CHNG 1 - TNG QUAN

1.1 Tm tt lch s ca nguyn t Arsen [20]

Nguyn t Arsen c hc gi kim nh gi kim ngi c Albertus Magnus (1193-1280) pht hin u tin. Mt s dng ha hc khc ca Arsen cng bt u c pht hin khi nn ha hc tch khi thut gi kim vo gia th k 18. Arsen c l l nguyn t lp k lc c mi lin h t nht vi con ngi do n c dng nh mt cht c khi con ngi bt u quan tm n ha hc. L do arsen c dng ph bin do tnh sn c, r tin, khng mu, khng mi. n cui th k 19, arsen khng cn c dng lm c dc nhiu na do s pht trin ca phng php xc nh Arsen c nhy v tin cy cao do Marsh thc hin nm 1836.

1.2 Tnh cht ca Arsen [20]

Arsen tn ti nhiu dng v c v hu c khc nhau. Nhng dng quan trng nht nh gi sc khe ca con ngi c trnh by bng 1.1. Arsen l nguyn t c mt khp ni, c tnh cht kim. Ha hc ca arsen phc tp v c nhiu hp cht khc nhau ca arsen hu c v arsen v c. Trong t nhin, n tn ti mt s dng khong, ch yu l dng arsenide ca ng, km, nickel, st, hay dng arsenic sulfide hay oxide. Trong nc, arsen thng tn ti dng arsenite hay arsenate. Cc hp cht arsen b methyl ha xut hin t nhin trong mi trng l kt qu ca cc hot ng sinh hc. Hp cht ph bin nht, arsenic (III) oxide, l sn phm ph trong qu trnh nng chy qung ng hay qung ch. 1.2.1 Hp cht arsen v c Hp cht ph bin nht l arsenic (III) oxide, cng thc phn t chung l As4O6, chu c nhit n 1073 0C, l sn phm ph trong qu trnh sn xut ng. Arsen trong arsenide kim loi hay arsenic sulfide b bay hi v oxy ha trong

qu trnh t nng qung v ngng t dng trioxide. Than cha arsen khi t nng cng sinh ra oxide arsen (III). Oxide arsen c im si thp (465 0C) v thng hoa nhit thp hn. p sut hi kh quyn nhit thng kh ln l mt c im quan trng nh hng n s phn b v di chuyn ca arsen trong mi trng. Kh nng ha tan ca As2O3 kh chm, khong 2 % 25 0C v 8.2 % 98 0C, dung dch c tnh acid nh v cha acid arsenous (H3AsO3). As2O3 d ha tan trong acid HCl hay dung dch kim. dng dung dch, arsen thng dng arsenate hay arsenite. Arsen v c ha tr 5 bao gm As2O5, acid arsenic v hp cht arsenate nh ch arsenate, calcium arsenate. Sodium arsenite v sodium arsenate rt d tan trong nc. Trng thi chuyn i ha tr c th xy ra trong dung dch nc, ty thuc vo pH v s c mt ca cc cht khc m arsen c th b oxy ha hay kh. Kim loi kim th kt hp vi anion arsenate to thnh dng mui t tan, do arsen c khuynh hng to thnh kt ta khi kt hp vi phosphate. 1.2.2 Hp cht arsen hu c Ha hc v arsen hu c rt phong ph v a dng. Lin kt C-As kh n nh iu kin pH v trng thi oxy ha ca mi trng. Mt s hp cht methylarsenic nh dimethylarsine, trimethylarsine l kt qu ca nhng hot ng sinh hc. Trong nc, cc cht ny b oxy ha thnh cc acid methylarsenic tng ng. Nhng hp cht arsen hu c khc nh arsenobetaine, arsenocholine, thng tm thy trong hi sn c kh nng chu c suy bin ha hc. Acid methylarsonic l acid hai chc, to thnh mui d tan vi kim loi kim. Cc acid alkylarsenic tham gia phn ng kh to thnh arsine tng ng, mt phn ng quan trng trong phn tch.

Bng 1.1 Mt s hp cht arsen v c v hu c thng dng

Tn Arsenite (arsenous acid) Arsenate (arsenic acid) Monomethylarsonic acid Monomethylarsonous acid Dimethylarsinic acid Dimethylarsinous acid Dimethylarsinoyl ethanol Trimethylarsine oxide Tetramethylarsonium ion Arsenobetaine Arsenobetaine 2 Arsenocholine Trimethylarsine Arsine Ethylmethylarsine Phenylarsonic acid

Vit tt AsIII AsV MMAV MMAIII DMAV DMAIII DMAE TMAO Me4As+ AB AB-2 AC TMAIII AsH3, MeAsH2, Me2AsH EtxAsMe3-x PAA

Cng thc ha hc As(OH)3 AsO(OH)3 CH3AsO(OH)2 CH3As(OH)2 (CH3)2AsO(OH) (CH3)2AsOH (CH3)2AsOCH2CH2OH (CH3)3AsO (CH3)4As+ (CH3)3As+CH2COO(CH3)3As+CH2CH2COO(CH3)3As+CH2CH2OH (CH3)3As (CH3)xAsH3-x (x=0-3) (CH3CH2)xAs(CH3)3-x (x=0-3) C6H5AsO(OH)2

Hnh 1.1 Mt s hp cht arsen hu c c pht hin trong mi trng bin.

Dng in m c th c pht hin mi trng trn cn

1.3 Cc ngun gc gy nhim mi trng [20]

1.3.1 Cng nghip Hai nn cng nghip ch yu lm arsen b nhim vo khng kh, nc v t l qu trnh lm nng chy kim loi mu v sn xut nng lng t nhin liu hnh thnh t xc ng vt b phn hy. Cc ngun gy nhim khc l sn xut v tiu th thuc tr su cha arsen v cht bo qun g. Mt nguyn nhn gy nhim arsen vo t, tip theo l vo h thng nc ngm, chnh l ph phm t cng nghip khai thc m kim loi. 1.3.2 Nng nghip Trc nm 1960, cc arsen v c nh ch arsenate, canxi arsenate, ng acetoarsenite c dng rng ri trong nng nghip. Ngy nay, mt s arsen hu c (MMA, DMA) vn cn c s dng. 1.3.3 Qun s Kh Lewisite (C2H2AsCl3) c dng trong Chin tranh th gii th I, c tnh st thng cao do gy bng da rt kh cha. Mt s hp cht arsen dng trn p m ng do c tnh gy kch ng da v mt. Acid dimethylarsinic, cht gy rng l c dng trong chin tranh Vit Nam. 1.3.4 Sn xut v ng dng Arsen c sn xut ch yu da vo qu trnh thu hi sn phm ph khi lm nng chy qung ng, ch, coban v vng. Arsen ch yu c dng trong cng nghip in t, luyn kim, trong nng nghip c dng lm thuc tr su, thuc gy rng l, cht bo qun g... Ngoi ra, arsen cn c ng dng trong cng nghip sn xut thy tinh, lm pho hoa, ceramic, cht dt nhum, sn chng st, dc phm. Trong lnh vc in t, gallium arsenide v indium arsenide c dng lm t bo nng lng mt tri, t bo quang in, cht bn dn, diode pht sng.

1.4 S phn b ca arsen trong mi trng [25]

C 3 dng bin i sinh hc ch yu ca arsen trong mi trng: Qu trnh oxy ha gia arsenite v arsenate Qu trnh kh v methyl ha arsen Qu trnh tng hp sinh hc ca cc dng arsen hu c.

Arsen phn b ch yu trong mi trng nc. i vi nc b oxy ha, arsen tn ti ch yu dng arsenate, nhng mi trng kh, v d nh trong nc ging su, dng arsenite chim u th. S methyl ha arsen v c thnh acid methylarsenic v acid dimethylarsenic lin quan n cc hot ng sinh hc trong mi trng nc. Mt s loi sinh vt bin tham gia vo qu trnh chuyn i arsen v c thnh hp cht hu c phc tp nh arsenobetaine, arsenocholine, arsoniumphospholipid. Trong mi trng t b oxy ha, arsen v c tn ti dng arsen (V), trong mi trng kh tn ti dng arsen (III). C nhiu bng chng v s methyl ha sinh hc trong t v qu trnh gii phng methylarsine vo khng kh. Hp cht arsen methyl ha cng c pht hin trong kh nh knh. Tuy nhin arsen dng kh tn ti ch yu dng v c. Ha hc ca arsen v c trong mi trng nc, c bit l pH v oxygen rt phc tp. Mt c im quan trng, iu kin lng kh CO2 cao, mui arsenate phn ly thnh 4 acid arsenic [As(V)]: H3AsO4, H2AsO4-, HAsO42-, AsO43-. Tuy nhin, trong mi trng kh nh s hnh thnh dng acid arsenous [As (III)]: H3AsO3, H2AsO3-, HAsO32-. Acid arsenic t c nht trong cc dng arsen v c, acid arsenous c hn v khng c php tn ti trong c th sng. Mt s ln cc phn ng sinh hc v ha hc, nh oxy ha kh, hp ph, kt ta, methyl ha v ha hi tham gia tch cc vo chu k hot ng ca nguyn t ny (Hnh 1.2). Cc phn ng ny kim sot s c mt ca arsen trong mi trng. Do , arsen gy hi cho con ngi ch t mt s dng arsen ch khng phi do tng dng arsen.

Hnh 1.2 Chu trnh ca Arsen trong mi trng

Cc phn ng ha hc v cc qu trnh vt l trong t nc v cn bn nh hng n qu trnh vn chuyn, phn b ca arsen trong mi trng. Lng oxy kim sot cc phn ng oxy ha kh arsenate arsenite. S hp thu v kt ta arsenate v arsenite ngn chn hot ng ca cc arsen ha tan. S gii phng arsenic dn dn t v bn lng hay s ha tan do qu trnh oxy ha ca arsenopyrite (FeAsS) chuyn ha arsen vo trong mi trng. S methyl ha arsenite thnh monomethylarsonic acid (MMA) hay dimethylarsinic acid (DMA) hnh thnh hp cht arsen hu c ng gp vo nhng phn ng sinh hc ch yu trong chu trnh arsen.

1.5 Ngun gc ca arsen trong hi sn [13]

Trong nc bin thng cha arsen vi hm lng khong 1 2 g/L (WHO, 2001). Hm lng ny gn nh khng i mc nc bin su, trong khi nc b mt hm lng ny thay i theo ma. Qu trnh kh v methyl ha bi cc vi sinh vt xy ra vng c nhiu nh sng, nhng tng i dng m nh sng mt tri c th xuyn qua thc hin qu trnh quang hp. Hu ht arsen v c c trong c th sinh vt bin khng phi t nc bin. Ngc li, ngun arsen ny ch yu t thc n, mt qu trnh tch ly tng ng vi mt chui trao i cht xy ra khi arsen tham gia vo trong chui thc n. Chui trao i cht bt u t nhng sinh vt ph du (rong ru, to) hp thu arsenate t nc bin qua h thng mng trao i cht. Sau khi hp thu, to nhanh chng kh c arsenate thng qua phn ng kh v methyl ha to thnh dng ng cha arsen v mt lng nh DMA cng cc hp cht arsen khc. Lng arsen trong to ln hn gp 1000 n 10 000 ln so vi trong nc bin. Trong sinh vt bin, dng arsen ch yu l arsenobetaine, hp cht As(V) cha 3 nhm methyl. AB c khp ni trong mi trng bin, c bit cc loi hi sn m con ngi dng lm thc phm. Cc nghin cu cho thy sinh vt bin cp cao hn khng tng hp arsenobetaine t arsenate. l do cc loi to khi cht v b phn hy s gii phng arsenosugar vo mi trng nc v trm tch, nh loi vi khun s chuyn ha thnh arsenobetaine, t i vo c th sinh vt bin. Cc th nghim cng cho thy vi khun trong nc bin c th chuyn ha MMA v DMA (tr arsenate) thnh AB.

1.6 c tnh
c tnh ca arsen thay i ty thnh phn v cu trc ha hc. Hu ht cc hp cht arsen u c, nhng c tnh th khc nhau rt nhiu. Cc dng arsen ch yu c tm thy trong hi sn l: As(V), As(III), MMA, DMA, TMAO, TMA, AC, AB. Ngoi ra cn c arsenosugar v arsenolipid. Dng arsenosugar chim s lng ln bao gm glycerosulfonate, glycerosulfate, glycerol

v glycerophosphate ca dimethylarsinylriboside. Dng arsen c hi nht trong thc phm l arsen v c. Cc dng arsen hu c khc c c thp hn nhiu, mt s trong gn nh l khng c hi. As(III) tn ti trong c th sng dng lin kt vi nhm SH ca cc protein v cc i phn t, lm c ch cc enzyme trao i cht gy ra ng c cp tnh. Triu chng ng arsen khng ph thuc vo dng arsen v c no tn ti, c l l do kt qu ca qu trnh chuyn i qua li gia As(III) v As(V) bi cc phn ng oxy ha kh trong c th sng. Do , vic phn bit hai dng arsen v c l khng cn thit. Kt qu l, vic d on mi nguy sc khe ca con ngi t vic dng hi sn ph thuc vo lng arsen v c tiu th qua thc n [24]. Arsen c th gy ra cc bnh v tim mch, da liu, huyt hc, gan, thn. Arsen cng c th gy ra ung th b phn sinh dc, b phn tit niu, c quan h hp v da.[22] Liu c gy cht LD50 (g/kg th trng) ca mt s dng arsen trong mi trng c th hin bng 1.2. Dng trimethyl hu nh khng c. Arsenocholine v trimethylarsine oxide t c hn As(III) 200 n 300 ln. Arsenobetaine thng c tm thy trong hi sn v l dng t c nht, khng th xc nh chnh xc LD50 v c tnh qu thp (> 10 g kg-1). c tnh ca As(III) c chng minh l do lin kt vi nhm thiol ca cc protein hot ng sinh hc lm c ch enzyme trao i cht.

Bng 1.2 Gi tr LD50 ca 8 dng arsen ph bin [20]

S c mt ca cc dng arsen trn l do qu trnh methyl ha sinh hc arsen v c. S methyl ha c th xy ra trong t, trm tch, ng vt v thc vt di nc hoc trn cn, gm c con ngi thng qua gin tip l nhng vi sinh vt. S methyl ha sinh hc arsen gm cc bc lp li ca qu trnh kh, methyl ha v oxy ha (Hnh 1.3).

Hnh 1.3 Qu trnh kh v methyl ha sinh hc arsen v c

1.7 Tng qut v phng php phn tch cc dng arsen [20]
1.7.1 Phng php xc nh tng hm lng arsen Hu ht cc phng php xc nh As u phi chuyn mu t dng rn sang dng lng. Dng lng cha tt c cc dng arsen trong . ph mu ta thng dng 2 phng php sau: Phng php v c ha mu kh: cht tr nung l cht oxy ha dng v c. Phng php v c ha mu t: thuc th l HNO3. Trong v c ha mu t, ph mu bng l vi sng gia nhit l mt phng php kh hu hiu c dng trong thi gian gn y. Li ch ca phng php ny l nhanh chng, gim nguy c nhim bn hay mt mu, tit kim thuc th ph mu. Ph mu bng l vi sng c 2 dng: dng kn v dng h. Dng kn thun li hn do p sut cao c th t c nhit cn thit ph mu vi acid c im si thp, v d nh acid nitric. K thut to hydride Hydride l qu trnh to dn xut ha hc sinh ra cc cht hydride d bay hi da trn phn ng ha hc vi mt tc nhn kh, thng l sodium tetrahydroborate (NaBH4). NaBH4 trong mi trng acid trung bnh l iu kin chung to hydride. NaBH4 phn hy hon ton to thnh hydro kh cht phn tch v hydride: BH4 - + 3 H2O + 6H H+ H3BO3 + 8 H

+ AsO33- + 3 H+ AsH3 + 3 H2O

K thut to hydride thng c dng xc nh cc nguyn t c kh nng to hydride nh As, Bi, Sb, Se v Sn. Dng kh tch hydride ra khi nn mu i vo h thng pht hin lm cn nhiu ph v cn nhiu ha hc c bn c loi tr. Cc yu t c th nh hng n qu trnh to hydride l nng acid, s to thnh cc dng bay hi khc, trng thi oxy ha ca nguyn t, nng NaBH4. Acid arsenous, acid arsenic, MMA, DMA, TMAO b kh trong mi trng acid bi NaBH4 to thnh arsine AsH3, CH3AsH2, (CH3)2AsH, (CH3)3As. Arsenosugar, cc dng arsen chnh trong cc loi thy hi sn cng to thnh

hydride. Arsenobetaine, arsenocholine, cation tetramethylarsonium khng th to thnh hydride nu khng c cc bc x l thm. Cc h c th ghp cp vi k thut hydride l ph hp thu nguyn t (AAS), ph pht x nguyn t (AES), ph hunh quang nguyn t (AFS), khi ph plasma ghp cp cm ng (ICP-MS), ph pht x plasma ghp cp cm ng (ICP-AES). Cc phng php ph nguyn t c u im nhy cao, gii hn pht hin thp. Tuy nhin, k thut ny li c hn ch nh khong tuyn tnh nh, ch p dng c i vi nguyn t c kh nng to hydride v khng th xc nh ng thi nhiu nguyn t.
Bng 1.3 Phng php xc nh tng arsen (theo National Research Council of Canada, 1999) [20]

Phng php K thut to hydride Ph hunh quang nguyn t Ph hp thu nguyn t l graphite Ph pht x ICP ICP-MS Phng php ph Ph hp thu nguyn t ngn la Ph hp thu nguyn t l graphite Ph pht x ICP ICP-MS 1.7.2 Phng php xc nh cc dng arsen

Gii hn pht hin

20 ng/L 2 ng/L 20 ng/L 0.1 ng/L 1 mg/L 1 g/L 10 g/L 0.05 g/L

Ngy nay, vi s pht trin cc k thut kt hp nh tnh v nh lng cc dng arsen, cc hp cht ny c dng d on c tnh ca arsen trong mu. Hu ht trng hp cn phi tch trc khi xc nh. Cc phng php nh tnh v nh lng arsen c th hin hnh 1.4.

Hnh 1.4 Phng php nh danh v nh lng cc dng arsen [20]

1.7.2.1 Phng php chit cc dng arsen Quy trnh chit c thc hin sao cho hp cht arsen khng b phn hy hay chuyn i ha hc. Cc k thut hin nay cha th tch ht tt c cc dng arsen trong mt bc, do cn thit phi c s kt hp cc phng php tch vi nhau. Cc dung mi chit arsen ph bin l methanol, hn hp methanol/nc, acid phosphoric Dng hn hp methanol/ nc hay methanol lm dung dch chit c nhiu thun li v cc dng hp cht khc t b chit cng methanol, dung mi d bay hi khi lm giu mu. Do , hiu sut chit c th t c 90% khi chit arsen trong sn phm thy sn cha nhiu arsenobetaine. Tuy nhin, methanol khng c dng chit arsen v c v hiu sut rt km. Phng php chit ch yu l lc, siu m, chit c kim sot p sut.

1.7.2.2 H sc k lng hiu nng cao (HPLC) [36] HPLC l mt phng php tch hu hiu ch cn mt lng mu nh v c th lin kt vi cc h thng pht hin khc. Hai dng sc k lng thng dng tch arsen l sc k ghp cp ion v sc k trao i ion. Sc k ghp cp ion Sc k ghp cp ion c dng phn tch arsen trung tnh v arsen dng ion. C hai k thut sc k ghp cp anion v sc k ghp cp cation u c pht trin tch ri cc dng arsen. Tetrabutylammonium (TBA, dng hydroxide v phosphate) l cation ghp cp ph bin tch As(III), As(V), MMA v DMA. phn gii ca nhng arsen ny ty thuc vo nng ca cation ghp cp, tc dng, pH ca pha ng. Khong pH ti u tch bn hp cht arsen ny l 5-7. i vi sc k ghp cp anion, tc nhn ghp cp l tetraethylammonium hydroxide (TEAH) dng tch AB v arsenosugar. Phng php ny c ng dng phn tch cc dng chuyn ha ca arsen trong nc tiu sau khi dng thc phm l cc loi rong bin hay to bin v nghin cu cc dng arsen trong mi trng. Sc k trao i ion C hai phng php sc k trao i cation v sc k trao i anion u c th dng phn tch cc dng arsen. Ty thuc vo c im ion ca hp cht arsen, sc k trao i anion dng phn tch As(III), As(V), MMA, DMA, trong khi trao i cation dng phn tch AB, AC, trimethylarsine oxide (TMAO) v Me4As+.

1.8 K thut ph pht x plasma ghp cp cm ng (ICP) [1,5,9]

1.8.1 Gii thiu Phng php ph pht x plasma ghp cp cm ng l mt trong nhng phng php ti u phn tch a nguyn t. y l mt cng c rt hu hiu cho php pht hin mc nng thp.

Ngun ICP s to ra plasma, l mt dng kh c nng lng ion ha cao c hnh thnh t s ghp cp cm ng ca mt kh tr nh argon vi mt t trng tn s cao to nn mt plasma n nh, c nhit cao (6000-10000 oK). Khi mu c a vo plasma nhit 10000 oK s ln lt b de-solvate ha, ha hi, nguyn t ha, kch thch v ion ha. Cc nguyn t, ion b kch thch s pht ra bc x ti bc sng c trng. Bc x c thu nhn v chuyn thnh tn hiu in t. Mt s thun li khi dng ICP-OES: Gii hn pht hin thp Khng c cn nhiu ha hc nh hng tng tc gia cc nguyn t cc thp ng v chnh xc cao.

Cc qu trnh din ra trong plasma Sau qu trnh phun sng, mu c a vo plasma dng sol kh. Khi cc sol kh di chuyn vo plasma, hng lot qu trnh xy ra. Cc qu trnh ny c tm tt hnh 1.5

Hnh 1.5 S cc qu trnh din ra trong plasma

u tin, cc ht sol kh b de-solvat ha to thnh cc ht mui rn. Tip , cc ht ny s ha hi sinh ra dng phn t pha kh. Cc phn t ny s b nguyn t ha ri ion ha. Nu mt nguyn t pht ra bc x, theo nh lut bo ton nng lng, nguyn t phi hp thu nng lng tng ng t ngun cp bn ngoi nh plasma. Nng lng chuyn ha vo nguyn t s a electron ln trng thi kch thch. Cc qu trnh kch thch ch yu ca cht phn tch bao gm: - S va chm electron: e- + M M* + e - S kt hp bc x ca ion v electron: M+ + e M* + h S pht x s xy ra khi nguyn t trng thi kch thch chuyn v trng thi nng lng thp hn v gii phng mt bc x photon. 1.8.2 Thit b ICP-OES l mt k thut phn tch nguyn t s dng ph pht ra t nhng nguyn t hay ion t do c to ra t ngun ICP. S h thng ICP-OES tiu biu c th hin hnh 1.6.

Hnh 1.6 S h thng ICP-OES

1.8.2.1

H thng a mu B to sng

C nhiu cch chuyn mu dng lng thnh dng hi; trong , hai cch ph bin l dng lc kh nn v lc c hc siu m. Hu ht cc b to sng dng trong h ICP l dng kh nn, s dng dng kh tc cao to thnh dng phun sng. B to sng dng lc kh nn rt ph bin trong k thut ph hp thu nguyn t ngn la, v cng l dng u tin dng trong ICP-OES, l dng ng tm (Hnh 1.7).

Hnh 1.7 - B to sng dng ng tm dng trong ICP-OES

dng ny, mu c a vo thng qua ng mao qun n vng p sut thp c to ra khi cho dng kh thi nhanh vo cui ng mao qun. p sut thp v dng kh tc cao s ph v dung dch to thnh dng hi sng. Hu ht cc b to sng dng ng tm ph bin (nh Meinhard) c lm t thy tinh, do rt d v v c kh nng b n mn nu dung dch cha acid HF. Bm Dng cht lng vo b to sng c kim sot bng bm nhu ng. Mc ch chnh ca bm l cung cp dng cht lng vo b to sng v bm dng thi ra khi bung phun sng. Cc ng dy dng trong bm nhu ng phi tng thch vi dung dch mu v phi c thng xuyn thay mi.

Bung phun mu vo plasma Ht sng mu sau khi c sinh ra t b to sng s di chuyn vo ngn uc (torch) ri vo plasma. V ch c mt lng nh hi mu c tim vo plasma nn cn c mt thit b phun mu t gia b to sng v ngn uc ICP. Thit b phun mu tiu biu c trnh by hnh 1.8.

Hnh 1.8 - Bung phun mu vo h ICP-OES

Chc nng chnh ca thit b phun mu l loi b lng ln git mu ra khi h hi sng. Chc nng th hai l lm phng cc xung xy ra trong qu trnh to sng, thng l do qu trnh bm mu. Thit b phun mu c thit k cho ht c ng knh nh hn hoc bng 10 m vo plasma. Thng thng lng mu vo plasma chim t 1 n 5% lng mu vo b to sng, phn cn li theo ng dn thi ra ngoi. 1.8.2.2 Ngun pht x Ngn uc (Torch) Ngn uc gm ba ng ng tm cho dng argon v dng sng mu thi qua (Hnh 1.9). Khong cch gia hai ng ngoi kh hp dng kh thi vo t tc cao. Vng ny c thit k dng kh xoy thng ng vo. Dng kh ny c nhim v lm mt thnh thch anh ca ngn uc, gi l dng lm mt, dng ngoi hay dng plasma. Vi kh argon trong h ICP, tc dng plasma trung bnh khong 7 15 L/pht.

Hnh 1.9 S ngn uc dng trong h ICP-OES

Vng gia dng ngoi v dng trong a kh trc tip vo plasma. Dng ny gi cho qu trnh phng in tch xa khi ng trung gian v ng tim mu ng thi chuyn mu vo plasma d dng hn. Dng ny c gi l dng b tr, tc trung bnh khong 2-3 L/pht. Dng kh cui cng a trc tip hi mu vo plasma gi l dng mu, tc dng khong 1 L/pht v c chc nng nh dng kh mang. Ngun pht tn s sng radio (RF power) Ngun pht tn s radio l cng c cung cp nng lng cho qu trnh sn sinh v duy tr s phng in trong plasma. Nng lng ny, thng thng t 500 1700 W, c chuyn vo kh plasma qua cun ti qun quanh u ngn uc. Cun ti, c nhim v truyn nng lng RF n plasma, c lm bng dy ng v c lm mt bng nc hoc kh trong sut qu trnh vn hnh. 1.8.2.3 Ngun thu nhn v pht hin bc x H thng truyn quang Bc x pht ra t vng plasma (c gi l vng phn tch thng thng NAZ) s vo vng o ph. Cho n gn y, vng phn tch c quan st t

plasma theo hng thng ng. Bc tip cn c in n vng ph ICP ny c gi l hng xuyn tm hay hng theo cnh ca plasma. (Hnh 1.10)

Hnh 1.10 - Bc tip cn vng ph ICP theo hng cnh

u nhng nm 1990, trn th trng xut hin dng ICP c bc tip cn n vng ph hng mi. Plasma xoay theo hng nm ngang v vng quan st theo hng trc ca plasma. (Hnh 1.11)

Hnh 1.11 - Bc tip cn vng ph ICP theo hng trc

Mt s thit b kt hp c hai bc tip cn trn. i vi cu hnh hng cnh, lng knh hi t kt hp vi h thng gng cho php o pht x cc chiu cao khc nhau trong plasma. Vic ny lm thit b linh ng hn, mc d n khng cn thit cho hu ht cc php phn tch. Vi cu hnh hng trc, vic o pht x chiu cao khc nhau khng quan trng. Tuy nhin, kh nng iu chnh h gng s n gin ha vic canh chnh ngn uc. B n sc Bc x pht ra t vng plasma c hng vo mt thit b quang hc gi l my n sc phn gii thnh tng tia n sc ring bit. Hu ht cc thit b o

ph pht x nguyn t hin nay u dng loi my n sc cch t. Bng cch xoay cch t ta la chn khe ra ca my n sc mt tia n sc c trng ca nguyn t ha hc cn xc nh. Cc b phn chnh ca my n sc gm c: - Khe vo: cung cp mt hnh nh hp ca ngun bc x a sc (cha phn gii). - Thu knh t chun trc: chuyn chm tia phn k thnh chm tia song song a sc (cha phn gii). - Cch t hoc lng knh: tch chm tia a sc thnh tng tia n sc, mi tia n sc i theo mt chiu ring. - Thu knh tiu im: chuyn hnh nh ca khe vo ln khe ra. - Khe ra: cho thot ra tia n sc yu cu v che mi tia khng yu cu. Hai dng ch yu ca my n sc c th hin hnh 1.12.

Hnh 1.12 a. B n sc loi hai gng

b. B n sc loi mt gng

Cch t l mt b phn quan trng trong b n sc. l mt bn ch nht hoc vung bng nhm, mt di gn vi mt hp kim km theo h thng c vi cp iu khin gc quay ca mt phng cch t, mt trn ngi ta dng mi dao kim cng to ra cc rnh phn x song song v cch u nhau. C hai loi cch t:

- Cch t echellette: l cch t c mt phng nhiu x l mt phng cha cnh di ca gc nh din ca rnh cch t. c im ca loi cch t ny l: Gc nghing nh, khong 100 - 350 Bc nhiu x lm vic m=1

Hnh 1.13 S cch t echellette

- Cch t echelle: l cch t c mt phng nhiu x l mt phng cha cnh ngn ca gc nh din ca rnh cch t. c im ca loi cch t ny l: Gc nghing ln, khong 630 Bc nhiu x lm vic m=75

Hnh 1.14 S cch t echelle

Trong h ICP-OES, cch t thng dng l cch t echelle. Nhng nm gn y xut hin nhng my n sc ghp cch t echelle v lng knh 300 (hoc mt cch t nhiu vch hn) phn gii ph nguyn t. Tia sng ra khi l nguyn t ha ln lt qua h quang hc lng knh-cch t echelle-lng knh. Nng sut phn gii c nng cao gp i trong loi my n sc ny. H quang in hnh ca dng cch t ny c th hin hnh1.15.

Hnh 1.15 S quang hc cch t echelle

Cch t echelle s tch bc x a sc theo cc bc sng to thnh nhng bc ph trng chp nhau. Thit b phn tn th hai, cng l cch t vi mt rnh dy hn s tch cc bc ph trng chp thnh dng hai chiu gi l echellogram. Mt phng tiu im ca my n sc cch t c th hin hnh 1.16, vi mt chiu l thang bc sng, cn chiu kia l bc nhiu x.

Hnh 1.16 - Mt phng tiu im ca my n sc cch t

Cch t echelle c nhng u im sau : H quang hc t hiu sut cao mi bc ph. Cch t nhiu x thng c ti u ha ti bc sng c trng theo mt bc c bit, thng thng l bc 1. H thng c phn gii cc tt v c dng nhng bc ph cao hn (bc cng cao phn gii cng tng). V dng bc nhiu x cao lm tng phn gii nn kch thc ca thit b c thu nh li. B d quang in Tia cng hng khe ra ca my n sc c chiu thng vo b d quang in chuyn ha thnh dng in tng ng. u d c dng ph bin nht trong h ICP-OES l n nhn quang (PMT). PMT l mt ng chn khng c cha cht cm quang, c gi l quang cathode, khi c nh sng chiu vo s sinh ra cc electron. Cc electron ny va p vo dynode sinh ra electron th cp. Cc electron th cp ny tip tc va p vo dynode sinh ra nhiu electron hn. Trong mt n nhn quang c th c nhiu dynode v mt anode. Dynode c ch bng BeO, GaP, CsSb...

Mt n nhn quang in hnh cha t 9 n 16 giai on i qua dynode. bc cui cng, anode s thu thp cc electron t dynode. Cng dng in o c ti anode s t l vi cng bc x chiu vo n nhn quang.

Hnh 1.17 S m t quang cathode, dynode v anode trong n nhn quang

u d CCD Ngy nay, nhng my ICP th h mi khng dng PMT na m dng u d CCD (Charge coupled device) hay SCD (Segmented array charge-coupled device). u d CCD hot ng da vo tnh cht nhy vi nh sng ca silic trng thi rn v nm trong nhm thit b da vo nn tng silic gi l thit b chuyn di in tch (CTD). minh ha nhng phn chnh ca CTD, chng ta xt n mt khi tinh th silic tinh khit rt cao (Hnh 1.18). Trn b mt nn silic l mt lp bo v bng

SiO2. Mi nguyn t silic lin kt vi nguyn t silic lin k to thnh mng tinh th ba chiu (Hnh 1.19).

Hnh 1.18 - T in kim loi oxide-Silic

Hnh 1.19 - S hp thu photon to thnh electron v l trng

Lin kt Si-Si s b ct t bi mt nng lng vi cng ln nh photon bc sng vng UV hay Vis. Khi lin kt b ct t, mt electron s c gii phng to thnh mt l trng trong cu trc mng tinh th. Nu p vo mt in th, electron t do s di chuyn ngc vi t trng p vo hoc hng vo b mt Si-SiO2 trong khi cc l trng s di chuyn cng chiu hay ngc chiu vi t

trng li khong trng tch in dng. S di chuyn ca cc electron v l trng trong mng tinh th sinh ra dng in t l vi lng photon va chm vo cu trc mng. Cc yu t CTD, cn c gi l pixel, c th thay i kch thc t 6-30 m v c sp xp dng xp hai chiu t 512 x 512 pixel n 4096 x 4096 pixel. Mi pixel c kh nng cha photon sinh ra in tch. Cch thu nhn v lu tr in tch nh th no l c s phn bit cc dng u d khc nhau. Thit b ICP chng ti dng phn tch trong bi vit ny s dng u d CCD. y l u d c dng xc nh ng thi nhiu bc sng. u d CCD ca thit b ICP-OES Varian 720-ES vi 70 ngn pixel cho hnh nh hai chiu t h quang hc echelle, cung cp bc sng lin tc t 167-785 nm, do c th loi tr cn nhiu ph. u d CCD nh ngha li khi nim tc trong ph nguyn t. y l k thut duy nht vi tc 1 MHz pixel cho kh nng c nhanh hn 80 ln so vi cc u d khc. Chng ta c th o ng thi 73 nguyn t ch trong thi gian 35 giy.