Explanatory Memorandum to COM(1980)831 - 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) - Main contents
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| dossier | COM(1980)831 - Proposal for a COUNCIL DIRECTlVE on methods for the surveillance and monitoring of the environments affected by wastes from ... |
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| source | COM(1980)831  |
| date | 11-12-1980 |
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COM (80)831
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Conformement au reglement (CEE, Euratom) n° 354/83 du Conseil du ler fevrier 1983 concernant I’ouverture au public des archives historiques de la Communaute economique europeenne et de la Communaute europeenne de I’energie atomique (JO L 43 du 15.2.1983, p.
1), tel que modifie par le reglement (CE, Euratom) n° 1700/2003 du 22 septembre 2003 (JO L 243 du 27.9.2003, p.
1), ce dossier est ouvert au public. Le cas echeant, les documents classifies presents dans ce dossier ont ete declassifies conformement a I’article 5 dudit reglement.
In accordance with Council Regulation (EEC, Euratom) No 354/83 of 1 February 1983 concerning the opening to the public of the historical archives of the European Economic Community and the European Atomic Energy Community (OJ L 43, 15.2.1983, p.
1), as amended by Regulation (EC, Euratom) No 1700/2003 of 22 September 2003 (OJ L 243, 27.9.2003, p.
1), this file is open to the public. Where necessary, classified documents in this file have been declassified in conformity with Article 5 of the aforementioned regulation.
In Obereinstimmung mit der Verordnung (EWG, Euratom) Nr. 354/83 des Rates vom 1. Februar 1983 uber die Freigabe der historischen Archive der Europaischen Wirtschaftsgemeinschaft und der Europaischen Atomgemeinschaft (ABI. L 43 vom 15.2.1983, S.
1), geandert durch die Verordnung (EG, Euratom) Nr. 1700/2003 vom 22. September 2003 (ABI. L 243 vom 27.9.2003, S.
1), ist diese Datei der Offentlichkeit zuganglich. Soweit erforderlich, wurden die Verschlusssachen in dieser Datei in Obereinstimmung mit Artikel 5 der genannten Verordnung freigegeben.
COMMISSION OF THE EUROPEAN COMMUNITIES
C0MC80) 831 final Brussels, 17 December 1980
environments affected by wastes from the titanium
dioxide industry
(Presented by the Commission to the Council)
C0M(80) 831 final
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 prevention and progressive reduction, with a view to its elimination, of pollution caused by waste from the titanium dioxide industry. •
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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 Member 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
. ■ \ • '
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 ./ - *
Procedure ior_ _dra_fjt_i_ng_tJhe_D_i_r_ec_ti_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.
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2.2. Aims of the Directive
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 of view.- by discharges of titanium dioxide ' waste/ of understanding pollution trends and of assessing the pro-
■ gressive reduction of pollution caused by these wastes. ,
3. ' Comments on'titanium dioxide ; ' '
• ' . ' ' ■ ' ' ' • '
3.1. £ijgm£n_^a_ry_p_ro£e_rt_i_es^ ‘ .. . •
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. anatase and rutile. As . a white pigment/ it is incomparable and irreplaceable. \
i. ’ • • . ’ • • 1 - . . , .' • • ’ • _ • . _ ' '
3.2. JJt^ljzjitj[on . ,, .
On account of its pigmentary properties this product has come .
. into widespread use in many areas/ principal among which are .
. paints and varnishes, paper, plastics, rubber, floor coverings, ceramics, andi synthetic fibres. The paint and varnish, industry accounts for more than half of the total consumption. .
3.3. Ti^ta£ijj7i_d_i_ox_id^e_m£njjf^ct_u_riing__pj^o_ce_ss^s_ , • * ■ \ . ,
. Manufacturing of titanium dioxide pigments consists in preparing -
high purity titanium dioxide from an ore in which it is present . ■
, 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.
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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 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_lphate_p£Ojcess ’ ,
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% Til^ . 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 precipitate the titanium selectively as hydroxide. This hydroxide is then calcined to give the titanium oxide.
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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,7H-,0)
4 C
commonly known as 'copperas', resulting from the . reduction and crystalization of the solutions formed from the ilmenite digestion stage. This liquor is made , up of a complex salt of titanium, ferrous and ferric sulphate; .
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(iii) mother liquor produced from the separation of titanium
gel after hydrolysis by filtration and/or decantation.
solution of ferrous sulphate contains the sulphates of amounts in the raw
This liquor is made up of a in sulphuric acid. It also the metals present in trace material;
(iv) various gel wash waters and waters from the scrubbing . of the calcination gases. They contain dilute sulphuric acid, traces of the salts of iron, titanium ancf other metals present in the ore. ,
3 .3.2. iJh_loHde_p£0_ces_s
The standard ore used in the chloride process is natural, rutile, a scarce ore very rich in TiC^ (approximately 96%), or alteran-tively concentrates generally obtained from ilmenite or synthetic
rutile. „
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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
.../...
tetrachloride, the titanium dioxide is obtained; the regenerated '
I 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 pretreatment leads to the same problems as those associated with waste from the sulphate .process.
3.4. _Coimp£s_i_t_i^on of_tjT_e_wa_st_ejs jfr_om_t_he_t_i_ta_n_2_urn diiox_ide_ Jndustry
3.4.1. In the sulphate process, the main wastes from the industry are:
insoluble substances, copperas, mother liquors or strong acids, wash waters or weak acids. ' >
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In the chloride process, the main process wastes are the chlorides . of manganese, magnesium, calcium, sodium, alumiqium, chromium, iron, vanadium, ZrO^, titanium dioxide, TiCl^ and chlorine.
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3.4.2. 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%); , : . ' '
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- suspended solids (oxides of Ti, Si, Fe, Al, Ca, Zr);
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- 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^, TlF^O); 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 conditions in which calcination takes place, the ratio of SO^: S0^ (calculated as F^SO^) 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 S0j. .
Principal ‘methods of waste disposal used by the titanium
dioxide industry 1 ■■ -
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.
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Mscha£ges_at_ _sea_
The two principal methods of disposal are: ,
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(i) by5 pipeline from the coast •
(ii) discharge at sea from special ships
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The first method normally requires prior.dilution 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. /
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/ dilution curve;
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(ii) on the basis of this curve, if a pH of 6 or more must
- : be reached within 5 minutes, the requisite dilution
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v * 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 dilution engendered by ‘ the propeller,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.
_Di_sch_a_rge _into_sur_fa^ejwaters .
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This method of disposal: is used for acid solutions once they have been neutralized. The neutralization products-are disposed of with the ferrous sulphates.. '
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4.3. on_lj3nd ■ r
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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
'. * - - s
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. ,
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4.4. Injection in[t_o_ujidj?r£r£und_strata_ . ,
With this disposal method, the previously neutralized acid ,
' solutions are pumped into subterranean strata.
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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
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. amounts of copperas (ferrous sulphates) are roasted and converted
, to sulphuric acid by the addition of sulphur.
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 copperas are ' . involved in these applications, ) , ' '
5. Methods of surveillance and monitoring of the environments affected
The methods for the survei llan.ce and monitoring of the environments 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
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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 discharges will make it possible to monitor changes in the environments affected.'
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Monitoring of the .following parameters shall be compulsory:
(a) In the water column .
— pH, the salinity of sea .water,, -dissolved oxygen, turbidity,
, hydrated 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, titanturn, chromium, cadmium, mercury, vanadium, nickel, copper, .zinc and lead;
(d) flora and fauna . , . ■ .
'diversity and relative abundance.
/ ...
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V . ' . ■ h
Monitoring of the following parameters shall be optional:
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- - the level of chromium, vanadium, zinc, lead, nickel, .
copper, manganese in the water column and sediment and the
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amounts of suspended solids. • '
5.2. 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
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general ecological assessment of the area surrounding the tipping, storage or injection point. , .
6. . 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 conditions 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 general rules to be observed for sampling
Minimum annual frequency for sampling and for the analysis '
of parameters , ■, • ' .
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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. ■
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 specified in each case by the competent authority in each Member State.
Where the results of measurements taken on samples from the discharge 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. .
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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 carrying out the analyses as rapidly as possible. ' .../...
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Many investigations have been made with a view to recommending methods by which water samples can be stored without their composition 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 conditions 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 conditions 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.
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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 pollution. The conventions are: , ' .
“ The Convention for the Prevention of Marine Pollution from Land-based Sources (Paris Convention) (75/437/EEC);
f- 1 , ’ , . * • ‘ 1 -
Convention for the Protection of the Mediterranean Sea
. against Pollution (Barcelona Convention); ,
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- 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'
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discharge of certain substances such as acid compounds whose .
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composition and auqntity are such that they may adversely affect . the quality of sea water or make the dumping or discharge of
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specific substances, such as titanium, chromium and acid compounds subject to the prior granting of a specific permit or to appropriate programmes and measurements to reduce pollution.
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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. -
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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. \
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. Finally, a Directive on pollution caused by certain dangerous 1
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 Directive1 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.
17
THE COUNCIL OF THE EUROPEAN COMMUNITIES '
Having regard to the Treaty establishing the European Economic Community, and in particular Articles 100 and 235 thereof,^
Having regard to Council Directive 78/176/EEC of 20 February 1978
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. on waste froc the titanium dioxide industry , and in particular
Article 7(3) thereof, .
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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
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such wastes must be accompanied, in particular, by measures to monitor the environment affected from a physical, chemical, biological and ecological point of view;
Whereas, in-order to monitor the quality required of the environments 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
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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;
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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- r 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
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ecological point of view, by the discharges of wastes from the titanium dioxide industry.
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Article 2
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For the purpose of this Directive:
(a) environment affected means surface water/ ground water,
a . a / . . ■
. 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; . .
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Cb) sampling point means the point at which the sample is
’ '. 7 ' ; • taken; ■ ! ■ . . ; . , - , , ■; •
' ' f V ' ' ' ‘ ' . ■' ■ ’ ‘ 1 ■■■' . ' - . ' • . . * '
/ 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 ' ‘ v '
1. The relevant parameters for the surveillance and monitoring of the - \ . environments referred to in Article 1 are shown jn Annexes 1 to 5,
• subdivided according to the receiving medium. ’
, -2. Where a parameter appears in the Mandatory1 column of the Annexes,
' f" sampling and analysis must be carried out in respect of the
environmental components stated. , ' .
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. ' '
\ . ' . 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.,
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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.. . , .../...
3. 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.
A. The sampling must be carried out in the zone directly affected by
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the discharges, special account being taken of local environmental, factors and the manner of discharge, i.e. whethej? intermittent or-continuous. 1 l ,
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. - ■
5. 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 environments’affected, the Member States shall take the ' requisite measures.
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' - Article 5 - - *7 .
1. 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. ’ ..
2. 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 significantly affect the analytical results. 7 , ,
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V Article 6 . ^ 1
- . . • • r • . .
* 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.' r
, ' . ' .• Article 7 -• 7 . . '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. ' .
•7 . ' . ■ Article 8 . '■ ■ - , • > ■ 7. _ ■
1. 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: • ,
* 22 - ' . ■ : '
' H '
(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;
- 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.
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. '
4. The Commission will 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.
, ' 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 ’ •
1. 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. .
• • i ' ' , _ - - '
2. The Committee shall draw up its rules of procedure.
Article 12 ,
1. Where the procedure laid down in this Article is to be followed, matters sha.ll be referred to the Committee by its Chairman,either
on his own initiative or at the request of the representative of
' 1 ' , . • • x ‘
the Member States. ' . ' : ■ -
2. 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.
(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 -
1 , • \ , - • ’ , 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:
V ."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 affected in the ' area concerned/ or
(c) Annex 11(B) is deleted.
. Article 14 .
The Member States shall bring into'force the laws; regulations and administrative provisions necessary to comply with this
■ *v ’ ■ 1 ' •-
. 1 . . .../...
Directive before 1 January 1983. They shall forthwith inform the Commission thereof.
2. 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.
ANNEX I
l(
PARAMETERS
r
SAMPLING FREQUENCY >
REFERENCE METHOD OF ANALYSIS
12
In the prevailing wind in the zone directly 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) _ . '
. - ■ . . • . .... . ■" I?
RECEIVING MEDIUM * SEA WATER (estuarine, coastal, open sea) . . . . . , . % ANNEX IJ
| COMPONENTS | - PARAMETERS | | MINIMUM ANNUAL -j SAMPLING 1 FREQUENCY j | , — ~s - , , * - . . REFERENCE METHOD OF ANALYSIS . 4 • . •• - • . k . - . • ■■ ' J | |
| IMPERATIVE | 1 ■ GUIDE. | |||
| Water column Non-fiItered water or s ' Vat er filtered through 0.45 jjm membrane r t | ■ , % Temperature | • - - | l 4 ... | Thermometry < |
| Salinity - | 4 | Conductimetry : | ||
| pH " L | 4 | Electrometry. Measurement is to be carried out jj on the spot at the time of sampling. J | ||
| Dissolved 0.. j ) 4 1 4 _ _:_ _i ■ | - Winkler method • j - Electrochemical method • - i | |||
| Turbidity or suspended matter , | . ' . ' | 4 ^ | ■ i Turbidimetry . | - Weighing after filtration through 0.45 um | . filter and drying at 105°C .■ . . j - Weighing after centrifugation (minimum time j 5 minutes, and average accerleration ; 2,800 and 3,200 g) j | |
| ' ■ , | Fe | j, ., c. . O | Atomic absorption spectrophotometry j Molecular absorption spectrophotometry jj | |
| - ■ - | -' ...... Ti | Mn, Ni, V, In, | 4 | _ ---- Atomic absorption spectrophotometry , 5 . i | |
| :—!—i | Cu, Pb | • -4 j | Atomic absorption spectrophotometry polarography | |
| Suspended solids | Fe | Cr . ! | -—-1-:- „ i After appropriate preparation of the sample, , j wet or dry mineralisation, and purification . ' __7 - --*• | |
| 4 | Atomic absorption spectrophotometry . . j Molecular absorption spectrophotometry | |
REFERENCE METHOD OF ANALYSIS
| MINIMUM ANNUAL SAMPLING FREQUENCY | |||||||||||||
| Hydrated oxides hydroxides of iron |
Atomic absorption spectrophotometry
Atomic absorption spectrophotometry polarography <>-
Extraction of the sample under dilute acid conditions (HCl; CH^OOH; HN03; HClO^/HNOj), measurement by atomic absorption spectrophotometry. The determination of iron by molecular absorption spectrophotometry can be made without interference if the extraction is made using CHjCOOH,
The same method of acid extraction must be used for all samples coming from the same site •
Sediments
In the top layer of sediment (0-1 cm.)
Fe, Ti
Cr, V, Zn, Pb, Ni, Cu, Mn
Identical methods to those for measurements in the water column. _
After appropriate preparation of the sample (wet or dry mineralisation and purification)
The Quantities of metals may be measured for a specific range of particle sizes
The quantities of metals are to be expressed in mg/kg of dry matter
'
J
-—— -f — -, ■ 1 ■ ’ r
Hydrated oxides i J }
hydroxides of J {
iron t ' {
' Identical methods to those for measurements in the water column .
| PARAMETERS | MINIMUM ANNUAL | ' , | ||
| COMPONENTS | - SAMPLING | . - ' - REFERENCE METHOD OF ANALYSIS j | ||
| ^ ‘ | . IMPERATIVE | GUIDE. | , FREQUENCY | : ■ ■■■■■' - ■ ■ : j |
| Living organisms | . . ■- ■ -■ ■ ■ ■ | |||
| Species representa- | j Cr, Cd, V; Hg, | 1 ", | Atomic absorption spectrophotometry.after | |
| - tive of the site: | Fe, Ti, Zn, Pb, | appropriate preparation of the composite sample - | ||
| molluscs, crusta- | j Ni,. Cu | of ground flesh (wet or dry'mineralisation and - | ||
| ceans apd fish and at | purification) , ' | |||
| least two inverte- | , ' | , ..... - ' - ' • ' . - ' • - • • K | ||
| - brates including, if | - For fish, the metals must be measured in ' t | |||
| possible, one benthic | j , | muscle. The sample should consist of at least f | ||
| organism (1) . ' < | 10 specimens. > " * | |||
| ■ H - The quantities of metals are to be expressed * | ||||
| r - - | ' - - | . ■ | 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. : ■ ’ j * | ||||
| Benthic flora and | Diversity and | 2 -■ ■ | . . i Qualitative and quantitative classification 5 | |
| fauna, fish ' * | relative | indicating the liste of species, the specimen . j | ||
| abundance | . - | count par species, the specimen count, density J | ||
| - - - , i | dominance, and in the case of fish,, the per- | |||
| ;■ ■ - . ' | centage showing morbid anatomical symptoms. • ' | |||
| ■ ■ ; • | - .. | ! 1 l . . .. ' ' ' , • t | - . ■ ■. / ' - . |
red mullet, herring, sole (or another appropriate benthic species). ■
SO
RECEIVING MEDIUM: FRESH WATER
| COMPONENTS . , | PARAMETERS ' | MINIMUM ANNUAL | ||
| .< IMPERATIVE j GUIDE | ) SAMPLING . FREQUENCY f ....... | i , KtFtKbNtb Mb 1 HUD OF ANALYSIS j • - - ' ' ' . ' | ||
| Water column - .Samples taken at a depth of 0.50 m below the surface at the same time of the year - On non-fiItered water or water filtered through a 0.45 fjtn membrane | . V ' . . pH* | 4 | - ' . ' • ’ ' .1 1 ' ‘ Electrometry. Measurement is to be carried out on the spot at the time of sampling. | |
| Dissolved 0^ | 4 | - Winkler method ✓ - Electrochemical method . ~ | ||
| Turbidity or suspended matter . ' | - ■ '• ■ | 4 | Turbidimetry ’ ' , . . - Weighing after filtration through 0.45 urn filter and drying at 105°C - Weighing after centrifugation-(minimum time 5 minutes, and average acceleration 2,800 and 3,200 g) and drying at 105°C. 1 ‘ | |
| Dissolved salts | ■ ■ - | ■; 4 ' | Electrometric measurement of conductivity at 20°C | |
| Fe | Cr | 4 • ■ | Atomic absorption spectrophotometry . Molecular absorption spectrophotometry | |
| Ti | - /Mn, Nr, V, Zn | .4" J Atomic absorption spectrophotometry , | ||
| Cu, Pb | 4 | Atomic absorption spectrophotmetry;polarOgraphy | |||
| Suspended solids | Fe | . _ , Cr . | . j After appropriate preparation of the sample, . j wet or dry mineralisation, and purification ■ • j_______:----— • 4 . j Atomic absorption spectrophotometry . j Molecular absorption spectrophotometry ' |
| COMPONENTS | PARAMETERS | MINIMUM ANNUAL | , REFERENCE METHOD OF ANALYSIS ' - - ■ . • ■ ( ‘ ' . | |
| IMPERATIVE | GUIDE | - SAMPLING ' FREQUENCY | ||
| S' * ' | Ti ' | Mn, Ni, V, Zn | \ | Atomic absorption spectrophotometry |
| Cu, Pb | 4 | Atomic absorption spectrophotometry- . . Polarography . | ||
| Hydrated oxides hydroxides of iron | 4 | Extraction of the sample under dilute acid conditions (HCl; CH^OOH; HN03; HCIC^/HNO,), measurement by atomic absorption spectrophotometry. 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. | ||
| Sediments On the top layer of sediment (0-1 cm.) I. | Fe, Ti | Cr, V, Zn, Pb, Ni, Cu, Mn | * 1 | Identical methods to those for measurements in - the water column. - After appropriate preparation of the sample (wet or dry mineralisation and purification) - The quantities of metals may be measured for a specific range of particle sizes - The quantities of metals are to be expressed in mg/kg of dry matter ' |
| Hydrated oxides hydroxides of iron | 1 | Identical methods to those for measurements in the water column . ' |
page 3 -
| COMPONENTS | PARAMETERS | MINIMUM ANNUAL | - • ■■■■•- . : ' f REFERENCE METHOD OF ANALYSIS | ^ - ■ ' •’ ii | |
| IMPERATIVE | GUIDE , | SAMPLING - . FREQUENCY | ||
| Living organisms Species representative of the substrate | ' " * ‘ Cr, Cd, V, Hg, Fe, Ti, Zn, Pb, Ni, Cu . ’ - | < 1 | . . ' 1 . • , Atomic absorption spectrophotometry after appropriate preparation of the composite sample of ground flesh. . , . - 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 list of species, the specimen i | |
| ' ' | abundance' | 2 ' | count per species, the specimen count, density j | |
| ■■ _ • ' | .. | | | ■ | dominance, and in the case of fish, the per- | |
| ‘ _ *_■ ■■ - . | 1 | centage. showing morbid anatomical symptoms ) | ||
| ■ " - : , | • - . . . : ' ,, - ■. , | |||
| ■' > | I | . - - .. ■ ’ ’ ■ . ; ' | ||
| ' ‘ | 1 . ■ , i | ■. , . ■ ■ \ ■■ ■ - |
■ . . - *4
RECEIVING MEDIUM; STORAGE AND DUMPING ON LAND . ' • ’ . ANNEX IV -
| ' | PARAMETERS | MINIMUM ANNUAL | ■ • f REFERENCE METHOD OF ANALYSIS j | |
| COMPONENTS | IMPERATIVE | GUIDE ■ | ' SAMPLING FREQUENCY | |
| . Running surface waters | ' • ' . ■ Acidity | 2 | ( . \ . . • ' • . ' - Titrimetry .. ' - ' ' t | |
| Water filtered through a 0.45 jjm membrane | ... . ’ • ' ‘ ■ A ~ | . „ (1) : Cr | • ■ : 2 ■ | - Atomic absorption spectrophotometry . ' i - Molecular absorption spectrophotometry |
| (a) from the storage area and evacu- ’ ated to the outside (not recycled) (b) around the site in the area | SO, , *' | ■■■'.■’ 2 ' ' . , | - Gravimetry- ' { ' - Complexometric titration with EDTA 1 - Molecular absorption spectrophotometry j | |
| V”> | • , ' ■ ' ‘ , X - Atomic absorption spectrophotometry ’ j | |||
| ■ affected by the storage and at a v point outside | B (1) | • 2 | - Atomic absorption spectrophotometry - j - Molecular absorption spectrophotometry : J . . > | |
| this area | i | Zn(1) | 2 . | Atomic absorption spectrophotometry * ■ ' •• ' f |
| Ground waters | Ca | 2 | ■ - ■ - - Atomic absorption spectrophotometry • - Complevometric titration | |
| Water filtered | • Pb(1) | -.--- 2 | . . - Atomic absorption spectrophotometry - Polarography - | |
| through a 0.45/um membrane | Ti . | --- | 2 a | - Atomic absorption spectrophotometry - . |
| Around the site including, where necessary, its outflow points. | K1.(1) Nl , | ' 2 \ | - Atomic absorption spectrophotometry | |
| Cl | 2. . | - Titrimetry (Mohr method) | ||
| , Cud) | •' J | - Atomic absorption spectrophotometry - - Polarography ' | ||
| . ' " | Mnd) | 2 | - Atomic absorption spectrophotometry | |
| • t |
| COMPONENTS | ’ PARAMETERS * ' ' | MINIMUM ANNUAL | -----:-!-;-ir • ■ . . •' '■ .. ■ ' :! ‘ REFERENCE METHOD OF ANALYSIS - I | |
| IMPERATIVE | | GUIDE | SAMPLING FREQUENCY | ||
| , ■ - ^ - | ... . , , . . . . . | |||
| Environment of the | ■ | - • ■ ■ \ - | ||
| storage and dumping | Visual | ' ■ 1 . • | Methods to be chosen by Member States | |
| site ' i„ | inspection | |||
| Topography and site | ■■ ■ - ; ' | • • ... . ' . N • > . ’ • • / ' " ■ . | ||
| management: . | • • - ■ •_ | ■ • ' . •• • . • • ■ . • • < , . < ' \ | ||
| effect ori sub soil | , - * - * | ■__, .. ■ ' . •. •- | - ' ■ ■ ■ - ■ i | |
| and on the etology | -■ ■ " . \ | |||
| of the site | . ' | ' ‘ .... ■ ■ - 1 | ||
| ■ ' ■ | - ' . *' ■ ' • • ' ■ |
3f
ANNEX V
RECEIVING MEDIUM: INJECTION
| ' COMPONENTS ' *. ‘ | .......— —— - PARAMETERS | MINIMUM ANNUAL | : ■ ■ . - t REFERENCE METHOD OF ANALYSIS j | |
| IMPERATIVE | GUIDE | ■ SAMPLING FREQUENCY^ | ||
| Surface waters Water filtered through a 0.45 yum . membrane ' Around the site in , the zone affected by the injection Ground waters Water filtered . through a 0.45 jjm membrane / Under and around . the site including outflow points | Acidity | \ | .. i | . - . , . 1 - Titrimetry • j j |
| r (1) Cr | i | • 1 • . ' £ - Atomic absorption spectrometry j - Molecular absorption spectrophotometry C | ||
| $05 ' ' . | . ' . | ■ i ' | ■ * ■ ■ 1 - Gravimetric analysis. - . - ' J - Complexometric titration with EDTA j - Molecular absorption spectrophotometry } | |
| v(1) | i . | - Atomic absorption spectrophotometry - • ( ' 4 | ||
| Fe(1) T ' | - ' ’ ■ - ■ - | . 1 ' | , . \ - Atomic absorption spectrophotometry j - Molecular absorption spectrophotometry • ! | |
| Zn(1) | i | - Atomic absorption spectrophotometry ; | ||
| Ca | i ■ | - —f - 1 - •• i | - Atomic absorption spectrophotometry - ' " - Complexometric titration | |
| Pb(1> | i ' ■ | - Atomic absorption spectrometry . - Polarography . . ' " --“ ~ | ||
| Ti 1 | -;- 1 , | ■- Atomic absorption spectrophotometry ■ | ||
| ' . ■ ' - • ' | ) | M.<1) Ni I | 1 | - Atomic absorption spectrophotometry - |
| Cl | 1 1 | - Titrimetry (Mohr method) | ||
| r" • ■ | „ (l) • Cu • | 1 ’ ■ 9----—"— - A . ' ~ Atomic absorption spectrophotometry ‘ • | -Polarography • | ||
| . : | M (1) Mn | —- '■ 1 ■ ■ i....... - -----— " '' — 1 | - Atomic absorption spectrophotometry . - |
| COMPONENTS | ’ PARAMETERS ' | MINIMUM ANNUAL | ■ ... .. . . .. ■ REFERENCE METHOD OF ANALYSIS ) " ■ ‘ ^ ' ' ■ -I | |||
| IMPERATIVE | GUIOt | SAnrLINo . FREQUENCY | ||||
| v- Environment Topography | \ . Ground . stability , | " ......" ' | i ■ ■ | Photographic and topographic survey | 1 | |
| Permeability' Porosity , | ' •• • ' - • • | . .1 . . | Punping tests : ^ Well-logging | - | | # |
(1) Also includes a quantitative analysis of the residue after filtration (suspended matter).