Document rxQq969DLqk73RXDxoG58rZVJ

{.-MaO SrMnw Reversed Liquid-Liquid Partition in Determination of j ixr polychlorinated Biphenyl (PCB) and Chlorinated Pesticides in Wate 4.2) *> 4.M *} 04 ).)? *#ff> 4.l a P.m P.49P a p oop P.449 * P.PII 4.40 * P PM |n|t AMtctj end Strep Jeneen* ' /CV-4*y. tVcerefry c/S-.rdkA:/.-. S-MOS.S-^M.- Method bueod on en cppricptlpn ol the common id Ilquld-ll4uld partition method ie deKribed Oxtreetlon of chlorineted peetlddee from ureter. " 1 the ureter In penned throufh n filter Rohm and Hut <}) and elvo found to be hig*:> tffiatm the extraction of chtorinaied pesticides from water, extraction of the Alter material gave, however, poor root* lelnlnf e mliture ef e-vndeenne end Good results both in extraction and recovery from ft Men >n< Ml fount l coommi In No. I-) | eviction* we Poe i* ! carried Into the li- teciof hey bkw led iolnlonnd make I meneeteerate en Chrenteeerb W, end peetlddee ere eluted with petroleum ____ ... j. When detected by meene ef e |ee tMemetoerephlc eyetem with en electron cepture (rledot. the MMiSvIty le U np/m' ef Undone with n Ttemple dep otjStlteri. The receuery ef nddedjmetl- ddee <ntie-UP% (DOT, 14%) and fer NS, tl-INft. OuaiNo' ucwt mu, many attempts have been made to material were found In a method baaed on the reversed hop liquid partition method with partition from water so hye phobixed carrier coated with a lipc^hi^c sutioawy pi followed by recovery from the column by mews ofsa amount of petroleum ether <10 ml). EXPERIMENTAL I uMn pouidwn cy. 1 the preaenee of chlorinated hydrocarbons in water. Reagents and Equipment. a-Undecane, (purum, bp. t i' A** two methods most often used are baaed either on con 196 *0 is shaken with portions of concentrated sulfuric i corvc Aulni method cm not be tMbnMcd houMit of the octuel tee for (be unknown jiMkw before elnnlni ! The ameulvc (V gous Extraction with an orpnJc solvent (/, 2) or adsorption a a finer containing activated carbon (J). These methods ^ however,'rather time consumini owing to a long ex* ndlon time, ioth from the water and from the carbon. The sensitivity of the different methods depends mostly on Sc way of detection and the used volume of water. Thus lata sbd Wayman (/) extracted several hundred liters of (p.a.) until the Kid is colorless. The undecans is then pa through column of Ktivatsd alumina (13 hours m 239 Petroleum ether (Skcllysolve B. b.p. 60-70 *0004*101 (p.a.) are distilled through a 1-meter column lifted * tadels and insulated with glass-wool and aluminum foil, head of the column is fitted to a Kill-head condenser Mfta for 90% reflux. The solvents are tested on the gas dime graph after evaporation to the same degree as in the anal; jeverpe when Ow W- nlcr with petroleum ether. The speed of extraction was kuhukw cowered U-| Hljsr/hour and recovery of added pesticide was 13-100%. Carbowux 4000 monoslearalc (CP 27) was obtained f Analytical Engineering Laboratories Inc. Chromoaorb . uelni nny M of ike trauc'of compounds was detected with an electron affinity was 00-80 mesh. HMDS treated, and acid washed (Jd ,4* IPX for the true end KmIKai. At- the InMtl vcluee ere i be prawned ernpirl- jurw. i of (he tllrelHM) dele rankled In the runet kucla ! Ihc 0.2-J40 ppb level. Rouen and Middleton (J) M aalvMed curbon and 2000 111era of water end eutneted k cMoriMIPd hydrocarbom from the carbon with chloderm.. The recovery mi 75-80% and the 2.5^>pm level :hed with infrarod detection. Brcidcnbach (J) found Pt )] Ihoun* ektrcction with ohloroform ww neceeury for oplctji recovery of the chlorinated hydrocarbon* from the Manviile). Sulfuric Kid was p.a. (Merck). The filter column was 30 cm x I cm i.d. with a gtaan# disk O 1 (100-120 a). A 10-ml graduated centrifuge tube was used. The gat chromatographic column borositicolc glass, 160 cm X 0.20 cm. AH the glassware is washed with detergent, bests# 1 mixture of sulfuric Kid-nitric Kid (4:1) to 70 *C and fit with distilled water. After cleaning, the glassware is chec i.4,7,cndl01eTcbk prtvkwly diying the tiler imterial for two by shaking with mhexane from which 10 *1 is injects# en yf velue, end the re loofo-c. gas chromatograph. The gas chromatogasph with . wee of chenfiiw die a of theee two methode win be found in un detector was a Varian Aerograph 204, with a Spsadn* te (neunenl of mini M. jropby thet OeJmeilK tla of colored Imperi- ilmoet no Inluenee w i | doa nor teke more review by Tharnburi and Bockman (4). Our Intentltn la the pretent work ha* been is develop an per method than the above menUoatd, la wbM U could be,. [udHe to teach the propoeed level of chlorinated hydroWorn in aatbral water In Sweden. of the oleopMllc character of the chlorinated a pouible method mlMu be bated on the coro- 0-1 mV recordK. Paper spaed was 12 inthss/hour. Gas Chromatography. The columns arc HMDS was , and filled with 10-100 mesh HMDS-treated Chromosort covered with either 4% methyl silicone oil (Sf 96), or fluorsllicone oil (QF I). The earrier gas is nitrogen pud with a 6-inch molecular sieve. Gas speed is about JO per minute. Detector and injector temperature ie 209 220 *C, respectively. The column temperature was cho eea e at of thrnHoe reverted phaae partition method, to give DDT a retention time of 20 minutes (about 199 * .hint method wO be of oriaaic material from water by meene of Prepareboa ef Cohan* Malarial Ten grams of Carbm |te XAD (a croaalinked polymer) wu tret ueed by 4000 monostearate and 30 grams of undecaac are dfaaai in 100 ml of acetone in a one-liter round-bottoms# fe jbwepied July 1. IN- ..... udhem, ImUtuM Ur Vttlm-ock LuMrdMbnkaitw. -**$ K/Wdm sdg STD. 114 ft. Stockholm. ' 4* iMm LaatbruksMgakofcn, Knat l Ufcum, 790 07, One hundred grams of Chromoaorb W is added fellow# additional acetone to cow alt support The amana evaporated in a rotavapor apparatus under slightly #b fehed pressure. Parbbea aad Prsdpltattea Procedure. Three gras L Kata sntf C H. Wayman, Anal Cmt., K1340 (1964). * A ARaam, aad E. M. Mlddtaon. IMA 01,179 (IMS). A w. frblwksch wef.,*lTn>*ld**flflcntio* and Measurement * - ` KyOocutai KxUta fe SurObot Wators," iIwofmlbssIwHr*iln^oarsPUwisl WsWr ft,sftabt ao Control 1 K Perkman. Ann. O41, 14MA the column material era weighed into the column whisk then fitted to the outflow of the water container by meant an all-glass fitting. In laboratory work, the lower an# the column Is connected to a water suction pump #d in field wort, to any other kind ofvacuum punq>. Hunts (9) Rohm A Haas, OWm. J*. Nrmi, 44, 54 (Jan. 17,19MI HONS 083969 ANALYTICAL CHEMISTRY, VOL. 42. NO. IJ. NOVEMSER IS70 U 2 IL Jg ft 3 8 * * 8 8 9 8 It i; t MSI* 9It t t sc s B * 8- P - - ft * a g ll I I * ft * 9 g 8 3 6 8= i !! * 9 9*38 Ill 98 S " A '2 a a Is 1 -*3 Hi 93 8 8 8 8 9 9 9 9 9 * W W m d v*v tn -it I? -i l It e H i S +T| +f. r+ J+ + + + + It s' jjj -f + ff tJLl ?? 8 as 9 iii mljiivlnl In give ho outflow kttlwn tA uml I Vl ml of per minute, l or iiniilysi-. of wnslc wtiivrs uml other wuin with hi||U purlictu cmitunl, the residue is cslittMli-tl svp;ir*tr| in the purlkic* uml in the water. Iteftwc tittering tutti wiUl' 300 mg of nlominiiin Kiilftilc per liter is iitbli'd uml nfi sedimentation of the solid, the water is decanted uml /vis^ through the filter. For extraction of the solid, see held pp L This two-step method will ulso avoid hlotkiigcs in the lohu*, Klutlnn of Oitorinated Hydrocarbon* from the C'fttw* When the nitration is finished, the suction is continued f* oo 0 few minutes. Petroleum other is then added to elute fc pesticides; 10 ml of the diluent is collected in u gradual centrifugation tube. The cxtruct is further prepared * analysed as described below. Extraction af Solid from Aluminum Sulfite FrecipltaUn The sediment is air dried and two grams or less is extract* with 6 ml of acetone in a small column <30 cm x I eta followed by 5 ml of petroleum ether. The cxtruct is collects in 25-ml bottle filled with distilled water and shaken. Tk petroleum ether to then treated as described below. j Treatment 6f Extract before Gas Chromatography. 0* ml of the extract is transferred to a J-ml test lube contain^ I ml of concentrated sulfuric acid. The lube to covered atf, aluminum foil, shaken carefully, and then centrifuged. TV* Figure In. < from dtotiWcd 6. Gat tbit rural water sulfuric add to chilled in a mixture of carbon dioxide ice ik{ Ketone. After decantation of the petroleum ether, a 10, j portion'is injected on the gas chromatograph. If the inject*; gives too low peaks, the remaining 9 mi is concentrated 0.9 ml in a 30 *C water bath with a stream of purified nitrogp and treated with sulfuric Kid as above. ! Gas Chromatographic Procedure. The extract to injvai on two columns, one SF 96 and one QF I. Neither of thaj columns gives a full separation of the chlorinated fcydn) carbons present in the water. The combination, howtmj give* a rather good possibility for calculations. ; ii was diflieu liters in 24 ho Rer#ery procedure w, inated insccti water. The Recoveryc ng/m ') are d range hardly find distilled RESULTS AND DISCUSSION j peaks on the These peaks . Development of Column Material. The most critical por: both the GC in this investigation was to develop the best composition r really are 8H the filter material, both with regards to absorption and i These peaks* desorption. , i very small a In addition to the column materials mentioned in Tahiti1 to distilled wa two others were tested <5, 6). Amberlite XAD-2 a croa mi any water linked non-ionic copolymer of styrene and divinylbenm The identifi absorbed the chlorinated hydrocarbons from the water ad mount preset high efficiency but the desorption from the filter was as! ef the 14 peak very easy. From PorapaJt, 100-120 mesh, with a sunk pesticides eve composition as Amberlite, some pesticides could be eluta system. This with recoveries over 50%, but impurities In the support mnl T DDE and I very difficult to remove. ! Nnounts were As shown in Table I, Chromosorb W, 60-80 mesh, covert! in this caaa l with mixture of Carbownx 4000 monoslcaraic and auadl (hromalogra* cane gave good results, while any of them alone gave ba, recoveries for the pesticides used. When the amount sj undecane was higher than 23-30 grams per 100 gram solid support, it ran out of the filter during the filtration pw cedure and the filter material was difficult to handle. ; Besidck Chromosorb W, Chromosorb P, 35-90 mesh, ad Sample Silica gel HMDS-treated, 50-72 mesh, were Died. TV* Tap water materials could not maintain the necessary amount of stsiiw i lacoming wait ary phase to give satisfactory recovery. ! Waste water w No diminished recovery could be seen after increasing 91 wdimcni witerfiow through the filter from 65 lo 1 ml per minute, to I kdimcnl Waste water w if the amount of Alter material was doubled from 2 to* sediment granw. the recovery waa increased. With 4 fffims, howev*1 Analysis eoadu Filter: i$ Flow speed: (6) W. A. Winsten, Anal. Cmim., M, 1334 (1962), ANALYTICAL CHEMISTRY, VOL. 42, NO. 13. NOVEMBER 1970 MONS 083970 shramatagraai Iw 8F M rehaaa ef extract (Mr logreai front ST N celutaa ef titnct Itai It, hlVMi rilical point iipoeltlon of tlpn and to M mi difficult to reach the (5 ml/min necessary to give 100 Wm in 24 hour*. Dreamy Experiments. The efficiency of the over-all procedure war rated by adding known amounts of chtoriartrd insecticides or polychlorinated biphenyl (PCD) to the aster. The recoveries are found In Table I. Recoveryexperiments at the ppq-level (pans per quadrillion, ram*) are difficult to verify, because a true blank In this nage hardly exists. For instance, It an Impossible to led distilled miter to fonify because the water itself gave ptsks on the gas chromatograph in this method (Figure la). Hew peaks most often correspond to BHC and lindane on both the OC columns. Where they come from, and If they reaMy ire BHC and lihdane has not been further essmined. lime peaks are responsible for the recoveries over 100); when I imp small amount (110 ppq or tourer) of standard Is added [ ndhtlDed water. A blank made by elution of the Alter with in any outer passing through was totally flee from peaks. Ike WentWestion of the peaks and the calculation of the mount present became very difficult because peaks from some dike 14 peaks Of f*CB overlapped those from the chlorinated rntiddet even when ueing the mentioned double* column gstria. This triads k Impossible to get a true calculation si DDE and DDD la the waste waters even when detectable mounts were Pfsseas. The calculation pf PCB Is possible s this case bachuse of the similarity between the sample `-------'-------- --* dtresnetograme from known standards Figure 2. Car chroaHtegrsa Irani SF M returns of astract freas sewage sitedgt solutions (Chophen A 40 and A SO, Bayer). Because of the thorough clean up with sulfuric acid, all eposy-containiag pesticides, such as dlsldrin, will be destroyed. This method can be justified because epoay-conlaialng pesticides are very rare in Sweden. SeaafIMIy. With a range setting of `/.ofhighest sensitivity, 10 ng/m* of lindane can be detected if the sise of the sample la 200 liters, the extract Is concentrated to 2 ml and 10 pi la injected. Results from Analyses ef Water. Natural and tap water from the water-works in LovO on Lake Malacca taken April -24 <kd 22,1Mg, were analysed for the presence ef BHC, lin dane, aldrin, DDE, DDD, DDT, and FCB (Figure D shows the chroemtogram from natural water), Table II shows that the values are of the same magnitude la bosh samples. Table II. CMerlaalad Hydrocarbons la Tap- aad Waste WaSars lampling 22/4/M ,24/4m Sampling Hmc Lto LovO Water Is !2 IkUt BHC 0.05 0.13 Undone 0.07 0.16 ng per kg water, jpt_ DOB DDD 0.07 0.22 0:06 0.24 DDT 0.20 0.11 24/4/M Hcnrludtl 10 22 24/4/M Hnr(kad*l 2.65 M 146 hunt 100 24/4/M HmrOudal 10 2 65 60 tor wtiir w*lywi: 1 <10% CBrto*x, 10% undNMW to Chrommorb W). 1*4 J00 MQNS 083971 PCB 0 1) o so 1350 1150 ANALYTICAL CHEMISTRY, VOL 42, NO. U, NOVEMBER 1S70 140 Waste wnier trnving the purificnlkm plant in HenrikKUl near Stockholm was analyzed April 24, 1961. The aediment Mid the water ware anatyjicd separately at described above. The mein, giwn In Tabijr I), show that the water Itaelf wu almost free from raaldunin reUlloo to the amount found in the aluminium sulfate sediment, indicating the good effect if the plant used the aluminium wlfaie precipitation in the clean ing procedure. The wtiJht of sediment plus aluminium hy droxide was 26) mg per fiUer of water. A sample of 10 liter* of waste water taken April 16 was im possible to analyte becaUc serious artifacts were present. The amount of the artifacts was so targe that the 10-ml ex tract from the water had jo be diluted 100 times to give peaks with the same height as 0.1 ng of aldrin. In the same way the extract from one-ftfth ov 0.6 gram of the solid had to be diluted to 1S0Q ml to give (he ptik height corresponding to 0.1 ng of aldrin. The artifacts gave throe peaks, (sec Figure 2, peaks X, r, and X) with the last peak having a retention time almost Jequal to aldrin on the Sf 96 column and exactly equal to ttn- dincontheQP! column. Ansoctonltril/n-hcxsfiepnrtltion(7) (DAW. Monte* mi f. A. MBs,/. Am. 00c* Agr. CV.MMX, *11 (M* followed by eluliofi with hexane from a silica gel ooiun* 1 did not remove the artifacts from the chlorinated hyUrocarba* J fraction. ofnahm When treating the extract with potassium hydroxide gj methanol, the artifacts disappeared. Analysis of highly cm centratcd extract on a combined gas chromatograph ms* mowo ms* This hvl sdmrptn* ipecirometer(LKH7f)0D)didnotgivesny result. Whcntki in the v* extract was cooled in carbon dioxide ice, cfytlaU appear^ [ icmpt'rMt* which eouid be analyzed on the mass spectrometer ($h tfg type of s> direct inlet) and shown to be elemental sulfur as S motec* | icently d Finally the three artifact peaks appeared on the pi chroma* I 'region Ms graph when a sulfur solution was injected giving proof tfc' phase to sulfur was responsible for these peaks. ' over span ry phusc ACKNOWLEDGMENT The authors gratefully acknowledge the help of Profem: O. Widmark, Die bead of the analytical institute at the Ifcj varsity of Stockholm, and civil engineer >. NuocL I ndwidef kmatigut* st*b ehos but also* Toitlvw composite Hocsivid for review March 9, 1970. Accepted My m composlib 197a I of a door Xt mole J mall, yieh Thua with mpe Variable Selectivity Stationary Phases for Gas Chromatography prrvturvs, torraipans curve. W melted to Raymond Aaaiao and P. P. McCren Aeeeerck Cnnvr, The Poxhore Company, Pexbom, Mw. MONS 0839li X,. Than peeler sot than subses A and ffae Tk performance *| * mw slots of chromatographic ttatienary phases I* described. th.lr aelectMty can bo manipulated over i wide tango merely by changing Vie column tomaoiMuro. Ry cemblnlnp eukeltnene differing In malting point nnd tnlute ootocflvlty, Foe puanlitative analytic, the tepar.tion of complex ndaunj has been accompUxhed by combininp different ilatio pMcec either at ceriet columiu or In a cinple column (S-Sy AH of theae method, reflect a need tar a stationery p eras traverr selectivittn mnsinpkae Ac Ptallenary pknan mixture le produced exhibiting en extended renpe o nfeWap. Since bpth Bin effective relume end eemPMlwn tl lb* melt ere strongly tempereture dependent, absolute nnd relative rntenSen vnlumne el thn e-(ut ere altered markedly by tempereture ever the treneltlen replen, resulting In vorytng degree, ef tpeciflcity through chelee e( the eppreprlete eelume tempereture. Peeltlve relative retenUen shtftt en Ihn erder ef M% have been eb* terved with e IP *C hwreeee In tnmpnrnture. It le hewn that the ebMW ef the nevel atetlenery pheee te Identify verleut ctoideg ef aelutee by e retention Indei whose selectivity can be varied over a larpe renm by aualp| latinp some convenient parameter loch ot the colnew so ike column peretun. A reoently reported method for peak idenilflcur (d) reliet on variation la the temperature dependences of t lien range r,, there ie Kovata Indices (7) for various ctaxaer of solutes, fin; rrtmlionm chinpee In selectivity with tempereture, however, are relMar for conventional ststloruiry phases. . wrlkce. -- rapidly beet W all i This paper describee a clan of stationary phase! wk; uodarpo reveniMe temperaturedependent composures fa P chanter to produce large variations In selectivity foe tore] be inereast I - rmethod le ae peed lee the two column method, end peiieuee the eddftMMl advantepe that lie specificity can be varied at win te obtain thn Met reaotutleo el a campion temple. A Nuance ov ptaea. chMrommaatleogrophic pramdurea have been clatset of solutes. These systems are not to be confuted tc the uee of liquid cryttal. (*) or conventional liquid teffcr operatod near their fracing point (P), where sltertities. i selectivity for different solutes can be attributed primarib charge in the physical state ofthe aotvesu. sad volume retention a The make E ie Ihe ns "mpoeition devtoed which owe Ihdr auceccc to the ucc of two dPTermt saee. Hots tuKonary pheicc, either alnply or in combination, For example, a widely inira technique for aolute MenUAcation Mi been the determination of retention behavior of the un known .ample on Iwo oohimiu of different selectivity (/, Xy (I) D. A. Uathtrd end 1. C Shurleck, in "Proersea la Oaa Chro- mstoerephy," I. H. jPuraatt, Ed., Inuncfcnoe, New York, KY..I*S.plt,t. ' O) 0. Ichomburg. In ^Advancee in Chromelceraphy- VoL ft I. C Otddo> and ft A Kelhr. Ed., M. pskksr, New York, KY.,IMt.P>ll. | (1) R. A Keller and O. K. Stewart. Akhl. On., 1ft I IK tin* ( (4) O.P.HildebrandandC.N.RaUlcy,Mt.,p4T ' (9) A. ft. Uttlewood end F. W. Wlllmott, IM., IP, 1091 (IW The ) N. C Saha and O. I>. Mhra.A OUw-s.sf' Set., ft 14 (l , (7) E. Konta, In -Advances in Chreemumaphy " Yoi. I. * ` iri\Giddinas and It. A Keller, Ed.. M. Dakkar. Haw Yeaf, N.i |l0 . 1*49. (5) H. Kelkar and ft Van Sekiviihoffan, In -Advansae la tk matoprephy,- VoL . j. C Oiddiapr and ft. A Kdbr, I. 1 ' M. Dekkw, New York. K ISIS, p S4T. ^ UH( (W) ft. Oeys sod H. prauad, /. Cue Cksiv'n'., ft 421 (fl* Ifl ftdA <b MftvrMRFO tX7A