Pollution pathways of pharmaceutical residues in the aquatic environment on the island of Mallorca, Spain.

This work determines the principal environmental pollution pathways of pharmaceuticals on the island of Mallorca (Spain). The evaluation was made on the basis of the quantification of pharmaceutical residues by liquid chromatography-tandem mass spectrometry in several environmental water samples, including wastewater-treatment plant effluents, municipal solid waste landfill leachates, groundwater (GW), and marine water. An overall set of 19 pharmaceuticals has been identified in the environment of the 27 human pharmaceuticals investigated in this study. WWTP effluents are the main source of discharge of the pharmaceuticals into the aquatic environment. The data indicate that reuse of treated domestic wastewater for irrigation (which supplies some 30 % of the total water demand in Mallorca) contributes to the contamination of GW. In addition, leaching from landfills is identified as another, but minor, possible source of introduction of pharmaceuticals to GW aquifers. Finally, WWTP effluents ending in the Mediterranean Sea, primarily highly urbanized coastal areas, cause pharmaceutical residues to occur in marine water bodies.

Implementation and optimisation of a high-temperature loading strategy of liquid standards in the quantification of volatile organic compounds using solid sorbents.

High-temperature liquid standard loading strategy onto solid sorbent traps for calibration of thermal desorption-GC-MS techniques for the analysis of volatile organic compounds is evaluated and optimised. With this proposed set-up, volatilised liquid-loaded standards interact in gas phase with solid sorbent particles. Response factor for 15 volatile compounds with different vapour pressures have been evaluated and compared with common strategies based on liquid matrix interactions. Using gas matrix strategy improves signal output in the range 10-700%. Average increase for benzene, toluene, ethylbenzene and xylenes is 480%. Reported systematic bias between liquid standards and gas samples are reduced, enhancing thermal desorption methodologies on one of its more important issues. In addition, the proposed system improves the average repeatability to a 3.2%, over 13 times some reported data. The use of an ultra-thin GC capillary column of 150 µm id performs better peak resolution in about 60% the time with usual 250 µm id capillary columns. The usefulness of this proposed optimised procedure has been proved in real air matrix samples, through a large study with the reliable characterisation of 93 different volatile compounds in the ambient air of a municipal solid waste treatment area.

Use of thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) on identification of odorant emission focus by volatile organic compounds characterisation.

Volatile organic compounds (VOCs) from several different municipal solid wastes' treatment plants in Mallorca (Spain) have been analysed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Ambient (immission) air was collected during February and March 2011 by active sampling onto sorbents Tenax™ TA and Carboxen™ 1000. The study presents the chemical characterisation of 93 volatile organic compounds (VOCs) from an overall set of 84 immission air samples. 70 VOCs were positively identified. The linear fit for all 93 external standard calibration, from 10 mg L(-1) to 150 mg L(-1) (n=4), was within the range 0.974

Analysis of cocaine and benzoylecgonine in urine by using multisyringe flow injection analysis-gas chromatography-mass spectrometry system.

In this paper, a method was described to determine cocaine (COC) and benzoylecgonine (BZE) in human urine samples by GC-MS detection. The extraction of analytes from urine samples was achieved in an Oasis hydrophilic-lipophilic balance column (20 mmx3.9 mm id, dp=25 microm; Waters, USA), incorporated in a multisyringe flow injection system, used for the sample treatment. Finally, to improve the volatility of the BZE, an in-line derivatization reaction with N,O-bis (trimethylsilyl) trifluoroacetamide with 1% trimethylchlorosilane was made microwave-assisted in order to reduce the reaction time. The results showed that the proposed method is a good alternative for the analysis of COC and BZE in urine samples because it offers advantages compared with those described in the literature, which include simplicity in the sample treatment, the sensitivity and selectivity necessary to determine the analytes of interest at low levels in the urine and high sample throughput.

Multi-pumping flow system for the determination of dissolved orthophosphate and dissolved organic phosphorus in wastewater samples.

A multi-pumping flow system (MPFS) for the spectrophotometric determination of dissolved orthophosphate and dissolved organic phosphorus in wastewater samples is proposed. The determination of orthophosphate is based on the vanadomolybdate method. In-line ultraviolet photo-oxidation is employed to mineralise organic phosphorus to orthophosphate prior to detection. A solenoid valve allows the deviation of the flow towards the UV-lamp to carry out the determination of organic phosphorus. Calibration was found to be linear up to 20 mg P L(-1), with a detection limit (3s(b)/S) of 0.08 mg P L(-1), an injection throughput of 75 injections h(-1) and a repeatability (R.S.D.) of 0.6% for the direct determination of orthophosphate. On the other hand, calibration graphs were linear up to 40 mg P L(-1), with a detection limit (3s(b)/S) of 0.5 mg P L(-1), an injection throughput of 11 injections h(-1) and a repeatability (R.S.D.) inferior to 2.3% for the procedures involving UV photo-oxidation.

The use of anion-exchange disks in an optrode coupled to a multi-syringe flow-injection system for the determination and speciation analysis of iron in natural water samples.

A combination of multi-syringe flow-injection analysis (MSFIA) technique with an optical fibre reflectance sensor for the determination of iron in water samples has been developed in this work. Anion-exchange solid phase extraction (SPE) disks have been used as solid phase. Ammonium thiocyanate has been chosen as chromogenic reagent for Fe(III). The complex Fe[SCN](6)(3-) is retained onto the SPE disk and spectrophotometrically detected at 480nm. The complex is eluted with 0.25moll(-1) hydrochloric acid in 75% ethanol. Total iron can be determined by oxidising Fe(II) to Fe(III) with hydrogen peroxide. A mass calibration was run within the range of 0.4-37.5ng. The detection limit (3s(b)/S) was 0.4ng. The repeatability (RSD), calculated from 9 replicates using 0.5ml injections of a 25microgl(-1) concentration, was 3.6%. The repeatability between five anion-exchange disks was 5.4%. An injection throughput of 7 injections per hour for a sampling volume of 1ml has been achieved. The applicability of the proposed methodology in natural water samples has been proved. The properties of anion-exchange and chelating SPE disks have been studied and compared.