Ammonium Nitrate 100 10 16. Aluminum Sulfate_ 100 1000 10 1000 17. Aldrin______________ 18. Toxaphene__________ 19. DDT 20. EPN 500 500 21. Malathion 145 145 145 145 22. Parathion__ 2.5 2.5 25 23. Dieldrln___ 0.03 24. Heptachlor_ 0.02 25. Sevln_______ 40 40 26. Chlordane__ 27. Fermate_________ 12 120 12 120 120 28. Lead Arsenate 2.5 0.3 2.5 29. Dlsodlum Methylarsenate_ 100 1000 1000 30. Phenylmercurie Chloride 0.07 0.7 31. 2,4-D (Acid)______________ " 900 900 32. 2,4,5-T (Acid) _________ 280 280 280 33. Ammonium Phosphate, Dibasic 10 100 10 NOTE: Instrumental measureable responses are Indicated by a change of 0.5 pH unit, gain In conductivity ot 5<J jnuioa or change In transmittance of 5t CCR 00004-0627 tton O O 70 O o o o o th fSi CO Table 5 Detection of Contaminants in Water from Susquehanna River (Concentrations of Hazardous Materials in mg/1 shoving a measureable response) Hazardous Materials " X* H <H ox: XG OM G0 N G CP >a> -au SC V a. *0rt c(0 u sac o3cO oo WM S3cs O oo 0) JJ u (Q ,e 0 'H fd a C 0 O CM H0 2 JS CO 1^ -5 1. Phenol 1 0) T3 H M O rH o 0 T3 rt O 0 rH S*4 2. Methyl Alcohol 3, Acrylonitrile 4. Chloroaulfonic Acid 5. Benzene ( 6. Ammonium Chloride 7. Phosphorus Pentesulflde 1000 1 100 1000 10 100 100 10 100 100 100 10 10 1000 1 10 1 1 10 10 8. Styrene 9. Acetone Cyanohydrin 10. Calcium Hypochlorite 11. Nonylphenol 12. Iaoprene 13. Xylenee 14. Nitrophenol 13. Ammonium Nitrate 16. Aluminum Sulfate 17. Aldrin 6.6 100 100 1000 100 100 1.7 1 1.3 10 100 10 100 10 100 1000 10 1000 10 100 , 1 1000 1 1000 18. Toxaphene i9. bbr 20. EPN 21. Kalathlon 22. Parathlon 23- Oleldrln 24. Heptachlor 145 145 2.5 500 500 145 145 145 25 2.5 0.3 25. Sevln 26. Chlordane 4 0.4 40 40 27. Fermate 28. Lead Arsenate 29. Dlaodlum Methylarsenate 30. Phenylmercurid Chloride 31- 2,4-D (Acid) 32. 2,4,5-T (Acid) 33. Ammonium Phosphate, Dibasic 12 2.5 0.07 90 280 or change in transmittante of 5% 120 12 12 12 2.5 0.3 100 1000 1000 0.7 90 280 280 t. 1000 i 10--0 i .t , ,, r--------- 1 ,,.,r1 , --1 i., - l , 100 f. j by a change of 0.5 pH unit, gain In conductivity of 50 jiahos/i SURVEY OF MARYLAND WATERS Natural waters from north central Maryland were sampled to determine range of properties and concentrations of natural constituents. Twenty-two water sampes were taken from a loop which reached from approximately 10 miles north of Baltimore, northwest to Emmitsburg, south toward Frederick, south-easterly towards Laurel, around Baltimore and hack to five miles south of the starting point. The names of the waters where known were noted; others were identified by their location. The selected detection methods were used to characterize the waters and to anticipate any nroblems which might arise in use of the kit. No difficulties were experienced in analysis. Generally speaking the waters were of high quality and changes in them due to contamination should be easy to detect. Only when samples were taken near the city of Baltimore, in the harbor area, did some of the background readings (e.g. conductivity, sulfate and chloride) get so high as to present a significant background. Data are summarized in Table 6. 26 CCR 000040629 ^able 6 Background of Natural Waters of North Central Maryland <N Water Source uH p * & 0C1 01 P\ on rH --i o JO H H N > Cfl q Hu3 u* rCoCJ JM(23 C P0C1 (0 *J E0C1 01 01 ^pk 01 *H C flJ U tQc. u* Bu u\ 9 CO o o cO E U3 Ho <!=?} H bC 55 32! C (toX rH Mj Xo tt e tx e 0) o M O X Bo 0ro1t M O3 ~r--~l- frt 6C B. B 1. Loch Raven Reservolr_ 10 6.9 139 4.8 20 <0.1 <0.1 10.4 0.1 2. Liberty Reservoir____ 10 6.9 136 6.2 40 <0.1 0.7 15.9 0.1 3. Stream West of Taneytown_ 10 7.1 165 7.5 30 <0.1 <0.1 9.1 0.1 4. Stream West of Taneytovn_ 10 7.1 135 5.7 30 <0.1 0.4 8.2 0.2 5. Stream West of Taneytown_ 10 7.2 249 4.8 40 18 0.3 0.8 25.4 0.2 6. Monacacy River, Rt 97 10 7.1 185 3.8 50 16 0.2 0.6 10.4 0.3 7. Stream East of Enmltsburg_ 10 7.4 165 2.2 40 12 <0.1 <0.1 5.0 0.2 8. Stream South of Emmitsburg 10 7.1 104 1.8 10 <0.1 <0.1 4.0 0.2 9. Stream Worth of Frederick^ 10 .to 10 Stream Worth of Frederick^ 10 .<1 11 Monacacy River, Rt 80______ 10 .12 Hawllngs Run__________________ 26 6.8 60 7.1 160 7.0 200 6.8 78 0.0 10 7.0 10 7.5 30 5.3 20 <0.1 <0.1 11 <0.1 <0.1 15 0.2 0.3 <0.1 <0.1 1.3 0.1 5.5 0.2 6.8 0.2 6.0 0.1 13. Pautuxent River, Rt 97_ 10 6.9 106 4.8 20 <0.1 <0.1 6.4 0.1 14. Cattail Creek 10 6.8 110 6.2 10 <0.1 <0.1 9.1 0.1 15. Pautuxent River, Rt 108_ 10 6.9 95 4.0 <0.1 <0.1 7.8 0.2 16. Stream Wear Brinklow 10 6.8 84 3.7 10 <0.1 <0.1 7.8 0.1 17. Middle Pautuxent River__ 10 7.3 130 4.8 <0.1 <0.1 13.4 0.1 18. Little Pautuxent River__ 10 7.2 142 4.0 <0,1 <0.1 17.7 0.2 19. Patapsco River, Rt 144 .20 Patapsco River, Baltimore_ .21 Patapsco River, Baltlmore_ .22 Falls Run 10 10 10 10 7.3 113 6.6 162 7.3 600 7.5 165 4.8 3.8 3.7 30 4.0 <0.1 0.3 12.5 0.2 12 <0.1 1.6 16.5 0.1 35 0.4 0.5 110.0 0.2 <0.1 <0.1 15.0 0.2 CCR 0 0 0 0 4 0 6 3 0 *Stains were less than l-2mm, tests considered negative. WOTE: All samples represent different Bources of water, or significantly different pointB of the same body of water. SECTION 5 FORMULATION OF DETECTION CONCEPT SELECTED TESTS Many of the reasons for selection or rejection of individual tests have been discussed (Experimental Studies). Unfortunately, selection is often based not necessarily on capability required, but on what is available. All-in-all every effort was made to assemble the best combination of tests from what is available, with emphasis placed on reaching previously set goals of the detector kit. Generally, procedures which are simple, reliable, stable and cpmmercially available (when possible) and lend themselves to the detection concept were selected. To maintain compactness, duplication of detection capability was avoided. For example, numerous metal tests were eliminated by adopting dithizone as a general heavy metals test. A summary of characteristics of the 15 procedures selected for the kit are given in Table 7 . PROJECTED DETECTION CAPABILITY A "paper analysis" was made to project the probability of detection of the 370 compounds listed in the Federal Pegister. Each compound was screened by comparison with the detection tests (except turbidity) listed in Table 7 ; that is, each compound was compared with a) data derived from laboratory test ing with contaminants from the model list, and b) data derived from handbooks. A compound was considered detectable by a particular test If it was judged that a saturated solution or 1000 mg/1 of the compound (whichever was less) has a significantly greater than 50? chance of responding. Where information was considered inadequate to make a satisfactory judgment, individual additional testing was considered. (For example, in this manner it was determined that 28 CCR 000040631 Detection Parameter Cholinesterase Inhibitors Type* Qualitative Bensene Qualitative Heavy Metals Qualitative TABLE 7 Summary of Methods Selected for Detector Kit Time, Types of Process Reagents** Min. Substances Detected Enzyme M30A1, Chemical ^8 Certain insecticides, very acid Ticket Agent Detector materials. Kit Max. Sena, in Nat. Hater, mg/1 <3 Detector Tube Bendlx/Gastec <2 Benzene, styrene, xylene, toluene, other organic materials. 1 Extraction/ Hach/Laboratory Test Tube < 1 Many metals. Also some organic materials. <10 Phenol Cyanide Qualitative Qualitative Extraction/ Cent. Tube Detector Tube Hach Kitagawa < 1 Phenolies. <1 Cyanide ion. Certain other organic and Inorganic materials. 1 10 pH Quantitative Meter Conductivity Quantitative Meter -- -- <1 Acidic or basic organic and inorganic materials. <1 Inorganic compounds and other materials with high ionic strength. <3 10 Nitrate Nitrogen Color Quantitative Spectro photometer Quantitative Spectro photometer Hach -- <6 Nitrate ion. Certain other organic and inorganic substances. < 1 Highly colored organic or inorganic substances. 10 <5 Sulfate Quantitative Spectro photometer Hach CIO Sulfate ion. 10 Phosphate Quantitative Spectro photometer Hach < 2 Phosphate ion. Certain arsenates arsenlteB and bromatsa. <1 Ammonia Nitrogen Quantitative Spectro photometer Hach <10 Hide range of organic and inor ganic ammonia containing materials <1 Chloride Fluoride Quantitative Spectro photometer Laboratory Quantitative Spectro Hach photometer <10 <- 2 Hide range of sulfides, bromides, cyanides, sulfides, thiosulfates, chlorides. Fluoride. Various inorganic and organic materials. 10 10 Turbidity Quantitative Spectro photometer -- <1 Low solubility materials. Hot determined * Quantitative in thia context naans that a numerical value la assigned to the data. ** Laboratory indicates reagents which are specially prepared. nitrites would respond to the nitrate test and sulfites were detected by the sulfate test, whereas, thiosulfates were not. Also, certain arsenates, arsenites and bromates respond to the phosphate test, but chromate does not). Extensive testing was conducted with heavy metals and ammonia con taining compounds. These data have already been reported under appropriate sections in Experimental Studies. Highlights of the "paper analysis" are given in Table 8 Data from this study indicate that 85% of the contaminants would respond to at least one parameter; 58%, 30% and 10% would respond to two, three, and four or more parameters respectively. (See complete data in Appendix A.) Because certain compounds don't show responses for the detection parameters doesn't necessarily mean non-detection. Rather, many of these structures are very complex and their reactivity cannot be predicted. Judging by some of the unexpected responses obtained with many of the detection methods it is to be expected that some of these materials are detectable by present methods. Table 8 Probability of Detection of Water Contaminants (Based on nominally 370 compounds) Detection Parameter Probable Responses Cholinesterase Inhibitors Benzene Heavy Metals Phenol Cyanide pH Conductivity Nitrate Nitrogen Color Sulfate Phosphate Ammonia Nitrogen Chloride Fluoride 16 20 102 12 11 66 2C1 18 50 23 18 58 72 24 USE CONCEPT Our goal was to develop a field kit using a standardized system so that results are easily obtained and interpreted by a senior technician. This goal, generally, has been met; tests are easy to perform, short and designed for ease of operation in the field. However, detecting almost any contami nant in any water background is a formidable task which requires ingenuity and the interpretive skills of a dedicated investigator. 30 [00^0633 CCR 00 The detection concept relies basically on three evaluations as shown: DETECTION CONCEPT General Assessment Relative Measurements 1. Appearance 9. pH 2. Color of Filtered Water 10. Conductivity 3. Color of Suspended Matter 11. Turbidity 12. Nitrate Nitrogen Spot Tests 13. Color 4, Cholinesterase Inhibitors 14. Sulfate 5. Benzene 15. Phosphate 6. Heavy Metals 16. Ammonia Nitrogen 7. Phenol 17. Chloride 8. Cyanide 18. Fluoride General Assessment procedures allow the operator to make a general evaluation of the water to be tested. That is, are there slicks present? -- is the water colored? -- is there a lot of suspended material?-- is the suspended material colored? Spot Tests are used to Indicate if a parti cular type of contaminant is present. A positive response to any of these tests should be considered contamination since it would Indicate compounds not normally found or desired in water. The final group of tests. Relative Measurements, is based on constituents of natural water. Contami nation is indicated by a significant increase in one of these parameters compared to uncontaminated water. To use the detection concept the Investigator must assess two major factors: a) The nature of the water source -- is it stationary, like a lake or pond, or is it moving like a stream or river? b) The nature of the contaminant -- is it specifically known or partially known, such that it may be acid or base, organic or Inorganic, phosphate containing, colored, etc? In situations where the contaminant is unknown, the investigator confronts the situation in an orderly fashion: (1) He immediately conducts the General Assessment evaluations. (2) He considers using the Spot Tests since these are simple to use and easy to evaluate. (3) He proceeds to the Relative Measurements. If the location of the contaminant is based on a relative measurement then he must make a comparison between the area of 31 CCR 000040634 suspected contamination and a clean source of water (reference sample). In the case of a stream, the reference sample may be taken at a location upstream from the contamination. If the body of water is a lake, he must use his best judgment and select an area believed to be clean. Once the reference sample is established, it is a matter of deciding which relative tests can be used In detecting significant changes. In cases where the specific contamination is known, the investigator proceeds directly to the applicable tests. For example, an investigator confronted with a spill of phosphoric acid would immediately perform pH, conductivity and phosphate tests and determine which is most suitable for this situation. A special data sheet for recording and reporting of contamination has been designed to correspond with the detection concept (see Appendix B, p. 10). design and fabrication of prototype kits A significant part of design was concerned with human factors considerations, i.e. man/machine interfaces. The purpose is to select procedures and instrumentation which make tests easy to perform and evaluate and which provide reliable information. Some of these factors have already been considered when procedures were selected. For example, use of test papers, color comparators and pH indicators are considered too subjective, particularly when measurements must be made relative to a reference sample. Use of a quality pH meter, conductivity meter and colorimeter is a prerquisite. Spot tests, which are also subjective, are adopted for use In the detection concept as gross tests to be used only on a "go no-go" basis. Some of the instruments considered for this program (e.g. the Chemtrix Type 40E pH meter and Chemtrlx Type 70 conductivity meter) have already been discussed. Much of the development data was obtained with the instruments; both meet the level of quality and performance required for the kit. Also, the Hach DR Colorimeter was used extensively and was found to be a highly satisfactory portable' colorimeter. The Mini-Spec 20 Spectrophotometer (marketed by Bausch and Lomb, Analytical Systems Division) was also considered briefly for the kit. A demonstration of the Mini-Spec 20, which is a full grating spectrophotometer about the size of a pocket calculator, showed it to be a sensitive, accurate and versatile Instrument. The feeling, however, is that it may be too delicate and sophisticated for field use; many of the pieces used are small and do not appear to easily lend themselves to operation under rugged conditions. Originally it was planned to integrate the best available instrumentation into a suitable carrying case. . A prime concern all-along was to restrict kit size and weight to maintain the man-portable concept. When it appeared the final package might become too large and unwieldy, instruments combining 32 CCR 000040635 several functions were sought. In fact, at that time, a 4 Function Water Analyzer (International Ecological Systems) was on the market. The instrument, which measured about 5x10x11 inches provided pH, conductivity, colorimeteric and thermal measurements. This item was considered until its continued availability, service and replacement parts became uncertain. Finally, a decision was made to adapt the DR-EL/2 portable test kit marketed by Hach which incorporates a spectrophotometer and a conductivity meter. Hach agreed to provide this item without the standard equipment or reagents. In addition, a Hach Model 1975 battery-operated pH meter was dismantled and reassembled into a special compartment fabricated into the lid of the case; when the case is open the pH meter faces the operator. The battery for the pH meter is next to the power supply for the spectrophoto meter and conductivity meter. A significant human factors advantage is gained by use of the spectrophotometer instead of a filter colorimeter since color filter changes are not required for the different colorimetric analyses. It was originally planned to use a case meeting military specifications for the detector kit. However, the Hach case by comparison, while not as rugged, is considerably lighter and less expensive. Also use of the Hach case significantly reduces special design and fabrication costs for the kit. A particularly important piece of equipment included in the kit is a plastic syringe with stainless steel head fitted with a glass fiber disc to filter the water sample. It is used for general assessment of the water sample and to process it for colorimetric analysis. Other necessary ancillary equipment or reagents were purchased from available sources or prepared in the laboratory. Many of the purchased reagents and equipment were repackaged in the kit in the interest of economy cf space. It must be remembered that only the detectcr tickets and suostrate are used from the M30A1 Chemical Agent Detector Kit, The Tris buffer is prepared in the laboratory (Experimental Studies, m. Enzyme Systems) since it must be washed with dithizone for use in the heavy metals test. An Operator's Manual (Appendix B) was prepared for use with the kit. It describes in detail the use concept, equipment and procedures used. A source listing for consumable parts is given. Hach manuals for the DR-EL/2 portable test kit and Model 1975 pH meter are also provided. In addition, laminated outlines of procedures are included for use in the field. Tests were conducted with the kits to demonstrate their fleldability. Modifications were made to the Operator's Manual as a result of these exercises. The detector kits resulting from this program are shown in Figures 1 and 2. CCR 000040636 33 HAZARDOUS MATERIALS DETECTOR KIT *? f A-feffe v `-V CO -T Figure 1 Hazardous Materials Detector Kit CCR 0 0 0 0 4 0 6 3 CCR 0 0 0 0 4 0 6 3 8 Figure 2 Hazardous Materials Detector Kit, In Use REFERENCES 1. Prober, R., "CRC Handbook of Environmental Control", Vol, III, Water Supply and Treatment. CRC Press, Cleveland, OH (1973). 2. Annual Book of ASTM Standards", Part 23, Water; Atmospheric Analysis, Philadelphia, PA (1973). 3. "Standard Methods for the Examination of Water and Wastewater", 13th ed., American Public Health Association, Washington DC (1971). 4. "Methods for Chemical Analysis of Water and Wastes", US Environmental Protection Agency, Analytical Quality Control Laboratory, National Environmental Research Center, OH (1971). 5. Wilder, I., Lafornara, J.P., Water and Sewage Works, 119, 82 (1972). 6. Duke, F.R. and Smith, G.F., Industrial and Engineering Chemistry, 12, 201 (1940). 7. Feigl, F., "Spot Teats in Organic Analysis", 7th ed., Elsevier Publishing Co., Amsterdam, Netherlands (1966). 8. Elsheimer, H.N., Kocken, R.L., Anal. Chem. 38, 145 (1966). 9. UtBumi, S., J. Chem. Soc. Japan 73, 835 (1952). 10. Fehringer, N.V., Ogger, J.D., J. Chromatog. 23, 95 (1966). 11. Kovacs, M.F., J. of the AOAC, 47_, 1097 (1964). 12. Abbott, D.C., Egan, H., Thomson, J.. J. Chromatog. 16, 481 (1964). 13. Kenner, R.A., Aboderin, A.A., Biochemistry, 1, 4433 (1971). 14. Bumhan, R., Calder, G.Y., Fritz, J.S., Junk, G.A., Svel, H.J., Willis, W., Anal. Chem., 44, 139 (1972). 15. Braun, R.A., Mosher, W.A., J. of the American Chemical Society, 80, 2749 (1958). 16. Mellan, I., "Organic Reagents in Inorganic Analysis", The Blakiston Co., Philadelphia, PA (1941). 17. Braun, T., Farag, A.B., Analytica Chimica Acta, 73, 301 (1974). 18. Berthelot, M., Repertaire de Chemil Applique, 1_, 284 (1859). 19. Searcy, R.L., Gaugh, G.S., Karotger, J.J., Berquist, L.M., Am. J. Med. Tech., 27, 255 (1962). 20. Chaney, A.L., Marbach, C.P., Clin. Chem., 8, 130 (1962), 36 CCR 000040639 LIST OF MANUFACTURERS AND SUPPLIERS 1 !* Anderson Laboratories Corporation, Fort Worth, TX 1 2- Bausch and Lomb, Analytical Systems Division, P.ochester, NY 1 3' Bendix/Gastec (Products available from National Environmental Instruments, Inc., Warwick, RI) I 4. Boehringer Mannheim GMBH, Biochemcial Department (Products available from Fisher Scientific Co.) 1 5* Chemtrix, Inc., Hillsboro, OR 6. Corning Glass Co. (Electrodes are available from VWR Scientific Division of Univar) 7. Hath Chemical Co., Ames IA 8. International Ecological Svstems Corporation, Mt. Laurel, NJ 9. Kitagawa (Products are available from Matheson Gas Products, East Rutherford, NJ) 10. Micro-Essential Laboratory, Brooklyn, NY 11. Rohm and Haas, Philadelphia, PA 12. Worthington Biochemical Corporation, Freehold, NJ 37 CCR 0000A0640 .ijbi alpelll-; a PROBABLE KESpu LSK.s u I UETELlOR KIT Id Al.M KHL\ LS I JHTED IN FEDERAL ItELlSJ MR, \OL. 10, NO, TO?), PEL, 75 r-J Acetaldehyde ________ Acetic acid___________ Acetic anhydride____ Acetone cyanohydrin Acetyl bromide_______ Acetyl chloride_____ Acrolein_______________ Acrylonitrile________ Adiponitrile_________ 00 Aldrin Allyl alcohol____ Allyl chloride______ Aluminum Bulfate____ Ammonla Ammonium Compounds: Ammonium acetate _ Ammonium benzoate Ammonium bicarbonate_______ Ammonium bisulfite_________ Ammonium bromide Ammonium carbamate________ Ammonium carbonate............. Ammonium chloride Ammonium citrate, dibasir Ammonium ferrocyanide _ Ammonium fluoborate Ammonium formate___________ Ammonium gluconate___ Ammonium hydroxide______ Ammonium hypcphosphlte CCR 0 0 0 0 4 0 6 4 1 .a. APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (continued) Ammonium Iodide Ammonium molybdate Ammonium nitrate Ammonium oxalate Ammonium pentaborate____ Ammonium silicofluoride Ammonium sulfaaate_______ to Ammonium sulfate CO Ammonium sulfide^,________ Ammonium sulfite Ammonium tartrate Ammonium thiocyanate____ Ammonium thisulfate Amyl acetate Anil ine_________ _________ Antimony Compounds: Antimony pentachlorlde_______ Antimony pentafluorlde_______ Antimony potassium tartrate Antitaony tribromide___________ Antimony trichloride_________ Antimony trlfluorlde_________ Antimony triiodide Antimony trioxlde Arsenic Compounds: Arsenic acid____________________ Arsenic disulfide_____________ Arsenic pentaoxlde____________ + ++ T + + + + + + T T T +_ + + T +_ + + + ++ ++ ++ + ++ + ~ + + T T +T ++ ++ + + T T + T Z^PO^OOOO VOJ APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (continued) Arsenic tribromide Arsenic trichloride Arsenic trifluoride Arsenic triiodlde Arsenic trloxide Arsenic trisulfide Cacodyllc acid Calcium arsenate Calcium arsenite Potassium arsenate Potassium arsenite Sodium arsenate Sodium arsenite Sodium cacodylste Benzene Benzoic acid Benzonltrlle Benzoyl chloride Benzyl chloride Beryllium Compounds: Beryllium chloride Beryllium fluoride Beryllium hydroxide Beryllium nitrate Beryllium phosphate Beryllium Bulfate Boric acid Brucine Butyl acetate ++ ++ ++ ++ + + + + + + + + + + + + + + + + + + + ++ + + + + + + + CCR 0 0 0 0 4 0 6 4 3 APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO, 250, DEC. 75 {continued) Butylamine Butyric acid Cadmium Compounds: Cadmium acetate Cadmium bromide Cadmium chloride Cadmium fluoborate Cadmium nitrate Cadmium Bulfate Calcium carbide Calcium hydroxide Calcium hypochlorite Calcium oxide Captan Carbaryl Carbon disulfide Catechol Chlordane Chlorine Chlorobenzene Chloroform Chlorosulfonlc acid Chromium Compounds: Ammonium bichromate Amnonium chromate Calcium chromate Chromic acid Chromic sulfate 10 H 4J H C M V c H O ,C U ec0o1 4<J0 01 X H > c c 401 X 01 XJC 01 TJ tH c (d EC o H > H U U d Co u CM iz; V 4J V* 4J o rH o U CM 01 4J 4ur$J X (0 cd 44 P. CQ oc rH O d .C g 6 CO << *iuH0o1 o rAH CJ 01 *H M O d H + + + + + + + + + + + + + + + + + + + + + + + + ++ + + ++ ++ + + + + T~ + ~^r + + T ++ + + ++ ++ + ++ + + CCR 0 0 0 0 4 0 6 4 4 APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (continued) C hoi. In h ib Benzene Heavy M etali Phenol C yanide pH C o n d u ctivit; N itra te N,, C olor S u lfa te P h o s p h a te Ammonia N^ C h lo rid e F lu o rid e Chromous carbonate Chromous chloride Chromoua oxalate Chromyl chloride Lithium bichromate Lithium chromate. Potassium bichromate Potassium chromate Sodium bichromate Sodium chromate Strontium chromate Zinc bichromate Cobalt Compounds: Cobaltous acetate Cobaltoua bromide Cobaltous chloride CobaltouB citrate Cobaltous fluoride Cobaltous formate Cobaltous iodide Cobaltous nitrate Cobaltous perchlorate Cobaltous succinate Cobaltous sulfamate O Cobaltous sulfate O 7> Copper Compounds: o o Cupric acetate o Cupric acetoaraenlte o -F o O' Ul + + + ++ + + + + + + + + + + + + + + + + + ++ + + + ++ + ++ + ++ + + + ++ + ++ + + ++ + ++ + + ++ + + ++ + + + + ++ + ++ ++ APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATE WANS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (cnmimied) *000 Cupric acetylacetonate Cupric bromide Cupric chloride Cupric formate Cupric gluconate Cupric glyclnate Cupric lactate Cupric nitrate Cupric oxalate Cupric aubacetate Cupric aulfate Cupric sulfate, ammonlated Cupric tartrate CuprouB bromide Cuprous iodide Coumaphoa Cresol Cyanide Compounds: Barium cyanide Calcium cyanide Hydrogen cyanide Potassium cyanide Sodium cyanide Zinc cyanide Cyanogen chloride Cyclohexane 2,4-D (acid) 2,4-D (eaters) Dalapon o a O' . CO XI H (fl Cl CN x: c a> > s; i4 41 JJ 01 at M Q) S 41 c rH 0) o H M 4) (J u 3 4? al cd T* u x: H >H H p- C V* Vj H e ro N G a] PQ cc T3 oj 41 vO PW 41 ,C >> ts O H X P* u ex CJ Si o in rH rH o O 3X U to P, O O0 E rH 3 b ,3 H < C_J P, ++ + ++ + + ++ + + ++ + + ++ ++ ++ + ++ ++ + +4 + + ++ + ++ + + ++ ++ + + ++ + + ++ + ++ -- -------- ++ + + ++ + + -4++ + + + ~ -T + + + -- -- -- + + APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (continued) c) Szs 03CM us o Nc u CQ sO 09 OS u3> u a0o 03 P. o (A UO aaa C3O 0ok !Oj DDT Dlazinon_ Dlcamba Dichlobenil_ Diehlone_____ Dichlorvos__ Dleldrln Diethylamlne___ Dlmethylamine__ Dini trob enzene_ Dinltrophenol__ Diquat_ Disulfoton_ Diuron Dodecyl benzenesulfonic acid Dodecyl benzenesulfonic acid, calcium salt Dodecyl benzenesulfonic acid isopropanol amine salt____________________ Dodecyl benzenesulfonic acid, sodium salt ________ Dodecyl benzenesulfonic acid, triethanolamine salt____________ Dursban______________________________ o Endoaulfan__________________________ o 73 Endrln Ethion________ Ethylbenzene____ Ethy1enediamlne_ Ethylenediamlne-tetraacetlc acid ~r T APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (routiniied) Fluorine Compounds: Aluminum fluoride Ammonium bifluorlde Ammonium fluoride Hydrofluoric acid Lithium fluoride Phosphorus pentafluoride Sodium bifluoride Sodium fluoride Stannous fluoride Formaldehyde Formic acid Fumaric acid Furfural Guthlon Heptachlor Hydrochloric acid Hydroquinone Hydroxylamine Iron Compounds: Ferric ammonium citrate Ferric ammonium oxalate Ferric chloride Ferric fluoride Ferric glycerophosphate Ferric nitrate Ferric phosphate Ferric sulfate .n ja rH H 0 xc 4J 41 H <1) X 01 c H T3 * H o 0) N e (0 O e <c0 & 4) 01 c PQ cu o u H C4 > tH 0] UU a fd -d M O Co M *H tH o CJ % u a; 4J 0k d -p X (0 D* UM (A HO aA to C4 X <d H oc 0 E 01 T3 tH M O rH U ok TJ pH O a --i tin + ++ ++ ++ ++ ++ ++ ++ ++ + + -- + + + .-- + + + + + + + + + ++ + + + + + + + + ++ + + + + + + CCR 0 0 0 0 4 0 6 4 8 APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (continued) FerrouB ammonium sulfate Ferrous chloride FerrouB oxalate Ferrous sulfate Isoprene Kelthane Lead Compounds: Lead acetate Lead arsenate Lead bromide Lead chloride Lead fluoborate Lead fluoride Lead iodide Lead nitrate Lead stearate Lead sulfate Lead sulfide Lead tetraacetate Lead thiocyanate Lead thiosulfate Lead tungstate Lindane Malathion Maleic acid Maleic anhydride X C w OJ c a) HN OC 0) u + o fH <0 OJ s (0 01 X + + + + 0) H T3 O H ee 01 flj X >. Pi u 4J > 4J O 3 TJ 33 ao P. o + + CN 2: OJ *J (4 M 4J t-i 55 M O H O u 01 u OJ 4 4J X CO CL * as rH O 3X CO p CM S3 ad rl C 0 01 3 0J M O e ++ +. + 01 TJ o 3 fx + + + + + + + + + + + + + + + ++ _____ + ++ + + + + + + + ++ + + X. _ APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (continued) Mercury Compounds: Mercuric acetate Mercuric ammonium chloride Mercuric bromide Mercuric chloride Mercuric cyanide Mercuric iodide Mercuric nitrate Mercuric oxide Mercuric sulfate Mercuric thiocyanate Mercurous chloride Mercurous iodide Mercurous nitrate Methoxychlor Methyl mercaptan Methyl methacrylate Methyl parathion Mevlnphos Molybdlc trioxlde Monoe thylamine Haled Naphthalene Naphthalenlc acid Nickel Compounds: Nickel acetate Nickel ammonium sulfate Nickel bromide 43 X c M 01 c u HN OC X 01 KJ A (0 rH (fl 4J Of X H O(3 id 01 01 X XAI 01 T3 cH CJ p. 4J > 4J U 3 Tc) CoJ CM X 0) td v* o 4J tH O U 0) J td uH3~t CO CM Q> X w id GJ *0a1 43 H Ow. c O 0i nH Ho 43 1 X< 43 CJ 01 TJ H Oa rH Pi + + + + + + t + f f t + + + + + + ++ ++ + + + + + + + + + + + + ++ + + ++ + ++ + CCR 0 0 0 0 4 0 6 5 0 A APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (continued) Nickel chloride Nickel fluoride Nickel formate Nickel hydroxide Nickel iodide Nickel nitrate Nickel perchlorate Nickel sulfate Nitric acid Nitrobenzene Nitrogen dioxide Nitrophenol Paraformaldehyde Parathlon Pentach1oropheno1 Phenol Phosgene Phosphoric acid Phosphorus Phosphorus oxychloride Phosphorus oentasulflde Phosphorus trichloride Polychlorinated biphenyls Potassium hydroxide Potassium permanganate Propionic acid Propionic anhydride Propyl alcohol Pyrethrlns Pvrogallic acid Quinoline Resorcinol 10 JO *H X 4<40 HC H oCr 4N Oc 01 X 4r A.-a__ __ V __ + + + + + + + + tH O c 01 i: at + T-0H31 (d >s u __ + + + + + + + + + + ++ + + + + 4H-1 CN -> X 4J U 404) T33 c 0 4 44 MO HO u... -.a.,-. u + ++ ++ + + ++ + + + ++ 01 U 4 tH 3 --10 + 4041 4<43x to o .e Pj . C4 P5 01 4 T5 cOfl H O R <C A_ + 01 *o M O r3H fa + + + + + ++ + + + + ++ + + + + '+ + + +4 + + + 1+ + + + + CCR 0 0 0 0 4 0 6 5 1 ill APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATE if? REGISTER, VOL. 40, NO. 250, DEC. ;r- 1 [; [ ED IN FEDERAL iML'f-:!) *O O o > O xo> o a hj Selenium Compounds: Sel nlc acid Selenium oxide Selenium oxychloride Sodium selenite Sodium Sodium bisulfite Sodium borate S dlum hydrosulfide Sodium hydroxide Sodium hypochlorite Sodium methylate Sodium nitrite Sodium phosphate, dibasic Sodium phosphate, monobasic Sodium phosphate, tribasic Sodium silicate Sodium sulfide Strychnine Styrene Sulfuric acid Sulfur monochloride 2,4,5-T (acid) 2,4,5-T (esters) Tannic acid TDK Tetraethyl lead Tetraethyl pyrophosphate Toluene XH 4J cd H r J >xi c M 0) c Cl N OE X0 o JJ Cl X a 4) rc Cl 'd o cc Cl o ja Ph o > H U O 3 T3 C o au *z; Cl 4J (fl H 4J a a> u i-t flU o m-j tH rS o3 r/i ua u OJ (0 43 H p. E (II 0 og XB Ph Cl Xf M O H jC o o TJ H Vi 9 O iH + + + +A t + + -- + + ++ ++ + + ++ -- ++ ++ -- + ++ +-- ++ ++ + + -- ~4 --_ + + + + + + ++ ++ ++ + -- + -- -- + + + -- -- APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (continued) Toxaphene Trichlorfon Tr1ch1oropheno1 Triethylamine Trimethylamine Uranium Compounds: cn Uranium peroxide o Uranyl acetate Uranyl nitrate Uranyl Bulfate Vanadium Compounds: Vanadium oxytrichloride Vanadium pentoxide Vanadyl sulfate Vinyl acetate Xylenol Xylene Zectran Zinc Compounds: Zinc acetate Zinc ammonium chloride Zinc anmonium sulfate Zinc borate Zinc bromide Zinc carbonate Zinc chloride Zinc fluoride a >s XtH rH to V *r4 CM CH X ii > 0) g w rH O X u 0) G 4) N G a) PO a* s: H O d c0) X pH 4> d *rl a 0 tn Ua H 41 O 4J 9 ad o u (3 V O u 2J 01 U Vi O ft U~i rH rH O9 u to 4J aa X H &. G 00 o 0 g* X1 CV < 01 4) *d H Vi Vi OO rH X rH9 tj + + + + + + + + + + + + + ++ + + + + + + + + ++ + ++ + ++ ++ ++ CCR 0 0 0 0 4 0 6 5 3 .Jt APPENDIX A PROBABLE RESPONSES OF DETECTOR KIT TO MATERIALS LISTED IN FEDERAL REGISTER, VOL. 40, NO. 250, DEC. 75 (continued) Zinc formate Zinc hydrosulfite Zinc nitrate Zinc permanganate Zinc phenolsulfonate Zinc phosphide Zinc potassium chromate Zinc propionate Zinc ailicofluorlde Zinc sulfate Zinc sulfate, monohydrate Zirconium Compounds: Zirconium acetate Zirconium ammonium fluoride Zirconium potassium fluoride Zirconium nitrate Zirconium oxychloride Zirconium Bulfate Zirconium tetrachloride H e M 01 G 1-1 VN oc $ Un ptHo q) 4J 01 X iH 01 o od G0) G (0 01 X xc U + + + + ++ + + + + + + 4- >H 4-1 O 3 T3 EC (X C o o ++ + ++ + + 52 40-11 (0 4H-1 + t t t + + 40J] M HCOOJ 40-1J Mtho i-1 3 CO to (X CO .Go {X + + + + <N 01 *crd4 T*HJ g BBo HO << U 0> T*MH3 O r3H F** + + + ++ + + + ++ + 4+ + CCR 0 0 0 0 4 -0 6 5 4