R O C Z N I K I G L E B O Z N A W C Z E , T . X I X , D O D A T E K , W A R S Z A W A 1968
JA N U S Z O STR O W SK I
THE ELIM IN A TIO N O F H ERBICID ES CARRYOVER EFFEC T BY T H EIR A D SO R PTIO N ON ACTIVATED CARBON
In stitu te of O rganic In d u stry, W arsaw
D iuron an d sim azine herbicides e x h ib it long resid u a l a c tiv ity and w ould th e re fo re be hazardo u s to sen sitiv e crops in ro ta tio n system s [1, 2, 6]. T h eir resid ues m igh t p ersist in th e soil and in ju re sensitive crops ro ta te d w ith p re -e m e rg e n tly sp ray ed p lants. R esidual c a rry o v e r of these herb icides ap p eared to be c o rre la ted w ith tim e, ra te an d m ethod of application [3]. K now ledge we have gained so fa r ind icates some pos
sibilities of liq u id atin g th e side effects of excessive accu m ulatio n of che m icals in soil [6].
E specially th e in te g ratio n of ph ysical and chem ical m ethods are v e ry prom ising in th is field th o u g h little success has so fa r been atta in e d . C a s t e l f r a n c o and D e u t s c h [5] rep o rted th a t in ac tiv a tio n of si m azine w as accelerated by ad dition of calcium po lysulfide to soil an d Z e m a n e k [11] noted th a t activ ate d carbon red u ced the p h y to to x icity of a tra zin e b u t in fo rm atio n on possibilities of soils am en d m en ts by in tro ductio n of th e chem icals and on th e m echanism of such am en d m en ts is lacking.
T hese stu d ies w ere an a tte m p t to assess th e role of a c tiv ate d carbon as a soil am en d m en t for sensitiv e p la n t grow ing in soil containing diuron or sim azine.
M A TE R IA L S A N D M ETH ODS
M u stard bioassays Sinapis alba L. w ere used to follow th e elim in ation of d iu ro n or sim azine residues in the soil. W axed p ap er pots w ere filled w ith 0.5 kg of coarse sandy soil. This soil ty p e w as used in all ex p erim en ts describ ed here. The m ech anical analysis an d organic m a tte r co n ten t of th e soil used is given in Tab. 1.
236 J. O strow sk i
T a b l e 1
The mechanical a n a ly s is and organic n a tte r content of the s o i l used in d i f f e r e n t experiments Sand 1 -0.05 mm S i l t 0 .0 5 -0 .0 0 2 inm Clay 0.002 mm Organic matter ~rO 88 10 2 0.83
H erbicides and ac tiv ate d carbon w ere applied in w a te r suspensions to th e soil su rface of th e pots (herbicides 1 p pm a.i. and ac tiv ate d carbon 2, 10 or 50 ppm on a ir d ry soil w eig h t basis). Carbon w as applied n e x t d ay a fte r herb icides tre a tm e n t. T hen th e pots received th e follow ing w a te r ap plications: 15 su rface m ilim eters of w a te r in 5 equal portion s w ith 3 or 2 days in te rv als. T he pots w ere seeded w ith w h ite m u sta rd s 15 days a fte r herb icides application. T w en ty seeds of m u sta rd w ere p la n te d in each pot. F o u r pots w ere p la n te d for each tre a tm e n t. 14 days a fte r p la n t ing a p hoto g rap h w as tak e n an d th e n m u sta rd s w ere cropped at th e soil line and the fresh w eig h t determ in ed .
S tu d ies on th e ad so rption of d iu ro n and sim azine on soil am ended w ith activ ate d carbon by ag itatio n of th e herbicides w ith 4 : 1 w a te r — soil m ix tu re or in soil colum ns u n d e r leaching conditions w ere ad d itio n a lly c arried out, and th e effect of am en ded soil as ad so rb e n t on th e fre sh w eig ht of m u sta rd tre a te d w ith d iu ro n or sim azine before or a fte r th e con ta c t w ith th e ad so rb en t w as ev alu ated . The adopted con cen tratio n s of h erb icides in ppm a.i. w ere as follows: 12.5 ppm in w a te r suspension an d 50 ppm if calculated p er air d ry soil w eigh t basis in a closed sy stem u n d e r shaking conditions an d 25 ppm in w a te r suspensions w hich corresponded ca 15 ppm p er air d ry soil w eight basis u n d e r leaching conditions. The d e p th of soil colum n 3 cm. The soil w as am en ded w ith 500 or 2500 ppm of activ ate d carbon. The solutions b efore or a fte r contact w ith th e ad so rb en t w ere applied on th e su rface of q u a rtz sand seeded w ith m u stard s. All tre a tm e n ts w ere rep lica ted fo u r tim es.
R E SU L T S A N D D IS C U S S IO N
The re su lts of th e elim inatio n of d iu ro n and sim azine resid u a l c a rry over by activ ated carbon (Carbopol H-4) are show n in Fig. 1 and 2.
T he e lim in a tio n of h erb icid es ca rry o v er e ffe c t 237
A stro n g in ac tiv a tin g capacity of carbon w as show n in th is ex p erim en t. T h e g ro w th in h ib ito ry effect of sim azine an d d iu ro n residues declined as th e carbon c o n ten t in th e soil increased. 2 ppm of C arbopol did not c o n tra - to x ific a te th e resid u es of herb icid es ap p lied in doses to get 1 ppm a.i. con c e n tra tio n on a ir d ry w eig h t basis. A t 10 ppm tec h n ica l carbon c o n c en tra tio n h erb icid es resid ues w ere still som e toxic to m u sta rd as in d icato r
Treatments
Fig. 1. E ffect of a ctiv a ted carbon as a so il am en d m en t on th e fresh w e ig h t of m ustard (S in a p is alb a L. gro w in g in so il
co n ta in in g 1 ppm sim a zin e (s) or diuron (d)
Fig. 2. C o n tra to x ifica tio n of sim a zin e and diuron resid u es in th e so il by a ctiv a ted carbon 50 ppm
crop. The re su lts confirm ed th a t n e ith e r d iuron nor sim azine p ersisted in av ailab le fo rm a fte r in tro d u c tio n of activ ate d carbon in 50 ppm per d ry w eig ht of soil. T he am o u n t of in ac tiv a tin g m a te ria l needed to in ac tiv a te th e resid u es of herb icid es in th e soil w as 50 tim es bigger. The value of th is in ac tiv a tin g q u o tie n t fo r atra zin e e stim ated by Z e m a n e k [11] u n d e r la b o ra to ry an d glasshouse conditions w as about 200 and in th e field over 100. O u r glasshouse tests do not elim in ate th e need for m ore ex te n d e d e x p e rim e n ts u n d e r field conditions. Soil in corp oration of Carbopol p ro
238 J. O stro w sk i
b ab ly w ill im prove in ju r y red u c tio n and give some possibilités for fu rth e r low ering of c o n tra to x ific a n t q u a n tity used. The a c tu a l resid u es of diu ro n or sim azine can be e stim ated by a n a ly tic a l or biological m ethod an d th e am o u n t of C arbopol n eeded to in ac tiv a te th e residues defined.
The in flu en ce of soil am en d m en t b y a c tiv ate d carbon on th e adso rp tio n of d iu ro n an d sim azine an d on re la tiv e g ro w th of the in d icatin g m u sta rd p lan ts is show n in Tab. 2.
T a b l e 2
I f i e c t oi amended s o i l as adsorbent on the f r e s h we ight o f mustard t r e a te d with diuron or simazine
before or a f t e r the c on ta c t w ith the adsorbent
Adsorbent r 1 Liustards i r e s h weight in j % of c o n t r o l j in a c l o s e d eq u il ib r iu m system under l e a c h i n g c o nd it ions ; Liuron in water ■ Before c o n ta c t 3 3 . 7 4 0 . 3 1 Unamended s o i l 4 3 . 2 4 5 . 1 ! S o i l amended 500 ppm С 105 .7 o 7 . 9 ! S o i l amended 2500 ppm С 1 0 1 .9 11 3 .2 ' Simazine in water j ! Before co n ta c t 3 5 . 5 3 4 . 9 Unamended s o i l ; 5 7 . 0 Э9.5 S o i l amended 50C ppm 0 105.3 3 3 .3 S o i l amended 2500 ppm С j 11 5. 3 109 .7 Water Unamended s o i l 1 2 2 .2 121. b S o i l amended 2Û0 ppm С 10 8. 8 1 0 4. 2 S o i l amended 2300 ppm С 1 1 2. 2 i 11 3 .2
A ll am en d m en ts of th e soil by activ ated carbon ad dition increased herbicides adsorption as w as in d icated a fte r eq u ilib ratio n on th e ro ta ry sh ak er an d in soil colum ns u n d e r leaching conditions. O nly soil a m e n d m en t w ith 500 ppm activ ate d carbon did not elim in ate th e p h y to tox ic am oun t of diuron fro m in p u t solution u n d e r leaching conditions, th o u g h th e m ovem ent of th is herbicide in soil pro file is lim ited [9]. Som e resid ues of sim azine at th is sam e soil co rrection could be d ete c te d in th e p erco late too. H erbicides b an d leaching dow n w ards in th e soil am end ed w ith 2500 ppm activ ate d carbon w as h ig h ly lim ited by adsorption. No h erb
ici-T he elim in a tio n of h erb icid es carryover e ffe c t 239
des could be d ete c te d in percolates. S uch th e a m en d m en t in re a l soil is even p erh ap s too rich for n e a rly all p la n t species send dow n th e ir roots v e ry quickly, often fa r deeper th a n d iu ro n or sim azine are able to p e n e tra te. C o n tam in ated soil zone and rooting h a b it an d fu n ction should be tak e n into consid eration discussing th e problem s of soil am en d m en ts [7, 8].
W orking u n d e r s lu rry conditions w e have in d ic a te d b y biological eva lu atio n th a t th e w hole am o u n t of d iu ro n or sim azine w as adsorbed by th e soil am end ed even w ith 500 ppm a c tiv ate d carbon. It m eans th a t 10 t i m es bigger am ou n t of co n tra to x ific a n t th a n h erb icides residues w as q u ite su fficie n t to adsorb an d elim in ate th e u n w a n te d resid u es of those h e rb i cides u n d e r a g ita te d s lu rry conditions.
Soil am en d m en t by ad d itio n of a c tiv ate d carbon w ould lessen h azardes fro m carry o v er. S uch th e in te g ratio n of chem ical w eeding and soil a m en d m en t creates new possibilities for application of d iu ro n an d sim azine in a g ric u ltu ra l practice. C arbopol H-4 is re la tiv e ly inexpensiv e pro du ct. The econom ics of d iffe re n t a g ric u ltu ra l crops are o ften such th a t some m oney can be used for elim ination of c a rry o v e r effect to achieve th e optim um grow ing conditions for plants.
R EFEREN CES
[1] B a k u n i a k I., O s t r o w s k i J.: B ad an ia nad p rzem ieszcza n iem się w g le b ie i n a stęp czy m d ziałan iem atrazinu i sim azin u . C h em iczn e Ś rodki O chrony R oślin a B iocen oza G leb, P A N , 1964, 60— 2.
[2] В r u n s V. F., C l o r e W. J., D a w s o n J. H.: W eed control in asparagus w ith m onuron and diuron. W ash in gton A gr. E xpt. Sta. B ull., 1962, 635.
[3] B u c h h o l z K. P.: F actors in flu e n c in g oat in ju ry from tria zin e resid u es in soil. W eeds 13, 1965, 4, 362— 7.
[4] В u r n s i d e O. C., F e n s t e r C. R., W i c k s G. A.: D issip a tio n and le a c h in g of m onuron, sim a zin e and a trazin e in N ab rask a soils. W eeds 11, 1963, 209. [5] C a s t e l f r a n c o P., D e u t s c h D. B.: A ctio n of p o ly s u lfid e ion on sim a
zin e in soil. W eed s 10, 1962, 244— 245.
[6] O s t r o w s k i J.: Z a g a d n ien ie uboczneg’o d zia ła n ia h erb icyd ów . Z eszy ty Probl. P ost. N au k R oln., 60, 1964— 1966, 155— 159.
[7] O s t r o w s к i J.: B ad an ia nad k o rzen io w y m p ob ieran iem n iek tó ry ch h e r b ic y dów . B iul. Inst. IOR, 31, 1965, 125— 34.
[8] O s t r o w s к i J.: M ech an izm y d zia ła n ia h erb icyd ów . P ost. N auk R oln., 4, 1965, 65— 93.
[9] O s t r o w s k i J.: L aboratory stu d ies on so il le a c h in g of som e h erb icid es for sugar b eet. J ou rn es In tern a tio n a les D ’É tudes sur le s D esh erb a g e S e le c tif on C ultures B ette r a v e s n arly L e Roi, 1967, 233— 37.
[10] S h e e t s T. J.: T he co m p a ra tiv e to x ic itie s of fou r p h en y lu rea h erb icid es in sev e r a l so il ty p es. W eeds, 6, 1958, 413.
[11] Z e m a n e k J.: S tu d iu m ru zn ych sp osob u in a k tiv a c ie atrazinu w pude. R ost. V yroba, 37, 1964, 959— 72.
240 J. O stro w sk i
J . O S T R O W S K I
RECHERCH ES SUR L ’É L IM IN A T IO N DE L ’A CTIO N R ESID U E L L E D ES H ER BIC ID E S, PA R VOIE D ’A D SO R P T IO N PA R LE C H A R B O N A C T IF
I n s t i t u t e d e l ’I n d u s t r i e O r g a n i q u e
R é s u m é
On d ém on tra la p o ssib ilité d’é lim in e r l ’in flu e n c e de l ’action r é sid u e lle du d iurone et de la sim a sin e par l ’a p p lica tio n du charbon a ctif — Carbopol. L ’in flu e n c e n é g a tiv e qui su ccèd e à l ’em p loi des h erb icid es fu t lim ité au fur et à m esu re de l ’au g m en ta tio n des doses du C arbopol.
L ’in tro d u ctio n du charbon a ctif eccro it le ca p a cité de sorp tion du sol p e r m e t ta n t l ’é lim in a tio n des résid u s b io lo g iq u em en t a ctifs des herb icid es.
La m éth od e proposée, d ’ajou ter du charbon a ctif au sol, rend p o ssib le l ’em p loi du diurone et de la sim a sin e en a g ricu ltu re dans une p lu s la rg e m esure.
J . O S T R O W S K I
U N T E R SU C H U N G E N Ü BER B E SE IT IG U N G DER H E R B IZ ID E N N A C H W IR K U N G A U F DEM W EGE DER A D SO R P T IO N D UR C H A K T IV E KOHLE
I n s t i t u t f ü r O r g a n i s c h e I n d u s t r i e in W a r s z a w a
Z u s a m m e n f a s s u n g
Es w ird au f die M öglich k eit der B eseitig u n g der N a ch w irk u n g von D iuron und S im azin durch A n w en d u n g der a k tiv e n K oh le — C arbopol, h in g e w ie se n . D ie n eg a tiv e N a ch w irk u n g obiger H erb izid e w ar, je nach der V ergrösseru n g der C arbopolgaben, im m er m eh r b egrenzt.
D ie A n w en d u n g der a k tiv en K o h le erh ö h te die S o rp tio n sfä h ig k eit des B odens, w a s die B eseitig u n g der b io lo g isch a k tiv en R ü ck stä n d e von H erb icid en erlaubte.
D ie v o r g e sc h la g e n e M eth od e ein er Z ugabe der a k tiv en K oh le zum B oden trägt zur M ö g lich k eitserw eiteru n g der D iu ro n - und S im a zin a n w en d u n g in la n d w ir tsc h a ft lich er P r a x is bei.
J . O S T R O W S K I
E LIM IN O W A N IE N A ST Ę PC Z EG O W PŁY W U H ER BIC Y D Ó W W DRODZE ICH A D SO R P C JI PRZEZ W ĘGIEL A K T Y W N Y
I n s t y t u t P r z e m y s ł u O r g a n i c z n e g o , W a r s z a w a
S t r e s z c z e n i e
W ykazano m o żliw o ść e lim in o w a n ia n astęp czego w p ły w u diuronu i sim a zy n y p rzez sto so w a n ie w ę g la a k ty w n eg o — C arbopolu. U jem n y w p ły w następ czy h erb i cyd ów b y ł ogran iczon y w m iarę zw ięk sza n ia d aw k i C arbopolu.
T he elim in a tio n of h erb icid es carryover e ffe c t 241
W p row ad zen ie w ęg’la a k ty w n eg o zw ięk sza ło zd olność sorp cyjn ą g le b y p o z w a la ją c na w y e lim in o w a n ie a k ty w n y c h b io lo g iczn ie p o zo sta ło ści h erb icyd ów .
P rop on ow an a m etod a w p ro w a d zen ia do g leb y w ę g la a k ty w n eg o stw arza szersze m o żliw o ści dla sto so w a n ia d iuronu i sim a zy n y w p ra k ty ce roln iczej.
Я . О С Т Р О В С К И И СС Л ЕД О ВА Н И Я ПО У С ТРА Н ЕН И Ю ПО СЛ ЕДЕЙ СТВИ Я ВЛ И Я Н И Я ГЕРБИ Ц И ДО В ПУТЕМ И Х А Д С О РБ И РО В А Н И Я Н А А К Т И В Н О М УГЛЕ И н с т и т у т О р г а н и ч е с к о й П р о м ы ш л е н н о с т и , В а р ш а в а Р е з ю м е Д ок азан о в озм ож н ость устр ан ен и я п осл едей стви я влияния ди ур он а и си м а- зи н а путем прим ен ения активного угля — карбополя. О трицательное в лия ние остаточн ы х количеств гербицидов ум еньш алось по мере повы ш ения д о зы карбополя. В в ед ен и е активного угля увел и ч и вает сорбцион ную способность почвы р а зр еш а я устранить биологически активны е остатки гербицидов. П редлагаем ы й метод п р ибавления активного угля к почве со зд а ет б ол ее благоприятны е усл ови я для ш ирокого прим ен ения ди ур он а и сим ази на в сел ь ск охозяй ств ен н ой практике. 16 R o c z n i k i g l e b o z n a w c z e
