🌿 Determination of hydrocarbon content C10–C40 (mineral oil) in solid waste by gas chromatography — about 20 g of sample is shaken for one hour with acetone and an n-heptane solution with retention time window standards, the organic layer is washed with water, cleaned up on a Florisil and sodium sulfate column and analysed by GC-FID; the result is the sum of areas between the n-decane and n-tetracontane peaks against a standard of two mineral oils, 100–10 000 mg/kg dry matter, PN-EN 14039

Environment PN-EN 14039

Overview

WHAT THE STANDARD COVERS. Scope from the PKN catalogue card of PN-EN 14039:2008 (Polish version), in full (our translation): “A method is given for the quantitative determination of hydrocarbon content (C10 to C40) by gas chromatography in solid waste. The method is applicable to hydrocarbon contents between 100 mg/kg and 10000 mg/kg expressed on a dry matter basis”. We read the text of the standard in the sample of SIST EN 14039:2005 (the text of EN 14039:2004 without changes) from the title page through the contents, foreword, introduction and Clauses 1–9 up to and including the beginning of 10.4.1. Outside the sample remain the rest of 10.4 (chromatographic conditions and procedure, calibration), calculation, Clause 11 (performance characteristics), 12 (test report) and Annexes A–E (example chromatograms, boiling points of n-alkanes, flow diagram, aqueous liquid waste, summary of requirements).

ACCORDING TO THE TEXT OF EN 14039:2004 (Clauses 1–9, 10.1–10.4.1). The standard was prepared by CEN/TC 292 “Characterization of waste” (secretariat NEN). Foreword: waste and sludge may contain hazardous substances (toxic, reactive, flammable, infectious), gases from microbiological or chemical activity are flammable and pressurize sealed bottles, and bursting bottles scatter shrapnel, dust or aerosol. Introduction: hydrocarbons have so far been determined mainly by infrared spectroscopy after extraction with halogenated solvents (1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloromethane); the standard gives a method by capillary gas chromatography without such solvents; results may not be comparable with those of the infrared method; the preferred extraction solvent is a mixture of acetone and n-heptane; for waste with large amounts of relatively high-boiling hydrocarbons the gravimetric method (EN 14345) can be used. Scope (1): quantitative determination of hydrocarbons C10–C40 in solid waste by gas chromatography, 100–10 000 mg/kg on a dry matter basis; all compounds boiling approximately at 175–525 °C are determined as hydrocarbons — n-alkanes from C10H22 to C40H82, isoalkanes, cycloalkanes, alkyl benzenes, alkyl naphthalenes and polycyclic aromatic compounds — provided they do not adsorb on Florisil; volatile hydrocarbons cannot be determined quantitatively, which affects e.g. petrol. Notes: from the chromatogram pattern (Annex A) and the boiling points of n-alkanes (Annex B) the approximate boiling range and nature of the hydrocarbons can be assessed; there is insufficient information on organic liquid waste; aqueous liquid waste is analysed according to EN ISO 9377-2 or the annex of the standard (entry on PN-EN ISO 9377-2). Normative references (2): prEN 14346 (dry matter), EN ISO 3696, ISO 8466-1. Definition (3.1): hydrocarbon content by gas chromatography is the sum of compounds extractable with acetone/n-heptane (2 + 1) that do not adsorb on Florisil and can be chromatographed on a non-polar capillary column with retention times between n-decane and n-tetracontane — mainly non-polar long-chain or branched aliphatic, alicyclic, alkyl-substituted aromatic or polycyclic aromatic compounds; the definition differs from that in EN 14345. Principle (4): a known amount of the homogenized sample is extracted with acetone and n-heptane by mechanical shaking or sonication, the organic layer is separated and washed twice with water, polar compounds are removed by chromatography on Florisil, and an aliquot of the purified extract is analysed by capillary gas chromatography with flame ionization detection; the total area between the retention time window standards (n-decane and n-tetracontane) is measured and quantified against an external standard of equal amounts of two different mineral oils; instead of heptane another non-polar solvent (e.g. petroleum ether, cyclohexane, n-hexane) may be used if its suitability is proven. Interferences (5): high concentrations of more polar compounds, e.g. animal and vegetable fats and oils, may exceed the capacity of the Florisil; up to 10 000 mg/kg of such compounds do not interfere. Reagents (6): water at least grade 3 according to EN ISO 3696; acetone, n-heptane; Florisil 150–250 µm, heated at least 16 h at 140 °C and stored in a desiccator over molecular sieve (or ready-made cartridges); anhydrous sodium sulfate; test solution of stearyl stearate (approx. 100 ± 1 mg in 100 ml of n-heptane, stable 6 months at 1–5 °C); retention time window solution — (30 ± 1) mg of n-tetracontane and 30 µl of n-decane (approx. 21 mg) in 1 l of n-heptane, used for all dilutions of the hydrocarbon standard and stored at room temperature; hydrocarbon calibration standard — approximately equal masses of two mineral oils dissolved in the window solution to approx. 8 g/l: the first with discrete peaks (e.g. diesel fuel without additives), the second with a higher boiling range giving a “hump” in the chromatogram (e.g. lubricating oil without additives); an independent control solution from the middle of the working range; system performance solution — even n-alkanes C10–C40 at approx. 50 mg/l each in n-heptane (resolution and detector response, retention times); clean-up column — plug of glass wool or PTFE frit, 2 g Florisil and 2 g sodium sulfate, prepared immediately before use. Hazards (7): acetone and n-heptane are highly flammable; care during centrifugation; pressure may build up in the extraction vessel — vent in a fume hood. Equipment (8): glassware heated or rinsed with acetone; shaker or ultrasonic bath; gas chromatograph with non-discriminating injection, FID and temperature-programmable oven; capillary column with non-polar phase (e.g. 100 % dimethylpolysiloxane, 5 % phenyl-), length at least 5 m, diameter 0.1–0.32 mm, giving baseline separation of n-alkanes; a pre-column is recommended; data system integrating the total chromatogram area with compensation of column bleed; extraction vessel at least 100 ml, tube 25 ml, separating funnel at least 500 ml, glass column approx. 10 mm. Storage (9): samples kept sealed, in the dark, at about 4 °C, extracted within one week; if not possible — at −18 °C or lower; homogenized before analysis. Blank (10.1): with each series, with all reagents but without sample; a blank greater than 10 % of the lowest value of interest requires checking every step. Water (10.2): dry matter is determined according to prEN 14346 in the sample or in each phase after phase separation; stable emulsions are analysed without phase separation. Extraction and clean-up (10.3): approx. 20 g of sample (to the nearest 0.1 g) into the vessel, (40 ± 1) ml of acetone, short shaking by hand, (20 ± 0.1) ml of window solution, shaking or sonication for 1 h; after settling as much liquid as possible into the separating funnel, two washes with 100 ml of water to remove acetone, organic layer into the tube, sodium sulfate until no lumps form; 10 ml of extract onto the Florisil column without pre-washing with solvent, collect the entire eluate, an aliquot into a GC vial. Notes: test portion 5–30 g (smaller when the sample absorbs the solvent, larger for sensitivity); alternative extraction (e.g. ASE) allowed if comparable; centrifugation speeds phase separation; alternatively cartridges with 2 g Florisil and 2 g sodium sulfate; it is very important that the Florisil is fresh and active and the extract free of acetone (less than 0.1 % by volume), especially when the sample contains PAH besides mineral oil — PAH must be adsorbed on the Florisil, and if distinct PAH peaks are seen in the GC-FID chromatogram, this should be reported.

STATUS (catalogue cards as of 03.10.2026). The card of PN-EN 14039:2008 (Polish version, published 28-01-2008, 23 pages, price group L) has no “Withdrawn” header: Health, Environment and Medicine Sector, KT 216 Waste, ICS 13.030.01, “Introduces: EN 14039:2004 [IDT]”, “Supersedes: PN-EN 14039:2005 — English version”. The card of PN-EN 14039:2005 (English version) — “Withdrawn” 28-01-2008, “Replaced by: PN-EN 14039:2008 — Polish version”; both introduce the same EN 14039:2004. The PKN search (term “PN-EN 14039”, 03.10.2026) shows no other editions.

HOW MANY LABORATORIES AND IN WHAT FORM (copy of the accreditation scope database, load up to 17.09.2026, read 03.10.2026). The number 14039 appears in 7 records at 5 laboratories: AB 213, AB 322, AB 418, AB 550, AB 646. One of the two AB 418 records in our copy is the TOC item from the neighbouring row of the PCA document (where PN-EN 13137:2004 is cited) — in the current AB 418 document the standard 14039 stands at two mineral oil items. In the current scopes on the PCA website (read 03.10.2026, issues from 17.11.2025 to 22.09.2026) AB 213, AB 322 and AB 646 give “PN-EN 14039:2008”, AB 418 — once with year and once without, AB 550 — twice without year. The “Laboratories” tab (“PN-EN 14039”) shows the same 5 laboratories; checked with the tab query on the production server labcoda.pl on 03.10.2026.

WHAT THE LABORATORIES TEST (PCA items). Waste with codes (AB 322, AB 646, AB 418, AB 550), solid recovered fuels (AB 550), bottom sediments (AB 418) and construction materials — sand, aggregate, slag (AB 213, AB 418). Item names: “Mineral oil content (hydrocarbons C10–C40)”, “Hydrocarbon content in the range C10 to C40 (mineral oils)”, “Mineral oil index” (AB 550). Technique everywhere: GC-FID. Ranges: (5.0–5000) mg/kg (AB 213), (5.0–10 000) mg/kg (AB 646), (10–10 000) mg/kg (AB 418), (50–10 000) mg/kg (AB 322); AB 550 gives no range. All four lower limits given lie below 100 mg/kg — the lower applicability limit of Clause 1; the upper ones do not exceed 10 000 mg/kg.

WHERE A SEEMINGLY CORRECT RESULT IS EASY. At storage: a sample kept at 4 °C longer than one week, and not frozen to −18 °C, does not meet the conditions of Clause 9; volatile fuel fractions (e.g. petrol) are not determined quantitatively by the method anyway (1). At clean-up: acetone left in the extract (above 0.1 % by volume) or inactive Florisil let PAH and polar compounds pass, which enter the sum as “hydrocarbons” — the result is too high; animal and vegetable fats above 10 000 mg/kg exceed the Florisil capacity (5, note 5 to 10.3). At calibration: the standard requires a standard of two different oils — one with discrete peaks and a second, higher-boiling one with a “hump” (6.8); a standard of a single oil is a deviation from the standard; the n-decane–n-tetracontane window standards are added to every sample (10.3), because they define the integration limits (4). At calculation: the result refers to dry matter determined on a separate portion (10.2) — a component of the calculation, not a measurement of this method (on dry matter — entry on PN-EN 14346); a blank greater than 10 % of the lowest value of interest requires searching for the cause (10.1). At the result: results of this method may not be comparable with the former infrared method (introduction) and with the gravimetric method EN 14345, which has a different definition (3.1, note 2); results in the interval below 100 mg/kg lie outside the scope of the standard.

WHAT WE DO NOT GIVE. We did not read the rest of 10.4, the calculation, Clauses 11–12 and the annexes, so we do not give chromatographic conditions, the way of determining the area and baseline, the calculation formula, precision data or report requirements beyond the statement on PAH. Nor do we give criteria for waste or soil, because we did not read the texts of regulations for this entry.

Method principle

Hydrocarbons are extracted from the moist sample with acetone and n-heptane, acetone is removed by washing with water, and polar compounds (e.g. fats, PAH) are retained by a Florisil column. The purified extract is separated on a non-polar capillary column with a flame ionization detector, and the whole area between the peaks of n-decane and n-tetracontane, added to every sample, is integrated; the area is converted against a standard of equal amounts of two mineral oils and related to dry matter.

Applications

• Solid waste — hydrocarbons C10–C40 (boiling at approx. 175–525 °C), 100–10 000 mg/kg dry matter (Clause 1)
• Assessment of the nature of contamination from the chromatogram pattern and the boiling points of n-alkanes (note 1 to Clause 1)
• Waste, bottom sediments, solid recovered fuels, construction materials (sand, aggregate, slag) — in the accreditation scopes of 5 laboratories at PCA

Key parameters

Standard

Standard number

PN-EN 14039:2008

Title (PL)

Charakteryzowanie odpadów — Oznaczanie zawartości węglowodorów w zakresie od C10 do C40 za pomocą chromatografii gazowej

Title (EN)

Characterization of waste — Determination of hydrocarbon content in the range of C10 to C40 by gas chromatography

Step-by-step procedure

1. Storage and dry matter

   Sample at 4 °C in the dark, extraction within one week (otherwise −18 °C); homogenization; dry matter on a separate portion according to prEN 14346. PN-EN 14039:2008 current (PKN catalogue card as of 03.10.2026).

2. Extraction

   approx. 20 g of sample + 40 ml acetone, shake briefly, add 20 ml window solution, 1 h shaking or sonication; vent the vessel in a fume hood.

3. Removal of acetone and drying

   Liquid into the separating funnel, wash twice with 100 ml of water, dry the organic layer with sodium sulfate.

4. Clean-up on Florisil

   10 ml of extract onto the column (2 g Florisil + 2 g Na2SO4), collect the entire eluate; fresh, active Florisil.

5. GC-FID

   Check the system with the n-alkane solution; measure the area between n-decane and n-tetracontane; blank with each series. Conditions and calculation — outside the sample read.

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• Acetone and n-heptane are highly flammable; special care during centrifugation; vent pressure in the extraction vessel in a fume hood (Clause 7)
• Waste and sludge may contain toxic, reactive, flammable or infectious substances; gases from samples may burst sealed bottles (foreword)

Frequently asked questions