PHNG PHP PHN TCH CC CH TIU HO HC TRONG NC T THC VT

Ngo Thuy Diem Trang, Ph.D. Department of Environmental Sciences College of Environment and Natural Resources Can Tho University, 10 Otc 2011
Standard Methods for the Examination of Water and Wastewater. 20th Ed. American Public Health Association, American Water Works Association, Water Environment Federation.1998.

*Mt s lu trong qu trnh phn tch mu - Tt c dung dch phn tch, mu nc (c tr lnh) cn phi c ra ngoi t nhit phng trc khi tin hnh phn tch - Lu , mi ha cht ha cht sau khi pha s dng cho mi ch tiu th c cch bo qun (chai ti, chai sng, lnh, nhit phng,) v thi gian bo qun hay thi hn s dng khc nhau (xem chi tit cho tng ch tiu bn di). Kt qu phn tch c th s b nh hng nu bo qun ha cht khng ng. - Tt c dng c phi c chun b sn 1 ngy trc khi thu mu v phn tch mu. - Tt c cc loi bnh nh mc, buret thy tinh khng c php sy. Ch kh t nhin nhit phng. - Dng c nn c tch ra ra trong 2 thng acid H2SO4 ring bit dnh cho P v N. Ring dng c phn tch COD khng cn ngm acid, ch cn ra sch bng nc my v trng k li nhiu ln bng nc ct (t 5-7 ln) sau khi hon tt vic phn tch mu. - Mu khng cn lc dnh cho phn tch TKN, COD, BOD, TP (nh mix u trc khi bm mu). Mu lc th s dng cho tt c cc ch tiu ha tan (nh mix u trc khi bm mu). - Pha long mu (TP, PO4-P, NO2-N, NO3-N, NH4-N, COD) cho php s dng pipet in t n ngng pha long max 10 ln (0.5 mL mu + 4.5 mL nc ct). Nu mun pha long cao hn >10 ln, th dng bnh nh mc 25 mL 100 mL (Lu : ch s dng 01 bnh pha long cho tt c cc mu, cho nn cn trng ra sch trc khi chuyn sang mu khc. V c gng ly th tch mu nhiu (cng nhiu cng tt) pha long, nh th s hn ch sai s bi ly qu t mu hay s dng qu nhiu nc ct). - Lu : tt c cc thao tc s dng dung dch H2SO4 m c cn c thc hin tht cn thn. Nu l bn ln da hay qun o, lp tc ra ngay di vi nc my.

- pH, DO, nhit v EC c o ti khu th nghim cng lc thi im thu mu nc (ghi li thi gian thu mu nc v c gng thng nht cng mt thi gian mi t thu mu) 1. TSS a. Dng c: - Giy lc 0,45m (Whatman) - a Petri - Cn (c 4 s thp phn) b. Phng php: * Chun b giy lc v a Petri 1 ngy trc khi thu mu ngoi ng: - Ghi tn trn a Petri (vd: S1.1 tc l sample 1 lc ln 1) trc khi t vo t sy. - Sy giy lc v a Petri (1050C trong 1 gi), ly ra vo bnh ht m (vn chuyn bnh ht m cn thn n gn t sy khi ly giy lc v a Petri ra trnh hin tng ht m t khng kh) trong khong 30 pht, cn ghi trng lng W0 (mg) (cn giy lc v a Petri ngay lp tc trc khi lc mu nc). Trnh tip xc bng tay vo giy lc, cho nn mi thao tc u phi s dng cy gp. - Trc khi lc mu, cho 20 mL of Distill water (DW) qua giy lc lm mu blank (2 ln lp li). Sau vi giy lc cho mu thc cng nn dng mt t DW ra giy v gip qu trnh filter hiu qu hn. Lc u mu trc khi dng mt lng mu (xc nh) lc qua giy lc (bm ht chn khng) (ty theo Organic Matter concentration hin din trong mu, nu OM cao nn dilute mu hoc c th dng lng mu t li) - em sy giy lc v a Petri (sau khi lc mu) 1050C trong 2 gi, ly ra vo bnh ht m (trong khong 30 pht), ghi trng lng W1 (mg) (sau t mu li t sy v cn li. Qu trnh ny c thc hin n khi trng lng khng i khng qu 0.0005 g gia 2 ln cn) Tnh kt qu: TSS (mg/L) = (W1-W0), mg*103/Vmu (mL) 2. TKN (Kjeldahl method, APHA 1998) (Distillation and Titration) (triplicate measurements in the lab) a. Dng c, ho cht: - Bnh tam gic 50mL, 250mL - Bnh tam gic Bnh chng ct - DD NaOH 40% (400 g/1000mL) - H3BO3 2% (20 g/1000mL)

Hn hp (K2SO4 : CuSO4 : Se) trn u theo t l 100:10:0.5 (hn hp cng ph mu) - H2SO4 (s dng ha cht Merck, dnh cho chun TKN) (nu t pha th 0.325 mL H2SO4 m c ln 1000mL t nng 0.01N ) - Ch th hin mu: s dng acic boric v methyl red v blue 0,05 g methyl >> thm alcohol 950 ln thnh 100 mL (tr lnh) 0,15 g methyl blue >> thm alcohol 950 ln thnh 100mL (tr lnh) Dung dch ch th mu: Mix 10 mL + 2 mL xanh + 1000mL H3BO3 2% b. Phng php: - Cho 20mL mu vo mi bnh tam gic (loi 50mL) - Cho vo mi bnh mt nhm hn hp ph mu (khong 1 mung nh y) - Tip tc thm vo 4mL H2SO4 (to maintain acid-salt balance and prevent digestion temperature) - un mu: vn nt 5 bp trng khong 30 pht sau vn ln nt 7 (Khong 2100C). i n khi mu chuyn t mu en > nu > xanh l cy > sang mu xanh da tri nht (c ht tinh th trng), th ngng un (thi gian un khong 2 - 3 ting). - S dng gin chng ct (titration) ca Kjeldahl. - Add 20mL dung dch ch th mu vo bnh hng trong gin Kjeldahl. - em mu i chun (bng H2SO4 0.01N) n khi dung dch trong bnh chuyn t mu en >> sang tm th dng (thc hin chun da theo mu trng). Ghi li th tch chun . Nng TKN trong mu c tnh theo cng thc: N-TKN (mg/L) = (V trung bnh mu tht V mu trng),mL x 0.01 x 14 x 1000/V mu, mL 4. TP (Total Phosphorus: Ascorbic Acid Method, APHA, 1998) (triplicate measurements in the lab) a. Dng c & ho cht: - ng nghim thu tinh c np y dnh cho TP - ng nh git - DD H2SO4 : pha long 50mL H2SO4 thnh 200mL bng nc ct - DD ph mu: Ly 10mL dung dch acid trn pha long thnh 200mL vi nc ct. Sau thm 10g K2S2O8. Ha cht ny s dng ngay sau khi pha (do ty theo s lng mu cn phn tch th gim th tch v ho cht theo t l tng ng) - Phenolphtalein - NaOH 2N: 80g NaOH trong 1L nc ct - DD H2SO4 5N: 14mL H2SO4 pha long thnh 100mL nc ct -

- Cc ho cht hin mu ging vi phn tch PO43b. Phng php: * Preliminary Acid Hydrolysis to hydrolyze all organic-P compounds to orthophosphate (cng ph mu trong autoclave bng acid) - Cho vo mi ng nghim 5mL mu, cho vo 1 git thuc th phenolphthalein. (Chun b tng t cho tt c ng nghim c dung dch chun (standard solution)). - Cho tip 0,4mL DD ph mu vo mi ng - y kn np ng nghim, em autoclave 30 pht p sut t 98 137kPa - Ly ra ngui, trung ho bng DD NaOH 2N (xut hin mu hng nht) sau cho thm mt t H2SO4 n khi dung dch mt mu (i vi mu nghi ng c Fe cao th p dng cch ny), cn nu khng th thm dd hin mu v c mu. - em ly tm nu mu c cn. - em cho hin mu ging vi PO43- (c mu 880 nm) 5. PO43- (Orthophosphate: Ascorbic Acid Method, APHA, 1998) (triplicate measurements in the lab) a. Dng c, ho cht: - ng nghim - Dung dch chun PO43- 5ppm (S dng dd chun PO43- 1000ppm pha long. Lu nn pha long lm nhiu ln trnh sai s: (pha t 1000 ppm >> 100 ppm >> 10ppm, chai 100ppm nn tr li trong t lnh pha tip cho nhng ln sau) - Dung dch H2SO4 5N (1): 14mL H2SO4 pha long thnh 100mL nc ct - K(SbO)C4H4O60.5H2O (2): Cn 0.2743g ho tan trong 100mL bng nc ct. Tr lnh trong chai thy tinh ti c np y. - (NH4)6MO7O24.4H2O (3): Cn 4 g ho tan trong bnh 100mL bng nc ct. Tr lnh trong chai thy tinh c np y - Acid ascorbic 0.1M (4): Cn 1.76g ho tan trong 100mL nc ct. Tr lnh trong chai thu tinh np y, ho cht ny s dng trong vng mt tun. - Hn hp hin mu: Trn u cc ho cht trn theo th t 25mL (1) + 2.5mL (2) + 7.5mL (3) + 15mL (4). Mix mi ln thm vo mt cht. Hn hp ny n nh trong 4 gi. (Tt nht nn ly cc cht 1, 2, 3 v 4 ra khi t lnh cho tr v room temperature trc khi mix). Ty theo s lng mu mi t phn tch m chun b lng dd hn hp hin mu va (trnh lng ph ha cht). b. Phng php: - Lc mu

Chun b dy ng chun t dung dch chun 5ppm, nng ti a cho php n 3mg/L. (Bao gm mu blank) - Cho 0.8mL cht hin mu vo mi ng nghim, lc u hn hp. em so mu bc sng 880nm. (Nn c mu ngay sau khi cho cht hin th mu trong thi gian khng qu 30 pht) 5. NO3- (Phng php Salicylate, APHA) (triplicate measurements in the lab) a. Dng c, ho cht: - Bnh tam gic 50mL - DD chun NO3- 1ppm - DD A: ho tan 0.5g Natri salicylate vi nc ct thnh 100mL - DD B: H2SO4 - DD C: 100g C4H4KNaO6.4H2O thnh 1000mL nc - DD D NaOH 10N: 400g NaOH thnh 1000mL nc ct b. Phng php: - Lc mu - Cho vo mi bnh tam gic 10mL mu v lp dy ng chun t dd chun 1ppm - Cho vo 1mL thc th A - em sy nhit 1050C n cn - ngui, cho vo 1mL thuc th B - Ch 10 pht, cho tip 20mL thuc th C v 5mL thuc th D (dung dch c mu vng anh nu c nitrate). - Ch 15 pht em so mu bc sng 410nm. 6. NH4+ (Salicylate method, modified version of a photometric method) (triplicate measurements in the lab) * Ghi ch: Tt c ha cht hin mu phn tch NH4 u phi tr trong chai ti, t trong t lnh v ch s dng c 2 tun. ng chun cao nht l 1ppm a. Dng c, ha cht: - ng nghim - Dung dch chun NH4+ 10ppm (pha t 1000 ppm >> 100 ppm >> 10ppm, chai 100ppm nn tr li trong t lnh pha tip cho nhng ln sau) Re1: Reagent 1. Salicylate/citrate Ho tan 34g natri salicylate v 300g trisodium citrate trong khong 950 mL nc ct. Thm 0.4g sodium nitroprusside. Khuy u co n khi tt c cc ha cht tan ht v ct ln ti vch bng nc ct.

Tr dung dch trong trong t lnh bng chai ti. C th s dng trong t nht hai tun. Re2: Sodium dichloroisocyanurate Ha tan 10g NaOH trong 500 mL nc v sau thm 0.8g Sodium dichloroisocyanurate (DIC, Dichloro s- triazine 2,4,6 (1H,3H,H) trione sodium salt) thnh dung dch. Khi ha tan hon ton, chuyn dung dch sang bnh nh mc 1 lt. Trn u v ct ln n vch. Tr dung dch trong chai ti 40C. Ch s dng dung dch trong 2 tun. b. Phng php: Lp dy ng chun nh sau: STT Cmu chun Vddc10ppm Vnc ct Reagent 1 Reagent 2 1 0.0 0.0 5 0.5 0.5 2 0.2 0.1 4.9 0.5 0.5 3 0.4 0.2 4.8 0.5 0.5 4 0.6 0.3 4.7 0.5 0.5 5 0.8 0.4 4.6 0.5 0.5 6 1.0 0.5 4.5 0.5 0.5 Ch 1 gi (trong thi gian ny, nn t mu vo ch ti hoc ph kn mu bng giy bc), em so mu bc sng 660nm 7. NO2- (Colorimetric Method, APHA) (triplicate measurements in the lab) Ha cht hin mu 80mL nc ct + 10mL H3PO4 85% +1g sulfanilamide + 0.1g N-1 napthylehthylendiamin dihyrocloride. Tr trong bnh ti. Phng php: Ly 5mL mu + 0.2mL dd hin mu, t 10 pht 2 gi. em so mu bc sng 543nm. 10. COD (Closed Reflux Method) (triplicate measurements in the lab) 1. Thuc th a. Dung dch chun digestion K2Cr2O7 0.01667M (0.1N) Ho tan 4.903g K2Cr2O7 ( sy kh 1500C trong thi gian 2h) vi 500 mL nc ct. Sau thm 167 mL H2SO4 v 33.3 g HgSO4 => lc u cho mui tan ht => lm ngui nhit phng => ln th tch thnh 1000 mL. b. Dung dch acid sulfuric Cn 5.5 g Ag2SO4 vo 500 mL H2SO4 (theo t l 5.5 g Ag2SO4/1Kg H2SO4). dung dch khong 2 ngy cho mui Ag2SO4 ho tan ht trong acid sulfuric => vn np chai acid tht knh v lc u. c. Ch th Ferroin indicator

Ho tan 1.485 g 1,10-Phenoltroline Monohydrate v 0.695 g FeSO4.7H2O vi nc ct thnh 100 mL (tr trong chai ti). d. Dung dch chun FAS 0.1 M Ho tan 39.2 g mui Fe(NH4)2(SO4)2. 6H2O vi mt t nc ct. Sau thm 20 mL H2SO4 => Lm ngui nhit phng => Ln th tch thnh 1000 mL (Dung dch sau khi pha xong tr trong ti). Dung dch ny phi c chun li hng ngy vi dung dch chun Digestion K2Cr2O7. d. 1 Cch chun - Dng Pippet rt 5 mL dung dch Digestion K2Cr2O7 vo beaker nh, lm mt nhit phng - Thm 1-2 git ch th Ferroin v chun vi FAS. d. 2 Tnh nng FAS VK2Cr2O7 0.01667M (mL) x 0.1 CM FAS = VFAS s dng (mL)

2. Qui trnh phn tch

Qui trnh ny ch p dng cho mu nc c COD trong khong 40-400mg/L. Khi hm lng COD trong mu thp th phi pha long dung dch K2Cr2O7 v dung dch FAS xung cho ph hp. Chun b dng c: trng ng nghim v bnh tam gic nh bng acid H 2SO4 20%, ra li bng nc tht sch v trng bng nc ct. Tin hnh: Thc hin qui trnh theo bng sau: Digestion Vessel Sample Digestion Dung dch Tng th ( Culture tubes) (mL) Solution acid Sulfuric tch (mL) (mL) (mL) 16 x 100 mm 2.5 1.5 3.5 7.5 20 x 150 mm 5 3 7 15 25 x 150 mm 10 6 14 30 Standard 10 mL ampules 2.5 1.5 3.5 7.5 Ch : Cho dung dch acid Sulfuric chy t t theo thnh ng nghim vo mu => khi ng nghim rt nng. V vy trong qu trnh phn tch phi mang gng tay m bo an ton. Vn tht cht np ng nghim v lc u mu bng my stirring t ng nghim hoc ampules vo thit b un COD, chuyn nhit v 1500C, chnh thi gian 120 pht. Sau 120 pht, my t tt => ly ng nghim ra => ngui nhit phng Chuyn mu t ng nghim qua bnh tam gic nh Cho vo mu 2 git ch th Ferroin Indicator => lc u nhanh

 Chun mu vi dung dch FAS 0.01 M (Cn pha long t FAS 0.1 M mi ln cn phn tch) im kt thc chun dung dch chuyn t mu xanh (Blue-green) sang mu nu (lu ngng chuyn mu cho blank v mu tht phi ging nhau) Mu trng : c tin hnh song song vi mu tht theo qui trnh sau : 2.5 mL nc ct + 1.5 mL Digestion solution + 3.5 mL dung dch acid Sulfuric => Cc bc cn li tin hnh ging nh mu tht.

3. Tnh kt qu
(A B) x M x 8000 COD (mgO2/L) = mL mu Trong ; A : mL FAS c s dng trong chun mu trng B : mL FAS c s dng trong chun mu tht M : Nng mol/l ca dung dch FAS (0.01) 8000 : ng lng gram ca oxy (8) x 1000mL