JAERI-Review JP0250004 Japan Atomic Energy Research Institute (1=319-1195 This report is issued irregularly. Inquiries about availability of the reports should be addressed to Research Information Division, Department of Intellectual Resources, Japan Atomic Energy Research Institute, Tokai-mura, Naka-gun, Ibaraki-ken T 319-1195, Japan. © Japan Atomic Energy Research Institute, 2001 m JAERI- Review 2001-043 0 (2001 ^ 10^ 29 (35CK 37Cl) (IRMS) (AMS) i^J;5 36C1 •. T 319-1195 JAERI- Review 2001-043 Recent Research Activities and Future Subjects on Stable- and Radio-isotopes of Chlorine in Environment Kouhei KUSHITA Nuclear Technology and Education Center (Tokai Site) Japan Atomic Energy Research Institute Tokai-mura, Naka-gun, Ibaraki-ken (Received October 29, 2001) This report reviews the recent studies on the stable- and radio-isotopes of chlorine from a viewpoint of environmental science, partly including historic references on this element. First, general properties, occurrence, and utilization of chlorine are described. Secondly, current status and research works on chlorine-compounds, which attract special attention in recent years as environmentally hazardous materials, are reported. Thirdly, research works on stable chlorine isotopes, 35C1 and 37C1, are described with a focus laid on the newly-developed techniques; isotopic ratio mass spectrometry (IRMS) and thermal ionization mass spectrometry (TIMS). Fourthly, recent research works on chlorine radioisotopes, 36C1 etc., are described, focusing on the development of accelerator mass spectrometry (AMS) and its application to geochemistry and others. Finally, taking account of the above-mentioned recent works on Cl isotopes, possible future research subjects are discussed. Keywords: Chlorine, Stable Isotope, Radioisotope, Environment, Isotopic Ratio Mass Spectrometry, Accelerator Mass Spectrometry, 35C1,37C1,36C1. JAERI-Review 2001-043 g #£ • ^ijfflfe^ 3 2.1 3 2.2 3 2.3 3 2.4 3 2.5 4 2.6 4 2.7 5 2.8 5 2.9 6 2.10 7 12 3.1 12 3.2 12 3.3 17 3.4 3.5 19 3.6 3.7 21 4. 30 4.1 30 4.2 31 4.3 31 4.4 (D:IRMS 32 4.5 (2):TIMS 35 4.6 4.7 36 4.8 37 4.9 38 JAERI- Review 2001-043 5. M.mtkfti&.mGLmz.m-tzw% 53 5.1 36c\mm&ffi^mm-f&ffiR 53 5.2 3Hc\m^ikm^mmi-^m^ 54 5.3 &mwi^wMi~zffliz 54 5.4 mT-jjmm/w^jjmmm^mm-f&miz 55 5.5 WiBlgiSC&Wtt&itfKllljI-rsWSS 56 5.6 ^ftsy^^§ii-sw5£ 57 5.7 ^£f^&@-f 3W2E 58 5.8 m¥/mM\^m^&ffiR 58 5.9 ^(DitiwWR 59 6. ^m$Lfc®t3z(DmM 79 6.1 mwimmmu.w-*m^tz9%MM 79 6.2 %%mw%Lftw$i.w\^£%^W)Lfo\kmfe 79 6.3 <£fe&Mn®.fo*Rl^tzM9?MM 80 7. Sifc 87 m & 87 88 iv JAERI-Review 2001-043 Contents 1 . Introduction 1 2 . Properties, Occurrence, Utilization of Chlorine 3 2.1 Discovery and Occurrence of Chlorine 3 2.2 Chlorine in the Ocean 3 2.3 Chlorine in the Atmosphere 3 2.4 Chlorine Isotopes 3 2.5 Chlorine as Single Substance 4 2.6 Inorganic Compounds of Chlorine 4 2.7 Organic Compounds of Chlorine 5 2.8 Analysis of Chlorine 5 2.9 Sodium Chloride 6 2.10 Life, Ocean, Human Body, and Chlorine 7 3 . Environmental Pollution and Chlorine 12 3.1 Halogenide Compounds in the Air 12 3.2 Organic Compounds of Chlorine Related with Drainage 12 3.3 Chlorination of Water 17 3.4 Environmental Endocrine Disrupters and PCDDs 18 3.5 Analysis of PCDDs 19 3.6 Chlorofluorocarbons (CFCs) and Destruction of the Ozone Layer 19 3.7 Warm-up of the Earth and Chemical Substances 21 4. Studies Using Chlorine Stable Isotopes (35CU 37C1) 30 4.1 Stable Isotope Ratio and Isotope Fractionation Factor 30 4.2 Studies of Stable Isotopes: Sulfur 31 4.3 Early Studies on Chlorine Stable Isotopes 31 4.4 Determination Method of Chlorine Stable Isotope Ratio (1):IRMS 32 4.5 Determination Method of Chlorine Stable Isotope Ratio (2): TIMS 35 4.6 Isotopic Effect 36 4.7 Geochemistry of Stable Isotopes 36 4.8 Applied Studies for Hydrology and Ground Water 37 4.9 Thermodynamics and Others 38 V JAERI-Review 2001-043 5. Studies of Chlorine Radioisotopes (36CU 38CK etc.) 53 5.1 Studies of 36C1 Measurement 53 5.2 Studies of 38C1 Measurement 54 5.3 Studies Related to Nuclear Bomb Experiments 54 5.4 Studies Related to Nuclear Power Generation and Nuclear Waste 55 5.5 Studies Related to Chlorine Radioisotopes Produced by Cosmic rays 56 5.6 Studies Related to Dating 57 5.7 Studies Related to Hydrology 58 5.8 Studies Related to Medicine and Labeling 58 5.9 Others 59 6 . Future Research Subjects on Chlorine 79 6.1 Research Subjects Using Chlorine Radioisotopes 79 6.2 Determination of Chlorine Stable Isotope Ratio by a Light Element Mass Spectrometer 79 6.3 Research Subjects Using Chlorine Stable Isotopes 80 7 . Conclusion 87 Acknowledgement 87 References 88 vi JAERI-Review 2001-043 1. chlorine Mo) L (cation) J&5}Tfe3^ b y ?^ ^ (anion) (Dfflfi "9 ^/V (PCB) 2,3,7,8- il 19 oo, (so 35Cl t 37Cl cD^fl^cD SI i: (-<t otctf Z.<DmM<n SI SI si (RI) -m, ^M»! 30 n¥mm(D RI & RI 36Cl «C RI (AMS) 36Cl , AMS - 1 - JAERI-Review 2001-043 si*3«fct*Ri - 2 - JAERI-Review 2001-043 2. 2.1 H2SO4, HN(X R.Glauber t± NaCl Id H2SO4 £{1^ffl £-ti:T HCl ^ i: £3§ I, U =t<D\k HC1 0 Lavoisier CO, M NFft^o<5l/^c0 1774 ^ Scheele « HC1 ^ MnO2 coS^i-^^^l^feco^Tk^M/i^^^^i-S^Xco^^-rsr tS:|8Ebfco 1811 ¥J.L. Gay-Lussac t Thenard ttiUac^ <t SiSTcW^RTIi*^ t *»?> dO^^Sr^flct^X., H. Davy (±^57-(-^ttJ;5 t LTML, -ocO^^-Cfc5 ir co^f^^T U -g^ -t*^, r<DfeS:ic!*i-5dr V ^TfgJ; <9 chlorine «k^f^ L/c0 HC1 tf'pm!k\Utfxq>K%1\,^t££tiZtf, Cl ^20{iL-C(130 n g/g)-T?foZ>of&ynk LTtt^-J^NaCK* U^ikKCU ^7-^-/1^^ KC1 •MgCl2-6H2O, ^ffil£ AgCK i&$$V>-EK^ CasCPO^sCl ft ¥ &&>%<, ^fSi^\^t.tiX\t^tc Cl $s HC1 Cl lkg ^ Cl 19 2.2 h Table 2.1 x-^ £^1"2 ) 2.3 3) (Fig. 2.D 2.4 (SI) 38C1 (RI) ^#ftf5 4) (Table 2.2 - 3 - JAERI-Review 2001-043 36ci 2.5 6'7) C O2, N2 © Ch fi. \ MnO2 V«D Ch t P4O1 ) ^\ Ch Ch 0 3 C, 4 50 ppmT-fi30-60 o Ch Au^Pt \ Ch o H2 2.3 f^^W Ch *S^E(t, H2O + Ch ^ H+ +Cl" + HCIO <D Ck-nHzO = 6 > Br2, h, S &ttiiroCh (i H2O2, NHs, CO, NO, SO2 /£ <B' iSi^ LT O2, NCh, COCh, NOCK SO2CI2 ££j5)<;-f 5o (Ch) (i, XDIWl-fiJSfbf^/l', ^^noifl/y, CCU, CHCb Jfe^ i^, Ti ^S^ 2.6 M * (HCl) H2 Ch d = 1.187 (-85°Ciit)0 0 100 g \Z 82.3 g T HCl-nH2O fin = 2, 3, 4, 6& HCl (HCl • aq) fi HCl itiS^tt 37.2 %, d = 1.19, j^J 12 M, ?£ FeCb -CLtfLtfUfe, **^^tl(± 108.584 °C, 20.222 %, m 6 Mo 3figg-t?(0.I M 92.6 %) #< W^Ji tSJS LT H2 §rffi1-o Au, Ag, &i, Nb, Ta, ftk*X~Wlik£tlX Ch &titf-o (ChO, CI2O3, CIO2, CI2O4, CI2O6, CI2O7, - 4 - JAERI-Review 2001-043 (CIOF, C10F3, C102F, CIO2F3, C103F 3?h &MMM&. (HCIO), m. (MCIO), mM^wt (Hcichh wMmmm. (MCM, mmm (HOOK mmm& (HC104), m&mmt& (MCICM (CINO3) 2.7 lit CH3C1 (-23.7 r) 0.920o (Table 2.3 M CH2CI2 : li, itfi 1.320 (20"C) (I3.2g^g, 20 ) CHCb, f -A' (PCB) (Aspergillus, Penicillium ft if) d^M,o(t bMtt nyt-r h tr^, tt0^ (Anaptychia, Buellia, Lecanora ^C if) 2.8 o ( +3 +4 (H +5 HClCbh +7 (ill Agco3 Agci - 5 - JAERI-Review 2001-043 V -, EPMA, ESCA, NMR, SIMS, ICP, ICP-MS (PCB, Lt, Kylin , Petrick HPLC & ECD-GC PCB 2.9 l3) Hallstatt , 19 itt,i 1.9 3- o 99 % fo 1/3 (1) (3) 2 800 ha, SMgffitfS 20 000 ha & !9 , ¥0 600 ^ t - 6 - JAERI-Review 2001-043 (4) (5) *^ 7 140 2.10 30 ^4fI 2000 (21%) , 3ff 5000 19 , * m )#>—jKl' to T Table 2.1 Table 2.4 \Z.7f?t«t 9 t , Na t Cl , t l4) - 1 - JAERI-Review 2001-043 - 8 - JAERI-Review 2001-043 Table 2.1 Main chemical components in the sea water2* fife ft ™«" mmm (mg/kg) (mmol/kg) (mg/kg) (¥) Na 0.5561 10,760 468.0 6.9 4.8x107 Mg 0.06679 1,294 53.2 3.9 l.OxlO7 Ca 0.02127 412 10.2 15.0 8.5xlO5 K 0.0206 399 10.2 2.1 5.9x106 Sr 0.00041 7.9 0.090 4 xlO6 Cl 1.0000 19,350 545.0 8.1 7.3xlO7 SO4 0.1400 2,712 28.2 10.6 7.9x106 HCO3 0.00749 145 2.38 55.9 8.0x104 Br 0.003473 67 0.84 1 xlO8 B 0.000240 4.6 0.39 1 xlO7 F 0.000067 1.3 0.068 5 xlO5 : 15 mg/kg, Si;2.9 mg/kg Table 2.2 Isotopes of chlorine4> m - t ?tJt (MeV), Zi(MeV) 33 + C1 2.511 s -21.004 3/2 j3 + /r4.51;y 0.841 (0.54) fdl 34C1 1.5262 s -24.440 0+ 0 + i3 +4.50 34mCl 32.23 m -24.294 3+ j3+53%, IT47% j3+2.47[34]{til, y 2.128(42), 0.146 (IT) {til 35C| (75.77 %) -29.014 3/2" a 43, / 15; a 0.48, Ip 0.59; a a'0.08 mb 36C1 3.01xl05 y -29.522 2+ ]3 "98%, EC2%, j3 "0.709; /3 +0.2; no y 37CI (24.23 %) -31.762 3/2+ a (0.7 s) 0.005, o (37 m)0.43, / 0.32 38 D C1 37.24 m -29.798 2 "C i3"4.91 (58), 2.77(11), 1.11(31); y 1.642(40), 2.168(55) 3SmC, 0.715 s -29.127 5" IT y 0.671 (99.95) 39 D C1 55.6 m -29.804 3/2" "C 13" 1.91 (85) {til; y 1.267 (54) {til 4OC] 1.35 m -27.540 2 13--7.5, -3.2; y 1.461 (77) {t!l : ate* off a .