🌿 Determination of polycyclic aromatic hydrocarbons (PAH, 16 compounds of the EPA list) in soil by high-performance liquid chromatography with UV or fluorescence detection — extraction with acetone and petroleum ether without drying (method A, slightly contaminated soils) or with toluene in a Soxhlet apparatus after drying (method B, more heavily contaminated soils), external calibration, PN-ISO 13877 (withdrawn)

Environment PN-ISO 13877

Overview

WHAT THE STANDARD COVERS. Scope from the PKN catalogue card of PN-ISO 13877:2004 (Polish version), in full (our translation): “Two methods for the determination of polycyclic aromatic hydrocarbons in soil by high-performance liquid chromatography with UV detection and fluorimetric detection are given”. We read the text of the standard in the sample of ISO 13877:1998 in the French version: table of contents, foreword, introduction, end of Clause 2 (the last three references), Clauses 3–6 and the beginning of Clause 7 up to 7.1.1 (extraction in method A, up to the second shaking). The first page of the text of the standard (title, Clause 1 “Scope” and the beginning of the references) is blank in the sample — we know the scope only from the PKN card. We do not have the further course of method A (phase separation, concentration, clean-up on aluminium oxide), the whole of method B, the chromatographic conditions, the calculation (8), the performance characteristics (9), the test report (10) or Annex A (wavelengths for UV and fluorescence detection) — we know them only from the table of contents.

ACCORDING TO THE TEXT OF ISO 13877:1998 (French version: foreword, introduction, Clauses 2 — end, 3–7.1.1). The standard was prepared by ISO/TC 190 “Soil quality”, subcommittee SC 3 “Chemical methods and soil characteristics”. Introduction: PAH are formed when organic matter is processed under pyrolytic conditions (heating or incomplete combustion with oxygen deficiency); in soil they occur diffusely at 1–10 µg/kg per component, in soils of areas used by man (industry, traffic) at 1–10 mg/kg per component, and in soils of (abandoned) industrial sites at several hundred mg/kg per component; PAH are of low volatility and poorly soluble in water, adsorb on solid surfaces and have a high affinity for organic matter, so they occur as a thin layer or fine particles, in clay soils also inside aggregates, and in more heavily contaminated areas in dust, soot or tar particles; this diversity makes a single method for all applications impossible, hence two methods: A — for slightly or non-contaminated soils, with a polar solvent (acetone) and mechanical shaking that breaks up the aggregates; B — for more heavily contaminated soils, with a less polar solvent dissolving PAH from soot and tar particles: the most effective would be the highly toxic benzene, so toluene with total extraction in a Soxhlet apparatus is prescribed (the French version gives the same expression “domaine des mg/kg” for both soil types). Both methods apply to all concentration ranges, but acetone extraction of highly contaminated soils and toluene extraction of slightly contaminated soils may give unsatisfactory results — the method is chosen according to the expected concentrations and the way PAH are bound in the soil. Other solvents (hexane, cyclohexane, methyl chloride, acetonitrile, tetrahydrofuran) and other techniques (ultrasound, supercritical fluid extraction — SFE) often give comparable results, but procedures not described in the standard are not covered by it and their users should not refer to it. It is recommended to obtain beforehand the approval of the public health authorities for the facilities and to train staff with a non-carcinogenic PAH, e.g. fluoranthene. References (end of Clause 2, visible in the sample): ISO 11464 (pretreatment of samples for physico-chemical analysis), ISO 11465 (dry matter and water content, gravimetric method), ISO 14507 (pretreatment of samples for the determination of organic contaminants). Principle (3): the soil is extracted with acetone without drying (method A) or with toluene after drying (method B; losses of naphthalene may occur when the soil is air-dried — Note 1); the extract is analysed by HPLC with a variable-wavelength UV detector or a fluorescence detector with variable excitation and emission wavelengths; quantification is from the signals (peak area or height) by external calibration; 16 compounds listed in 5.11 can be determined (PAH called EPA priority pollutants), for other PAH the method has to be validated; fluorescence detection does not allow acenaphthylene to be measured (Note 2). Apparatus (4): balances with 0,01 g and 0,01 mg accuracy (the latter only for standards), drying oven according to ISO 11465; for method A — 500 ml conical flask, 1000 ml separating funnel, horizontal shaker up to 200 strokes per minute, concentration device (e.g. Kuderna-Danish or rotary evaporator), water bath up to 100 °C, chromatography column for clean-up with an internal diameter of 1 cm; for method B — Soxhlet apparatus of about 30 ml with cellulose or glass-fibre thimbles, 100 ml flask and reflux condenser (the thimbles are washed with toluene if a blank value cannot be excluded), 50 and 100 ml volumetric flasks; for analysis — HPLC with UV or fluorescence detector (with fluorescence, degassing of the mobile phase is necessary, e.g. with helium), reversed-phase separation column for PAH with a guard column (extends the life of the column with soil samples), data recording system. Reagents (5): of residue-analysis grade and free of PAH; blank values are determined periodically, usually after introduction of new batches; solvent batches containing PAH are replaced or distilled (e.g. in a 1 m Vigreux column); acetone, petroleum ether (boiling range 40–60 °C) and toluene — analytical or residue-analysis grade; anhydrous sodium sulfate; basic or neutral aluminium oxide with a specific surface of 200 m²/g, activity super I according to Brockmann; methanol or acetonitrile of HPLC grade; double-distilled or deionized water for extraction (A) and ultrapure water for the mobile phase; helium for degassing; nitrogen for concentration (check that no impurities are introduced, e.g. from plastic tubing). Reference substances (5.11): naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[ah]anthracene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene — with CAS numbers. Standard solutions (5.12): warning — do not prepare PAH standards from solid substances without equipment meeting all safety rules; about 5 mg of each substance (weighed to 0,01 mg) in a 100 ml flask made up with methanol or acetonitrile; 1 ml of this stock solution, by pipette accurate to 1 %, into an ampoule sealed after cooling in liquid nitrogen and stored in an explosion-proof refrigerator — stable for at least 1 year; standard solution — the content of an ampoule into a 100 ml flask made up with acetonitrile (method A) or toluene (method B); for very low concentrations with fluorescence detection — in acetonitrile and further diluted 1:10; commercial solutions are recommended (5.13 — strongly). Sampling and sample pretreatment (6): sampling according to ISO 10381-5 in agreement with the laboratory, containers not affecting the PAH content (glass or metal), sample mass 500–1000 g, a detailed sampling report recommended; further information on storage and pretreatment — ISO 14507; stones and other materials larger than 10 mm that are clearly not contaminated are separated and weighed, and the result recorded; larger particles suspected of contamination are crushed and analysed separately or together with the fine fraction — the procedure followed is given in the test report; samples are stored in the dark and preferably cool (e.g. 4 ± 2 °C) and analysed as soon as possible (microbial degradation, especially in agricultural soils); in method B the sample is air-dried according to ISO 11464, agglomerated soils are crushed in a mortar, sieved to the 2 mm fraction, the mass fractions < 2 mm and > 2 mm recorded and the analytical sample taken from the fraction < 2 mm; soils with a high content of materials of industrial origin (ashes, bricks), or when these materials are to be examined — the whole sample is crushed to particles < 2 mm (typical of brownfield sites). Extraction in method A (7.1.1): about 20 g of soil (to 0,1 g) in a 500 ml conical flask, 200 ml acetone, close, shake vigorously mechanically for 15 min; add 100 ml petroleum ether and shake again for 15 min — the sample ends here.

STATUS (catalogue cards as of 03.10.2026). The card of PN-ISO 13877:2004 (Polish version, published 08-12-2004, 23 pages, price group L) has the header “Withdrawn”: withdrawal date 19-11-2020, Health, Environment and Medicine Sector, KT 191 Soil Chemistry, ICS 13.080.10, “Introduces: ISO 13877:1998 [IDT]”; the card does not name a replacing standard. The PKN search engine (query “PN-ISO 13877”, 03.10.2026) shows only this edition (the other hits are PN-EN 13877 — concrete pavements). The card of PN-EN 17503:2022-07 (English version; soil, sludge, treated biowaste and waste — PAH by GC or HPLC, KT 191) has no “Withdrawn” header and in the field “Replaces” lists PN-EN 16181:2018-09 and PN-EN 15527:2008 — not PN-ISO 13877. ISO document: according to the iTeh catalogue (read 03.10.2026) ISO 13877:1998 has the status “Withdrawn” (stage 95.99, stage date 10-12-2014), and the Slovenian SIST ISO 13877:1999 — “Withdrawn” since 14-11-2022. What this means for the result: withdrawal by PKN does not change the content of the method or remove the standard from the regulation — the Regulation of the Minister of the Environment of 1 September 2016 on the method of assessing contamination of the earth surface (Journal of Laws 2016 item 1395; the only amending act, Journal of Laws 2024 item 1657, does not concern Annex 3) in Annex 3 names for 10 PAH (naphthalene, anthracene, chrysene, benzo(a)anthracene, dibenzo(a,h)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(ghi)perylene, indeno(1,2,3-c,d)pyrene) the reference methodology “Test procedure based on PN-ISO 13877” with HPLC with UV or FL detector or UPLC with UV or FL detector, and alternatively GC-MS based on PN-ISO 18287.

HOW MANY LABORATORIES AND IN WHAT FORM (copy of the accreditation scope database, data up to 17.09.2026, read 03.10.2026). The number 13877 appears in 15 records at 9 laboratories: AB 005, AB 127, AB 165, AB 447, AB 550, AB 869, AB 1059, AB 1249, AB 1302. In the current scopes on the PCA website (read 03.10.2026, issues from 18.12.2025 to 22.09.2026) seven give “PN-ISO 13877:2004” (AB 1059 in the form “PN- ISO 13877:2004”, with a space), AB 165 and AB 550 — the designation alone without the year. The “Laboratories” tab (“PN-ISO 13877”) shows 8 laboratories — all except AB 1059, whose entry with a space after “PN-” does not start with this key; checked with the tab query on the production server labcoda.pl on 03.10.2026.

WHAT THE LABORATORIES TEST (items in PCA scopes). “Content of polycyclic aromatic hydrocarbons (PAH)” in soil and ground — all 9; AB 550 also in waste (many codes), in secondary fuels (SRF) and in solid fuels. Technique: HPLC with fluorescence detection (HPLC-FLD) — 7 laboratories, UHPLC-FLD — AB 550, HPLC-FLD and HPLC-UV — AB 1249. Number of compounds listed: 10 at AB 1302 (exactly the ten PAH of Annex 3 to the regulation), 12 at AB 127, 13 at AB 447, 15 at AB 005, AB 869 and AB 1059 (all of the list in 5.11 except acenaphthylene), 16 at AB 1249 (with acenaphthylene 10–1000 mg/kg — and the only one with UV detection). Ranges: from 0,0060 mg/kg (benzo(a)pyrene at AB 1249) to 1000 mg/kg; AB 447 lists “benzo(a)fluoranthene” (0,01–1 mg/kg) — there is no compound of this name in the list in 5.11. The sum of PAH “from calculation” is given by AB 005, AB 127, AB 447, AB 869, AB 1059 and AB 1249. AB 1249 applies the standard “excluding item 7” together with its own instruction I-13, i.e. without the extraction procedure of the standard; AB 165 cites PN-ISO 13877 and PN-EN 17503 jointly for HPLC-FLD.

WHERE A SEEMINGLY CORRECT RESULT IS EASY TO GET. Sampling and storage: a plastic container can change the PAH content (glass or metal are allowed), and storage in light and warmth and delay — especially with agricultural soils — lower the result through microbial degradation (6). Pretreatment: in method B air drying can cause losses of naphthalene (Note 1 in Clause 3); separating large particles without recording whether they were contaminated changes what the result refers to (6). Choice of extraction: acetone for a highly contaminated soil (soot, tar) and toluene for a slightly contaminated soil may give unsatisfactory results — both methods are formally applicable to all concentration ranges, so the error does not come from exceeding the range (introduction). Detection: the fluorescence detector does not measure acenaphthylene (Note 2) — a “16 PAH” sum calculated from fluorescence results alone has one component less, and the sum at laboratories with 15 compounds in the scope does not include acenaphthylene. Reagents: solvents containing PAH and nitrogen from plastic tubing give blank values — check after every new batch (5.1, 5.10). Calculation of the PAH sum: the components are measurement results of this method, but the list of components depends on the laboratory (10, 12, 13, 15 or 16) — when comparing sums from different laboratories, the list must be checked.

WHAT WE DO NOT GIVE. We do not have Clause 1 (blank page in the sample — scope only from the card), 7.1 after the second shaking or method B, the clean-up on aluminium oxide, the HPLC conditions (columns, mobile phase, gradient), the UV and fluorescence wavelengths of Annex A, the calculation, the limits of quantification or the results of interlaboratory trials of Clause 9 — so we give none of these values.

Method principle

PAH are extracted from soil with acetone and petroleum ether without drying (method A) or with toluene in a Soxhlet apparatus after air drying (method B), the extract is concentrated and cleaned up, and the 16 compounds are separated by reversed-phase high-performance liquid chromatography and detected with a variable-wavelength UV detector or a fluorescence detector; the content is determined from peak area or height by external calibration.

Applications

• Soil and ground — PAH in the assessment of contamination of the earth surface (reference methodology for 10 PAH in Annex 3 to Journal of Laws 2016 item 1395); 9 laboratories in PCA scopes
• Soils of brownfield sites with materials of industrial origin (ashes, bricks) — crushing of the whole sample to < 2 mm (Clause 6)
• Waste, secondary fuels (SRF) and solid fuels — in the scope of one laboratory, outside the scope of the standard (the standard concerns soil)

Key parameters

Standard

Standard number

PN-ISO 13877:2004

Title (PL)

Jakość gleby — Oznaczanie wielopierścieniowych węglowodorów aromatycznych — Metoda z zastosowaniem wysokosprawnej chromatografii cieczowej

Title (EN)

Soil quality — Determination of polynuclear aromatic hydrocarbons — Method using high-performance liquid chromatography

Step-by-step procedure

1. Sample

   Sample according to ISO 10381-5, 500–1000 g into glass or metal; store dark and cool, analyse as soon as possible; separate and weigh stones > 10 mm. PN-ISO 13877:2004 withdrawn 19-11-2020 (PKN catalogue card as of 03.10.2026), still named in Journal of Laws 2016 item 1395, Annex 3.

2. Choice of method

   Method A (acetone, undried soil) — slightly contaminated soils; method B (toluene, Soxhlet, soil air-dried and sieved to 2 mm) — soils with soot, tar, industrial materials.

3. Extraction A

   About 20 g of soil, 200 ml acetone, 15 min shaking; 100 ml petroleum ether, again 15 min; then separation, concentration and clean-up according to 7.1 (we do not have the text).

4. Standards and calibration

   Standard solution from the ampoule into 100 ml acetonitrile (A) or toluene (B); with fluorescence and low concentrations — in acetonitrile, diluted 1:10; external calibration.

5. HPLC and result

   Reversed-phase separation, UV or fluorescence detection (acenaphthylene only UV); conditions, wavelengths and calculation according to 7.3–8 and Annex A (we do not have the text).

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• Some PAH (e.g. benzo[a]pyrene) are carcinogenic — the standard warns against preparing standards from solid substances without suitable equipment and recommends training staff with non-carcinogenic fluoranthene
• Acetone, petroleum ether, toluene and acetonitrile are flammable; Soxhlet extraction and concentration — in a fume hood, standards in an explosion-proof refrigerator

Frequently asked questions