1、Designation: D 4453 02 (Reapproved 2006)Standard Practice forHandling of Ultra-Pure Water Samples1This standard is issued under the fixed designation D 4453; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision
2、. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This practice2covers concepts for handling ultra-purewater samples needed for the measurement of ever-decreasinglevels of specifie
3、d impurities that are encountered in theoperation of modern high-pressure boilers and turbines. Thehandling of blanks associated with the analysis of ultra-purewater samples is also covered by this practice. The techniquespresented can help the investigator increase the accuracy ofanalyses performed
4、.1.2 This practice is applicable to water and steam samplesfrom “zero solids treated” once-through or drum-type boilers,reactor coolant water, electronic grade water, or any otherprocess water where analyte concentrations are in the low partsper billion (micrograms per litre) range.1.3 This standard
5、 does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific hazardsstatements are
6、given in 5.2.3.5, 5.1, and 5.3.7.2. Referenced Documents2.1 ASTM Standards:3D 1066 Practice for Sampling SteamD 1193 Specification for Reagent Water3. Significance and Use3.1 The determination of trace impurities (on the order ofparts per billion) in ultra-pure water places extreme require-ments on
7、all aspects of the analytical system. This is particu-larly true when ubiquitous species such as sodium and chlorideare of interest because they can potentially be introduced ascontaminants at almost every step of an analytical procedure.Contamination can occur during sample collection, duringsample
8、 storage by leaching of improperly cleaned containers,during sample transfer, and by handling with pipets, syringes,etc., and during the actual analysis by contaminated reagentsand sample cells and loop systems. It is also possible that tracecontaminants can be lost from samples by volatilization or
9、precipitation, by diffusion into the matrix of the containermaterial, and by “plating out” on the walls of sampling lines byflow phenomena.3.2 Strict adherence to a given procedure is necessary toachieve good results at trace levels of analysis because verysmall differences in procedure execution wi
10、ll affect precisionand the addition or loss of nanogram amounts of analyte mayaffect the accuracy of a determination.4. Reagents and Materials4.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. It is intended that all reagents shall conform tothe specifications of the Committee
11、on Analytical Reagents ofthe American Chemical Society, where such specifications areavailable.4Other grades may be used, provided it is firstascertained that the reagent is of sufficiently high purity topermit its use without lessening the accuracy of the determi-nation.4.2 Purity of Water Referenc
12、e to high-purity water shallbe understood to mean water conforming to SpecificationD 1193, Type I reagent water, post treated with an organicremoval cartridge or demineralized water which has addition-ally been polished using a cartridge water purification systemwith an organic removal cartridge and
13、 0.2-m final filter.4.3 Hydrochloric Acid (1 + 1)Dilute concentrated hydro-chloric acid with an equal quantity of high purity water.4.4 Nitric Acid (1 + 1)Dilute concentrated nitric acid withan equal quantity of high purity water.4.5 Nitric Acid, ultra-pure.4.6 Methanol.4.7 n-hexane.1This practice i
14、s under the jurisdiction of ASTM Committee D19 on Water andis the direct responsibility of Subcommittee D19.03 on Sampling of Water andWater-Formed Deposits, Surveillance of Water, and Flow Measurement of Water.Current edition approved July 1, 2006. Published July 2006. Originally approvedin 1985. L
15、ast previous edition approved in 2002 as D 4453 02.2This practice suggests the use of specific techniques. As new techniques aredeveloped or required by lower limits, revision of this practice will likely be needed.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM
16、Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4“Reagent Chemicals,American Chemical Society Specifications,”Am. Chemi-cal Soc., Washington, DC. For suggestions on the testing of reagents not l
17、isted bythe American Chemical Society, see “Analar Standards for Laboratory Chemicals,”BDH Ltd., Poole, Dorset, U.K., and the “United States Pharmacopeia.”1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4.8 Nitrogen, organic-free.5.
18、Procedure5.1 Environmental ConditionsAny processes that mightcontaminate the analytes should be excluded from the samplingand handling area, e.g., smoke, volatile organic solvents, etc.(Warningwhen performing trace organic analyses, do notallow the use of volatile organic solvents or smoking at thes
19、ame time and within the area.)5.2 Sample Containers and Their Treatment:5.2.1 Analysis of Trace Metals:55.2.1.1 Bottles made from the following materials should beadequate: TFE-fluorocarbon FEP, HDPE, LDPE, Polypropy-lene, and polycarbonate. Caps should be made of the samematerial or, if not availab
20、le, the caps should be lined with oneof the suggested materials.5.2.1.2 Fill the bottle with HCl (1 + 1) and allow to stand for48 h at room temperature (80C for TFE-fluorocarbon), thenempty and rinse with high purity water.5.2.1.3 Fill the bottle with HNO3(1 + 1) and allow to standfor 48 h at room t
21、emperature (80C for TFE-fluorocarbon),then empty and rinse with high purity water.5.2.1.4 Fill the bottle about one third full with high puritywater, cap, shake, and empty. Wear disposable polyethylenegloves when handling the bottles from this point onward. If acontaminated surface is touched, remov
22、e and replace the glove.5.2.1.5 Repeat 5.2.1.4.5.2.1.6 Completely fill the bottle with high purity water,cap, and allow to soak for 48 h.After filling, place the bottle ina polyethylene bag and seal the bag during the storage period.The high-purity water should be changed at weekly intervalsduring l
23、ong storage periods.5.2.2 Analysis of Other Trace Ions:65.2.2.1 Containers made from the following materialsshould be adequate: HDPE, LDPE, polysulfone, polycarbon-ate, polystyrene, polypropylene, and polymethyl pentene. Thetemperature of the samples should not be above 50C whentaken or during the s
24、torage period to prevent leaching from thecontainers. (See 5.3.3.)5.2.2.2 Fill the bottle one third full with high purity water,cap, shake, and empty. Wear disposable polyethylene gloveswhen handling the bottles from this point onward. If acontaminated surface is touched, remove and replace the glov
25、e.5.2.2.3 Repeat 5.2.2.2.5.2.2.4 Completely fill the bottle with high purity water,cap, and allow to soak for a minimum of 1 day and a maximumof 5 days. After filling, place the bottle in a polyethylene bagand seal the bag during the storage period. The high-puritywater should be changed at 5-day in
26、tervals during long storageperiods.5.2.3 Analysis of Trace Organics (Acid and Base Neutrals):5.2.3.1 The sample bottle must be borosilicate glass with aTFE-fluorocarbon-lined or aluminum-lined cap.5.2.3.2 Wash in hot detergent water and rinse with tap waterthree times.5.2.3.3 Rinse three times with
27、high purity water.5.2.3.4 Bottles must be either heated to a minimum of400C in a muffle furnace (or dry heat sterilizer) for at least 30min or solvent rinsed as in 5.2.3.5.5.2.3.5 Rinse with solvents in the following order: metha-nol, n-hexane. Gloves worn during the solvent rinse maycontain plastic
28、izers (phthalates) that may cause contamination.Polyurethane, polyethylene, or nitrile rubber gloves are notlikely to have phthalates and should be used. (Warningwhenrinsing with solvents, use a fume hood with proper exhaustflow.)5.2.3.6 Dry with organic-free nitrogen to drive off thevolatile solven
29、ts.5.2.3.7 Immediately cap the bottle with a TFE-fluorocarbon-lined or aluminum-lined cap which has beenpreviously cleaned using the same method.5.2.4 Analysis of Trace Volatile Organics:5.2.4.1 The sample container must be glass with a TFE-fluorocarbon-lined septum and screw cap properly tightened
30、toprovide a hermetic seal.5.2.4.2 Wash in hot detergent water, and rinse with tap waterthree times.5.2.4.3 Rinse three times with high-purity water.5.2.4.4 Heat the vials and septa at 105C for 1 h, then coolto room temperature in an enclosed contaminant-free area. Capthe vials with the TFE-fluorocar
31、bon lining of the septum down.5.3 Sampling:5.3.1 Errors due to the sampling process can be minimizedusing an on-line measurement technique. A proper choice ofmaterials to conduct the sample to the measuring instrumentand the samples residence time in transit can affect the finalaccuracy.5.3.2 Some o
32、f the same precautions followed in the prepa-ration of the sample containers must also be followed whencollecting grab samples (see above). It is recommended thatsample conditioning condensers, coolers, and associated fit-tings and valves be of stainless steel and maintained leak free(See Practice D
33、 1066). Condensate temperature should be50C and preferably near ambient temperature.5.3.3 Any samples to be stored more than 24 h should berefrigerated (4C). Samples requiring trace PO4=,NO3,NH4+,and SO4=determinations should be refrigerated at 4C at thetime of collection. These species are subject
34、to biologicaldegradation.5.3.4 Establish a continuous flow in a well-flushed samplingline (24 h recommended). Do not readjust the flow rate lessthan 45 min before sampling. (See Practice D 1066.)5.3.5 Put on disposable polyethylene gloves before handlingthe sample bottle. Empty the bottle, rinse wit
35、h the sample(including cap) three times, fill only to the rim to prevent ionictransport in the water film on the outside of the sample bottle.Replace the bottle in the plastic bag and collect a duplicatesample.5.3.6 Samples collected for the analysis of non-alkali tracemetals should be acidified to
36、a pH of 2 with 1 mLof ultrapureHNO3per 500 mL of sample. The concentrated acid should beadded to the sample bottle so as to keep its contact time with5Except alkali and alkali earth metals.6Ions such as Na+,K+,Cl,Ca+2,Mg+2,F,Br,NH4+,NO3,SO4=, and PO4=.D 4453 02 (2006)2the bottle to a minimum.7Fill t
37、hese bottles just to the rim toavoid loss of the acid. Replace the bottle in the plastic bag andcollect a duplicate sample.5.3.7 When sampling for volatile organics the vial should befilled to overflowing so that a convex meniscus is formed. Thecap and septum with the TFE-fluorocarbon side down is p
38、lacedon the meniscus and sealed allowing no air into the vial.(Warningavoid warming the bottle to prevent breakage.)5.3.8 In the event an automatic sampler is being used, caremust be taken during set-up, and blank water must be runthrough the sampler following the initial set-up to assureadequate ri
39、nsing prior to use.5.4 Analytical Blank:5.4.1 The ability to control the level of the analytical blankhas seriously affected the accuracy of modern methods of traceelement analysis. Often it is the variability in the blankcorrection and not the absolute value of the blank that affectsthe accuracy of
40、 the analysis. As the variability becomes asignificant percentage of the sample amount, more determina-tions of the blank are necessary so that the variability can beestimated with some degree of reliability. It is a mistake to basethe blank correction on a single determination. At least threereplic
41、ate runs for the blank determination as well as thesubsequent analyses of each sample are recommended.5.4.2 All precautions observed in the preparation of bottlesfor sampling of ultra-pure water shall also be observed forbottles used in the preparation of analytical blanks.5.4.3 When acidifying samp
42、les for trace metals, also acidifythe blank with the same amount of acid.6. Keywords6.1 analysis; container; contamination; ion; samplingASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this sta
43、ndard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years an
44、dif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee,
45、which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-295
46、9,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).7This prevents the formation of ion-exchange sites on the bottles internalsurface.D 4453 02 (2006)3
