1、 STD-ANSI IT4-43-ENGL 3998 0724150 0551821 368 ANSI/PIMA IT4.43-I998 STDmANSI IT4.43-ENGL LA II 0724350 055L822 2T4 I ANSVPIMA lT4.43-1998 Revision and redesignation of ANSVNAPM 1T4.43-1993 American National Standard for Photography (Processing) - Effluents - Determination of Total Cyanide Secretari
2、at Photographic their existence does not in any respect preclude anyone, whether he has approved the standards or not, from manufacturing, marketing, purchasing, or using products, processes, or procedures not conforming to the standards. The American National Standards Institute does not develop st
3、andards and will in no circumstances give an interpretation of any American National Standard. Moreover, no person shall have the right or authority to issue an interpretation of an American National Standard in the name of the American National Standards Institute. Requests for interpretations shou
4、ld be addressed to the secretariat or sponsor whose name appears on the title page of this standard. CAUTION NOTICE: This American National Standard may be revised or withdrawn at any time. The procedures of the American National Standards Institute require that action be taken periodically to reaff
5、irm, revise, or withdraw this standard. Purchasers of American National Standards may receive current information on all standards by calling or writing the American National Standards Institute. Standard Published by American National Standards Institute, Inc. 11 West 42nd Street, New York, NY 1003
6、6 Copyright O 1999 by American National Standards Institute All rights reserved. No part of this publication may be reproduced in any form, in an electronic retrieval system or otherwise, without prior written permission of the publisher. Printed in the United States of America STDWANSI IT4.43-ENGL
7、1998 0724150 0551824 077 W Contents Page Foreword ii Introduction . III 1 Scope 1 2 Normative references 1 3 Principle 2 . 4 Reliability . 3 5 Safety and operational precautions . 4 6 Materials and reagents 5 7 Apparatus 8 8 Sampling and sample preparation 10 9 Procedure 10 Tables 1 Cyanide ion stan
8、dard mixes 8 2 Aliquot and 40 g/l NaOH for dilution 11 3 Silver nitrate solution . 13 Figures 1 2 Typical calibration curve for the colorimetric procedure 12 Annex A Bibliography 14 Cyanide distillation apparatus . 9 i STDmANSI IT4.43-ENGL 3778 W 0724350 O553825 TO3 Foreword (This foreword is not pa
9、rt of American National Standard ANSVPIMA lT4.43-1998.) This American National Standard is one of a series devoted to the analysis of photo- graphic processing effluents. It represents a revision and redesignation of ANSI/ NAPM lT4.43-1993 and has been prepared in the IS0 format. Technical changes i
10、n- clude information on amine interferences in the method. This standard contains one annex, which is for information only and is not considered part of this standard. Suggestions for improvements of this standard will be welcome. They should be sent to the Photographic e-mail: . This standard was p
11、rocessed and approved for submittal to ANSI by PIMA Technical Committee on Photographic Processing, IT4. Committee approval of the standard does not necessarily imply that all committee members voted for its approval. At the time it approved this standard, the IT4 Committee had the following members
12、: Joseph M. Rao, Chairman John Gignac, Secretary Organization Represented Name of Representative Photographic it encompasses the field of analysis of the total cyanide content in a photo- graphic effluent. This standard is intended for use by individuals with a working knowledge of analyti- cal tech
13、niques. Some of the procedures use caustic, toxic, or otherwise hazardous chemicals. Safe laboratory practice for the handling of chemicals requires the use of safety glasses or goggles, and in some cases other protective apparel such as rub- ber gloves, face masks, and aprons. Normal precautions fo
14、r the safe performance of any chemical procedure shall be exercised at all times, but specific details have been provided for hazardous materials. Hazard warnings are designated by an appropriate letter enclosed in angle brackets I“. These are defined in clause 5 and then used throughout the text. M
15、ore detailed information on hazards, handling, and use of these chemicals may be available from the manufacturer. Photographic laboratories can establish conformity to effluent regulations only by chemical analysis. If this cannot be done in-house, an outside laboratory should be used. Photographic
16、processing effluents may contain low concentrations of free cyanide and often contain the complex cyanide, ferrocyanide. When performed on aliquots of the same sample, the total cyanide analysis and the free cyanide analysis give a good characterization of cyanide in photographic processing effluent
17、s. DANGER: Reagents and samples handled in this standard contain cyanide. It is possible for toxic hydrogen cyanide gas to form if handled improperly. Use these materials in a well ventilated fume hood. The recommended method for the determination of free cyanide in photographic ef- fluents by the m
18、icrodiffusion method may be found in American NationalStandard for Phofography (Processing) - Effluents - Determination of free cyanide, ANS I/PI MA IT4.41-1998. A companion test method for the determination of the ferrocyanide and ferricyanide ion by spectrophotometry in photographic processing eff
19、luents is avail- able in American National Standard for Photography - Processing wastes - Analysis of cyanides - Part I: Determination of hexacyanoferrate (10 and hexacyanoferrate (II0 byspectrometry, ANSVIS0 7766-1 :I 993, ANWPIMA lT4.38-1998. Precautionary labeling detailed in this standard is dir
20、ected primarily to the avoidance of injury from a single accidental exposure to a chemical. Many products present no hazard in normal handling and storage, but precautions required in the performance of any chemical procedure shall be exercised at all times. The warning and caution notices for chemi
21、cal reagents used in this standard are based on those listed in American National Standard for Hazardous industrial chemicals - Precautionaty la- belling, ANSI 2129.1-1994, and provide guidance that was in existence as of the date of issue of that standard. Specific warning and caution notice applic
22、able to this stan- dard, but not covered in ANSI 2129.1, are incorporated in the appropriate clauses of this standard. iii STDOANSI IT4.43-ENGL 3998 0724350 0553827 886 I AMERICAN NATIONAL STANDARD ANSIIPIMA lT4.43-1998 American National Standard for Photography (Processing) - Effluents - Determinat
23、ion of Total Cyanide 1 Scope This standard describes a method for determining the total cyanide in photographic effluents, based on the modified cyanide determination described in American National Standard for Photography (Processing) - Effluents - Determination of Free Cyanide, ANSVPIMA IT4.41-199
24、8. It measures both free cyanides and complex cyanides. 2 Normative references The following standards contain provisions which, through reference in this text, constitute provisions of this American National Standard. At the time of publication, the editions indicated were valid. All stan- dards ar
25、e subject to revision, and parties to agreements based on this American National Standard are encouraged to investigate the possibility of applying the most recent editions of the standards indicated below. ANSVIS0 7766-1:1993, ANSIIPIMA lT4.38-1998, Photography - Processing wastes - Analysis of cya
26、- nides - Part I: Determination of hexacyano ferrate (Il) and hexacyano ferrate (Ill) by spectrometry ANSVNAPM lT4.36-1995, Photography (Processing) - Photographic processing solutions - pH calibration and measurements - Test methods ANSVNAPM lT4.99-1996, Photography - Photographic-grade chemicals -
27、 Test methods (Part I: Gen- eral) ANSVPIMA IT4.41-1998, Photography (Processing) - fluents - Determination of free cyanide ANSI 21 29.1-1 994, Hazardous industrial chemicals - Precautionary labeling ASTM D2036-1991, Standard test methods for cyanide in water“ I SO 5667- 1 : 1 980, Water quality - Sa
28、mpling - Part I: Guidance on the des of sampling programs? IS0 566721 991, Water quality - Sampling - fart 2: Guidance on sampling technique2 IS0 5667-3: 1 994, Water quality - Sampling - Part 3: Guidance on the preservation and handling of sam- pies“ IS0 6353-1 :i 982, Reagents for chemicalanalysis
29、 -Part I: General test method.? IS0 6353-21 983, Reagents for chemical analysis - fart 2: specifications - First serieg Available from ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428. *) Available from the American National Standards Institute, 11 West 42“d Street, New York, NY 10036. 1 STD
30、-ANSI IT4.43-ENGL 1998 = 0724150 0553828 712 m ANSVPIMA lT4.43-1998 IS0 6353-3: 1 987, Reagents for chemical analysis - Part 3: Specifications - Second series” l Standard methods for the examination of water and waste water, 19th ed. 1 99!3 2 Kanno, S. et al., Formation of cyanide ion by the reactio
31、n of organic compounds with nitrous acid or other reagents. I. The formation mechanism of cyanide ion from aniline and nitrous acid, Chemosphere, 7, 657, (1978) 3 Kanno, S. et al., Formation of cyanide ion or cyanogen chloride through the cleavage of aromatic rings by nitrous acid or chlorine. IV. O
32、n the reaction of aromatic hydrocarbons with hypochlorous acid in the presence of ammonium ion, Chemosphere, 11,663, (1982) 4 Kanno, S. et al., Formation of cyanide ion or cyanogen chloride through the cleavage of aromatic rings by nitrous acid or chlorine. V. On the reaction of aromatic amines or p
33、henolic compounds with hypochlor- ous acid in the presence of ammonium ion, Fac. Pharm. Sci, 11, 669 (1982) 5 Leung, L. K. et al., Normal pulse polarographic quantification of cyanide and sulphide by anodization of mercury, Anal. Chem. Acta, 131, 167 (1981) SI Nonomura, M., Endogenous formation of h
34、ydrogen cyanide during the distillation for the determination of total cyanide, Toxicol. Env. Chem., 17,47 (1988) 7 Nonomura, M., ion chromatographic determination of cyanide compounds by chloramine-t and con- ductivity measurement, J. Chrom., 465, 395 (1 989) BI Nonomura, M., Pretreatments for the
35、Determination of Total Cyanide - Interferences, effects of re- ducing agents and additives, Intern. J Envir. Anal: Chem., 35, 253 (1 989) 9 Owerbach, D., Analysis and sample stability of cyanides in industrial effluents, J. Water Pollution Con- trolFed, 52, 2647 (1980) lo Rosenstreter, J. et al., Tr
36、ace determination and speciation of cyanide ion by atomic absorption spec- troscopy, Anal. Chem., 63, 682, (1 991) ll Stara, V. et al., Fast-scan differential pulse polarographic determination of cyanide, Collect, Czech. Chem. Commun., 47,2214, (1982) 1 21 Handbook for analytical quality control in
37、water and waste water laboratories, environmental protec- tion agency environmental monitoring and support laboratod 1 31 Handbook for monitoring industrial wastewate? 3 Principle The total cyanide method given in this standard is based on the distillation of hydrogen cyanide, HCN, with sulfuric aci
38、d and a magnesium chloride catalyst into an alkaline receiving solution. The sample is placed in a boiling flask, along with magnesium chloride solution and sulfuric acid. Distillation of the sam- ple with sulfuric acid readily converts the simple alkali cyanides and cadmium, copper, nickel, silver,
39、 and zinc cyanides to hydrogen cyanide. Decomposition of the stable complex iron cyanides (hexacyanofer- rates) is hastened with the magnesium chloride catalyst. 3, Available from the American Public Health Association, American Water Works Association, and the Water Envi- ronmental Foundation, 1015
40、 15* Street, NW, Washington, DC 20005. 4, Available from the Regional Environmental Protection Agency Publication Office. 5, Available from the Environmental Protection Agency, Office of Technology Transfer, Washington, DC 20460. 2 STD-ANSI IT4.43-ENGL L998 M 0724350 0553829 659 m ANSVPIMA lT4.43-19
41、98 Hydrogen cyanide gas and water vapor are evolved from boiling the sample solution and are separated by refluxing and by means of an air stream. The water vapor is returned to the distilling flask and the hydro- gen cyanide is carried over into a sodium hydroxide solution. The distilled cyanide io
42、n is then determined colorimetrically using the Chloramine-T method or optionally determined by titration with silver nitrate if the cyanide content is greater than 1 mg/l. 4 Reliability 4.1 Statistical reliability According to the American Public Health Association (APHA) Standard Methods 1,6? the
43、silver nitrate ti- tration for cyanide (CN-) levels above l mg/l has a coefficient of variation (100dx) of 2.0% for distilled samples or for relatively clear samples without significant interferences. The data, though obtained using the referenced method with mercuric chloride, will also apply to th
44、e method described in this standard. Using this method on one simulated photographic processing effluent, one laboratory found 95% confi- dence limits of 10.1 mg/l at a level of 2 mg/l, based on 26 pairs of data. The 95% confidence limits for six- teen standard samples (beheen 0.020 mg/l and 0.200 m
45、g/l CN-) were found to be approximately 10.010 mg/l CN?. 4.2 Interferences The EPA approved total cyanide method, ASTM D2036, is based on distillation of HCN with sulfuric acid and magnesium chloride catalyst into an alkaline receiving solution. The specified finishing step consists of either a silv
46、er complexometric titration, a Chloramine-T colorimetric measurement, or a specific ion electrode measurement. The method given in this standard is also based on the distillation of HCN with sulfuric acid and magnesium chloride catalyst into an alkaline receiving solution. The ANSI method speci- fie
47、s the Chloramine-T colorimetric finishing step or a potentiometric titration with silver nitrate. Recent studies 2, 6, 91 have shown that organic compounds can react with amines when present to- gether in wastewater to form cyanide under distillation conditions. Simulated color developing and photo-
48、 graphic processing solutions were examined in one study 8. Hydroxylamine sulfate and organic com- pounds such as EDTA, glycols, alcohols, acetic acid, and aromatic amines were mixed together. Cyanide was detected from both solutions using EPA distillation conditions even though it had not been adde
49、d. In general, it appears that various nitrogen containing compounds can produce HCN in the presence of organic compounds under various conditions. Dissolved chlorine, or chloramines commonly found in pub- lic water supplies are also active cyanide formers as confirmed by mass spectrometry 3, 41. In order to address these interferences, other analytical methods have been used to avoid distillation artifacts. These include methods such as ion chromatography 7, atomic absorption spectroscopy lo, and polarography There are o
