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Dissertations, Theses, and Masters Projects Theses, Dissertations, & Master Projects
1983
Organic toxic substances monitoring in Virginia
Robert Emile. Croonenberghs College of William and Mary - Virginia Institute of Marine Science
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Recommended Citation Croonenberghs, Robert Emile., "Organic toxic substances monitoring in Virginia" (1983). Dissertations, Theses, and Masters Projects. Paper 1539616622. https://dx.doi.org/doi:10.25773/v5-vdbf-8m78
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University Microfilms International 300 N. Zeeb Road Ann Arbor. Ml 48106
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Croonenberghs, Robert Emile
ORGANIC TOXIC SUBSTANCES MONITORING IN VIRGINIA
The College of William and Mary in Virginia PH.D.
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International300 N. Zeeb Road, Ann Arbor, MI 48106
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University Microfilms International
ORGANIC TOXIC SUBSTANCES MONITORING IN VIRGINIA
A Dissertation
Presented to
The Faculty of the School of Marine Science
The College of William and Mary in Virginia
In Partial Fulfillment
Of the Requirements for the Degree of
Doctor of Philosophy
by
Robert Emile Croonenberghs
1983 APPROVAL SHEET
This dissertation is submitted in partial fulfillment of
the requirements for the degree of
Doctor of Philosophy
£ Robert E. Croonenberghs
Approved, May 1983
N. Bartlett Theberge, T LL.M., T V f (Co-Chairman)
Robert J. Hug^etPh (Co-Chairman)
Craig L. Smith, Ph.D.
Michael E. Bender, Ph.D.
Randolph A. Coleman, Ph.D., Department of Chemistry, College of William and Mary DEDICATION
This dissertation is dedicated to my family, including both Tooey's side and my side, for their love, encouragement and support. Especially, it is dedicated to Tooey, who made life most enjoyable during the rigors. The timely completion of the work must be credited to the arrival of James Pierre. TABLE OP CONTENTS
Page Dedication...... iii Table of Contents...... iv Acknowledgements...... vi List of Tables...... vii List of Figures...... ix Abstract...... x
Chapter I. Introduction and Hypothesis...... 2
1.1 Introduction...... 2 1.2 Hypothesis...... 6
Chapter II. Methods...... 7
2.1 Toxic Substances Used in Virginia...... 7 2.2 Analytical Requirements...... 18
Chapter III. Results...... 20
3.1 Critical Conventional Procedures...... 20 Evaporative Loss Potential...... 21 Stability...... 23 Solubility...... 24 Liquid Chromatography...... 25 GC and GC/MS...... 28 3.2 Analytical Properties of "Compounds" 29 Detectable by Conventional Techniques.... 29 Possibly Detectable by Conventional Techniques...... 32 Not Detectable by Conventional Techniques...... 34 3.3 Toxic Effects...... 37 3.4 Judgement of Need for Special Monitoring. 37 Volatiles...... 39 Non-volatiles...... 41 Miscellaneous Analytical Procedures 43 3.5 Proposed Analytical Procedures...... 47 Volatiles...... 48 Nitrofurans...... 51 Benzidine...... 52 Chloramphenicol...... 53 Sulfamethazine...... 53 Cupferron...... 54 Anionic Dyes ...... 55 Cationic Dyes ...... 61
Chapter IV. Discussion and Conclusions...... 63
iv 4.1 Discussion...... 63 4.2 Proposals for implementation...... 69 4.3 Conclusions...... 73
Literature Cited...... 74
Appendix...... 106
v ACKNOWLEDGEMENTS
My deepest appreciation for help on this work extends to Dr. Craig Smith, for spending many hours patiently explaining concepts in organic chemistry. His insights were acutely perceptive, and his direction throughout the work was extremely helpful. Many thanks are due to my two co-chairmen. Dr. Bob Huggett was a great help in my early work on Kepone, instilling a confidence in my ability to conduct research. Mr. Bart Theberge, LL.M., educated me in the realities of bureaucracies, and provided me with legal and management tools which I now find indispensable. I wish to thank Dr. Mike Bender for his help over the years, and Dr. Randy Coleman for his participation on my committee. Ms. Janice Meadows, Assistant Librarian, was most helpful in the retrieval of far too many journal articles. Ms. Susan Carter was helpful in so many instances, I can only say thanks. Thanks also to the many other friends at VIMS who helped me along the way. LIST OF TABLES
Page Table 1. Toxic organic "compounds" involved in production in Virginia which were researched by this work ...... 11
Table 2. "Toxic" organic substances involved with production in Virginia, but omitted from research by this work 17
Table 3. "Compounds" which are detectable by conventional analytical techniques 30
Table 4. "Compounds" possibly detectable by conventional analytical techniques 33
Table 5. "Compounds" which are not detectable by conventional techniques...... 35
Table 6. Volatile and potentially volatile "compounds" of potential concern in long term environmental accumulation... 40
Table 7. Non-volatile "compounds" of potential concern in long term environmental accumulation...... 42
Table 8. Miscellaneous non-detectable or possibly detectable "compounds" of potential concern in long term environmental accumulation...... 45 Table 9. Costs for implementation of analytical procedures...... 72
vii LIST OF FIGURES
Page
Figure 1. Proposed analysis plan for toxic substances monitoring in Virginia 49
viii ABSTRACT
This project attempts to identify toxic organic substances used in Virginia, which cannot be detected by conventional analytical procedures. A list from the Virginia Bureau of Toxic Substances Information which contained substances reported as used in manufacture or produced in Virginia was cross-referenced with the Master File of toxic substances compiled pursuant to the Toxic Substances Control Act. Organic chemicals appearing on both lists were thus identified as toxic substances used in Virginia, and were the subjects of this research. Due to the reporting requirements of the Virginia Toxic Substances Information Act, the 113 "compounds" do not include substances used solely in repair work in Virginia. In addition, since chemicals used only as pesticides or drugs were not included in the Master File, these types of substances do not appear in the list of 113 "compounds".
Conventional organic analytical procedures were studied, and five basic critical parameters which could impair analysis were determined: volatility, stability, solubility, adsorption in liquid chromatography, and problems in GC and GC/MS. The literature was then researched for these critical parameters to indicate the ability of conventional techniques to detect the 113 "compounds". "Compounds" which were either not detectable or possibly detectable by conventional techniques were assessed for potential long term environmental accumulation. An analytical technique, involving a minimum of steps, was then developed to analyze specifically for those "compounds" requiring special monitoring. ORGANIC TOXIC SUBSTANCES MONITORING IN VIRGINIA CHAPTER 1
INTRODUCTION AND HYPOTHESIS
1.1 Introduction
The years 1974 to 1977 represent a period of nearly unprecedented public concern over toxic pollutants in food.
Three major instances of widespread environmental and human contamination by organic pollutants resulted from intentional discharges and accidental mishaps. In May 1974 polybrominated biphenyls (PBBs) were discovered in Michigan's human population and livestock, in December 1975 the James
River in Virginia was closed to fishing and shellfishing as a result of high Kepone concentrations, and in February 1976 the Hudson River was essentially closed to commercial fishing due to high concentrations of polychlorinated biphenyls
(PCBs).
A particularly distressing similarity in all three cases appeared: an environmental problem existed well before the contaminants were identified in human food. Widespread human contamination continued while the regulatory agencies tried to understand and effectively react to the situation. A method was obviously needed to shorten this time lag between the appearance of problems and effective agency responses
(Cooper and Farace 1979) .
Congress responded to public pressure through major legislative enactments. The Federal Insecticide, Fungicide
2 and Rodenticide Act Amendments of 1975 (PIPRA) significantly
increased control over the sale and use of pesticides and
related chemicals (7 USCA, Sec. 136b.) The Toxic Substances
Control Act (TSCA), passed in October 1976, required the determination of substances which should be given priority by
EPA for testing to determine adverse effects on human health
and the environment (15 USCA, Sec. 2603(e.)). The Resource
Conservation and Recovery Act of 1976 (RCRA) instituted
controls over the storage, transportation and disposal of
toxic wastes (42 USCA, Sec. 6921 - Sec. 6931) . The Clean
Water Act of 1977 (CWA) amended requirements concerning
priority pollutants (33 USCA, Sec. 1317(a.)). The General
Assembly of Virginia passed the Toxic Substances Information
Act in 1976 to develop a central repository of information
concerning chemicals used in Virginia (Code of Virginia, Sec.
32.1-239 - 32.1-245) .
Though these legislative efforts were made both to
prevent pollution events and to shorten the response time,
additional measures are undoubtedly still needed. Current
monitoring practices for toxic substances typically involve
the creation of lists of compounds most likely to cause
pollution problems, with analysis specifically for those
compounds. This list oriented approach is generally employed
because analysis for all possible compounds in a sample
involves an unrealistic amount of time and effort.
Researchers at the Virginia Institute of Marine Science
- William and Mary (VIMS) have collaborated in the
3 1
development of an analytical procedure designed to "extract,
identify and quantitate as broad a spectrum of organic
compounds as possible with gas chromatography and gas
chromatography-mass spectrometry" (Bieri et al. 1981) . This
technique stores analytical instrument responses to samples
in a computer, with the potential for selective peak
identification at a later time if desired. Should the
concentration of an unidentified substance increase over
time, or should a new substance suddenly appear at an
alarmingly high concentration, efforts can be focused on
identifying that questionable compound. Therefore the method
allows for a broad band scan of organic toxics, with
identification procedures limited to a reasonable number of
the extracted substances. It is the hope of researchers at
VIMS that Virginia will adopt this monitoring procedure, and
take advantage of its superior potential to detect, with a
minimum of additional effort, unsuspected environmental
organic pollutants. At this time, the state is pursuing
implementation of at least a portion of this technique.
Whether Virginia adopts the broad band analytical
procedure as proposed by VIMS, or whether it maintains
conventional monitoring techniques, the state's operating
paradigm would necessarily be that the effort is satisfactory
(i.e. that either of these approaches are sufficient, within
reasonable limits, to detect those organic compounds most
likely to cause long term pollution problems in Virginia).
Paradigms, once established, tend to restrict creative
4 1
approaches. To expand beyond the accepted view, as
exemplified by testing the paradigm, usually requires a
significant expenditure of time and effort. If however, the
ultimate goal of environmental monitoring for toxic
substances is to assure that no problems exist, then
paradigms concerning monitoring must constantly be
challenged. The primary objective of this dissertation is to
challenge the effectiveness of the current monitoring
paradigm by determining if there are toxic chemicals,
manufactured or used in production in Virginia, which cannot
be detected by conventional analytical techniques and which
may pose long term problems of environmental accumulation.
The final objective of this dissertation was to develop
an analytical technique capable of detecting those
pollutants, not detectable by conventional procedures, that
could be an environmental problem in Virginia. This
technique could be selectively used in addition to
conventional procedures to provide an additional measure of
protection to the public with a minimum of effort.
5 1.2 Hypothesis
Conventional analytical techniques are capable of identifying and quantitating toxic organic substances manufactured or used in production in Virginia which may be transported to the marine environment, and which may pose long term pollution problems.
6 CHAPTER II
METHODS
2.1 Toxic Substances Used in Virginia
The determination of "toxic" substances used in Virginia could best have been accomplished by cross-referencing lists of chemicals deemed toxic by EPA, with a list of all substances used in Virginia. Unfortunately, the lists of substances that were available from the respective agencies responsible for compiling this type of information, did not contain the exact information desired. Thus, the compounds investigated by this work are not intended to portray an all inclusive list of all toxic compounds used in Virginia. This section explains the derivation of the chemicals investigated by this study.
The Virginia Toxic Substances Information Act, as amended in 1977, requires all manufacturers in Virginia to report to the state all chemicals manufactured or used as raw materials in their production process. Since the law applies only to manufacturers, chemicals used in repair are not required to be reported (Sec. 32.1-244 Virginia State Code).
For example, the Newport News Ship Building and Dry Dock
Corporation must report those compounds used in the manufacture of ships, but not those chemicals used for repair. Nevertheless, it is assumed that probably the majority of chemicals used in Virginia, especially those used
7 in large quantities, would fall within the mandate of the
law, and thus were incorporated into this study.
The Virginia Bureau of Toxic Substances Information
(BTSI) catalogues information on these mandated compounds.
This listing included the substances held confidentially on
record by the Bureau. Since the companies using these
confidential chemicals were not identified, the confidentiality of their uses by industry was maintained.
Substances on the BTSI list were specifically identified by
the Chemical Abstract System's (CAS) numerical designation.
This numerical code, developed and used by CAS, provides an
unambiguous numerical designation for specific chemicals.
Work by the Interagency Testing Committee (ITC), as mandated
by TSCA (15 USCA, Sec. 2603(e.)), was used to determine the
toxicity of the substances reported to the BTSI. This Act
required the ITC to determine which chemicals or mixtures,
used in the U.S., should be given priority for study by the
EPA in its determination of adverse human and environmental
effects. The Committee first developed an Initial Listing of
3649 compounds which were gleaned from previously existing
lists of potentially hazardous substances, as developed by
federal agencies and other organizations. The ITC also
incorporated readily available chemical information, and used
subjective judgement where toxicity data were limited. In
addition, compounds exceeding 1 million pounds net annual
production were included in the Initial Listing. This
Initial Listing should not be confused with the EPA's
8 Candidate List of Chemical Substances which contained all chemicals used in U.S. production during 1977.
The Master Pile of 2046 compounds was developed as a subset of the Initial Listing by deleting substances used primarily as pesticides, drugs, or food additives, and thus not subject to regulation by TSCA. However, deleted compounds with significant commercial uses that fell under the jurisdiction of TSCA were retained in the Master File.
Chemicals produced annually in excess of 10 million pounds were also retained. Subsets of the Master File were further developed for purposes of TSCA, but were not pertinent to this work (Toxic Substances Control Act Interagency Testing
Committee, 1977).
In an effort to identify as many toxic chemicals used in
Virginia as possible, the BTSI's list was cross-referenced with the Initial Listing of the ITC by comparing CAS numbers.
Compounds that appeared on both the BTSI's list and the
Initial Listing totaled 579 organic substances. A month of searching the literature for these substances clearly indicated their number to be too large to research in a reasonable amount of time.
The list of "Virginia substances" from the BTSI was then cross-checked with the smaller Master File of the ITC, and a more manageable number (124) of substances was obtained.
Many of the chemicals omitted by using the Master Listing were some of the more environmentally widespread and toxic compounds, such as pesticides and herbicides. However, these pesticides and herbicides are much more closely regulated through the Federal Insecticide, Fungicide, and Rodenticide
Act (7 USCA, Sec. 136) . In addition, pesticides that are used in Virginia, along with many other related chemicals, are specifically monitored by state and federal agencies.
Since there is a higher degree of awareness concerning certain substances, this dissertation addresses those potentially dangerous compounds for which there is a significantly lower degree of awareness. Thus, an effort has been made to understand the least regulated and studied compounds (Table 1).
All the organic compounds derived from comparing the toxic chemicals list (Master File) and the list of "Virginia substances" were not researched. Substances of low toxicity which occurred in the Master File due to high production values, and some naturally occuring compounds of low toxicity, were deleted. In addition, complex mixtures of numerous organic substances (e.g. gasoline) were omitted.
Table 2 contains the list of these 11 deleted substances.
The substances selected for study in this work are henceforth referred to as "compounds". To determine whether these "compounds" were detectable by conventional techniques required a definition of those techniques. Though specifics may vary from one conventional analytical scheme to another, certain basic steps are germane. These germane procedures were identified and used as the basis for comparison of the
"compounds'" amenability to conventional analytical
10 Table 1. Toxic organic "compounds" involved in production in Virginia which were researched by this work.
CAS # 10CI Name and Common name
50-00-0 Formaldehyde 50-06-6 2,4,6(lH,3Hf5H)-Pyrimidinetrione, 5-ethyl-5- phenyl- Phenobarbitol 50-50-0 Estra-1,3,5(10)-triene-3,17-diol(17B)-3 -benzoate Estrogen 50-55-5 Yohimban-16-carboxylic acid, 11,17-dimethoxy- 18-[(3,4,5-trimethoxybenzoyl)oxy]-methyl ester, (3B,16B,17A,18B,20A)- Reserpine 50^78-2 Benzoic acid, 2-(acetyloxy)- Salicylic acid acetate 51-79-6 Carbamic acid, ethyl ester Urethane 53-16-7 Estra-1,3,5(10)-triene-17-one, 3-hydroxy- Estrone 54-21-7 Benzoic acid, 2-hydroxy-, monosodium salt Sodium salycilate 56-23-5 Methane, tetrachloro Carbon tetrachloride 56-75-7 Acetamide, 2,2-dichloro-N-[2-hydroxy-l- (hydroxymethyl-2-(4-nitrophenyl)ethyl]-, [R-(R*,R*)]- Chloramphenicol 57-39-6 Aziridine, 1,1',1'1-phosphinylidynetris[2- methyl- Metepa 57-68-1 Benzenesulfonamide, 4-amino-N-(4,6-dimethyl- 2-pyr imidinyl)- Sulfamethazine 57-85-2 Androst-4-en-3-one, (17B)-(1-oxopropoxy)- Testosterone propionate 59-87-0 Hydrazinecarboxamide, 2-[(5-nitro-2-furanyl) methylene]- Furacin 60-29-7 Ethane,1,1'-oxybis- Ethyl ether 62-44-2 Acetamide, N-(4-ethoxyphenyl)- Phenacetin 65-45-2 Benzamide, 2-hydroxy- Salicylamide 67-45-8 2-Oxazolidinone, 3-[[(5-nitro-2-furanyl) methylene]amino]-
11 1
Furazolidone 74-31-7 1,4-Benzenediamine, N,N'-diphenyl- 75-00-3 Ethane, chloro- 75-07-0 Acetaldehyde 75-08-1 Ethanethiol 75-44-5 Carbonic dichloride Phosgene 75-55-8 Aziridine, 2-methyl- Propylenimine 77-78-1 Sulfuric acid, dimethyl ester Dimethyl sulfate 78-00-2 Plumbane, tetraethyl- Tetraethyllead 78-30-8 Phosphoric acid, tris(2-methylphenyl) ester Tri-o-cresyl phosphate 79-10-7 2-Propenoic acid Acrylic acid 79-46-9 Propane, 2-nitro- 80-08-0 Benzenamine, 4,4'-sulfonylbis- Dapsone 80-62-6 2-Propenoic acid, 2-methyl-, methyl ester Methyl methacrylate 81-88-9 Ethanaminium, N-[9-(2-carboxyphenyl)-6- (diethylamino)-3H-xanthen-3-ylidene]-N- ethyl-, chloride Rhodamine B 84-66-2 1,2-Benzenedicarboxylic acid, diethyl ester Diethyl phthalate 85-83-6 2-Naphthalenol, 1-[[2-methyl-4-[(2- methylphenyl)azo]phenyl]azo]- Cl Solvent Red 24 86-30-6 Benzenamine, N-nitroso-N-phenyl- Diphenylnitrosamine 87-29-6 Benzoic acid, 2-amino-3-phenyl-2-propenyl ester Cinnamyl anthranilate 91-64-5 Benzopyran-2-one Coumarin 92-87-5 [1,1'-Biphenyl]-4,4'-diamine Benzidine 94-36-0 Peroxide, dibenzoyl Benzoyl peroxide 95-53-4 Benzenamine, 2-methyl- o-Toluidine 96-33-3 2-Propenoic acid, methyl ester Methyl acrylate 96-45-7 2-Imidazolidinethione Ethylene thiourea 97-77-8 Thioperoxydicarbonic diamide, tetraethyl- Disulfiram 97-88-1 2-Propenoic acid, 2-methyl-, butyl ester Butyl methacrylate
12 1
98-51-1 Benzene, 1-(1,1-dimethylethyl)-4-methyl- p-tert-Butyl toluene 98-83-9 Benzene, (1-methylethenyl)- 100-37-8 Ethanol, 2-(diethylamino)- 100-42-5 Benzene, ethenyl- Styrene 100-74-3 Morpholine, 4-ethyl- 101-14-4 Benzenamine, 4,4'-methylenebis[2-chloro- MOCA 101-73-5 Benzenamine, 4-(1-methylethoxy)-N-phenyl- 4-Isopropoxydiphenylamine 101-77-9 Benzenamine, 4,4'-methylenebis- Methylenedianiline 101-83-7 Cyclohexanamine, N-cyclohexyl- Dicyclohexylamine 102-77-2 Morpholine, 4-(2-benzothiazolylthio)- Sulfenamide M 103-23-1 Hexanedioic acid, bis(2-ethylhexyl)ester Di(2-ethylhexyl)adipate 105-60-2 2H-Azepin-2-one, hexahydro- Caprolactam 108-20-3 Propane, 2,2'-oxybis- Isopropyl ether 108-67-8 Benzene, 1,3,5-trimethyl- Mesitylene 112-62-9 9-Octadecenoic acid (Z)— , methyl ester Methyl oleate 117-84-0 1.2-Benzenedicarboxylic acid, dioctyl ester Di-n-octyl phthalate 119-93-7 [1,1'-Biphenyl]-4,4'-diamine, 3,3'-dimethyl- o-Tolidine 120-93-4 2-Imidazolidinone Ethyleneurea 123-31-9 1,4-Benzenediol Hydroquinone 123-72-8 Butanal Butyraldehyde 123-86-4 Acetic acid, butyl ester N-Butyl acetate 126-99-8 1.3-Butadiene, 2-chloro- Chloroprene 127-19-5 Acetamide, N,N-dimethyl- 127-47-9 Retinol acetate Vitamine A acetate 128-37-0 Phenol, 2 ,6-bis(1,1-dimethylethyl)-4-methyl- 2,6-Di-tert-butyl cresol 128-44-9 l,2-Benzisothiazol-3(2H)-one, 1,1-dioxide, sodium salt Sodium salt of saccharin
13 129-17-9 Ethanaminium, N-14-[[4-(diethylamino)phenyl] (2 , 4-disulfophenyl)methylene]-2,5- cyclohexadien-l-ylidene]-N-ethyl-hydroxide, inner saltf sodium salt C.I. Acid Blue 1 135-20-6 Benzenamine, N-hydroxy-N-nitroso-ammonium salt Cupferron 135-88-6 2-Naphthalenamine, N-phenyl- B-Phenylnaphthylamine 136-23-2 Zinc, bis(dibutylcarbamodithioato-S,S1)- 140-11-4 Acetic acid, phenylmethyl ester Benzyl acetate 140-88-5 2-Propenoic acid, ethyl ester Ethyl acrylate 141-23-1 Octadecanoic acid, 12-hydroxy-methyl ester Methyl 12-hydroxystearate 142-47-2 L-Glutamic acid, monosodium salt Monosodium glutamate 151-56-4 Aziridine Ethylenimine 518-47-8 Spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3- one, 3',6'-dihydroxy-disodium salt C.I. Acid Yellow 73 Uranin 546-88-3 Acetamide, N-hydroxy- 555-43-1 Octadecanoic acid, 1,2,3-propanetriyl ester Tristearin 573-58-0 1-Naphthalenesulfonic acid, 3,3'-[[l,l'- biphenyl]-4,4'-diylbis(azo)]bis[4-amino- disodium salt C.I. Direct Red 28 Congo Red 584-84-9 Benzene, 2,4-diisocyanato-l-methyl- Isocyanic acid methylphenylene 614-45-9 Benzenecarboperoxoic acid, 1,1-dimethylethyl ester tert-Butyl perbenzoate 680-31-9 Phosphoric triamide, hexamethyl- Hexametapol 842-07-9 2-Naphthalenol, l-(phenylazo)- C.I. Solvent Yellow 14 860-22-0 lH-Indole-5-sulfonic acid, 2-(1,3-dihydro-3- oxo-5-sulfo-2H-indole-2-ylidene)-2,3-dihydro -3-oxo-disodium salt C.I. Acid Blue 74 Indigo Carmine 915-67-3 2,7-Naphthalenedisulfonic acid, 3-hydroxy-4- [(4-sulfo-l-naphthalenyl)azo]-trisodium salt Amaranth F.D. & C. Red No. 2 1321-65-9 Naphthalene, trichloro-
14 1338-23-4 2-Butanone peroxide Methyl ethyl ketone peroxide 1665-48-1 2-0xazolidinone, 5-[(3,5-dimethylphenoxy) methyl]- 1694-09-3 Benzenemethanaminium, N-[4[[4-(dimethylamino) phenyl][4-[ethyl[3-sulophenyl)methyl]amino] phenylj methylene]-2,5-cyclohexad ien-1- ylidene]-N-ethyl-3-sulfo-hydroxide, inner salt, sodium salt C.I. Acid Violet 49 1934-21-0 lH-Pyrazole-3-carboxylic acid, 4,5-dihydro-5- oxo-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo] -trisodium salt C.I. Food Yellow 4 F.D. & C. Yellow No. 5 2223-93-0 Octadecanoic acid, cadmium salt Cadmium stearate 2238-07-5 Oxirane 2,2'-[oxybis(methylene)]bis- Bis(2,3-epoxypropyl)ether 2353-45-9 Benzenemethanaminium, N-ethyl-N-[4-[[4-[ethyl [(3-sulfophenyl)methyl]amino]phenyl](4- hydroxy-2-sulfophenyl)methylene]-2,5- cyclohexadien-l-ylidene]-3-sulfo-hydroxide, inner salt, disodium salt F.D. & C. Green No.3 2465-27-2 Benzenamine, 4,4'-carbonimidoylbis[N,N- dimethyl-monohydrochloride C.I. Basic Yellow 2 2580-78-1 2-Anthracenesulfonic acid, l-amino-9,10- dihydro-9,10-dioxo-4-[[3-[[2-(sulfooxy) ethyl]sulfonyl]phenyl]amino]-disodium salt Reactive Blue 19 2602-46-2 2,7-Naphthalenedisulfonic acid, 3,3'— [[1,1'— biphenyl]-4,41-diylbis(azo)]bis[5-amino-4- hydroxy-tetrasodium salt C.I. Direct Blue 6 2610-05-1 1,3-Naphthalenedisulfonic acid, 6,6'— [(3,3*— dimethoxy[1,1'-biphenyl]-4,41-diyl)bis(azo)] bis[4-amino-5-hydroxy-tetrasodium salt C.I. Direct Blue 1 2646-17-5 2-Naphthalenol, 1-[(2-methylphenyl)azo]- C.I. Solvent Orange 2 2650-18-2 Benzenemethanaminium, N-ethyl-N-[4-[[4-[ethyl [(3-sulfophenyl)methyl]amino]phenyl] (2-sulfophenyl)methylene]-2,5-cyclohexadien -l-ylidene]-3-sulfo-hydroxide, inner salt, diammonium salt C.I. Acid Blue 9 2783-94-0 2-Naphthalenesulfonic acid, 6-hydroxy-5-[(4- sulfophenyl)azo]-disodium salt C.I. Food Yellow 3
15 4548-53-2 1-Naphthalenesulfonic acid, 3-[(2,4-dimethyl -5-sulfophenyl)azo]-4-hydroxy-disodium salt C.I. Pood Red 1 F.D. & C. Red No. 4 5002-47-1 Decanoic acid, 2-[4-[3-[2-(trifluoromethyl)- 10H-phenothiazin-10-yl]propyl]-1- piperazinyl]ethyl ester Fluphenazine decanoate 5141-20-8 Benzenemethanaminium, N-ethyl-N-[4-[[4-[ethyl [(3-sulfophenyl)methyl]amino]phenyl](4- sulfophenyl)methylene]-2,5-cyclohexadien-l- ylidene]-3-sulfo-hydroxide, inner salt, disodium salt C.I. Acid Green 5 13927-77-0 Nickel, bis(dibutylcarbamodithioato-S,S')- 14239-68-0 Cadmium, bis(diethylcarbamodithioato-S,S')- 15180-02-6 l,8-Naphthyridine-3-carboxylic acid, 1-ethyl- 1,4-dihydro-4-oxo-7-(phenylmethyl)- Amfonellic acid 25301-02-4 Phenol, 4-(1,1,3,3-tetramethylbutyl)-polymer with formaldehyde and oxirane Triton WR-1339 25322-68-3 Poly(oxy-1,2-ethanediyl)-a-hydro-w-hydroxy- Polyethylene glycol 26761-40-0 1,2-Benzenedicarboxylic acid, diisodecyl ester Diisodecyl phthalate
16 Table 2. "Toxic" organic substances involved with production in Virginia, but omitted from research by this work.
CAS# COMMON NAME REASON FOR OMISSION
57-88-5 Cholesterol Common plant product 58-08-2 Caffeine Common and used in food. 63-42-2 Lactose Common sugar in nature. 69-79-4 Maltose Common sugar in nature. 71-36-3 Butanol Common alcohol in nature. 73-24-5 Adenine Common amino acid. 142-82-5 Heptane Common in nature. 630-08-0 Carbon monoxide Common in the environment 1401-55-4 Tannic acid Common plant product. 8002-05-9 Petroleum Too complex. 8006-61-9 Gasoline Too complex.
17 techniques.
2.2 Analytical Requirements
The analytical requirements of the "compounds", as they
related to these basic conventional procedures, were primarily determined by literature search. Since the
"compounds" had been uniquely identified by the CAS numbering
code, it was possible to determine the unique CAS name and
subsequent analytical information for the "compounds" in each
Consolidated Index (Cl) period. Though the CAS name is
occasionally changed from one indexing period to the next,
the CAS number never changes for a substance. In an effort
to maintain uniformity throughout this work, formal CAS
"compound" names in Tables 1 and 3-115 reflect those names
used in the 10th Cl (volumes 86-95). In addition, the formal
CAS nomenclature was hyphenated exactly as appears in the
10th Cl. Future CAS nomenclature changes will be
cross-referenced in the CAS Index Guide, thus facilitating
the updating of this work.
Extensive use was made of the Consolidated Indexes at
the campus of William and Mary in Williamsburg. However,
since the 10th Consolidated Index (10-CI) for the interval
1976 to 1981 had not been printed, most references for that
period were manually determined from each volume. The
commercial retrieval capacity of Dialog was used as an aid to
locate part of the material for the years 1966 to 1981. In
18 addition to using Chemical Abstracts, bibliographic searches were made, and some letters were sent to authors for information not listed in articles.
The objective in researching the analytical information for the "compounds" was not to locate all relevant information pertaining to them. Rather, the attempt was made to obtain three references to substantiate a point. This often was not possible, especially for solubility data, since the information was rarely indexed by Chemical Abstracts, and thus required "blind" searching. The search for a particular piece of information was terminated when it was subjectively believed that a reasonable point of diminished returns had been well surpassed. However, the literature search was usually conducted to the extent necessary or possible to find needed information.
19 CHAPTER III
RESULTS AND COMMENTS
3.1 Critical Conventional Procedures
Conventional analytical techniques for a broad spectrum of organic pollutants might involve any number of steps.
Generally however, samples of either sediment or organisms are used for long term pollutant monitoring schemes, because they provide concentrations integrated over time. Water samples primarily indicate a more instantaneous value. In addition, sediments and organisms generally magnify concentrations of trace compounds, and if they do not, these chemicals are usually of little concern due to the dilution potential of the estuarine environment.
Samples are usually placed in a relatively inert container and stored at subfreezing temperatures until extraction. Though they can be extracted as wet (aqueous) samples, a freeze dried sample eliminates phase separation steps, and thus reduces the chance of nonvolatile sample loss. Loss of highly volatile substances during freeze drying does occur however. The solvent, usually slightly polar, is often concentrated using evaporative techniques, followed by any combination of separatory techniques such as gel permeation chromatography (GPC), column chromatography
(CC), thin layer chromatography (TLC), or high pressure liquid chromatography (HPLC). Identification of the
20 fractionated samples is normally conducted by GC or GC-MS.
The columns used in these instruments for broad band identification are usually quite inert, and contain a relatively non-polar liquid phase.
The following subsections explain how these conventional techniques were categorized into fundamental processes.
These fundamental processes were then logically developed into five parameters which could impair analysis: volatility, stability, solubility, adsorption in liquid chromatography, and problems with GC and GC/MS.
Evaporative Loss Potential
Significant losses of various types and amounts of
"compounds" can occur due to evaporation. Obviously, careless technique such as evaporation of solvents to dryness will result in significant losses of even mildly volatile compounds. Of specific interest however, are the limitations of conventional procedure, and these can be condensed into two primary considerations, i.e. volatization during freeze drying and the evaporation from solvents.
Conventional techniques often involve extraction with a very light solvent such as a chlorinated hydrocarbon or an ether. The extracted substances may then be transferred from the lighter solvent to a less volatile solvent such as toluene, either to decrease solvent evaporation, or to provide a solvent suitable for a particular analytical instrument. Though losses may occur during any evaporative step, maximum loss will occur by the time the solvent with the highest boiling point is evaporated. Thus "compounds" with a boiling point near or less than that of toluene (110.6 degrees C.), a solvent commonly used as a working solvent, were considered to be too volatile for conventional procedures involving solvents.
An estimate of the critical degree of volatility in substances, which would still allow those substances to
remain in a sample during freeze drying, was empirically deduced from work done at VIMS (Bieri et al. 1981). The lightest substance detected in their environmental samples was naphthalene (B.P. 218 degrees C.), and lab experiments
indicated some naphthalene is lost during freeze drying.
Since surface chemistry affects the retention of substances on a substrate during the freeze drying process, one cannot assume boiling points to be an exact indication of volatility. A better indication of volatility could have been obtained by using vapor pressures, but they were usually not available. Despite these limitations, it is assumed that
"compounds" with a B.P. near that of naphthalene are near
the limits of retention during the freeze drying process.
Additional information such as temperatures required for GC was also used as an indication of volatility.
The data for these two volatily critical steps were
compiled and presented through a rating system based on their
evaporative potential, as best as could be deduced from the
22 available data. Ratings were listed as either high, moderate, low or nil. A rating of high indicated the loss potential was so great as to require special analytical techniques. A moderate volatility signified one could use conventional analytical techniques, but that quantitative losses could occur unless careful techniques were executed.
One would not expect losses to occur with compounds of a low rating, unless careless procedures were followed to the extreme. Nil indicates it is almost impossible to lose a
"compound" by volatization.
Stability
In order for substances to be stable to conventional technique, they must be at least somewhat stable in water, oxygen, light and heat, since these conditions are generally present. Instability to any of these conditions, or any indications of lability during analysis were presented in
Appendix Tables 1-113. If no analytical stability problems were noted by researchers, the "compounds" were indicated as probably being sufficiently stable for conventional analysis.
Of course, even though researchers may not have reported lability problems, stability under all conventional conditions is not necessarily proven.
Indications of stability in the environment are considerably more tenuous than those ratings during analysis, due to the paucity of information. Apparent stability to
23 analysis, and the lack of evidence indicating short
environmental lifetimes, has been interpreted as an
indication of probable environmental stability. This conservative approach is taken so that "compounds" are
considered long-lived until proven otherwise. Though some
extra effort may be occasionally involved, relatively stable
compounds will not be missed due to erroneous assumptions
about lability. If additional information is found to
indicate a "compound" is environmentally short-lived, a
reevaluation of its need for specific monitoring can be made
in the event it should require nonconventional techniques.
Solubility
As indicated earlier, the question of solubility of a
"compound" in various solvents was one of the most difficult
types of information to find when not listed in a handbook.
Often abstracts had to be relied upon, and when used, they were corroborated with other abstracts as much as possible.
Unfortunately, simple solubility does not necessarily
indicate extractability, and the majority of all analytical work on these "compounds" has been done with pure solutions
or simple mixtures rather than complex environmental samples.
Though partitioning is probably the major mechanism by which
extraction occurs, it may be possible that the solvent would
not always penetrate totally into the matrix for partitioning
to occur. In addition, the vastly complex interactions
24 between organics and inorganics in sediments defy extraction predictions (Bieri et al. 1981). However, it should be remembered that conventional soxhelet-type repetitive extraction procedures have been proven quite efficient in extracting numerous types of substances from environmental samples. Thus, evidence of general solubility in solvents of intermediate polarity was interpreted as sufficient proof of extractability, unless analytical information indicated otherwise.
Liquid Chromatography
Many forms of liquid chromatography (LC) may be used during the conventional analysis of complex mixtures. The primary purpose of LC is usually to separate substances into fractions of different chemical characteristics, thus reducing the complexity of a particular aliquot. LC is often considered to incorporate either normal- or reversed-phase chromatography, though for the purposes of this discussion,
GPC will also be considered.
Normal-phase chromatography involves a polar stationary phase, and a non-polar or a non-polar followed by a polar solvent system. Reversed-phase chromatography involves a non-polar stationary phase, and either a polar or a polar followed by a non-polar solvent system.
Reversed-phase chromatography is commonly performed on a silica gel whose entire surface is covered by chemically
25 bonded octadecylsilane. This configuration presents a hydrocarbon surface to the solutes which are retained on the stationary phase by relatively weak van der Waals forces.
Since these adsorptive forces are weak, problems of irreversible adsorption are almost non-existant, and so reversed-phase LC was not considered by this work as a procedure which could result in sample loss.
Normal-phase LC involves adsorption onto active polar sites, and when silica gel is used as the stationary phase, adsorption can be quite strong. This active site adsorption is generally accepted to result from hydrogen bonding (Young and McNair 1976), which can be a much stronger bonding force than the van der Waals forces. These hydrogen bonding forces can be sufficiently strong to prevent the elution of certain strongly polar substances, thus resulting in sample loss.
Therefore, the ability of solvents to elute the "compounds" from silica gel was considered to be the crucial step in judging conformity to conventional LC. References indicating the nonaqueous mobility of the "compounds" on silica gel, whether in TLC, CC, or HPLC, was considered adequate proof of amenability to LC. Performance, as indicated by theoretical plates and resolution, is not germane to this consideration, only the probability of elution is of concern.
GPC is a relatively new method of fractionating extracted samples by the use of inert porous beads.
Molecules are primarily separated by size and shape. Smaller molecules, which can pass through the pores in the beads,
26 follow a longer path. Larger compounds are excluded from passing into the beads, follow a shorter path around the beads, and thus are eluted quicker. However, size exclusion is not the only factor during GPC affecting substances containing double bonds. Interactions between pi-bonding electron clouds slows the passage of substances, especially aromatics, past phenyl groups on the resin polymers. For example, coronane, a very large polynuclear aromatic (PNA) of six rings, is one of the last PNA's of a standard mixture of substances to elute from the column (Defur, pers. commun.).
Due to these conflicting retention tendencies in GPC, the prediction of the fraction in which a "compound" will elute is often nearly impossible. Since most of the very large biogenic substances elute first, this fraction is very complex, rarely contains substances of toxic interest, and is extremely difficut to analyze. Therefore, this lipid fraction is generally not analyzed, and if a "compound" should elute in the fraction, it probably would not be detected. There were a few "compounds" identified as probably eluting in this lipid fraction, but generally no attempt was made to estimate the fraction in which a
"compound" might elute. It is the responsibility of the analyst to experimentally determine the lipid fraction volume which is not apt to contain the generally smaller and toxic compounds.
27 GC and GC/MS +
Conventional GC and GC/MS instrumentation parameters are
essentially identical up to their point of detection.
Typically glass capillary columns and packed columns are
deactivated with trimethylsilyl groups (e.g. HMDS), and
coated with an inert and relatively non-polar liquid phase.
GCs are usually equipped with a broad spectrum detector such
as a flame ionization detector (FID) or a thermal
conductivity detector (TCD). The nitrogen/phosphorous
detector (NPD) and the electron capture detector (ECD) are
more sensitive to specific types of substances, but their
application in general substances monitoring should remain
auxiliary to the broad spectrum detectors. Column
temperatures are generally programmed from an easily
attainable low temperature of 35-75 degrees C., to a maximum
of 270-280 degrees C. Injection port temperatures vary, but
generally approximate the maximum temperature attained by the
column.
Since conventional instrumentation parameters for GC and
GC/MS are essentially identical, assessment of the
detectability of the "compounds" by the two types of
instruments can be considered together. "Compounds" were
researched for volatility and heat stability within the
temperature range, for response by various detectors, and for
adsorption problems.
28 3.2 Analytical Properties of the "Compounds"
The following subsections refer to the ability of conventional analytical procedures to detect the "compounds".
The basic critical parameters from section 3.1 were used to evaluate the amenability of the "compounds" to conventional procedures, and the results are listed in Appendix Tables
1-113. Those "compounds" which can.be conventionally detected were labeled as detectable by conventional techniques, and those which cannot were labeled as not detectable by conventional techniques. "Compounds" for which information was lacking concerning these critical analytical parameters, were labeled as possibly not detectable by conventional techniques.
Detectable by Conventional Techniques
Approximately one third of the "compounds" researched were found to be reasonably amenable to standard analytical procedures (Table 3). However, one cannot assume these
"compounds" would be accurately recovered if conventional techniques were used, because numerous factors enter into any analysis scheme. The best estimate of recovery rates is obtained by processing standards through the exact analytical techniques being employed.
One should be aware of certain unfavorable tendencies in
29 Table 3. "Compounds" which are detectable by conventional analytical techniques.
CAS # Common Name 50-06-6 Phenobarbitol 50-50-0 Estrogen 50-55-5 Reserpine 50-78-2 Salicylic acid acetate 51-79-6 Urethane 57-85-2 Testosterone propionate 62-44-2 Phenacetin 65-45-2 Salicylamide 74-31-7 N,N1-Diphenyl-1,4-benzenediamine 78-30-8 Tri-o-cresyl phosphate 80-08-0 Dapsone 84-66-2 Diethyl phthalate 86-30-6 Diphenylnitrosamine 91-64-5 Coumarin 97-77-8 Disulfiram 98-83-9 (1-Methylethenyl)benzene 101-14-4 MOCA 101-73-5 4-Isopropoxydiphenylamine 101-77-9 Methylenedianiline 102-77-2 Sulfenamide M 103-23-1 Di(2-ethylhexyl)adipate 105-60-2 Caprolactam 112-62-9 Methyl oleate 117-84-0 Di-n-octyl phthalate 119-93-7 o-Tolidine 123-72-8 Butyraldehyde 128-37-0 2,6-Di-tert-butyl cresol 135-88-6 B-Phenylnaphthylamine 136-23-2 Bis(dibutylcarbamodithioato-S,S')zinc 140-11-4 Benzyl acetate 141-23-1 Methyl 12-hydroxystearate 555-43-1 Tristearin 680-31-9 Hexametapol 842-07-9 C.I. Solvent Yellow 14 1321-65-9 Tr ichloronaphthalene 13927-77-0 Bis(dibutylcarbamodithioato-S,S')nickel 14239-68-0 Bis(diethylcarbamodithioato-S rS 1)cadmium 25322-68-3 Polyethylene glycol 26761-40-0 Diisodecyl phthalate
30 many of the "compounds" classified as detectable by conventional techniques. Slight thermal instability at high
GC temperatures occurs with some "compounds" (50-06-6,
86-30-6, 95-53-4, 101-14-4, 136-23-2, 555-43-1, 13927-77-0,
14239-68-0), though results should be sufficiently accurate
for environmental monitoring purposes. Other "compounds"
exhibit adsorption or tailing problems in GC unless
conventionally inert columns are used (50-78-2, 51-79-6,
123-72-8, 141-23-1). Metal carbamates (136-23-2, 13927-77-0
and 14239-68-0) have been shown to exchange ligands in GC
columns, thus producing artifacts in the form of hybrid
carbamates. Some "compounds" require high GC column
temperatures (80-08-0, 136-23-2, 555-43-1, and 13927-77-0),
though these temperatures (270-280 degrees C.) are not above
the upper end of conventional ranges. In some cases
derivatization has often been used for better volatization
and separation (50-50-0, 50-55-5, 57-85-2, and 25322-68-3),
though this is not necessary.
As a result of these somewhat undesirable
characteristics in many "compounds" rated as detectable, one
must interprete results with some care. Should any of these
more difficult "compounds" appear at significantly elevated
concentrations, one might consider more specialized
analytical techniques to insure accuracy. However, as
indicated above, one would expect conventional procedures to
produce reasonably accurate results for these "compounds"
31 Possibly Detectable by Conventional Techniques
"Compounds" of uncertain detectability by standard analytical techniques are listed in Table 4. A conservative classification approach was used which was biased towards
inclusion, as opposed to exclusion, of "compounds" as possibly not detectable. Therefore, some cases of uncertain amenability to conventional techniques may be more predictable than indicated.
The reasons for the "compounds'" inclusion in Table 4 can be classified according to uncertainty at each of the major analytical steps. Some "compounds" are of questionable volatility for quantitative recovery (78-00-2, 79-46-9,
95-53-4, 97-88-1, 100-42-5, 108-67-8 and 123-86-4). Other
"compounds" may not be sufficiently soluble in some common
solvents (96-45-7) or may react once extracted into a solvent
(77-78-1, 79-10-7, 123-31-9). Occasionally, references to
separations on silica gel with organic solvents could not be
found, and when those "compounds" were known or suspected to be polar, they were listed as possibly detectable (100-37-8,
101-83-7, 127-19-5 and 584-84-9). Since one cannot easily
foretell the heat stability of substances at GC temperatures,
"compounds" were included when no GC references could be
found (85-83-6 and 2646-17-5). Compounds for which
analytical information was almost totally lacking were also
included in this list (87-29-6, 100-74-3, 546-88-3,
32 Table 4. "Compounds" possibly detectable by conventional analytical techniques.
CAS # Common Name
77-78-1 Dimethyl sulfate 78-00-2 Tetraethyllead 79-10-7 Acrylic acid 79-46-9 2-Nitropropane 85-83-6 C.I. Solvent Red 24 87-29-6 Cinnamyl anthranilate 95-53-4 o-Toluidine 96-45-7 Ethylene thiourea 97-88-1 Butyl methacrylate 100-37-8 2-(Diethylamino)ethanol 100-42-5 Styrene 100-74-3 4-Ethylmorpholine 101-83-7 Dicyclohexylamine 108-67-8 Mesitylene 123-31-9 Hydroquinone 123-86-4 N-Butyl acetate 127-19-5 N ,N-Dimethylacetamide 546-88-3 N-Hydroxyacetamide 584-84-9 Isocyanic acid methylphenylene 1665-48-1 5-[(3,5-Dimethylphenoxy)methyl]-2- oxazolidinone 2238-07-5 Bis(2,3-epoxypropyl)ether 2646-17-5 C.I. Solvent Orange 2 5002-47-1 Fluphenazine decanoate 15180-02-6 Amphonellic acid 25301-02-4 Triton WR-1339
33 1665-48-1, 2238-07-5, 5002-47-1, 15180-02-6 and
25301-02-4).
Not Detectable by Conventional Techniques
The classification of "compounds" as not detectable by standard analytical procedures (Table 5) is the most definite of the three classes of detectability, because they exhibit certain characteristics that prevent conventional analysis.
The most common problem being that they are too non-volatile for GC. Most of these non-volatile "compounds" are salts, though one is a metal chelate (135-20-6), and the rest are either large or highly adsorptive (53-16-7, 56-75-7, 57-68-1 and 120-93-4) . Another major cause preventing conventional analysis is because they are too volatile and are lost prior to GC (50-00-0, 56-23-5, 57-39-6, 60-29-7, 75-00-3, 75-07-0,
75-08-1, 75-44-5, 5-55-8, 80-62-6, 96-33-3, 98-51-1,
108-20-3, 126-99-8, 140-88-5, 151-56-4 and 614-45-9). A few
"compounds" are too heat labile for GC temperatures (59-87-0,
67-45-8, 94-36-0, 127-47-9 and 1338-23-4), and one (92-87-5) significantly degrades during solvent evaporation unless preventative measures are employed.
34 Table 5. "Compounds" which are not detectable by conventional analytical techniques.
CAS # Common Name
50-00-0 Formaldehyde 53-16-7 Estrone 54-21-7 Sodium salycilate 56-23-5 Carbon tetrachloride 56-75-7 Chloramphenicol 57-39-6 Metepa 57-68-1 Sulfamethazine 59-87-0 Furacin 60-29-7 Ethyl ether 67-45-8 Furazolidone 75-00-3 Chloroethane 75-07-0 Acetaldehyde 75-08-1 Ethanethiol 75-44-5 Phosgene 75-55-8 Propylenimine 80-62-6 Methyl methacrylate 81-88-9 Rhodamine B 92-87-5 Benzidine 94-36-0 Benzoyl peroxide 96-33-3 Methyl acrylate 98-51-1 p-tert-Butyl toluene 108-20-3 Isopropyl ether 120-93-4 Ethyleneurea 126-99-8 Chloroprene 127-47-9 Vitamine A acetate 128-44-9 Sodium salt of saccharin 129-17-9 C.I. Acid Blue 1 135-20-6 Cupferron 140-88-5 Ethyl acrylate 142-47-2 Monosodium glutamate 151-56-4 Ethylenimine 518-47-8 C.I. Acid Yellow 73 573-58-0 C.I. Direct Red 28 614-45-9 tert-Butyl perbenzoate 860-22-0 C.I. Acid Blue 74 915-67-3 Amaranth 1338-23-4 Methyl ethyl ketone peroxide 1694-09-3 C.I. Acid Violet 49 1934-21-0 F.D. & C. Yellow No. 5 2223-93-0 Cadmium stearate 2353-45-9 F.D. & C. Green No. 3 2465-27-2 C.I. Basic Yellow 2 2580-78-1 Reactive Blue 19 2602-46-2 C.I. Direct Blue 6 2610-05-1 C.I. Direct Blue 1 2650-18-2 C.I. Acid Blue 9
35 Table 5.
2783-94-0 C.I. Food Yellow 3 4548-53-2 F.D. & C. Red No. 4 5141-20-8 C.I. Acid Green 5
36 3.3 Toxic Effects
In an effort to determine the toxicity of the
"compounds", the 1980 edition of the Registery of Toxic
Effects of Chemical Substances (RTECS), produced by the
National Institute for Occupational Safety and Health, was used. Though RTECS references many types of information, such as LD-50 and LC-50 data, this information was not used except for the aquatic toxicity ratings. Of more concern than lethal action, are the effects of chemicals in sublethal doses, since only trace levels generally exist in the environment. The meanings of the abbreviated notations used in Appendix Tables 1-113 can be found in Appendix Table 114, as adapted from RTECS (1980).
3.4 Judgement of Need for Special Monitoring
Since approximately two thirds of all "compounds" studied may not be amenable to conventional analytical techniques, one must determine whether they are of a significant risk to warrant the additional expense of specialized analysis. Consideration must be given to toxicity, probable environmental lifetime, possibility of bioconcentration, concentrations allowed in foods, etc. As an initial risk assessment, these characteristics were studied to determine whether a "compound" could be considered to be of concern in trace amounts in the environment. More rational management decisions concerning the need for specialized analysis can be made once the known risks versus the expenses of analysis have been evaluated.
In deciding whether substances are of sufficient long term concern to warrant monitoring, one can obviously eliminate environmentally short lived compounds which degrade to non-toxic substances. Though these short lived substances may be extremely toxic in the immediate vicinity of a discharge, toxic effects would not be expected in distant areas.
"Compounds" which were found to be either not detectable or possibly not detectable by conventional procedures are rated below as to whether they merit special monitoring attention. This section is subdivided according to the physical properties restricting the substances from detectability by conventional techniques, since some of these properties largely determine the need for special monitoring.
The primary reasons preventing conventional analysis were that "compounds" were either too volatile or simply non-volatile.
38 Volatiles +
Volatile "compounds", herein defined as those with
sufficient vapor pressures to evaporate during conventional
analysis, usually pose little threat of long term
environmental accmulation problems. Most of these substances
are probably too volatile to be retained, in either the
aqueous environment or in organisms, at concentrations near
the PPM range. However, there is a transition range in vapor
pressures wherein "compounds" may be lost during analysis,
yet have sufficiently low vapor pressures to be retained in
sediments and animals at environmentally significant
concentrations. For example, naphthalene has been shown to
significantly concentrate in estuarine sediment and in
oysters, yet also to partially evaporate during freeze drying
(Bieri et al. 1981).
Table 6 contains all "compounds" too volatile and
potentially too volatile for conventional analysis. These
volatiles were rated as to whether they might be of concern
in long term monitoring, with respect to potential for
bioaccumulating, as opposed to being a problem in drinking
water. This rating was somewhat subjective where data were
limiting, but the attempt was made to be consistent. For
example, compounds with a B.P. near that of naphthalene (218
degrees C.) and which appear relatively stable, were rated
as potentially of concern. Both the highly lethal and the
suspected carcinogenic or teratogenic "compounds" were rated
39 Table 6. Volatile and potentially volatile "compounds" of potential concern in long term environmental accumulation.
CAS # Common Name Of Concern
50-00-0 Formaldehyde No 56-23-5 Carbon tetrachloride No 57-39-6 Metepa Yes 60-29-7 Ether No 75-00-3 Chloroethane No 75-07-0 Acetaldehyde No 75-08-1 Ethanethiol No 75-44-5 Phosgene No 75-55-8 Propylenimine No 77-78-1 Dimethyl sulfate No 78-00-2 Tetraethyllead Yes 79-10-7 Acrylic Acid Yes 79-46-9 2-Nitropropane Yes 80-62-6 Methyl methacrylate Yes 95-53-4 o-Toluidine Yes 96-33-3 Methyl acrylate Yes 97-88-1 Butyl methacrylate Yes 98-51-1 p-tert-Butyl toluene Yes 100-37-8 2-(Diethylamino)ethanol Yes 100-42-5 Styrene Yes 100-74-3 4-Ethylmorpholine Yes 108-20-3 Isopropyl ether Yes 108-67-8 Mesitylene No 123-86-4 n-Butyl acetate Yes 126-99-8 Chloroprene No 127-19-5 NfN-Dimethylacetamide Yes 140-88-5 Ethyl Acrylate Yes 151-56-4 Ethylenimine No 614-45-9 t-Butyl perbenzoate Yes
40 as potentially of concern when apparently stable and not extremely volatile. Volatiles which are reactive in the environment, or are known to be readily metabolized, were rated as not of concern.
Non-volatiles
The "non-volatile" compounds are immediately of more concern than the volatiles, because they are more likely to remain in the aqueous ecosystem unless they are degraded.
Table 7 lists the "compounds" which are non-volatile in the
GC, their common names and whether they are rated as potentially of concern. These "compounds" were considered to be of potential concern unless they occurred naturally, were known to be unstable, or were allowed in food.
The largest grouping of the non-volatile "compounds" consists of the acidic and basic dyes. These dyes are generally complex organic molecules containing ionically bound metals or halides. A similar "compound" is the metal chelate cupferron (135-20-6) . Though the literature was not exhaustively searched for the bioconcentration potential or the environmental fate of these dyes and cupferron, it is obvious that very little of this research has been conducted on them. As a group, these "compounds" are apparently relatively stable. Since 16 out of these 17 ionic compounds pose at least some question concerning teratogenic or carcinogenic effects, they form a class of potentially toxic Table 7. Non-volatile "compounds" of potential concern in long term environmental accumulation.
CAS # Common Name Of Concern
Acidic Dyes 81-88-9 Rhodamine B Yes 129-17-9 C.I. Acid Blue 1 Yes 518-48-8 Uranin Yes 573-58-0 Congo Red Yes 860-22-0 Indigo Carmine Yes 915-67-3 Amaranth Yes 1694-09-3 C.I. Acid Violet 49 Yes 1934-21-0 F.D. & C. Yellow No. 3 Yes 2353-45-9 F.D. & C. Green No. 3 Yes 2580-78-1 Reactive Blue 19 Yes 2602-46-2 C.I. Direct Blue 6 Yes 2610-05-1 C.I. Direct Blue 1 Yes 2650-18-2 C.I. Acid Blue 9 Yes 2783-94-0 C.I. Food Yellow 3 Yes 4548-53-2 F.D. & C. Red No. 4 Yes 5141-20-8 C.I. Acid Green 5 Yes
Basic Dye 2465-27-2 C.I. Basic Yellow 2 Yes
Miscellaneous "Compounds" 53-16-7 Estrone No 54-21-7 Sodium Salycilate No 56-75-7 Chloramphenicol Yes 57-68-1 Sulfamethazine Yes 120-93-4 Ethyleneurea No 128-44-9 Sodium Saccharin No 135-20-6 Cupferron Yes 142-47-2 Monosodium Glutamate No 2223-93-0 Cadmium Stearate No
42 substances whose environmental occurrence and fate is relatively unknown. In addition, direct inputs of Rhodamine
B are added to the Bay as a water mass tracer in oceanographic work. The author believes that some work should be undertaken to determine whether these ionic
"compounds" are concentrating in the Chesapeake Bay. Other non-volatile "compounds" of sufficient toxicity and stability which are believed to warrant some form of monitoring are chloramphenicol (56-75-7) and sulfamethazine (57-68-1).
Monitoring for the following non-volatile "compounds"
(Table 6) was believed unnecessary for various reasons. For instance, relatively rapid degradation in the environment to non-toxic substances occurs with ethylene urea (120-93-4) and estrone (53-16-7). The toxicity of cadmium octadecanoate
(2223-93-0) results from the ionic cadmium, which dissociates in water and follows the fate of other environmental ionic cadmium. MSG (142-47-2) is a salt of a common compound in nature, and therefore not of concern in environmental monitoring. Sodium salicylate (54-21-7) and saccharin
(128-44-9) are used in food.
Miscellaneous Analytical Properties
In addition to the volatile and non-volatile
"compounds", there were 21 "compounds" which were not detectable or possibly not detectable by conventional techniques. The need for special monitoring of these 21 "compounds" was assessed by the same standards as were used with the non-volatiles, and they are listed in Table 8. Thus
Tables 6-8 contain all "compounds" that would or might not be detected by conventional monitoring procedures, and an assessment of their need for monitoring.
Of the five "compounds" indicated earlier as too heat labile for conventional analysis, two (94-36-0 and 1338-23-4) would be expected to degrade fairly rapidly to relatively non-toxic substances in the environment, and thus are not of long term concern. Another heat labile "compound" (127-47-9) is used as a vitamin supplement, and is only toxic at the mg/day dosage. The last two "compounds" (59-87-0 and
67-45-8) are unstable to light and would rapidly degrade in many environmental situations, though conceivably they could be long lived at depth in the turbid estuarine environment.
Since these latter two "compounds" could possibly be of concern, perhaps some limited monitoring should be considered.
Benzidine (92-87-5) is potentially of major concern, and would be largely lost during conventional analysis. The
"compound" is apparently fairly stable, is a known human carcinogen, and may bioconcentrate. Due to its unusual property of degrading in most solvents during their evaporation, effective monitoring for the chemical generally has not been accomplished, and thus little is known of its environmental fate. Therefore, special analytical procedures to monitor for this substance are recommended.
44 Table 8. Miscellaneous non-detectable or possibly detectable "compounds" of potential concern in long term environmental accumulation.
CAS # Common Name Of Concern
59-87-0 Furacin Yes
67-45-8 Furazolidone Yes
79-10-7 Acrylic acid No
85-83-6 C.I. solvent red 24 Yes
87-29-6 Cinnamyl anthranilate Yes
92-87-5 Benzidine Yes
94-36-0 Benzoyl peroxide No
100-37-8 2-Diethylaminoethanol Yes
100-74-3 4-Ethylmorpholine Yes
101-83-7 Dicyclohexylamine Yes
127-19-5 N,N-Dimethylacetamide Yes
127-47-9 Vitamine A acetate No
546-88-3 N-Hydroxyacetamide Yes
584-84-9 Isocyanic acid methylphenylene Yes
1338-23-4 MEK Peroxide No
1665-48-1 2-Oxazolidinone, 5—[(3r5— Yes dimethylphenoxy)methyl]-
2238-07-5 Bis(2,3-epoxypropyl)ether Yes
2646-17-5 C.I. solvent orange 2 Yes
5002-47-1 Fluphenazine decanoate Yes
15180-02-6 Amphonellic acid Yes
25301-02-4 Triton WR-1339 Yes
45 Acrylic acid (79-10-7) poses the problem of polymerizing readily in oxygen, and would probably polymerize upon extraction into a solvent. This substance may well be reactive in the environment, but no references concerning environmental fate were found. Whether it would be of long term environmental concern is uncertain but doubtful.
Special monitoring is not recommended since the polymer would be visible by standard analytical technique, and since the monomer is probably environmentally unstable and may well be analytically visible.
A few "compounds" are highly suspected of adsorbing too strongly to silica gel for conventional analysis. Three of these substances may be sufficiently long lived to pose monitoring concerns (100-37-8, 101-83-7 and 127-19-5).
Another chemical (584-84-9) is slowly hydrolyzed in water to a further degradable carcinogenic compound, but the initial . hydrolysis rate is uncertain and as such the "compound" would have to be considered of concern in monitoring. Analyzing for these adsorptive substances however, can easily be accomplished by the use of cyano or amino normal-phase columns.
The final group of "compounds" to address for the need of monitoring are those with basically uncertain analytical requirements. Two of these chemicals (85-83-6 and 2646-17-5) are known to be amenable to conventional technique up to the point of GC, and since both are suspected animal carcinogens, testing for amenability to GC is recommended. Of the eight
46 "compounds" for which very little analytical information could be found, four (87-29-6, 546-88-3, 2238-07-5 and
25301-02-4) pose at least some question concerning their teratogenic or carcinogenic effects, and one (15180-02-6) was not listed in RTECS. It is suggested that these eight
"compounds" (including 100-73-4, 1665-48-1 and 5002-47-1), be tested specifically by the state for amenability to conventional analytical technique.
3.5 Proposed Analytical Procedures
As mentioned earlier, a substantial amount of research has been conducted at VIMS concerning an analytical technique for monitoring toxic organic pollutants in the Chesapeake Bay
(Bieri et al. 1981) . This technique involves state-of-the-art procedures including freeze drying, soxhelet extraction, separation by GPC and HPLC, and identification with computer assisted GC and GC/MS. Analysis of samples by this procedure should recover and identify all "compounds" of the present work listed as amenable to conventional analytical techniques. In addition, the procedure easily avoids the problem of irreversible adsorption of "compounds" to silica gel during separation, since the polarity of the
HPLC column is greatly reduced. Positive identification by
GC/MS can be limited to those compounds which are increasing . in the Bay, or which suddenly appear in a sample at alarmingly high concentrations. Thus, effective monitoring
47 for a wide range of substances can be accomplished without identifying all peaks recovered from a sample. This analytical technique is recommended as the basic tool to monitor for organic pollutants in Virginia's estuarine environment.
Since the broad band technique of Bieri et al. (1981) will not detect all the toxic "compounds" used in Virginia, an analytical scheme for these "invisible compounds" is presented below. The "compounds" are grouped according to analytical requirements, and their respective subsections are organized in a sequence one might follow if analyzing for all potential "compounds". This analysis scheme is summarized in
Figure 1.
Volatiles Analysis
Most of the work concerning volatile organic compounds has been undertaken with water and wastewater. Futama et al.
(1981) reviewed the literature and concluded that volatiles are best analyzed in the lab by purging water with inert gas, trapping the organics on an adsorbent, and thermally desorbing them into a GC. Numerous types of adsorbents have been used, including porous polymers like Tenax GC and
Chromosorb 103 (Mieure and Dietrich 1973, Zlatkis et al.
1974, Kuo et al. 1977, Dirinch et al. 1980, Barnes et al.
1981), XAD resin (Stepan and Smith 1977), activated charcoal
(Grob 1973) and silica gel. Varying degrees of success have
48 Figure 1. Proposed analysis plan for toxic substances monitoring in Virginia.
Volatiles Sample Nitrofurans Benzidene Broad Band Technique Chloramphenicol Sulfamethazine Cupferron
save solid residue
Anionic Dye Analysis
save solid residue
Cationic Dye Analysis
49 been met with these adsorbents for different organics.
Consequently, one might be inclined to use a combination of
adsorbents when monitoring for a broad spectrum of possible volatile organics.
Fortunately, some analyses for volatile organics in media other than water have been conducted. May et al.
(1975) vapor stripped volatiles from wet sediment with
nitrogen, trapped the volatiles and desorbed them into a GC.
Solvent extraction techniques have been used on wet fish
samples (Pearson and McConnell 1975), but compounds more
volatile than the solvent are lost. Easley et al. (1981)
report simple headspace analysis is not sufficiently
sensitive with aqueous fish samples, and have developed a
procedure which would appear satisfactory for a broad-banded monitoring program.
Easley et al.'s (1981) technique involves the
homogenization of 1 gram of previously frozen tissue in a 25
or 40 ml vial with 10 ml of reagent water. The sample is
sonified with the microprobe approximately 0.25 inches below
the water's surface, while the vial rests in an ice bath. An
impinger-type purging device is immediately fitted, and the
vial is placed in a 70 degree C. water bath. The sample is purged with a stream of inert gas bubbles and transferred to
a trap. The trap, 26 cm by 1/8 inch, is composed of three
equal parts of Tenax, silica gel and activated charcoal.
Once purging is complete, the trap is back flushed while
rapidly being heated, and the organics are blown into the GC
50 at a column temperature of 20 degrees C. Though they
recommend an injector port temperature of 170 degrees C., a
temperature of 145 degrees C. would prevent the decomposition of tert-butyl perbenzoate (614-45-9).
A far simpler analytical procedure might be based on work by Pearson and Me Connell (1975), and be designed primarily for those volatiles in which we are interested
(i.e. those of relatively high vapor pressures). This
technique would involve soxhlet extraction of frozen and ground wet samples with a light solvent like methylene
chloride. The resulting fraction could be very complex, but by using low injection port temperatures (145 degrees C.), many of the complex substances would be left in the injection port liner. Recovery rates may be somewhat reduced due to partitioning problems with aqueous samples, but the ease of the method warrants some testing for applicability. This
technique may prove to be an acceptable compromise since the
extra workload required for the analysis of all volatiles is probably not worthwhile.
Nitrofurans Analysis
Analysis for the nitrofurans, furacin (59-87-0) and
furazolidone (67-45-8), is an involved procedure best presented by Ryan et al. (1975). Briefly the procedure
involves the hydrolysis of the nitrofurans to
5-nitrofuraldehyde in aqueous acid with a number of
51 additional extraction and centrifugation steps. Analysis must be performed with light exclusion techniques to prevent photodecomposition. Due to the involved analytical procedures and the probable environmental instability, monitoring should be primarily limited to special areas where problems are believed most likely to occur.
Benzidine Analysis
A simple alteration of conventional analytical technique will allow the successful analysis of benzidine (92-87-5).
The addition, prior to concentration, of 15% methanol in methylene chloride or chloroform (Riggins and Howard 1979) , or 25% methanol in diethyl ether (Jenkins and Baird 1975), will prevent decomposition of the benzidine during solvent evaporation. Unfortunately, the addition of methanol to the solvent will probably affect the characteristic retention times of compounds in the GPC and HPLC, such that this modification of procedure cannot be incorporated into the routine broad band analytical procedure. Specific analysis for benzidine will probably be required, and will therefore limit the amount of analysis that can be done.
52 Chloramphenicol Analysis +
Derivatization is required to provide sufficient
volatization for the GC of chloramphenicol (56-75-7), and as
such the trimethylsilyl derivatives are usually formed.
Apparently, derivatization with a mixture of
hexamethyldisilazane and trimethylchlorosilane in pyridine
yields the most satisfactory results. Probably the easiest
derivatization method would be to evaporate an aliquot of the
broad band extract in a small screw cap septum vial and add
1.0 ml Tri-Sil (Pierce). An excess of derivatizing agent is
desired, otherwise relative quantities are unimportant.
Shake for 30 seconds to dissolve, allow to stand for 5
minutes, and inject into the GC (Pierce 1982) .
Sulfamethazine Analysis
Sulfamethazine (57-68-1) requires derivatization to
provide sufficient volatility, and the easiest method is
probably acylation. Typically heptafluorobutyric acid
anhydride (HPB) is used as the derivatizing agent, though
pentafluoropropionic acid anhydride could also be used. An
aliquot of the broad band extract should be dried in a screw
cap vial, followed by the addition of 0.1ml of a 0.05M
trimethylamine solution in benzene and 10 ul of the
anhydride. The vial should be capped, heated for 15 minutes
53 at 50 degrees C., allowed to cool, diluted with 1 ml. water and shaken for an additional minute. Add 1 ml. of 5% aqueous ammonia, shake for 5 minutes, centrifuge and inject the benzene phase into the GC (Pierce 1982).
Cupferron
Cupferron (135-20-6) poses analytical problems similar to the ionic dyes which will be discussed in detail next.
Cupferron occurs environmentally as a metal chelate which is soluble in many organic solvents, and thus would occur in the broad band solvent extracts of samples. However, since the chelate is non-volatile in the GC, special separation and identification techniques are required. An aliquot of the broad band sample can be taken from the HPLC fraction in which the cupferron has been shown to elute. Preliminary analysis by atomic absorption spectrophotometry of either this HPLC fraction, or of the initial broad band sample extract, would indicate the presence or absence of iron.
Since iron is the principle metal chelated in the environment, if iron is not detected, analysis for cupferron may be terminated. However if iron is detected, further analysis is needed to determine whether the organic portion is cupferron or another chelating agent. Therefore evaporate the aliquot to dryness to remove some volatiles, heat might be used to drive off more interferring substances should the cupferron prove to be heat stable. CC could be used to
54 clean-up the sample, followed by HPLC for quantitation.
Further clean-up by TLC or CC would be needed for solid probe
M.S. confirmation. Research is needed to determine retention times and clean-up methods since there is little
information in the literature.
Anionic Dye Analysis
Due to the anionic nature of the carboxylic and sulphonic dyes, their analytical requirements differ from conventional organic procedures, yet their extraction can be
incorporated into the proposed broad-banded analytical technique without requiring additional sample material.
Analytical schemes for these dyes generally employ preextraction with a relatively non-polar solvent to remove high fat concentrations. Solvents for preextraction have
included n-hexane (Takashita et al. 1972), chloroform
(Gilhooley et al. 1972, Graichen 1975), petroleum ether
(Hurst et al. 1981), and methylene chloride (Van Peteghem et
al. 1981). Though Gilhooley et al. (1972) added Celite to
samples prior to preextraction, more recent work by Hurst et
al. (1981) omits Celite, and Van Peteghem et al. (1981)
recommend not using it. Preextraction of dye samples with methylene chloride is therefore analogous to the extraction
technique of Bieri et al. (1981) . The sediment and oyster
sample residues, remaining after soxhelet extraction, can
then be used for the analysis of the ionic dyes.
55 Extraction of the anionic dyes from solid matrices has usually been effected with aqueous solutions. Gilhooley et
al. (1972) and Van Peteghem et al. (1981) used methanol-ammonia solutions. Steurle (1979) used a 50% urea
solution buffered to pH of 7.6 for fish extractions. Bailey
(1980) used ammonium acetate, acetonitrile and water. Boley
et al. (1981) used pure water in their extraction of acid
dyes from crushed samples, concentrated the dyes on a Sep-Pak
C-18 cartridge, and eluted them with methanol. However,
Graichen (1975) used a liquid anion exchange resin (Amerlite
LA-2) in hexane and butanol, usually at either an acidic or basic pH, followed by elution of the dyes from the resin with water. Though most anionic dyes identified in this work would probably withstand acidic or basic extraction, the dye
FD & C Blue No. 2 (860-22-0) would rapidly deteriorate
(Gilhooley et al. 1972, Graichen 1975, Lepri et al. 1978,
Boley 1981) and should be extracted at a near neutral pH.
Van Peteghem et al. (1981) used an aqueous solution of
cetrimide (l-Hexadecanaminium,N,N,N-trimethyl-, bromide) to
form an ion-pair with the dye, followed by extraction with
methylene chloride at a pH of 2.5. Of course a solution this
acidic would degrade the FD and C No. 2 if present.
Perhaps the most inclusive technique for the extraction
of acidic dyes would employ Graichen's (1975) exchange resin
extraction procedure on past the point of elution from the
resin with water. Cetrimide could then be added to the
water, and the cetrimide-dye ion-pairs extracted with
56 methylene chloride. Knox and Laird (1976) indicated the dyes would primarily exist as relatively nonpolar ion-pairs in a water:cetrimide solution of approximately 99:1. The organic solvent fraction can then be concentrated under a stream of inert gas, and thus be ready for HPLC of the ion-pairs.
The majority of the qualitative work on anionic dyes has consisted of paper chromatography (PC) and TLC (Parrish 1968,
Chiang and Chen 1970, Hoodless et al. 1971, Takashita et al.
1972, Pearson 1973, Lepri et al. 1978, Home and Dudley
1981) . However this work usually involved the analysis of dyes for purity.
Quantitative analytical techniques have been attempted with differing amounts of success. Comparisons of spot intensities between unknowns and standards have been used in
TLC and PC. Spectrophotometry (Graichen 1975, Lyle and
Tehrani 1979) has been used on solutions, and electrophoresis
(Yeh 1977) has been attempted. Unfortunately, these techniques are probably not sufficiently sensitive for environmental samples. GC is a favorite tool for quantitation in environmental samples, but the vaporization of dye salts is nearly impossible within the limits of normal analytical conditions. However, Me Ewen et al. (1977) were able to identify sulphonated dyes by solid probe insertion into the MS.
HPLC seems to be the new method of choice for quick and efficient quantitation of highly polar substances such as acid dyes (Wittmer et al. 1975). Reverse-phase, ion-pair
57 HPLC is the most commonly used analytical technique for dyes in the recent literature. Usually a solution of a counter-ion such as tetrabutylammonium is used in reverse-phase work (Clark and Miller 1978, Joyce and Sanger
1979, Masiala-Tsobo 1979, Lawrence et al. 1981, Puttemans et al. 1981, DeBeer and Dierickx 1982). Horvath et al. (1977) have discussed reverse-phase ion-pair formation in detail.
Another counter-ion receiving considerable emphasis in the literature has been cetrimide. Knox and Laird (1976) introduced the concept of "soap chromatography" with the detergent cetrimide as the counter-ion for pairing anionic dyes. They found conventional adsorption and ion-pair partition techniques using tetraalkylammonium counter-ions did not prevent tailing of various naphthalenesulphonic acids on silica gel columns, whereas cetrimide was successful. The formation of these cetrimide ion-pairs with both carboxylic and sulphonic acid dyes, toxic dye types most commonly used in Virginia, is readily accomplished (Terweij-Groen et al.
1978, Van Peteghem and Bijl 1981) .
The advantage gained in using cetrimide over tetraalkylammonium ions, is that normal-phase HPLC can be employed. Both normal-phase and reverse-phase HPLC have been conducted with cetrimide by Knox and Laird (1976) and by
Chudy et al. (1978) . The former researchers believed normal-phase (silica gel) and reverse-phase column efficiencies to be about equal. The latter investigators indicated reverse-phase columns generally better separate the
58 cetrimide-dye ion-pairs, but that normal-phase (silica gel) still had an adequate number of theoretical plates to be of practical use.
All references concerning the HPLC of acid dyes, including the cetrimide bound type, used water in the mobile phase. Knox and Laird (1976) indicated water acts to reduce retention of the ion-pairs on the silica by replacing the n-propanol on the active sites of the silica. Since the ion-pairs are lipophillic, they are not attracted to the water layer adsorbed on the active sites. By correctly balancing the concentrations of water and propanol, sufficient sites for proper retention and separation of the ion-pairs is accomplished.
Unfortunately, to use water in an HPLC previously run with non-aqueous solvents requires careful cleaning and bothersome work. It would be far preferable and expedient to maintain the usual solvents in the HPLC if possible. There are no references in the literature concerning normal-phase
HPLC of the "compound" dyes with the cyano or amino columns of reduced adsorption potential. It is suggested that since the cetrimide-dye ion-pairs are relatively stable and quite soluble in organic solvents (Knox and Laird 1976, Tribalat et al. 1978) , that separation and quantitation by conventional cyano or amino columns is entirely possible, and should be tried prior to using an aqueous mobile phase. Ideal separation of the dyes may not be necessary, simply a characteristic retention time by the dye is enough to alert
59 investigators to its possible presence.
Confirmation of the dye types would probably require MS.
Since even the ion-pairs of the dyes are relatively non-volatile, the solid phase insertion probe would have to be used (McEwen et al. 1977) . The use of this probe requires relatively pure compounds to prevent numerous substances from simultaneously fragmenting and thus negating identification.
Purification of the HPLC aliquot containing the suspected dyes might easily be accomplished by TLC. The cetrimide-dye ion-pairs could be used directly from the HPLC aliquot by spotting on silica gel and eluting with one or more solvent schemes. Visualization of the chromatographed spots may be difficult due to typically low environmental concentrations, and will have to be experimentally determined. Relatively high concentrations are generally needed for TLC. Van Peteghem and Bijl (1981) worked with reference solutions of 250ppm, yet to concentrate environmental sample extracts to this extent might result in high concentrations of interfering polar compounds.
Experimentation would be needed to learn the degree of concentration possible. Column chromatography in combination with TLC might be very useful in providing extra separation of components. In both cases of TLC and column chromatography, eluants of methanol-acetone (1:1) with 0.1M cetrimide could be used (Van Peteghem et al. 1981) .
If spots are visible on the silica gel, they can be
60 scraped off the plates, eluted with methylene chloride, evaporated to dryness, and inserted into the MS. If spots are not visible on the TLC plates, yet dye presence is suspected, a standard mixture of suspected dyes could be chromatographed alongside the sample on a TLC plate vertically divided between the ascending standard and unknown. Areas of the unknown side of the TLC plate horizontally adjacent to the known chromatographed dye spots could be analyzed.
Cationic Dye Analysis
Though there are numerous toxic anionic dyes involved in production in Virginia, currently only one toxic cationic dye is used, C.I. Basic Yellow 2 (2465-27-2). Neither conventional analytical techniques nor the proposed anionic dye technique will recover this dye, so an analytical scheme is offered. Since this proposed cationic technique involves sufficient work to be of considerable expense, it is not recommended that analysis for this dye be given high priority. However, once the effort is made to check for the dye, some exploratory analysis for the presence of other ionic amine dyes might be attempted.
Normal-phase HPLC of amines can be accomplished with an organic eluant by previously forming an ion-pair between the amine and an aqueous acid such as 0.1M HC104, a strong oxidizing agent (Eksbourg and Schill 1973, Karger et al.
61 1974, Persson and Karger 1974) . The amine exists as a cation in aqueous solution, but partitions into an organic phase
(e.g. a higher alcohol) as the ion-pair (Knox and Laird
1976) . Since the cationic dye will form an ion-pair in an organic solvent, these dyes can probably be analyzed by a technique similar to that for anionic dyes. After conventional soxhelet extraction of the sample with methylene chloride, followed by extraction with the exchange resin in hexane and butanol for anionic dyes, acidify the sample residue to a 0.1M solution with HC104. Extract the cationic dye-acid ion-pairs from the solution with octanol, concentrate the sample by boiling it down, and quantitate in the HPLC by a cyano or amino normal-phase column with non-aqueous eluants. Experimentation with a standard would determine retention times and optimal HPLC conditions. As with the anionic dyes, TLC and perhaps columnn chromatography would be required to separate out individual solutes. For
TLC separation, Goshima et al. (1977) used BuOH - 1M NaCI
(1:1) with 0.01N HC1 (pH 2.1), though this mixture would add more solutes to the solution. Once components were relatively purified, identification could be accomplished by solid probe insertion into the MS as with the anionic dyes.
62 CHAPTER IV
DISCUSSION AND CONCLUSIONS
4.1 Discussion
Care should be taken in the use of this dissertation not to assume that all or most of the toxic substances used in
Virginia were included in this work. Actually a review of the list of "compounds" studied by the work will reveal the absence of many toxic substances one would expect to find there. For example, one might expect such common solvents as benzene and the chloroalkanes to be included on the list. In addition such common plasticizers as the phthalates might be expected, though very few of these appeared in Table 1.
There are several possible reasons why so many known toxics did not appear, though one reason seems most likely - they were not included in the Master File. An explanation of possible reasons why these obvious omissions did not appear in this work follows next.
In cross-referencing the BTSI list of Virginia's chemicals with the Initial Listing of the ITC, 715 organic and inorganic substances used in Virginia were indicated as being toxic. When that number proved too large to work with and the BTSI list was cross-referenced with the Master File of the ITC, only 159 organic and inorganic substances were obtained. These 159 chemicals supposedly included all toxic substances produced or used in manufacture in Virginia which are not used soley as drugs or pesticides (unless their total
U.S. production exceeded 10 million pounds in 1977).
The reduction in numbers of chemicals obtained by
switching from the cross-referencing with the Initial Listing
(715) to the cross-referencing with the Master File (159),
amounted to a 78% reduction. However, the 3609 substances in
the Initial Listing were reduced by only 43%, down to 2046
substances in the Master File. Thus, a 35% greater reduction
occurred in the numbers of chemicals obtained from the the
cross-referencing of the BTSI list with the Master File than would be expected. The chemicals which appeared in the list of 715 substances, but which did not appear among the 159
substances, consisted primarily of common types. The usual
solvents like benzene and the chlorinated alkanes were present among these deleted substances, along with the plasticizers and numerous pesticides.
The question then arises as to why these common solvents
and plasticizers would be deleted from the Master File. The
only chemicals the ITC was supposed to delete were those
substances previously regulated by FIFRA or the Food, Drug
and Cosmetic Act (FDCA). If any of those previously
regulated chemicals had uses subject to TSCA regulation, then
they were to be reincluded within the Master File.
During my background research of the 579 organic
substances (those organics extracted from the 715 organic and
inorganic substances obtained from the BTSI list
cross-referenced with the Initial Listing), I often noted
64 uses for the more common substances which were different from
their usual uses. A glance through a handbook such as the
Merck Index will often reveal pesticidal type uses for
compounds such as solvents. These varied uses for the more
common compounds leads me to suspect that the list of pesticides and herbicides regulated by FIFRA was probably
expansively developed. Thus, many of the more common
compounds were included as being under the jurisdiction of
FIFRA, and therefore were deleted from the Master File. The
list of compounds under regulation by the FDCA may have also
been expansively developed. Phenol, once used topically in medicine and known as carbolic acid, was another of the
substances present in the Initial Listing yet deleted from the Master File. Why these substances were not reincluded in
the Master File is not known, but it would seem they should have been reincluded since benzene and phenol are certainly widely used as other than a drug or pesticide.
While the primary reason for the omission of many of the well known toxic substances from Table 1 seems to be due to
their deletion from the Master File, other reasons may also
exist. There is the potential that numerous industries are
delinquent in their reporting to the Virginia BTSI. For
example, the lack of toluene from the BTSI's list of
Virginia's chemicals is conspicuously absent. However,
discussions with BTSI personnel indicate the level of
resistance to reporting, while constant, is not
insurmountable and they believe their files are relatively complete.
Another potential cause for certain "toxic" organic substances not appearing in Table 1 could be that no one considered them sufficiently toxic to be listed, or they were not known to be toxic. Though these events probably have occurred with some chemicals, this sequence of events is certainly not a probable reason for the omission of those substances commonly believed to be toxic.
While keeping in mind the limitations on the number of substances included in this dissertation, the work is proposed to be used as a working document. One of the premises of the work was that it was to investigate those substances not commonly known to environmental chemists.
Thus, the work serves as a core to which can be added new information as it becomes known to investigators. Additional data can be filled into the tables present, and new tables can be developed for any substances of interest to the readers. By using the tabular form presented, one can be sure to assess the basic critical steps involved in determining whether other substances are likely to be amenable to conventional techniques. The maintenance of such tabular records allows all personnel in a lab to benefit from the small bits of information about which others become aware.
As indicated earlier, since this dissertation is, in part, a product of the state and federal toxics information network, the quality of this work is dependent upon and
66 reflects upon the quality of the state and federal work. It would appear that Virginia has a good representation in its
files of the chemicals involved in manufacture instate. Of
course a listing of all chemicals used in Virginia would be
optimal. At the federal level however, it would appear that
the Master File of the ITC, which may have functioned well
for the purposes of TSCA, does not lend itself well to other
uses. This is unfortunate because the description of the
Master File would lead one to believe it would function well
as an indicator of toxic substances, other than those used
primarily as drugs or pesticides.
This breakdown in the usefulness of the Master File
reflects upon a greater issue which has been a central tenet
of this dissertation. This tenet asserts that lists tend to
become their own problem. The reliance upon lists to lead
one towards a reliable monitoring program will suffer from
the omission of substances which have been left out for any
of a wide range of possible reasons. One such reason derives
from the artificial territoriality in jurisdiction over
substances. Another problem with lists resulting from this
artificiality, may be expected from substances which have not
been assigned a CAS identification number. Without these CAS
numbers it is nearly impossible, in working with lists
containing substance names, to be certain of their structure.
As a result, these unidentified substances tend to receive
less attention.
It is interesting to note that none of the three
67 chemicals, which were used earlier as examples of major environmental contamination events, appeared in Table 1.
Kepone is no longer manufactured in the U.S., nor are PBBs
(McNally 1978), so these substances would not appear in the table. However, though PCBs are no longer used as raw materials in production in Virginia, they may well be used in existing hydraulic systems and transformers throughout the state. There is the potential for these to leak and contaminate nearby areas, yet PCBs are not present on the
BTSI list as a result of the specifics of the reporting requirements. The point at issue is that there are numerous potential reasons for the omission of compounds from lists.
Of course, due to the notoriety and ubiquitous occurence of
PCBs, they probably would be specifically analyzed.
Thus, it is emphasized again, that the primary monitoring scheme for toxic substances in the Chesapeake Bay should not continue in its list-oriented manner. By analyzing for a particular list of chemicals, one can only
"see" that for which one is "looking". For the State to maintain monitoring programs which are limited to lists, is to ignore the lesson that should have been learned by the
Kepone incident. There is a need to anticipate those toxic compounds which may escape notice and accumulate in the environment, yet one must also attempt to analyze for as many substances as is reasonably possible to detect unsuspected toxic substances. The closure of the James River to certain types of fishing for the past 7 years should continually remind us of the consequences which can arise from ignoring the unexpected.
4.2 Proposals for Implementation
The following is an assessment of the cost and effort that would be required to implement a monitoring scheme for the identification of those toxic substances, used in the state, which were deemed not detectable by conventional techniques. It is emphasized that the analytical scheme proposed by this work for the identification of those non-detectable "compounds" has not been tested, and includes only those considered in this study. The scheme suggested is based on theory and the modification of demonstrated methodologies, and is offered as a beginning for future work.
In order for the state to seriously consider monitoring for these substances, a substantial financial commitment will be needed to further refine and improve these techniques.
Rather than target the costs of implementation of these procedures towards a specific laboratory, estimates are provided to indicate basic costs of the entire program.
Other benefits could be derived from these same resources, since they would not be used to their full capacity.
The level of personnel experience required for development of the technique is anticipated to differ from that required for implementation of the monitoring scheme. A
Ph.D. chemist, skilled in the development of new procedures,
69 and experienced in mass spectrometry, will be needed to develop the new techniques. For the monitoring program, a
Ph.D. chemist experienced in mass spectrometry will be required. In both the research and monitoring phases, two assistants with appropriate chemical backgrounds will be needed. It should be anticipated that several years may be required to determine effective analytical procedures.
In addition to sufficiently qualified analytical chemists, state-of-the-art analytical equipment will be needed. An advanced GC/MS with electron impact, chemical ionization, and solid probe capability will be required, along with several GCs equipped with differing detectors.
Both the GC and the GC/MS should be interfaced with a computerized data system to allow efficient handling of data and comparisons of results over time. Liquid chromatographic capabilities such as HPLC must also be anticipated.
Once the analytical procedures have been developed, implementation of the monitoring program can commence.
Initial sampling should be directed at a system-wide approach with emphasis in the large tributaries to the Chesapeake Bay.
Perhaps three samples should be taken from each of the four major rivers in Virginia, plus other samples from smaller systems including the Elizabeth River. Such a large system approach would miss small localized areas of pollution, but would allow an initial overview with a maximun of perhaps 50 samples per year. Should a problem be perceived, then a site specific approach can be used. This site specific approach
70 might employ the use of the BTSI's list of chemicals, which should be compiled by use in watersheds. NPDES permits could also be used in conjunction with the "watershed list" to indicate potential sources of the contaminants.
As Table 9 indicates, the projected costs for implementation of this program would amount to approximately
$510,000 in the first biennium, and $245,000 in the second biennium.
71 Table 9. Costs for implementation of analytical procedures.
Personnel Year 1 Year 2 Year 3 Year 4
Chemist D 40.000 41.000 42.000 43.000 (Fringe-30%) 12.000 12,300 12,600 12,900 Chemist A 16,000 17.000 18.000 19.000 (Fringe-30%) 4.800 5.100 5.400 5.700 Chemist A 16,000 17.000 18,000 19.000 (Fringe-30%) 4.800 5.100 5.400 5.700
Equipment
GC/MS 200,000 GC-FID 20,000 GC-ECD 20,000 GC-NPD 20,000 HPLC 30,000 Repair 5,000 7,000 10,000 10,000
Solvents etc. 10,000 4,000 4,500 5,000
Sampling 1,000 1,000 4,000 4.000
Totals $399,600 $109,500 $119,900 $124,300
72 4.3 Conclusions
1. Conventional analytical techniques are neither capable of identifying nor quantitating all toxic organic substances used in production in Virginia which may pose long term pollution problems.
2. Alternative analytical techniques which are proposed for "compounds" not detectable by conventional analysis should receive some attention by the state, though rigorous monitoring is not recommended.
3. Though this work employs a list-oriented approach to monitoring for toxic substances, it is recommended the state adopt analytical procedures capable of broad band monitoring.
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105 APPENDIX
This appendix contains tables of the toxic organic "compounds" used in manufacture or produced in Virginia with summaries of their detectability by conventional analysis. In addition, a table of selected abbreviations is included.
106 Appendix Table 1.
CAS # 50-00-0
Formaldehyde
STRUCTURE: HCHO
M.F. C-H2-0 M.W. 30.03 B.P. -19.5 C.
TOXICITY Toxic Effects Reported: ETA, IRR Aquatic Toxicity Rating: TLm96: 100-10 ppm.
USE Disinfectant, fungicide, in the manufacture of phenolic resins, artificial silk and cellulose esters, dyes, explosives, and in photographic processing.
ANALYTICAL SUMMARY Too volatile for conventional techniques. Too reactive for solvent extraction procedures.
EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High
STABILITY Highly reactive, environmentally short lived. Fairly stable when adsorbed onto activated charcoal, Tenax-GC or Molecular Sieve 13X (Yokouchi et al. 1979), though likely to react in extracted solution.
SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in water, alcohol and ether.
LC Evaporation prior to LC in conventional techniques. Probably too reactive in solution to remain stable for LC.
107 Appendix Table 1.
GC and GC/MS Low column temperatures needed for adequate separation. Derivatization for GC has been used to decrease volatility and reactivity (Hoshika and Takata 1976, Janos et al. 1980, Neitzert and Seiler 1981), but techniques without derivatization including headspace sampling, have been shown to be highly successful (MacDonald and Brady 1974, Yokouchi et al. 1979, Klug and Schmidt 1981, Barcello and Eek 1980).
108 Appendix Table 2.
CAS # 50-06-6
2,4,6(1H,3H,5H)-Pyrimidinetrione, 5-ethyl-5-phenyl-
STRUCTURE: H3C-H2C
NH
II
M.F. C12-H12-03-N2 M.W. 232.26 M.P. 174-178 C.
TOXICITY Toxic Effects Reported: TER, NEO
USE In estrogenic hormone therapy.
ANALYTICAL SUMMARY Derivatization aids in preventing adsorption and decomposition problems in GC, but it is not necessary.
EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low
STABILITY Heat stable but may tend to decompose when chromatographed on less than conventionally inert columns (Christopherson and Rasmussen 1980). Unstable in alkaline media.
109 Appendix Table 2.
SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in water (slightly), methanol, propanol, diethyl ether, methylene chloride, chloroform, carbon tetrachloride, and benzene.
LC Amenable to normal-phase. TLC on silica gel with acetone:chloroform (Beniczky-Augusztin and Tasi-Toth 1973) .
GC and GC/MS Amenable to conventional techniques. Derivatization as the methyl or the trimethylsilyl derivatives have been used to prevent decomposition (Christopherson and Rassmussen 1980) and to improve separation (Abraham 1977) , though others indicate it is helpful but is not necessary (Osiewicz et al. 1974, Marigo et al. 1977), or not needed with highly inert columns (Jaramillo and Driscoll 1979, Riva et al. 1980, Cailleux et al. 1981) .
110 Appendix Table 3.
CAS * 50-50-0
Estra-lf3,5(10) -triene-3,17-diol(17B)-3-benzoate
STRUCTURE: OH
C-
M.F. C25-H28-03 M.P. 191-196 C.
TOXICITY Toxic Effects Reported: ETA, TER, CAR Review: Carcinogenic Determination: Animal Positive
USE Drug
ANALYTICAL SUMMARY Derivatization is helpful but is not mandatory for GC analysis.
EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low
STABILITY Probably stable to conventional analytical techniques. No indication of lability was found.
Ill Appendix Table 3.
SOLUBILITY Probably soluble in most solvents of intermediate polarity. Soluble in: water, alcohol, acetone, ether, chloroform (Roman et al. 1979), heptane, and olive oil.
LC Amenable to normal-phase. CC on silicic acid with ethyl etherspetroleum ether (Cavina et al. 1971). CC on silica gel with ethanol:methanol:heptane (Roman et al. 1979).
GC and GC/MS Amenable to conventional techniques. Standard technique involves the formation of the more volatile trimethylsilyl derivative (Moretti et al. 1969, Gazdag et al. 1977, Roman et al. 1979), but derivatization is not mandatory (Mestres and Berges 1972).
112 Appendix Table 4.
CAS # 50-55-5
Yohimban-16-carboxylic acid, 11,17-dimethoxy-18-[(3,4,5,- trimethoxybenzoyl) oxy]-methyl ester, (3B,16B,17A,18B, 20A) -
STRUCTURE: H3C-0
0-CH3
0-CH3
H3C-0-C=0 O-C 0-CH3 0-CH3 0
M.F. C33-H40-N2-O9 M.W. 608.7
TOXICITY Toxic Effects Reported: ETA, TER, CAR Status: Carcinogenic bioassay indicates carcinogenic in mouse and rat.
ANALYTICAL SUMMARY Requires high column temperatures. Derivatization can be used to increase volatility.
EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low
113 Appendix Table 4.
STABILITY Sufficiently stable to conventional analytical techniques. Develops fluorescence from exposure to light, acids, or oxidizing agents by losing one H+ and forming a double bond to form 3-dehydroreserpine (Higuchi and Brockmann-Hanssen 1961, Sams and Huffman 1978).
SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Somewhat selectively soluble in solvents due to its large size. Soluble in: hot water, (slightly), hot alcohol (slightly), ether (slightly), methylene chloride, chloroform, ethyl acetate, heptane, benzene (slightly).
LC Amenable to normal-phase. CC on silica gel with methanol (Verpoorte and Svendsen 1974) . HPLC on silica gel with hexane:isopropanol:chloroform: diethylamine (Butterfield et al. 1978). TLC on silica gel with methyl ethyl ketone:hexane (Stohs and Scratchley 1975) .
GC and GC/MS Amenable to conventional techniques with high column temperatures. Since this is a heavy compound, either high column temperatures in the range of 285 decrees C. (Pantarotto et al. 1977) or esterification to the 3,4,5- trimethoxybenzoate (Settimj et al. 1976) is needed for proper volatility.
114 Appendix Table 5.
CAS # 50-78-2
Benzoic acid, 2-(acetyloxy)-
STRUCTURE: uuti 02-CH3
M.F. C9-B8-04 M.W. 180.17 M.P. 135 C.
TOXICITY Toxic Effects Reported: PUL, SYS, GIT, TER
USE Drug
ANALYTICAL SUMMARY Amenable to conventional techniques. Requires derivatization or an inert column to prevent severe tailing.
EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from solvent: Low
STABILITY Relatively stable to conventional analytical procedure, though it hydrolyzes in water.
SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, ether, ethyl acetate, chloroform, methylene chloride (Harrison et al. 1980), hexane, benzene (slightly) .
115 Appendix Table 5.
LC Amenable to normal-phase. CC on silica gel with methanol (Strojny and deSilva 1975) . TLC on silica gel with chloroformiacetone, ethyl acetate, and acetone (Owen et al. 1978).
GC and GC/MS Amenable to conventional techniques with inert columns. Severe tailing can be prevented with inert columns (McMartin and Street 1966, Nieminen 1971, Snelzwar 1980, Osselton et al. 1980),or by derivatization with N,0-bis(trimethylsilyl)trifluoroacetamide (Christopherson and Rasmussen 1980, Street 1969), or with BF3 in methanol (Crippen and Freimuth 1964) .
116 Appendix Table 6.
CAS # 51-79-6
Carbamic acid, ethyl ester
STRUCTURE NH2-COO-CH2-CH3
M.F. C3-H7-02-N M.W. 89.09 M.P. 48.5-50 C. B.P. 182-184 C.
TOXICITY Toxic Effects Reported: ETA, NEO, CAR Review: Carcinogenic Determination: Animal Positive
USE Organic solvent, intermediate in organic synthesis, preparation of amino resins, solubilizer for pesticides and fumigants.
ANALYTICAL SUMMARY Amenable to conventional techniques. Requires a fairly inert GC column to prevent tailing.
EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low to Moderate Evaporation from Solvent: low
STABILITY Stable to conventional analytical procedures. A fairly stable compound in neutral conditions, though incompatible with acids and alkalies.
SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, ether, methylene chloride, chloroform, benzene, pyrimidine, glycerol, olive oil.
117 Appendix Table 6.
LC Amenable to normal-phase. TLC on silica gel with acetone:chloroform (Heyndrickx et al. 1965) . CC on alumina plus silica gel with methylene chloride: methanol (Joe et al. 1977).
GC and GC/MS Amenable to conventional techniques with inert columns. This adsorptive compound can cause tailing problems resolvable either by derivatization as the trimethylsilyl derivative (Nery 1969), as the perfluoroacyl derivative (Walker et al. 1974), or through the use of inert columns (Zielinski and Fishbein 1965, Joe et al. 1977) .
118 Appendix Table 7.
CAS # 53-16-7
Estra-1,3,5(10)-trien-17-one, 3-hydroxy-
STRUCTURE:
H3C
HO
M.F. C18-H22-02 M.W. 270.38 M.P. 260-262 C.
TOXICITY Toxic Effects Reported: ETA, NEO, TER Review: Carcinogenic Determination: Animal Positive
USE Drug, preparation of 19-nor steroids.
ANALYTICAL SUMMARY Hydrolysis of steroid conjugates followed by derivatization is required for GC.
EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low
STABILITY Stable to conventional analytical procedures. Stable to acids though acidic solvolysis causes some destructive cleavage (Pinelli and Formento 1972) .
119 Appendix Table 7.
SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Apparently more soluble in water than organic solvents. Soluble in: water, hot alcohol, hot acetone (slightly), ether (slightly), hot chloroform (slightly), benzene (slightly).
LC Amenable to normal-phase. TLC on silica with hexane:ethanol (Lin and Heftmann 1981) .
GC and GC/MS Hydrolysis of steroid conjugates followed by derivatization is required for GC. Quantitative analysis is generally accepted to require enzymatic hydrolysis (Pinelli and Formento 1972, Joe et al. 1978, Zweig et al. 1980) , and possibly acidic solvolysis (Leunissen and Thijssen 1978) . Derivatization to prevent severe tailing (Roman et al. 1981) is generally performed with silylating agents.
120 Appendix Table 8.
CAS # 54-21-7
Benzoic acid, 2-hydroxy-, monosodium salt
STRUCTURE: COO * Na
M.F. C7-H5-03-Na M.W. 160.11
TOXICITY Toxic Effects Reported: IRR, TER
USE Drug, frostproofing concrete, corrosion inhibitor, fireworks.
ANALYTICAL SUMMARY Requires organic extraction from acidic aqueous solution as salicylic acid for analysis.
EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Low (as the acid)
STABILITY Stable' to conventional analytical procedures. No indication of lability was found.
SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in polar solvents including water, alcohol and glycerol. The acid is more effectively extracted from aqueous solution with ethers than halogenated hydrocarbons (Ranee et al. 1975), though the acid is favorably soluble in methylene chloride and hexane.
121 Appendix Table 8.
LC Amenable to normal-phase. TLC of the acid form on silica gel with methanol (Strojny and deSilva 1975) , and with chloroform:acetone/ ethyl acetate, acetone, and chloroform:methanol (Owen et al. 1978) .
GC and GC/MS The acid is amenable to conventional techniques with relatively inert columns. The salt will not vaporize. Adsorption of the acid to the column (Nikelly 1964) , is resolvable as the trimethylsilyl derivative (Thomas et al. 1973) , or with reasonably inert columns (Kaempe 1974, Beringer and Moeller 1977, Osselton et al. 1980).
122 Appendix Table 9.
CAS # 56-23-5
Methane, tetrachloro
STRUCTURE: C-C14
M.P. C-C14 M.W. 153.84 B.P. 76.7 C.
TOXICITY Toxic Effects Reported: SYS, CNS, PUL, GIT, ETA, CAR, NEO Review: Carcinogenic Determination: Positive Human and Animal Aquatic Toxicity Rating: TLm 96: 100-10 ppm
USE Dry cleaning, solvent, extraction of oil from flowers and seeds, pesticides.
ANALYTICAL SUMMARY Too volatile for conventional analytical techniques. Low column temperatures are required. Special detector required.
EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Probably would be lost during freeze drying. Could be retained during evaporation of methylene chloride, but probably would be lost during evaporation of isopropanol or toluene.
STABILITY Stable to conventional analytical procedure. The common occurance in drinking water and river water indicates some environmental stability.
123 Appendix Table 9.
SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: alcohol, chlorinated hydrocarbons, acetone, ether, benzene.
LC Amenable to normal-phase.
GC and GC/MS Difficult to separate from most solvents by GC. Column temperatures of 75 to 95 degrees C. are optimal (Michael et al. 1980, Reddrop et al. 1980). ECD provides superior response to PID.
124 Appendix Table 10.
CAS # 56-75-7
Acetamide, 2,2-dichloro-N-[2-hydroxy-l-(hydroxymethyl)-2- (4-nitrophenyl]ethyl)-,[R-(R*,R*)]-
''02 STRUCTURE:
HO-C-H K-C-NHCO-CHC12 H- M.F. C11-H12-05-N2-C12 M.W. 323.15 M.P. 151 C. TOXICITY Toxic Effects Reported: CAR, CNS, BLD, TER Review: Carcinogenic Determination: Human Suspected USE Drug ANALYTICAL SUMMARY Derivatization is required for volatization in the GC. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. Stable in neutral and acid solutions. 125 Appendix Table 10. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. More soluble in polar than nonpolar solvents. Soluble in: water (slightly), alcohol (very), ether (slightly), acetone (very), chloroform, ethyl acetate, acetonitrile. LC Amenable to normal-phase. TLC on silica gel with methanol:chloroform and methanol: acetone (Bossuyt et al. 1976) . GC and GC/MS Derivatization, usually as the trimethylsilyl derivative, needed for adequate volatility (Hollstein et al. 1981, Nakagawa et al. 1975, Janssen and Vanderhaeghe 1973, Bentley et al. 1963). ECD responds poorly despite the chlorine atoms (Wal et al. 1979), and FID is normally used. 126 Appendix Table 11. CAS # 57-39-6 Aziridine,!,!',1''-phosphinylidynetris[2-methyl- STRDCTURE: CII3 0 CH3 N CH3 M.P. C9-H18-0-N3-P M.W. 215.24 B.P. 90-92 C. TOXICITY Toxic Effects Reported: CAR, TER Review: Carcinogenic Determination: Animal Suspected USE Chemosterilant, in crease proofing and flameproofing textiles. ANALYTICAL SUMMARY Too volatile for conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Could be retained during evaporation of methylene chloride, hexane, and isopropanol, but probably would be lost during evaporation of toluene and higher boiling solvents. STABILITY Apparently stable to conventional analytical techniques. No reference to lability was found. 127 Appendix Table 11. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, methanol, ethanol, chloroform, benzene. LC Probably amenable to normal-phase. No references to organic normal-phase chromatography were found in the literature. Somewhat adsorptive to GC columns, yet the structure and the low B.P. hint it may not be extremely adsorptive in LC. GC and GC/MS FPD is the most sensitive. Amenable to conventional techniques, though some tailing is apt to occur {Bowman 1966, Seawright et al. 1973, Bowman 1975) unless highly inert columns are used. 128 Appendix Table 12. CAS # 57-68-1 Benzenesulfonamide, 4-amino-N(4,6-dimethyl-2-pyrimidinyl)- STRUCTURE: CH3 CH3 M.F. C12-H14-N4-02-S M.W. 278.32 TOXICITY Toxic Effects Reported: ETA USE Antibacterial ANALYTICAL SUMMARY Derivatization is required for GC analysis. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Apparently stable to conventional analytical procedures. No indication of lability was found. The compound is relatively biodegradable, but will bioaccumulate somewhat (Coats et al. 1976). SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, acid, alkali, alcohol, acetone, methylene chloride, (Manuel and Steller 1981), chloroform (Kiger and Kiger 1966) . 129 Appendix Table 12. LC Amenable to normal-phase. TLC on silica gel with ethersmethanol (DeZeeuw 1970) and with chloroform:methanol (Kiger and Kiger 1966) . GC and GC/MS Derivatization required for GC due to the typically low volatility and tailing of sulphonamides. Derivatives may be produced as either the perfluoroacyl derivative (Gyllenhaal and Ehrsson 1975, Goodspeed et al. 1978) or as a methylated derivative (Garland et al. 1980, Manuel and Steller 1981) . 130 Appendix Table 13. CAS # 57-85-2 Androst-4-en-3-one, (17-B)- (1-oxopropoxy)- STRUCTURE: H3C 0-C-CH2-CH3 H3C M.F. C22-H32-03 M.W. 344.48 M.P. 118-122 C. TOXICITY Toxic Effects Reported: TER, ETA Review: Carcinogenic Determination: Animal Positive USE Drug ANALYTICAL SUMMARY Amenable to conventional techniques, though hydrolysis and derivatization for GC is often performed. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. No reference to lability was found. 131 Appendix Table 13. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: alcohol, ether, chloroform, pyridine, heptane, vegetable oil. LC Amenable to normal-phase. CC on silicic acid with ethyl etherrpetroleum ether (Cavina et al. 1971). GC and GC/MS Amenable to conventional techniques. Techniques often involve derivatization as the TMS derivative (Gazdag et al. 1977) and as the oxime (Koshy et al. 1975) to improve separation between similar steroids, however conventional GC techniques can be used {Cavina et al. 1970, Youssef et al. 1972) Hydrolysis of steroid conjugates prior to GC is not mandatory, though occasionally executed (James et al. 1972) . 132 Appendix Table 14. CAS # 59-87-0 Hydrazinecarboxamide, 2-[(5-nitro-2-furanyl)methylene]- STRUCTURE: o M.F. C6-H6-N4-04 M.W. 198.14 TOXICITY Toxic Effects Reported: NEO, TER, ETA Review: Carcinogenic Determination: Indefinite USE Antimicrobial drug. ANALYTICAL SUMMARY Unstable to heat or light. Derivatization is required for GC. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low Solvents containing this polar compound are often evaporated to dryness during analysis (Cieri 1979, Vilim and Macintosh 1979) . STABILITY Heat labile above 50 C. (Vilim and Macintosh 1979) . Photosensitive to natural and artificial light (Ryan et al. 1975) . Exposure to light would shorten its environmental lifetime. 133 Appendix Table 14. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, acetone, chloroform, benzene: cyclohexane. LC Amenable to normal-phase. TLC on silica gel with benzene:cyclohexane (Narbutt-Mering 1973) . CC on silica gel with chloroform:methanol (Cieri 1979) . GC and GC/MS Technique involves the formation of a heat stable derivative as the 5-nitrofuraldehyde which is common to all nitrofurans, and thus is incapable of identifying specific parent compounds (Ryan et al. 1975) . 134 Appendix Table 15. CAS # 60-29-7 Ethane,1,11-oxyb i s- STRUCTURE: CH3-CH2-0-CH2-CH3 M.F. C4-H10-O M.W. 74.12 B.P. 34.6 C. TOXICITY Toxic Effects Reported: IRR Aquatic Toxicity Rating: TLm96: over 1000 ppm USE Solvent for waxes, fats, and gums; extraction of ingredients from plants; in manuf. of gun powder. ANALYTICAL SUMMARY Too volatile for conventional analysis. Low GC column temperatures required for good peak separation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High STABILITY Stable to conventional analytical procedures. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: water (slightly), lower aliphatic alcohols, ether, acetone, chloroform, benzene, oils, ligroin. LC Amenable to normal-phase. 135 Appendix Table 15. GC and GC/MS Low column temperatures required for good separation, otherwise amenable to conventional chromatography (Bertoni et al. 1981, Drucker 1981). 136 Appendix Table 16. CAS # 62-44-2 Acetamide, N-(4-ethoxypheny1)- STRUCTURE: NH-C0-CH3 0-CH2-CH3 M.F. C10-H13-O2-N M.W. 179.21 M.P. 134-135 TOXICITY Toxic Effects Reported: CNS, CAR Review: Carcinogenic Determination: Human Suspected USE Drug ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. No indication of lability was found. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Apparently somewhat selectively soluble. Soluble in: water (slightly), alcohol, ether (slightly), ethyl acetate, acetone (slightly), chloroform, benzene (slightly), pyrimidine. 137 Appendix Table 16. LC Amenable to normal-phase. TLC on silica gel with acetone-chloroform (Ebel and Herold 1976) . GC and GC/MS Amenable to conventional GC techniques. Analysis by conventional GC techniques (Kaempe 1974, Berninger and Moeller 1977, Baker 1977, Osselton et al. 1980). 138 Appendix Table 17. CAS # 65-45-2 Benzamide, 2-hydroxy- STRUCTURE: M.F. C7-H7-02-N M.W. 137.13 M.P. 140 C. TOXICITY Toxicity Effects Reported: TER USE Bactericide ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, ether, chloroform. LC Amenable to normal-phase. CC on silica gel with methanol (Strojny and deSilva 1975). TLC on silica gel with chloroform:acetone ethyl acetate, acetone chloroform:methanol (Owen et al. 1978). 139 Appendix Table 17. GC and GC/MS Amenable to cpnventional techniques. GC by conventional procedures (Alber et al. 1971, Moffat 1975, Berninger and Moeller 1977) . 140 Appendix Table 18. CAS # 67-45-8 2-Oxazolidinone, 3-[[(5-nitro-2-furanyl)methylene]amino]- STRUCTURE: M.F. C8-H7-N3-05 M.W. 225.16 TOXICITY Toxic Effects Reported: POL USE Drug ANALYTICAL SUMMARY Unstable to heat or light. Derivatization is required for G.C. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low Solvents containing this compound are often evaporated to dryness (Cieri 1979, Vilim and Macintosh 1979) . STABILITY Heat labile at temperatures below volatization, and photosensitive to natural and artificial light (Ryan et al. 1979, Smallidge et al. 1981). Exposure to environmental light would shorten this compound's lifetime. 141 Appendix Table 18. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, chloroform (Guinebault et al. 1981), methylene chloride (Winterlin et al. 1981), benzene:cyclohexane. LC Amenable to normal-phase. TLC on silica gel with benzene:cyclohexane (Narbutt-Mering 1973) . CC on silica gel with chloroform-methanol (Cieri 1979) . GC and GC/MS Technique involves the formation of a heat stable derivative as the 5-nitrofuraldehyde which is common to all nitrofurans and thus is incapable of identifying specific parent compounds (Ryan et al. 1975). 142 Appendix Table 19. CAS # 74-31-7 1 ,4-Benzenediamine, N,N'-diphenyl- STRUCTURE: M.P. C18-H16-N2 M.W. 260.36 TOXICITY Toxic Effects Reported: ETA USE Antioxidant, heat stabilizer for rubber. ANALYTICAL SUMMARY Amenable to conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Apparently stable to conventional analytical procedures. No indication of lability was found, though little information was available. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: acetone, tetrahydrofuran (Protivova et al. 1974), hexane, cyclohexane (Kompisova et al. 1966), ethanol, benzene (Zijp 1957a), carbon tetrachloride (Zijp 1957b). 143 Appendix Table 19. LC Amenable to normal-phase. TLC on silica gel with carbon tetrachloride:acetone (Gormoryova 1970) with benzenetethyl acetate:acetone (Simpson and Currell 1971), with chloroform:hexane (Simpson 1972), and with benzene:hexane, ether benzene:diethyl ether, and benzene:ethanol (Protivova et al. 1974.) GC and GC/MS Amenable to conventional techniques. GC by conventional techniques (Wise and Sullivan 1962, Kochel and Jaroszynska 1974, Protivova et al. 1974). 144 Appendix Table 20. CAS # 75-00-3 Ethane, chloro- STRUCTURE: CH3-CH2-CI M.P. C2-H5-C1 M.W. 64.52 B.P. 12.3 C. TOXICITY Toxic Effects Reported: CNS Aquatic Toxicity Rating: TLm96: over 1000 USE Topical anesthetic, solvent. ANALYTICAL SUMMARY Too volatile for conventional techniques. Low GC column temperatures provide better separation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High STABILITY Stable to conventional analytical procedure. A relatively stable compound. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water (slightly), alcohol, ether, chlorinated hydrocarbons. LC Amenable to normal-phase. 145 Appendix Table 20. GC and GC/MS Low column temperatures provide better separation. GC by conventional procedures with low column temperatures (Grimsrud and Miller 1980, Nawrocki et al. 1980, Easley et al. 1981. 146 Appendix Table 21. CAS # 75-07-0 Acetaldehyde STRUCTURE: CH3-CHO M.F. C2-H4-0 M.W. 44.05 B.P. 20.8 C. TOXICITY Toxic Effects Reported: IRR, TER USE Manufacture of paraldehyde, acetic acid, butanol, perfumes, flavors, aniline dyes, plastics, synthetic rubber; silvering mirrors; hardening gelatin fibers. ANALYTICAL SUMMARY Too volatile for conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High STABILITY Stable to conventional analytical procedures. A common metabolite in plants and animals. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, acetone and benzene. LC Amenable to normal-phase. 147 Appendix Table 21. GC and GC/MS Low column temperatures provide better separation of sample peaks. Derivatization as the 2 ,4-dinitrophenylhydrazones provides longer retention times and better peak separation (Linko et al. 1978), though it is not necessary with low column temperatures (Kuo et al. 1977, Hoshika and Muto 1978, Mendenhall et al. 1980). 148 Appendix Table 22. CAS # 75-08-1 Ethanethiol STRUCTURE: CH3-CH2-SH M.F. C2-H6-S M.W. 62.13 B.P. 35 C. TOXICITY Toxic Effects Reported: CNS USE Odorant for natural gas; manuf. of plastics, insecticides, antioxidants. ANALYTICAL SUMMARY Too volatile for conventional techniques. Low GC column temperatures provide better peak separation. EVAPORATIVE LOSS POTENTIAL Freeze Drying : High Evaporation from Solvent: High STABILITY Stable to conventional analytical procedures. An anaerobic metabolic product of organic matter (Jenkins et al. 1980) . SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water (slightly), alcohol, ether, acetone, dilute alkali. LC Probably amenable to normal-phase with polar solvents. 149 Appendix Table 22. GC and GC/MS Low column temperatures provide better peak separation. GC by conventional procedures at low column temperatures (Pearson 1976, Vitenberg et al. 1977, Jenkins et al. 1980) . 150 1 Appendix Table 23. CAS # 75-44-5 Carbonic dichloride STRUCTURE: C1-C0-C1 M.F. C-0-C12 M.W. 98.92 B.P. 8.2 C. TOXICITY Toxic Effects Reported: IRR Highly poisonous gas. USE Manuf. of rayon, carbon tetrachloride, xanthogenates, soil disinfectants, electronic vacuum tubes. ANALYTICAL SUMMARY Too volatile for conventional techniques. Low column temperatures aid in GC peak separation. Probable decomposition in conventional LC. Special GC detector required. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High STABILITY Decomposes in alcohol. Slowly hydrolyzed by water. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: glacial acetic acid, chloroform, carbon tetrachloride, toluene, benzene, and most liquid hydrocarbons. LC Probable decomposition in alcohol. 151 Appendix Table 23. GC and GC/MS ECD is far more sensitive than FID. Low column temperatures aid in peak separation. Other than the above limitations, amenable to conventional technique. Conventional GC with low column temperatures and ECD (Singh 1976, Baiker et al. 1978, Reichert et al. 1979), though adsorption problems have been noted (Esposito et al. 1977). 152 Appendix Table 24. CAS # 75-55-8 Aziridine, 2-methyl- STRUCTURE: CH3 M.F. C3-H7-N M.W. 57.11 B.P. 64-68 C. TOXICITY Toxic Effects Reported: CAR Review: Carcinogenic Determination: Animal Positive ANALYTICAL SUMMARY Too volatile for conventional techniques. LC requirements uncertain. Adsorption and tailing tend to be a problem in GC. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Could be retained during evaporation of methylene chloride but probably would be lost during evaporation of hexane and higher boiling solvents. STABILITY Possibly too reactive for solvent extraction, though sufficiently stable for headspace and vapor stripping techniques. Aziridines are very reactive and hydrolyze rapidly in acidic solutions to alkanolamines, but are stable in alkaline solutions (Shimomura et al. 1973). 153 Appendix Table 24. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Aziridine is soluble in: water, alcohol, ether, acetone, benzene, general organic solvents. LC Requirements for chromatography are uncertain. Adsorption might be a problem due to the polar and reactive nature of the molecule. GC and GC/MS Low column temperatures provide better separation of p e a k s . Adsorption and tailing tend to be a problem, and KOH has been used in columns to reduce tailing (diLorenzo and Russo 1968, Raulin et al. 1980), though this is apparently not mandatory (Hillers et al. 1978). Conventional inert columns would probably reduce adsorption. 154 Appendix Table 25. CAS # 77-78-1 Sulfuric acid, dimethyl ester STRUCTURE: (CH3-0)2-S02 M.F. C2-H6-04-S M.W. 126.13 B.P. 188 C. TOXICITY Toxic Effects Reported: ETA Review: Carcinogenic Determination: Human Suspected Aquatic Toxicity Rating: TLm96: 100-10 ppm USE Methylating agent in manuf. of many organic chemicals; war gas. ANALYTICAL SUMMARY Potential evaporative loss during freeze drying. A reactively unstable compound. Specialized injection into GC helpful. Special detector helpful. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate to High Evaporation from Solvent: Moderate GC columns often 100-125 degrees C. STABILITY Quantitative losses could occur in conventional analysis. Hydrolysis in water is rapid above 18 degrees C. Reactive with amines and phenols, and is used as a methylating agent for them. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, ether, dioxane, acetone, aromatic hydrocarbons, carbon disulfide (sparingly), aliphatic hydrocarbons (sparingly). 155 Appendix Table 25. LC Apparently amenable to normal-phase. Elution from silica gel with acetone (Gilland and Bright 1980) . GC and GC/MS Specialized injection techniques and detector are helpful. Column conditioning with injections of the compound prior to analysis for the unknown provides more reproducible results (Sidhu 1981), though thermal desorption from polymer trap into the GC has been performed (Ellgehausen 1975) . FPD produces a 5X greater response than FID (Gilland and Bright 1975) . 156 Appendix Table 26. CAS # 78-00-2 Plumbane, tetraethyl STRUCTURE: Pb(CH2-CH3)4 M.F. C8-H20-Pb M.W. 323.45 B.P. @200 C. TOXICITY Toxic Effects Reported: CAR Review: Carcinogenic Determination: Animal Suspected Aquatic Toxicity Rating: TLm96: under 1 ppm USE Additive in gasoline. ANALYTICAL SUMMARY Possibly too volatile for freeze drying. Extraction should be performed quickly after sampling. Specialized detector helpful. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate to High Evaporation from Solvent: Moderate Exhibits a high vapor pressure (Chau et al. 1979) . STABILITY Somewhat unstable in air and water, so extraction should be initiated quickly. Stable in organic solvents. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in alcohol, ether, petroleum ether, benzene. Practically insoluble in water. LC Readily amenable to normal-phase. 157 Appendix Table 26. GC and GC/MS Readily amenable to GC. ECD is more sensitive than FID (Chau et al. 1976), though FID is often used conventionally (Radziuk et al. 1979, Estes et al. 1980), or doped with silane for better sensitivity (DuPuis and Hill 1979, Jonghe et al. 1980). GC/MS poses no special problems (Nielson et al. 1981) . 158 Appendix Table 27. CAS # 78-30-8 Phosphoric acid, tris(2-methylphenyl) ester STRUCTURE: 0 — P — 0 CH3 ,CH3 M.P. C21-H21-04-P M.W. 368.36 B.P. @265 C. TOXICITY Toxic Effects Reported: CNS USE Plasticizer, flame-retardant,' in cellulosic molding, fluid in hydraulic systems. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. No indication of lability was found. 159 Appendix Table 27. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: alcohol, ethyl acetate:toluene, hexane, all common solvents. Compound has a high octanol:water partition coefficient Muir et al. 1981) . LC Amenable to normal-phase. TLC on silica gel with methylene chloride:carbon tetrachloride:hexane:ethyl acetate, also with hexane: carbon tetrachloride;ethyl acetate (Bloom 1973) . CC on silicic acid and Celite with benzene:diethyl ether and TLC on silica gel with isopropanol:hexane (Sugden et al. 1980) . CC on alumina with hexane:diethyl ether (Muir et al. 1981) . GC and GC/MS Amenable to conventional techniques. GC analysis by conventional procedures with both FID (Bloom 1973, Nakamura et al. 1980) and NPD (LeBel et al. 1981, Muir et al. 1981). 160 Appendix Table 28. CAS # 79-10-7 2-Propenoic acid STRUCTURE; CH2=CH-COOH M.F. C3-H4-02 M.W. 72.06 B.P. 141 C. TOXICITY Toxic Effects Reported; SEV, TER Aquatic Toxicity Rating; TLm96: 100-10 ppm USE In the manufacture of plastics. ANALYTICAL SUMMARY Possibility of sample loss during freeze drying is unclear. Polymerizes readily in the presence of oxygen, which would affect quantitative results. LC characteristics are uncertain, but it may be strongly adsorptive. EVAPORATIVE LOSS POTENTIAL Freeze Drying; Moderate to High Evaporation from Solvent; Moderate The compound has been converted to the tetra-n- butylammonium salt prior to freeze drying, possibly to prevent polymerization or vaporization (Korte 1981). GC column temperatures commonly 115-120 degrees C. STABILITY Polymerizes readily in the presence of oxygen. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in; water, alcohol, ether, acetone, carbon disulfide, benzene. 161 Appendix Table 28. LC Uncertain characteristics. No references to organic normal-phase chromatography were found. Possibly too adsorptive for elution from silica gel with organic solvents. GC and GC/MS Amenable to conventional GC. Though derivatization as the benzyl derivative will reduce adsorptive tendencies (Korte 1981), analysis of the underivatized compound on an inert column is acceptable (Noble and Cerkawski 1973, Pileire 1978, Beaune et al. 1980, Muller and Baerns 1981) . 162 Appendix Table 29. CAS # 79-46-9 Propane, 2-nitro- STRUCTURE: CH3-C(N02)H-CH3 M.F. C3-H7-02-N M.W. 89.09 B.P. 120.3 C. TOXICITY Toxic Effects Reported: GIT, ETA Aquatic Toxicity Rating: TLm96: 100-10 ppm. USE Solvent for cellulose acetate, vinyl resin lacquers, synthetic rubbers, fats and oils; intermediate in organic synthesis. ANALYTICAL SUMMARY Possibly too volatile for conventional techniques. Low GC column temperatures result in better peak separation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Possibly High Evaporation from solvent: Moderate GC column temperatures occasionally of 50-60 degrees C. STABILITY Stable to conventional analytical procedures. A relatively stable compound once widely used as a solvent. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, chloroform, ethylene dichloride, many organic solvents LC Amenable to normal-phase. CC on silica gel with chloroform and ethylene dichloride (Scott and Kucera 1973) . 163 Appendix Table 29. GC and GC/MS Low column temperatures result in better peak separation. GC by conventional procedures with low column temperatures (Bethea and Adams 1962r Fear and Burnet 1965, Boneva et al. 1978, Jarosiewicz and Szychlinski 1980) . 164 Appendix Table 30. CAS # 80-08-0 Benzenamine, 4,4'-sulfonylbis- STRUCTURE: H.P. C12-H12-02-N2-S M.W. 248.30 M.P. 175-176 C. TOXICITY Toxic Effects Reported: SYS, RBC, CAR, NEO Status: NCI carcinogenesis bioassay positive for rat and negative for mouse. USE Hardening agent in the curing of epoxy resins; drug. ANALYTICAL SUMMARY High column temperatures are needed for sufficient volatility. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. Compound hydrolyzes slowly in humans (Burchfield et al. 1973) . SOLUBILITY Probably sufficiently soluble for trace analysis in most solvents of intermediate polarity. Soluble in: water (practically insoluble), methanol, ethanol, acetone, ethyl acetate, ethylene dichloride. 165 Appendix Table 30. LC Amenable to normal-phase. CC on silica gel with ethyl acetate (Gordon and Peters 1970, Murray et al. 1975). TLC on silica gel with chloroformsmethanol (Armasescu and Manda 1974) . GC and GC/MS High column temperatures (270-280 C.) are required for proper volatization, otherwise amenable to conventional procedures. Derivatization to the 4,4'-diiododiphenyl sulfone will increase detector sensitivity (Kazinik et al. 1971, Burchfield 1973) . 166 Appendix Table 31. CAS # 80-62-6 2-Propenoic acid, 2-methyl-, methyl ester STRUCTURE: CH2=C(CH3)-C02-CH3 M.F. C5-H8-02 M.W. 100.13 B.P. 100 C. TOXICITY Toxic Effects Reported: IRR, CNS, TER, ETA Review: Carcinogenic Determination: Indefinite Aquatic Toxicity Rating: TLm96: 1000-100 ppm USE In manufacture of acrylic films. ANALYTICAL SUMMARY Too volatile for conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Much of the compound probably would be lost during freeze drying. Could be retained during the evaporation of methylene chloride, hexane, and isopropanol, but probably would be lost during the evaporation of toluene and higher boiling solvents. STABILITY Stable to conventional analytical procedures. No reference to lability was found. SOLUBILITY Soluble in most solvents of intermediate polarity. Soluble in: water (slightly), alcohol, diethyl ether, acetone, methyl ethyl ketone, tetrahydrofuran, chlorinated and aromatic hydrocarbons. 167 Appendix Table 31. LC Amenable to normal-phase. HPLC on silica with hexane:diethyl ether (Aitzetmuller and Eckert 1978). GC and GC/MS Amenable to conventional techniques at low column temperatures. Low column temperatures are required for peak separation Gatriel and Mao 1965, Hollifield et al. 1980) . Amenable to conventional columns (Junk et al. 1974, Ashes and Haken 1975) . 168 Appendix Table 32. CAS * 81-88-9 Ethanaminium, N-(9-(2-carboxyphenyl-6-(diethylamino)-3H-xanth en-3- ylidene)-N-ethyl-f chloride STRUCTURE: (C2H5)2N COOH M.F. C28-H31-03-N2-C1 M.W.479 TOXICITY Toxic Effects Reported: ETA Review: Carcinogenic Determination: Animal Positive USE Dye; used as a tracer in oceanography. ANALYTICAL SUMMARY Too polar for conventional analysis. The use of a counter-ion renders the ion-pair soluble in nonpolar solvents and amenable to normal-phase separation, identification and quantification, with the potential for solid probe MS identification. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from solvent: Nil 169 Appendix Table 32. STABILITY Probably stable to air, water and light, though heat stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in water and alcohol, slightly soluble in HC1 and NaOH. LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 170 Appendix Table 33. CAS # 84-66-2 1,2-Benzenedicarboxylic acid, diethyl ether STRUCTURE: COO-C2H5 COO-C2H5 o M.F. C12-H14-04 M.W. 222.23 B.P. 295 C, TOXICITY Toxic Effects Reported: IRR, TER USE In the manufacture of celluloid; solvent for cellulose acetate in the manufacture of varnishes and dopes; fixative for perfumes. ANALYTICAL SUMMARY Readily amenable to conventional techniques, EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. A relatively stable compound. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in : alcohol, acetone, ether, benzene, and many other organic solvents. 171 Appendix Table 33. LC Amenable to normal-phase. HPLC on a normal-phase LiChrosorb NH2 column with isopropanol:hexane (Bieri et al. 1981). GC and GC/MS Readily amenable to conventional techniques. GC by conventional procedures (Mayer et al. 1972, Bloom 1972, Friocourt et al. 1979, Ehrhardt and Derenbach 1980) . 172 Appendix Table 34. CAS # 85-83-6 2-Naphthalenol, 1-[[2-methyl-4-[(2-methylphenyl)azo]phenyl]az o]- STRUCTURE; M.F. C24-H20-N4-0 M.W. 380.43 M.P. 181-188 C. TOXICITY Toxic Effects Reported: ETA Review: Carcinogenic Determination: Animal Positive USE Dyef fat stain, drug. ANALYTICAL SUMMARY Response to GC conditions are uncertain. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY No indication of lability was found, though few analytical references exist. Probably fairly stable to conditions of water, air, and light since it is used as a dye, though heat stability is uncertain. 173 Appendix Table 34. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: alcohol, acetone, phenol, chloroform, benzene, petrolatum, parafin, oils and fats. LC Amenable to normal-phase. TLC on silica gel with benzene, xylene, petroleum ether: acetone, petroleum etherschloroform (Rai 1971), and with acetone (Mathews 1975) . CC on Florisil with acetone (Whittle 1977). CC on silica with chloroformihexane (Ohnishi et al. 1977). GC Responses to GC conditions are uncertain. No references to GC were found. 174 Appendix Table 35. CAS # 86-30-6 Benzenamine, N-nitroso-N-phenyl- STRUCTURE: O H N M.F. C12-H10-O-N2 M.W. 198.24 TOXICITY Toxic Effects Reported: CAR, ETA Status: NCI Carcinogenesis Bioassay: Rat Positive Mouse Negative USE Bactericide for jet fuels; in developer solutions for dyes; acrylate polymerization inhibitor. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low Analytical technique has included evaporation of solution to dryness under vacuum (Yasuda 1963) . STABILITY Relatively stable to conventional analytical procedures, though it exhibits some thermal instability. 175 Appendix Table 35. SOLUBILITY Probably sufficiently soluble for trace analysis in solvents of intermediate polarity. Soluble in: methanol, acetone, n-pentane-2-propanol, methylene chloride (Drescher and Frank 1978). LC Amenable to normal-phase. HPLC on silica with n-pentane:2-Propanol, n-pentane: diethyl ether, and n-pentane:methanol (Vodicka et al. 1978) . GC and GC/MS Amenable to conventional techniques. Though some authors have reported thermal degradation into n-phenyl benzenamine (122-39-4) during GC (Palframan et al. 1973, Sopranetti and Reich 1977), other work indicates the "compound" is unstable on polar columns (Pensabene et al. 1972), and that it will quantitatively chromatograph on relatively.inert, nonpolar columns (Gough and Webb 1974, Sauter et al. 1981) . 176 Appendix Table 36. CAS * 87-29-6 Benzoic acid, 2-amino-3-phenyl-2-propenyl ester STRUCTURE: C02-CH2-CH=CH M.F. C16-H15-02-N M.W. 253.32 TOXICITY Toxic Effects Reported: NEO Review: Carcinogenic Determination: Animal Suspected ANALYTICAL SUMMARY Analytical parameters for this compound remain uncertain. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Uncertain Evaporation from Solvent: Uncertain Compound was used in perfume (Opdyke 1975), so it may be volatile despite its M.W. STABILITY Uncertain SOLUBILITY Uncertain Probably soluble in most conventional organic solvents of intermediate polarity since it has a somewhat sterically hindered amine function, and contains aromatic groups. LC Uncertain properties. Compound may not be strongly adsorptive to silica since the amine function is probably somewhat sterically 177 Appendix Table 36. hindered. GC and GC/MS Uncertain properties. May be volatile since it was used in perfume. Possible column adsorption by the amine function may be mitigated by steric hinderance. Heat stability is uncertain. 178 Appendix Table 37. CAS * 91-64-5 Benzopyran-2-one STRUCTURE 0 M.F. C9-H6-02 M.W. 146.14 M.P. 71 C. B.P. 297-299 C. TOXICITY Toxic Effects Reported: ETA Review: Carcinogenic Determination: Animal Positive USE In deodorants; in electroplating. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, ether, acetone, chloroform, pyrimidine, alkali. 179 Appendix Table 37. LC Amenable to normal-phase. TLC on polyamide-silica gel plates with diethyl ether: hexane (Chiang et al. 1972) . TLC on silica gel with 4-methyl-2-pentane:acetone: petroleum ether (Copenhauer and Carver 1964). CC on silica gel with chloroform, ethyl acetate Minamikawa et al. 1962) . GC and GC/MS Amenable to conventional techniques. GC by conventional procedures (Brown and Shyluk 1962, Furuya and Kojima 1967, Dekert 1972). 180 Appendix Table 38. CAS # 92-87-5 [1,1*-Biphenyl]-4,41-diamine STRUCTURE: H2 M.F. C12-H12-N2 M.W. 184.23 B.P. @400 C. TOXICITY Toxic Effects Reported: CAR, ETA Review: Carcinogenic Determination: Human Suspected Aquatic Toxicity Rating: TLm96: 10-1 ppm USE In the manufacture of benzidine dyes. ANALYTICAL SUMMARY Requires special solvent evaporation techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Unstable in methylene chloride, chloroform (Riggin and Howard 1979), and ether (Jenkins and Baird 1975) during solvent reduction unless solution is made up to 15-25% methanol prior to concentration. Somewhat heat labile to Kuderna-Danish concentration, but stable to rotary evaporation (with methanol present). SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water (slightly), alcohol, ether, methylene chloride, chloroform, benzene. 181 Appendix Table 38. LC Amenable to normal-phase. TLC on silica gel with benzene:acetone (Thielemann 1980), with methanol:acetone, toluene:pyridine:methylene chloride, toluene:pyridine:propanol(Petronio and Russo 1980), and with hexane:methyl-tert-butyl ether (Nowicki 1981). GC and GC/MS Amenable to conventional techniques. Derivatization as the heptafluorobutyryl derivative has been performed for ECD (Nony and Bowman 1980), though derivatization is unnecessary for conventional FID (Jenkins and Baird 1975, Schulze et al. 1978, Hurst et al. 1981) or for MS (Sauter et al. 1981) . 182 Appendix Table 39. CAS # 94-36-0 Peroxide, dibenzoyl STRUCTURE O 0 M.P. C14-H10-04 M.W. 242.22 M.P. 103-106 C. B.P. 249 C. TOXICITY Toxic Effects Reported: PUL Toxic Effects of Benzoic Acid: SKN USE Oxidizer in bleaching oils, flour, etc.; catalyst in plastics industry. ANALYTICAL SUMMARY Too heat labile for GC analysis.. Primary degradation product is benzoic acid which is amenable to conventional technique. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Beat labile, may explode when heated. Easily reduced - primarily to benzoic acid, a common natural product. 183 Appendix Table 39. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, chloroform, ether, acetone, carbon disulfide, toluene, benzene, olive oil. Benzoic acid is soluble in most conventional solvents of intermediate polarity. LC Amenable to normal-phase. TLC on silica gel with xylene, toluene, chlorobenzene, carbon tetrachloriderchloroform, petroleumsacetone (Kavcic et al. 1972) . TLC of benzoic acid on silica gel with chloroform:acetone, ethyl acetate, acetone, chloroform:methanol (Owen et al. 1978) . GC and GC/MS Too heat labile for GC conditions. Benzoic acid is readily amenable to GC (Karaz et al. 1974, Foster and Wainwright 1978). 184 Appendix Table 40. CAS # 95-53-4 Benzenamine, 2-methyl- STRUCTURE: CH3 Q •NH2 M.P. C7-H9-N M.W. 107.15 B.P. 200-202 C. TOXICITY Toxic Effects Reported: MMI, ETA, NEO Review: Carcinogenic Determination: Human Suspected USE Manufacture of dyes; printing textiles blue-black? making colors fast to acids. ANALYTICAL SUMMARY Sample volatization may occur during freeze drying. Some sample loss may occur by heat degradation in GC. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate to High Evaporation from Solvent: Low to Moderate GC column temperatures of 92-100 degrees C. occasionally used. STABILITY The a-specific rotation is unstable at melting point temperatures but the b-specific rotation is stable. 185 Appendix Table 40. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water (slightly), alcohol, ether, tetrahydrofuran (Protivova and Popsil 1974), carbon tetrachloride. Amenable to normal-phase. TLC on silica gel with methanol:acetone (Petroio and Russo 1980), and with xylene:methyl ethyl ketone:ethyl acetate (Srivastava and Chauhan 1980) . CC on silica gel with ethanol:heptanol (Wood and Anderson 1975) . HPLC on silica with chloroformscyclohexane (Young and McNair 1975) . GC and GC/MS Amenable to conventional techniques. Though derivatization as the permethyl derivative has been used to reduce adsorption (Chiavari and Guimanini 1981), many authors have shown polar columns to perform entirely satisfactorily (Pank et al. 1976, Ivanyuk and Kolvevskaya 1977, Dalene et al. 1981, Uppal et al. 1981), and one would expect highly inert columns to be adequate. 186 Appendix Table 41. CAS # 96-33-3 2-Propenoic acid, methyl ester STRUCTURE: CH2=CH-C02-CH3 M.F. C4-H6-02 M.W. 86.09 B.P. 80.5 C. TOXICITY Toxic Effects Reported: IRR Aquatic Toxicity Rating: TLm96: 1000-100 ppm USE In the manufacture of leather finishes, textile and paper coatings and plastic films. ANALYTICAL SUMMARY Too volatile for conventional techniques. Low column temperatures provide better separation of GC p e a k s . EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Could be retained during evaporation of methylene chloride and hexane, but probably would be lost during evaporation of isopropanol and higher boiling solvents. STABILITY Apparently stable to conventional analytical procedures. No reference to lability was found. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water (slightly), alcohol, ether, acetone, benzene. 187 Appendix Table 41. LC Probably amenable to normal-phase since it is not highly polar and does not contain highly reactive functional groups. GC and GC/MS Low column temperatures provide better separation of GC peaks. GC by conventional procedures (Denker and Wolf 1970, Ashes and Haken 1975, Brown and Purnell 1979, Dirinck et al. 1980) . 188 Appendix Table 42. CAS # 96-45-7 2-Imidazolidinethione STRUCTURE: s II HN'/ 'X NH VJ M.F. C3-H6-N2-S M.W. 102.17 M.P. 203-204 C. TOXICITY Toxic Effects Reported: TER, CAR Review: Carcinogenic Determination: Animal Positive USE Bactericide, fungicide, vulcanization accelerator, photographic bleach accelerator. ANALYTICAL SUMMARY Probably amenable to conventional technique, though solubility in some conventional solvents may be limiting. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Photosensitive, with primary degradation to glycine. Stable to other conventional analytical procedures. Rapid degradation in the environment to fundamental compounds (Rhodes 1977, Pease and Holt 1977). 189 Appendix Table 42. SOLUBILITY Probably sufficiently soluble for trace analysis in solvents of intermediate polarity since analytical work has been done with such solvents, despite handbook listings as insoluble. Soluble in: water, methanol, ethanol, ethylene glycol, pyridine. "Insoluble" in: acetone, ether, chloroform, benzene, ligroin. Solvents of intermediate polarity used in analysis: methylene chloride (Otto et al. 1977, Lazzarini et al. 1980), chloroform (Fishbein and Fawkes 1965, Kobayashi 1981), ethyl acetate (Hirvi et al. 1979), acetate:benzene (DiBello and Celon 1967) . LC Amenable to normal-phase. TLC on silica gel with chloroform (Fishbein and Fawkes 1965) and with ethanol:chloroform:benzene (Rhodes 1977) . CC on silica gel with chloroform:methanol (Kobayashi et al. 1981). HPLC on Spherisorb CN with hexane:ethanol (Farrington and Hopkins 1979). GC and GC/MS Amenable to conventional techniques. Derivatization as the s-butyl derivative (Haines and Alder 1973, Onley 1977) and as the perfluoroacyl derivative (Nash 1975) have been used to prevent additional "compound" from being formed from its precursor in the GC. However, other authors believe the additional "compound" produced by temperature effects is slight (Farrington and Hopkins 1979, Hirvi et al. 1979), and that non-derivatized analysis is more accurate since derivatization does not occur quantitatively (Otto et al. 1977) . 190 Appendix Table 43. CAS # 97-77-8 Thioperoxydicarbonic diamide, tetraethyl- STRUCTURE: (CH2H5)2N-CS-S-S-CS-N(C2H5)2 M.F. C6-H20-N2-S4 M.W. 296.54 M.P. 70 C TOXICITY Toxic Effects Reported: NEO Review: Carcinogenic Determination: Indefinite Status: NCI Carcinogenesis Bioassay: Negative USE Rubber accelerator, seed disinfectant, fungicide, drug. ANALYTICAL SUMMARY Amenable to conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low Evaporation to dryness under reduced pressure at 50 degrees C. (Davidson and Wilson 1979) . STABILITY Stable to conventional analytical procedures. No indication of lability was found. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, ether, acetone, chloroform, carbon disulfide, benzene. 191 Appendix Table 43. LC Amenable to normal-phase. HPLC on silica with heptane:tetrahydrofuran:methanol (Jensen and Faiman 1980), and with isopropanol:heptane (Pederson 1980). GC and GC/MS Amenable to conventional techniques. GC under conventional conditions (Baker et al. 1979, Davidson et al. 1979). 192 Appendix Table 44. CAS # 97-88-1 2-Propenoic acid, 2-methyl-, butyl ester STRUCTURE: CH2-C(CH3)-C02-(CH2)3-CH3 M.F. C8-H14-02 M.W. 142.22 B.P. 160 C. TOXICITY Toxic Effects Reported: TER Aquatic Toxicity Rating: TLm96: 1000-100 ppm. USE In polymers with synthetic and natural textiles. ANALYTICAL SUMMARY Potential volatization during freeze drying. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate to High. Evaporation from Solvent: Moderate GC column temperatures of 150 degrees C. commonly used. STABILITY Stable to conventional analytical procedures. No indication of lability was found. SOLUBILITY Probably sufficiently soluble for trace analysis in solvents of intermediate polarity. Soluble in: alcohol, acetone. The methyl ester is soluble in: methyl ethyl ketone, tetrahydrofuran, esters, chlorinated and aromatic hydrocarbons. LC Amenable to normal-phase. HPLC on silica with hexane:diethyl ether (Aitzetmuller and Ekert 1978) . 193 Appendix Table 44. GC and GC/MS Amenable to conventional techniques. GC analysis by conventional procedures (Germain and Haken 1969, Ashes and Haken 1971, Rygle 1980, Komrokova and Kuznetsova 1981). 194 Appendix Table 45. CAS # 98-51-1 Benzene, 1-(1,1-dimethylethyl)-4-methyl- STRUCTURE: CK3 I CH3-C-CH3 O CH3 M.F. C11-H16 M.W. @148 B.P. 169.12 TOXICITY Toxic Effects Reported: IRR, CNS USE By-product in isoprene rubber production. ANALYTICAL SUMMARY Probable evaporation during freeze drying. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: Moderate Recovered from ambient air over a cotton field (Hedin 1976) . GC column temperature of 65 degrees C. has been used. STABILITY Stable to conventional analytical procedures. No indication of lability was found. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: tetrahydrofuran, benzene. 195 Appendix Table 45. LC Should be amenable to normal-phase since it has no highly reactive functional groups nor is it strongly polar. GC and GC/MS Amenable to conventional techniques. GC analysis by conventional procedures (Sanders and Maynard 1968, Svob and Deur-Siftar 1974, Gerasimenko et al. 1981) . 196 Appendix Table 46. CAS # 98-83-9 Benzene, (1-methylethenyl)- STRUCTURE: H3C /CH2 6 M.F. C9-H10 M.W. 118.19 B.P. 165.5 C. TOXICITY Toxic Effects Reported: IRR Aquatic Toxicity Rating: TLm96: 100-10 ppm USE Occurs in coal distillates. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate Evaporation from Solvent: Moderate Sufficiently volatile to be quantitated in air (Ivanenko and Ivanova 1976, Shchukina and Aizvert 1977) , yet sufficiently nonvolatile to be retained in freeze dried sediment (Steinheimer et al. 1981) . STABILITY Stable to conventional analytical procedures. No indication of lability was found. 197 Appendix Table 46. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: methanol (Gawell and Larsson 1980), ethanol, isopropanol ether (Daukaeva 1978), chloroform (Ivannko and Ivanova 1976), methylene chloride (Bulkin et al. 1971), benzene (Gerasimenko et al. 1981). LC Amenable to normal-phase. CC on silica gel with isopropanol (Saltanova 1976) , with ethanol (Shchukina and Aizvert 1977), and on silica with tetrahydrofuran (Vyskyrebentsev et al. 1980) and methylene chloride (Steinheimer et al. 1981). GC and GC/MS Amenable to conventional techniques. GC by conventional procedures (Willis 1967, Rohrschneider and Jaeschke 1974, Tirgan and Sharifi-Sandjani 1980, Gerasimenko et al. 1981) . 198 Appendix Table 47. CAS # 100-37-8 Ethanol, 2-(diethylamino) STRUCTURE: (C2H5)2N-(CH2)2-OH M.F. C6-H15-N-0 M.W. 117.19 B.P. 163 C. TOXICITY Toxic Effects Reported: only LD values reported. USE As a catalyst for many polymerizing reactions. ANALYTICAL SUMMARY Possible volatization during freeze drying. Too polar for certain types of normal-phase. Derivatization is useful in reducing adsorption on GC columns. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate to High Evaporation from Solvent: Moderate Has been reported in the atmosphere (Pomazova and Volokhova 1975) . Due to its adsorptive nature, the potential for loss during freeze drying may be lower than is indicated. STABILITY Apparently stable to conventional techniques despite its polarity. Stable in HC1 (Wood and Nichols 1978). SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, acetone, ether, chloroform Verweij et al. 1972), benzene. 199 Appendix Table 47. LC Too polar for certain types of normal-phase. Unclear whether alcohol will elute the compound from silica gel. Immobile on silica gel with cyclohexane:chloroform: diethylamine and on alumina with chloroformsmethanol and with chloroform:diethylamine. Mobile on alumina with the addition of aqueous acids or base (Verweij et al. 1972). Polar organic solvents probably would elute this compound from silica gel modified with cyano or amino groups. GC and GC/MS Amenable to conventional techniques. Analysis without derivatization can be accomplished, but inert columns are needed (Ishizuka et al. 1964) . Trimethylsilyl derivatization (White and Swafford 1973) or derivatization with benzaldehyde to form dibenzylidene derivatives (Wood and Nichols 1978) helps alleviate adsorption problems. 200 Appendix Table 48. CAS # 100-42-5 Benzene, ethenyl- STRUCTURE: C6 H5-CH=CH2 M.F. C8-H8 M.W. 104.14 B.P. 145.2 C. TOXICITY Toxic Effects Reported: IRRf CNS, ETA Status: NCI Carcinogenesis Bioassay: Mouse Indefinite Rat Negative Aquatic Toxicity Rating: TLm96: 100-10ppm USE In the manufacture of plastics, synthetic rubber, and resins. ANALYTICAL SUMMARY Probably too volatile for freeze drying. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: Moderate Standard analytical procedure usually involves either wet extraction, vapor stripping, or headspace analysis. GC column temperature of 60 degrees C. has been used. STABILITY Stable to conventional analytical procedures. A relatively stable compound. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: alcohol, ether, acetone, carbon disulfide, toluene, benzene, cyclohexane (Tweet and Miller 1963), cyclohexanone (Wilkinson et al. 1964) . 201 Appendix Table 48. LC Amenable to normal-phase. CC on silica gel with benzene:chloroform (Kohlschuetter et al. 1966). GC and GC/MS Amenable to conventional techniques. Conventional procedures, generally at moderate temperatures with FID (Liebich and Woll 1977, Hites et al. 1979, Gilbert and Shepherd 1981, Heydanek and McGorrin 1981, Varner and Breder 1981) . 202 Appendix Table 49. CAS # 100-74-3 Morpholine, 4-ethyl- STRUCTURE: N I CH2 CH3 M.F. C6-H13-0-N M.W. 115.20 B.P. 138-139 C. TOXICITY Toxic Effects Reported: IRR USE As a catalyst in the manuf. of polyisocyanurate and polyurethane foams. ANALYTICAL SUMMARY Uncertain, though possibly amenable to conventional technique. Volatility, stability, LC, and GC properties remain uncertain. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate to High Evaporation from Solvent: Moderate STABILITY Uncertain Probably stable to conventional GC analysis. Since there are no highly reactive functional groups, it may be fairly stable to conventional analysis, but evidence is limited. 203 Appendix Table 49. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, ether, acetone, benzene. Probably soluble in chlorinated hydrocarbons since the polar morpholine is soluble in chloroform (Brock and Louth 1955) , and the instant compound (100-74-3) should be less polar than morpholine. LC Probably amenable to normal-phase since the compound may not be highly polar and apparently does not contain highly reactive functional groups. The relatively similar benzothiazolylthio N-substituted morpholine (Table 56) has been shown to be amenable to normal-phase. GC and GC/MS Uncertain, though probably amenable to conventional analytical techniques. GC of 4-methyl morpholine on a highly polar column (Puerst and Mannetslaetter 1968). The successful GC of morpholine without derivatization (Tombropoulos 1979, Ramsey et al. 1980) supports the limited evidence that the instant compound (100-74-3) would not cause severe adsorption problems on inert columns. 204 Appendix Table 50. CAS # 101-14-4 Benzenamine, 4,4'-methylenebis[2-chloro- STRUCTURE C l H2N chhCS~NH2 C l M.F. C13-H12-N2-C12 M.W. 267.17 M.P. 120 C TOXICITY Toxic Effects Reported: CAR, ETA Review: Carcinogenic Determination: Animal Positive USE Cross-linking agent for epoxy resins, vulcanizing agent for urethane rubber. ANALYTICAL SUMMARY Amenable to conventional techniques. Derivatization as the trifluoroacetyl derivative is helpful for accurate GC quantitation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Possibly moderate This compound has a significant vapor pressure slightly above the melting point. STABILITY Tendency for slight decomposition during GC (Rapport and Morales 1979), otherwise stable to conventional procedures. 205 Appendix Table 50. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: methanol, ether. 4 ,4'-methylenebisbenzenamine is very soluble in water, alcohol and benzene, and soluble in chloroform. LC Amenable to normal-phase. TLC on silica gel with benzene:acetone (Lesiak and Orlikowska 1973), and with heptane:acetone (Leonova and Ushakova 1977) . CC on Gas Chrom S with acetone (Sawicki 1975) and on Tenax GC and silica gel with methanol (Purnell and Warwick 1980). GC and GC/MS Amenable to conventional techniques. Reasonable accuracy can be obtained by conventional technique Sawicki 1975, Yasuda 1975, Perelekhova 1980), though trifluroacetyl derivatives provide more accurate results by preventing slight solute degradation (Linch et al. 1971, Ebell et al. 1981). 206 Appendix Table 5i. CAS # 101-73-5 Benzenamine, 4-(1-methylethoxy)-N-phenyl- STRUCTURE: M.F. C15-H17-0-N M.W. 227.33 TOXICITY Toxic Effects Reported: NEO ANALYTICAL SUMMARY Probably amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Relatively stable to conventional techniques. Slowly oxidized at 100 degrees C. (Tsurugi et al. 1971). SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in acetone. Diphenylamine, a similar compound, is soluble in: alcohol, ether, carbon disulphide, chloroform, toluene, benzene. 207 Appendix Table 51. LC Probably readily amenable to normal-phase. No information on LC was found in the literature. Adsorption probably would not be a problem since diphenylamine is amenable to normal-phase. TLC of diphenylamine on silica gel with benzene, toluene, and chloroform (Belomestnova 1981), also with methanol: acetone, toluene:pyridine:acetone, toluene:pyridine: chloroform (Petronio and Russo 1980) . GC and GC/MS Amenable to conventional GC (Tsurugi et al. 1971) . Diphenylamine is also, amenable to conventional GC (Luke and Cossens 1980, Kinberger et al. 1981) . 208 Appendix Table 52. CAS # 101-77-9 Benzenamine, 4,41-methylenebis- STRUCTURE H2N- H2 M.F. C13-H14-N2 M.W. 198.26 M.P. 91.5-92 C. B.P. 398-399 C. TOXICITY Toxic Effects Reported: SYS, ETA Review: Carcinogenic Determination: Indefinite USE In the preparation of azo dyes; corrosion inhibitor. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Probably stable to conventional analytical procedures. No indication of lability was found. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, tetrahydrofuran (Bauer and Richter 1981), chloroform, benzene. 209 Appendix Table 52. LC Amenable to normal-phase. TLC on silica gel with acetone:benzenescyclohexane Michonska-Cebromska and Wencel 1973), with benzene: acetone (Lesiak et al. 1976), and with chloroform: methanol (Dukhovnaya and Yun 1981) . CC on microporous silica with chloroform (Young and McNair 1976) . GC and GC/MS Amenable to conventional GC techniques. GC by conventional procedures (LiGotti et al. 1970, Kazinak et al. 1971, Braun and Lee 1972, Krasnova et al. 1977) . 210 Appendix Table 53. CAS # 101-83-7 Cyclohexanamine, N-cyclohexyl- STRUCTURE: (C6-Hll)2NH M.F. C12-H23-N M.W. 181.31 B.P. 255.8 C. TOXICITY Toxic Effects Reported: ETA Review: Carcinogenic Determination: Indefinite USE In manufacture of insectides, plasticizers, corrosion inhibitors, rubber chemicals, dyestuffs, emulsifying agents, dry cleaning soaps, acid gas absorbents, etc. ANALYTICAL SUMMARY Adsorption in LC may be a problem. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Probably relatively stable to conventional analytical procedures. No reference to lability was found. A strong base which readily forms adducts with solvents. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: water, ether, chloroform, and the usual organic solvents. 211 Appendix Table 53. LC Adsorption may be a problem in normal-phase since it is a strong base. No references to organic solvent chromatography on silica gel were found. GC and GC/MS Probably amenable to conventional analytical techniques. Adsorption problems such as tailing may be a problem, though the available literature is not clear on this. Derivatization as the 4'-nitroazobenzene-4-carboxamide for GC has been reported (Neurath and Luttich 1968). An analysis without derivatization has been accomplished on a DCMS treated capillary column treated with KOH in Carbowax 20M (Caddy et al. 1973). Apparently, the analysis of the underivatized compound on a conventional packed column has been successful (Znamenskaya et al. 1974). 212 Appendix Table 54. CAS # 102-77-2 Morpholine, 4-(2-benzothiazolythio)- STRUCTURE A“\ f 0 ( \___ / M.F. C11-H12-0-N-S2 M.W. 252.37 TOXICITY Toxic Effects Reported: NEO USE Vulcanization accelerator. ANALYTICAL SUMMARY Amenable to conventional techniques. Special detector is useful. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. It is used in the rubber industry as an accelerator which may indicate a certain reactivity. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: acetonitrile and hexane (Eto et al. 1980), benzene n-heptane:ethyl acetate and acetone (Sullivan et al. 1976) . 213 Appendix Table 54. LC Amenable to normal-phase. TLC on silica gel with benzene, benzene:ethyl acetate, heptanesethyl acetate, acetone (Sullivan et al. 1976). GC and GC/MS Amenable to conventional GC analysis. FPD is particularly sensitive with the optical filter at 394 nm (Eto et al. 1980) . 214 Appendix Table 55. CAS # 103-23-1 Hexanedioic acid, bis(2-ethylhexyl)ester STRUCTURE: C4H9-CH(C2H5)-CH2-02C-(CH2)4-C02CH2-CH(C2H5)-C4H9 M.P. C22-H42-04 M.W. 370.64 B.P. 214 C. TOXICITY Toxic Effects Reported: only LD data reported USE Plasticizer in PVC. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate Evaporation from Solvent: Moderate STABILITY Stable to conventional analytical procedures. No indication of lability was found. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: alcohol, ether, acetone, methylene chloride, tetrahydrofuran, acetic acid. LC Amenable to normal-phase. TLC on silica gel with methylene chloride, petroleum ether:diethyl ether, isooctane:ethyl acetate, methylene chloride:chloroform:hexane:ethyl acetate (Bloom 1975) . 215 Appendix Table 55. GC and GC/MS Amenable to conventional procedures. GC by conventional FID procedures (Krishen 1971, Hites and Biemann 1975, Sheldon and Hites 1978, Ogino et al. 1979). 216 Appendix Table 56. CAS # 105-60-2 2H-Azepin-2-one, hexahydro STRUCTURE aN M.F. C6-H11-0-N M.W. 113.16 M.P. 70 C. B.P. 139 C. TOXICITY Toxic Effects Reported: IRR USE Manufacture of polyamide fibers. ANALYTICAL SUMMARY Amenable to conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate Evaporation from Solvent: Moderate Apparently sufficiently polar to prevent ease of volatization from substrates. GC column temperatures commonly 180-200 degrees C. STABILITY Stable to conventional analytical procedures. No indication of lability was found. Degradation in soil after 5-7 days (Dodolina and Sergienko 1977) . 217 Appendix Table 56. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, ether, chloroform, and other chlorinated hydrocarbons, cyclohexane, benzene, petroleum fractions. LC Amenable to normal-phase. TLC on silica gel with chloroform:acetone (Agafonova and Strigina 1979), and on alumina with chloroform:acetone (Tsendrovskaya et al. 1971). GC and GC/MS Amenable to conventional GC techniques. GC by conventional FID procedures (Ongemach and Moody 1967, Fritz et al. 1969, Fedotova et al. 1978, Yankov et al. 1978, Hamaguchi et al. 1979). 218 Appendix Table 57. CAS # 108-20-3 Propane, 2,2'-oxybis STRUCTURE: (CH3)2CH-0-CH(CH3)2 M.F. C6-H14-0 M.W. 102.17 B.P. 68-69 C. TOXICITY Toxic Effects Reported: IRR Aquatic Toxicity Rating: TLm96: 1000-100 ppm USE Solvent ANALYTICAL SUMMARY Too volatile for conventional techniques. Low column temperatures provide better separation of GC p eaks. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Could be retained during evaporation of methylene chloride, but probably would be lost during evaporation of hexane and higher boiling solvents. STABILITY Apparently stable to conventional procedures as a trace compound. As a pure solution, it tends to form peroxides and may explode on shaking. No reference to lability as a trace compound was found. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water (slightly), alcohol, ether, and acetone. 219 Appendix Table 57. LC Probably amenable to normal-phase. GC and GC/MS Low column temperatures provide better peak separation. GC by conventional procedures with low column temperatures (Bezus et al. 1974, Chastrette and Tagand 1974, Korol et al. 1980, Jonsson and Mathiasson 1981). 220 Appendix Table 58. CAS # 108-67-8 Benzene, 1,3,5,-trimethyl- STRUCTURE: CH3 H3C M.F. C9-H12 M.W. 120.19 B.P. 164.7 C. TOXICITY Toxic Effects Reported: CNS USE Aluminum electrodeposition baths, lubricating oils. ANALYTICAL SUMMARY Possible evaporative loss during freeze drying. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate to High Evaporation from Solvent: Moderate STABILITY Stable to conventional analytical procedures. No indication of lability was found. No highly reactive functional groups are present. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: alcohol, diethyl ether, petroleum ether, acetone, carbon tetrachloride, benzene. 221 Appendix Table 58. LC Amenable to normal-phase. HPLC on silica gel with n-pentane (Kuras et al. 1980). GC and GC/MS Amenable to conventional techniques. GC by conventional procedures (Chlesler et al. 1978, Hester and Meyer 1979, Kalashnikova et al. 1979, Nabivach and Kirilenko 1980) . 222 Appendix Table 59. CAS # 112-62-9 9-Octadecenoic acid (Z)-, methyl ester STRUCTURE: CH3-(CH2)7-CH=CH-(CH2)7-COO-CH3 M.F. C19-H36-02 M.W. 296.55 B.P. (20 torr) 218.5 C. TOXICITY Toxic Effects Reported: ETA USE In manufacture of oils and soft soap; in polishing compounds for waterproofing textiles; in driers; thickening lubricating oils. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. Tends to separate out in the lipid fraction. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. No indication of lability was found. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. LC Amenable to normal-phase. TLC on silica gel with benzene:ethyl acetate (Seher and Josephs 1969) . CC on silica gel impregnated with silver nitrate and eluted with toluene (Ackman and Hooper 1974). 223 Appendix Table 59. GC and GC/MS Amenable to conventional GC techniques. GC by conventional procedures with FID (Ottenstein et al. 1976r Ackman and Sebedio 1978, Karasek et al. 1978, Hockel et al. 1980, Kobayshi 1980), and by GC/MS (Vine 1980) . 224 Appendix Table 60. CAS # 117-84-0 1,2-Benzenedicarboxylic acid, dioctyl ester STRUCTURE: ,C02-CH2-(CH2)6-CH3 ''C02-CH2- (CH2) 6-CH3 M.F. C24-H38-04 M.W. 390.62 TOXICITY Toxic Effects Reported: TER USE In aerosol resins. ANALYTICAL SUMMARY Amenable to conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low Techniques have included extraction from freeze dried sediment and evaporation of solvent to dryness (Brownlee and Strachan 1976, Fox 1976). STABILITY Stable to conventional analytical procedures. Recovery from water 5 km from release site (Brownlee and Strachan 1976) and from sediment (Hites et al. 1979) indicates some environmental stability. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: acetone, methylene chloride, chloroform, toluene (Komaita et al. 1975), cyclohexane, hexane. 225 Appendix Table 60, LC Amenable to normal-phase, TLC on silica gel with methylene chlorider chloroform: diethylamine, cyclohexanesdiethylamine (Bloom 1972), and with hexane:diethyl ether (Kaneshima et al. 1974). GC and GC/MS Amenable to conventional GC techniques. GC by conventional procedures with FID (Brownlee and Strachen 1976, Fox 1976, Betty and Karasek 1978, Grenier-Loustalot et al. 1978, Sauter et al. 1981). 226 Appendix Table 61. CAS # 119-93-7 [1,1*-Biphenyl]-4,4'-diamine, 3,3'-dimethyl- STRUCTURE: H3C CH3 M.F. C14-H16-N2 M.W. 212.32 M.P. 131-132 C. TOXICITY Toxic Effects Reported: CAR, ETA Review: Carcinogenic Determination: Animal Positive USE In color test strips for clinical analysis. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. No indication of lability was found. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water (slightly), alcohol, ether, benzene. 227 Appendix Table 61. LC Amenable to normal-phase. TLC on silica gel with ethyl ether:cyclohexane (Frank and Koudelkova 1979), and with methanol:acetone, toluene: pyridine:acetone, toluene:pyridine:methylene chloride (Petronio and Russo 1980) . GC and GC/MS Probably amenable to conventional techniques. Derivatization with fluorinating agents for increased ECD sensitivity has been performed (Bowman 1980, Nony and Bowman 1978, Lowrey et al. 1980), though it probably is not necessary for FID, since similar substances such as benzidine (Table 40), and 3,3'-dichlorobenzidene (Nony and Bowman 1978) do not require derivatization. 228 Appendix Table 62. CAS # 120-93-4 2-Imidazolidinone o STRUCTURE: " HN NH M.P. C3-H6-N2-0 M.W. 86.10 M.P. 131 C. TOXICITY Toxic Effects Reported: CAR USE Manufacture of high polymers, finishing agents for textiles and leather, plasticizers, lacquers, adhesives, insecticides. ANALYTICAL SUMMARY Derivatization is required for GC. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. No indication of lability was found. Nitrosation in animals to nitrosoethyleneurea occurs readily (Sander 1972), and it is carcinogenic in rats (Druckrey et al. 1967). SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, acetone, ether (slightly), chloroform, benzene. 229 Appendix Table 62. LC Amenable to normal-phase. TLC on silica gel with ethyl acetatesmethanol (DiBello and Celon 1967) , with ethyl acetateschloroform (Jordan and Neal 1979), and with chloroformsmethanol (Iverson et al. 1980) . GC and GC/MS Derivatization is required for GC. The pentafluorobenzamide derivative provides sufficient volatility for analysis (Newsome 1978) . 230 Appendix Table 63. CAS # 123-31-9 1,4-benzenediol STRUCTURE OH OH M.F. C6-H6-02 M.W. 110.11 M.P. 170-171 C B.P. 285-287 C. TOXICITY Toxic Effects Reported: Only LD data reported. Review: Carcinogenic Determination: Indefinite USE Photographic processing; antioxidant. ANALYTICAL SUMMARY Amenable to conventional techniques. Analysis of sample should not be delayed. Oxidizes to quinone, which is also amenable to conventional analysis. Sum of quinone and hydroquinone should be taken into account. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Probably sufficiently stable for conventional analysis. Oxidizes in air to quinone, which has received a carcinogenic rating of indeterminate. Oxidation may cause quantitative losses if the sample is stored too long. 231 Appendix Table 63. ’ SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, acetone, ether, methylene chloride, benzene (slightly). Extraction is most efficient from acidified water with methylene chloride (Hunt et al. 1977). Quinone is also probably sufficiently soluble in solvents of intermediate polarity. LC Amenable to normal-phase. TLC on silica gel with benzene:acetone (Thielemann 1973), with benzene:methanol (Danch and Chmielowski 1974), and with benzene:methanol, benzene:ethyl acetate (Smith et al. 1974) . Quinone is also amenable to normal-phase. TLC of quinone on silica with chloroform:hexane (Aue and Wickramanayake 1980) . GC and GC/MS Amenable to conventional techniques. Though derivatization as the trimethylsilyl derivative will prevent tailing (Severson et al. 1980), conventional inert columns will do the same (Kusy 1971, Hunt et al., Radecki et al. 1979). Quinone has also been shown amenable to conventional GC techniques (Moeckel and Veltwish 1978), though derivatization is more accurate as either the bistrifluoroacetate or as the bistrimethylsilyl ether (Roeper and Heyns 1977) . 232 Appendix Table 64. CAS # 123-72-8 Butanal STRUCTURE: CH3-CH2-CH2-CHO M.F. C4-H8-0 M.W. 72.10 B.P. 74.8 C. TOXICITY Toxic Effects Reported: IRR Aquatic Toxicity Rating: TLm96: 10-1 ppm. USE Manufacture of rubber accelerators, synthetic resins, plasticizers. ANALYTICAL SUMMARY Too volatile for conventional techniques. Low column temperatures provide better GC peak separation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Compound could be retained during evaporation of methylene chloride, and probably hexane, but would be lost during evaporation of isopropanol and higher boiling solvents. STABILITY Stable to conventional analytical procedures. No reference to lability was found. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: water, ethanol, ether, ethyl acetate, acetone, chloroform, toluene, benzene, and many other solvents. 233 Appendix Table 64. LC Amenable to normal-phase. CC on silica gel with MeOH (Magin 1980) . GC and GC/MS Low column temperatures provide better peak separation. Derivatization as the benzyloxime derivative has been used to reduce tailing (Magin 1980), though GC has been successful with polar columns (Ryan 1980, Urano et al. 1981) , and by more conventional procedures (Hoshika 1981) . 234 Appendix Table 65. CAS # 123-86-4 Acetic acid, butyl ester STRUCTURE: CH3-C00-(CH2)3-CH3 M.F. C6-H12-02 M.W. 116.16 B.P. 125-126 C. TOXICITY Toxic Effects Reported: IRR Aquatic Toxicity Rating: TLm96: 100-10 ppm USE Manufacture of lacquer, artificial leather, photographic films, plastics, safety glass. ANALYTICAL SUMMARY Probably too volatile for freeze drying. Low GC column temperatures provide better peak separation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: Moderate Often exists as an atmospheric contaminant (Brown and Purnell 1979, Barnes et al. 1981) . GC column temperatures of 70 and 81 degrees C. have been used. STABILITY Stable to conventional analytical procedures. Often used as a solvent. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: water (slightly), alcohol, ether, acetone, carbon disulfide, toluene, most hydrocarbons. 235 Appendix Table 65. LC Amenable to normal-phase. This compound does not contain highly reactive functional groups, and is not strongly polar. TLC on silica gel as the eluant (Home and Dudley 1981, al. 1981) . GC and GC/MS Low column temperatures provide better peak separation, otherwise amenable to conventional techniques. GC by conventional procedures with TCD (Chastrette and Tagand 1974) and FID (Yabumoto et al. 1977, Brown and Purnell 1979, Calixto and Raso 1981) . 236 Appendix Table 66. CAS # 126-99-8 1,3-Butadiene, 2-chloro- STRUCTURE: CH2=C(Cl)CH=CH2 M.F. C4-H5-C1 M.W. 88.54 B.P. 59.4 C. TOXICITY Toxic Effects Reported: Only LD data reported. Review: Carcinogenic Determination: Human Suspected Aquatic Toxicity Rating: TLm96: 100-10 ppm USE Common by-product in rubber and plastics industry. ANALYTICAL SUMMARY Too volatile for conventional techniques. Low column temperatures provide better GC peak separation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Solvent Evaporation: High Could be retained during evaporation of methylene chloride, but probably would be lost during evaporation hexane and higher boiling solvents. STABILITY Compound is stable to conventional analytical procedures. No indication of lability was found. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water (slightly), ether, acetone, benzene, and other organic solvents. LC Amenable to normal-phase. 237 Appendix Table 66. GC and GC/MS Low column temperatures provide better peak separation, otherwise readily amenable to conventional techniques (Sassu et al. 1968, Gizhlaryan et al, 1976, Casper 1977, Shabel and Caspar 1980). 238 Appendix Table 67. CAS # 127-19-5 Acetamide, N,N-dimethyl- STRUCTURE: CH3-CO-N(CH3)2 M.F. C4-H9-0-N M.W. 87.12 B.P. 163-165 C. TOXICITY Toxic Effects Reported: SYS, TER USE Solvent for many organic reactions and in industrial applications. ANALYTICAL SUMMARY Possible evaporative loss during freeze drying. Adsorption in LC may be a problem. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate to High Evaporation from Solvent: Moderate GC column temperature of 50 degrees C. has been used. STABILITY Probably stable to conventional analytical techniques. No indication of lability was found. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, acetone, ether, chloroform, benzene, most organic solvents. LC Adsorption may be a problem. No references to normal-phase could be found. 239 Appendix Table 67. GC and GC/MS Amenable to conventional techniques. GC by conventional procedures (Butcher 1977, Sergeeva and Agranonskii 1978, Gladkov et al. 1980, Saint-Jalm and Moree-Testa 1980) . 240 Appendix Table 68. CAS # 127-47-9 Retinol acetate STRUCTURE CH3 CH3 CH3 Si-CH=CH-C=CH-CH=CH-C=CH-CH2-0-C-CH3I CH3 CII3 M.F. C22-H32-02 M.W. 328.54 M.P. 57-58 TOXICITY Toxic Effects Reported: TER USE Vitamin supplement. ANALYTICAL SUMMARY Unstable to light or oxygen. Derivatization is required to prevent decomposition in GC. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Unstable to light, oxygen and heat (Fenton et al. 1973) . SOLUBILITY Probably sufficienly soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: methanol, ethanol, hexane:diethyl ether, chloroform (Holasova and Blattna 1976), and hexane (Wollard and Wollard 1981) . Appendix Table 68. LC Amenable to normal-phase. HPLC on silica with heptane:diisopropyl ether (Aitzetmueller et al. 1979). TLC on silica gel with hexanesdiethyl ether (Parizkova and Blattna 1980) . GC and GC/MS Too heat labile for GC analysis. Requires hydrogenation with platnium oxide to the stable perhydro-retinol derivative (Fenton et al. 1973). 242 Appendix Table 69. CAS I 128-37-0 Phenol, 2,6-bis(1,1-diroethylethy1)-4-methyl- STRUCTURE ,C (CH3) 3 H3C- ■OH C (CH3) 3 M.F. C15-H24-0 M.W. 220.39 M.P. 70 C. B.P. 265 C. TOXICITY Toxic Effects Reported: Only LD data reported. Status: NCI Carcinogenesis Bioassay Negative. USE Antioxidant for food, animal feed, synthetic rubbers, plastics animal and vegetable oils, and soaps; in paint and ink. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvents: Low STABILITY Stable to conventional analytical procedures. Easily degraded in model ecosystems (Inui et al. 1979). SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, petroleum ether, chloroform, 243 Appendix Table 69. toluene, benzene, most hydrocarbon solvents. LC Amenable to normal-phase. TLC on silica gel with hexane (Lipshtein et al. 1973). TLC on alumina-silica gel with chloroform (Miles 1974). GC and GC/MS Amenable to conventional techniques. GC by conventional technique (Radecki and Grzybowski 1978, Ramsey et al. 1980, Spitz 1980, Sedea and Toninelli 1981) . 244 Appendix Table 70. CAS # 128-44-9 l,2-Benzisothiazol-3(2H)-onef 1,1-dioxide, sodium salt STRUCTURE: O M.F. C7-H4-03-N-S-Na M.W. 205.16 M.P. 228-230 C. TOXICITY Toxic Effects Reported: NEO, ETA Review: Carcinogenic Determination: Animal Positive USE To stabilize drugs containing a phenothiazine nucleus; sweetner in foods. ANALYTICAL SUMMARY Organic extraction from acidic aqueous solution is required. Derivatization is required for GC. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Low STABILITY Stable to conventional analytical procedures. Not metabolized by humans (Hartvig et al. 1978) . A stable ionic compound in aqueous solution. 245 Appendix Table 70. SOLUBILITY Insoluble, as the salt, in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and hot alcohol. Extractable, as the imide, from aqueous acidic solution with chloroform (Hussein et al. 1976, Okamoto 1973) or ether (Li and Hsao 1980) . LC The salt form is not amenable to normal-phase, though the imide is amenable. TLC of the imide on silica gel with acetone and chloroform:methanol (Owen et al. 1978). GC and GC/MS The ionic sodium salt will not vaporize in the GC. The imide form is derivatized to provide sufficient volatility (Szinai and Roy 1976) , as either the methyl derivative (Conacher and O'Brien 1970, Hartvig et al. 1978 Yamamoto et al. 1979), or the trimethylsilyl derivative (Ratchik and Viswanathan 1975, Ito al. 1976). 246 Appendix Table 71. CAS * 129-17-9 Ethanaminium, N-[4-[[4-(diethylamino)phenyl](2,4- disulfophenyl)methylene]-2,5-cyclohexadien-l-ylidene]-N -ethyl-hydroxide, inner salt, sodium salt STRUCTURE: Na-03S S03 ,C- =N (C2H5)2 (C2H5) 2N M.F. C27-H31-06-N2-S2-Na M.W. 566.7 TOXICITY Toxic Effects: NEO, CAR, ETA Review: Carcinogenic Determination: Animal Positive USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. 247 Appendix Table 71. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica gel. Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 248 Appendix Table 72. CAS # 135-20-6 Benzenamine, N-hydroxy-N-nitroso-ammonium salt STRUCTURE ^NO •N NONH4 M.F. C6-H9-02-N3 M.P. 163-164 C TOXICITY Toxic Effects Reported: ETA, CAR Status: NCI Carcinogenesis Bioassay: Positive for Mouse and Rat USE As a reagent to separate Cu and Fe from other metals; to precipitate metals from solution. ANALYTICAL SUMMARY Exists environmentally as chelates with metals. The metal chelate is nonvolatile at GC temperatures. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil Environmental samples will contain the compound as the nonvolatile metal chelate. STABILITY Basically stable to conventional analytical techniques. Exchange reactions with chelated metals occur in aqueous organic solutions (Zolotov et al. 1969) Unstable in acidic solution and upon drying from acidic solution if the acid remains in contact. 249 Appendix Table 72. SOLUBILITY Possibly sufficiently soluble for trace analysis, as the metal chelate, in conventional solvents of intermediate polarity. Highly soluble in polar solvents such as water and alcohol. Soluble in chloroform as the acid (Hilderbrand and Pickett 1975), also in chloroform as the chelate with many metals (Stary and Smizanska 1963, Kim 1963). LC Probably amenable to normal-phase as the metal chelate. TLC on silica gel mixed with EDTA apparently has been performed (Nishimoto and Toyoshima 1965) . GC and GC/MS Not volatile, at GC temperatures, as the environmentally present metal chelate. Requires temperatures above 1000 degrees C. (Hilderbrand and Pickett 1975). No references to the GC of the acid form were found. 250 » Appendix Table 73. CAS # 135-88-6 2-Naphthalenamine, N-phenyl- H I M.F. C16-H13-N M.W. 219.30 M.P. 108 C. TOXICITY Toxic Effects Reported: NEO Review: Carcinogenic Determination: Animal Suspected USE Antioxidant for rubber and grease. ANALYTICAL SUMMARY Amenable to conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low Sample in solvent can be evaporated to dryness in a partial vacuum (Protivova et al. 1974) . STABILITY Stable to conventional analytical techniques. No indication of lability was found. It is used as an antioxidant in rubber. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: alcohol, acetone, benzene:hexane, benzene: diethyl ether, iso-octane. 251 Appendix Table 73. LC Amenable to normal-phase. HPLC on a cyanopropyl column with iso-octane (Majors 1970) . TLC on silica gel with benzene:hexanef benzene:diethyl ether, benzene:ethanol (Protivova et al. 1974) . GC and GC/MS Amenable to conventional techniques. GC by conventional procedures with ECD (Vieth et al. 1979), and with FID (Lukyanova et al. 1976, Ivanenko and Ivanova 1977, Styskin et al. 1978) . 252 Appendix Table 74. CAS # 136-23-2 Zinc, bis(dibutylcarbamodithioato-S,S')- STRUCTURE: [CH3-(CH2)3]2N-CS-S-Zn-S-CS-N[(CH2)3-CH3]2 M.F. C18-H36-N2-S4-Zn M.W. 474 TOXICITY Toxic Effects Reported: ETA USE Antioxidant for lubricating oils, heat stabilizer for fluoropolymers, vulcanization accelerator. ANALYTICAL SUMMARY Basically amenable to conventional techniques. Relatively high GC column temperatures are required. GC injection port temperatures should not greatly exceed column temperatures. Ligand substitution easily occurs in the GC column. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Metal chelates are subject to thermal degradation at high temperatures (Masaryk et al. 1975, Sucre and Jennings 1980) . SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Resonably soluble in many organic solvents, especially chlorinated hydrocarbons. 253 Appendix Table 74. LC Amenable to normal-phase. HPLC on silica with chloroform, methylene chloride: n-pentane, methylene chloride:carbon tetrachloride, chloroform:cyclohexane (Lehotay et al. 1979). GC and GC/MS Basically amenable to conventional techniques, though the tendencies exist for ligand substitution and for thermal degradation. Injection port and column temperatures must be a compromise between those sufficient for rapid volatization yet below those causing thermal degradation, approximately 240-275 degrees C. (Krupcik et al. 1979, Riekkola 1980) . Accurate qualitative and quantitative results are more difficult with environmental samples due to the ease with which ligands exchange between metal bisdialkyldithiocarbamate complexes in the column. For example, ligand exchange will result in a third analytical peak when only two complexes occur in the sample (Lehotay et al. 1979, Liska et al. 1979). 254 Appendix Table 75. CAS * 140-11-4 Acetic acid, phenylmethyl ester STRUCTURE: CH2-C02-CH3 H.F. C9-H10-O2 M.W. 150.17 B.P. 213-218 C. TOXICITY Toxic Effects Reported: IRR USE In perfumery; solvent for cellulose acetate and nitrate. ANALYTICAL SUMMARY Amenable to conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Moderate Evaporation from Solvent: Low STABILITY Stable to conventional analytical techniques. This class of esters has been used as the derivatized form of low molecular weight organic acids for GC (Korte 1981) . SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: alcohol, ether, acetone, chloroform (Dakshinamorty and Rao 1958), toluene (Pavlova et al. 1972), hexane (Manzini and Crescenzi 1977), benzene. 255 Appendix Table 75. LC Probably amenable to normal-phase. A relatively nonpolar compound without strongly active sites. TLC on alumina with benzene (Oba and Kawai 1962). GC and GC/MS Amenable to conventional techniques. GC by conventional analytical procedures (Junk et al. 1974 Habboush and Al-Rubaie 1978, Palaveeva et al. 1979, Korte 1981, Verzele et al. 1981) . 256 Appendix Table 76. CAS # 140-88-5 2-Propenoic acid, ethyl ester STRUCTURE: CH2=CH-COO-CH2-CH3 M.F. C5-H8-02 M.W. 100.11 B.P. 99.4 C. TOXICITY Toxic Effects Reported: IRR Review: Carcinogenic Determination: Indefinite Aquatic Toxicity Rating: TI»m96: 1000-100 ppm USE In the manufacture of water emulsion paint vehicles, textile and paper coatings, leather finish resins, and adhesives. ANALYTICAL SUMMARY Too volatile for conventional analysis. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Could be retained during evaporation of methylene chloride, hexane and isopropanol, but probably would be lost during evaporation of toluene and higher boiling solvents. STABILITY Relatively stable to conventional analytical procedures, though it tends to polymerize during distillation. SOLUBILITY Soluble in most conventional solvents of intermediate polar ity. Soluble in: water (slightly), alcohol, ether, acetone, methyl ethyl ketone, chloroform, toluene, benzene, cyclohexane. 257 Appendix Table 76. LC Probably amenable to normal-phase since it is not highly polar. GC and GC/MS Amenable to conventional GC techniques. GC by conventional procedures (McCormick 1968, Danboy and Deneubourg 1971, Ashes and Haken 1975, Parsons and Mitzner 1975, Brown and Purnell 1979) . 258 Appendix Table 77. CAS # 141-23-1 Octadecanoic acid, 12-hydroxy-methyl ester STRUCTURE: CH3-(CH2)5-CHOH-(CH2)10-COO-CH3 M.F. C19-H38-03 M.W. 314.57 M.P. 56.5-57 C. TOXICITY Toxic Effects Reported: ETA ANALYTICAL SUMMARY Amenable to conventional analytical techniques. Derivatization is useful in GC, but is not mandatory. Will probably separate out in the lipid fraction. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical techniques. No indication of lability was found. SOLUBILITY Probably sufficiently soluble for trace analysis in most solvents of intermediate polarity. Soluble in: methanol (Henke and Schubert 1980) , diethyl ether:light petroleum, chloroform, benzene. LC Amenable to normal-phase. CC on silica with hexane:isopropanol (Neff and Frankel 1980). TLC on silica gel with diethyl ether:light petroleum Morris and Wharry 1965) . 259 Appendix Table 77. GC and GC/MS Derivatization is helpful but is not required. Hydroxy fatty esters typically tail and have long retention times with polar substrates, so derivatization is usually performed as the trimethylsilyl or trifluoroacetate derivative (Freedman 1967, Leu and Anderson 1974, Frankel et al. 1977). This ester however, may be analyzed conventionally without severe tailing, though it may not separate well from similar compounds (Freedmans et al. 1965, Freedmans 1967, Heintz et al. 1970). 260 Appendix Table 78. CAS * 142-47-2 L-Glutamic acid, monosodium salt STRUCTURE: COOH I H2N-C-H I H-C-H I H-C-H I C O O N a M.F. C5-H8-04-N-Na M.W. 169.12 TOXICITY Toxic Effects Reported: SYS, TER USE Flavoring in food. ANALYTICAL SUMMARY Insoluble in solvents of intermediate polarity. Adsorption in LC may be a problem. Derivatization for GC is required. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil (as the ionic compound) Low (as the acid) STABILITY Stable to conventional analytical procedures. Stable to normal cooking and processing (Armand et al. 1976) . Naturally occuring in living organisms and subject to metabolic processes. 261 Appendix Table 78. SOLUBILITY Insoluble in solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Adsorption in LC could be a problem, no references to nonagueous chromatography on silica gel could be found. GC and GC/MS Derivatization to provide volatility is required. GC analysis as the trimethylsilyl derivative (Tatsuka et al. 1978, Conacher et al. 1979) and as the N-trifluoroacetic-n-butyl ester derivative (Gal and Schilling 1972). 262 Appendix Table 79. CAS # 151-56-4 Aziridine H STRUCTURE: I N H2C— ~CH2 M.F. C2-H5-N M.W. 43.07 B.P. 56 C. TOXICITY Toxic Effects Reported: NEO, CAR, ETA Review: Carcinogenic Determination: Animal Positive USE In the manufacture of triethylenemelamine. ANALYTICAL SUMMARY Too volatile for conventional analysis. Probably too reactive in solvents. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Could be retained during evaporation of methylene chloride, but probably would be lost during evaporation of hexane and higher boiling solvents. STABILITY Probably would react with other compounds once freely mobile in solvent. Polymerizes easily. Strongly basic, and is very reactive, especially in acidic environments where it hydrolyzes rapidly to ethanolamine (Shimomura et al. 1973) . Too reactive to have a long half-life in the environment. 263 Appendix Table 79. SOLUBILITY Soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, ether, acetone, benzene, organic solvents. LC Adsorption may be a problem in normal-phase. Due to the strongly basic nature of this compound it may strongly bind to silica gel. GC and GC/MS Either polar stationary phases (DiLorenzo and Russo 1968, Sile et al. 1969, Anderson et al. 1974) or inert columns are needed to prevent adsorption and tailing problems. Due to the adsorptive nature of this compound, low column temperatures are not required for good peak separation from the solvent. 264 Appendix Table 80. CAS # 518-47-8 Spiro[isobenzofuran-1(3H),9'-[9H]xanthen)-3-one, 3*6'- dihydroxy-disodium salt STRUCTURE: Na • 0 M.F. C20-H10-05-Na2 M.W. 376.27 TOXICITY Toxic Effects Reported: ETA USE As a marker to detect waste discharges, sources of springs, etc. ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. STABILITY Probably stable to air, water, and light, though heat 265 Appendix Table 80. stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica gel. Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 266 Appendix Table 81. CAS # 546-88-3 Acetamide, N-hydroxy- STRUCTURE: CH3-C0-NH0H M.F. C2-H5-02-N M.W. 75.08 M.P. 88 C. TOXICITY Toxic Effects Reported: TER ANALYTICAL SUMMARY Analytical requirements remain unclear. Very little information could be found on this or homologous hydroximic acids. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Uncertain SOLUBILITY Uncertain, though probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: benzene:2-pentanol:2-octanol LC Amenable to normal-phase. TLC on silica gel with benzene:2-pentanol:2-octanol (Soler et al. 1976). GC and GC/MS Uncertain 267 Appendix Table 82. CAS # 555-43-1 Octadecanoic acid, 1,2,3-propanetriyl ester STRUCTURE: [CH3-(CH2)16-C02-CH2]2CH-OCO-(CH2)16-CH3 M.F. C57-H110-O6 M.W. 891.45 M.P. 55-72 C. TOXICITY Not listed in RTECS USE In sizing textiles. ANALYTICAL SUMMARY Basically amenable to conventional techniques. Relatively high column temperatures are required. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Relatively stable to conventional analytical techniques, though there is some indication of thermal degradation at high temperatures (Yonese et al. 1977). SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: alcohol (hot better than cold), diethyl ether and petroleum ether (hot better than cold), chloroform, hexane, heptane, benzene. LC Amenable to normal-phase. HPLC on silica with hexane:isopropanol, hexane:ethane (Kiuchi et al. 1975). 268 Appendix Table 82. GC and GC/MS Relatively high column temperatures (270 C.) required. GC by conventional procedures with FID and relatively high column temperatures (Takagi and Itabashi 1977, Yonese et al. 1977, Mares et al. 1978, Aneja et al. 1979, Traitler and Prevot 1981) . 269 Appendix Table 83. CAS # 573-58-0 1-Naphthalenesulfonic acid, 3,3'-[[l,l,-biphenyl]-4,4l- diylbis(azo)]bis[4-amino-disodium salt STRUCTURE: NH2 NH2 ■N=N' N=N> no S03* Na S03*Na M.F. C32-H22-06-N6-S2-Na2 M.W. 696.67 TOXICITY Toxic Effects Reported: TER USE Dye, biological stain. ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. 270 Appendix Table 83. SOLUBILITY Uncertain, possibly sufficiently soluble for partial extraction by conventional solvents of intermediate polarity. Soluble in: water, ethanol, acetone (very slightly), ether (practically insoluble). Insoluble in chlorinated hydrocarbon solvents. LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 271 Appendix Table 84. CAS # 584-84-9 Benzene, 2,4-diisocyanato-l-methyl- STRUCTURE wro OCN CH3 M.F. C9-H6-02-N2 M.W. 174.15 M.P. 19.5-21.5 C B.P. 251 C. TOXICITY Toxic Effects Reported: PUL, IRR Review: Carcinogenic Determination: No Data Aquatic Toxicity Rating: TLm96: 10-1 ppm Toxic Effects Reported for (95-80-7): CAR Review: Carcinogenic Determination: Animal Positive Status: NCI Carcinogenesis Bioassay: Mouse Positive Rat Positive USE In the manufacture of polyurethane foams and other elastomers. ANALYTICAL SUMMARY May strongly adsorb to silica gel. Somewhat unstable to conventional analytical techniques. Derivatization for stability is helpful but not mandatory. The primary degradation product (95-80-7) is probably amenable to conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low 272 Appendix Table 84. STABILITY Somewhat unstable to conventional analytical procedures. Derivatization to stabilize the compound during analysis is helpful but apparently not mandatory since 96hr static aquatic toxicity tests have been conducted and analyzed without derivatization (Curtis et al. 1979). Strongly electron absorbing (Wheals and Thomson 1967). Reacts slowly with water to form 4-methyl-l,3- benzenediamine (95-80-7) (Johnson et al. 1980), which is easily degraded by activated sludge (Matsiri et al. 1975). Would not be environmentally long lived. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: alcohol, ether, acetone, chloroform, benzene, chlorobenzene, kerosene, olive oil. 4-Methyl-l,3-benzenediamine is probably soluble in most conventional solvents of intermediate polarity. LC Possibly strongly adsorptive in normal-phase due to its electrophilic character. No examples of normal-phase elution with organic solvents were found in the literature. The N-(4-nitrobenzyl)-N-propylamine derivative is amenable to conventional normal-phase LC (Dunlap et al. 1976, Vogt et al. 1979) . 4-Methyl-l,3-benzenediamine has apparently been chromatographed on silica gel with chloroform:ethanol (Boitsov et al. 1976) . GC and GC/MS Amenable to conventional techniques,' though derivatization may provide more accurate quantitative results. Analysis with FID of the N-(4-nitrobenzyl)-N-propyl-3-(4- nitrobenzyl)) urea has been used (Dunlap et al. 1976, Vogt et al. 1977, Sangoe 1979), though conventional analyses without derivatization by ECD (Wheals and Thomson 1967, Curtis et al. 1979), and by FID (Nenasheva 1976) have been successful. 4-Methyl-l,3-benzendiamine has been analyzed by conventional GC procedures (Willeboordse et al. 1968, Boufford 1968) . 273 Appendix Table 85. CAS # 614-45-9 Benzenecarboperoxoic acid, 1,1-dimethylethyl ester STRUCTURE: M.F. C11-H14-03 M.W. 194.25 B.P. 75-76 C TOXICITY Toxic Effects Reported: ETA USE Catalyst for cross-linking polyesters. ANALYTICAL SUMMARY Too volatile for conventional techniques. Requires low injector and column temperatures for GC analysis. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High Could be retained during evaporation of methylene chloride and probably hexane, but probably would be lost during evaporation of isopropanol and higher boiling solvents. STABILITY Decomposes at 111 degrees C. (Noller and Bolton 1963). This compound would tend to decompose at conventional GC temperatures. 274 Appendix Table 85. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: acetone, ethyl acetate, chloroform, hexane, benzene. LC Amenable to normal-phase. TLC on silica gel with benzene, ethyl acetate, acetone, methylene chloride:chloroform (Krull and Mandelbaum 1976) . HPLC on silica with propanol-hexane (Cornish et al. 1981). GC and GC/MS Too heat labile for conventional temperatures, resulting in the chromatography of degradation products. Low temperatures have been successfully used in solid probe (Krull and Mandelbaum 1976) and low injection and column temperatures (max. of 148 C.) have been successful in GC (Cerveny et al. 1972). 275 Appendi* Table 86. CAS # 680-31-9 Phosphoric triamide, hexamethyl- STRUCTUREs [(CH3)2N]3PO M.F. C6-H18-0-N3-P M.W. 179.20 TOXICITY Toxic Effects Reported: CAR Review: Carcinogenic Determination: Animal Positive USE Solvent, de-icing additive for jet fuels, insect chemosterilant, as a chemical mutagen. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low to Moderate Evaporation from Solvent: Low STABILITY Stable to conventional analytical conditions. No indication of lability was found. SOLUBILITY Soluble in most solvents of intermediate polarity. Soluble in: methanol, ethanol, isopropanol, acetone, chloroform, phenol, toluene, hexane, benzene. LC Amenable to normal-phase. TLC on silica gel with methanol, ethanol, isopropanol, acetone:chloroform, phenol, benzene:ethnol (Terranova and Schmidt 1967) . 276 Appendix Table 86. GC and GC/MS Amenable to conventional analytical techniques. GC by conventional procedures with FID (Terranova and Schmidt 1967) and with FPD (Bowmann 1975, Sass and Parker 1980). 277 Appendix Table 87. CAS # 842-07-9 2-Naphthalenol, 1-(phenylazo)- STRUCTURE: HO. ■N=N' M.F. C16-H12-0-N2 M.W. 248.3 M.P. 131-133 C. TOXICITY Toxic Effects Reported: ETA, CAR Review: Carcinogenic Determination: Animal Positive Use Dye ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Probably relatively stable to conventional analytical conditions. Apparently slow photooxidation occurs by reaction of the singlet "0" with the hydrazone tautomeric species Griffths and Hawkins 1977). 278 Appendix Table 87. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in petroleum ether:acetone, petroleum ether: chloroform, chloroformzhexane, xylene, benzene. LC Amenable to normal-phase. TLC on silica gel with benzene, xylene, petroleum ether: acetone, petroleum etherzchloroform (Rai 1971), and on alumina with benzene (Smith 1966) . CC on a cyanopropyl column with chloroformzhexane and on silica gel with benzene (Ito et al. 1979). GC and GC/MS Amenable to conventional techniques. GC by conventional procedures with FID (Ichihara et al. 1980) . 279 Appendix Table 88. CAS # 860-22-0 lH-Indole-5-sulfonic acid, 2-(l,3-dihydro-3-oxo-5-sulfo- 2H-indole-2-ylidene)-2,3-dihydro-3-oxo-disodium salt STRUCTURE: Na-03S S03•Na M.F. C16-H8-08-N2-S2-Na2 M.W. 466.37 TOXICITY Toxic Effects Reported: NEO USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. STABILITY Very sensitive to oxidizing agents. Decomposes easily in alkaline solution (Graichen and Molito 1963, Gilhooley et al. 1972), in acidic solution, and with heat (Boley et al. 1981). 280 Appendix Table 88. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica gel. Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 281 Appendix Table 89. CAS # 915-67-3 2,7-Naphthalenedisulfonic) acid, 3-hydoxy-4-[(4-sulfo-l- naphthalenyl)azo]-trisodium salt STRUCTURE: H0 S03-Na Na*03S' •N=N- S03•Na M.F. C20-Hll-010-N2-S3-Na3 M.W. 604.48 TOXICITY Toxic Effects Reported: TER, CAR Review: Carcinogenic Determination: Indefinite USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. 282 Appendix Table 89. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. Anaerobically decomposed in sludge after 10 days, but only slightly decomposed aerobically (Tonogai et al. 1978). SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol (slightly). LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 283 Appendix Table 90. CAS # 1321-65-9 Naphthalene, trichloro- STRUCTURE: M.F. C10-H5-C13 M.W. 231.5 M.P. 65-131 C. TOXICITY Toxic Effects Reported: Only LD data reported. ANALYTICAL SUMMARY Amenable to conventional techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical techniques. No indication of lability was found. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: chloroform, toluene, hexane, light petroleum: diethyl ether. LC Amenable to normal-phase. HPLC on microporous silica with hexane (Brinkman and Rymer 1976). 284 Appendix Table 90. GC and GC/MS Readily amenable to conventional techniques. GC by conventional procedures (Challen and Kucera 1967, Armour and Burke 1971, Goerlitz and Law 1972, Beland and Geer 1973, Stalling and Huckins 1973). GC/MS by conventional procedures (Erickson et al. 1978a). 285 Appendix Table 91. CAS # 1338-23-4 2-Butanone peroxide STRUCTURE: CH3-C0-C(00H)H-CH3 M.F. C4-H8-03 M.W. 92 TOXICITY Toxic Effects Reported: GIT, ETA USE Catalyst for polyesters. ANALYTICAL SUMMARY Probably too volatile and labile for quantitative conventional analysis. EVAPORATIVE LOSS POTENTIAL Freeze Drying: High Evaporation from Solvent: High STABILITY A reactive, labile compound which would be environmentally short lived. Explodes when heated and is corrosive. Would tend to react with other solutes to form simple hydrocarbons and would degrade in the GC. SOLUBILITY Uncertain. No reference to solubility in pure solvents was found, though Fijolka and Gnauck (1966) indicate it is soluble in benzene:acetic acid and toluene:carbon tetrachloride: acetic acid. LC Uncertain. No references to nonaqueous normal-phase LC were found. 286 Appendix Table 91. GC and GC/MS Probably too heat labile for GC temperatures, 287 Appendix Table 92. CAS # 1665-48-1 2-Oxazolidinone, 5-[(3,5-dimethylphenoxy)methyl]- STRUCTURE: H3C H3C M.F. C12-H15-03-N M.W. 221.25 M.P. 121.5-123 C. TOXICITY Toxic Effects Reported: CNS USE Muscle relaxant. ANALYTICAL SUMMARY Analytical requirements remain uncertain. No analytical information, except for ionic resonance spectra (Sammul et al. 1964), could be found for this or similar compounds. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporative Loss Potential: Low STABILITY Uncertain SOLUBILITY Uncertain, though possibly relatively soluble in most conventional solvents of intermediate polarity. 288 Appendix Table 92. LC Uncertain GC and GC/MS Uncertain 289 Appendix Table 93. CAS # 1694-09-3 Benzenemethanaminium, N— [4 —[[4-(dimethylamino)phenyl][4- [ethyl[3-sulfophenyl)methyl]amino]phenyl]methylene]-2,5 -cyclohexadien-l-ylidene]-N-ethyl-3-sulfo-hydroxide, inner salt, sodium salt STRUCTURE: M.F. C39-H41-06-N3-S2-Na M.W. 734.94 TOXICITY Toxic Effects Reported: ETA, CAR Review: Carcinogenic Determination: Animal Positive USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. 290 Appendix Table 93. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica gel. Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 291 Appendix Table 94. CAS # 1934-21-0 lH-Pyrazole-3-carboxylic acid, 4,5-dihydro-5-oxo-l-(4- sulfophenyl)-4-[(4-sulfophenyl)azo]-trisodium salt STRUCTURE: S 0 3 •Na M.F. C16-H9-09-N4-S2-Na3 M.W. 534.39 TOXICITY Toxic Effects Reported: ALR USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. 292 Appendix Table 94. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. Undergoes significant anaerobic degradation after 10 days, yet remains relatively stable aerobically (Tonogai et al. 1978) . SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica gel. Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 293 Appendix Table 95. CAS # 2223-93-0 Octadecanoic acid, cadmium salt STRUCTURE: CH3-(CH2)16-COO-Cd-OCO-(CH2)16-CH3 M.P. C36-H70-O4-Cd M.W. 697 TOXICITY Toxic Effects Reported: CNS, CVS USE Heat stabilizer for PVC. ANALYTICAL SUMMARY Special solvents may be required. LC requirements are uncertain. Too nonvolatile for GC. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil STABILITY Stable to air, light and water, though heat stability is uncertain. A relatively stable compound. SOLUBILITY Uncertain solubility characteristics for conventional solvents of intermediate polarity. No references concerning the solubility of this compound were found. Other metal stearates were found to be generally soluble in: pyridine, dioxane and acetic anhydride; and with solubility varying from soluble to practically insoluble in: water, alcohol, acetone, ether, chloroform, carbon tetrachloride, toluene, and benzene. 294 Appendix Table 95. LC Uncertain. No references concerning nonaqueous LC were found in the literature for this or other metal stearates. GC and GC/MS GC not possible as this is a nonvolatile salt. 295 Appendix Table 96. CAS # 2238-07-5 Oxirane, 2,2'-[oxybis(methylene)]bis- STRUCTURE: CH20CH-CH2-0-CH2-CH0CH2 M.F. C6-H10-O3 M.W. 130.16 TOXICITY Toxic Effects Reported: ETA ANALYTICAL SUMMARY Analytical requirements remain unclear. No references to the analysis of "bis-structured" oxirane ethers were found in the literature. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Possibly moderate to high. Evaporation from Solvent: Possibly moderate to high. STABILITY Uncertain. Possibly quite unstable due to the epoxy groups. SOLUBILITY Uncertain, though probably sufficiently soluble for trace analysis in most common solvents of intermediate polarity. LC Uncertain. GC and GC/MS Uncertain. Oxirane is amenable to conventional analysis by GC (Zagar 1972 Pfeilsticker et al. 1975, Lebedeva and Likhtman 1980, Pujol-Forn et al. 1981). 296 Appendix Table 97. CAS # 2353-45-9 Benzenemethanaminium, N-ethyl-N-[4- [ [4[ethyl [ (3- sulfophenyl)methyl]amino]phenyl](4-hydroxy-2- sulfophenyl)methylene]-2,5-cyclohexadien- l-ylidene]-3-sulfo-hydroxide, inner salt, disodium salt STRUCTURE j M.P. C37-H36-010-N2-S3-Na2 TOXICITY Toxic Effects Reported: NEO Review: Carcinogenic Determination: Animal Positive USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. 297 Appendix Table 97. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 298 Appendix Table 98. CAS # 2465-27-2 Benzenamine, 4,4'-carbonimidoylbis[N,N-dimethyl- monohydrochlor ide STRUCTURE: Nil ’Cl (CH3) 2N"\V_x/ \V_^//'N(CH3) 2 M.P. C17-H21-N3-C1 M.W. 321.89 TOXICITY Toxic Effects Reported: NEO, ETA USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. 299 Appendix Table 98. SOLUBILITY Insoluble in conventional solvents of intermediate polarity; Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 300 > Appendix Table 99. CAS # 2580-78-1 2-Anthracenesulfonic acid, l-amino-9,10-dihydro-9,10- dioxo-41[3-[[2-(sulfooxy)ethyl]sulfonyl]phenyl]amino] -disodium salt STRUCTURE: O NH2 S03 *Na S02-CH2-CH2-0-S03•Na NH M.F. C22-H16-011-N2-S3-Na2 M.W. 626.56 TOXICITY Toxic Effects Reported: ETA USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. 301 Appendix Table 99. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 302 Appendix Table 100. CAS # 2602-46-2 2,7-Naphthalenedisulfonic acid, 3,3'-[[1,1'-biphenyl]-4, 4 '-diylbis(azo)]bis[5-amino-4-hydroxy-, tetrasodium salt STRUCTURE: M.F. C32-H20-O14-N6-S4-Na4 M.W. @932 TOXICITY Toxic Effects Reported: ETA, TER, NEO, CAR Status: NCI Carcinogenesis Biossay: Rat Positive Mouse Negative USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. 303 Appendix Table 100. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica gel. Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 304 Appendix Table 101. CAS * 2610-05-1 1,3-Naphthalenedisulfonic acid, 6 , 6 [ ( 3 , 3 '-dimethoxy[1, 1'-biphenyl]-4,4'-diyl)bis(azo)]bis[4-amino-5-hydroxy -tetrasodium salt STRUCTURE: CH30 OCH3 H2N OH \ ----/ HO NH2 Na•03S S03‘Na M.F. C34-H24-016-N6-S4-Na4 M.W. @992 TOXICITY Toxic Effects Reported: TER USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. 305 Appendix Table 101. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica gel. Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 306 * Appendix Table 102. CAS # 2646-17-5 2-Naphthalenol, 1-[(2-methylphenyl)azo]- STRUCTURE: HO N=N CH3 M.F. C17-H14-0-N2 M.W. 262.33 TOXICITY Toxic Effects Reported: NEO, CAR Review: Carcinogenic Determination: Animal Positive USE Dye ANALYTICAL SUMMARY Analytical requirements for GC remain uncertain. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Probably Low Evaporation from Solvent: Probably Low STABILITY Uncertain. Probably fairly stable to air, water and light since it is used as a dye, though heat stability is uncertain. 307 Appendix Table 102. SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: ethanol (Hoodless et al. 1971), chloroform (Pearson 1973), xylene, benzene. LC Amenable to normal-phase. TLC on silica gel with benzene, xylene, petroleum ether: acetone, and petroleum ether:chloroform (Rai 1971). HPLC on silica gel with chloroform:hexane (Ohnishi et al. 1977) . GC and GC/MS Uncertain. No references to the GC of this compound or similar compounds could be found in the literature. 308 Appendix Table 103. CAS # 2650-18-2 Benzenemethanaminium, N-ethyl-N- [4-[[4-[ethyl[(3- sulfophenyl)methyl]amino]phenyl](2-sulfophenyl) methylene]-2,5-cyclohexadien-l-ylidene] -3-sulfo-hydroxide, inner salt, diammonium salt STRUCTURE: M.F. C37-H36-09-N2-S3-(H3-N)2 M.W. 783.01 TOXICITY Toxic Effects Reported: NEO, ETA USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. 309 Appendix Table 103. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 310 Appendix Table 104. CAS * 2783-94-0 2-Naphthalenesulfonic acid, 6-hydroxy-5-[(4-sulfophenyl) azo]-disodium salt STRUCTURE: HO N=N S03-Na M.F. C16-H10-O7-N2-S2-Na2 M.W. 452.38 TOXICITY Toxic Effects Reported: Only LD data reported. Review: Carcinogenic Determination: Indefinite USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. 311 Appendix Table 104. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 312 Appendix Table 105. CAS # 4548-53-2 1-Naphthalenesulfonic acid, 3-[(2,4-dimethyl-5- sulfophenyl)azo]—4—hydroxy—disodium salt STRUCTURE; M.F. C18-Hl4-07-N2-S2-Na2 H.W. 480.44 TOXICITY Toxic Effects Reported: CAR, ETA Review: Carcinogenic Determination: Indefinite USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. 313 Appendix Table 105. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 314 Appendix Table 106. CAS # 5002-47-1 Decanoic acid, 2-[4-[3-[2-(trifluoromethyl)-10H- phenothiazin-10-yl]propyl)-1-piperazinyl)ethyl ester STRUCTURE: CH2-(CH2)2-N N-(CH2)2-O-CO-(CH2)8-CH3 CF3 M.F. C32-H44-02-N3-S-F3 M.W. 591.85 TOXICITY Toxic Effects Reported: PSY ANALYTICAL SUMMARY Analytical limitations remain largely uncertain. Possibly not significantly volatile for, or stable to, GC analysis. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low No references to volatility were found, but the compound is very large and one can assume a low. volatility. STABILITY Uncertain. Metabolism of similar compounds by organisms tends to cleave off the aldehyde and leave the parent alcoholic compound, fluphenazine (Hansen and Larsen 1974). 315 Appendix Table 106. SOLUBILITY Uncertain. Soluble in sesame oil. This ester compound (5002-47-1) is more lipophilic than the parent compound, which is an alcohol (Tjaden et al. 1976) . LC Strong adsorption should not be a problem due to its lipophillic nature. Reverse-phase chromatography has been researched (Goldstein and Vunakis 1981, Heyes and Salmon 1978). GC and GC/MS Possibly too nonvolatile or too heat labile for GC conditions. No references to the GC analysis of this or similar esters were found, though the parent alcohol, fluphenazine, has been successfully derivatized with acetic acid anhydride and analyzed by GC (Hansen and Larsen 1974). Some GC work may have been done by Deaconeasa (1978) . 316 Appendix Table 107. CAS # 5141-20-8 Benzenemethanaminium, N-ethyl-N-[4-[[4-[ethyl[(3- sulfophenyl)methyl]amino]phenyl](4-sulfophenyl) methylene]-2,5-cyclohexadien-l-ylidien]-3-sulfo hydroxide, inner salt, disodium salt STRUCTURE N(C2H5)CH2 N (C2H5JCH2 M.F. C37-H34-09-N2-S3-Na2 M.W. 792.85 TOXICITY Toxic Effects Reported: NEO, CAR USE Dye ANALYTICAL SUMMARY Too polar for conventional analytical techniques. The use of a counter-ion renders the ion-pair soluble in slightly polar organic solvents, and amenable to normal-phase separation, identification, and quantification, with the potential for solid probe MS confirmation. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Nil 317 Appendix Table 107. Evaporation from Solvent: Nil This is an ionic compound, thus almost nonvolatile. STABILITY Probably stable to air, water, and light, though heat stability is uncertain. SOLUBILITY Insoluble in conventional solvents of intermediate polarity. Soluble in very polar solvents including water and alcohol. LC Too polar for organic solvent chromatography on silica g e l . Either an ion-pairing or an aqueous eluant is required for normal-phase. GC and GC/MS Too nonvolatile for GC. Solid probe insertion into the MS may be employed. 318 Appendix Table 108. CAS # 13927-77-0 Nickel, bis(dibutylcarbamodithioato-S,S')- STRUCTURE: [CH3-(CH2)3]2N-CS-S-Ni-S-CS-N[(CH2)3-CH3]2 M.F. C18-H36-N2-S4-Ni M.W. 467.51 M.P. 86-87 C. TOXICITY Toxic Effects Reported: ETA USE Antioxidant for polypropylene, urethane rubber, neoprene, transformer oils, and polyamide tire cords. ANALYTICAL SUMMARY Relatively high GC column temperatures are required. GC injection port temperatures should not greatly exceed column temperatures. Ligand substitution easily occurs in GC column. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Metal chelates are subject to thermal degradation at high temperatures (Masaryk et al. 1975, Sucre and Jennings 1980) . SOLUBILITY Probably sufficiently soluble for trace analysis in conventional solvents of intermediate polarity. Soluble in: alcohol, methylene chloride, chloroform. Bis(diethyldithiocarbamato)nickle is soluble in toluene and benzene (Ahmad and Aziz 1978). 319 ’Appendix Table 108. LC Amenable to normal-phase. HPLC on silica with chloroform:cyclohexane (Liska et al. 1979). GC and GC/MS Basically amenable to conventional techniques, though the tendencies exist for ligand substitution and for thermal degradation. Injection port and column temperatures must be a compromise between those sufficient for rapid volatization yet below those causing thermal degradation, approximately 240-275 degrees C. (Krupcik et al. 1979, Riekkola 1980). Accurate qualitative and quantitative results are more difficult with environmental samples due to the ease with which ligands exchange between metal bisdialkyldithiocarbamate complexes in the column. For example, ligand exchange will result in a third analytical peak when only two complexes occur in the sample (Lehotay et al. 1979, Liska et al. 1979). 320 Appendix Table 109. CAS # 14239-68-0 Cadmium, bis(diethylcarbamodithioato-S,S')- STRUCTURE: (CH3-CH2)2N-CS-S-Cd-S-CS-N(CH2-CH3)2 M.F. C10-H20-N2-S4-Cd M.W. 408.96 M.P. 254 C. TOXICITY Toxic Effects Reported: ETA ANALYTICAL SUMMARY Basically amenable to conventional techniques. Relatively high GC column temperatures are required. GC injection port temperatures should not greatly exceed column temperatures. Ligand substitution easily occurs in the GC column. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Metal chelates are subject to thermal degradation at high temperatures (Masaryk et al. 1975, Sucre and Jennings 1980) . SOLUBILITY Probably sufficiently soluble for trace analysis in most conventional solvents of intermediate polarity. Soluble in: alcohol, chloroform, toluene. LC Amenable to normal-phase. HPLC on silica with chloroform:cyclohexane (Liska et al. 1979), and on a cyanopropylsilylated silica gel column with toluene (Gaetani et al. 1979). 321 Appendix Table 109. GC and GC/MS Basically amenable to conventional techniques, though the tendencies exist for ligand substitution and for thermal degradation. Injection port and column temperatures must be a compromise between those sufficient for rapid volatization yet below those causing thermal degradation, approximately 240-275 degrees C. (Krupcik et al. 1979, Riekkola 1980). Accurate qualitative and quantitative results are more difficult with environmental samples due to the ease with which ligands exchange between metal bisdialkyldithiocarbamate complexes in the column. For example, ligand exchange will result in a third analytical peak when only two complexes occur in the sample (Lehotay et al. 1979, Liska et al. 1979). 322 Appendix Table 110. CAS # 15180-02-6 l,8-Naphthyridine-3-carboxylic acid, l-ethyl-l,4-dihydro- 4-oxo-7-(phenylmethyl)- STRUCTURE: UZHD H2C COOH 0 M.F. C18-H16-03-N2 M.W. @308 TOXICITY Uncertain, not listed in RTECS 1980. ANALYTICAL SUMMARY Analytical limitations remain uncertain. Possibly amenable to conventional techniques, though tailing of GC peaks may be a problem resolvable by derivatization. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY No analytical references for this compound were found. References to a similar compound, naldixic acid (389-08-2), did not indicate lability. SOLUBILITY Probably sufficiently soluble for trace analysis in conventional solvents of intermediate polarity. The similar carboxylic acid naldixic acid (389-08-2) , is soluble in: methanol, ethanol, ether, chloroform, toluene. 323 Appendix Table 110. LC Probably amenable to normal-phase since moderately polar to polar solvents have been used to chromatograph the similar naldixic acid on silica gel. TLC of naldixic acid on silica gel with chloroform: acetone, ethyl acetate, acetone, chloroform:methanol. GC and GC/MS Analytical limitations remain uncertain. No references to GC were found. The chemically similar naldixic acid (389-08-2) tends to tail unless derivatized to the methyl, butyl, or silylated derivative (Wu et al. 1978, Roseboom et al. 1979) . Derivatization of the instant compound (15180-02-6) may not be required to obtain a peak, though it may be needed to accurately quantitate. 324 Appendix Table 111. CAS # 25301-02-4 Phenol, 4-(1,1,3,3-tetramethylbutyl)- polymer with formaldehyde and oxirane STRUCTURE: M.F. (C14-H22-0.C2-H4-0.C-H2-0)x M.W. 280 per monomer TOXICITY Toxic Effects Reported: TER USE Therapeutic detergent. ANALYTICAL SUMMARY Analytical properties remain uncertain. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Oxidized by metals. Incompatible with tetracyclines. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, chloroform, carbon tetrachloride, carbon disulfide, toluene, benzene. LC Uncertain. No information was recovered. 325 Appendix Table 111. GC and GC/MS Uncertain. No information was recovered. Appendix Table 112. CAS # 25322-68-3 Poly(oxy-1,2-ethanediyl)-a-hydro-w-hydroxy- STRUCTURE: H(0-CH2-CH2)nOH n>4 M.W. >194 TOXICITY Toxic Effects Reported: ETA USE As water soluble lubricants for rubber molds, textile fibers, and metal forming operations; in food and packaging cosmetics, water-based paints, paper coatings, polishes and ceramic glazes. ANALYTICAL SUMMARY Derivatization is sometimes used in GC to increase volatility but it is not required. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical techniques. Used as GC liquid phase which is typically nonreactive. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: water, alcohol, acetone, ether, chloroform, benzene. 327 Appendix Table 112. LC Amenable to normal-phase. TLC on silica gel with chloroform:ethanol (Safiullina et al. 1978) . CC on silica gel with chloroformrmethanol (Rosen 1963) . TLC on alumina with chloroformiethanol (Yudina et al. 1972) . GC and GC/MS Amenable to conventional technique. Derivatization as either the acetyl or trimethylsilyl derivative will increase volatility (Chadwich et al. 1977, Deaconeasa and Constantinescu 1980, Blaetzinger et al. 1981), however derivatization is not mandatory (Bouska and Phillips 1980, Deaconeasa and Constantinescu 1980, Grob 1980). Polymers of 14 units (M.W. 634) elute at about 308 degrees C. (Grob 1980), thus representing an approximate upper size limit of volatility for underivatized polymers. 328 Appendix Table 113. CAS # 26761-40-0 1,2-Benzenedicarboxylic acid, diisodecyl ester STRUCTURE 0 II C-O-(CH2)9-CH3 C-O-(CH2)9-CH3 II O M.F. C28-H46-04 M.W. @446 TOXICITY Uncertain, not listed in RTECS 1980. USE Plasticizer in PVC. ANALYTICAL SUMMARY Amenable to conventional analytical techniques. EVAPORATIVE LOSS POTENTIAL Freeze Drying: Low Evaporation from Solvent: Low STABILITY Stable to conventional analytical techniques. SOLUBILITY Probably soluble in most conventional solvents of intermediate polarity. Soluble in: methylene chloride, hexane. Phthalates tend to be soluble in alcohol, ether, acetone, benzene. 329 Appendix Table 113. LC Amenable to normal-phase. HPLC on silica with isooctane:methylene chloride: isopropanol (Kuo et al. 1981). GC and GC/MS GC by conventional procedures with FID (Hites 1973, Burnes et al. 1975, Grenier-Loustalot 1978, Ramsey et al. 1980) . 330 Table 114. Selected abbreviations. A. Notations Descriptive of the Toxicology (Adapted from RTECS 1980) Abbreviation Definition ALR Allergic systemic reaction such as might be experienced by individuals sensitized to penicillin. BCM Blood clotting mechanism effects - any effect which increases or decreases clotting time. BLD Blood effects - effects on all blood elementslectrolytes, pH, protein, oxygen earring or releasing capacity. BPR Blood pressure effects - any effect which increases or decreases any aspect of blood pressure. CAR Carcinogenic effects - production of malignant tumors. CNS Central nervous system effects - includes effects such as headaches, tremor, drowsiness, convulsions, hypnosis, anesthesia. COR Corrosive effects - burns, desquamation. CUM Cumulative effects - where substance is retained by the body in greater quantities than is excreted, or the effect is increased in severity by repeated body insult. CVS Cardiovascular effects - such as an increase or decrease in the heart activity through effect on ventricle or auricle, fibrillation, auricle, fibrillation, constriction or dilation of the arterial or venous blood. DDP Drug dependence effects - any indication of addiction or dependence. ETA Equivocal tumorigenic agent - some evidence of tumorigenic effects. EYE Eye effects - irritation, diploplia, cataracts, eye ground, blindness by affecting 331 Table 114. Selected abbreviations. the eye or the optic nerve. GIT Gastrointestinal tract effects - diarrhea, constipation ulceration. GLN Glandular effects - any effect on the endocrine glandular system. IRR Irritant effects - any irritant effect on the skin eye, or mucous membrane. MLD Mild irritation effects - used exclusively for primary irritation data. MM I Mucous membrane effects - irritation, hyperplasia, changes in ciliary activity. MOD Moderate irritation effects - used exclusively exclusively for primary irritation data. MSK Musculo-Skeletal effects - such as osteoporosis, muscular degeneration. NEO Neoplastic effects - production of benign tumors. PNS Peripheral nervous system effects. PSY Psychotropic effects - exerting an effect upon the mind. PUL Pulmonary system effects - effects on respiratory pathology. RBC Red blood cell effects - includes the several anemias. SEV Severe irritation effects - used exclusively for primary irritation data. SKN Skin effects - such as erythema, rash, sensitization of skin, petechial hemmorage. SYS Systemic effects - effects on the metabolic and excretory function of the liver or kidneys. TER Teratogenic effects - nontransmissible changes produced in the offspring. WBC White blood cell effects - effects on any of the cellular units other than erythrocytes, 332 Table 114. Selected abbreviations. including any change in number or form. B. Notations Descriptive of Analysis CC Column Chromatography GC Gas Chromatography GC/MS Gas Chromatography/Mass Spectrometry HPLC High Pressure Liquid Chromatography TLC Thin Layer Chromatography 333