ARCHIVES HISTORIQUES
DELACOMMISSION
COLLECTION RELIEEDES
DOCUMENTS "COM"
COM(75)339
Vol.1975/0137

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COMMISSION OFTH3EUROPEAN COMMUNITIES
COM(75)339 final
Brussels ,14July 1975
Proposal for a
COUNCIL DIRECTIVE
onwaste from the titanium dioxide industry
(submitted totheCouncil bytheCommission )
COM(75 )339final

ΜΓ7/47/75-Ε
EXPLANATORY MEMORANDUM
INTRODUCTION
ThisDirective isbasedontheprinciples laiddownintheProgramme of
ActionoftheEuropean Communities ontheEnvironment of20December 1973,
0JNoC112,andinparticular theprinciple of"preventin/?,reducing and,
asfaraspossible,eliminating pollution andnuisances "(TitleIpage5).
Atpresentthevastmajority offactories manufacturing titanium dioxide
(TiOg)dumptheirwasteatseaorinestuaries,relyingonthebuffereffect
oftheseatoneutralize theacidpartofthewasteandonthecapacity of
theoxygenpresenttoconverttheferroussulphatetoferricsulphate ,the
otherwaste(variousoxidesofheavymetals)sinkingnaturallytothesea
bed.
Atthesametime,itmustberealizedthatthedemandfortitanium dioxide
ontheEuropean marketisincreasing andthattheproducers hopetodouble
theircapacityintenyears,eitherbyextending existingfactories orby
settingupnewones.
Theprocessgenerally usedinEuropeisthe"sulphate process"*.Toobtain
TiOgfromthecommonestores(ilmeniteandslag),thesehavetobetreated
withsulphuricacid.Obtaining onetonneofTiO^involves2.6tonnesof
waste,whichconsists mainlyofsulphuric acidandironsulphate .Assuming
thatauthorization weregivenfordumpingatsea,andalsoassumingthat
production weredoubled,marinepollution fromthiswastewouldbealmost
boundtodoubleinturn.•
Awholeseriesofpollution controlcampaigns havebeenconducted atthe
presentdumpinggrounds;thesecampaigns havebeensponsored bynational
authorities orsometimes bytheproducers themselves .
*Chapter 1ofthetechnical reportderlsindetailwiththissection.

*4»4*«ï'Y-s*
ItisclearfroraananalysisoftheresultsoftheEecontrolsthatw^ste
fromtheTiOgindustryispotentially orrctu-llyharmful.These?dverse
effectsonthemarineenvironment predueebove?11torcidity,thepresence
offerroussulphp.te ^ndprobablyothermetals(heavymet-Is).
Theeffectsinquestion csntrkethefollowing variousforms,depending on
themethodandplaceofdumping;;
1.Reducedoxygenation andpHofthewaterandincreased concentration of
Feandheavymet?Is.
2.a)Temporary shortageofthezooplrrikton biomsssrndinducement ofeffects
leadingtoadeterioration ofthemorphological structure ofits
components ;
b)repulsion anddeparture ofsomespeciesoffish;
c)reductionofthebiomsss,production andspecificdiversity ofbenthic
and/ornectobenthic biocenoses inthedischarge ?=rea.Inmoresevere
cases,r.llanimallifemaydisappear .
3.Changeinthecolour,transparency andturbidity ofthew?ter?ndtemporary
reduction ofphotosynthesis ,ofphytoplankton mdinprimrryproduction ,
p?rticul?rly inthecaseofsurfacedumping.Theseabedbecomescovered
withironoxidesandwithoxidesofothermetsiswherethedunpingis
carried outinestuaries andinshallow water.
4.Ontheotherhand,thereisnoevidenceofanytoxiceffectsonman
fromtheconsumption ofspeciesoffishcaughtinthedumpingrreas.
Itistherefore advisable gr-?du^lly toreducethedumpingatseaofthis
wasteoverareasonable andrealistic period.Pert1ofthetechnical
reportcontainsaninventoryofthewastefromtheproduction ofTiOg.
Thesewasteshsvebeenclassified infourmajorcategories corresponding
tothewasteproductsdischarged byfactories atdifferent stagesof
production .Thesecategories are:
./•

\09 SF.747/75-S
i)insoluble matterremaining pfterfiltration
ii)"copperas"(ferroussulphate )
iii)strongacids
iv)werkacidsorweakliquors
Thereportelsoconsidered howandatwhatpricethiswastecould "bedisposed
of"byeitherconversion orrecycling .Itshouldbeborneinmindth?tthe
processing costvaluesdstebacktotheendof1^73andthebeginning of
1S74andmustbeupdatedtotdceaccountofchangesintheeconomic situa­
tion.Astudyonthisisbeingcarriedout:itisnevertheless truethat
thefiguresgiveninthereportremainfullyv?lidforthepurposeof
assessing thehighcostoftreatment inrelationtoproduction costsand
toallowcomp^xison ofthevarioussolutions proposed .
C(MEM'SPITSOIfflOFTHEARTICLES ANDANNEXES
TheaimofthisDirective isgradually toreduceendthentoeliminate pollu-
tionofthesea,bywastefromthetitaniuu dioxideindustry .
l)Severalstagesareenvisagedduringthetransition periodtoallowindustry
toadaptfromthepresentsituation toonewhereth$eisalmosttotal
elimination ofdumpingatsea. .......
Stage1;1>75-1January 1973
Duringthisperiodexisting andnewplantswillbe?bletodumptheir
wasteatseaorinestuaries subjecttopriorauthorization (Arts.4and
5)andanecologies *,1controloftheenvironment (Art.j).
Stage2;1Janurry1978-1January1981
Existingplantswillhavetobeequippedwithtreatmentfacilities such
that"thepollutionaftertreatmentisnotgreaterthaji "JO'%ofthetotal
untreated pollution"(Art .8(3)).Theseprovisions correspond toa30$
reductioninpollution ;theremaining TO^canbedumpedatse?orin
/
•i•

estuaries (Arts.4".nd5andArt.8).
Newplrntswillhavetobeequipped withtreatment facilities suchthat
"thepollution aftertreatment isnotgreaterthm30ofthetotfl
untreated pollution"(Art .8-2).Theserequirements represent a70',s
reduction inpollution ;theremaining 30pcanbedumpedatse:-orin
estuaries (Arts.4and5andArt.0).
Thiswillmeanthatinthefirstinstancethetotalpollution iscon­
tainedandthatthereafter itwillbegintodrop.
Stage3'•1January1981-1January1905
Existingplantswillhavetobeequipped withtreatment facilities
suchthat"thepollution aftertreatment doesnotexceed30ofthe
totaluntreated pollution "(Art.8-3andAnnexII).Thiscorresponds
tothesituationofnewplantsinStage2,wherethereisa70jlreduction
inpollution ,theremaining 30/obeingdumpedstseaorinestuaries
(Arts.4and5andArt.8).
Thesituation forthenev:plantsisthesameasinthesecondstage.
Thiswillleadtoasignificant reduction ofthetotalpollution .
Stage4:from1January1963onvrarc's
Existingandnewpl?ntswillberequiredtotreattheireffluentin
suchawaythatonly5'hofthetotaluntreated pollution remains
tobedumpedatseaorinestuaries (Arts.8/2–3and9-4)«
Totalpollution willbereducedby95

»y» EiîV/47/75-E
2)Therearetherefore threeaspectstothisDirective ,namely:
i)priorauthorization
ii)ecological controloftheenvironment
iii)themeasureswhichareto"betpkento"reduceand
eliminate pollution andnuisances ".
1.Thechoiceofthedumpingareaandthewastecharacteristics must "be
tcikenintoconsideration andtheinteraction between themmustbe
carefully examined.Thencedumpingatsea,canonlybecarriedout
undercertainconditions (Art.5)snclstorageonlandmustmeetcer­
tainrequirements (Art.6).
2.Duringtheperiodinwhichdumpingatseaisstillbeingcarriedout,
theremustbeanecological controloftheenvironment ;marineenvi­
ronmentcontrolcampaignswilltherefore benecessary (Art.1),
Controlswillcoveracutetoxicity ,larvaldevelopment andbioaccumu *-.
lationtestsinthepelagicchains.
3.Firmsinthissectorx*illhaveto:
a.)storeonlandtheinsoluble matterremainingafterfiltration ;
b)makecertainreductions inthetotalpollution (either30fi,"70'/o
or95,°)Article'3+AnnexIi).
Thesereductions areb?sedonperfectly feasible techniques .With
plantsusingilmenite,forexrmple,areductionof30°jowouldmean
■frhfttheferroussulphate hadbeentreated,70th?ttheferrous
sulphateandthestrongacidshadbeentreated,and55^thatthe
ferroussulphate ,strongacidsandthebulkoftheweakacidshad
beentreated. ... -
3)Itshouldbepointedoutthatthethreeandsixyearperiodsrespectively
shouldenablefirmstomakethenecessary adjustments underrealistic
economic andtechnical ,conditions .(SeePart-I,para.2and3oftech­
nicaldocument.)

Ifj«
Inthecr.seofr.euplants,construction projectswill "beabletotske
accountoftheserequirements (ferroussulphate endstrongacids).
Inthecaseofexistingplants,treatment cfferroussulphrtc (dehydra­
tion+roastingortippingonpreparedspoilheaps)cm"becarriedout
duringthisthree-year period.Theproposedsix-ye-rperiodshould
allowtheseunitsachoiceinthetreatment ofstrongacids.Thepro­
posedten-year periodfora'fj,'Jreduction seemstobereasonable for
perfecting thetreatment ofwoaltacids.
ApartfromthefactthatthisDirective willservetoeliminate almost
nilmarinepollution fromthistypeofwaste,itsapplication willencou­
ragewasterecycling .
3.LEGALCONSIDERATIONS
SeveralIlemberStateshavealreadypassedlawson-amongotherthings-
thedisposal ofwastefromthetitanium dioxideindustry .
TheGermanLav?of7June1972onwastedisposal requires bothlocalautho­
ritiesandprivateindividuals tousecpcci-1plantsforthetreatment ,
storage anddisposal ofsolidwaste.
Likewise theFrenchLawof1917oninductrirlestablishments whichare
dangerous ,insanitary orcarryonnoisyornoxioustradesappliestotita­
niumdioxidemanufacturers byvirtueofthef-ctthattheyprocessmineral
oresusing,amongotherthings,sulphuric acidwhichcancauseadverse
changesinwater(cfNo2>3inthenomenclature tothislaw).TheOrders
issuedbythePrefetpursuant totheabovementioned lrwauthorizing the
setting-up ofindustrial establishments aresubjecttoconditions which
govern,rmongotherthings,thedischarge ofeffluentintowatercourses.
Anewdraftlawmakestheseconditions evenstricter andstipulates that
anyauthorization grantedmusttakeaccountofthedangersordrawbacks
whichtheindustrial establishment inquestion maypresentasregardsnature
andtheenvironment andmustlrydowninstall -tionandoperating conditions
concerning ,inparticular ,thepurification anddisposalofeffluent ,wastes
andresidues .
•/.

-7- EN7/47/75-E
InItaly,itisthePishinsCode(Law9^3of1965)whichappliesto
discharges atsea.
IntheotherMemberStates,generallawsonthe.protection ofwater,air
andsoilapply.
. >
Theattached proposalforadirective basedonArticle 100oftheEEC
Treatytherefore setsouttoharmonize theselawsandthuscreatea
coherentsetofprovisions whichcanapplyinallMemberStates,
UnderArticle 100oftheTreatytheOpinionoftheEuropean Parliament and
theEconomic andSocialCommittee isrequired. ■
I

EïïV/47/75-E
Anncx
ProosalforaCouncilDirective onwrstefromthe
titanium dioxideindustry
THECOUNCIL OPTHEEUROPEAN COIiiUNITIES ,
HavingregrrdtotheTre?,tyestablishing theEuropean Economic Community ,
andinparticular Article 100thereof .;
Havingregardtotheproposr.1 fromtheCommission ;
HavingregardtotheOpinionoftheEuropornParliament ;
HavingregardtotheOpinionoftheEconomic andSocialCommittee ;
Whereaswastefromthetitanium dioxideindustryisliabletoboharmful
tohumanhealthandtotheenvironment ,including aquaticfloraandf?un?;
whereasitistherefore appropriate gradually toreduceandthentoeliminrto
pollution causedbythedumpingatseaofsuchwastes ;
Where?stheProgramme ofActionoftheEurope:nCommunities ontho
Environment (l)adoptedbytheCounciloftheEuropean Communities and
representatives oftheliomberStatesmeetingintheCouncil ,inthe
declaration of22November 1973,referstotheneedtoundertake Community
actionagainstcertaintypesoftoxicwasteandinparticular wastefrom
thetitanium dioxideindustry ;
Whereasnational l~wsonwastefromthetitanium oxideindustry varyfrom
oneMemberStatetoanother ;whereasthesedisparities arelikolyto
constitute barrierstotradewithintheComriiunity rndwilltherefore hrve
adirecteffectonthefunctioning oftheCommonIlarkct ;
WhereasESCCouncilDircotive No (2)concernswastedisposalin
general ;whereasforparticularly dangerous wasteitisrdvisr.ble toley
downaspecialsystemoffering everyguarantee thathumanhealthandtho
environment isprotected againstthohrrafuleffectscausedbythedischarge ,
(1)OJNoC112,20December IS73
(2)0J

-2- Eir//47/7-s
s
dumpingoruncontrolled tippingofsuchifastes ;whereasthisshouldbe
thecasewithwastofromthotitanium dioxideindustry ;
Whereas,inordertoattainthoseobjectives thereshouldbemachinery
forpriorauthorization ofalldischarges ofwastefromthemanufacture
oftitanium dioxideintowatercourses,laiccsandthesea,andfor
dumpingatseaorstorageonorintheground;whereasforindustrial
establishments locatedintheterritory ofaIlemberState,this
authorization nustbograntedbythecompetent authority ofthisState}
whereasforindustrial establishments locatedintheterritory ofa
non-member State,theauthorization mustbeissuedbythocompetent
authority oftheIlemberStrfceinvhoseterritory thewasteisstoredor
deposited ;
Ifhereasitisalsoadvisable tomalcetheissueOfthisauthorization
subjecttospecificconditions ,notonlyforthedumpingofwasteatsea
ordischarge thereofintoestuaries butalsoforstoragethereofonor
inthesoil;
Whereas,toensureeffective monitoring ofthemarineenvironment ,itis
essential thatanydischarge carriedoutinamaritime cresoranestuary
beaccompanied byasystematic follow-up onthegeneralecologyofthe-
environment •
Whereas,inordertoprotecttheseassurrounding theCommunity ,itis
essential tolawdownlevelstowhichdischarges ofpollutants nustbe
reduced ;whereastheselevelsmustbereachedinsuccessive stagesover
amaximumperiodoftenyearsfromthedate,ofentryintoforce :ofthe
Directive ;whereasexistingornewindustrial establishments andnew
capacities addedtoexistingindustrial promises mustuseanti-pollution
techniques inordertoachievetheselevelswithintherequired time-
limits;

ENWA7/7e)-F.
HASADOPTED THISDIEECTTVE :
Article 1
1,Theaimofthis"Directive isthegradualroduction andtheelimination
fromthosoaofpollution caused "bywastefromthetitanium dioxide
industry *
2.ForthepurposesofthisDirective :
(a)"waste"meansanyresiduefromthetitaniumdioxidemar.ufe.cturing
process ;
("b)"disposal"meanstheremoval,transportation ,treatment ,recycling
orrecoveryofwastes,thostorageanddepositing thereofonorin
thesoiland/orthedischargethereofintowatercourses,lakes
padthosoa,anddumpingatecr.j
(c)"existingindustrial establishments "meansthoseindustrial
establishments whichhavereachedtheirfullproduction capacity
beforethedrtoofentryintoforceofthisDirective ;
(d)"newindustrial establishments "meansthoseindustrial establishments ,
whichareinthecourseofbeingsetupandwhichhavenotreached
theirfullproduction capacity atthedateonwhichthisDirective
enteredintoforce,togetherwithallindustrial establishments
whicharesetupafterthisdate.

-4- EKV/47/75
Article 2
IlemberStatesshrlltakethenecessary measurestoensurethatthevmote
isdisposed of:
-withoutendangering humanhealth;
-withoutriskofcontamination towater,airorthesoilortotheflora
paidfauna;
-withoutadversely affecting beautyspotsfindthecountryside .
Article 3
IlemberStates ,shrlltricethenecessary measurestopromotethetreatment ,
recycling andrecovery ofwastes.
Article 4.
Thedischarge ofwasteintowrtercourses,lrkesandthesea,dumpingat
seaorstorageonorinthegroundshall "besubjecttoapriorauthorization
issuedtythecompetent authority oftheStateinwhoseterritory the
industrial establishment islocated.
Asregardswastefromindustrial establishments locatedintheterritory
ofanon-aember State,thisauthorization shrllbeissuedbythecompetent
authority intheHciaberStateinwhoseterritory thosewastesarestored
ordeposited . <
Article 5
1«Inthecaseofdumpingatseaordischarge intoestuaries ,thecompetent ■
authority shall,onthebasisoftheinformrtion suppliedinaccordance
withAnnex1,granttheauthorization referredtoinArticle4oncon­
ditionthat:
(a)thereisnoadverseeffectonboating,fishing,leisureactivities ,
oreextraction ,desalination ,fishandshellfish breeding ,onregions
ofspecialscientific valueandonotherlegitimate usesofthesea;
/.

-5- Em/47/75-E
(t>)noothermeansofdestruction ordisposalexists,
2.Irrespective ofthemethod "bywhichandthoextenttowhichtlaoeffluent
inquestionistreated,authorization shellnotbegrantedifthelevel
ofdilutionisinadequate toensurethatthepHofthereceiving water,
beyondtheactualdischarge point,doesnotexceedthepHvalueatwhich
acutetoxicityiscaused.
Article 6
Inthecaseofstorageonorinthesoil,thoauthorization referredtoin
Article4shall,irrespective ofthemethodandextentoftreatment ofthe
effluentinquestion,besubjecttothefollowing conditions :
(a)discharge intounderground strataisprohibited ;
(b)insoluble subst-nces remainingafterfiltration sh."!!bostoredonland
inconditions suchthattheydonotadversely affectthegroundwater;
(c)ferroussulphatetreatment products,strongandwe?I:acidsandwaste
otherthantheinsoluble substsjaces remaining afterfiltration mry,if
theyaxenotsubsequently used,bestoredonlandprovidedtheydonot
adverselyaffectthegroundwater.
Article 7
1.Irrespective ofthemethodandextentoftreatment oftheeffluent which
istobedischarged ,anydischarge intoamaritime areaorintoan
estuaryshallbeaccompanied byasysten?tic follow-up onthegeneral
ecologyoftheenvironment .
2.Thisfc>llov/-upshallincludeinparticular :
(a)anecological inventory ofthecurrentstateoftheareaaffected
bytherelases.Thisrequirement shallbefulfilled whennew
industrial establishments aresetuporwhencapacityisincreased
inexistingindustrial establishments :

-6- EN7/47/75-E
(b)samplingspeciesofmolluscs,crustaceans ,fishsxidplankton
organisms .
Thissamplingshallbocarriedoutregularly laya"bodyappointed "bythe
MemberStateinwhoseterritory theindustrial establishment islocated.
IntheCaseofcross-frontier pollution ,thebodyinquestionshallbe
appointed bytheCommission .
•. r
Apartfroathemonitoring ofchangesinthemarineenvironment ,testsfor
acutetoxicity shs-.llbocrrriedoutregularly onspeciesofmollusc,-
crustacean ,fishandplarJctcn whicharecommonly foundintherelease
area.Overaperiodof36hours,andataneffluentdilutionof1/5000,
thesetestsshallnot,for80pofthespeciestested,giveriseto
noreality.Thetestsslir.llbesupplemented bytestson1-rvaldevelop­
ment,whichshallonsuchastoensuretotalsurvivalofthelavaeafter
24hoursataneffluentdilutionof1/5000.
Uhenthesecheclcshavebeencompleted ,discharge operations shallbo
suspendedif:
(a)anexamination ofthegener:-,lecologyofthearerreveelsamcrlced
deterioration ofth?±ecology ;
(b)testsfortoxicityinducedbytheaccumulation ofmetalsinfood
chainsindicate oilaccumulation hazardous tohuarnhe'lthr
(c)theresultscfthetestsforacutetoxicityareatvariancewiththe
valuessotoutabove.
Article 8 ■
"emberStatesshalltricethenecessary measurestoensurethatexisting
andnewindustrial establishments areequippedwitheffluent treatment
plant.
JLsfrom1January1578"thetotalpollution aftertreatment fromnew
industrial establishments sh-11beless'than30'%ofthetotaluntreated
pollution ,endasfrom1JanuaryIS35i"tshallbelossthan5%

7- Eir,/47/75-E
3.Asfrom1Janutxy101o,totclpollution aftertreatment from,existing
industrial establishments shall "belessthan70ofthetotaltintrested
.pollution jas,from1JanuarylS-'Sl,itshall "belessthan30,jandas
from1January 1985itshr.llbelessthan55*
4.Thistotaluntreated pollution shall,inaccordance withAnnexII,be
defined "bypollution ottogoryandbythetypeoforeused.
Article 9-
Existingindustrial establishments whichincrersetheirproduction capacity
afterthedr.teofentryintoforceofthisDirective shr-.llberequired
eitherto:
(a)complywiththerequirements ofArticle8(2)astotheproportion ,
corresponding totheincreaseinproduction ,andofArticle8(3)as
totheproportion corresponding totheformerproduction ,onthedates
onwhicheachoftheserequirements entersintoforcej
orto:
(b)applyeenercltreatment inbothexisting endnowestablishments sothat
thetotalpollution aftertreatment doesnotexceedthesumofthe
10,
memberStatesBayadoptstricterregul-tion3withoutprejudicetothepro­
visionsofthisDirective . 7
Article 11
AnnexesIandIIshallformanintegralpartofthisDirective .
•rArticle 12
LcmberStatesshellputintoforcethemeasuresneededinordertocomply
withthisDirectivewithinanrocinuraperiodofeighteenmonthsofitsnoti­
fication andshallforthwith informtheCornmission thereof.
IienberStatesshallensurethatthetextsoftheprovisions ofnational
lawwhichtneyadoptinthefieldcoveredbythisDirective arecommuni­
catedtotheCommission .
Article 13
ThisDirectiveisaddressed totheIlembcrStates.

SFV747/75-S
ANIIF.X1
Provisions governing thedumping*ofwastestseaenddischarging into
estuaries .
1.v-.astechar.'ctcristics .
(a)Quantity andcomposition ;
(b)Quantityofsubstancesandiarterials which,eratobedumpedordischar­
geddaily(weekly,irontly);
(c)Forrainwhichthewasteistotiedumpedordischarged ,i.e.,solid,
semi-solid ,liquid;
(d)Physicalproperties (inparticular solubility anddensity),chemical
properties ,"biochemical properties (oaygendemand,nutritional v?lue)
andbiological properties (presenceofviruses,"bacteria,yeast,para­
sites,etc.);
(e)Toxicity ;
«
(f)Persistency ;
(g)Accumulation inthe"biological matterorsediment ;
(h)Chemicalandphysicalchangesoccurringinthewasteafterdischarge ,in
particular theformation ofnewcompounds ;.
(i)Probability ofanychangeswhichwoulddecreasethemarketingpotential
ofnatureresources (fish,molluscs,etc.).
^•Characteristics ofthedumpingordischarge areaandmethodsemployed
(a)Geographical situation ,depthofx-jratoranddistancefromthecoast;
(b)Locationinrelationtolivingcreaturesintheadultorgrowingstage;
(c)Locationinrelationtoamenityareas;
(d)Whereapproprirte ,methodscfpackaging ;
(e)Initialdilutionlevelachievedbytheproposeddischarge method *
(f)Dispersion ,horizontal displacement andverticalmixingcharacteristics;
(g)Existence andeffectsofcurrentandpreviousdischarging anddumpingin
thearea(including accumulation effects).
*V.ithinthemeaningoftheLondonConvention onthedumpingofwssteatses<

ANNEX 2
Untreated wastefromthesulphate process
(calculated pertonneofTiC^manufactured end
expressed inkilogrrjnmes )
j 1 1 ■
i
Norwetir-n j.uctralirji Canadian .nriclied
|Ilmenites
1Ilraenites Slag Ore
1CategoryI SO.Ions 4.250 3,170 2.830 *,330
IPollution(acid)
+ + + +
*
;Ironcations$20 680 170 55
Total Η5,200 3,850 3.000 Η2,400
'
Category2jOthermetal
Pollutionications j
i-110 100 200 η20
*Allowing foradditions duringm?jiuir.cture .

ANNEX 2(continued .)
Untreated wr.stefromthesulphrvte process
(calculated pertonneofTiC>2nanufrctured and
expressedinlcilogivaues )EH\r/47/75-B
1 •,(I
|Clilormeused
I'
CateroryIClIons(c.cidity)
Pollution +
IroiP'
Total
Crtcsory 2|Othormetal
Pollution cationsHNcturalRutile
1,G60
70
-r
i
70
16Synthetic Rivtilo
1,860
55
+
25
80
25Australien Il^enitce
2,500-2,000
S70to680
h
4)0
H1,3)0
35
(1)Valuesinsertedhereforrecordonly.
(2)Allowingforadditionsduringmanufacture .

Annex2
Thopollution catcariesaffected laythereductions required underArticles
8and9asfollows :
Category 1:pollution laydirecttoxicity
-50.ions,acidity(sulphuric ?.cidprocess)
-CLions?.cidity(chlorineprocess)
-Fecations(bothprocesses )
Category 2:pollution "byindirecttoxicity
-cationsofmetalsotherthaniron(Ti,Cr,v",Hi,etc..)
(bothprocesses). . 1

COItilSSION OPTHE
EUIÎOPEAH COMHUNITIESENV.47/75E
POLLUTION CAUSED BYTHETITANIUM DIOXYDE INDUSTRY
TECHNICAL REPORT

EHV//17/75-
Orig.:F
POLLUTION CAUSED BYTHETITANIUII DIOXIDE INDUSTRY
TECHNICAL REPORT
General
Part1-TheTiO_industry–– IT
CHAPTER I
CHAPTERII
CHAPTERIII
CHAPTER IV4
5
6
7
8
8THEPROPERTIES ANDUSES0?TiOg p.
l)Pigmentary properties
2)Uses p.
3)Economicsituation p.
:THEPROCESSES p.
:THERAWIIATERIALS p.
:WASTEFROMTHEPRODUCTION OFTiO. p.
I.GENERAL p.
II.SULEiATE PROCESS p.11
1)H::steproductsinherentintheprocess
2)Elimination crtreatment ofthewa3te
products inherent intheprocess p.21
1.Definition
2.Listofthemainme;nsofelimination
andtreatment thatcan"beenvisaged
for"wasteproducts inherent inthe
process" p.21
3.Treatment procedure endfinrlwaste
products t>.25
A.AES
3.BASICDATA
C.COSTASSESSMENT
D.RECAPITULATION
III.CHLORINE PR0CESS
wasteproducts inherent intheprocess
1.General
2.A.Wasteproducts corresponding tonatural
rutileore p.35
B.Wasteproducts corresponding tosynthetic
rutileore p.36
C.Wasteproducts corresponding to
Australian ilmcnite ore p.37
3.Treatments p.38
A.Effluents considered p.38
B.Hainprocesses p.35p.21
p.25
p.25
p.26
p.28
p.30
P.33

ENV/47/75-E
Orig.îF
Part2-Ecological aspects
CHAPTER V:ESTHIA3E OFTHEPHYSICO-CHEHIC /iCHANGES
DUETODISCHARGES
CHAPTER VI:STUDYOFTHEBIOLOGICAL EFFECTS OFDISCHARGES
Thedifferent aspectsoftheproblem
SECTIONI.THESHORT-TERM EFFECTS
1)Dataonthebehaviour ofthe
marinefloraend.frunainthe
vicinity ofthedischarges
2)Experimental dataontheir
beh?viour atdifferent
concentrations oftheeffluent
Determination ofacutetoxicity
thresholds
Results
...3)Estimateofthedirect
consequences ofthedischarges
onmarinefloraandfauna
SECTIONII.THELONG-TERM EFFECTS '.
l)The"naturel"accumulation
procese
2)Studiesofaccumulation and
inducedtoxicity carriedout
inlaboratories
3)Observations ofheavy-metal
contentsofthemarineorganisms
collected inthedischarge area
SECTIONIII.CONCLUSION
CONCLUSIONSp.42
P.49
P.50
P.50
P.53
P.57
p.60
p.63
p.63
p.66
p.6Ç
P-72
P.74
\

ENV/47/75-E
Orig .ÎP
PART 1
THE TITANIUM DIOXIDE INDUSTRY

-2- ENV/47/75-E
Orig.îP
GENERAL -'■– - ---»•–» •-
Themodernworldneedsanumberofmanufactured products inorderto
provideeverycitizenwithacertainstandard andqualityoflife.
Thewayinwhichthesevariousproductsareobtainedattheindustrial
levelcanhasummarized "bythefollowing equation :
Ravimaterial +materials usedforprocessing +energy • -j.
«product+waste(solid,liquidorgaseous).,
Onethingistherefore obvious:everything thatisputinatthebeginning
isstillthereattheend.
Inthecaseofcertainindustries ,thegreaterpartoftheoriginal
materials isprocessed andlittlewasteappearsintheproduction chain
(thepetrochemical industry,forinstance).Inotherindustries ,however,
therawmaterialisrelatively poorinbasicconstituents ofthefinished
product,andtheamountofmaterialcontributed fortheprocessing ofthe
rawmaterial isconsiderable . ' ■-
Thisistrueofthetitanium-oxide-producing industry .Onetonneof
TiOg"involvesabout2.6tofwasteinthemostwidelyusedprocess,
notcountingtheconsump&^an ofwater.' ■

-3- iarv/47/75-S
Orig.sF
CHAPTER 1-THEPROPERTIES ANDUSESOFTiO?
l)Pigmentary properties
Titanium dioxidei3atpresentregarded asthebestwhitepigment.
Themainproperties whichhelptogiveitthissuperiority areexamined
below.
Itshouldbenotedthatthetwocommercial formsofthispigment,"anatase"
and"rutile",correspond totwocrystalline formsoftitaniumdioxide.
Thesamenamesareusedtodesignate thesimilarcrystalline formswhich
aretobefoundinnaturewithalowerdecreeofpurity.
Theessential qualityofapigmentisitsopacity,thatis,itspower
ofreflection whendispersed inamedium.
Thislight-reflecting powerisduetothereflection oflightatthe
crystal-medium interfaces .Thispowerwilldependontherefractive
indexofthecrystaland,foragivenpigmentconcentration ,onthe
numberofcrystalfacets.
Theformervalueisinherent inthecrystal ,whilethelatterisimproved
byverysmallcrystalsizes,whichmusthoweverbegreaterthanaminimum
sizeconnected withthewavelength ofthelighttobereflected .
Titanium dioxide
-whichhasthehighestrefractive indexofalltraditional pigments
(averageindexofsyntheticrutileforawavelength of450nm:2.921);
-ofwhichcrystals ofoptimum
synthetically ;size(0.05-1«5a0canbeproduced
-whichhasverygoodtransparency inthevisiblerange
istherefore averyeffective pigment .

«4- 3NV/47/75-E
Orig.ïF
Rutileandanatasedifferbytheirbehaviour intheultra-violet range.
Thisbehaviour producesdifferences inthelight-fastness ofthepaints
inwhichtheyareused. -•
Lastlyitshouldbenotedthatcoatings ofmetaloxidemakeitpossible
toimprovethewettability anddispersibility ofthepigments andthus
toenhancethequalityofthedispersions .
2)Uses
Thefundamental characteristics ofrutileandanatasecrystals havebeen
noted.Theseproperties haveledtoverywidespread useoftitanium
dioxideinmanyfields.
Majorcategories worthyofmentionares(l)
-paintsandvarnishes 5($<
-papers ^ ' 2(>o
-plas;les 10$
-rubber H.%
■-floorcoverings . . 4%
-inks;: ,2.5
-ceramics - 2.5$
-synthotic ffbres .( • -1.2%
--miscellaneous ,including cosmetics
andpharmaceut icalproducts ■ '5-3%
Consumption ofthispigmerjt,owingtoitsfieldofapplication ,maybe
regardedasanindexofacountry'sdegreeofindustrial development .
Withregardtothedistribution ofitsapplication bysectors,thismay
varyfromcountrytocountry,butitshouldinanycasebonotedthat'
paintsandvarnishes represent morethanhalfoftotalconsumption ,while
theothersectorsrepresent proportions rangingfrom3to15$ofthetotal
Inalltheseapplications ,titaniumdioxideisasuspension inthevarious
media.
(l)Thedistribution ofusesshowncorresponds tothesituation inthe
UnitedStates.Thisdistribution istakenfromthestudy
EPA-230/1-73-015datingfrom1973.

Orig.sF
3)Economiesituation
Itisobviousthatthefutureoftitaniumdioxideisboundupwiththe
development ofitstraditional fieldsofapplication .Theeffectsof
competition fromsimilarproducts areslightinthesefields.
Theaverageannualgrowthinworldconsumption oftitanium dioxidewas
estimated in1974atabout5/£*Thisratemay,however,beexpectedto
increase inthenextfewyears„
Bytheendof1974thissubstantial demandhadledtoariseinprices,
whichwerearound595unitsofaccount(U.A.)pertonneofanataseand
720U.A.pertonneofrutile(mid-December 1974pricesperconsignment
of20tonnes).
ThepricesofJapaneseproductsarethehighest,followed byEuropeanprices,
exceptforthoseinPranceandGreatBritain,whichv/eresubjecttotaxation
asfrom1stJuly1974-Lastly,Americanpricesappeartobelower.
Countries
Pricesnot
including tax
20tconsignments!
USA
UA/kgB1LLGIUII
UA/kgFRANCE
UA/lcgFIID.REP.
ofGERMANY
UA/kgNETT1ER--
LAITDS
UA/kg1■ I
ITALY
UA/kg–:»G.B.
UA/iccI
July1974Anatase
Rutile0,45C
0.5000.570
0.C160.333
0.5300.432
O.6740»5ol
0.6710.5C5
0.7130»3o0
0.424
TheJuly1974pricesinUA/kgarabasedonquotations onlothJuly1974,assuming
thatoneUA=50Belgianfrancs,asgivenby"European Chemical News",Vol.25
No.642.

-5- ENV/47/75-E
Orig .îF
CHAPTER II-PROCESSES
Description ofprocesses
Themethod ofmanufacturing titanium dioxide pigments consists ofpreparing
atitanium dioxide ofvery high purity from anorewhich already contains
it,butmixed with other elements .
There isnoindustrial process forthepreparation oftitanium dioxide
which enables ittobeextracted selectively .
Actually theonly twoexisting industrial processes consist ofanattack
onthewhole oftheorefollowed byselective operations toextract the
titanium compound ..Afinal stage enables thetitanium dioxide tobe
obtained from theintermediate compound .
These twomethods aretheso-called "sulphate "and "chlorine "processes .
Inthecase ofthesulphate process thewhole oftheore isattacked by
sulphuric acid ,andthen titanium hydroxide isselectively precipitated .
Finally titanium dioxide isobtained bycalcination ofthehydroxide .
Inthecase ofthechlorine process thewhole oftheoreischlorinated
andthetitanium tetrachloride formed isfirst ofallseparated from the
other chlorides bymechanical means andthen distilled .Finally the
titanium dioxide isobtained byoxidation ofthetitanium tetrachloride .
(Thechlorine process isgenerally used only with ores which arerich
intitanium (rutile ).Only onefirm hassucceeded inapplying this
process topoorer ores (ilmenite ).)

~7- aw/O'/i>
OriA,'o:F
CHAPTERIII-THERA!JJLVT2RULS
Alltitanium dioxidei3prepared fronnaturalore.Thetitaniumis
contained inthelattermainlyintheformofirontitsnate inthe
caseofthemoreordinaryores(ilmenite)andalreadyintheformof
crystallised Ti02(rutileform)inthericherores.
Whilereserves oforeoftherutiletypearesmallandbecoming exhausted ,
reserves ofordinary oressuchasilmonite areextremely large.In
particular ,thereareenormousdeposits oftheminCanadaandNorway *
Asawhole,oreavailability shouldnotcreateanyproblemsduring
theney:t75years.However,averygreatresearch anddevelopment
effortisatpresentbeingmadeforthepreparation ofanorovery
richinTi(>2(syntheticrutile)fromtheilmenite-type ore,inviev/
oftheenvironmental problems createdbyoresoftheilmenite type.

EHV/47/75-E
Orig .:F
CHAPTER IV-WASTE FROM THE PRODUCTION OPTiOp
SECTION I.GENERAL
Inthis chapter ,twocategories of"waste "will bediscussed :.
a)thewaste products inherent intheprocess ,resulting from the
.carrying outoftheproduction process ,that is,from thevarious
separations taking place intheprocess itself before anytreatment ;
b)thefinal waste products ,which areobtained after elimination or
treatment oftheprocess waste products .These final waste products
maybeidentical totheprocess waste products ifthefactory does
notcarry outanyelimination ortreatment .But ,bydefinition .
"elimination ortreatment ofprocess waste products "ioregarded
asembracing anyintervention which leads toachange intheir
characteristics ,which canrange from mere dilution inorder to
reduce their concentration tovery elaborate operations which .<
radically change thenature ofthewaste ..
Before going into this question ofwaste products inmore detail ,it
isinteresting tonote that theproduction ofthe "Ti02 "pigment industry
is .very simple todefine ,because itconsists ofhigh --purity titanium
dioxide .Inallevaluations ,theparticular additives which enable
theperformance ofthepigments tobeimproved ,andalso theresidual
quantities ofimpurities ,which areextremely small ,will bedisregarded .
Asproduction consists only oftitanium dioxide ,allrawmaterials
other than titanium dioxide will ofnecessity bediscarded atoneof
thestages oftheprocess .Moreover ,asproduction oftitanium dioxide
iscarried outwith acertain yield ,there will also besome titanium
dioxide inthewaste products .
That iswhy ,inSection II,forthesulphate process ,four cases of
production ofTiO?based onthefollowing ores areconsidered :

-9- 2NV/47/75--E
Orit,\:F
'•Norwegian ìlnenite
~Australian ilmenite
"Canadian slag
-Enrichedore(hypothetical )containing aboutQ&/oofTi02
(maximumpossibleforsulphateprocess).
Similarly ,inSectionIII,forthechlorineprocess,threecasesof
production basedonthefollowing oresareconsidered :
-naturalrutile
-synthetic rutile
-ilmenite (hypothetical ).
Foreachofthesetypesofproduction ,accountwillbetaicen
-ofthequantities ofrawmaterials employed ;
-ofthetotalweightsofwasteproducts corresponding totheseraw
materials ;
-ofthemaincategories ofwasteproducts ,statingtheirnature
andquantity .
Weshallthusseehowthevariousoriginal'constituents aredistributed
inthemainprocesswasteproducts ,

PROCESS DIAGRAM
i1...,i!■■
ore
>•
>
//MPRûCKiS
E2so4////^/''100fo//////I
■*'//.1
Iron// -
Additives <'• ^Product
Waste
products
inherent in
theprocess.Treatment of
WasteproductsFinal
waste
productsTiOp
Waste
products
RAVI
MATERIALSPROCESSING PRODUCT AND
HASTEPRODUCTS

-11- E1W/47/75-2
Orig.:F
SECTIONII.SULPHAT3 PROCESS
l)Wasteproductsinherentinprocess
Generr.1
Itshouldnotbethepurposeofthecalculations presented inthis
chaptertoascertain theexactcompositions ofeffluents .
Thereasonwhysuchacalculation hasnevertheless beenattempted
isratherinordertoachieveacoherentoverallanalysis based
onwell-defined hypotheses .
Thesehypotheses canbearguedaboutandthecalculations adjusted ,
buttheydomakepossible,asfarasthemainwasteproductsare
concerned ,avalidquantitative approachforthedifferent typesof
production anddifferent factorycapacities representing -themain
European producers .
Fourmaincategories ofwasteproducts corresponding topossible
groupings ofthewasteproducts inherentintheprocessareconsidered :
-theinsoluble substances remaining afterfiltration
(wasteproductl)
-the"copperas"(i.e.ferroussulphate)compounds
(wasteproduct 2)
-the"strongacids"(wasteproduct 3)
-the"weakacids"(wasteproduct4)
obtainedaftertheoperations schematically showninthefollowing
illustration (Table2).

Taoie2 -12-
lit'2-«ULniiïS PRCC3S3ENV/47/75-E
Oriff.sP-
ILM3NITE o-
flocculent ,
agents
Iron ■o
flocculent
agents
genasof
TiCly,
24
powderofZn°­(solid)..–v(O­
(solid)/^ .VAP
*ATTACK )
DISSOLVING ;
■1r––~l~î
o fr/separation ).»jwashing |.,'„
» i
I–i i
M ,■REDUCTION " ; ■j
•'" i !
« - * '
■;rTT^ 1
0■. ■»(separation J 1 ;
: 1 ;IrimnimATt TfiAmTAW I 4I;*jCRYSTALLISATION | 'j ,.
!•.•; l_ | 1
« i «' 'i./.*. »\
(separation }1■ t>)washinfe -
•• i–p.
I Ó
! ! VAP •:
, CONCENTRATION ^ ,
.'' HYDROLÏSIS
'»
s
"f...,.fseparation J '■■■■■)
; i
' IIII IIiIIIII■!■I.1■■■
0u1WASHING-REDUCTION ^ , NJ(liquid)"JUIUUUAXV /XT•11 ) 1 11 1 1if.AV–*\– i¥
"1' GAZS I
:,. : zzi>t
;• CALCINATION ;J
;4^, 1r
jFINISHING I(liquid)0^

TablG3 -1.1- J^C^xL:$
WASTEPRODUCTS CORRESPONDING TOOREA.NORWEGIAN ILKEBITE
ORIGINAL ORE
INORHEGIAIT ILMENITE
«£
(TiOpI44-45Ί1130.000
FeO 33-34 8C7oOO
Fe02Û3 12-13 ;312.500
SiOp 2.5-3.0 Go,100
IZrO? -
AI2O3 O.0-O.7 I
1I15,000
P2O5<0,03 0.700
lînO 2-0.3 5.000
MtO 4»5-5»5 125.000
Cr20->0.07 1.700
V205O.I5--O.I7 4.000
CaO 0.2-0.3 6.200
NaoO
<0.04 I<1.000J
!2^p*ra ©IGrammes j
Ni Cl-113 253.000
!Zn 57-93 I67.OOO
ICu 6<-0.2<13.000
Cd <3-1.9 <-4.000
Pb.3q !<2.3eaoh
Sb,HS
li1mijO<2.5eachIYield:C3.5&
r~.~
Wasteproducts
S
J"V
Correspondis weithtofore:2,500xg
N.3.:Thetotalcfthecolunndoesnotcorrespond to
2,500k£,astheweights -ofeachconstituent have
averagevaluesrelatedtodifferent compositions of
ilnemte .
iv-1 -,-1 "«-v•. !''liin -hrôtPRODUCT
TiO?:1tonne
FATALWASTEPRODUCTS
Iexpressedasquantities
(ofmetal(iq,)
Ti 78.000
ffp j
I755,000
Si 32.000
Zr
Al 4.000
P 0.142
Mn 3-C70
75.000
Cr 0,559
l.OoO
!Ca 4-275
ingrammes J
S <1000
m
1253=000
Zn 1C7.000
Cu 1S.000
Cd 4.000
Pb,3e <25each
Sb,Hfe|<7,9each|
;lll£
"1.1-ta."1
--ν\->1

-14- ENV/47/75-E
Orig .:P
NORWEGIAN ILMEHITE
-.'•v.- '■•*•••
Thequantities shown below relate to1tonne offinished product andare
based onthevalues inthepreceding table .
Waste product 1-Insoluble substances " .–"■»•■■• -
... . . . 81kg (Si02tTi02,Al202»MgO,Cr^,P2®5 »
81kg
162kgMnO,VgO^,CaO,Si,Ni,Zn,Cu,Cd,
Be,Sb,Hg)
HgO (assuming HoO«50$oftotal weight )
Waste product 2-Copperas
3,372 kg
+
+460kg
23kg '
3,855 kg
Waste product 3-Strong acid
727kg
+
+
+
+
V..34kg
41kg
11,482 kg
5,127 kg
7,411 kgvarious sulphates ,including 2,941kg
PeSO ,7H20
H2O.
freeHgSO .
various sulphates ,including 585kgof
PeSO . ■'4 ' ,
TiOg insuspension
TiO„insolution ; 1
H2SO4 (exp.as10#)concentration 20fj
H2° -
Waste product 4-Weak acid
391kg
+
+
+
+28kg
22kg
300kg
5.753 kg
e.ooc kgvarious sulphatas ,including 315kgof
PeSO -
TiOg insuspension .,
TiO_insolution
HgSO^(exp.as100f')concentration 10$
K0

Table 4 -15 ENV/47/75-S
Orig .:F
WASTE PRODUCTS CORRESPOND !^ TOORE B.AUSTRALIAN ILMENITS
ORIGINAL ORS
AUSTRALIAN ILMENITE
% ^5
Ti°o I55-4 1130.000
FaO I23.8 x 1485.450
Fe.O
ί16.9!344.800
SiO» 0.15 3.060
ZrOp-
A120, 0.94 19.200
250.08 I.65O
MnO 0.72 14.700
Mg0 0.27 5.5OO
Cr200.14 2.850
250.17 3.500
CaO 0.02 0.400
Na.O
*2°
S 0.01 0.200
Ni
Zn*" 1
Cu
Cd
Ρο,Βθ
Sb.HgYield :88.5%
Waste products
>Π 9PRODUCT
TiOgî 1tonne
FATAL WASTE PRODUCTS I
(Expressed asquantities
ofmetal (kg) |
Ti 76.000
498.000
Si 1.400
Zr
Al 5.080
F 0.330
m 11.370
Mg 3.300
Cr 0.940
0.920
Ca 0.280
S 0.200
Ni
Zn
ιmm
ICu
Cd
Pb,Be
Corresponding weight cfore :2,040 kg.
N.B.iThetotal ofthecolumn does notcorrespond to
2.040 kg,astheweights ofeach constituent have
average values related todifferent compositions of
ilmenite .
Nevertheless ,thecomplex information inthis table makes
itpossible toassess theoverall quality andquantity of
thewaste products .

-16-.EOT/4',7Y^.
Crlg .:F
AUSTRALIE IICTITB
Thequantities shown "below relate to1tonne offinished product and -
are "based onthevalues inthepreceding table .
Waste product 1-Insoluble substances ■
20kg (Si02,'Ti02,A1203,KgO,C^Oj^0 t
MnO,V20^,CaO,Si,Ni,2n,Cu,Cd,
Be,Sb,Hg) . :
+ 20kg FLO (assuming ILO=50>oftotal weight )
40kg
Waste product 2–Copperas
1,768kg
+ 241kg
+ 12kgvarious sulphates ,including 1,725 kg
FeSO^,7H20 •;
h2O •
free F^SO .
2,021 kg
T/fes+e product 3-Strong acid
637kg
+
+
+
+34kg
38kg
1,250 kg
4.291 kgvarious sulphates ,including 584kg
ofPeSO
TnOg insuspension
Ti0oinsolution
EpSO .(e::p«as10O'/o)concentration 20$
Η2° . ....
0,250kg
Waste product 4-TTe^-k acid
■ 343kg
+
+
+
+28kg
21kg
672kg
5,663 kgvarious sulphates ,including 314kg
ofPeSO .
Ti02tasuspension
Ti0oinsolution
HpSO ^.(exp.as100$ )concentration 10%
ILO
*,727kg

-17- ELJV/47/73-E
r i:- Origr?
WASTEPRODUCTS CORRPISPCttTDWGv TOORBC.CAIADIM SLAG
ORIGINALOREJ
CAN.ADIAITSLAG
^ kgj
TiOp i70,72 1130.000i
FeO 12,15 194,138
Pe203 1,50 23,960
Si02 3,5-5,0 67.100
2r02
A1203 4,0-6,0 79,890
P205 0.025 0-399
IMn.0 0,2 3,195
'HgO 4,5-5,5 79,892
Cr203 0,25 3,994
V205 |!0,5-0,6 8,788
CaO j1,2 19,174 !
Ïïa20 .!1
I–l
i
»
K20 j
J
S |ofC5 ο,7?ε
ì\T10 i0,085 1,358
Zh 1,1i
[ * 1
[CuO |!0,015 0,239
Cd!•"I ΐ
Pb,Bei„
! 0,07
iSb,Hg
i.I·-■■■■'
| ιI-
-,,,!■■■■ ,LYield88,5/a
PRODUCT
Tx02:1tonne
>WasteProducts
N,
1r– "■
Corresponding veightofore:1,600k£.
2uB»:Thetotalofthecolumndoes .not
correspond to1,600kg,astheve.l/rhts
•ofe~,c.'iconstituent haveav.3ra.f0velu.ee
'related'todifferent compositions of[FATALWASTEPRODUCTS
L..,
Expressed asQuantities
ofmetal(kg)
T1 |78,000
pe 159,751
Si.31.3
Zr
'Lu 21.14
p
10,081
jl-ii
kg2,472
47,935
ICr
t1,314
iv.2,3:»
Ca!13,210
lATarai- i
P Iî0,798
Mi !"..068
{
Zn «(1,1)
bu \ρα 0yl89
ρ
ι(0,07) |
i
ΙI
Uovertheleps ,thecomplex5nf6nxation in
thistablamakesitpossiolstoarmors
theoverallcuaiityandquantityofthe theoverall cua
wastoproduots.

-18- ET07/75-E
Orig:F
CANADIAN SLAG ■ !.V.'.' ..;
Thequantities shown "belowrelateto,.1tonne ;offinished productand
are"basedoilthevalueinthepreceding table,■■
Wasteproduct 1-Insoluble substances
107kg
•+.107kg
214kg
Wasteproduct 2–Copperrs
–;' *None'
Wasteproduct 3-Strongacid
630kg ;
+34kg
.+33kg
v+1,440kg
+5f063kg
7,200kg
Wasteproduct 4–Weakacid
339kg
+
+
+
+28kg
19kg
778kg
6,624kg
7,780kg(Si02,Ti027A1203,MgO,Cr203PgC
ì&iO,V2ÒiCaO,Si,Ni,Zti,Cu,Cd,
Be..J3b,/Hg)
H20(assuming H20=50$oftotalweight)
ί
varioussulphates ,including 303kg
ofPeSO.–4
Ti02insuspension
Ti02insolution
HgSO^(exp.as100$)concentration
h26
varioussulphates ,including 163kg
ofFeS0„4
TiOginsuspension
Ti02insolution
H->S0.(exp,as100%)concentration 10$
HO

-19-
WASTEPRODUCTS CORRESPONDING TOORED.
ECTRICHED MINERAL (Hypothetical )
(SimilertoCanadianslag)ENV/47/75-E
Orig:F
ORIGINAL ORE
EMRICHED ORE
% kg
bio2 88,00 1130,000
beO 5,0064,204\
pe203 0,50 6,420
Bi02 1,65 21,187
Zr02
1A1203 2,00 25.681
P205 0,01 0,128
Ϊ£η0 0.08 1,027
IgO 2,00 25,681
Cr203 0,10 1,284
V205 0J20 2,568
CaO 0,40 5,136
CIa20
A20
Ρ 0,02 0,256
FiO 0,03 0,385
pn
Eu 0.01 0,128
Ρ
Pb.Be
JYield88.5%PRODUCT
TiO_:1tonne
VJasteproducts ;
r
jjFATALWASTEPRODUCTS |
Expressed ascruantities
ofmetal(kg)
ITi 78,000
FB 52,133
Si 9,746
IZr
Al 6,779
P 0,026
il 0,795
Pig 15,408
Cr 0,422
0,680
Ca 3,538
bla
Ρ 0,256
pi1.068
Zn mm
Cu
j0,101
Corresponding weightofore:1,284kg

-20- EÏÏV/47/75-E
Orig:P
ENRICHED ORE
Thequantities shovrnbelowrelr,tgto1tonneoffinished productand
are"basedonthe.valuesinthepreceding table.
Wasteproduct 1-Insoluble substances
57kg(Si02,Ti02,Al203,Mg0,Cr203,P^,
MnO,VgO^,CaO,Si,Ni,Zn,Cu,Cd,
Be,Sb,He)
–+'•57kg•H20(assumingHgO=50$oftotalweight)
114kg
Wasteproduct 2-Copperas '
None .
Wasteproduct 3-Strongacid
- 185kgvarioussulphates ,including $8kg
ofPeSO.4
+34kgTi02insuspension
+ 31kg TiOoinsolution
+19395kgH^SO.(exp,as100^)concentration 20%
+5,330kgH20
6,975kg
Wasteproduct 4~Weakacid
100kgvarioussulphates ,including 53kg
ofPeSO.
+28kg^^2BUSPens*on
+17kg ;-Ti02insolution
+;,750kgH2S°4(exP»as1
+6,605kgH20+;,750kg^2^4(exp*as100^)concentration 10$
7,500kg

-21- ENV/47/75-E
OrigïF
2)Disposalortreatment of"theirp.steproductsinherentintheprocess
1–Definition
"Elimination ortreatment ofwasteproductsinherentintheprocess"
isunderstood tomeananyintervention whichleadstoachange
intheircharacteristics ,whichcanrangefrommeredilutionin
ordertoreducetheconcentration toveryelaborate operations
radically changing thenatureofthewaste.
2–Listofthemainmethods ofelimination andtrcatr.ent th^tcan "be
envisaged for"wasteproducts inherent intheprocess"
DISCHARGE H3T0THESEA(l)*Thiscanbedonedirectfromthecoast
orbyscattering overthesea.This
methodiswidelyusedforsolublewaste
products (copperasandacidsolutions).
Injection intounderground Thisremiresspecialgeological conditions ,
strata ItsuseintheUnitedStates(DuPont)has
givenrisetostrongcriticism .The
"injected "effluents mustnotcontain
suspensions whichmightclogthewell.
STORAGE ONLAND(2) Thisisusedforinsoluble wasteproducts.
Storage onlandofsolublewasteproducts
("copper£„s")raisesmoreproblems owing
totheirsolubility andtheirlarge
.quantities .Thecompany TKANN&MULHOUSE ,
inThann(France),storesonlandinsoluble
products ,"copperas "andtheneutralisation
productsofitsacidliquors(output
20,000tonnesperannumofTiO^).
NEUTRALISATION (3) Thismethod,whichresultsinaverylarge
volumeofneutralisation product,isvery
littleused.Itscostishigh.Atpresent,
inEurope,onlyTHANN&IIULHOUSE usesthis
methodforitsacidliquors(atThenn).In
theUnitedStates,"SCK"neutralises the
diluteacidfraction .Theneutralised
products areredilutedanddiscarded .
(*)Onlythenumberedmethodscenbeenvisaged ,apriori,inthe
European context.

Production ofgypsum :
LURGI COPPERAS *
DRYING PROCESS (4)
Fluidised–bed drying
ofcopperas compounds
LURGI FLUIDISED-3ED
ROASTING PROCESS (5)
ROASTETG BïAROTARY
PUffîTACE (6V-22- EITV/47/75-E
Orig :F
Production ofgypsum from theneutralisation
oftheacid liquors requires aspecial local'
context .IntheUnited States the American
Cyanauid company is "building afactory for
producing building components ofgypsum .It
should "benoted that inthis oase there areno
local gypsum resources ;moreover ,thelocal types
ofbuildings arewell suited totheuseofsuch
amaterial .
This method enables "copperas "conpounds tobe
dehydrated bychanging them into iron sulphate
monohydrate ,which canberoasted ina
fluidised –bedfurnace (there isanexisting
unit atSpinetta ,Italy ,andonebeing built (
atCelje,Yugoslavia ),
Process employed byBAYER toenable iron sulphate
toberoasted inrotary furnaces .
TheLURGI roasting process mekes itpossible
totreat iron sulphate monohydrate ("copperas "
after dehydration )orconcentrated acids (70$)
containing salts insolution .Oneobtains ,from
thesolid orliquid substance fedin,onthe
onehandSOgwhich canbedirectly used ,inan
HgSO^synthesising unit and,ontheother hand ,
themetal oxides corresponding ?to.thesalts in
solution .There isnoexperience yetofworking
with liruid feed .
This -technique ,which isanoldone ,makes it
possible totreat "copperas "compounds after
dehydration orsalts precipitated during
concentration ofacid liquors .Actually theneed
tousesulphur orpyrites tobring about
combustion leads totheproduction ofquantities
ofHgSO^greatly inexcess oftherequirements
ofaTi02 unit .Thismethod hasbeen employed
marginally byBayer –Titangesellschaft -Pigment
Chemie inGermany andbyBritish Titan Products
atGrimsby (Great Britrin ).

-2.3- 32'7V/47/75-E
Orir-:P
"EEWJERSEY ZH'TG"
PROCESS (7)
LURGIACID-
CCNCEÎTTRATICN
PROCESS (8)
BAYERACII>-
COITCENTRAT ION
PROCESS (9)
BAYEF-3ERTRATTS
ACIl>-COIÍCEtTTRATIOIÍ
PROCESS (10)
Production of
superphosphateThisprocesscmbeusedfortreating acid
liquors.Aftertreatnent puresulphuric acid
isobtained ,together withironsulphate
nonohydra.te nixedwiththeotherelementspresent
inthesolution .Atpresenttheonlyplant
basedonthisprocessisasnailpilotinthe
UnitedStates.
Thisprocess "treats"acidliquorsbybringing
thenuptoaconcentration of70$.Theacid
isnotevaporated ,andthe70%acidstill
contains allthesaltsinsolution .TToactual
unitbasedonthisprinciple .
Bayerusesaprocessofconcentration bysubmerged
flcne.Thisprocesshasprovedvery
unsatisfactory .
Thisprocessforconcentration ofacidlicuors
usesafilnevaporator .Thereisstilllittle
information aboutthopossibilities ofusingit
intheTi0oindustry.
Superphosphate isafertiliser theuseofwhich
inEaropehasconsiderably declined .Itis
obtained byattacking naturaltricalcium phosphate
withsulphuric acid.Atpresentonlyonestate-
ownedcompanyinPolandusesthisprocess,which
requires priorconcentration oftheacidlienors
uptoCj%

•24- EMV/47/75-E
Orig:F
Amnoniun sulphate
production
.I.P.P.PR0C2SS(11)Thisprocessenablesamoniunsulphatetobe
produced fronacidliquors.Ishihara Sangyo
Kaishaholdstherightstoaprocessmaking
possible theoptintratreatment ofacidliquors
bythismethod.Ammonium sulphateisnolonger
usedinEurope,andthismethodisthusoflittle
interestatpresent,atleastinEurope.
Thisprocessenablesdissolved sulphates tobe
treated.Itthusmakesitpossible totreat
eitheracidliquorsaloneoracidliquorsin
wtichthe"copperas "compounds havebeen
previously redissolved .Theproducts obtained
eresulphurandhydroxides andsulphides ofthe
metalsinsolution .
Totheseprocesses shouldbeaddedthoseoftheBUTTNER andSAINT
GOBAMcompanies ,described as"newtechniques "inthefieldofacid
concentration .
Note:IntheNetherlands thereisasystemoftaxation ofeffluents .
Itsanountatpresentrepresents about3»5/SofthecostofTiO^.
IItissaidthatthistaxistobedoubledeveryyear.

-25- EMV/47/75-E
Orig;F
SECTION 3–Treatmont unitsandfinalwasteproducts
A.AHIS
InSection 2alisthasbeengivenoftheprocesses
whichcouldbeusedforthetreatment ofwasteproducts
inherent intheproduction process.
Inthissectionanr.tteaptwillbecade,bycombining
thevariousproposedprocesses ,toestablish couplete
treatment units.Thereareobviously verymany
possibilities ,andonlythomostcharacteristic ones
havebeenconsidered .
Furthermore ,depending onthedegreeoftreatment
whichitisdesiredtoachieve,theunitsproposed can
eitherboadoptedasawholeorsomeoftheirconstituent
partsreplaced orevenomitted.
$hecapitalinvestments rndoperating costsinvolved
foreachoftheseunitewillbestated.Thecapital
investemtn figuresarebf-sedonlyondesigndata
available atpresent,andtheoperating costshave
beencalculated ontheb-sisofvaluesrecorded at
afixeddate(endof1973)^ndarenowbeingupdated
inthelightofthepresenteconomicsituation .The
characteristics andvolumes ofthefinaleffluents will
alsobegiven.
Thesesolutions willbeconsidered forthedifferent
typesofrawmaterials .

-26- ENV/47/75-E
OrigîP
B.BASICDATA
Belowendonthefollowing page,theweightsofeffluents tobe
treatedcorresponding toanoutputofTi02of100tonnesperday
aregivenforthefourtypesofrawmaterials.
4
1■' I----- 1Norwegian
ilmeniteAustralian
ilneniteCanadaan
slag.Enriched
iore
I
» ι
1)DTS0IXJBI^
STJBS'fAMCSS
Totalweicht 16t/d
i.·. I
3.8t/d21t/d11t/d
IVolumeifd=2*
i32m3/d 7.6m*yd 42m/d 22itfVd
"Dry"weight**8t/d 1.9t/d10.5t/d5-5t/d
2)COPPERAS t/d- t/d t/d[
It/d :
!Totalweight 385 !202
PeSO.,1.1/2fl^O189 111 doesnot
existdoesnot
exist
KgSO 20.4 1.1 !
ι
exp.inH^SO^,
exp.inPe2°3122
169
i62
99I
i
»
*d:densityoftheinsoluble substances asawhole
(d»2isahypothetical value)
**represents theweightoftheinsoluble substances if
waterisexcluded fromthen.;

27 ETÏV/47/75-E
OrigîP
Norwegian
ilmeniteAustralian
ilmeniteCanadien
slag •Enriched
ore
3)ACIDLIQUOR
(hypothetical
concentration
20<£)
Totalweight
H2°.
Free
PeSOB2SO4
4
Varioussulphates
HpSO.(free+,
combined )
Exp,in
Exp.insulphur
4)DILUTEACID
(hypothetical
concentration
Totalveirfït
Free
h2O
PeSO,
Varioussulphates
HpSO.(free+
com'bined)
Exp.inPegO^
iExp.insulphurt/d
741
512
140
58
14
195;
61
64t/d
625
429;.
125
58
5.
165
61;
54
t/d
800
80
675
31•
8
106
33
35t/d
672
67
566
•31:
3
89
33
29t/d
720
506
144
30
32
184
31
60
t/d
778
78
652
16
18
99
17
32t/d
697
533.
140
10
9
152
11
50
t/d
750
75
660
5
5
82
5
27

-28- MV/47/75-E
Orig:F
C.GOSTAS3ESHÎ.M:T
?)Cardta!investment
Foreach-treatmentunitthetotalcapitalinvestment isdetermined
fromthecapitalinvestments foreachconstituent part.These
arsfortheperiodend1973-beginning 1974andmusttherefore
adjustedinthelightofthepresenteconomicsituation.
Allowance hasalsobeenmadeforthepriceofrecovering thesulphur
orsulphuric acidasthecasemaybe,excluding allotherproducts ,
particularly FeO.
b)Enerconsuintion '.
* –iiwr-M.ii– ttm
Foreachtreatment theenergyconsumptions forthedifferent types
ofrawmaterials havebeenestablished .
Forthepriceoffueloil,anaveragepriceof50U.A.pertonne
hasbeenassumed.Itshouldbe"noted,however,thattheprocesses
treatinggasescontaining S0?arenotinterfered withbytheuseof
verysulphurous fueloilsuchas"vacuumresidues".Thesetwo
processes aretheroastingprocess (LURGl)andtheI.F.P.process *
Thevalueofthe"vacuumresidues",alwayslessthanthatoffuel
oiljwilldependontheparticular situations ofeachpetroleum
group,thelocationoftherefinery anditsdistance fromthe
consuming factory.
'Depending onthesituation ,the"vacuumresidue"maycostthe
consumerbetween80'foand(exceptionally )60$ofthepriceof
ordinary heavyfueloil.Inthepresentcasethepossible use
of"distillation -"residues "costing40U.A.pertonnehasbeen
assumed.
Note;Itwillberecalledthat,forroasting,sulphurcanbe-need
asafuel,whichinsomecasesmaizesitpossible toreduce
consumption offueloil.Thispossibility dependsgreatly
onlocalconditions ;itshouldmerelybeborneinmindthat
thefuel–oilconsumptions shownforroastingarehighvalues.

-20- EMV/47/75-S
Orig:F
Ev-products
Inpractice weshallconsider onlythreecategories of"by–products :
-sulphur
–sulphuric acid
-ferricoxide(part)orferrichydroxide (part).
Asulphur "credit"willbeincluded incaseswherethesulphates
and/orsulphuricacidaredecomposedintheformofS0^or
elenienta-rysulphur.
A"sulphuric acid"creditwillbeincluded wherever recycling cfthis
acidcanbedonedirectly andtherefore deesnotentailadditional
capitalexpenditure .
Thesavingsarebasedonthefollowing values:
sulphur :52U.A«/t
stilphuricacid::29U.A./t
Note:Asthepriceofsulphurvariesgreatly,atreatment ccst
corresponding toasulphurpriceof30U.A./tandthus
toasulphuric acidpriceof22U.A./th-:.salsobeen
given.
Withregardtoironinoxideorhydroxide fcrir..only
ironobtained fromcopperaswillberegarded ass.by-product
whichmaypossibly bereusable ,butitsvaluewillbe
assumedtobezero.

30 T32TV/47/75-E
D.RECAPITULATION
Treatment unitswhichcanbeenvisaged
forthetitanium dioxideindustry
..Constituent processes-1Capitalinvestment
Ref.(U.A./t.perannum
ofTiOjWasteproducts
aftertreatment
(Dehydration )–Lurgi II1n 263(ironoxide)
Roasting –Lurgi Ironoxides+various
Concentration –Lurgi CaSO,Fe(0H)2
Neutralisation Slag 195water
(Dehydration )–Lurgi
(Roasting)-Lurgi
IFPprocess
Neutralisation(Dehydration )–--Lurgi IIIla
Roasting -Lurgi
Concentration –F.J.Z Slag
Neutralisation
III273(ironoxide)
(ironoxides+various
195Cai394,Fe(0H)2
Water
Ilm, 338(ironoxide)
Fe(0H)p+various
,...sulphates -•«
Slag245245CaSO-,Fe(OH), \J<-*KJJ
Water
Ilm 339(ironhydroxide )
IFPprocess IV Fe(OH)0-fcvarious
sulphates
Slag 254Water
(Dehydration)–Lurgi (ironoxide) :
(Roasting)-Lurgi VIla 351Fe(0H)„+various
sulphates
IFPprocess ■ 'Slag 259Water
(Dehydration )-Lurgi (ironoxide)
Roasting -Lurgi VI Ilm 312Ironoxide+various
Concentration -N.J.Z. Slag 233water
Note1:Thesubstances inbrackets disappearifslagisused
Note2;Thewasteproductsmarked(o)maybereusable.Theyhavebeen
assigned zerovalueintheeconomic calcvilations .

-31- EW47/75-E
Co3tofthemainraethodc oftreatment whichcan "be
envisaged forthetitanium dioxideindustry
(Sulphateprocess)
TreatmentKawHypotheses
Katerial
Fueloil:50UA/t
Su"!plnir52UA/t
Hp30,29UA/t£ .·±Puoioil50UA/t
+diatorss.40UA/t
Sulphur 52UA/t
29UA/tFueloil50UA/t
H-di¡-.t.rea.45UA/u
Sulphur 30UA/t
H30^,22UA/t
UA/tofTi02 UA/tofTiCU UA/tofTiO
I Ilia. 97.3 90.8 113.6
Slag 77 72.8 86
II Un. 77«4" 747 95.2
Slag 53.8 53.4 64.7
III Xlui« 134 124.2 145J
Slag 105.6 97.6 110.8
IV Ilm. 126 100 130
Slag 94.3 82.9 112.2
V Un. 122 108 138.4
Slag 89.3 77»9 112.2
VI lin. 95.4 92.1 108
Slag 52.1 50.9 66,4
Kote~Thisisanestimatemadeattheendof1973/beginningof1974.
Amoreup-to-dateestimateis"beingprepared .

-32- EtJV/47/75-E
Specialcharacteri .stiesofthemainmethodsoftreatment whichcan
beenvisagedforthetitaniumdioxide"industry (sulphateprocess)
TREATII3HT I-lowcost
–concentration processnotyetindustrially proved
–neutralisation wasteproductsratherinconvenient
tostore ,
TRKITIxEfW ?II-Same-comments asforTreatment I
TREATI-E3HT III–Juxtaposition ofseveralfairlyreliable processes
-highcost
-neutralisation wasteproductsratherinconvenient
tostore
TREATIIENT IV-onlyoneprocessused(IPP)
-relatively highcost
-finalwasteproducts apriorilessconvenient than
oxides
TREATIIENT ¥-completofquitereliable processos
-ratherhighcost "<.■
–finalwasteproducts apriorilessconvenient
thanoxides
TPJUiVTIIIiZT VI-"Concentration section"notindustrially proven
–costsensitive totheconcentration ofthewec'Jcacid
-finalwasteproductsfairlyconvenient tostore
and/orpossibility ofreuse.

-33 2F//47/75-
SECTION III .CHLORIÎTE PROCESS
",-Ja'ote product sinherent inthe process
*τ.}■– ,ι·Κι·ι· Μΐΐίΐίΐ:· ^■υι^ φ··^– »
1.General
a)Introduction
Asalready mentioned ,theonly purpose ofthecalculations made in
this section istogive orders ofmagnitude forthequantities .of
wa3te products tobeconsidered *
Admittedly ,inview ofthefact that thechlorine process islittle
used inEurope endthat theinformation about isisgenerally
confidential ,ithasonly been possible tomake rather rough
hypotheses forthis process .
However ,although these hypotheses mayprove inaccurate ,thequantitative
approaoh tothetotal effluents remains valid .
b)Hypotheses
Wehave assumed that :
~theoverall operating yield is$8$inrelation totheTiOginvolved ,
excluding thefinishing (surface treatment )stage .This type of
treatment hasalready been 3een forthesulphate process .Uith regard
toeffluents ,itleads only todilute salt solutions andasmall
quantity ofTiOg insuspension .
-Thezirconium oxide present intheore isnotattacked .
-All the other metals andmetalloids are chlorinated .
-1/Softheraworeislost inthe"blow-offs "ofthefluidised
bedandbyentrainment intheprocess gases .
-0.5%ofthetitanium dioxide islostintheformofTiCl^.
-2%ofthechlorine necessary forthechlorination ofthetitanium
dioxide islo3t through combination with hydrogen from the
reduction coke and the ore .

-34- ENV/47/75-E
-FortheTiCl."oxidation "section
.0.5%oftheTiO,involvedislostinsolidform
.withregardtotheeffluents resulting frompossible liquefaction
ofthechlorine ,theseareverytraditional innatureandhave
beendisregarded inthepresenttechnical report.
)?ist'ribut~iori ofthedifferent wasteproducts
Ithasalreadybeenseeninthedescription ofthechlorine process
thatthefourmajorsourcesofwasteproducts are:.
.wasteproduct 1.–"blow–off "fromthefluidised bed
wasteproduct2-"residues"ofthedistillation ofTiCl^
„wasteproduct3–"venting"fromthedistillation oftheTiCl^
.wasteprod-act4-wastefromtheoxidation stage.
Themeltingandevaporation temperatures ofthechlorides ofthe
different metalsmakeitpossible tosomeextenttopredictthe
distribution ofthesechlorides inthewasteproducts .Furtherir.'ore ,
certainhypotheses havebeenmadeforthedistribution ofthelosses
ofore,TiCl^andchlorine.
.Wasteproduct 1
The•AoleoftheZr02,I&iClg5IlgCl^,CaCl^,FaCl.
Kalfoftheorelosses.
0'product 2
ThewholeoftheSNbCI,,A1CI,,CrCloJFoC?._3'3' 5
ThevanadiumispresentintheformofVOCIg
Halfoftheorelosses.
.rvasteproduct 3
ThewholeoftheSiCl^,PC13(POCl^)
ThewholeofthelossesofHG1andTiCl.ν

-35- KÏV/s7/75-E
2-A.WASTEPRODUCTS (ERnESPOEDIlPJ TOSTATURAL JtUTILE ORE
ORIGINAL ORE PROPUCT
FATURAL RUTILEmiO?:1tonne
% kg
~1J3r\Otfr
TiO 96.6O 1020.400xxtjxuyv.o
FATAL WASTEPRODUCTS
PcO
Fe2°3
Si02
Zr020.35
0.353c696
3.696expressed ,
quantities
(kg")as
ofuetal
0.65 6.866 Ti 12.240
AlpO 0.45 4.752 Pa 1.219
p2°5
IJhO0.05
0.020.5?-7
0.211Si
Zr1.700
5.032
ïfeO 0.06 0.633 Al 1.254
Cr~0 0.30 3.169 Iva3teProducts Ρ 0.106
v2°5
CaO0.66 6.971 ;in 0.163
0.01 0.1057T,~> --0.380
Na.O Cr 1.0^2
K~0 V 1.074
S Ca 0.072
h20lia
Co mmC!
c Ni
ÏTbO~ 0.30 3.169■Zn
E 0.20 2.113 Cn
Cu
1Tb
K2,352
2.111
Total1056kg
Typicalcomposition
Distribution ofeffltients :
wasteproduct 1:14kg/tofTiOp(ZrO-+variouschlorii
wasteproduct2:30kg/tofTiOp(+variouschlorides )
wasteproduct 3:591-S/t0-TiO(+variouschlorides )

-36- EtTV/47/75-E
2-B,WASTE PRODUCTS CORRESPONDING TOSYNTHETIC RUTILE ORE
(Benelitetype)
ORIGINAL ORE
SÏMÎIÎÎPIC RUTILE "
Ti02
FeO
Pe2°3kg
951020.40
'1.8 18.96
2.0 21.60Yield93%PRODUCT
Ti0o:1tonne
FATALWASTEPRODUCTS
Expressed as
quantities cfmetal
(kg)
Various 1.2 13.09Ti,
Fe12.240
22.665
WasteproductsVarious
(13.09)
Correspondmg weightofore:1074kg
Distribution ofeffluentss
Wasteproduct 1:14kg/tofTiO^
Wasteproduct2:90kg/tofTiO^
Wasteproduct3:59kg/tofTiO-

2-C.WASTEPRODUCTS CORRESPONDING TOAUSTRALIA IIZZEUTE ORE
ORIGINAL GRE PRODUCT
AUSTRALIAÎT IUIENÏTEYield9G%TiO„:1tonne
afkg
TiOp 55«41020»20FATAL 'WASTEPRODUCTS
FeO
Fe2°3
So0223.8
16.9 '
0.15433.351
311.350
2.763expressed m
quantities ofmetal
(l'-g)••
ZrO Ti 12.240
A1~0 0.94 17«337 Fe 449.513
P25
Ilîn00.0c 1.439 Si 1.264
0.72 13.274 Zr
lîgO 0.27 4.966 Al 4.569
Cr0,0.14 2,753 Ρ 0.297
2e)0.17 3.160 lin 10.267
CaO 0.02 0.361 2.979
Na„0 Cr 0084^
^2°Wasteproducts V 0.830
nO 0.01 0.180 Ccl 0.252
MCrtJ 0.100
Zn ITi
Cu Zn
Cd Cu
Pb,Be Ce•
Sb,Hg Pb,Be
Corresponding weightofore1.842kg
N.B.Thetotalofthecolumndoesnotcorrespond to2,040kg,asthevreights
ofeachconstituent haveaveragevaluesrelatedtodifferent compositions
ofilraenite .
Distribution ofeffluents :
Wasteproduct1s44kg/tofTiO^(ZrO+variouschlorides +ore)
Wasteproduct2:1,339kg/tofTi02(variouschloridesincluding1,304kgofFeCl^)
Wasteproduct3$76kg/tofTiO„(variouschlorides )

38- Emy47 /75-E
Treatments
A.Effluent 3considered
A3stated earlier ,thechlorine process islittle used inEurope .In
allcases theinstalled capacity issmall .
Moreover ,these units atpresent usenatural rutile ,that is,anore
veryrichinTiC^(about 96$),which therefore gives risetoonlyfairly
minor quantities ofeffluents .
These twofactors mean that theproblem oftheeffluents ofthechlorine
process does notreally arise inEurope .
nevertheless ,themain treatments which canbeenvisaged inthis case
will beexamined ,firstly because even though thechlorine process is
atpresent little U3ed inEurope ,itisnevertheless under certain
conditions avalid alternative tothesulphate process ,andsecondly
because thepossibilities ofdevelopment ofsynthetic rutile orthe
possibility ofusing apoorer oremay lead toachange inthepresent
positions .
Itmaybenoted that intheUnited States ,where thechlorine process
isvery widespread andwhere DuPont issaid tousearelatively poor
oreinoneofit3factories ,theproblem oftheeffluents ofthis
process hasarisen .
.DuPont ,which isthecompany most involved inthis direction ,hasnot
yetsucceeded ,despite major research efforts andstrong economic
incentives ,inperfecting theregeneration ofthechlorine byoxidation
oftheby-product chlorides .
After having envisaged discharge into underground strata ,itwould
appear that IhiPont hasdecided tooptfordischarge atsea .

-39-
Thefollowing will notbeconsidered inthis chapter :
-theeffluents ofthe "regeneration "unit forthechlorine tobe -recycled ,
asthese aretraditional andnotspecific tothis industry ;
-theeffluents corresponding tothefinishing operations (surface
treatment );these arenotpeculiar tothi3 process .
Weshall deal here with the treatment ofthe chlorides which are formed
simultaneously with thetitanium tetrachloride andwhich areseparated in
thefurther course oftheprocess .
Three sources ofwaste products forthis type ofeffluent and forthis
process have "been listed .These effluents areidentified as"waste
product 1,2and 3"»
B I?ain processes
Theconsiderations regarding thedischarge ofeffluents into underground
strata oratseawill not berepeated here .These eventualities have
already been examined tirithin theframework ofthe *"sulphate "process
(page 21).
Itmaybenoted ,however ,that these aretheonly twomethods which have
been adopted inpractice intheUnited States ;underground discharge has
incidentally been strongly criticised .
Theonly twoprocesses xirhich seem torepresent apossible treatment for
this type ofeffluent areones which enable themetallic chlorides tobe
broken down into oxide3 ,thechlorine then being combined toform HC1 .
Actually these twoprocesses arefairly similar inprinciple ,themain
difference being their type offeed :
–chlorides insolution inonecase ,
-solid chlcrideE inthe other case .
The companies holding therights tothese processes areWOODALL DUCIOIAII
and LURGI respectively .

«•»40••
\Emy47/75-E
Itshould also benoted that thecompany "CHLORINE TECHNOLOGY Ltd",
which isengaged intherecuperation ofilnenite ,issaid toheld the
rights toaprocess fortheoxidation ofthechlorides ,hutthis isnot
yetregarded asvery satisfactory .There isnodoubt ,however ,that
companies other than those enumerated above arelikely todevelop
processes which would bebased onsimilar principles .
Itmayalso bementioned that inthetwocases referred toabove itis
aquestion ofadapting existing ,proven processes whose application has
notyet ,however ,been tested inthis particular field .

-41 EETV//7/
PART 2
ECOLOGICAL ASPECTS

-41a- EW/47/75-E
GENERAL
Examination ofthe restilts already obtained •
Examination ofinternational scientific documentation onthe effects of
discharging theresidues from theproduction oftitanium dioxide into
theeealeads ustoregard these waste products aspotentially oractually
harmful tothemarine aquatic medium .
Thedegree ofharmfulness oftheresidues mayvary depending ontheir
composition ,themethod ofdischarge andthecharacteristics ofthe
receiving medium .Theadverse effects ontheenvironment areduemainly
totheacidity ,tothepresence offerrous sulphate andprobably tothe
other metals (heavy metals )which arealso present .
Depending onthecases ,theadverse effects ontheenvironment cantake
thefollowing forms :
1)reduction oftheoxygenation andpHofthewater andincrease ofthe
concentration ofiron andother heavy metals .Theduration andextent
ofthese effects depend onthephysico-chemical characteristics ofthe
waste products ,andespecially their concentration ;
2)a)temporary depletion ofthezooplanktonic biomass andproduction of
effects leading toadeterioration inthemorphological structure
ofitacomponent parts *;
b)repulsion andremoval ofcertain species offish ;
c)reduction ofthebiomass andoftheproduction anddiversity of
specie3 ofthebenthic and/ornactobenthic biocenoses inthe
discharge area .Inmore serioua cases allanimal life may
disappear .

-41b- ENV/47/75-E
3)deterioration inthecolour ,transparency andturbidity ofthewater
andtemporary reduction ofphotosynthesis ,phytoplankton andprimary
production ,especially ineases where thewaste isdischarged cnthe
surface .Covering ofthe soabed with ferric oxides rjidoxides of
other metals where thewaste isdischarged inestuaries andplaces where
thewater isshallow ;
4)ontheother hand ,there have been noreports ofdangers oftoxicity
forhuman beings duetoeffects produced bytheconsumption ofspecies
from theplaces where thewaste hasbeen discharged .
Thedegree towhich theabove-mentioned phenomena occur varies depending
01:.thedifferent methods ofdischarge .There isnot ,however ,asingle
case inthescientific literature published ormentioned bythevarious
experts ofthe Ilember States inwhich oneormore ofthese phenomena have
not been recorded .
All this leads tcthe conclusion that discharge into the sea ofwaste
from theproduction ofTiOgmust becontrolled andeven suspended within
acertain period inorder toprevent damage tothemarine environment ,
now and inthe future .
Asanillustration ofthe effect ofthedisposal ofeffluents ofthe
TiOg industry ,theresults ofthe"Vlhite Book"published byPrance in
connection with thedischarging oftheMontedison company 'swaste products into
into theMediterranean Seaarereproduced onthefollowing pages .

42- EN7/47/75-E
CHAPTER V-ESTIMATE OFTHE PHYSICO-CHEMICAL CHANGES DUE
TOTHE DISCHARGES
Thefollowing analysis deals mainly with thephysico-chemical changes
(inpH,saturation indices ,change innatural concentration ,etc.)which
nayhecaused bydischarges such asthose made bytheMontedison
company . •
1)Three ma.jor factors must "beconsidered
Ashasbeen stated earlier ,thewaste products arecharacterised by:
-high acidity duetothepresence oflarge quantities offree
sulphuric -acid intheeffluents :wemust therefore assess the
reactions ofseawater when faced with the introduction of330
tonnes ofpure sulphuric acid perday .
++ ._ '-ahigh content ofdivalent iron Fe :thecommonest form of
++-+■iron inthe sea istnvalent iron Pe tthe .
oxidation inseawater must therefore beconsidered .
-abynomeans negligible content ofheavy metals such astitanium ,
chromium ,vanadium ,cadmium ,etc .
2)Reaction ofsulphuric acid
Seawater isamedium with avery strong buffer capacity with regard
toacids andbases .This buffer capacity isbound upwith thebalance
ofthecarbon dioxide gas ,bicarbonate –carbonate system .Ittakes
3milli-equivalents ofstrong acid perlitre totransform the
carbonates andbicarbonates into carbon dioxide gasandreach apH
ofabout 6. •
Onthisbasis itcanbecalculated that ittakes 12m^ofseawater
to"buffer "onelitre ofpure sulphuric acid (pHbrought back toa
value of6orabove ).

-43 EW//!7/75-E
Itisassumed (Americanpapers)that15mofseawatercompletely
neutralise 1litreofpuresulphuric acid.
Onthe"ba3i3oftheabovevalues(330tonnesofH?S0^dischargedperday)
aneutralisation volumeof
lliUIMOO.2,300,000 m
isobtained .
Inordertoestablish anorderofmagnitude ,theareawithinwhicha
dailydischarge isneutralised naybeestimated atabout30hectaresif
itisassumedthatthedischarged wastediffuses slowlyinavertical
direction whatever thedepthatwhichitisdischarged andthatitonly
affectsalayerofwaterabout10nthick(cf.theconclusions ofthe
C.N.E.X.0 ,reportonhorizontal andverticaltransmissions inthearea).
Theoxidation ofdivalent ironintotrivalentiron
Whileseaitfater hasabuffercapacity asregardsacid-base equilibria ,
thepositionisdifferent asregardsoxida\ion-reduction couples.That
iswhyitmustbeassumedthathighoxygendemandscanonlybesatisfied
byutilisation oftheoxygendissolved intheseawater.
2+Ifweassumethatittalcesonemolecule ofoxygentooxidise 4Feions
into4Feions,wearriveatthefollowing calculation :
140tonnesofdivalent irondischarged perday
needinordertobeoxidised :
1^032x7"»20tonnescfoxygen
Itmaybementioned inthisconnection thatthisrepresents approximately
theoxygendemandofthesewageofatownwith:
20yl0,»350,000inhabitants (1)
(1)Thisisanimportant pointandenablesustorelatethesedischarges
tothoseofthecoastal townsoftheCoted'AzurandtheGulfofGenoa.

-44- ENV/47/75-E
Theavailable data concerning "this area indicate aquantity ofdissolved
oxygen of8mg/litre ,or8g/m\Thevolume ofwater required for
complete oxidation ofthewaste istherefore (assuming that the
oxidation takes place near thesvirface ):
?P.O,Q.-ot;nnnnng–=dt500 ,000m
(itwill "benoted that there isafair degree ofsimilarity between this
value andthevolume required to"buffer "theeffluent ,although itis
necessary toemphasise theapproximate nature oftheabove twocalculations ,
thesole purpose ofwhich istoprovide orders ofmagnitude .)
63
*•Itwould however bemisleading topicture anactual volume of3•10m
affected bythesulphuric acid :infact ,only 'programmes of
measurements carried out onthe spot can permit amore accurate
determination ofthevoluae involved ,which isprobably smaller owing to
theturbulences which appear atthesurface ofthestreams ofwaste
products andwhich have theeffect ofspreading outtheperiod during
which thedilution phenomenon takes place .
–Similarly ,theoxidation ofthedivalent iron into trivalent iron
isprobably along-term phenomenon :theexperimental results obtained
both attheplace ofthewaste discharges andintheNorth Seaorin
HewYork Bayrepresent aslow oxidation ,which never reduces theoxygen
saturation index ofthearea bymore than 30^.
Itistherefore logical toassume that thedischarges ofwaste products
cause theformation ofamass ofwater with asmall oxygen deficit ,but
much larger involume than hasbeen envisaged .

-45- Θτν/47/75-Ε
4) eand "behaviour oftheheavy elements cucli aschromium ,vanadium .
c?A".im andtita n:.un
Ithasbeen thought necetsary todevote aparagraph torecalling
certain overall data concerning thepresence andpossible role of
such elements ,which have recently ledtotheadoption of3ome
contradictory attitudes .
1-Itmust berecalled inthefirst place that allthese elements
arenaturally present inseawater ,asi3shown bythefigures
taken from Riley andSkirow (1965 )andIvanoff (1972 )inthe
following comparative table .
Elements Weight present in
1kgofrock
(average )inmgConcentration
sea water in
ng/1mWeight present in
1kgofpelagic ,
sediment intigResidence tme in
the sea in
yoars (1)
Si 275,000 3 199,000οo103
Al 83,000 0,01 65,000 100
Fe 52,000 0.01 41,000 140
22,000 1,300 17,000 4.510'
Ti 6,300 0.001 3,500 160
iïn 930 0.002 3,200 1,400
V 120 0.002 330 104
Cr 65 0.00005 80 350
Cd 0. 0,0001o5 105
Pb150,00003 160 2103
(1)The "residence tine"ofanelement intheseaisequal totheaverage time for
which this element remains inthesoawater before disappearing bysedimentation
orbiological absorption .Ashort residence time foranelement which iE
assumed tobetoxic (afavourable factor from theoverall point ofview )is
therefore not areassuring criterion from thepoint ofview oftheconsumer
oftheproducts ofthesea ,insofar asthis rapid elimination ispartly achieved
thanks toconcentration phenomena inthebiological chains .

f-46– EN7/47/75-E
Itwill thus beseen that thechemical composition ofrocks isfairly -
close tothat ofsediments .Ontheother hand ,therelative composition
ofseawater isentirely different from that oftheearth 1scrust ,a
fact which implies theexistence intheseaofprocesses which limit the
concentration ofcertain elements although they arecontinually provided
byrivers ,run-off water andwind-borne matter .
Theintensity oftheaction produced bythese .mechanisms onthevarious
elements iswell represented bythe "residence times ",which canrange
from around 100years foraluminium ,iron andtitanium toseveral tens
ofmillions ofyears forcertain alkaline andalkaline-earth substances .
Theprocesses ofregulation ultimately tend toeliminate certain
elements from seawater byincorporating them inthesediments .They
arephysico-chemical (formation ofcomplexes ,co-precipitation ,
absorption andionexchanges ontheparticles oratthesediment levels )
andbiological innature .(Many marine organisms selectively concentrate
certain elements .During mineralisation oforganic matter ,aportion
sediments andrepresents aloss fortheseawater ).
•2–With regard more specifically totitanium ,itwill beseen that this
element isoneofthemain constituents oftheearth 'scrust ,representihg
about 0.5$ byweight .Itisalmost equally abundant insediments .It
ispresent invery lowconcentration inseawater ;itsresidence time
hasbeen estimated at160years .Byitscharacteristics iti3closely
akin tothe three most abundant constituents ofthe earth 'scrusts
silicon ,aluminium andiron .Titanium isregarded asphysiologically
inert .
Thetrace elements ,hexavalent chromium (l)andabove allcadmium are
well-known fortheir toxicity .Vanadium would also appear tobetoxic ,
(1)Chromium isharmful initshexavalent form ,butintheseaitisquickly
changed back toitsless dangerous trivalent form .Thechromium contained
inthewaste from themanufacture oftitanium dioxide isalready inthe
form ofatrivalent oxide .

-47- ES-TV/47/75–E
butthereisasyetrelatively littleliterature onthispoint.
3–Inordertogiveaclearerideaoftheactualscaleofthetraceelements
discharged withthewasteproducts oftheMontedison company ,itvas
therefore thoughtworthwhile ,onthebasisoftheforegoing information ,to
preparethefollowing table:
Elements Weightprésentin3000t
ofrockinkgweightprc3entinthe3000tof
wasteproducts fronthemanufacture
of150tofTiO^/ds-yO/
(ke)
Fo 156,000 145,000
Ti 18,900 7,800
M 2,790 1.750
V 360 710
Pb 45 30
ci 1.5 30
Cr 195 100
Thistablebringsoutthesimilarity whichexist3betweenthequantities
ofheavymetalspresentinthewasteandinthosameweightofrocks;
butthissimilarity isrelative ,becauseitmustbepointedoutthatthe
effluents containvanadium andcadmiuminlargerproportions thanthe
rocks.
Suchfigures donotwarrantthedrawingofanyconclusion regarding the
directorinducedtoxicityattributable toheavymetalsinthowaste
products :partoftheseisdissolved intheliquideffluent ,uhichis•••
nottrueofthosewhicharecontained inrocks.

-43- ENV/47/75-E
When theeffluents arediluted ,alarge .proportion ofthemetal3
precipitate inmineral form andproduce asediment onthesea "bed .
The phonoriena ofindirect toxicity arebound upwith thetwoportions
(dissolved andprecipitated )ofthemetal salts inthewaste .
Thecomparison made iatherefore only ofoverall value ,being
quantitatively valid inrelation tothegeochemistry ofthewhole of
theLi^rrian basin .Itshould furthermore berecalled that this area
naturally receives quite substantial quantities ofheavy metals naturally
entrained byrivers asthe soil iswashed anderoded .

-49- ENV/47/75-E
CHAPTER VI-STUDY OFTHE BIOTJUGICAL EFFECT OP
EPb'UJSNT DISCHARGES
The ,different aspects oftheproblem
Thestudy ofthepossible effect ofthedischarging ofindustrial ,
effluents into thesea isanextremely complex matter .Forthis
effect has twodifferent aspects :
-ashort-tern effect bydirect or"acute "poisoning ,which caneven
lead tothekilling ofliving beings intheimmediate vicinity of
thedischarge area ,Inthespecific case ofthewaste products of
Ilontecatini Edison ,thjjeffect will bemainly duetotheir high
sulphuric acid and iron content .
-anindirect long-term toric effect bytheaccumulation ofcertain
elements infood chains *This phenomenon does notnecessarily lead
tomajor disorders inmarine life itself .Problems mayarise ,however ,
atthe level ofhuman consumption offish ormolluscs which have
accumulated high contents ofunxlesirable elements inthegeographical
area ofthewar,te discharges .
Inthecase ofthedischarges oftheIlontedison company ,their indirect
toxicity maybeduototheir content ofheavy metals :titanium ,
vanadium ,cadmium andchromium .
Forthepurpose ofstudying thebiological influence ofthewaste products
itistherefore necessary todistinguish between these twomain directions
ofinvestigation ,They canbecovered :
-bybiological observations "onthespot "
–bylj.Doratory e.xperiments ,

-50- EÎÎY/47/75-E
Theritudieeofdirectorindirecttoxicity carriedoutmlaboratories
areall"basedonobservations ofthebehaviour ofmarineplantsor
animalsplacedforfairlylongperiodsinvariable concentrations of-
theeffluent undertest.
Itisimportant toemphasise this"time"a3pectattheoutset,since
inthenaturalenvironment acertainnumberofthespeciestested
willtendtofleefromthemostactivezoneofthev;astematterand
willfinallyonlybeexposedforrelatively shortperiodstotheweakest
dilutions ofeffluents , •
Ilanyinvestigations havebeenmadeintothetoxicity ofthewaste
products oftheMontedison companyorofsimilarwaste.
Theresultsatpresentknownwillbegiven,inthelightofthe
foregoing ,underthefollowing mainheads:
-analysis oftheshort-term effects
-analysisofthepossible long-terra effects.
SECTIONI-THEoHCRT-TEPJ ;EFF3CTS
1)Dataonthebehaviour ofthemarineflorg,andfaunainthevicinity
'ofthedischarges
a)Bohaviour ofmacro_3copic animais
Itisimportant toemphasise thispoint,whichmayhaveledto
misunderstandings inrecentmonths:ithasneverbeenpossible
toobserveinthedischarge goneanyabnormal mortality of
macroscopic animals suchasfish,molluscs ormarinemammals .

-51- 2!TV/47/75-E
Orig.:F
Furthermore ,noneofthevariousreportsofthefivemissions
carriedoutonthespot "byFrenchtechnicians mentions thepresence
ofbodiesofanimals onthesurfaceofthewater.
Withregardtothestranding ofspcm-whales andcetaceans which ,
hastakenplacefairlyrecentlyintheMediterranean ,thecon­
clusionsofthereportoftheIiistitutScientifique etTechnique
desPSchesliaritimes areasfollows :
"Withregardtochestrandings ofcetaceans inCorsica,viehave
"beenabletoanalysethemuscleandfatofasperm-whale strrnded
nearBonifaccio .Itappearsthatthomercurycontentrecorded
ishigh(about4nig/kgwetweight),butthefactthatthecontent
ofotherheavymetalsisinnowayabnormal suggeststhatthe
Montedison wasteproducts ,whichdonotcontainmercury ,are'not
thereasonforthedeathofthisanimal.Thehighjiercurycontent
maybeattributable tothewa,steproducts ofthechlorine industry
discharged intothoGulfofGenoa ,andtothedischarging atseaof
thewastefrommercurymines."
Furthermore ,examination ofthevariousforeignreports modeon
discharge locations intheNorthSeaorNewYorkBayleadto
identical conclusions :nodeathsofpelagicorevenbenthic
fish(althoughsuchdischarges aremadeatdepthsof20to30m)
havebeenreportedintheareasinquestion .
Itseemslikelythatthemacroscopic animalsintheimmediate
vicinityofthewaterswherethoeffluents aremostconcentrated
fleefromthenandthusescapetheinime&iate toxiceffectofthe
waste;theprobability ofmacroscopic animalsbeingdirectly
engulfedinthewastedischarges andaffected bytheiracute
toxicityis.moreover ,likelytobelow.Onlyadditional

-52- m/47/75-E
Orig.:P
experiments couldmakeitpossibletoestablish ,onthe"basis
ofanamountofdatalargeenoughtobestatistically processable
whetherornotthefishstockshaveappreciably changedinthe
discharge area*.
b)Behaviour ofplanktoninthedischarge rroa
Itwilleasilybeunderstood tha;ta,studylikethisisdifficult
tocarryoutonthespotforpurelytechnical reasons.Itis
therefore discussed inmuchgreaterdetailinconnection with
thepresentation oftheresultsobtainedinthelaboratory :
itshouldimoreover benotedthatplankton doesnotpossessany
meansenablingittofleefromthedischarge area:thelaboratory
studytherefore givesanexceptablerepresentation oftheactual
behaviour ofplanktoninthemedium *
Itis,however,worthwhilementioning theconclusion ofan
American studymadeonthedischarge ofsimilarwasteproducts
inNewYork3ay.
TheNational Research CounciloftheNational AcademyofSciences
FishandWildlife Service,mentionsthat "zooplanktonic
erganisns wereimmobilised byexposuretotheeffluent .Butthey
generally renusedtheiractivity andappeared normalaftertwo
orthreeminutes,evenwhenremaining inthecontaminated
water.
Specimens placedinsamplestakenfromthewashlessthanone
iininuteafterthepassageofthelighterdidnotreaxt.Assoon
asthiswaterhadbeendilutedhalf-and-halfwithuncontnminated
seawatertheyreactedandstartedtoswimaboutagain".
Itwillbenotedthattheseexperiments carriedout"insitu"
donotprovideanyaccurateexperimental data(concentration ,
speciesobserved...),buttheyleadustoexcludeanyimmediate
large-scale mortality ofzooplankton inthewashofthelighter
whichdischarges theeffluents intothesea.

-53- ENV/47/75-E
Orig.:F
Bethatasitmay,thisstudyconcludes that"thevolumeofacid
waterofeachdischarge issosnailcoupprod withthoTtfater
available thattheeffects onthezoopl -nktonandphytoplankton
willbonegligible ".*
2)Experimental dataonthebehaviour ofmarinefloraandfruna
withdifferentconcentrations oftheeffluent
Determination ofacutetoxicity thresholds
a)ReportoftheInstitutScientifique etTechnique desPêches
Maritimes
Measurements ofacutetonicity weremcdeonthefollowing
marinecreatures :
1phytoplanktonic alga :Phacodactylum Tricornutum
1zooplanktonic crustacer.n :ArtemiaSalina
3lamellibranch molluscs :CstreaEdulis(oy3ter)
CardiumEdule(cockle)
IlytilusEdulis(mussel)
1gasteropod mollusc :Littorinalittorca (winkle)
2crustaceaiu :Cr-.ngoncra.ngon (shrimp)
Palaemonserrâtus(prawn)
2fish ;Pometoschistus minutus
Elvcrs(post-larvae of
AnguiliaAnguilia).
Theexperiment s.wereperformed onlotsof10animalsmglass
crystallisers withacapacityof4lfeachofwhichreceived
21ofsolution .Asuitable aeration wasmaintained by
bubbling throughout thoperiodofthetests.
Thedeadanimalswereremoved andthecumulative mort°iity
percentages after4-8and96hourswererecorded .
*N.B.Translator 'snote:,,Thesetwoquotations ,re-translated fromthe
Frenchversionofthereportinquestion ,shouldbecheckedwith
theEnglishoriginal .

-54- ENV/47/75-E
Orig.:P
Results
ThegrowthcurvesofPhaedactylum tricornutum forthe
different dilutions oftheeffluent aregiveninFig.1.
Wefindthatthegrowthintheculturewithadilution
ofl/l0,000ispractically normal.
Adilutionof1/5000showsagrotvthofapproximately 65£
ofthegrowthofthereference culture.
Adilutionof1/3000corresponds verynoticeably withthe
concentration whichreducesthegrowthofthecultureby
half,ortheLD50.
Lastly,dilutionsof1/2000and1/1000appearincompatible
withthedevelopment ofPhaedactylum tricornutum .Butit
wouldappearthatthepEvaluesofthecultures atthesetwo
dilutions arelargelyresponsible fortheabsenceofgrowth.
Thecumulative mortality percentages after48and96hoursare
showninFig,2.
WeobservethattheArteraiaeshowthegreatestsensitivity ,
since45*50an&100$ofthepopulation dieatthe
dilutionsofl/3000,1/2000andl/lOOOrespectively after
96hours.
Shrimpsandthetwofishtestedarealsosensitive ,because
thedilutionof1/1000causesthedeathofthewholeofthe-*
populations after96hours.
I
Lastly,forPalaemonserratus,Ostreaedulis,Cardiumedulis,
MytilusedulisandLittorinalittorea ,nomortality isfound
atthe5dilutions tested.
Kecantherefore concludethattheeffluentisacutelytoxic

120
110
100
90
80
70
6o
50
40
30
20
10
0yy- m747/75-E
Qng.
reierence
lj ^^__|i/ioooa
_
//
ï/5~CÔÔ
Jfp/L
7JJL I
ι "11/α.υυυ ■ 1■– –123 45^7 ?<^Ξ

EM/47/75-E
Orig.:F
Fi"VT>e?■•Percentrge
dilation oEortrlity c:t4oand>6
fïhocffluent .hoursdepending onthe
1/100001/5000l/30001/2000l/l000
^.rtemia46h 0 0 A A 100
sr.lma
96h 0 16 45 50 100
42-h 0 0 0 0 0
rciicicmua –
serra .tue96h 0 0 0 0 0
Crrngon48h 0 0 0 0 66
crangon
h 0 0 O 0 100
Ostrea48h 0 0 0 0 0
ednlis
56h 0 0 0 0 0
Crrdiua48h 0 0 0 0 0
edule
96h 0 0 0 0 0
ilytilus48h 0 0 0 0 0
edulis
96h 0 0 0 0 0
Littorina .4oh 0 0 0 0 0
]ittorea .
9oh 0 0 0 0 0
Pomatoschistus48h 0 0 0 0 100
ninutus
96h 0 0. 0 0 100
Elvers
Anguilla –48h 0 0 0 0 100

ÏS.-V//7/75-E
Orig.:P
forconcentrations rangingfrom1/5000to1/cOOO(thelf,ttor
concentration not"beingfataltotheorganisms "butret\n'.i.ic
.thegrowthofsomeofthem).
b)Resultsprovided bytheCentred'EtudesetdeRecherches do
Biologieetd'Océanographie ï-Iédicales (C.E.R.B.O.ïi.)
Theworkdone "byCEHBOiirevealedtoxicity thresholds ofthe
sameorderofmagnitude asthoseobserved bytheI.S.T.P.H. ,
i.e.vaiyingtoxicities forconcentrations ofl/'lOOOto
l/l0,000(seethe-resultsbelou).Itshouldbopointedout
thatthetoxicdilutionofl/35,000isrecordedforthenost
sensitive fish,butafterast:^yof10daysinpollutedwfter,
whichrepresents artificial conditions .
Results
1.Pelagictypechain
-Phytoplancton :Anterior ,ella¿aponic?1/1,000
-Zooplanlcton :Artemiasalina 1/1,000
-Fish :Carassius auraius l/2,000
2.Benthictypechain
-Marinebacteria :between 1/1,000and1/10,000
-Annelida :Nercisdiversicolori aLout1/2,000
3.Neriticcrustacorntypechain
-ForEai'inebrcteria thethresholds hc.dbeendetermined
duringearlierexperiments .•–Fish :Labrusbergylta 1/16,000
-CruBta.ce ans-ilolluSCS :jvytilusedulxs :
:Leander cerratusabout1/3,000
1/2,000
4.NeriticnolJusctypech.?in
-Phytoplankton :Diogenes sp
-ï'clluscs :Kytilusedulis1/2,000to1/3,000
1/8,000

-5o- ENV/47/75-®
Orig.;F
c)Foreignexperiments
Interesting studieshavebeenmadeinNei*YorkBaybythe
WoodsHoleOceanographicInstitution ,Massachusetts .
Someofthesegivethefollowing resultsoftoxicity studies
"invitro"oncopepoda andphytoplankton gathered closeto
thedischarge area;theresultsaresummarised asfollows :
"Theexperiment onthedevelopment ofphytoplankton didnot
showanysignificant effectonthegrowthofphytoplanlcton
foraconcentration ofl/l0,000.
After12dnys "boththecultureinthediluteeffluent and
thereference culture showedanincrease inthenumberof
cellsofthosemeorderofmagnitude ,withoutanyapparent
changeinthediversity ofthespecies.
Thestudiesofchlorophyl aandofcarbonpr.rticles confirm
theaboveresults.
Theredoesnotappeartobeanyeffectonthesurvival ofthe
eggsorthedevelopment ofthecopepod "pneudodiaptomus
coronatus "insolutions withconcentrationsofwasteacidof
10-5and10-6byvolume.Attheseconcentrations thoperiod
ofdevelopment fromtheeggstagetotheadultstrgeinfiltered
andunfiltered effluent was13to14days-,whereasthereference
inseawater(waterfromtheWoodsHolebridge)indicated 13
drys.Intlios-nee:cperinent ,bvetwithan-cidconcentration
of1C-,',theeggsditnodhatch,highnorfcality ofnnupliiwas
observed ,ortheperiodofdevelopment fror.itheeggtotherdult
waslongerthruthatobservedinthereference srmple.Owing
tothefactthatthenaupliiandtheadultsdisplrj^ed ,when
examined ,rnaccumulation ofironontheirexo-slceletons rnd
theirappendages ,filtered wasteacidwasusedin'anotherseries
ofanalysesduringwhichthemortality rnddevelopment timesin•
eachofthe10-4wa.steacidconcentrations ~ndinthereference
concentration werecompared.Intwocfthesesolutions nocopcpod
reachedtheadultstage.

-53r,- EN-../47/75-E
Orig.:P
Inthetwoothersthedevelopment tin:3wr.slengthened f-jorr .
3to7daysinconp~rison withthetinesobservedtobe
t<?Jcentoreachenidentic?.!degreeofevolution inthe
reference samplefromtheWoodsHolebridge."*
*N.B.Translator 'sNote:Heretoo,comparethisre-trrjnslation
withtheEnglishoriginrl .

/
-59- EN1F/4Ï/75-E
Orig .:P
d)Acute toxicity thresholds
Itisobviously difficult todraw anyfinal conclusions from
.results ofstudies carried outondifferent organisms under
conditions which aresometimes dissimilar ;moreover ,some
figures putforward display relet ively large discrepancies .
Theresults r„sawhole can ,however ,"besummarised asfollows
-atadilution ofl/l0,000 theeffluents display notaxipity
orinhibition ofgrowth inrelation tothe phytoplanlcton
elements (alltheresults agree onthis point );
-with regard tozooplankton ,thetoxicity threshold isfor
dilutions of1/2,000 tol/5,000 .However ,certain stages
ofdevelopment aresensitive todilutions down tol/l00,000
(.tjierican experiment );
<-formolluscs theresults diverge r.nd ,intheworst cc.se ,
give toxicities foradilution of1/8,000$
-forcrust aceans ,thetoxic dilutions a.rearound l/2,000 ;
-lastly ,thegrowth ofmarine bacteria ,isnormal fora
dilution ofl/l0,000 .
Itcantherefore beconcluded that thedirect toxicity effects
oftheeffluent only appear below adilution ofl/l0,000 .

-60- 3r-747/75■-E
Qiig.F
3;Estimate ofthec1ire";t■"onF-eyvcicg'pfthec"i^chr:,r ,--e3or.ta~.rine
•faun?,andflorr(Theeffectofsludge-type wasteisexcluded
fromthecalculations )
Itappearsthatacertainproportion ofthe"biomass"(total
bodyoflivingmatter)isaffectedbythedirecttoxicityofthe
wasteproducts whentheseareinsufficiently diluted.Partof
thefoodstockofthezoneinquestion canthusbeaffected.
Itisriskytoattempttomakeapreciseestimateoftheannual
lossoflivingmatterduetothewasteproducts ;ashasjust
beenseen,thetoxicitythresholds varydepending ontheanalyses
made,anditisalsonecessary tomakerssumptions concerning the
diffusion ofthewasteproducts ,theprimaryproductivity ofthe
area,etc.
Nevertheless ,itispossibletom?lcethefollowing estimates ;
a)Ph^topianktonicproductivity inthedischarge '.re?,(prinary
productivity2
oTheonlyd?tawhichwepossessconcerning thezonewere
published byKondratieva (1970)«Primaryproduction was
about5nigofcarbonperm^perd?yatthesurface,inllarch
1968.Thisvalue,withthoseoftheotherstations onthe
Ligurian Sea,isoneofthehighestthattheauthorhasbeen
abletoobtainfromthevarious measurements whichheh?sruede
throughout theMediterranean .Itseems,however,that
Kondratieva' sresultsaresuspectintermsofabsolute velues.
Itseemsmorereasonable toacceptthefiguresofI-linas(i960)
relatingtotheLaboratory Buoy(42°47'N,7°29'E).,In
these,annualprimaryproduction isestimrted at76fcof
carbonper(aggregate production forthewholedepth).

OOE,- KKV/47/75-E
Orig.sF
b)Estimateofthelossofprimaryproductivity duetothedirect
effectsofthewasteproducts
Onthebasisofadischarge of3,000tonnesofeffluents per
day(orabout2,500withadensityof1.2)itisfoundthat
thevolumenecessary todilutetheeffluent 10,000timesis
.25,000,000 M3.(ItWESnotpossibletornekeallowance ,in
thisestimr.te,forthescreening effectofthesludge
discharge.)Inviewofthefactthr.tthehorizontal rates

-61- L'NY/47/75-E
Orig.:F
ofdurnsion rrerauchhigherthenthevcrtio;1r-,tes(itcan
"beassumedthatthethickness ofthevc-lmaoeffected isless
than70m(lin.itdepthoftheeuphotic zone(l)).Ifitis
assumedthatinthe0-70razoneprimrryproductivity is
independent ofdepthitwillbeseenthat,foradepthof
70maffected bythedischarge ,thesurfe.eeareaaffected
2byinsufficient dilution oftheeffluentia350,000 nior
36hectares .
Itisnecessary tomakeanassuption hereregarding thetime
whichthewasteproducts taketodilutedowntothethreshold
ofl/l0,000:ifweassumethatinonedaythemediumreverts
tonormalconditions (andtherefore thatthewasteproducts
ofthenertdaywillbedischarged intoazonewhichcanbe
regardedasintact),itcanbeassumedthatthroughout the
year36hectareswillbeperrnmently lostfortheproduction
ofthezone.
Takingtheprimary-productivity figureadoptedinsection3a),
thisrepresents alossof:
360,000x0.076=27,360kgofcarbonperyear.
If,furthermore ,itisassumed (figurestakenfromRile;'-and
Skirrow)that10g^.mraesofbiomasscorrespond to1gr?inmeof
organiccarbon,weobtain v.lossofprimaryproductivity
(phytoplankton )of273,600kgperyear.
If,lastly,itisassumedthat1000gofphytoplankton r.cke
possiblethegrowthof10gofplanktonivorous fishorof
1grammeofcarnivorous fish,thisgivesanannuallossof
halieutic resources oftheorderofsever?!hundreds of
kilogrammes peryear.
)Zonewherephotosynthesis occurs.Alens-shapedregionofhigh
productivity islocatednotfarawayfromthezone.Thedepthof
thisvjouldapneartobe150-200 111.

62- EN1//47/75-E
Orig .ÎP
The argument isbased ,onanumber ofparameters which are
difficult toassess andareobviously arbitrary innature .
Even allowing formargin oferror ofabout 10,itwill be
seen that the loss ofnutritional resources due tothe direct
action ofthewaste products isextremely limited .
Itmust berecalled ,however ,itwasnotpossible totpke into
account the role ofthewaste product discharged ;itwould
certainly benegligible ,inview oftliepresence ofahigh-
productivity ares close tothedischarge zone .
Heremore than elsewh erethenumber ofassw.pt ions involved
calls forthe greatest caution .Neverthel ess,the lowvalue
ofthe figures obtained shoul dbenoted ;ittallies with the
results oftheobservations imj&e atthe site ofthedischarges
inNewYork Bay ,which lead totheconclusion that theloss
ofhalieutic resources isnegligible .
This judguent needs ,however ,tobequalified by"onthe spot "
observation oftheeffect ofthedischarges onlocal fishing ,
andbydiscussion -cnthefollowing pages -ofthelong-tern
effect ofthewaste products discharged from the point ofviow
ofaccumulation phenomena .

/'■»/'
Ori^.:F
SECTIONII-THELONG-TOP:. -!EFFECTS
VJehavealready "touched ,upontheimportance fromaphysico-chemical
pcintofviewoftheintroduction ofthehervyret.rIscontained inthe
effluents .
Wemustnowexaminewhatarethepossiblebiological consequences ,
oftheaccumulation oftheseelements alongthefoodchains.These
consequences con"bestudiedintwoways:
-thefirstconsists ofthereproduction ,invitro,ofphenomena
ofchronicpoisoning ;
-thesecond,morepromising wayconsists ofon-the-spotobservation
ofthecontent ofundesirable elements inanimals fishedor
gathered inthegeographical areaofthedischarges inorderto
drewconclusions astothedangersentailed "bythi-iringestion .
Thisapproach mustallowfortheextremevariability ofthe
resultsobtained andbebasedonasufficiently largenumberof
analysestobringoutclearlytheeffectofthewasteproducts
themselves .
Itwouldseemusefalfirstofalltorecallsomedctaconcerning
thephenomena ofconcentration oftheelements encountered inthe
effluents .
l)The"natural"accumulation processes
a)Thedifferent contentsobservedinthenaturalmedium
Ashasbeenemphasised elsewhere ,titanium ,chromium ,vanadium
endcadmiumarenaturally presentinsc.?water,inextremely
smallproportions .
Thenaturaltracesoftheseelements areconcentrated bycertain
organisms .

-64- EFV/47/75-E
Orig.:F
Thusthefollowing contents haveteenobserved ,inNewZealand
filialveorganisms (BrocksandHurasby,1265,quoted "byHome).
Averagecontentinppm(ug/gramme).dryweight
Scallop Oyster Ilussel
Iron 2,915 680 1,960
Chromium 10 3 16
Vanadium 9 3 5
Cadmium 250 35 10
Similarly thefollowing proportions arefoundinthefleshof
certainmarinoorganisms (ISTPIIfiguresquotedintheGIPLI
report,1973).
Contentsinppm(up/gramme)drymatter:
Chromium :fish:0.02to1
Cadmium :fish:0.15to3
algae:0.0006.
.Dataconcerning thecontentoftitanium ,vanadium andaluminium
inmarineorganisms aremorerarelyfound.
Information fromC.E.R.B.O.M. mentions that:
"inthespecialised literature itisassumedthatfornon-polluted
fish,titanium andvanadium arenotdetectable ;withregardto
aluminium ,theaverageproportions areoftheorderof10-6g/g
dryweightoffish",
b)Toxicityofthesedifferent elementsforhumanbeings
Theacceptable dosesinfoodstuffs are:
1mg/kgoffish )
jforcadnium(freshx/ei;ght)
5m^/kginmolluscs )
0.1mg/'lcgincertainfoodstuffs forchronium.

-€5- E„:.,.,7,7>2
0:.dg.:F
(ISTPHfiguresmentioned ,intheGIPIIreport.)
Withregardtotitanivjn andvanadium ,theredonotappeartobe
anynationalorinternational stcjidaixisoftoxicity ,Furthermore ,
therearenoresultstobefoundofworkconcerning thetoxicity
ofthesetwoelements ,whichuptonowhavenot"beenthesubject
ofmanypublications .
Professor 3RIS0Nmentions ,inaletteraddressed totheCIESKand
passedtousbytheChairman ofthe"Campaign againstuarine
pollution "Committee ofthatinternational organisation :
"Titaniunsaltsareinthemselves harmless ,sincetheyareinsoluble ,
withafewexceptions (bromides ,chlorides ,fluorides ,iodides...).
Thesolublesaltsareveryunstable andrapidlydecompose inthe
atmosphere .Inthepurestcte,someofthemnreregarded as
irritants ,butthishasnothingtodowiththepresentsubject.
Themostrecenttreatises ontoxicology statethatnocaseof
poisoning bytitanium oritssaltsisknown.Titanium oxideis,
aseveryone knows,widelyusedfortherapeutic purposes .Itis
administered inveryheavydoses,severaltensofgrammesperdry.
Coirretitanium contains 9goftitanium anhydride per10grammes
and2to3dosesperday,i.e.30grammes,areabsorbed .
"Bismntitane "contains 7*4grammesoftitanium anhydride and2.5
grammesofbismuthsub-nitrate per10grammes ;hereagainone
ortwodosesaretakenperdry,makingabout20grrmmes.For
mypartIusetheseproducts alotandmakeupmanyprescriptions
forthem.
Titanium oxideisincludedinthecomposition ofmanyointments ,
thebestknownbeing"Hetatitane".Thesulphatementioned (in

M+
m m EKV/47/75-E
Orig.:P
theletterfromMr.PAOLETTI (l))isbothinsoluble andunstable,
andtheanalyses presented intheItalianpapersshowthatithas
ahighcontentofH2S04andironsulphate ,butobviously the
sulphuric acidisimmediately dilutedandneutralised whenit
reachesthereceiving seawater ,!1
However,adocument provided byCERBOIImentionsthat:
"Russianworkshaveshownthatingestion oftitanium (TiC13)in
theorganismofrabbits(2mg/kg)ledafteracertainperiod(129
days)tocertainmetabolic disturbances ^Otherdisturbances are
producedbytileingestionof0.CF>ng/kgofTiClJ.Inthesame
documentattention isdrawntometabolic disturbances resulting
fromexcessive ingestion ofvanadium."
2)Studiesofaccumulation andinducedtonicitycarriedoutinlaboratories
a)ReportoftheI.S.T.P.M.
Atthedateofpublication ofthefirstreportoftheI.S.T.P.K.
(February),onlyoneshortexperiment onconcentration phenomena
hadbeenperformed ;theanimalssurviving afterfourdaysinthe
effluents ofdifferent concentrations andthereference anim?ls
displayed nodetectable differences intheircontentofironand
cadmium.
Amuchlongerinvestigation (scheduledtoextendover3to4months)
isinprogress :Arter.iaSalinatrillbogrownfromdiatomcultures
inaneffluentdilutedtol/5000.andtheArtemiaSalinawillitself
(l)AnexpertoftheItalianscientific commission .

»»τ»7V^ι-.Γ;·'Γ
"beused,tofeedshrimps raidalsofish.Theresultsof"this
studywillbeknowninJuno.
b)Resultsfror.CERBOII
.A.CCÎTCBITTÏÏATIONPHEKOI-ÎEITA
CERBOIIsucceeded inmeasuring thephenomena ofinducedconcentration
byreconstituting inthelaboratory fourmajoralimentarychainsof
,thecoecnenvironment :themethodemployed ,consistsofbreeding
theelements ofthefourchainsintrnlcocontaining varirbledilu­
tionsoftheeffluents .Eachalincntr.rystagewhichhasthus
possibly accumulated theundesirrble substances fromthewaste
natterservesasfoodforthehigherstage,whichitselfisplaced
inadilutesolution oftheeffluent .Lastlytheeffectofthe
concentration phenomena onthefinalconsur.er (mouse)istested.
Theresultsreported byCEIlBOI,areasfollows :
"l)Heriticcrustrceanchain,consisting ofmicro-organisms ,
molluscs ,shrimps (exposuretopoisoningfor2weeksforeach
ofthecomponents ):
-Themolluscs (mussels)hrdtitaniumcontentsrangingfrom
2to4ug/'gandvanadiumcontentsragingfror.i0.5to1ug/g,
whereasthereference SMiplesh:dtitaniumcontents belowthe
detection limitandvrnadiun contentsofaround0.1ug/g,the
concentration factorbeing6to13fortit^niun and80to170
forvanadium ,incomparison withthecontentsofthetested
polluted water.
-thecrustaceans (shrinps)hrdcontentsof5to7.5ug/gof
titanium and2.6to2.£u&'gofv-nadiun ,whereasthereference
samples showednodetectable contentoftitr.niur.v andcontents
of0.5ug/gforvanadiua,theconcentr?tion incomparison with
thetestedwaterbeing16to25fortitr-nium rnd430to4S0for
vanrdiiaa.(Thedegreeofdilutionoftheeffluent was
1/50,000.)
/

-Oo– ϊ3Γ7>,7/75-Β
On/*.:F
2)Bonthicchainconsisting ofnicro-orr^ni sms,pnnelida and
fishwhichhrdlivedinatrnl:ina1/50,000dilutionof
theeffluent foroneweekinthecaseofthemicro-organisms
andannelida andfortwomonthsinthecaseofthefish:
-Theannelidacontained from25to65ug/goftitaniunand
from1.5to19.5u-z/£ofvanadium,wherepsthecontentsof
thereference s?:npleswererespectively luj/j'oftitaniunand
anundetectable proportion forvrnadium .Theconcentration
factorranges "between400and1,000fortitanium andbetween
1,250and2,500forvanadiumincomparison withthecontents
ofthosemetalsinthetestedwatersamples.
-Thebenthicfish(blennies)contained from0.3to0.6Mr/g-
weti^tter-oftitanium andbetween0.5and1.1ug/gof
vanadium,whilethereference samples'contents werebelow
thedetectable limitfortitaniumand0.3ug/gforvanadium,
sothattheconcentration factorsincomparison with,the
pollutedwaterwere5to10fortitanium and400to600for
vanadium .
3)Pelagicchaincomposedofphytoplankton,zooplankton (exposure
topoisonforaperiodof8dcys)andfish(exposurefor15
days).Dilutiontested:l/l0,000.
Titaniumcontentsrangingfrom6to16ug/gwetmatter,end
contentsof1.5ug/gofvanadiumwereobservedinfish,whereas
thereference spriples showednodetectable contentofeither
titanium orvanadium ,theconcentration.ratiosbeingofthe
orderof20to55fortitanium andaround250forvanadium in
comparison withthoconcentration ofthesemetalsinthetested
water."

••T »-•
Ci'ij,:
4)fleritic molluscchrir.
Theconcentrations observed ,arcnotincluded ,intheresults
reported .
Theresults obtpinedatCEP30IIthusconfirmthosementioned
insub-section II-l)with'regardtothepossibility of
accumulation ofvanrsdium andtitanium .
Ontheotherhand,noindication wasgivenbythisorganisation
concerning thepossible accumulation factorsofchronica and
cadmium.
B.Withregardtotheinducedtoxicities observedinvitro,itshould
benotedthatnophenomenon ofthishindwasijounddurinj (TJKBOK's
experiments ;whilethesameexperiments porforraed onother
industrial effluents (effluents ofpapermillsendofceramics
factories )hedinfretledtothederthofthefinalconsumers
(mice),nonortality wasfoundatthisst-£ebyC2RB0I1,which
concludos : v . •
"lloacutetoxicity ifasfoundatthelevelofthefinalconsumer
afterthesuccessive consumption ofthelaststagesofthefour
marinetrophodynamic chains."Triosemedocumentstates,however :
"althoivjh,inthemediumterm,thereworenolethalmanifestations
inthel:.nd-b".sod consumer,laiouledgo ofthelor-j-tcrmeffects
'ofcertainofitsconstituents docsnotexcludethepossibility
ofdelryedpathological iuanifestr.tions".
3)Observationoftheheavy-metal contentsofthemarineorganisms
collected ,inthedischrr^earea.
tiedonotatpresenthavemanyresultsofthiskind.OnlyCERBOIi
reportsontwoseriesofanalyses :thefirstconcernsfishprovided
bytheVeterinary ServicesDepartment oftheAjaccioPrefecture (the
placewheretheywerecaughtisnotstated);thesecondconcerns

-70- ENV/47/75-E
0ri.*>:F
fishsentbyBantiafishermen ashavingteencaughtnorthofCapCorse,
CEKDOi!rericrksinthisconnection thatitdidnotitself -arrrnccfor
thesetwoamplestobetaken,whichn?yintroduce artefacts .
Theresultsofthoseanalyses areasfollows j
FISHSUPPLIED BYTHEVETERINARY SERVICES DEPARTIiENT OFTIE
AJACCIO PÏE333CTUH3
Samples Titaniwn Vanediuia Aluminium
Sea.bassmuscle
intestine
liver
heradN.D.
N.D.
N.D.
N.D.N.D.
N.D.
N.D.
1.331.35
6.35
9-36
6.30
Oca-brcammuscle
intestine
liver
hecdN.D.
N.D.
N.D.
.N.D.N.D.
2.47
IT.D*
1.931.24
£.87
7.46
5.90
Bre?inir.uscle
intestine
liver
hoadN.D.
N.D.
N.D.
N.D. 'N.D.
I.63
II.D.-
2.061.39
2.45
14.92
6.18
FISEPROVIDUD BYBilSïIAFISIEKOÎ ,*SHAVING BEENCAUGHT
NOP.THOFCAPCOIïSE
Sonples Titrniua Vanadium Aluminiun
Raymuscle
intestine
{JlllSN.D.
N.D.
N.D.N.D.
N.D.
N.D.1.79 ■
-V1.44
4.94
Sword-fish muscle 1.50 1.50 110
Octopus tentacle 8.45 N.D. .84.53
N.D.anotdetectable .

-71-
i-1^7/47/75-2
Cri,".:F
Ittrillhenotedthr.ttitanium ionotdetectable inmostoftho
srmplcs,exceptfortliosword-fish muscleandtheoctopustentacle .
Onthootherhand,whileallthoediblepart3oftheanimals(except
forthesword-fish )containnovanadium,relatively highcontentsof
thiselement arefoundintheviscerarMherds.
Thesefirstresultsmayappearsignificant .Itisextremely difficult ,
however,todrawanydefinitive conclusions from'them.
Acertainnumberofpointsrequiremorethorough consideration :
1)Tlieliterature rr,relycontains .contents layorgans "butratheraverage
contentsforeachorganism :theproportions ofvanadium andtitanium
tobeconsidered foracoraprrison \;ithotherresultsshouldtherefore
becorrected byaveraging thoresultsfoundinthevisceraaidherds
withthoseforthemuscles ofthefish.
2)Iloreover,itisratherdifficult toexplainthehighcluminiun
contents foundinthedifferent orgsaisus ?thereisusuallylittle
information available ontheconcentration factorsofthiselement,
whichincidentrlly doesnotappearinverylargequantities intho
effluents .
3)Ashasalreadybeenemphasised ,thereisatpresentsshortageof
overalldataontheactualtoxicities oftitanium andvanadium .
Itwouldtherefore beuseful,asafirststage,toexaminethe
proportions ofcrdinium andchromium contained inmoxineorganisms ,
asthecontentsoftheseelements havealreadybeenthesubjectof
detailedinvestigations lerdingtotheestablishment ofstandards ;
knowledge ofthocontentsoftitanium andvanadium ,while
interesting initself,doesnotatpresentenableonetoestimate
thepossible dangersofconsumption ofmarineproducts ,owingto
tholackofreference dataontheproportions contained inanimals
collected inunpolluted areasoftheilediterrmean .

-72- EUV/47/75-E
Orir.:F
K.3.Furtherresultsworereported byCER30IIinacomnunicat ion
datediCthApril1$73.
..."but,furthemore ,attherequestoftheVeterinary Services
Department ofthePrefecture ofCorsica,wehavecarriedouta.
scriesofmeasurements onfishcaughtoffCorsicawhichhave
beensenttousrogulrrly forthelastfeuweeks.Thesestaples
enabledustofindaveragevaluesof0./2tita-nium,0.51for.
vanadiumand0,40formercury (micro^amc/rpr-Tiaac-wetweight).
Thisstudyisinprogress e„tpresent.Heshallkeepyouinformed
oftheresultsobtained subsequently .•
Thefollowing twopointsmpybonoted:
1)Thetitenimcontentsarehigherthanpreviously ,whilethe
vanadium contents ,presented asaveragevalues,correspond to
theprecious values.
2)Themercurycontents,althoiv^hliifh,remainbelowtheacceptable
thresholds .Inviewofthefactthattherehesneveruptonow
beenr,nyreportofthepresenceofmercuryintheeffluents ,it
appearsdifficult atpresenttolinkthecontents observed with
theItaliandischarges ."

-73- î3lïV/<;7/75-E
Orig.:F
SDCTIOIIIII-FCOLOGICAL /iSPSOTS-CONCLCSICN
Theanalysisofthoscientific andbibliogrrphical drtacompiledin
ailefforttogainaclearerideaofthedetailsandeffectsofthe
wasteproducts discharged "bythoIlontcdison companyenablesusto
drawsomeconclusions , .
Theindustrial wairteproductsintheseadisplayanappreciable
directtonicity duetotheiracidityandtheirironcontent,
•whichcouses,inthewakeofthedischarging vessel,i.e.ina
linitcdvolumeofwater,thedisappearance ofthospecieswhich
areunabletofleeorwhichcannotwithstand 1/10,000dilutions
oftheeffluentintheno&ima(thisbeingthethreshold value
obtainedforprolonged strays);plan!:tonisprobablytheraain
victimofthismodeofpoisoning ,althoughtheestimateofthe
quantities perdcyaffected bythowastoproductsresultsin
lowvalueswhenneasurcdintheLigurirn Sea.
Ithasnotsofr.rbeenpossibletodenonstrato theresidual
toxicity ofthesewasteproducts ,i.e.thehamfulnos3 which
racyresultinthelongrunfromthesystematic introduction
intothenediuuoftheheavynotalswhichtheycontrin.
Chemicalanalysis ofthewasteproducts hasshownthatthey
didinfactcontainsrr.llproportions ofrosidualtoxic
substances .Thestudiescarriedoutinvitroh?.voenabled
thepossibility ofaccumulation ofthosesubstances alongthe
alimentary cheintobeder.onstrcted .Furthermore ,thepresence
ofresidue!elements incertainfishtrlcenfromthodischarge
area,wouldappeartoconfirmthisobservation ,although
responsibility forthepresenceofthosesubstances inthe
animalscollected cannotwithabsolutecertainty beattributed ,
toMontedison ^wasteproducts.Itshouldmoreover berecalled
thatithasnotbeenpossibletodatetoprovethechronic
toxicityofthesubstances contained inllontodison 'sindustrial
wasteproducts eveninthelaboratory .

SNV/47/75
Ori-j.:F
However,inviewoftheabsenceofdefinite conclusions 011this
point,violence iscalledforuntilsuchtineasthe
organisations uhicharcatpresentstillengagedinlon^-terw
experiments m?i:eknowntheirresults.

-74- ENV.47/75E
CONCLUSIONS

ENV.47/75E
CONCLUSIOÎTS
Theproduction capacity oftitanium dioxydefactories inEuropeoftheNine
is840.000tonnesperyear(tpa).Thisrepresents 39$ofworldcapacity
(2175000tpa)andisdividedupasfolloxfs :
741000tpa(88$)forthesulphateprocess
99000tpa(12$)fortheclorineprocess.
Facotring discharging intotheChannelortheNorthSeaaccountfor727000tpa
(87$)andfactories discharging intotheMediterranean accountfor50000
tpa(6$).Twofactories (63000tpa,or7$)treattheirwasteonland.
Atpresent,discharge levelsareasfollows :
(1)intheNorthSeaandtheChannel,eitherinestuaries orontheopen
sea: ?•
4100t/daySO^Hgexpressedas100$concentration
3000t/dayFeSO^^H^O (ferroussulphate)
1300t/dayFeSO^dischargedwiththe"acidwaters"(SO^H^)
(2)intheMediterranean :
335t/daySO^Hgexpressedas100$concentration inthe
>formofneutralized products(2600t/day)
580t/dayFeSO^fHgOareatpresentstoredonland.
Awholeseriesofecological pollution monitoring campaigns havebeen .
carriedoutintheactualdischarge areasjthesecampaigns havebeen ■
investigated bythenationalauthorities orsometimes bythemanufacturers
themselves .
Itisclearfromananalysis oftheresultsofthesecontrolsthatwaste
fromtheTi02industryispotentially oractually harmful.Theseadverse
effectsonthemarineenvironment aredueabovealltoacidity,thepresence
offerroussulphate andprobablyothermetals(heavymetals).

-76- ENV .47/75S
Theeffects inquestion cantake thefollowing various foras ,depending
onthemethod andplace ofdipping :
(1)reduced oxygenation andpHofthewater andincreased concentration of
Fcandheavy metals ;
(2)(a)temporary shortage ofthezooplankton biomass andinducement of
effects leading toadeterioration ofthemorphological structure
ofitscomponents ;
(b)repulsion andloss ofsome species offish :
(c)reduction ofthebiomass ,production andspecific diversity of
benthic and/ornectobenthic biocenoses inthedischarge area .In
more severe cases ,allanimal life mrydisappear •
(3)change inthecolour ,transparency andturbidity ofthewater and
temporary reduction ofphotosyntheses ,ofthephytoplanlcton andof
primary production ,particularly inthecase ofsurface dumping .The
seabed becomes covered with iron oxides and the oxides ofother
metals where thedumping iscarried outinestuaries and inshallow
water •
(4)ontheother hand ,there isnoevidence ofanytoxic effects onman
from theconsumption ofspecies offish caught inthedischarge areas .
Part 1ofthis report contains aninventory ofthewaste from theproduction
ofTi02 .These wastes have been classified into four major categories cor­
responding tothewaste products discharged byfactories atdifferent
stages ofproduction .These categories are :
1.insoluble matter remaining after filtration
2."copperas "(ferrous sulphate )
3.strong acids
4.weak acids orweak liquors .

-77- ENV.47/75E
Itwouldseemfairtosuggestthatindustries inthissectorshould,
withincertain reasonable timelimits :
a)storeonlandtheinsoluble matterremainingafterfiltration r
b)makecertainreductions inthetotalpollution (either30$,10%or95$)•
Thesereductions arebasedonperfectly feasible techniques .Forplants
usingIlneniteforexemple,areduction of
30c/owouldmeanthattheferroussulphate hasbeentreated,
70$thattheferroussulphate andthestrongacidshadbeentreated,and
95$thattheferroussulphate,strongacidsandthebulkoftheweakacids
hadbeentreated .
Thereportisalsoconsidered howandatwhatpricethiswastecouldbedispo­
sedofeitherbyconversion orrecycling (seep.28andfollowing).
Itshouldbeborneinmindthattheprocessing costvaluesdatebackto
theendof1973andthebeginning of1974andmustbeupdatedtotake
accountofchangesintheeconomicsituation .Astudyonthisisbeing
carriedout'jhowever,thefiguresgiveninthereportremainvalidfur
thepurposeofassessing thehighcostoftreatment inrelationtopro­
ductioncostsajidforcomparing thevarioussolutions proposed .