Tiiu ban Sinh thai, Moi tncdng vd qudn ly Bien ^ BIEN DONG TICH TU KIM LOAI NANG TRONG M O T SO LOAI RONG Nguyen Binh Thuat, Biii Minh Ly, D^ing Xuan Cirdng, Lam Thu Ngan, Le Nhu* Hau Vien Nghien cdu va iTng dung cdng nghe Nha Trang, 02 Hiing Vuong - Nha Trang - Khanh Hda Email: ngdinhthiiat(5).nitra.ac.vn O nhiim kim logi ndng da tdng len nhicng thdp ky gdn day vd da trd thdnh mgt vdn de quan trgng cdc co quan qudn ly mdi trudng Asen, cadimi, thiiy ngdn vd chi ndm so cdc nguyen tS vi luong co dnh hudng Idn vd cd cdc nguy co cao nhdt ddi vdi sice khde ngudi Muc dich cua nghien cieundy Id theo doi sv tich luy Cd, Pb, Hg vd As mgt sd mdu rong thu thdp tie cdc viing ven bien Khdnh Hda Do chiing toi quan tdm din (1) xdc dinh phgm vi ndng kim logi nang cdc lodi rong biin d Khdnh Hda, (2) md td theo thdi gian su biin doi cua nong dg kim logi ndng cdc lodi rong bien Mdu dugc thu gom vdo thdng 3, 4, cdc ndm 2009, 2010, 2011 Thdnh phdn chi, asen, thity ngdn vd cadimi dugc xdc dinh lodi rong phd biin tgi vimg bien Khdnh Hda Hdm luong cua cdc kim logi (mg/kg kho) dugc tim thdy ndm khodng gidi han: Pb (0,02-0,46), As (0,0322.91), Hg (0,02-0,59) vd Cd(0.03-1,16) Abstract CHANGES IN HEAVY METAL ACCUMULATION (Cd, Pb, Hg and As) OF THE SEAWEEDS Pollution from heavy metals has increased in recent decades and has become an important concern for environmental agencies Arsenic, cadmium, mercury and lead are among the trace elements that have the greatest impact and carry the highest risk to human health The aim of the present study is to compare the accumulation ofCd, Pb, Hg and As in the seaweeds collectedfrom the coast of Khanh Hoa Because of that, we were interested to (1) determine the concentration range of heavy metals in seaweed species in Khanh Hoa: (2) describe the temporal variation of heavy metal concentrations in the seaweeds Seasonal collections were done in March, April, May 2009, 2010, 2011 Lead, arsenic, mercury and cadmium contents were determined in species of seaweed in Khanh Hoa The concentration ranges found, expressed in mg/kg dry weight, were: Pb (0.02-0.46) As (0.03-22.91), Hg (0.02-0.59) and Cd (0.03-1.16) Keywords: lead; cadmium; arsenic; mercury; seaweed 17 178 /fp/ nghi Khoa hgc vd Cdng nghj biin loan qudc lan thic I MO DAU Rong biin tir lau da dugc biet den la mdt phan quan trpng he sinh thdi ven bd Nd la nai cu tni va la ngudn thuc an cho cac sinh vat bien va ban than rong bien la noi tich tu cac khoang chit, cac kim loai da lugng va vi lugn^ cd nude bien, As, Cd, Pb, Hg la cac nguyen td vi lugng mang tinh dgc td dugc hap thu cd rong biin Tir vai chuc nam lai day cac nha khoa hpc da khang dinh dgc tinh ciia nguyen td As phu thudc vao trang thai hda tri va dang iien ket hiJu co hoac vd co ciia nd [5] Ham lugng Cd cho phep cd mat rong biin dimg lam thuc pham nam khoang tir 0,1 den 3ppm tiiy thudc vao quy djnh cua moi nude [4] Ham lugng cho phep cua Pb rong bien lam thyc phim cho ngudi chip nhan tai Nhat la 0,9ppm Ham lugng cho phep ciia Hg rong biin diing lam thuc phim chap nhan tai Nhat la 0,5ppm [9] Hien nay, san phSm tir cac loai rong bien dugc su dung nhu thuc an bd dudng cao cap dugc ua chuong nhieu d cac nude Au, M^ [1] Trong y dugc rong bien la ddi tugng cd chda nhieu hgp chat cd hoat tinh sinh hgc cd tiem nang ling dung linh vyc dugc hgc [2] Trong tieu chuan dang ky cdc san pham che bien tir rong bien sir dung y dugc, thyc pham cac kim loai Cd, Pb, As, Hg ludn la cac chi tieu quan trpng dugc de cap den O Viet Nam, van de xac djnh cac kim loai nang dpc hai da dugc quan tam nghien cuu tir nhieu nam trudc, viec nghien cuu cd y nghia ve sy thay ddi ham lugng kim loai nang theo thdi gian tir cac mau rong bien sudt thdi ky sinh trudng Ngoai ra, thdng qua ket qua cd the danh gia che dinh dudng cua nhieu loai ddng vat an rong cd the anh hudng den sire khde cua chiing Qua viec xac djnh ham lugng cac kim logi cac mau rong cd the kiem soat su anh hudng ciia cac kim loai tir cac san pham su dyng nguyen lieu rong bien IL PHirONG PHAP VA NGUYEN LIEU Quang phd hip thy nguyen tOr Id graphit (QPHTNT-LG) tir lau la phuang phap dugc sir dung rdng rai de xac djnh ham lugng cac nguyen td kim loai cac mau y hoc, sinh hpc, dugc pham, thyc pham nhd cd dd nhay cao d mure ppb Mdt loat cac cai tiln Idn ve thiet bi nhu su dung hetfiongbd chinh nIn, cac chit cai biin hda hoc da lam giam thilu va loai trir cacylu td anh hudng cac loai iihilu nhu nhilu hda hgc, nhieu ion hoa, nhieu nen, nhieu phat xa, nhilu phd; hip thy nIn hay hip phu khdng chpn lpc nen phuong phap QPHTNT-LG la mpt cdng_ cy hihi ich dl djnh lugng As, Cd, Hg va Pb cac mau y sinh hpc, dugc pham, thuc pham va mdi trudng [8] Thiet bi May quang phd hip thy nguyen tu Thermo Elemental-Model Solaar M6 Dual Zeeman Atomic Absorption Spectrometer, thilt bj tiem miu ty ddng FS95, den catot rdng HCL data eroded, dugc dieu khien bing may tinh vdi phan mem dieu khiln Solar Version 27 Cac che dp quang phd dugc dan bang 1.1 va 1.2, sir dung hieu ung hi?u chinh nen Zeeman Tieu ban Sinh Ihai, Moi mr&ti^ va quan ly Bien 179 Bans I Cdc dieu kien quang hap thu nguyen tir sir diing lo graphit logi "PyrolyticaUy Coaled Electrographite "[11] Thong so As Cd Hg Pb X(nm) 193,7 228.8 253,7 217,0 Dp rpng khe (nm) 0,5 0,5 0,5 0,5 Thoi gian (s) 3 3 Kieu Dien tich Dien tich Dien tich Dien tich Dong den (%) 90 50 90 90 Bcm^ Chicmig trinh nhiet cita Id graphit sic dung logi "PyrolyticaUy Coaled Electrographite "[11] Nguyfin As Cd Hg Pb Nhiet (°C)' Thdi gian luu(s) Tdc gia nhiet (°C/s) Luu lugng (L/phut) Say kho 100 Tro hoa 1.200 30 10 0,2 20 150 Nguyen tu lioa 0,2 2.600 Lam sach 16 2.700 0,2 Say kho 100 30 10 0,2 Tro hoa 800 20 150 0,2 Nguyen tir hoa 1.200 0 Lam sach 16 2.500 0,2 Biroc Say kho 100 30 10 0,2 Tro hoa 200 20 150 0,2 Nguyen tir hoa 750 0 Lam sach 16 2.500 0,2 Say kho 100 30 10 0,2 Tro hoa 800 20 150 0,2 Nguyen tir hoa 1.200 0 Lam sach 16 2.500 0,2 Hpi nghj Khoa hoc va Cong nghe biin todn quoc lan thir 180 Hoa chat - HNO3 nong 70% (Merck); chuin As lg/1 pH3 (Fluka); chuAn Cd lg/1 (Fluka); chuin Pb lg/1 (Fluka);'chuin Hg lg/1 (Fluka); Pd lg/1 (Fluka); Mg IgA (Fluka); Ni lg/1 (Fluka); nuoc sieu sach; Pd(N03)2 sir dung lam chit cai bien hoa hoc cho nguySn to Kg va Cd, Ni(N03)2 sir dung lam chat cai biSn hoa hpc cho As va Mg(N03)2 sir dung lam chat cai biin hoa hpc cho Pb; argon 99,9% tir Xi nghifp Hod ky nghe Nha Trang; chuin 10"', 10"^ 10"', 10"*, 10"^ (g/1) ciia cac nguyen t6 Cd, Pb, Hg, As dirge chuin bj tir cac dung dich g6c ban diu lg/1 voi nuac sieu sach Can 0,5g mlu kho vao binh pha mlu dung tich 55ml dua vao 5ml axit nitric, day nip lai va van chat (moment luc 2,3Nm), chay v6i chuang trinh nhiet dp nhu bang 1.3 Bane Chuang Irinh nhiet dp ciia Id vi song Stage Cdng suat eye dai (W) 0) 1200 % Cdng suat Toe gia nhiet (phut) Nhiet ("C) Thai gian giir nhiet (phut) 20 200 30 100 (So binh >20) NguySn lieu Rong biin thupc nganh rong luc, rong dd, rong nau dugc thu thap tir sdng C^i, Ddng Bd, Sdng Ciu, Hdn Chdng, Hdn Dd ciia loai rong vao cac thang 3, 4, ciia cac nam2009,2010,2011 Bdng Ten khoa hgc, tin mdu, vi tri vd ngdnh cua cdc mdu rong nghiin ciru TT Ten khoa hpc Ten mau Nganh Vftrithumlu Ulva lactuca I Rong luc Song Cai Ulva reticulata II Rong luc Song Cai G tenuistipitata III Rong D6ng B6 G bailiniea IV Rong Song ciu Sargasum serratum V Rong nau Hon Chong S oligocystum VI Rong nSu Song Cai Turbinaria ornata VII Rong nau Hon Do Tiiu ban Sinh thdi, Moi tncdng vd qudn ly Bien 181 III KfeT QUA VA THAO LUAN Bans Hdm luong cdc kim logi biin dgng theo thdi gian cua lodi rong Mau Trung binh nam 2009 Trung binh nam 2010 Ham lugng ((ig/g) Ham lupng (^g/g) Cd II III IV V VI VII 0,07 Pb Ktt Hg As Cd 0,10 0,36 0,08 Pb Ktt 0.14 0,06 0,09 0,33 0,15 0,06 0,49 0,07 0,28 0,38 Ktt Ktt 0,27 0,07 0,31 0,3< 0,07 0,05 0,58 0,24 0,10 4,23 0,47 0,08 0,19 0,25 0,34 12,9 0,25 0,05 14,1 0,37 0,06 14,4 0,52 0,14 Hg 0,09 0,09 Ktt Ktt 0,27 0,06 0,09 As 0,38 0,36 3,95 0,18 11,8 14,1 13,4 Nam 2011 Thang Ham luong (ng/g) As Cd Pb 0,07 Ktt Hg Ktt 0,47 0,07 Ktt 0,08 0,45 0,09 Ktt 0,24 0,32 TB 0,08 Ktt, 0,11 0,41 0,03 Ktt 0,12 0,53 0,26 0,05 0,07 0,24 0,15 0,12 0,07 0,15 TB 0,15 0,06 0,09 0,31 0,05 0,02 Ktt 0,03 1,16 0,04 Ktt 0,06 0,16 Ktt 0,11 11,22 TB 0,42 0,07 Ktt 3,79 0,24 0,16 Ktt 0,16 0,29 0,46 Ktt 0,16 0,19 0,33 Ktt 0,17 TB 0,24 0,32 Ktt 0,16 0,36 0,05 Ktt 13,98 0,32 0,07 0,59 10,04 0,05 0,03 0,09 9,27 TB 0,24 0,05 0,23 11,10 0,30 0,03 Ktt 5,57 0,46 0,11 0,04 11,13 0,51 0,08 0,10 22,91 TB 0,32 0,07 0,05 13,20 0,35 0,26 0,13 18,10 0,55 0,19 0,09 10,59 0,55 0,08 0,02 10,12 TB 0,48 0,18 0,08 12,94 Qua bang ta nhan thay Cd va As1 diu cd hiu het cac loai rong, Pb khong tim thay rong Ulva lactuca Rieng Hg hai rong G Tenuistipitata va G bailiniea 182 //p; nghj Khoa hgc vd Cdng nghe biin todn quoc Idn lin khdng tim thiy Riosmena-Rodriguez R cho rang qua trinh tich liiy kim loai nSng d moi loai sinh vat tiiy theo nhu ciu qua trinh phat trien, mdi trudng ty nhien cd the anh hudng cac sinh vat dac biet la sinh vat nhay cam nhu rong bien [13] Ham lugng cac kim loai cac mlu rong nhin chung nam it cd sy thay ddi Idn, vi vay chiing tdi dua sd lieu cac thang gin day nhit cua nSm 2011 cac loai rong de thao luan Nguyen td Cd cd ham lugng thap nhat 0,03pg/g d rong Ulva reticulata vao thang va cao nhat la 0,55pg/g d rong Turbinaria ornata vao thang 4, So sanh vdi loai rong V Rigida (Canakkale, Turkey) nhan thay Cd cd ham lugng cao nhat vao miia he 0,05(j,g/g va thap nhit vao miia thu 0,001pg/g [10] Griselda Margarita Rodriguez-Figueroa da khao sat loai rong Padina diirvillaei va nhan thay rang ham lugng Cd thap nhat la l,45pg/g vao thang va cao nhit vao thang dat din 9,lpg/g [7] Ham lugng Pb rong G Bailiniea cd ham lugng cao nhat vao thang dat 0,46pg/g va thap nhat d thang dat 0,16|ig/g Rddenas de la Rocha S ham lugng Pb cao nhat la mSu rong thu tai Nhat Ban len den 0,85|j,g/g va thap nhat la tai Phap vdi ham lugng 0,31iig/g [14] Rong Sargasum serratum va S Oligocystum hap thu kim loai cao nhat vao thang 4, Griselda Margarita Rodriguez-Figueroa khao sal rong Padina durvillaei nhan thay ham lugng Pb thap nhat la l,5^tg/g vao thang va cao nhat vao thang dat den 30|ig/g [7] Qua bangl nhan thay ham lugng Hg cao nhat la 0,59fig/g ddi vdi rong Sargasum serratum vao thang va thap nhat 1^ 0,02|ig/g vao thang ddi vdi rong Turbinaria ornata Ddi vdi Hg cac tai lieu dac biet quan tam nd tdn tai thyc phim dudi dang vo co hay hihi ca va ham lugng cd vugt nguong cho phep ddi vdi an toan thyc phim [6] Ham lugng As cua loai rong Ulva reticulata la 0,9iig/g thu thap vao thang 5/2007 so sanh vdi mau dang khao sat cd thip hon nhung van nam cimg ngudng [12] Ham lugng As cua mau rong tai thdi diem thu miu phan tich cao han muc cao nhit cua loSi rong Porphyra [14] Ham lugrig As cao nhit hip thu d loai rong S Oligocystum dat 22,91pg/g vao thang va thdp nhdt cung d loai rong la 5,57pg/g vao thang Rddenas de la Rocha S khao sat ham lugng As rong Laminaria ong nhan thdy ham lugng As cao nhat la miu rong thu tai Phap len din 53,lpg/g va thip nhit la tai Tay Ban Nha vdi ham lugng 30,l^g/g, cdn Han Qudc ham lugng As dat 40,0^g/g nim giiia hai gia tri tren [14] IV KET LUAN Da xac djnh ham lugng cac kim loai Cd, Pb, Hg va As biin ddng theo thdi gian mpt sd loai rong Nhin chung su tich tu cac kim loai d mot sd loai rong nghien cuu neu so sanh vdi cac loai rong ciing loai tren thi gidi cd thi ndi rong biin ciia ta tich tu thip kim loai nhung ddi vdi kim loai khac thi cd the cao han va tiiy thupc vao loai rong Nhirng ket qua nghien ciru ve hien trang han lugng cac kim loai Cd, Pb, Hg va As rong bien bien ddng theo thdi gian d bai chi la nhGng thdng tin ban diu D I cd thi kit l u ^ va cd each nhin tdng quan va toan dien han cin nghien cuu bd sung them so lieu vl mdi truang nude noi rong sinh trudng phat trien va cac dpng vat ton tai noi dy su dung rong bien nhu la nguon thirc an qua trinh phat triin ciia chiing Tiiu ban Sinh thdi, Moi tricdng vd qudn ly Bien TAI LIEU THAM KHAO [1] A guide to the seaweed industry, 2003, FAO [2] Andrea Desiree HoJtkamp Svenja Kelly Roland Ulber and Siegmund Lang 2009, Fucoidans and fucoidanases-focus on techniques for molecular structure elucidation and modification of marine polysaccharides, Applied Microbiology and Biotechnology, Volume 82, Number 1,1-11 [3] Caliceti M., E Argese, A Sfriso, B Pavoni, 2002, Heavy metal contamination in the seaweeds of the Venice lagoon, Chemosphere, 47,443-454 [4] Concepcidn' Almela, M Jesiis Clemente, Dinoraz Velez, Rosa Montoro, Total arsenic, inorganic arsenic, lead and cadmium contents in edible seaweed sold in Spain, 2006, Food and Chemical Toxicology, 44, 190M908 [5] Feldmann J., John K and Pengprecha, P., 2000, Arsenic metabolism in seaweedeating sheep from Northern Scotland, Fresenius J Anal Chem., 368, 116-121 [6] Food & Tech Magazine http://tapchithucpham.com/?p=n59 [7] Griselda Margarita Rodriguez-Figueroa, Evgueni Shumilin, Ignacio SanchezRodriguez, Heavy metal pollution monitoring using the brown seaweed Padina durvillaei in the coastal zone of the Santa Rosalia mining region, Baja California Peninsula, Mexico, 2009, J Appl Phycol, 21:19-26 [8] Jordi Sardans, Fernando Montes, Josep Penuelas, 2010, Determination of As, Cd, Cu, Hg and Pb in biological samples by modern electrothermal atomic absorption spectrometry, Spectrochimica Acta Part B, 65, 97-112 [9] Kazutosi Nisizawa Hiroyuki Noda Ryo Kikuchi and Tadaharu Watanabe 1987, The main seaweed foods in Japan, Hydrobiologia, 151, 5-29 {\0\ Mehtap Ustunada, Hiiseyin Erdugan, Selehatlin Yilmaz, Riza Akgul, Veysel Aysel, Seasonal concentrations of some heavy metals (Cd, Pb, Zn, and Cu) in Ulva rigida J Agardh (Chlorophyta) from Dardanelles (Canakkale, Turkey), Environ Monit Assess, Received: January 2010 / Accepted: 29 July 2010 [11] Methods Manual, Atomic Absorption Spectrometry, Thermo Elemental Issue 3,01-01 [12] Nguyin Dinh Thuit Nghien cdu phan tich lien tuc (on-line) d ^ g Asen mdt sd ddi tugng mdi trudng biin bing phuong phap lien hgp sic ky Idng va hip thy nguyen tu Luan an Tiln sy Hda hpc ViSn Hda hpc Vien Khoa hpc va Cdng nghe Viet Nam Ha Ndi 2009 [13] Riosmena-Rodriguez R., A Talavera-Saenz, B Acosta-Vargas, S C Gardner, Heavy metals dynamics in seaweeds and seagrasses in Bahia Magdalena, B.C.S., Mexico, 2010, J Appl Phycol, 22,283-291 [14] Rodenas de la Rocha S., F.J Sanchez-Muniz, M Gomez-Juaristi, M.T Larrea Marin, 2009, Trace elements determination in edible seaweeds by an optimized and validated ICP-MS method Journal of Food Composition and Analysis, 22, 330-336 Ngudi dgc nliQn xet: TS Nguyin Dire Cu ... M^ [1] Trong y dugc rong bien la ddi tugng cd chda nhieu hgp chat cd hoat tinh sinh hgc cd tiem nang ling dung linh vyc dugc hgc [2] Trong tieu chuan dang ky cdc san pham che bien tir rong bien... chiing Qua viec xac djnh ham lugng cac kim logi cac mau rong cd the kiem soat su anh hudng ciia cac kim loai tir cac san pham su dyng nguyen lieu rong bien IL PHirONG PHAP VA NGUYEN LIEU Quang phd... 30 100 (So binh >20) NguySn lieu Rong biin thupc nganh rong luc, rong dd, rong nau dugc thu thap tir sdng C^i, Ddng Bd, Sdng Ciu, Hdn Chdng, Hdn Dd ciia loai rong vao cac thang 3, 4, ciia cac