⚗️ Chlorophenols and pentachlorophenol (PCP) in water and wastewater — GC

Physicochemistry PN-EN 12673

Overview

WHAT THIS STANDARD DESCRIBES. The scope from the PKN catalogue card of the current edition (PN-EN 12673:2004, Polish-language version), in full and in the spelling of the card: "Opisano metodę oznaczania techniką chromatografii gazowej 19 chlorofenoli (2-,3-, i 4-chlorofenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- i 3,5-dichlorofenol, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- i 3,4,5-trichlorofenol, 2,3,4,5-, 2,3,4,6- i 2,3,5,6-tetrachlorofenol i pentachlorofenol) w wodzie do picia, gruntowej, deszczowej, morskiej i powierzchniowej oraz w ściekach, która pozwala na oznaczenie chlorofenoli w zakresie stężeń od 0,1 mikrog/l do 1 mg/l, w zależności od jakości próbki oznaczonej i od czułości wykrywania związku (liczba atomów chloru w cząsteczce). W niektórych przypadkach, gdy całkowite rozdzielenie izomerów nie jest możliwe, poprzestaje się na podaniu wartości sumarycznej. Metoda może być stosowana do oznaczania innych chlorowcowych pochodnych fenoli pod warunkiem przeprowadzenia walidacji w każdym przypadku" [A method is described for the determination by gas chromatography of 19 chlorophenols (2-, 3- and 4-chlorophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dichlorophenol, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-trichlorophenol, 2,3,4,5-, 2,3,4,6- and 2,3,5,6-tetrachlorophenol and pentachlorophenol) in drinking water, groundwater, rainwater, seawater and surface water and in wastewater, which allows chlorophenols to be determined in the concentration range from 0.1 µg/l to 1 mg/l, depending on the quality of the sample determined and on the detection sensitivity for the compound (the number of chlorine atoms in the molecule). In some cases, where complete separation of the isomers is not possible, only a sum value is given. The method may be applied to the determination of other halogenated derivatives of phenols, provided that validation is carried out in each case]. The edition was published on 14 July 2004, has 26 pages and is maintained by KT 122 Water Quality — Chemical Testing — Organic Substances, ICS 13.060.50; it implements EN 12673:1998 and replaces PN-EN 12673:2002 in the English-language version.

TWO CARDS, TWO UNITS. The card of the 2002 edition (English-language version, withdrawn on 14 July 2004 and replaced by the Polish edition) has the same description of the scope with one difference of substance: the lower limit there is "0,1 mg/l", not "0,1 mikrog/l" — a thousand times more (the other differences between the two cards are only in wording, e.g. "w wodach podziemnych" [in groundwaters] versus "gruntowej" [ground water]). Both editions implement the same European document, EN 12673:1998, as identical ([IDT]), so the difference cannot come from the standard, only from the description on one of the cards. The requirement of the regulation for pentachlorophenol — a limit of detection of 2 µg/l — falls within the range on the card of the current edition; it would not fall within the range on the card of the withdrawn edition. In this entry we give the range from the card of the current edition.

WHY THIS ENTRY WAS CREATED. The standard was selected from the list of reference methodologies in Annex No. 12 to the regulation of the Minister of Maritime Economy and Inland Navigation of 12 July 2019 (Journal of Laws 2019 item 1311). Item 44 of this annex reads: "Pentachlorofenol (PCP) — chromatografia gazowa (GC) — PN-EN 12673" [pentachlorophenol (PCP) — gas chromatography (GC)], with the requirement: limit of detection 2 µg/l, accuracy and precision ± 50% at a concentration equal to twice the limit of detection. Explanatory note 3 to the annex defines the limit of detection as the concentration corresponding to the signal calculated from the blank value increased by three times the standard deviation, and adds that it is also determined from the results of at least ten blank samples, after rejecting outlying results with Dixon's test.

HOW MANY LABORATORIES AND IN WHAT FORM. All notations of the number 12673 in the reference-document field (reading of 23.09.2026): 10 entries at 7 laboratories, in four forms. "PN-EN 12673:2004" — 5 entries at 5 laboratories; "PN-EN 12673:2004 M" — 2 at 1; "PN-EN 12673:2004 IN-125 wydanie 3 z dnia 18.03.2019 r." — 2 at 1 (data of the laboratory's instruction glued onto the designation of the standard); "PN-EN 12673" without a year — 1 at 1. No laboratory cites the 2002 edition. The "Laboratories" tab searches for notations beginning with "PN-EN 12673", so it covers all four forms and shows the complete set.

NINETEEN COMPOUNDS IN THE STANDARD, ONE IN THE REGULATION. The standard describes the determination of nineteen chlorophenols, while the regulation requires one for wastewater — pentachlorophenol. Different practices can be seen in the scopes. AB 213, AB 313 and AB 412 name the test "Stężenie chlorofenoli" [chlorophenol concentration] (at AB 412 with the typo "Steżenie"). AB 418 and AB 1095 — "Stężenie pentachlorofenolu (PCP)" [pentachlorophenol (PCP) concentration], and AB 1095 separately also "Stężenie 2,4,6-trichlorofenolu" [2,4,6-trichlorophenol concentration]. AB 300 and AB 005 give the compounds in the test name itself, e.g. "Stężenie chlorofenoli pentachlorofenol (PCP) 2,4,6 trichlorofenol" [chlorophenol concentration: pentachlorophenol (PCP), 2,4,6-trichlorophenol]. AB 213 lists among its parameters seventeen items covering eighteen compounds — one of them is "2,4+2,5-dichlorofenol", i.e. precisely the sum value that the card permits when the isomers cannot be separated. A citation of this standard therefore does not mean that the laboratory determines all nineteen compounds; the laboratory's scope says which ones.

THE STANDARD NEXT TO COMPOUNDS OUTSIDE ITS LIST. Two of the ten entries (AB 300) concern phenol and cresols — "Stężenie fenolu i krezoli" [phenol and cresols concentration] and "Suma krezoli (z obliczeń)" [sum of cresols (calculated)]. The card permits the method to be applied to other HALOGENATED derivatives of phenols after validation in each case; phenol and cresols have no chlorine in the molecule. The laboratory cites the standard for them together with its own instruction (IN-125).

WHO DETERMINES PENTACHLOROPHENOL IN WATER AND WASTEWATER. There are seven entries, at seven laboratories, in which the test name or a parameter names pentachlorophenol and the object of testing is water or wastewater: six cite PN-EN 12673, one (AB 700) — its own procedure. In the whole set pentachlorophenol occurs in 20 entries at 15 laboratories; the other entries concern other matrices — including wood and wood-based materials, paper, textiles and leather, soil, waste, secondary fuels — and other documents.

WHAT WE DO NOT GIVE. We did not have the text of the standard — PKN makes it available for a fee (26 pages). The card speaks of the technique (gas chromatography), the list of compounds, the matrices and the concentration range. We do not give the sample preparation, the extraction method, any derivatisation, the column or the detector.

Method principle

According to the standard's card: the nineteen chlorophenols listed by name are determined by gas chromatography (GC), in the range from 0.1 µg/l to 1 mg/l; the limit depends on the quality of the sample and on the detection sensitivity for the compound, and the latter — on the number of chlorine atoms in the molecule. Where the isomers cannot be completely separated, a sum value is given. The method can be applied to other halogenated derivatives of phenols after validation in each case. WE DO NOT GIVE the sample preparation, extraction, any derivatisation, the column or the detector — we did not have the text of the standard.

Applications

• Drinking water, groundwater, rainwater, seawater and surface water — scope of the standard according to the card
• Wastewater — scope of the standard according to the card; when testing for the purposes of Journal of Laws 2019 item 1311, the methodology indicated for pentachlorophenol (Annex No. 12, item 44)
• Other halogenated derivatives of phenols — according to the card only after validation in each case

Key parameters

Standard

Standard number

PN-EN 12673:2004

Title (PL)

Jakość wody — Oznaczanie niektórych wybranych chlorofenoli w wodzie z zastosowaniem chromatografii gazowej

Title (EN)

Water quality — Gas chromatographic determination of some selected chlorophenols in water

Step-by-step procedure

1. Establishing the list of compounds determined

   The standard covers nineteen chlorophenols, while the regulation requires one for wastewater — pentachlorophenol. Record which compounds the laboratory determines: the citation of the standard alone does not say so.

2. Checking the requirement of the regulation

   For wastewater the method is to ensure a limit of detection for pentachlorophenol of 2 µg/l and accuracy and precision of ± 50% at a concentration equal to twice the limit of detection (Annex No. 12, item 44; definition of the limit of detection — explanatory note 3).

3. Determination

   WE DO NOT GIVE the sample preparation, the extraction or the chromatographic conditions — we did not have the text of the standard.

4. Sum result

   Where the isomers cannot be completely separated, the standard permits a sum value to be given (card). Note this in the report: a sum and the result for a single compound are different quantities.

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• We do not describe the hazards associated with the reagents and solvents — we do not know their list, because we did not have the text of the standard; the safety data sheets of the substances used in the laboratory apply, including those of the chlorophenol standards

Frequently asked questions