CA2107006A1

CA2107006A1 - Fixant for mixed organic and inorganic contaminated materials and method for making and using same

Info

Publication number: CA2107006A1
Application number: CA 2107006
Authority: CA
Inventors: Jeffrey P. Newton
Original assignee: HARBOUR REMEDIATION & TRANSFER INC.
Current assignee: Harbour Remediation & Transfer Inc
Priority date: 1993-09-27
Filing date: 1993-09-27
Publication date: 1995-03-28

Abstract

ABSTRACT OF THE DISCLOSURE
FIXANT FOR MIXED ORGANIC AND INORGANIC CONTAMINATED
MATERIALS AND METHOD FOR MAKING AND USING SAME
A toxic waste fixant for detoxification of a contaminated includes a mixture of ferric sulfate, of from about fifteen to nineteen percent weight manganese sulfate, of from about fifteen to about nineteen weight percent;
organophilic clays, of from about thirty-seven to about forty-six weight percent;
an oxidizer, of from about sixteen to about nineteen weight percent; and aluminum sulfate, of from about zero to about 12.5 weight percent. All or part of the ingredients in said fixant may be added as a pretreatment into contaminated materials such as soils, sediments, or sludges. The pretreatment can range from zero to one-hundred weight percent to material. The fixant is blended intovarious mixtures of Portland cement, and or blast furnace slag, or lime, or gypsum, or coal fly ash, or cement filn dust as a means to derive a chemical fixation treatment for contaminated soil, sediments, and sludges to prevent the excess leaching of organic and inorganic compounds and elements.

Description

2 ~ 0 7 ~

FI~CANT FOR MIXED ORGANIC kND INORGANIC COhlTAMlN~TED
MATERU~LS AND ME~HO~ FOR IllAlCiN~3 AND USING SAM~ :
ACK~P~OLIND OF THE INVE~LC ~ ~- :

l-his inven~on re~ates ~o ~e field of toxi ~ e ~eatmen~7 and, more particularly,o a to~ac ~Naste fb~ant tor prevenb-ng ffl~ leaching of organlc and inorg~nic ~o~cs at unacce7~able l~v~ls ~rom mat3rials such as soils, ssdimerlts7 and sludges and cause a signrFicant r~duction in ~he inherent toxici~ concen~ation of a corltarninated ma~erials by cl~emical 1 necharisms as well as a method ~or m~king an~ using that ffx~n~

The probbm o~ ~e safe disposal oF t~ . waste material~ is a pressing one Wi~
me ~ver incr~asing genera~on ~ hazaldous materi~s in our in~ustnal soci~
~sre is a growlng demand for s~ ols on th8 handling and disposal of all ~rms of toxic wast~. In response to th,a~ demand, l~gisla~res, bo~ stat~ and fedsral, have passsd l~ws llm~rg the I ount and nature o~ wastes wh~ch may b~ discharged Into ~ ern~ronmer~ re has b~n a gr~at deal o~ movement of la~s to make ~ese la~Hs more sl:rlngel~t, and re~ching ~e ~oals setforffl in ~e laws may soon ~eoome much more d~ cul~

To~c wastes ar~ legally defined ln the ~arious statutes and regula~ons ~ealing w-~ thei~ handllng and trea~ment, b I ~ey may be broadly defined as any ma~erial generated as a by-product oF I n indus~ial proce~ capable o~ ha\~ing an adverse impa~: upon ~ environmel[ if discharged wl~out ~e~bnent llle s~ e6 and regula~ons also s~ for~ ~he standards to be met by the indus~y which generates the waste, glenerally by sefflng maximum limits of a speci~ied number of parts-per-milDon (pprn)~ parts ~r l~illion (pp~), or parts per ~ll~n ~ppt) of ~e tre~ wast~æ founcl in ~ t~t sampl~s, as measured rela~ve to a leaching or solven~ extrac~ion test standar~. It is ~us ~e ~oal o~ to~c~c waste ~ea~nont processes to reduce the lev~ls of the waste presellt and or leaching in 21070~
:
an excessive degree in ~e ~ sampbs ~ ~e lowest lev~s possible, a~ least ~ : ~
a lev~ below me mandate~ maximum. : .

Known m~ods of ~a~ng to~c wastes i, in terms of s~bileation~ dfrica~on or chemica flxation methods, include~ for example the five broa~ categories of sorption, lim~fly ash pozolan process, pozzolan-Portiand oemen~ systems.
therrnoplas~-c micro~n~aps~affon7 and Imacroencapsula~on.

Sorp~on inwhfes add ng a solid to ma~eri~ containing ~e waste t~ be ~reated.
The solid soaks up any llquid presen~ and may produce a soll-like mate~al ContaininQ th~ waste, and is most suitable for applications involv~ng the :::
~eabnent of non-readve, no~iodsgrada~le wastes. Typical solids su~able ~or ~ ~ :
use in sorp~on indude a~vated carbon, anhydrous sodium silicate, V~ObS :
fonns of gypsum, ~lite, clays, expande~ mica, zeofites, coal ~y asll, cement Wlndust, and lime .
Ume~iy-~sh pozolanic ptocesses utilize a finely divided, no~iline silica In fly ash, and the cadum in th~ lime ~o produce a low-stteng~ cementation. -The treated was~s are entrapped Iwithin the pozzolan concrete ma~c (microencapsulatiorl~, thereby rem~/ing them from contact with the enYironment a~

Pozzo an-Por~and syst~ms us~ Por~ cernent and fly ash, or o~er pozzolan : :
matenals to produc~ a s~ronger t~pe¦ of wastelconcrete composHe. Waste con~lnment results from microencapsula~on of ~e waste in ~he concre~e matri~ Soluble silicates may be add~d to accelerate hardening and me~al co~inment ¦

Therrnoplasb-c microencapsulation Invollles blending fine par~culate waste w~
me~ed asphalt or other mat~ Liquid alnd volatils phases associated w-lth ~e --wa~ re isoiated in a mass o~ cooled, hardened, asphalt The re~ultant ma~rial can bs bu~ed w-~oln a con~ainl~r.

Microencapsula~on systems oontain w ~e by isolabng large m~ses o~ ~e ~:
was~e u~ng ~oms form of ~acketing m 'ateriai me most carefully resea~ched 2 ~`
,::

-- 21~7~

.
sys~ems uss a ~dr~lm or polye~yiene jacket fused over a monolithic block ~f soli~ied wastes.

T~se syst~ns. are us~Ful, and approp Iriate ~or many applica~ons, ~ut th~y are not suitable for meeting ~I current state and feder~ laws and for all ~pes of materials There s~ill exists a needl for ~ solld~icaffon/stabiliza~donmD~ation system for trea~ng toxic wa~es to prevent t~e leaching of impennissible levels o~ ~e3e-0rsanic and inorganic w~stes¦into ~e environn~en~ p~rticularly soi~, sediments, and ~udges that con~in rela~vely high levels of organics as well as inorganic to~dc eon~tuen~. more thus exists a n~d for a new matenal which ~an be used in certain applica~ons fol th~ disposal or con~ainment of some ~ese forms ol' tt)xic was~es to a gr~brldegree ~an h~retofore known Accordingly, it is an obiect ol the invention to pro~de a toxic waste fixant which ov~rcomes ~e drawbacks o~ the pnor ar~ It is a fur~er object o~ ~e invenbon to provide a toxic waste tixant which ren~ers m~ed organic ~nd inor~anic t~ac wastes nor~leachabie to a great~r degree than ~own methods I

It is a still turthsr o~ f the in~enffonl to provide a toxic waste fixan~ wiffl an improved microstruchure In ~e pres Inc~ of high concentra~ons o~ acid, leaching soivent~, salt water or other concl~ions whi~h m~y impair ~e leaching res~nce ot ~ ~ar~

Bri~fly ~tabd, there is provided a toxi c waste fixant for detoxification of a ~ontamin~ted soil, sediment, an~ or sludge material. ~he fixant includes nineteen weight pero~nt of f0rric suKa~; ¦nineteen w~ight percent of manganese x sulfab; fort~f six weight psr~ent of van ous org~nophilic smec~lte clays; and sDct~en w~igh~ percent ~f an oxidizing ag~nt such as potassium or ~odlum persulfate or po~ssium permanganate This fb~arlt is ff~on ~dded to various m~ ures of Po~and cement, blast furnace slag, gypsum, lime ( cacium oxide ), co~ fly ash, soil, and cement k~n dus~L As a ~urttler point r~ardlng U~e use o~ ~e ~ rt may ~e added In whole or in palt to so~ as a pre~eatment agent which su~sequ~n~y becomes part o~ the ov~rall - ' ' ..

treated mam~ Pr~reatment i5 defired as Initial step or steps in the s~biliza~on~ca~on proc~s in ~ ch a soil, sedim~r~t. or sludge is mixed with a m~c buildins mat~l suc~ as soU, sand, cement, fly ash, cernent, etc ~at allows the hnal treatrn~nt with the fixant and cement, slag, etc mb~ture ~o a~hiev~ r erid state phy~ical ar~ aching proper~es Ac~rding to an embodim~nt of the iren'don, there is prov~ded a ~Ixant ~r chemlcally and physically bonding organi~ and inorgar~ic ~xic wastes, said ant cornprising a mi~ure of: ferric s~ffa~a, manganese sulfa~e, org~nophmc srnecffl~ clays, an oxid~zer, such as potass~um or sodi~lm p~rsulfate, combir,led with a rnix~re o~ cern~n~, slag, ancl ~urn~
~ - .
According tO a featur4 of the inver~o~ re is providecl a fixant for ~e~ffng toxic wastes comprlsln~: a oement of R~y percent of the w~lght of said fixant, blastfumaceslag,o~ y~nep~rcent~F~eweigh~aidf~ant,gypsum,ofsbc percent of the wei~ht oF sal-d fu~ant, org~nophilic smec~te clays, ~F SD~ peroent oF
the weight of sa~d ffi~ant, ~erric s~ate, q ~5 percsllt of the weig~t oF said fKant, mangan~s~ suiFate, oF 2.5 percent of ffls w~gh~ o~ said Fixan~, and potassium orsodium persuKate, of ~ nt of the weigh;t ~ said fbcan~

According to a fur~er fea~ur~ of the invention, there Is pr~v~ded a me~o~ of trea~ng a soil, s~diment, and or slud~e mat~nal ~ontaining a to~dc waste, c~mpnsing t~e steps of: rnixing ~ said fix~nt including a cement, slag, gypsum, organophaic days, ferrk sulfat~, mangarle~;e sul~at~, and po~ssium or sodium persulfat~, ~din~ ~a~d ~K~nt to said contaminat~d n~tenal, whereby sai~ l'Kant a~res in said matenal, ancl rerders said to~ac waste su~stanbally l~leacha~le relaffve to the to~c consffluents after ~ea~nent. A secondary ~
impor~nt obJective is to r~uce the pr~sence of the toxiG cor stihlents D~ ffle contarnina~d soil, sedimert, or ~udge by some form of chemical reacbon.
; , ': ,' The above, and o~er o~j~ots, fe~tures and advan~ges o~ ~e present invention ~11 beoome apparent from ~e followin5 cbscnpbon ~ .
'~

~ ~;'., ~ 21~7~

.
DErA~LED DESÇRIPT10~ OF T~ PF~FERP~ED EMB0131MENT
Th~ invenbon is d7r~ cl to ~e rnanufa~re and use of a ~Kar~t ~or ~eating toxic wastes found in a contarninated soil! slu~ge, or sedim~n~ m~terial In ~e follow~ng description of ~e pr~ferred er~odiment of the invention, the materi~
is ~ soil corltairling ~e toxic was~, b~rt tRiS is not intended to be limitabve,merely illustrative.

~he ~mcac~ of ff~ trea~nent of soils containin~ organic and inorganic toxic wastss is mea~w~ by th~ rractlon~ p Drtion o~ tlle soil conslstiRg of the t~ac was~s, In ppm (parts per mill~on)7 pqb (parts per billion), or ppt (parts per trillion~ as appropriate v~rsus ~e a lount of such toxic wastes capable of lea~n~ng from ~e ~ontamina~eci soil under both leach and solverlt extrac~on tests as measured by ff~e GC/I~JIS.
. .
I have d~term~ned that the f~cant, d~ ~fined as 3S mix~ure of farric sutfate, mansane~e sulfate, organopnDic ciays, ¦and an oxidizer, such as p~tassi~lT or sodiurn persulfat~, combmecl wffl a mD~tur~ of cement, blast ~urnaoe slag, and gypsum, presents muoh improved ~niTcy in ~e ~eatment of toxiG inorganic and organlc contaminated ~oils, secbrnents, and sludges. These ocn~amina~
materials may contain such tox~cs a~ lead, mercury, arsenicl chromium, cadmium, PCBs, polynuclear aromati I, ~enzene, toluene, ~lenes, volatile organics, ~enatedorganics, 8tG ¦

Whil~ ths mechanism o~ the reactlon is not fully understood, a ful~
llndsrstandlng is not a r~quirement foq patentablllty. Th8 mechanisms have been obse~Yed and are disclos~ herein Ito provide as much insight as posslble into ~e rnechanisms of the trea~nen~ activlty afforded by the fixar~ The oom~ on and ac~ r ~ ~e inver~on I e descr~bed in deta~l ~e ~xant eff~s chemical change in ~el structur~ of ta~nc by ~or example ionic exchan~e, su~s~on reaotions, int~rmolecular forces ( dipole-dipole, hydrogsn ~onds, London force~, bimljolecular displacement, and vaflous organ~metaiiic bon~ng o~ ffle ~oxic c~ Iponents i~ ~ie cor~arninated materi~.
These changes convsr~ ~he toxic waste into innocuous compounds and complexes there~y lowerlng t~e overall leYels of tiree toxic components ~-- 2 ~ ~ 7 ~

remalniny in the material af~r treatmerlt The fKant binds the tox~c consff~ents into a hardening conuet~ ma~

Specifiically ~e f~ant is added to a I nd mixtur~ to form a new mixture, this cornbined mixbure for ~ea~ng toxic was~ comprises: a ~en~. of fr-~ percer7~
weight of said fKant, ~last furnac~ sla~, of th~ one peroent o~ ~e weight said Fixant, gypsum, o~ six percent o~jff e weight of said fixant, organophilic sme~te clays, of six percent of the weight ~F said ffxan~ femc sulfate, of ~5 ~:
percent of ffle weight of said fD~arrt, m~ngane~ sul~ate, of ~5 percer7~ of the w~ight ~f said fixant, and po'tassiurn or sedlum p~rsulfate, of two percent of the w~ight of said fixan~ :' ~':
The fixant is ~en blended in~o ~ combl n~ mb~re of; Por~and cement, is fi~
percent ~y weight of thB com~ined mlxture; blast furnace slag, is thirty-one percer~ by weight of ~e combined mi I re; and oF gypsum, is six percent by weigh~ of ffle combined mixture The ~nt is ~irteen peroent by weight of the .: : :
combined mixturQ. Portiand c~ment, slalg and gypsum are commonly available :articl~ o~ comrn~rce. Their combinaltion, ~y themselv~s and in various.
combination~, have b~ perfo~med m~ny ffm~s in the art for trea~ng tox~c . .
w~stes, such as in the described so p~on ancl pozolan-Portland cemerrt :
systen s ..
The fbcant can also be blended into a mi ~re wllich ~e Por~and cement portion oF the pr~viously giv~n combin~cl mixtu e can be subsfflu~ y an exp~nded slag por~on in which the blast ~umace¦slag can range ~rom fo~r to seventy peroen~ igh~ combined mixtl~re In ff-is pi~rticuiar mlxture, Portland æm~t would range from zero to forty~bne per~t of the com~ined mixture.
L~me, calclum o~dd~, can be addecl ~rom~ zero to forl~r p~rcent ~y wei~ht of ~e combined mbc~fe, and gyps~lm, which can be a~de~ to ~he combined mixture ~om zero to t N~lve percent by w~igiTt of ~ combined mbchlre.
. : .
In add~on the pr~viously ~Iven ~ormuli ~tion o- the ~Kant can be alter~ to impro~ ~e leac~ ~esting resul~ m ~@rtaln cases by adding ialuminum sulfate, 7rom ~Nelve to nineiteen peir~nt by wslght of the fixant. Tllerefore the ~rmulation of ~e fixant ean ba a mixtlre ferric sulfate, manganese sulfate, organophilic clays, an oxidizer such as potassium or sodium persulfate or !

2107~`t~
. .

po~sslum pennanganate, and aluminhrll sulfate. therefor~ a version of ~e for~ulation of. ~e f7xar~ becomes:
Component I Percent ~y w~
Ferr~c sulfate 15.6 Manganese sui~ate 15.
Organophllic clays 37.55 Potasslum or sodiun ~ p~rsul~ate ~ 75 Aluminum sulFate 1:~
..
I have ~so discovered ~at improved resu~l~s in tha Lse Or the fixant in the tr~l8, .t ~ ~rg~n,lc con$ant toxic wast j m~P,r br . ealkad by the ad~ of an 7ntercal~t70n com,~u:?d S~l as o~a~ 7ilic sme~ c~ays to ~e7 ~;~r.~ Th~
i~iteroalaP70n compo~nd comprlses a ~m~ y process~l or tre2~B~ clay mineral ~f ffte srr ec~te g~oup. ~e ola~ mine.~als, such as sodium bentonite or hectorite, are pr~7s~d with ammoniul;n compounds such as amines, purines or p~rfdiF es7 for 1m~ing organopi~ilio ~rop~r thereto Smec~tes may alscr b~
pr~cesseci with glycols, gly~rols or off~r polyheclfic alcohols to render ~hem suitable for use in ~e ~Ixan~ Sultable i It2rcaia~ion com,oounds or o-ganophiliGclays are comm rc~ally avaDable.

The microstructurQ of ma~erials trea e~ with the fxant exhtbit increased durabillty, comparcd ~ known systems,l In ff e preser~e ~f high a 3), in various le~c~ing solvetlts, salt wat~r, er o~her ~nd~ons .in yYh.iCh i~ wou!d bç~Impaired.
.. ...
Fur~errnore, ffle fixant ~; relaffvely inexp en~ , so r~ may compare favor~bly to o~er, less ~e3ir~1e, a~ma~ives. su~h as incinera~ion or c:ontinement to t~xic w~ dumps.

Trea~ng a soil, sediment, or sludge mat~ ~na7 containing a orga.l.c and inGrgai~sc -L~ac wastes w~ the t'D~arft produces a subst~r;cs ha~ing a oom~
Ie four or more ~nnecti~e neLwor~c, inorganic polymer Th resultar,. - -macromolecules comprlse selected pol~ valerr~ organic ~lements ~a. reac~ in a poly~unc~nal manner, a~d produce ~anched and cro~s-link0d polymers having R den-eity slJfflolç~llt to cause some IPI~J (Interp~neh-al~ng P~lymer neh~ork) bond~ng. ~hc resul~r~ p~lyme~s alsQ have a hlgh res~s~ance to acids ~ :

:`:

21~70~S - -or other naturally occ~lrnn~ rior~t~s, S~uctural bonding in the polyrner is primarily i~nic and covalen~ There is a two-phase reac~ion in which ~e t~xic componerrts a~ complexed first In a rapid reaction, and then permanently complexed further in ~e building ~ ~ macromolecules which conffnue to gener~te o~er a long period of time.

T~e first phas~ of ~e~ation ~nerat~s , irrevsrsi~le colloidal s~uctures and ion exc~anges ~ulth to~ac n~tals and orQanics ~y means of ~he ir~ercala~fon compounds and intermsdiary hydrati~n products. In a high percentage of reactions with halogenat~d hydrocafi~ons~ a bimolecular dispiacement or 8ut~ tuffon occurs as the ~rst ~tep in the linking mechanism to th~ second phase macromolec~lles. Var~us organometallic bondin~ is llkely with a~ded m~i oompounds in ~e fhtar~
In ~e second phase, ~e g~nera~on I f ~e mac~omolecule framework, also involYes a rela~veiy irr4vers~b1e colloid syrthes!s This is a slower reac~ion, how~ver, going from sol ~o gel, and ffnally to a crys~lline, ~re~dimensional, inorganic polyrner~ The treate~ ma~llal should b~ a~le to pass ourrently proposed lea~ ng s~ndards wl~in ~irom seven to ~venty-eigm days. 0~
partlcula~ impor~ance ~n ~e bondT~g of the hazardous elements and cornpoun~s i3 ffl~ ds~relopment ~ second phase reac~on ~ sulpho-~erri-~luminate hydra~s, Th~ bonciing charlactenstics and struch~ral durability are v~iad t~ ac~omm~ate ~ p~-cula~ applicaffon ~y va~y~ng tl-e composi~

Speclflc examples will illustr~te the e Fflcacy of the f xartt ~n t~e illus~a~reappUca~ons.

~XAblPLE l;

ThQ r~ture ~F ffle wast~ is in ~e ~orrn o~ I ntamlnated soîîs an~ In order to ~eat ~is was~e an app~ach h~d to bs developed so ~at th~ ~r coutd b~ mîx~d efFcctively wKh the cem~nfflious ~ased mix~re wE~}ich Includes a fk~nt descrlbed pfaYiously in a ~lurry fornl, fflat is mixe~ w~ water The ~ar t used in ~s example includes nineteen weight p~rcent of femc sul~ate; nineteen wei~ht g , ; -... - ,,........ ~ ... . .. . . . .

70~6 percentof manganese su~ate;fo~y sK¦weight percent cf vanous organophilic smec~ clays; and sixteen weight percent of an o~adizing agent, potassium persulfa~. This fixant is then added~ into a secon~ m~ure compnsing- a o~nen~ cn~y pencen~o~the weightoflsaidfixan~ blasthuma¢e slag, ~ thi~y- ~:
one percento~the weight said flxan~ gyps~, ~ six pe~oe n~ offfle weight sai~f~an~ organophnic~me~e ~ays, ~ sixperoe~ ofthe w~g~ of 5~ fixant, femcsu~e,of ~5 percen~ofthe ~iglhtofsaid ~xant, manganese ~u~ate, o~
æ5 peroentc~the weightofs~dfixan~ and potassium persulf~te,oFhNo per~e~
~ the w~ght~ ~dffxan~
. ~ ~
C~he~ oons~ain~ wers ~at we dld not, ~dd excess~e b~king ~gentstothe that would expand ~he volume o~ contaminated mat~nals that neede~ ~ be t~eated any more Uhan nec~ssary. Also too large addl~ons of cement or pozolan mat~nal would generat~ oonstderable heat ~ hydra~on and bo~ o~ a considerab~ arnoun~ ~ ~ol~ ar~ se ri-volaffleto~c oompounds. What was WOltte~d out was fflQ fOIlOWIng:

We flrst InKed IOW levels of various I :OmPIeX;ng agents,femc sulfa~e an~
organophilic clays,this mi~ r~ was 85 ~eight ~ercant organophilic ~ays and 15 w~ghtpero~ntfen~c su~a~e,i~ a gN~n ~mountc~ the con~ninated soil This compl~xing agent m~nhr~ was a~de~ia~3.7% ~y weightbothe soil. Then :. :
thlssdi w ~lendsdirtDth~tarata ~a~o ~ ~ee pa~ssoiito on~ pa~tar This 3av~ a m-D~ur~fftatwas~#~able at 20Ph¦ by ~eigh~ of blend~d soilandtar w~h the the above ~iesw ~ed mix~ure offikan~, oemen~ slag, and gypsum. The tollowin~ are ~hi TC U resul~ we ob~ d en ~is ~ea~ed waste aRer 2 seven day cur~ The uncon~ne~ comp~sssNe ~rength of t~e samples excee~ed 100 psiIn ~ casethe~xant ~assd mb~ure¦based ma~e~s pe~onn~d be~er ~an other a~smpbad fonnula~ons. We b~ielve thatin ~e case c~ high levels Cf backyroun~ s~Nratedlong ch~h hydrocalrbonsinthe wa~e andtha~the use of or~ano~aysare b~n~rsu~d ~ ~-s cond~onthanfixa~on m~ures~hatdo no~. -Th~ below listed cont~minu~s are the major ones. There are a mulfflude of x mpoundstn minorconce~affons. ~ :~
.

-: 2~70~

Lead 200 h:~ 13,000 ~.01 P~A compounds 02 to 70 c0.001 B~nzene 0.007 to 0.67 :

.r ~ample ( Untreated Numbe~loyy Reflect T~r Onhr ~,ln~ R~n~e (ppm~Treated (~?P~
~?d 37to 100 ¦C0.01 PNA compoL~s 1,0~0 to 50,Q00 Naph~alene ~.52 An~racene O Q8 ene 0t~3,~00 001 T~e PNA (polynuclear arorna~c~ comp sunds leachlng will ~e reduced as ~e treated m~rbc ages or could be improvecl consider~bly by ad~mg a ~igh~ly h~gh~r loading of f~nt plus ~ cemQn~ ~Ind or slag, and or gypsum, and or lime, ` `
and or fly ash mkeur~ T~is is only a preliminary study U~at giv~s an indicaffon of ` : :
~at is po~bl with fflis category of w~ste w~ f~a~on fonnulation sc deffnecl.

C:om~ned FonnlJl~on ¦ P~roentbyW~
~emc su~ate ¦ ~5%
Manganese ~ 5%
Po~ rsuffats ~ o orgar~phirlc smec~ cl4ys 1 6.0h ;
Por~and ~ment , 50.0%
31a~tfurna~eslag 1 31.0%
6~h .
EXAIJIPLE~

In ~N0 r~c~nt analys5s ~ number of chemical f'oca~on/stabilizaffon deslgns were benc~ tes~ed in a ~eatrnen~ of a spik~ l~oil sample~ from Miami~ Flon~a, wi~
seven vola~ organi~ COIT pounds (VO¢:s). The m~x~ng of ~e samples for the ~0 1 ~:

-~" 21071~

TCiP tes~, prescni~ed U.S.E P.A. Ieaching ~est proce~uresr took place in a oon~rolled ancl enclosed a~nosphere, and the samples were checked for the deg~ee of volatiiization or loss of ~e ~ 'OCs during mbdng and curing wi~ ~e fixant plus cement, ~ypsurn, and slac ~ Temperatur~ pro~les of the samples :
b~fore and du~in~ ~reatrnent were al~o plo~ed.

In Test 1 soil samp~es were spiked with the following compounds and concen~affons:
Benzene 75 ppm, Chiorobenzene 150 ppm, m~ ene 10 ppm, 1,1 dTchloro~ne tO ppm, 1,3 dlch~oroprol ~ylen~ 10 ppm, car~on tetra~f~loride 10 ppm, and ~hyi benzene 10 ppm. In Test2 ffle soil sarnple w~s spTked urlth 362 - r ppm of ~ichb~iene, TCE. ~ ~ .

Untreated soll sampIes ~eached totaI o rganics on average appro~ama~ely 200 ppm using the TCU.

All Test 1 sampIes were treat~ 16% 1 ~y weig~t of soiI w~h ~e ~xant ~e~tsnent m~tenal, wi~ a 30 day cure. Sampbs ill Test 2 were tre~t~d a~t 20~t. by weight oF soll. AII referenoes beIow to TCE are frem Test 2 Only ~e fixant, ffle combInecl formuIa~on is de~crbed In ExampIe 1, oemer~t, and hln dust were test~ in T~st 2 wffll TCE. ~ : -l~nol ~on of Trea~ Detec~ble E ctraction Data (ppb~
Combined fb~ant Formulabon - All tox~cs were non detectable : -Cement -220 benzen~, 3800 chlorob I ne, 15~ e~yl benzene, 300 xylQne LimeAaln dust - 856 ~nzene, 987~ chlorobenzene, 576 e~yl benzene, TCE
45~xyl~ne ~ Detec~a~le Leach Da~ (ppb~
Combined FD~a~ Formulaffon - All tox~cs are non~et~ble Cement - 38 ~en2ene, 1151 chloroben~ne, g TCE :Umelkiln dust -140 benzene, 1213 chloroben2ene, 21 TCE

The starang temperature o~ ~e sarnpleslwa~ 17C in Test 1 and 16C in Test 2, ~e combined ~ Nent to 28G in Test¦1 and 23C in Test 2, cemsnt w~t to 30C in T~st 1 and 29C in Test ~ and lime/kiln dust went to 36C in Test 1 and :

21070~

29C in Test ~ T~ VOCs lost into ~e ~r cluring mbdng and curing were 1.5%
in Tes~ 1 and 9.9/O in Test ~ for ffle conlbined ~ 5.1% in Test 1 and 6 5% inTes~ 2 for ~m~nt, snd 6 4% in Test 1 ar~d 7 4% in Test 2 for lime/lciln dust ~his air leaching should be reduced sign~can~y if the applic~on is ~one in-place, und~rground, insteacl of in ~ open in ~n above ground mixer.

Con~en~a~ion Added (PPM~ I .
Benzene Chorobenz~3ne xybne ~yl bereen~
Test 1 7~ 150 10 10 TCE Test 2 - 362 B~nzene Chlor~bereenexylene e~yl~ ene TCE
Cement 38 1151 9 ~ .
LK Dust 1~0 1213 21 Fb~ ~ ' ' ~enzene Chlorobenzene xyl~ne e~ylbe~eene Cement ?~a 3~0 300 150 -~
~Y Dust 856 987~ 4~0 576 FKant Th0 s~ng ~mp~rab~ e mat~ ~as 17C ~n Test 1 and 16C in Test 2 ~nd a level o~ trea~nent in TeSt 1 at 15/J l~y weigt~t to con~minate~ soil and 20% inTes~2. ¦ ~ ~

Test1 Test~ ~TCE) ~.
Cement 30C 5.t% :~9C 6.5%
IU< Dust 36C 6.4% 29C 7.4%
i~ æ 1~% 23C 0.9%

liXAMPLE lll ¦ - 1Fxa~Q~ ~le lll P~ by Weigi~ :
O~ganophO~ 5.~f l~erric u~ate 2~2%
Manganese sul~a~ 22~/o i , .
~, . . - .
. , , . ~ . . .. ~ : ; - ' `' ' 2~70~

Combined Forrnula~onPercent bv Weiaht Por~ c~nent ~4%
Bastfllrnaoeslag 31% :
Gy~um 6h Fe~ic su~e 2~f, - ~:
Man~anese suffa~e . 2%
Organophirc days 'I 5/0 The fixant fron~ Example I was blende~ into a sandy soil contarninated wiffl PC~s The sample averaged 8000lppm of ~ontaminates. Extrac~on by ultr~sonic hexane technique yielded 1300 ppm o~ PCB. The sample ~as ~aeated identically t~ that of Exampl~ 1, except ~Lt ~e ~eatrnent b~el w~ ent~r-ff~e . ~ -weight percent ~25%~. Allowin~ for dilutlon of the sample ~y ffle i~rotuc~on of t~nt, sevent~-one (71%) o~ ~e PCBs were ~onverted ~nto an inert inorganic -organic compl@xes..

Under ttle EP Toxicit~ Tes~ wffll glass I ~Iber filter, only 80 ppt leached. This ~ple c~ from four to five weeks belFore testing. ~

Th~ examples sh~w ~e rema~ble I ults adlieved by ~e use d ffie fo~n~ :

Having described pr~rr~d embocliment~ Of ~e inv~nffon, i~ ~s to ~e ~mderstood that ~e inv~n~on is no~ limit~ oselprecise embodEmen~sj and t71at vanous: ~ ~
chan~es and mod~ a'dons may ~e ~ cted therein by one s~illed In ~he art: :
WittlOUt depar~ng trom ffle scope or s~lirit o~ the In~en~on as dafined in the appended ~a~ms.

Claims

1. A fixant for fixing toxic wastes, said fixant comprising a mixture of organophilic clays, ferric sulfate, manganese sulfate, and an oxidizer.

2. The fixant of Claim 1, further comprising: the oxidizer can be sodium persulfate.

3. The fixant of Claim 1, further comprising the oxidizer can be potassium permanganate.

4. The fixant of Claim 1, further comprising: the oxidizer can be potassium persulfate.

5. The fixant of Claim 1, can also include: aluminum sulfate.

6. The fixant of Claim 1, wherein said organophilic clay includes a clay mineralof the smectite group.

7. The fixant of Claim 6, wherein said clay mineral can be sodium bentonite.

8. The fixant of Claim 6, wherein said clay is pre-treated with a compound including ammonium.

9. The fixant of Claim 8, wherein said compound is selected from the group consisting of: amines, purines, and pyridines.

10. The fixant of Claim 8, wherein said clay material is treated with a polyhedric alcohol.

11. The fixant of Claim 1, wherein the said weight of the ferric sulfate is fifteen to nineteen weight percent of the fixant.

12. The fixant of Claim 1, wherein the said weight of the manganese sulfate is fifteen to nineteen weight percent of the fixant.

13. The fixant of Claim 1, wherein the said weight of the organophilic clays is thirty-seven to forty six weight percent of the fixant.

14. The fixant of Claim 1, wherein the said weight of the oxidizer is sixteen tonineteen weight percent of the fixant.

15. The fixant of Claim 5, wherein the said weight of the aluminum sulfate is from zero to 12.5 weight percent of the fixant.

16. The fixant of Claim 1, may be mixed with various percentages of cement, and or blast furnace slag, or lime (calcium oxide), or gypsum, or coal fly ash, cement kiln dust.

17. The fixant of Claim 5, may be mixed with various percentages of cement, and or blast furnace slag, or lime (calcium oxide), or gypsum, or coal fly ash, cement kiln dust.

18. the fixant of Claim 1, may be mixed in all or in component parts with soil, sediment, or sludge as a chemical fixation/stabilization pretreatment.

19. The fixant of Claim 18, may be mixed into soil, sediment, or sludge in zero to one-hundred weight percent.

20. A method of treating a soil, sediment, or sludge material containing a toxic waste, comprising the steps of:
mixing the fixant of Claim 1 or Claim 5, said fixant including a cement, and or blast furnace slag, or gypsum, or coal fly ash, or cement kiln dust, or lime;

adding said fixant to said contaminated soil, sediment, or sludge material, whereby said fixant cures in said material, and renders said toxic waste substantially less leachable with respect to the environment after said treatment.