🌿 Determination of 16 polycyclic aromatic hydrocarbons (PAH) in soil, sewage sludge, treated biowaste and waste — extraction, concentration and clean-up chosen for the matrix (aluminium oxide, silica gel or gel permeation chromatography), measurement by GC-MS with at least four deuterated internal standards or by HPLC with UV-DAD or fluorescence detection; lower limit of application from 10 µg/kg d.m. (soils, sludge, biowaste) to 100 µg/kg d.m. (solid waste), PN-EN 17503

Environment PN-EN 17503

Overview

WHAT THE STANDARD COVERS. The scope on the PKN catalogue card of PN-EN 17503:2022-07 (English version) begins (our translation): “This document specifies different methods for the quantitative determination of 16 selected polycyclic aromatic hydrocarbons (PAH) (see Table 2) in soil, sewage sludge, sludge, treated biowaste and waste using GC-MS or HPLC-UV-DAD/FLD covering a wide range of PAH contamination levels”; the card then reproduces the whole of Clause 1 of the standard — Table 2 with CAS numbers, the lower limits of application, the remark on decision tables, the possibility of determining other PAH after validation and the exclusion of sampling (content consistent with the description of Clause 1 below). We read the text of the standard in the iTeh sample of SIST EN 17503:2023 (text of EN 17503:2022, English): from the title page through the European foreword, introduction and Clauses 1–6 up to and including 7.6.5 of Clause 7 (reagents). Outside the sample remain 7.6.6 onwards (other standard solutions), Clause 8 (apparatus), 9 (sample storage and preservation), 10 (procedure — extraction, clean-up, measurement, calibration, decision tables), 11 (performance characteristics), 12 (precision), the test report and Annexes A (repeatability and reproducibility data) and B (example conditions and chromatograms for GC-MS, HPLC-FLD and GC-MS/MS).

ACCORDING TO THE TEXT OF EN 17503:2022 (Clauses 1–6, 7.1–7.6.5). The standard was prepared by CEN/TC 444 “Environmental characterization of solid matrices” (secretariat NEN); CEN approved it on 3 January 2022. It replaced EN 15527:2008 and EN 16181:2018 — it was created by merging EN 16181 (originally a technical specification from the “HORIZONTAL” project, validated by CEN/TC 400 with the support of BAM) with EN 15527 (CEN/TC 292); as far as possible it agrees with the method for PCB in EN 17322 (PKN withdrew the Polish PN-EN 17322:2021-01 on 08.01.2026 and replaced it with PN-EN ISO 18475:2026-01 — cards as of 03.10.2026) and has been tested for ruggedness. Validation was carried out on sandy soil, sludge from a municipal waste water treatment plant, compost and waste (contaminated soil, building debris, waste wood, roofing tar, shredder light fraction) — Table 1. Scope (1): quantitative determination of 16 PAH (naphthalene, acenaphthene, acenaphthylene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene) in soil, sludge, treated biowaste and waste by GC-MS or HPLC-UV-DAD/FLD; sediments — when the user demonstrates suitability; with fluorescence detection acenaphthylene cannot be measured. Lower limit of application: from 10 µg/kg dry matter for soils, sludge and biowaste to 100 µg/kg dry matter for solid waste; for some samples (e.g. bitumen) 100 µg/kg cannot be reached. The matrices differ so much that a single procedure cannot be described — the standard contains decision tables for choosing extraction and clean-up. Other PAH may be determined after in-house validation. Sampling is not part of the standard (e.g. EN 14899, ISO 5667-12, EN ISO 5667-13). Definitions (3): critical pair — a pair of PAH separated to a defined degree (e.g. R = 0.5); internal standard — added from the beginning, corrects for losses and matrix effects (usually deuterated PAH); injection standard — added before injection into the GC-MS, to calculate the recovery of internal standards; extraction standard — checks extraction efficiency, not used for calculation. Principle (4): modules are chosen for the sample, and the laboratory must show that the criteria are met; internal standards check the whole combination of modules but say nothing about the efficiency of extracting PAH bound to the matrix; after pre-treatment — extraction, concentration, clean-up if necessary, for HPLC a change of solvent to a polar water-miscible one; GC-MS on a capillary column of low polarity or HPLC with a reversed-phase column. Interferences (5): containers of steel, aluminium or glass, no plastics, away from light; during storage PAH adsorb on the walls. GC-MS: dibenz[a,h]anthracene and indeno[1,2,3-cd]pyrene separate poorly but differ in mass; required resolution e.g. 0.8 between benzo[b]- and benzo[k]fluoranthene and between benzo[a]pyrene and benzo[e]pyrene; benzo[b]fluoranthene and benzo[j]fluoranthene cannot be separated; triphenylene may be unresolved from benz[a]anthracene and chrysene — this shall be stated in the report. HPLC: fluorescing or quenching compounds may overlap naphthalene and phenanthrene; incompletely removed extraction solvent gives broadened or double peaks of 2- and 3-ring PAH, and toluene — a broad peak interfering with naphthalene; perylene overlaps benzo[b]fluoranthene but can be suppressed by the choice of wavelength. Safety (6): certain PAH are highly carcinogenic; standards are best purchased ready-made; contamination of vessels is detected with 366 nm UV light; hexane is neurotoxic. Reagents (7): blank below 50 % of the lowest reporting limit; for extraction acetone, toluene, petroleum ether 40–60 °C (hexane-like solvents 40–98 °C allowed), anhydrous sodium sulfate, sodium chloride, a keeper substance against evaporation to dryness (e.g. octane, nonane). Clean-up A — basic or neutral aluminium oxide, deactivated with about 100 g/kg water, conditioned about 16 h, usable two weeks; B — silica gel 60 (63–200 µm), heated at least 3 h at 450 °C, before use at least 5 h at 130 °C and deactivated with 10 % water, usable two weeks; C — gel permeation chromatography (GPC) on Bio-Beads S-X3 type packing in cyclohexane with ethyl acetate 1 : 1. For HPLC acetonitrile or methanol and ultra-pure water. For GC-MS at least four deuterated internal standards (Table 3 gives deuterated counterparts of the 16 PAH; 13C-labelled ones are also allowed); for highly contaminated samples the standards may be added in two steps (first unlabelled ones to the sample — at least two, then at least four deuterated ones to the aliquot of extract); for HPLC the standard can be e.g. 6-methylchrysene or 1-methylnaphthalene; injection standards e.g. 1-methylnaphthalene-d10, triphenylene-d12, perylene-d12. Primary solutions about 0.4 mg/ml (about 10 mg in 25 ml), stored in the dark at (5 ± 3) °C, stable for at least one year; internal and injection standards in an amount giving a peak at least ten times the detection limit.

STATUS (as of 03.10.2026). The card of PN-EN 17503:2022-07 (English version, published 21-07-2022, 55 pages, price group U) has no “Withdrawn” header: Health, Environment and Medicine Sector, KT 191 Soil Chemistry, ICS 13.030.01 and 13.080.10, “Introduces: EN 17503:2022 [IDT]”, “Replaces: PN-EN 16181:2018-09 — English version, PN-EN 15527:2008 — English version, PN-EN 16181:2018-09 — Polish version”. We did not find a Polish language version of PN-EN 17503 in the catalogue (the card of the Polish version at the address ending in “p” does not exist, 03.10.2026). According to the title page of the sample, the Slovenian SIST EN 17503:2023 replaced SIST EN 15527:2009, SIST EN 16181:2018 and also SIST ISO 13877:1999 — an ISO standard that the European foreword of EN 17503 does not list among those replaced. The Knowledge Base has a separate entry on PN-ISO 13877 — “Determination of polycyclic aromatic hydrocarbons (PAH, 16 compounds of the EPA list) in soil by high-performance liquid chromatography with UV or fluorescence detection”; AB 165 cites both standards in one item.

HOW MANY LABORATORIES AND IN WHAT FORM (copy of the accreditation scope database, data up to 17.09.2026, read on 03.10.2026). The number 17503 appears in 11 records at 5 laboratories: AB 165, AB 199, AB 418, AB 550, AB 719. In the current PCA documents (read on 03.10.2026, issues from 26.01.2026 to 22.09.2026) the number appears in 8 items of the same 5 laboratories (AB 550 — 4, the others 1 each); there are more records in the copy because the AB 719 item with two techniques is split into three records in the copy and the AB 199 item into two. Notation: “PN-EN 17503:2022-07” at four laboratories, “PN-EN 17503” without the year at AB 165 (together with PN-ISO 13877); AB 550 cites its in-house procedure IB_SL_38_01 of 31.03.2025 alongside in all four items. The “Laboratories” tab (“PN-EN 17503”) shows the same 5 laboratories — checked with the tab query on the production server labcoda.pl on 03.10.2026.

WHAT THE LABORATORIES TEST (items in PCA). Soil or soils and ground — HPLC with fluorescence detection: AB 165 (together with PN-ISO 13877, without a list of compounds), AB 199 (15 compounds, (0.001–10) mg/kg, dibenzo(a,h)anthracene from 0.002, naphthalene from 0.003, acenaphthene from 0.007 mg/kg), AB 418 (15 compounds, (0.010–100) mg/kg, and the sum of PAH by calculation); AB 719 — HPLC-FLD for 10 compounds (lower limits 0.10 or 0.20 mg/kg, upper 20 or 40 mg/kg) and HPLC-DAD for six (fluorene, phenanthrene, fluoranthene, pyrene, acenaphthene (2.0–40) mg/kg, acenaphthylene (4.0–40) mg/kg). None of the laboratories with fluorescence detection lists acenaphthylene with it — as Clause 1 provides. AB 550 — GC-MS in soil and ground, in secondary fuels (SRF) and in waste (codes and DAB-11 groups, including sewage sludge): 19 compounds at (0.01–100) mg/kg each — the 16 of the standard plus benzo(e)pyrene, benzo(j)fluoranthene and “benzo(a)fluoranthene” — and the sum of PAH by calculation; at the DAB-11 waste item the PCA document carries the marking “A, C, E, H”, which is not in the part of the standard read, so we do not explain it.

WHERE A SEEMINGLY CORRECT RESULT IS EASY. In sampling and storage: the standard excludes plastic containers and exposure to light, and during storage PAH are lost by adsorption on the walls — the more, the longer the sample waits (5.1). In GC-MS measurement: benzo[b]fluoranthene cannot be separated from benzo[j]fluoranthene (5.2) — the result for benzo[b]fluoranthene includes both compounds, and when a laboratory reports them separately (like AB 550, which cites an in-house procedure alongside the standard), the basis for such a separation has to be sought outside the standard; triphenylene unresolved from benz[a]anthracene and chrysene raises them and must be stated in the report. In HPLC: fluorescence does not see acenaphthylene (1), and incompletely evaporated toluene interferes with naphthalene and 3-ring PAH (5.3). In checking the procedure: good recoveries of internal standards do not prove that PAH bound in the matrix have been extracted (4). In calculating the sum of PAH: a calculated sum depends on which compounds the laboratory measures — with 15 compounds (without acenaphthylene) and with 19 compounds these are different sums, although both appear in scopes as “sum of PAH”.

WHAT WE DO NOT GIVE. We have not read Clauses 8–12 or the annexes, so we do not give the extraction procedures (solvents, time, technique), the decision tables for choosing modules, the chromatographic conditions, the identification criteria, the calibration and calculation or precision data. Nor do we give limit values for PAH in soil, sludge or waste — we have not read the texts of the regulations for this entry.

Method principle

A pre-treated sample of soil, sludge, biowaste or waste is extracted with a suitable solvent with addition of internal standards (for GC-MS at least four deuterated PAH), the extract is concentrated and, if necessary, cleaned up on aluminium oxide, silica gel or by gel permeation chromatography — the combination of modules is chosen for the matrix. The PAH are separated on a capillary column of low polarity and measured by mass spectrometry (GC-MS) or, after a change of solvent to a polar one, separated in reversed phase and measured with a UV-DAD or fluorescence detector (HPLC); identification and quantification are based on relative retention times and signals against standards.

Applications

• Soil, sewage sludge, treated biowaste and waste — 16 PAH from 10 µg/kg d.m. (soils, sludge, biowaste) and from 100 µg/kg d.m. (solid waste) (1)
• Sediments — when the user demonstrates suitability; other PAH — after in-house validation (1)
• Soil and ground, secondary fuels, waste — in the accreditation scopes of 5 laboratories in PCA (HPLC-FLD, HPLC-DAD, GC-MS)

Key parameters

Standard

Standard number

PN-EN 17503:2022-07

Title (PL)

Gleba, osady ściekowe, uzdatnione bioodpady oraz odpady — Oznaczanie wielopierścieniowych węglowodorów aromatycznych (WWA) z zastosowaniem chromatografii gazowej (GC) i wysokosprawnej chromatografii cieczowej (HPLC)

Title (EN)

Soil, sludge, treated biowaste and waste — Determination of polycyclic aromatic hydrocarbons (PAH) by gas chromatography (GC) and high performance liquid chromatography (HPLC)

Step-by-step procedure

1. Storage and pre-treatment

   Glass or metal containers, no light; sample pre-treatment according to the referenced standards (EN 15002, EN 16179, EN ISO 16720). PN-EN 17503:2022-07 current (PKN card as of 03.10.2026).

2. Internal standards and extraction

   Addition of internal standards before extraction (for GC-MS at least four deuterated); the extraction procedure is chosen according to the matrix — we do not give the details (Clause 10).

3. Concentration and clean-up

   Concentration of the extract; clean-up A (aluminium oxide), B (silica gel) or C (GPC) as required by the matrix; for HPLC change of solvent to a polar one.

4. Measurement

   GC-MS — with check of resolution of critical pairs; HPLC-UV-DAD/FLD — no acenaphthylene with fluorescence; blank below 50 % of the lowest reporting limit.

5. Report

   Result on dry matter; benzo[b]fluoranthene together with benzo[j]fluoranthene; information on unresolved triphenylene if it occurred.

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• Certain PAH are highly carcinogenic — avoid contact with samples, extracts and standard solutions; standards are best purchased ready-made (6)
• PAH solutions in solvents are disposed of as toxic waste; contamination of vessels is detected under 366 nm UV light (6)
• Hexane is neurotoxic — precautions are required (6)

Frequently asked questions