Determination of estrogenic steroids in surface water and wastewater by liquid chromatography-electrospray tandem mass spectrometry

An analytical method is presented which permits trace level determination of 17alpha-ethynylestradiol (EE2), 17beta-estradiol (E2), and estrone (E1). Using this method, the estrogenic steroids were analyzed in drinking water, surface water, and wastewater (sewage influents and effluents) at concentrations down to 0.1 ng/L. Sample volumes between 100 and 500 mL are concentrated using automated solid-phase extraction. Analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Applying simple clean-up procedures and internal standard calibration, recovery losses resulting from matrix-dependent ion suppression during electrospray ionization could be compensated for all of the investigated compounds. Recoveries around 100% were obtained for all analytes after correction using the internal standards. Limits of quantification (LOQ) were between 0.1 and 0.4 ng/L for purified sewage, surface, ground, and drinking water and between 1 and 2 ng/L in the case of raw sewage. Water treatment by wastewater treatment plants (WWTPs) or by a surface water treatment plant affected the removal of all estrogenic steroids. Thus, E1, E2, and EE2 were removed in the municipal WWTPs to the extent of 93%, 93%, and 80%, respectively. In the effluents of the WWTP in Ruhleben (Berlin, Germany), E1, E2, and EE2 were detected at the low ng/L level. E2 and EE2 were, however, not present in the Berlin surface water above the LOQ (0.2 ng/L). E1 was the only compound that could be detected in surface water samples. After additional surface water treatment it was still detectable but only at trace-level concentrations with a mean value of 0.16 ng/L.     

Optimisation of derivatisation for the analysis of estrogenic compounds in water by solid-phase extraction gas chromatography-mass spectrometry

An optimisation of derivatisation methods for the simultaneous determination of endocrine disrupting chemicals (EDCs) in water by solid-phase extraction (SPE) gas chromatography-mass spectrometry (GC-MS) was developed in this study. Seven highly potent EDCs including 17β-estradiol (E2), estrone (E1), 16α-hydroxyestrone, 17α-ethynylestradiol (EE2), bisphenol A, 4-nonylphenol and 4-tert-octylphenol were selected as the target compounds. The SPE technique, followed by the derivatisation with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) was used for the extraction recoveries of compounds from water and effluent samples. The stability of the silylation derivatives under different reaction conditions was investigated. The combined use of BSTFA and pyridine as derivatisation reagents, together with the use of hexane as the final solvent, was preferred in order to generate more stable derivatives of EDCs. The relative response factor (RRF) of all derivatives except that of EE2 was stable 120 h after derivatisation. The addition of pyridine as derivatisation reagent with BSTFA can prevent the conversion of EE2 to other products during the reaction. Several parameters that may affect the recovery of EDCs, such as the SPE flow rate, and water properties including aquatic colloid content and surfactant concentration were tested. The results showed that the flow rate (1-25 mL min⁻¹), colloid concentration (0-50 mg L⁻¹) and surfactants concentration (0-10 μg L⁻¹) did not cause significant decrease in the EDCs recovery.     

Selective pressurized liquid extraction of estrogenic compounds in soil and analysis by gas chromatography-mass spectrometry

A selective pressurized liquid extraction (SPLE) method, followed by gas chromatography–mass spectrometry (GC–MS), for the simultaneous extraction and clean-up of estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), estriol (E3) and bisphenol A (BPA) from soil samples is described. The on-line clean-up of soil by SPLE was achieved using different organic matter retainers, including silica, alumina and Florisil, the most effective being silica. Thus, different amounts of silica, in conjunction with different extraction solvents (acetone, ethyl acetate, isohexane and dichloromethane), either alone or in combination, were used to extract the target chemicals from spiked soil samples. It was shown that 3 g silica resulted in satisfactory rates of recovery of target compounds and acetone:dichloromethane (1:3, v/v) was efficient in extracting and eluting estrogenic compounds for SPLE. Variables affecting the SPLE efficiency, including temperature and pressure were studied; the optimum parameters were 60 °C and 1500 psi, respectively. The limits of detection (LODs) of the proposed method were 0.02–0.37 ng g⁻¹ for the different estrogenic chemicals studied. The outputs using the proposed method were linear over the range from 0.1 to 120 ng g⁻¹ for E1, E2, EE2, 0.2–120 ng g⁻¹ for E3, and 0.5–120 ng g⁻¹ for BPA. The optimized method was further verified by performing spiking experiments in natural soil matrices; good rates of recovery and reproducibility were achieved for all selected compounds and the method was successfully applied to soil samples from Northeast Scotland, for the determination of the target compounds.     

Determination of dissolved iron(III) in estuarine and coastal waters by adsorptive stripping chronopotentiometry (SCP)

An adsorptive stripping chronopotentiometric (SCP) method has been developed for quantification of dissolved iron in estuarine and coastal waters. After UV-digestion of filtered samples the Fe(III) ions in non-deoxygenated samples were complexed with solochrom violet RS (SVRS). The complexes were then accumulated by adsorption on the surface of a mercury-film electrode. The stripping step was performed by applying a constant current of −17 μA. Sensitivity and detection limit were 15 ms nmol⁻¹ L (270 ms μg⁻¹ L) and 1.5 nmol L⁻¹ (84 ng L⁻¹), respectively, for 60-s electrolysis time. Compared with the only other chronopotentiometric method available for measurement of iron in natural waters, our procedure is fifty times more sensitive in a quarter of the electrolysis time. It therefore enables detection of the concentrations currently found in estuarine and coastal waters. The method was successfully used to study the behaviour and seasonal variations of dissolved iron in the Penzé estuary, NW France.     

牛奶、母乳中全氟化合物分析方法的研究

建立了HPLC-ESI-MS/MS联用技术测定奶制品中12种全氟化合物(PFCs)的方法.12种全氟化合物包括9种常见PFCs和2种调聚酸及一种全氟磺酰胺.对比了MTBE液-液萃取、甲酸、乙腈和甲醇萃取这4种萃取方法对12种全氟化合物的萃取和回收效果.最终选用甲醇作为萃取溶剂,并选取WAX作为固相萃取柱对萃取的溶液进行净化,方法对12种PFCs的加标回收在83.5%～113.3%之间,检出限0.005～0.092 μg/L.最后完成了对纯牛奶,早餐奶和母乳样品中12种PFCs的分析.     

Monitoring of environmental phenolic endocrine disrupting compounds in treatment effluents and river waters, Korea

The last two decades have witnessed growing scientific and public concerns over endocrine disrupting compounds (EDCs) that have the potential to alter the normal structure or functions of the endocrine system in wildlife and humans. In this study, the phenolic EDCs such as alkylphenol, chlorinated phenol and bisphenol A were considered. They are commonly found in wastewater discharges and in sewage treatment plant. In order to monitor the levels and seasonal variations of phenolic EDCs in various aquatic environments, a total of 15 water samples from the discharged effluent from sewage and wastewater treatment plants and river water were collected for 3 years. Ten environmental phenolic EDCs were determined by GC-MS and laser-induced fluorescence (LIF). GC-MS analysis revealed that most abundant phenolic EDCs were 4-n-heptylphenol, followed by nonlyphenol and bisphenol A during 2002-2003, while 4-t-butylphenol and 4-t-octylphenol were newly detected in aquatic environments in 2004.The category of phenolic EDCs showed similar fluorescence spectra and nearly equal fluorescence decay time. This makes it hard to distinguish each phenolic EDC from the EDCs mixture by LIF. Therefore, the results obtained from LIF analysis were expressed in terms of the fluorescence intensity of the total phenolic EDCs rather than that of the individual EDC. However, LIF monitoring and GC-MS analysis showed consistent result in that the river water samples had lower phenolic EDCs concentration compared to the effluent sample. This revealed a lower fluorescence intensity and the phenolic EDCs concentration in summer was lower than that in winter. For the validation of LIF monitoring for the phenolic EDCs, the correlation between EDCs concentration acquired from GC-MS and fluorescence intensity from LIF was obtained (R = 0.7379). This study supports the feasibility of the application of LIF into EDCs monitoring in aquatic systems.     

Analysis by liquid chromatography‐tandem mass spectrometry of biophenolic compounds in olives and vegetation waters,Part I

Biophenolic compounds constitute a complex mixture in olives and derived products. In this work, ion‐spray tandem mass spectrometry coupled with liquid chromatography is applied to the identification and quantification of biophenols present in complex matrices such as olives and vegetation waters. The extraction and purification method for the biophenol present in both the matrices is reported. Using this approach the main biophenols found, in three different variety of olives, were: tyrosol, hydroxytyrosol, oleoside methyl ester, oleoside dimethyl ester, and oleuropein. In vegetation water the biophenols are present in lower amounts than in olives.     

Voltammetric in situ measurements of trace metals in coastal waters

Developments in instrument miniaturisation and automation have resulted in the manufacture of portable electrochemical instrumentation for continuous trace-metal measurements from the banks of estuaries and on board ships. The most recent developments in flow cells with gel-coated iridium (Ir) micro-electrode arrays have resulted in submersible in situ voltammetric probes that allow long-term trace-metal monitoring at sub-nanomolar concentrations in coastal waters. This article overviews the design and the application of field-deployable voltammetric instrumentation for trace-metal monitoring.     

Determination of herbicides by solid phase extraction gas chromatography-mass spectrometry in drinking waters

A solid phase extraction (SPE) method has been optimized for the gas chromatography-mass spectrometry (GC-MS) simultaneous determination of herbicides belonging to the following different families: carbamate (molinate), atrazines (atrazine, propazine, simazine, ametryne, cyanazine, terbutylazine, deethylterbutylazine, deethylatrazine), dinitroaniline (trifluralin, pendimethalin), chloroacetamide (alachlor, metolachlor). Different solid substrates have been compared (C18, cyano, styrene-divinylbenzene, phenyl, graphitic carbon). The type of conditioning and elution solvent, its volume, and the sample flow rate have been considered as variables affecting the recovery yields of the herbicides.The optimized experimental conditions are C18 phase conditioned with 3 mL acetone, loaded with 1 L water sample at 5 mL min⁻¹, and eluted with 3 mL acetone. Good recoveries (included between 79% and 99%) and R.S.D. (included between 2% and 12%) have been obtained for all analytes, except for deethylatrazine whose recovery was 46 ± 7%. The recovery of deethylatrazine increases up to 94 ± 17% if a non-porous graphitic carbon is coupled to the C18 phase, keeping the other parameters constant as optimized. The optimized method has been successfully checked for the identification and quantitation of the selected herbicides in raw and drinking water samples, with quantitation limits as low as 0.01 μg L⁻¹, fully in agreement with the current legislation. The method is easily routinable. After development, the method is currently routinely applied for the analysis of herbicides in waters and, up today, more than one thousand samples have been analysed at the “Laboratorio della Società Metropolitana Acque di Torino” (Laboratory of the Municipal Waterworks of Turin) in charge of the control of drinking water quality in Torino.     

Nanofiltration and ultrafiltration of endocrine disrupting compounds, pharmaceuticals and personal care products

Reports of endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have raised substantial concern among important potable drinking water and reclaimed wastewater quality issues. Our study investigates the removal of EDC/PPCPs of 52 compounds having different physico-chemical properties (e.g., size, hydrophobicity, and polarity) by nanofiltration (NF) and ultrafiltration (UF) membranes using a dead-end stirred-cell filtration system. EDC/PPCPs were applied to the membrane in one model water and three natural waters. Experiments were performed at environmentally relevant initial EDC/PPCP concentrations ranging typically from 2 to <250 ng/L. EDC/PPCP retention was quantified by liquid and gas chromatography with mass spectroscopy–mass spectroscopy. A general separation trend due to hydrophobic adsorption as a function of octanol–water partition coefficient was observed between the hydrophobic compounds and porous hydrophobic membrane during the membrane filtration in unequilibrium conditions. The results showed that the NF membrane retained many EDC/PPCPs due to both hydrophobic adsorption and size exclusion, while the UF membrane retained typically hydrophobic EDC/PPCPs due mainly to hydrophobic adsorption. However, the transport phenomenon associated with adsorption may depend on water chemistry conditions and membrane material.     

Electrocatalytic detection of phenolic estrogenic compounds at NiTPPS|carbon nanotube composite electrodes

A Ni(II)tetrakis(4-sulfonatophenyl) porphyrin (NiTPPS)|carbon nanotube composite electrode that shows strong catalytic and antifouling capability was developed to detect a series of phenolic endocrine compounds including bisphenol A, nonylphenol and ethynylestradiol. This electrode was fabricated by electropolymerizing NiTPPS complexes on a carbon nanotube-modified glassy carbon electrode. Optimized experimental parameters including a hydrodynamic potential of 0.7 V for flow injection analysis (FIA) and a NiTPPS surface coverage of 2.2 nmol cm⁻² (standard deviation 0.2 nmol cm⁻²; n = 6) were obtained for detection of the endocrine disrupting compounds. The sensor responded well to all the tested compounds with limits of detection ranging from 15 nmol L⁻¹ to 260 nmol L⁻¹ (based on three times S/N ratio) under FIA conditions. Both carbon nanotubes and NiTPPS account for the excellent performance of the composite modified electrode.     

Occurrence of endocrine-disrupting compounds in reclaimed water from Tianjin,China

Continuous disposal of endocrine-disrupting compounds (EDCs) into the environment can lead to serious human health problems and can affect plants and aquatic organisms. The determination of EDCs in water has become an increasingly important activity due to our increased knowledge about their toxicities, even at low concentration. The EDCs in water samples from the reclaimed water plant of Tianjin, northern China, were identified by gas chromatography (GC)–mass spectrometry (MS). Important and contrasting EDCs including estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), 4-tert-octylphenol (OP), 4-nonylphenol (NP), bisphenol A (BPA), di-n-butyl phthalate (DnBP), diisobutyl phthalate (DIBP), and di(2-ethylhexyl)phthalate (DEHP) were selected as the target compounds. Concentrations of steroid hormones, alkylphenolic compounds and phthalates ranged from below the limit of detection (LOD) to 8.1 ng L⁻¹, from <LOD to 14.2 ng L⁻¹, and from 1.00 μg L⁻¹ to 23.8 μg L⁻¹, respectively. The average removal efficiencies for target EDCs varied from 30% to 82%. These results indicate that environmental endocrine disrupting compounds are not completely removed during reclaimed water treatment and may be carried over into the general aquatic environment.     

Polypyrrole‐coated alginate/magnetite nanoparticles composite sorbent for the extraction of endocrine‐disrupting compounds

Magnetite nanoparticles incorporated into alginate beads and coated with a polypyrrole adsorbent were prepared (polypyrrole/Fe₃O₄/alginate bead) and used as an effective magnetic solid‐phase extraction sorbent for the extraction and enrichment of endocrine‐disrupting compounds (estriol, β‐estradiol and bisphenol A) in water samples. The determination of the extracted endocrine‐disrupting compounds was performed using high‐performance liquid chromatography with a fluorescence detector. The effect of various parameters on the extraction efficiency of endocrine disrupting compounds were investigated and optimized including the type and amount of sorbent, sample pH, extraction time, stirring speed, and desorption conditions. Under optimum conditions, the calibration curves were linear in the concentration range of 0.5–100.0 μg/L, and the limit of detection was 0.5 μg/L. The developed method showed a high extraction efficiency, the recoveries were in the range of 90.5 ± 4.1 to 98.2 ± 5.5%. The developed sorbent was easy to prepare, was cost‐effective, robust, and provided a good reproducibility (RSDs < 5%), and could be reused 16 times. The developed method was successfully applied for the determination of endocrine‐disrupting compounds in water samples.     

The use of molecularly imprinted polymers for the multicomponent determination of endocrine‐disrupting compounds in water and sediment

The method employing molecularly imprinted polymers for the extraction and clean up of endocrine‐disrupting compounds (estrogens, bisphenol A, and alkylphenols) from water and sediment is described. The identical extraction/clean‐up and LC‐MS/MS condition were used for the analysis of both types of samples. The method showed high recoveries ranging from 90 to 99% with excellent precision (intrabatch: 3.6–9.3%; interbatch: 5.6–11.4% for water; intrabatch: 4.3–8.5%; interbatch: 6.1–9.6% for sediment). The LOD was in the range of 0.7–1.9 ng/L and 0.3–0.6 ng/g for water and sediment, respectively. Overall extraction on molecularly imprinted polymers substantially enhanced sample clean‐up. The difference in efficiency of clean‐up was particularly pronounced when a large sample volume/weight was extracted and analyzed. Finally, the method was successfully applied for the analysis of 20 water and sediment samples.     

Critical evaluation of the determination of pharmaceuticals, personal care products, phenolic endocrine disrupters and faecal steroids by GC/MS and PTV-GC/MS in environmental waters

An analytical method is described for the determination of a broad range of emerging and priority pollutants, together with sewage molecular markers in environmental waters. The step-by-step study of the GC/MS analyses focuses on the effects of experimental variables using a large volume injection (LVI) technique [a programmed temperature-vaporising (PTV) inlet], the evaluation of a clean-up step using classical and newer sorbents (i.e. Al-N, Fl, NH₂, PSA, Si, CN and DIOL), and the revision of how organic matter [i.e. humic acids (HA) content] affects method performance. Reproducibility and recoveries from spiked coastal water samples at different analyte concentrations (100, 250 and 500 ng L⁻¹) as well as with different levels of spiked humic acids (2, 10 and 20 mg L⁻¹) are reported indicating a good performance of the extraction procedure with low levels of HA (<10 mg L⁻¹). The presence of HA is a critical parameter during the solid-phase extraction (SPE) procedures. Of the clean-up sorbents tested, CN and DIOL proved most efficient in cleaning-up the extracts with recoveries in the range of 66-77% and 100-114%, respectively for the selected analytes. Both GC/MS and PTV-GC/MS instrumental configurations were tested using final sewage effluents, riverine, estuarine and coastal water samples. However, limited applicability of the PTV inlet is reported for environmental applications, affording only a modest improvement in chromatographic signal-to-noise ratios.     

Application of chemometric methods to the investigation of main microcontaminant sources of endocrine disruptors in coastal and harbour waters and sediments

Identification, resolution and distribution of main microcontaminant sources of endocrine disruptors in Spanish harbours, coastal waters and sediments are investigated using chemometric methods. We investigated eighteen different endocrine disruptor chemical compounds, including non-ionic surfactants, their degradation products and linear alkylbenzene sulfonates, found in a total number of 74 samples (35 water samples and 39 sediment samples) over a period of 16 months from March 1999 to July 2000, and in 32 different geographical sites along the Spanish Mediterranean Coast (e.g. Barcelona, Tarragona, Almeria Harbour, Malaga and the Bay of Cadiz). Main environmental contamination sources of these endocrine disruptor compounds were investigated and interpreted according to their chemical composition and according to their resolved geographical distribution profiles.An erratum to this article can be found at     

Determination of pyrithione in natural waters by cathodic stripping voltammetry

A method was developed to determine the biocide pyrithione in natural waters. The method is based on cathodic stripping voltammetry (CSV) in the presence of Triton-X-100, which is used to separate the peak from interfering thiol compounds. Optimised conditions include a Triton-X-100 concentration of 4 ppm and a pH adjusted to 9 using ammonia buffer. The adsorption potential for pyrithione was −0.10 V and the peak occurred at −0.2 to −0.3 V. Detection was by differential-pulse CSV. The detection limit in UV-digested seawater was 1.5 nM for a deposition time of 60 s. In principle, this limit of detection could be lowered by extending the adsorption time, but in practice this may not be possible due to interferences by other organic compounds (surfactants and thiol compounds) in natural waters.     

Determination of dissolved manganese in natural waters by differential pulse cathodic stripping voltammetry

A procedure based on differential pulse cathodic stripping voltammetry on the graphite electrode is described for the determination of dissolved manganese in natural waters buffered at pH about 6.5 with acetate solution. In order to avoid interference of iron(II) the addition of fluoride is used. The limit of detection is 3 g/l for a deposition time of 6 min. Acidification and UV-irradiation are recommended for samples containing dissolved organic matter. Results of manganese determination in table mineral waters are reported and the possibility of manganese speciation is discussed.     

Determination of thallium in natural waters by electrothermal atomic absorption spectrometry

Thallium is determined in natural waters by electrothermal atomic absorption Spectrometry after preconcentration. Thallium is oxidized and retained as the tetrachlorothallate (III) ion on an anion exchange column, followed by elution with ammonium sulfite solution. A concentration factor of 400 is achieved. The detection limit of the method is 3.3 ng/1.