title: Determination of total and available fractions of PAHs by SPME in oily wastewaters: overcoming interference from NAPL and NOM.
abstract: OBJECTIVE
  Polycyclic aromatic hydrocarbons (PAHs) are often found in oily wastewaters. Their presence is usually the result of human activities and has a negative effect on the environment. One important step in addressing this problem is to evaluate the effectiveness of PAH removal by biological processes since these are the most cost-effective treatments known today. Many techniques are presently available for PAH determination in wastewaters. Solid phase microextracion (SPME) is known to be one of the most effective techniques for this purpose. When analyzing complex matrices with substances such as natural organic matter (NOM) and non-aqueous phase liquids (NAPL), it is important to differentiate the free dissolved PAH from matrix-bonded PAH. PAHs associated with the bonded fraction are less susceptible to biological treatment. The present study concerns the development of a simple and suitable methodology for the determination of the freely dissolved and the total fraction of PAHs present in oily wastewaters. The methodology was then applied to an oily wastewater from a fuel station retention basin.
  
  
  METHODS
  Headspace SPME was used for analyzing PAH since the presence of a complex or dirty matrix in direct contact with the fiber may damage it. Four model PAHs-anthracene, fluorene, phenanthrene, and pyrene-were analyzed by GC-MS. Negligible depletion SPME technique was used to determine the free fraction. Total PAH was determined by enhancing the mass transfer from the bonded phase to the freely dissolved phase by temperature optimization and the use of the method of standard additions. The PAH absorption kinetics were determined in order to define the optimal sampling conditions for this method. The fitting of the experimental data to a mathematical model was accomplished using Berkeley Madonna software. Humic acid and silicon oil were used as model NOM and NAPL, respectively, to study the effect of these compounds on the decrease of SPME response. Then, the method was evaluated with wastewater from a fuel station spill retention basin.
  
  
  RESULTS
  The SPME kinetic parameters-k (1) (uptake rate), k (2) (desorption rate), and K (SPME) (partition coefficient)-were determined from experimental data modeling. The determination of the free fraction required 15-min sampling to ensure that PAH depletion from sample was below 1%. For total PAH, a 30-min extraction at 100 degrees C ensured the maximum signal response in the GC-MS. For the determination of free and total PAHs, extractions were performed before reaching the SPME equilibrium. The wastewater used in this study had no free fraction of the analyzed PAHs. However, the four studied PAHs were found when the method for total PAH was used.
  
  
  CONCLUSIONS
  The addition of NOM and NAPL dramatically decreased the efficiency of the SPME. This decrease was the result of a greater partition of the PAHs to the NAPL and NOM phases. This fact was also observed in the analysis of the fuel station spill retention basin, where no free PAH was measured. However, using the method of standard addition for the determination of total PAH, it was possible to quantify all four PAHs.
  
  
  CONCLUSIONS
  The method developed in the present study was found to be adequate to differentiate between free and total PAH present in oily wastewater. It was determined that the presence of NOM and NAPL had a negative effect on SPME efficiency.
  
  
  CONCLUSIONS
  The presence of binding substances had a great influence on SPME kinetics. Therefore, it is of extreme importance to determine their degree of interference when analyzing oily wastewaters or results can otherwise be erroneous. Other factors influencing the total PAH determinations should be considered in further studies.
authors.affiliation: Institute for Biotechnology and Bioengineering, Centre of Biological Engineering, University of Minho, Campus de Gualtar, 4710-057, Braga, Portugal.
authors.forename: Rui B
authors.initials: RB
authors.lastname: Gomes
authors.forename: Regina
authors.initials: R
authors.lastname: Nogueira
authors.forename: José M
authors.initials: JM
authors.lastname: Oliveira
authors.forename: João
authors.initials: J
authors.lastname: Peixoto
authors.forename: António G
authors.initials: AG
authors.lastname: Brito
mesh_terms: D004784:Environmental Monitoring; D009930:Organic Chemicals / Q000032:analysis*; D010578:Petroleum / Q000032:analysis*; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D052617:Solid Phase Microextraction / Q000379:methods*; D013696:Temperature; D014865:Waste Disposal, Fluid; D014874:Water Pollutants, Chemical / Q000737:chemistry*
chemical_list: D009930:Organic Chemicals; D010578:Petroleum; D011084:Polycyclic Aromatic Hydrocarbons; D014874:Water Pollutants, Chemical