Document e7D7oaDmG5Ox1mMq68Djjjv5M

a. & P f opy- f o *----' --- . F ile No.: R. A.220-. . ., THE ASSOCIATSD..-.JQCTBL .COMPANY LIMITED 3 S&&fiGH AND, DH^ LO m t E^ P m R r ^ IT r M adsaL M a 'T'TT>T* THE DECOOTAMIN/.TION OF SLUICE FROM LEADED GASOLINE STORAGE "TANKS' - EXPERIENCE TO.THE END OF io 5 " ~ ~ ` `" AUTHOR: E0 V. BROWETT APPROVED: E. V. BROWETT SUMMARY; An account is given in th is Note of two t r i a l s th a t have been performed according to the Ethyl Corporation procedure fo r the decontam ination of sludge by w eathering and of one t r i a l in which potassium permanganate was used as docontaminant* E ffe ctiv e decontam ination was not a ch ie v e d .in any of thes tria ls . 1 h, K. F o sso tt 2t <^r. R. 0. GibsoT\Afenggor, Engineering Dept ./Manager, Production 3. Manager, Besearch & Development D ept., . Bapt0, A*" Sales Manager 5 - 1 0 . S e c re ta r y 3 Company S a fe ty Com aittee 1 1 . Mr0 E. V. Browett 12 - 1/U Inform ation Department,, H 0009771 I t i s necessary fo r O il Companies to remove sludge from leaded g aso lin e sto rag e tanks from time to tim e. The d isp o sa l of such sludge presen ts an in cre asin g ly d i f f i c u l t problem* This sludge i s contaminated vibh T.E.L. and o th er organolead compounds and Any technique o f d isp o sa l of the sludge must include effe ctiv e decontamination. Standard p ra c tic e to d ate has been to fcury t h i s m a te ria l but space fo r ''b u ria l grounds" i s d i f f i c u l t to fin d a t some r e f i n e r i e s . Ethyl Corporation have recommended a method of d isp o sa l in which th e sludge i s allowed to "weather" in the open fo r a few weeks and i t i s claimed th a t decontam ination i s "thereby effected* This Note o u tlin e s th e Company's experience w ith the "Weathering" technique and w ith a proposed method involving decontamination of the sludge by treatm ent with potassium permanganate. N either method appears to give s a tis f a c to r y re s u lts ,. 2.1 Procedure recety"'0^ 0'* w ^ During I960, Ethyl Corporation published a procedure fo r the decontam ination by weathering o f sludgo from ie;-ded gaso lin e storage tanks. E ssen tially , th is procedure involves spreading tho sludge in a la y e r of not more than th re e inches in th ick n ess on the ground. The s i t e se le c te d may be bare ground or i t may be covered w ith grass c r w ith concrete. I t must be f a i r l y smooth and s u f f ic ie n tly w ell drained to prevent w ater-logging and should be so lo cated th a t a ir can c irc u la te freely over the surface of the sludge0 I t is sta te d th a t the spread sludge must be l e f t for e b le a s t four weeks, a f te r which i t sifc be tre a te d as any other non-toxic v a sts m a te ria l. The four week period a p p lie s when the ambient iem poiature i s above 32 ^ ., and during th is time exposure to the sun i s sta te d to be d e sira b le but not mandator;/- The s a fe ty p recau tio n s deemed t o be necessary are also given. ' . Ethyl Corporation provided fig u res shoving reductions in to ta l organic lead as below;- b u r inches th ic k patch ( l ) 3.3 p,p.m . to 0.3 p.p.m , in 31 days. (2) 377 p.p.m . to 19.6 p.p.m , in 2 days, Two inch th ic k patch (1) 38.2 p..p,m, to 0 ,6 p.p.ja, in 31 days. (?.) 56 p.p.m . to 2.7 p.p.m . in 2 days. In each of these cases, values are given sep ara tely fo r T.E.L, and "other organic lead"., those fo r "other organic lead" being low and approxim ately constant in each of th ese four t r i a l s . Tice remarkable red u ctio n s in the t o t a l organolead content of those sludges are due to the reduction of the T.E-L. content in each case. ' K 0009772 - 2- 2=2 A n alytical. Methods provided.by Ethyl Corporation Attached to the copy o f the procedure for decontamination by weathering, received from Ethyl Corporation in i9 6 0 , was a copy o f th e ir A n alytical Procedure No.192* This i s a method fo r the determina tio n o f organic lead confounds in gasolin e storage tank sludge> in which tetra eth y l lead aid "other organolead compounds*1 are determined sep arately. In v estig a tio n s in our la b o ratories showed th at th is method did not d iffe r e n tia te q u a n tita tiv ely between T.E.L. and tr ie th y l lead s a lt s . Ethyl Corporation were approached.in mid~196l on th is point and in August, 19&L, we received th e ir rep ly acknowledging th a t cur fin d in gs were correct, but sta tin g th at th e ir A n alytical Procedure No192 was applicable only to sample-, containing le s s than 10 p.p.m . organic lea d . They a lso sen t a copy o f "Determination o f tetr a eth y l lead and i t s decomposition products in gasolin e storage tank sludge* which comprised four a n a ly tica l procedures, "A*, "B*, SC" and "D*. Procedure "D* was the same as A n alytical Method No.192, but with a number o f footn otes which had not been on the previous , v ersio n . Procedures "A*, and 9C* together enable the tetra eth y l lead; tr ie th y l lead and d ieth y l lead contents o f a sludge to be determined* We have found th ese procedures to be r e lia b le and have used them in seme o f the more recent work reported below. These methods have been o f greet value to u s. 2 .3 Weathering t r ia l carried..out in France Early in 1961, a t r ia l wen carried out a t a Mobil O il depot a t Haut-Irdre, near Nantes, in which sludge from a leaded gasolin e storage tank was allowed to "weatherB0 P eriod ic determ inations o f the to ta l organic lead content were undertaken by Octel-Kuhlaann a t Paimboeuf. The a n a ly tica l method used consisted o f extraction o f the sludgo with banaene follow ed by d estru ction o f the' organic matter and gravim etric determ ination o f the extracted le a d . Th r e su lts obtained are tabulated below i- Bes u its of A nalcos,, luring. i Exposure time i f e removed from tank !(i I One month I p days i 50 days 60 days 70 day& 80 dayu 90 daysi ICO days, 100 dayfl, a fter miring 110 dayp 110 dayp, a fte r mixing 120 days; ! 130 A & J S Total organic lead,p.p.m . f i I 9O 1 i1 ' 1 200 200 170 it i i 80 i 11 t 70 110 f 140 1 150 ( ! 34P i 1,40 i 200 i ! I 4O 200 0 0 0 9 7 7 .3 - 3- Thus, there was no sig n ific a n t reduction in the organic lead content o f the sludge a fte r weathering for about four months. This i s certa in ly in co n sisten t w ith the claim s made by Ethyl Corporation. W aathagina-tgiftl carrled .ou t a t Fewler This t r ia l was started during the f i r s t week in September, 1961* The sludge used was taken from a tank o f 96,000 b arrels capacity th at had been tilled fo r several d iffe r e n t grades o f g a so lin e . The aaount o f alddge in the tank was rather le s s than had been expected? The s it e se lec ted for the weathering t r ia l wag a grassy jatch a few fe e t outside the bund w all o f the tank0 The t&afe yas washed down with water and the washings pumped to the weathering site*, The xcess liq u id soon disappeared;, mainly by natural drainage# The sludge was then trans ferred to the weathering s it e by wheelbarrows and spread in a layer about two inches thick# The to ta l area covered was about $3 yards by 10 yards and o f t h is , an area about four yards square was roped o f f separately and need as the t e s t area Half o f th is was raked over nos per week and . the other h a lf remained unraked* The weather during the period o f the t r ia l was ty p ic a l o f the English autumn and the temperature did not f a l l below 32 ?# a t ary time during th is period# Duplicate samples o f the "weathered sludge were taken p erio d ica lly by Esso fo r a n a ly sis by them selves and by th is Company in order to fo llo w the progress in decontam ination, each sample comprising portions fro a number o f d iffe r e n t p o sitio n s on the s i t e . The samples taken on the 14th , Z lst and 28th days th a t were submitted to th is Cosspary were extracted with methanol according to Ethyl Corporation a n a ly tica l procedure *A* and the extract was divided in to two parts* The to ta l organic lead content was determined separately in each, portion - on one by the Ethyl Corporation a n a ly tica l procedure "B* and on th e other by & method developed in our lab o ra to ries in which the organic lead is converted to the inorganic sta te and then determined by a mixed colour d lth iaom method a t pH 9*0. The other samples received were divided in to two p a rts. One part was analysed by the Ethyl Corporation procedures *d *B* 2Sk* other portion was extracted w ith a solven t comprising 5 parts by volume o f metteanel ar4 2 parts by volume o f carbon te trachiocrlde 0 The lead in the axtsraet weub then soaverted to the inorganic sta te and detersdwsd by the mixed colour d ith izo n s method# I t can bs seen from Table 2 th a t the r e su lts obtained by tv methods were in sa tisfa c to r y agreement on m ost, but not a l l , o f the samples# * KE 0009774 - 4- lBJ M&Xt a .o l' ..M a r ..Qr^t^ g.. Lai d JfctejflA nftttong pujcju^ , s ha fra^L st fw lm , Exposure 1 time j in days . | From tank j1 !2 1 17 2n1 1! 28 ; 5i i 66 | 98 I1' ..TOTAL OUXMtuA/vFK'XCv/ Il&E sJJ.t ZgaArX.,-Jg-a A3 F,P,Mi i X S T ! Raked Portion . ... . ............. . Unraked Portion . ! A ss.Octal ! Ethyl Corn* Asi* O ctel Ethyl Corp. j method method method method .... 1 ! U9 1 228 172 1 182 ! 156 1 135 i 118 | 101 ! 85 i 80 i 86 .............. ..... 159 207 156 184 162 191 170 138 165 87 84 165 167 135 202 150 115 109 94 93 83 ; 72 164 J 167 132 188 16 1 156 . 138 144 173 74 .... ,.7t .... C ertain samples taken during th is t r i a l were analysed by Ethyl C orporation procedures "AM, and "C" in order to determ ine the r e la tiv e amounts o f T.E.L. and o th er organolead compounds p resen t in the sludges, The r e s u lts o btained, expressed as p.p.m , T.E.L. by weight, are given in Table 3 R esu lts o f Analy se s fo r..T1^ and. " ^ l i ^ - ^gg:7vnolgJ3d^ 1 ____Raked. P o rt ion Exposure | time | Other . organs ' .......... . Unraked .Portion j Other organo v1 ! days . i. T.E.L. ,,,..JL9.4_________ i T o ta l._ T. E. La .1 i lead. .. .Total, 2 j) w 1 - tI 'w * 112 ; 20 132 ! 14 159 21 161 28 1 129 32 ! 191 9 , 170 es 129 ! 9 -' 138 9 138 112 i 3 144! 98 i '66 18 84 68 76 j i !3 Thus-, i t was ahovm th a t the bulk of the organole&d p resen t in the sludge was p resen t as te tr a e th y l le a d . This i s c o n siste n t w ith the r e s u lts rep o rted by Ethyl C orporation H it the r a te a t which th e T.EeL. a ta appeared from the sludge during the weathering process va3 very slew KE 0009775 Vw The claim s made by Ethyl Corporation for the rate o f decontamination were c le a rly not su b stan tiated , d esp ite the fa c t th a t the conditions under which the t r ia l was performed wore v e il w ithin the range o f conditions la id down by Ethyl Corporation* 3* DSCOhTAMINmQ BT K>TASSIUM Ph&lAISAHATE IN AQUEOUS ACETOUS 3 ci fflresrjPgAl^ L.xsxk 3. 1, 1 ig g sj& a a l.g j - ja ia t o .vjLth .v g /lg u a < ta c o n t^ ln fia ta In October, 195$* Sdles Manager, requested an in v e stig a tio n in to the p o s s ib ility o f chdinical decontam ination o f sludgo from loaded gasolin e storate tanks* Laboratory t r ia ls were carried out In 1959 ' , ad a r e su lt o f which i t vaa concluded th at the use o f potassium permanganate and acetone might be the answer to th i3 problem. In th is work, the e ffe c tiv e n e ss o f decontamination was assessed by measurement o f lea d in -a ir concentration above the treated sludge and the use o f potassium permanganate and acetone reduced the le a d -in -a ir values to zero, No analyses for organic lead content, before or a fte r treatm ent, were carried out. I t was recommended th at th is technique be in v estig a ted further and a fie ld t r ia l was even tu ally organised in 1961 (Section 3,2f below )a Meanwhile, other relevant laboratory in v estig a tio n s into the e ffe c t o f potassium permanganate have been carried out, 3 .1 o2 Later... experim ental treatm ent a.-aladrajtflth agraftagftmAa After the Ethyl Corporation methods o f a n a ly sis ver mode a v a ila b le, they were used to examine sludge th a t had been treated with potassim s permanganate in the laboratory,, Two samples o f sludge were taken and two t r ia ls were performed on each. In each t r i a l , 25 g o f the 3ludge was treated with 5 m l, o f acetone and a weighed; amount o f potassium permanganate. I t was then shaken for two hcurg0 Hydroxylmine sulphato and methanol were then added and the mixture shaken gain to destroy the excess permanganate and sim ultaneously extract tfee organolead oompenxndc, The extract was analysed according to the a n a ly tica l procedures ''B* and C* and the r e su lts are given in Table A. ' 000977g - 6- im & jk M & w t f l i - f l i f l g A M t f / Before L_ Total organic Sludgy load as p0p,m, sample T0S,L , V t. B feO ^.g. A ! Bi t I 207 20? do 80 1 .5 2.5 1 .5 2,5 Other organo Total organo f i K . t . lead as lead as J p.p*a. p .p .a . T.E.L, j pp#a, Th.. j D . jjB 109 94 54 63 1 ` 163 | j 157 33 j A** ! 31 38 .. . i ! ' 64. ' 42 ! These r e s u l ts show th a t th e org an ic lea d oontent o f sludge i s considerably reduced by the type o f treatm en t, bu t t h a t more severe cord i t io ns and longer re a c tio n tim es would be needed before th e sludgo could be regarded as "decontam inated" , I t may be noted t h a t the v alu es obtained fo r "o th o r organo lo ad " ., les d ie th y l lead and t r i e t h y l lea d compounds, a re much higher p roportio n s o f t o t a l organic lead th an was th e case when a m p le s obtained during th e weathering t r i a l were analysed by the sane technique, 3o2 Chemical decontam ination t r ia l carried out .st Pawley I t wag arranged th a t a f i e l d t r i a l of tb s technique of de contam ination by potassium permanganate should be undertaken a t Fawley, using some of th e sludge from 'he same storage tank as th a t used in th e w eathering t r i a l , k concrete mixer was charged w ith about 600-lb, o f sludge, a sample o f which was taken fo r d eterm ination of i t s o rganic le a d oontent. The sludge was mixed and a lo a d - in - a ir t o s t was mod by sampling th e atmosphere inside the mixer barrel, The attem pted docontsm im tion was c a rrie d out l a two sta g e s . F i r s t l y , a s lu rry o f 6 - lb 0 of p o ta s s lm permanganate in 2 -^ allo n s of acetone wias added, followed by mixing fo r 45 minutes, Secondly, a f u r th e r 6 - lb 0 of potassium permanganate in 1 -g a llo n o f acetone was addedp followed by & mixing Jbr a f u r th e r 75 sd t g c The content f th e s ix e r were then allowed to stand evornighto 3h sludge be ce a d ark er brown colour during the perarangsnate treatm ent, p ossibly due to the oxidation of ferrous iro n to th f e r r i c s t a t e , bei th e a d d itio n o f the com paratively sm all volmes of acetone did not r e s u lt in a separate liq u id phase an any time during the t r i a l .. I t was not r i s i b l e , th e re fo re , to see whether or not excess permanganate was present., K 0009777 L e sd -in -e ir t e s ta were ad in sid e th e mixer and samples o f sludge were taken fo r organic load determ ination a t the nd o f each stage and also -.fte r standing o v e rn ig h t, The r e s u l t s obtained are given in Table 5 TABLE 5 BaatfLtg of Azfelzas&j&dg forts*, OhsalaJ. ffpooBtartnatioB , . .. -- . .J', ifiTi.Wr------ ....... -- - L o ad -in -air ! te s t inside i mixer Saflfole uc.B bi/ciuft, Total organ j lead contest j of sludge as, 10 Before treatm ent ! 20 After f i r s t stage [ 3o A fter second Stage A, f t t e r standing ; overnight > 20 12,5 3 <1 i ! j 147 159 47 4S i These r e s u lts in d ic a te a ra p id re d u c tio n of the organic lead content to about one th ir d o f th e o r ig in a l le v e l, but not down to a le v e l t h a t would in d ic a te s a tis f a c to r y decontam ination, d e sp ite the vary lo v le& d -ln -a ir co n cen tratio n th a t was achieved. u xm Q m m m m Q n.31. i m a m I t i s w oll known th a t a l l organolend compounda a re th erm ally u n stab le and can be ra p id ly decomposed, to in o rg an ic lead csoapounds by heating to f a ir ly high tem peratures. Thus, i t should be possible to dcontaminate sludge from loaded gasoline storage tanks by heating under co n tro lle d c o n d itio n s0 Such a technique vxmld be more c e rta in in i t s o p eratio n th an w eathering o r chemical decontam ination and may deserve aorious consideration. 5. STANDARDS OF DBCOETiHIMiTIOI .s The inform ation a v a ila b le from Ethyl C orporation about th e i l "weathering* procedure includes excerpts from & F ie ld B u lle tin in which referen ces a re made tc th e lo v o l to which the org an ic load content should r redwood. 0009778 For example: .' (l) " I f the sample taken a f t e r fcrtii* weeks of w eathering has a lea d content of 0,002 vt* % o r loss* no H ire samples neod be taken". and (2) "Whenever the weathered sludge analyses 0*002 wi* js organic lea d or less* i t nmy be considered safe and th e sludge may then be tr e a te d as any oth er non-haz&rdous waste m aterial". Thus* i t appears th a t Ethyl C orporation accept a standard of 20 p.p.me of organic lea d (equ iv alen t to about JO p.p.m . of T .E .L .) a s in d ic a ti ng s a tis f a c to r y decontamination* This i s much le s s s trin g e n t than th e standard s t h a t have been ap p lied by t h i s Company from time to tim e in not d is s im ila r circum stances. When req u ire d to a s s e s s th e to x ic hasard a sso c ia te d with gaso lin e tank sludge th a t has been buried and may have to be removed* we have tended to regard samples containing organolead compounds in amounts down to th e eq u iv alen t of J p.p.m . T.E.L. as presenting a toxic ha*ard0 There i s obviously a need to agree on a lim itin g erganolead content below which t h is type of sludge may be considered safe to handle Ary proposed decontamination procedure can then be designed to reduce the organs lea d content "to below the l i m i t . 6. CONCmsIONS The claim s made by Ethyl C orporation fo r t h e i r procedure fo r docontarein iio n by weathering have not been su b s ta n tia te d by the r e s u l ts obtained from two t r i a l s in which t h i s Company has had an in te r e s t - one in Franco and one in England. The one t r i a l th a t has been performed using potassium permanganate aa the deoontsminant .in th e presence o f acetone was not successful although a lower t o t a l organic lea d content was a tta in e d in two hours by t h i s technique than was achieved in two months by the w eathering procedure In order to a sse ss th e development o f the permanganate method or any other procedure* i t w ill be necessary to define "effe ctiv e decontamination" in q u a n tita tiv e terms o f the f i n a l erganolead content o f the sludge. The lim it quoted by Ethyl Corporation may be higher th an t h i s Company would be prepared to accept^ . W. Towers? Kf 000977$