pesticide which is highly toxic to fish The still not clearly underst - PDF document

SO2 'ON bHOd3N H3HV3S3H 3NM pesticide which is highly toxic to fish. The still not clearly understood. Atmospheric transport from cotton- is presently the most however, does different geographical regions particular, concentrations the immediate the Great Lakes have decreases have Midwestern sites not conceivable that env

ironmental chlorination reactions, not involving the manufacture generating materials closely laboratory and Toxaphene-like materials aqueous chlorination monoterpenes, camphene, limonene, a- pinene and 8-pinene complex polychlorinated primarily dependent exposed to product mixtures had striking less extensive substantial ch

lorination clllorinated compounds could be mistaken for biologically degraded Toxaphene Toxaphene-like mixtures under environmental conditions. the actual extent such mixtures and the degree they may samples remain to be A. and Karen A. Marley Toxaphene-Like Contaminants paper Pulp Bleaching Water Resources Center Research

Report 205, 27pp.. University of Toxaphene/ monoterpenes/ chlorination/ pulp bleaching/paper polychlorinated terpenes Toxaphene usage as 1973, year (1986) data have obtained (Swackhamer unpublished) on sampling areas. Fish Lake (a essentially undisturbed Bay (a site near the Michigan Lake Huron) contained roughly a whol

e-fish basis. indicate no significant decrease Toxaphene concentrations Toxaphene has been used Great Lakes Region since 1960's. Its use has a post-emergent corn insecticide, has also an insecticide on small grains. These uses have however, accounting for less Toxaphene concentrations Great Lakes have shown declining, even thoug

h the southern states now no (Schmitt, et (23, monoterpene derived from turpentine oleoresin sulfite and kraft with the being far the widely used. FIGURE a kraft pulp mill. pulp bleaching the unbleached operations which typically include (in strong acid chlorination, alkaline extraction, C102 Acidic and alkaline are not

combined, sewered separately. Both the acidic extracts contain toxic constituents. Diterpene resin guaiacols, chloroacetones, and other unknown have Landner et al., 1977; McKague which are high the most effluents. Among the compounds found sesqui-, and diterpenes. substances have been found outfall (Yamoka, 1979; pu

lp bleaching the acidic chlorination reaction temperature 15-30°C (Dence and conditions insure majority of the chlorine applied will C12, rather than HOCl or c~o', other water treatment procedures. When chlorine the following equilibria rapidly develop: C12 + H2 0 + Ht + ~1- + HOCl pKa = 3.4 HOC~+ H+ + oc

l- pKa Molecular chlorine form encountered solvent- cn~~taining systems and has different and greater reactivity toward organic compounds synt.hesized chlorine gas C1 other organic reaction with aqueous solution, although mechanistic Toxaphene-like compounds should There is extensive literature on chlorinated terpene

solvents (Jennings little, however, has particularly under pulp bleaching with hypochlorous aqueous acetone (Buchbaner et al., 1984). a-terpineol water (Bjorseth the environment routiriely detected in wat.er the southern agricultural regions of some analyses, was also detected samples (Stanley et Toxaphene was samples

after the 1973-74 application season the southeastern over the western North Atla~itic long range (Bidleman and the level Toxaphene usage the Great been relatively suggested that the only means explaining its occurrence atmospheric transport FIGURE 2 fish are pue HI qJosqe 03 pasn seM 1IaM uoysaauur ale3rlrso~oq

palooc~--~a?e~ Q '(r~ 'pua~u~~ '3111 'ssnI9 a3~) due1 JO~RA A~n3~aw z2.1anb a-~nssa~d wnypau ey~oueg-pe~ua3 JleM 002 a dq pa~e~aua% seM J~%TI laloyAeJ.\[n .spunoduo3 pa~eur~o1qz~ A~rlZi~q JOJ A111?~3adsa 'aIqa!TaJ I sAe~~e ~ou aJe sor7e.I ado~osr aq7 pue a1qrsy~l wopIas sr rro! +j.q aqj

9 apow I3 aql UI .auaqdaxoJ 30 sJauosr 0113- 13 u~ouy jo sauy7 uoy7ua7aa aqj 02 uosy~edwo3 pua aIqe1reAe eJJ3ads 1e~JJed aq3 uo paseq aJaM s1uauu2~sse ' sa1n3a1ou pa~euy~o~q3 ~aq%!q aq7 JOJ : s, lI3-s , '13 ' spunodwo3 pa~euy~o1q3 JaMo1 aqJ OJ paJywr1 seM ~uawu%ysse 33exa JaAaMoq 'sa

uy~o1q3 jo Jaqwnu pue Jq%ra~ ~e1n3a1ou auruJaJap 03 Jduia~~~! 02 paurwnxa aJaM e.1~3ads ssew '(8861 'qa1es) auaqdexo~ %uyd~y~uapy ~03 sysd1eue i3[\pySaJ ap~3~Jsad u~ pasn poqJau paqsr1qeJsa ue SF srq~ .paaIosaJ aq uea synad d~eqs 08-OL A~aJewrxo~dda 139 AJe~Iyde3 dq a~qe~edas ~ou aJe aua

qduxo~ 30 s2uauoduo3 002 IIQ 'suJaJJed ynad pua sauyl uor2uaJa.I JOJ sa3ua~aja.1 se pasn uaql aJaM swc?~%o~euo~q3 lu~Jd.Ia%uyj ZuyJ1nsa.I aqJ, 'MIS pua IJ q~oq Aq sw-39 6q pazAIeua pue pa~ada~d aJaM auaqdexo~ jo suoyJn1os 7302s '(~~61 'aa%~aq1aq3rg pue appng) suoqac?3o~pAq paJeur.xoIqn Jaq

qo pua s,g3d se q3ns sa3ue~sqns %uy~aj~a~u~ 611e~2ua7od u! 3uasa.1d JOU an pue aJnJxyu auaqdexo~ aql uy suoq~e3o~pdq pa~euyao1qz~ aqI uy 7uez1rjyu%ys 7sow aq2 ~61 pue 961 '191 '6s1 suer Juau%eq aq7 MIS ~od .sapou (MIS) %uy~o~yuo~ uo~ pa~~~a~ag JO (IJ,) uo~ 1eqoJ aq7 u~ Jaqlra pal3811

0:) SBM eJea .Aa OL Je %uyJn~ado apou uo!2ezTuoy uo~~3a~a aqJ u! pa33a1103 aJaM a e.1~3ads ssa~ '3, 002 IB day aJaM axnos uor pue saur1 JajsueJ7 '7~od uoTJ3acuI '(P1oq UFw 9 JaJJa) uTw/30 E 2e 30 OPZ-OSI Jo OPZ-OP UoJJ were made between uader dark conditions. every case were observed.

(cf. Table chlorination seemed to be on the length reaction and mixture was Under dark short reaction longer reaction times lo four C1 -c13 isomers 2 predominated, and up to C15 compounds were was left to react overnight (T=15 the predominant products shifted C14-C1 case the camphene remained after minute reaction tim

e and minutes it no longer detectable. Thus the reaction camphene was iuitially compounds were proceeding from the lower exposed to simulate sunlight exposure) C1 compounds were formed with mostly C13-CIgts actual sunlight complex mixture different compounds were resolved of the chlorinated products mixture and Toxaphene.

They C1 -C12 are relatively rT1 &$ c 1 ID " t] 8 1 t-'. m 0 0 H'l 0 1 r- 3 a 0 3 r ID 3 t-'. X R E d t-'. P, C R 5 n t-'. 0 X P, u f m -I w ma s.- "I- IU- c. M- E- N_ A 8-1 8- 3- 1- PI- #" .suo~x!puo3 YJRP pue xqFiy1 q3oq Japlln aues aql A1le3~seq aJaM saJnlxru ~

onpo~d aqJ -sl3npo~d pa~eun%Axo pauado A~q~ssod aJaM ~33npo~d ~oreu aqJ .pa3npo~d aJaM spunoduo3 o.lolq3yp 8 1 CONCLUSIONS Complex chlorinat.ed terpenes (similar is in Clp, acid chlorination stage bleachitig. heavily chlorinated may possibly biologically degraded Toxaphene or other chlorinated the highly ch

lorinated material proceeds the free radicals an initiator present. In the case reactions, the Pulp bleaching carried out a closed no sunlight present. There that the the pulp bleaching process react It is not known certain what initiators present, again possible. Even the chlorination terpenes were high yield processes, the lar

ge volume of may mean that quantities of Toxaphene-like material could Prodl~ction pulp is tonnes/year. 'l'he discharge of organically bound chlorine has beer1 estimat-ed at 5 kg/tonne pulp for an approximate total of (Kririgstad and Ljndstrom, only a very small fraction (- 1%) has been characterized wit11

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