🧯 Sampling of waste gases for the determination of organic compounds — PN-Z-04008-4

Environment PN-Z-04008-4

Overview

STATUS (state of the PKN card on 22.09.2026). PN-Z-04008-4:1999 is CURRENT — the card contains no withdrawal note and no "Replaced by" row. Publication 27-05-1999, 8 pages, ICS 13.040.40, technical body KT 280 (Air Quality).

A NOTE ON THE NUMBER: THE PN-Z-04008 SERIES HAS SHEETS ON TWO DIFFERENT SUBJECTS. The number PN-Z-04008 is associated with workplace air, and this is what sheet 7 is — PN-Z-04008-7:2002 "Principles of sampling air in the working environment and of interpreting the results" (current, with the amendment Az1:2004). Sheet 4, which this entry concerns, describes something else: the sampling of WASTE GASES, i.e. EMISSIONS. The difference is visible on the cards in two fields: sheet 7 is maintained by KT 159 (Chemical and Dust Hazards in the Working Environment) and has ICS 13.040.30 (workplace atmospheres), sheet 4 is maintained by KT 280 (Air Quality) and has ICS 13.040.40 (stationary source emissions). The series number therefore does not determine the subject of the standard — the technical body and the ICS classification decide. We note this because we made this mistake ourselves before we looked at the card, and detected it only by a measurement on the accreditation scopes, where all entries with this standard have the test object "Gazy odlotowe" [waste gases].

WHAT THE STANDARD COVERS AND WHAT IT DOES NOT. The standard describes SAMPLING and PREPARATION FOR ANALYSIS. The determination itself — chromatographic separation, detection, calibration — is outside it. Citing the number PN-Z-04008-4:1999 alone in an accreditation scope therefore does not say by which determination the result was obtained or what its uncertainty is; it says only how the sample reached the laboratory. This is the same observation we recorded for other sampling standards: a scope row with the standard number alone describes an activity or a document, not a test carried out.

THREE WAYS OF SAMPLING. The card of the standard states the scope unambiguously: sampling and preparation of samples of waste gases using (1) adsorption on ACTIVATED CARBON with solvent desorption, (2) adsorption on SILICA GEL with solvent desorption and (3) ABSORPTION IN ABSORPTION SOLUTIONS. The choice of method is not arbitrary — it depends on which compounds are to be determined. A RESERVATION ABOUT THE NEXT SENTENCE: here we describe GENERAL ANALYTICAL PRACTICE, not the content of the standard, whose text we did not have; we do not know what selection criteria its annex gives. In practice activated carbon binds non-polar and weakly polar compounds, silica gel is used for polar compounds that activated carbon does not release on desorption, and absorption solutions — for compounds that react chemically with the reagent in the impinger. The standard contains annexes: guidelines for carrying out PRELIMINARY TESTS, for calculating the results, and information useful for SELECTING the method of sampling and sample preparation. The very fact that the choice of method received a separate annex is content here: there is no single default sampling mode for all organic compounds.

"WITH PARAMETERS SIMILAR TO AIR" IS A CONDITION OF APPLICATION, NOT A DESCRIPTION. The title of the standard contains a restriction that is easy to read as an ornament. The standard concerns waste gases with parameters SIMILAR TO AIR. What exactly this condition requires — what limits of temperature, humidity and composition — WE DO NOT KNOW, because we did not have the text of the standard; we only know that the condition exists and that it stands in the title. From general analytical practice, not from the standard, it is known why such a restriction is imposed at all: a hot, wet gas or one with a high solvent concentration changes the behaviour of the sorbent bed. Either way, a standard with this restriction in its title is not a universal document for sampling from every emission source — and a laboratory citing it for a gas that differs from air should be able to indicate on what basis it considered the condition fulfilled.

WHAT THE ACCREDITATION SCOPES GIVE — A LIMIT IN MASS, NOT IN CONCENTRATION. A measurement on the database of scopes (22-09-2026, 84 entries with this standard) shows a regularity that follows directly from the fact that this is a sampling standard: the ranges declared with it are most often given AS MASS IN THE SAMPLE, not as a concentration — for example "(2 – 1000) µg w próbce" [µg in the sample] for phenol and cresols, "(10 – 1000) µg w próbce" [µg in the sample] for methanol, "(0,002 – 4) mg w próbce" [mg in the sample] for N,N-dimethylacetamide. The reason is the same as for the determination of sodium hydroxide in air according to PN-Z-04435:2011 (a separate entry in this database): a limit expressed in mg/m³ depends on the volume of gas drawn, so a laboratory that does not fix a single volume in advance gives the limit in mass. Some scopes give both numbers at once, for example "(0,520 – 800) mg/m³" with "(0,0260 – 4,00) mg w próbce" [mg in the sample] — and only the pair gives complete information.

"EMISJA ZWIĄZKÓW ORGANICZNYCH (Z OBLICZEŃ)" [EMISSION OF ORGANIC COMPOUNDS (CALCULATED)] — A CALCULATED QUANTITY, NOT A MEASURED ONE. In 23 scope entries with this standard the methodology reads "Emisja związków organicznych (z obliczeń)" [emission of organic compounds (calculated)], next to 20 entries with the methodology "Pobieranie próbek do oznaczania stężeń związków organicznych" [sampling for the determination of concentrations of organic compounds]. Emission (mass per unit of time) is not measured — it is calculated from the concentration and the volume flow of the gas, and the flow comes from a separate measurement according to another standard. A result marked "(z obliczeń)" [calculated] therefore has an uncertainty composed of at least two components and must not be treated as a direct measurement. The same situation occurs with total nitrogen calculated from three determinations according to PN-C-04576-14:1973 — that standard has its own entry in this database.

A NATIONAL STANDARD THAT OUTLIVED THE EUROPEAN ONE. A related method — the determination of the mass concentration of individual gaseous organic compounds using activated carbon and solvent desorption — was described by PN-EN 13649:2005 (implementing EN 13649:2001). That standard was WITHDRAWN on 08-08-2018, and its card does not indicate a successor of the same rank; what is in circulation, however, is a document of LOWER rank and a later date — CEN/TS 13649:2014, with a broader title, because it also covers thermal desorption. PN-Z-04008-4:1999, a NATIONAL standard twenty years older, remains current. We have not established whether CEN/TS 13649:2014 formally replaced EN 13649:2001 — publishers' catalogue descriptions point to this, but they are summaries, not the document.

WHAT WE DO NOT GIVE. We did not have the text of PN-Z-04008-4:1999 — the standard is sold for a fee and has no international counterpart whose sample extract could be viewed. Everything above comes from the PKN catalogue card (scope, title, publication data, technical body, ICS) and from a measurement on the database of accreditation scopes. WE THEREFORE DO NOT GIVE: the masses of sorbent in the tube and the size of the back-up layer, the permissible breakthrough, the list of desorption solvents or the required desorption efficiency, the recommended flow rates and sample volumes, the composition of the absorption solutions, or what exactly the preliminary tests in the annex cover. All these quantities affect the result. We point this out separately because, when searching for the content of this standard, we received a description containing precisely such details — repeated from our own query, not from any source; they were not included in the entry.

Method principle

A metered volume of waste gas with parameters similar to air is passed through an element that captures volatile organic compounds. The standard provides three ways: adsorption on activated carbon followed by solvent desorption, adsorption on silica gel with solvent desorption, and absorption in absorption solutions. The choice of method depends on the nature of the compounds to be determined and is the subject of a separate annex of the standard, as are the guidelines for preliminary tests and for calculating the results. The resulting solution — the eluate after desorption or the absorption solution — is the sample for analysis by gas chromatography, which itself remains outside the scope of this standard.

Applications

• Measurements of emissions of individual volatile organic compounds from industrial installations
• Sampling for the determination of phenol and cresols, methanol, N,N-dimethylformamide and N,N-dimethylacetamide, 1,3-dioxolane and 1,3,5-trioxane in waste gases
• Measurements for the purposes of integrated permits and balancing of volatile organic compounds
• Reading an accreditation scope in which "Emisja związków organicznych (z obliczeń)" [emission of organic compounds (calculated)] appears separately next to sampling
• Deciding whether a given scope row concerns the sampling or the whole determination

Key parameters

Standard

Standard number

PN-Z-04008-4:1999 (wersja polska)

Title (PL)

Ochrona czystości powietrza — Pobieranie próbek — Pobieranie próbek gazów odlotowych (emisja) o parametrach zbliżonych do powietrza i ich przygotowanie do analizy metodą chromatografii gazowej

Title (EN)

Air purity protection — Sampling — Sampling of waste gases (emission) with parameters similar to air and their preparation for gas chromatography analysis

Step-by-step procedure

1. Checking whether the standard applies

   Establish whether the waste gas has parameters SIMILAR TO AIR — the condition stands in the title of the standard. We do not give the limits of this condition: we did not have the text of the standard, so we do not know how it is defined there. Check this in the standard itself before citing it.

2. Choosing the sampling method

   Select one of the three methods depending on the nature of the compounds to be determined: activated carbon (non-polar and weakly polar), silica gel (polar), absorption solution (chemically reacting). The standard contains a separate annex on this — the choice is not arbitrary.

3. Preliminary tests

   Carry out preliminary tests according to the guidelines in the annex of the standard. Their purpose is to check whether the adopted sampling method and sample volume are appropriate for the given emission source and the compounds to be determined.

4. Taking the sample

   Pass a metered volume of gas through the capturing element. Record the volume: with this standard the determination range is usually declared as mass in the sample, and conversion to a concentration in mg/m³ is impossible without the volume.

5. Preparing the sample for analysis

   Subject the sorbent to solvent desorption, or collect the absorption solution from the impingers quantitatively and make up to a known volume. The resulting solution is the sample for chromatographic analysis.

6. Determination — outside the scope of the standard

   Carry out the determination by gas chromatography according to the laboratory's own test procedure. The standard indicates the technique in its title, but does not describe the separation, detection or calibration — look for these elements in the laboratory's procedure, not in the standard.

7. Calculating the result

   Calculate the result according to the guidelines in the annex of the standard. Relate the concentration to the gas volume and to the adopted reference conditions, and give the result together with them.

8. Distinguishing concentration from emission

   If the scope includes "Emisja związków organicznych (z obliczeń)" [emission of organic compounds (calculated)], remember that this is a quantity calculated from the concentration and the volume flow of the gas, which comes from a separate measurement. Mark it in the report with the annotation "(z obliczeń)" [calculated] and do not present it as a result of a direct measurement.

Required equipment and apparatus

Reagents, media and consumables

Health and safety (OHS)

• Sampling at the emission source takes place on the measurement platform with hot gases — the rules for working at height and protection against burns from the probe apply
• The solvents used for desorbing the sorbents are volatile, flammable and harmful — carry out the desorption under an efficient fume hood, in chemically resistant gloves
• The compounds determined (phenol, cresols, dimethylformamide, dimethylacetamide) are toxic, and some are toxic to reproduction — an exposure assessment of the persons taking the samples is required, not only of those carrying out the analysis
• After sampling, sorption tubes contain concentrated pollutants — transport and store them tightly closed, in accordance with the requirements for samples, and treat used ones as hazardous waste
• Report the result with the volume of gas collected and with the reference conditions — a limit expressed in mg/m³ without the sample volume is an incomplete number

Frequently asked questions