Determination of polycyclic aromatic hydrocarbons in environmental waters from southern Spain by using a continuous solid-phase extraction system and gas chromatography-mass spectrometry
Andrés J. Rascón
A , Abdelmonaim Azzouz A and Evaristo Ballesteros A B
+ Author Affiliations
- Author Affiliations
A Department of Physical and Analytical Chemistry, Escuela Politécnica Superior de Linares, University of Jaén, 23700 Linares, Jaén, Spain.
B Corresponding author. Email: eballes@ujaen.es
Environmental Chemistry 15(6) 351-361 https://doi.org/10.1071/EN18106
Submitted: 23 May 2018 Accepted: 10 July 2018 Published: 23 August 2018
Environmental context. Polycyclic aromatic hydrocarbons are widespread carcinogenic compounds resulting from incomplete combustion of fossil fuels. We report a robust analytical method suitable for detecting these compounds at trace levels in various types of environmental waters. The method allows for accurate monitoring of the levels and behaviour of these priority environmental pollutants.
Abstract. Human exposure to polycyclic aromatic hydrocarbons (PAHs) is a major challenge for the scientific community. The European Commission and the European Food Safety Agency have declared PAHs as priority pollutants, and sanctioned their quantification and monitoring in water and foods, owing to their carcinogenic, teratogenic, and mutagenic properties. We report a method for determining sixteen PAHs in various types of environmental water samples collected from various sources and places in the south of Spain. The target compounds were preconcentrated to a reduced volume (350 µL) with an automatic solid-phase extraction system and determined by gas chromatography–mass spectrometry. Optimising the operational variables, such as the type and nature of sorbent, and analytical variables resulted in a very low limit of detection (0.01–0.3 ng L−1), high accuracy and precision (RSD < 7.5 %), and recoveries of 86–102 % from 200 mL of sample. The method was applied to a variety of environmental water samples, many of which were found to contain PAHs at different levels, depending on the nature and origin the sample. In any case, such levels were lower than the maximum tolerated limits except for sea and waste water. In the case of waste water, a comparison between influent and effluent from the waste water treatment plant was performed to assess the effect over the environment after their treatment, where a reduction of the presence of PAHs in the samples was observed.
Additional keywords: determination of pollutants, water analysis.
References
Avino P, Notardonato I, Perugini L, Russo MV (2017). New protocol based on high-volume sampling followed by DLLME-GC-IT/MS for determining PAHs at ultra-trace levels in surface water samples. Microchemical Journal 133, 251–257.| New protocol based on high-volume sampling followed by DLLME-GC-IT/MS for determining PAHs at ultra-trace levels in surface water samplesCrossref | GoogleScholarGoogle Scholar |
Barco-Bonilla N, Romero González R, Plaza-Bolaños P, Fernández-Moreno JL, Frenich AG, Martínez Vidal JL (2011). Comprehensive analysis of polycyclic aromatic hydrocarbons in wastewater using stir bar sorptive extraction and gas chromatography coupled to tandem mass spectrometry. Analytica Chimica Acta 693, 62–71.
| Comprehensive analysis of polycyclic aromatic hydrocarbons in wastewater using stir bar sorptive extraction and gas chromatography coupled to tandem mass spectrometryCrossref | GoogleScholarGoogle Scholar |
Boffetta P, Jourenkova N, Gustavsson P (1997). Cancer risk from occupational and environmental exposure to polycyclic aromatic hydrocarbons. Cancer Causes & Control 8, 444–472.
| Cancer risk from occupational and environmental exposure to polycyclic aromatic hydrocarbonsCrossref | GoogleScholarGoogle Scholar |
Cheng X, Forsythe J, Peterkin E (2013). Some factors affecting SPME analysis and PAHs in Philadelphia’s urban waterways. Water Research 47, 2331–2340.
| Some factors affecting SPME analysis and PAHs in Philadelphia’s urban waterwaysCrossref | GoogleScholarGoogle Scholar |
Delgado B, Pino V, Ayala JH, González V, Afonso AM (2004). Nonionic surfactant mixtures: a new cloud-point extraction approach for the determination of PAHs in seawater using HPLC with fluorimetric detection. Analytica Chimica Acta 518, 165–172.
| Nonionic surfactant mixtures: a new cloud-point extraction approach for the determination of PAHs in seawater using HPLC with fluorimetric detectionCrossref | GoogleScholarGoogle Scholar |
EFSA (2012). Panel on Contaminants in the Food Chain (CONTAM); Scientific Opinion on Mineral Oil Hydrocarbons in Food. EFSA Journal 10, 2704
European Commission (2002). Scientific Committee on Food. Polycyclic Aromatic Hydrocarbons – Occurrence in foods, dietary exposure and health effects. Available at http://ec.europa.eu/food/fs/sc/scf/out154_en.pdf [verified 20 May 2018].
European Commission (2013). Directive 2013/39/EU of the European Parliament and of the Council of 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy Text with EEA relevance. Official Journal of the European Union L226, 1–17.
Fontanals N, Marcé RM, Borrull F (2005). New hydrophilic materials for solid-phase extraction. TrAC Tends in Analytical Chemistry 24, 394–406.
| New hydrophilic materials for solid-phase extractionCrossref | GoogleScholarGoogle Scholar |
Hagestuen ED, Campiglia AD (1999). New approach for screening polycyclic aromatic hydrocarbons in water samples. Talanta 49, 547–560.
| New approach for screening polycyclic aromatic hydrocarbons in water samplesCrossref | GoogleScholarGoogle Scholar |
Kabziński AKM, Cyran J, Juszczak R (2002). Determination of polycyclic aromatic hydrocarbons in water (including drinking water) of Łódź. Polish Journal of Environmental Studies 11, 695–706.
López-López JA, Ogalla-Chozas E, Lara-Martín PA, Pintado-Herrera MG (2017). Solvent bar micro-extraction (SBME) based determination of PAHs in seawater samples. The Science of the Total Environment 598, 58–63.
| Solvent bar micro-extraction (SBME) based determination of PAHs in seawater samplesCrossref | GoogleScholarGoogle Scholar |
Ma J, Xiao R, Li L, Yu J, Zhang Y, Chen L (2010). Determination of 16 polycyclic aromatic hydrocarbons in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with gas chromatography-mass spectrometry. Journal of Chromatography A 1217, 5462–5469.
| Determination of 16 polycyclic aromatic hydrocarbons in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with gas chromatography-mass spectrometryCrossref | GoogleScholarGoogle Scholar |
Mollahosseini A, Rokue M, Mojtahedi MM, Toghroli M, Kamankesh M, Motaharian A (2016). Mechanical stir bar sorptive extraction followed by gas chromatography as a new method for determining polycyclic aromatic hydrocarbons in water samples. Microchemical Journal 126, 431–437.
| Mechanical stir bar sorptive extraction followed by gas chromatography as a new method for determining polycyclic aromatic hydrocarbons in water samplesCrossref | GoogleScholarGoogle Scholar |
Montuori P, Triassi M (2012). Polycyclic aromatic hydrocarbons loads into the Mediterranean Sea: Estimate of Sarno River inputs. Marine Pollution Bulletin 64, 512–520.
| Polycyclic aromatic hydrocarbons loads into the Mediterranean Sea: Estimate of Sarno River inputsCrossref | GoogleScholarGoogle Scholar |
Okoli CP, Adewuyi GO, Zhang Q, Guo Q (2016). QSAR aided design and development of biopolymer-based SPE phase for liquid chromatographic analysis of polycyclic aromatic hydrocarbons in environmental water samples. RSC Advances 6, 71596–71611.
| QSAR aided design and development of biopolymer-based SPE phase for liquid chromatographic analysis of polycyclic aromatic hydrocarbons in environmental water samplesCrossref | GoogleScholarGoogle Scholar |
Ozaki N, Takamura Y, Kojima K, Kindaichi T (2015). Loading and removal of PAHs in a wastewater treatment plant in a separated sewer system. Water Research 80, 337–345.
| Loading and removal of PAHs in a wastewater treatment plant in a separated sewer systemCrossref | GoogleScholarGoogle Scholar |
Plaza-Bolaños P, Frenich AG, Martínez Vidal JL (2010). Polycyclic aromatic hydrocarbons in food and beberages. Analytical methods and trends. Journal of Chromatography A 1217, 6303–6326.
| Polycyclic aromatic hydrocarbons in food and beberages. Analytical methods and trendsCrossref | GoogleScholarGoogle Scholar |
Poster PL, Schantz MM, Sander LC, Wise SA (2006). Analysis of polycyclic aromatic hydrocarbons (PAHS) in environmental samples: a critical review of gas chromatographic (GC) methods. Analytical and Bioanalytical Chemistry 386, 859–881.
| Analysis of polycyclic aromatic hydrocarbons (PAHS) in environmental samples: a critical review of gas chromatographic (GC) methodsCrossref | GoogleScholarGoogle Scholar |
Qin N, He W, Kong XZ, Liu WX, He QS, Yang B, Xu FL (2013). Ecological risk assessment of polycyclic aromatic hydrocarbons (PAHs) in the water from a large Chinese lake based on multiple indicators. Ecological Indicators 24, 599–608.
| Ecological risk assessment of polycyclic aromatic hydrocarbons (PAHs) in the water from a large Chinese lake based on multiple indicatorsCrossref | GoogleScholarGoogle Scholar |
Rascón AJ, Azzouz A, Ballesteros E (2018). Assessing polycyclic aromatic hydrocarbons in cereal-based foodstuffs by using a continuous solid-phase extraction system and gas chromatography–mass spectrometry. Food Control 92, 92–100.
| Assessing polycyclic aromatic hydrocarbons in cereal-based foodstuffs by using a continuous solid-phase extraction system and gas chromatography–mass spectrometryCrossref | GoogleScholarGoogle Scholar |
Sarria-Villa R, Ocampo-Duque W, Páez M, Schuhmacher M (2016). Presence of PAHs in water and sediments of the Colombian Cauca River during heavy rain episodes, and implications for risk assessment. The Science of the Total Environment 540, 455–465.
| Presence of PAHs in water and sediments of the Colombian Cauca River during heavy rain episodes, and implications for risk assessmentCrossref | GoogleScholarGoogle Scholar |
Siemers AK, Mänz JS, Palm WU, Ruck WKL (2015). Development and application of a simultaneous SPE-method for polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, heterocyclic PAHs (NSO-HET) and phenols in aqueous samples from German Rivers and the North Sea. Chemosphere 122, 105–114.
| Development and application of a simultaneous SPE-method for polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, heterocyclic PAHs (NSO-HET) and phenols in aqueous samples from German Rivers and the North SeaCrossref | GoogleScholarGoogle Scholar |
Sun S, Jia L, Li B, Yuan A, Kong L, Qi H, Ma W, Zhang A, Wu Y (2018). The occurrence and fate of PAHs over multiple years in a wastewater treatment plant of Harbin, Northeast China. The Science of the Total Environment 624, 491–498.
| The occurrence and fate of PAHs over multiple years in a wastewater treatment plant of Harbin, Northeast ChinaCrossref | GoogleScholarGoogle Scholar |
USEPA (2014). EPA Method 8270d. Semivolatile Organic compounds by gas chromatography/mass spectrometry. Available at https://www.epa.gov/sites/production/files/2015-12/documents/8270d.pdf [verified 20 May 2018].
USEPA (2015). EPA Method 610 for organic chemical analysis of municipal and industrial wastewater. Available at https://www.epa.gov/sites/production/files/2015-10/documents/method_610_1984.pdf [verified 20 May 2018].
Wang Y, Wang J, Mu J, Wang Z, Cong Y, Yao Z, Lin Z (2016). Aquatic predicted no-effect concentration of 16 polycyclic aromatic hydrocarbons and their ecological risks in surface seawater of Liaodong bay, China. Environmental Toxicology and Chemistry 35, 1587–1593.
| Aquatic predicted no-effect concentration of 16 polycyclic aromatic hydrocarbons and their ecological risks in surface seawater of Liaodong bay, ChinaCrossref | GoogleScholarGoogle Scholar |
Wei MC, Jen JF (2007). Determination of polycyclic aromatic hydrocarbons in aqueous samples by microwave assisted headspace solid-phase microextraction and gas chromatography/flame ionization detection. Talanta 72, 1269–1274.
| Determination of polycyclic aromatic hydrocarbons in aqueous samples by microwave assisted headspace solid-phase microextraction and gas chromatography/flame ionization detectionCrossref | GoogleScholarGoogle Scholar |
Wenzl T, Simon R, Anklam E, Kleiner J (2006). Analytical methods for polycyclic aromatic hydrocarbons (PAHs) in food and the environment needed for new food legislation in the European Union. TrAC Trends in Analytical Chemistry 25, 716–725.
| Analytical methods for polycyclic aromatic hydrocarbons (PAHs) in food and the environment needed for new food legislation in the European UnionCrossref | GoogleScholarGoogle Scholar |
Werres F, Balsaa P, Schmidt TC (2009). Total concentration analysis of polycyclic aromatic hydrocarbons in aqueous samples with high suspended particulate matter content. Journal of Chromatography A 1216, 2235–2240.
| Total concentration analysis of polycyclic aromatic hydrocarbons in aqueous samples with high suspended particulate matter contentCrossref | GoogleScholarGoogle Scholar |
Whitcomb JL, Campiglia AD (2001). Screening potential of solid-phase extraction and solid surface room temperature fluorimetry for polycyclic aromatic hydrocarbons in water samples. Talanta 55, 509–518.
| Screening potential of solid-phase extraction and solid surface room temperature fluorimetry for polycyclic aromatic hydrocarbons in water samplesCrossref | GoogleScholarGoogle Scholar |
Yang RT (2003). ‘Adsorbents: fundamentals and applications’ (John Wiley & Sons, Inc.: Hoboken, NJ)
Zhang ZL, Hong HS, Zhou JL, Yu G (2004). Phase association of polycyclic aromatic hydrocarbons in the Minjiang River Estuary, China. The Science of the Total Environment 323, 71–86.
| Phase association of polycyclic aromatic hydrocarbons in the Minjiang River Estuary, ChinaCrossref | GoogleScholarGoogle Scholar |
Zhi H, Zhao Z, Zhang L (2015). The fate of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in water from Poyang Lake, the largest freshwater lake in China. Chemosphere 119, 1134–1140.
| The fate of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in water from Poyang Lake, the largest freshwater lake in ChinaCrossref | GoogleScholarGoogle Scholar |
