CELEX: 51980PC0831
Language: en
Date: 1980-12-17
Title: Proposal for a COUNCIL DIRECTlVE on methods for the surveillance and monitoring of the environments affected by wastes from the titanium dioxide industry (Presented by the Commission to the Council)

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COM (80) 831
Vol. 1980/0262
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 ---pagebreak--- COMMISSION OF THE EUROPEAN COMMUNITIES
                                             COM(80)831 final
                                             Brussels , 17 December 1980
                                                  '''ô  v  V
                                     hl             N
                                     .            ^   ^
                                                           M
                                                          /^/
                            Proposal           -
                           COUNCIL DIRECTlVE
      on methods for the surveillance and monitoring of the
       environments affected by wastes from the titanium
                           dioxide industry
           ( Presented by the Commission to the Council )
C0M(80 ) 831 final
 ---pagebreak---  Introduction
In implementation of the Action Programme of the , European
Communities on the Environment of 20 December 1973 , the Council
adopted on 20 February 1978 ( 78 / 176 / EEC) the Directive on waste
from the titanium dioxide, industry , the aim of which is the pre­
vention and progressive reduction , with a view to its elimination ,
of pollution caused by waste from the titanium dioxide industry . •
                                                       .  /
              * .     ■                        -                     ,
The Directive stipulates the measures to be taken to achieve this
end, in particular-, the prior authorizations for waste discharge
issued by the competent authority of the Mpmber State in whose
territory the waste is produced and the drawing up of programmes
for the progressive reduction of pollution with a view to its
                                                 Ν
ultimate elimination .                                       .
Article 7 of the Directive also stipulates that the Commission will
within one year of notification of the Directive , submit to the
                                                  /
Council a proposal on the procedures for the surveillance and
monitoring of the environments affected by waste from this
industry .                                        '
Comments on the proposed Directive                  -
Pr^cedurj? ior_ ^r^fj^i_ng_tJhe_D_i_r_ec_t i_ve
The Commission has brought together a group of national experts
to assist it in drafting the technical part of the Directive .
This group , which has met three times , has advised the Commission
on the methods of surveillance and monitoring to be used and, in
particular , on the list of the relevant parameters to be measured
throughout the Community and on the minimum annual frequency of
sampling with respect to the different environments receiving
waste from the titanium dioxide industry .
 ---pagebreak--- Aims_crf th_e _D i_r e_ctJ_ve                          , - ■                 . .
This Directive will - on the basis of the parameters selected -
provide the means of identifying pollution levels in those parts
of the environment affected - from a physical / chemical , biological
and ecological! point cf view              by discharges of titanium dioxide -
waste , of understanding pollution trends and of assessing the pro­
gressive reduction of pollution caused by these wastes .
Comments on' titanium dioxide ;                                     '
P ijg/n e^nt^a_r y_p_r^o£e_r tj_e^       1
In its erystaline form , titanium dioxide is currently regarded as
having the highest refractory index of all the Conventional pig­
ments in both its allotrophic forms , i.e. anataae and rutile .                  As ■
a white pigment , it is incomparable and irreplaceable .
Ut i IjzjitTon
On account of its pigmentary properties this product has come
into widespread use in many areas , principal among which are
paints and varnishes , paper , plasties , rubber , floor coverings ,
ceramics , andi synthetic 'fibres .          The paint' and varnish, industry
accounts for more than half of the total consumption .
Ti^a£ij^_d_i_°x_id^e_m£njjf^c t_u_riing__pj^o_c e_s s^s_        ,     *  '
Manufacturing of titanium dioxide pigments consists in preparing
high purity titanium dioxide from an ore in which it is present .
                           ' . '                             -1   '    ,   •
already but mixed with other substances ..                          ^
There' is no industrial process for manufacturing titanium dioxide
by which titanium dioxide can be extracted' selectively .                The
only two existing industrial processes involve digestion of the
ore , followed by selective operations to, extract , the titanium compound
 ---pagebreak---                                        - 4 -
         In a final stage , the titanium dioxide is obtained from the
         intermediate compound .
         These two processes are known as the 'sulphate' and 'chloride'
         processes' respectively .         ' ,       >
         In the first process , the ore is opened up by sulphuric acid and
         then the titanium hydroxide is precipitated selectively . Finally ,
         the titanium oxide is obtained by calcination of the hydroxide .
         In the chloride process , the ore is chlorinated and the resultant
                                   V .       •     -   '
         titanium tetrachloride is first separated from the other chlorides
         mechanically and then distilled . Finally , the titanium oxide is
         obtained by oxidation of the titanium tetrachloride .
         In Europe , the sulphate process is the one most commonly used .
3.3.1 . _Su_lpj]_a_te process            *     *
         The ore used is either ilmenite or slag .
               /                .               .      •
        -     Ilmenite is a mineral complex of titanium and iron containing
             on average 55% Ti(>2 and approximately 30% iron;
        - slag is obtained from iron ore which contains some 70% Ti *^ ,
              10% iron as oxide plus metallic iron .
         The main stages involved in the separation of TiO^ from other
         compounds are to dissolve nearly all the ore and then to pre­
         cipitate the titanium selectively as hydroxide .   This hydroxide
         is then calcined to give the titanium oxide .
                                                          \
 ---pagebreak---                                           - 5 -
           The main waste products are :
                     (i)   residue from the ore digestion process .
                           This insoluble residue is composed of unattached ore
                           and insoluble silica ;
                   ( ii ) ferrous sulphate in the form of heptahydrate ( SO^Fe^TH^O) ,
                           commonly known as " copperas ", resulting from the
                           reduction and crysta lization of the solutions formed
                           from the ilmenite digestion stage .    This liquor is made
                           up of a complex salt of titanium - ferrous and ferric
                                    i I
                           sulphate ;
                                                                ν
                                                                  \
                 ( iii )   mother liquor produced from the separation of titanium
                           gel  after hydrolysis by filtration and / or decantation .
                           This liquor is made up of a solution of ferrous sulphate
                           in sulphuric acid .  It also contains the sulphates of
                           the metals present in trace amounts in the raw
                           material ;
                   ( iv)   various gel wash waters and waters from the scrubbing
                         . of the calcination gases .   They contain dilute sul­
                           phuric acid, traces of the salts of iron , titanium ancf
                           other metals present in the ore .
3 .3 . 2 . _Ch 1 0£ide_p£0_ces_s
            The standard ore used in the chloride process is natural, rutile ,
            a scarce ore very rich in TiOg (approximately 96%), or alteran-
            tively concentrates generally obtained from ilmenite or synthetic
            rutile .                                ■    ,
                                                           ,                          1
            The process consists in obtaining titanium tetrachloride from
            the high-temperature chlorination of a rutile and carbon mixture .
            After condensation , purification and oxidation of the titanium
                              i
 ---pagebreak---                              - 6 -
 tetrachloride , the titanium dioxide is obtained ; the regenerated
 chlorine is recycled .          .
 This process generates only small amounts of waste but is little
 used in Europe.'  But although this process uses concentrates of
 ilmenite , it does involve an iron removal stage .        This pre­
 treatment leads to the same problems as those associated with
 waste from the sulphate .process .
_Compos2tion of the wastes from the titanium dioxide jmJujstry
 In the sulphate process , the main wastes from the industry are :
 insoluble substances , copperas , mother liquors or strong acids ,
wash waters or weak acids .                                    " >
                     i               r
 In the chloride process , the main process wastes are the chlorides
of manganese , magnesium , calcium , sodium , aluminium , chromium ,
 iron , vanadium, ZrO_, titanium dioxide, TiCt ^ and chlorine .
                                       I -
The detailed composition of titanium dioxide manufacturing wastes
varies according to the ores used, the manufacturing processes and
the way in which the solid, liquid and gaseous wastes are treated
at each stage of the process .
Liquid wastes
Generally , these wastes have the /following features :
-   high acidity ;                                                   .
                           »                             '
-   a high iron content , mainly in the form of iron sulphate .
    ( 0.8 to 14%);     , :   .
-   suspended solids ( oxides of Ti , Si , Fe , Al , Ca , Zr );
 ---pagebreak--- -    dissolved metals , normally in the following concentrations
     ( in mg / l ):
     Mn : 400 to 1400 ; Cr : 4 to 225 ; Zb : 1 to 125 ; V : 75 to 110 ;
     Ni : 4 to 50; Cu : 0.1 to 10; Pb : 3 to 6 ; As : 0.04 to 4 ;
     Cd : <£0.1 ; Hg : <£0.005 .
Solid wastes
                                                                       /
These are made up of copperas , arising from the processing of
raw materials in the sulphate process and by the neutralized
residues of ore or slag . Copperas contains^ some 90% of iron
sulphate present as FeSO^, 7(^0); the remaining fraction is
made up of titanium dioxide , magnesium sulphate , free sulphuric
acid and water of crystallization .          The neutralised residues
from the sulphate process contain ore or slag which is
insoluble at 200°C in 90% sulphuric acid together with filter
aids ; the waste products from the chloride process comprise
unattacked ores , coke and metal hydroxides .x            '   .
Gaseous waste
Principal among these are SO^ and S0^ which are formed from the
residual sulphuric acid ( 100-120 kg per tonne TiO^) and the
sulphur contained in the fuel used to initiate combustion when
the hydrated titanium oxide is calcined .          Depending on the con­
ditions in which calcination takes place , the ratio of SO^: SO^
 ( calculated as             ranges " from 1:1.92 to 1:2.80 . The amount
of gaseous waste produced in the manufacture of one tonne of
titanium dioxide ranges from 12 to 22.4 kg SOg and 53.6 to
60.2 kg SO,.
 ---pagebreak--- 4.       Principal 'methods of waste disposal used by the titanium
         dioxide industry                 '                             -
         The effects' on biotopes due to the various properties of the
         wastes are closely linked to the nature of the receiving medium .
         Sea waters are most frequently used for this , but in certain
         special circumstances the wastes may be discharged in fresh
         water , stored on land or injected underground into deep strata .
                                                                      /
4.1 .   _Dij^cha_rc^es_at_ _sea_
         The two principal methods of disposal are :
                                      ►                         :   '
               (i)    by^ pipeline from the coast                 •
                                 '1                            •,
              <ii>    discharge at sea from special ships
  • '                   1           "X
         The first method normally requires prior . di lution of the effluent
      ^ and a discharge point which favours rapid dispersal of the
         effluent .    The acidic solutions are neutralized by dilution and
        by the buffer effect .
        The second method, namely discharge at sea , necessitates the use
        of specially-equipped tanker ships which enable the acid effluent
        to be discharged directly into the ship 's wake , thus providing
         rapid dilution and conveyance of the effluent to greater depths .
        This method is used for soluble wastes ( ferrous sulphate and
        acid solutions ).                                                     J
         When titanium dioxide waste is discharged from a ship , the
        predominant short-term chemical impact is caused by the
         reduction in pH .       According to the guidelines laid down by the
         Oslo Convention on discharges of titanium dioxide waste, the pH
        of the receiving waters must reach 6 within a maximum of 5
        minutes after discharge .                                     /
 ---pagebreak--- Since the pH of wastes varies according to their source and that
different types of ship may be used ( differences in size and
speed) , the following measurements should be taken before the
permitted level of discharge is decided :
         (i)      the pH at different dilutions of the receiving water
                  should bfe calculated in such a way as to produce a pH /
                  di lut ion curve ;
                                                      I
                                              ■   ' .    -  - > ■
       ( ii )     on the basis of this curve , if a pH of 6 or more must
                  be reached within 5 minutes - the requisite dilution
            ; \                          '              ■ r
               ' can be calculated;
     ( iii )     -the. rate of discharge can be worked out depending on
                  the required dilution on the basis of experimental work
                  carried out on the ship itself' ( using tracers ) or by
                  calculation (using general formulae for the minimum
                  dilution in the ship 's wake ).
                             »                  •
Another possibility is direct measurement of the pH of the waste
                                            \
dissolved in the ship 's wake during the discharge operation .
these conditions also presuppose that- the di lution engendered by
the propel ler , wake will be adequate to reduce the density
difference between the sea water /waste mixture and the receiving
water to a sufficiently low level to prevent the formation of
dense layers which would impede the subsequent mixing process .
 D i_sch_a_rge _int o_s r_f a_çejw at erj>
 This method of disposal: is used for acid solutions once they have
 been neutralized . The neutralization products- are disposed of
 with the ferrous sulphates ..
 ---pagebreak---                                                     - 10 -
  4.3 *   Storage on land
         This type of storage on " tips                       is used by small capacity
         titanium dioxide plants and is most frequently used for the small
          fraction of insoluble waste materials ( i.e." those which cannot
                                                        •                                               v
         be dissolved by sulphuric acid when the ore is opened up ).
          Furthermore , the acid effluent from this industry can be
         neutralized by calcium carbonate and slaked lime ( CaCOH^) and then'
         stored on land .         The same is true for the ferrous sulphates .
                  I                    '■                   1               !                       '
                     . '      ' '           - , ' ' '                             ,   •   I
4.4 .   _Injectioj2 int_o underground strata
         With this disposal method, the previously neutralized acid
         solutions are pumped into subterranean strata .
                                   ■ .    '                                   ι
                                            y  -                          '     •         . . - *
4.5 .    Re_cy_ct_i_n£ £f_tjie_wj3s^e_p£odu£t_s
         In some production plants the dilute sulphuric acid solutions
         are recovered, reconcentrated and used again . . In others , varying
                           "•                         .                             *                 ,
         amounts of copperas ( ferrous sulphates ) are roasted and converted
         to sulphuric acid by the addition* of sulphur .
        y
         Other potential outlets for these products have been contemplated.
                                                          '
         for example : iron oxi^e pigments , flux for the cement industry ,
         weed killer and in water treatment for the production of
         drinking water .         But only small quantities of copperais are
'        involved in these applications ,                             )                 -         ~
 5.      Methods of surveillance and monitoring of the environments affected
         The methods for the survei I lan.ce and monitoring of the environ­
         ments receiving TiO., wastes discharged at sea or into fresh water , ,
         stored or dumped on land or injected into underground strata are
         based on the provisions of Annex II B of the Directive on waste
 ---pagebreak--- from the titanium dioxide industry , adopted by the Council on
20 February 1978 ( 78 / 176 / EEC) .
Where the waste is discharged into fresh water or dumped /
immersed at sea,, the following .three .components shall be
monitored :      the water column,, living .organisms and the sediment .
Periodic .checks on the state of the area affected by the dis­
charges will mak« it possible to monitor changes in the environ­
ments affected .
                                                 ' '                   v
               A   .
Monitoring of the io,I lowing parameters shall be compulsory :
 (a )  In the water column
       –   pH,, the sa linity of sea .water , dissolved oxygen , turbidity
           hydra ted iron oxides and hydroxides in suspension ,
           concentration of dissolved salts , toxic metals ;
 .Ob ) In suspended solids and in sediment
       –   hydrated iron oxides and hydroxides and toxic metals ;
  Cc ) In living organisms (having due regard to the species typical
       of the discharge zone)
       –   the levels of iron, titanium , chromium, cadmium , mercury ,
           vanadium., nickel., copper, ^zinc and lead;
  ( d)  Flora and fauna
        Diversity and relative abundance .
 ---pagebreak---   Monitoring of the following parameters shall be optional :
                                       s
  -  the level of chromium , vanadium , zinc , lead, nickel ,
     copper , manganese in the water column and sediment and the
     amounts of suspended solids .
  In the case of storage , tipping or injection , the monitoring shall
. include :
  - tests to' ensure that surface waters and ground waters have
     not been contaminated .  These tests relate to a control of
     acidity , the levels of iron ( dissolved and in suspension ),
     calcium, chlorides, titanium and sulphates ancj to the
     environment of the storage sites , i.e. the permeability ,
     porosity , structure and stability of the soil ,!i and to a
                                                      i '
     general ecological assessment of the area surrounding the
     tipping, storage or injection point .
  Sampling
  The greatest attention should be paid to the taking of samples
  which should be regarded as a preliminary phase in the analysis
  process .
  The methods of sampling should be such as to ensure that the con­
  ditions in which the measurements are taken can be reproduced and
  that the methods are representative of the conditions prevailing
  in the surrounding environment . Article 4(4) of this proposal for
  a directive lays down the generaJL rules to be observed for sampling .
 ---pagebreak--- Minimum annual frequency for sampling and for the analysis
of parameters ,
                      /            "           '              ,
The frequency of sampling and analysis is the minimum number of
sampling operations and analyses to be carried out each year in
respect of the various parameters described in the foregoing
chapter and depending on the different environments affected by
the discharge of waste from the titanium dioxide' industry .
                          .               ' Λ
The samples should be taken having due regard to local environ­
mental and discharge conditions , i.e * whether the discharges
are intermittent or continuous , the exact Site of the sample
taking and its distance from the discharge point should be speci­
fied in each case by the competent authority in each Member State .
Where the results of measurements taken on samples from the dis­
charge zone are consistent or show a significant improvement in
environmental quality over the previous year , the frequency of
sampling and analysis may , with the prior agreement of the
Commission , be reduced by the Member State concerned .
Accordingly , the Member States should communicate to the -
 Commission the results of these measurements and state the
 frequency they propose to adopt .
 Preservation and transport of samples '
 As stated in Article 5 , the type of container used for sampling
 and packaging should not influence the analytical results .
 The volume of such sampling bottles should be such as to enable
 the specified measurements to be carried out in optimum conditions
 of reproducibility . Since the characteristics of the sample wafer
 may alter quite rapidly under the action of the various organisms
 it contains , such changes as may occur between the moment of
 sampling and analysis should be kept to a strict minimum by carry­
 ing out the analyses as rapidly as possible .
 ---pagebreak---                          - 14-
Many investigations have been made with a view to recommending
methods by which water samples can be stored without their compo­
sition being affected .  But it is impossible to lay down any hard
and fast rules which would cover every case and every situation
and to which there would be no exceptions .   The samples needed to
measure the parameters should be transported to the laboratory
for examination at the earliest opportunity .   If immediate
analysis is not possible , the samples should be kept under con­
ditions where the containers are protected from any outside
contamination and no change in the state of their contents is
possible .
Methods of measurement
The reference methods of measurement for each parameter selected
for the surveillance and monitoring of the environments affected'
are shown in the Annexes to this proposal .
Laboratories in the Member States using other methods must ensure
that the results obtained are equivalent or comparable to those
given in the Annexes .
The result obtained from the samples and methods of measurement
must be representative of the true average quality of the water
analysed .  The various operations needed to achieve this result
may lead to errors ; it is vital that, such errors be detected
and then eliminated or reduced .
The Annexes to this proposal for a Directive lay down the con­
ditions in which the measurements of certain parameters must be
carried out in view of the risk that their value may change
during the transport or protracted storage of the water samples in
containers . This is the case with temperature and pH .
 ---pagebreak---                                     - 15 -
10 . Action at international and Community level
     In the campaign against freshwater and sea water pollution ,
     the Community is a Contracting Party to international conventions
     aimed at reducing and eventually eliminating this type of pollu­
     tion .   The conventions are :
     -    The Convention for the Prevention of Marine Pollution from
          Land-based Sources ( Paris Convention ) ( 75 / 437 / EEC) ;
     ^    Convention for the Protection of the Mediterranean Sea
          against Pollution ( Barcelona Convention );
                                                           ' i
     -    Protocol for the Prevention of Pollution of the Mediterranean Sea
          by Dumping from Ships and Aircraft (77 / 585 / EEC);
     -    Convention on the Protection of the Rhine against Chemical
        , Pollution ( 77 / 585 / EEC).
      On 17 May 1980., the Community also signed the Protocol on the
      protection of the Mediterranean Sea against pollution from Land-
      based sources .
                                                                   /
      Specific articles of these Conventions either ban the dumping or'
      discharge of certain substances such as acid compounds whose
                              t
      composition and auqntity are such that they may adversely affect
      the quality of sea water or make the dumping or discharge of
                                            ι
      specific substances , such as titanium , chromium and acid com­
      pounds subject to the prior granting of a specific permit or to
      appropriate programmes and measurements to reduce pollution .
 ---pagebreak--- The Community participates as an observer in the Convention for the
Prevention of Marine Pollution by Dumping from Ships and Aircraft ,
signed in Oslo on 15 February 1972 .        The Community is closely    ♦
following the work being done under the auspices of the Standing
Advisory Committee to the Scientific Councils of the Oslo             1
Convention and the Joint Working Party on monitoring and continuous
surveillance under the Oslo and Paris Conventions ; this work concerns
the monitoring and continuous surveillance of the sea areas into ,
which titanium dioxide wastes are discharged .
In January 1976 , moreover / the Commission put forward a proposal
for a Council Directive on the dumping of wastes at sea ( OJ C 40 ,
20 February 1976 ) which contains a brief review of the legal
situation regarding this method of dumping at sea .                \
    ■ "■ .  ...    -    t                ..    ■ ■ ■ ,           –
Finally , a Directive on pollution caused by certain dangerous
substances discharged into the aquatic environment of- the
Community ( 76 / 464 / EEC) stipulates that pr'ior authorization must
be obtained for any discharge into waters likely to contain one
of the substances specified in Annex II , such as titanium , zinc ,
vanadium , chromium etc .
Consultation of the European Parliament and the Economic and
Social Committee
                                                             \
Since this proposal for a Directive 1 is based on Article 7 of
Directive 78 / 176 / EEC , consultation of the European Parliament
and of the Economic and Social Cbmmittee is obligatory , as
stipulated in paragraph 3 of . this Article .                  ■
 ---pagebreak--- THE COUNCIL OF THE EUROPEAN COMMUNITIES
Having regard to the Treaty establishing the European Economic
Community , and in particular Articles 100 and 235 thereof ,*.
                                                              4
Having regard to Council Directive 78 / 176 / EEC of 20 February 1978
                                               1
on waste froc the titanium dioxide industry , and in particular
Article 7(3 ) thereof,
                     ' 1  -
Having regard to the proposal from the Commission ,
Having regard to the opinion of the European Parliament ,
Having regard to the opinion of the Economic and Social Committee ,
Whereas , irrespective of t-he method and extent of the treatment of
wastes from the titanium dioxide industry , the discharge ,             ^
dumping at sea , storage , tipping or injection into the ground of
                                                                  f
such wastes must be accompanied, in particular , by measures to
monitor the environment affected from a physical , chemical , biolo­
gical and ecological point of view ;
Whereas , in-order to monitor the quality required of the environ­
ments affected a regular minimum number of samples should be taken
annually so that the parameters specified in the Annexes may be
measured ; whereas the number of these sampling operations could be '
 reduced in the light of the results obtained ; whereas to ensure
                                                 »
that the monitoring is effective , samples should also be taken in
a zone deemed to be unaffected by the discharges in question ;
 Whereas in connection with the analyses carried out by the Member '
 States , common reference methods of measurement should be fixed for
 determining the parametric values which define the physical , chemical
 biological and ecological characteristics of the environments
 affected ;
 ^ JO L 54, 25 February 1978                                    .     1
 ---pagebreak---                                    - 18 -
                                                      ■
   Whereas , for the purposes of surveillance / Member States are at
   all times free to measure parameters other than those prescribed
   by this Directive ;                                      "
                             ' ■                          *
   Whereas the Member States should communicate to the Commission .
   details of the methods of surveillance and monitoring of the
, environments affected ; whereas it is appropriate that the Commission
   should draw up a consolidated report to be sent to the Member States ;
   Whereas certain natural circumstances are outside the control of
   Member States and that , accordingly , provision must be made for
   derogation , in certain cases , from this Directive ;
                      I                             ■   '     '
   Whereas technical and scientific progress may require the rapid
   adjustment of specific provisions contained in the Annex ; whereas
   to facilitate implementation of the requisite measures , a procedure
   should be laid down to establish close cooperation between the
   Member States and the Commission through a Committee on adapta­
   tion to scientific and technical progress ;
   HAS ADOPTED THIS DIRECTIVE
                                 Article One
   This Directive lays down - pursuant to Article 7(3 ) of Directive
   78 / 176 / EEC - the methods , for the surveillance and monitoring of the
   environments affected from a physical , chemical , biological and
                                         \ 1 -,
   ecological point of view , by the discharges of wastes from the
   titanium dioxide industry .
                                  Article 2       .
 "                       t '                    '
   For the purpose of this Directive :
   (a)     'environment affected' means surface water , ground water ,
 ---pagebreak---                                                     - 19 *
                       the sea ,. the land surface and underground strata and the air
                       into or on which wastes from the- titanium dioxide industry
                       are discharged or stored;
                Cb)    'sampling point * means the point at which the sample is
 '. ,   '            • taken ;        '                               ,
                Cc )    'reference method of measurement * means a measurement prin­
                       ciple or the concise description of a method for determining
                       the parameters specified in the Annexes to this Directive .
  ■           \            '                      Article 3             »
    1.          The relevant parameters for the surveillance and monitoring of the
            . environments referred to in Article Tare shown jn Annexes 1 to 5 ,
                subdivided according to the receiving medium .                   '
■ 2.            Where a parameter appears in the 'mandatory * column of the Annexes ,
       ' sampling and analysis must be carried out in respect of the
                ■/                          ■ Λ '        -       · ·.
                environmental components stated .                                            '
                         .        ■                 ■< ■    -I   ,
    3.          Where a parameter appears in the 'guide' column pf the Annexes , the
                Member States shall endeavour to perform the sampling and analysis
                                        * ,
                operations for the environmental components shown .                ' '
                                                                              <■       f
                                                  Article 4        ,      '                ■-
- 1.            The competent authorities in the Member States shall determine the
                 frequency of sampling and analysis for each parameter in respect
                of a given zone in which discharge ," tipping , dumping , storage ,
                 deposition or underground injection takes place ..
          /                               »       •                         '
    2.           The frequency of sampling and analysis may not be less than the
                 minimum frequencies shown in the Annexes to this Directive .        The •
                 sampling periods must , as far as possible , be spread over the year
                  in such a way as to obtain a representative picture of the quality
                 of the environments affected ..               .
 ---pagebreak---                           - 20 -
The competent authority in each Member. State shall determine -
on a case by case basis - the exact site at which samples are to
be taken / the distance of this site from the nearest pollutant
discharge point and the depth or height at which the samples, must
be taken . A general description must be given of the sampling
point which will include its permanent features , capable of being
codified, and other administrative or geographical information .
The description shall be made only once when the typical sampling
point iS designated ,               V.
The sampling must be carried out in the zone directly affected by
                                                  i
the discharges , special account being taken of local environmental ,
                               •           .      $              -
factors and the manner of discharge, i.e. whethej? intermittent or-
continuous .
In the cas£ of tidal waters , the samples must be taken at the
same depth and under the same conditions , i.e. the same time in
relation to high tide, tidal coefficient etc .
Where the competent authority finds that the resutts of measure­
ments on the samples / taken in a discharge zone during the previous
year are both constant and significant and show that the quality
of the environments affected has been detected, the frequency of
sampling and analysis may - with the Commission 's agreement - be
reduced by the Member State concerned;
To this end, the Member States shall   communicate to the Commission
the results of such measurements and   notify it of the frequency
they intend to adopt ; the Commission  may make its agreement subject
to certain conditions , in particular  the duration of the reduction
in frequency . In the likelihood of any deterioration in the quality
of the envi ronments' affected, the Member States shall take the
requisite measures .
                                                    •• /■•
 ---pagebreak---                          Article 5
The reference methods of measurement to be used to determine the
relevant parametric values are specified in the Annexes .
Laboratories using other methods must eqsure that the results
obtained are equivalent or comparable .
The containers used to carry the samples , the agents or methods
used to preserve a part sample with a view to analysis of one or
more parameters , the transport and storage of samples and their
preparation for. analysis must be such that they do not signifi - ~
cant ly- affect the analytical' results .
                         Article 6
                                     • ·            ·  <
In order toassess the state of progress in the surveillance and     \
monitoring of the various environments affected from a physical ,
chemical , biological and ecological point of view, the competent
authorities in the Member States shall ensure that samples are
taken and analyses performed in respect of each environmental
component specified in the Annexes to this Directive in a zone    '
deemed to be unaffected by the discharges under surveillance.'
                      '  Article 7
Member States may , at any time , measure parameters other than those
 laid down by- this Directive relevant to the surveillance and
monitoring of the environments affected .
                         Article 8
 The following information shall be given by the Member States in
 the report they are Required to submit to the Commission pursuant
 to Article 14 of Directive 78 / 176 / EEC :
 ---pagebreak---                     *           - 22 -
                           • 'i                                 »
      (a ) details of the methods of surveillance and monitoring
           carried out by the bodies appointed in accordance with
           Article 7(2 ) of Directive 78 / 176 / EEC;
      (b ) the details referred to in point ( a ) above shall , in respect
           of each environment affected by the discharges , include the
           following information :
           -   the results of the measurements of the parameters listed
               in the " mandatory " and " guide" columns provided that the
               latter parameters are measured;
 ι.                                       ·
           -   the methods of measurement and analysis with their limit
               of detection , accuracy and precision ;
           -   the descriptions of the sampling point ;
           -   a description of the sampling methods used .
                                            I
2.    In implementation of this Article , the first set of data to be
     communicated is that gathered during the third year following
     notification of this Directive .
3.   The Commission shall , with the prior agreement of the Member
      State concerned , publish a summary of the information thus
     obtained .
A.   The Commission wi 1 1 assess the effectiveness of the environmental
      surveillance and monitoring procedure and will - no later than
      six years after notification of this Directive- place before the
      Council , where appropriate , proposals to improve this procedure
      and, if necessary , to harmonize the methods of measurement
    " including the limit of detection , accuracy and precision and the
      sampling methods .
 ---pagebreak---                           Article 9
Member States may derogate from this Directive in the event of
flooding or natural disaster or on account of exceptional weather
conditions..                                                        '
                          Article 10              ■ *
The requisite amendments to adapt the methods of analysis and
the G S I parameters shown in the Annexes to scientific and
technical progress shall be adopted in accordance with the pro- .
cedure laid down in Article 12 .       '
                          Article 11
                           ' /           •     -,             '   '   ^
A Committee on adaptation to technical progress ( hereinafter
referred to as the " Committee") consisting of representatives
                                                          ■
of the Member States and chaired by a Commission representative , is
is hereby set up .    .
The Committee shall draw up its rules of procedure .
                          Article 12
 Where the procedure laid down in this Article is to be followed,         .
matters sha.ll be referred to the Committee by its Chai rman , either
on his own initiative or at the request of the representative of
the Member States .     ' *■                               :    ■
The Commission representative shall submit to the Committee a
 draft of the measures to be adopted .     The Committee shall deliver
 its opinion on the drAft within a time-limit set by the Chairman
 in the light of the urgency of the matter .          It shall act by a
 majority of 41 votes , the votes of the Member States being weighted
 as provided for in Article 148(2 ) of the Treaty .          The Chairman
 shall not vote .
 ---pagebreak---  (a ) The Commission shall adopt the proposed measures where they ;
      are in accordance with the opinion of the Committee .
( b)  Where the proposed measures are at variance with the opinion
      of the Committee / or if no opinion is adopted, the Commission
      shall , without delay , submit a proposal to the Council
      concerning the measures to be taken .           The Council shall act
      by qualified majority ;
(c )  If/ within three months of the proposals being submitted to
      it / the Council , has not acted, the proposed measures shall
      be adopted by the Commission .
                            Article 13
           , ,• / •   '   .      '•           ' • ' %   v        '         ' ■
Directive 78 / 176 / EEC is hereby amended as follows :
(a)   In Article 7(1 ) the words "and of the environment concerned
      having regard to its physical , chemical , biological and
      ecological aspects " shall be deleted .
< b)  Article 8 , paragraph 1 point C is amended as follows :
      " If the results of the monitoring provided for in Article 1
      of Directive                  EEC concerning the methods of
      surveillance and monitoring of environments affected " show
      a deterioration in the specific environment iaffected in the
      area concerned, or
(c)   Annex 11(B) is deleted .
                            Article 14
The Member States shall bring into 1 force the laws ; regulations
and administrative provisions necessary to comply with this
 ---pagebreak--- Directive before 1 January 1983 .   They shall forthwith inform
the Commission thereof .
The Member States shall communicate to the Commission the texts
of the main provisions of national law which they adopt in the
field covered by this Directive .
                                                     i
                         Article 15
This Directive is addressed to the Member States .
 ---pagebreak---                                                                                                                                      ANNEX I
        R ECEIVING MEDIUM : AIR
                             |              ~             PARAMETERS            j
                                                                                                  1
                                                                                   MINIMUM ANNUAL j           REFERENCE METHOD OF ANALYSIS
                                                                                         SAMPLING J
               COMPONENTS    j                                jf                j       FREQUENCY I
                             !     IMPERATIVE                 I       GUIDE   - I
  I ■ I  ■                            I I ■ I ■ Éi. I I   I 1 -  ■              „■
                                    «                               '     ' ^   i
                                                                                      .   12        In the prevailing wind in the zone directly
\       Air*                      SO2                                                               affected by the discharge .
                                                                                                    In accordance with those given in Annex II
                                                                                                    of the Directive of 15 July 1980 on air
                   '                                    \                                           quality limit values and guide values for
                                                                                                    sulphur dioxide and suspended particulates .
                                                                                                    ( O.J. L 229 of 30 August 1980 , pages 30-48)
                                                                                                          ( 80 / 779 / CEE ) -    '
             Ν               II                               ■
                                I
 ---pagebreak---     RECEIVING MEDIUM - SEA WATER ( estuarine , coastal , open sea )
       COMPONENTS
                                          |                PARAMETERS                       J MINIMUM ANfyMAL                         –––
                                                                                                                                       ■ '
                                                                                                                                               ■ –                          <
                                                                                                                                                                           ''
                                                                   ■             :          j     SAnPLIMG
                                          | IMPERATIVE               .
                                                                            GUIDE           f
                                                                                            j
                                                                                            I
                                                                                                 FREQUENCY
                                                                                                                                   . REFERENCE METHOD OF ANALYSIS
                                                                                                                                            .
                                                                                                                                                                          i
                                                                                                                                                                           S
                                                                                                                                                                           »
 t
    Water column
    Non-filtered water
    or
                                         i
                                                 %
                                              Temperature
                                        j Salinity
                                                                                           1L <4                  I
                                                                                                                     Thermometry
                                                                                                                  I Conduct imetry
                                                                                                                                           _____
                                                                                                                                                                         |
                                                                                                                                                                          |
 | -Water filtered
 j
 {
    through 0.45 urn
   membrane
                                       ! pH
                                       i                         L                                 • ■ l            Electrometry . Measurement is to be carried out
                                                                                                                    on the spot at the time of sampling .
                                                                                                                                                                         |
                                                                                                                                                                         J
I                                           Dissolved 0^                                                            - Winkler method
                                                                                                                                                                         It
                                                                                                                                                                         4
r
i                                           ■      –■  - .     -j!.                    !       ■              ·     - Electrochemical method                          - i
                                      I                                                  I                       j                                                       j
                                       i    Turbidity                                              4     .
                                            or suspended                               I
                                                                                                                    Turbidimetry                                         |
                                            matter
                                                                                                                    - Weighing after filtration through 0.45 urn        |
                                       j;                ,                            I
                                                                                      I
                                                                                      I
                                                                                                                     . filter and drying at 105°C
                                                                                                                    - Weighing after centrifugation (minimum time       !
                                                                                                                                                                         J
                                                                                      I
                                                                                                                       5 minutes , and average accerlerat ion           f
                                                                 i       :          71                         i
                                                                                                                       2,800 and 3,200 g)                                j
                                            Fe                  I■■
I
I
I
                                                                                     l?
                                                                                                   «          It    Atomic absorption spectrophotometry
                                                                                                                    Molecular absorption spectrophotometry
                                                                                                                                                                        |<
                                            11                 ! Mn, Ni , V, Zn, j
                                    «                                                1                                                                                   j
                                                                                                                    Atomic absorption spectrophotometry       ,          3
                                                                                     5
                                                                                                                                                                - .     i
                                                               !
                 -
                                    *
                                    I                          I Cu, Pb              !           -4   .
                                                                                                              j Atomic absorption spectrophotometry polarography
                                                                                                              r
                                                                                                                                                                         I
   Suspended solids
                                                                                                              i wet
                                                                                                              3
                                                                                                                    After appropriate preparation of the sample ,
                                                                                                                         or dry mineralisation , and purification
                                            Fe                             Cr                      4                Atomic absorption spectrophotometry             , j
           H  ■ II Tl ^ ■ 1 1 M | | ^                                  .           _J                               Molecular absorption spectrophotometry              j
 ---pagebreak---                                                                             k
                                                                                                                                                              n
                                                                                                                                                     ANNEX II
                                                                                                                                                     page 2
                                                                                      1
                                         PARAMETERS                           MINIMUM ANNUAL
         COMPONENTS                                                               SAMPLING                                REFERENCE METHOD OF ANALYSIS           j
                           | IMPERATIVE                GUIDE _
                                                                               •
                                                                                 FREQUENCY
                                  «
                                                                                                                                                                 (
                              Ti
                                                      Mn> Ni, V, Zn j               A                    Atomic absorption spectrophotometry                     |
                           I                     j Cu, Pb
                                                 I
                                                                           j .4                       f
                                                                                                         Atomic absorption spectrophotometry
                                                                                                         polarography
                                                                                                                 -                      ,
                                                                                                                                                      (>
                                                                                                                                                                 |
                                                                                                                                                                 E
                              Hydrated oxides                                       4
                              hydroxides of
                                                 I                                                       Extraction of the sample under dilute acid              g
                                                    *                                                   conditions ( HCl ; CH^COOH; HNO3 ; HCl O^ / HNO.,),      ;
                              iron                                                                      measurement by atomic absorption spectrophotometry. '
                                                                       I
                                                                                                        The determination of iron by molecular absorption        {
                                                                                                        spectrophotometry can be made without inter -            £
                                                                                                         ference if the extraction is made using CH,COOH .       S
                                                                                                        The same method of acid extraction must be used          J
                                                                         I              - ' "           for alt samples coming from the same site              • |
    Sediments                                                                                         i                                                     ■
                                                                                                      i               ,
    In the top layer of       Fe, Ti               Cr , V, Zn , Pb ,                1                 i  Identical methods to those for measurements in tht
    sediment ( 0-1 cm .)                           Ni , Cu , Mn                                         water column .
                                             y
                                                                                                        After appropriate preparation of the sample ( wet
                                                                                                        or dry mineralisation and purification )
                                    J, -
                                                                                                        -   The cfuantities of metals may be measured for
                                                                                                            a specific range of particle sizes
                                                                                                        -   The quantities of metals are to be expressed
                                                                 ; i                                        in mg / kg of dry matter
                                                            ;     _J
                                               •          ,          ■         ....           , – < ^
                             Hydrated oxides J                       J             1                \ Identical methods to those for measurements in             }
                             hydroxides of     {                     j                              j   the water column                                          !
I
i
  •    '            '
                         .
                             iron              t                     I                              I
 ---pagebreak---                                                                                                                                            In
                                                                                                                                  ANNEX II
                                                                                                                                  page 3
                                            PARAMETERS             MINIMUM ANNUAL
       COMPONENTS                                                     SAMPLING                       REFERENCE METHOD OF ANALYSIS
                               IMPERATIVE                          , FREQUENCY
                                                       GUIDE .
Living organisms
 Species representa - j       Cr , Cd, V,' Hg ,                                   Atomic absorption spectrophotometry . after
 tive of the site :       j   Fe , Ti , Zn , Pb ,                                 appropriate preparation of the composite sample         -
molluscs , crusta -       I  Ni ,. Cu                                             of ground flesh ( wet or dry "mineralisation and
 ceans   apd TI
    JUS apa  fish  and at|
                sn ana  aq                                                        pur i f icat ion )
 least
    ist two inverte- ]
brdtes    including,, if I
    ites including                                                                    For fish , the metals must be measured in
possible-,        benthic
    ssible, one bent   hie -                                                         muscle . The sample should consist of at least
organism ( 1 )                                                                        10 specimens .
                                                                                  -  The quantities of metal 's are to be expressed
                                                                                     in mg / kg of wet matter
                                                                                  For the molluscs and crustaceans , the metals must
                                                                                  be measured in the flesh . The sample should
                                                                                  consist of at least 50 specimens .         ~
                                                                                     The quantities of metals are to be expressed
                                                                                     in mg / kg of wet matter .
Benthic flora and            Diversity and                                        Qualitative and quantitative classification
fauna , fish                 relative                                             indicating the liste of species , the specimen
                             abundance                                            count per species , the specimen count , density
                                                                                  dominance , and in the case of fish ,, the per­
                                                                                  centage showing morbid anatomical symptoms . .
 C ) Species representative of the discharge site : such as mytilus edulis , crangon crangon , flounder , plaice, cod, mackerel ,
        red mullet , herring, sole ( or another appropriate benthic species ).
 ---pagebreak---                                                                                                                                                                                    10
                                                                                                                                                         , ANNEX III
       RECEIVING MEDIUM : FRESH WATER
                                                  PARAMETERS                            MINIMUM ANNUAL
                                                                                                            J
                                                                                                               r_                                  """                                !
1          COMPONENTS
                                                                                            SAMPLING . I                            REFERENCE METHOD OF ANALYSIS                         i
                                  - IMPERATIVE           j|        GUIDE                    FREQUENCY       |
                                                         !                                                 J
       Mater column                                                                                                        ■      ,                                     -                t
     . depth
       Samplesof taken  at a J
                   0.50 m
                                                                         ~ ' •    i
                                                                                                               !                  "           .                                       N- L
       below the surface at      . pH "                                                       4                !   Electrometry .     Measurement is to be carried out                   t
       the same time of the                      1
                                                                                                               j on the spot at the time of sampling .                                    |
 I year                     - j     Dissolved 0oc
                                                        i
                                                        |i
                                                                                              4    . - ' '     | - Winkler method
                                                                                                                   - Electrochemical method
                                                                                                                                                                -                         H
 P     On non-f i Itered      '                                                                                                                                     " '    '
                                                                                                                                                                             •
                                                                                                                                                                               "
                                                                                                                                                                                          \x /
                                                                                                                                                                                          »*
       water or water
       filtered through a          Turbidity or                                               4                     Turbidimetry ' '                         ,                 ■          j
       0.45       membrane          suspended
                                   matter                                                                           - Weighing after filtration through 0.45 urn                           |
                                                                                                                       filter and drying at 105°C                                          {
                                                                                                                    - Weighing after centri fugat ion- (minimum time                       ]
                                                                                                                       5 minutes , and average acceleration                                 i
                                                             - -
                                                                                                                       2,800 and 3,200 g) and drying at 105°C . 1                          j
                                                           h-        :         –
 I
  I
            ■                       Dissolved
                                    salts     -
                                                       j
                                                                                   i
                                                                                     -■       4 - - !I Electrometric measurement of conductivity at 20°C |
                                                                                                       .     I
                                                                                                             I
                                    Fe            .
                                                    '
                                                       i
                                                         I
                                                                    Cr
                                                                                 f
                                                                                 !
                                                                                            .4               i
                                                                                                               ! Molecular
                                                                                                               " ––
                                                                                                                     Atomic absorpti  on spectrophotometry
                                                                                                                               absorption    spectrophotometry                   •           j
                                                                                                                                                                                             j
                                                                                                                                                                                             ft
         ■      •         ■■        Ti                   | - ,Mn , Nr, V, Zn i               .4                | Atomic absorption spectrophotometry                                         |
                                                                                   r–
                                                                                                               ( Atomic absorption spectrophotmetry;polarOgraphy                             |
                                      1               ^
                                                         I     Cu , Pb
                                                       I                           i      ■      .
  J :                   :     ii        –                  i
                                                           »     .         -
                                                                                   i
                                                                                                                [ After appropriate preparation of the sample,                                j
  |
  i
        Suspended solids      J
                              i
                                                           i                                                    j wet or dry mineralisation, and purification                                  j
  I
                                     Fe                  I                                                      ) Atomic absorption spectrophotometry                                          |
                                                         i
                                                                    Cr
                                                                                   I
                                                                                   t
                                                                                               4                { - Molecular absorption spectrophotometry                                     j
                                                                                                               i  . I        –  ■»     ■"     ■ – ■i « ■   ■       ■ 11' 1
                                                                                                                                                                  ■••/•••
 ---pagebreak---                                                                                                                                ANNEX III
  r*"–" 1            ■                                                                                                         page 2
                             I               PARAMETERS                 J MINIMUM ANNUAL.
          COMPONENTS                                 –––––––––
                                                                                                      REFERENCE METHOD OF ANALYSIS
                                                                        I    FREQUENCY
                             I    IMPERATIVE               GUIDE
                               Ti   %                 Mn , Ni , V , Zn  E~H_                Atomic absorption spectrophotometry
                                                   I      Cu, Pb              •          .1 Atomic absorption spectrophotometry-
                                                                                            Polarography
                               Hydrated oxides                                4             Extraction of the sample under dilute acid
                               hydroxides of                                                conditions ( HCl ; CH^COOH; HN03 ; HCIO^ / HNO-),
                               iron                                                         measurement by atomic absorption spectrophotometry .
                           i
                                              .  i                                          The determination of iron by molecular absorption
                                                                                            spectrophotometry can be made without interference
    \  *               *                                                                    if the extraction is made using CH^COOH .
                                                                                            The same method of acid extraction must be used
                                                                                            for all samples coming from the same site .
                                                                                          I                            :                       ;
      Sediments                                                                           \     ■ ■                      ■
      On the top layer of      Fe , Ti                Cr , V, Zn , Pb ,       1             Identical methods to those for measurements in           -
      sediment ( 0-1 cm .)                            Ni , Cu , Mn                        ! the water column .
                                                                                            After appropriate preparation of the sample ( wet
                                                                                            or dry mineralisation and purification)
                                                                                          I                       "
                                                                                            -  The quantities of metals may be measured for
                                                                                          !    a specific range of particle sizes
                                                                                          i
                                                                                          | - The quantities of metals are to be expressed
                                                                                               in mg / kg of dry matter                    - ■   ' .
                               Hydrated oxides                                1             Identical methods to those for     measurements in
                               hydroxides of                                                the water column         .
                               iron
I
I
                                                                        10
 ---pagebreak---                                                                              •  % ■  -
                                                                                                                                                           ANNEX  III
                                                                                                                                                           page 3   -
                                                                                                                *
                          |                 PARAMETERS                     ( MINIMUM ANNUAL jI
                                                                                     r A uni t kir         I
                                                                                                                               REFERENCE METHOD OF ANALYSIS                   j
                                                                           iaHnrLiiiu - . K
I     COMPONENTS
I
                          j IMPERATIVE
                            -,–––.                ( ■"■V "
                                                           GUIDE ,
                                                                   ■ ' "
                                                                                    FREQUENCY
                                                                                                                          -       -          ■          "             "• >V   I
                                   *              j
  Living organisms                                                        i                                         ■     •               V '                                 .j
                              Cr , Cd, V, Hg ,                                          1                         Atomic absorption spectrophotometry after
  Species representa­
  tive of the substrate       Fe , Ti , Zn , Pb ,                                                                appropriate preparation of the composite sample
                              Ni , Cu                                                                            of ground flesh .
                                                                                                                  -   The quantities of metals are to be expressed
                                                                                                              i       in mg / kg of wet matter                              –
             :          1                                                1r-                        :    • Ï
  Benthic flora and           Diversity and
                                                                         iI
                                                                         II
                                                                                                                  Qualitative and quantitative classification                  «
                              relative .
                                                                         i
                                                                                                                  indicating the list of species , the specimen                 1
                                                                         !i            2           "
  fauna , fish                                                           I
                              abundance'                                                                          count per species , the specimen count , density              j
                                                                                                                  dominance, and in the case of fish, the per-                  j
                                                                   •     i
                                                                         a
                                                                                                                  centage showing morbid anatomical symptoms                     «
                                                        !■    '■ i   ' ■
                                                                                            • '             I
                                                                                                      \ ■' i                 *    "                                     '
                                                                                                                               X'                            '        /
                                                                           I
                                                                           I
                                                                                                                  ■                            ;          '                   ...
                                                                               ï                  B
 ---pagebreak---                                                                                                                                                                        3$
 RECEIVING MEDIUM :  STORAGE AND DUMPING ON LAND                                                                                                            ANNEX IV
                           y .■ iw .l,» na^n.ii
                                                                                                                                  -            ––                                ,
                                               PARAMETiÏRS                - '              MINIMUM ANNUAL
      COMPONENTS
                                 IMPERATIVE
                                                        |       GUIDE
                                                                                               SAMPLING
                                                                                               FREQUENCY
                                                                                                                                   REFERENCE METHOD OF ANAllYSIS                |
                                                                                                                                                                                t
                                    *
                                                                                                                                                             ■  .          ■
Running surface
waters
                               Acidity                                                           2           ;     - Titrimetry
Water filtered                                                rCr (1 >                   ■       2                 - Atomic absorption spectrophotometry                          i
throuyh a 0.45 pm                                                                                                  - Molecular absorption spectrophotometry
membrane                 |
                      .  I                                                             .
                                                                                                                                        .           .                           n
(a ) from the storage 'î S0 4.                      .                                         ' 2      '           - Gravimetry .         "                                     '
      area and evacu­                                                                                            ' - Complexometric titration with EDTA                         I
      ated to the                                                                                                  - Molecular absorption spectrophotometry                     |
      outside ( not
      recycled )
                                                                                                               !                                         •                      I
                                                                                                               !                                                                *
( b ) around the site
      in the area
                                                              v«>                                2
                                                                                                               | - Atomic absorption spectrophotometry                       ' jj
      affected by the          cFe (D
      storage and at a
                                                                                                 2                 - Atomic absorption spectrophotometry                -       j
                                                                                                               ! - Molecular absorption spectrophotometry                       J
v.    point outside       i              _            .                                          –
                                                                                                               !                                       .                        i
      this area
                                                                                                                   Atomic absorption spectrophotometry                           «
                                                                                                                                                           _   ;         ;       i
                                                                                                                                                                                 i
Ground waters
                                Ca
                                                        |                            '
                                                                                                 2
                                                                                                               i
                                                                                                                   - Atomic absorption spectrophotometry
                                                                                                                   - Comple*ometric titration     .
                                                                                                                                                                     •           J
                                                                                                                                                                                 j
Water filtered
                                                            • Pb(1)                j             2.
                                                                                                               i
                                                                                                                   - Atomic absorption spectrophotometry
                                                                                                                   - Polarography
                                                                                                                                                       __
through a 0.45 ^um
membrane                                                                      n                  –           jj
                                                                                                             i
                                                                                                                   - Atomic absorption spectrophotometry                         }
                                          ,           ,
Around the site
including , where
                                                ■
                                                                                   j              2          I ~ Atomic absorption spectrophotometry                              j
                                                                                                ~~2.     ' ~j - Titrimetry (Mohr method)                                          |
                                                          –        ■    ...  ... . t
necessary , its out­
flow points .
                           ~                          I                            i
                                                               Cu<1)               J              2
                                                                                                     -
                                                                                                            f - Atomic absorption spectrophotometry
                                                                                                            I - Polarography
                                                                                                                                                                              i
                                                                                                                                                                                  I
                                                               Mn ( 1 )            1              2         j        Atomic absorption spectrophotometry                          I
                        I                             i                            ,
 ---pagebreak---                                                                                                                                                       ANNEX IV
                                                                                                                                                      page 2
                                              PARAMETERS       " '
                                                                                                             -      –   ––•–;––-–,            ; –                      ff
                                                                                      MINIMUM ANNUAL
             COMPONENTS
                        ** '  '      IMPERATIVE "| \ ' GUIDE                             SAMPLING
                                                                                       , FREQUENCY                      REFERENCE METHOD OF ANALYSIS - |
                                                                                                                                          .    ,                   –j.
M
    Environment of the                                                                      - ■   N
  ] storage and dumping        I   Visual                    V -.          ,     '         1          ■-       Methods to be chosen by Member States                   |
  I site                           inspection        I
  I Topography and site                                ■               ■
                                                                                   =■-. : -v              !        ' v-.     :    ;
  I management :                                                                                           :                                      ■             '      \
  ] effect on sob soil               ■    •              -   .     ,
                                                                                                  ' ■
                                                                                                               .      \                     ~        . . • '       ' ,
  I and on the efcotogy      j   ■
                                                         -■■ ■   .       - -                    .      ; 1!                         ' .          \ :           : .
  | of the site              jI                     I   - -          -         I                                 ;              :                          ––          I
    ( 1 ) Also includes a quantitative analysis of the residue after filtration ( suspended matter ) ,
                                                                             <
 ---pagebreak---                                                                                                                                                            ANNEX V   r> jr
         RECEIVING MEDIUM :    INJECTION
                            l'  ■■     1
                                             PARAMETE: RS                        MINIMUM ANNUAL                                                                            r
                                                                                                                              REFERENCE METHOD OF ANALYSIS                 j
          COMPONENTS                                                                      SAMPLING
                                     IMPERATIVE
                                                        J     GUI.DE                     FREQUENCY^
                                                                                                                                                                           i
! Surface waters                  AcicJity             Ji   :             !                    - :.:Jj - T ftrimetry                                "         •    .       i
   Water filtered
                                                          rCr <1 >                             1                   - Atomic absorption spectrometry                        J
   through a 0.45 yum
  membrane                                                                I                                        - Molecular absorption spectrophotometry                j
  Around the site in ,                                               ■"j                       1                   - Gravimetric analysis.                                 I
   the zone affected by                                                  i                                         - Complexometric titration with EDTA                    f
  the injection                                  .    !1                 I                              _J[ - Molecular absorption spectrophotometry                       j
                                                        j  vnJ                                 1    "              - Atomic absorption spectrophotometry                   |
                                                                                                                           -                                               ii
   Ground waters                                                           i                            :                                         .                        *
   Water filtered .
   through a 0.45 jjm
                                   _ (1)
                                   Fe
                                    f
                                                        l              "
                                                                           i                   1 ''            \
                                                                                                               !
                                                                                                                   - Atomic absorption spectrophotometry
                                                                                                                   - Molecular absorption spectrophotometry
                                                                                                                                           :    –
                                                                                                                                                                           5
                                                                                                                                                                            »
                                                                                                                                                                            i
                              ––"1
                                                                                                                 –                                                          i
   membrane      ,
                                                           Zn ( 1 )        !"                  1            I - Atomic absorption spectrophotometry                         j
                                                                                                               j - Atomic absorption spectrophotometry                      j
                                                                             * –f   ~
                                                        !
                                   Ca                                                          1
                                                        I                                                      | - Complexometric titration                                 j
   Under and around .                                      Pb ( 1 )                            1                   - Atomic absorption spectrometry
   the site including                                                                                              - Polarography .
   outflow points                                       !      •'                                            i
       -                   I
                               •«                                          '       '   -
                                                                                                1
                                                                                                      '   -
                                                                                                             I
                                                                                                             i
                                                                                                               i - Atomic absorption spectrophotometry                       j
                                                   H
                                                      I
                                                                                                !              i - Atomic absorption spectrophotometry                        1
                                                      l                                                        i                               ––                       –- i
                            i       a
                                                    r
                                                                           !
                                                                                     -
                                                                                               –
                                                                                                ^              | - Titrimetry (Mohr method)
                                                                                                               I                ; :
                                                                                                                                                                              j
                            |                                  "•>    • !j
                            I '                            Çu                                   t              «       Atomic absorption spectrophotometry
          f "
                            I         '                                                                        | - Polarography                                  '
                                                                           | ■ ■          ■'                1
                                                           Mn              i                    1               I      Atomic absorption spectrophotometry
 L ,
     .
              -             »
                                                                              ■  i           '    ■ 1
                                                                                                              I      '  '
                                                                                                                                                          ––  /
                                                                                                                                                                              i
 ---pagebreak---                                                             L
                                                                                                                                    s&
              /             .           .
                                                                                                           •  '             ANNEX V
                                                                                                                            page 2
                                       PARAMETERS             { MINIMUM ANNUAL
 COMPONENTS            j
                                                                    r- kMn i   rm /»
                                                                                               REFERENCE METHOD OF ANALYSIS
                             IMPERATIVE
                             "               !
                                                    GUIDÇ     IOMl'ir L 1IVU .
                                                                   FREQUENCY
                                \
 Envi ronment
 Topography                Ground                                       1    '       Photographic and topographic survey
                           stability       ,
                           Permeabi lityA                            ' 1             Puriping tests                     ^
                           Porosity               '  •    •                          Well-logging
                         I                                    I
( 1 ) Also includes a quantitative analysis of the residue after filtration ( suspended matter ).
                                                                                                                                       \