Determination of drugs in surface water and wastewater samples by liquid chromatography-mass spectrometry: methods and preliminary results including toxicity studies with Vibrio fischeri.

In the present work a combined analytical method involving toxicity and liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) was developed for the determination of pharmaceutical compounds in water samples. The drugs investigated were the analgesics: ibuprofen, ketoprofen, naproxen, and diclofenac, the decomposition product of the acetyl salicylic acid: salicylic acid and one lipid lowering agent, gemfibrozil. The selected compounds are acidic substances, very polar and all of them are analgesic compounds that can be purchased without medical prescription. The developed protocol consisted, first of all, on the use Microtox and ToxAlert 100 toxicity tests with Vibriofischeri for the different pharmaceutical drugs. The 50% effective concentration (EC50) values and the toxicity units (TU) were determined for every compound using both systems. Sample enrichment of water samples was achieved by solid-phase extraction procedure (SPE), using the Merck LiChrolut EN cartridges followed by LC-ESI-MS. Average recoveries loading 11 of samples with pH=2 varied from 69 to 91% and the detection limits in the range of 15-56 ng/l. The developed method was applied to real samples from wastewater and surface-river waters of Catalonia (north-east of Spain). One batch of samples was analyzed in parallel also by High Resolution Gas Chromatography coupled with Mass Spectrometry (HRGC-MS) and the results have been compared with the LC-ESI-MS method developed in this work.

LC-MS determination of linear alkylbenzene sulfonates and their carboxylic degradation products in influent and effluent water samples and sludges from sewage-treatment plants.

Linear alkylbenzene sulfonates (LAS) have been determined in samples of the influent and the effluent, and in the sludge, from sewage-treatment plants (STP). LAS and sulfophenyl carboxylate compounds (SPC) were isolated by solid-phase extraction (SPE) with the polymeric phase Isolute ENV, then determined by liquid chromatography-electrospray mass spectrometry (LC-ESI-MS). The method enabled unequivocal identification of C10-C13 LAS by monitoring the ion at m/z 183 and the base peak corresponding to the [M-H]- ion. Average recoveries varied from 77-93% and the linear range of the method varied from 0.2 to 10 microg L(-1), with a limit of detection ranging from 10 ng L(-1) to 1.5 microg L(-1) when 200 mL waste water were preconcentrated. For sewage sludge, recoveries varied from 58 to 90% and the linear range was between 0.2 and 100 microg L(-1), with a detection limit ranging from 0.4 to 120 microg kg(-1) when 2.5 g sewage sludge was extracted. Unequivocal identification and determination of some metabolites of the LAS, the sulfophenyl carboxylate compounds (SPC), was achieved by monitoring [M-H]- ions.

Determination of non-ionic surfactants and polar degradation products in influent and effluent water samples and sludges of sewage treatment plants by a generic solid-phase extraction protocol.

Non-ionic polyethoxylated surfactants (nonylphenol polyethoxylates, alcohol polyethoxylates), their breakdown products (polyethylene glycol, polyethoxylated nonylphenol carboxylates and polyethoxylated alcohol carboxylates) and other compounds were identified and measured in various waste-water treatment samples (influent, effluent and sludge). A generic protocol involving the use of sequential solid-phase extraction (SSPE) with octadecylsilica and styrene-divinylbenzene cartridges in series and differential elution was used. Fractionated extracts were analyzed by liquid chromatography-mass spectrometry (LC-MS) using atmospheric pressure chemical ionization (APCI) in the positive and negative ionization modes. For sewage treatment plant (STP) sludge, the extraction protocol involved lyophilization of the sludge followed by sonication with MeOH-CH2Cl2 (7 + 3) and final clean-up using the SSPE protocol. Limits of detection for target analytes ranging from 1.1 to 4.1 micrograms L-1 for water samples and from 0.11 to 0.28 mg kg-1 for sludge were achieved. The results obtained demonstrated the inefficient removal of the target analytes in physico-chemical STPs whereas their elimination factors in STPs with biological treatment reached average values of 77, 92 and 98% for alcohol polyethoxylates, nonylphenol polyethoxylates (NPEOs) and polyethylene glycols (PEGs), respectively. Quantitative elimination of coconut fatty acid diethanolamide (CDEA) surfactants in the activated sludge process occurred. In contrast, total removal of NPEOs led to the formation of persistent and toxic metabolites such as nonylphenol which was present in treated effluent as well as in sludge samples with average concentrations ranging from 15.0 to 251.2 micrograms L-1 and from 13.5 to 74.2 mg kg-1, respectively. Polyethoxylated carboxylates and short chain NPEOs were also detected at similar levels in the effluents and sludges. In addition, a linear correlation between the total phenolic concentration (Total Ph) measured by the 4-aminoantipyrine method and the total concentration of nonylphenolic compounds (Total NP) measured by SSPE-LC-APCI-MS was observed.