ARCHIVES HISTORIQUES
DELACOMMISSION
COLLECTION RELIEE DES
DOCUMENTS "COM"
COM (80)831
Vol.1980/0262

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COMMISSION OFTHEEUROPEAN COMMUNITIES
COM(80)831 final
Brussels ,17December 1980
'''ô vVhl NM^
. ^/^/
Proposal -
COUNCIL DIRECTlVE
onmethods forthe surveillance andmonitoring ofthe
environments affected bywastes from thetitanium
dioxide industry
(Presented bytheCommission totheCouncil )
C0M(80 )831 final

Introduction
Inimplementation oftheActionProgrammeofthe,European
Communities ontheEnvironment of20December1973,theCouncil
adoptedon20February1978(78/176/EEC)theDirectiveonwaste
fromthetitaniumdioxide ,industry,theaimofwhichisthepre­
ventionandprogressive reduction,withaviewtoitselimination,
ofpollutioncausedbywastefromthetitaniumdioxideindustry.•
./
*. ■ - ,
TheDirectivestipulatesthemeasurestobetakentoachievethis
end,inparticular -,thepriorauthorizations forwastedischarge
issuedbythecompetentauthorityoftheMpmberStateinwhose
territorythewasteisproducedandthedrawingupofprogrammes
fortheprogressive reductionofpollutionwithaviewtoits
Νultimateelimination . .
Article7oftheDirectivealsostipulatesthattheCommissionwill
withinoneyearofnotification oftheDirective,submittothe
/
Councilaproposalontheproceduresforthesurveillance and
monitoringoftheenvironments affectedbywastefromthis
industry. '
CommentsontheproposedDirective -
Pr^cedurj ?ior_^r^fj^i_ng_tJhe_D_i_r_ec_t i_ve
TheCommissionhasbroughttogetheragroupofnationalexperts
toassistitindraftingthetechnicalpartoftheDirective.
Thisgroup,whichhasmetthreetimes,hasadvisedtheCommission
onthemethodsofsurveillance andmonitoringtobeusedand,in
particular,onthelistoftherelevantparameterstobemeasured
throughouttheCommunityandontheminimumannualfrequencyof
samplingwithrespecttothedifferentenvironments receiving
wastefromthetitaniumdioxideindustry.

Aims_crf th_e _Di_re_ctJ_ve ,- ■ ..
This Directive will -onthe basis ofthe parameters selected -
provide the means ofidentifying pollution levels inthose parts
oftheenvironment affected -from aphysical /chemical ,biological
andecological !point cfview bydischarges oftitanium dioxide -
waste ,ofunderstanding pollution trends andofassessing thepro­
gressive reduction ofpollution caused bythese wastes .
Comments on'titanium dioxide ; '
Pijg/ne^nt^a_r y_p_r^o£e_r tj_e^ 1
Initserystaline form,titanium dioxide iscurrently regarded as
having thehighest refractory index ofalltheConventional pig­
ments inboth itsallotrophic forms ,i.e. anataae andrutile .As ■
awhite pigment ,itisincomparable and irreplaceable .
UtiIjzjitTon
Onaccount ofitspigmentary properties this product has come
into widespread use inmany areas ,principal among which are
paints andvarnishes ,paper ,plasties ,rubber ,floor coverings ,
ceramics ,andisynthetic 'fibres .Thepaint' andvarnish ,industry
accounts for more than half ofthetotal consumption .
Ti^a£ij^_d_i_°x_id^e_m£ njjf^ct_u_riing__pj^o_c e_ss^s_ , * '
Manufacturing oftitanium dioxide pigments consists inpreparing
high purity titanium dioxide from anore inwhich itispresent .
'.' -1 ' , •
already but mixed with other substances .. ^
There' isnoindustrial process formanufacturing titanium dioxide
bywhich titanium dioxide can beextracted' selectively .The
only twoexisting industrial processes involve digestion ofthe
ore ,followed byselective operations to ,extract ,thetitanium compound

-4-
Inafinal stage ,thetitanium dioxide isobtained from the
intermediate compound .
These twoprocesses areknown asthe 'sulphate' and 'chloride'
processes' respectively . ' , >
Inthefirst process ,theore isopened upbysulphuric acid and
then thetitanium hydroxide isprecipitated selectively .Finally ,
thetitanium oxide isobtained bycalcination ofthehydroxide .
Inthechloride process ,theore ischlorinated andtheresultant
V . • - '
titanium tetrachloride isfirst separated from theother chlorides
mechanically andthen distilled .Finally ,thetitanium oxide is
obtained byoxidation ofthetitanium tetrachloride .
InEurope ,thesulphate process istheonemost commonly used .
3.3.1 ._Su_lpj]_a_te process * *
Theoreused iseither ilmenite orslag .
/ . . •
-Ilmenite isamineral complex oftitanium and iron containing
onaverage 55%Ti(>2 andapproximately 30%iron ;
-slag isobtained from ironorewhich contains some 70%Ti*^ ,
10% iron asoxide plus metallic iron .
Themain stages involved intheseparation ofTiO^fromother
compounds are todissolve nearly all theoreandthen topre­
cipitate thetitanium selectively ashydroxide .This hydroxide
isthen calcined togive thetitanium oxide .
 
\

-5-
The main waste products are :
(i)residue from the oredigestion process .
This insoluble residue iscomposed ofunattached ore
and insoluble silica ;
(ii)ferrous sulphate intheformofheptahydrate (SO^Fe^TH^O ),
commonly known as"copperas ",resulting from the
reduction and crysta lization ofthe solutions formed
from the ilmenite digestion stage .This liquor ismade
upofacomplex salt oftitanium -ferrous andferric
iI
sulphate ;
ν
\
(iii)mother liquor produced from the separation oftitanium
gel after hydrolysis byfiltration and/ordecantation .
This liquor ismade upofasolution offerrous sulphate
insulphuric acid .Italso contains the sulphates of
the metals present intrace amounts inthe raw
material ;
(iv)various gel wash waters and waters from the scrubbing
.ofthecalcination gases .They contain dilute sul­
phuric acid,traces ofthesalts ofiron,titanium ancf
other metals present inthe ore.
3.3.2._Ch10£ide_p£0_ces_s
The standard ore used inthechloride process isnatural ,rutile ,
ascarce orevery rich inTiOg (approximately 96%),oralteran -
tively concentrates generally obtained from ilmenite orsynthetic
rutile . ■ ,
, 1
The process consists inobtaining titanium tetrachloride from
thehigh-temperature chlorination ofarutile and carbon mixture .
After condensation ,purification andoxidation ofthetitanium
i

-6-
tetrachloride ,thetitaniumdioxideisobtained;theregenerated
chlorineisrecycled..
Thisprocessgeneratesonlysmallamountsofwastebutislittle
usedinEurope.'Butalthoughthisprocessusesconcentrates of
ilmenite,itdoesinvolveanironremovalstage.Thispre­
treatmentleadstothesameproblemsasthoseassociatedwith
wastefromthesulphate .process.
_Compos2tionofthewastesfromthetitaniumdioxidejmJujstry
Inthesulphateprocess,themainwastesfromtheindustryare:
insolublesubstances,copperas,motherliquorsorstrongacids,
washwatersorweakacids. ">
i r
Inthechlorideprocess,themainprocesswastesarethechlorides
ofmanganese,magnesium,calcium,sodium,aluminium,chromium,
iron,vanadium,ZrO_,titaniumdioxide,TiCt^andchlorine.
I-
Thedetailedcomposition oftitaniumdioxidemanufacturing wastes
variesaccordingtotheoresused,themanufacturing processesand
thewayinwhichthesolid,liquidandgaseouswastesaretreated
ateachstageoftheprocess.
Liquidwastes
Generally,thesewasteshavethe/followingfeatures:
-highacidity; .
» '
-ahighironcontent,mainlyintheformofironsulphate .
(0.8to14%);,:.
-suspendedsolids(oxidesofTi,Si,Fe,Al,Ca,Zr);

-dissolved metals ,normally inthefollowing concentrations
(inmg/l):
Mn:400to1400;Cr:4to225;Zb:1to125;V:75to110;
Ni:4to50;Cu:0.1to10;Pb:3to6;As:0.04 to4;
Cd:<£0.1 ;Hg:<£0.005 .
Solid wastes
/
These are made upofcopperas ,arising from theprocessing of
rawmaterials inthe sulphate process and bytheneutralized
residues oforeorslag.Copperas contains ^some 90%ofiron
sulphate present asFeSO^,7(^0);theremaining fraction is
made upoftitanium dioxide ,magnesium sulphate ,free sulphuric
acid andwater ofcrystallization .Theneutralised residues
from the sulphate process contain ore orslag which is
insoluble at200°C in90% sulphuric acid together with filter
aids ;the waste products from thechloride process comprise
unattacked ores,coke andmetal hydroxides .x ' .
Gaseous waste
Principal among these are SO^and S0^which areformed from the
residual sulphuric acid (100-120 kgpertonne TiO^)andthe
sulphur contained inthefuel used toinitiate combustion when
the hydrated titanium oxide iscalcined .Depending onthe con­
ditions inwhich calcination takes place ,theratio ofSO^:SO^
(calculated as ranges "from 1:1.92 to1:2.80 .The amount
ofgaseous waste produced inthe manufacture ofone tonne of
titanium dioxide ranges from 12to22.4 kgSOgand53.6 to
60.2 kg SO,.

4.Principal'methodsofwastedisposalusedbythetitanium
dioxideindustry ' -
Theeffects'onbiotopesduetothevariouspropertiesofthe
wastesarecloselylinkedtothenatureofthereceivingmedium.
Seawatersaremostfrequentlyusedforthis,butincertain
specialcircumstances thewastesmaybedischargedinfresh
water,storedonlandorinjectedunderground intodeepstrata.
/
4.1._Dij^cha_rc^es_at __sea_
Thetwoprincipalmethodsofdisposalare:
► :'
(i)by^pipelinefromthecoast •
'1 •,
<ii>dischargeatseafromspecialships
•' 1 "X
Thefirstmethodnormallyrequiresprior.dilutionoftheeffluent
^andadischargepointwhichfavoursrapiddispersalofthe
effluent.Theacidicsolutionsareneutralized bydilutionand
bythebuffereffect.
Thesecondmethod,namelydischargeatsea,necessitates theuse
ofspecially-equipped tankershipswhichenabletheacideffluent
tobedischargeddirectlyintotheship'swake,thusproviding
rapiddilutionandconveyanceoftheeffluenttogreaterdepths.
Thismethodisusedforsolublewastes(ferroussulphateand
acidsolutions). J
Whentitaniumdioxidewasteisdischarged fromaship,the
predominantshort-termchemicalimpactiscausedbythe
reductioninpH.Accordingtotheguidelineslaiddownbythe
OsloConventionondischargesoftitaniumdioxidewaste,thepH
ofthereceivingwatersmustreach6withinamaximumof5
minutesafterdischarge. /

Since thepHofwastes varies according totheir source and that
different types ofship may beused (differences insize and
speed ),the following measurements should betaken before the
permitted level ofdischarge isdecided :
(i)thepHatdifferent dilutions ofthereceiving water
should bfecalculated insuch awayastoproduce apH/
dilution curve ;
I
■ ' . - -> ■
(ii)onthebasis ofthis curve ,ifapHof6ormore must
bereached within 5minutes -the requisite dilution
;\ ' ■r
'can becalculated ;
(iii) -the .rate ofdischarge canbeworked outdepending on
the required dilution onthebasis ofexperimental work
carried outontheship itself' (using tracers )orby
calculation (using general formulae fortheminimum
dilution inthe ship 'swake ).
» •
Another possibility isdirect measurement ofthepHofthewaste
\
dissolved inthe ship 'swake during thedischarge operation .
these conditions also presuppose that -the dilution engendered by
thepropel ler ,wake will beadequate toreduce thedensity
difference between theseawater /waste mixture andthereceiving
water toasufficiently lowlevel toprevent theformation of
dense layers which would impede thesubsequent mixing process .
Di_sch_a_rge _into_s r_fa_çejwaterj>
This method ofdisposal :isused foracid solutions once they have
been neutralized .Theneutralization products -aredisposed of
with the ferrous sulphates ..

-10-
4.3*Storageonland
Thistypeofstorageon"tipsisusedbysmallcapacity
titaniumdioxideplantsandismostfrequentlyusedforthesmall
fractionofinsolublewastematerials (i.e."thosewhichcannot
• v
bedissolvedbysulphuricacidwhentheoreisopenedup).
Furthermore,theacideffluentfromthisindustrycanbe
neutralizedbycalciumcarbonateandslakedlime(CaCOH^)andthen'
storedonland.Thesameistruefortheferroussulphates.
I '■ 1 ! '
.''' -,''' , •I
4.4._Injectioj2int_oundergroundstrata
Withthisdisposalmethod,thepreviouslyneutralizedacid
solutionsarepumpedintosubterranean strata.
■.' ι
y- ' • ..-*4.5.Re_cy_ct_i_n££f_tjie_wj3s^e_p£odu£t_s
Insomeproductionplantsthedilutesulphuricacidsolutions
arerecovered,reconcentrated andusedagain..Inothers,varying
"• . * ,
amountsofcopperas(ferroussulphates)areroastedandconverted
tosulphuricacidbytheaddition *ofsulphur.
Otherpotentialoutletsfortheseproductshavebeencontemplated.
y '
forexample:ironoxi^epigments,fluxforthecementindustry,
weedkillerandinwatertreatmentfortheproductionof
drinkingwater.Butonlysmallquantitiesofcopperaisare
'involvedintheseapplications , ) - ~
5.Methodsofsurveillance andmonitoringoftheenvironments affected
ThemethodsforthesurveiIlan.ceandmonitoringoftheenviron­
mentsreceivingTiO.,wastesdischargedatseaorintofreshwater,,
storedordumpedonlandorinjectedintoundergroundstrataare
basedontheprovisionsofAnnexIIBoftheDirectiveonwaste

from thetitanium dioxide industry ,adopted bythe Council on
20February 1978 (78/176/EEC).
Where the waste isdischarged into fresh water ordumped /
immersed atsea,,thefollowing .three .components shall be
monitored :thewater column ,,living .organisms and the sediment .
Periodic .checks onthestate ofthe area affected bythedis­
charges will mak«itpossible tomonitor changes intheenviron­
ments affected .
'' v
A .
Monitoring oftheio,Ilowing parameters shall becompulsory :
(a)Inthe water column
–pH,,the salinity ofsea .water ,dissolved oxygen ,turbidity
hydra tediron oxides and hydroxides insuspension ,
concentration ofdissolved salts ,toxic metals ;
.Ob)Insuspended solids andinsediment
–hydrated iron oxides and hydroxides andtoxic metals ;
Cc)Inliving organisms (having due regard tothe species typical
ofthe discharge zone )
–thelevels ofiron,titanium ,chromium ,cadmium ,mercury ,
vanadium .,nickel .,copper ,^zinc and lead;
(d)Flora and fauna
Diversity andrelative abundance .

Monitoring ofthe following parameters shall beoptional :
s
-the level ofchromium ,vanadium ,zinc ,lead ,nickel ,
copper ,manganese inthewater column and sediment and the
amounts ofsuspended solids .
Inthe case ofstorage ,tipping orinjection ,themonitoring shall
.include :
-tests to'ensure that surface waters andground waters have
not been contaminated .These tests relate toacontrol of
acidity ,the levels ofiron (dissolved and insuspension ),
calcium ,chlorides ,titanium andsulphates ancjtothe
environment ofthestorage sites ,i.e. thepermeability ,
porosity ,structure andstability ofthesoil ,!iandtoa
i '
general ecological assessment ofthearea surrounding the
tipping ,storage orinjection point .
Sampling
Thegreatest attention should bepaid tothetaking ofsamples
which should beregarded asapreliminary phase intheanalysis
process .
Themethods ofsampling should besuch astoensure that the con­
ditions inwhich themeasurements aretaken canbereproduced and
that themethods arerepresentative oftheconditions prevailing
inthesurrounding environment .Article 4(4)ofthis proposal for
adirective lays down the generaJL rules tobeobserved forsampling .

Minimum annual frequency forsampling and for the analysis
ofparameters ,
/ " ' ,
The frequency ofsampling andanalysis istheminimum number of
sampling operations andanalyses tobecarried outeach year in
respect ofthevarious parameters described intheforegoing
chapter anddepending onthedifferent environments affected by
thedischarge ofwaste from thetitanium dioxide' industry .
. 'Λ
The samples should betaken having due regard tolocal environ­
mental anddischarge conditions ,i.e *whether thedischarges
areintermittent orcontinuous ,theexact Site ofthesample
taking and itsdistance from thedischarge point should bespeci­
fied ineach case bythe competent authority ineach Member State .
Where theresults ofmeasurements taken onsamples from thedis­
charge zone are consistent orshow asignificant improvement in
environmental quality over theprevious year ,the frequency of
sampling andanalysis may,with theprior agreement ofthe
Commission ,bereduced bytheMember State concerned .
Accordingly ,theMember States should communicate tothe -
Commission the results ofthese measurements and state the
frequency they propose toadopt .
Preservation andtransport ofsamples '
Asstated inArticle 5,thetype ofcontainer used forsampling
andpackaging should notinfluence theanalytical results .
Thevolume ofsuch sampling bottles should besuch astoenable
thespecified measurements tobecarried out inoptimum conditions
ofreproducibility .Since thecharacteristics ofthesample wafer
mayalter quite rapidly under theaction ofthevarious organisms
itcontains ,such changes asmayoccur between themoment of
sampling andanalysis should bekept toastrict minimum bycarry­
ingouttheanalyses asrapidly aspossible .

-14-
Manyinvestigations havebeenmadewithaviewtorecommending
methodsbywhichwatersamplescanbestoredwithouttheircompo­
sitionbeingaffected.Butitisimpossibletolaydownanyhard
andfastruleswhichwouldcovereverycaseandeverysituation
andtowhichtherewouldbenoexceptions.Thesamplesneededto
measuretheparametersshouldbetransported tothelaboratory
forexamination attheearliestopportunity .Ifimmediate
analysisisnotpossible,thesamplesshouldbekeptundercon­
ditionswherethecontainersareprotectedfromanyoutside
contamination andnochangeinthestateoftheircontentsis
possible.
Methodsofmeasurement
Thereferencemethodsofmeasurement foreachparameterselected
forthesurveillance andmonitoringoftheenvironments affected'
areshownintheAnnexestothisproposal.
Laboratories intheMemberStatesusingothermethodsmustensure
thattheresultsobtainedareequivalentorcomparabletothose
givenintheAnnexes.
Theresultobtainedfromthesamplesandmethodsofmeasurement
mustberepresentative ofthetrueaveragequalityofthewater
analysed.Thevariousoperationsneededtoachievethisresult
mayleadtoerrors;itisvitalthat,sucherrorsbedetected
andtheneliminated orreduced.
TheAnnexestothisproposalforaDirectivelaydownthecon­
ditionsinwhichthemeasurements ofcertainparametersmustbe
carriedoutinviewoftheriskthattheirvaluemaychange
duringthetransportorprotractedstorageofthewatersamplesin
containers.Thisisthecasewithtemperature andpH.

-15-
10. Action atinternational and Community level
Inthe campaign against freshwater and seawater pollution ,
the Community isaContracting Party tointernational conventions
aimed atreducing andeventually eliminating this type ofpollu­
tion .The conventions are :
-The Convention for the Prevention ofMarine Pollution from
Land-based Sources (Paris Convention )(75/437/EEC);
^Convention for the Protection ofthe Mediterranean Sea
against Pollution (Barcelona Convention );
'i
-Protocol for the Prevention ofPollution ofthe Mediterranean Sea
byDumping from Ships andAircraft (77/585/EEC);
-Convention onthe Protection ofthe Rhine against Chemical
,Pollution (77/585/EEC).
On17May 1980 .,the Community also signed the Protocol onthe
protection ofthe Mediterranean Seaagainst pollution from Land-
based sources .
/
Specific articles ofthese Conventions either ban the dumping or'
discharge ofcertain substances such asacid compounds whose
t
composition andauqntity are such that they may adversely affect
thequality ofsea water ormake the dumping ordischarge of
ι
specific substances ,such astitanium ,chromium andacid com­
pounds subject totheprior granting ofaspecific permit orto
appropriate programmes and measurements toreduce pollution .

The Community participates asanobserver inthe Convention for the
Prevention ofMarine Pollution byDumping from Ships andAircraft ,
signed inOslo on15February 1972 .The Community isclosely ♦
following the work being done under theauspices ofthe Standing
Advisory Committee totheScientific Councils ofthe Oslo 1
Convention and theJoint Working Party onmonitoring and continuous
surveillance under the Oslo and Paris Conventions ;this work concerns
themonitoring and continuous surveillance ofthe sea areas into ,
which titanium dioxide wastes are discharged .
InJanuary 1976,moreover /the Commission put forward aproposal
for aCouncil Directive onthe dumping ofwastes atsea (OJ C40,
20February 1976 )which contains abrief review ofthe legal
situation regarding this method ofdumping atsea. \
■"■ . ... - t .. ■ ■ ■ , –
Finally ,aDirective onpollution caused bycertain dangerous
substances discharged into theaquatic environment of-the
Community (76/464/EEC)stipulates that pr'ior authorization must
beobtained for any discharge into waters likely tocontain one
ofthe substances specified inAnnex II,such astitanium ,zinc,
vanadium ,chromium etc.
Consultation ofthe European Parliament and the Economic and
Social Committee
\
Since this proposal for aDirective 1isbased onArticle 7of
Directive 78/176/EEC,consultation ofthe European Parliament
andofthe Economic and Social Cbmmittee isobligatory ,as
stipulated inparagraph 3of .this Article . ■

THE COUNCIL OFTHE EUROPEAN COMMUNITIES
Having regard totheTreaty establishing the European Economic
Community ,andinparticular Articles 100 and 235thereof ,*.
4
Having regard toCouncil Directive 78/176/EECof20February 1978
1onwaste froc thetitanium dioxide industry ,and inparticular
Article 7(3)thereof ,
'1 -
Having regard tothe proposal from the Commission ,
Having regard totheopinion ofthe European Parliament ,
Having regard totheopinion ofthe Economic andSocial Committee ,
Whereas ,irrespective oft-he method andextent ofthetreatment of
wastes from thetitanium dioxide industry ,the discharge , ^
dumping atsea,storage ,tipping orinjection into the ground of
f
such wastes must beaccompanied ,inparticular ,bymeasures to
monitor the environment affected from aphysical ,chemical ,biolo­
gical andecological point ofview ;
Whereas ,in-order tomonitor thequality required ofthe environ­
ments affected aregular minimum number ofsamples should betaken
annually sothat the parameters specified inthe Annexes may be
measured ;whereas the number ofthese sampling operations could be '
reduced inthelight oftheresults obtained ;whereas toensure
»
that themonitoring iseffective ,samples should also betaken in
azone deemed tobeunaffected bythe discharges inquestion ;
Whereas inconnection with the analyses carried out bythe Member '
States ,common reference methods ofmeasurement should befixed for
determining theparametric values which define thephysical ,chemical
biological andecological characteristics ofthe environments
affected ;
^JOL54,25February 1978 . 1

-18-
■
Whereas ,for the purposes ofsurveillance /Member States areat
all times free tomeasure parameters other than those prescribed
bythis Directive ; "
'■ *
Whereas the Member States should communicate tothe Commission .
details ofthe methods ofsurveillance andmonitoring ofthe
,environments affected ;whereas itisappropriate that the Commission
should draw upaconsolidated report tobesent tothe Member States ;
Whereas certain natural circumstances are outside the control of
Member States andthat,accordingly ,provision must bemade for
derogation ,incertain cases ,from this Directive ;
I ■ ' '
Whereas technical andscientific progress may require the rapid
adjustment ofspecific provisions contained inthe Annex ;whereas
tofacilitate implementation oftherequisite measures ,aprocedure
should belaid down toestablish close cooperation between the
Member States and the Commission through aCommittee onadapta­
tion toscientific andtechnical progress ;
HAS ADOPTED THIS DIRECTIVE
Article One
This Directive lays down -pursuant toArticle 7(3)ofDirective
78/176/EEC-the methods ,forthesurveillance andmonitoring ofthe
environments affected from aphysical ,chemical ,biological and
\ 1-,
ecological point ofview,bythedischarges ofwastes from the
titanium dioxide industry .
Article 2 .
" t ' '
For the purpose ofthis Directive :
(a)'environment affected' means surface water ,ground water ,

-19*
the sea,.the land surface and underground strata and theair
into oronwhich wastes from the -titanium dioxide industry
are discharged orstored ;
Cb)'sampling point *means thepoint atwhich the sample is
'.,' •taken ; ' ,
Cc)'reference method ofmeasurement *means ameasurement prin­
ciple orthe concise description ofamethod fordetermining
the parameters specified inthe Annexes tothis Directive .
■ \ ' Article 3 »
1. The relevant parameters for thesurveillance andmonitoring ofthe
.environments referred toinArticle Tare shown jnAnnexes 1to5,
subdivided according tothereceiving medium .'
■2. Where aparameter appears inthe 'mandatory *column ofthe Annexes ,
'sampling andanalysis must becarried outinrespect ofthe
■/ ■Λ' - ··.
environmental components stated . '
. ■ ■< ■ -I ,
3. Where aparameter appears inthe'guide' column pfthe Annexes ,the
Member States shall endeavour toperform the sampling andanalysis
* ,
operations for the environmental components shown . ' '
<■ f
Article 4 , ' ■-
-1. The competent authorities inthe Member States shall determine the
frequency ofsampling andanalysis for each parameter inrespect
ofagiven zone inwhich discharge ,"tipping ,dumping ,storage ,
deposition orunderground injection takes place ..
/ » • '
2. The frequency ofsampling andanalysis may not beless than the
minimum frequencies shown inthe Annexes tothis Directive .The •
sampling periods must,asfar aspossible ,bespread over theyear
insuch away astoobtain arepresentative picture ofthequality
ofthe environments affected .. .

-20-
The competent authority ineach Member .State shall determine -
onacase bycase basis -the exact site atwhich samples are to
betaken /thedistance ofthis site from thenearest pollutant
discharge point and thedepth orheight atwhich thesamples ,must
betaken .Ageneral description must begiven ofthesampling
point which will include itspermanent features ,capable ofbeing
codified ,andother administrative orgeographical information .
Thedescription shall bemade only once when thetypical sampling
point iSdesignated , V.
The sampling must becarried out inthezone directly affected by
i
thedischarges ,special account being taken oflocal environmental ,
• . $ -
factors andthemanner ofdischarge ,i.e. whethej ?intermittent or-
continuous .
Inthecas£ oftidal waters ,thesamples must betaken atthe
same depth andunder the same conditions ,i.e. the same time in
relation tohigh tide ,tidal coefficient etc .
Where thecompetent authority finds that the resutts ofmeasure­
ments onthesamples /taken inadischarge zone during theprevious
year are both constant and significant and show that thequality
oftheenvironments affected hasbeen detected ,thefrequency of
sampling andanalysis may -with the Commission 'sagreement -be
reduced bytheMember State concerned ;
Tothis end,theMember States shall communicate tothe Commission
theresults ofsuch measurements andnotify itofthefrequency
they intend toadopt ;the Commission maymake itsagreement subject
tocertain conditions ,inparticular theduration ofthereduction
infrequency .Inthelikelihood ofanydeterioration inthequality
oftheenvironments' affected ,theMember States shall take the
requisite measures .
••/■•

Article5
Thereferencemethodsofmeasurement tobeusedtodeterminethe
relevantparametricvaluesarespecifiedintheAnnexes.
Laboratories usingothermethodsmusteqsurethattheresults
obtainedareequivalentorcomparable.
Thecontainersusedtocarrythesamples,theagentsormethods
usedtopreserveapartsamplewithaviewtoanalysisofoneor
moreparameters,thetransportandstorageofsamplesandtheir
preparationfor.analysismustbesuchthattheydonotsignifi-~
cantly-affecttheanalytical'results.
Article6
•· ·<
Inordertoassessthestateofprogressinthesurveillance and\
monitoringofthevariousenvironments affectedfromaphysical,
chemical,biologicalandecologicalpointofview,thecompetent
authorities intheMemberStatesshallensurethatsamplesare
takenandanalysesperformedinrespectofeachenvironmental
componentspecifiedintheAnnexestothisDirectiveinazone'
deemedtobeunaffectedbythedischargesundersurveillance.'
'Article7
MemberStatesmay,atanytime,measureparametersotherthanthose
laiddownby-thisDirectiverelevanttothesurveillance and
monitoringoftheenvironments affected.
Article8
ThefollowinginformationshallbegivenbytheMemberStatesin
thereporttheyareRequiredtosubmittotheCommissionpursuant
toArticle14ofDirective78/176/EEC:

*-22-
•'i »
(a)detailsofthemethodsofsurveillance andmonitoring
carriedoutbythebodiesappointedinaccordancewith
Article7(2)ofDirective78/176/EEC;
(b)thedetailsreferredtoinpoint(a)aboveshall,inrespect
ofeachenvironmentaffectedbythedischarges,includethe
followinginformation :
-theresultsofthemeasurements oftheparameterslisted
inthe"mandatory"and"guide"columnsprovidedthatthe
latterparametersaremeasured;
ι. ·
-themethodsofmeasurement andanalysiswiththeirlimit
ofdetection,accuracyandprecision;
-thedescriptions ofthesamplingpoint;
-adescription ofthesamplingmethodsused.
I
2.Inimplementation ofthisArticle,thefirstsetofdatatobe
communicated isthatgatheredduringthethirdyearfollowing
notification ofthisDirective.
3.TheCommissionshall,withtheprioragreementoftheMember
Stateconcerned,publishasummaryoftheinformation thus
obtained.
A.TheCommission wi11assesstheeffectiveness oftheenvironmental
surveillance andmonitoringprocedureandwill-nolaterthan
sixyearsafternotification ofthisDirective-placebeforethe
Council,whereappropriate,proposalstoimprovethisprocedure
and,ifnecessary,toharmonizethemethodsofmeasurement
"includingthelimitofdetection,accuracyandprecisionandthe
samplingmethods.

Article 9
Member States may derogate from this Directive inthe event of
flooding ornatural disaster oronaccount ofexceptional weather
conditions .. '
Article 10 ■*
Therequisite amendments toadapt the methods ofanalysis and
the GSIparameters shown inthe Annexes toscientific and
technical progress shall beadopted inaccordance with the pro- .
cedure laid down inArticle 12. '
Article 11
'/ • -, ' '^
ACommittee onadaptation totechnical progress (hereinafter
referred toasthe"Committee ")consisting ofrepresentatives
■
ofthe Member States andchaired byaCommission representative ,is
ishereby set up. .
The Committee shall draw upitsrules ofprocedure .
Article 12
Where theprocedure laid down inthis Article istobefollowed , .
matters sha.ll bereferred tothe Committee byits Chai rman,either
onhis owninitiative oratthe request ofthe representative of
the Member States . ' *■ : ■
The Commission representative shall submit tothe Committee a
draft ofthe measures tobeadopted .The Committee shall deliver
itsopinion onthedrAft within atime-limit set bythe Chairman
inthelight ofthe urgency ofthematter .Itshall act bya
majority of41votes ,the votes ofthe Member States being weighted
asprovided forinArticle 148(2 )oftheTreaty .The Chairman
shall not vote .

(a)TheCommissionshalladopttheproposedmeasureswherethey;
areinaccordancewiththeopinionoftheCommittee.
(b)Wheretheproposedmeasuresareatvariancewiththeopinion
oftheCommittee/orifnoopinionisadopted,theCommission
shall,withoutdelay,submitaproposaltotheCouncil
concerningthemeasurestobetaken.TheCouncilshallact
byqualifiedmajority;
(c)If/withinthreemonthsoftheproposalsbeingsubmittedto
it/theCouncil ,hasnotacted,theproposedmeasuresshall
beadoptedbytheCommission.
Article13
,,•/•' .'• '•'%v ' '■
Directive78/176/EECisherebyamendedasfollows:
(a)InArticle7(1)thewords"andoftheenvironment concerned
havingregardtoitsphysical,chemical,biologicaland
ecologicalaspects"shallbedeleted.
<b)Article8,paragraph 1pointCisamendedasfollows:
"IftheresultsofthemonitoringprovidedforinArticle1
ofDirective EECconcerningthemethodsof
surveillance andmonitoringofenvironments affected"show
adeterioration inthespecificenvironmentiaffectedinthe
areaconcerned,or
(c)Annex11(B)isdeleted.
Article14
TheMemberStatesshallbringinto1forcethelaws;regulations
andadministrative provisionsnecessarytocomplywiththis

Directivebefore1January1983.Theyshallforthwithinform
theCommissionthereof.
TheMemberStatesshallcommunicatetotheCommissionthetexts
ofthemainprovisionsofnationallawwhichtheyadoptinthe
fieldcoveredbythisDirective.
i
Article15
ThisDirectiveisaddressedtotheMemberStates.

RECEIVING MEDIUM :AIR
| ~ PARAMETERS j
COMPONENTS j jf j! IMPERATIVE I GUIDE -I
I■ I■ II■I■Éi.I I I 1- ■ „■
« ' '^ i
\Air* SO2
' \
Ν II ■
IANNEX I
1
MINIMUM ANNUAL j
SAMPLING J
FREQUENCY IREFERENCE METHOD OFANALYSIS
.12 Intheprevailing wind inthe zone directly
affected bythe discharge .
Inaccordance with those given inAnnex II
oftheDirective of15July 1980 onair
quality limit values andguide values for
sulphur dioxide and suspended particulates .
(O.J. L229of30August 1980,pages 30-48 )
(80/779/CEE ) - '

RECEIVING MEDIUM -SEAWATER (estuarine ,coastal ,open sea)
COMPONENTS| PARAMETERS JMINIMUM ANfyMAL––– ■– <
■' ''
.REFERENCE METHOD OFANALYSIS
S
. »
i|IMPERATIVE■ : j SAnPLIMG
GUIDE f FREQUENCY
j
. I
Water column
Non-filtered water
or
t
| -Water filtered
jthrough 0.45 urn
{membrane
I
r
i%
Temperature 14 Thermometry |
i
jSalinity L <I _____
IConduct imetry |
!pH
iL • ■■ lElectrometry .Measurement istobecarried out |
onthespot atthetime ofsampling . J
Dissolved 0^
■ – ■ - . -j!. !■ ·It
-Winkler method 4
-Electrochemical method -i
I
iTurbidity
orsuspended
matter
j; ,I
I
I
I
II
4 .j j
Turbidimet ry |
-Weighing after filtration through 0.45 urn |
.filter anddrying at105°C J
-Weighing after centrifugation (minimum time !
5minutes ,andaverage accerlerat ion f
2,800 and3,200 g) j
I
I
IFe Ii : 71 i
■ ■ l « I
? tAtomic absorption spectrophotometry |
Molecular absorption spectrophotometry <
«
*
- I11 !1
Mn,Ni,V,Zn,jj
Atomic absorption spectrophotometry , 3
- . i
!
I5
Cu,Pb ! -4 jAtomic absorption spectrophotometry polarography I
Suspended solids
H ■IITl^■11M| |^Fe Cr
. _J. r
i
3After appropriate preparation ofthesample ,
wet ordrymineralisation ,andpurification
4 Atomic absorption spectrophotometry ,j
Molecular absorption spectrophotometry j

k
n
ANNEX II
page 2
COMPONENTSPARAMETERS1
MINIMUM ANNUAL
SAMPLING
FREQUENCY
•REFERENCE METHOD OFANALYSIS jj
|IMPERATIVE GUIDE _
«
Ti Mn>Ni,V,Znj A(
Atomic absorption spectrophotometry |
I jCu,Pb j.4Atomic absorption spectrophotometry |polarography (> E
Hydrated oxides
hydroxides of
ironI
I
*
I4
I -' "f - ,
Extraction ofthesample under dilute acid g
conditions (HCl;CH^COOH ;HNO3;HClO^/HNO.,), ;measurement byatomic absorption spectrophotometry .'
Thedetermination ofiron bymolecular absorption {
spectrophotometry can bemade without inter - £
ference iftheextraction ismade using CH,COOH . S
The same method ofacid extraction must beused Jforaltsamples coming from thesamesite •|
Sediments
Inthe top layer of
sediment (0-1 cm.)
I • ' '
i
.Fe,Ti
y
J, -Cr,V,Zn,Pb,
Ni,Cu,Mn
;i
; _J1i ■
i ,
iIdentical methods tothose for measurements intht
water column .
After appropriate preparation ofthe sample (wet
ordrymineralisation andpurification )
-Thecfuantities ofmetals may bemeasured for
aspecific range ofparticle sizes
-Thequantities ofmetals aretobeexpressed
inmg/kgofdrymatter
• , ■ .... ,– <^Hydrated oxides J J 1 \
hydroxides of { j j
iron t I IIdentical methods tothose formeasurements in }
the water column !

COMPONENTSPARAMETERS
IMPERATIVE GUIDE.MINIMUMANNUAL
SAMPLING
,FREQUENCYANNEXII
page3In
REFERENCE METHODOFANALYSIS
Livingorganisms
Speciesrepresenta-jtiveofthesite:jmolluscs,crusta-I
ceansapdfishandat|
leasttwoinverte-]brdtesincluding,ifI
possible-,onebenthic
organism (1)Cr,Cd,V,'Hg,
Fe,Ti,Zn,Pb,
Ni,.Cu
JUSapaTIsnanaaq
isttwoinverte-]itesincluding,ifI
ssible,onebenthie-Atomicabsorptionspectrophotometry .after
appropriatepreparationofthecompositesample -
ofgroundflesh(wetordry"mineralisation and
purification)
Forfish,themetalsmustbemeasuredin
muscle.Thesampleshouldconsistofatleast
10specimens.
-Thequantitiesofmetal'saretobeexpressed
inmg/kgofwetmatter
Forthemolluscsandcrustaceans,themetalsmust
bemeasuredintheflesh.Thesampleshould
consistofatleast50specimens.~
Thequantitiesofmetalsaretobeexpressed
inmg/kgofwetmatter.
Benthicfloraand
fauna,fishDiversityand
relative
abundanceQualitative andquantitative classification
indicatingthelisteofspecies,thespecimen
countperspecies,thespecimencount,density
dominance,andinthecaseoffish,,theper­
centageshowingmorbidanatomical symptoms..
C)Speciesrepresentative ofthedischargesite:suchasmytilusedulis,crangoncrangon,flounder,plaice,cod,mackerel,
redmullet,herring,sole(oranotherappropriatebenthicspecies).

10
,ANNEX III
RECEIVING MEDIUM :FRESH WATER
PARAMETERSJ
MINIMUM ANNUAL
SAMPLING .I
FREQUENCY |
Jr_ """ !
REFERENCE METHOD OFANALYSIS i
1 COMPONENTS
-IMPERATIVE j
!|GUIDE
Mater column ■, - t
.Samples taken ata J
depth of0.50 m
below the surface at
the same time ofthe.pH "
1~' • i
4! " . N-L
!Electrometry .Measurement istobecarried out t
jonthespotatthetimeofsampling . |
Iyear - j
P Onnon-f iItered 'i
Dissolved 0o |c i4 .-''|-Winkler method  - H
-Electrochemical method
• \x/"' '" »*
water orwater
filtered through a
0.45 membraneTurbidity or
suspended
matter
- -4 Turbidimetry '' , ■ jj
-Weighing after filtration through 0.45 urn |filter anddrying at105°C {
-Weighing aftercentri fugation-(minimum time ]
5minutes ,andaverage acceleration i
2,800 and3,200 g)anddrying at105°C . 1 j
I ■
IDissolved j
salts -h- : –
-■4-- !IElectrometric measurement ofconductivity at20°C |
Fe . i
' ICr
fi . I
I.4 i!Atomic absorption spectrophotometry • j Molecular absorption spectrophotometry j
■ • ■■ Ti |!
-,Mn,Nr,V,Zni .4"–– ft
|Atomic absorption spectrophotometry |
1 ^
I
ICu,Pbr–
i ■ . (Atomic absorption spectrophotmetry;polarOgraphy |
J : : i
|Suspended solids J
i ii–i
» . -
ii[After appropriate preparation ofthesample , j
jwetordrymineralisation ,andpurification j
I
Fe I
iCr
I 4
t)Atomic absorption spectrophotometry |
{-Molecular absorption spectrophotometry j
i .I – ■» ■" ■–■i « ■■ ■ 11'1
■••/•••

ANNEXIII
r*"–" 1 ■ page2
COMPONENTSI PARAMETERSJMINIMUMANNUAL.
REFERENCE METHODOFANALYSIS
IIMPERATIVE–––––––––
GUIDEIFREQUENCY
Ti% Mn,Ni,V,ZnE~H_Atomicabsorptionspectrophotometry
ICu,Pb•.1Atomicabsorptionspectrophotometry- Polarography
i
\ * *Hydratedoxides
hydroxidesof
iron
.i4 Extractionofthesampleunderdiluteacid
conditions(HCl;CH^COOH;HN03;HCIO^/HNO-),
measurement byatomicabsorptionspectrophotometry .
Thedetermination ofironbymolecularabsorption
spectrophotometry canbemadewithoutinterference
iftheextractionismadeusingCH^COOH.
Thesamemethodofacidextraction mustbeused
forallsamplescomingfromthesamesite.
Sediments
Onthetoplayerof
sediment (0-1cm.)Fe,Ti Cr,V,Zn,Pb,
Ni,Cu,Mn1I : ;
\ ■■ ■
Identicalmethodstothoseformeasurements in-
!thewatercolumn.
Afterappropriatepreparation ofthesample(wet
ordrymineralisation andpurification )
I "-Thequantitiesofmetalsmaybemeasuredfor
!aspecificrangeofparticlesizes
i
|-Thequantitiesofmetalsaretobeexpressedinmg/kgofdrymatter -■'.
I
IHydratedoxides
hydroxidesof
iron1 Identicalmethodstothoseformeasurements in
thewatercolumn .
10

•% ■-
ANNEX III
page 3-
*
| PARAMETERS (MINIMUM ANNUAL jrAuni tkir I
I REFERENCE METHOD OFANALYSIS j- - ■ " "•>V II COMPONENTS
jIMPERATIVEGUIDE ,iaHnrLiiiu -.KFREQUENCY
I
Living organisms
Species representa­
tive ofthe substrate-,––– . (
* j
Cr,Cd,V,Hg,
Fe,Ti,Zn,Pb,
Ni,Cu■"■V " ■'"
i
1■ • V ' .j
Atomic absorption spectrophotometry after
appropriate preparation ofthecomposite sample
ofground flesh .
-Thequantities ofmetals aretobeexpressed
i inmg/kgofwetmatter –
: 1
Benthic flora and
fauna ,fishDiversity and
relative .
abundance'1
i
I
i
I
!
• i
ar- : •Ï
I
I
i 2 "Qualitative andquantitative classification «
indicating thelist ofspecies ,thespecimen 1
count perspecies ,thespecimen count,density j
dominance ,andinthecaseoffish,theper- jj
centage showing morbid anatomical symptoms «
!■ '■ i '■
• ' I
\■' i
I
I* " '
X' ' /
■ ; ' ...
ï B

RECEIVING MEDIUM :STORAGE AND DUMPING ON LAND3$
ANNEX IV
COMPONENTSy.■iw .l,»na^n.ii
PARAMETi
IMPERATIVEÏRS -'
| GUIDEMINIMUM ANNUAL
SAMPLING
FREQUENCY- –– ,
REFERENCE METHOD OFANAllYSIS |
Running surface
waters
Water filtered
throuyh a0.45 pm
membrane |
. I
(a)from thestorage '
area and evacu­
ated tothe
outside (not
recycled )
(b)around the site
inthe area
affected bythe
storage and ata
v.point outside
this area
Ground waters
Water filtered
through a0.45 ^um
membrane
Around the site
including ,where
necessary ,itsout­
flow points .*
Acidity 2 ;t
■ . ■
-Titrimetry
r(1>Cr ■■ 2 -Atomic absorption spectrophotometry i
-Molecular absorption spectrophotometry
îS0. .
4.
'2 '. . n
-Gravimetry . " '
'-Complexometric titration with EDTA I
-Molecular absorption spectrophotometry |
v«> 2! • I
! *
|-Atomic absorption spectrophotometry 'j
c(DFe
i2j-Atomic absorption spectrophotometry -j
!-Molecular absorption spectrophotometry J
! . i_ . –
Atomic absorption spectrophotometry «
_ ; ; i
Ca|2i
-Atomic absorption spectrophotometry • J
-Comple*ometric titration j
•Pb(1) j'
2.i .
-Atomic absorption spectrophotometry
-Polarography
i __n – j
ij-Atomic absorption spectrophotometry }
, ,
■ j 2 I~Atomic absorption spectrophotometry j~ I– ■... ... .t
i ~~2. '~j-Titrimetry (Mohrmethod ) |
Cu<1) J2 f-Atomic absorption spectrophotometry i
- I-Polarography I
Mn(1) 1 2 j Atomic absorption spectrophotometry I
I i,

ANNEX IV
page 2
COMPONENTS
** ' 'PARAMETERS "'
IMPERATIVE "|\'GUIDEMINIMUM ANNUAL
SAMPLING
,FREQUENCY-––– •– ;––-– , ;– ff
REFERENCE METHODOFANALYSIS - |
Environment ofthe- ■N. , – j.
]storage anddumpingIVisual V-. , ' 1 ■- Methods tobechosen byMember States |
Isite inspection I
ITopography andsite■ ■ =■-. :-v ! 'v- . : ;
Imanagement : : ■ ' \
]effect onsobsoil■ •- . ,' ■
. \ ~ . . • ' ' ,
Iandontheefcotogy j■-■■ ■ . -- . ;1! ' . \: :.
|ofthesite jI I-- - I
; : –– IM
(1)Also includes aquantitative analysis ofthe residue after filtration (suspended matter ),
<

RECEIVING MEDIUM:INJECTIONANNEXVr>jr
COMPONENTSl'■■1
PARAMETE
IMPERATIVE:RS
JGUI.DEMINIMUM ANNUAL
SAMPLING
FREQUENCY ^r
REFERENCEMETHODOFANALYSIS j
!SurfacewatersAcicJity Ji:!-:.:Ji
j-Tftrimetry " •.i
Waterfiltered
througha0.45yum
membrane
Aroundthesitein,
thezoneaffectedby
theinjection
Groundwaters
Waterfiltered .
througha0.45jjm
membrane ,
Underandaround .
thesiteincluding
outflowpoints
- Ir<1>Cr
I1-Atomicabsorptionspectrometry J
-Molecularabsorptionspectrophotometry j
.!■"j
i
1 I1
_J-Gravimetricanalysis. I
-Complexometric titrationwithEDTA f
[-Molecularabsorptionspectrophotometry j
jvnJ1"-Atomicabsorptionspectrophotometry |
- ii
_(1)Fe
f
l "i :
i1''. *
\-Atomicabsorptionspectrophotometry 5
!-Molecularabsorptionspectrophotometry »
:– i––"1 Zn(1)!"1 I– i
-Atomicabsorptionspectrophotometry j
Ca!
I*–f~
1 j-Atomicabsorptionspectrophotometry j
|-Complexometrictitration j
Pb(1)
! •'1
i-Atomicabsorptionspectrometry
-Polarography .
•« 1 I
''- '- ii-Atomicabsorptionspectrophotometry j
f"
.
L,-H
I
l !i-Atomicabsorptionspectrophotometry 1
i –– –-i
r
ia-^|-Titrimetry(Mohrmethod) j
|
I'
I'"•> •!Çu!– I ;:
jt «Atomicabsorptionspectrophotometry
|-Polarography '
»Mn|■■■' 1
i1IAtomicabsorptionspectrophotometry
I ––i
■i' ■1 '' /

L
/ . .s&
• ' ANNEX V
page 2
COMPONENTS jPARAMETERS {MINIMUM ANNUALr-kMn irm /»REFERENCE METHOD OFANALYSIS
IMPERATIVE
" !GUIDÇIO Ml'irL1IVU.FREQUENCY
Envi ronment
Topography\
Ground
stability ,
Permeabi lity A
Porosity
I' • •1 '
'1
IPhotographic and topographic survey
Puriping tests ^
Well-logging
(1)Also includes aquantitative analysis ofthe residue after filtration (suspended matter ).
\