JP2016130734A - Plasma spectroscopic analysis method and plasma spectroscopic analysis apparatus - Google Patents
Plasma spectroscopic analysis method and plasma spectroscopic analysis apparatus Download PDFInfo
- Publication number
- JP2016130734A JP2016130734A JP2016003555A JP2016003555A JP2016130734A JP 2016130734 A JP2016130734 A JP 2016130734A JP 2016003555 A JP2016003555 A JP 2016003555A JP 2016003555 A JP2016003555 A JP 2016003555A JP 2016130734 A JP2016130734 A JP 2016130734A
- Authority
- JP
- Japan
- Prior art keywords
- plasma
- sample
- electrodes
- analysis method
- spectroscopic analysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004611 spectroscopical analysis Methods 0.000 title claims abstract description 34
- 238000004458 analytical method Methods 0.000 claims abstract description 79
- 238000001514 detection method Methods 0.000 claims abstract description 35
- 239000000523 sample Substances 0.000 claims description 78
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 30
- 229910052753 mercury Inorganic materials 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000012491 analyte Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229910052793 cadmium Inorganic materials 0.000 claims description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 210000002700 urine Anatomy 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 4
- 210000004369 blood Anatomy 0.000 claims description 4
- 239000008280 blood Substances 0.000 claims description 4
- 235000013305 food Nutrition 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012472 biological sample Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- 229910052770 Uranium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- 210000004209 hair Anatomy 0.000 claims description 2
- 210000000282 nail Anatomy 0.000 claims description 2
- 210000003296 saliva Anatomy 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 210000004243 sweat Anatomy 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 16
- 239000012141 concentrate Substances 0.000 abstract description 2
- 210000002381 plasma Anatomy 0.000 description 87
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 229910052755 nonmetal Inorganic materials 0.000 description 5
- 239000013307 optical fiber Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- FGGPAWQCCGEWTJ-UHFFFAOYSA-M sodium;2,3-bis(sulfanyl)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(S)CS FGGPAWQCCGEWTJ-UHFFFAOYSA-M 0.000 description 2
- ACTRVOBWPAIOHC-XIXRPRMCSA-N succimer Chemical compound OC(=O)[C@@H](S)[C@@H](S)C(O)=O ACTRVOBWPAIOHC-XIXRPRMCSA-N 0.000 description 2
- AGBQKNBQESQNJD-SSDOTTSWSA-N (R)-lipoic acid Chemical compound OC(=O)CCCC[C@@H]1CCSS1 AGBQKNBQESQNJD-SSDOTTSWSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- MDNSLPICAWKNAG-UHFFFAOYSA-N 2-(2,5-dioxopyrrol-1-yl)propanoic acid Chemical compound OC(=O)C(C)N1C(=O)C=CC1=O MDNSLPICAWKNAG-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YTGJWQPHMWSCST-UHFFFAOYSA-N Tiopronin Chemical compound CC(S)C(=O)NCC(O)=O YTGJWQPHMWSCST-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- AGBQKNBQESQNJD-UHFFFAOYSA-N alpha-Lipoic acid Natural products OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- PGLTVOMIXTUURA-UHFFFAOYSA-N iodoacetamide Chemical compound NC(=O)CI PGLTVOMIXTUURA-UHFFFAOYSA-N 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 235000019136 lipoic acid Nutrition 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229960005346 succimer Drugs 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229960002663 thioctic acid Drugs 0.000 description 1
- 229960004402 tiopronin Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45C—PURSES; LUGGAGE; HAND CARRIED BAGS
- A45C11/00—Receptacles for purposes not provided for in groups A45C1/00-A45C9/00
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45C—PURSES; LUGGAGE; HAND CARRIED BAGS
- A45C13/00—Details; Accessories
- A45C13/002—Protective covers
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45C—PURSES; LUGGAGE; HAND CARRIED BAGS
- A45C13/00—Details; Accessories
- A45C13/04—Frames
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45C—PURSES; LUGGAGE; HAND CARRIED BAGS
- A45C13/00—Details; Accessories
- A45C13/10—Arrangement of fasteners
- A45C13/12—Arrangement of fasteners of press-button or turn-button fasteners
- A45C13/123—Arrangement of fasteners of press-button or turn-button fasteners of press-buttons
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45C—PURSES; LUGGAGE; HAND CARRIED BAGS
- A45C11/00—Receptacles for purposes not provided for in groups A45C1/00-A45C9/00
- A45C2011/002—Receptacles for purposes not provided for in groups A45C1/00-A45C9/00 for portable handheld communication devices, e.g. mobile phone, pager, beeper, PDA, smart phone
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Biomedical Technology (AREA)
- Biophysics (AREA)
- Hematology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Urology & Nephrology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Molecular Biology (AREA)
- Geology (AREA)
- Combustion & Propulsion (AREA)
- Plasma & Fusion (AREA)
- Remote Sensing (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Plasma Technology (AREA)
- Electron Tubes For Measurement (AREA)
Abstract
Description
本発明は、プラズマ分光分析方法およびプラズマ分光分析装置に関する。 The present invention relates to a plasma spectroscopic analysis method and a plasma spectroscopic analysis apparatus.
試料中の分析対象物を分析する方法として、プラズマ発光を利用した分析方法が知られている。前記分析方法に関し、特許文献１には、高周波プラズマ質量分析装置を用い、試料を分析する方法が開示されている。また、特許文献２および３には、狭小部を有するプラズマ発生装置を用い、試料中でプラズマを発生させ、プラズマ発光を分析することで試料を分析する方法が開示されている。さらに、特許文献４および５には、液体の試料中でプラズマを発生させ、プラズマ発光を分析することで試料を分析する方法が開示されている。 As a method for analyzing an analysis object in a sample, an analysis method using plasma emission is known. Regarding the analysis method, Patent Document 1 discloses a method of analyzing a sample using a high-frequency plasma mass spectrometer. Patent Documents 2 and 3 disclose a method of analyzing a sample by using a plasma generator having a narrow portion, generating plasma in the sample, and analyzing plasma emission. Further, Patent Documents 4 and 5 disclose a method of analyzing a sample by generating plasma in a liquid sample and analyzing plasma emission.
しかしながら、特許文献１の方法では、適切な前処理を行わないと、他の物質の混入により分析結果が変わるという問題があった。また、特許文献２および３の方法では、夾雑物がある試料を使用した場合、および試料の液量を減らす前処理をする際に異物等が混入した場合、前記夾雑物および前記異物が前記狭小部に詰まり測定できなくなるという問題があった。さらに、特許文献４および５の方法では、分析感度が低いという問題があった。 However, the method of Patent Document 1 has a problem in that the analysis result changes due to mixing of other substances unless appropriate pretreatment is performed. In addition, in the methods of Patent Documents 2 and 3, when a sample with contaminants is used, and when foreign matter or the like is mixed during pretreatment to reduce the amount of the sample liquid, the contaminants and the foreign matter are narrowed. There was a problem that it could not be measured due to clogging. Furthermore, the methods of Patent Documents 4 and 5 have a problem of low analysis sensitivity.
そこで、本発明は、簡便、且つ分析感度の高いプラズマ分光分析方法の提供を目的とする。 Accordingly, an object of the present invention is to provide a plasma spectroscopic analysis method that is simple and has high analytical sensitivity.
前記本発明の課題を解決するために、本発明のプラズマ分光分析方法（以下、「分析方法」ともいう。）は、
試料の存在下、一対の電極への電圧印加により、少なくとも一方の電極の近傍に前記試料中の分析対象物を濃縮する濃縮工程、および
前記一対の電極への電圧印加によりプラズマを発生させ、前記プラズマにより生じた前記分析対象物の発光を検出する検出工程を含むことを特徴とする。
In order to solve the above-described problems of the present invention, a plasma spectroscopic analysis method of the present invention (hereinafter also referred to as “analysis method”) includes:
In the presence of the sample, by applying a voltage to the pair of electrodes, a concentration step of concentrating the analyte in the sample in the vicinity of at least one electrode, and generating a plasma by applying the voltage to the pair of electrodes, It includes a detection step of detecting light emission of the analysis object generated by the plasma.
本発明のプラズマ分光分析装置（以下、「分析装置」ともいう。）は、一対の電極、容器および受光部を含み、
前記容器は、透光部を含み、
前記一対の電極は、前記容器内に配置され、
前記容器の外部には、前記一対の電極への電圧印加により発生した発光を、前記透光部を通して前記分析対象物の発光を受光可能な受光部が配置され、
前記本発明のプラズマ分光分析方法に使用することを特徴とする。
The plasma spectroscopic analyzer of the present invention (hereinafter also referred to as “analyzer”) includes a pair of electrodes, a container, and a light receiving unit,
The container includes a translucent part,
The pair of electrodes are disposed in the container,
A light receiving part capable of receiving light emitted by applying voltage to the pair of electrodes and receiving light emitted from the analysis object through the light transmitting part is disposed outside the container.
The plasma spectroscopic analysis method of the present invention is used.
本発明のプラズマ分光分析方法は、簡便、且つ分析感度が高い。このため、本発明のプラズマ分光分析方法によれば、例えば、試料に前処理を行わず、簡便、且つ高い感度で試料を分析できる。 The plasma spectroscopic analysis method of the present invention is simple and has high analytical sensitivity. For this reason, according to the plasma spectroscopic analysis method of the present invention, for example, the sample can be analyzed with ease and high sensitivity without pretreatment of the sample.
＜プラズマ分光分析方法＞
本発明のプラズマ分光分析方法は、前述のように、試料の存在下、一対の電極への電圧印加により、少なくとも一方の電極の近傍に前記試料中の分析対象物を濃縮する濃縮工程、および前記一対の電極への電圧印加によりプラズマを発生させ、前記プラズマにより生じた前記分析対象物の発光を検出する検出工程を含むことを特徴とする。本発明の分析方法は、前記濃縮工程および前記検出工程を含むことが特徴であり、その他の工程および条件は、特に制限されない。
<Plasma spectroscopy method>
In the plasma spectroscopic analysis method of the present invention, as described above, the concentration step of concentrating the analyte in the sample in the vicinity of at least one electrode by applying a voltage to the pair of electrodes in the presence of the sample, and the above It includes a detection step of generating plasma by applying a voltage to a pair of electrodes and detecting light emission of the analyte generated by the plasma. The analysis method of the present invention is characterized by including the concentration step and the detection step, and other steps and conditions are not particularly limited.
一般的に、試料中の分析対象物を効率よく分析するためには、例えば、前記試料に対して、前記試料の全体積（全液量）を濃縮によって低減する前処理を施すことで、前記試料の全体積において単位体積あたりの分析対象物量を増加させていた。しかしながら、本発明によれば、以下の理由から、前記試料の全体積を低減する前処理は不要である。すなわち、本発明の分析方法によれば、前記試料の全体積を低減させなくても、前記濃縮工程において、前記一対の電極への電圧印加により、少なくとも一方の電極の近傍に前記試料中の分析対象物を濃縮、すなわち前記電極の近傍において局所的に前記分析対象物を集積することができる。このため、続く前記検出工程において、前記分析対象物が集積した電極側にプラズマを発生させることで、局所的に高濃度となった分析対象物を効率よく分析できる。しがたって、本発明の分析方法によれば、例えば、使用する試料において前記分析対象物が低濃度の場合であっても、例えば、分析に先立ち、前記試料に対する前記前処理を行うことなく、簡便に、高い感度で前記試料を分析できる。さらに、本発明の分析方法は、少なくとも一方の電極の近傍に分析対象物を集積し、前記電極側にプラズマを発生することで、効率よい分析を可能にできるため、例えば、前記先行技術文献に記載されているように、狭小部をそなえる分析装置を必須とはしない。このため、例えば、前述のような、前記試料中の夾雑物による分析装置の詰まり等を回避でき、夾雑物による分析の影響を受け難いことから、例えば、前記夾雑物を含む試料であっても、前記夾雑物を除去する前処理等も不要である。 In general, in order to efficiently analyze an analyte in a sample, for example, the sample is subjected to a pretreatment for reducing the total volume (total liquid amount) of the sample by concentration, The amount of analyte per unit volume was increased in the total volume of the sample. However, according to the present invention, the pretreatment for reducing the total volume of the sample is unnecessary for the following reasons. That is, according to the analysis method of the present invention, the analysis in the sample is performed in the vicinity of at least one of the electrodes by applying a voltage to the pair of electrodes in the concentration step without reducing the total volume of the sample. It is possible to concentrate the object, that is, to accumulate the analysis object locally in the vicinity of the electrode. For this reason, in the subsequent detection step, by generating plasma on the electrode side on which the analysis object is accumulated, the analysis object having a locally high concentration can be efficiently analyzed. Therefore, according to the analysis method of the present invention, for example, even if the analyte is in a low concentration in the sample to be used, for example, without performing the pretreatment on the sample prior to analysis, The sample can be analyzed easily and with high sensitivity. Furthermore, the analysis method of the present invention enables efficient analysis by accumulating analytes in the vicinity of at least one electrode and generating plasma on the electrode side. As described, an analyzer with a narrow portion is not required. For this reason, for example, it is possible to avoid the clogging of the analyzer due to the contaminants in the sample as described above, and it is difficult to be affected by the analysis by the contaminants. In addition, pretreatment for removing the impurities is not necessary.
本発明の分析方法において、前記試料は、例えば、検体である。前記検体は、液体の検体でもよいし、固体の検体でもよい。前記検体は、例えば、前記検体の未希釈液をそのまま液体検体として使用してもよいし、前記検体を媒体に、懸濁、分散または溶解した希釈液を液体検体として使用してもよい。前記検体が固体の場合、例えば、前記検体を前記媒体に懸濁、分散または溶解した希釈液を液体検体として使用することが好ましい。前記媒体は、特に制限されず、例えば、水、緩衝液等があげられる。前記検体は、例えば、生体由来の検体（試料）、環境由来の検体（試料）、金属、化学物質、医薬品等があげられる。前記生体由来の検体は、特に制限されず、尿、血液、毛髪、唾液、汗、爪等があげられる。前記血液検体は、例えば、赤血球、全血、血清、血漿等があげられる。前記生体は、例えば、ヒト、非ヒト動物、植物等があげられ、前記非ヒト動物は、例えば、ヒトを除く哺乳類、魚介類等があげられる。前記環境由来の検体は、特に制限されず、例えば、食品、水、土壌、大気、空気等があげられる。前記食品は、例えば、生鮮食品または加工食品等があげられる。前記水は、例えば、飲料水、地下水、河川水、海水、生活排水等があげられる。 In the analysis method of the present invention, the sample is, for example, a specimen. The specimen may be a liquid specimen or a solid specimen. As the sample, for example, an undiluted solution of the sample may be used as a liquid sample as it is, or a diluted solution suspended, dispersed or dissolved in the sample as a medium may be used as a liquid sample. When the sample is solid, for example, it is preferable to use a diluted solution in which the sample is suspended, dispersed or dissolved in the medium as the liquid sample. The medium is not particularly limited, and examples thereof include water and a buffer solution. Examples of the specimen include biological specimens (samples), environmental specimens (samples), metals, chemical substances, pharmaceuticals, and the like. The biological sample is not particularly limited, and examples thereof include urine, blood, hair, saliva, sweat, and nails. Examples of the blood sample include red blood cells, whole blood, serum, plasma and the like. Examples of the living body include humans, non-human animals, plants, and the like, and examples of the non-human animals include mammals other than humans, seafood, and the like. The environment-derived specimen is not particularly limited, and examples thereof include food, water, soil, air, and air. Examples of the food include fresh food and processed food. Examples of the water include drinking water, groundwater, river water, seawater, and domestic wastewater.
前記分析対象物は、特に制限されず、例えば、金属、化学物質等があげられる。前記金属は、特に制限されず、例えば、アルミニウム（Ａｌ）、アンチモン（Ｓｂ）、ヒ素（Ａｓ）、バリウム（Ｂａ）、ベリリウム（Ｂｅ）、ビスマス（Ｂｉ）、カドミウム（Ｃｄ）、セシウム（Ｃｓ）、ガドリニウム（Ｇｄ）、鉛（Ｐｂ）、水銀（Ｈｇ）、ニッケル（Ｎｉ）、パラジウム（Ｐｄ）、白金（Ｐｔ）、テルル（Ｔｅ）、タリウム（Ｔｌ）、トリウム（Ｔｈ）、スズ（Ｓｎ）、タングステン（Ｗ）、ウラン（Ｕ）等の金属があげられる。前記化学物質は、例えば、試薬、農薬、化粧品等があげられる。前記分析対象物は、例えば、１種類でもよいし、２種類以上でもよい。 The analysis object is not particularly limited, and examples thereof include metals and chemical substances. The metal is not particularly limited. For example, aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), cadmium (Cd), cesium (Cs) , Gadolinium (Gd), lead (Pb), mercury (Hg), nickel (Ni), palladium (Pd), platinum (Pt), tellurium (Te), thallium (Tl), thorium (Th), tin (Sn) , Metals such as tungsten (W) and uranium (U). Examples of the chemical substance include reagents, agricultural chemicals, and cosmetics. The analysis object may be one type or two or more types, for example.
前記分析対象物が金属の場合、前記試料は、例えば、前記検体中の金属を分離するための試薬を含んでもよい。前記試薬は、例えば、キレート剤、マスキング剤等があげられる。前記キレート剤は、例えば、ジチゾン、チオプロニン、メソ−２，３−ジメルカプトコハク酸（ＤＭＳＡ）、２，３−ジメルカプト−１−プロパンスルホン酸ナトリウム（ＤＭＰＳ）、エチレンジアミン四酢酸（ＥＤＴＡ）、ニトリロ三酢酸（ＮＴＡ）、エチレンジアミン-N,N'-ジコハク酸（ＥＤＤＳ）、αリポ酸等があげられる。本発明において、「マスキング」は、ＳＨ基の反応性を不活性にすることを意味し、例えば、ＳＨ基の化学修飾により行うことができる。前記マスキング剤は、例えば、マレイミド、Ｎ−メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−フェニルマレイミド、マレイミドプロピオン酸、ヨードアセトアミド、ヨード酢酸等があげられる。 When the analysis object is a metal, the sample may include, for example, a reagent for separating the metal in the specimen. Examples of the reagent include chelating agents and masking agents. Examples of the chelating agent include dithizone, thiopronin, meso-2,3-dimercaptosuccinic acid (DMSA), sodium 2,3-dimercapto-1-propanesulfonate (DMPS), ethylenediaminetetraacetic acid (EDTA), nitrilotri Examples include acetic acid (NTA), ethylenediamine-N, N′-disuccinic acid (EDDS), α-lipoic acid, and the like. In the present invention, “masking” means inactivating the reactivity of the SH group, and can be performed, for example, by chemical modification of the SH group. Examples of the masking agent include maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, maleimidopropionic acid, iodoacetamide, iodoacetic acid and the like.
前記試料は、例えば、ｐＨを調整した試料（以下、「ｐＨ調整試料」ともいう。）でもよい。前記ｐＨ調整試料のｐＨは、特に制限されない。前記試料のｐＨの調整方法は、特に制限されず、例えば、アルカリ性試薬、酸性試薬等のｐＨ調整試薬が使用できる。 The sample may be, for example, a sample with adjusted pH (hereinafter also referred to as “pH adjusted sample”). The pH of the pH adjusted sample is not particularly limited. The method for adjusting the pH of the sample is not particularly limited, and for example, a pH adjusting reagent such as an alkaline reagent or an acidic reagent can be used.
前記アルカリ性試薬は、例えば、アルカリおよびその水溶液等があげられる。前記アルカリは、特に制限されず、例えば、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、アンモニア等があげられる。前記アルカリの水溶液は、例えば、アルカリを水または緩衝液で希釈したものがあげられる。前記アルカリの水溶液において、前記アルカリの濃度は、特に制限されず、例えば、０．０１〜５ｍｏｌ／Ｌである。 Examples of the alkaline reagent include alkali and an aqueous solution thereof. The alkali is not particularly limited, and examples thereof include sodium hydroxide, lithium hydroxide, potassium hydroxide, and ammonia. Examples of the aqueous alkali solution include those obtained by diluting an alkali with water or a buffer solution. In the aqueous alkali solution, the concentration of the alkali is not particularly limited, and is, for example, 0.01 to 5 mol / L.
前記酸性試薬は、例えば、酸およびその水溶液等があげられる。前記酸は、特に制限されず、例えば、塩酸、硫酸、酢酸、ホウ酸、リン酸、クエン酸、リンゴ酸、コハク酸、硝酸等があげられる。前記酸の水溶液は、例えば、酸を水または緩衝液で希釈したものがあげられる。前記酸の水溶液において、前記酸の濃度は、特に制限されず、例えば、０．０１〜５ｍｏｌ／Ｌである。 Examples of the acidic reagent include acids and aqueous solutions thereof. The acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, acetic acid, boric acid, phosphoric acid, citric acid, malic acid, succinic acid, and nitric acid. Examples of the acid aqueous solution include those obtained by diluting an acid with water or a buffer solution. In the acid aqueous solution, the acid concentration is not particularly limited, and is, for example, 0.01 to 5 mol / L.
前記電極は、特に制限されず、例えば、固体電極があげられ、具体例として、棒電極等があげられる。前記電極の材料は、特に制限されず、固形導電材料であればよく、例えば、前記分析対象物の種類に応じて、適宜決定できる。前記電極の材料は、例えば、非金属でもよいし、金属でもよいし、これらの混合物でもよい。前記電極の材料が非金属を含む場合、前記電極の材料は、例えば、１種類の非金属を含んでもよいし、２種類以上の非金属を含んでもよい。前記非金属は、例えば、炭素等があげられる。前記電極の材料が金属を含む場合、前記電極の材料は、例えば、１種類の金属を含んでもよいし、２種類以上の金属を含んでもよい。前記金属は、例えば、金、白金、銅、亜鉛、スズ、ニッケル、パラジウム、チタン、モリブデン、クロム、鉄等があげられる。前記電極の材料が２種類以上の金属を含む場合、前記電極の材料は、合金でもよい。前記合金は、例えば、真鍮、鋼、インコネル（登録商標）、ニクロム、ステンレス等があげられる。前記一対の電極は、例えば、同じ材料でもよいし、異なる材料でもよい。 The electrode is not particularly limited, and examples thereof include a solid electrode, and specific examples thereof include a rod electrode. The material of the electrode is not particularly limited as long as it is a solid conductive material, and can be appropriately determined according to, for example, the type of the analysis object. The electrode material may be, for example, a non-metal, a metal, or a mixture thereof. When the material of the electrode includes a nonmetal, the material of the electrode may include, for example, one type of nonmetal or two or more types of nonmetal. Examples of the nonmetal include carbon. When the material of the electrode includes a metal, the material of the electrode may include, for example, one type of metal or two or more types of metal. Examples of the metal include gold, platinum, copper, zinc, tin, nickel, palladium, titanium, molybdenum, chromium, and iron. When the electrode material includes two or more kinds of metals, the electrode material may be an alloy. Examples of the alloy include brass, steel, Inconel (registered trademark), nichrome, and stainless steel. The pair of electrodes may be made of the same material or different materials, for example.
前記電極の大きさは、特に制限されず、例えば、前記試料と接液可能な大きさであればよい。前記電極が棒電極である場合、前記電極の直径は、例えば、０．０２〜５０ｍｍ、０．０５〜５ｍｍであり、前記電極の長さは、例えば、０．１〜２００ｍｍ、０．３〜５０ｍｍである。前記一対の電極の大きさは、同じでもよいし、異なってもよい。 The size of the electrode is not particularly limited, and may be a size that can come into contact with the sample, for example. When the electrode is a rod electrode, the diameter of the electrode is, for example, 0.02 to 50 mm, 0.05 to 5 mm, and the length of the electrode is, for example, 0.1 to 200 mm, 0.3 to 50 mm. The size of the pair of electrodes may be the same or different.
前記濃縮工程は、前述のように、試料の存在下、一対の電極への電圧印加により、少なくとも一方の電極の近傍に前記試料中の分析対象物を濃縮する工程である。前記一対の電極は、例えば、前記試料に接触（接液）している。前記濃縮工程において、前記電極の近傍は、特に制限されず、例えば、後述する検出工程において、プラズマが発生する範囲があげられる。本発明において、前記電極の近傍は、例えば、電極上も含む。 As described above, the concentration step is a step of concentrating the analyte in the sample in the vicinity of at least one electrode by applying a voltage to the pair of electrodes in the presence of the sample. The pair of electrodes are in contact (wetted) with the sample, for example. In the concentration step, the vicinity of the electrode is not particularly limited, and examples thereof include a range where plasma is generated in the detection step described later. In the present invention, the vicinity of the electrode includes, for example, the electrode.
前記濃縮工程において、例えば、前記分析対象物の一部を前記電極の近傍に濃縮してもよいし、前記分析対象物の全部を前記電極の近傍に濃縮してもよい。 In the concentration step, for example, a part of the analysis object may be concentrated near the electrode, or the entire analysis object may be concentrated near the electrode.
前記濃縮工程では、後述する検出工程において、前記分析対象物の検出に使用する電極、すなわちプラズマが発生する電極に前記分析対象物を濃縮するように、前記電極の電荷条件を設定することが好ましい。前記電荷条件は、特に制限されず、例えば、前記分析対象物が正の電荷を有する場合、前記プラズマが発生する電極が負の電荷を有するように電荷条件を設定すればよい。また、例えば、前記分析対象物が負の電荷を有する場合、前記プラズマが発生する電極が正の電荷を有するように電荷条件を設定すればよい。 In the concentration step, it is preferable that the charge condition of the electrode is set so that the analysis target is concentrated on the electrode used for detection of the analysis target, that is, the electrode where plasma is generated, in the detection step described later. . The charge condition is not particularly limited. For example, when the analysis object has a positive charge, the charge condition may be set so that the electrode generating the plasma has a negative charge. For example, when the analysis object has a negative charge, the charge condition may be set so that the electrode generating the plasma has a positive charge.
前記分析対象物の濃縮は、例えば、電圧によって調節できる。このため、当業者であれば、前記濃縮がおきる電圧（以下、「濃縮電圧」ともいう。）を適宜設定できる。前記濃縮電圧は、例えば、１ｍＶ以上、４００ｍＶ以上であり、その上限は、特に制限されない。前記濃縮電圧は、例えば、一定でもよいし、変動してもよい。また、前記濃縮電圧は、例えば、プラズマが発生しない電圧でもよい。 The concentration of the analyte can be adjusted by voltage, for example. For this reason, those skilled in the art can appropriately set the voltage at which the concentration occurs (hereinafter also referred to as “concentration voltage”). The concentration voltage is, for example, 1 mV or more and 400 mV or more, and the upper limit is not particularly limited. The concentration voltage may be constant or may vary, for example. Further, the concentration voltage may be a voltage at which plasma is not generated, for example.
前記濃縮電圧を印加する時間は、特に制限されず、前記濃縮電圧に応じて、適宜設定できる。前記濃縮電圧を印加する時間は、例えば、０．２〜４０分、１〜５分である。前記一対の電極への電圧印加は、例えば、連続的に印加してもよいし、非連続的に印加してもよい。前記非連続的な印加は、例えば、パルス印加があげられる。前記電圧印加が非連続的な場合、前記濃縮電圧を印加する時間は、例えば、前記濃縮電圧を印加している時間の合計の時間でもよいし、前記濃縮電圧を印加している時間と前記濃縮電圧を印加していない時間との合計の時間でもよい。 The time for applying the concentrated voltage is not particularly limited, and can be appropriately set according to the concentrated voltage. The time for applying the concentration voltage is, for example, 0.2 to 40 minutes or 1 to 5 minutes. The voltage application to the pair of electrodes may be applied continuously or discontinuously, for example. Examples of the non-continuous application include pulse application. When the voltage application is discontinuous, the time for applying the concentration voltage may be, for example, the total time for applying the concentration voltage, or the time for applying the concentration voltage and the time for concentration. The total time may be the time when no voltage is applied.
前記電極への電圧の印加は、電圧印加手段により行うことができる。電圧印加手段は、特に制限されず、例えば、前記電極間に電圧を印加できればよく、公知の手段として電圧器等が使用できる。前記濃縮工程において、前記電極間の電流は、例えば、０．０１〜２００ｍＡ、１０〜６０ｍＡ、１０〜４０ｍＡに設定できる。 The voltage can be applied to the electrodes by a voltage applying means. The voltage application means is not particularly limited, and for example, it is sufficient if a voltage can be applied between the electrodes, and a voltage device or the like can be used as a known means. In the concentration step, the current between the electrodes can be set to 0.01 to 200 mA, 10 to 60 mA, and 10 to 40 mA, for example.
前記検出工程は、前述のように、前記一対の電極への電圧印加によりプラズマを発生させ、前記プラズマにより生じた前記分析対象物の発光を検出する。 As described above, in the detection step, plasma is generated by applying a voltage to the pair of electrodes, and light emission of the analysis object generated by the plasma is detected.
前記検出工程は、前記濃縮工程と連続的に行ってもよいし、非連続的に行ってもよい。前者の場合、前記検出工程は、前記濃縮工程の終了と同時に前記検出工程を行う。後者の場合、前記検出工程は、前記濃縮工程の終了後から所定時間内に検出工程を行う。前記所定時間は、例えば、前記濃縮工程後、０．００１〜１０００秒、１〜１０秒である。 The detection step may be performed continuously with the concentration step or may be performed discontinuously. In the former case, the detection step is performed simultaneously with the end of the concentration step. In the latter case, the detection step is performed within a predetermined time after the end of the concentration step. The predetermined time is, for example, 0.001 to 1000 seconds and 1 to 10 seconds after the concentration step.
前記検出工程において、「プラズマを発生させる」とは、プラズマを実質的に発生させることであり、具体的には、プラズマ発光の検出において、実質的に検出可能な発光を示すプラズマの発生を意味する。具体例として、プラズマ発光の検出器により、プラズマ発光が検出可能であるといえる。 In the detection step, “to generate plasma” means to substantially generate plasma. Specifically, in detection of plasma emission, it means generation of plasma that exhibits substantially detectable light emission. To do. As a specific example, it can be said that plasma emission can be detected by a plasma emission detector.
実質的なプラズマの発生は、例えば、電圧によって調節できる。このため、当業者であれば、実質的に検出可能な発光を示すプラズマを発生させるための電圧（以下、「プラズマ電圧」ともいう。）は、適宜設定できる。前記プラズマ電圧は、例えば、１０Ｖ以上、１００Ｖ以上であり、その上限は、特に制限されない。前記プラズマが発生する電圧は、例えば、前記濃縮が起こる電圧に対して、相対的に高い電圧である。このため、前記プラズマ電圧は、前記濃縮電圧に対して、高い電圧であることが好ましい。前記プラズマ電圧は、例えば、一定でもよいし、変動してもよい。 Substantial plasma generation can be adjusted, for example, by voltage. For this reason, those skilled in the art can appropriately set a voltage (hereinafter, also referred to as “plasma voltage”) for generating plasma exhibiting substantially detectable light emission. The plasma voltage is, for example, 10 V or more and 100 V or more, and the upper limit is not particularly limited. The voltage generated by the plasma is, for example, a voltage that is relatively higher than the voltage at which the concentration occurs. For this reason, it is preferable that the plasma voltage is higher than the concentrated voltage. The plasma voltage may be constant or may vary, for example.
前記プラズマ電圧を印加する時間は、特に制限されず、前記プラズマ電圧に応じて、適宜設定できる。前記プラズマ電圧を印加する時間は、例えば、０．００１〜０．０２秒、０．００１〜０．０１秒である。前記一対の電極への電圧印加は、例えば、連続的に印加してもよいし、非連続的に印加してもよい。前記非連続的な印加は、例えば、パルス印加があげられる。前記電圧印加が非連続的な場合、前記プラズマ電圧を印加する時間は、例えば、１回の前記プラズマ電圧を印加している時間でもよいし、前記プラズマ電圧を印加している時間の合計の時間でもよいし、前記プラズマ電圧を印加している時間と前記プラズマ電圧を印加していない時間との合計の時間でもよい。 The time for applying the plasma voltage is not particularly limited, and can be set as appropriate according to the plasma voltage. The time for applying the plasma voltage is, for example, 0.001 to 0.02 seconds and 0.001 to 0.01 seconds. The voltage application to the pair of electrodes may be applied continuously or discontinuously, for example. Examples of the non-continuous application include pulse application. When the voltage application is discontinuous, the plasma voltage application time may be, for example, a time during which the plasma voltage is applied once, or a total time during which the plasma voltage is applied. Alternatively, the total time of the time during which the plasma voltage is applied and the time during which the plasma voltage is not applied may be used.
前記検出工程において、前記プラズマが発生する電極は、例えば、前記一対の電極の接液面積を異なる接液面積とすることで調節できる。具体的には、一方の電極の接液面積を他方の電極に対して接液面積を小さくすることで、前者に、プラズマを発生させることができる。このため、本発明において、前記一対の電極は、前記試料との接液面積が異なる一対の電極であり、前記一対の電極のうち、前記試料との接液面積が小さい電極が、プラズマ発生により前記分析対象物を分析する電極であることが好ましい。前記一対の電極の接液面積が異なる場合、前記一対の電極の接液面積の差は、例えば、０．００１〜３００ｃｍ２、１〜１０ｃｍ２である。本発明において、「接液面積」は、前記試料と接する面積を意味する。前記接液面積の調節方法は、特に制限されず、例えば、前記試料に浸漬する前記電極の長さを異なる長さにする方法、前記試料と接する電極の一部を絶縁性材料により被覆する方法等があげられる。前記絶縁性材料は、特に制限されず、例えば、樹脂、シリコーン、ガラス、紙、セラミックス、ゴム等があげられる。前記樹脂は、例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリエチレンテレフタレート、ポリメタクリレート、ポリアミド、飽和ポリエステル樹脂、アクリル樹脂、ポリブチレンテレフタレート（ＰＢＴ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリメチルペンテン（例えば、登録商標ＴＰＸ）等の熱可塑性樹脂、尿素樹脂、メラミン樹脂、フェノール樹脂、フッ素樹脂ガラスエポキシ等のエポキシ樹脂、不飽和ポリエステル樹脂等の熱硬化性樹脂等があげられる。前記シリコーンは、例えば、ポリジメチルシロキサン等があげられる。 In the detection step, the electrode from which the plasma is generated can be adjusted, for example, by setting the wetted areas of the pair of electrodes to different wetted areas. Specifically, plasma can be generated in the former by reducing the liquid contact area of one electrode with respect to the other electrode. Therefore, in the present invention, the pair of electrodes are a pair of electrodes having different liquid contact areas with the sample, and of the pair of electrodes, an electrode having a small liquid contact area with the sample is generated by plasma generation. The electrode is preferably used for analyzing the analysis object. When the wetted areas of the pair of electrodes are different, the difference in wetted area of the pair of electrodes is, for example, 0.001 to 300 cm 2 , 1 to 10 cm 2 . In the present invention, the “wetted area” means an area in contact with the sample. The method for adjusting the liquid contact area is not particularly limited. For example, the electrode immersed in the sample has a different length, and the electrode in contact with the sample is covered with an insulating material. Etc. The insulating material is not particularly limited, and examples thereof include resin, silicone, glass, paper, ceramics, and rubber. Examples of the resin include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polymethacrylate, polyamide, saturated polyester resin, acrylic resin, polybutylene terephthalate (PBT), polyetheretherketone (PEEK), polymethylpentene ( Examples thereof include thermoplastic resins such as registered trademark TPX), epoxy resins such as urea resin, melamine resin, phenol resin and fluororesin glass epoxy, and thermosetting resins such as unsaturated polyester resin. Examples of the silicone include polydimethylsiloxane.
前記検出工程において、前記発生したプラズマの発光は、例えば、連続的に検出してもよいし、非連続的に検出してもよい。前記発光の検出は、例えば、発光の有無の検出、発光の強度の検出、特定の波長の検出、スペクトルの検出等があげられる。前記特定の波長の検出は、例えば、前記分析対象物が、プラズマ発光時に発する特有の波長の検出があげられる。前記発光の検出方法は、特に制限されず、例えば、ＣＣＤ（Charge Coupled Device）、分光器等の公知の光学測定機器が利用できる。 In the detection step, the light emission of the generated plasma may be detected, for example, continuously or discontinuously. Examples of the light emission detection include detection of the presence or absence of light emission, detection of the intensity of light emission, detection of a specific wavelength, detection of a spectrum, and the like. The detection of the specific wavelength includes, for example, detection of a specific wavelength that the analysis object emits during plasma emission. The light emission detection method is not particularly limited, and for example, a known optical measurement device such as a CCD (Charge Coupled Device) or a spectroscope can be used.
前記電極への電圧の印加は、電圧印加手段により行うことができる。電圧印加手段は、例えば、前述の説明が援用できる。前記検出工程において、前記電極間の電流は、例えば、０．０１〜１０００００ｍＡ、５０〜２０００ｍＡに設定できる。 The voltage can be applied to the electrodes by a voltage applying means. As the voltage applying means, for example, the above description can be used. In the detection step, the current between the electrodes can be set to, for example, 0.01 to 100,000 mA and 50 to 2000 mA.
本発明の分析方法は、さらに、検出工程における検出結果から、前記試料中の前記分析対象物の濃度を算出する算出工程を含んでもよい。前記検出結果は、例えば、前述の発光の強度等があげられる。前記算出工程において、前記分析対象物の濃度は、例えば、検出結果、および検出結果と試料中の前記分析対象物の濃度との相関関係に基づき、算出できる。前記相関関係は、例えば、前記分析対象物の濃度が既知である標準試料について、前記本発明の分析方法により得られた検出結果と、前記標準試料の前記分析対象物の濃度とをプロットすることにより求めることができる。前記標準試料は、前記分析対象物の希釈系列が好ましい。このように算出を行うことによって、信頼性の高い定量が可能となる。 The analysis method of the present invention may further include a calculation step of calculating the concentration of the analysis object in the sample from the detection result in the detection step. Examples of the detection result include the above-described emission intensity. In the calculation step, the concentration of the analysis target can be calculated based on, for example, a detection result and a correlation between the detection result and the concentration of the analysis target in the sample. The correlation is, for example, plotting the detection result obtained by the analysis method of the present invention and the concentration of the analyte in the standard sample for a standard sample having a known concentration of the analyte. It can ask for. The standard sample is preferably a dilution series of the analyte. By calculating in this way, reliable quantification is possible.
本発明の分析方法において、前記一対の電極は、透光部を含む容器内に配置されていてもよい。この場合、前記検出工程において、前記透光部を通して前記分析対象物の発光を受光可能に配置された受光部により前記発光を検出する。前記容器、前記透光部、前記受光部等の説明は、例えば、後述する本発明の分析装置の説明を援用できる。 In the analysis method of the present invention, the pair of electrodes may be disposed in a container including a light transmitting part. In this case, in the detection step, the light emission is detected by a light receiving portion arranged so as to be able to receive light emission of the analysis object through the light transmitting portion. For the description of the container, the light transmitting part, the light receiving part and the like, for example, the description of the analyzer of the present invention described later can be used.
＜プラズマ分光分析装置＞
本発明のプラズマ分光分析装置は、前述のように、一対の電極、容器および受光部を含み、前記容器は、透光部を含み、前記一対の電極は、前記容器内に配置され、前記容器の外部には、前記一対の電極への電圧印加により発生した発光を、前記透光部を通して前記分析対象物の発光を受光可能な受光部が配置され、前記本発明のプラズマ分光分析方法に使用することを特徴とする。本発明の分析装置は、前記本発明の分析方法に使用することが特徴であり、その他の構成および条件は、特に制限されない。本発明の分析装置によれば、前記本発明の分析方法を簡便に実施できる。本発明の分析装置は、例えば、前記本発明の分析方法と互いの説明を援用できる。
<Plasma spectroscopy analyzer>
As described above, the plasma spectroscopic analyzer of the present invention includes a pair of electrodes, a container, and a light receiving unit, the container includes a light transmitting unit, and the pair of electrodes are disposed in the container, and the container A light receiving portion capable of receiving light emitted by applying a voltage to the pair of electrodes and receiving light emitted from the analysis object through the light transmitting portion is disposed outside the device, and is used in the plasma spectroscopic analysis method of the present invention. It is characterized by doing. The analysis apparatus of the present invention is characterized by being used in the analysis method of the present invention, and other configurations and conditions are not particularly limited. According to the analyzer of the present invention, the analysis method of the present invention can be easily implemented. The analysis apparatus of the present invention can use, for example, the analysis method of the present invention and the mutual explanation.
本発明の分析装置の一例について、図面を参照し説明する。また、図面においては、説明の便宜上、各部の構造は適宜簡略化して示す場合があり、各部の寸法比等は、実際とは異なり、模式的に示す場合がある。 An example of the analyzer of the present invention will be described with reference to the drawings. In the drawings, for convenience of explanation, the structure of each part may be simplified as appropriate, and the dimensional ratio of each part may be schematically shown, unlike the actual case.
図１において、（Ａ）は、本実施形態の分析装置の模式透視斜視図であり、（Ｂ）は、（Ａ）において、Ｉ−Ｉ方向からみた模式断面図である。図１（Ａ）および（Ｂ）に示すように、本実施形態の分析装置１０は、一対の電極１、２、容器４、および受光部５を含み、容器４は、透光部３を含み、容器４の外部には、一対の電極１、２への電圧印加により発生した発光を、透光部３を通して前記分析対象物の発光を受光可能に配置された受光部５が配置されている。また、電極１は、容器４の底面に対して垂直方向に配置され、その先端は、透光部３と当接するように配置されている。電極２は、容器４の側面から内部に向かって配置されている。電極１は、絶縁性材料６により被覆されている。本実施形態の分析装置１０において、前記分析対象物を含む試料は、例えば、容器４の筒内に、電極１、２と接するように導入される。本実施形態において、分析装置１０は、縦置き型の分析装置としているが、分析装置１０は、この実施形態に限定されず、例えば、横置き型の分析装置としてもよい。 1A is a schematic perspective view of the analyzer of the present embodiment, and FIG. 1B is a schematic cross-sectional view as viewed from the II direction in FIG. As shown in FIGS. 1A and 1B, the analyzer 10 of the present embodiment includes a pair of electrodes 1, 2, a container 4, and a light receiving unit 5, and the container 4 includes a light transmitting unit 3. The light receiving unit 5 is disposed outside the container 4 so as to be able to receive light emitted by applying voltage to the pair of electrodes 1 and 2 through the light transmitting unit 3. . The electrode 1 is disposed in a direction perpendicular to the bottom surface of the container 4, and the tip thereof is disposed so as to contact the light transmitting part 3. The electrode 2 is disposed from the side surface of the container 4 toward the inside. The electrode 1 is covered with an insulating material 6. In the analyzer 10 of the present embodiment, the sample containing the analysis object is introduced into the cylinder of the container 4 so as to be in contact with the electrodes 1 and 2, for example. In the present embodiment, the analyzer 10 is a vertically installed analyzer, but the analyzer 10 is not limited to this embodiment, and may be a horizontally installed analyzer, for example.
本実施形態において、電極１は、その表面の一部を絶縁性材料６により被覆されているが、絶縁性材料６は、任意の構成であり、あってもよいし、なくてもよい。また、本実施形態において、電極１、２は、容器４の異なる面に配置されているが、電極１、２の配置位置は、特に制限されず、例えば、任意の位置に配置できる。 In the present embodiment, a part of the surface of the electrode 1 is covered with the insulating material 6, but the insulating material 6 may have any configuration and may or may not be present. Moreover, in this embodiment, although the electrodes 1 and 2 are arrange | positioned in the different surface of the container 4, the arrangement position of the electrodes 1 and 2 is not restrict | limited in particular, For example, it can arrange | position in arbitrary positions.
本実施形態において、電極１と透光部３とは接しているが、本発明はこれに限定されず、例えば、電極１が透光部３から離れて配置されてもよい。電極１と容器４の底面との距離は、特に制限されず、例えば、０〜２ｃｍ、０〜０．５ｃｍである。 In this embodiment, although the electrode 1 and the translucent part 3 are in contact, this invention is not limited to this, For example, the electrode 1 may be arrange | positioned away from the translucent part 3. The distance in particular of the electrode 1 and the bottom face of the container 4 is not restrict | limited, For example, it is 0-2 cm and 0-0.5 cm.
透光部３の材料は、特に制限されず、例えば、一対の電極１、２への電圧印加により発生した発光を透光する材料であればよく、前記発光の波長に応じて、適宜設定できる。透光部３の材料は、例えば、石英ガラス、アクリル樹脂（ＰＭＭＡ）、ホウケイ酸ガラス、ポリカーボネート（ＰＣ）、シクロオレフィンポリマー（ＣＯＰ）、メチルペンテンポリマー（ＴＰＸ（登録商標））等があげられる。透光部３の大きさは、特に制限されず、例えば、一対の電極１、２への電圧印加により発生した発光を透光可能な大きさであればよい。 The material of the translucent part 3 is not particularly limited, and may be any material as long as it is a material that transmits light emitted by applying a voltage to the pair of electrodes 1 and 2, and can be appropriately set according to the wavelength of the light emission. . Examples of the material of the translucent part 3 include quartz glass, acrylic resin (PMMA), borosilicate glass, polycarbonate (PC), cycloolefin polymer (COP), and methylpentene polymer (TPX (registered trademark)). The size of the translucent part 3 is not particularly limited, and may be any size as long as it can transmit light emitted by applying a voltage to the pair of electrodes 1 and 2.
本実施形態において、容器４は、有底筒状であるが、容器４の形状はこれに限定されず、任意の形状としてよい。容器４の材料は、特に制限されず、例えば、アクリル樹脂（ＰＭＭＡ）、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、ポリ塩化ビニル（ＰＶＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリスチレン（ＰＳ）等があげられる。容器４の容積は、例えば、０．３〜０．５ｃｍ３である。容器４が有底筒状である場合、容器４の直径は、例えば、０．４〜５０ｃｍ、１〜５ｃｍであり、その高さは、例えば、０．３〜５０ｃｍ、０．７〜２ｃｍである。 In the present embodiment, the container 4 has a bottomed cylindrical shape, but the shape of the container 4 is not limited to this, and may be an arbitrary shape. The material of the container 4 is not particularly limited, and examples thereof include acrylic resin (PMMA), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polyethylene terephthalate (PET), and polystyrene (PS). . The volume of the container 4 is, for example, 0.3 to 0.5 cm 3 . When the container 4 has a bottomed cylindrical shape, the diameter of the container 4 is, for example, 0.4 to 50 cm and 1 to 5 cm, and the height thereof is, for example, 0.3 to 50 cm and 0.7 to 2 cm. is there.
受光部５は、特に制限されず、例えば、ＣＣＤ、分光器等の公知の光学測定機器があげられる。受光部５は、例えば、分析装置１０の外部に配置された前記光学測定機器に前記発光を伝送する伝送手段でもよい。前記伝送手段は、例えば、光ファイバー等の伝送路があげられる。 The light receiving unit 5 is not particularly limited, and examples thereof include known optical measurement devices such as a CCD and a spectroscope. The light receiving unit 5 may be, for example, a transmission unit that transmits the light emission to the optical measurement device arranged outside the analyzer 10. Examples of the transmission means include a transmission path such as an optical fiber.
容器４の製造方法は、特に制限されず、例えば、射出成型等により、成型体を製造してもよいし、プレート等の基材に凹部を形成することで製造してもよい。その他、容器４等の製造方法は、特に制限されず、例えば、リソグラフィ、切削加工等があげられる。 The manufacturing method of the container 4 is not particularly limited, and for example, a molded body may be manufactured by injection molding or the like, or may be manufactured by forming a recess in a substrate such as a plate. In addition, the manufacturing method of the container 4 or the like is not particularly limited, and examples thereof include lithography and cutting.
つぎに、本発明の実施例について説明する。なお、本発明は、下記の実施例により制限されない。 Next, examples of the present invention will be described. In addition, this invention is not restrict | limited by the following Example.
（実施例１）
本発明の分析方法により、水銀を感度よく分析できることを確認した。
Example 1
It was confirmed that mercury can be analyzed with high sensitivity by the analysis method of the present invention.
（１）プラズマ分光分析装置
前記実施形態の分析装置を準備した。具体的には、有底筒状の透明ＰＭＭＡ製容器（高さ１５ｍｍ×直径φ１０ｍｍ）を準備した。前記容器の底部の中央には、石英ガラスを配置した。前記容器内に、電極１と電極２とを配置した。前記電極１は、前記容器底面に対して垂直方向に配置した。そして、電極１の先端が、前記容器の底部の石英ガラスに当接するように配置した。電極１は、直径０．１２ｍｍの真鍮棒を使用した。電極１は、先端から０．３ｍｍまでを露出し、その他の領域を絶縁したものを使用した。電極２は、電極１に対して垂直方向であって、前記容器の側面から内部に向かって配置した。電極２は、直径２．５ｍｍの炭素電極棒を使用した。また、前記石英ガラスを介して、電極１の先端と対面するように光ファイバーを配置した。前記光ファイバーは、直径４００μｍ 単芯の光ファイバーを使用した。また、前記光ファイバーは、凹面グレーティング方式の分光器（自家調製）に接続した。
(1) Plasma spectroscopic analyzer The analyzer of the above embodiment was prepared. Specifically, a bottomed cylindrical transparent PMMA container (height 15 mm × diameter φ10 mm) was prepared. Quartz glass was placed in the center of the bottom of the container. The electrode 1 and the electrode 2 were arrange | positioned in the said container. The electrode 1 was arranged in a direction perpendicular to the bottom surface of the container. And the front-end | tip of the electrode 1 was arrange | positioned so that it might contact | abut to the quartz glass of the bottom part of the said container. The electrode 1 was a brass rod having a diameter of 0.12 mm. The electrode 1 was used by exposing 0.3 mm from the tip and insulating the other regions. The electrode 2 was arranged in a direction perpendicular to the electrode 1 from the side of the container toward the inside. The electrode 2 was a carbon electrode rod having a diameter of 2.5 mm. Further, an optical fiber was disposed so as to face the tip of the electrode 1 through the quartz glass. As the optical fiber, a single core optical fiber having a diameter of 400 μm was used. The optical fiber was connected to a concave grating type spectroscope (self-prepared).
（２）プラズマ分光分析
０．３ｍＬの０．１ｍｏｌ／Ｌ 硝酸水溶液に、１００ｐｐｂとなるように塩化水銀を溶解し、これを水銀試料とした。つぎに、前記分析装置の前記容器の内部に、前記水銀試料を導入した。そして、電極１と電極２との間に、電極１が陰極（カソード）となり、電極２が陽極（アノード）となるよう、下記の濃縮条件で電圧を印加し、電極１の近傍に前記水銀を濃縮した。
(2) Plasma spectroscopic analysis Mercury chloride was dissolved in 0.3 mL of 0.1 mol / L nitric acid aqueous solution so as to be 100 ppb, and this was used as a mercury sample. Next, the mercury sample was introduced into the container of the analyzer. A voltage is applied between the electrode 1 and the electrode 2 under the following concentration conditions so that the electrode 1 becomes a cathode (cathode) and the electrode 2 becomes an anode (anode). Concentrated.
（濃縮条件）
印加電圧：３０Ｖと０Ｖとの繰り返し
パルス幅：５０μｓ
Ｄｕｔｙ：９９％
印加時間：５００ｍｓ
印加回数：１ｓ間隔で２５０回
(Concentration conditions)
Applied voltage: 30V and 0V repetition Pulse width: 50μs
Duty: 99%
Application time: 500 ms
Number of applications: 250 times at 1s intervals
前記濃縮直後に、さらに、電極１と電極２との間に、電極１が陽極となり、電極２が陰極となるよう、下記のプラズマ発生条件で電圧および電流を印加し、発生したプラズマ発光の各波長における発光強度（カウント値）を測定した。また、コントロール（比較例）は、前記濃縮を行わなかった以外は同様にして、発生したプラズマ発光のスペクトルを測定した。 Immediately after the concentration, a voltage and a current are applied under the following plasma generation conditions so that the electrode 1 becomes an anode and the electrode 2 becomes a cathode between the electrodes 1 and 2. The emission intensity (count value) at the wavelength was measured. The control (comparative example) measured the spectrum of the generated plasma emission in the same manner except that the concentration was not performed.
（プラズマ発生条件）
印加電圧：１５０Ｖと０Ｖとの繰り返し
パルス幅：５０μｓ
Ｄｕｔｙ：８０％
印加時間：１００ｍｓ
(Plasma generation conditions)
Applied voltage: 150V and 0V repetition Pulse width: 50μs
Duty: 80%
Application time: 100 ms
この結果を図２に示す。図２は、水銀ピーク付近のスペクトルを示すグラフである。図２において、横軸は、波長を示し、縦軸は、発光強度（カウント値）を示す。また、図２において、実線は、実施例の結果を示し、破線は、比較例の結果を示す。図２に示すように、実施例は、比較例に対して、水銀特有のプラズマ発光の波長である２５３．６５ｎｍ付近において、カウント値が増加した。なお、図２においては、２５３．８８ｎｍにピーク（水銀ピーク）が観察されるが、これは、前記分光器の測定誤差を含むためである。これらの結果から、本発明の分析方法は、前記濃縮を行わない前記特許文献４および５の分析方法に対して、分析感度が高いことがわかった。 The result is shown in FIG. FIG. 2 is a graph showing a spectrum near the mercury peak. In FIG. 2, the horizontal axis indicates the wavelength, and the vertical axis indicates the emission intensity (count value). In FIG. 2, the solid line indicates the result of the example, and the broken line indicates the result of the comparative example. As shown in FIG. 2, in the example, the count value increased in the vicinity of 253.65 nm, which is the wavelength of plasma emission unique to mercury, as compared with the comparative example. In FIG. 2, a peak (mercury peak) is observed at 253.88 nm, because this includes a measurement error of the spectrometer. From these results, it was found that the analysis method of the present invention has higher analysis sensitivity than the analysis methods of Patent Documents 4 and 5 in which the concentration is not performed.
（３）異なる分析対象物の濃度におけるプラズマ分光分析
０．３ｍＬの０．１ｍｏｌ／Ｌ 硝酸水溶液に、所定濃度（１０ｐｐｂ、５０ｐｐｂ、１００ｐｐｂ）となるように塩化水銀を溶解した以外は、前記実施例１（２）と同様にして、水銀ピークのカウント値を測定した。
(3) Plasma spectroscopic analysis at concentrations of different analytes Example 1 except that mercury chloride was dissolved in 0.3 mL of a 0.1 mol / L nitric acid aqueous solution to a predetermined concentration (10 ppb, 50 ppb, 100 ppb). The count value of the mercury peak was measured in the same manner as 1 (2).
この結果を図３に示す。図３は、水銀濃度と水銀ピークにおけるカウント値との相関を示すグラフである。図３において、横軸は、水銀の濃度を示し、縦軸は、発光強度（カウント値）を示す。図３に示すように、水銀の濃度依存的にカウント値が増加した。これらの結果から、本発明の分析方法によれば、幅広い濃度で分析対象物を分析可能なことがわかった。 The result is shown in FIG. FIG. 3 is a graph showing the correlation between the mercury concentration and the count value at the mercury peak. In FIG. 3, the horizontal axis indicates the mercury concentration, and the vertical axis indicates the emission intensity (count value). As shown in FIG. 3, the count value increased depending on the mercury concentration. From these results, it was found that according to the analysis method of the present invention, the analysis object can be analyzed in a wide range of concentrations.
（実施例２）
本発明の分析方法により、尿検体中の鉛を感度よく分析できることを確認した。
(Example 2)
It was confirmed that lead in urine samples can be analyzed with high sensitivity by the analysis method of the present invention.
（１）プラズマ分光分析
尿検体に、１００ｐｐｂとなるように鉛を溶解した。つぎに、０．２ｍｏｌ／Ｌ 水酸化リチウムとなるように、水酸化リチウムの粉末を添加した。そして、前記水銀試料に代えて、前記鉛試料を用いた以外は、前記実施例１（２）と同様にして、発生したプラズマ発光のスペクトルを測定した。また、コントロール（比較例）は、前記濃縮を行わなかった以外は同様にして、発生したプラズマ発光のスペクトルを測定した。
(1) Plasma spectroscopic analysis Lead was dissolved in a urine specimen so as to be 100 ppb. Next, lithium hydroxide powder was added so as to be 0.2 mol / L lithium hydroxide. And the spectrum of the generated plasma emission was measured in the same manner as in Example 1 (2) except that the lead sample was used instead of the mercury sample. The control (comparative example) measured the spectrum of the generated plasma emission in the same manner except that the concentration was not performed.
この結果を図４に示す。図４は、鉛ピーク付近のスペクトルを示すグラフである。図４において、横軸は、波長を示し、縦軸は、発光強度（カウント値）を示す。また、図４において、実線は、実施例の結果を示し、破線は、比較例の結果を示す。図４に示すように、実施例は、比較例に対して、鉛特有のプラズマ発光の波長である３６８．３４ｎｍ付近において、カウント値が増加した。なお、図４においては、３６８．５２ｎｍにピーク（鉛ピーク）が観察されるが、これは、前記分光器の測定誤差を含むためである。これらの結果から、本発明の分析方法は、前記濃縮を行わない前記特許文献４および５の分析方法に対して、分析感度が高いことがわかった。 The result is shown in FIG. FIG. 4 is a graph showing a spectrum near the lead peak. In FIG. 4, the horizontal axis indicates the wavelength, and the vertical axis indicates the emission intensity (count value). Moreover, in FIG. 4, a continuous line shows the result of an Example and a broken line shows the result of a comparative example. As shown in FIG. 4, in the example, the count value increased in the vicinity of 368.34 nm, which is the wavelength of plasma emission peculiar to lead, as compared with the comparative example. In FIG. 4, a peak (lead peak) is observed at 368.52 nm because it includes a measurement error of the spectrometer. From these results, it was found that the analysis method of the present invention has higher analysis sensitivity than the analysis methods of Patent Documents 4 and 5 in which the concentration is not performed.
（２）異なる分析対象物の濃度におけるプラズマ分光分析
尿検体に、所定濃度（１０ｐｐｂ、５０ｐｐｂ、１００ｐｐｂ）となるように 硝酸鉛を溶解した。つぎに、０．２ｍｏｌ／Ｌ 水酸化リチウムとなるように、水酸化リチウムの粉末を添加した鉛試料を、前記水銀試料に代えて用いた以外は、前記実施例１（２）と同様にして、鉛ピークのカウント値を測定した。
(2) Plasma spectroscopic analysis at different analyte concentrations Lead nitrate was dissolved in urine specimens to a predetermined concentration (10 ppb, 50 ppb, 100 ppb). Next, in the same manner as in Example 1 (2) except that a lead sample to which lithium hydroxide powder was added so as to be 0.2 mol / L lithium hydroxide was used instead of the mercury sample. The count value of the lead peak was measured.
この結果を図５に示す。図５は、鉛濃度と鉛ピークにおけるカウント値との相関を示すグラフである。図５において、横軸は、鉛の濃度を示し、縦軸は、発光強度（カウント値）を示す。図５に示すように、鉛の濃度依存的にカウント値が増加した。これらの結果から、本発明の分析方法によれば、幅広い濃度で分析対象物を分析可能なことがわかった。また、本発明の分析方法は、夾雑物を含む試料である尿検体においても、前記分析対象物を分析可能であることがわかった。 The result is shown in FIG. FIG. 5 is a graph showing the correlation between the lead concentration and the count value at the lead peak. In FIG. 5, the horizontal axis represents the lead concentration, and the vertical axis represents the emission intensity (count value). As shown in FIG. 5, the count value increased depending on the lead concentration. From these results, it was found that according to the analysis method of the present invention, the analysis object can be analyzed in a wide range of concentrations. Further, it was found that the analysis method of the present invention can analyze the analysis target object even in a urine sample that is a sample containing impurities.
（実施例３）
本発明の分析方法により、カドミウムを感度よく分析できることを確認した。
Example 3
It was confirmed that cadmium can be analyzed with high sensitivity by the analysis method of the present invention.
前記鉛試料に代えて、０．２ｍｏｌ／Ｌ 水酸化リチウム溶液に１ｐｐｍとなるようにカドミウムを溶解したカドミウム試料を用いた以外は、前記実施例２（１）と同様にして、発生したプラズマ発光のスペクトルを測定した。また、コントロール（比較例）は、前記濃縮を行わなかった以外は同様にして、発生したプラズマ発光のスペクトルを測定した。 Plasma luminescence generated in the same manner as in Example 2 (1) except that a cadmium sample in which cadmium was dissolved to 1 ppm in a 0.2 mol / L lithium hydroxide solution was used instead of the lead sample. The spectrum of was measured. The control (comparative example) measured the spectrum of the generated plasma emission in the same manner except that the concentration was not performed.
この結果を図６に示す。図６は、カドミウムピーク付近のスペクトルを示すグラフである。図６において、横軸は、波長を示し、縦軸は、発光強度（カウント値）を示す。また、図６において、実線は、実施例の結果を示し、破線は、比較例の結果を示す。図６に示すように、実施例は、比較例に対して、カドミウムのプラズマ発光の波長である２２８．８０ｎｍ付近において、カウント値が増加した。なお、図６においては、２２８．９ｎｍにピークが観察されるが、これは、前記分光器測定誤差を含むためである。これらの結果から、本発明の分析方法は、前記濃縮を行わない前記特許文献４および５の分析方法に対して、分析感度が高いことがわかった。 The result is shown in FIG. FIG. 6 is a graph showing a spectrum near the cadmium peak. In FIG. 6, the horizontal axis indicates the wavelength, and the vertical axis indicates the emission intensity (count value). Moreover, in FIG. 6, a continuous line shows the result of an Example and a broken line shows the result of a comparative example. As shown in FIG. 6, in the example, the count value increased in the vicinity of 228.80 nm, which is the wavelength of plasma emission of cadmium, as compared with the comparative example. In FIG. 6, a peak is observed at 228.9 nm because this includes the spectroscopic measurement error. From these results, it was found that the analysis method of the present invention has higher analysis sensitivity than the analysis methods of Patent Documents 4 and 5 in which the concentration is not performed.
（実施例４）
本発明の分析方法により、水銀を感度よく分析できることを確認した。
Example 4
It was confirmed that mercury can be analyzed with high sensitivity by the analysis method of the present invention.
０．３ｍＬの０．１ｍｏｌ／Ｌ 硝酸水溶液に、１０ｐｐｂとなるように塩化水銀を溶解し、水銀試料とした以外は、前記実施例１（２）と同様にして、発生したプラズマ発光のスペクトルを測定した。また、コントロール１（比較例１）は、前記濃縮を行わなかった以外は同様にして、発生したプラズマ発光のスペクトルを測定した。 Except that mercury chloride was dissolved in 0.3 mL of 0.1 mol / L nitric acid aqueous solution so as to be 10 ppb and used as a mercury sample, the generated plasma emission spectrum was obtained in the same manner as in Example 1 (2). It was measured. Control 1 (Comparative Example 1) measured the spectrum of the generated plasma emission in the same manner except that the concentration was not performed.
コントロール２（比較例２）は、０．３ｍＬの０．１ｍｏｌ／Ｌ 硝酸水溶液に、５ｐｐｍとなるように水銀を溶解したものを前記水銀試料とした。また、コントロール２は、前記プラズマ分光分析装置に代えて、狭小部を有する樹脂製セル（ＬｅｐｉＣｕｖｅ、株式会社マイクロエミッション社製）および前記樹脂製セル測定用のプラズマ分光分析装置（ハンディ元素分析ＭＨ−５００、株式会社マイクロエミッション社製）を用い、添付のプロトコルにしたがって、前記水銀試料において発生したプラズマ発光のスペクトルを測定した。コントロール３（比較例３）は、前記水銀試料に代えて、０．１ｍｏｌ／Ｌ 硝酸水溶液を用い、前記樹脂製セルおよび対応するプラズマ分光分析装置を用いた以外は、コントロール２と同様にして発生したプラズマ発光のスペクトルを測定した。 Control 2 (Comparative Example 2) was prepared by dissolving mercury in 0.3 mL of a 0.1 mol / L nitric acid aqueous solution so that the concentration was 5 ppm. In addition, instead of the plasma spectroscopic analyzer, the control 2 is a resin cell having a narrow portion (LepiCube, manufactured by Microemission Co., Ltd.) and a plasma spectroscopic analyzer for measuring the resin cell (handy elemental analysis MH-). 500, manufactured by Microemission Co., Ltd.), and the spectrum of plasma emission generated in the mercury sample was measured according to the attached protocol. Control 3 (Comparative Example 3) was generated in the same manner as Control 2 except that a 0.1 mol / L nitric acid aqueous solution was used instead of the mercury sample, and the resin cell and the corresponding plasma spectroscopic analyzer were used. The plasma emission spectrum was measured.
この結果を図７に示す。図７（Ａ）は、１０ｐｐｂの水銀溶液を分析した際のスペクトルを示すグラフであり、（Ｂ）は、狭小部を有した分析装置において、５ｐｐｍの水銀溶液を分析した際のスペクトルを示すグラフである。図７（Ａ）および（Ｂ）において、横軸は、波長を示し、縦軸は、発光強度（カウント値）を示す。また、図７（Ａ）において、実線は、実施例の結果を示し、破線は、比較例１の結果を示す。図７（Ｂ）において、実線は、比較例２の結果を示し、破線は、比較例３の結果を示す。図７（Ａ）に示すように、実施例は、比較例１に対して、水銀ピークにおいて、カウント値が、約９００カウント増加した。また、図７（Ｂ）に示すように、比較例２は、比較例３に対して、水銀特有のプラズマ発光の波長である２５３．６５ｎｍ付近である２５３．００ｎｍにおいて、カウント値が、約５００カウント増加した。なお、図７（Ｂ）においては、２５３．００ｎｍにピークが観察されるが、これは、前記樹脂製セル測定用のプラズマ分光分析装置の測定誤差を含むためである。これらの結果から、本発明の分析方法は、狭小部を有する樹脂製セルを使用する方法と比較して、１／５００の水銀濃度でも、約２倍のカウント値が得られることがわかった。すなわち、本発明の分析方法は、特許文献２および３の分析方法に対して、分析感度が高いことがわかった。 The result is shown in FIG. FIG. 7A is a graph showing a spectrum when a 10 ppb mercury solution is analyzed, and FIG. 7B is a graph showing a spectrum when a 5 ppm mercury solution is analyzed in an analyzer having a narrow portion. It is. 7A and 7B, the horizontal axis indicates the wavelength, and the vertical axis indicates the emission intensity (count value). In FIG. 7A, the solid line indicates the result of the example, and the broken line indicates the result of the comparative example 1. In FIG. 7B, the solid line indicates the result of Comparative Example 2, and the broken line indicates the result of Comparative Example 3. As shown in FIG. 7A, in the example, the count value increased by about 900 counts at the mercury peak as compared with Comparative Example 1. Further, as shown in FIG. 7B, the second comparative example has a count value of about 500 at 253.00 nm, which is around 253.65 nm, which is a wavelength of plasma emission peculiar to mercury. Count increased. In FIG. 7B, a peak is observed at 253.00 nm, because this includes a measurement error of the plasma spectroscopic analyzer for resin cell measurement. From these results, it was found that the analysis method of the present invention can obtain a count value approximately twice as high even at a mercury concentration of 1/500, as compared with a method using a resin cell having a narrow portion. That is, it was found that the analysis method of the present invention has higher analysis sensitivity than the analysis methods of Patent Documents 2 and 3.
以上、実施形態および実施例を参照して本発明を説明したが、本発明は、上記実施形態および実施例に限定されるものではない。本発明の構成や詳細には、本発明のスコープ内で当業者が理解しうる様々な変更をできる。 As mentioned above, although this invention was demonstrated with reference to embodiment and an Example, this invention is not limited to the said embodiment and Example. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.
この出願は、２０１５年１月１３日に出願された日本出願特願２０１５−００３７９５を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2015-003795 for which it applied on January 13, 2015, and takes in those the indications of all here.
本発明のプラズマ分光分析方法は、簡便、且つ分析感度が高い。このため、本発明のプラズマ分光分析方法によれば、例えば、試料に前処理を行わず、簡便、且つ高い感度で試料を分析できる。このため、本発明は、例えば、プラズマ発生を利用した元素等の分析に、極めて有用である。 The plasma spectroscopic analysis method of the present invention is simple and has high analytical sensitivity. For this reason, according to the plasma spectroscopic analysis method of the present invention, for example, the sample can be analyzed with ease and high sensitivity without pretreatment of the sample. For this reason, this invention is very useful for the analysis of the element etc. which utilized plasma generation, for example.
１、２ 電極
３ 透光部
４ 容器
５ 受光部
６ 絶縁性材料
１０ 分析装置
DESCRIPTION OF SYMBOLS 1, 2 Electrode 3 Translucent part 4 Container 5 Light-receiving part 6 Insulating material 10 Analyzer
Claims (12)
前記一対の電極への電圧印加によりプラズマを発生させ、前記プラズマにより生じた前記分析対象物の発光を検出する検出工程を含むことを特徴とする、プラズマ分光分析方法。 In the presence of the sample, by applying a voltage to the pair of electrodes, a concentration step of concentrating the analyte in the sample in the vicinity of at least one electrode, and generating a plasma by applying the voltage to the pair of electrodes, A plasma spectroscopic analysis method comprising a detection step of detecting light emission of the analysis object generated by plasma.
前記一対の電極のうち、前記試料との接液面積が小さい電極が、プラズマ発生により前記分析対象物を分析する電極である、請求項１記載のプラズマ分光分析方法。 The pair of electrodes are a pair of electrodes having different liquid contact areas with the sample,
2. The plasma spectroscopic analysis method according to claim 1, wherein an electrode having a small liquid contact area with the sample of the pair of electrodes is an electrode for analyzing the analysis object by generating plasma.
前記容器は、透光部を含み、
前記容器の外部には、前記透光部を通して前記分析対象物の発光を受光可能な受光部が配置されている、請求項１から５のいずれか一項に記載のプラズマ分光分析方法。 The pair of electrodes are disposed in a container,
The container includes a translucent part,
The plasma spectroscopic analysis method according to any one of claims 1 to 5, wherein a light receiving unit capable of receiving light emitted from the analysis object through the light transmitting unit is disposed outside the container.
前記容器は、透光部を含み、
前記一対の電極は、前記容器内に配置され、
前記容器の外部には、前記一対の電極への電圧印加により発生した発光を、前記透光部を通して前記分析対象物の発光を受光可能な受光部が配置され、
請求項１から１１のいずれか一項に記載のプラズマ分光分析方法に使用することを特徴とする、プラズマ分光分析装置。 Including a pair of electrodes, a container and a light receiving section;
The container includes a translucent part,
The pair of electrodes are disposed in the container,
A light receiving part capable of receiving light emitted by applying voltage to the pair of electrodes and receiving light emitted from the analysis object through the light transmitting part is disposed outside the container.
A plasma spectroscopic analysis apparatus, which is used in the plasma spectroscopic analysis method according to any one of claims 1 to 11.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160004239A KR102420443B1 (en) | 2015-01-13 | 2016-01-13 | Plasma spectrochemical analysis method and plasma spectrochemical analyzer |
| EP16151054.0A EP3045895A1 (en) | 2015-01-13 | 2016-01-13 | Plasma spectrochemical analysis method and plasma spectrochemical analyzer |
| US14/994,277 US10101275B2 (en) | 2015-01-13 | 2016-01-13 | Plasma spectrochemical analysis method and plasma spectrochemical analyzer |
| CN201610022123.4A CN105784675B (en) | 2015-01-13 | 2016-01-13 | Plasma spectroscopic analysis method and plasma spectroscopic analysis apparatus |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015003795 | 2015-01-13 | ||
| JP2015003795 | 2015-01-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016130734A true JP2016130734A (en) | 2016-07-21 |
| JP6656931B2 JP6656931B2 (en) | 2020-03-04 |
Family
ID=56415426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016003555A Active JP6656931B2 (en) | 2015-01-13 | 2016-01-12 | Plasma spectroscopic analysis method and plasma spectroscopic analyzer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6656931B2 (en) |
| KR (1) | KR102420443B1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018063242A (en) * | 2016-10-07 | 2018-04-19 | アークレイ株式会社 | Method for plasma spectroscopic analysis and inhibitor of plasma emission derived from non-target |
| EP3364182A1 (en) | 2017-02-16 | 2018-08-22 | ARKRAY, Inc. | Electrolysis device |
| EP3363932A1 (en) | 2017-02-16 | 2018-08-22 | ARKRAY, Inc. | Electrolysis device |
| EP3425374A1 (en) | 2017-07-05 | 2019-01-09 | ARKRAY, Inc. | Plasma spectroscopy analysis method |
| EP3425375A1 (en) | 2017-07-05 | 2019-01-09 | ARKRAY, Inc. | Plasma spectroscopy analysis method |
| JP2019078559A (en) * | 2017-10-20 | 2019-05-23 | アークレイ株式会社 | Carbon-containing electrode processing method and measuring container |
| EP3561493A1 (en) | 2018-04-26 | 2019-10-30 | ARKRAY, Inc. | Plasma spectroscopy analysis method |
| JP2019191052A (en) * | 2018-04-26 | 2019-10-31 | アークレイ株式会社 | Plasma spectroscopic analysis method |
| JP2019192413A (en) * | 2018-04-20 | 2019-10-31 | アークレイ株式会社 | Wire connection structure and measurement unit |
| JP2019191051A (en) * | 2018-04-26 | 2019-10-31 | アークレイ株式会社 | Measuring system and temperature adjustment method for measuring device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3306314B1 (en) * | 2016-10-07 | 2021-01-20 | ARKRAY, Inc. | Plasma spectroscopic analysis method and inhibitor of plasma emission derived from non-target |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010537211A (en) * | 2007-08-27 | 2010-12-02 | アルカテル−ルーセント | A system for analyzing low-pressure gases by emission spectroscopy. |
| WO2012048308A2 (en) * | 2010-10-08 | 2012-04-12 | Photon Machines, Inc. | Spark emission particle detector |
| US20130148117A1 (en) * | 2011-12-09 | 2013-06-13 | Human Services, Centers For Disease Control And Prevention | Method and apparatus for aerosol analysis using optical spectroscopy |
| JP2013205389A (en) * | 2012-03-29 | 2013-10-07 | Nagoya Univ | Emission analyzer and atomizer |
| US8559004B1 (en) * | 2011-03-29 | 2013-10-15 | Zhou Zhou | Method and appratus for emission spectroscopy utilizing a flat plate for sample holding and excitation |
| US20130321804A1 (en) * | 2012-05-29 | 2013-12-05 | Centers For Disease Control And Prevention | Electrode-assisted microwave-induced plasma spectroscopy |
| JP2015506484A (en) * | 2012-02-07 | 2015-03-02 | マテリアリティクス，エルエルシー | Method and system for analyzing a sample |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006059808A1 (en) | 2004-12-03 | 2006-06-08 | Kabushiki Kaisha Toyota Jidoshokki | Submerged plasma-use electrode, submerged plasma generating device and submerged plasma generating method |
| JP4986824B2 (en) | 2007-11-27 | 2012-07-25 | Ｊｘ日鉱日石金属株式会社 | Analytical method of high-frequency plasma mass spectrometer for trace precious metals |
| RU2368895C1 (en) * | 2008-05-20 | 2009-09-27 | Открытое Акционерное Общество "Научно-Производственное Предприятие "Буревестник" | Method of emission analysis for determining elementary composition using discharge in liquid |
| WO2011099247A1 (en) | 2010-02-10 | 2011-08-18 | 国立大学法人愛媛大学 | Electrode for plasma in liquid, plasma in liquid generator device, and plasma generation method |
| JP5530222B2 (en) | 2010-03-02 | 2014-06-25 | 国立大学法人北陸先端科学技術大学院大学 | Plasma generating means, plasma generating apparatus and elemental analysis method |
| JP5705591B2 (en) * | 2011-03-07 | 2015-04-22 | 株式会社日立ハイテクノロジーズ | Plasma spectrometer |
| CN102445445B (en) * | 2011-10-08 | 2013-08-21 | 中国地质大学（武汉） | Method and device for detecting metal ions by adopting liquid dielectric barrier discharge (DBD) emission spectrum |
-
2016
- 2016-01-12 JP JP2016003555A patent/JP6656931B2/en active Active
- 2016-01-13 KR KR1020160004239A patent/KR102420443B1/en active IP Right Grant
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010537211A (en) * | 2007-08-27 | 2010-12-02 | アルカテル−ルーセント | A system for analyzing low-pressure gases by emission spectroscopy. |
| WO2012048308A2 (en) * | 2010-10-08 | 2012-04-12 | Photon Machines, Inc. | Spark emission particle detector |
| US8559004B1 (en) * | 2011-03-29 | 2013-10-15 | Zhou Zhou | Method and appratus for emission spectroscopy utilizing a flat plate for sample holding and excitation |
| US20130148117A1 (en) * | 2011-12-09 | 2013-06-13 | Human Services, Centers For Disease Control And Prevention | Method and apparatus for aerosol analysis using optical spectroscopy |
| JP2015506484A (en) * | 2012-02-07 | 2015-03-02 | マテリアリティクス，エルエルシー | Method and system for analyzing a sample |
| JP2013205389A (en) * | 2012-03-29 | 2013-10-07 | Nagoya Univ | Emission analyzer and atomizer |
| US20130321804A1 (en) * | 2012-05-29 | 2013-12-05 | Centers For Disease Control And Prevention | Electrode-assisted microwave-induced plasma spectroscopy |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018063242A (en) * | 2016-10-07 | 2018-04-19 | アークレイ株式会社 | Method for plasma spectroscopic analysis and inhibitor of plasma emission derived from non-target |
| EP3364182A1 (en) | 2017-02-16 | 2018-08-22 | ARKRAY, Inc. | Electrolysis device |
| EP3363932A1 (en) | 2017-02-16 | 2018-08-22 | ARKRAY, Inc. | Electrolysis device |
| JP2018131660A (en) * | 2017-02-16 | 2018-08-23 | アークレイ株式会社 | Electrolysis device |
| CN108489964A (en) * | 2017-02-16 | 2018-09-04 | 爱科来株式会社 | Electrolysis unit |
| CN108489964B (en) * | 2017-02-16 | 2022-06-24 | 爱科来株式会社 | Electrolysis device |
| US10551323B2 (en) | 2017-07-05 | 2020-02-04 | Arkray, Inc. | Plasma spectroscopy analysis method |
| JP2019015562A (en) * | 2017-07-05 | 2019-01-31 | アークレイ株式会社 | Plasma spectroscopic analysis method |
| EP3425374A1 (en) | 2017-07-05 | 2019-01-09 | ARKRAY, Inc. | Plasma spectroscopy analysis method |
| EP3425375A1 (en) | 2017-07-05 | 2019-01-09 | ARKRAY, Inc. | Plasma spectroscopy analysis method |
| US10539548B2 (en) | 2017-07-05 | 2020-01-21 | Arkray, Inc. | Plasma spectroscopy analysis method |
| JP2019078559A (en) * | 2017-10-20 | 2019-05-23 | アークレイ株式会社 | Carbon-containing electrode processing method and measuring container |
| JP2019192413A (en) * | 2018-04-20 | 2019-10-31 | アークレイ株式会社 | Wire connection structure and measurement unit |
| JP2019191051A (en) * | 2018-04-26 | 2019-10-31 | アークレイ株式会社 | Measuring system and temperature adjustment method for measuring device |
| JP2019191053A (en) * | 2018-04-26 | 2019-10-31 | アークレイ株式会社 | Plasma spectroscopic analysis method |
| JP2019191052A (en) * | 2018-04-26 | 2019-10-31 | アークレイ株式会社 | Plasma spectroscopic analysis method |
| US11143595B2 (en) | 2018-04-26 | 2021-10-12 | Arkray, Inc. | Plasma spectroscopy analysis method |
| JP7007986B2 (en) | 2018-04-26 | 2022-01-25 | アークレイ株式会社 | Plasma spectroscopic analysis method |
| JP7019505B2 (en) | 2018-04-26 | 2022-02-15 | アークレイ株式会社 | Plasma spectroscopic analysis method |
| EP3561493A1 (en) | 2018-04-26 | 2019-10-30 | ARKRAY, Inc. | Plasma spectroscopy analysis method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6656931B2 (en) | 2020-03-04 |
| KR102420443B1 (en) | 2022-07-13 |
| KR20160087359A (en) | 2016-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6656931B2 (en) | Plasma spectroscopic analysis method and plasma spectroscopic analyzer | |
| CN105784675B (en) | Plasma spectroscopic analysis method and plasma spectroscopic analysis apparatus | |
| JP3932368B2 (en) | Plasma generator | |
| JP6851946B2 (en) | Plasma spectroscopic analysis method and non-target-derived plasma emission suppressor | |
| US20180024069A1 (en) | Plasma spectroscopic analysis method and plasma spectroscopic analyzer | |
| EP3425375B1 (en) | Plasma spectroscopy analysis method | |
| JP2018021902A (en) | Plasma spectroscopic analysis method and plasma spectroscopy analyzer | |
| US10295471B2 (en) | Plasma spectroscopic analysis method and inhibitor of plasma emission derived from non-target | |
| US10551323B2 (en) | Plasma spectroscopy analysis method | |
| JP2018131659A (en) | Electrolysis device | |
| JP7019505B2 (en) | Plasma spectroscopic analysis method | |
| JP6871088B2 (en) | How to clean carbon electrodes | |
| CN108489964B (en) | Electrolysis device | |
| CN110412016B (en) | Plasma spectrum analysis method | |
| JP6480210B2 (en) | Plasma generating chip, plasma generating apparatus, and plasma spectroscopic analysis method | |
| Mincu et al. | DETERMINATION OF BISPHENOL A FROM WATER SAMPLES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20170113 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20170124 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20181213 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190911 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20191023 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191213 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200204 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200205 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6656931 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |