1. TIU CHUN QUC GIA TCVN 6716 : 2013 ISO 10298 : 2010 KH V HN HP KH - XC NH TNH C CA KH HOC HN HP KH Gas and gas mixture - Determination of toxicity of gas or gas mixture Li ni u TCVN 6716:2013 thay th TCVN 6716:2000 (ISO 10298:1995). TCVN 6716:2013 hon ton tng ng ISO 10298:2010. TCVN 6716:2013 do Ban k thut tiu chun quc gia TCVN/TC 58 Chai cha kh bin son; Tng cc Tiu chun - o lng - Cht lng ngh, B Khoa hc v Cng ngh cng b. KH V HN HP KH - XC NH TNH C CA KH HOC HN HP KH Gas and gas mixture - Determination of toxicity of gas or gas mixture 1. Phm vi p dng Tiu chun ny lit k s liu t cc ti liu v tnh cc c thng gp nht ca cc kh gip phn loi kh v hn hp kh. 2. Thut ng v nh ngha Trong tiu chun ny s dng cc nh ngha sau: 2.1. Nng gy cht LC50 (lethal concentration LC50) Nng ca kh (hoc hn hp kh) trong khng kh c cung cp cho mt ln phi nhim ca mt nhm chut bch mi trng thnh (chut c v ci) trong chu k thi gian ngn (24h hoc t hn) lm mt na s chut b cht trong vng t nht 14 ngy. 2.2. Mc c (toxicity level) Mc c ca kh v hn hp kh CH THCH 1: Trong TCVN 6551 (ISO 5145), Tnh c ca kh v hn hp kh c chia thnh ba nhm: - Nhm 1: khng c [kh LC50 > 5000 ppm (theo th tch)] - Nhm 2: c [khi 200 ppm < LC50 5000 ppm (theo th tch)] - Nhm 3: rt c [khi LC50 200 ppm (theo th tch)] Trong - LC50 gi tr tng ng vi 1h phi nhim trong kh; - ppm (theo th tch) ch phn triu, tnh theo th tch. CH THCH 2: Trong GHS cc mc c ht phi gm bn hng: Hng 1: Gy cht ngi nu ht phi 0 ppm < LC50 100 ppm (theo th tch) Hng 2: Gy cht ngi nu ht phi 100 ppm < LC50 500 ppm (theo th tch) Hng 3: Nhim c nu ht phi 500 ppm < LC50 2500 ppm (theo th tch) Hng 4: C hi nu ht phi 2500 ppm < LC50 20000 ppm (theo th tch)]

2. CH THCH 3: Trong GHS, tr s LC50 tng ng vi 4h phi nhim. Do , tr s LC50 c trnh by trong Ph lc A (xem 3.2.2) cn phi chia cho 2 (tc l ). Trong iu B.2 c s gii thch v vic chia cho 2. 3. Xc nh tnh c 3.1. Yu cu chung Tnh c c th c xc nh theo phng php th (3.2) i vi mt hn hp kh m n tn ti cc s liu ca kh thnh phn hoc thng qua phng php tnh ton (3.3). V l do bo v ng vt, cn trnh cc th nghim tnh c bng s ht th ch nhm phn loi hn hp kh, nu nh tnh c ca tng kh thnh phn c. Trong trng hp ny, tnh c c xc nh ph hp vi 4.2. 3.2. Phng php th 3.2.1. Tin hnh th Phi s dng phng php th nghim c quc t cng nhn nh OECD TG 403[43], khi cc s liu mi v tnh c c xt n v a vo trong tiu chun ny. 3.2.1. Tnh kt qu i vi kh sch Tnh c ca kh sch c lit k trong Ph lc A, trong gi tr ca LC50 tng ng vi 1h phi nhim. Mt s gi tr ny c nh gi ph hp vi Ph lc B. 3.3. Phng php tnh Gi tr LC50 ca hn hp kh c tnh bng cng thc sau: LC50 = 50 1 LC Ci Trong Ci l s mol (phn t gam) ca thnh phn c th i trong hn hp kh; LC50i l nng gy cht ca thnh phn c th i [LC50 < 5000 ppm (theo th tch)] tnh bng phn triu theo th tch. Sau khi tnh c gi tr LC50, hn hp c phn loi ph hp vi 2.2. CH THCH: Hiu ng ng thi khng c xt n phn trn, do thiu cc s liu khoa hc. Ph lc A (tham kho) Gi tr LC50 i vi cc kh c v hi c dng trong hn hp kh Bng A.1 lit k gi tr LC50 v ti liu tham kho cho tng kh mt. Bng A.2 lit k gi tr LC50 v ti liu tham kho cho tng loi hi. Bng A.3 quy nh ch tiu cho cc kh oxi ha. Bng A.1 Danh sch cc kh vi tr s LC50 v ngun ti liu Kh Tn thng dng S CASa S UN LC50 b /1h (theo th tch) Lu Ti liu tham kho (xem th mc) 3. Amoniac 7664-41-7 1005 7338 (1) Arsin 7784-42-1 2188 178 (62) Arsenic pentaflorua 7784-36-3 3308 178 Tng t nh arsin Bo triclorua 10294-34-5 1741 2541 (1) Bo triflorua 7637-07-2 1008 864 (44) Brom clorua 13863-41-7 2901 290 c nh gi t clorin Cacbon monoxit 630-08-0 1016 3760 c hiu chnh theo thi gian (6) Cacbonyl florua 353-50-4 2417 360 (5) Cacbonyl sunfua 463-58-1 2204 1700 c hiu chnh theo thi gian (7) Clorin 7782-50-5 1017 293 (1) Clorin pentaflorua 13637-63-3 2548 122 (8) Clorin triflorua 7790-91-2 1749 299 (8) Clorifloetylen 79-38-9 1082 2000 c hiu chnh theo thi gian (10) Clometan 74-87-3 1063 5133 (54) Cyanogen 460-19-5 1026 350 (11) Cyclopropan 75-19-4 1027 220000 "Khng c" - LCLO - Xm c hiu chnh theo thi gian Cyanogen clorua 506-77-4 1589 80 c hiu chnh theo thi gian (12) Deuteri clorua 7698-05-7 1789 3120 Deuteri selenua 13536-95-3 2202 51 Ging nh hydro selenua Deuteri sunfua 13536-94-2 1053 710 Tng t hydro sunfua Diboran 19287-45-7 1911 80 c hiu chnh theo thi gian (13) Diclo silan 4109-96-0 2189 314 (52) Dimetyl amin 124-40-3 1032 5290 c hiu chnh theo thi gian (67) Dinit trioxit 10544-73-7 2421 57 c tnh ton t s phn ly thnh NO2 Etylen oxit 75-21-8 1040 2900 c hiu chnh theo thi gian (18) Flo 7782-41-4 1045 185 (19) German 7782-65-2 2192 620 (55) Hexafloaxeton 684-16-2 2420 470 c hiu chnh theo thi (56) 4. gian Hydro bromua 10035-10-6 1048 2860 (51) Hydro clorua 7647-01-0 1050 2810 (45) Hydro iodua 10034-85-2 2197 2860 Tng t nh hydro bromua Hydro selenua 07883-07-5 2202 51 (57) Hydro sunfua 07783-06-4 1053 712 (1) Hydro telurua 07783-09-7 3160 51 Tng t nh hydro selenua Metyl bromua 74-83-9 1062 850 c hiu chnh theo thi gian (23) Metyl mercaptan 74-93-1 1064 1350 c hiu chnh theo thi gian (24) Ete metyl vinyl (b cm) 107-25-5 1087 > 40000 Ngun cha c kim chng ti 64000 ppm Monoetylamin 75-04-7 1036 16000 c hiu chnh theo thi gian (25) Monometylamin 75-04-7 1061 7110 (46) Kh ht ci 4 LCLO - con ngi - c hiu chnh theo thi gian (17) Nit monoxit 10102-43-9 1070 115 Ging nh nit dioxit Nit dioxit 10102-44-0 1067 115 (28) Nit triflorua 7783-54-2 2451 6700 (48) Nitrosyl clorua 2696-92-6 1069 35 c hiu chnh theo thi gian LCLO chut (29) Oxi diflorua 7783-41-7 2190 26 (8) Ozon 10028-15-6 9 c hiu chnh theo thi gian (30) Phosgen 75-44-5 1076 5 c hiu chnh theo thi gian (32) Phosphin 7803-51-2 2199 20 c hiu chnh theo thi gian (64) Phospho pentaflorua 07647-19-0 2198 261 Nhn c t phn hy vi HF - Phospho triflorua 7783-55-3 3308 436 Nhn c t phn hy vi HF - Selen hexaflorua 7783-79-1 2194 50 c hiu chnh theo thi gian (39) Silan 7803-62-5 2203 19000 c hiu chnh theo thi gian (1) Silic tetraflorua 7783-61-1 1859 992 (5) 5. Stibin 7803-52-3 2676 178 Tng t arsin - Lu hunh dioxit 7446-09-5 1079 2520 (35) Lu hunh tetraflorua 7783-60-0 2418 40 (36) Sulfuryl florua 2699-79-8 2191 3020 (1) Telu hexaflorua 7783-80-4 2195 25 c hiu chnh theo thi gian (39) Tetrafloetylen 116-14-3 1081 2000 Trifloaxetyl clorua 354-32-5 3057 10 Ging nh tricloaxetyl clorua Trifloetylen 359-11-5 1954 2000 c hiu chnh theo thi gian Ly t clotrifloetylen Trimetylamin 75-50-3 1083 7000 LCLO - c hiu chnh theo thi gian (66) Vonphram hexaflorua 7783-82-6 2196 160 Nhn c t phn hy vi HF Vinyl bromua (b cm) 593-60-2 1085 > 40000 Vinyl clorua (b cm) 75-01-4 1086 - Vinyl florua (b cm) 75-02-5 1860 > 40000 (47) a CAS = Chemical Abstract System b Xem 3.2.2 c LCLO = Tr s thp ca nng gy cht ngi. Bng A.2 - Danh mc cc hi c ha lng c vi tr s LC50 v ngun ti liu Kh Tn thng dng S CASa S UN LC50 b /1h (theo th tch) Lu Ti liu tham kho (xem th mc) Antimon pentaflorua 7783-70-2 1732 30 Xm [2] Arsenic triflorua 7784-35-2 1556 178 Tng t nh arsin Bis (triflometyl) peoxit 927-84-4 10 c tha nhn (cht bo v) Bo tribromua 10294-33-4 2692 950 Thu c t HBr v BF3 Bromin clorua 13863-41-7 2901 290 c nh gi t clorin Bromin pentaflorua 7789-30-2 1745 25 c hiu chnh theo thi gian v hiu ng [4] Bromin trflorua 7787-71-5 1746 180 c nh gi t flo [4] Bromoaceton 598-31-2 1569 260 Tng t nh cloroaceton Deuteri florua 14333-26-7 1100 Dibromdiflometan 1868-53-7 1941 27000 LCLO - c hiu chnh 6. theo thi gian Diclo (2-clovinyl) asin 8 c ngoi suy t tim tnh mch 8 Dietylamin 109-89-7 1154 8000 c hiu chnh theo thi gian [67] Dietyl km 557-20-0 1366 Khng c c tha nhn (cht bo v) [15] Diphosgen 503-38-8 1076 2 Thu c t phosgen (cht bo v) Etyldicloarsin 598-14-1 1892 7 LCLO - con ngi - c iu chnh theo thi gian [17] Heptaflobutironitril 375-00-8 10 c tha nhn (cht bo v) Hydroxianua 74-90-8 1613 144 c iu chnh theo thi gian [59] Hydro florua 7664-39-3 1052 1307 Tr s trung bnh ca 5 nghin cu [61] Iodua pentaclorua 7783-66-6 2495 120 Ging nh CIF5 Metyl clorosilan 993-00-0 2534 2810 c chnh theo ng lng HCl Metyldicloasin 593-89-5 1556 7 Tng t vi etyldicloroarsin 10 Metyl diclorosilan 75-54-7 1242 1785 [49] Niken cacbonyl 13463-39-3 1259 20 c hiu chnh theo thi gian [27] Pentaboran 19624-22-7 1380 10 c hiu chnh theo thi gian [31] Pentaflobutyronitril Khng lit k 10 Pentaflopropionitril 422-04-8 10 c tha nhn (cht bo v) Perclorylflorua 7616-94-6 770 c hiu chnh theo thi gian [12] Perflobut-2-en 360-89-4 12000 Khng c - LCLO - c hiu chnh theo thi gian Phenylcarbaminclorua 622-44-6 1672 5 Tng t nh phosgen - Propylen oxit 75-56-9 1951 7140 c hiu chnh theo thi gian [60] Silic tetraclorua 10026-04-7 1818 1312 [49] Telu hexaflorrua 7783-80-4 2195 25 c hiu chnh theo thi gian [39] Ch tetraetyl 78-00-2 1649 63 [37] Tetraflohidrazin 10036-47-2 100 c hiu chnh theo thi [38] 7. gian Ch tetrametyl 75-74-1 800 c hiu chnh theo thi gian [65] Tionyl clorua 7719-09-7 1836 500 [58] Triclo silan 10025-78-2 1295 2780 [50] Trietyl nhm 97-93-8 Khng c c tha nhn (cht bo v) Trietylboran 97-94-9 1400 c hiu chnh theo thi gian [13] Trifloacetonitril 353-85-5 500 c hiu chnh theo thi gian v hiu ng c c t tricloacetonitril Trimetylstibin 178 Ging nh stibin uran hexaflorua 7783-81-5 2978 25 Ging nh telu hexaflorua a CAS = Chemical Abstract System b Xem 3.2.2 Bng A.3 - Ch tiu i vi kh c tnh oxi ha Loi Ch tiu 1 Bt c loi kh no c th cung cp oxi gy chy hoc gp phn lm chy cc vt liu khc mnh hn so vi khng kh CH THCH: "Bt c loi kh no c th cung cp oxi gy chy hoc gp phn lm chy cc vt liu khc mnh hn so vi khng kh" c ngha l kh hoc hn hp kh sch vi cng sut oxi ha ln hn 23,5% nh c xc nh theo phng php quy nh trong TCVN 6550:2013 (ISO 10156:2010). Ph lc B (tham kho) La chn gi tr LC50 cho tng loi kh B.1. Quy nh chung Khi la chn s liu t cc ti liu v tnh c xng cp ca cc loi kh, kh khn l kinh nghim. iu gii thch cho v d ca cc cng b nhng nm gn y, m n khng th t c kt qu ca php th tiu chun. Tuy nhin s liu ca cc ngun bo co tr nn c gi tr i vi cc chi tit ca n trong vic x l v tng hp thng tin. Hn na, r rng l c s thiu ton b cc thng tin v tnh c xng cho nhiu loi kh. V th cn phi c gng ln trong vic phi hp tt c cc thc t c b sung cho cc tnh cht c ca cc kh. B.2. iu chnh thi gian Trong php th tnh c xng, mi lin h liu lng - s phn ng c th c th hin bng phng trnh W = c x t Trong : W l hng s c trng cho tc dng xy ra, ngha l s cht chim 50% s ng vt b phi nhim; 8. c x t l liu dng c biu th nh l tch s ca nng v thi gian phi nhim. Phng trnh ny, c gi l qui tc Haber, c th s dng c khi chu k bn phn r sinh hc ca mt cht ang xem xt, cng ko di hn th cng hp l so vi thi gian phi nhim. i vi kh v hi c tc gii c hoc thi ra ng k trong thi gian ang xem xt, mi lin quan gia nng v thi gian c pht hin v c miu t tt hn bng phng trnh: W = c x t0,5 Khi ngoi suy t 4h n 1 h phng trnh W = c x t0,5 d on gi tr LC50 thp hn so vi qui tc Haber. Trn kha cnh an ton, nguyn tc ny c UN Transport Recommendations (Khuyn co chuyn giao ca Lin Hp Quc) p dng trong vic thng qua h s chuyn 2 cho php phn loi vt liu trn c s s liu 1 h - LC50. Mt khc qui tc Haber d on LC50 thp hn kh chuyn t 1h n 4 h - LC50. S dng tt c cc s liu c th c v tnh c xng cp di cc ch phi nhim khc nhau, cn s dng li gii thch tng qut hn. Vic s dng chu k 1 h nh l im i chiu, - i ln t cc chu k ngn hn, php ngoi suy tuyn tnh c u tin hn; - i xung t cc chu k di hn, h s chuyn c s dng. Tuy nhin, kt qu th i vi chu k ngn hn 0,5 h khng c dng, v n c coi l khng tin cy. B.3. Chn ng vt T s liu trn con ngi, nu sn c, thng l khng c c bt k mi lin h no gia liu lng - s phn ng, nghin cu c tnh ca cc cht, ng vt th nghim c s dng l ng vt mu nng. Tr khi c ch th ngc nhau, nh l nhy cm qu cao hoc qu thp ca chut so vi cc ng vt khc hay so vi ngi, chut l loi c u tin trong phn ln cc php th tnh c thng thng. V vy s liu LC50 ca chut thng d tm thy. Nu khng c chut, s liu ca ng vt gn ging vi chut v khi lng c dng nh gi. B.4. iu chnh hiu ng Thay cho LC50, thut ng LCLO thng xut hin trong cc ti liu bo co v c s d liu. LCLO (tr s thp nng gy cht) c nh ngha nh l nng thp nht ca mt cht trong khng kh, khc vi LC50, i lng c ghi chp trong cc ti liu tham kho chnh thc nh l nguyn nhn gy cht ngi hoc ng vt. ng tic, vic s dng nh ngha ny khng chc chn khng nh rng liu LC50 l nh hn hoc ln hn gi tr ny hay khng. Tuy nhin, c v hp l s dng ng thi LCLO nu nh n l thng tin v nng xp x gy cht ngi. phn loi cc kh, khng yu cu chnh xc cao hn, nhng cng thc tnh ton i vi hn hp kh yu cu ly gi tr LC50 xc nh. Gi tr LC khc c ly thay cho LC50 khi m thng tin b sung chng t n ng nh vy. B.5. S ng ha Mt s cht c biu th vi cc c tnh sinh l bit khi c cu to ha hc lin quan tng t. Mi quan h hot ng - cu to phi c coi trng ht mc c th. Hn na trong mt vi v d, nh hng tnh c ln ng h hp da trn cc phn ng c bn nh l s thy phn cc kh khc nhau khi c mt ca hi m a ti cng nguyn tc phn ng. B.6. Cc cch p dng khc Cch ny ch c th c dng khi c mt s la chn cui cng. i khi tnh c xng ca cc cht lng d bay hi c nh gi trn c s triu chng ngoi ng tiu ha khc, c bit l vim bn trong mng bng (i.p.), gi tr LD50. C s tng quan tng i tt gia LC50 v LD50 i.p. cng c h thng hn vi cc hot cht cp. Ly cc thuc tr su c hi lm v d, c th thy rng mt LD50 i.p. tng ng vi mt liu lng theo 9. khi lng c th trong cc php o sol kh m cc con chut ht vo trong thi gian 4h. Chng hn mt LD50 i.p. ca 100 mg/kg c th chp nhn s tng ng vi 4h - LC50 ca khong 1mg/lt khng kh. B.7. Kt lun Vic la chn mt gi tr LC50 cho mt cht kh ring bit tun theo thut ton logic c gii thiu trn Hnh C.1. Tiu chun o nn dng l LC50 CHUT nui trong 1h. Khi thiu cc d liu c gi tr cho cc thng s chnh xc ny th cc gi tr LC50 CHUT c chn cho cc thi gian khc vi 1h nhng gn vi thi gian 1 h nht, loi b tt c cc s liu ng vi thi gian nh hn 0,5 h. Nu khng c c cc s liu LC50 tin cy i vi chut RAT, cn chn con vt tip sau l chut MUS, sau theo th t sau: th, chut bch, mo, ch, kh v ng vt c v. Nn dng cc d liu i vi thi gian 1 h. Nu khng tm thy cc s liu tin cy ca LC50 i vi bt k con vt no th cn tm mt gi tr LCLO c th tin cy c vi vic dng cng mt h thng cp bc cc con vt. Nu khng nhn c gi tr LC50 hoc LCLO c th tin cy c, mt gi tr c chn tm thi, da trn mt, mt s kt hp hoc tt c cc iu kin sau: a) S phn ng (phn hy) ca sn phm trong khng kh; b) S tng t vi sn phm tng ng LC50; c) S so snh vi cc mc nguy him c cng b khc, v d) S tng quan ti tr s LD50 i.p. Hnh B.1 - La chn thut ton logic 10. 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[67] SMYTH, H.F. et. al Archives of Industrial Hygiene and Occupational Medicine 1951, Volume 4, pp. 119-122 in IUCLID [68] TCVN 6551(ISO 5145) Chai cha kh - u ra ca van chai cha kh v hn hp kh - La chn v xc nh kch thc. [69] TCVN 6550:2013 (ISO 10156:2010), Kh v hn hp kh - Xc nh kh nng chy v kh nng oxy ha chn u ra ca van chai cha kh.