Tcvn

tIu chun vIt nam

TCVN 6663-14 : 2000 ISO 5667-14 : 1998

cht lng nc ly mu phn 14: hng dn m bo cht lng ly mu v s l mu nc mi trng

Water quality Sampling Part 14: Guidance on quality assurance of environmental water sampling and handling

H ni - 2000

Li ni u
TCVN 6663-14 : 2000 hon ton tng ng vi ISO 5667-14 : 1998. TCVN 6663-14 : 2000 do Ban k thut Tiu chun TCVN/TC 147 Cht lng nc bin son, Tng cc Tiu chun o lng Cht lng ngh, B Khoa hc Cng ngh v Mi trng ban hnh.

tiu chun vit nam

TCVN 6663-14 : 2000

Cht lng nc Ly mu Phn 14: Hng dn m bo cht lng ly mu v x l mu nc mi trng

Water quality Sampling Part 14: Guidance on quality assurance of environmental water sampling and handling

Cnh bo: Phi xem xt v gim thiu mi nguy c v tun th cc quy nh v an ton. Xem cc ch an ton trong ISO 5667-1, bao gm c vic ly mu t thuyn v trn sng.

1 Phm vi p dng
Tiu chun ny a ra hng dn v la chn v s dng cc k thut m bo cht lng khc nhau lin quan n vic ly mu th cng nc mt, nc ung, nc thi, nc bin v nc ngm. Ch thch Cc nguyn tc chung nu ra trong tiu chun ny c th p dng cho vic ly mu bn v cn
lng trong mt s trng hp.

2 Tiu chun trch dn

ISO 5667-1: 1980, Cht lng nc - Ly mu - Phn 1: Hng dn lp cc chng trnh ly mu TCVN 5993-1996 (ISO 5667-3: 1985), Cht lng nc - Ly mu - Hng dn bo qun v x l mu.

3 nh ngha
Cc nh ngha sau y c p dng cho tiu chun ny (TCVN 6663-14: 2000 /ISO 5667-14:1998)

3.1 ng
gn nhau v s tng ng gia mt kt qu kim tra v gi tr i chng c chp nhn. [ISO 3534-1]

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Ch thch Khi nim ng, khi p dng vo mt lot cc kt qu kim tra, bao gm s kt hp ca cc
yu t sai s hoc lch ngu nhin v h thng.

3.2 chch
s khc nhau gia k vng ca kt qu kim tra v gi tr i chng c chp nhn. [ISO 3534-1] Ch thch lch l sai s ton b mang tnh h thng, ngc li vi sai s ngu nhin. C th c mt hoc
nhiu thnh phn sai s mang tnh h thng gp phn to ra lch. lch cng ln phn nh s sai khc h thng cng ln so vi gi tr i chng c chp nhn .

3.3 chnh xc
gn nhau v s tng ng gia cc kt qu c lp thu c trong nhng iu kin quy nh. [ISO 3534-1] Ch thch 1 S bin ng i km theo cc kt qu kim tra do cc thao tc ly mu lp s bao gm bin
ng t qu trnh phn tch cng nh cc nguyn nhn t qu trnh ly mu. C th so snh sai s ngu nhin ca vic ly mu lp vi sai s ngu nhin t phn tch lp trn cng mu suy ra sai s do ly mu so vi sai s ngu nhin tng.

Ch thch 2 chun xc ch ph thuc vo s phn b cc sai s ngu nhin v khng lin quan n gi tr
thc hay gi tr l thuyt (ISO 3534-1). Php o chun xc c th hin theo lch chun. chun xc c ci thin l c th hin khi lch chun c gi tr nh.

Ch thch 3 "Tnh c lp" ca cc kt qu kim tra phn nh gii hn m ti cc kt qu thu c theo

cch khng b nh hng bi kt qu phn tch mu trc (ISO 3534-1). Cc php o nh lng chun xc rt ph thuc vo cc iu kin quy nh. Nhng thut ng thng c bit n nh l " lp li" v " ti lp" lin quan n cc loi iu kin quy nh nht nh. " lp li" t ng ng vi cc php o c tin hnh trong nhng iu kin c kim sot (bi cng mt bin php, c tun th cht ch trong cng mt phng th nghim); cn " ti lp" cp ti cng mt bin php song c dng trong nhiu phng th nghim khc nhau.

3.4 tnh i din

l mc trong iu kin ca tt c cc mu nc c ly t thu vc phn nh iu kin ca nc cn nghin cu

3.5 tng hp
mc tho thun v mt kim sot cc sai s ngu nhin v sai s h thng

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3.6 vt liu i chng c chng nhn (CRM)
vt liu n nh v ng nht, c thnh phn gn khp vi thnh phn ca mu cn phn tch, nng cc thnh phn cn phn tch trong vt liu c bit vi mt bt nh xc nh. Ch thch Trong hu ht cc phn tch ha hc, c th c c kh nng truy nguyn ca php o bng mt
lot hiu chnh cho thy khng c s mt mt cc thng s cn xc nh hoc s nhim bn trong qu trnh x l mu. Kh nng truy nguyn ny c th da vo phn tch CRM.

3.7 gi tr mu trng
gi tr quan st thu c khi tin hnh php o trn mt mu ging ht mu cn nghin cu, song khng cha cht cn xc nh. Ch thch Cc mu trng ti hin trng l nhng mu trng trong phng th nghim c mang ra hin
trng, c x l nh mu tht v c phn tch kim tra quy trnh ly mu.

[ISO/TR 13530]

3.8 gi tr mu thm
lng bit v thnh phn cn xc nh c b sung vo mu, thng l tnh sai s h thng ca mt h thng phn tch bng phng php pht hin. [ISO/TR 13530]

3.9 tm thy
l mt lng ti thiu no bit ca mt cht cn phn tch c thm vo mu m c th o c bng mt h thng phn tch. Ch thch gi tr pht hin c tnh t s khc nhau gia cc kt qu phn tch ca phn mu c thm v
phn mu khng thm v thng c tnh bng phn trm (%).

[ISO/TR 13530]

3.10 biu kim sot

l biu c cc gii hn trn v gii hn di, trong cc gi tr ca mt s php o thng k ca mt lot mu tht, mu thm v mu trng, c lp thnh biu v thng tng ng vi ngy thng hoc th t s mu. Ch thch 1 Biu thng c mt ng trung tm d nhn ra xu th ca cc gi tr c xc nh trn
biu v mt trong hai gii hn kim sot.

[ISO 3534-2]

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Ch thch 2 Trong mt s biu kim sot, cc gii hn kim sot c da trn cc s liu ca ring l
lp trn biu ; trong khi vi mt s biu khc th cc gii hn kim sot ny li da vo cc tiu chun c chp nhn hoc cc gi tr quy nh p dng cho c trng thng k c dng.

Ch thch 3 Biu tng tch ly l mt dng biu kim sot. Dng biu ny dng pht hin nhng
thay i nh thng xuyn theo xu th m c th nu dng biu kim sot Shewhart th cha chc pht hin ra. Nguyn tc c bn ca dng biu tng tch ly ph bin nht l da trn gi tr c lp ln biu l tng tch ly ca cc lch ca cc thng k mu lin tip so vi mt gi tr ch. Khi c mt thay i no v qu trnh, tng s tr v khng. To ca mi im c v s l tng i s ca to im trc v lch hin ti so vi gi tr ch.

Cc biu tng tch ly thng c phn tch qua cc im hng ln trn bng phng php chng, s xut hin mt du hiu nu ng tng tch lu giao nhau hay chm ng bin ca th (ISO 3534-2).

3.11 biu kim sot Shewhart

l biu kim sot cho thy qu trnh c c kim sot v mt thng k hay khng [ISO 3534-2 v ISO 8258] Ch thch c th l mt biu dng cc c trng nh tnh (v d, phn khng ph hp) nh gi mt
qu trnh, hoc c th l mt biu dng cc c trng nh lng (v d, s trung bnh v dy) nh gi mt qu trnh. Mt s v d l:

Biu gi tr trung bnh - cc gi tr trung bnh c v thnh th kim sot gi tr trung bnh ca mt bin s;

Biu gi tr cc dy mu c v thnh th kim sot thay i ca mt bin s;

Biu lch chun - cc lch chun ca mu c v thnh th kim sot thay i ca mt bin s;

Biu bin thin - bin thin ca mu c v thnh th kim sot thay i ca mt bin s; Biu C - s lng cc sai li (theo mi l, tng ngy, tng my, v.v...) c v trn biu .

3.12 gii hn can thip trn [di]

gi tr thng k ang xt no nm gii hn trn [di], hay nm ngoi khi nht thit phi thc hin mt hnh ng can thip [ISO 3534-2] Ch thch Cc gii hn ny da trn gi thit l ch 0,3% cc kt qu phn b bnh thng s nm ngoi
nhng gii hn ny. iu c ngha chc chn rng nhng nguyn nhn ph hay cha chc chn gy ra thay i cng vn c th tn ti v c th phi tin hnh xc nh v gim thiu cc nguyn nhn .

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3.13 gii hn cnh bo kim sot trn [di]
gi tr thng k ang xt no vi xc sut cao nm gii hn di [trn] ( gii hn trn hoc di), hay nm gia khi qu trnh ang c kim sot . [ISO 3534-2] Ch thch 1 Khi gi tr thng k c tnh ton t mt mu nm ngoi cc gii hn cnh bo nhng nm trong
gii hn can thip, nhn chung cn tng cng gim st qu trnh v c th p dng cc quy tc can thip trong mt s qu trnh nht nh.

Ch thch 2 Ti cc gii hn cnh bo, cn ch n kh nng c cc iu kin ngoi kim sot, tuy nhin
khng cn c tin hnh thm bin php.

Ch thch 3 Cc gii hn cnh bo lun lun nm trong gii hn can thip . Ch thch 4 Cc gii hn cnh bo thng c xc nh sao cho thng thng ch 5% kt qu nm bn
ngoi cc gii hn . Trong mt s trng hp nht nh, cc kt qu lin tip nm ngoi gii hn cnh bo biu th rng cc nguyn nhn gy ra s thay i l hin hu v cn c bin php can thip nhn bit

v gim bt cc sai s.

Ch thch 5 Cc gii hn c tnh t lch chun ca gi tr thng k c xem xt ca t nht l 20 mu.

Cc gii hn cnh bo v can thip c p dng cho cc kt qu ly mu ring l.

3.14

ng trung tm

l ng thng trong biu kim sot th hin gi tr trung bnh theo mt thi gian lu di hoc mt gi tr c xc nh trc ca php o thng k c lp thnh th. [ISO 3534-2]

4 Ngun sai s ly mu
Cc ngun gy sai s bao gm nhng ngun sau y: a) Nhim bn Nhim bn c th do cc vt liu ca thit b ly mu gy ra (bnh ly mu v bnh ng mu), do s nhim bn ln nhau gia cc mu v do cch bo qun, lu kho khng thch hp v do cc b tr vn chuyn mu. b) Tnh khng n nh ca mu Loi bnh ly mu v bnh ng mu s dng c th nh hng n bn vng ca cht cn xc nh trong khong thi gian t lc ly mu n lc phn tch do tnh khng bn vng c hu ca bn thn mu v do cc iu kin trong mu c lu gi v vn chuyn. c) Bo qun mu khng ph hp

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Vic la chn cc bnh ly mu v bnh ng mu nh hng n s thng nht gia cht cn xc nh vi cc gii php bo qun c th c, nh c trnh by c th trong TCVN 5993: 1995 (ISO 5667-3). d) Ly mu khng ng Ly mu sai khc vi quy trnh ly mu, hoc bn thn quy trnh ly mu sai c th l mt ngun gy sai s. e) Ly mu t nhng thu vc khng ng nht. f) Vn chuyn mu (xem iu 6)

5 Cc k thut kim sot cht lng qu trnh ly mu

5.1 Khi qut
TCVN 5992: 1995 (ISO 5667-2) nh ngha ly mu l qu trnh ly mt phn c coi l i din ca mt vng nc (hoc bn hoc cn lng), nhm kim tra cc c tnh khc nhau c qui nh ca nc. Hng dn v quy trnh kim sot cht lng di y c th c dng nhn dng v nh lng cc sai s lin quan n vic ly mu. Ti liu ny khng nhm xem xt ton b vic m bo cht lng p dng cho ly mu. Tuy nhin, phi nhn mnh rng cc bin php kim sot cht lng cp di y s phi c p dng nghim tc nht trong bi cnh kim sot cht lng c t chc tt. iu ny bao gm c vic xem xt ton b phng php ly mu xem c thch hp vi mc ch d nh khng. Trong , cn cn nhc vic la chn cc k thut ly mu, v tr ly mu, s lng v loi mu phi ly, o to nhn vin ly mu, vn chuyn mu, bo qun v lu gi mu. Phng php la chn phi c vit thnh ti liu y v phi lp mt h thng lu gi v ghi chp ti liu. Mt chng trnh kim sot cht lng thch hp c th gm mt hoc tt c cc k thut lit k di y. Vic kim sot cht lng ly mu ph thuc vo mc tiu ca chng trnh, song t nht 2 % cng sc phn tch nn dnh cho vic qun l cht lng ly mu. Nh cp trc y, cc bin php kim sot cht lng ly mu c ba mc tiu chnh sau y: a) Cung cp c phng thc gim st v pht hin cc sai s ly mu v do l mt bin php loi cc d liu khng hp l hoc sai lc; b) Chng minh c rng cc sai s ly mu c kim sot mt cch thch hp; v c) Ch ra c s bin ng ca vic ly mu v t truy nguyn c kha cnh rt quan trng ca sai s. Cc k thut kim sot cht lng c miu t di y l:
ly cc mu lp kim tra chnh xc ca qu trnh ly mu;

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s dng cc mu trng ti hin trng gim st cc ngun gy nhim bn mu;

s dng cc mu thm khi kim sot cht lng nh gi n nh ca mu trong qu trnh

vn chuyn v lu mu.

5.2 Cc mu lp kim sot cht lng

Mc ny c th dng cho hng lot phng php kim sot cht lng nhm nh gi sai s ngu nhin lin quan vi cc mc khc nhau n qu trnh ly mu : a) bin ng do phn tch: lp li cc php phn tch i vi cng mt mu trong phng th nghim nh gi sai s phn tch nht thi b) bin ng do phn tch + ly mu con/vn chuyn mu: phn tch cc mu lp ly ti hin trng (B1 v B2) t mu chung (B) (mu ly c bng cch p dng mt ln quy trnh ly mu). S khc nhau gia cc s liu nh vy s cho c c lng v s bin ng do phn tch cng vi s bin ng do ly mu (gm c vic lu mu nhng khng tnh n cc nh hng t bnh ly mu). c) thay i do phn tch + do ly mu tng : phn tch cc mu t mu chung thu c bng cch p dng ring r quy trnh ly mu. Cch ny ch ra s thay i ca ton b qu trnh ly mu v phn tch (A1 v A2). Mi lin h gia cc bin ng ly mu khc nhau trong v d b) v c) c minh ho di dng gin trong hnh 1. im ly mu

B tng mu n

A1 2 mu n

A2

B1

B2

Chia lm 2 mu con

a1

a2

b11

b12

b21

b22

Hnh 1 - Mi lin h gia cc bin ng khc nhau do ly mu

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S khc nhau gia A1 v A2 cho php c lng cc bin ng trong qu trnh ly mu (ly mu, bnh cha, lu mu v phn tch). S khc nhau gia B1 v B2 (c th hin di dng gi tr trung bnh ca b11 & b12, v b21 & b22) cho php c lng cc bin ng do phn tch v bin ng trong qu trnh ly mu (gm vic lu mu nhng khng tnh n thay i do bnh ng mu). S khc nhau gia cc phn tch lp b11 & b12, v b21 & b22 cho php c lng tp trung ca kt qu phn tch. Vic phn tch cc mu lp cho php c lng c s gp phn ca sai s phn tch i vi tt c cc v d trong hnh 2 n hnh 7. So snh gia cc c lng khc nhau v bin ng m t trn c th dng phn nh nhng ngun quan trng nht to ra bt nh ca php o. iu ny c minh ha trong bng 1 v bng 2 di y. Bng 1 - bin ng phn tch Mu s Kt qu lp - 1 -2 c lng ca bin ng (1 bc t do) Ch thch c lng ca bin ng (gi tr trung bnh ca cc lch nu trn) vi 7 bc t do =
0,020 23.

1 1,61 1,55 0,001 8

2 1,72 1,98 0,033 8

3 2,21 1,99 0,024 2

4 1,38 1,55 0,014 45

5 2,25 2,44 0,018 05

6 2,8 2,55 0,031 25

7 1,74 1,55 0,018 05

Cc kt qu lp sau y c c t mt lot mu nc thi, mi mu c chia lm hai phn mu phn tch. Cc mu ny c phn tch v cho nhng kt qu di y. Bng 2 - bin ng phn tch + ly mu con/vn chuyn mu

Mu s Kt qu lp - 1 -2 c lng bin ng (1 bc t do)

1 2,66 1,85 0,328 1

2 1,66 2,22 0,156 8

3 2,31 1,44 0,378 5

4 1,99 1,55 0,096 8

5 1,85 2,54 0,238 1

6 1,81 2,65 0,352 8

Ch thch 1: c lng bin ng phn tch v bin ng x l mu - vi 6 bc t do = 0,258. Ch thch 2: Nng mu c chn phi tng t nh nng c chn trong bng 1.

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Hai gi tr c lng v bin ng do phn tch v bin ng do phn tch + ly mu con/vn chuyn mu c th c so snh nh p dng mt cch thch hp php kim tra F (F-test) : gi tr F thu c = 12,75. Gi tr F t cc bng ny (vi 7 v 6 bc t do v mc xc sut l 95%) = 4,2. Gi tr F quan st c ln hn cc gi tr bng 1 v bng 2 - do c l do tin rng c nhng ngun gy bin ng quan trng giai on ly mu/x l mu. Trong trng hp cc mu c ly, v d xc nh amoniac, c th xem xt kh nng phi lu n vic bo qun mu hoc kh nng nng b thay i trong giai on ly mu.

5.3 Cc mu trng ti hin trng

K thut ny c th dng phn nh cc sai s lin quan n vic nhim bn bnh cha mu v qu trnh ly mu (xem hnh 2). Trong phng th nghim, chia mu nc loi ion ra lm hai phn, Phn A v Phn B. Gi phn A li trong phng th nghim. Mang Phn B ra hin trng v chia lm hai phn mu nh b1 v b2. Phn mu b1 phi c x l dng bnh ly mu v k thut cng ging nh mu tht cng tt. Phn mu b2 phi c gi li v a tr li phng th nghim m khng tin hnh bt c x l no ti hin trng. Phn mu b1 c x l nh mt mu tht, cng vi phn mu b2 khng c s dng, c a v phng th nghim phn tch.

Nc loi ion

Chuyn ra hin trng

Phn A (Gi li trong phng th nghim)

Phn B (Chia nh)

Phn mu b1 (X l nh mu tht)

Phn mu b2 (Khng s dng)

Hnh 2 - Cc mu trng ti hin trng dng nc loi ion So snh kt qu ca Phn A v phn mu b1 xc nh ra sai s do ly mu, x l v vn chuyn mu. 11

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So snh kt qu ca phn A v phn mu b2 xc nh ra sai s do vic vn chuyn mu. So snh kt qu ca phn mu b1 v phn mu b2 xc nh ra sai s do nhim bn bnh ly mu hoc qu trnh ly mu.

5.4 Ra thit b (cc bnh ly mu)

K thut ny c th dng phn nh cc sai s lin quan n vic nhim bn cc thit b ly mu v qu trnh ly mu do khng xc ra sch cc bnh ly mu (xem hnh 3). Cc quy trnh lin quan n cc mu trng ti hin trng c th c s dng ti ch ngay sau giai on ly mu. Trong phng th nghim, chia mt mu nc loi ion thnh hai phn, Phn A v Phn B. Gi Phn A li trong phng th nghim. Mang Phn B ra hin trng v chia lm hai phn mu nh b1 v b2. Phn mu b1 s phi c x l cho vic ra bnh ly mu vi k thut cng ging vi cc mu tht cng tt. Phn mu b2 c gi li v a tr li phng th nghim m khng c mt x l no ti hin trng. Phn mu b1, cng vi phn mu b2 khng c s dng, c a v phng th nghim phn tch. So snh kt qu ca Phn A v phn mu b1 xc nh ra sai s do vic cha lm sch k cc bnh ly mu. So snh kt qu ca phn A v phn mu b2 xc nh ra sai s do vic vn chuyn mu. So snh kt qu ca phn mu b1 v phn mu b2, xc nh ra sai s do nhim bn bnh ly mu hoc qu trnh ly mu v cha lm sch k cc bnh ly mu.

Nc loi ion

Chuyn ra hin trng

Phn A (Gi li trong phng th nghim)

Phn B (Chia nh)

Phn b1 (Ra thit b v x l nh mu tht)

Phn b2 (Khng s dng)

Hnh 3 - Ra thit b bng mu trng (nc loi ion)

5.5 Hiu sut lc

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5.5.1 Khi qut K thut ny dng xc nh sai s lin quan n vic nhim bn bnh ly mu v qu trnh ly mu c lin quan n vic lc. Khi c yu cu lc mu ti hin trng, th cc mu trng hin trng v/hoc cc mu dng m bo cht lng theo tiu chun u phi c x l bng vic s dng cc quy trnh lc ging nh dng cho mu tht. 5.5.2 Lc mu trng (nc loi ion) K thut ny dng phn nh bt k sai s no lin quan n bnh ly mu, thit b lc, qu trnh ly mu v vic nhim bn mu (xem hnh 4). Trong phng th nghim, chia mt mu nc loi ion ra lm hai phn, Phn A v Phn B. Gi phn A li trong phng th nghim. Mang Phn B ra hin trng v chia lm hai phn mu nh b1 v b2. X l phn mu b1 dng bnh ly mu v thit b lc v cng mt k thut cng ging vi vi cc mu tht cng tt. Phn mu b2 c gi li v a tr li phng th nghim, khng c mt x l no ti hin trng. Phn mu b1 c x l nh mu tht, cng vi phn mu b2 khng c s dng, c a v phng th nghim phn tch. Nc loi ion

Chuyn ra hin trng

Phn A (Gi li trong phng th nghim)

Phn B (Chia nh)

Phn b1 (Lc v x l nh mu tht)

Phn b2 (Khng s dng)

Hnh 4 - Lc mu trng (nc loi ion) So snh kt qu ca Phn A v phn mu b1 xc nh ra sai s do lc khi ly mu, do x l mu khi ly mu v vn chuyn mu. So snh kt qu ca phn A v phn mu b2 xc nh ra sai s do vic vn chuyn mu. So snh kt qu ca phn mu b1 v phn mu b2 xc nh ra sai s do nhim bn bnh ly mu hoc cc qu trnh ly mu trong khi lc

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5.5.3 Lc mu m bo cht lng bng phng php thm Phng php ny c th dng xc nh ra cc sai s lin quan n bnh ly mu, thit b lc, cc qu trnh ly mu, v tnh khng n nh ca mu v nhim bn mu (xem hnh 5). Trong phng th nghim, chun b mt mu mi trng c phn tch trc bng cch thm vo mu mt lng bit ca cht cn xc nh. Lng cht cn xc nh thm vo phi c chn sao cho cc php o c tin hnh i vi nng c th thu c chnh xc tt nht. Chia mu ra lm hai phn, Phn A v Phn B. Phn A c gi li trong phng th nghim. Phn B c mang ra hin trng v chia ra thnh hai phn b1 v b2. Phn mu b1 s c x l vi vic dng bnh ly mu v thit b lc cng nh k thut cng ging vi mu tht cng tt. Phn mu b2 c gi li v a tr li phng th nghim, khng c bt c x l no ti hin trng. Phn mu b1 c x l nh mu tht, cng vi phn mu b2 khng c s dng, c a v phng th nghim phn tch.

mu thm

Chuyn ra hin trng

Phn A (Gi li trong phng th nghim)

Phn B (Chia nh tip)

Phn b1 (Lc v x l nh mu tht)

Phn b2 (Khng s dng)

Hnh 5 - Lc mu thm m bo cht lng So snh kt qu ca Phn A v phn mu b1 xc nh ra sai s do ly mu, bao gm cc qu trnh ly mu, thit b lc, khng n nh mu v vn chuyn mu So snh kt qu ca phn A v phn mu b2 xc nh ra sai s do vic vn chuyn mu. So snh kt qu ca phn mu b1 v phn mu b2 xc nh ra sai s do nhim bn cc bnh ly mu, thit b lc v cc qu trnh ly mu, v cc sai s do mu khng bn vng v mu b nhim bn.

5.6 Cc mu thm
5.6.1 Khi qut

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K thut ny dng nh gi sai s h thng ca qu trnh ly mu, bao gm vic xc nh cc sai s lin quan n bnh ly mu b nhim bn v qu trnh ly mu. K thut ny c bit c gi tr trong vic xc nh cc sai s do mu khng n nh, bao gm vic hao ht cc cht cn xc nh do bay hi, hp th hoc cc yu t sinh hc; v d, cc cht cn xc nh nh cc hp cht hu c d bay hi, kim loi vt (khi lc mu) v cc cht dinh dng. C hai k thut chnh, l thm mu vo nc loi ion (xem hnh 6) v thm vo mu mi trng (xem hnh 7). 5.6.2 Cc mu thm vo nc loi ion Trong phng th nghim, chia mt mu thm t nc loi ion thnh hai phn, Phn A v Phn B. Phn A c gi li trong phng th nghim. Phn B c mang ra hin trng v chia nh thnh ba phn b1 b2,, v b3. Phn mu b1 c x l, dng bnh ly mu cng ging nh i vi cc mu tht cng nhiu cng tt. Phn mu b2 c gi li v a tr li phng th nghim, khng c bt c mt x l thm no ti hin trng. Phn mu b3 s phi c thm vi nng bit ca cht cn xc nh v sau c chia nh lm hai phn b3 (i) v b3(ii). Phn mu b3 (i) s c x l dng cng bnh ly mu v cng mt k thut cng ging cc mu tht cng tt Phn mu b3(ii) c gi li v mang tr li phng th nghim, khng c thm bt c x l no ti hin trng.

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TCVN 6663-14 : 2000

Nc loi ion

Chuyn ra hin trng

Phn A (Gi li trong phng th nghim)

Phn B (Chia nh)

Phn b1 (X l nh mu tht)

Phn b2 (Khng s dng)

Phn b3 (c thm vo)

Phn b3(i) Bnh cha mu (nh mu tht)

Phn b3(ii) (khng s dng)

Hnh 6 - Mu nc loi ion c thm

Mu mi trng c thm

Chuyn ra hin trng

Phn A (Gi li trong phng th nghim)

Phn B (Chia nh)

Phn b1 (X l nh mu tht)

Phn b2 (Khng s dng)

Hnh 7 - Mu mi trng c thm

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TCVN 6663-14 : 2000

Chuyn cc phn mu b1, b2, b3(i) v b3(ii) tr li phng th nghim phn tch. So snh kt qu ca Phn A v phn mu b1 xc nh sai s do qu trnh x l khi ly mu v vn chuyn. So snh kt qu ca Phn A v phn mu b2 xc nh ra sai s do vic vn chuyn mu. So snh kt qu ca Phn A v phn mu thm vo b3(ii) xc nh ra cc sai s do bt k mt s khng n nh no ca mu, b nhim bn v vn chuyn mu. So snh kt qu ca Phn A v phn mu thm vo b3(i) xc nh ra sai s do x l mu v vn chuyn, v cc sai s do bt k mt s khng n nh, b nhim bn no ca mu. So snh kt qu ca phn mu b1 v phn mu b2 xc nh ra sai s do nhim bn bnh ly mu v x l khi ly mu (loi tr cc sai s do vn chuyn). So snh kt qu ca phn mu b2 v b3(ii) xc nh ra sai s do mu khng n nh v b nhim bn. So snh kt qu ca phn mu b3(i) v b3(ii) xc nh ra sai s do s nhim bn cc bnh ly mu hoc do cc qu trnh ly mu. 5.6.3 Mu mi trng c thm L tng nht l mu nn c thm hin trng ti thi im ly mu. Vic ny c th cn chuyn gia c chuyn mn v c th khng thng dng i vi phn tch thng nht. C th chun b ti phng th nghim mt mu mi trng c phn tch t trc bng cch thm cht cn xc nh vo mu. Lng cht cn xc nh b sung ny phi c chn sao cho php phn tch c tin hnh nng m ti thu c chnh xc cao nht. Chia mu ny thnh hai phn, Phn A v Phn B. Gi phn A li trong phng th nghim. Mang Phn B ra hin trng v li c chia lm hai phn mu nh b1 v b2. Phi x l phn mu b1 dng bnh ly mu v k thut cng ging vi cc mu tht cng tt Phn b2 c gi li v a tr li phng th nghim, khng c thm bt k mt x l no ti hin trng. Phn mu b1 c x l nh mu tht, cng vi phn mu b2 khng s dng, c a v phng th nghim phn tch. So snh kt qu ca Phn A v phn mu b1 xc nh ra sai s do x l mu v vn chuyn. So snh kt qu ca phn A v phn mu b2 xc nh ra sai s do vic vn chuyn mu. So snh kt qu ca phn mu b1 v phn mu b2 xc nh ra sai s do nhim bn bnh ly mu v qu trnh ly mu v cc sai s do mu khng n nh v b nhim bn.

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TCVN 6663-14 : 2000 6 Vn chuyn, n nh v lu mu

Cn tham kho TCVN 5993: 1995 (ISO 5667-3) xem hng dn v cch x l v bo qun mu. iu c bn l phi cn thn m bo tt c cc cht bo qun c chun b v pha ch chnh xc. o v ghi li ngay ti ch nhit mu . Cc thng s vt l (v d nh pH, kh ha tan, cht rn l lng) phi c xc nh ti ch hoc ngay sau khi ly mu cng sm cng tt. Cn m bo cc bnh ng mu phi c a ti phng th nghim ging nh cc mu thng nht. Nn y kn bnh ng mu v trnh b nh hng ca nh sng v nhit cao qu, v cc tnh cht ca mu c th nhanh chng b bin i do trao i kh, cc phn ng ha hc v s trao i cht ca cc sinh vt c th c mt trong mu. Cn m bo nhng mu khng th phn tch ngay th c n nh ngay. C th lm lnh mu xung 4 oC; v bo qun trong thi gian di hn, lm lnh xung n - 20 oC nh hng dn trong TCVN 5993: 1995 (ISO 5667-3). Trong trng hp ny, phi m bo mu tan hon ton trc khi s dng, v qu trnh ng lnh c th gy ra s tp trung ca mt s thnh phn phn trong ca mu, l phn ng bng sau cng. Cc mu c th c bo qun bng cch thm ha cht vo vi nhng lng thch hp. Cn chn bin php bo qun khng lm nh hng n vic phn tch tip theo hoc nh hng n cc kt qu. Ghi li tt c cc bc bo qun trong bo co th nghim. Ch thch Cc mu m bo cht lng trong vn chuyn, n nh v lu gi phi c x l bng cc
qu trnh y ht nh i vi mu th nghim.

7 Phn tch v gii trnh cc s liu kim sot cht lng

Mc ch ca h thng kim sot cht lng l m bo rng tin cy ca cc s liu ly mu l nht qun vi cc tiu ch tin hnh yu cu.

7.1 Biu kim sot Shewhart

Biu Shewhart l loi biu c s dng rng ri nht (xem ISO 8258). y l dng biu m trn bin s cn quan tm c v lin tip nhau. Cc gi tr o c s c so snh vi gi tr kim sot. Ch cn kim tra trc tip trn biu l c th thu c nhiu thng tin (xem hnh A.1 v A.2)

7.2 Lp biu kim sot khi ch c hai kt qu th lp

Biu ny c dng mt th, trn sai lch gia hai php xc nh lp, d, c lp thnh biu . d = R1- R2 trong : R1 R2 l kt qu phn tch ca mu u tin l kt qu phn tch ca mu th hai

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TCVN 6663-14 : 2000

iu c bn l phi lun lun ly kt qu ca ln phn tch th nht tr i kt qu ln th hai v v ra trn biu vi lu n du ca n. Gi tr mong i i vi biu ny phi l 0. lch chun ca mu tng ng, sd, c tnh theo cng thc:

sd =
trong D di

(d i D) 2
m 1

i =1

l sai lch trung bnh gia cc mu lp trn m l mu, v l cc sai lch ring l

Ph lc A a ra th d v mt biu kim sot i vi s liu lp v tm thy.

8 Nhn bit mu v ghi chp

Miu t tng im ly mu. Trong trng hp c chng trnh di hn, khng cn nhc li cc iu kin c tho thun v khng thay i. Trong trng hp ny, ch cn trnh by cc php o ti ch situ) v cc bin s v d nh iu kin thi tit v cn ghi li nhng quan st khng bnh thng. Khi ly mu, v nhng l do c bit, cn cung cp cc thng tin chi tit, k c l do ly mu v cc bc bo qun tin hnh. (in

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TCVN 6663-14 : 2000 Ph lc A (tham kho) Biu kim sot A.1 Th d v biu kim sot vi s liu lp (hnh A.1)
Sai lch kt qu

Gii hn can thip Gii hn cnh bo

Gii hn cnh bo Gii hn can thip

S mu kim sot

Hnh A.1 - Biu Shewhart i vi mu kim sot lp

Cc cht rn l lng c xc nh trong mt lot nc thi cng nghip gim st tun th vi tiu chun thi gii hn l 30mg/l. Cc v d nu trong hnh A.1, l mt lot cc mu lp c ly ca nc thi c nng cht rn l lng trong khong c quan tm: 20mg/l n 40mg/l. Gi thit l lch chun ca ly mu v phn tch l khng i trong ton b gii hp ny. iu ny cho php c lng c tp trung ca qu trnh ly mu v kim tra c n trn c s phn tch thng nht. Vi mi trng hp, mt mu nc thi tng c ly v ng nht cn thn. Sau mu tng ny c chia thnh cc mu con, p dng quy trnh ly mu to ra cc mu th nghim lp. Mi mu th nghim ny c phn tch mt ln. Bng A.1 trnh by cc s liu phn tch ca 20 mu lp. Km theo l biu kim sot tng ng. Gi tr trung tm ca biu c c nh ti gi tr trung bnh vi sai gia cc s liu lp. Gii hn kim sot can thip v gii hn cnh bo c v tun t lch chun 3 v 2.

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TCVN 6663-14 : 2000

Bng A.1 - S liu v cht rn l lng ca cc mu lp kim sot cht lng

Gi tr o c mg/l Ln th nht 33,2 25,6 38,2 28,8 31,4 34,6 22,4 27,2 22,0 34,0 24,6 23,8 33,6 37,4 29,2 30,0 36,4 37,2 33,6 28,0 Vi sai trung bnh lch chun ca sai lch Ln th hai 36,0 26,2 34,8 27,2 29,8 32,2 24,6 26,8 23,2 32,8 22,6 23,0 35,2 36,6 31,4 31,2 35,8 39,4 35 26,4

sai lch mg/l

- 2,8 - 0,6 3,4 1,6 1,6 2,4 - 2,2 0,4 - 1,2 1,2 2,0 0,8 - 1,6 0,8 - 2,2 - 1,2 0,6 - 2,2 - 1,4 1,6 1,0 0,471 8

Ch thch: lch chun quan st c th hin chnh xc kt qu phn tch cng nh v ly mu

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TCVN 6663-14 : 2000 A.2 Th d v biu kim sot i vi tm thy (hnh A.2)
Cc s liu di y (xem bng A.2) lin quan n vic xc nh nng vt ca thu ngn trong nc sng. Vi mi l phn tch, mt php th nghim tm thy i vi mu thm c tin hnh bng cch phn tch mt mu nc sng trc v sau khi thm vo mt lng 90 ng/l. Cc chi tit ca qu trnh thm nh sau: C = Nng ca dng dch thm = 100 g/l V = Th tch lng mu ly = 1 998,2 ml W = Th tch lng thm vo = 1,8 ml S = Nng o c trong mu c thm (xem phn di) U = Nng o c trong mu khng c thm (xem phn di) Phn trm tm thy c tnh nh sau: % Tm thy = 100. [S. (V + W) - U . V]/C . W

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TCVN 6663-14 : 2000

Bng A.2 - S liu t th nghim tm thy i vi mu thm Nng khng L mu, s c thm , U ng/l 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 tm thy trung bnh (%) lch chun ca tm thy (%) 14 15 25 8 15 3 8 25 13 19 7 28 9 8 33 2 1 8 14 34 12 Nng c thm, S ng/l 90 100 115 103 104 88 95 108 92 104 94 108 98 87 120 84 84 88 89 120 91 84,5 94,5 100 105,6 98,9 94,4 96,7 92,2 87,8 94,5 96,7 88,9 98,9 98,9 96,7 91,1 92,2 88,9 83,3 95,3 87,8 93,2 5,55 tm thy %

Biu kim sot tm thy (xem hnh A.2) c lp bng gi tr trung bnh hoc c lng ban u ca lch chun. Ch thch Khng nn p dng mong i tm thy 100% nu nh tm thy quan st c c v b lch.
Gii php tt nht l dng biu da trn tm thy trung bnh ca khong 20 kt qu ban u hay c lng nh vy. Sau khi lm xong vic quan trng l sot xt xem c s thay i no trong tm thy tht da theo mc tiu phn tch v lp li biu cho ph hp.

Ch thch lch chun c lng = 5,5 (dng lp biu )

lch chun tnh c = 5,55 (t t nht 20 kt qu).

116

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TCVN 6663-14 : 2000

Gii hn can thip 105 Dy tm thy 94 Trung bnh tm thy Gii hn cnh bo

83

Gii hn cnh bo

72

Gii hn can thip

10

15

20 S mu

Ch thch lch chun c lng = 5,5 (dng lp biu )

lch chun tnh c = 5,55 t t nht 20 kt qu.

Hnh A.2 - Biu kim sot Shewhart i vi tm thy

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TCVN 6663-14 : 2000 Ph lc B (tham kho) Ti liu tham kho

[1] ISO 3534-1:1993, Thng k - Thut ng v K hiu - Phn 1: Xc sut v cc thut ng thng k chung Statistics Vocabulary and symbols Part 1: Probability and general statistical terms. [2] ISO 3534-2:1993, Thng k - Thut ng v K hiu - Phn 1: Kim sot cht lng bng thng k. Statistics Vocabulary and symbols Part 2: Statistical quality control. [3] TCVN 5992:1995(ISO 5667-2:1991), Cht lng nc - Ly mu - Hng dn k thut ly mu Water quality Sampling Part 2: Guidance on sampling techniques. [4] ISO 8258:1991, Biu kim sot Shewhart Shewhart control charts. [5] ISO/TR 13530:1997, Hng dn chung v kim sot cht lng phn tch i vi phn tch nc General guidance to analytical quality control for water analysis. [6] Gardner, M. J., Wilson, A. L. v Cheesman, R. J. (1989) Hng dn v kim sot cht lng phn tch i vi cng nghip nc, NS30, WRc, Medmenham, Anh quc A manual on analytical Quality Control for Water Industry, NS30, (1999). WRc, Medmenham, UK.

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