🌿 Copper and its compounds in workplace air — AAS, PN-Z-04106 series (both standards withdrawn)

Environment PN-79/Z-04106

Overview

TWO STANDARDS, BOTH WITHDRAWN — AND THIS IS THE MAIN THING TO KNOW ABOUT THIS DETERMINATION. The PN-Z-04106 series has two sheets describing the determination of copper at workplaces. **Sheet 02 of 15 June 1979** (2 pages) was withdrawn on **07-12-2016**. **Sheet 3 of 21 March 2002** (7 pages), on copper fume and dust determined by flame AAS, was withdrawn on **30-01-2020**. Both PKN catalogue cards have the header "Withdrawn" and a filled-in "Withdrawal date" row; checked on 23.09.2026. Today there is no national standard for this determination in the PN collection.

THE SCOPE OF SHEET 02 — AND THE LIMITATION IT CONTAINS. The card states: "Metodę stosuje się do oznaczania miedzi i jej związków w powietrzu otaczającym stanowiska pracy. Metoda jest specyficzna wobec żelaza, manganu, niklu i chromu. W przypadku jednoczesnego występowania w badanym powietrzu wymienionych metali, np. podczas spawania…" [The method is used for determining copper and its compounds in the air surrounding workplaces. The method is specific with respect to iron, manganese, nickel and chromium. Where the listed metals occur simultaneously in the air under test, e.g. during welding…]. The sentence breaks off on the card, so we do not give its ending — but the beginning alone is enough to see what the reservation concerns: **welding produces a multi-metal aerosol**, and the method was described as specific precisely with respect to these four elements.

THE OLDER STANDARD HAS MORE CITATIONS THAN THE NEWER ONE — A MEASUREMENT THAT SHOWS IT. Reading of 23.09.2026 on the copy of the database of scopes: sheet 02 in the old scheme ("PN-79/Z-04106…") — 21 entries at 17 laboratories; the same sheet in the new scheme ("PN-Z-04106-02:1979") — 7 entries at 4 laboratories; **sheet 3 of 2002 — 17 entries at 15 laboratories**. The whole series: 45 entries at 35 laboratories. The 1979 standard, withdrawn earlier, thus has 28 entries at 21 laboratories in total — more than its newer counterpart. **The withdrawal of the newer sheet in 2020 did not move laboratories back to the older one; it simply left both without a successor.**

WHAT THIS MEANS FOR A LABORATORY — AND WHY IT IS NOT A VIOLATION. The withdrawal of a standard does not invalidate the accreditation in which the standard appears, nor does it prohibit its use. A reference document in a scope may be withdrawn if the method remains useful and the laboratory can demonstrate its validity — and in the determination of copper this situation is forced, because there is no successor. The reader of a report should, however, know that the cited standard is not a current document; the same reservation applies to the determination of ammonia (PN-71/Z-04041), described in a separate entry of this database.

THE LIMIT VALUE — ONE, BUT EXPRESSED AS THE ELEMENT. The list of maximum admissible concentrations, in the wording given by the regulation of 26 March 2026 (Journal of Laws 2026 item 447), carries under **item 394 "Miedź [7440-50-8] i jej związki nieorganiczne – w przeliczeniu na Cu" [copper and its inorganic compounds — as Cu] — NDS 0.2 mg/m³**, without a short-term value. The wording "w przeliczeniu na Cu" [as Cu] means that the result of the determination is given as the mass of copper, regardless of the compound in which it occurred in the air — and this is also how atomic absorption spectrometry measures, since it sees the element, not the compound. § 2 of the amending regulation does NOT mention copper, so the value applies directly (checked on 23.09.2026 on the text of the act).

SCALE OF CITATIONS AND FOURTEEN FORMS OF NOTATION. The core "04106" occurs in 45 entries at 35 laboratories, in fourteen different forms. The most frequent: "PN-Z-04106-3:2002" 13 times, "PN-79/Z-04106.02" 10, "PN-79/Z-04106/02" 7, "PN-Z-04106-02:1979" 2. The rest are notations with additions — the number of an own instruction ("EV-IR-68 wydanie 1"), the number of a procedure ("PB_06 edycja 6"), an exclusion of clauses ("z wył. pkt.7 i pkt.10") and three variants of the exclusion of clause 9.1 for sheet 3, written once with the full word "punktu", once "pkt" and once "pkt." [all three: clause].

CORRECTION OF THIS PARAGRAPH (23.09.2026) — IT WAS WRONG IN TWO WAYS. A sentence stood here saying that for sheet 3 "three laboratories exclude the same clause 9.1, each with a different abbreviation". A repeated reading of the notations record by record shows something else: • "PN-Z-04106-3:2002 z wyłączeniem pkt 9.1" — AB 1065; • "PN-Z-04106-3:2002 z wyłączeniem pkt. 9.1" — **THE SAME laboratory AB 1065**, a second notation of the same content in a different form of the abbreviation; • "PN-Z-04106-3:2002 z wyłączeniem punktu 9.1 i 10.1" — AB 340, and this is a **DIFFERENT SCOPE OF EXCLUSION**: two clauses, not one. SO THERE ARE TWO LABORATORIES, NOT THREE, AND ONLY ONE DECLARES THE EXCLUSION OF EXACTLY CLAUSE 9.1. The first defect is the unit — notations were counted, while the text said "laboratories". The second is non-disjoint categories — the notation excluding two clauses landed in one bag with those excluding one, because it matched the pattern. THE OBSERVATION ABOUT THREE FORMS OF THE ABBREVIATION REMAINS TRUE and is even stronger than it was: since ONE laboratory writes the same exclusion in two different forms in its own scope, the spread of forms is not a difference between laboratories, but a lack of convention within a single document. THE SCALE OF THIS PHENOMENON IN THE WHOLE SET (measurement of 23.09.2026): the exclusion of clause 9 is written in SIXTEEN ways, 70 occurrences in total — from "z wyłączeniem pkt 9" (10 times) through "z wyłączeniem punktu 9.2" (7) to "z wyłączeniem pkt. 9.1.4.3" (5). A pattern searching for one form will find between one and ten of the seventy.

A GAP IN THE COLLECTION OF STANDARDS, NOT A BACKLOG OF THE LABORATORIES — THIS MUST BE SAID PLAINLY (supplement of 23.09.2026). The above could lead to the conclusion that thirty-five laboratories work with outdated documents through their own negligence. This is not so. Today there is NO national standard at all in the collection of Polish Standards for the determination of copper in workplace air: sheet 02 was withdrawn on 07-12-2016, sheet 3 on 30-01-2020, and neither got a successor. A laboratory that would like to cite a document in force HAS NOTHING TO CITE — it would have to write its own procedure and demonstrate its equivalence itself, and for a determination performed for forty years according to a standard, this would be a step backwards, not progress. THEREFORE THE CORRECT READING OF THESE NUMBERS IS: thirty-five laboratories cite withdrawn standards because the withdrawal left them no choice. The withdrawal of the newer sheet did not move anyone back to the older one — it left both without a successor, and the laboratories with what they already had in their scope. No laboratory on its own can remedy the lack of a document in the PN collection.

Method principle

The aerosol containing copper and its compounds is retained on a filter while a known volume of air from the workplace is drawn through it. The sample is digested, and the resulting solution is introduced into an atomic absorption spectrometer — in the flame version (sheet 3) or according to the procedure of sheet 02. The absorbance is measured at the copper resonance line of 324.8 nm, and the content is read from the calibration curve. The result is given AS COPPER, in line with the wording of the limit value. The method measures the element, so it does not distinguish metallic copper from its inorganic compounds — and the limit value does not distinguish them either, which is a rare case of agreement between technique and regulation.

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
• Welding shops and workplaces where non-ferrous metals are cut — a multi-metal aerosol
• Copper smelters and foundries, rolling mills and wire-drawing plants
• Electroplating shops — copper baths and pickling processes

Key parameters

Standard

Standard number

PN-Z-04106-02:1979 (wersja polska)

Title (PL)

Ochrona czystości powietrza -- Badania zawartości miedzi i jej związków -- Oznaczanie miedzi i jej związków na stanowiskach pracy metodą absorpcyjnej spektrometrii atomowej

Title (EN)

Air purity protection — Testing for content of copper and its compounds — Determination of copper and its compounds at workplaces by atomic absorption spectrometry

Step-by-step procedure

1. Sampling

   Draw a known volume of air from the worker's breathing zone through the filter.

2. Digestion

   Digest the filter in accordance with the test procedure based on the standard.

3. Measurement

   Measure the absorbance of the solution by AAS at the copper resonance line; read the concentration from the calibration curve.

4. Calculation

   Calculate the concentration of copper in air from the mass in the solution, the volume of the solution and the volume of air drawn; give the result as Cu.

5. Reference to the limit value

   Compare the exposure index for the work shift with the NDS of 0.2 mg/m³. The list sets no short-term value, so short-term measurements have no reference threshold.

6. RESERVATION IN THE REPORT

   State that the cited standard is WITHDRAWN, together with the withdrawal date, and that there is no document replacing it in the PN collection. For welding workplaces, note the presence of other metals in the aerosol.

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• Acids for digestion — corrosive; work in a fume hood, wearing chemically resistant gloves and safety goggles
• Welding fume contains, besides copper, other metals, including manganese and chromium, as well as nitrogen oxides — the assessment of exposure at such a workplace requires the determination of several agents
• Acetylene–air flame: check the tightness of the gas installation

Frequently asked questions