[Show abstract][Hide abstract] ABSTRACT: A direct, simple and solvent-free method based on headspace stir bar sorptive extraction and thermal desorption gas chromatography with mass spectrometry was developed to determine 13 musk fragrances (six polycyclic musks, three nitro musks and four macrocyclic musks) in sludge without sample treatment. The optimal headspace stir bar sorptive extraction conditions were achieved when a polydimethylsiloxane stir bar was exposed for 45 min in the headspace of a 10 mL vial filled with 100 mg of sludge mixed with 0.2 mL of water stirred at 750 rpm at 80°C. The stir bar was then desorbed in the thermal desorption gas chromatography and mass spectrometry system, obtaining LODs between 5 ng/g and 30 ng/g. The method applicability was tested with sewage sludge from two urban wastewater treatment plants and from a potable water treatment plant. Results showed galaxolide and tonalide to be the most abundant musk fragrances found in wastewater treatment plants with maximal concentrations of 9240 and 7500 ng/g, respectively. Maximum concentration levels between 35 and 635 ng/g were found for musk ketone, musk moskene, traseolide, phantolide and celestolide in this kind of samples. Concentrations below LOQs of phantolide, galaxolide, tonalide and musk ketone were found in sludge from the potable water treatment plant.This article is protected by copyright. All rights reserved
Journal of Separation Science 03/2014; 00:1-8. · 2.59 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Different sampling methods involving the collection of biogas by Tedlar bags or adsorption tubes, and different GC-MS injection systems, loop injection or cold trap injection (with bags or by tube desorption), were compared to establish the best method to determine the minority compounds in biogas from sewage treatment plants (STPs). A study of parameters is included, such as the stability of compounds in Tedlar bags or cartridges and the adsorption effect of some less volatile compounds in the thermal desorption system (TD). The optimized methods allowed to determine most compounds at low mgm(-3) levels. Among them, maximum values of D5 (4.84mgm(-3)), decane (95-118mgm(-3)) and H(2)S (2223mgm(-3)) were found in biogas samples.
[Show abstract][Hide abstract] ABSTRACT: Personal-care products (PCPs) are organic chemicals widely used in human life daily. Among the most recently studied PCPs, we can find ultraviolet filters, preservatives, antimicrobials, musk fragrances, insect repellents and siloxanes. PCPs are increasingly important emerging organic contaminants due to their presence in environmental waters.We present a review of the most important extraction and chromatographic techniques used to determine PCPs in waters. We also review data regarding the occurrence of these compounds in different kinds of environmental waters and the removal of these compounds in sewage-treatment plants.
[Show abstract][Hide abstract] ABSTRACT: A solid-phase extraction and liquid chromatography-tandem mass spectrometry (SPE/LC-MS-MS) method was developed and validated for the simultaneous determination of nicotine, five drugs of abuse (morphine, cocaine, codeine, methadone, and 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine) and four metabolites (dihydrocodeine, 6-acetylmorphine, 11-nor-carboxy-Δ(9)-tetrahydrocannabinol, and benzoylecgonine) in water samples. A Fused-Core™ particle column was used as an alternative to sub-2-μm particles in chromatographic separations to work with low backpressures and high efficiencies in short analysis times. Drugs were extracted from waste and surface water with SPE using Oasis MCX cartridges. Electrospray (ESI) in positive and negative mode and tandem MS selected reaction monitoring mode were used for identification and quantification. Calibration by linear regression analysis with deuterated internal standards was used to compensate the matrix effects. Limits of detection were found as low as 0.5-1 ng/L (surface water) and 1-50 ng/L (wastewater). The method was applied to the analysis of different kinds of samples. Wastewater from a sewage treatment plant was collected from three sampling points (after primary, secondary, and tertiary treatments) for a week. The analysis of the samples revealed a significant presence of these drugs in samples from primary treatments, where maximum concentrations of nicotine (1105 ng/L) and benzoylecgonine (3336 ng/L) were found. Most of the compounds showed values between <LOQ and 52 ng/L after tertiary treatment. When surface waters from the Ebro River were analyzed, only benzoylecgonine showed levels between 19 and 35 ng/L.
Journal of Separation Science 05/2011; 34(10):1091-101. · 2.59 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: This paper describes the presence of 33 pharmaceuticals and hormones in waters from two sewage treatment plants (STPs) situated
in Catalonia, in northeastern Spain. The target compounds were one psychoactive stimulant, one antiepileptic, four analgesics
and non-steroidal anti-inflammatories, one lipid regulators, two anti-ulcer agents, nine antibiotics (sulfonamides and macrolides),
two beta-blockers, two metabolites, and 11 hormones (free and conjugates). The determination was performed using liquid chromatography
coupled to tandem mass spectrometry after enrichment by solid-phase extraction with Oasis HLB sorbent. Most of the pharmaceuticals
were found in both influent and effluent samples from the two STPs. The most frequently detected were caffeine, acetaminophen,
carbamazepine, diclofenac, ibuprofen, naproxen, sulfamethoxazole, sulfapyridine, sulfathiazole, ranitidine, omeprazole, estrone
3-sulfate, and estradiol 17-glucuronide. Specifically, the highest concentrations found in influents were 19,850ng/L (acetaminophen),
9,945ng/L (caffeine), 4,215ng/L (ibuprofen), 5,695ng/L (sulfamethoxazole), and 5,140ng/L (sulfathiazole). Most of the
pharmaceuticals present in influent waters were found in effluents at lower concentrations. The highest concentrations in
effluents were 970ng/L (caffeine), 670ng/L (sulfamethoxazole), 510ng/L (bezafibrate), and 1,032ng/L (diclofenac).
Water Air and Soil Pollution 01/2011; 217(1):267-281. · 1.75 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Stir-bar-sorptive extraction (SBSE) with liquid desorption (LD) and ultra-high-performance liquid chromatography-electrospray ionization triple-quadrupole tandem mass spectrometry (UHPLC-(ESI)MS-MS) were used for analysis of six personal care products in environmental water: four UV filters (2,2-dihydroxy-4-methoxybenzophenone, benzophenone-3, octocrylene, and octyldimethyl-p-aminobenzoic acid) and two antimicrobial agents (triclocarban and triclosan). Experimental conditions that affect SBSE-LD sorption efficiency (extraction time and temperature, sample pH, and ionic strength) and desorption efficiency (solvent, temperature, and time) were optimized. The method proved to be sensitive--a 50-mL sample was used to determine these compounds in environmental waters at trace levels. The detection limits of the analytical method were 2.5 ng L(-1) for river water and 5-10 ng L(-1) for effluent and influent sewage water. In river waters, benzophenone-3 was found at levels from 6 ng L(-1) to 28 ng L(-1) and triclosan at levels <LOQ. Benzophenone-3 was found between 75 and 127 ng L(-1) in influent sewage, whereas concentrations of benzophenone-3 and triclosan were commonly below 25 ng L(-1) in effluent sewage.
Analytical and Bioanalytical Chemistry 08/2010; 397(7):2833-9. · 3.66 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Personal care products (PCPs) are widely used emerging contaminants which can cause adverse environmental effects. This paper reports the development and validation of a method based on solid-phase extraction (SPE) and ultra-high-performance liquid chromatography-electrospray ionisation-tandem mass spectrometry (UHPLC-(ESI)MS-MS) for simultaneously determining eleven PCPs: 4 preservatives (methylparaben; ethylparaben; benzylparaben; propylparaben); 2 antimicrobial agents (triclocarban and triclosan) and 5 UV filters (2,4-dihydroxybenzophenone; 2,2-dihydroxy-4-methoxybenzophenone; benzophenone-3; octocrylene and octyldimethyl-p-aminobenzoic acid) in environmental waters in only 9 run minutes of chromatographic separation. The SPE was carried out with two polymeric cartridges (Oasis HLB and Bond Elut Plexa). The recoveries obtained with Bond Elut Plexa were between 69% and 101% for 500 mL of river waters, with the exception of octyldimethyl-p-aminobenzoic acid (46%). Limits of detection for 500 mL of river water were in the range of 1-5 ng/L. Oasis HLB was chosen for wastewater samples with recoveries between 38% and 92% (250 mL of effluents) and 36-89% (100mL of influents). In both wastewater samples, octyldimethyl-p-aminobenzoic acid and methylparaben showed the lowest recoveries (20% and 27%). The method revealed benzophenone-3 as having the highest concentration levels ( 7 ng/L) in river waters. Most of PCPs determined were found in influent waters being methylparaben and propylparaben the ones found at highest concentration with values of 5613 and 1945 ng/L, respectively. In effluent waters, significant lower levels of some PCPs were found, being benzophenone-3 the one found at the highest concentration (100 ng/L).
Journal of Chromatography A 10/2009; 1216(42):6994-7000. · 4.61 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A sensitive method for simultaneously determining eleven free and conjugated steroid estrogens has been developed using liquid chromatography-(electrospray)triple quadrupole-mass spectrometry (LC-(ESI)MS-MS) in negative mode with application to environmental aqueous matrices. Two selected reaction monitoring (SRM) transitions per compound were used, one of which was used for quantification and the second one for confirmation. The procedure includes a solid-phase extraction with an Oasis HLB solid-phase cartridge. Recoveries in 500 mL of river water spiked at 50 ng/L for sulfate estrogens and 100 ng/L for the rest of the compounds were 46-87%, except for E2, which had lower values (32%). Recoveries in wastewater were higher than 49% and 30% for all the compounds, except E2-17A and E2-17G (lower than 26% and 28%, respectively), in effluent (250 mL) and influent (100 mL), respectively. Ion suppression is a well-known phenomenon when using ESI; thus its impact on method recovery made us consider this effect when quantifying our samples. Limits of detection varied from 2 to 30 ng/L in river water and 10 to 100 ng/L in sewage water. The method was used to determine the target compounds in the Ebro river water where none of the analytes were found. In effluent and influent water samples, EE2, E1-3S and E2-3S were determined at concentration levels ranging from 35 to 160 ng/L.
[Show abstract][Hide abstract] ABSTRACT: This paper describes a method for determining 11 pharmaceuticals in various water sources by SPE followed by LC-(ESI) MS. SPE was carried out with Oasis HLB and the recoveries were 33-67% for 250 and 100 mL sewage water, 55-77% for 500 mL river water and 72-98% for 1 L tap water, with the exception of sulfamethoxazole and omeprazole which showed lower recoveries in all kinds of sample. The LODs in river water were of 5 ng/L for sulfadiazine, trimethoprim, sulfamethazine, sulfamethoxazole, and ranitidine and 10 ng/L for the other compounds. The highest concentrations found in river waters were for sulfamethoxazole (50 ng/L). In influent sewage waters, ranitidine was the most commonly detected compound with a maximum value of 0.24 microg/L.
Journal of Separation Science 08/2008; 31(12):2182-8. · 2.59 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A method was developed to determine 11 pharmaceutical compounds in water samples. The method uses SPE and HPLC coupled to MS (LC/MS) using ESI in both positive and negative modes. Three different sorbents were compared for the extraction of analytes from river and sewage treatment plant (STP) waters and OASIS HLB provided the best results. For the solid-phase extraction of 500 mL of river water samples, the recoveries were between 41 and 101% with the exception of acetaminophen, salicylic acid and naproxen. The LODs were between 3 and 5 ng/L for all the compounds, except naproxen which had an LOD of 15 ng/L. Acetaminophen, caffeine, carbamazepine, bezafibrate and ibuprofen were found in three of the tested river samples at ng/L levels and among them, the highest values were for caffeine and bezafibrate with 305 and 363 ng/L, respectively. For the influent and effluent water samples of the STP, volumes of 100 and 250 mL were used, respectively, to obtain acceptable recoveries. All the compounds showed recoveries between 33 and 91% for effluent samples and 33-72% for influent samples, with the exception of acetaminophen, salicylic acid and bezafibrate, which had lower recoveries. The method developed enabled pharmaceuticals in the influent and effluent sewage waters to be determined in five campaigns carried out between February 2004 and June 2005. Several pharmaceuticals were found in the influent samples: for instance, maximum concentrations of ibuprofen and caffeine were 6 and 40 microg/L, respectively.
Journal of Separation Science 02/2007; 30(3):297-303. · 2.59 Impact Factor