Part 1 METHOD OF MEASURING THE VALUES OF PARAMETERS

No. in Annex I to the 1975 Directive	Parameters		Limit of detection^f1	Precision^f2	Accuracy^f3	Method of measurement
General note: Samples taken at the abstraction point are analysed and measured after sieving (wire mesh sieve) to remove any floating debris such as wood or plastic.
1 For waters classified as DW1, Schedule 2 limit.
2 For waters classified as DW2 and DW3.
3 For waters classified as DW3.
4 For waters classified as DW1, DW2 and DW3, Schedule 1 limit.
5 For waters classified as DW2, Schedule 1 limit, and DW3.
6 For waters classified as DW2 and DW3, Schedule 2 limit.
7 Mixture of six standard substances all of the same concentration to be taken into consideration: fluoranthene; 3, 4-benzofluoranthene; 11, 12-benzofluranthene; 3, 4-benzopyrene; 1, 12-benzoperylene; indano/1, 2, 3-ed/pyrene.
8 Mixture of three substances all of the same concentration to be taken into consideration: parathion, hexachlorocyclohexane, dieldrin.
9 If the samples contain so much suspended matter as to require special preliminary treatment, the accuracy values shown in this Part of Schedule 3 may as an exception be exceeded and will be regarded as a target. These samples must be treated so as to ensure that the analysis covers the largest quantity of substances to be measured.
10 As this method is not in current use in all Member States it is not certain that the limit of detection required for checking values in the 1975 Directive can be attained.
11 Absence in 5,000 m1 (for waters classified DW1, Schedule 2 limit) and absence in 1,000 m1 (for waters classified DW2, Schedule 2 limit).
12 “Limit of detection” means the minimum value of the parameter examined which it is possible to detect.
13 “Precision” means the range within which 95% of the results of measurements made on a single sample, using the same method, are located.
14 “Accuracy” means the difference between the true value of the parameter examined and the average experimental value obtained.
1	pH	pH unit	–	0.1	0.2	– Electrometry. Measured in situ at the time of sampling without prior treatment of the sample.
2	Coloration (after simple filtration)	mg/1 Pt Scale	5	10%	20%	– Filtering through a glass fibre membrane. Photometric method using platinum-cobalt scale.
3	Total suspended solids	mg/1 SS	–	5%	10%	– Filtering through a 0.45μm filter membrane, drying at 105°C and weighing
						– Centrifuging (for at least 5 mins with mean acceleration of 2,800 to 3,200g) drying at 105°C and weighing.
4	Temperature	°C	–	0.5	1	– Thermometry. Measured in situ at the time of sampling without prior treatment of the sample.
5	Conductivity at 20°C	μs/cm	–	5%	10%	– Electrometry.

No. in Annex I to the 1975 Directive	Parameters		Limit of	Precision detection	Accuracy	Method of measurement recommended for the container	Materials
6	Odour	dilution factor at 25 °C	–	–	–	– By successive dilutions.	Glass.
7	Nitrates	mg/1 NO₃	2	10%	20%	– Molecular absorption spectrophotometry.
8	Fluorides	mg/1 F	0.05	10%	20%	Molecular absorption spectrophotometry after distillation if necessary. Ion selective electrodes.
10	Dissolved iron	mg/1 Fe	0.02	10%	20%	Atomic absorption spectrophotometry after filtering through a filter membrane (0.45μm). Molecular absorption spectrophotometry after filtering through a 0.45μm filter membrane.
11	Manganese	mg/1 Mn	0.01^f4 0.02^f5	10% 10%	20% 20%	Atomic absorption spectrophotometry Atomic absorption spectrophotometry Molecular absorption spectrophotometry.
12	Copper^f6	mg/1 Cu	0.005 0.02^f7	10% 10%	20% 20%	Atomic absorption spectrophotometry Polarography Atomic absorption spectrophotometry Molecular absorption spectrophotometry Polarography.

No. in Annex I to the 1975 Directive	Parameters		Limit of detection	Precision	Accuracy	Method of measurement	Materials recommended for the container
13	Zinc	mg/1 Zn	0.01 0.02	10% 10%	20% 20%	Atomic absorption spectrophotometry Atomic absorption spectrophotometry Molecular absorption spectrophotometry.
14	Boron	mg/1 B	0.1	10%	20%	Molecular absorption spectrophotometry Atomic absorption spectrophotometry	Materials not containing boron in any significant quantities.
19	Arsenic	mg/1 As	0.002 0.01^f8	20%	20%	Atomic absorption spectrophotometry Atomic absorption spectrophotometry Molecular absorption spectrophotometry.
20	Cadmium	mg/1 Cd	0.0002 0.0015	30%	30%	Atomic absorption spectrophotometry Polarography.
21	Total Chromium	mg/1 Cr	0.01	20%	30%	Atomic Absorption spectrophotometry Molecular absorption spectrophotometry.
22	Lead	mg/1 Pb	0.01	20%	30%	Atomic absorption spectrophotometry Polarography.
23	Selenium	mg/1 Se	0.005			– Atomic absorption spectrophotometry.
24	Mercury	mg/1 Hg	0.0001 0.0002^f9	30%	30%	– Flameless atomic absorption spectrophotometry (cold vaporisation).
25	Barium	mg/1 Ba	0.02	15%	30%	– Atomic absorption spectrophotometry.
26	Cyanide	mg/1 CN	0.01	20%	30%	– Molecular absorption spectrophotometry.
27	Sulphates	mg/1 SO₄	10	10%	10%	Gravimetric analysis. EDTA compleximetry. Molecular absorption spectrophotometry.
28	Chlorides	mg/1 C1	10	10%	10%	Titration (Mohr’s method). Molecular absorption spectrophotometry.
29	Surfactants (reacting with methylene blue)	mg/1 (laury1 sulphate)	0.05	20%		– Molecular absorption spectrophotometry.
30	Phosphates	mg/1 P₂O₅	0.02	10%	20%	– Molecular absorption spectrophotometry.
31	Phenols (phenol Index)	mg/1 C₆H₅OH	0.0005 0.0015	0.0005 30%	0.0005 50%	Molecular absorption spectrophotometry 4-aminoantipyrine method. Paranitraniline method.	Glass.
32	Dissolved or emulsified hydrocarbons	mg/1	0.01 0.04	20%	30%	Infra-red spectrometry after extraction by carbon tetrachloride Gravimetry after extraction by petroleum ether.	Glass.
33	Polycyclic aromatic hydrocarbons	mg/1	0.00004	50%	50%	– Measurement of fluorescence in the UV after thin layer chromatography. Comparative measurement in relation to a mixture of six control substances with the same concentration^f10.	Glass or aluminium.
34	Total pesticides (parathion, hexachlorocyclohexane, dieldrin)	mg/1	0.0001	50%	50%	– Gas or liquid chromatography after extraction by suitable solvents and purification. Identification of the constituents of the mixture. Quantitative analysis^f11.	Glass.
35	Chemical oxygen demand (COD)	mg/1 0₂	15	20%	20%	– Potassium dichromate method.
36	Dissolved oxygen saturation rate	%	5	10%	10%	Winkler’s method Electrochemical method.	Glass.
37	Biochemical oxygen demand (BOD₅) at 20°C without nitrification	mg/1 0₂	2	1.5	2	– Determination of dissolved oxygen before and after five day incubation at 20 °C ± 1°C in complete darkness. Addition of a nitrification inhibitor.
38	Nitrogen by Kjeldahl method (except in NO₂ and NO₃)	mg/1 N	0.3	0.5	0.5	– Mineralisation, distillation by Kjeldahl method and ammonium determination by means of molecular absorption spectrophotometry or titration.
39	Ammonium	mg/1 NH₄	0.01 0.1	0.03 10%	0.03 20%	– Molecular absorption spectrophotometry.
40	Substances extractable with chloroform	mg/l	^f12			– Extraction at neutral pH value by purified chloroform, evaporation in vacuo at room temperature, weighing of residue.
43	Total coliforms	/100ml	5 500^f13			Culture at 37 °C on an appropriate specific solid medium (such as Tergitol lactose agar, Endo agar, 0.4% Teepol broth) with filtration or without filtration and colony count. Samples must be diluted or, where appropriate, concentrated in such a way as to contain between 10 and 100 colonies. If necessary, identification by gasification. Method of dilution with fermentation in liquid substrates in at least three tubes in three dilutions. Sub-culturing of the positive tubes on a confirmation medium. Count according to MPN (most probable number). Incubation temperature: 37°C ± 1 °C.	Sterilised glass.
44	Faecal coliforms	/100ml	2 200			Culture at 44 °C on an appropriate specific solid medium (such as Tergitol lactose agar, Endo agar, 0.4% Teepol broth) with filtration or without filtration and colony count. Samples must be diluted or, where appropriate, concentrated in such a way as to contain between 10 and 100 colonies. If necessary, identification by gasification. Method of dilution with fermentation in liquid substrates in at least three tubes in three dilutions. Sub-culturing of the positive tubes on a confirmation medium. Count according to MPN (most probable number). Incubation temperature 44 °C ± 0.5 °C.	Sterilised glass.
45	Faecal streptococci	/100 ml	2 200			Culture at 37 °C on an appropriate solid medium (such as sodium azide) with filtration or without filtration and colony count. Samples must be diluted or, where appropriate concentrated in such a way as to contain between 10 and 100 colonies. Method of dilution in sodium azide broth in at least three tubes in three dilutions. Count according to MPN (most probable number).	Sterilised glass.
46		Salmonella^f14	1/5,000ml 1/1,000ml			Concentration by filtration (on membrane or appropriate filter). Inoculation into pre-enrichment medium. Enrichment and transfer into isolating gelese – Identification.	Sterilised glass.

Annotations

Footnotes

f1

“Limit of detection” means the minimum value of the parameter examined which it is possible to detect.

f2

“Precision” means the range within which 95% of the results of measurements made on a single sample, using the same method, are located.

f3

“Accuracy” means the difference between the true value of the parameter examined and the average experimental value obtained.

f4

For waters classified as DW1, Schedule 2 limit.

f5

For waters classified as DW2 and DW3.

f6

If the samples contain so much suspended matter as to require special preliminary treatment, the accuracy values shown in this Part of Schedule 3 may as an exception be exceeded and will be regarded as a target. These samples must be treated so as to ensure that the analysis covers the largest quantity of substances to be measured.

f7

For waters classified as DW3.

f8

For waters classified as DW1, DW2 and DW3, Schedule 1 limit.

f9

For waters classified as DW2, Schedule 1 limit, and DW3.

f10

Mixture of six standard substances all of the same concentration to be taken into consideration: fluoranthene; 3, 4-benzofluoranthene; 11, 12-benzofluranthene; 3, 4-benzopyrene; 1, 12-benzoperylene; indano/1, 2, 3-ed/pyrene.

f11

Mixture of three substances all of the same concentration to be taken into consideration: parathion, hexachlorocyclohexane, dieldrin.

f12

As this method is not in current use in all Member States it is not certain that the limit of detection required for checking values in the 1975 Directive can be attained.

f13

For waters classified as DW2 and DW3, Schedule 2 limit.

f14

Absence in 5,000 m1 (for waters classified DW1, Schedule 2 limit) and absence in 1,000 m1 (for waters classified DW2, Schedule 2 limit).