( A i , Figure 4). The inlet t o the tree is vlcsed. Evacuation of the furnace hy the rotary backing pump (28, Figure 3) is begun through the bypass h e . When the pressure has fallen t o about 0.05 mni. of mercury, the two-stage mercury diffusion pump .(26, Figure 3) is brought into operation, and evacuation continued until the pressure has fallen t o 5 X 10-5 inm. of mercury. This pump has a (6apacity of 70 t o 80 micron-liters per .econd up to a maximum backing presw r e of 0.35 mm. of mercury. The four-stage mercury diffusion pump (17: Figure 3) is then brought into op(.ration, th(J valve in the bypass line vlosed (16, Figurc: 3), and the line through the gas collection system ..pened. Meanwhile, t h e gas collection system has been held under vacuum during removal and replacement of the Eurnacc hoad and preliminary rvaruntion of t h r furnace unit. The motor generator is now s w i t c h d on, :mrl power supplitd t o the coil. The cirucihle temlwratui,e is slowly raised to 2200" C'., so t h a t the Dressurr in the furnace unit ~icwsnot tsxcred I micron at. any tinit,. T!iv tc~rnporatul.c~ is inaintaind at 2200' C. until thtx blank m t r has fallen to a satisfactory level;.e.. ahout 0.15 ml. of gas per hour. I t is then reduced t o 1600" C., and 3J grams of steel are addrtl to thc vrucihle. Rat,h t,cnipcrature is raised Lo t h e reachon level and held thert. L:ntil the f'lank rate has :wc*omt. (:oni t a n t . A samplc of t h e blank gas c~vnlved is no\\-takc,ri ior anaiysis.
vi nwtai in the run. Finally, a check is mad(. of the volume of the h l m k gas and a sample taken for analysis. This concludcs the run. The opparatcs has been successfull\. w i p l o y d in the determination of thc gas rontcnts of a uidr vsriety of chromium metal and chromiumalloy samples, using a steel bath as the reaction inediuni. Titanium nwtal aiic! titanium alloj-s havr also h e w siircessfully :tnal!-zcd using a stwl hath. ACKNOWLEDGMENT
Th(5 authors thank the Chief Sciciitist, Acstralian Defencr Scientific Scriice, Department of Supply, Melbourne, Australia, for pvrmission to puhlish this paper. INCHES O
U
Figure 6. Scaled diagram of furnace tube and crucible assembly
Thc systc.111 is evacuatcd and the first metal samplc addcd t o the hath. T h r gas eiolvtd from the metal sample is i.ollec*ted and measured, and a suitable volume transferred by the Toepler puml) t o a gas holder for analysis. Resi~lualgas is pumped away. T h r sequence of addition of a metal saniple, gas rollcction, mcasurtnirnt, sampling, and wacuation of rcsitlual gas from the system is rep(xatrd for ravh sample
LITERATURE CITED
(1) Booth, E., Bryant, F.J., Parker, A , , ' i d y s t 82, 50 (1057).
( 2 ) Horton, W. S., Brady, J., ASAI,. CHEM. 25, 1891 (1953). ( 3 ) MrI)onald, R. S.,Fagel, J. E., Jhlis, E. R.,!bid., 27, 1682 (1955). ( 4 ) hlclllet,t, 31. W., 7 ' r m . v . . l r r t . SOC. Jlelals 41, 870 (1949). (.i) llartiii, G. S., Lench, Arthur, J . Sci I n s t r . 36, 141 (1059) ( 6 ) Soloman, FI. .A,, Swcinth Itvport, Hcterogencity of Stwl Ingots Committee. Iron anti Stwl liist., p. 82, 1037. ( 7 ) \Valter, i ) . I., . A s . ~ I . . (:HEM. 22, 297 (19.50).
l t s c ~ ~ v sfor u review 1 )cwnil)rr 22, 1058.
Arceptcd l l q y 4, 1959.
Chlorinated Insecticides in Surface Waters A. A. ROSEN and
F. M. MIDDLETON
Robert A. Toft Engineering Center, Department of Health, Education, and Welfare, Public Health Service, Cincinnuti 26, Ohio
*
in the ewluation of the quality of jurtace waters, a general monitoring xocedure that -an detect Q variety of mrnmon inse:+wdes In concentrations betow Those 'oxic to aquatic life is perwired. This result is accomplished 2y combinirg the processes of carbon Plter sampling, adsorption chroma:ograDhy, and infrared spectrophovnetrv. The above method has >roved sufficiently sensitive TO identify PSS than 10 p.p.b. of eight chlorinated insecticides in river water. A quantitative estimate is also obtainea. 'he method qas been tested with alarin, benzene hexachloride, chlordan, DDD, DDT, dieldrin endrin. and meth7xychlor.
'7 H L O R I N A ' ~ ~ , U ,>rganic. insecticides :'an finti their way :o surface m t t w ny the ninofi of rain water from :,re:itPc! crot,!rtnti or fnrw.: areas. h;: +he
direct application to bodies of w a t u ab in mosquito control, and hy the unintentional covering of surfacr waters during airplanr spraying of adjacrnt lar,d arcas. Thv most iwmmonly observed resuit of this pollution is tktniagc. to thc fish population--1,.g., 0:. Zainting t , h c L flesh ( I ) , by tlestroying thc food supply (S), or by direct poisoning. Fish kills have h e m causeri by insrc:tii*i(lr concentrations below 10 p.p.b. (4. 16). X disagrerable tastc i s imilartcd to drinking: n.attir by 20 p.p.b. of licnzene hexachloride (i7 ) . Thv quan+,ities of rhlorinatcd insecticidcs that havt. bwn encountt,rcd s o far in surfarr waters drawn upon ior puMic iuppiirs arc n r ~ l hcloa. l \vhat &rec.oiisidcwti tn h levels toxic to humans ( 7 ) . For ilSr in the mduation of watrr quality, appropriatc analytirai ii1pthds for chlorinated insecticic!rs havo iiistinctivc requirements. Although srnsitivities to 1 CJr 2 c.p.h. :m ttrsirahlt:. ' 4 0 1 . 31, NO. 10, OCTOBER 1959
* 1729
tight representative chlorinated insectid e s have shown sufficient similarities in solubility properties and chromatoTraphic behavior %hata single procedure serves for both sampling and analysis. The essential steps of this procedure are: concentration and recovery by a d s o r p tion in a filter containing active caibon, removal of other interfering pollutants by chromatography on alumina, and infrared spectroscopy of the recovered insecticide. MATERIALS
Aldrin (1,2,3,4,10,1O-hexachloro-1,4, 1 a.5,8,8a-hexahydro-l ,4-endo-ex~5,Miinethanonaphthalene). Benzene hexachloride (1,2,3,4,5,6hexachlorocyclohexane). Chlordan (1,2,4,5,6,7,8,8-octachloro2,3.3n.4,7,7a - hexahydro - 4,7 methnnoindene). p,p’-DDD 11.1 - dichloro - 2,2 - bis(p-chloropheny1)ethane J. C D T [1,1,1 - trichloro - 2,2 - bis(pchloropheny1)ethane 1. Dieldrin (1,2,3.4,10,10 - hexachloro6,7 - epoxy - 1,4,4a,5,6,7,8,8a octahvdro - 1,4 - e h e z o - 5,Mimethanonaphthalene). :>ndrin (1,2,3,4,10,10 - hexachloro6 7 - epoxy - 1 ,4,4a35,6,7,8,8a-octahydroI ,4 - endo-endo - 5.8 - dimethanonaphthalene). Methoxvchlor 11.1.1 - trichloro - 2.2-
-
-
of w t i v e alumina while the insecticides pass through with the solvent. T h e chromatographic d u m n is prepared in a i9-mm. inside diameter tube (Scienti5c Glsss Apparatus Co. ND.5-1663). T h e adsorbent is Fisher adsorption alumina, 80 to 200 mesh. While applying vacuum momentarily to the delivery tip of the column, portions of the alumina are added to a height of 14 cm. The tube is tapped after each addition to pack the adsorbent. The use of vacuum is kept to a minimum to prevent drawing moist air through the column, which
K-;: E -
--r1
_. ..
-1-
p r t i a l l y inactivates the adsorbent. 3uffjcielit chloroform is added to v e t ,111 the alumina; about 24 mi. (1 coluinn voiume) are required. A weighed portion of the carbon filter extract, from 0.25 to 0.5 gram of solids dissolved in 3 ml. of chloroform, is added to the column, which is developed with the same solvent until 3 column volumes of effluent have been collected. The filtrate is reduced to 1 ml. on a steam bath in a stream of dry air, then transferred to a vacuum oven at 50’ C. for 1 hour to remove the remaining solvent. The residue
m
i----r----
Figure 1. Principal infrared bands of insecticides
i I I1
i I
4 --!
t
’-i
DIELDRIN
-.
bis(p-metGoxypheAyl)ethane]. Analytical reference grades supplied by various manufacturers were used as standards in colorimetric analyses and to obtain reference infrared spectra. The experiments on isolation €rom other water contaminants eniployed commercial formulations or technical concentrates, thus including the possible interfering effects of solvents, emulsifiers, and impurities.
WAVENUMBERS IN Wl 5
PROCEDURE
Concentration and Recovery. A carbon filter technique has been derioped €or sampling traces of organic %r:l,stanresin water. It is especially r h i $0 water samples of several w a n d gallons, where the connCIations of organics may be in the . t i t 3 3er billion range. T h e adSCJP tl(i )rganics are recovered Sy :dl m g the carDon with chloroform , f i + , %sed on the sensitivity of r a ! d step and over-ail recovery C’IU LPR B wa ter sample containing L LO vg. ( 1 ; chlordan cr 4 mg. t h e r insectirides is desirable. iter referred to above hoids a ri:n 11 ,wtive c-arbon IS inches high 3 riches in diameter, which is ’ L ~ L A ie +or 5000 gallons of water. For iit’r uatcr samples ‘,he filter size (’ t’i r 6,spondingly reduced. When :”’ f msecticide i s high a m i , i L i ~r :t c~hniqw to use is liquidx,raction ($1, which is niorr i 4-ir.irr ?lie carnon tilter. ?“hromatography. Many oxygentirlmp organic compounds t h a t er’ n!rzretl interference are re: s : v d ti0 z rhromat,ographic aoiumn 7
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WAVE NMI~RS
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MICROWS
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