30(4), 363 368 Tap chi CAc KHOA HOC VE T R A I DAT 12 2008 ^ '''' KHA NANG HAP PHU ARSEN (III vA V) CUA LATERIT DA ONG HA TAY NGUYEN TRUNG MINH, N G U Y I N DLTC CHUY I Md DAU Trong v6 Trai Ddt, arsen (A[.]
30(4), 363-368 T a p c h i C A c KHOA HOC VE T R A I DAT 12-2008 ^' KHA NANG HAP PHU ARSEN (III vA V) CUA LATERIT DA ONG HA TAY NGUYEN TRUNG MINH, N G U Y I N DLTC C H U Y I Md DAU Trong v6 Trai Ddt, arsen (As) cd ham lugng tir 1-2 mg/kg, dd chinh la ngudn gay nhiem mOi trudng nude mat vd nude ngdm Nhu da biet nhi^u van lieu, arsen tac dOng xdu de'n he tudn hoan, he thdn kinh Theo luat ve cdc vdn de mOi trudng (CERCLA) [231 As la nguyen td dOc hai nhdt danh sach cac nguyen td dOc hai nam 2005 (bang 1) Bdng Thiir t u doc hai cua mot so nguyen to ho^ hoc va gidi han cho phep moi trudng nude theo CERCLA [23] Nguyen to Arsen (As) Chi (Pb) Thuy ngan (Hg) Cadiini (Cd) Crom (Cr (VI)) Kem (Zn) Mangan (Mn) Ddng (Cu) Selen (Se) Bac (Ag) Antimon (Sb) Thir tu dOc hai 01 02 03 08 18 74 115 133 147 213 222 Gidi han cho phep (ing/1) 0,01 0,015 0,002 0,005 0,01 5,0 0,05 1,3 0,05 0,05 0,006 V6mat sinhhgc, Ascdthe'gay 19 benh khac nhau, dd cd ung thu da va phdi Ne'u nhiem dOc it Ihi gay cac benh rung tdc, budn nOn, siit can, ung thu, giam tri nhd ; ne'u nhi^u thi gay tu vong Mat khac As cd vai trd thay ddi nuclein, tdng hgp protit va hemoglobin As anh hudng den thuc vat nhu mOt chat can, lam giam manh nang sua't trao ddi chdt DOc tinh cila cac hctp chdt As ddi vdi sinh vat dudi nude giam ddn theo ddy Arsen -> Arsenit -^ Arsenal -> hgp cha't As hthi co Trong mOi trudng sinh thai, cac dang hop chat As (111) ed dOe tinh cao hon As (V) khoang 60 Idn cd phan irng vdi cac men qua trinh chuye'n hoa cua co the 11, 6, 131 Moi trudng khu la dieu kien thuan lgi cho nhieu hgp chdt As (V) chuye'n sang As (111) Trong dieu kien pH trung tinh As (III) khd bi tach khdi nude hon As (V) bdi cac qua trinh hdp phu ha\' ddng ke't tila deu bi thie'u sire hiit tTnh dien 12, 121 Trong nude ngdm thOng thudng cd tdi 96 % As tdn tai dudi dang ion As (III) 118,211 Ham lugng A,s(V), As(lll) cao nude ngdm dang Id vdn de mOi trudng nghiem dac biet la d cac nude Tay Bengal, dn DO Bangladesh, Trung Qudc, Dai Loan va DOng Nam A, dd cd Viet Nam 118,81 Viet Nam cd viing nhiem As 11, 15, 201 nhu sau : - Viing nui vdi cac da bie'n ddi nhiet dich, quang va vd phong hda cung nhu ddt phat trien tren chiing Ngudn nhiem la cac qua trinh tu nhien - Mot sd noi d ddng bang, nude ngdm ed ham lugng As vugt TCVN Ngudn nhiem la cac qua trinh tu nhien - Ddi duyen hai (trdm tich bie'n•^'en bd) vdi ngudn nhiem chil )'e'u la hoat dOng nhan sinh dac biet la su dung thudc trir sau, diet cd, vu hda hoc Nhi^u loai ngu\'en lieu khoang tu nhien dugc danh gia la cd kha nang hdp phu As cao vdi gia thdnh re, de sir dung vdi quy mO khac Hien dang cd nhieu cOng trinh tren the gidi nghien ciru ve kha nang hdp phu As cda zeolit tu nhien va da niii lira |51, md sdt tu nhien 1221, oxisol [ 141, biin dd [71, md mangan sdt [3[, siderite [9-111, cd mOt sd cOng trinh nghien ciru ve laterit da ong hdp phu As [19[ Trong mdt sd nam gdn day laterit da ong dugc cac nha khoa hoc chii)' den cdc tinh chat hod ly khac cila nd Muc tieu nghien ciru ciia chung tOi Id : 1) danh gia kha nang hdp phu As(lll) va As(V) ciia laterit 363 da ong Ha Tay mOi trudng nude ; 2) kha nang irng dung thuc tiln cila loai vat lieu n DOI TUONG VA PHUONG PHAP NGHIEN CUU Laterit phan bd nhieu viing cila nude ta nhu cac khu vuc ria ddng bang sdng Hdng (Quang Ninh, Vinh Phuc, Phu Thg, Ha Tay, Ha NOi, Hoa Binh, Ninh Binh), sOng Ma (Thanh Hod), sOng Ca (Nghe An), ,sOng Cuu Long (Bien Hoa, Ba Ria) va Tay Nguyen (Ddc NOng, Kontum, Tay Ninh) Trong de tai nghien ciru chiing tOi sii dung laterit da ong cua viing Son Tay (Ha Tay) Khu vuc nghien cim thuOc td ban dd Ha Ndi (Ban dd dia chdt va khoang san - Cue Dia cha't va Khoang san Viet Nam - 2001, td F-48-XXV1II, ty le 1:200.000) noi da ghi nhan dugc diem da ong, chu ye'u d phia bdc va phia tay III THUC NGHIEM, KET QUA vA Thanh phdn khoang vat ciia laterit dugc xac dinh bang phuong phap nhieu xa tia X (XRD) Ket qua phan tich cho thdy cd mat cdc khoang vat sau: kaolinit, coalingite, rectorite, microcline LUAN Viec xir ly mdu laterit da ong va cac thi nghiem nghien ciru dac tinh ha'p phu cHa nd tie'n hanh d Phdng "Thi nghiem Hod (Vien Dia cha't, Vien KH & CN Viet Nam) vd Phdng "Thi nghiem Hoa ly (Khoa Hoa hgc, trudng Dai hgc Su pham Ha NOi) Hoa cha't tinh khie't: mudi AsHNa204.7H20 va AsNaOj dugc sir dung cQa hang Ruka, than hoat tinh (PAC) cua hang Merck : Carbon Graphite 1.04206.2500 K34597206 522, cd hat < 50 ^m Cac thi nghiem thuc hien vdi laterit da ong nguyen khai va than hoat tinh (PAC) ciing dieu kien de so sanh cac thOng sd hoa ly va hdp phu Bdng Ke't qua xac djnh p h i n nguyen to cua da ong bSng phuong phap XRF Nguyen td (%) Nguyen td (%) Si Fe AI Mg Ti K Pb 39,2323 29,3010 24,0442 4,9363 1,6872 0.3927 0,0981 V Mn Cr Zr Rb Zn Sr 0,0904 0,0796 0,0753 0,0394 0,0130 0,0096 0,0009 Kie'u vd phong hda laterit khu vuc la kie'u laterit da ong tren cac trdm tich phu sa cd va da luc nguyen thuOc cac he tdng Ngdi Chi, Thac Ba d cac chan ddi thdp dO ddc nhd Mdu laterit da ong nghien ciru dugc phan tich dinh lugng bdng phuong phap huynh quang tia X (XRF) tai phdng MOi trudng, Trung tam An toan birc xa va MOi trudng thuOc Vien Khoa hgc Ky thuat Hat nhan {bang 2) Ket qua phan tich mdu cho thdy ham lugng cac nguyen td chii ye'u la Si, thir hai la Fe, AI Ngoai cdn cd nhieu nguyen td khac gdm Mg, K, Ti, V, Cr, Mn, Zn THAO / Thi nghiem vdi ion A^*: mu6i AsHNa204 7H,0, dp tinh khiei 98,5% Thi nghiem thuc hien di6u kien nhiet dO khOng : 29,0 °C, nhiet dO dung dich 28,5 °C, dO dm 81 %.Cdhat laterit da ong 0,16-0,2 mm ; Ke't qua the' hien d bdng va hinh la,b De' xac dinh cac hang sd Freundlich ta xay dung dd thi theo hai true logq^ va logCj, {hinh 2a b) Ke't qua tinh toan cdc thOng sd theo Freundlich [4[ dugc the hien d bdng Bdng Ke't qua thi nghiem ve dung ludng hap phu (q,) ion As** cua laterit da ong nguyen khai va than hoat tinh (PAC) Laterit da ong nguyen khai Ndng dd As"'^* Cac ban ddu (Co) Ndng As^^ Dung luong Hieu sudt loai die'm dung sau hap phu hdp phu (qj, bd As *khdi dich, mg/1 ^ H ' ^ " ^ T ^ dung dich, % tng/kg dich, mg/1 I 364 • 0,024 0,12 0,6 15 75 0,0072 0,0088 0,309 1,911 1,937 7,120 0,42 2,78 7,27 27,21 326,49 1696,73 70,04 92,68 48,44 36,29 87,10 90,50 Than hoat tinh PAC Ndng As'^* r,, , ,_ , ,' , Dung luong Hieu sudt loai sau hap phu , „- u \ ,^,, J • hap phu (q,), bd As * khdi (C) dung „ dung dich, % dich, mg/1 75,75 0,0058 0,45 0,0240 2,40 80,03 0,308 7,30 48,68 1,123 46,92 62,57 27,294 1192,48 63,60 04 ong - As'* f Mudi AsNa02 dO tinh khie't 99 % Ke't qua thi nghiem the hien d bdng va hinh 3a 3b De xac dmh cac hdng sd Freundlich la xay dung dd thi theo hai true logq, va logC, {hinh 4a 4b) Ke't qua tinh toan cac thOng sd theo Freundlich dugc the' hien d bang « a) 1500 ?1000 ^ ^ ^ ^ Q 500 y = 22 763x-12 173 ^ ^ ^ ' ^ R^ = 9995 Bdng 19^^^ Ket q u a t i n h t o a n cac t h o n g s o theo F r e u n d l i c h * c h o laterit da o n g n g u y e n khai va t h a n * h o a t t i n h v d i cac i o n As^* va A s ' * 20 40 Nong dung djch ban d i u {Co), mg/1 Cha't ha'p phu Ion kim loai R^ 1/n Kr(x 10 ) Laterit da ong As A.S-' As As 0.903 0,951 0,977 0.891 1.048 0,813 0.901 0.887 8.7 21.9 PAC-As'* •;;+• Than hoat tinh * Xem each tinh [4| Oa ong - As"*" Hinh Dung lugng hdp phu cila da ong (a), than hoat tinh (PAC) (b) vdi As'" Do thi Freundlich 1000 Nong dp dung dich ban d^u (Co), mg/1 ^M a) 0) 0> 500 c Q da ong - As 40 ^ ^ ^ ' ^ ^ ^ ^ ^ y = 13 x » 4238 R- = 9996 ^ a) _30 40 60 20 Nong dung dich ban d3u {Co), mg/1 y = 0477X • 0607 a R^ = 903 |2 1.0 1000 C^^"^ V— *10 30 20 b) irpl Log{Ce) « Ihl Freundlich Than PAC - As" b) y = 09006x-1 0531 R2 = 9766 ^^^^i:;;;:::^^ ^^^^;;s;:::=^^^^^^ Nong dung dich ban d^u (Co) mg'l | Hinh Dung luong hdp phu cua da ong (a), than hoat tinh (PAC) (b) vdi As'* 15 20 25 30 35 40 Log (Ce) Hinh Dd Ihi Freundlich da ong (a), than hoat tinh PAC (b) ha'p phu As"* 2) Thi nghiim vdi ion As* Thi nghiem dieu kien nhiet dO khong : 29,0 °C, nhiei dung djch : 28,5 °C, dO dm : 81 % Tren cac dd thi bieu dien mdi tuong quan giira dung luong hdp phu vdi ndng dO dung dich (hinh la \'a 3a) deu chua xudt hien die'm cue dai va vdn theo xu hudng di len vdi r"= 0.9995, chirng td kha nang hdp phu cila laterit da ong vtii As ", As " rdt tdt 75 ing/l dung luc;rng hdp phu q, cila da ong vdi As'* dat gdn 1.700 mg/kg vdi As"* la 1.053 mg/kg, kha nang hdp phu dat tren 90 % va 56 '^k vdi l\s\ As"* tuong irng ndng dO dung dich ban ddu 365 0,120 mg/1 (gdp 12 Idn tieu chudn cho phep nude an udng theo quyet dinh sd 1329/2002/BYT) kha nang hdp phu cila laterit da ong deu dat tren 92,6 % vdi ca ion A.s^*, As'* (bang 3, 5) Dung dich sau hdp phu deu dat tieu chudn nude an udng ciia Viet Nam Bdng Ket qua thi nghiem ve dung ludng ha'p phu [q,] ion As'* cua laterit da ong nguyen khai va than hoat tinh (PAC) Laterit da ong Than hoat tinh PAC Ndng As" * - — — ,^ Ndng As a c ban ddu (Co) Nong 10 As Dung lugng Hieu sudt loai Dung lugng Hieu sua't loai die'm dung ^;,^" hap phu hdp phu (q,), bd As* khdi sau ha'p phu ha'p phu (qc), bd As* khdi (C) dung dich, mg/1 (C) dung mg/kg mg/kg duns dich, % dung dich, % ' djch, mg/1 dich, mg/1 0,024 0,12 0,6 15 75 0,0059 0,0088 0,216 0,436 6,320 33,027 0,45 2,78 9,59 64,09 216,95 1048,99 0.0095 0,0104 0,410 1,143 3,016 32,864 75,46 92,63 63,96 85,46 57,90 56,00 06 thi Freundlich : da ong - 60,29 91,30 31,67 61,90 79,90 56,20 0,36 2,74 4,75 46,41 299,56 1053,29 Do thi Freundlich : than PAC - As " As'- • b) V = 8 x - 0104 R2 = 8906 o e x - 6593 R' = 9506 (*^ \ ^ \ 1,5 2.5 3.5 4.5 Log(Ce) Hinh Dd thi Freundlich da ong (a), than hoat tinh PAC (b) ha'p phu As'* Kha nang hdp phu ciia laterit da ong vdi As * d nhirng die'm cd ndng dO thdp (nhd hon 0,6 mg/1) xdp xi than PAC nhung d die'm 75 mg/1 lai Idn hon hdn (1,42 Idn) cdn vdi qua trinh hdp thu As * su chenh lech xdy d diem ndng dO 0,6 mg/1 va mg/1 {bang 6) Bdng So sanh dung lUdng hap phu As3+, As5+ ciia laterit da ong va than hoat tinh Ndng (mg/1) 0,024 0,12 0,6 15 75 qc(mg/kg) laterit (As ) 0,420 2,780 7,266 • 326,487 1.696,73 q^ (mg/kg) than (A.S) 0,454 2,401 7,301 46,918 1192,48 Rieng vdi su hdp phu arsen tren the' gidi da cd nhieu loai vat lieu tu nhien dugc thu nghiem va dat nhirng ke't qud nhdt dmh (bdng 7) Qua bang so sanh tren cd the nhan thdy laterit 366 q,da qi; than 0,93 1,16 0,99 1,42 qc(mg/kg]^ laterit (As" ) 0,453 2,778 9,591 64,090 216,152 1048,99 qc.(mg/k|0 than (A.S" ) 0,362 2,739 4,794 46,414 299,561 1053,29 q, da q^ than 1,25 1,01 1,99 1,38 0,72 0,99 da ong Ha Tay, cd kha nang hdp phu rdt tO't vdi ^^sen, dung lugng hdp phu cao hon hdn so vdi cac ^j^j ,jg^ ju ^f^i^n i^^ac da dugc cOng bd tren the gidi va tuong duong than hoat tinh cila hang Merck Bdng So sanh ket qua ha'p phu arsen cua laterit da ong nguyen khai Ha Tay vdi mot so loai vat lieu tif nhien tren the gidi Chdt ha'p phu Ion Sdt md tu jihien Gi sat (md mangan) Feldspar tu nhien Hematite tu nhien Siderite tu nhien Clinoptilotile As(V) 400 99 As(III) As(V) 537 208 72 As(V) 219 100 As(V) 520 As(III) 1040 As(V) 100 qma,(mg/kg) % ha'p phu Ngudn tai lieu 1192,5 1053,3 1696,7 1049,0 [31 97 [111 [5] 63,6 56,2 90,5 56 Acta [3[ S CHAKRAVARTr-, V DLREJA G BHATTACHARWA S MAlTf, S BHATTACHARIEE, 2002 : Water Res 36, 625 [211 [171 Than hoat As(V) tinh A.s(III) Laterit da As(V) ong Ha Tay As(III) [2| M BISSEN P.M FRIMMEL, 2003 Hydroehim Hydrobiol 31 97 ] Tac gia bang KET LUAN Dung lugng ha'p phu As (V) cila laterit da ong nguyen khai Ha Tay (1697 mg/kg) cao hon han so vdi than hoat tinh PAC (1193 mg/kg) d ndng dd dung dich la 75 mg/1 2- Dung lugng ha'p phu As (III) cda laterit da ong Ha Tay (1049 mg/kg) tuong duong vdi than hoat tinh PAC (1053 mg/kg) d ndng dO dung dich Id 75 mg/1 3- Vdi ndng dO arsen (V vd III) dung dich la 0,12 mg/1, sau dugc hdp phu bang laterit da ong thi ndng dO dung dich la 0,0088 mg/1 thdp hon ndng dO cho phep (0,01 mg/1 - tieu chudn nude sinh hoat cda BO Y te") va kha nang loai bd arsen khdi dung dich dat 92,6 % Trong dd, ciing di^u kien nhu tren than hoat tinh chi cd kha nang loai bd arsen khdi dung dich dat 80 de'n 91 % Nhu vay laterit da ong Ha Tay hoan toan cd the' dung lam vat lieu ha'p phu arsen nude TAI UEU DAN 111 D VAN AI MAI TRONG NHUAN, NGUYfiN KHAC VINH, 2007 : MOt sd diem phan bd arsen tu nhien va vdn de nhiem arsen mOi trudng d Viet Nam - http://w\vw.monre.gov.vn BO TN va MTVN | | NGUYgN DLfC CHLY, NGUYEN TRUNG MINH, 2008 : Budc ddu nghien cim su hdp phu ion Pb** cua da basalt Phudc Long, Viet Nam Tap chi Khoa hgcDHSPHaNOi Vol , 726-754 [51 M.R ELIZALDE-GONZALEZ, J MATTUSCH, W.D EINICKE R WENNRICH, 2001 : Chem Eng J 81,787 [6[ J.F FERGUSON J GAVIS, 1972 : Water Res 6, 7259 [71 H GEN9-FUHRMAV, J.C TJELL D MCCONCHIE, O SCHUILING 2003 J Colloid Interface Sci 264, 327 [8[ H.M GUO, Y.K WAs'G G.M SHPEIZER S VAN, 2003 : J Environ Sci Health A 38, 2565 | | H.M GUO D STCBEN, Z BERNER, 2007 : Sci Total Environ 377 142 \ 10[ H.M GUO D STl'BEN Z BERNER 2007 : Appl Geochem 22, 1039 11 11 HUAMING GUO DORIS STL'BEN ZSOLT BERNER, 2007 : Adsorption of arsenic (III) and arsenic (V) from groundwater using natural siderite as the adsorbent Journal of Colloid and Interface Science, 315 47-53 12 E.O KARTINEN J.M MARTIN 1995 : Desalination 103, 79 |13[ N.E KORTE, Q FERN/WDO, 1991 Rev Environ Control, 21 / Crit [14] A.e.g LADEIRA V.S.T CIMINELU, 2004 : Water Res 38 2087 [15[ TRAN HIEU NHUE, 2007 : nhiem mOi trudng nude arsen va eOng nghe xu ly phuc vu cdp nude sinh hoat Trang thOng tin dien td BO Xay dung [16] JO NRIAGU, in : W.T FRANKEN'BERGER (Ed.), 2002 : Environmental Chemistry of Arsenic, Dekker, New York, [17[ D.B SINGH G PR.ASAD DC RLPAINWAR, 1996: Colloids Surf 111.-^9 [181 PL SMEDLEi' DG KINNIBLIRGH 2002 : Appl Geochem 17 517 367 [19| NGUYEN QUANG TRUNG, NGUYEN THI PHUONG THAO, 2004 : Study of arsenic removal from groundwater by laterite mineral Advances in Natural Sciences Vol 5, 2,173-179 [20] MAI THANH TRUYET, 2007 : O nhiem arsenic: Phuong hudng giai quye't - http://vastvietnam.org/ truyet/trgquas.html - 2007 [21 [ F WAGNER, Z BERNER, D STUBEN, in : J BUNDSCHUH, P BHATFACHARYA D CHANDRASEKHARAM (Eds.), 2005 : Natural Arsenic in Groundwater : Occurrences, Remediation and Management, Taylor & Francis, Balkema, [22[ W, ZHANG, R SINGH, E PALING, S DELIDES, 2004 : Miner Eng 17,577 [23] Comprehensive Environmental Response, Compensation and Liability Act (CERCLA), USEPA, 2005 [24| National Research Council, Arsenic in Drinking Water : 2001 Update, National Academy Press, Washington, DC, 2001 368 SUMMARY The adsorptive capacity of As (III) and (V) of Ha Tay laterites The investigated results indicat that the adsorptive capacity of As (V) onto Ha Tay latehte (1697mg/kg) is larger than one of PAC (1193 mg/kg) The adsorption capacities of As (III) onto laterite and PAC are equivalent (1050 mg/kg) When initial concentration of arsenic (V and III) in solution is 0.12 mg/1 (12 times large than regulatory limits), final concentration of As after adsorbed by laterite is 0.008 mg/1 that is smaller than regulatory limits and arsenic removal from solution is 92.6 % With the same condition, PAC can remove only 80-91 % arsenic from solution Conclusion : Ha Tay laterite can be used as an adsorption material for arsenic ion in groundwater Keyword : Adsorption, arsen (III, V), Ha Tay laterite Ngdy nhgn bdi : 23-6-2008 Vien Dia chdt (Vien KH&CN Viet Nam) Khoa Hod hgc (DHSP Hd Noi) ... hoat As (V) tinh A.s(III) Laterit da As (V) ong Ha Tay As(III) [2| M BISSEN P.M FRIMMEL, 2003 Hydroehim Hydrobiol 31 97 ] Tac gia bang KET LUAN Dung lugng ha''p phu As (V) cila laterit da ong nguyen... Ninh Binh), sOng Ma (Thanh Hod), sOng Ca (Nghe An), ,sOng Cuu Long (Bien Hoa, Ba Ria) va Tay Nguyen (Ddc NOng, Kontum, Tay Ninh) Trong de tai nghien ciru chiing tOi sii dung laterit da ong cua viing... nhien Hematite tu nhien Siderite tu nhien Clinoptilotile As (V) 400 99 As(III) As (V) 537 208 72 As (V) 219 100 As (V) 520 As(III) 1040 As (V) 100 qma,(mg/kg) % ha''p phu Ngudn tai lieu 1192,5 1053,3