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KH NNG HP TH AMMONIA CA ZEOLITE T NHIN TRONG MI TRNG NC CC MN KHC NHAU

Nguyn L Hong Yn v Trng Quc Ph 1

ABSTRACT
Zeolite is recently used extensively to reduce toxic gas such as ammonia (unionized ammonia, N-NH3 and ionized ammonia, N-NH4+) in the intensive shrimp and fish ponds. However, the efficiency of zeolite is highly variable in different ecological conditions, particularly in different salinities. In order to determine the effects of salinity on ammonia absorption of zeolite, two experiments were undertaken in indoor and outdoor conditions, respectively. Each experiment consisted of six treatments, including 0, 5, 10, 15, 20 and 25o/oo randomly designed in 500 L composite tanks without aeration during the experiment courses. The results showed that zeolite peformed well in freshwater with highest ammonia uptake, one gram zeolite has absorbed 0.12 mg TAN. The absorbability of ammonia tendentiously decreased in increased salinities. However, increase of dissolved oxygen concentration and reduction of hardness after treating zeolite were observed. Saturation in ammonia absorbption was recorded after twelve hours of application. Keyword: Zeolite, TAN, absorability Title: Ammonia absorbability of natural zeolite in different water salinities

TM TT
Trong nui tm c thm canh, Zeolite c s dng nhm mc ch lm gim TAN (NH3 v NH4+), trong mi trng. Tuy nhin hiu qu ca Zeolite vn cn nhiu bin ng cc iu kin sinh thi khc nhau. Th nghim v nh hng ca nng mui ln kh nng hp th TAN ca Zeolite c thc hin trong iu kin phng v ngoi tri nhm xc nh kh nng hp thu TAN ca zeolite. Mi th nghim gm 6 nghim thc: 0, 5, 10, 15, 20 v 25%o. Kt qu cho thy zeolite c tc dng hp thu TAN tt nht trong mi trng nc ngt, 1g zeolite c kh nng lm gim 0,12 mg TAN. mn cng cao tc dng hp th TAN ca zeolite cng gim. Zeolite c tc dng lm tng hm lng oxy ha tan. Sau 12 gi x l, zeolite khng cn kh nng hp th TAN. T kha: Zeolite, TAN, hp th

1 M U Trong nui trng thy sn, c bit l cc m hnh nui thm canh, cht lng nc l mt trong nhng nhn t c nh hng rt ln n sc kho vt nui. Sau thi gian nui, cc loi kh c tch t nn y ao nui s lm tm c chm ln, pht sinh dch bnh lm gim t l sng v nng sut nui. ci thin tnh trng tch t kh c y ao v cht lng mi trng nc, cc nh khoa hc nghin cu nhiu bin php khc nhau nh s dng cc bin php sinh hc, s
1

B mn Thy sinh hc ng dng- Khoa Thy sn- i hc Cn Th

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dng ha cht, trong Zeolite hin nay c cc nh nng a chung. Trong nui trng thy sn, c nhiu tc gi nhn nh, Zeolite l mt trong nhng sn phm c tc dng tt trong vic ci tao mi trng nc, hp thu kh c. Mt lng ln Zeolite c s dng trong sut v nui tm cng nh c. Zeolite c th lm gim lng ammonium trong h thng tun hon nui thy sn nc ngt n 97% (http://www.Zeolyst.com/html/faq.html. 17/2/2005). Tuy nhin, Boyd (1995) t vn v hiu qu ca vic s dng Zeolite, ng cho rng kh nng hp th NH4+ ca Zeolite b gim thp trong nc mn v kh nng ny cng thp khi mn cng tng. Bn cnh , c kin cho rng khng th s dng Zeolite trong cc ao nui nc mn lm gim hm lng Ammonia trong ao nui, (http://www.fishdoc.co.uk/water/ammonia.htm., 4/3/2005). S hp ph NH4+ ca Zeolite b kim ch mnh bi nng cao cc cation ha tan trong nc l v cc hc ca Zeolite b nc lp y nn khng th hp ph cc loi kh c (GESAMP). Nh vy vic s dng Zeolite trong nc l l vn cn quan tm v nghin cu. Kh nng hp th Ammonia ca Zeolite t nhin trong mi trng nui trng Thy sn c thc hin nhm kho st kh nng hp thu kh NH3, ci thin mi trng ca Zeolite t c th xut khuynh hng s dng mt cch c hiu qu. 2 PHNG PHP NGHIN CU Nghin cu gm 2 th nghim v tin hnh trong 2 iu kin khc nhau. Th nghim 1 tin hnh trong b c th tch 10lt/b, khng c nn y, b tr trong iu kin phng. Th nghim 2 tin hnh trn b Composite 500lt, nn y ct bn khong 10cm. Mi th nghim gm 6 nghim thc vi cc mn khc nhau: 0, 5, 10, 15, 20, 25%o c pha t nc t 90%o v nc my thnh ph v b tr hon ton ngu nhin. Zeolite c s dng l Zeolite t nhin dng ht, c thnh phn SiO2>70% v s dng vi liu lng 15mg/L (theo khuyn co ca nh sn xut). C hai th nghim c tin hnh trong iu kin khng sc kh. Hm lng m ammonia c to ra trong mi b th nghim 1 v 2 bng cch b sung NH4Cl v bt c c hm lng protein l 59% vi liu lng 1.96g mt ln/ngy. Theo Boyd (1998), lng Nitrogen th hin dng NH4+ cho php trong ao nui thy sn nm trong khong 0.2 2 mg/L, do khi s dng mt lng d bt c bn vo b, to s pht trin sau 5 ngy. Hm lng TAN c kim tra hng ngy vo lc 14 gi (thi gian pH v nhit tng cao nht trong ngy). Trong nui trng thy sn gii hn ti u ca kh ammonia < 0.1mg/L, tnh c ca n tng khi pH v nhit tng, do khi hm lng NH3>0.1mg/L hay thi im nhit v pH cao nht trong ngy cng vi hm lng TAN ln hn 2mg/L, tin hnh x l Zeolite liu lng 15 mg/L TAN c thu mu 2 gi/ln sau khi x l Zeolite v c phn tch xc nh hm lng bng phng php Indophenol-blue. S bin ng Oxy trc v sau khi x l Zeolite 2 gi c xc nh bng my o YSI-DO200

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3 KT QU V THO LUN 3.1 Th nghim 1 3.1.1 Bin ng Oxy trc v sau khi x l Zeolite 2 gi Sau khi x l Zeolite hm lng oxy tt c cc nghim thc u tng hn so vi trc ti thi im cha x l (Hnh 1). Hm lng oxy tng cao nht nghim thc 1 t 4,59 tng ln 4,95mg/L. Mc d s gia tng l khng ng k nhng khc bit c ngha thng k (P<0,05) so vi oxy trc khi x l Zeolite v khc bit c ngha thng k (P<0,05) so vi nghim thc 2, 3, 5, 6. Theo quan st khi x l Zeolite vo nc hin tng si bt li ti xy ra. iu ny c th l do Zeolite c cu trc l nhng ti rng, bn trong c cha khng kh, khi tip xc vi nc, hin tng nc trn vo lp y khong trng y khng kh khuch tn ra ngoi gy nn hin tng si bt gip gia tng lng oxy ha tan trong nc. C th v c im ca Zeolite l kh nng trao i ion v tnh hp th, nh m tham gia vo qu trnh ty u, o nc v cung cp oxy ha tan cho c v tm nui (Chen Kong Jung,1988) do vy nhiu cng ty, nh sn xut c khuyn co nn x l Zeolite lc chiu ti nhm gia tng lng oxy vo ban m cung cp cho vt nui.
5.20 5.00

Oxy (mg/L)

4.80 4.60 4.40 4.20 4.00

NT 1 NT 2 NT 3 NT 4 NT 5 NT 6

Nghim thc Oxy trc Oxy sau

Hnh 1: Bin ng hm lng oxy trc v sau khi x l Zeolite 2gi-TN1

3.1.2 Bin ng TAN: Total Ammonia Nitrogen Vi cng hm lng TAN l 2mg/L ban u, sau khi x l Zeolite vi liu lng 15g/m2, sau 2 gi hm lng TAN bt u gim v gim mnh tt c cc nghim thc sau 4 gi. Hm lng TAN nghim thc 1 gim 42,2% cn 1,15mg/L sau 2 gi, v gim nhanh n 82% (1,64mg/L) cn 0,36 mg/L sau 4 gi x l Zeolite. Sau 12 gi x l Zeolite, hm lng TAN nghim thc 1 t mc thp nht (cn 0,22 mg/L), gim 88,9% (1,78 mg/L) so vi ban u v khc bit c ngha thng k so vi cc nghim thc khc (Bng 1). Hm lng TAN gim mt cch ng k cc nghim thc 1, 2 c mn ln lt l 0, 5%o v khc bit c ngha thng k (P<0,05) so vi cc nghim thc khc ti cc thi im thu mu (Bng 1). Cc nghim thc c mn t 5 n 25 %o c hm lng TAN gim cao nht ti thi im 8 gi sau x l v khong thi gian sau khi x l Zeolite 8 gi n 16 gi th kh nng hp thu TAN ca Zeolite b suy gim, hm lng TAN gim i gn nh khng thay i tt c cc nghim
3

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thc qua cc ln thu mu (Bng 1). mn cng tng hm lng TAN gim i sau khi x l Zeolite cng thp v thp nht nghim thc 6 ( mn 25%o), sau 8 gi x l Zeolite TAN suy gim l 0,5 mg/L v khc bit khng c ngha thng k (P>0,05) so vi nghim thc 4, 5 c mn l 15 v 20%o.
Bng 1: Hm lng TAN (mg/L) gim i cc nghim thc c mn khc nhau Th nghim 1

Thi gian sau x l Zeolite NT 1 (0) NT 2 (5 ) NT 3 (10) NT 4 (15) NT 5 (20) NT 6 (25)

4 gi 1,640,04a 1,400,05 b 0,960,11 c 0,460,02 d 0,560,08 d 0,480,03 d

8 gi 1,690,04a 1,440,01 b 0,790,04 c 0,620,03 d 0,610,01 d 0,570,02 d

12 gi 1,780,01a 1,390,01 b 0,790,01 c 0,660,04 d 0,610,01 de 0,580,01 e

16 gi 1,760,01a 1,390,01 b 0,790,02 c 0,660,05 d 0,610,01 de 0,580,02 e

Cc gi tr trong cng mt ct c cng ch ci th khc bit khng c ngha thng k (P>0,05)

Nghim thc 4, 5, 6 c mn 15, 20, 25%o, s bin ng hm lng TAN khc bit khng c ngha thng k. Hm lng TAN gim thp nht nc c mn 25%o, sau 8 gi gim 28% v gim 29% sau 14 gi x l Zeolite. Nu so snh gia nghim thc 1 v 6 th hm lng TAN nghim thc 1 (0%o) c lng TAN gim cao nht sau 12 gi x l (1,78 mg/L) nhiu gp 3 ln nghim thc 6 (28,8% hay 0,58 mg/L) v khc bit c ngha (P<0,05) so vi cc nghim thc khc. Khi tin hnh th nghim vi hm lng Zeolite x l l 10mg/L trong nc c mn t 0 n 30%o, Emadi et al, (2001) c kt lun, vi mn cng tng th kh nng trao i ion NH4+ ca Zeolite cng gim. Kt qu cho thy i vi nc c mn cao hn 30%o, s dng Carbon hot tnh s c trin vng nhiu hn s dng Zeolite trong vic loi b Ammonia. Bn cnh , kh nng hp th Ammonia ca Zeolite cng gim khi trong nc c nhiu ion Ca2+, Mg2+, Na+ (Boyd, 1995). Theo http://www.badgerminingcorp.com/asp/sb (ngy 1/3/2005) th Zeolite c s dng loi b nhng kh c trong tri ging, ao nui c nc ngt t hiu qu rt tt. Nh vy, nc c mn cng cao th kh nng hp th TAN ca Zeolite cng gim. 3.2 Th nghim 2 3.2.1 Bin ng Oxy trc v sau khi x l Zeolite 2 gi Do Zeolite c x l vo khong thi gian nhit v pH cao nht trong ngy (14 gi) nn sau 2 gi x l Zeolite, lc ny cng nh sng cao gip gia tng qu trnh quang hp, y nhanh s gia tng pH. Oxy to ra t quang hp cng vi s khuch tn ca khng kh t nhng khong trng trong cu trc Zeolite do cc phn t nc trn vo lp y, do hm lng oxy tng tt c cc nghim thc sau khi x l Zeolite. Mc d hm lng oxy tng nhng khc bit khng c ngha thng k (P>0,05) tt c cc nghim thc. Do mt to cc nghim thc khc nhau nn nh hng n hm lng oxy ha tan cc nghim thc. Hm lng oxy ha tan tng ln th nghim ny cao hn hn th nghim 1. Hm lng oxy ha tan nghim thc 6 l thp nht tuy
4

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nhin lng oxy tng ln cao nht (0,13 mg/L) so vi cc nghim thc cn li sau khi x l Zeolite 2 gi. Nguyn nhn c th do nghim thc 6 c mt to thp hn cc nghim thc khc nn trong qu trnh x l Zeolite chm xung t b bao ph bi vt cht hu c nn hm lng oxy thot ra nhiu t nhng hc rng ca phn t Zeolite. Theo Reynolds v Williford (1987, 1988), khi x l Zeolite lng xung, nhanh chng b bao ph bi cht hu c nn y, vt cht l lng trong ct nc lm gim t l hp thu cc ion ca Zeolite trong ct nc.
7.00 6.50

Oxy (mg/L)

6.00 5.50 5.00 4.50 4.00

NT 1 NT 2 NT 3 NT 4 Nghim thc NT 5 NT 6

Oxy trc

Oxy sau

Hnh 2: Bin ng oxy trc v sau khi x l Zeolite 2 gi - Th nghim 2

3.2.2 Bin ng TAN (Total Ammonia nitrogen) Sau khi x l Zeolite, TAN c theo di 2 gi/ln v hm lng ny u gim tt c cc nghim thc. Hm lng TAN gim nhiu nht v r nht nghim thc 1 (60%), nghim thc c mn 0%o, gim t nht nghim thc 6 (10%), k n l nghim thc 5 (20%) so vi nng TAN ban u (Bng 2)
Bng 2: Hm lng TAN suy gim cc nghim thc sau khi x l Zeolite - Th nghim 2

Thi gian sau x l Zeolite NT 1 (0) NT 2 (5 ) NT 3 (10) NT 4 (15) NT 5 (20) NT 6 (25)

4 gi 1,080,13a 1,010,36a 0,780,17ab 0,240,18 c 0,360,04 bc 0,100,09 c

8 gi 1,290,17a 1,190,30a 0,950,07ab 0,450,20 c 0,480,11 bc 0,230,04 c

12 gi 1,310,16a 1,270,37a 1,180,25ab 0,560,22 bc 0,530,11 c 0,200,15 c

16 gi 1,320,16a 1,290,35ab 1,200,23ab 0,670,27 bc 0,530,13 c 0,240,17 c

Cc gi tr trong cng mt ct c cng ch ci th khc bit khng c ngha thng k (P>0,05)

Sau 4 gi x l Zeolite, lng TAN gim nhanh nht nc ngt (1,08mg/L) v khc bit c ngha thng k so vi nghim thc 4, 5, 6. Lng TAN gim chm nht l nghim thc c mn cao nht (25%o), sau 2 gi lng TAN gim 3%, t 2,48 mg/L gim xung 2,4 mg/L (Hnh 3). Sau khi x l Zeolite 16 gi, hm lng TAN nghim thc 1 gim 60% (1,32 mg/L), gp 3 ln so vi nghim thc 5 (gim 20% hay 0,53 mg/L) v gim gp 6 ln so vi nghim thc 6 (gim 10% hay 0,24 mg/L) v khc bit c ngha thng
5

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k so vi ba nghim thc 4, 5, 6 (Bng 2). Trong th nghim hm lng TAN suy gim vi t l thp hn t l gim TAN ca th nghim thm d tt c cc nghim thc. i vi th nghim thm d, sau 4 gi x l Zeolite, hm lng TAN gim n 82% nc ngt gp 2 ln s suy gim hm lng TAN nghim thc 1 trong th nghim ny (gim 49%). Trong iu kin th nghim, mt lng d bt c c bn vo lm gia tng hm lng TAN trong nc v to ra thm mt lng vt cht hu c lng t nn y. y chnh l nguyn nhn gy nn s km hp thu TAN ca Zeolite. Theo Reynolds v Williford (1987, 1988), trong ao nui tm thm canh, lng vt cht hu c ha tan tng theo thi gian nui v lm gim hiu qu hp th ca Zeolite, bn cnh khi x l Zeolite lng xung, nhanh chng b bao ph bi cht hu c nn y, vt cht l lng trong ct ncnn t l hp thu cc ion ca Zeolite trong ct nc b gim. S hp thu TAN ca Zeolite tng dn v sau c khuynh hng chm li sau khi x l Zeolite c 8 gi. Sau 12 gi, kh nng lm gim TAN ca Zeolite khng cn, s bin ng hm lng TAN khng ng k tt c cc nghim thc. Hm lng TAN nghim thc 1 (0%o) v nghim thc 2 (5%o) l tng ng nhau v khc bit khng c ngha thng k, tuy nhin chng khc bit rt c ngha thng k so vi cc nghim thc cn li ti cc thi im thu mu.
3.00 2.50 2.00 1.50 1.00 0.50

Hm lng TAN (mg/L)

0
NT 1

2
NT 2

6 8 10 Thi gian (gi)

NT 3 NT 4

12

14
NT 5

16
NT 6

Hnh 3: Bin ng TAN cc mn khc nhau sau khi x l Zeolite TN2

Qua nh gi bng mt thng sau khi x l Zeolite, lng vt cht l lng trong nc th nghim gim, nc trong, iu ny rt ph hp vi kt qu ca NACA (1994), mi trng nc sau khi x l Zeolite cht lng nc c ci thin, gim hm lng cht rn l lng trong nc (Total Suspended Solid), y c th l nguyn nhn lm hm lng TAN gim i th nghim ny khng cao. Kt qu ny ph hp vi kt qu ca Emadi et al. (2001), sau khi x l Zeolite (dng bt mn) 4 gi, TAN tip tc suy gim hm lng nhng khc bit khng c ngha thng k (P>0,05). mn c nh hng n kh nng hp thu TAN ca Zeolite trong nc, cc nghim thc c mn cao th hm lng TAN suy gim theo thi gian cng t. Theo nhn nh ca GESAMP (2001), s hp ph NH4+ ca Zeolite b kim ch mnh bi cc cation ha tan trong nc l vi nng cao v cc hc rng ca Zeolite b nc lp y nn khng th hp ph cc loi kh c.
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Ti thi im thu mu, vi pH t 8,2 n 8,4 v nhit t 30 n 31oC th hm lng NH3 chim t 12,32% n 18,21% (Boyd, 1995). Nh vy khi s dng Zeolite, i vi nc ngt (nghim thc 1) sau thi gian 16 gi, x l Zeolite liu lng 15mg/L, hm lng NH3 gim i 0,24 mg/L (t 0,4mg/L xung cn 0,16mg/L). Cc nghim thc c mn cng cao th lng TAN mt i cng thp, do t l NH3 tn ti trong mi trng gim i khng ng k. Nh vy, trong cc m hnh nui thy sn, Zeolite c kh nng hp th TAN tt nht trong nc ngt v nc c mn cng cao th kh nng ny cng gim 4 KT LUN Zeolite t nhin c kh nng lm gim TAN cao nht mi trng nc ngt. Qua th nghim thm d, vi hm lng ban u 2mg/L sau 16 gi x l vi liu lng Zeolite 15 mg/L, TAN gim 88% (1,76mg/L) cn 0,24 mg/L, tng ng 1g Zeolite lm gim 0,12 mg TAN Tc dng ca Zeolite cng gim khi mn cng tng v hm lng vt cht hu c lng t nn y cng nhiu Zeolite c tc dng lm gim TAN trong khong thi gian t 8-12 gi sau khi x l, trn khong thi gian trn hm lng TAN gn nh khng thay i. Do Zeolite nn c s dng trong trng hp hm lng TAN tng cao t ngt TI LIU THAM KHO
Boyd. Claude.E, 1995. Water quality for Pond aquaculture. Deparment of Fisheriesand Allied Aquacultures- Auburn University- Alabama. 428pp Boyd. Claude.E, 1998. Water quality for Pond aquaculture. Reseach and Development series No.43 August 1998, International Center for Aquaculture and Aquatic Enviroments Alabana Agriculture Experiment station Auburn University.37pp Chen Kong Jung, 1988. K thut phn loi v s dng khong Daimetin (Zeolite) trong nui thy sn. Emadi H., J. E. Nezhad and H. Pourbagher, 2001. Invitro comparision of Zeolite and Activated Carbon as Ammonia Absorbants in Fish Culture.In Naga, the ICLARM Quarterly. Vol.24, No 1&2 GESAMP (nhm hn hp cc chuyn gia v kha cnh khoa hc trong bo v mi trng bin), 2001. Hng ti vic s dng an ton v hiu qu cc ho cht trong nui trng thy sn ven bin. Cc nghin cu v bo co ca GESAMP. No 65 http://www.Zeolyst.com/html/faq.html. (17/2/2005). http://www.fishdoc.co.uk/water/ammonia.htm (4/3/2005) http://www.badgerminingcorp.com/asp/sb (ngy 1/3/2005) NACA 1994, The envioronmental management of coastal aquaculture. An asseessment of shrimp culture in Southern Thailand. Final report to the office of Environmental Policy and Planning, Network of Aquaculture Centres in Asia-Pacific, January 1994. Reynolds W.R. & C.W. Williford (1987) Zeolite ammonia removal from catfish pond waters. Report of the US Geological Survey Water Resources Division. Mississippi University. MS. 1987. 33 pp. Reynolds W.R. & C.W. Williford (1988) Zeolite ammonia removal from catfish pond waters. Report of the US Geological Survey Water Resources Division. Mississippi University. MS. 1988. 26 pp.