Abstract :

In r e c e n t y e a rs th e re h a s b e e n a n
in c re a s in g in te r e s t in th e p o s s ib ility o f th e u s e o f
n a tu ra l a lu m in o s ilic a te s in a g ric u ltu re a n d
e n v iro n m e n ta l p ro te c tio n . Z e o lite s a re a la rg e g ro u p
o f (c lu s te r s ilic a te s ) a lu m in o s ilic a te m in e ra ls w ith
d iffe re n t c h e m ic a l c o m p o s itio n . D u e to th e ir u n iq u e
p h y s ic a l a n d c h e m ic a l p ro p e r tie s (h ig h s o rp tio n
c a p a c ity a n d io n -e xc h a n g e , io n - e xc h a n g e
s e le c tiv ity a n d s tru c tu ra l th e rm a l s ta b ility ), th e y c a n
b e u s e d fo r e xa m p le in th e p r o d u c tio n o f m in e ra l
fe rtiliz e rs . Z e o lite s c a n a ls o b e u s e d a s a m e d iu m o f
th e a c tiv e s u b s ta n c e s i.e . p e s tic id e s , h e r b ic id e s ,
fu n g ic id e s o r p e s tic id e s . T h e ir a d d itio n in c r e a s e s
p la n t p ro d u c tio n le v e ls a n d b io lo g ic a l a c tiv ity o f th e
s o il. A ls o z e o lite ’ s e xc e lle n t s o rp tio n p ro p e rtie s c a n
b e u s e d fo r th e re m e d ia tio n o f s o ils c o n ta m in a te d
w ith h e a v y m e ta ls . T h e h is to ry , s tru c tu re , p ro p e r tie s
a n d a p p lic a tio n o f n a tu r a l z e o lite s is p re s e n te d in
th is p u b lic a tio n , b a s e d o n th e re le v a n t lite ra tu re .
INTRODUCTION :

T h e firs t z e o litc m in e ra l, s tilb ite , w a s

d is c o v e re d in 1 7 5 6 b y S w e d is h c h e m is t a n d
m in e ra lo g is t A xe l F r e d ic k a C ro n s te d t. H e n o te d th a t
d u r in g h e a tin g , th is n a tu ra l m in e ra l in te n s iv e ly lo s e s
w a te r a n d n a m e d it u s in g th e G re e k w o rd s : d z e o
b o il a n d lith o s s to n e , r o c k . (P o la t e t a l., 2 0 0 5 ).
C u rr e n tly , th e re a re o v e r 4 0 k n o w n ty p e s o f n a tu ra l
z e o lite s , b u t o n ly s e v e n o f th e m (c lin o p tilo lite ,
c h a b a z ite , m o r d e n ite , e rio n ite ,fe rrie rite , a n a lc im e ,
p h ilip s ite ) a r e b e in g e xp lo ite d . A m o n g n a tu ra l
z e o lite s m o s t c o m m o n a n d m o s t s tu d ie d m in e r a l is
c lin o p tilo lite ; n o t o n ly b e c a u s e o f its h ig h o c c u r e n c e
in n a tu re a n d th e lo w e s t p ric e , b u t a ls o b e c a u s e o f
its u n iq u e p h y s ic o c h e m ic a l p r o p e rtie s (H u b ic k i e t a l.,
2 0 0 0 ). R ic h d e p o s its o f th e c lin o p tilo lite ,th e
s o -c a lle d c lin o p tilo lite tu f fs a r e p re s e n t, a m o n g th e
o th e rs , in th e C a rp a th ia n M o u n ta in s . It is e s tim a te d
th a t th e re a re d e p o s its o f th e n a tu r a l z e o lite o f o v e r
a b illio n to n n e s in th e v illa g e S o kir n ic a (V a s y lij e t
a l.,19 9 8 ). C lin o p tilo lite e tu ff s c o n ta in fro m 7 0 to
9 0 % o f c lin o p tilo lite a n d h a v e a c le a r c o lo r w ith a
tin g e o f w h ite , g ra y , g re e n o r p in k d e p e n d in g o n th e
p re s e n c e o f im p u ritie s . A s s o c ia te d m in e r a ls a re
m o n tm o rillo n ite , s e la d o n ite , c h lo rite , c ris to b a lite a n d
p y ro g e n ic m in e r a ls - q u a rtz , p la g io c la s e , b io tite a n d
K -f e ld s p a r. C u rre n tly , th e r e a re th re e w a y s o f
c la s s if y in g z e o lite s . T h e firs t m e th o d is b a s e d o n th e
to p o lo g y o f th e f ra m e w o rk (th e th re e le tte r c o d e ),
(M e ie r e t a l. 19 9 6 ). T h e s e c o n d w a y is c la s s ific a tio n
in te rm s o f th e s o -c a lle d "S e c o n d a ry b u ld in g u n its "
(S B U ’ s ), (B re c k 1 9 7 4 ). T h e th ird s c h e m e is s im ila r
to th e c la s s ific a tio n ty p e S B U (B re c k 1 9 7 4 ) in c lu d in g
th e c h ro n o lo g y in w h ic h z e o lite s w e re d is c o v e re d
(B a e rlo c h e r e t a l., 2 0 0 7 ).

Structure and properties of zeolites :

Z e o lite s a re m in e r a ls n a tu ra lly fo rm e d in
th e re a c tio n o f v o lc a n ic a s h w ith s u rfa c e w a te r o r
g ro u n d w a te r. T h e y c a n a ls o a ris e in th e
n o n - v o lc a n ic e n v iro n m e n t d u rin g a n in te r a c tio n
b e tw e e n th e s a lin e s o il p a rtic le s w ith s tro n g b a s ic
s o lu tio n s .T h e y a re c r y s ta llin e , h y d ra te d
a lu m in o s ilic a te s o f m e ta ls , in c lu d in g c a lc iu m ,
m a g n e s iu m , s o d iu m , p o ta s s iu m ,s tr o n tiu m a n d
b a riu m . D u e to th e ir in n e r s tr u c tu r e th e y a re
c h a ra c te r iz e d b y u n iq u e p h y s ic o c h e m ic a l p ro p e rtie s :
h ig h a n d c a tio n e x c h a n g e s o rp tio n c a p a c ity ,
io n - s e le c tiv ity , m o le c u la r s ie v in g , c a ta ly tic a c tiv ity
a n d h ig h th e rm a l s ta b ility u p to 7 5 0 ° C .T h e p rim a ry
b u ild in g u n it o f z e o lite fra m e w o rk is te tra h e d ro n , th e
c e n tre o f w h ic h is o c c u p ie d b y a s ilic o n o ra lu m in u m
a to m s , w ith fo u r o xy g e n a to m s a t th e
v e rtic e s .S u b s titu tio n o f S i4 + b y A l3 + p ro v id e s th e
n e g a tiv e c h a rg e o f th e fra m e w o rk , w h ic h is b a la n c e d
b y m o n o v a le n t o r d iv a le n tc a tio n s lo c a te d a t th e
s u rfa c e . T h e a lu m in o s ilic a te fra m e w o rk ,d e f in in g th e
s tru c tu re ty p e , is th e m o s t s ta b le c o m p o n e n t.T h e
S c h e m a tic s tru c tu re o f th e n a tu ra l z e o lite :

The use of zeolites in agriculture :

N a tu ra l a n d s y n th e tic z e o lite s d u e to
th e ir u n iq u e p h y s ic o c h e m ic a l p r o p e rtie s , h a v e
fo u n d w id e a p p lic a tio n in m a n y fie ld s re la te d to
a g ric u ltu re . T h e y a re b e in g in c re a s in g ly u s e d in th e
p ro d u c tio n o f m in e ra l fe rtiliz e rs w ith s lo w re le a s e
a n d a s c a rrie rs o f a c tiv e in g re d ie n ts o f h e rb ic id e s ,
fu n g ic id e s a n d p e s tic id e s .O n e o f th e m a in
a d v a n ta g e s o f u s in g z e o lite a d d itiv e to fe rtiliz e rs is
th e ir b e n e f ic ia l e ff e c t o f re te n tio n o f n u trie n ts in th e
s o il.T h e n u trie n ts a re re le a s e d g r a d u a lly , n o t o n ly in
th e firs t y e a r o f th e v e g e ta tio n p e rio d b u t a ls o in th e
s e c o n d o r th e fo llo w in g y e a r s . T h e m o s t im p o rta n t
n u trie n ts n e c e s s a ry fo r p ro p e r g ro w th a n d
d e v e lo p m e n t o f p la n ts , a re n itro g e n , p o ta s s iu m ,
c a lc iu m a n d m a g n e s iu m . T h e y a ffe c t n o t o n ly th e
s iz e o f th e c r o p b u t a ls o its q u a lity . Z e o lite s h a v e th e
a b ility to re ta in n u trie n ts in th e to p s o il, w h ic h a re
s lo w ly a n d g ra d u a lly le a c h e d fro m th e s o il. T h is
a llo w s th e u s e o f s m a lle r d o s e s o f fe rtiliz e r, w h ic h is
a s s o c ia te d w ith a re d u c tio n in th e c o s t o f c ro p
p ro d u c tio n .T h e a d d itio n o f z e o lite to th e f e r tiliz e r h a s
a s ig n ific a n t im p a c t o n th e c o n te n t o f a s s im ila tiv e
fo rm s o f n itro g e n in th e s o il, e s p e c ia lly o n lig h t a n d
s a n d y s o ils .. B e c a u s e th e s o il d o e s n ’ t a b s o rb
n itra te s , th e s e a r e w a s h e d o u t f ro m th e s o il. T h e
fo rm o f n itro g e n th a t ta k e s th e lo n g e s t to le a c h fro m
th e s o il is a n a m id e .T h e f e r tiliz e r o f h ig h n itr o g e n
c o n c e n tr a tio n in th e f o rm o f a n a m id e is u r e a (a b o u t
4 6 % b y w e ig h t), w h ic h is u s e d fo r th e p r o d u c tio n o f
m in e ra l fe rtiliz e rs fo r s e v e ra l re a s o n s .Z e o lite s a re
b e in g u s e d to p r o d u c e th is ty p e o f
fe rtiliz e r.P r o d u c tio n o f th e fe rtiliz e r c o n s is ts o f
h e a tin g th e z e o lite to 4 0 0 ° C .. T h e fe r tiliz e r o f th is
ty p e c a n c o n s is t o f a b o u t 17 w t% o f n itr o g e n . U re a ,
w h ic h is b e in g c lo s e d o n z e o lite s tu b u la r ta k e s a
s lo w c o n v e rs io n to a m m o n iu m io n s .A n in te r e s tin g
a p p lic a tio n o f z e o lite s is th e p ro d u c tio n o f
a n tib a c te r ia l a g e n ts . T h e y a re o b ta in e d b y
in tro d u c in g A g + io n s in to z e o lite s tru c tu re .
A n tib a c te ria l a c tiv ity is d u e to s lo w re le a s e o f th e
a c tiv e o xy g e n . S tu d ie s h a v e s h o w n th e e f fic a c y
a g a in s t b a c te r ia s u c h a s P s e u d o m o n a s a e r u g in o s a ,
E s c h e ric h ia c o li, S ta p h y lo c o c c u s a u r e u s m

The use of zeolites in soil remediation :

In c re a s e o f s o il p o llu tio n b y h e a v y m e ta ls
is o n e o f th e m a in p r o b le m s o f m o d e r n a g ric u ltu re .
T h e in c re a s e d a c c u m u la tio n o f m e ta ls in s o ils is
h ig h ly in flu e n c e d b y h u m a n a c tiv ity a n d th e r e la te d
d e v e lo p m e n t o f in d u s tr y a n d irra tio n a l u s e o f
fe rtiliz e rs . H e a v y m e ta ls m a y p e rs is t in th e s o il fo r
h u n d re d s o f y e a rs , w h ic h is a s s o c ia te d w ith th e ris k
o f th e ir in c lu s io n in a tro p h ic c h a in . M e th o d s o f th e
p re v e n tio n o f c h e m ic a l d e g r a d a tio n o f s o ils a re a
c o m p le x a n d d e p e n d o n m a n y fa c to rs . T h e m a in
fa c to r d e te rm in in g th e s o lu b ility o f h e a v y m e ta ls in
s o il is lo w p H . T h is is e xp la in e d b y th e fa c t th a t th e re
is a s lo w d is s o lu tio n o f th e o xid e s o f iro n , a lu m in iu m
a n d m a n g a n e s e a n d a ls o th e r e le a s e o f h e a v y
m e ta ls fro m th e p rim a ry a n d s e c o n d a ry m in e r a ls in
a c id ic e n v iro n m e n ts . T h e u s e o f z e o lite s in a c id ic
s o ils c a u s e a n in c re a s e in p H th a t s ig n ific a n tly
a ff e c ts re d u c tio n in h e a v y m e ta ls s o lu b ility a n d
b io a v a ila b ility fo r p la n ts . E xc e p t o f io n e xc h a n g e
re a c tio n s , th e p H in c re a s e p ro m o te s th e a d s o rp tio n
o f h e a v y m e ta ls o n th e s u rfa c e o f z e o lite s a n d th e ir
o xid e s p re c ip ita tio n .T h e u s e o f z e o lite s s ig n ific a n tly
re d u c e d th e u p ta k e o f c a d m iu m a n d le a d b y
w h e a t.S tu d ie s c o n c e rn in g th e e ffe c ts o f v a rio u s
a d d itiv e s o n a c h a n g e o f th e s o lu b ility o f
le a d ,c a d m iu m a n d z in c h a v e s h o w n th a t z e o lite s
s ig n if ic a n tly re d u c e d th e s o lu b ility o f le a d a n d
c a d m iu m in p o llu te d s o ils . A s a re s u lt th e ir c o n te n t
h a s s ig n ific a n tly d e c re a s e d in lu p in e w h ite
c o m p a re d to p la n ts g r o w n w ith o u t th e u s e o f
a d d itiv e s .

Conclusion :
U n d e r th e p re s e n t re q u ire m e n ts o f
e c o lo g ic a l a g ric u ltu re th e re a r e w id e a re a s o f u s e
fo r a n a tu ra l,in e r t a n d n o n - to xic m a te ria l s u c h a s th e
n a tu ra l z e o lite . D u e to its s tru c tu re a n d p ro p e r tie s
z e o lite m a y b e u s e d a s a s lo w - re le a s in g c a rr ie r o f
a g ro c h e m ic a ls o f v a rio u s k in d s a n d fe rtiliz e rs .
N a tu r a l z e o lite s a re e ffe c tiv e in im p ro v in g s o il
p ro p e rtie s a n d tre a tin g c o n ta m in a te d s o il. A w id e
ra n g e o f a p p lic a tio n s o f z e o lite p ro m o te s th e p u r s u it
o f o th e r p o s s ib ilitie s fo r th e ir u s e .