⚗️ Total chromium in water and wastewater — colorimetric method with diphenylcarbazide, concentration range 0.01–10 mg/l; spectrophotometric method in accreditation scopes; PN-C-04604-02:1977 (withdrawn standard)

Physicochemistry PN-77/C-04604/02

Overview

WHAT THE STANDARD COVERS. The "Scope" field of the PKN card, in full: "The method is used for determining the content of total chromium in water and wastewater, in the concentration range 0.01÷10 mg/l." (our translation). The method is defined by the title: colorimetric with diphenylcarbazide. We did not have the text of the standard (4 pages).

STATUS (cards as of 13.10.2026). The card of PN-C-04604-02:1977 (Polish version) bears the heading "Withdrawn": publication 21-05-1977, "Withdrawal date: 14-11-2012", 4 pages, price group B, Health, Environment and Medicine Sector, KT 121 Water Quality — Chemical Tests — Inorganic Substances, "Replaces: PN-C-04604-02:1972 - Polish version", ICS 13.060.50; there is no "Replaced by" field. Sheet 00 of the series, "General provisions and scope of the standard" ("The subject of the standard are methods for determining the content of chromium (total Cr, trivalent Cr3+, hexavalent Cr6+) in water and wastewater", our translation), was withdrawn on the same day. The PKN search under "PN-C-04604" (13.10.2026) returns 11 items of the series, all withdrawn, among them sheet 07:1977 (total chromium by the manganometric method), sheet 08:1977 (hexavalent and trivalent chromium) and sheet 09:1990 (chromium(VI) by a semi-quantitative method with a colorimetric test). We do not name a standard that would replace this sheet.

IN THE REGULATION. Regulation of the Minister of Maritime Economy and Inland Navigation of 12 July 2019 on substances particularly harmful to the aquatic environment and the conditions to be met when discharging wastewater into waters or into the ground (Journal of Laws 2019 item 1311; status "in force" in the Sejm ELI database, entry into force 16.07.2019). Annex 4, Table II, item 28 — the highest permissible value of total chromium in industrial wastewater: 1 mg Cr/l for the tanning industry, 0.5 mg Cr/l for other types of wastewater; Annex 6, item 9 (wastewater from the cleaning of waste gases from the thermal treatment of waste): chromium and its compounds expressed as chromium 0.5 mg/l. Annex 12 "Reference methodologies for the analysis of samples of wastewater and of rainwater or snowmelt water", item 18 "Total chromium": atomic absorption spectroscopy with flameless atomisation (PN-EN ISO 15586) and with flame atomisation (PN-EN 1233), inductively coupled plasma atomic emission spectrometry (PN-EN ISO 11885) and inductively coupled plasma mass spectrometry (PN-EN ISO 17294-2); this sheet is not there. Item 19 "Hexavalent chromium": molecular absorption spectrophotometry (photocolorimetry) — PN-C-04604-8 — and ion chromatography — PN-EN ISO 10304-3. Notes to the annex: the reference method is chosen from standardised methodologies, and the determination range in the standard is to correspond to the concentration range in the wastewater tested; if a listed standard has been replaced and withdrawn, the new Polish Standard is regarded as the recommended one.

HOW MANY LABORATORIES AND IN WHAT FORM (copy of the accreditation scope database from the production server, refreshed on 12.10.2026). Number 04604/02 appears in 7 records at 7 laboratories; in the current PCA documents (read on 12–13.10.2026; issues from 03.12.2024 — AB 986 — to 12.08.2026 — AB 199) — in 6 rows at 6 laboratories. We do not confirm the seventh, AB 396: its page in the PCA public information bulletin list (read on 12.10.2026) gives "Accreditation valid until: 06-08-2026" and has no link to a scope document. A search of all downloaded PCA documents found no laboratories outside the database copy, no row with the number is set in bold italics, and no pages are repeated in any document. Notations: "PN-77/C-04604/02" — AB 447, AB 739, AB 986; "PN-77/C-04604.02" — AB 199 (next to PN-77/C-04604.08), AB 396, AB 932; "PN-77/C-04604-02" — AB 1436. The "Laboratories" tab looks for notations BEGINNING with the search term: "PN-77/C-04604/02" — 3 laboratories, "PN-77/C-04604.02" — 3, "PN-77/C-04604-02" — 1 — checked with the tab query on the labcoda.pl production server on 13.10.2026; this page searches with "PN-77/C-04604/02", so the tab shows 3 of the 7 laboratories.

WHAT THE LABORATORIES TEST (database copy and PCA documents). Test object: wastewater — AB 396, AB 447, AB 739; water, wastewater — AB 199, AB 932, AB 986, AB 1436. Characteristic: total chromium — AB 396, AB 739, AB 932, AB 986, AB 1436; "chromium concentration" — AB 447; chromium(VI) — AB 199 (together with sheet 08). Technique: spectrophotometric method — all. Ranges: 0.005–1.4 mg/l — AB 199; 0.01–10 mg/l — AB 396; 0.010–10.0 mg/l — AB 447, AB 932; 0.02–10 mg/l — AB 739; 0.020–10.0 mg/l — AB 986; 0.02–2.0 mg/l — AB 1436.

ALONGSIDE THIS STANDARD. In the entry with this standard: sheet 08 (PN-77/C-04604.08) — AB 199. In separate entries: chromium(VI) according to sheet 08 — AB 396 (database copy), AB 447, AB 739, AB 986, AB 1436, and chromium(III) calculated according to sheet 08 — AB 396, AB 447, AB 986, AB 1436; chromium(VI) according to PN-EN ISO 18412:2007 — AB 199 (5.0–50 µg/l) and AB 1436 (water, 0.004–0.25 mg/l); chromium according to PN-EN 1233:2000 by FAAS — AB 1436 (0.50–50.0 mg/l); total chromium and chromium(VI) by in-house procedure PB 037 (flow coulometry, 0.005–1.0 mg/l) — AB 932. Chromium in water and wastewater is determined by 166 laboratories in the database copy (entries with chromium in the test description or parameters, excluding COD, with water or wastewater as the test object, excluding sediments, soils, waste, air, feed, food, cosmetics, fertilisers and biological material): PN-EN ISO 11885 is cited by 68, PN-EN ISO 15586 by 47, PN-EN ISO 17294-2 by 42, sheet 08 by 31, PN-EN 1233 by 28, PN-EN ISO 18412 by 19, this sheet by 7, PN-EN ISO 23913 by 2 (AB 313, AB 1158), PN-EN ISO 18724 by AB 127; the other documents are mainly in-house procedures. The determination according to sheet 08, PN-EN ISO 11885, PN-EN ISO 15586, PN-EN ISO 17294-2 and PN-EN ISO 18412 is described in separate Knowledge Base entries.

WHERE A SEEMINGLY CORRECT RESULT IS EASY TO GET. First — form of chromium: sheet 02 concerns total chromium, while AB 199 cites it for chromium(VI) together with sheet 08; total chromium, chromium(VI) and chromium(III) are different quantities — check in the report which one is given. Second — regulation: all 7 laboratories have wastewater as the test object, while Annex 12 of the regulation, Journal of Laws 2019 item 1311, lists PN-EN ISO 15586, PN-EN 1233, PN-EN ISO 11885 and PN-EN ISO 17294-2 for total chromium in wastewater, not this sheet. Third — range: the card gives 0.01–10 mg/l, while the range of AB 199 starts at 0.005 mg/l, below the lower limit on the card; AB 1436 ends its range at 2.0 mg/l. Fourth — status: the sheet has been withdrawn since 14.11.2012 without a successor, the whole PN-C-04604 series is withdrawn. Fifth — tab and list: because of the three notations of the number, the "Laboratories" tab of this page shows 3 of the 7 laboratories, and we do not confirm one of the seven (AB 396) in PCA.

WHAT WE DO NOT GIVE. We did not have the text of the standard — we do not give the preparation and mineralisation of the sample, the way chromium is converted into the determined form, the reagent concentrations, the wavelength, the calibration, interfering substances, the calculation formula or the precision.

Method principle

Total chromium in water and wastewater is determined by the colorimetric method with diphenylcarbazide in the concentration range 0.01–10 mg/l (PKN card); in accreditation scopes — the spectrophotometric method. WE DO NOT GIVE the sample preparation, reagents, wavelength or formula — we did not have the text of the standard.

Applications

• Water and wastewater — total chromium in the range 0.01–10 mg/l (PKN card; withdrawn sheet in the accreditation scopes of 7 laboratories in the database copy, 6 in PCA)
• Industrial wastewater — highest permissible values of total chromium 1 mg Cr/l (tanning industry) and 0.5 mg Cr/l (other wastewater), Journal of Laws 2019 item 1311, Annex 4, Table II, item 28; the reference methodologies in Annex 12 are other standards

Key parameters

Standard

Standard number

PN-C-04604-02:1977

Title (PL)

Woda i ścieki — Badania zawartości chromu — Oznaczanie chromu ogólnego metodą kolorymetryczną z dwufenylokarbazydem

Title (EN)

Water and wastewater — Tests for chromium content — Determination of total chromium by the colorimetric method with diphenylcarbazide

Step-by-step procedure

1. Sample

   Water or wastewater; WE DO NOT GIVE the preparation. PN-C-04604-02:1977 withdrawn on 14-11-2012 (card as of 13.10.2026).

2. Colour reaction

   With diphenylcarbazide (title of the standard); WE DO NOT GIVE the conditions.

3. Measurement

   Colorimetric (PKN card), spectrophotometric in accreditation scopes; WE DO NOT GIVE the wavelength.

4. Result

   Total chromium in mg/l in the range 0.01–10 mg/l (PKN card); chromium(VI) and chromium(III) — other sheets of the series.

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• Safety rules of a chemical laboratory and the safety data sheets of the reagents used
• SUBJECT-MATTER NOTE: total chromium, chromium(VI) and chromium(III) are different quantities; for total chromium in wastewater the regulation (Journal of Laws 2019 item 1311, Annex 12) lists other standards

Frequently asked questions