CELEX: 51975PC0339
Language: en
Date: 1975-07-14
Title: Proposal for a COUNCIL DIRECTIVE on waste from the titanium dioxide industry (submitted to the Council by the Commission)

ARCHIVES HISTORIQUES
DE LA COMMISSION
COLLECTION RELIEE DES
DOCUMENTS "COM"
COM (75) 339
Vol. 1975/0137
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 ---pagebreak--- COMMISSION OF TH3 EUROPEAN COMMUNITIES
                                   COM(75)339 final
                                   Brussels , 14 July 1975
                           Proposal for a
                          COUNCIL DIRECTIVE
            on waste from the titanium dioxide industry
            ( submitted to the Council by the Commission )
  COM(75 ) 339 final
 ---pagebreak---                                                              ΜΓ7/47/75-Ε
EXPLANATORY MEMORANDUM
 INTRODUCTION
This Directive is based on the principles laid down in the Programme of
Action of the European Communities on the Environment of 20 December 1973 ,
0J No C112 , and in particular the principle of "prevent in/?, reducing and ,
as far as possible , eliminating pollution and nuisances" (Title I page 5 ).
At present the vast majority of factories manufacturing titanium dioxide
 (TiOg ) dump their waste at sea or in estuaries , relying on the buffer effect
of the sea to neutralize the acid part of the waste and on the capacity of
the oxygen present to convert the ferrous sulphate to ferric sulphate , the
other waste ( various oxides of heavy metals ) sinking naturally to the sea
bed .
At the same time , it must be realized that the demand for titanium dioxide
on the European market is increasing and that the producers hope to double
their capacity in ten years , either by extending existing factories or by
setting up new ones.
The process generally used in Europe is the " sulphate process"*.    To obtain
TiOg from the commonest ores ( ilmenite and slag), these have to be treated
with sulphuric acid. Obtaining one tonne of TiO^ involves 2.6 tonnes of
waste , which consists mainly of sulphuric acid and iron sulphate .   Assuming
that authorization were given for dumping at sea, and also assuming that
production were doubled , marine pollution from this waste would be almost
bound to double in turn. •
A whole series of pollution control campaigns have been conducted at the
present dumping grounds ; these campaigns have been sponsored by national
authorities or sometimes by the producers themselves .
* Chapter 1 of the technical report derls in detail with this section.
 ---pagebreak---                                        * 4 »                    4* « ï' Y - s *
It is clear frora an analysis of the results of theEe controls that w^ste
from the TiOg industry is potentially or rctu-lly harmful . These ?dverse
effects on the marine environment pre due ebove ? 11 to rcidity , the presence
of ferrous sulphp.te ^nd probably other metals (heavy met - Is ).
The effects in question csn trke the following various forms , depending on
the method and place of dumping;;
1 . Reduced oxygenation and pH of the water and increased concentration of
    Fe and heavy met ? Is .
2 . a) Temporary shortage of the zooplrrikton biomsss rnd inducement of effects
        leading to a deterioration of the morphological structure of its
        components ;
    b ) repulsion and departure of some species of fish ;
    c ) reduction of the biomsss , production and specific diversity of benthic
        and/or nectobenthic biocenoses in the discharge ?= rea. In more severe
        cases , r.ll animal life may disappear.
3 . Change in the colour , transparency and turbidity of the w?ter ?nd temporary
    reduction of photosynthesis , of phyto plankton md in primrry production ,
    p?rticul?rly in the case of surface dumping.    The seabed becomes covered
    with iron oxides and with oxides of other met sis where the dunping is
    carried out in estuaries and in shallow water.
4. On the other hand , there is no evidence of any toxic effects on man
    from the consumption of species of fish caught in the dumping rreas .
It is therefore advisable gr-?du^lly to reduce the dumping at sea of this
waste over a reasonable and realistic period .    Pert 1 of the technical
report contains an inventory of the waste from the production of TiOg .
These wastes hsve been classified in four major categories corresponding
to the waste products discharged by factories at different stages of
production.     These categories are :
                                                               ./•
 ---pagebreak---                                           \ 09                    SF.747/75 -S
                  i)  insoluble matter remaining pfter filtration
                 ii ) "copperas" ( ferrous sulphate )
                iii ) strong acids
                 iv)  werk acids or weak liquors
The report elso considered how and at what price this waste could "be disposed
of "by either conversion or recycling.         It should be borne in mind th?t the
processing cost values dste back to the end of 1^73 and the beginning of
1S74 and must be updated to tdce account of changes in the economic situa­
tion.    A study on this is being carried out : it is nevertheless true that
the figures given in the report remain fully v?lid for the purpose of
assessing the high cost of treatment in relation to production costs and
to allow comp^xison of the various solutions proposed .
C(MEM'S PIT SOIffl OF THE ARTICLES AND ANNEXES
The aim of this Directive is gradually to reduce end then to eliminate pollu-
tion of the sea, by waste from the titaniuu dioxide industry .
l ) Several stages are envisaged during the transition period to allow industry
    to adapt from the present situation to one where th$e is almost total
    elimination of dumping at sea.                                 ... . ...
    Stage 1 ; 1>75 - 1 January 1973
    During this period existing and new plants will be ?ble to dump their
    waste at sea or in estuaries subject to prior authorization (Arts . 4 and
    5 ) and an ecologies*, 1 control of the environment (Art . j ).
    Stage 2 ; 1 Janurry 1978 - 1 January 1981
    Existing plants will have to be equipped with treatment facilities such
    that "the pollution after treatment is not greater thaji "JO '% of the total
    untreated pollution"(Art . 8 ( 3 )). These provisions correspond to a 30 $
    reduction in pollution ; the remaining TO ^ can be dumped at se ? or in
                                                                            /
                                                                         • i •
 ---pagebreak--- estuaries ( Arts . 4 ".nd 5 and Art . 8 ).
New plrnts will have to be equipped with treatment facilities such that
"the pollution after treatment is not greater thm 30        of the totfl
untreated pollution"(Art . 8-2 ).    These requirements represent a 70 ',s
reduction in pollution ; the remaining 30 p can be dumped at se :- or in
estuaries ( Arts. 4 and 5 and Art . 0 ).
This will mean that in the first instance the total pollution is con­
tained and that thereafter it will begin to drop.
Stage 3 '• 1 January 1981 - 1 Janua ry 1905
Existing plants will have to be equipped with treatment facilities
such that " the pollution after treatment does not exceed 30      of the
total untreated pollution "( Art . 8-3 and Annex II ).  This corresponds
to the situation of new plants in Stage 2 , where there is a 70 jl reduction
in pollution , the remaining 30 /o being dumped st sea or in estuaries
( Arts . 4 and 5 and Art . 8 ).
The situation for the nev: plants is the same as in the second stage .
This will lead to a significant reduction of the total pollution .
Stage 4 : from 1 J anuary 1963 onvr arc's
Existing and new pl?nts will be required to treat their effluent in
such a way that only 5 'h of the total untreated pollution remains
to be dumped at sea or in estuaries ( Arts . 8/2–3 and 9-4 )«
Total pollution will be reduced by 95
 ---pagebreak---                                           » y »                      EiîV/47/75-E
2 ) There are therefore three aspects to this Directive , namely :
                      i ) prior authorization
                     ii ) ecological control of the environment
                    iii ) the measures which are to "be tpken to "reduce and
                          eliminate pollution and nuisances ".
    1 . The choice of the dumping area and the waste characteristics must "be
        tciken into consideration and the interaction between them must be
        carefully examined . Thence dumping at sea, can only be carried out
        under certain conditions ( Art . 5 ) sncl storage on land must meet cer­
        tain requirements ( Art . 6 ).
    2 . During the period in which dumping at sea is still being carried out ,
        there must be an ecological control of the environment ; marine envi­
        ronment control campaigns will therefore be necessary ( Art . 1 ),
        Controls will cover acute toxicity , larval development and bioaccumu*- .
        lation tests in the pelagic chains .
    3 . Firms in this sector x*ill have to :
        a.) store on land the insoluble matter remaining after filtration ;
        b ) make certain reductions in the total pollution ( either 30 fi ," 70 '/o
            or 95 , °) Article '3 + Annex Ii ).
            These reductions are b?sed on perfectly feasible techniques .         With
             plants using ilmenite , for exrmple , a reduction of 30 °jo would mean
            ■frhft the ferrous sulphate had been treated , 70      th?t the ferrous
             sulphate and the strong acids had been treated, and 55 ^ that the
             ferrous sulphate , strong acids and the bulk of the weak acids had
            been treated.                              .     ..               -
3 ) It should be pointed out that the three and six year periods respectively
    should enable firms to make the necessary adjustments under realistic
    economic and technical , conditions.      (See Part- I , para. 2 and 3 of tech­
    nical document .)
 ---pagebreak---                                          If j «
        In the cr.se of r.eu plants , construction projects will "be able to tske
        account of these requirements ( ferrous sulphate end strong acids ).
        In the case of existing plants , treatment cf ferrous sulphrtc ( dehydra­
        tion + roasting or tipping on prepared spoil heaps ) cm "be carried out
        during this three-year period.     The proposed six-ye - r period should
        allow these units a choice in the treatment of strong acids .      The pro­
        posed ten-year period for a 'fj ,'J reduction seems to be reasonable for
        perfecting the treatment of wo alt acids .
        Apart from the fact that this Directive will serve to eliminate almost
        nil marine pollution from this type of waste , its application will encou­
        rage waste recycling.
3 . LEGAL CONSIDERATIONS
    Several Ilember States have already passed laws on - among other things -
    the disposal of waste from the titanium dioxide industry .
    The German Lav? of 7 June 1972 on waste disposal requires both local autho­
    rities and private individuals to use cpcci-1 plants for the treatment ,
    storage and disposal of solid waste .
    Likewise the French Law of 1917 on induct rirl establishments which are
    dangerous , insanitary or carry on noisy or noxious trades applies to tita­
    nium dioxide manufacturers by virtue of the f-ct that they process mineral
    ores using , among other things , sulphuric acid which can cause adverse
    changes in water ( cf No 2>3 in the nomenclature to this law ).      The Orders
    issued by the Prefet pursuant to the abovementioned lrw authorizing the
    setting-up of industrial establishments are subject to conditions which
    govern , rmong other things , the discharge of effluent into water courses .
    A new draft law makes these conditions even stricter and stipulates that
    any authorization granted must take account of the dangers or drawbacks
    which the industrial establishment in question may present as regards nature
    and the environment and must l r y down install - tion and operating conditions
    concerning , in particular , the purification and disposal of effluent , wastes
    and residues .
                                                                          •/.
 ---pagebreak---                                     - 7 -                     EN7/ 47/ 75 -E
In Italy, it is the Pi shins Code ( Law 9^3 of 1965 ) which applies to
discharges at sea.
In the other Member States , general laws on the. protection of water, air
and soil apply.
                                 .                                 >
The attached proposal for a directive based on Article 100 of the EEC
Treaty therefore sets out to harmonize these laws and thus create a
coherent set of provisions which can apply in all Member States ,
Under Article 100 of the Treaty the Opinion of the European Parliament and
the Economic and Social Committee is required.                 ■
                                             I
 ---pagebreak---                                                                  EïïV/ 47/75-E
                                                                 Anncx
             Pro osal for a Council Directive on wrste from the
                           titanium dioxide industry
THE COUNCIL OP THE EUROPEAN COIiiUNITIES ,
Having regrrd to the Tre?,ty establishing the European Economic Community ,
and in particular Article 100 thereof .;
Having regard to the proposr.1 from the Commission ;
Having regard to the Opinion of the Euro porn Parliament ;
Having regard to the Opinion of the Economic and Social Committee ;
Whereas waste from the titanium dioxide industry is liable to bo harmful
to human health and to the environment , including aquatic flora and f?un?;
whereas it is therefore appropriate gradually to reduce and then to eliminrto
pollution caused by the dumping at sea of such wastes ;
Where ? s the Programme of Action of the Europe : n Communities on tho
Environment ( l ) adopted by the Council of the European Communities and
representatives of the liomber States meeting in the Council , in the
declaration of 22 November 1973 , refers to the need to undertake        Community
action against certain types of toxic waste and in particular waste from
the titanium dioxide industry ;
Whereas national l~ws on waste from the titanium oxide industry vary from
one Member State to another ; whereas these disparities are likoly to
constitute barriers to trade within the Comriiunity rnd will therefore hrve
a direct effect on the functioning of the Common Ilarkct ;
Whereas ESC Council Dircotive No           ( 2 ) concerns waste disposal in
general ; whereas for particularly dangerous waste it is rdvisr.ble to ley
down a special system offering every guarantee that human health and tho
environment is protected against tho hrraful effects caused by the discharge ,
( 1 ) OJ No C 112 , 20 December IS 73
( 2 ) 0J
 ---pagebreak---                                    -2 -                    Eir//47/7 -s
                        s
dumping or uncontrolled tipping of such ifastes ; whereas this should be
the case with wast o from tho titanium dioxide industry ;
Whereas , in order to attain those objectives there should be machinery
 for prior authorization of all discharges of waste from the manufacture
of titanium dioxide into water courses , laiccs and the sea, and for
dumping at sea or storage on or in the ground ; whereas for industrial
 establishments located in the territory of a Ilember State , this
 authorization nust bo granted by the competent authority of this State }
whereas for industrial establishments located in the territory of a
non-member State , the authorization must be issued by tho competent
authority of the Ilember Strfce in vhose territory the wast e is stored or
deposited ;
Ifhereas it is also advisable to malce the issue Of this authorization
subject to specific conditions , not only for the dumping of waste at sea
or discharge thereof into estuaries but also for storage thereof on or
in the soil ;
Whereas , to ensure effective monitoring of the marine environment , it is
essential that any discharge carried out in a maritime cres or an estuary
be accompanied by a systematic follow-up on the general ecology of the -
environment •
Whereas , in order to protect the seas surrounding the Community, it is
essential to law down levels to which discharges of pollutants nust be
reduced ; whereas these levels must be reached in successive stages over
a maximum period of ten years from the date , of entry into force : of the
Directive ; whereas existing or new industrial establishments and new
capacities added to existing industrial promises must use anti-pollution
techniques in order to achieve these levels within the required time-
limits ;
 ---pagebreak---                                                                ENWA7 /7e) -F.
HAS ADOPTED THIS DIEECTTVE :
                                    Article 1
1, The aim of this "Directive is the gradual roduction and the elimination
    from tho soa of pollution caused "by waste from the titanium dioxide
    industry*
2 . For the purposes of this Directive :
    ( a) "waste" means any residue from the titanium dioxide mar.ufe.ct uring
          process ;
    ("b ) "disposal " means the removal , transportation, treatment , recycling
          or recovery of wastes , tho storage and depositing thereof on or in
          the soil and/or the discharge thereof into water courses , lakes
          pad tho soa, and dumping at ecr.j
    ( c ) " existing industrial establishments" means those industrial
          establishments which have reached their full production capacity
          before the drto of entry into force of this Directive ;
    ( d) "new industrial establishments" means those industrial establishments ,
          which are in the course of being set up and which have not reached
          their full production capacity at the date on which this Directive
          entered into force , together with all industrial establishments
          which are set up after this date .
 ---pagebreak---                                      - 4 -                     EKV/47/75
                                   Article 2
Ilember States shrll take the necessary measures to ensure that the vmote
is disposed of :
- without endangering human health ;
- without risk of contamination to water , air or the soil or to the flora
   paid fauna ;
- without adversely affecting beauty spots find the countryside.
                                   Article 3
Ilember States, shrll trice the necessary measures to promote the treatment ,
recycling and recovery of wastes.
                                   Article 4.
The discharge of waste into wrter courses , lrkes and the sea, dumping at
sea or storage on or in the ground shall "be subject to a prior authorization
issuedty the competent authority of the State in whose territory the
industrial establishment is located .
As regards waste from industrial establishments located in the territory
of a non-aember State , this authorization shrll be issued by the competent
authority in the Hciaber State in whose territory those wastes are stored
or deposited.                                       <
                                   Article 5
1 « In the case of dumping at sea or discharge into estuaries , the competent ■
    authority shall , on the basis of the informrtion supplied in accordance
    with Annex 1 , grant the authorization referred to in Article 4 on con­
    dition that :
    ( a) there is no adverse effect on boating, fishing, leisure activities ,
         ore extraction , desalination , fish and shellfish breeding, on regions
         of special scientific value and on other legitimate uses of the sea ;
                                                                    /.
 ---pagebreak---                                       -5 -                     Em/47/75-E
     (t>) no other means of destruction or disposal exist s,
2 . Irrespective of the method "by which and tho extent to which tlao effluent
     in question is treated , authorization shell not be granted if the level
     of dilution is inadequate to ensure that the pH of the receiving water,
     beyond the actual discharge point , does not exceed the pH value at which
     acute toxicity is caused .
                                    Article 6
In the case of storage on or in the soil , tho authorization referred to in
Article 4 shall , irrespective of the method and extent of treatment of the
effluent in question, be subject to the following conditions :
( a) discharge into underground strata is prohibited ;
(b ) insoluble subst-nces remaining after filtration sh."!! bo stored on land
       in conditions such that they do not adversely affect the ground water ;
( c ) ferrous sulphate treatment products , strong and we?I: acids and waste
       other than the insoluble substsjaces remaining after filtration mry , if
       they axe not subsequently used , be stored on land provided they do not
       adverse ly affect the ground water.
                                    Article 7
1 . Irrespective of the method and extent of treatment of the effluent which
     is to be discharged , any discharge into a maritime area or into an
     estuary shall be accompanied by a systen?tic follow-up on the general
     ecology of the environment .
2 . This fc>llov/-up shall include in particular :
     ( a) an ecological inventory of the current state of the area affected
          by the relases .  This requirement shall be fulfilled when new
          industrial establishments are set up or when capacity is increased
          in existing industrial establishments :
 ---pagebreak---                                      - 6 -                     EN7/ 47/75-E
 (b ) sampling species of molluscs , crustaceans , fish sxid plankton
      organisms.
This sampling shall bo carried out regularly lay a "body appointed "by the
Member State in whose territory the industrial establishment is located.
In the Case of cross-frontier pollution , the body in question shall be
appointed by the Commission.
                                                          • .   r
Apart froa the monitoring of changes in the marine environment , tests for
acute toxicity shs-.ll bo crrried out regularly on species of mollusc , -
crustacean , fish and plarJctcn which are commonly found in the release
area.    Over a period of 36 hours , and at an effluent dilution of 1/5000 ,
these tests shall not , for 80 p of the species tested , give rise to
no reality.    The tests slir.ll be supplemented by tests on 1-rval develop­
ment , which shall on such as to ensure total survival of the lavae after
24 hours at an effluent dilution of 1/5000.
Uhen these checlcs have been completed , discharge operations shall bo
suspended if :
( a ) an examination of the gener:-,l ecology of the arer reveels a mcrlced
      deterioration of th?± ecology ;
(b ) tests for toxicity induced by the accumulation of metals in food
      chains indicate oil accumulation hazardous to huarn he'lthr
( c) the results cf the tests for acute toxicity are at variance with the
      values sot out above .
                                    Article 8                          ■
"ember States shall trice the necessary measures to ensure that existing
and new industrial establishments are equipped with effluent treatment
plant .
JLs from 1 January 1578 "the total pollution after treatment from new
industrial establishments sh-11 be less 'than 30 '% of the total untreated
pollution , end as from 1 January IS35 i"t shall be loss than 5 %
 ---pagebreak---                                               7 -                       Eir,/ 47/75 -E
    3 . As from 1 Janutxy 101o , totcl pollution after treatment from, existing
         industrial establishments shall "be less than 70         of the total tint rested
       . pollution j as ,from 1 January lS-'Sl , it shall "be less than 30 ,j and as
         from 1 January 1985 it shr.ll be less than 5 5*
    4. This total untreated pollution shall , in accordance with Annex II , be
         defined "by pollution ottogory and by the type of ore used.
                                        Article 9 -
    Existing industrial establishments which increrse their production capacity
    after the dr.te of entry into force of this Directive shr-.ll be required
    either to :
    ( a) comply with the requirements of Article 8(2 ) as to the proportion ,
          corresponding to the increase in production , and of Article 8(3 ) as
          to the proportion corresponding to the former production , on the dates
          on which each of these requirements enters into force j
          or to :
    (b) apply eenercl treatment in both existing end now establishments so that
          the total pollution after treatment does not exceed the sum of the
                                                10,
 member States Bay adopt stricter regul -t ion3 without prejudice to the pro­
 visions of this Directive.                                     7
                                     Article 11
 Annexes I and II shall form an integral part of this Directive.
                                • r  Article 12
Lcmber States shell put into force the measures needed in order to comply
with this Directive within a nrocinura period of eighteen months of its noti­
fication and shall forthwith inform the Cornmission thereof.
Iienber States shall ensure that the texts of the provisions of national
law which tney adopt in the field covered by this Directive are communi­
cated to the Commission.
                                    Article 13
This Directive is addressed to the Ilembcr States.
 ---pagebreak---                                                                     SFV747/ 75-S
                                    A N II F. X   1
Provisions governing the dumping* of waste st sea end discharging into
estuaries .
1 . v-.aste char.'ctcristics .
 ( a) Quantity and composition ;
 ( b ) Quantity of subst ances and iarterials which, era to be dumped or dischar­
         ged daily (weekly , irontly) ;
( c ) Forra in which the waste is to tie dumped or discharged , i.e. , solid ,
        semi-solid , liquid ;
( d ) Physical properties ( in particular solubility and density), chemical
       properties , "biochemical properties ( oaygen demand , nutritional v?lue )
       and biological properties ( presence of viruses , "bacteria, yeast , para­
        sites , etc.);
( e ) Toxicity ;                                        «
( f) Persistency ;
( g) Accumulation in the "biological matter or sediment ;
(h) Chemical and physical changes occurring in the waste after discharge , in
       particular the formation of new compounds ;.
( i ) Probability of any changes which would decrease the marketing potential
       of nature resources ( fish , molluscs , etc .).
^ • Characteristics of the dumping or discharge are a and met hods employed
( a)   Geographical situation , depth of x-jrat or and distance from the coast ;
(b)    Location in relation to living creatures in the adult or growing stage ;
(c)    Location in relation to amenity areas ;
( d)   Where approprirte , methods cf packaging;
( e)   Initial dilution level achieved by the proposed discharge method *
( f)   Dispersion, horizontal displacement and vertical mixing charact eristics ;
( g)   Existence and effects of current and previous discharging and dumping in
       the area ( including accumulation effects ).
* V.ithin the meaning of the London Convention on the dumping of wsste at ses<
 ---pagebreak---                                                               ANNEX         2
                                                 Untreated waste from the sulphate process
                                           ( calculated per tonne of TiC^ manufactured end
                                                         expressed in kilogrrjnmes )
                                     j 1 1   ■
                                     i
                                         Norwetir-n                  j.uctralirji          Canadian   . nriclied
                                     |
                                     1
                                         Ilmenites                   Ilraenites              Slag         Ore
1 Category I        SO . Ions               4.250                        3,170              2.830        *, 330
I Pollution              ( acid)
                                                 +                         +                  +             +
                                 *
                                                 $20                       680                170             55
               ;    Iron cations
                    Total              Η    5,200                        3,850              3.000   Η    2,400
             '
  Category 2 j      Other met al
                                    i
  Pollution         cations         j          -   110                     100                200           η 20
                                    i
                 * Allowing for additions during m?jiuir.cture .
 ---pagebreak---                                                                                                            EH\r/47/75-B
                                                            ANNEX      2 ( continued.)
                                           Untreated wr.ste from the sulphrvte process
                                       ( calculated per tonne of TiC>2 nanufrctured and
                                                    expressed in lcilogivaues )
                                               Nctural Rutile                 Synthetic Rivtilo   Australien Il^enitce
            1          •       , (I
            |    Clilorme used                         1,G60                         1,860        2,500     - 2,000
            I '
                Cl Ions ( c.cidity)               70                                   55         S70 to 680
Caterory I
                                                                                        +               h
Pollution                +                          -r
                       IroiP'                       i                                  25              4)0
                       Total               H      70                                   80       H    1,3)0
Crtcsory 2 |    Othor metal
                cations                            16                                  25              35
Pollution
 ( 1 ) Values inserted here for record only.
 ( 2 ) Allowing for additions during manufacture.
 ---pagebreak---                                                               Annex 2
Tho pollution cat caries affected lay the reductions required under Articles
8 and 9     as follows :
Category 1 : pollution lay direct toxicity
             - 50 . ions , acidity ( sulphuric ?.cid process)
             - CL ions ?.cidity ( chlorine process )
             - Fe cations ( both processes )
Category 2 : pollution "by indirect toxicity
             - cations of metals other than iron (Ti , Cr , v", Hi , etc..)
               (both processes ).          .                      1
 ---pagebreak---   COItilSSION OP THE
EUIÎOPEAH COMHUNITIES
                                                                ENV . 47/75 E
                      POLLUTION CAUSED BY THE TITANIUM DIOXYDE INDUSTRY
                                      TECHNICAL REPORT
 ---pagebreak---                                                                  EHV/ /1 7/75-
                                                                 Orig. : F
              POLLUTION CAUSED BY THE TITANIUII DIOXIDE INDUSTRY
                                   TECHNICAL REPORT
     General
     Part 1 - The TiO_ industry
               ––        IT
CHAPTER I
               THE PROPERTIES AND USES 0? TiOg                              p.
               l ) Pigmentary properties
               2 ) Uses                                                     p.   4
               3 ) Economic situation                                       p.   5
CHAPTER II   : THE PROCESSES                                                p.   6
CHAPTER III  : THE RAW IIATERIALS                                           p.   7
CHAPTER IV   : WASTE FROM THE PRODUCTION OF TiO .                           p.   8
               I. GENERAL                                                   p.   8
              II . SULEiATE PROCESS                                         p. 11
                   1 ) H::ste products inherent in the process
                   2 ) Elimination cr treatment of the wa3te
                       products inherent in the process                     p. 21
                       1 . Definition
                       2 . List of the main me ; ns of elimination
                            and treatment that can "be envisaged
                            for "waste products inherent in the
                            process "                                       p. 21
                       3 . Treatment procedure end finrl waste
                            product s                                       t>. 25
                                                                            p.
                            A. AES                                          p. 25
                            3 . BASIC DATA                                  p. 26
                            C. COST ASSESSMENT                              p. 28
                            D. RECAPITULATION                               p. 30
             III . CHLORINE PR0CESS                                         P. 33
                   waste products inherent in the process
               1 . General
               2 . A. Waste products corresponding to natural
                       rutile ore                                           p. 35
                   B. Waste products corresponding to synthetic
                       rutile ore                                           p. 3 6
                   C. Waste products corresponding to
                       Australian ilmcnite ore                              p. 37
               3 . Treatments                                               p. 38
                   A. Effluents considered                                  p. 38
                   B. Hain processes                                        p. 35
 ---pagebreak---                                                               ENV/47/75-E
                                                               Orig. î F
     Part 2 - Ecological aspects
CHAPTER V   : ESTHIA3E OF THE PHYSICO-CHEHIC /i CHANGES
              DUE TO DISCHARGES                                          p. 42
CHAPTER VI : STUDY OF THE BIOLOGICAL EFFECTS OF DISCHARGES               P. 49
              The different aspects of the problem
              SECTION I.    THE SHORT-TERM EFFECTS                       P. 50
                            1 ) Data on the behaviour of the
                                marine flora end. fruna in the
                                vicinity of the discharges               P. 50
                            2 ) Experimental data on their
                                beh?viour at different
                                concentrations of the effluent
                                Determination of acute toxicity
                                thresholds                               P. 53
                                Results                                  P. 57
                       .. . 3 ) Estimate of the direct
                                consequences of the discharges
                                on marine flora and fauna               p. 60
              SECTION II .  THE LONG-TERM EFFECTS ' .                   p. 63
                            l ) The "naturel " accumulation
                                procese                                 p. 63
                            2 ) Studies of accumulation and
                                induced toxicity carried out
                                in laboratories                         p. 66
                            3 ) Observations of heavy-metal
                                contents of the marine organisms
                                collected in the discharge area         p. 6Ç
              SECTION III . CONCLUSION                                  P- 72
CONCLUSIONS                                                             P. 74
                                                                  \
 ---pagebreak---                               ENV/47/75-E
                              Orig. Î P
        PART      1
THE TITANIUM DIOXIDE INDUSTRY
 ---pagebreak---                                     - 2 -                     ENV/47/75-E
                                                              Orig . î P
GENERAL         -  '■ –          -       - - -» •     –    »   • -
The modern world needs a number of manufactured products in order to
provide every citizen with a certain standard and quality of life .
The way in which these various products are obtained at the industrial
level can ha summarized "by the following equation :
Ravi material + materials used for processing + energy             •          - j.
                         « product + waste ( solid, liquid or gaseous ). ,
One thing is therefore obvious : everything that is put in at the beginning
is still there at the end.
In the case of certain industries, the greater part of the original
materials is processed and little waste appears in the production chain
(the petrochemical industry, for instance ).        In other industries, however,
the raw material is relatively poor in basic constituents of the finished
product, and the amount of material contributed for the processing of the
raw material is considerable .                          '                ■-
This is true of the titanium-oxide-producing industry.         One tonne of
TiOg "involves about 2.6 t of waste in the most widely used process,
not counting the consump&^an of water .   '       ■
 ---pagebreak---                                         - 3 -                  iarv/47/7 5-S
                                                               Orig . s F
                     CHAPTER 1 - THE PROPERTIES AND USES OF TiO?
l ) Pigmentary properties
    Titanium dioxide i3 at present regarded as the best white pigment .
    The main properties which help to give it this superiority are examined
    below .
    It should be noted that the two commercial forms of this pigment , "anatase "
    and " rutile ", correspond to two crystalline forms of titanium dioxide .
    The same names are used to designate the similar crystalline forms which
    are to be found in nature with a lower decree of purity .
    The essential quality of a pigment is its opacity, that is , its power
    of reflection when dispersed in a medium .
    This light-reflecting power is due to the reflection of light at the
    crystal-medium interfaces .   This power will depend on the refractive
    index of the crystal and, for a given pigment concentration , on the
    number of crystal facets .
    The former value is inherent in the crystal , while the latter is improved
    by very small crystal sizes, which must however be greater than a minimum
    size connected with the wavelength of the light to be reflected .
    Titanium dioxide
    - which has the highest refractive index of all traditional pigments
       ( average index of synthetic rutile for a wavelength of 450 nm : 2.921 );
    - of which crystals of optimum size ( 0.05 - 1«5a0 can be produced
      synthetically ;
    - which has very good transparency in the visible range
    is therefore a very effective pigment .
 ---pagebreak---                                               « 4 -                   3NV/47/75-E
                                                                      Orig . ï F
    Rutile and anatase differ by their behaviour in the ultra-violet range .
    This behaviour produces differences in the light-fastness of the paints
    in which they are used .                        -•
    Lastly it should be noted that coatings of metal oxide make it possible
    to improve the wettability and dispersibility of the pigments and thus
    to enhance the quality of the dispersions .
2 ) Uses
    The fundamental characteristics of rutile and anatase crystals have been
    noted .    These properties have led to very widespread use of titanium
    dioxide in many fields .
    Major categories worthy of mention ares            (l )
    - paints and varnishes                                      5($<
    - papers             ^          '                           2(>o
    - plas ; les                                                10$
    - rubber                                                     H.%
  ■ - floor coverings           .       .                        4%
    - inks    ;     :                                       ,    2.5
    - ceramics                    -                              2.5$
    - synthotic ffbres      . (             •                  - 1.2%
 - - miscellaneous , including cosmetics
       and pharmaceut ical products       ■                   ' 5-3%
    Consumption of this pigmerjt , owing to its field of application, may be
    regarded as an index of a country 's degree of industrial development .
    With regard to the distribution of its application by sectors, this may
    vary from country to country, but it should in any case bo noted that '
    paints and varnishes represent more than half of total consumption , while
    the other sectors represent proportions ranging from 3 to 15$ of the total
    In all these applications, titanium dioxide is a suspension in the various
    media .
    ( l ) The distribution of uses shown corresponds to the situation in the
          United States .   This distribution is taken from the study
          EPA-2 30/1-7 3-015 dating from 1973 .
 ---pagebreak---                                                                  Orig. s F
  3 ) Economie situation
      It is obvious that the future of titanium dioxide is bound up with the
      development of its traditional fields of application .     The effects of
      competition from similar products are slight in these fields .
      The average annual growth in world consumption of titanium dioxide was
      estimated in 1974 at about 5/£ *  This rate may, however , be expected to
      increase in the next few years „
      By the end of 1974 this substantial demand had led to a rise in prices,
      which were around 595 units of account (U.A. ) per tonne of anatase and
      720 U.A. per tonne of rutile ( mid-December 1974 prices per consignment
      of 20 tonnes ).
      The prices of Japanese products are the highest , followed by European prices ,
      except for those in Prance and Great Britain, which v/ere subject to taxation
      as from 1st July 1974 - Lastly, American prices appear to be lower .
                            !                                          1 ■       I
                                                                                   –:     »
  Countries            USA    B1LLGIUII FRANCE  FIID . REP . NETT1ER--     ITALY   G.B.
                                                of GERMANY   LAITDS
Prices not
                      UA/kg    UA/kg    UA/lcg     UA/kg      UA/kg        UA/kg   UA/icc I
including tax
20 t consignments
July 1974 Anatase     0,45C    0.570    0.333      0.432      0»5ol        0.5C5   0»3o0
            Rutile    0.500    0.C16    0.530      O.674      0.671        0.713   0.424
The July 1974 prices in UA/kg ara based on quotations on loth July 1974, assuming
that one UA = 50 Belgian francs , as given by "European Chemical News ", Vol . 25
No . 642 .
 ---pagebreak---                                       - 5 -               ENV/47/75-E
                                                          Orig. î F
                           CHAPTER II - PROCESSES
Description of processes
The method of manufacturing titanium dioxide pigments consists of preparing
a titanium dioxide of very high purity from an ore which already contains
it , but mixed with other elements .
There is no industrial process for the preparation of titanium dioxide
which enables it to be extracted selectively.
Actually the only two existing industrial processes consist of an attack
on the whole of the ore followed by selective operations to extract the
titanium compound . . A final stage enables the titanium dioxide to be
obtained from the intermediate compound .
These two methods are the so-called " sulphate" and "chlorine" processes .
In the case of the sulphate process the whole of the ore is attacked by
sulphuric acid, and then titanium hydroxide is selectively precipitated .
Finally titanium dioxide is obtained by calcination of the hydroxide .
In the case of the chlorine process the whole of the ore is chlorinated
and the titanium tetrachloride formed is first of all separated from the
other chlorides by mechanical means and then distilled . Finally the
titanium dioxide is obtained by oxidation of the titanium tetrachloride .
(The chlorine process is generally used only with ores which are rich
in titanium (rutile ). Only one firm has succeeded in applying this
process to poorer ores ( ilmenite ).)
 ---pagebreak---                                      ~ 7 -                  aw /O' /i >
                                                            OriA,'o : F
                       CHAPTER III - THE RA!J JLVT2RULS
All titanium dioxide i3 prepared fron natural ore .     The titanium is
contained in the latter mainly in the form of iron titsnate in the
case of the more ordinary ores ( ilmenite ) and already in the form of
crystallised Ti02 ( rutile form ) in the richer ores .
While reserves of ore of the rutile type are small and becoming exhausted ,
reserves of ordinary ores such as ilmonite are extremely large .        In
particular, there are enormous deposits of them in Canada and Norway *
As a whole, ore availability should not create any problems during
the ney:t 75 years . However, a very great research and development
effort is at present being made for the preparation of an oro very
rich in Ti(>2 ( synthetic rutile ) from the ilmenite-type ore , in viev/
of the environmental problems created by ores of the ilmenite type .
 ---pagebreak---                                                                     EHV/47/75-E
                                                                    Orig. : F
                         CHAPTER IV - WASTE FROM THE PRODUCTION OP TiOp
SECTION I. GENERAL
           In this chapter, two categories of "waste" will be discussed : .
           a) the waste products inherent in the process, resulting from the
              . carrying out of the production process, that is, from the various
                separations taking place in the process itself before any treatment ;
           b ) the final waste products, which are obtained after elimination or
                treatment of the process waste products . These final waste products
                may be identical to the process waste products if the factory does
                not carry out any elimination or treatment .  But , by definition.
                " elimination or treatment of process waste products" io regarded
                as embracing any intervention which leads to a change in their
                characteristics, which can range from mere dilution in order to
                reduce their concentration to very elaborate operations which .<
                radically change the nature of the waste ..
           Before going into this question of waste products in more detail , it
           is interesting to note that the production of the "Ti02 " pigment industry
           is . very simple to define , because it consists of high- -purity titanium
           dioxide . In all evaluations, the particular additives which enable
           the performance of the pigments to be improved, and also the residual
           quantities of impurities, which are extremely small , will be disregarded.
           As production consists only of titanium dioxide, all raw materials
           other than titanium dioxide will of necessity be discarded at one of
           the stages of the process . Moreover, as production of titanium dioxide
           is carried out with a certain yield, there will also be some titanium
           dioxide in the waste products .
           That is why, in Section II , for the sulphate process , four cases of
           production of TiO? based on the following ores are considered :
 ---pagebreak---                                   - 9 -                 2NV/47/75--E
                                                        Orit,\ : F
      '• Norwegian ìlnenite
      ~ Australian ilmenite
      " Canadian slag
      - Enriched ore (hypothetical ) containing about Q&/o of Ti02
         (maximum possible for sulphate process ).
Similarly, in Section III , for the chlorine process , three cases of
production based on the following ores are considered :
      - natural rutile
      - synthetic rutile
      - ilmenite (hypothetical ).
For each of these types of production, account will be taicen
- of the quantities of raw materials employed ;
- of the total weights of waste products corresponding to these raw
  materials ;
- of the main categories of waste products , stating their nature
  and quantity .
We shall thus see how the various original' constituents are distributed
in the main process waste products ,
 ---pagebreak---                                PROCESS               DIAGRAM
                                  i1 .  . .,i !■■
                                                              Product
                                                                                               TiOp
  ore
                        >  •
                         >
                       / /M PRûCKiS
 E2so4          / ///                             Waste                         Final         Waste
             ^      / ' '                         products                      waste
 100fo             / //                                                                       products
                /// I
                                                  inherent in  .  Treatment of  products
                                                  the process
                                                                 Waste products
  ■* '//. 1
  Iron        /
            /    -
Additives <'  •              ^
                                       PROCESSING                                      PRODUCT AND
   RAVI
                                                                                      HASTE PRODUCTS
MATERIALS
 ---pagebreak---                                                 - 11 -                E1W/47/75-2
                                                                      Ori g . : F
SECTION II . SULPHAT3 PROCESS
             l ) Waste products inherent in process
                 Generr.1
                 It should not be the purpose of the calculations presented in this
                 chapter to ascertain the exact compositions of effluents .
                 The reason why such a calculation has nevertheless been attempted
                 is rather in order to achieve a coherent overall analysis based
                 on well-defined hypotheses .
                 These hypotheses can be argued about and the calculations adjusted,
                 but they do make possible, as far as the main waste products are
                 concerned, a valid quantitative approach for the different types of
                 production and different factory capacities representing- the main
                 European producers .
                 Four main categories of waste products corresponding to possible
                 groupings of the waste products inherent in the process are considered :
                      - the insoluble substances remaining after filtration
                          (waste product l )
                      - the " copperas" ( i.e. ferrous sulphate ) compounds
                          (waste product 2 )
                      - the " strong acids" (waste product 3 )
                      - the "weak acids" ( waste product 4 )
                 obtained after the operations schematically shown in the following
                 illustration ( Table 2 ).
 ---pagebreak---        Ta oie 2                                                                - 12 -                                 ENV/47/75-E
                                                                                                                      Oriff.s P-
                                               lit'2 - «ULniiïS PRCC3S3
                                                                                        VAP
   ILM3NITE       o-
                                    *                ATTACK                                   )
                                                  DISSOLVING                                                                                  ;
                              ■ 1                          r––                                           ~l~î
                                                                                                                                    ( solid ) ..–v
 flocculent
    agents
                 ,o                   fr/ separation                             )        .            » jwashing | . , ' „                       (O­
                                                           »                                                   i
     Iron      ■ o
                                          I                             –i                                    i
                                    M           ,■ REDUCTION"                         ;                                                   ■ j
                     •    ' "            i                                            !
                                                                                                      «     -            *                    '
  flocculent                   ■ ; r                      TT                   ^                                                             1
    agents       0 ■.                ■» ( separation                            J              1                          ;
                                          :                                         1I                                   ;4  II
                       ;              *j CRYSTALLISATION |
                                            rimnimATt TfiAmTAW
                                                                                                                          '  j               ,      .
                       !          •. •;                                              l_                                      |               1
                       «                                    i                                         «'                  'i       ./.*. » \
                                           ( separation                          }1
                                                                                ••
                                                                                            ■                        t>)washinfe-
                                                                                                                       i–p.
                                                                                                                                      (solid)/^ .
                                                            I                                                               Ó
                                         !                  !                            VAP                                             • :
                       ,                          CONCENTRATION                           ^            ,
   genas of
    TiCly,       .     '        '                   HYDROLÏSIS
                                  '»
                       s
                   " f . . . , . f separation                                   J                '■ ■          ■ ■■ )           (liquid) 0^
                                      ;                      i
                                       '     I      III  I Ii   II III ■ ! ■ I .1 ■■■
   2 4           0                  u 1WASHING - REDUCTION^
                                                        " JUIUUUAXV/XT •                 11
                                                                                                  ,                 N J
                                                                                                                    )    1
                                                                                                                                (liquid )
                                                                                                                                11    1     1 if.  A  V
powder of Zn     °­  –*\                                –                           i            ¥
                      "1              '                                                 GAZ      S           I
                        : ,.                         :                                  zzi> t
                       ;•                         CALCINATION                                      ;        J
                       ; 4^,             j         FINISHING
                                                              1                     I
                                                                                                            r
 ---pagebreak---                Tabl G 3                                              -1 .1 -                             J             ^
                                                                                                         C^xL : $
                                WASTE PRODUCTS CORRESPONDING TO ORE A. NORWEGIAN ILKEBITE
                   ORIGINAL ORE
I             NORHEGIAIT ILMENITE
                           «£
                                                             Yield :      C3.5&                                         PRODUCT
( TiOp I                 44-45 Ί         1130.000
                                                            r~.~
                                                                                                                 TiO ?:    1 tonne
       FeO               33-34            8C7oOO
       Fe02Û3            12-13         ;   312.500
       SiOp            2.5-3.0              Go , 100
                                                                                                            FATAL WASTE PRODUCTS
I ZrO?                        -
       AI2O3           O.0-O.7 I            15,000                                                     I expressed as quantities
                                    1
                                              0.700
                                                                                                       (          of metal (iq,)
       P2O5           < 0,03
       lînO                 2-0.3             5.000                                                        Ti                  78.000
                                                                                                       f fp        j          755,000
       MtO             4»5-5»5             125.000                                                     I
                                                             Waste products                                Si                  32.000
       Cr20 ->           0.07                 1.700
       V205           O.I5--O.I7              4.000      S                                  "V
                                                                                                           Zr
       CaO            0 . 2-0.3               6.200                                                        Al                   4.000
       NaoO                                                                                                P                    0.142
                                                                                                                                3-C70
                       < 0.04        I      < 1.000 J                                                      Mn
                                                                                                                               75.000
                !       2^p*ra ©       I Grammes j
                                                                                                           Cr                   0,559
       Ni                Cl-113            253.000
                                                                                                                                l.OoO
 ! Zn                     57-93            I67.OOO
                                                                                                        ! Ca                    4-275
  I Cu                  6 < -0.2          < 13.000
        Cd               < 3-1.9          <- 4.000                                                                    in grammes       J
        Pb . 3q                        ! <2.3 eaoh                                                         S               <1000
                                                        J
        Sb,HS
  li 1 mi
                  j O                    < 2.5 each I                                                      m
                                                                                                           Zn
                                                                                                                    1
                                                                                                                              253=000
                                                                                                                              1C7.000
                                                                                                           Cu                  1S.000
                                                                                                           Cd                   4.000
                                                                                                           Pb , 3e          < 2 5 each
        Correspondis weitht of ore : 2,500 xg
                                                                                                           Sb,Hfe |         < 7,9 each |
        N.3. :      The total cf the colunn does not correspond to
                    2,500 k£ , as the weights - of each constituent have
                    average values related to different compositions of
                    ilnemte .
                             iv -1             -,    -1    " « -v •.        !      ''liin
                                                                                   ; lll£ 1 -h-tarôt
                                                                                                   ."1
                                                                              "1 .         -- ν\-> 1
 ---pagebreak---                                         - 14 -                   ENV/47/75-E
                                                                 Orig. : P
     NORWEGIAN ILMEHITE
                                                                -.'•v.-         ' ■•*•• •
     The quantities shown below relate to 1 tonne of finished product and are
     based on the values in the preceding table.
     Waste product 1 - Insoluble substances                   "         . – " ■»•■■• -
  .. . .          .      81 kg              (Si02t Ti02, Al202» MgO, Cr^, P2®5»
                                             MnO, VgO^, CaO, Si, Ni, Zn, Cu, Cd,
                                             Be, Sb, Hg)
                         81 kg               HgO (assuming HoO « 50$ of total weight )
                        162 kg
     Waste product 2 - Copperas
                      3,372 kg             various sulphates, including 2, 941 kg
                                           PeSO , 7H20
              +         460 kg             H2O.
              +          23 kg '           free HgSO .
                      3,855 kg
    Waste product 3 - Strong acid
                        727 kg             various sulphates, including 585 kg of
                                           PeSO .                         ■'
                                                4                         '                 ,
              +          34 kg             TiOg in suspension
              +          41 kg             TiO„ in solution               ;                 1
              +     1 1,482 kg             H2SO4 (exp. as 10#) concentration 20fj
              +       5,127 kg             H2°                                            -
                      7,411 kg
V ..
    Waste product 4 - Weak acid
                        391 kg             various sulphatas, including 315 kg of
                                           PeSO-
              +          28 kg             TiOg in suspension                .,
              +          22 kg             TiO_ in solution
              +         300 kg             HgSO^ (exp. as 100f') concentration 10$
              +       5.753 kg             K 0
                      e.ooc kg
 ---pagebreak---        Table 4                              - 15                ENV/47/75-S
                                                                Orig . : F
                 WASTE PRODUCTS CORRESPOND!^ TO ORE B. AUSTRALIAN ILMENITS
         ORIGINAL ORS
     AUSTRALIAN ILMENITE
              %           ^5             Yield : 88.5%                      PRODUCT
 Ti°o I     55-4        1130.000
                                                                         TiOgî 1 tonne
 FaO      I 23.8   x   1 485.450
 Fe.O     ί 16.9       ! 344.800
 SiO »       0.15          3.060                                    FATAL WASTE PRODUCTS I
 ZrOp         -
                                                                 (Expressed as quantities
 A1 20 ,     0.94         19.200                                         of metal (kg)   |
   2 5
             0.08          I.65O                                    Ti          76.000
 MnO         0.72         14.700                                               498.000
 Mg0         0.27          5.5OO                                    Si           1.400
 Cr20        0.14          2.850                                    Zr
   2 5
             0.17          3.500        Waste products              Al           5 . 080
 CaO         0.02          0.400  >   Π                  9          F            0.330
 Na.O                                                               m           11.370
 *2°                                                                Mg           3.300
 S           0.01          0.200                                    Cr           0.940
 Ni                                                                              0.920
 Zn                                                                 Ca           0.280
              *"      1                                                          0.200
                                                                    S
 Cu
                                                                    Ni
 Cd
                                                                    Zn            mm
 Ρο , Βθ                                                          ι
                                                                  I Cu
 Sb.Hg
                                                                    Cd
                                                                    Pb, Be
Corresponding weight cf ore : 2,040 kg.
N. B. i  The total of the column does not correspond to
         2.040 kg, as the weights of each constituent have
         average values related to different compositions of
         ilmenite .
         Nevertheless, the complex information in this table makes
          it possible to assess the overall quality and quantity of
         the waste products .
 ---pagebreak---                                     - 16 -                     . EOT/4',7Y^.
                                                                 Crlg . : F
 AUSTRALIE IICTITB
 The quantities shown "below relate to 1 tonne of finished product and -
 are "based on the values in the preceding table .
 Waste product 1 - Insoluble substances               ■
                          20 kg       (Si02 , 'Ti02 , A1203 , KgO, C^Oj ^0 t
                                      MnO, V20^, CaO, Si, Ni, 2n , Cu, Cd,
                                      Be , Sb , Hg )                         . :
           +              20 kg       FLO ( assuming ILO = 50> of total weight )
                          40 kg
Waste product 2 – Copperas
                     1,768kg          various sulphates , including 1,725 kg
                                      FeSO^, 7H20 •;
           +             241 kg       h2O               •
           +              12 kg       free F^SO .
                     2,021 kg
T/fes+e product 3 - Strong acid
                         637 kg       various sulphates , including 584 kg
                                      of PeSO
           +              34 kg       TnOg in suspension
           +              38 kg       Ti0o in solution
           +         1,250 kg         EpSO . (e::p« as 1 0O'/o) concentration 20$
           +         4.291 kg         Η2°       .         ....
                     0 , 250 kg
Waste product 4 - TTe^-k acid
     ■                   343 kg       various sulphates , including 314 kg
                                      of PeSO .
           +              28 kg       T i02 ta suspension
           +              21 kg       Ti0o in solution
           +             672 kg       HpSO^. (exp. as 100$) concentration 10%
           +         5,663 kg         ILO
                     *, 727 kg
 ---pagebreak---                                                             - 17 -                           ELJV/47/73-E
                                                            r     i :-                       Origr ?
                      WASTE PRODUCTS CORRPISPCttTDWGv TO ORB C. CAIADIM SLAG
                      ORIGINAL ORE                       J
              C A N .A D I A IT        SLAG                   Yield 88,5/a
                                                                                              PRODUCT
                             ^                     kg     j
                                                                                      Tx02 :        1 tonne
      TiOp          i   70,72                1130.000 i
     FeO                12,15                   194,138
     Pe203                1,50                   23,960                           [FATAL WASTE PRODUCTS
                                                                                  L.   .   ,
     Si02              3,5-5,0                   67.100
                                                                                   Expressed as Quantities
       2r02                                                                        of metal (kg )
      A1203            4,0-6,0                   79,890
      P205
                                                                                   T1            | 78,000
                         0.025                     0-399
I Mn.0                   0,2                       3,195
                                                                                 pe                 159,751
                                                                                  Si     .           31 .3
   ' HgO              4,5-5,5                    79,892     >Waste Products
                                                                           N,      Zr
    Cr203                0,25                     3,994     1 r  –     " ■
                                                                              'Lu                    21.14
        V205      |! 0,5-0,6                      8,788
                                                                                  p                   0,081
        CaO       j      1,2                     19,174 !                       1
    Ïïa20      .  !1I
                                                          l                    jl-ii                  2,472
       K20
                          –                               i
                                                          »
                                                          j
                                                                               kg                    47,935
                                                          J
                                                                               ICr                    1,314
    S             |      o f C5                   ο,7?ε                         t
   ì\T 10         i      0,085                    1,358
                                                                               iv .                   2,3 :»
                                                                                  Ca              ! 13,210
    Zh
                                       [
                                                  1,1
                                                    *
                                                          i
                                                          1                    lATa
                                                                               ra               i     -        i
[ CuO              |!    0,015                    0,239
    Cd
                                                                               P                I î   0,798
                    !     •"           I                  ΐ                      Mi              !    " .. 068
   Pb,Be            i     „                       0,07                                          {
                    !
                    I      ·-■■■■'     I            -                            Zn              « ( 1,1 )
i Sb,Hg                                                                       bu                 \ 0 y l89
i    .
                    |                ι                                        ρα
                                         -, ,,!■■■■   ,   L
                                                                              ρ                      (0,07 )   |
                                                                                                               i
  Corresponding veight of ore :                       1,600 k£.               ι
  2uB »: The total of the column does .not
             correspond to 1,600 kg, as the ve.l/rhts                         Ι                 I
        •    of e~,c.'i constituent have av.3ra.f0 ve lu.ee
            'related 'to different compositions of
             Uovertheleps , the complex 5nf6nxation in
             this tabla makes it possiols to armors
             the overall
             the  overall cua   cuaiity and quantity of the
             wasto produo ts .
 ---pagebreak---                                            - 18 -                   ET07/75-E
                                                                   Orig : F
 CANADIAN SLAG              ■     !. V.'.'               . .     ;
 The quantities shown "below relate to ,. 1 tonne; of finished product and
 are "based oil the value in the preceding table , ■■
 Waste product 1 - Insoluble substances
                         107 kg                  (Si02, Ti027 A1 203, MgO, Cr203 PgC
                                                ì&iO, V2Ò i CaO, Si , Ni , Zti , Cu, Cd,
                                                Be . . J3b , /Hg)
             •    + .    107 kg                 H20 (assuming H20 = 50$ of total weight )
                         214 kg
 Waste product 2 – Copperrs
–; '           *         None '                                ί
 Waste product 3 - Strong acid
                         630 kg ;               various sulphates , including 303 kg
                                                of PeSO .
                                                    –4
                 +        34 kg                 Ti02 in suspension
           .     +        33 kg                 Ti02 in solution
          v +         1,440 kg                  HgSO^ (exp. as 100$) concentration
                 +    5f063 kg                  h26
                      7,200 kg
 Waste product 4 – Weak acid
                         339 kg                 various sulphates , including 1 63 kg
                                                of FeS0„4
                 +        28 kg                TiOg in suspension
                 +        19 kg                Ti02 in solution
                 +      778 kg                 H->S0 . (exp, as 100%) concentration 10$
                +     6,624 kg                 HO
                      7,780 kg
 ---pagebreak---                                            - 19 -                   ENV/47/ 75-E
                                                                     Orig : F
                      WASTE PRODUCTS CORRESPONDING TO ORE D .
                         ECTRICHED MINERAL ( Hypothetical )
                                ( Similer to Canadian slag )
           ORIGINAL ORE
           EMRICHED ORE
                                           Yield 88.5%               PRODUCT
                   %           kg                                 TiO_:    1 tonne
bio2           88,00    11 30,000
beO             5,00       64,204 \
pe203           0,50        6,420                          j FATAL WASTE PRODUCTS     |
Bi02             1,65      21 , 187
                                                             Expressed as cruantities
 Zr02                                                         of metal (kg )
1A1203          2,00       25.681                          ITi              78,000
P205            0,01        0,128                             FB            52,133
Ϊ£η0            0.08         1,027
                                                              Si             9,746
  IgO            2,00       25,681       VJaste products ;  IZr
 Cr203           0,10        1,284                       r    Al             6,779
 V205            0J20        2,568                            P              0,026
  CaO            0,40        5,136                             il            0,795
 CIa20
                                                            Pig             15,408
 A 20
                                                               Cr            0,422
 Ρ               0,02        0,256                                           0,680
 FiO             0,03        0,385                             Ca            3,538
 pn                                                         bla
 Eu              0.01        0,128      j
                                                            Ρ                0,256
 Ρ                                                           pi              1.068
 Pb.Be
                                                               Zn             mm
                                                               Cu            0,101
 J
                                                             j
    Corresponding weight of ore : 1,284 kg
 ---pagebreak---                                          - 20 -                 EÏÏV/47/75-E
                                                                Orig: P
ENRICHED ORE
The quantities shovrn below relr,tg to 1 tonne of finished product and
are "based on the . values in the preceding table .
Waste product 1 - Insoluble substances
                     57 kg        (Si02, Ti02, Al203 , Mg0, Cr203, P^,
                                  MnO, VgO^, CaO, Si , Ni , Zn , Cu, Cd,
                                  Be , Sb , He)
       – +     ' • 57 kg •        H20 (assuming HgO = 50$ of total weight )
                    114 kg
Waste product 2 - Copperas                        '
                    None .
Waste product 3 - Strong acid
  -                 185 kg        various sulphates , including $8 kg
                                  of PeSO .
                                           4
           +         34 kg        Ti02 in suspension
           +         31 kg        TiOo in solution
           +    1 9 395 kg        H^SO . (exp, as 100^) concentration 20%
           +    5,330 kg          H20
                6,975 kg
Waste product 4 ~ Weak aci d
                    100 kg        various sulphates , including 53 kg
                                  of PeSO .
           +         28 kg        ^^2        BUSPens*on
           +         17 kg    ; - Ti02 in solution
           +;    , 750 kg         H2S°4 (exp*
                                  ^2^4    (exP» as 100^)
                                                    1    concentration 10$
           +    6,605 kg          H20
                7,500 kg
 ---pagebreak---                                          - 21 -                   ENV/47/75-E
                                                                  Origï F
2 ) Di sposal or treatment of "the irp.ste products inherent in the process
    1 – Definition
         "Elimination or treatment of waste products inherent in the process "
          is understood to mean any intervention which leads to a change
          in their characteristics , which can range from mere dilution in
          order to reduce the concentration to very elaborate operations
          radically changing the nature of the waste .
    2 – List of the main methods of elimination and trcatr.ent th^t can "be
         envisaged for "waste products inherent in the process "
         DISCHARGE H3T0 THE SEA ( l )* This can be done direct from the coast
                                        or by scattering over the sea .      This
                                        method is widely used for soluble waste
                                        products ( copperas and acid solutions ).
         Injection into underground     This re mires special geological conditions ,
         strata                         Its use in the United States ( DuPont ) has
                                        given rise to strong criticism .      The
                                        " injected" effluents must not contain
                                        suspensions which might clog the well .
         STORAGE ON LAND ( 2 )          This is used for insoluble waste products .
                                        Storage on land of soluble waste products
                                         (" copper£„s ") raises more problems owing
                                        to their solubility and their large
                                      . quantities .     The company TKANN & MULHOUSE ,
                                        in Thann (France ), stores on land insoluble
                                        products , " copperas " and the neutralisation
                                        products of its acid liquors ( output
                                        20,000 tonnes per annum of TiO^).
         NEUTRALISATION ( 3 )           This method , which results in a very large
                                        volume of neutralisation product , is very
                                        little used .     Its cost is high . At present ,
                                        in Europe , only THANN & IIULHOUSE uses this
                                        method for its acid liquors ( at Thenn ). In
                                        the United States , "SCK" neutralises the
                                        dilute acid fraction . The neutralised
                                        products are redi luted and discarded .
   (*) Only the numbered methods cen be envisaged , a priori , in the
        European context .
 ---pagebreak---                                   - 22 -               EITV/47/75-E
                                                       Orig : F
Production of gypsum : Production of gypsum from the neutralisation
                       of the acid liquors requires a special local'
                       context .   In the United States the American
                        Cyanauid company is "building a factory for
                       producing building components of gypsum . It
                       should "be noted that in this oase there are no
                       local gypsum resources ; moreover , the local types
                       of buildings are well suited to the use of such
                       a material .
LURGI COPPERAS*        This method enables "copperas " conpounds to be
DRYING PROCESS (4 )    dehydrated by changing them into iron sulphate
                       monohydrate , which can be roasted in a
                       fluidised–bed furnace (there is an existing
                       unit at Spinetta, Italy, and one being built (
                       at Cel je , Yugoslavia ),
Fluidised–bed drying   Process employed by BAYER to enable iron sulphate
of copperas compounds  to be roasted in rotary furnaces .
LURGI FLUIDISED-3ED    The LURGI roasting process mekes it possible
ROASTING PROCESS (5 )  to treat iron sulphate monohydrate ("copperas"
                       after dehydration ) or concentrated acids (70$)
                       containing salts in solution . One obtains , from
                       the solid or liquid substance fed in , on the
                       one hand SOg which can be directly used, in an
                       HgSO^ synthesising unit and, on the other hand,
                       the metal oxides corresponding? to. the salts in
                       solution .   There is no experience yet of working
                       with liruid feed .
ROASTETG Bï A ROTARY   This- technique , which is an old one , makes it
PUffîTACE ( 6 V        possible to treat "copperas " compounds after
                       dehydration or salts precipitated during
                       concentration of acid liquors . Actually the need
                       to use sulphur or pyrites to bring about
                       combustion leads to the production of quantities
                       of HgSO^ greatly in excess of the requirements
                       of a Ti02 unit . This method has been employed
                       marginally by Bayer – Titangesellschaft - Pigment
                       Chemie in Germany and by British Titan Products
                       at Grimsby (Great Britrin ).
 ---pagebreak---                                  - 2.3 -               32'7V/47/75-E
                                                       Or ir- : P
"EEW JERSEY ZH'TG "    This process cm be used for treating acid
PROCESS (7 )           liquors . After treatnent pure sulphuric acid
                       is obtained , together with iron sulphate
                       nonohydra.te nixed with the other elements present
                       in the solution .  At present the only plant
                       based on this process is a snail pilot in the
                       United States .
LURGI ACID-            This process "treats " acid liquors by bringing
CCNCEÎTTRATICN         then up to a concentration of 70$ . The acid
PROCESS ( 8 )          is not evaporated , and the 70% acid still
                       contains all the salts in solution . TTo actual
                       unit based on this principle .
BAYER ACII>-           Bayer uses a process of concentration by submerged
COIT CENTRAT ION       flcne .  This process has proved very
PROCESS ( 9 )          unsatisfactory .
BAYEF- 3ERTRATTS       This process for concentration of acid licuors
ACIl>-COIÍCEtTTRATIOIÍ uses a filn evaporator .  There is still little
PROCESS ( 10 )         information about tho possibilities of using it
                       in the Ti0o industry .
Production of          Superphosphate is a fertiliser the use of which
superphosphate         in Earope has considerably declined .      It is
                       obtained by attacking natural tricalcium phosphate
                       with sulphuric acid .  At present only one state-
                       owned company in Poland uses this process , which
                       requires prior concentration of the acid lienors
                       up to Cj%
 ---pagebreak---                                      • 24 -               EMV/47/75-E
                                                          Orig : F
  Amnoniun sulphate      This process enables amoniun sulphate to be
  production             produced fron acid liquors . Ishihara Sangyo
                         Kaisha holds the rights to a process making
                         possible the opt intra treatment of acid liquors
                         by this method . Ammonium sulphate is no longer
                         used in Europe , and this method is thus of little
                         interest at present , at least in Europe .
. I.P.P. PR0C2SS ( 11 )  This process enables dissolved sulphates to be
                         treated . It thus makes it possible to treat
                         either acid liquors alone or acid liquors in
                         wtich the "copperas " compounds have been
                         previously redissolved .    The products obtained
                         ere sulphur and hydroxides and sulphides of the
                         metals in solution .
  To these processes should be added those of the BUTTNER and SAINT
  GOBAM companies , described as "new techniques " in the field of acid
  concentration .
 Note : In the Netherlands there is a system of taxation of effluents .
        Its anount at present represents about 3»5/S of the cost of TiO^.
  I     It is said that this tax is to be doubled every year .
 ---pagebreak---                                  - 25 -                EMV/47/75 - E
                                                       Orig ; F
SECTION 3 – Treatmont units and final waste products
            A. AHIS
               In Section 2 a list has been given of the processes
               which could be used for the treatment of waste products
               inherent in the production process .
               In this section an r.tteapt will be cade , by combining
               the various proposed processes , to establish couplete
               treatment units .  There are obviously very many
               possibilities , and only tho most characteristic ones
               have been considered .
               Furthermore , depending on the degree of treatment
               which it is desired to achieve , the units proposed can
               either bo adopted as a whole or some of their constituent
               parts replaced or even omitted .
               $he capital investments rnd operating costs involved
               for each of these unite will be stated .   The capital
               investemtn figures are bf-sed only on design data
               available at present , and the operating costs have
               been calculated on the b-sis of values recorded at
               a fixed date ( end of 1973 ) ^nd are now being updated
               in the light of the present economic situation .   The
               characteristics and volumes of the final effluents will
               also be given .
               These solutions will be considered for the different
               types of raw materials .
 ---pagebreak---                                                  - 26 -                  ENV/47/75-E
                                                                         Origî P
    B. BASIC DATA
        Below end on the following page , the weights of effluents to be
        treated corresponding to an output of Ti02 of 100 tonnes per day
        are given for the four types of raw materials .
                           Norwegian        Australian         Canada an      . Enriched
                      4    ilmenite            ilnenite          slag         i    ore
     -----
               1 ■'    I
                       1
                                                                              I
»                      ι
  1 ) DTS0IXJBI^
      STJBS'fAMCSS
                                         .·  .      I
  Total weicht             1 6 t/d   i
                                               3.8 t/d         21 t/d           11 t/d
I Volume if d = 2*
i
                           32 m3/d             7.6 m*yd        42 m /d          22 itfVd
  "Dry" weight**             8 t/d             1 .9 t/d        10.5 t/d         5-5 t/d
                                                                              [
  2 ) COPPERAS                 t/d-                    t/d          t/d       I      t/d :
! Total weight             385         ! 202
  PeSO ., 1.1/2 fl^O       189              111                does not         does not
                                                                exist            exist
  KgSO                      20.4                1.1        !
                                                            ι
  exp . in H^SO^,          122               62                             I
  exp . in Pe2°3           169               99
                                                                            i
                         i                                   »
       * d:    density of the insoluble substances as a whole
                 (d » 2 is a hypothetical value )
      ** represents the weight of the insoluble substances if
          water is excluded from then .              ;
 ---pagebreak---                                     27                  ETÏV/47/75-E
                                                        Origî P
                       Norwegian    Australian     Canadien     Enriched
                       ilmenite       ilmenite       slag •       ore
 3 ) ACID LIQUOR               t/d           t/d        t/d            t/d
     (hypothetical
       concentration
       20<£)
 Total weight           741           625           720          697
 H2° .                  512          429 ; .        506          533 .
 Free
         B2SO4           140          125           144          140
 PeSO
       4
                          58            58           30           10
 Various sulphates        14             5 .         32            9
 HpSO . (free + ,       195 ;         165           184          152
           combined )
 Exp , in                 61            61 ;         31           11
 Exp . in sulphur         64            54           60           50
 4 ) DILUTE ACID                t/d            t/d      t/d            t/d
     (hypothetical
       concentration
 Total veirfït          800           672           778          750
 Free                     80           67            78           75
                        675          566            652          660
 h2O
 PeSO ,                   31 •       • 31 :          16            5
 Various sulphates         8             3           18            5
 HpSO . (free +         106            89            99           82
           com'bined )
 Exp. in PegO^            33           33            17            5
iExp . in sulphur         35           29            32           27
 ---pagebreak---                                         - 28 -               MV/47/75-E
                                                             Orig : F
C. GOST AS3ESHÎ.M:T
?) Card ta! investment
      For each -treatment unit the total capital investment is determined
      from the capital investments for each constituent part .      These
      ars for the period end 1973 - beginning 1974 and must therefore
      adjusted in the light of the present economic situation .
      Allowance has also been made for the price of recovering the sulphur
      or sulphuric acid as the case may be , excluding all other products ,
      particularly FeO .
b ) Ener
  *
                consuintion
             –ii wr-M.ii – ttm
                                                             '  .
      For each treatment the energy consumptions for the different types
      of raw materials have been established .
      For the price of fuel oil , an average price of 50 U.A. per tonne
      has been assumed . It should be "noted , however, that the processes
      treating gases containing S0? are not interfered with by the use of
      very sulphurous fuel oil such as "vacuum residues ".     These two
      processes are the roasting process ( LURGl ) and the I.F.P. process *
      The value of the "vacuum residues", always less than that of fuel
      oilj will depend on the particular situations of each petroleum
      group , the location of the refinery and its distance from the
      consuming factory .
    ' Depending on the situation , the "vacuum residue " may cost the
      consumer between 80'fo and ( exceptionally) 60$ of the price of
      ordinary heavy fuel oil .     In the present case the possible use
      of "distillation -" residues " costing 40 U.A. per tonne has been
      assumed .
     Note ; It will be recalled that , for roasting, sulphur can be- need
              as a fuel , which in some cases maizes it possible to reduce
              consumption of fuel oil . This possibility depends greatly
              on local conditions ; it should merely be borne in mind that
              the fuel–oil consumptions shown for roasting are high values .
 ---pagebreak---                                      - 20 -             EMV/47/75-S
                                                        Orig : F
Ev-products
In practice we shall consider only three categories of "by–products :
- sulphur
– sulphuric acid
- ferric oxide (part ) or ferric hydroxide ( part ).
A sulphur " credit " will be included in cases where the sulphates
and/or sulphuric acid are decomposed in the form of S0^ or
e lenient a-ry sulphur .
A " sulphuric acid " credit will be included wherever recycling cf this
acid can be done directly and therefore dees not entail additional
capital expenditure .
The savings are based on the following values :
                         sulphur           : 52 U.A« /t
                         stilphuric acid : : 29 U.A./t
Note : As the price of sulphur varies greatly, a treatment ccst
        corresponding to a sulphur price of 30 U.A./t and thus
        to a sulphuric acid price of 22 U.A./t h-:.s also been
        given .
        With regard to iron in oxide or hydroxide fcrir.. only
        iron obtained from copperas will be regarded as s. by-product
        which may possibly be reusable , but its value will be
        assumed to be zero .
 ---pagebreak---                                                30                   T32TV/47/75 -E
          D. RECAPITULATION
                      Treatment units which can be envisaged
                           for the titanium dioxide industry
                                        - 1 Capital investment              Waste products
.    . Constituent processes      Ref .     ( U.A./t.per annum              after treatment
                                                  of TiOj
 ( Dehydration ) – Lurgi           I        I1n           263      ( iron oxide )
Roasting          – Lurgi                                          Iron oxides + various
Concentration – Lurgi                                              CaSO , Fe(0H)2
Neutralisation                              Slag          195      water
  ( Dehydration ) –--Lurgi        II        Ila           273      ( iron oxide )
Roasting          - Lurgi                                          ( iron oxides + various
 Concentration – F.J.Z                      Slag          195      Cai394, Fe(0H)2
Neutralisation                                                     Water
 ( Dehydration ) – Lurgi                    Ilm ,         338      ( iron oxide )
 ( Roasting)      - Lurgi        III                               Fe(0H)p + various
                                                        ,     . .. sulphates - •«
IFP process                                 Slag 245      245      CaSO - , Fe(OH ),
                                                                   \J <-*KJ   J
Neutralisation                                                     Water
                                            Ilm           339      ( iron hydroxide )
IFP process                       IV                               Fe(OH)0 -fc various
                                                                   sulphates
                                            Slag          254      Water
 (Dehydrati on ) – Lurgi                                           ( iron oxide )           :
 (Roasting)       - Lurgi          V        Ila           351      Fe(0H)„ + various
                                                                   sulphates
IFP process ■                           '  Slag           259      Water
( Dehydration ) - Lurgi                                            ( iron oxide )
Roasting          - Lurgi         VI        Ilm           312      Iron oxide + various
Concentration - N.J.Z.                     Slag           233      water
    Note 1 :   The substances in brackets disappear if slag is used
    Note 2 ; The waste products marked ( o ) may be reusable . They have been
               assigned zero value in the economic calcvilations .
 ---pagebreak---                                              - 31 -                     EW 47/75-E
                   Co3t of the main raethodc of treatment which can "be
                      envisaged for the titanium dioxide industry
                                     ( Sulphate process )
              Kaw
                                                      Hypotheses
 Treatment
            Katerial
                         Fuel oil : 50 UA/t      Puoi oil         50 UA/t Fuel oil        50 UA/t
                         Su"! plnir 52 UA/t      + diato r ss . 40 UA/t H- di¡-.t . rea . 45 UA/ u
                         Hp30 ,
                          £    .·±
                                       29 UA/t   Sulphur          52 UA/t Sulphur         30 UA/t
                                                                  29 UA/t H 30^,          22 UA/t
                              UA/t of Ti02           UA/t of TiCU             UA/t of TiO
   I          Ilia .                97.3                   90.8                     113.6
              Slag                  77                     72.8                      86
   II         Un .                  77 «4  "               74 7                      95.2
              Slag                  53.8                   53.4                      64.7
   III        X lui «              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 ~ This is an estimate made at the end of 1973/beginning of 1974 .
       A more up-to-date estimate is "being prepared .
 ---pagebreak---                                       - 32 -                  EtJV/47/75-E
    Special characteri .sties of the main methods of treatment which can
    be envisaged for the titanium dioxide" industry ( sulphate process)
TREATII3HT I     - low cost
                 – concentration process not yet industrially proved
                 – neutralisation waste products rather inconvenient
                   to store ,
TRKITIxEfW? II   - Same -comments as for Treatment I
TREATI-E3HT III  – Juxtaposition of several fairly reliable processes
                 - high cost
                 - neutralisation waste products rather inconvenient
                   to store
TREATIIENT IV    - only one process used ( IPP)
                 - relatively high cost
                 - final waste products a priori less convenient than
                   oxides
TREATIIENT ¥     - complet of quite reliable processos
                 - rather high cost                                " <.■
                 – final waste products a priori less convenient
                   than oxides
TPJUiVTIIIiZT VI - " Concentration section" not industrially proven
                 – cost sensitive to the concentration of the wec'Jc acid
                 - final waste products fairly convenient to store
                   and/or possibility of reuse .
 ---pagebreak---                                                              - 33               2F//47 /75-
SECTION III .          CHLORIÎTE PROCESS
          ",-Ja'ote product s Μΐΐίΐίΐ:·^
         *τ.} ■–,ι ·Κι·ι·
                                   inherent
                                         ■ υι ^
                                                in the process
                                                        φ··^–   »
           1.       General
              a) Introduction
                    As already mentioned , the only purpose of the calculations made in
                    this section is to give orders of magnitude for the quantities . of
                   wa3te products to be considered *
                    Admittedly , in view of the fact that the chlorine process is little
                   used in Europe end that the information about is is generally
                    confidential , it has only been possible to make rather rough
                   hypotheses for this process .
                   However , although these hypotheses may prove inaccurate , the quantitative
                    approaoh to the total effluents remains valid .
             b) Hypotheses
                    We have assumed that :
                   ~ the overall operating yield is $8$ in relation to the TiOg involved,
                          excluding the finishing ( surface treatment ) stage . This type of
                          treatment has already been 3een for the sulphate process . Uith regard
                          to effluents , it leads only to dilute salt solutions and a small
                          quantity of TiOg in suspension .
                   - The zirconium oxide present in the ore is not attacked .
                   - All the other metals and metalloids are chlorinated .
                   - 1 /S of the raw ore is lost in the "blow-offs" of the fluidised
                         bed and by entrainment in the process gases .
                   - 0.5% of the titanium dioxide is lost in the form of TiCl^.
                   - 2% of the chlorine necessary for the chlorination of the titanium
                          dioxide is lo3t through combination with hydrogen from the
                          reduction coke and the ore.
 ---pagebreak---                                       - 34 -                  ENV/47/75-E
 - For the TiCl . " oxidation" section
       . 0.5% of the TiO, involved is lost in solid form
       . with regard to the effluents resulting from possible liquefaction
          of the chlorine , these are very traditional in nature and have
         been disregarded in the present technical report .
) ?ist'ribut~iori of the different waste products
  It has already been seen in the description of the chlorine process
  that the four major sources of waste products are :          .
      . waste product 1. – "blow–off" from the fluidised bed
         waste product 2 - "residues" of the distillation of TiCl^
      „ waste product 3 – "venting" from the distillation of the TiCl^
      . waste prod-act 4 - waste from the oxidation stage .
  The melting and evaporation temperatures of the chlorides of the
  different metals make it possible to some extent to predict the
  distribution of these chlorides in the waste products .         Furtherir.'ore ,
  certain hypotheses have been made for the distribution of the losses
  of ore , TiCl^ and chlorine .
        . Waste product 1
           The •Aole of the Zr02 , I&iClg 5 IlgCl^, CaCl^, FaCl .
           Kalf of the ore losses .
        0'       product 2
           The whole of the SNbCI 3'
                                  ,, A1 CI 3'
                                           ,, CrCloJ FoC ?._5
           The vanadium is present in the form of VOCIg
           Half of the ore losses .
        . rvaste product 3
           The whole of the SiCl^, PC13 (POCl^)                      ν
           The whole of the losses of HG1 and TiCl .
 ---pagebreak---                                            - 35 -                       KÏV/s 7/75-E
              2 - A. WASTE PRODUCTS (ERnESPOEDIlPJ TO STATURAL JtUTILE ORE
        ORIGINAL ORE                                                     PROPUCT
       FATURAL RUTILE                                                 miO? :  1 tonne
           %           kg
                                         ~ 1 J3 r\Otfr
                                      x xtjxu yv.o
TiO      96.6O      1020 . 400                                 FATAL WASTE PRODUCTS
PcO
                                                               expressed, a s
Fe2°3     0.35         3 c 696                                 quantities of uetal
          0.35         3.696                                    (kg")
Si02
Zr02      0.65         6 . 866                                 Ti                 12.240
AlpO      0.45         4.752                                   Pa                  1 . 219
p2°5      0.05         0.5?-7                                  Si                   1.700
IJhO      0.02         0.211                                   Zr                  5.032
ïfeO      0.06         0.633                                   Al                   1.254
Cr~0      0.30         3.169         Iva3te Products           Ρ                   0.106
v2°5      0.66         6.971                                   ; in                0.163
CaO       0.01         0.105                                   7T,~>
                                                                                 --0.380
Na.O                                                           Cr                  1 . 0^2
K~0                                                            V                   1.074
S                                                              Ca                  0.072
h20                                                            lia
                                                               C!
Co         mm
c                                                              Ni
ÏTbO~     0.30         3.169                                  ■Zn
E         0.20         2.113                                   Cn
                                                               Cu
                                                               1Tb                2,352
                                                               K                  2.111
Total 1056 kg
Typical composition
                       Distribution of effltients :
                       waste product 1 : 14 kg/t of TiOp       ( ZrO- + various chlorii
                       waste product 2 : 30 kg/t of TiOp       (+ various chlorides )
                       waste product 3 :    59 1-S/ t 0 - TiO  (+ various chlorides )
 ---pagebreak---                                            - 36 -                  EtTV/ 47/75-E
          2 - B,   WASTE    PRODUCTS CORRESPONDING TO SYNTHETIC RUTILE ORE
                                      (Benelite type )
         ORIGINAL ORE                                                  PRODUCT
                                        Yield 93%
      SÏMÎIÎÎPIC RUTILE   "                                        Ti0o :   1 tonne
                         kg
                                                              FATAL WASTE PRODUCTS
Ti02         95      1020.40
FeO          '1.8       18.96                                 Expressed as
              2.0      21.60                                  quantities cf metal
Pe2°3                                                         (kg)
                                                              Ti ,              12.240
Various       1.2       13.09                                 Fe                22.665
                                                                              Various
                                                                              ( 13.09 )
                                        Waste products
                  Correspondmg weight of ore :    1074 kg
                  Distribution of effluentss
                  Waste product 1 : 14 kg/t of TiO^
                  Waste product 2 : 90 kg/t of TiO^
                  Waste product 3 : 59 kg/t of TiO-
 ---pagebreak---            2 - C.    WASTE PRODUCTS CORRESPONDING TO AUSTRALIA IIZZEUTE ORE
           ORIGINAL GRE                                                  PRODUCT
        AUSTRALIAÎT IUIENÏTE                                          TiO „ : 1 tonne
                                         Yield 9G%
               af
                            kg
                                                             FATAL 'WASTE PRODUCTS
TiOp        55 «4      1020 » 20
FeO         23.8         433.351                             expressed m
                                                             quantities of metal
Fe2°3       16.9   '     311.350
So02         0.15          2.763
                                                              (l'-g)        •  •
ZrO                                                          Ti                  12.240
A1~0         0.94         17 « 337                           Fe                449.513
                           1.439                             Si                   1 . 264
P2 5         0.0c
Ilîn0        0.72         13.274                             Zr
lîgO         0.27          4.966                             Al                   4.569
Cr 0 ,       0.14          2,753                             Ρ                    0.297
             0.17          3.160                             lin                 10.267
   2 e)
CaO          0.02          0.361                                                  2.979
Na„0                                                         Cr                   0 0 84^
                                        Waste products                            0.830
 ^2°                                                         V
n
O            0.01          0.180                             Ccl                  0.252
M                                                            Cr
                                                             tJ                   0.100
Zn                                                           ITi
Cu                                                           Zn
Cd                                                           Cu
Pb , Be                                                      Ce     •
Sb , Hg                                                      Pb , Be
   Corresponding weight of ore 1 . 842 kg
   N.B.   The total of the column does not correspond to 2,040 kg , as the vreights
          of each constituent have average values related to different compositions
          of ilraenite .
   Distribution of effluents :
   Waste product 1s 44 kg/ t of TiO^ (ZrO + various chlorides + ore)
   Waste product 2 : 1,339 kg/t of Ti02 (various chlorides including 1,304 kg of FeCl^)
   Waste product 3$ 76 kg/t of TiO„ (various chlorides )
 ---pagebreak---                                       38 -                  Emy47/75-E
Treatments
A. Effluent 3 considered
   A3 stated earlier , the chlorine process is little used in Europe .   In
   all cases the installed capacity is small .
   Moreover , these units at present use natural rutile , that is , an ore
   very rich in TiC^ (about 96$) , which therefore gives rise to only fairly
   minor quantities of effluents .
   These two factors mean that the problem of the effluents of the chlorine
   process does not really arise in Europe .
   nevertheless , the main treatments which can be envisaged in this case
   will be examined , firstly because even though the chlorine process is
   at present little U3ed in Europe , it is nevertheless under certain
   conditions a valid alternative to the sulphate process , and secondly
   because the possibilities of development of synthetic rutile or the
   possibility of using a poorer ore may lead to a change in the present
   positions .
   It may be noted that in the United States , where the chlorine process
   is very widespread and where DuPont is said to use a relatively poor
   ore in one of it3 factories , the problem of the effluents of this
   process has arisen .
 . DuPont , which is the company most involved in this direction , has not
   yet succeeded , despite major research efforts and strong economic
   incentives , in perfecting the regeneration of the chlorine by oxidation
   of the by-product chlorides .
   After having envisaged discharge into underground strata , it would
   appear that IhiPont has decided to opt for discharge at sea.
 ---pagebreak---                                          - 39 -
  The following will not be considered in this chapter :
  - the effluents of the "regeneration" unit for the chlorine to be - recycled ,
      as these are traditional and not specific to this industry ;
  - the effluents corresponding to the finishing operations ( surface
      treatment ); these are not peculiar to thi3 process .
  We shall deal here with the treatment of the chlorides which are formed
  simultaneously with the titanium tetrachloride and which are separated in
  the further course of the process .
  Three sources of waste products for this type of effluent and for this
  process have "been listed . These effluents are identified as " waste
  product 1 , 2 and 3" »
B I ?ain processes
  The considerations regarding the discharge of effluents into underground
  strata or at sea will not be repeated here . These eventualities have
  already been examined tirithin the framework of the* " sulphate" process
   ( page 21 ).
  It may be noted , however , that these are the only two methods which have
  been adopted in practice in the United States ; underground discharge has
  incidentally been strongly criticised .
  The only two processes xirhich seem to represent a possible treatment for
  this type of effluent are ones which enable the metallic chlorides to be
  broken down into oxide3 , the chlorine then being combined to form HC1 .
  Actually these two processes are fairly similar in principle , the main
  difference being their type of feed :
              – chlorides in solution in one case ,
              - solid chlcrideE in the other case .
  The companies holding the rights to these processes are WOODALL DUCIOIAII
  and LURGI respectively .
 ---pagebreak---                                      «•» 40 ••             Emy47/7 5-E
                                                  \
It should also be noted that the company " CHLORINE TECHNOLOGY Ltd" ,
which is engaged in the recuperation of ilnenite , is said to held the
rights to a process for the oxidation of the chlorides , hut this is not
yet regarded as very satisfactory . There is no doubt , however , that
companies other than those enumerated above are likely to develop
processes which would be based on similar principles .
It may also be mentioned that in the two cases referred to above it is
a question of adapting existing , proven processes whose application has
not yet , however , been tested in this particular field .
 ---pagebreak---         - 41           EETV/ / 7/
     PART    2
ECOLOGICAL     ASPECTS
 ---pagebreak---                                      - 41a -                EW/47/75-E
GENERAL
Examination of the restilts already obtained •
Examination of international scientific documentation on the effects of
discharging the residues from the production of titanium dioxide into
the eea leads us to regard these waste products as potentially or actually
harmful to the marine aquatic medium .
The degree of harmfulness of the residues may vary depending on their
composition , the method of discharge and the characteristics of the
receiving medium . The adverse effects on the environment are due mainly
to the acidity , to the presence of ferrous sulphate and probably to the
other metals (heavy metals) which are also present .
Depending on the cases , the adverse effects on the environment can take
the following forms :
1 ) reduction of the oxygenation and pH of the water and increase of the
    concentration of iron and other heavy metals . The duration and extent
    of these effects depend on the physico-chemical characteristics of the
    waste products , and especially their concentration ;
2 ) a) temporary depletion of the zooplanktonic biomass and production of
       effects leading to a deterioration in the morphological structure
       of ita component parts*;
    b) repulsion and removal of certain species of fish ;
    c) reduction of the biomass and of the production and diversity of
       specie3 of the benthic and/or nactobenthic biocenoses in the
       discharge area .  In more serioua cases all animal life may
       disappear .
 ---pagebreak---                                       - 41b -               ENV/47/ 75-E
3) deterioration in the colour , transparency and turbidity of the water
     and temporary reduction of photosynthesis , phytoplankton and primary
     production , especially in eases where the waste is discharged cn the
     surface . Covering of the soa bed with ferric oxides rjid oxides of
     other metals where the waste is discharged in estuaries and places where
     the water is shallow ;
4) on the other hand , there have been no reports of dangers of toxicity
     for human beings due to effects produced by the consumption of species
     from the places where the waste has been discharged .
The degree to which the above-mentioned phenomena occur varies depending
01:. the different methods of discharge . There is not , however , a single
case in the scientific literature published or mentioned by the various
experts of the Ilember States in which one or more of these phenomena have
not been recorded .
All this leads tc the conclusion that discharge into the sea of waste
from the production of TiOg must be controlled and even suspended within
a certain period in order to prevent damage to the marine environment ,
now and in the future .
As an illustration of the effect of the disposal of effluents of the
TiOg industry , the results of the "Vlhite Book" published by Prance in
connection with the discharging of the Montedison company 's waste products into
into the Mediterranean Sea are reproduced on the following pages .
 ---pagebreak---                                             42 -                      EN7/47/75-E
           CHAPTER V - ESTIMATE OF THE PHYSICO-CHEMICAL CHANGES DUE
                              TO THE DISCHARGES
 The following analysis deals mainly with the physico-chemical changes
(in pH , saturation indices , change in natural concentration , etc .) which
 nay he caused by discharges such as those made by the Montedison
 company .                                       •
 1 ) Three ma.jor factors must "be considered
     As has been stated earlier , the waste products are characterised by :
        - high acidity due to the presence of large quantities of free
           sulphuric- acid in the effluents : we must therefore assess the
           reactions of sea water when faced with the introduction of 330
           tonnes of pure sulphuric acid per day.
                                                   ++                  . _       '
        - a high content of divalent iron Fe          :    the commonest form of
                                                      ++-+■
           iron in the sea is tnvalent iron Pe              t the.
           oxidation in sea water must therefore be considered .
        - a by no means negligible content of heavy metals such as titanium ,
           chromium , vanadium , cadmium , etc .
 2) Reaction of sulphuric acid
     Sea water is a medium with a very strong buffer capacity with regard
     to acids and bases . This buffer capacity is bound up with the balance
     of the carbon dioxide gas , bicarbonate–carbonate system . It takes
     3 milli-equivalents of strong acid per litre to transform the
     carbonates and bicarbonates into carbon dioxide gas and reach a pH
     of about 6 .                         •
     On this basis it can be calculated that it takes 12 m^ of sea water
     to "buffer" one litre of pure sulphuric acid (pH brought back to a
     value of 6 or above ).
 ---pagebreak---                                       - 43                    EW//! 7/7 5-E
 It is assumed ( American papers ) that 15 m of sea water completely
neutralise 1 litre of pure sulphuric acid .
On the "ba3i3 of the above values ( 330 tonnes of H?S0^ discharged per day)
a neutralisation volume of
                      lliUIMOO . 2,300,000 m
is obtained .
In order to establish an order of magnitude , the area within which a
daily discharge is neutralised nay be estimated at about 30 hectares if
it is assumed that the discharged waste diffuses slowly in a vertical
direction whatever the depth at which it is discharged and that it only
affects a layer of water about 10 n thick ( cf . the conclusions of the
C.N.E.X.0 , report on horizontal and vertical transmissions in the area).
The oxidation of divalent iron into t rival en t iron
While seaitfater has a buffer capacity as regards acid-base equilibria ,
the position is different as regards oxida\ ion-reduction couples .     That
is why it must be assumed that high oxygen demands can only be satisfied
by utilisation of the oxygen dissolved in the sea water .
                                                                     2+
If we assume that it talces one molecule of oxygen to oxidise 4 Fe       ions
into 4 Fe     ions , we arrive at the following calculation :
                       140 tonnes of divalent iron discharged per day
need in order to be oxidised :
                       1^0    32
                           x 7" » 20 tonnes cf oxygen
It may be mentioned in this connection that this represents approximately
the oxygen demand of the sewage of a town with :
                       20yl0, » 350,000 inhabitants ( 1 )
( 1 ) This is an important point and enables us to relate these discharges
      to those of the coastal towns of the Cote d'Azur and the Gulf of Genoa .
 ---pagebreak---                                        - 44 -                 ENV/47/75-E
 The available data concerning "this area indicate a quantity of dissolved
 oxygen of 8 mg/litre , or 8 g/m\ The volume of water required for
 complete oxidation of the waste is therefore (assuming that the
oxidation takes place near the svirface) :
                           ?P.O,Q. - o t;nn nnn
                              g– = d t 500 , 000 m
 ( it will "be noted that there is a fair degree of similarity between this
value and the volume required to "buffer" the effluent , although it is
necessary to emphasise the approximate nature of the above two calculations ,
the sole purpose of which is to provide orders of magnitude .)
                                                                        6 3
*• It would however be misleading to picture an actual volume of 3 • 10 m
    affected by the sulphuric acid : in fact , only 'programmes of
    measurements carried out on the spot can permit a more accurate
    determination of the voluae involved , which is probably smaller owing to
    the turbulences which appear at the surface of the streams of waste
    products and which have the effect of spreading out the period during
    which the dilution phenomenon takes place .
– Similarly, the oxidation of the divalent iron into trivalent iron
    is probably a long-term phenomenon : the experimental results obtained
    both at the place of the waste discharges and in the North Sea or in
    Hew York Bay represent a slow oxidation , which never reduces the oxygen
    saturation index of the area by more than 30^.
It is therefore logical to assume that the discharges of waste products
cause the formation of a mass of water with a small oxygen deficit , but
much larger in volume than has been envisaged .
 ---pagebreak---                                                - 45 -                  Θτν/47/75-Ε
         4)      e and "behaviour of the heavy elements cucli as chromium , vanadium .
             c?A".im and titan :.un
            It has been thought necetsary to devote a paragraph to recalling
            certain overall data concerning the presence and possible role of
            such elements , which have recently led to the adoption of 3ome
            contradictory attitudes .
             1 - It must be recalled in the first place that all these elements
                  are naturally present in sea water , as i3 shown by the figures
                  taken from Riley and Skirow ( 1965) and Ivanoff ( 1972 ) in the
                  following comparative table .
  Elements     Weight present in     Concentration  m  Weight present in    Residence tme in
               1 kg of rock          sea water in      1 kg of pelagic,     the sea in
               ( average ) in mg        ng/1           sediment in tig      yoars ( 1 )
     Si            275,000                3                 199,000
                                                                                   ο
                                                                                   o    103
     Al             83,000                0,01               65,000              100
     Fe             52,000                0.01               41 , 000            140
                    22,000            1,300                  17,000                4.5  10'
     Ti              6,300                0.001               3,500              160
     iïn               930                0.002               3,200          1 , 400
                                                                                        4
     V                 120                0.002                   330             10
     Cr                  65               0.00005                   80           350
     Cd                   0.              0,0001                  o
                                                                                   5    105
     Pb                                   0,00003                 160              2    10 3
                         15
( 1 ) The "residence tine" of an element in the sea is equal to the average time for
      which this element remains in the soa water before disappearing by sedimentation
       or biological absorption . A short residence time for an element which iE
      assumed to be toxic (a favourable factor from the overall point of view) is
      therefore not a reassuring criterion from the point of view of the consumer
       of the products of the sea , insofar as this rapid elimination is partly achieved
      thanks to concentration phenomena in the biological chains .
 ---pagebreak---                                            f- 46 –                  EN7/47/75-E
        It will thus be seen that the chemical composition of rocks is fairly-
        close to that of sediments . On the other hand , the relative composition
        of sea water is entirely different from that of the earth 1 s crust , a
        fact which implies the existence in the sea of processes which limit the
        concentration of certain elements although they are continually provided
        by rivers , run-off water and wind-borne matter .
        The intensity of the action produced by these .mechanisms on the various
        elements is well represented by the "residence times", which can range
        from around 100 years for aluminium , iron and titanium to several tens
        of millions of years for certain alkaline and alkaline-earth substances .
        The processes of regulation ultimately tend to eliminate certain
        elements from sea water by incorporating them in the sediments . They
        are physico-chemical (formation of complexes , co-precipitation,
        absorption and ion exchanges on the particles or at the sediment levels)
        and biological in nature . (Many marine organisms selectively concentrate
        certain elements .  During mineralisation of organic matter , a portion
        sediments and represents a loss for the sea water) .
• 2 – With regard more specifically to titanium , it will be seen that this
        element is one of the main constituents of the earth 's crust , representihg
        about 0.5$ by weight . It is almost equally abundant in sediments . It
        is present in very low concentration in sea water ;    its residence time
        has been estimated at 160 years . By its characteristics it i3 closely
        akin to the three most abundant constituents of the earth 's crusts
        silicon , aluminium and iron .  Titanium is regarded as physiologically
        inert .
        The trace elements , hexavalent chromium ( l ) and above all cadmium are
        well-known for their toxicity .   Vanadium would also appear to be toxic ,
  ( 1 ) Chromium is harmful in its hexavalent form , but in the sea it is quickly
        changed back to its less dangerous trivalent form . The chromium contained
        in the waste from the manufacture of titanium dioxide is already in the
        form of a trivalent oxide .
 ---pagebreak---                                        - 47 -                  ES-TV/47/7 5–E
    but there is as yet relatively little literature on this point .
3 – In order to give a clearer idea of the actual scale of the trace elements
    discharged with the waste products of the Montedison company , it vas
    therefore thought worthwhile , on the basis of the foregoing information , to
    prepare the following table :
  Elements     Weight présent in 3000 t     weight prc3ent in the 3000 t of
               of rock in kg                waste products fron the manufacture
                                            of 150 t of TiO^/ds-y
                                                           O/
                                                                 ( 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
    This table brings out the similarity which exist 3 between the quantities
    of heavy metals present in the waste and in tho same weight of rocks ;
    but this similarity is relative , because it must be pointed out that the
    effluents contain vanadium and cadmium in larger proportions than the
    rocks .
    Such figures do not warrant the drawing of any conclusion regarding the
    direct or induced toxicity attributable to heavy metals in tho waste
    products :  part of these is dissolved in the liquid effluent , uhich is • ••
    not true of those which are contained in rocks .
 ---pagebreak---                                   - 43 -                  ENV/47/75-E
When the effluents are diluted , a large .proportion of the metal3
precipitate in mineral form and produce a sediment on the sea "bed .
The phonoriena of indirect toxicity are bound up with the two portions
( dissolved and precipitated) of the metal salts in the waste .
The comparison made ia therefore only of overall value , being
quantitatively valid in relation to the geochemistry of the whole of
the Li^rrian basin . It should furthermore be recalled that this area
naturally receives quite substantial quantities of heavy metals naturally
entrained by rivers as the soil is washed and eroded .
 ---pagebreak---                                        - 49 -                ENV/47/75-E
                 CHAPTER VI - STUDY OF THE BIOTJUGICAL EFFECT OP
                                EPb'UJSNT DISCHARGES
The , d ifferent aspects of the problem
The study of the possible effect of the discharging of industrial,
effluents into the sea is an extremely complex matter . For this
effect has two different aspects :
- a short-tern effect by direct or "acute" poisoning , which can even
  lead to the killing of living beings in the immediate vicinity of
  the discharge area , In the specific case of the waste products of
  Ilontecatini Edison , thj j effect will be mainly due to their high
  sulphuric acid and iron content .
- an indirect long-term toric effect by the accumulation of certain
  elements in food chains * This phenomenon does not necessarily lead
  to major disorders in marine life itself . Problems may arise , however ,
  at the level of human consumption of fish or molluscs which have
  accumulated high contents of unxlesirable elements in the geographical
  area of the war,te discharges .
  In the case of the discharges of the Ilontedison company , their indirect
  toxicity may be duo to their content of heavy metals : titanium ,
  vanadium , cadmium and chromium .
For the purpose of studying the biological influence of the waste products
it is therefore necessary to distinguish between these two main directions
of investigation , They can be covered :
- by biological observations "on the spot "
– by lj.Doratory e.xperiments ,
 ---pagebreak---                                             - 50 -                   EÎÎY/47/75-E
        The ritudiee of direct or indirect toxicity carried out m laboratories
        are all "based on observations of the behaviour of marine plants or
        animals placed for fairly long periods in variable concentrations of -
        the effluent under test .
        It is important to emphasise this " time" a3pect at the outset , since
        in the natural environment a certain number of the species tested
        will tend to flee from the most active zone of the v;aste matter and
        will finally only be exposed for relatively short periods to the weakest
        dilutions of effluents ,         •
        Ilany investigations have been made into the toxicity of the waste
        products of the Montedison company or of similar waste .
        The results at present known will be given , in the light of the
        foregoing , under the following main heads :
                     - analysis of the short-term effects
                     - analysis of the possible long-terra effects .
SECTION I - THE oHCRT-TEPJ ; EFF3CTS
        1 ) Data on the behaviour of the marine florg, and fauna in the vicinity
           ' of the discharges
        a) Bohaviour of macro_3copic animais
             It is important to emphasise this point , which may have led to
             misunderstandings in recent months :  it has never been possible
             to observe in the discharge gone any abnormal mortality of
             macroscopic animals such as fish , molluscs or marine mammals .
 ---pagebreak---                              - 51 -                    2!TV/ 47/ 75-E
                                                       Orig. : F
Furthermore , none of the various reports of the five missions
 carried out on the spot "by French technicians mentions the presence
 of bodies of animals on the surface of the water .
With regard to the stranding of spcm-whales and cetaceans which,
has taken place fairly recently in the Mediterranean , the con­
 clusions of the report of the Iiistitut Scientifique et Technique
des PSches liaritimes are as follows :
 "With regard to che strandings of cetaceans in Corsica, vie have
"been able to analyse the muscle and fat of a sperm-whale strrnded
near Bonifaccio .    It appears that tho mercury content recorded
 is high ( about 4 nig/kg wet weight ), but the fact that the content
of other heavy metals is in no way abnormal suggests that the
Montedison waste products , which do not contain mercury , are' not
the reason for the death of this animal .     The high jiercury content
may be attributable to the wa,ste products of the chlorine industry
discharged into tho Gulf of Genoa, and to the discharging at sea of
the waste from mercury mines . "
Furthermore , examination of the various foreign reports mode on
discharge locations in the North Sea or New York Bay lead to
 identical conclusions :    no deaths of pelagic or even benthic
 fish ( although such discharges are made at depths of 20 to 30 m )
have been reported in the areas in question.
 It seems likely that the macroscopic animals in the immediate
vicinity of the waters where tho effluents are most concentrated
 flee from then and thus escape the inime&iate toxic effect of the
waste ; the probability of macroscopic animals being directly
engulfed in the waste discharges and affected by their acute
toxicity is . moreover , likely to be low.    Only additional
 ---pagebreak---                                  - 52 -                     m/ 47/75-E
                                                            Orig. : P
     experiments could make it possible to establish , on the "basis
     of an amount of data large enough to be statistically processable
     whether or not the fish stocks have appreciably changed in the
     discharge area*.
b ) Behaviour of plankton in the discharge rroa
     It will easily be understood tha;t a, study like this is difficult
     to carry out on the spot for purely technical reasons .    It is
     therefore discussed in much greater detail in connection with
     the presentation of the results obtained in the laboratory :
     it should imoreover be noted that plankton does not possess any
     means enabling it to flee from the discharge area : the laboratory
     study therefore gives an except able representation of the actual
     behaviour of plankton in the medium *
     It is , however , worth while mentioning the conclusion of an
    American study made on the discharge of similar waste products
     in New York 3ay.
     The National Research Council of the National Academy of Sciences
     Fish and Wildlife Service , mentions that      " zooplanktonic
     erganisns were immobilised by exposure to the effluent .    But they
     generally renused their activity and appeared normal after two
     or three minutes , even when remaining in the contaminated
    water.
     Specimens placed in samples taken from the wash less than one
    iininute after the passage of the lighter did not reaxt .   As soon
     as this water had been diluted half-and-half with uncontnminated
     sea water they reacted and started to swim about again".
     It will be noted that these experiments carried out " in situ"
     do not provide any accurate experimental data ( concentration,
     species observed ...), but they lead us to exclude any immediate
     large-scale mortality of zooplankton in the wash of the lighter
    which discharges the effluents into the sea.
 ---pagebreak---                                      - 53 -                    ENV/47 / 75-E
                                                               Orig. : F
       Be that as it may , this study concludes that "the volume of acid
       water of each discharge is so snail coupprod with tho Ttfater
       available that the effects on the zoopl - nkton and phyto plankton
       will bo negligible ".*
2 ) Experimental data on the behaviour of marine flora and fruna
    with differ e nt concentrations of the efflue nt
    Determination of acute toxicity thresholds
    a) Report of the Institut Scientifique et Technique des Pêches
       Maritimes
       Measurements of acute tonicity were mcde on the following
       marine creatures :
         1 phytoplanktonic alga             : Phacodactylum Tricornutum
         1 zooplanktonic crustacer.n        : Artemia Salina
         3 lamellibranch molluscs           : Cstrea Edulis ( oy3ter )
                                              Cardium Edule ( cockle )
                                              Ilytilus Edulis ( mussel )
         1 gasteropod mollusc               : Litt orina littorca (winkle )
         2 crust ace aiu                    : Cr-.ngon cra.ngon ( shrimp)
                                              Palaemon serrât us ( prawn)
         2 fish                             ; Pometoschistus minutus
                                              Elvcrs ( post-larvae of
                                                   Angui lia Angui lia).
       The experiment s . were performed on lots of 10 animals m glass
       crystallisers with a capacity of 4 l f each of which received
       2 1 of solution.     A suitable aeration was maintained by
       bubbling throughout tho period of the tests .
       The dead animals were removed and the cumulative mort °iity
       percentages after 4-8 and 96 hours were recorded.
* N.B. Translator 's note : ,, These two quotations , re-translated from the
        French version of the report in question , should be checked with
        the English original .
 ---pagebreak---                              - 54 -                     ENV/47/75-E
                                                        Orig. : P
Results
The growth curves of Phaedactylum tricornutum for the
different dilutions of the effluent are given in Fig. 1 .
We find that the growth in the culture with a dilution
of l/l0,000 is practically normal.
A dilution of 1/5000 shows a grotvth of approximately 65 £
of the growth of the reference culture .
A dilution of 1/3000 corresponds very noticeably with the
concentration which reduces the growth of the culture by
half , or the LD 50.
Lastly, dilutions of 1/2000 and 1/ 1000 appear incompatible
with the development of Phaedactylum tricornutum.      But it
would appear that the pE values of the cultures at these two
dilutions are largely responsible for the absence of growth.
The cumulative mortality percentages after 48 and 96 hours are
shown in Fig, 2 .
We observe that the Art eraiae show the greatest sensitivity ,
since 45 * 50 an& 100$ of the population die at the
dilutions of l/3000 , 1/2000 and l/lOOO respectively after
96 hours .
Shrimps and the two fish tested are also sensitive , because
the dilution of 1/ 1000 causes the death of the whole of the - *
populations after 96 hours .
                                       I
Lastly , for Palaemon serratus , Ostrea edulis , Cardium edulis ,
Mytilus edulis and Littorina littorea, no mortality is found
at the 5 dilutions tested.
Ke can therefore conclude that the effluent is acutely toxic
 ---pagebreak---                yy   -          m747 /75-E
                               Qng.
                                    reierence
120
110
       l j                             io ooa^^__|i/
100       _
 90
 80
                      //
                                     ï/5 ~CÔÔ
 70
 6o
 50
 40       Jfp/L
 30
 20
    7 JJL                                         I
 10
  0     ι   "11/ α. υυυ ■ 1 ■– –
     123     4            5^7                  ? <^Ξ
 ---pagebreak---                                                                       EM/47/75-E
                                                                      Orig. : F
      Fi "VT>e ?■ • Percent rge Eortrlity c:t 4 o and >6 hours depending on  the
                    dilation o f ïho cffluent .
                                 1/10 000    1/5 000     l/3 000    1/2 000      l/l 000
                     46 h            0           0          A          A           100
^. rtemia
 sr.lma
                     96 h            0          16         45         50           100
                     42- h           0           0          0          0             0
rciicicmua        –
 serra.tue
                     96 h            0           0          0          0             0
                     48 h            0           0          0          0            66
Crrngon
crangon
                         h           0           0          O          0           100
                     48 h            0           0          0          0             0
Ostrea
ednlis
                     56 h            0           0          0          0             0
                     48 h            0           0          0          0             0
Crrdiua
edule
                     96 h            0           0          0          0             0
                     48 h            0           0          0          0             0
ilytilus
edulis
                     96 h            0           0          0          0             0
                     4o h            0           0          0          0             0
Littorina.
] ittorea .
                     9o h            0           0          0          0             0
                     48 h            0           0          0          0           100
Pomat oschistus
ninutus
                     96 h            0           0  .       0          0           100
Elvers
                     48 h            0           0          0          0           100
Anguilla          –
 ---pagebreak---                                                                 ÏS.-V//7/75 -E
                                                                Orig. : P
     for concentrations ranging from 1/5 000 to 1/ cOOO ( the lf,ttor
     concentration not "being fatal to the organisms "but ret \ n'.i.ic
  . the growth of some of them ).
b) Results provided by the Centre d'Etudes et de Recherches do
    Biologie et d' Océanographie ï-Iédicales ( C.E.R.B. O.ïi. )
    The work done "by CEHBOii revealed toxicity thresholds of the
    same order of magnitude as those observed by the I.S.T.P.H. ,
    i.e. vaiying toxicities for concentrations of l/'lOOO to
    l/l0,000 ( see the - results belou ). It should bo pointed out
    that the toxic dilution of l/35,000 is recorded for the nost
    sensitive fish , but after a st:^y of 10 days in polluted wfter ,
    which represents artificial conditions .
    Results
    1 . Pelagic type chain
         - Phyt o plancton    : Anterior, ella ¿ aponic ?       1/ 1,000
         - Zooplanlcton       : Artemia salina                  1/ 1,000
         - Fish               : Carassius aurai us              l/2,000
    2 . Benthic type chain
         - Marine bacteria : between 1 / 1,000 and 1/ 10,000
         - Annelida          : Nercis di versicolori aLout 1/ 2,000
       • – Fish              : Labrus bergylta                  1/ 16,000
    3 . Nerit ic c rust acorn type chai n
         - For Eai'ine brcteria the thresholds hc.d been determined
           during earlier experiments .
         - ilolluSCS         : jvytilus edulxs :          about 1/ 3,000
         - CruBta.ce ans     : Leander cerratus                 1/2,000
   4 . Neritic nolJusc type ch.?in
         - Phytoplankton     : Diogenes sp                      1/2 , 000 to 1/3,000
         - ï'clluscs         : Kytilus edulis                   1/8,000
 ---pagebreak---                                     - 5o -                     ENV/ 47/ 75-®
                                                                Orig. ; F
c ) Foreign experiments
    Interesting studies have been made in Nei* York Bay by the
    Woods Hole Oceano graphic Institution , Massachusetts.
    Some of these give the following results of toxicity studies
    " in vitro " on copepoda and phytoplankton gathered close to
    the discharge area ;     the results are summarised as follows :
    "The experiment on the development of phytoplankton did not
    show any significant effect on the growth of phytoplanlcton
    for a concentration of l/l0,000.
    After 12 dnys "both the culture in the dilute effluent and
    the reference culture showed an increase in the number of
    cells of tho seme order of magnitude , without any apparent
    change in the diversity of the species.
    The studies of chlorophyl a and of carbon pr.rticles confirm
    the above results .
    There does not appear to be any effect on the survival of the
    eggs or the development of the copepod " pneudodiaptomus
    coronatus " in solutions with concent rat ions of waste acid of
    10-5 and 10-6 by volume.       At these concentrations tho period
    of development from the egg stage to the adult strge in filtered
    and unfiltered effluent was 13 to 14 days-, whereas the reference
    in sea water (water from the Woods Hole bridge ) indicated 13
    drys .    In tlio s-ne e:cperinent , bvet with an - cid concentration
    of 1C- ,' , the eggs dit nod hatch , high norfcality of nnuplii was
    observed , or the period of development fror.i the egg to the rdult
    was longer thru that observed in the reference srmple .         Owing
    to the fact that the nauplii and the adults displrj^ed , when
    examined , rn accumulation of iron on their exo-slceletons rnd
    their appendages , filtered waste acid was used in 'another series
    of analyses during which the mortality rnd development times in •
    each of the 10-4 wa.ste acid concentrations ~nd in the reference
    concentration were compared.        In two cf these solutions no copcpod
     reached the adult stage .
 ---pagebreak---                                    - 53r, -                  EN-../47/75 -E
                                                             Orig. : P
      In the two others the development tin: 3 wr.s lengthened f-jorr.
      3 to 7 days in conp~rison with the tines observed to be
      t<?Jcen to reach en identic ?.! degree of evolution in the
      reference sample from the Woods Hole bridge ."*
* N.B. Translator 's Note : Here too , compare this re-trrjnslation
        with the English originrl .
 ---pagebreak---                                        /
                                 - 59 -                   EN1F/ 4Ï/75-E
                                                          Orig. : P
d) Acute toxicity thresholds
     It is obviously difficult to draw any final conclusions from
  . results of studies carried out on different organisms under
    conditions which are sometimes dissimilar ; moreover , some
    figures put forward display relet ively large discrepancies.
    The results r„s a whole can, however , "be summarised as follows
    - at a dilution of l/l0,000 the effluents display no taxipity
       or inhibition of growth in relation to the phytoplanlcton
       elements ( all the results agree on this point );
    - with regard to zooplankton, the toxicity threshold is for
       dilutions of 1/ 2,000 to l/5,000. However , certain stages
       of development are sensitive to dilutions down to l/l00,000
       (.tjierican experiment );
    <- for molluscs the results diverge r.nd , in the worst cc.se ,
       give toxicities for a dilution of 1/8,000$
    - for crust aceans , the toxic dilutions a.re around l/2,000 ;
    - lastly, the growth of marine bacteria, is normal for a
       dilution of l/l0,000.
    It can therefore be concluded that the direct toxicity effects
    of the effluent only appear below a dilution of l/l0,000.
 ---pagebreak---                                         - 60 -                          3r-7 47/75 ■-E
                                                                        Qi ig. F
3 ; Estimate of the c1 ire ";t ■"onF- eyv c icg' pf the c"i^chr:,r,--e3 or. ta~ .rine
     •faun?, and florr ( The effect of sludge-type waste is excluded
     from the calculations )
     It appears that a certain proportion of the "biomass" ( total
     body of living matter ) is affected by the direct toxicity of the
     waste products when these are insufficiently diluted .                Part of
     the food stock of the zone in question can thus be affected.
     It is risky to attempt to make a precise estimate of the annual
     loss of living matter due to the waste products ; as has just
     been seen , the toxicity thresholds vary depending on the analyses
     made , and it is also necessary to make rssumptions concerning the
     diffusion of the waste products , the primary productivity of the
     area , etc.
     Nevertheless , it is possible to m?lce the following estimates ;
     a) Ph^t opi ankt onic productivity in the discharge '.re ?, ( prinary
          product ivity2
   o     The only d?ta which we possess concerning the zone were
         published by Kondratieva ( 1970 )«        Primary production was
         about 5 nig of carbon per m^ per d?y at the surface , in llarch
         1968 .  This value , with those of the other stations on the
         Ligurian Sea , is one of the highest that the author has been
         able to obtain from the various measurements which he h?s ruede
         throughout the Mediterranean.         It seems , however , that
         Kondratieva' s results are suspect in terms of absolute velues .
         It seems more reasonable to accept the figures of I-linas ( i960 )
         relating to the Laboratory Buoy ( 42° 47' N,7° 29' E )., In
         these , annual primary production is estimrted at 76 fc of
         carbon per      ( aggregate production for the whole depth ).
 ---pagebreak---                                   OOE, -                 KKV/47/75-E
                                                         Orig. s F
b) Estimate of the loss of primary productivity due to the direct
   effects of the waste products
   On the basis of a discharge of 3,000 tonnes of effluents per
   day ( or about 2,500      with a density of 1.2 ) it is found that
   the volume necessary to dilute the effluent 10,000 times is
 . 25,000,000 M3 .   ( It WES not possible to rneke allowance , in
   this estimr.te , for the screening effect of the sludge
   discharge.)   In view of the fact thr.t the horizontal rates
 ---pagebreak---                                  - 61 -                    L'NY/ 47/75 -E
                                                           Orig. : F
     of durnsion rre rauch higher then the vcrtio ; 1 r-,tes ( it can
    "be assumed that the thickness of the vc-lmao effected is less
    than 70 m ( lin.it depth of the euphotic zone ( l )).  If it is
     assumed that in the 0 - 70 ra zone primrry productivity is
     independent of depth it will be seen that , for a depth of
    70 m affected by the discharge , the surfe.ee area affected
                                                              2
    by insufficient dilution of the effluent ia 350,000 ni       or
    3 6 hectares .
    It is necessary to make an assuption here regarding the time
    which the waste products take to dilute down to the threshold
    of l/l0,000 :   if we assume that in one day the medium reverts
    to normal conditions ( and therefore that the waste products
    of the nert day will be discharged into a zone which can be
    regarded as intact ), it can be assumed that throughout the
    year 36 hectares will be perrnmently lost for the production
    of the zone .
    Taking the primary-productivity figure adopted in section 3a) ,
    this represents a loss of :
            360,000 x 0.076 = 27,360 kg of carbon per year.
    If , furthermore , it is assumed ( figures taken from Rile;'- and
    Skirrow ) that 10 g^.mraes of biomass correspond to 1 gr?inme of
    organic carbon , we obtain v. loss of primary product ivity
    ( phytoplankton ) of 273,600 kg per year.
    If , lastly , it is assumed that 1000 g of phytoplankton r.cke
    possible the growth of 10 g of planktonivorous fish or of
    1 gramme of carnivorous fish , this gives an annual loss of
    halieutic resources of the order of sever ?! hundreds of
    kilogrammes per year.
) Zone where photosynthesis occurs.     A lens- shaped region of high
  productivity is located not far away from the zone.      The depth of
  this vjould apnear to be 150-200 111.
 ---pagebreak---                               62 -                  EN1// 47/ 75 -E
                                                    Orig. Î P
The argument is based, on a number of parameters which are
difficult to assess and are obviously arbitrary in nature.
Even allowing for margin of error of about 10 , it will be
seen that the loss of nutritional resources due to the direct
action of the waste products is extremely limited.
It must be recalled , however , it was not possible to tpke into
account the role of the waste product discharged ;   it would
certainly be negligible , in view of tlie presence of a high-
productivity ares close to the discharge zone.
Here more than elsewhere the number of assw.pt ions involved
calls for the greatest caution. Neverthel e ss , the low value
of the figures obtained should be noted ; it tallies with the
results of the observations imj&e at the site of the discharges
in New York Bay , which lead to the conclusion that the loss
of halieutic resources is negligible.
This judguent needs , however , to be qualified by "on the spot "
observation of the effect of the discharges on local fishing,
and by discussion - cn the following pages - of the long-tern
effect of the waste products discharged from the point of viow
of accumulation phenomena.
 ---pagebreak---                                                                         / '■ » / '
                                                                     Ori ^. : F
SECTION II - THE LONG -TOP:.-! EFFECTS
       VJe have already "touched, upon the importance from a physico-chemical
       pcint of view of the introduction of the hervy ret .r Is contained in the
       effluents .
       We must now examine what are the possible biological consequences ,
       of the accumulation of these elements along the food chains .      These
       consequences con "be studied in two ways :
       - the first consists of the reproduction , in vitro , of phenomena
          of chronic poisoning ;
       - the second , more promising way consists of on-the -spot observation
          of the content of undesirable elements in animals fished or
          gathered in the geographical area of the discharges in order to
          drew conclusions as to the dangers entailed "by thi-ir ingestion.
          This approach must allow for the extreme variability of the
          results obtained and be based on a sufficiently large number of
          analyses to bring out clearly the effect of the waste products
          themselves .
       It would seem usefal first of all to recall some dcta concerning
       the phenomena of concentration of the elements encountered in the
       effluents .
       l ) The " natural " accumulation processes
           a) The different contents observed in the natural medium
              As has been emphasised elsewhere , titanium , chromium , vanadium
              end cadmium are naturally present in sc .? water , in extremely
              small proportions .
              The natural traces of these elements are concentrated by certain
              organisms .
 ---pagebreak---                                   - 64 -                      EFV/47/75-E
                                                              Orig. : F
    Thus the following contents have teen observed, in New Zealand
    filialve organisms (Brocks and Hurasby , 1265 , quoted "by Home ).
                         Average content in ppm ( ug/gramme ) .dry weight
                           Scallop             Oyster               Ilussel
        Iron               2,915                680                   1,960
        Chromium              10                   3                     16
        Vanadium                9                  3                      5
        Cadmium              250                 35                      10
    Similarly the following proportions are found in the flesh of
    certain marino organisms ( ISTPII figures quoted in the GIPLI
    report , 1973 ).
    Contents in ppm ( up/gramme ) dry matter :
    Chromium : fish : 0.02 to 1
    Cadmium    : fish : 0.15 to 3
                 algae : 0.0006 .
 . Data concerning the content of titanium , vanadium and aluminium
    in marine organisms are more rarely found.
    Information from C.E.R.B.O.M. mentions that :
    " in the specialised literature it is assumed that for non-polluted
    fish , titanium and vanadium are not detectable ; with regard to
    aluminium , the average proportions are of the order of 10-6 g/g
    dry weight of fish",
b ) Toxicity of these different elements for human beings
    The acceptable doses in foodstuffs are :
    1 mg/kg of fish                )
                                   j for cadnium ( fresh x/ei;ght )
    5 m^/kg in molluscs            )
    0.1 mg/'lcg in certain foodstuffs for chronium.
 ---pagebreak---                              - €5 -                    E„:., .,7 , 7>2
                                                       0:.dg. : F
( ISTPH figures mentioned, in the GIPII report .)
With regard to titanivjn and vanadium , there do not appear to be
any national or international st c jidaixis of toxicity,   Furthermore ,
there are no results to be found of work concerning the toxicity
of these two elements , which up to now have not "been the subject
of many publications .
Professor 3RIS0N mentions , in a letter addressed to the CIESK and
passed to us by the Chairman of the " Campaign against uarine
pollution" Committee of that international organisation :
"Titaniun salts are in themselves harmless , since they are insoluble ,
with a few exceptions ( bromides , chlorides , fluorides , iodides ...).
The soluble salts are very unstable and rapidly decompose in the
atmosphere .  In the pure stcte , some of them nre regarded as
irritants , but this has nothing to do with the present subject .
The most recent treatises on toxicology state that no case of
poisoning by titanium or its salts is known.      Titanium oxide is ,
as everyone knows , widely used for therapeutic purposes.          It is
administered in very heavy doses , several tens of grammes per dry.
Coirre titanium contains 9 g of titanium anhydride per 10 grammes
and 2 to 3 doses per day , i.e. 30 grammes , are absorbed.
"Bismntitane " contains 7*4 grammes of titanium anhydride          and 2.5
grammes of bismuth sub-nitrate per 10 grammes ; here again one
or two doses are taken per dry , making about 20 grrmmes. For
my part I use these products a lot and make up many prescriptions
for them.
Titanium oxide is included in the composition of many ointments ,
the best known being "Het atitane". The sulphate mentioned ( in
 ---pagebreak---                                     m
                                       M +
                                           m                  EKV/47/75-E
                                                              Orig. : P
        the letter from Mr. PAOLETTI ( l )) is both insoluble and unstable ,
         and the analyses presented in the Italian papers show that it has
         a high content of H2S04 and iron sulphate , but obviously the
         sulphuric acid is immediately diluted and neutralised when it
        reaches the receiving sea water,! 1
        However , a document provided by CERBOII mentions that :
        "Russian works have shown that ingestion of titanium ( TiC13 ) in
        the organism of rabbits (2 mg/kg) led after a certain period ( 129
        days ) to certain metabolic disturbances^    Other disturbances are
        produced by tile ingestion of 0. CF> ng/kg of TiClJ.  In the same
        document attention is drawn to metabolic disturbances resulting
        from excessive ingestion of vanadium."
2 ) Studies of accumulation and induced tonicity carried out in laboratories
     a) Report of the I.S.T.P.M.
        At the date of publication of the first report of the I.S.T.P.K.
        (February) , only one short experiment on concentration phenomena
        had been performed ; the animals surviving after four days in the
        effluents of different concentrations and the reference anim?ls
        displayed no detectable differences in their content of iron and
        cadmium.
        A much longer investigation ( scheduled to extend over 3 to 4 months )
        is in progress : Arter.ia Salina trill bo grown from diatom cultures
        in an effluent diluted to l/5000 . and the Artemia Salina will itself
( l ) An expert of the Italian scientific commission.
 ---pagebreak---                                        »» τ»7 V
                                                                  ^ι-.Γ ;·' Γ
     "be used, to feed shrimps raid also fish.         The results of "this
      study will be known in Juno .
b ) Results fror. CERBOII
 .   A. C CÎTCBITTÏÏATION PHEKOI-ÎEITA
     CERBOII succeeded in measuring the phenomena of induced concentration
     by reconstituting in the laboratory four major aliment ary chains of
   , the coecn environment :         the method employed, consists of breeding
     the elements of the four chains in trnlco containing varirble dilu­
     tions of the effluents .         Each alincnt r.ry stage which has thus
      possibly accumulated the undesirrble substances from the waste
     natter serves as food for the higher stage , which itself is placed
      in a dilute solution of the effluent .          Lastly the effect of the
     concentration phenomena on the final consur.er (mouse ) is tested.
     The results reported by CEIlBOI , are as follows :
      " l ) Heritic crust rcean chain , consisting of micro-organisms ,
            molluscs , shrimps ( exposure to poisoning for 2 weeks for each
            of the components ) :
            - The molluscs ( mussels ) hrd titanium contents ranging from
              2 to 4 ug/'g and vanadium contents raging fror.i 0.5 to 1 ug/g,
              whereas the reference SMiples h:d t it anium contents below the
              detection limit and vrnadiun contents of around 0.1 ug/ g, the
              concentration factor being 6 to 13 for tit^niun and 80 to 170
              for vanadium , in comparison with the contents of the tested
              polluted water.
            - the crustaceans ( shrinps ) hrd contents of 5 to 7.5 ug/g of
              titanium and 2.6 to 2.£ u&'g of v-nadiun , whereas the reference
              samples showed no detectable content of titr.niur.v and contents
              of 0.5 ug/g for vanadiua , the concentr?tion in comparison with
              the tested water being 16 to 25 for titr-nium rnd 430 to 4S0 for
              vanrdiiaa.   (The degree of dilution of the effluent was
              1/50,000. )
                                   /
 ---pagebreak---                              - Oo –                      ϊ3Γ7>,7/75-Β
                                                         On /*. : F
2 ) Bonthic chain consisting of nicro-orr^ni sms , pnnelida and
    fish which hrd lived in a t rnl: in a 1/50,000 dilution of
    the effluent for one week in the case of the micro-organisms
    and annelida and for two months in the case of the fish :
    - The annelida contained from 25 to 65 ug/g of t it aniun and
       from 1.5 to 19.5 u-z/£ of vanadium , whereps the contents of
       the reference s?:nples were respectively luj/j'of t it aniun and
       an undetectable proportion for vrnadium.     The concentration
       factor ranges "between 400 and 1,000 for titanium and between
       1,250 and 2,500 for vanadium in comparison with the contents
       of those metals in the tested water samples .
    - The benthic fish (blennies ) contained from 0.3 to 0.6 Mr/g -
       wet i^tter - of titanium and between 0.5 and 1.1 ug/g of
       vanadium , while the reference samples' contents were below
       the detectable limit for titanium and 0.3 ug/g for vanadium ,
       so that the concentration factors in comparison with, the
       polluted water were 5 to 10 for titanium and 400 to 600 for
       vanadium .
 3 ) Pelagic chain composed of phyto plankton , zooplankton ( exposure
     to poison for a period of 8 dcys ) and fish ( exposure for 15
     days ). Dilution tested : l/l0,000.
     Titanium contents ranging from 6 to 16 ug/g wet matter , end
     contents of 1.5 ug/g of vanadium were observed in fish , whereas
     the reference spriples showed no detectable content of either
     titanium or vanadium , the concent rat ion. ratios being of the
     order of 20 to 55 for titanium and around 250 for vanadium in
     comparison with tho concentration of these metals in the tested
     water."
 ---pagebreak---                                                                  •  • T       »-•
                                                                  Ci'i j, :
         4 ) fleritic mo llusc chrir.
              The concentrations observed, arc not included, in the results
              reported.
              The results obt pined at CEP30II thus confirm those mentioned
              in sub-section II-l ) with 'regard to the possibility of
              accumulation of vanrsdium and titanium.
              On the other hand , no indication was given by this organisation
              concerning the possible accumulation factors of chronica and
              cadmium.
        B. With regard to the induced toxicities observed in vitro , it should
            be noted that no phenomenon of this hind was ijound durinj (TJKBOK 's
            experiments ; while the same experiments porforraed on other
            industrial effluents ( effluents of paper mills end of ceramics
            factories ) hed in fret led to the derth of the final consumers
            ( mice ), no nortality was found at this st-£e by C2RB0I1, which
            concludos :                               v        .            •
            "llo acute toxicity ifas found at the level of the final consumer
            after the successive consumption of the last stages of the four
            marine trophodynamic chains ."     Trio seme document states , however :
            " althoivjh , in the medium term , there wore no lethal manifestations
            in the l:.nd-b".sod consumer, laiouledgo of the lor-j-tcrm effects
          ' of certain of its constituents docs not exclude the possibility
            of delryed pathological iuani fe st r.t io ns" .
3 ) Observation of t he heavy-metal conte nt s of the marine organisms
     collected, in the disch r r^e area.
    tie do not at present have many results of this kind.          Only CERBOIi
    reports on two series of analyses :       the first concerns fish provided
    by the Veterinary Services Department of the Ajaccio Prefecture (the
    place where they were caught is not stated ); the second concerns
 ---pagebreak---                                          - 70 -                  ENV/47/75-E
                                                                 0ri .*> : F
       fish sent by Bant i a fishermen as having teen caught north of Cap Corse ,
       CEKDOi! rericrks in this connection that it did not itself - arrrncc for
       these two amples to be taken , which n?y introduce artefacts.
       The results of those analyses are as follows j
            FISH SUPPLIED BY THE VETERINARY SERVICES DEPARTIiENT OF TIE
                                AJACCIO PÏE333CTUH3
  Samples                           Tit aniwn        Vanediuia       Aluminium
                 muscle               N.D.             N.D.              1.35
Se a. bas s
                 intestine            N.D.             N.D.              6.35
                 liver                N.D.             N.D.              9-36
                 herad                N.D.             1.33              6 . 30
                 muscle               N.D.             N.D.              1.24
Oca-brcam
                 intestine            N.D.             2.47              £.87
                 liver                N.D.             IT.D *            7.46
                 hecd             .   N.D.             1.93              5 . 90
                 ir.uscle             N.D.             N.D.              1.39
Bre?in
                 intestine            N.D.             I.63              2.45
                 liver                N.D.             II . D. -        14.92
                 ho ad                N.D. '           2.06              6.18
              FISE PROVIDUD BY BilSïIA FISIEKOÎ ,*S HAVING BEEN CAUGHT
                                NOP.TH OF CAP COIïSE
  Sonples                           Tit rniua        Vanadium        Aluminiun
                 muscle               N.D.             N.D.                1.79 ■
Ray              intestine            N.D.             N.D.            -V 1.44
                 {JlllS               N.D.             N.D.               4.94
Sword-fish       muscle               1.50             1.50            110
Octopus          tentacle             8.45             N.D.           . 84.53
  N.D. a not detectable .
 ---pagebreak---                                 - 71 -                       1^7/47 /75-2
                                      i-                     Cri ,". : F
It trill he noted thr.t titanium io not detectable in most of tho
srmplcs , except for tlio sword-fish muscle and the octopus tentacle .
On tho other hand , while all tho edible part3 of the animals ( except
for the sword-fish ) contain no vanadium , relatively high contents of
this element are found in the viscera rM herds .
These first results may appear significant .      It is extremely difficult ,
however , to draw any definitive conclusions from' them.
A certain number of points require more thorough consideration :
1 ) Tlie literature rr,rely contains .contents lay organs "but rather average
    contents for each organism :   the proportions of vanadium and titanium
    to be considered for a coraprrison \;ith other results should therefore
    be corrected by averaging tho results found in the viscera aid herds
    with those for the muscles of the fish .
2 ) Iloreover , it is rather difficult to explain the high cluminiun
    contents found in the different orgsaisus ? there is usually little
    information available on the concentration factors of this element ,
    which incidentrlly does not appear in very large quantities in tho
    effluents .
3 ) As has already been emphasised , there is at present s shortage of
    overall data on the actual toxicities of titanium and vanadium .
    It would therefore be useful , as a first stage , to examine the
    proportions of crdinium and chromium contained in moxine organisms ,
    as the contents of these elements have already been the subject of
    detailed investigations lerding to the establishment of standards ;
    knowledge of tho contents of titanium and vanadium , while
    interesting in itself, does not at present enable one to estimate
    the possible dangers of consumption of marine products , owing to
    tho lack of reference data on the proportions contained in animals
    collected in unpolluted areas of the ilediterrmean.
 ---pagebreak---                              - 72 -                        EUV/47/75-E
                                                           Orir. : F
K.3. Further results wore reported by CER30II in a comnunicat ion
      dated iCth April 1$73 .
... "but , furthemore , at the request of the Veterinary Services
Department of the Prefecture of Corsica , we have carried out a .
scries of measurements on fish caught off Corsica which have
been sent to us rogulrrly for the last feu weeks .       These staples
enabled us to find average values of 0. / 2 t it a-nium , 0.51 for .
vanadium and 0,40 for mercury (micro^amc/rpr-Tiaac - wet weight ).
This study is in progress e„t present .     He shall keep you informed
of the results obtained subsequently. •
The following two points mpy bo noted :
1 ) The titenim contents are higher than previously , while the
    vanadium contents , presented as average values , correspond to
    the precious values .
2 ) The mercury contents , althoiv^h liifh , remain below the acceptable
    thresholds .  In view of the fact that there hes never up to now
    been r,ny report of the presence of mercury in the effluents , it
    appears difficult at present to link the contents observed with
    the Italian discharges . "
 ---pagebreak---                                           - 73 -                    î3lïV/ <;7/75-E
                                                                    Ori g. : F
SDCTIOII III - FCOLOGICAL /iSPSOTS - CONCLCSICN
        The analysis of tho scientific and bibliogrrphical drt a compiled in
         ail effort to gain a clearer idea of the details and effects of the
        waste products discharged "by tho Ilontcdison company enables us to
        draw some conclusions ,             .
        The industrial wairte products in the sea display an appreciable
        direct tonicity due to their acidity and their iron content ,
     • which couses , in the wake of the discharging vessel , i.e. in a
         linitcd volume of water , the disappearance of tho species which
         are unable to flee or which cannot withstand 1/ 10,000 dilutions
        of the effluent in the no&ima (this being the threshold value
        obtained for prolonged strays ); plan!:ton is probably the raain
        victim of this mode of poisoning, although the estimate of the
        quantities per dcy affected by tho wasto products results in
        low values when neasurcd in the Ligurirn Sea.
        It has not so fr.r been possible to denonstrato the residual
        toxicity of these waste products , i.e. the hamfulnos3 which
        racy result in the long run from the systematic introduction
        into the nediuu of the heavy notals which they contrin.
        Chemical analysis of the waste products has shown that they
        did in fact contain srr.ll proportions of rosidual toxic
        substances .   The studies carried out in vitro h?.vo enabled
        the possibility of accumulation of those substances along the
        alimentary chein to be der.onstrcted.   Furthermore , the presence
        of residue! elements in certain fish trlcen from tho discharge
        area, would appear to confirm this observation , although
        responsibility for the presence of those substances in the
        animals collected cannot with absolute certainty be attributed         ,
        to Montedison^ waste products .   It should moreover be recalled
        that it has not been possible to date to prove the chronic
        toxicity of the substances contained in llontodison 's industrial
       waste products even in the laboratory .
 ---pagebreak---                                                           SNV/47/75
                                                          Ori-j. : F
However , in view of the absence of definite conclusions 011 this
point , violence is called for until such tine as the
organisations uhich arc at present still engaged in lon^-terw
experiments m?i:e known their results.
 ---pagebreak---   - 74 -    ENV . 47/75 E
CONCLUSIONS
 ---pagebreak---                                                             ENV . 47/75 E
 CONCLUSIOÎTS
 The production capacity of titanium dioxyde factories in Europe of the Nine
 is 840.000 tonnes per year ( tpa). This represents 39$ of world capacity
 (2 175 000 tpa) and is divided up as folloxfs :
         741 000 tpa ( 88$) for the sulphate process
          99 000 tpa ( 12$) for the clorine process .
Facotring discharging into the Channel or the North Sea account for 727 000 tpa
 ( 87$) and factories discharging into the Mediterranean account for 50 000
tpa ( 6$) . Two factories ( 63 000 tpa, or 7$) treat their waste on land .
At present , discharge levels are as follows :
 ( 1 ) in the North Sea and the Channel , either in estuaries or on the open
       sea :                               ?  •
                   4 100 t/day SO^Hg expressed as 100$ concentration
                   3 000 t/day FeSO^^H^O ( ferrous sulphate)
                   1 300 t/day FeSO^ discharged with the "acid waters" (SO^H^)
( 2 ) in the Mediterranean :
                   335 t/day SO^Hg expressed as 100$ concentration in the
                        >     form of neutralized products (2 600 t/day)
                   580 t/day Fe SO^fHgO are at present stored on land.
A whole series of ecological pollution monitoring campaigns have been      .
carried out in the actual discharge areas j these campaigns have been ■
investigated by the national authorities or sometimes by the manufacturers
themselves .
It is clear from an analysis of the results of these controls that waste
from the Ti02 industry is potentially or actually harmful . These adverse
effects on the marine environment are due above all to acidity , the presence
of ferrous sulphate and probably other metals ( heavy metals ).
 ---pagebreak---                                       - 76 -                 ENV . 47/ 75 S
The effects in question can take the following various foras , depending
on the method and place of dipping :
( 1 ) reduced oxygenation and pH of the water and increased concentration of
      Fc and heavy metals ;
( 2 ) ( a) temporary shortage of the zooplankton biomass and inducement of
            effects leading to a deterioration of the morphological structure
            of its components ;
      ( b) repulsion and loss of some species of fish :
      ( c ) reduction of the biomass , production and specific diversity of
            benthic and/or nectobenthic biocenoses in the discharge area . In
            more severe cases , all animal life mry disappear •
( 3 ) change in the colour , transparency and turbidity of the water and
      temporary reduction of photosyntheses , of the phytoplanlcton and of
      primary production , particularly in the case of surface dumping . The
      seabed becomes covered with iron oxides and the oxides of other
      metals where the dumping is carried out in estuaries and in shallow
      water •
( 4 ) on the other hand , there is no evidence of any toxic effects on man
      from the consumption of species of fish caught in the discharge areas .
Part 1 of this report contains an inventory of the waste from the production
of Ti02 . These wastes have been classified into four major categories cor­
responding to the waste products discharged by factories at different
stages of production .       These categories are :
         1 . insoluble matter remaining after filtration
         2 . "copperas " ( ferrous sulphate )
         3 . strong acids
         4 . weak acids or weak liquors .
 ---pagebreak---                                     - 77 -                 ENV . 47/75 E
 It would seem fair to suggest that industries in this sector should ,
 within certain reasonable time limits :
 a) store on land the insoluble matter remaining after filtration r
 b ) make certain reductions in the total pollution ( either 30$ , 10% or 95$) •
 These reductions are based on perfectly feasible techniques . For plants
 using Ilnenite for exemple , a reduction of
 30c/o would mean that the ferrous sulphate has been treated ,
70$ that the ferrous sulphate and the strong acids had been treated , and
95$ that the ferrous sulphate , strong acids and the bulk of the weak acids
       had been treated .
The report is also considered how and at what price this waste could be dispo­
sed of either by conversion or recycling ( see p. 28 and following).
It should be borne in mind that the processing cost values date back to
the end of 1973 and the beginning of 1974 and must be updated to take
account of changes in the economic situation . A study on this is being
carried out 'j however , the figures given in the report remain valid fur
the purpose of assessing the high cost of treatment in relation to pro­
duction costs ajid for comparing the various solutions proposed .