f̂lP chi Khoa hoc Truimg Dgi hgc Cdn Thu Phdn 4 Khoa hoc Tu nhien Cong nghi va Moi tnrang i i (2014) 109 116 Tap chi Khoa hoc Trifcing Dai hoc Can Thd website sj ctu edu vn DU" LirONG HOAT CHAT THUOC[.]
^flP chi Khoa hoc Truimg Dgi hgc Cdn Thu Phdn 4: Khoa hoc Tu nhien Cong nghi va Moi tnrang- i i (201 Tap chi Khoa hoc Trifcing Dai hoc Can Thd website: sj.ctu.edu.vn DU" LirONG HOAT CHAT THUOC BAO VE THU'C VAT QUINALPHOS TRONG NU'dC TREN RUONG LUA VA SONG RACHOf TINH HAU GIANG Pham Van Toan', Nguyin Phan Nhan^ va Bui Thi Nga' 'Khoa Moi trucmg & Tai nguyen Thien nhien, Trucmg Dgi hoc Cdn Tha ^ Nghien cuu sinh Moi truong dat vd nuac Khoa Moi truong & Tdi nguyen Thien nhien Thong Un Chung: Ngay nhgn: 11/04/2014 Ngdy chdp nhdn: 28/08/2014 Title: The residue concentrations of pesticide Quinalphos in surface water in rice fields and rivers in Hau Giang Province TdkhAa: du lugng, Quinalphos, rugng Ilia, kenh ngi dong, song rgch, tinh Hgu Giang Keywords: Residue, Quinalphos, rice fields Irrigation canals, main rivers, Hau Giang province ABSTRACT In this study, active ingredient Quinalphos was selected to measure and assess its concentration in surface water at rice fields, irrigation canals and main rivers in the Hau Giang province, in two rice crops, the Winter-Spring 2012 and the Autumn-Summer 2013 The study results revealed that the concentrations of Quinalphos were detected at all surveyed water bodies and the detected frequencies were gradually decreasedfromthe rice fields to the main rivers and the irrigation canals with 40% 50% and 67%, respectively The average concentrations of Quinalphos detected in the irrigation canals and main rivers in the Autum-Summer crop were higher than that in the Winter-Spring crop, Among the sampling locations at the irrigation canals and main rivers several measured concentrations exceeded the threshold value of acute 48 hour ECso toxicity for aquatic invertebrate animal (0,66 fig/L) In the annual monitoring program of the province, the concentration in surface water should be monitored for pesticides which are commonly used and laxic to aquatic animals and the accumulation of these compounds in food chain are needed to be researched, TOM TAT Hoat chdt Quinalphos thugc goc ldn hiru co dugc chgn de quan trac ndng nude mat rugng kenh ngi ddng vd song rgch d tinh Hdu Giang vdo vti liia Dong Xudn 2012 vd He Thu 2013 Kit qud nghien cuu cho thdy du lugng cua hogt chdt Quinalphos deu hien dien d cdc thi^ vuc khdo sdt vdi tdn sudt phdt hien gfdm ddn tu rugng lua song rgch den kenh ngi dong, ldn lugt chiem 40% 50% vd 67% Nong hogt chdt Quinalphos d kenh ngi dong vd song d vu He Thu cao han vu Dong Xudn Trong tai mgt so vi tri khdo sdt, nong cua Quinalphos nude dd vugt ngudng gay dgc cdp tinh ECso doi vdi dgng vdt thuy sinh khong xirang song (0,66 pg/L) Trong chuong trinh quan trac nude mgt hdng ndm cita tinh, cdn theo doi du lugng cua cdc logi thuoc bdo ve thuc vgt dang dugc su dung bien moi trudng nude mat G l d l THIPU Di d t a bao dupe nang suit lua, ding tiioi 6k ngan ch?n sv tan pha ciia djch hai cang theo chieu hudng cue doan dnh hudng cfta bien ddi ^ , ^ " ; "f"" '^ " ',* """I * " * ' ' ' ' * ° '* K*^' ^^' (^^TV) cang tang Trong tong so thuoc Tap chi Khoa hgc TrudngDgi hgc CSn Tho PhSn A: Khoa hgc Tif nhiin Cdng nghi vd Mdi Irudng: 33 (2014): 109-1 ft dupe nhip khiu hing nam, cd Udn 53% duac su dyng tai khu vyc DBSCL Trong cdc logi thudc thudng dupe su dung cd khoing 50% logi thudc thudc nhom II v i III (mftc dp ddc trung binh va nhe) theo sy phin logi cua t i chftc Y tl Thd gidi (WHO) (Pham Van Toin, 2013) Cac logi fliuic thudng dupe sft dung thudc nhdm conazoles, pyretiuoids, biopesticides vi carbamate Nhdm thudc ldn huu ca vin cdn duac su dyng nhung vdi tin suit thip Mdt sd loai thudc thudc eic gdc niy nhu cypermethrin, diazinon, quinalphos, propieonazole, profenofos dpc vdi cdc logi ddng vat thuy sinh, dgc bift li ca (Cagauan, 1995, Cong et al., 2008; US EPA, 2009) Cic nghien cftu gin diy cho thiy rang ngudi ddn sft dyng va bao quin thuoc khdng hop ly chiem ty If cao Day la i^;uyen nhdn cua sy phdt tan du lupng thuic vio ngudn nude Tuy nhidn, nhung nghidn cftu quan trie vl du lupng thudc thudng sft dung gin day tiong khu vyc rit It Mpt sd khdo sat tmdc day d Viet Nam da cho thiy rang du lupng eua hogt chit thuoc BVTV Uong nude, Uong uim tich tin tgi vdi ndng dd kha cao (Viet et al., 2000; Minh et al., 2007; Carvalho et al., 2008; Pham Manh Hoai et al., 2011) Ket qui dgc nghien cftu eua Pham Van Toan et al (2013) dii vdi 15 hogt chit dupe sft dung phd biln d khu vye DBSCL cho thiy ning dp trung binh cfta cic boat chdt nude m^t di d ngudng 3,34 pg/L, ndng dp cao nhdt ghi nhdn duoc Id cfta hoat chat isoprothiolane (11.24 pg/L) vifc sft dyng thuic, trinh trgng su dyng v i bio quin thuic khdng hpp ly cung li tiiyc trang cua dja phuang, Khd ning phdt tin ciia du lupng thuic vio mdi trudng nude la rit ldn Tuy nhidn, cdng tic quan trie chit lupng mdi trudng nude hing nam cfta tinh thi du lupng cua thuic BVTV Quinalphos ehua dupe quan tim Theo kit qud nghien cftu cua Bui Thi Nga vd ctv (2013), boat chit Quinalphos dupe ngudi din sft dyng, vdi ten thuong mgi phi biln la Kmalux 25EC, Sk phdng trft nhen gie v i siu hgi Hoat chit niy dupe xep vdo loai CO thdi gian tdn luu Uong nude liu, khoing 39 ngiy (d 20*'C vi pH = hoic 7) va cd dp ddc cap tfnh cao ddi vdi ci v i cic loii thfty smh khdng xuong sdng, dupe xep vio dp ddc loai II (df ddc ttamg bmh theo phin logi cfta WHO) (PPDB, 2014) Bai vilt trinh biy kit qui nghien cftu du lupng cfta hogt chit Quinalphos Uong mdi trudng nude trdn eae logi hinh thfty vyc khdc eua tinh PHUONG PHAP VA PHUONG TIEN Thdi gian nghien cdu Nghien cftu duac thyc hifn tft thing nim 2012 din thing nim 2013 Mlu nude dupe liy hai dot, lan lupt vio cic vu Ddng Xuin (tft thdng 10/2012 din thdng 1/2013) vd He Thu (tft thdng den thdng 5/2913) d thdi dilm Ifta dupe kliodng 50 tudi sau xg Dia diem nghien cuu Sdn xuat ndng nghiep tai Hiu Giar^ khdng ngftng phdt uiln theo xu the chung d Ddng bang sdng Cftu Long Difn tich dat ddnh cho sdn xuit ndng nghifp cfta tinh chidm khoang 82,7% ting difn tich San lupng lua toin tinh nam 2012 dat 1.179.889 tin (Nidn gidm tiidng ke tmh Hiu Giang, 2012) Cf Hiu Giang, canh tie Ifta cd thi tiln hinh ca ba vy: Ddng Xudn, He Thu va Thu Ddng nam d phdn ldn dia bin cfta tinh Theo thing ke cfta Chi eye bdo ve thyc vit tinh Hgu Giang, hing nam luong thudc BVTV dupe su dyng trung binh khodng 2.807 tin Ben canb su gia tang vl Dia dilm nghidn eftu thufc dja bin cfta ba huyfn Long My, Phung Hifp v i Vj Thfty tinh Hiu Giang Diy Id ba huyfn cd difn tich canh tdc lua ldn cfta tinh Mdu nude dupe liy ben mdng Ida, kdnh nfi ding v i cic sdng, rgch Xi No, Nang Mau, Cii Ldn, Lai Hieu, Quin Lp Phyng Hifp vi rgch Mil Dim thudc dia bin tinh H^u Giang Du lupng thudc bio vf thyc vit dupe phin tich tai phong thi nghifm khoa Mdi trudng va Tii nguyen Thien nhien v i jphdng thi nghifm Chuyen siu, Trudng Dal hpc Cdn Tha Tgp chiKhoa hgc Tmdng Dai Iigc Cdn Tha Phdn A: Khoa hoc Tu nhiin, Congnghi vd Moi trudng: 33 (2014): 109-116 Hinh 1: Ban the hien siu vi tri thu miu nude tren dja ban nghien cuu Ghi chu: XN: Xd No; NM Ndng Mau, CL: Cdi Ldn: LH: Ldi Hiiu; QL Qudn Ld Phung Hiip; MD: Mdi Ddm Phuong phap thu mlu Tgi mdi vi tri thu didm: Uong mpng lua, tiong kdnh npi ddng va song raeh ehinh Trong dd, tai vi tri rgeh Mai Dam chi rapt diem rgch dupe thu miu Tai mdi rupng, mau dupe thu ngau nhien; tgi mdi kenh ndi ding va sdng rgeh chinh, mdu (tgi dau ngudn, gifta ngudn, cudi nguin) dupe thu Miu nude Uong kenh vd sdng rach duac thu each mit nude 20 cm, d vj tri giua kenh Cac miu dupe thu theo cich thu miu td hpp eua diem, tgi mdi diem khoang lit nude dupe thu rdi dupe trdn ddu xd lit; sau liy lit, chfta chai thfty tinh de van chuyen ve phong thi nghifm Mau dupe thu theo tieu chuin nganh 10 TCN 386-99: Quy dinh ve phuang phap liy mSu kilm dinh du lupng thuic BVTV Phuang phap phin tich du luong thuic BVTV vi xft ly sd lifu Du lupng thudc Quinalphos Uong nude dupe chilt tich va phan tich theo phuang phdp duac Uinh bay Pham Van Toan (2013), duac hieu chmh Cu till nhu sau: - Miu nude (1 Lit) sau thu dupe axit hda bing dung dich HCI &i dua pH nude vl 2-2,5, dupe trft lanli va chujin ve phdng thi n ^ f m Tgi phdng thi nghifm, mlu dupe trft Ignh d 4''C - Lpc tdch bd can ling nude bang giiy lgc tiifty tinh Whatman 47 ^m Trich liy 500 ml miu sau lpc - Mudi hoa mdu bang dung dich NaCl 15% nham tang dd phin cue cua dung dich tdch chide Sau them 100 \d -HCH (deltahexachlorocyclohexane) lam chit ding hanh qua trinh phan tich - Mau dupe chiet tdch theo phuang phip chidt pha rin bing cdt lgc Strata C18-E (500mg) Cpt lpc dupe boat hda bang cdch cho Idn lupt ml n-hexane HPLC (Hi^-performance liquid chromatography), ml ethyl acetate HPLC, ml methanol HPLC va I ml nude HPLC qua cpt lpc Cgt dupe trang sach bai^ nude HPLC va lam khd bang hut chan khdng 30 phut Chit phin tich dupe rfta tft cdt bing eich cho lin lupt ml ethyl acetate, ml n-hexane qua cpt lpc Dung djch rfta dupe chfta binh qui Id Thdm vai gigt Toluen lam chdt gift chdt can phdn tich Cho bay hoi dung djch va chuyen phan cdn lgi sau bay hai vao vial Chdt ndi chudn Fluorene - dlO (1 |ig) dupe cho vao vial Toluene dupe cho vio vial de thd tich dgt mL Vial dupe trft ddng d -20''C din phin tich Du lupng cua Quinalphos dupe phin tich bang may sac ky Shimadzu GC - 2010 ghep vdi khii phi Shimadzu GCMS - QP2010, cd tich hpp bp tiem mau ty dgng Shimadzu AOC — 20S May sic ky dupe lap dat cdt dan mao quin Rxi@5Sil MS WAnter: dai 30 m, duong kinh ti-ong Tgp chi Khoa hgc Trudng Dgi hgc CSn Tho Phdn A: Khoa hgc Tu nhien Cdng nghi vd Mdi trudng: 33 (2014): 109-116 Kinalux 25EC Cd ban 2/3 ngudi din dupe hdi di sft dyng thuic niy dl tru nhfn gie Tfty theo lupng nude mpng v i tiiy theo thdi dilm phun so vdi thdi dilm liy mau tren mdng md ning dd du lupng Quinalphos tgi cac mdng khac 0,25 mm vi dp ddy 0,5 jim Khi Heli dugc sft dung Idm mang vdi tic dp ddng khdng dii li 1,0 mL/phftt Chuong Uuih nhiet dugc dp dyng nhu sau: 1) Nhift dp ban diu 70''C dupe gift phftt; 2) tang nhift dp len vdi tic df 15°C/phftt din 200°C vi gift Uong phftt; 3) tilp tyc tang nhift dp vdi tic dp 8''C/phut din 300°C v i gift Uong 10 phut Nhift dp cfta budng tiem dupe hifu chinh d 250*'C Till tich mii lin tiem li pL Viec xac dinh du lupng thuic Quinalphos uong miu nude dupe tiiyc hifn dya vio chit npi chuin Fluorene dlO CJ vy He Thu dilu kifn canh tdc khdng thu^ lpi nhu vy Ddng Xuin Thdi tilt cd nhieu biln dii thit thudng ndn tao dilu kidn thuin lpi cho nhilu dich hgi phit sinh Trong dd, siu riy li dii tupng mi ngudi din ludn phii chft y phdng trft Vi v$y, tin suit sft dung thudc cao Ning df cua hogt chit Quinalphos dupe tai cic vi tri vu He Thu dao dfng tft 0,01•^0,02 pg/L Ning dp du lupng dupe phat hien cao nhdt la 0,02 pg/L mpng d vi ui Xa No s i lifu tiiu tiidp dupe kilm Ua sy phin bi chuin bing phuang phap Kolmogorov-Sinimov d mftc 1^ n ^ i a p = 0,05 Trong nghien eftu nay, dft lifu ve ndng df cfta Quinalphos nude mat tgi cdc v\ tri cd phin bi khdng chuin Kilm dinh phi tham si Mann Wblmey dupe ip dung dl so sdnh ndng dp eua Quinalphos mdu nude dupe thu tai cic vi tri gifta vy Ddng Xuin vi vy He Thu Kit qud phin tich cbo thiy ndng df cfta hogt chit Quinalphos nude trdn rudng khac bift cd y nghTa giuB vy Ddng Xuin v i vu Hd Thu (P = 0,02*) Tgi thdi didm tidn hinh thu miu tren rupng d ca vy ddu giai dogn lua tft 50-55 ngdy tudi d cic mdng dupe cbpn khao sit, hogt chit Quinalphos d i dupe phun it nhit la hai lin din thdi dilm thu miu Tuy nhidn, ndng dd du lupng thuic dgc dupe Uong vy Ddng Xuin thudng cao ban vy He Thu Didu cd thi la ning dp du lupng thuic BVTV mdi tmdng nude ngoai phy Ihuf c vio die tinh thudc vi ylu to mdi trudng thi edn phy thudc vao tin suit phun xit, lieu lupng va thdi gian phun (Pham Van Toan, 2011) Tgi thdi dilm thu miu vy He Thu da cd xuit hifn mua diu mfta nen cd the ndng df thuic mgng da hi pha loang bdi nude mua Mat khic, myc nude trdn cdc mdng cd sy khic tfty theo kinh nghidm canh tic cua mdi ndng hd Theo khao sat, myc nude cic mgi^ liy miu dao dpng tft 20 cm K I T QUA VA THAO LUAN 3.1 Du lupng thuoc Quinalphos nude tgi cac thuy vyc u, Trong rugng lua Ning df cua hogt chit Quinalphos trSn rudng Ifta vy Ddng Xuin dupe dao dpng tft 0,01-^0,78 fig/L Trong do, ndng dp eua hogt chit dupe phat hifn cao nhit la d vj Ui sdng Cii Ldn (0,78 pg/L), d vi tri kenh Ldi Hieu vi kenh Quin Lp Phung Hifp dudi ngudng phit hien (0,003 pg/L) Qua phdng van ndng hp cfta nhdm nghien cftu (Qudch Hii Lgi, 2013) thi vifc phun xit thuic trft sau ray bit diu tft giai dogn Ifta 30 ngdy tudi v i cu cich 710 ngdy thi phun ldn Tai cic mpng thu miu, boat chit Quinalphos dupe dftng vdi tdn thuong mai Id Bing 1: Ning dd boat chat Quinalphos nude tren rupng LH QL CL NM XN Vu Ddng XuSn1 Tan suat N^ng M NSng d$ phiit hifn thap nhat cao nh^t (n=3,%) (Hga.) (MSrt-) KPH KPH KPH KPH 33 KPH 0,78 66 KPH 0,31 100 0,01 0,04 P = 0,02* Tan suat phit hien (n-3 33 0 100 66 ,%) VvlHe Thu Nong d^ thap nhat (us«.) KPH KPH KPH 0,012 KPH N^ng a^ cao nhit (US/L) 0,01 KPH KPH 0,02 0,02 Ghi chu: - *:Khdc biet co y nghta ihdng ki vS nong dg Quinalphos nude giiia tren rugng vu Dong Xudn vd v^ Hi Thu (Kiim dfnh Mann Whitney, muc y nghia 5%) - XN NM, CL LH, OL: ldn lugt la cdc v/ tri tgi Xd No, Ndng Mau, Cdi Ldn, Ldi Hiiu Qudn Lg Phvng Hiip -KPH Khdngphdihiin 112 Tap chi Khoa hgc Trudng Dgi hgc Cdn Tho Phdn A: Khoa hgc Tu nhien Cong nghi vd Moi Irudng: 33 (2014): 109-116 b Trong kenh ngi dong Ket qui phin tich cho thiy ndng dd cfta bogt chit Quinalphos Uong nude d kdnh ndi ddng d vu Ddng Xuin dao dfng tft 0,01 -^ 0,14 pg/L Du lupng cua hogt chit dupe phit hifn d hiu hit cdc vi tri kenh, tru vj tri thupc kdnh Qudn Ld Phung Hifp Kdnh ndi ding li nai cip hogc tilp nhan nude true tiep tft mpng lua Do do, nude Uong kenh cd thd bi nhilm thuic BVTV tft nude dupe thai tft rupng sau phun thudc hogc tft nhieu rudng khac ngoii cdc mpng dupe chpn de quan fric KeiiJi ndi ddng d tit cd cic vi tri ed cung dgc diem Id chiu tdc ddng ciia thuy triSu Do vay, hudng dong chdy vd myc nude kdnh ludn thay ddi hang ngdy Chinh vi vgy, neu mdt chit nao CO Uong nude kenh thi no ludn dupe xao Udn va pha loing Diy li ly de cd thd giai thich tai mi hogt chat Quinalphos d kenh xuit hifn d 4/5 vi Ui mie dft khong phit hifn hogt chit d Uong mpng tai Lii Hieu Uong vy Ddng Xuin vd ndng dp phit hifn t^ kdnh din d Xd No cao hon d Uong mpng Xi No Uong vy Ddng Xuin 3,9 lin Bang 2: Nong dp hogt chat Quinalphos nude kenh npi ding Vu Bong Xuan Vu He Thu vi tri thu mlu Tan sudt phat Ndng thap Nong TSn suat; phat Ndng d§ thip Ndng dd hiln (n=31, %) nhSt (ug/L)cao nhat (ug/L) hien (n=.3, %) nhat (^g/L)cao nhat (ug/L) LH 66 KPH 0,01 100 0,19 0.38 QL KPH KPH KPH KPH CL 100 0,01 0,02 KPH KPH NM 100 0,01 0,05 100 0,01 0,02 XN 100 0,05 0,14 100 0,05 0,58 P = 0,03« Ghi chu: - *Khdc biit c6 y nghia thdng ke ve nong Quinalphos Irong nude kenh ndi ddng giua v^i Ddng Xudn va vu He Thu (Kiim dinh Mann Whitney, muc y nghia 5%) - XN NM, CL LH, QL: ldn lufri la cdc vi Iri tai Xd No, Ndng Mau, Cdi Lan, Ldi Hiiu, Qudn Lg Phting Hiip - KPH: Khdng phdi hiin Ndng dd hogt chit Quinalphos dupe phdt hifn d vy He Thu dao dpng tft 0,01 ^ 0,58 pg/L, ning dp cao nhit dupe phat hien la 0,58 pg/L d nude Uong kdnh thufc vi tri Xd No Co sy khac biet cd y nghTa d mftc 5% gifta vy Dong Xuan va He Thu (P^ 0,03) ve ndng df eua tiiudc kenh Ket