🌿 Five solvents from nitrocellulose products at once — gas chromatography, PN-Z-04023-02 (withdrawn)

Environment PN-89/Z-04023

Overview

ONE STANDARD, FIVE SUBSTANCES. The scope from the PKN catalogue card: "Ustalono metodę polegającą na adsorpcji par substancji wydzielających się z wyrobów nitrocelulozowych na węglu aktywnym, desorpcji dwusiarczkiem węgla i chromatograficznej analizie otrzymanego roztworu. Metodę stosuje się do oznaczania w mieszaninie acetonu, alkoholi, np: etylowego, n-butylowego, toluenu, ksylenu wydzielających się z wyrobów lakierowych w powietrzu na stanowiskach pracy" [A method is established consisting in the adsorption on activated carbon of the vapours of substances emitted from nitrocellulose products, desorption with carbon disulphide and chromatographic analysis of the resulting solution. The method is used for determining, in a mixture, acetone, alcohols, e.g. ethyl and n-butyl alcohol, toluene and xylene emitted from coating materials into workplace air]. The standard was published on 29 April 1989, has four pages, is maintained by KT 159 — and **was withdrawn on 07-07-2015**; the card has the header "Withdrawn".

FIVE LIMIT VALUES FOR ONE DETERMINATION. Each of the substances has its own item and its own thresholds in the list (wording given by the regulation of 26 March 2026, Journal of Laws 2026 item 447): **acetone** item 4 — NDS 600 mg/m³, NDSCh 1800; **ethanol** item 219 — NDS 1900 mg/m³, without a short-term value; **butan-1-ol** item 70 — NDS 50 mg/m³, NDSCh 100, with the "skin" notation; **toluene** item 533 — NDS 100 mg/m³, NDSCh 200; **xylene** (mixture of isomers) item 332 — NDS 100 mg/m³, NDSCh 200. The spread is thirty-eightfold: from 50 mg/m³ for butanol to 1900 for ethanol. **One chromatographic determination therefore gives five results, each of which is compared with a different value — and for each of them the limit of quantification of the method means something different.**

BUTAN-1-OL HAS A TRANSITIONAL PROVISION. It is mentioned directly in § 2 of the amending regulation: **§ 2(4)(3) provides that "w ciągu dwóch lat od dnia wejścia w życie niniejszego rozporządzenia dla butan-1-olu wartość NDSCh wynosi 150 mg/m3" [within two years of the date of entry into force of this regulation, the NDSCh value for butan-1-ol is 150 mg/m3]** — instead of 100 mg/m³ from the table. The regulation was promulgated on 1 April 2026 and entered into force a day later, so the higher value applies until 2 April 2028. Whoever compares the result of a short-term measurement with the table will today apply a threshold stricter by half than the regulation requires. **This is exactly the layer we described for lead and asbestos: a value from the table is sometimes suspended by a paragraph that cannot be seen in the table.** The other four substances have no transitional provision.

WITHDRAWN, BUT NOT ABANDONED — AND A MEASUREMENT THAT SHOWS IT. Reading of 23.09.2026 on the copy of the database of scopes: notations in the old scheme ("PN-89/Z-04023…") are **56 entries at 14 laboratories**, in the new one ("PN-Z-04023-02:1989") — 19 entries at 9. The ratio of entries to laboratories is 4.0 in the old scheme and has a simple cause: five substances determined with one standard are five separate rows in an accreditation scope, each with its own measuring range. A laboratory that determines all five enters this standard five times.

THE CORE "04023" CATCHES TWO COMPLETELY DIFFERENT STANDARDS — THE EIGHTH CASE OF THIS CLASS IN THE DATABASE. Matching by the number alone, without anchoring the letter element, gives 112 entries at 55 laboratories. Of these, **35 entries at 34 laboratories are PN-R-04023:1996 — a standard from the R series, i.e. the agricultural one**, which has nothing to do with the determination of solvents. A core without a boundary therefore inflates the result here by half, mixing two series of standards. We recall the rule we worked out together: **the shorter the number, the more dangerous a core without an anchor — with five-digit numbers that have a letter element one must always anchor.**

WHAT THIS ENTRY DOES NOT GIVE. We do not have the text of the standard — PKN makes it available for a fee, and the card contains no limit-of-quantification values. Therefore **we do not give the lowest determinable concentrations for any of the five substances**, nor the sample volume. The card only states that the standard gives the apparatus, the preparation of reagents and the course of the determination. The card of this standard does not give the limits of quantification, and guessing by analogy with other carbon–disulphide methods would be inventing a number.

TWELVE FORMS OF NOTATION FOR ONE STANDARD — AND ONE OF THEM HAS THE WRONG YEAR (supplement of 23.09.2026). Measurement of all notations of the core 04023 with sheet 02: 76 entries in TWELVE forms. The most numerous: "PN-89/Z-04023/02" 30 times at 7 laboratories and "PN-Z-04023-02:1989" 17 times at 8 — i.e. the old and the new numbering scheme, both forms of the same 1989 standard. BUT ONE ENTRY, AT ONE LABORATORY, READS "PN-Z-04023-02:1998" — THE YEAR 1998 INSTEAD OF 1989. There is no standard with this designation: the PKN catalogue card knows PN-Z-04023-02:1989 (publication 29-04-1989) and no edition from 1998. This is a transposition of the last two digits, i.e. the same class as a typo in a designation — with the difference that it looks entirely credible: the year 1998 lies between the existing edition and today, and nobody will question it without checking the catalogue. THE OTHER FORMS OF THE SAME STANDARD SHOW THE WHOLE RANGE OF MINOR DISTORTIONS: "PN-89-Z-04023/02" (a hyphen instead of a slash after the year), "PN-89/Z-04023/02 pkt.8 i pkt..14" (a double full stop in the reference), "PN-89/Z-04023.02 IR-230/W5-08.03.2019" and "PN-89/Z-04023/02 IN-59 wyd. 3 z dnia 18.12.2025 r." (data of the test procedure glued onto the designation — the date 2025 next to a standard from 1989). OF THE TWELVE FORMS, THREE ARE DISTORTED, AND FOUR CARRY DESIGNATIONS FROM OUTSIDE THE STANDARD ITSELF.

Method principle

Air from the workplace is drawn through a tube with activated carbon, on which the vapours of all five substances are adsorbed at once. After sampling, carbon disulphide is poured over the sorbent to desorb the analytes, and the resulting solution is separated chromatographically — each substance gives a separate peak, identified by its retention time and measured separately. Carbon disulphide is the solvent of choice here because it gives a negligible signal in the flame ionisation detector and does not mask the peaks. The concentrations in air are calculated separately for each substance, from its mass in the solution and the volume of air drawn.

Applications

• Periodic measurements of occupational exposure required by the regulation of the Minister of Health on tests and measurements of agents harmful to health in the working environment
• Paint shops for wood products and furniture — nitrocellulose products
• Production of paints, lacquers and nitro thinners
• Spraying and drying workplaces for coatings

Key parameters

Standard

Standard number

PN-Z-04023-02:1989 (wersja polska)

Title (PL)

Ochrona czystości powietrza -- Badania zawartości (w mieszaninach) szkodliwych substancji wydzielających się z wyrobów lakierowych nitrocelulozowych -- Oznaczanie acetonu, alkoholi: etylowego, n-butylowego, toluenu i ksylenu

Title (EN)

Air purity protection — Testing for content (in mixtures) of harmful substances emitted from nitrocellulose coating materials — Determination of acetone, ethyl and n-butyl alcohols, toluene and xylene

Step-by-step procedure

1. Sampling

   Draw a known volume of air from the worker's breathing zone through a tube with activated carbon.

2. Desorption

   Desorb the analytes with carbon disulphide in a tightly closed vial.

3. Chromatographic separation

   Analyse the solution by gas chromatography; identify the five peaks by their retention times.

4. Calculation

   Calculate the concentration in air separately for EACH substance from its mass in the solution and the volume of air drawn.

5. Reference to the limit values

   Compare each result with ITS OWN value: acetone 600/1800, ethanol 1900, butan-1-ol 50/100, toluene 100/200, xylene 100/200 mg/m³. FOR BUTAN-1-OL check the date: until 2 April 2028 the short-term value is 150 mg/m³ under § 2(4)(3), not 100 mg/m³ from the table.

6. Combined exposure

   Where several solvents with a similar effect occur simultaneously, assess the combined exposure in accordance with the rules of the regulation on NDS values — the sum of the ratios of the concentrations to the limit values.

7. RESERVATION IN THE REPORT

   State that the cited standard has been WITHDRAWN since 07-07-2015, together with the justification for continued use of the method.

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• Carbon disulphide is highly toxic and extremely flammable — work only in a properly functioning fume hood, away from sources of ignition
• Butan-1-ol has the "skin" notation in the list — absorption through the skin may be as important as by inhalation; wear gloves when sampling at painting workplaces
• Vapours of nitro solvents form explosive mixtures with air — explosion hazard zones apply in paint shops

Frequently asked questions