Sensitive determination of acidic drugs and triclosan in surface and wastewater by ion-pair reverse-phase liquid chromatography/tandem mass spectrometry

A new method is presented for the determination of 12 acidic pharmaceuticals (non-steroidal anti-inflammatory drugs and bezafibrate), including two metabolites from aqueous samples, together with triclosan as a personal care product. Ion-pair liquid chromatography (IP-LC) with electrospray ionisation tandem mass spectrometry (ESI-MS) in the negative ion mode was employed. The ion-pairing agent (tri-n-butylamine) increased the signal intensity for all acidic analytes and detection limits of 6-200 ng/L were obtained by multiple reaction monitoring. This allows analysis of wastewater samples by direct injection into the LC/MS system without the need for a preceding enrichment step. When combined with a solid-phase extraction (SPE) step, limits of quantification between 0.15 and 11 ng/L were obtained from 100-mL sample volumes, which is adequate for most applications. The occurrence of matrix effects was studied and standard addition was required for reliable quantification after SPE from wastewater. The method was finally applied to surface and wastewaters, with analyte concentrations ranging from below the detection limit up to 5.5 microg/L.     

Solid phase microextraction of macrolide, trimethoprim, and sulfonamide antibiotics in wastewaters

In this work, we optimize a solid phase microextraction (SPME) method for the simultaneous collection of antibiotics (sulfonamides, macrolides, and trimethoprim) present in wastewaters. The performance of the SPME method is compared to a solid phase extraction (SPE) method. Analytes in both cases were quantified by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) with electrospray ionization. The advantages offered by SPME in this application are: decreased sample volume requirements, ease of sample processing and extraction, decreased cost, and most importantly, elimination of electrospray matrix effects. Despite having higher limits of quantification (16-1380 ng/L in influent and 35-260 ng/L in effluent), nearly all of the compounds found to be present in Edmonton Gold Bar wastewater by SPE were measurable by SPME (i.e., sulfamethoxazole, trimethoprim, erythromycin, and clarithromycin), with values similar to those obtained using the former method. Limits of quantification for the SPE method for the measured compounds were 4.7-15 ng/L and 0.86-6.1 ng/L for influent and effluent, respectively.     

Determination of benzothiazoles from complex aqueous samples by liquid chromatography-mass spectrometry following solid-phase extraction

A method was developed for the determination of benzothiazoles from municipal wastewater, which may originate from their use as corrosion inhibitors, vulcanization accelerators or fungicides. Extraction is performed by SPE using a polymeric sorbent, followed by LC-MS analysis with electrospray ionization. Due to the diversity of the analytes, two LC-MS runs are required: 2-aminobenzothiazole, benzothiazole and 2-methylthiobenzothiazole are detected in the positive ion mode, while benzothiazole-2-sulfonic acid (BTSA), 2-mercaptobenzothiazole and 2-hydroxybenzothiazole are determined in the negative ion mode. Limits of quantification range from 20 to 200 ng/L in treated wastewater. Reliable quantification with R.S.D.s below 25% is achieved by standard addition in a limited number of samples of each sample series. A significant reduction of matrix effects in positive electrospray ionization is achieved by reducing the flow directed into the ESI-interface. When applied to untreated municipal wastewater most analytes were found at concentrations in the high ng/L- to low microg/L-range with the most polar BTSA being the dominant compound of this class. Removal of benzothiazoles in biological wastewater treatment appears to be limited.     

Multiresidue methods for the analysis of pharmaceuticals,personal care products and illicit drugs in surface water and wastewater by solid-phase extraction and ultra performance liquid chromatography–electrospray tandem mass spectrometry

The main aim of the presented research is to introduce a new technique, ultra performance liquid chromatography-positive/negative electrospray tandem mass spectrometry (UPLC-ESI/MS/MS), for the development of new simultaneous multiresidue methods (over 50 compounds). These methods were used for the determination of multiple classes of pharmaceuticals (acidic, basic and neutral compounds: analgesic/anti-inflammatory drugs, antibiotics, antiepileptics, beta-adrenoceptor blocking drugs, lipid regulating agents, etc.), personal care products (sunscreen agents, preservatives, disinfectant/antiseptics) and illicit drugs (amphetamine, cocaine and benzoylecgonine) in surface water and wastewater. The usage of the novel UPLC system with a 1.7 microm particle-packed column allowed for good resolution of analytes with the utilisation of low mobile phase flow rates (0.05-0.07 mL min(-1)) and short retention times (method times of up to 25 min), delivering a fast and cost-effective method. SPE with the usage of Oasis MCX strong cation-exchange mixed-mode polymeric sorbent was chosen for sample clean-up and concentration. The influence of mobile phase composition, matrix-assisted ion suppression in ESI-MS and SPE recovery on the sensitivity of the method was extensively studied. The method limits of quantification were at low nanogram per litre levels and ranged from tenths of ng L(-1) to tens of ng L(-1) in surface water and from single ng L(-1) to a few hundreds of ng L(-1) in the case of wastewater. The instrumental and method intraday and interday repeatabilities were on average less than 5%. The method was successfully applied for the determination of pharmaceuticals in the River Taff (South Wales) and a wastewater treatment plant (WWTP Cilfynydd). Several pharmaceuticals and personal care products were determined in river water at levels ranging from single ng L(-1) to single microg L(-1).     

Role of the retaining precolumn in large-volume on-column injections of volatiles to gas chromatography

In the present study the retaining precolumn, which is commonly used in a set-up for large-volume on-column injections, or when solid-phase extraction (SPE) or liquid chromatography is coupled to gas chromatography (CC), was removed after varying its length from the standard length of 3 m down to zero. A dramatic increase of the evaporation rate of the injected organic solvent was obtained from a typical value of 100 microl/min up to 300 microl/min. The increased evaporation rate allowed (i) injection of a larger volume in the same retention gap, (ii) faster injection/transfer of the organic solvent and (iii) reduction of the transfer temperature. As volatile compounds under partially concurrent solvent evaporation conditions are easily lost once the organic solvent has been removed via a solvent-vapour exit (SVE), the parameters for large-volume injection, i.e. the evaporation rate and injection speed, were optimised using accurate measurements of the real flow-rate of the carrier gas into the GC system. All these options have been evaluated over the last 4 years. In order to demonstrate that omitting the retaining precolumn had no effect on the application range of the on-column interface, analytes as volatile as benzene were injected into GC-MS using 50-200 microl of n-pentane solutions. Contaminants were extracted from river water and wastewater into n-pentane using in-vial liquid-liquid extraction. The detection limits for benzene, toluene, ethylbenzene and m-xylene were approximately 10 ng/l. To obtain optimum results the SVE had to be closed 1 s before the end of evaporation. Several brands of n-pentane were analysed to check for the presence of benzene. Most of them contained interfering compounds and benzene at the low microg/l level and therefore had to be cleaned by means of column chromatography. As another example C8-C17 alkylphenones were extracted from wastewater with n-hexane. Detection limits were 10-40 ng/l.     

Determination of haloacetic acids in aqueous environments by solid-phase extraction followed by ion-pair liquid chromatography-electrospray ionization mass spectrometric detection.

Haloacetic acids (HAAs) were determined in different water samples by a new, fast and simple analysis method based on enrichment of 50-ml water samples at pH 1.8 by solid-phase extraction (SPE) followed by liquid chromatography (LC) separation and electrospray ionization mass spectrometric detection in the negative ionization mode. Deprotonated (M-H)-haloacetates and decarboxylated (M-COOH)- ions were detected. Different polymeric SPE sorbents were tested, and LiChrolut EN was found to be the best material for the extraction. Complete LC separation of all compounds could only be achieved by ion-pair chromatography using triethylamine as volatile ion-pairing reagent. The detection limits were in the low microg/l range. High microg/l concentration levels for the chlorinated and brominated haloacetates were found in drinking water from a drinking water treatment plant in Barcelona, and the corresponding tap water. In swimming pool water samples from Catalonia mg/l levels and in surface river water from Portugal microg/l values were detected. These results confirm other recent reports on the ubiquitous occurrence of HAAs in aqueous environments.     

Simultaneous determination of NSO-heterocycles, homocycles and their metabolites in groundwater of tar oil contaminated sites using LC with diode array UV and fluorescence detection

For monitoring groundwater at tar oil contaminated sites a simple method of analysis was developed for the simultaneous detection of several NSO heterocyclic compounds, homocyclic compounds, mobile two- and three-cyclic PAHs and selected metabolites. The groundwater samples are enriched using SPE with polymer material at pH 4. Chromatographic separation and detection is performed by LC with diode array UV or fluorescence detection. The recoveries of 25 selected compounds were mostly between 80-110% and the detection limits were 0.4-2.4 microg/L for UV detection and for the fluorescence detectable compounds 0.4-140 ng/L. The method was successfully applied to groundwater samples from a wood preserving facility. Especially benzo(b)thiophene showed an increasing dominance downgradient of the source. Detection of metabolites, such as 1-hydroxyiso-, 2-hydroxyquinoline and 2-hydroxy-4-methylquinoline, 2-naphthoic acid, and 1-indanone, indicating in situ biodegradation, was confirmed by LC-ESI-MS analysis.     

Determination of 76 pharmaceutical drugs by liquid chromatography–tandem mass spectrometry in slaughterhouse wastewater

A multi-residue method for the analysis of 76 pharmaceutical agents of nine classes of drugs (tetracyclines, macrolides, fluoroquinolones, β-agonists, β-blockers, diuretics, sedatives, sulfonamides and chloramphenicol) in slaughterhouse wastewater and a receiving river is presented. After simultaneous extraction with an Oasis HLB solid-phase extraction (SPE) cartridge and further purification using an amino SPE cartridge, analytes were detected by liquid chromatography–electrospray ionization-tandem mass spectrometry in positive or negative ion mode. Standard addition was used for quantification to overcome unavoidable matrix effects during ESI-MS analysis. Recoveries for most analytes based on matrix-matched calibration in different test matrices were >60%. The method quantification limits of 76 pharmaceuticals were in the range 0.2–30 ng/L. Nineteen compounds of 76 drugs were found in raw and treated slaughterhouse wastewater from four main slaughterhouses in Beijing. Sulfanamides (sulfanilamide, sulfameter), fluoroquenones (ofloxacin, pefloxacin, norfloxacin, ciprofloxacin, enrofloxacin), tetracyclines (tetracycline, oxytetracycline) and macrolides (kitasamycin, tylosin, erythromycin) were most frequently detected, with the highest levels up to ∼3 μg/L in slaughterhouse wastewater and ∼1 μg/L in treated wastewater. Illicit drugs for animal feeding such as clenbuterol and diazepam were commonly detected in slaughterhouse wastewater. These analytes were also observed in a river receiving slaughterhouse wastewater, with a highest level of up to 0.2 μg/L.     

Liquid chromatography-(tandem) mass spectrometry for the follow-up of the elimination of persistent pharmaceuticals during wastewater treatment applying biological wastewater treatment and advanced oxidation

The persistent and hardly eliminable pharmaceutical compounds carbamazepine, diazepam, diclofenac and clofibric acid were monitored in municipal wastewater by electrospray LC-MS and LC-MS-MS in positive and negative mode under high resolution and high mass accuracy conditions. While biological treatment by conventional and membrane bioreactors failed, the advanced oxidation methods using ozone (O3), O3/UV or hydrogen peroxide in combination with UV (H2O2/UV) successfully led to the complete elimination of these compounds. Target compounds could be confirmed as permanently present pollutants in Aachen-Soers wastewater in concentrations between 0.006 and 1.9 microg l(-1). Pharmaceuticals were determined after extraction using either C18 solid-phase extraction or by directly injecting them into the column without pre-concentration, achieving limits of quantification of 0.001 or 0.00001 microg l(-1), respectively.     

Simultaneous determination of methyl tert.-butyl ether and its degradation products,other gasoline oxygenates and benzene,toluene, ethylbenzene and xylenes in Catalonian groundwater by purge-and-trap-gas chromatography-mass spectrometry

In Catalonia (northeast Spain), a monitoring program was carried out to determine methyl tert.-butyl ether (MTBE), its main degradation products, tert.-butyl alcohol (TBA), tert.-butyl formate (TBF), and other gasoline additives, the oxygenate dialkyl ethers ethyl tert.-butyl ether, tert.-amyl methyl ether and diisopropyl ether and the aromatic compounds benzene, toluene, ethylbenzene and xylene (BTEX) in 21 groundwater wells that were located near different gasoline point sources (a gasoline spill and underground storage tank leakage). Purge-and-trap coupled to gas chromatography-mass spectrometry was optimised for the simultaneous determination of the above mentioned compounds and enabled to detect concentrations at ng/l or sub-microg/l concentrations. Special attention was given to the determination of polar MTBE degradation products, TBA and TBF, since not much data on method performance and environmental levels are given on these compounds in groundwater. All samples analysed contained MTBE at levels between 0.3 and 70 microg/l. Seven contaminated hot spots were identified with levels up to US Environmental Protection Agency drinking water advisory (20-40 microg/l) and a maximum concentration of 670 microg/l (doubling the Danish suggested toxicity level of 350 microg/l). Samples with high levels of MTBE contained 0.1-60 microg/l of TBA, indicating (but not proving) in situ degradation of parent compound. In all cases, BTEX was at low concentrations or not detected showing less solubility and persistence than MTBE. This fact confirms the suitability of MTBE as a tracer or indicator of long-term gasoline contamination than the historically used BTEX.     

Development of a multi-residue analytical method,based on liquid chromatography–tandem mass spectrometry,for the simultaneous determination of 46 micro-contaminants in aqueous samples

A multi-residue analytical method based on high-performance liquid chromatographic separation, electrospray ionization with tandem mass spectrometric detection (HPLC/MS–MS) was developed for the simultaneous analysis of 46 basic, neutral and acidic compounds covering a wide range of polarity (log K_OW < 0–5.9). The compound list included selected iodinated contrast media, analgesics, anti-inflammatories, stimulants, beta-blockers, antibiotics, lipid regulators, anti-histamines, psychiatric drugs, herbicides, corrosion inhibitors and the gastric acid regulator pantoprazole. The main feature of the presented method was a simultaneous solid phase extraction (SPE) of all analytes followed by simultaneous separation and detection by HPLC/MS–MS with electrospray ionization in both positive and negative polarization within the same chromatogram. Optimization of electrospray drying gas temperature resulted in using a temperature gradient on the ion source. Six different polymeric sorbents for SPE were compared with respect to recoveries, taking into account the specific surface of each sorbent. Method quantitation limits (MQL) in surface and seawater ranged from 1.2 to 28 ng/L, in wastewater from 5.0 to 160 ng/L, respectively. In order to demonstrate the applicability of the method, river water, treated wastewater and seawater were analyzed.     

Rapid determination of five antibiotic residues in swine wastewater by online solid-phase extraction–high performance liquid chromatography–tandem mass spectrometry

A simple and quick online solid-phase extraction (SPE) coupled to liquid chromatography (LC)/tandem mass spectrometry (MS/MS) for the determination of the five antibiotics (florfenicol, FF; lincomycin, LCM; oxytetracyclin, OTC; tylosin, TS; valnemulin, VLM) in swine wastewater has been developed. After filtration, aliquots (100 μl) of wastewater samples were directly injected to a column-switching LC system. Some matrix interference was removed by washing up SPE column with 0.2% formic acid solution and acetonitrile. Antibiotics eluted from SPE column were separated on analytical column by converting switching valve and were detected by MS/MS. Calibration curves using the method of standard addition had very good correlation coefficients (r > 0.99) in the range of 0.1 to 2 ng/ml. The intra-day precision of the method was less than 12% and the inter-day precision was between 6 to 17%. The detection limits were 0.01–0.1 ng/ml. When this method was applied to wastewater samples in swine facilities, four compounds (LCM, OTC, TS, and VLM) were detected.     

Rapid analysis of triazolopyrimidine sulfoanilide herbicides in waters and soils by high-performance liquid chromatography with UV detection using a C18 monolithic column

In this work, the simultaneous analysis of five triazolopyrimidine sulfoanilide herbicides (flumetsulam, florasulam, metosulam, cloransulam-methyl, and diclosulam) by HPLC using UV detection and a C18 monolithic column is proposed. The mobile phase which was composed of ACN, water, and formic acid was pumped at a high flow rate (5 mmL/min) providing an analysis time of all the compounds in less than 2.3 min. The LODs were in the low microg/L range (i.e. between 60 microg/L for flumetsulam and 90 microg/L for florasulam) and the calibration curves showed good linearity (R2 > 0.9949). The method was applied to the analysis of these compounds in spiked mineral and tap waters and soils after an SPE preconcentration procedure using C18 cartridges. Mean recovery values ranged between 35 and 110% for water samples providing LODs of the whole procedure in the low ng/L level, down to 280 ng/L, and between 77 and 92% for soil samples with LODs down to 9.38 microg/kg. This is the first time that this family of pesticides is simultaneously analyzed in both types of samples by HPLC and also using a monolithic column.     

Determination of beta-blockers and beta2-agonists in sewage by solid-phase extraction and liquid chromatography-tandem mass spectrometry

A method using solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed for the determination of 12 beta-blockers and beta(2)-agonists in wastewater samples. Extraction of the drugs was effected by an Oasis MCX cartridge with a strong cation resin adsorbent. Matrix coextractives were removed from the SPE cartridge by methanol prior to the elution of the drugs with a mixture of dichloromethane, 2-propranol, and ammonium hydroxide. The extract was analyzed by LC-MS/MS with electrospray ionization operating in the positive mode. Recovery of the 12 compounds was in most cases better than 85% at the fortification levels of 500 and 50 ng/L, with standard deviations between 3 and 7%. Based on a concentration factor of 250, the method detection limits ranged from 6 to 11 ng/L for the target compounds. No degradation of these drugs in spiked sewage effluent samples was observed over a storage period of 7 days at 4 degrees C in the dark. Many beta-blockers were detected in the 14 wastewater samples collected from seven Canadian sewage treatment plants; those occurring at the highest concentrations were atenolol, acebutolol, sotalol, and metroprolol, with overall median concentrations of 1370, 339, 282, and 257 ng/L, respectively. However, there was only a small decrease in the median concentrations of these beta-blockers between the primary and final effluent, suggesting that these drugs are not easily removed by the sewage treatment processes. As a result of selective extraction and effective removal of coextractives, no matrix effect was observed for the samples during LC-MS/MS analyses.     

Simultaneous determination of the endocrine disrupting compounds nonylphenol, nonylphenol ethoxylates, triclosan and bisphenol A in wastewater and sewage sludge by gas chromatography-mass spectrometry

An integrated analytical method for the simultaneous determination of 4-n-nonylphenol (4-n-NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), bisphenol A (BPA) and triclosan (TCS) in wastewater (dissolved and particulate phase) and sewage sludge was developed based on gas chromatography-mass spectrometry. Chromatographic analysis was achieved after derivatization with bis(trimethylsilyl)trifluoroacetamide (BSTFA). Extraction from water samples was performed by solid-phase extraction (SPE). The optimization of SPE procedure included the type of sorbent and the type of the organic solvent used for the elution. Referred to solid samples, the target compounds were extracted by sonication. In this case the optimization of the extraction procedure included the variation of the amount of the extracted biomass, the duration and the temperature of sonication and the type of the extraction organic solvent. The developed extraction procedures resulted in good repeatability and reproducibility with relative standard deviations (RSDs) less than 13% for all the tested compounds for both types of samples. Satisfactory recoveries were obtained (>60%) for all the compounds in both liquid and solid samples, except for 4-n-NP, which gave recoveries up to 35% in wastewater samples and up to 63% in sludge samples. The limits of detection (LODs) of the target compounds varied from 0.03 (4-n-NP) to 0.41 microg l(-1) (NP2EO) and from 0.04 (4-n-NP) to 0.96 microg kg(-1) (NP2EO) for liquid and solid samples, respectively. The developed methods were successfully applied to the analysis of the target compounds in real samples.     

An LC-MS method for the determination of pharmaceutical compounds in wastewater treatment plant influent and effluent samples

Pharmaceuticals are continually introduced into the environment as a result of industrial and domestic use. In recent years they have emerged as environmental pollutants. An analytical method has been developed allowing for simultaneous detection and identification of 20 pharmaceutical compounds from various therapeutic classes using solid phase extraction (SPE) followed by liquid chromatography-electrospray ionisation mass spectrometry (LC-MS/MS). The limits of detection and limits of quantitation for the method were in the ng/L-microg/L range. The method was applied to influent and effluent samples from three wastewater treatment plants (WWTPs). Fifteen compounds were identified in the sample matrix with salicylic acid and ibuprofen being the most abundant at 9.17 and 3.20 microg/L respectively.     

Analysis of perfluorooctanesulfonate and related fluorochemicals in water and biological tissue samples by liquid chromatography-ion trap mass spectrometry

A method for the determination of perfluorinated compounds (PFCs) in various water and biological tissue samples was developed and validated. The contents of selected PFCs (i.e., perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA) and perfluorodecanoate (PFDA)) in water samples were extracted by the C(18) solid-phase extraction (SPE). The biological tissue samples (frozen-dried fish and oysters) were simply extracted by liquid-solid extraction with MTBE and adding tetrabutylammonium hydrogensulfate (TBA) as an ion-pairing reagent. The analytes were then identified and quantitated by liquid chromatography-ion trap negative electrospray mass spectrometry (LC-ESI ion-trap-MS). Limits of quantitation (LOQ) were established between 0.5 and 6 ng/l in 250 ml of water sample, while 5-50 ng/g (dry weight) for biological tissue sample. Intrabatch and interbatch precision with their accuracy at two concentration levels were also investigated. Precision for these three PFCs, as indicated by RSD, proved to be less than 11 and 17%, respectively. The total contents of PFOA, PFOS and PFDA were detected in concentrations of up to 400 ng/l in various water samples, while up to 1,100 ng/g in fish and oyster samples. PFOA and PFDA was the major PFCs detected in water samples and biological tissue samples, respectively.     

Simultaneous determination of isoflavones and lignans at trace levels in natural waters and wastewater samples using liquid chromatography/electrospray ionization ion trap mass spectrometry

A high-performance liquid chromatography/electrospray ionization ion trap mass spectrometry (HPLC/ESI-MSn) method has been developed for the trace determination of phytoestrogens in aquatic environmental samples. The method includes solid-phase extraction (SPE) and analysis using liquid chromatography/electrospray ionization ion trap mass spectrometry. The aquatic environmental samples, influent of a wastewater treatment plant (WWTP) and creek water, were adjusted to pH approximately 5 before extraction. The analyzed phytoestrogens were identified by an MSn method and quantified against a deuterated internal standard (genistein-3',5',6,8-D4). In negative ion mode, 0.1% formic acid was employed in acetonitrile/water mobile phase. The method detection limits ranged from 0.5 to 10 ng/L in WWTP influent and from 0.1 to 5 ng/L in creek water. Average SPE recoveries for the analyzed phytoestrogens ranged from 85 to 95%, with a relative standard deviation (RSD) (%) ranging from 3.9 to 6.5. The concentrations of the six analyzed phytoestrogens varied from 0.2 to 600 ng/L with high levels of enterolignans (enterolactone and enterodiol) found in the collected wastewater. The method is shown to be suitable for the determination of phytoestrogens in aquatic environmental samples at nano- and sub-nanogram per liter levels.     

Perfluorinated compounds (PFCs) in groundwater and aqueous soil extracts: using inline SPE-LC-MS/MS for screening and sorption characterisation of perfluorooctane sulphonate and related compounds

Perfluorinated compounds (PFCs) have been recognised as emerging pollutants of global relevance. A fully automated method with inline solid-phase extraction coupled to electrospray ionisation liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) is presented and used for characterisation of soil adsorption and desorption for six PFCs: perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorobutane sulphonate (PFBS), and perfluorooctane sulphonate (PFOS). The method reduces sample turnaround time and solvent consumption and is suitable for low volume sampling. The only sample preparation necessary for water samples was sedimentation by centrifugation. The method has a total runtime of 21 min including inline sample cleanup (2 min for injection and SPE, 14 min for the chromatographic separation, 5 min for reconditioning). Negative AP-ESI with selective reaction monitoring (SRM) was used and the method was documented for quantification of the six environmentally important PFCs in subsoil matrix and related aqueous matrixes (groundwater and drainage water). Linearity was demonstrated in the range 5 to 2,500 ng/l and the LOD was between 2 and 8 ng/l in groundwater. Adsorption was characterised by linear Freundlich isotherms for all six compounds in two agricultural top soils (A horizon, sandy and clayey soil).Variability in sorption characteristics for soil types as well as compound properties were found, and correlation between the organic carbon normalised sorption coefficient (K _OC) and PFC molecular weight was demonstrated. The K _d values were in the range 0.1 to 33 (l/kg), and 0.3 to 65 (l/kg) for sorption and desorption respectively.     

Comparison of different liquid chromatography methods for the determination of corticosteroids in biological matrices

Various extraction techniques can be combined with column liquid chromatography (LC) and ultraviolet (UV) or mass spectrometric (MS) detection for the determination of synthetic corticosteroids in biological matrices. Target analysis of low concentrations of 25 microg/kg of dexamethasone in feed can be performed by combining immunoaffinity chromatography (IAC) and LC with UV detection. A straightforward multi-analyte procedure is obtained by tandem solid-phase extraction (SPE) and subsequent LC-UV. However, the limits of detection for feed samples are then relatively poor, viz. 100 microg/kg. A multi-analyte method which meets modern demands of about 5 microg/kg detection limit requires one-step SPE combined with LC-MS analysis. As regards urine corticosteroids can be determined down to a level of 0.5 microg/l by either SPE-LC-MS- MS or SPE(IAC)-LC-MS.