Water quality - Determination of polycyclic aromatic hydrocarbons (PAH) in whole water samples using liquid solid extraction combined with gas chromatography mass spectrometry (GC-MS)

This European Standard specifies a method for the determination of 7 polycyclic aromatic hydrocarbons (PAH) in whole water samples as listed in Table 1. The method uses solid-phase disk extraction (SPE-disk) in combination with gas chromatography-mass spectrometry (GC-MS). It is applicable to the analysis of PAHs in surface water, which may contain suspended particulate matter (SPM) up to 500 mg/l (whole water samples), drinking water and groundwater.
The lower and upper limit of the working range depends on the matrix, on the specific compound to be analyzed and on the sensitivity of the mass spectrometric detection unit. The limit of quantification (LOQ) determined in the validation is given in Table 1. The upper limit of the working range is approximately 2 000 ng/l.
This method is, with some modification may also be suitable for the analysis of waste water. This method is applicable to other PAH ), provided the method is validated for each PAH.
(...)

Wasserbeschaffenheit - Bestimmung von polycyclischen aromatischen Kohlenwasserstoffen (PAK) in Gesamtwasserproben mittels Flüssig/Fest-Extraktion in Verbindung mit Gaschromatographie-Massenspektrometrie (GC-MS)

Diese Europäische Norm legt ein Verfahren für die Bestimmung von 7 polycyclischen aromatischen Kohlenwasserstoffen (PAK) in Gesamtwasserproben fest, wie in Tabelle 1 angegeben. Das Verfahren verwendet Festphasenextraktions-Scheiben (SPE-Disk, en: solid-phase extraktion disk) in Kombination mit Gaschromatographie Massenspektrometrie (GC-MS). Die Norm gilt für die Analyse von PAK in Oberflächenwasser, mit einem Schwebstoffanteil bis zu 500 mg/l (Gesamtwasserproben), Trinkwasser und Grundwasser.
Die untere und obere Grenze des Arbeitsbereichs hängt von der Matrix, der zu bestimmenden Substanz und der Empfindlichkeit des Massenspektrometers ab. Die Bestimmungsgrenze (BG) nach der Validierung des Verfahrens ist in Tabelle 1 angegeben. Die obere Arbeitsgrenze beträgt ungefähr 2 000 ng/l.
Dieses Verfahren darf mit Modifikationen auch für Abwasser angewendet werden. Dieses Verfahren ist zur Bestimmung weiterer PAK anwendbar ), wenn es für diese PAK jeweils validiert wurde.
(...)

Qualité de l'eau - Dosage des hydrocarbures aromatiques polycycliques (HAP) dans des échantillons d'eau totale par extraction liquide-solide avec couplage chromatographie en phase gazeuse-spectrométrie de masse (CG-SM)

La présente Norme européenne spécifie une méthode pour le dosage de 7 hydrocarbures aromatiques polycycliques (HAP) répertoriés dans le Tableau 1, contenus dans des échantillons d'eau considérés dans leur intégralité. Cette méthode utilise une extraction en phase solide avec disques (disques SPE) combinée à une chromatographie en phase gazeuse-spectrométrie de masse (CG-SM). Elle s'applique à l'analyse des HAP dans les eaux de surface, lesquelles peuvent contenir jusqu'à 500 mg/l (échantillons d'eau totale) de particules en suspension (MES), dans l'eau potable et dans les eaux souterraines.
Les limites inférieure et supérieure du domaine de travail dépendent de la matrice, du composé à analyser et de la sensibilité du détecteur par spectrométrie de masse. La limite de quantification (LQ) déterminée lors de la validation est donnée dans le Tableau 1. La limite supérieure du domaine de travail est d'environ 2 000 ng/l.
Avec quelques modifications, la méthode peut également être adaptée à l'analyse des eaux résiduaires. Cette méthode est applicable aux autres HAP  ), à condition qu'elle soit validée pour chaque HAP.
(...)

Kakovost vode - Določevanje policikličnih aromatskih ogljikovodikov (PAH) v celotnem vzorcu vode z ekstrakcijo tekoče-trdno v kombinaciji s plinsko kromatografijo/masno spektrometrijo (GC/MS)

Razvoj metode za kvantitativno določevanje policikličnih aromatskih ogljikovodikov (PAH) v celotnih vzorcih vode z uporabo plinske kromatografije/masne spektrometrije (GC-MS). Obravnavani so naslednji posamezni policiklični aromatski ogljikovodiki:
Ta analitska metoda določa določevanje policikličnih aromatskih ogljikovodikov, ki izpolnjujejo naslednje zahteve:
– analiza celotnih vzorcev vode, ki vsebujejo do 0,5 g/l trdnih delcev;
– meja določljivosti (LOQ) mora biti enaka ali manjša od 30 % EQS;
– merilna negotovost mora biti enaka ali manjša od 50 %;
– pred medlaboratorijskim potrjevanjem morajo biti metode v celoti preverjene interno in testirane glede robustnosti;
– evropska medlaboratorijska študijska primerjava bo potekala v skladu s standardom ISO 5725.

General Information

Status
Published
Public Enquiry End Date
31-Jan-2014
Publication Date
01-Nov-2015
ICS
13.060.50 - Examination of water for chemical substances
Technical Committee
KAV - Water quality
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
12-Oct-2015
Due Date
17-Dec-2015
Completion Date
02-Nov-2015
Directive
2000/60/EC - Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy (substitutes Directive Reference 01/991 - Common Position on WFD)
Mandate
M/424 - Mandate for standardisation addressed to CEN for the development or improvement standards in support of the water framework directive
Ref Project
EN 16691:2015 - Water quality - Determination of selected polycyclic aromatic hydrocarbons (PAH) in whole water samples - Method using solid phase extraction (SPE) with SPE-disks combined with gas chromatography mass spectrometry (GC-MS)

Overview - EN 16691:2015 (Water quality, PAH determination)

EN 16691:2015 is a CEN European Standard for the determination of selected polycyclic aromatic hydrocarbons (PAH) in whole water samples. The method combines solid‑phase extraction (SPE‑disk) with gas chromatography–mass spectrometry (GC‑MS) to quantify seven target PAHs (anthracene, fluoranthene, benzo[b]‑ and benzo[k]‑fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3‑cd]pyrene). It applies to surface water (including whole water with suspended particulate matter up to 500 mg/L), drinking water and groundwater. The working range depends on matrix and instrument sensitivity; the upper limit is approx. 2 000 ng/L and validated limits of quantification (LOQ) for each PAH are provided in the standard.

Key topics and technical requirements

  • Sampling and preservation: Guidance consistent with EN ISO 5667 series; store samples at (3 ± 2) °C and avoid plastics or organic materials (use glass or stainless steel where possible).
  • Extraction: Use of SPE‑disks (liquid–solid extraction) with internal standards added before extraction; batch consistency of SPE disks recommended to ensure reproducible recoveries.
  • Concentration & clean‑up: Evaporation to concentrate extracts; optional silica clean‑up for complex surface water matrices (Annex D).
  • GC‑MS analysis: Low‑resolution mass spectrometry with electron impact (EI) ionization (typically SIM mode) for identification and quantification. An injection standard is added prior to injection.
  • Calibration & QA: Calibration by internal standards, blank measurements and recovery correction. Chromatographic resolution requirements (e.g., R > 0.8 for specific co‑eluting PAH pairs such as anthracene/phenanthrene and benzo[a]/benzo[e]pyrene) to avoid misidentification.
  • LOQs: Validated LOQs are listed for each compound (e.g., anthracene 0.24 ng/L, benzo[a]pyrene 0.33 ng/L, fluoranthene 2.1 ng/L).

Applications and users

EN 16691:2015 is used for:

  • Regulatory and compliance monitoring under the EU Water Framework Directive (WFD) and related EQS programs.
  • Environmental laboratories and testing facilities performing PAH analysis in whole water samples.
  • Water utilities, environmental consultancies, research institutions and public authorities assessing contamination in surface water, groundwater and drinking water.
  • Adaptation (with validation) for wastewater testing where required.

Related standards

  • EN ISO 5667 (sampling guidance)
  • EN ISO 17993, ISO 7981, ISO 28540, ISO/TS 28581 (other PAH methods in water)
  • The standard references validation, calibration and QC practices to meet WFD monitoring requirements.

Keywords: EN 16691:2015, water quality standard, PAH determination, SPE‑disk extraction, GC‑MS, whole water samples, suspended particulate matter, benzo[a]pyrene, LOQ, Water Framework Directive.

Frequently Asked Questions

SIST EN 16691:2015 is a standard published by the Slovenian Institute for Standardization (SIST). Its full title is "Water quality - Determination of polycyclic aromatic hydrocarbons (PAH) in whole water samples using liquid solid extraction combined with gas chromatography mass spectrometry (GC-MS)". This standard covers: This European Standard specifies a method for the determination of 7 polycyclic aromatic hydrocarbons (PAH) in whole water samples as listed in Table 1. The method uses solid-phase disk extraction (SPE-disk) in combination with gas chromatography-mass spectrometry (GC-MS). It is applicable to the analysis of PAHs in surface water, which may contain suspended particulate matter (SPM) up to 500 mg/l (whole water samples), drinking water and groundwater. The lower and upper limit of the working range depends on the matrix, on the specific compound to be analyzed and on the sensitivity of the mass spectrometric detection unit. The limit of quantification (LOQ) determined in the validation is given in Table 1. The upper limit of the working range is approximately 2 000 ng/l. This method is, with some modification may also be suitable for the analysis of waste water. This method is applicable to other PAH ), provided the method is validated for each PAH. (...)

This European Standard specifies a method for the determination of 7 polycyclic aromatic hydrocarbons (PAH) in whole water samples as listed in Table 1. The method uses solid-phase disk extraction (SPE-disk) in combination with gas chromatography-mass spectrometry (GC-MS). It is applicable to the analysis of PAHs in surface water, which may contain suspended particulate matter (SPM) up to 500 mg/l (whole water samples), drinking water and groundwater. The lower and upper limit of the working range depends on the matrix, on the specific compound to be analyzed and on the sensitivity of the mass spectrometric detection unit. The limit of quantification (LOQ) determined in the validation is given in Table 1. The upper limit of the working range is approximately 2 000 ng/l. This method is, with some modification may also be suitable for the analysis of waste water. This method is applicable to other PAH ), provided the method is validated for each PAH. (...)

SIST EN 16691:2015 is classified under the following ICS (International Classification for Standards) categories: 13.060.50 - Examination of water for chemical substances. The ICS classification helps identify the subject area and facilitates finding related standards.

SIST EN 16691:2015 is associated with the following European legislation: EU Directives/Regulations: 2000/60/EC; Standardization Mandates: M/424. When a standard is cited in the Official Journal of the European Union, products manufactured in conformity with it benefit from a presumption of conformity with the essential requirements of the corresponding EU directive or regulation.

You can purchase SIST EN 16691:2015 directly from iTeh Standards. The document is available in PDF format and is delivered instantly after payment. Add the standard to your cart and complete the secure checkout process. iTeh Standards is an authorized distributor of SIST standards.

Standards Content (Sample)


2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.OLQVNRWasserbeschaffenheit - Bestimmung von polycyclischen aromatischen Kohlenwasserstoffen (PAK) in Gesamtwasserproben mittels Flüssig/Fest-Extraktion in Verbindung mit Gaschromatographie-Massenspektrometrie (GC-MS)Qualité de l'eau - Dosage des hydrocarbures aromatiques polycycliques (HAP) dans des échantillons d'eau totale par extraction liquide-solide avec couplage chromatographie en phase gazeuse-spectrométrie de masse (CG-SM)Water quality - Determination of polycyclic aromatic hydrocarbons (PAH) in whole water samples using liquid solid extraction combined with gas chromatography mass spectrometry (GC-MS)13.060.50VQRYLExamination of water for chemical substancesICS:Ta slovenski standard je istoveten z:EN 16691:2015SIST EN 16691:2015en,fr,de01-december-2015SIST EN 16691:2015SLOVENSKI
STANDARD
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 16691
September
t r s w ICS
s uä r x rä w r English Version
Water quality æ Determination of selected polycyclic combined with gas chromatography mass spectrometry Qualité de l 5eau æ Dosage des hydrocarbures des échantillons d 5eau totale æ Méthode par extraction chromatographie en phase gazeuseæspectrométrie de
Wasserbeschaffenheit æ Bestimmung von ausgewählten polycyclischen aromatischen Kohlenwasserstoffen Verbindung mit Gaschromatographie This European Standard was approved by CEN on
t y June
t r s wä
egulations which stipulate the conditions for giving this European Standard the status of a national standard without any alterationä Upætoædate lists and bibliographical references concerning such national standards may be obtained on application to the CENæCENELEC Management Centre or to any CEN memberä
translation under the responsibility of a CEN member into its own language and notified to the CENæCENELEC Management Centre has the same status as the official versionsä
CEN members are the national standards bodies of Austriaá Belgiumá Bulgariaá Croatiaá Cyprusá Czech Republicá Denmarká Estoniaá Finlandá Former Yugoslav Republic of Macedoniaá Franceá Germanyá Greeceá Hungaryá Icelandá Irelandá Italyá Latviaá Lithuaniaá Luxembourgá Maltaá Netherlandsá Norwayá Polandá Portugalá Romaniaá Slovakiaá Sloveniaá Spainá Swedená Switzerlandá Turkey andUnited Kingdomä
EUROPEAN COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre:
Avenue Marnix 17,
B-1000 Brussels
t r s w CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Membersä Refä Noä EN
s x x { sã t r s w ESIST EN 16691:2015

Suitable gas chromatographic conditions and example chromatograms — GC-conditions . 19 Annex B (informative)
Repeatability and reproducibility data . 22 Annex C (informative)
Dilution Schedules for standards . 26 Annex D (informative)
Silica clean-up . 28 Annex E (informative)
Examples of suitable solid-phase extraction disks (SPE-disks) . 29 Bibliography . 30 SIST EN 16691:2015

g/mol
ng/l anthracene C14H10 178,23 204–371–1 120–12–7 0,24 fluoranthene C16H10 202,26 205–912–4 206–44–0 2,1 benzo[b]fluoranthene C20H12 252,32 205–911–9 205–99–2 0,56 benzo[k]fluoranthene C20H12 252,32 205–916–6 207–08–9 0,44 benzo[a]pyrene C20H12 252,32 200–028–5 50–32–8 0,33 benzo[ghi]perylene C22H12 276,34 205–883–8 191–24–2 0,44 indeno[1,2,3-cd]pyrene C22H12 276,34 205–893–2 193–39–5 0,42 a EC Number: European inventory of existing commercial substances (EINECS) or European list of notified chemical substances (ELINCS). b CAS-RN: Chemical Abstracts Service Registry Number. c For the determination of the LOQ the procedure given in NEN 7777+C1:2012 [12] was used. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 1042, Laboratory glassware - One-mark volumetric flasks (ISO 1042) EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696) EN ISO 5667-1, Water quality - Sampling - Part 1: Guidance on the design of sampling programmes and sampling techniques (ISO 5667-1)
1) During the inter-laboratory validation trial the method was tested for all 16 EPA PAH (see Annex B). SIST EN 16691:2015

Key: X
time Y
intensity tR1, tR2
retention time of eluting substances 1 and 2 in seconds (s) wb1, wb2
peak width at the base of each peak in seconds (s) Figure 1 — Resolution of chromatographic peaks −=+R2R1b1b2()2ttRww (1) where R is the resolution; tR1, tR2
Retention time of eluting substances 1 and 2 in seconds (s); wb1, wb2
peak width at the base of each peak in seconds (s). 5 Reagents The reagents shall be free from impurities possibly interfering with the GC-MS analysis. Use solvents and reagents of sufficient purity, i.e. with negligibly low impurities compared with the concentration of analytes to be determined. As reagents use, as far as available, “residual grade”, “picograde” or better in order to obtain clean blanks. Check blanks regularly and establish proper charge control. If necessary, apply additional cleaning steps. SIST EN 16691:2015

2) PAH stock solutions are commercially available. Examples are for instance CIL ES-2528 d-PAH cocktail: 100 mg/l in benzene-d6 and NIST SRM 1647e: 1 mg/l to 20 mg/l in acetonitrile. These examples are given only as information for the users of this European Standard and do not constitute an endorsement by CEN of these products. SIST EN 16691:2015

6.3 Glass autosampler vials, brown glass, capacity e. g. 2 ml, with inert cap and PTFE-coated septum. 6.4 Capillary gas chromatograph with mass spectrometric detector (GC-MS), using EI-ionization mode, gas supply in accordance with the respective manufacturer’s instructions. 6.5 Capillary column, high resolution, low bleeding, for gas chromatography (see 4.2 for requirements and Annex A for an example). 6.6 One-mark volumetric flasks, according to EN ISO 1042, class A. 6.7 Pasteur pipettes. 6.8 Molecular sieve beads, pore diameter 0,4 nm. 6.9 Vacuum device for solid-phase extraction, extraction box or automated workstation for solid-phase extraction. 6.10 Solid-phase extraction disk, inner diameter between 40 mm and 60 mm packed with an appropriate reversed phase adsorbent material (see Annex E for examples). 6.11 Desiccator. 6.12 Erlenmeyer with glass stopper. 6.13 Equipment for concentrating the eluates by evaporation, e. g. rotary evaporator, adjustable for constant vacuum and with a temperature-controlled water bath, or stripping equipment using nitrogen gas. 6.14 Glass bottles, brown/green glass, narrow-necked, flat-bottomed, 1 000 ml, with PTFE cap liner. 6.15 Balance, with an accuracy of ± 0,1 g. 6.16 Glass wool, rinsed with iso-hexane (5.4). 7 Sampling For sampling, use thoroughly cleaned, flat bottomed sample containers (6.1). Preservation and handing of the sample can be found in EN ISO 5667-3 Store the sample at (3 ± 2)°C, protected from light, until the extraction is carried out. Ensure that the extraction is carried out within the maximum preservation time, as specified in EN ISO 5667-3, to avoid losses. It is generally recommended to carry out the extraction as soon as practicable to minimize potential adsorption to the glass wall which could be a potential interference if glassware is re-used. SIST EN 16691:2015
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The article describes the development of a method for measuring polycyclic aromatic hydrocarbons (PAHs) in water samples using gas chromatography mass spectrometry (GC-MS). The method is designed to analyze whole water samples that contain up to 0.5 g/L of suspended solids. It specifies that the limit of quantification (LOQ) should be less than or equal to 30% of the EQS (equivalent quality standard) and the measurement uncertainty should be less than or equal to 50%. The method needs to be validated and tested for ruggedness before being used in interlaboratory comparisons.

기사 제목: SIST EN 16691:2015 - 수질 - 액상 고체 추출법과 가스 크로마토그래피 질량 분석법(GC-MS)을 결합한 전수 샘플에서 다환포화탄화수소(PAH)의 분석 기사 내용: GC-MS를 이용하여 전수 샘플에서 PAH의 양적 결정을 위한 방법 개발. 다음 개별 PAH들이 고려됩니다: 이 분석 방법은 다음 요구 사항을 충족하는 PAH의 결정을 명시합니다: - 분석 대상은 최대 0.5 g/L의 분산 고형물을 포함하는 전수 샘플입니다. - 정량한계(LOQ)는 법적인 기준값(EQS)의 30% 이하입니다. - 측정 불확도는 50% 이하이어야 합니다. - 방법은 성립 검증 후 상호 연구소 검증 전에 완전히 내부 확인되고 시험되어야 합니다. - ISO 5725에 따라 유럽 상호 연구소 비교 연구가 실시됩니다.

記事タイトル：SIST EN 16691:2015 - 水質 - 液体固体抽出とガスクロマトグラフィ質量分析（GC-MS）を組み合わせた全水サンプル中の多環芳香族炭化水素（PAH）の定量決定 記事内容：GC-MSを用いて水中のPAHを定量する方法の開発について説明しています。以下の個別のPAHを考慮しています： この分析方法では以下の要件を満たすPAHの定量が規定されています： - 懸濁固形物を最大0.5 g/L含む全水サンプルの分析 - 定量限界（LOQ）はEQS（等価基準値）の30%以下であること - 測定の不確かさは50%以下であること - 方法は相互較正前に完全に内部で検証され、堅牢性がテストされる必要があります - ISO 5725に従い、ヨーロッパの相互較正研究が行われます。