‘ -‘ § ‘ I‘ ~ ——. '§ ~ § ~ ‘ E ‘ ~ _ ACCUMULATION OF CHLORINATED HYDROCARBON INSECTICIDES FROM MUCK SOIL IY CERTAEN VEGETABLE CROPS (0—: \]_x _4 I CID—Kw “was: {or the Dog». of M. 5. MICHEGAN S'FATE UNIVERSITY Salih Mene 1967 ingu- n' “hf-1 Inns 3 mam .3 ’" ‘ p; g 137mm 3 4372;53an State 3% University '=_‘..—_- - I -w, '_ THESlS ch! 91! 23 In We: amass or mm m mmm rm m SOIL I! 033““ V‘WX‘J CHOPS ty am: that Bantam analyses for 901‘, alarm. dinlénn, haptachlor. lad awarding «to undo to intact the“ W in not can, can!“ can than munch. on! in mu. «lay. and paw stall in this none. ”no man!“ an applied 61mm to 9“ nil in n“: a: 33 “no" of ”my par nor. m m M “and 1m tho I“! on in 16. 1966. 8011 who ma minced II I31 16 a! July 11 III but): not! and vague-Mo m3.“ um college-d on Am: 16 an “pa-bar 7. 1966. lb. mu- mo mum by an magma, bf mum. “ 1991M tandem“. him" “at.“ indium chi: mum of M. saunas. kph-chin. ablation. and am: can pm: It unduly high 10.10 in not not! "and with than mucus. 1e Illa ”pun m‘mcmum. aumumm—ymum 0.01). mm mud on flu out! cont-dual mrby an. «and ”on. In. ud finial hem- ” bun boa up. «an d in. madman. hu obtain“ that that «mu. cola-y. and ”um any Mu manta we: of m, «cum. mm. W. and mm tru m not! mm «m annual: huh hall 0! all. “Infield”.- AW?!“ 0" Wm HENRI). MOM rm m IOU. I! “ISA" mum CROP! 3! um: lone & mu Manta to Michigan But. [hint-icy 1- nrttnl fulfill-nut of tho matron-n: to: tho dost-u of mm or 801m Deplflmne of Entomology 1967 fiWW I mu m:- to mun qupucuuin to Dr. Iota-3.3. ' mu... bop-rm: of hmlogy. for his gamma throw: uh mm a! mo "and: and critical min-cm 0! this . ~ .flflfli'tc~ amofianmuuallupuummquum “to... man-- I. m. cumin. w: a! mug. Ir. 3; J. in... W63: may. no! a. n. A. mm. W .1 hen-aw. m «was up man:- m n- ame“ «a. and mum a an. min-”w out.“ an “up I. W. a. "you as W mu Macaw to mutual. iii Page W1“ .COCOCQ....CCOCOCOC‘OCQOQO.C...‘.......-....O-..-. lbctoru In£1u¥ac1n¢ turnlntinco and Blatrtbucton of. Illnctictdoa §..-....-.-.-....-...--....-..1-.........--... Influnaco of Ibraulattou,.Appltclttan. and Cavur Crop ----- Inna-nu of m: 1y... uni-acute. unsure. «a “about.“ «-awe-f-o-u-«uu-noon-youn-un...... 13110.net o! cultt'utton Praoctcoa --------.-..-...-.....-. lrnaclocatto- of Inn-cttcidal Inntduoc than 8011 into cm” «on--. OD-..O...“OCOOCCOOOOO-.“-.O.G0.0-..“...-.--- mm m m Conuocfiooo...oust.-.90.-..-.fioaqp-ooqo-dou “1‘,“ 0--....- Onuhuuucoooo ooogoucoooooooodooaouocgguuu Intracttoa o£.flofil 801.100 for tho nutcrninnttol o! III-cttctdal tinting: .....-..-..--......-...--.-.....--... Ixtroctto|.o£ Illaaetcldal Inside». fro-‘Vb'otnblon ------- 9010-0 Ciro-Itosrlphlc Clotnwflp of Iatracc. .....-.....--.- “. ammufly mlnt. ucuocmaoconoocnnocuochQ-coann m” m Dims!" ‘0.“'-G--ICC-ccuo‘oouéccnoooccoaouuon-.- “‘1“. m ‘ton'. on."cacao-ouncann-ouc.-.o.¢ooonuoouu- “l’t‘u‘ “M cocoooom-Qononnoonoouuoo coo-uncoonuooo iv 1 11 11 17 18 18 19 21 21 23 .— ,— -u m....._.— _...-..- t —~— oun— ~——~.- .....‘._ .——.~ Ml um an 0! W (met-Ind) Page Mt‘¢t‘.! ”I’m 1. “t1. fmonocuoucucom.-.?26 mung-1 hum 1n the manual“ ---«--------«- 29 m Onoconuunanon-um...-”onwabooonooo.cooooooo--. 33 mn acuoéuooounoconon.--«as..-on-“oooococooqoooooucaup-- 34 hblc 10w 3-1. 1-1: 1.18! 0! ms m1. 1 p... I. f mum Foundation and In. of Application m”... 12 2 - “Inn Man Hana Cont-at 01 um.- m-«v-«umu-n 22 3 - Anna 0! humid-1 hum W In luck I.“ ....... 28 t - ”up! Macao. “ 1a 7.00qu ~mmm-w 30 vi km or In!!!” ”a. nun our. .mouuuocoumba 14 x 0 PM: “‘1‘” "nun-woman- m WHO-”um... 6 2 - Vogue-b1. 8m tn Hon ............. 1 vii 2-! 91': eh! en ft: m I“ M I011 INTRODUCT ION l‘ha tam "puticida raaiduaa" ratara to dcpcaita of cm or non paticidaa. and poaaibly their natabolitaa, on or below tha mtaca of a biological and aft»: adibla anhatanca (1.1.1:. 1966). tha mama of pacticidal miduaa in out anvircnnant haa craataa ”I“ that aura auburn hcfm tha introduction of anthatic chaniaala to! past central. According to Liak (1966), naticidaa taco-a nauuu dimtly or indiractly; by dim: application on crop. or animala. plant nptakc from tract“ «11. drift a: tn 0!! (rc- adjaccct W «A... and ”-9th cant-ninaticc. anch aa miduaa in scat. milk. and agga pickad up from bad cantaining taaiduaa. The com. of DDT raaiduaa on food waa capottad at laaat aa aarly aa 1%! and vaa fix-at aha-u in nan in 1948 (Bayaa. 1966). In ramt yam than haa been an public ccncarn “gard- ing tho autcnt to which ”atlaidal miduca arc found in wild lita. Nat-a (1966) notad that raaiduaa of chlorinatad hydrocarbon inaac- tlcidaa an M in ui-ala W tha world. Chlorinatad hydrant-baa icaacticidaa. which paralat for aural yam. an ma paraiataat than umoyhcayhom chanicala vhcaa halt-lim in Calla "up from dcya to acmal neutha (Lichtauataic. 1966). Insect the: anti mm mm 1am: film 1m I 110101 mph 11m Ma 1 Mill. "sou 111601} 10 d“ th. P1 lichtt m W .31....” mm“ 9.12 2.1.92.2...“ r tin 2!. W3. Boila ara baing contaminated aithcr through ”fallout" attai- crap apraying for inaact control or through dim: aoil trut- Iaat with lumticidaa. ”untamed c! inaaoticidcl rniduca in aoila dapauda on a minty of factor” primarily tha inucticida itaalf. rata of appli- cation. lmlaticn, can: crop that came» ”utilisation a! tha iaaacticidaa ma tha ”11. «11 typa which data-1m binding or "Ruins of the inaacticida. tauparatura which inflame» both the 1-» through ”utilisation and tha breakdown at tho imaticida by biological ad aha-teal facet". mm which apparatly can» a “ulna-act of thc inaacticidca Iron tho coil partial“. alarms- i‘ia-a cm smut «gradation at tha mama... and aail «mu; tin practice- that mam. tha diaappaaranca o! inacticidca “on um. 1: inc baa: ahcun that «In dittamt miatiaa of tha a.- ch arm in cell tractad with «rain inaccticidac about Vidal) ditfarant manta a! inaacticidal miduaa (LichtanatainJQGG). Mm 2! W- m. as! 9.229.! Em- “ «tar-inc tha cflact of coda as application add a com: crap on tha paraiatanca and urtical distribution of inaacticidaa in aoila, Lichtanatain at a1.. (1962) appliad aldrin and haptachlor either to tha aoil who. only at incorporated into tha aoil hy rotatilling to appraimctaly tin inch". Tun to thraa tinca ma inaacticidal mid' one: . these perm insect left c employ were: rated of res 0011 a alum into ti mum that u malt: 5101031 by the loclted cum 1-! m. f rcoidooo wcro rocovcrod tron oltolfo-cmrcd ploto thou from follow coco. Tho donoo cover crop opporontly provocto volatilizotioo of thou inaocticidol roaiduoo, probably owing to o reduction in air mot clooo to tho ooil ourfaco and to difforoocoo in ooil ton- porotoro. Volotilimioo my ho tho major footer in tho loao of iooooticidal rooiduoo occurring in ooila whoro tho inaocticido to loft on tho ooil ourtoco following application. Aldrin woo oppliod hploying {our opplicotion voriabloo. Two or thooo onlicotiooo mos omloion loft on tho ooil oorfoco ood tho cmloioo tumor- rotod into tho ooil (Lichtoootoio ot o1... 196A). rho grootoot looo o! rooiduca occurred in aoila whoro tho inoocticido woo loft on tho ooil ourtooo following an mloioo opplicotion. 'rho sraotoot por- oiotonco of rooiduoo woo found ottor granular had boon incorporotod into tho oppor 4 to 5 inch ooil loycr. rho highoot roto of aldrin oyouridotioo occurred in mloiomtrootod ooilo. It woo coocludod thot tho uoo c! on inoooticidol omloion io aoil trootnout probably rooolta in o lorgcr rooiduo ourfoco exposed to ottocko by voriouo biological. physical, ond chaiool foctoro. “may olao ahowod that tho poootratioo of inoocticidol rooiduoo into tho call was affoctod by tho oodo of opplicotion. Smollor mto of. rooiduoo woro trons- locotod into corroto grown in tho grmulor-trootod ooilo. Insecti- cidol rooiduoo from gronolor application to ooil oro not oo mil- oblo for biologicol, chcmicol. ond phyoicol brookdown ond roloaoo tot .tronolocotion through tho root oyotom into tho crop tioouo co cooporod with rooidooa froth mloioo trootmcnta oi ooil. ' ‘ Horrio cod Lichtonotoin (1961) reported that inoocticido vopou woro given off from oldrin. hoptachlor. ond dioldrin troat" od ooilo. No ovidoooo of volotilirotion woo obtoinod for ooilo W with. DDT. An incroooo in tho roto of inoocticido rolotil- isotioo from tho ooil rooultod from incrooooo in iuaoctioido concou- trotion in tho ooil. ooil noiotuo. and rolotivo humidity of air wooing ovor tho curfaoo of tho all. A docroooo in rolotilicotion woo ootod in dry ooilo cootoioios iocroooino «unto oi' oloy cod «sonic oottor and in vat ooilo cootoinins incrooolng mt! of organic oottor. “Wait-211m:- mm. mm- mm- m. Inoocticidoo poroiu longer in ooilo of high organic lotto: thou in thooo of low organic oottor cont-ht (Lichtoootoio ond loholo. 1960). During tho ozporinont. tho: onliad oldrin to Qua-t: oond. floiniiold aond. Corringtoo loom, ood mch ooilo to otody ito Motion and poroiotooco. Procticolly all tho aldrin toxicmta diooppoorod tron tho. Qoorto oond. yoooibly owing to tho oboonco of ony orgooic matter to which tho inoocticido could hovo boon bound. Tho mlloot want of dioldrio woo formed in tho Ploinfiold sand with oonoidorobly moro owing in tho moth ooil (organic matter mromimotoly 30 per-cont). Lichtcnotoin cod Schulz (1961) also found that insecticide persistence was influenced by ooil types. DDT and oldrin were found to be more persistent in a crack ooil then in e Miami silt-loom. Lichtenstein end Schult (1961) as well no Barrio (1967) hove reported that the peroiotcnco of insecticides lo effected by cell moisture. Harrio' otudy of three ooil types .. randy-loom. clay, and neck - indicoted that tho influence of ooil mioture on inoecticido bioectivity woo dependent on ooil type. The toxicity of an ineecticide in moist ooil depondo not only on the affinity of the active oito on the ooil pertieleo for the specific insecti- cide. but aloe on the ability of the insecticide to compete with water for theae active eitoo. Harrie (1964) noted that while the mineral fraction of the toil appeoro to be primarily responsible for eboorptiou in the dry etote, the presence of increasing moie- turo rooulto in deactivation of the mineral fraction. Conversely. in the pretence of couture, the organic fraction romaine highly active. Lichtenstein (1959) danonotrated that certain inoocticidee were oboorbod to the orgonic matter of the ooil to such an extent that in a neck ooil no phytotoucicity woo noticeable md the break-- down of the insecticide woo clawed down. It it also poeoible that the inaecticideo are dieeolvod in the organic matter of a wk soil and therefore are loco available for metabolism or pick-up by plante. (innocently. in a nick ooil the inacticido which to least otrongly W by the organic notter ie the moot effective and the inoecti— cidewbichianoetotronsly eheorbodbytheorgonicncttoriotdxo leaet affective. . Epoxidation of inoocticidoo in ooil to influenced by moisture and ooil type (Lichtenotcin and Schulz. 1961). Moiature enhances the releoee of volatile insecticideo from ooil partial“ and aloe influenced the breakdown of other insecticidal by wry of hydrolyeio. in addition. attache of nieroorgmim on insecticidal chenicolo require oertoin moisturo‘oonditiouo (Lichtenstein. 1966). no clue reported that nicroorgonimol in ooil attack mime insecticideo. Dne to nicrobiologicol activitice. aldr‘in ie midiaod to ‘dio‘ldrin. Degradation of parathion one either by hydrolyoio or by reduction to it. anion form depending on populations of ooil nioroorsooima. In ooilo boring a law nicrooraenianpopuletion or in dry eoilo where W have little activity. aldrin woo retained longer we none or. nonly well ”into of dieldrin were forced frcn the aldrin peanut (nichtenotein and Ethnic. 1960). Leaching we not notice» ou in new.“ me one local: noticeeble in reach our Wain. 1958). Soil- muun m cm to he «1 mm: factor in the mint-ace of insecticidal. ho lunaticido loco woo found in m ooilo (Lichtenotoin ad Schulz. 1959). In e11 tho experimnte conducted by Lichtonotoin end Schulz (1959) the dieoppeeronce of oldrln at well no heptoohlor was comparatlvoly rapid (eldrln recover- od‘wnn'83.8 ppm.at 6'c and 13.7 ppm.at ee‘b) when the 3°11. were ammuduacwmmmmotwk.Lawmuunu%manudwm not! temperature: influence volntlllzntion and breakdown of some Wtuide. o W 2; Cultggglon m. Cultlvntlon of the soil ha been reported to increase the dlseppalunce of lnsoctlcldal residue! from tavern). types 01,0011 (Lichtenstein. 1966). Frequent toll dleklng could poee’lbl; nerve as a method torreduclng the outdo. level 0! volntllo louotlcldet ln 0011:. Young and newline (1958) dmttntod thlt hoptachlor will not acououlato to dangerous levels in cultivated tolls when applied an a call treatment or as a £91m Iptny in the want. recomndod for efficient insect control. granglocgggg 2g geectlclde; ggeldge from 32011 1:152 Gregg. Different“ in tnmttcldo absorption have been noted between various trope and even between different path of the name crap (Llchtenateln, 1966). In the past few years insecticides of the chlorinated hydro- carbon typo hm been ohm to trmlocete from‘tolll into various plant. (Ssh. and McDonald, 1957). Recently, Bruce at 11.. (1966) dmtutod the tranolocntlon of eldrln. dieldrln. and heptnchlor end it. amide into barley. corn, oats. soybeans, and peanut needs grown on heptn’chlor or Aldrin treated soll. Licgtgwfite" (:,‘ fl) “.2 he} 50a; wit” .3}; , ddne (-1, (IL. A. 3 -I."~“1 t=.l-U '3‘ .08 ”'2 Sn. Ll- (‘.~ i‘tlL Lu “:8. ”£1 cldel are translocated from CUutuUaLJLgh b¢140 Luld glam; YES"? .1 u'. 1.1.5.111 a .‘c 5.15.21 :0 It»: a “.53 -..;’ 1.1:..0 arm”, .1.- .3 b9: 33 dedfiq. M}: an} r .8 , ‘L):O, v ' ' 011;], :1“? it $1.11; -14? l a)- 1-,“, a‘ '. “‘ i .24» .1.ka an}; 1 A; ‘ Ls‘. .' .LLL..0U ”A llr"l"l ‘- Kc also {wand that carrots not only absorbed moxx in72::1 ,.. .‘ . . _ u- .,.<:1‘..~ . . - :. biz] ' '1 ‘ . V 1’ 5;; 1‘: ‘r I: ..‘::I“ \‘h O y'- ,3 }“- 5.’-‘n\‘ :‘.1'J l'k“‘. I.’ ‘ . z ' . 1 ‘ .. I ' . ’- ‘ 1 «:13 a: file c1nalua. than mcenr.2w .n ..e {-11. lueucLi- tissues. agree :.3;‘ W83 ..‘1 2:1 U’ 0 ride than vacer heenratena by wniru an insecticide applied to soil nay cautaug- nete Ln. nt~iel port! of plants grovn in that so}; are: rain or uldr:1”y1aua1 ixw' 9.8n1fi.u 31 in: i 3 L gm-v;.u1hch 8'811 amount: f‘ . es' 7 :u.1 on tic L11 3-, yuT -fl . Ia the ln~ ;;122 - p k 1 ;HI' :13 L p ;L3.’.n: ta 1‘; 13’ 138‘ L; '. 3-, .13! ;;=.'..‘....“;-u?. :“'I‘eLr-~CL‘Jn (a: LI..- C.szn;-ouno t1“ -a.~.,_,l'. .m' rat: 8 followed hw translucet.ou for: the eerie; “Sit! of Cue piart (Llchfzu' stein and &;nu1z, 116“). It was observed Ldat plants gzzwn in aldrln or heptenflior tr~nted sand contained resi?;.c of uuly tk respective thxidus. $23.7“fi fn'féaZJA :53: n'o:K2f tnTlv? t L2"‘u3 aldrln "a“ p7*?‘;: fn tn; 93' 'fi tz‘ :;v;. u' ” l gt 7 in .-t to tzllty. 't {*‘0‘TI' (in I» (" '1' THE. '73:; tithit-L'tfg‘n o." be; techie": and capacielly ~ .‘ I .~ 9 .. Q . _ ' I C _ Q " _ ('1'. 1:. ..n ‘ pet-'41:. Lu l-y‘I-tt‘;¢.4 l -ULLL‘LKO with t;¢1£-ud and heptachlur egoxlde treated send, snowed rue :everse experiment, only dieldrin or heptachlor epoxlde in the aerial parts of the planted. Aldrin or heptachlor residues ocmld not be detected in either the sand or the plant tissues (Lichtenstein, 1953). . Pee plant: atom in and treated with turban-14 labeled DDT did not that any trmolocetion of. this insecticide (Lichtenstein and Sm. 1960). Lichtanitoln (1960) showed that oldrin we; more rapidly converted to dicldrln in soils than was hoot-chlor to it! amide. Also. the residue data obtained from crop analyses indicated that the tat. of cpouidntion o£ eldrin ‘and heptaohlor within tha plant tissue was in any on»: very oinilar .md appeared to be dependent upon the particular: crop. It as preposed that thin could be due to the pram of certain biological system which may effect the epanidation of aldrin and heptochlor or to Mount Won rates for the parent oompomde and their widen from the toils. . Unpealod Watoee were found to bontain higher levels of mammal; residues than any other crap except Motl- Residues of DDT. chlordane. eldrin. and dieldrin have been than to persist in sandy loan for at least three : yearn (Terrie dd Ingolahc. 1953), They 11” indicated that chlordane and dieldrin were in potato“ three years after the soil was treated with these chemicals. Gannon and Decker (1958) found that a one pomd per acre treatment of aldrin on alfalfa yielded aldrin residues which had diaaipated to 0.1 ppm eight days after Spraying, while the dieldrln produced took 25 days to drop to this lovol. This in of mortanco homes the epoxido is the more persistent of the two. Glnsaer (1955) ban further show that carrota taken from aldrin treated beds bore dieldrin residues. Such comroruona my be advantagoma for insect control. tine. the conpmuuis produced are not only toxic but also or. more paralatent than are the parent materials. They may explain the prolonged insecticidal efficiency obtained in soils treated with Aldrin and hoptachlar (Gannon and Bigger. 1958). " A knowledge of tho intricate processes of pesticide metabo- lism is the key to tho development of morn selective pestloldao, to the study and solution of the important problm of peat room-- can“ to puttcmea. and to tho developmnt of biodegradable pesticide: that will not cause problem of environmental contamina- tlon” (Matcalf. 1966) . 10 IQTERIALS AND if. THODS ' The Michigan State University Muck Experimental Farm located in Clinton County epproximstely ten miles northeast of the campus mused forthis study. Inspection ottha formusedmnot previously tmted specifically with my insecticide. DDT and deild-rin sprays used on adjacent cross had drifted onto it. however. the land had not been cultivated prior to this study. Selection of this port of. the form was based on the law insecticidal 'contminetion. Soil and hegetcble‘ couples were analyzed in the fisticide monarch Laboratories ofi the Entmlogy Department of Michigan State University.” not, eldrin. dieldrin, chlordane, md heptcchlor were applied in water it 23 gallons of spray per more on May 16, 1966 (Table 1). The fwd was disked lightly imdictcly after insecticide 'epplicsu tion to incorporete the insecticides into the soil. Plot outlines mchowninrigure land 2. " 55%. Soil couples were collected on July 11. Augist 16. and Septerber 7. 1966. Samples were obtained with 3 soil auger and ten 3/4" by 6" cores were randomly collected from each plot. the samples were placed in polyethylene bags and stored at 45% until cnslyzed. The mining staple was kept st ~15.C for further nib-empling in cm referee analyses were necessary. The data for each sample were recorded on laboratory record sheets. 11 1‘ ‘P‘A‘éph' Table l. Inoctioido formulation ad lot. of Application W W 99‘! 3 I. c. Chlordane I I. c. hackle: 2 I. C. Aldrin 2 I. C. Molina 1.3 I. c. Untrootod ......... W... 30 lb. 10 gal. 12 15. 1t 91. 6 1o. 3 «I 6 1b. 3 ill. 6 lb. A gal. * “hm inaction!“ won oppliod in rotor at 23 gallons of array par ocro. 12 mm. 1. III. “laced “all no “Vidal into mu sowquar-nuuaumom “HM“ in» us so» 23 {at plow. Mylo: tau-mummmu vifimhhlmmmm m mama.» WI. our“. “our“. mm. and W102. clout tint on ruthenium—outflow. thou. Mficplouhopri-rily hula-don! muamotmmwm «luv-tun. to: not at a. Mn. an... 25‘ ‘ fildnhn 291 #4 reate 77A Hulda; 0mg n W Wt. Aoflntrgatgd Aldrin wvwx— DDI;;e+ 53’ ‘14 Figure 1. Plot Outline East Plot Middle Plot West Plot liar. 1.! WI- com in no 02 tho plots. color-y, you“, and two "riot“. of carrot-”tor. planted in ouch plot. u.- if n O 5093. no; t. 3,98. 16 Vegetable Imple- were obtained on Mguot 16 and Septflor 7. 1966. Tboy «oh consisted of tooproximtcly two pounds of randomly luloctod‘vogotobloo. ho 5mg. you obtained from tho outor ' row of nob plot. ‘ I; ' i .Vogotablu were Itorod at 45.6 until coolyoio. During only“: of tbo'ylant “who, it no moron-y to roducc tho vog- uu mm in .1»; mm they um mum. run m m. by tuning the vogctoblu and randomly «looting 100 grams of tho alto“ for analysis. Tho root of tho canplc in tho bag was otorod W ‘t 4.5.0. mommmmmaw “mi mmmmmwmmmmm urn 0W rmdmly Iron “Karat aim a! has and wished mmmrrlmyurm. ngrmmbomwisbodmd “Whommudotmmmwntuu. quumw-m calm: (hamxlooproponol. 3:1) 'mmnmzoomumunamnuumm m a Enroll wrist-notion obokor for 20 minim. After “tuna clam-to alloutboorscuiomdaqmm loyarotoupnrato, tboorgmin loyormdcomtodintooooparotory funnel. Tho ox- Mammodtwmtmoningzoomofhcmtm- ,woylnol and decanting tho organic layer «oh that into the 1-7: appropriato separator)! funnel. The isopropanol in the combined «garlic attract! woo removed by washing with distilled water 6 or ,7 than (until no odor of alcohol could be detected). The olohhol-tm homo woo dried over anhydrous sodium oulfato (10 to 20 arm) for thirty minute: to remove any water and was thou ultorod through Whotmon No. 2 filtor paper into o 500 m1 coda-ted cylindor. Th0 mm: of oxtraot was recorded and it on thou concmtrotod in o Kudorno-n-nioh concontrotor to opprmri- umly lo o1. . W 3; gnaoctigida; m 513 Zeggtgbleso A oimilor oxtroction proceduro woo and for tho vogotobloo except that tho I‘licod 100 gram oomph woo blondod in a war-log Blondor for thrco uimtoo with 400 ml of "tho oolvcnt. Tho oxtroct m mom-on ond then filtered into o oeparatory fmnol through o gloo- wool plug. Tho comma: was rinsed with 50 ml distilled ntor oath than. which was also filtered. K oloan cohtoinor was mod for ooch oomplo to provont crooo-contunmotioh. M W W 2: W An nbnorben: mixturo o! Florioil® l Colitfi, 5:1. deactivotod with up to 12% motor cud otondordicod for olution proportion with nothoxyohlor woo and for calm clean-up of tho extrwto. Ono centimeter of onhydrou oodium oulfoto. 10 gram of the Florioil l Calico 18 and 1 cm coht‘imtor top layer of? Modulus radian oulfiato were placed in o clam 22 m a 530 m clwoaatosmphio colum. rho com wmttodwithhamoondoirhuhbloointhoaboorbontlmr wont-modbytoappinathocolm. mumsmouomdtodroin fmthoculmmtilitraochodthotopofwouppcromm W. mcmwmumemmmmom ammummmumoummom ddodtothocolmo ism-alwlmwlomokm‘mooam mammmmummuimumwm Mmmumlmlmmmammmmmml- laminar. mmfimoddodtothooolunmilsoonm oollooudlamwlmlo nook. Amumaexmuum uflon®liuodcowmtuwmhtfuomuomuomo mmtmmmeummomm-mm Wear. Mm.mohmlancmtrwodwtoso mumionwithootmofon. ommmiwdmimdwithuolmmmon mmmwm‘mmummly. thorouoimfi mmmwmmbmwuzso'c. mmwmhmuzoo‘c.wmmw Mmm¢325°co mnumaholn-mdmma l9 40 ml/min through the column and at 120 fill/bin for the discharge. Using coz. the sensitivity was maximized. A two microliter aliquot of the domed-up extract was injected into the column uoing o Hamilton lWroliter syringe. Stmderd oolutiono were injected into the zoo chrometogreph to permit quantitative analyoeo to be made. Free the peeluobteined. otmderd out." were redo each day oempleo were run end reoiduee present in the oompleo were quontitoted. 20 PESLLTS AND DISCUSS I'll w _e_n_d_ Storage. The smnple analyzed must he representa- tive of the crap, product. or soil impacted and for this reason a sufficiently large simple must be taken (Zoeig, 1963). Obtain- ing a rmdom sample gives material in the field or plant on equal chance of being selected for the analysis. thus providing a repre- sentative sample. Rmdom couples of one-half to one kilogram were obtained for the chemical analyses. i The quality of some tissues changes during low temperature otorags and their enelysis should be convicted in the shortest possible interval after sampling (Sutherland, 1965). Due to the nun- bar of samples involved , analyses could not be completed on the day of collection and samples were frozen until analyzed. "This should be taken into consideration as possibly altering detected pesticide]. residue values. Insecticidal residue levels were calculated on s dry-weight basis. Soil samples as collected may very widely in mois- ture content. thus results are usually calculated on the dry-weight basis (Teasley and Con. 1966). Average percent water content in the amiss is tabulated in Table 2. The soil contsined enough moisture ( mr 50 percent ) so that it was not necessary to add water, as is reccmndcd for soil samples containing less than 25 percent water, to insure Optician extraction of insecticidal residues (Shell Chemical 60;, Analytical Method ModS/GA" 1964). 21 Table 2. Average l’ercont water content of swine lupin “11.3“" ““1111. out 16, me 53 _ as no so so ”to 7. 1966 51 7‘ W 73 ' 79 . My ooil eagles are Collected on July ll, 1956. 22 Analytical Methods. Most analytical procedures require a. solvent extraction of the sample prior to the actual analysis. Any extraction depends upon 1 high solubility of the chemicals in the solvents used and intimate mixture of the solvents and pesticide (Gunther and Ellen, 1955). The method employed to ex- tract pesticides from soil and plant material was either shaking of solvent and sample or blending of the sample with the solvent using s Waring Blender. This blending provides for the quantita- tive removsl of internal and external pesticidal residues. Originally, blending was performed using s single. non-polar solvent. This type of extraction has been shown to be inefficient for pesti- cides end to produce quite vsrisble results. The blending technique employing a cmbinstion of polar and non-polar solvents has been shown to give both high extraction efficiency and consistent results (Wheeler end Freer, 1966). Boxenezisopmpsnol (3:1) mixtures were used for extraction of all samples in this project. The isOpropsnol was used as a point solvent to form a hanogeneous mixture with the plant juices or soil moisture and thus extract the polar plant or soil contents. The spolsr materials in the samples partitioned into the non-polar (hexane) solvent phase. Home will extract most of the cmonly used chlorinated hydrocarbon pesticides (McKinley et sl.. 1964). The distribution of the insecticide between water- slcohol-hexsne, as used in this method, has been shown to be entirely 23 in favor of the hexane phase (O'fionnell at al.. 1954). Thus, little less would be eXpected during the subsequent. step when the alcohol-water layer was discarded and alcohol in the hexane layer has washed out with water.) Bmver, a certain amount of insecti- cide could be lost during the extraction by incomplete extractinn due to insecticide binding with plant canpments. slight solvent leakage from the blendor, and materials adhering to the containers. Column chranatographic clean-up of extracts was done to separate the insecticide firm interfering plant materials before gas chromatographic analysis. The purpose was to reduce the inter- fering materials to a negligible mount. especially the metal- ccntaining compomds such as chlorophyll. Metals are known to re- tain chlorine molecules of chlorinated materials to some extent in the gas chrmtographic inlet. thus reducing the accuracy of the determination (O'Donnell at al” 1954). Column chromatography of extracts of glycerin-free crops over a magnesia (Florian.® a Celita®) colunn removes the pigments and mat of the wares (O'Donnell at al.. 1954). Gas chranatography was used for the residue analysis. It is a method of separating materials based on partitioning of the materials between a gas and a liquid or a solid phase. Some of the basic problems encountered with this method are mentioned in the following quotation. ”Gas chromatographic techniques have problems 24 of altered mobilities and resolution due to extraneous material. These materials may also adhere to the interior of certain detectors with e resultant loss in sensitivity. These problems are enhanced due to the required repetitive use of columns and detectors" (McKinley at £11.. 1964). Chlorinated hydrocarbons and crgenOphosphates can be separated chrometogrephicslly and detected quantitatively by a single procedure. The success of gas chromatography for these applications is due in part to the fact that the detection systems distinguish pesticides from other organic compounds normally found in the samples (Giuffrids end Bostwick, 1966). There are many reasons for less than absolute quentitetion of pesticidsl residues by gas chromatography. Among the more obvious reasons are the following which were numerized by Cessil in 1962: a) thermal decomposition or ismsrizetion in the injection block or column, b) catalytic activity of the aluminum alloy used in the block or column. c) catalytic activity of the solid support in the chromatographic column. and d) the liquid substrate in the column is not ideally suited for all pesticides. All these factors can contribute to low recoveries. Residue results were calculated according to the following formula: 500 3: ppm from standard curve ppm in semis - w W dry weight of sample in grams 25 Data obtained from analysis of soil and vegetable samples are presented in Tables 3 and 4 whnlltthe figures indicate parts per'million of residues found in soil treated with certain insecticides and in “saunas grown in the soil. insecticidal Residues.ig'§gilg. The insecticidal residues in the muck soil in which vegetables were green and which had been treated with DDT, aldrin, dieldrin, heptachlor, and chlor- dane showed the expected rapidinitial decrease followed by a slower disappearance. Later, heptschlor treated plots showed a slight increase in the total amount of residues detected. These latter results are not easily explained. DDT. aldrin, dieldrin, and chlordane residues decreased during the experiment in the plots treated with these chemicals. Loss of aldrin and chlor- dane was somewhat faster than that of DDT. dieldrin, and heptachlor residues. Table 3 summarizes the residue levels for soil samples collect- ed on three dates. DDT residue levels were the highest of the five after the insecticides had been applied and dished into the toil, followed by chlordane, heptachlor, dieldrin. and aldrin, in that order. Untreated plots showed contamination by DDT. its degradation products, and trace amounts of aldrin and dieldrin. The amount 26 of aldrin epoxide (dieldrin) found in each aldrin treated plot was larger on.August 16 and September 7, 1966 than on July 11, 1966. It appears that aldrin was converted to disldrin in the soil as was heptachlor to its epoxide. Decomposition of DDT to D131) and DDS also occurred. In general, all the insecticides applied to the soil woudd persist for appreciable periods in the muck soil. Chlordane and aldrin appeared less persistent than the others. These insecticides are probably lost true the soil mainly by chemical degradation, volttilization. or bacterial decanpoai- tion. Generally. these factors are influenced by temperature, however. this is not easily demonstrated in this project be- cause the disappearance rata did not increase during the manner period with its high toweratores. Leaching is responsible for little loss of. chlorinated hydrocarbon insecticides from soil and does not carry appreciable mts of residues to deeper soil (Edwards, 1966). Lichtenstein (1958. 61) showed that less insecticide was leached in soils rich in organic matter than in mineral soils. Results indicate that the insecticides were bound by organic matter in the muck soil. Edwards (1957) obtained a highly significant correlation between the retention of aldrin in soil and the organic matter content of the soil. Harris (1964) indicated that the influence of organic matter in the soil can be 27 Table 3. Ataom'lta of Insecticidal Residues Found in Mum: $011. (in ppm, dry weight: basis) Sample Collecting, Hepha- Da tea DDT Aldrin Dialdrin ch30: Chlordane u—A— 4 _¥ .___;. #4. A._ __. w J01)! 3.1, 1:66 57.101) 7.6(A) 9.60.) 11.005.) 23.30;) 51.3(3) 6.2(2) 9.1(3) 10.8(3) 23.3(2) 34.6(M) 3.2(M0 7.1(m) 13.1(M) 22.6(M) 55-400 8.5(3’) 12.60:!) 9.00!) 19.40:) Aug. 16, 1966 33.7(1) 2.801) 6.2(A) 3.201) 6.1(A) .0(E) 0.6(3) .301) 17.204) . 10%) 0.606) 61.3(3) 4.5(E) 8.1(2) 21.0(M) 1.6(M) 8.5(H) 30.1(w) 2.4(W) 1.5(w) UWO Sept. 7, 1366 16.80%) LUCA) (LUCA) 4.50.) 0.2(A) 17.103) 1.503) 6.20:) 6.00?) 0.901) 20.3(M) 0.8(M) &.1(M) 0.0(M) 0.1(M) 13.0(U) 0.8(w) 1.7(W) 7.5(w) 0 4(2) Note. A I Average 8 - East plot. M '- Hiddle plot U In West plot 28 regulated by soil moisture. The organic matter content of the soil strongly effects the amount of insecticide absorbed in moist Ioil, honever, in dry soil it has little effect. Harris and Lichtenstein (1961) found that less nldrin.wae lost by volatilize- tion from wet ooil rich in organic matter than from mineral eoile. The highest level of insecticidal residue found in the soil was DDT which bee been shown to be the least weter-eoluble. The sole- bilitieo of the other insecticide. need are. in order of increas- ing solubility, dieldrin, chlordane, heptechlor. and eldrin, which corresponds in general with the order of their persistence. Harris (1964) concluded that effectiveneeo an e toil insecti- cide was inversely related to water solubility. According to Edwnrde (1966), microorganisms are more active. in wet than in dry coil and this can can” faster disappearance of insecticides. In thin experiment, nicroorgenim or other factor. effected the epoxidation and degradation of the insecticides. insect icicle; Reaidgos 33 £119. Vegeggleg. Table A aumerizea the residues of DDT, eldrin. dieldrin, heptechlor. and chlordane found in carrot- (Gold Pat: and Denver 126), potatoes, and celery for two newline deteo. Crops grown during the owner of 1966 in the treeted plot. contained measurable amount! of the respective pesticides or resulting product: when analyzed. In general, the 29 "fivue &. beacon. ow unannnnnweee meson no