A new method of evaluation of element pollutant mobility in sediments

The application of a strong chelating agent for the screening test of element mobility in sedimentary systems was investigated. Single-step and sequential extraction procedures were applied to four sediment samples collected from an industrially polluted region of Eastern Slovakia. A sequential extraction procedure (SEP), recommended by the Institute for Reference Materials and Measurements (IRMM), was applied and used as a reference extraction method. A single-step extraction with 0.05 mol dm⁻³ ethylenediaminetetraacetic acid (EDTA) was adapted for sediments when extraction conditions were optimised. The extraction efficiency of the single-step procedure was compared with that of SEP. The contents of elements extracted by Na2EDTA were in good agreement with the sum of the first three steps of the SEP for Fe, Mn, and Co. Na₂EDTA can therefore be considered capable to extract the majority of elements associated with the reducible sedimentary phase — bound to Fe and Mn oxides in the regional geological conditions of the monitored region. Thus, Na₂EDTA extraction of Fe and Mn can serve as an economical, time-saving supplementary test for the IRMM procedure. This paper is dedicated to the memory of Erika Krakovská Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Inert matrix and Na4EDTA improve the supercritical fluid extraction efficiency of fluoroquinolones for HPLC determination in pig tissues

A supercritical fluid extraction method combined with high-performance liquid chromatography-fluorescence detection was developed for the determination of enrofloxacin, danofloxacin, and ciprofloxacin in pig muscle, lung, and kidney samples. The optimal SFE conditions were 80 °C, 300 kg/cm², 30% methanol for 40 min as a dynamic extraction time, in addition to 0.2 g Na₄EDTA and 7.0 g sea sand in the extraction vessel. The use of Na₄EDTA and sea sand on SFE extraction resulted in improvement of the recoveries of ciprofloxacin, a polar and hydrophilic compound, as well as enrofloxacin and danofloxacin. Overall, the recoveries ranged from 86.7 to 113.1% using the Na₄EDTA/sea sand-assisted SFE extraction method. The Na₄EDTA/sea sand-assisted SFE-HPLC-FLD validated method was successfully carried out in pig tissues, and proved to be specific, sensitive, reliable, and accurate. The method was also applied satisfactorily for accurate quantitative residue analysis in incurred pig tissues.     

121Sb Mössbauer spectra of alkali metal antimonides M3Sb (M3 = Na3, K3, Na2K, Rb3)

¹²¹Sb Mössbauer spectra for M₃Sb (M₃ = Na₃, K₃, Na₂K, Rb₃) were measured at 12 K. The values of isomer shift (d) and quadrupole coupling constant suggest that the valence state of antimony in M₃Sb is –3. The d values increase in the order Rb₃Sb<K₃Sb<Na₃Sb<Na₂KSb. The differences in d values are discussed by examining M–Sb distances and bond valence for M–Sb interactions. Some covalent interactions between alkali metal atoms and antimony atom are suggested.     

Adsorption characteristics of metal-EDTA complexes onto hydrous oxides

The adsorption characteristics of a variety of metal-EDTA complexes onto hydrous oxides, principally aluminum oxide (γ-Al₂O₃), were examined in aqueous solution. Adsorption of these complexes increased with increasing proton concentration due to the formation of surface complexes between EDTA and the surface hydroxo groups, specifically the AlOH₂⁺ surface groups. The pH-dependent adsorptive behavior and the magnitude of adsorption of the “free” EDTA species were similar to those of the metal complexes. The results also showed that the adsorption of “free” EDTA was exothermic, while the adsorption of Ni(II)-EDTA complexes was endothermic in the lower pH region (3.5) and exothermic at higher pH values (6.0). This implied that the surface preferred the NiHEDTA⁻¹ species rather than the NiEDTA⁻² species. Specific adsorption of the metal complexes was evidenced by the charge reversal exhibited by the γ-Al₂O₃ particles at the highest surface loadings. A quantitative model was formulated based on the pH-dependent speciation of the oxide surface, speciation of the metal complexes in solution, and ζ potential measurements. This model proved valid over a wide range of pH (3–10) and for both high (>50% coverage) and low (<10% coverage) surface loadings.     

Liquid chromatography-hydride generation-atomic fluorescence spectrometry hybridation for antimony speciation in environmental samples

Atomic fluorescence spectrometry was used as an element-specific detector in hybridation with liquid chromatography (LC) and hydride generation for the speciation of Sb(III), Sb(V) and trimethylantimony dichloride (TMSbCl₂). The three species were poorly resolved in a single chromatogram but good results were obtained by anion-exchange chromatography, using a mobile phase with 20 mM EDTA and 8 mM hydrogenphthalate to separate Sb(III) and Sb(V) and 1 mM carbonate at pH 10 to separate Sb(V) and TMSbCl₂. Calibration graphs were linear between 2 and 100 μg l⁻¹. Detection limits were 0.9, 0.5 and 0.7 μg l⁻¹ for Sb(III), Sb(V) and TMSbCl₂, respectively. The method was applied to the speciation of antimony in environmental samples.     

A comparison of an optimised sequential extraction procedure and dilute acid leaching of elements in anoxic sediments, including the effects of oxidation on sediment metal partitioning

The effect of oxidation of anoxic sediment upon the extraction of 13 elements (Cd, Sn, Sb, Pb, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As) using the optimised Community Bureau of Reference of the European Commission (BCR) sequential extraction procedure and a dilute acid partial extraction procedure (4 h, 1 mol L⁻¹ HCl) was investigated. Elements commonly associated with the sulfidic phase, Cd, Cu, Pb, Zn and Fe exhibited the most significant changes under the BCR sequential extraction procedure. Cd, Cu, Zn, and to a lesser extent Pb, were redistributed into the weak acid extractable fraction upon oxidation of the anoxic sediment and Fe was redistributed into the reducible fraction as expected, but an increase was also observed in the residual Fe. For the HCl partial extraction, sediments with moderate acid volatile sulfide (AVS) levels (1-100 μmol g⁻¹) showed no significant difference in element partitioning following oxidation, whilst sediments containing high AVS levels (>100 μmol g⁻¹) were significantly different with elevated concentrations of Cu and Sn noted in the partial extract following oxidation of the sediment. Comparison of the labile metals released using the BCR sequential extraction procedure (ΣSteps 1-3) to labile metals extracted using the dilute HCl partial extraction showed that no method was consistently more aggressive than the other, with the HCl partial extraction extracting more Sn and Sb from the anoxic sediment than the BCR procedure, whilst the BCR procedure extracted more Cr, Co, Cu and As than the HCl extraction.     

Vanadium in Italian waters: monitoring and speciation of V(IV) and V(V)

In this work, a highly sensitive method was developed to separate vanadium (IV) from vanadium (V), which are both contained in water at trace levels. A suitable strong anionic exchange column (SAX) loaded with disodium ethylendiaminetetraacetic acid (Na₂EDTA) was used to trap both vanadium species dissolved in 10–100 ml of water at pH 3. The vanadyl ion was selectively eluted by means of 15 ml of an aqueous solution containing Na₂EDTA, tetrabutylammonium hydroxide (TBA⁺OH⁻), and isopropanol (ⁱPr-OH) and was subsequently determined by atomic absorption spectroscopy with electrothermal atomization. The concentration of vanadate ion was calculated by subtracting the vanadyl concentration from the total concentration of vanadium. The optimal conditions for a selective elution were evaluated. The recovery of vanadium (IV) was 95% or better. The proposed method provides a simple procedure for the speciation of vanadium in aqueous matrices. The collection of the two forms could easily be carried out at the sampling site. Therefore, the risk of changing the concentration ratio between vanadium species was widely reduced. The detection limits were 1 μg/l for both species, when a 10-ml sample was eluted through the column. The method was applied successfully to vanadium speciation on different kinds of Italian volcanic water: Mount Etna (Sicily), Lake Bracciano and Castelli Romani (Latium).     

Studies on ion exchange equilibria and kinetics VI. Prediction of ion exchange equilibria of UO 2 2+ −Na+−H+ ternary system

Experimental data are reported for the ion exchange equilibria of the binary systems UO ₂ ²⁺ –H⁺, UO ₂ ²⁺ –Na⁺ and Na⁺–H⁺, and of the ternary system UO ₂ ²⁺ –Na⁺–H⁺ on a strong acid cation exchange resin 001X7 at 25 °C. It is found that the equilibria for any pairs of ions are essentially the same in binary and ternary mixtures and that the prediction method proposed by our laboratory for SO ₂ ^2– –Cl^––NO ₃ ^– -201X7 strong base anion exchange resin system is also applicable to the ternary system studied in this paper. The predictions of the ternary system UO ₂ ²⁺ –Na⁺–H⁺ based solely on the binary data without using resin phase activity coefficients are consistent with the experimental data.     

Determination of ochratoxin A in foods: state-of-the-art and analytical challenges

The work presented describes the application of different analytical approaches for study of aluminium mobility in rock, soil, and sediment samples affected by mining activity (secondary quartzites with sulfidic deposits). For this purpose we used a combination of the single extractions, the optimized BCR three-step sequential extraction procedure (SEP), and reactive aluminium determination after chelating ion-exchange on Ostsorb (Iontosorb) Salicyl by a batch technique with flame atomic absorption spectrometry quantification. The single extraction agents H₂O, KCl, NH₄Cl, and BaCl₂ were found to be the best for the quantitative estimation of the aluminium mobility in rocks, soils, and sediments caused by acidification of the environment. This fact was confirmed by reactive aluminium determination in the same samples. The vast majority of the aluminium content of samples after application of the optimized BCR three-step SEP is in the residues. The available fraction of aluminium extracted by dilute CH₃COOH in the first step of this procedure correlates with the reactive aluminium content. The amounts of aluminium released in the second and the third steps and the sums from steps 1–3 of this procedure are closely associated with the aluminium content values obtained by the single dilute HCl leach. The accuracy of results obtained was verified with only informative values for individual fractions of the BCR three-step SEP because of the absence of suitable certified or standard reference materials. The amounts of the reactive aluminium determined in samples was in the range 12–82% of total soluble Al in the filtered H₂O extracts. It was confirmed that the acidified polluted samples contain the most of reactive Al content, which is responsible for its toxicity.     

Development of a non-chromatographic method for the speciation analysis of inorganic antimony in mushroom samples by hydride generation atomic fluorescence spectrometry

A simple and sensitive method has been developed for the direct determination of toxic species of antimony in mushroom samples by hydride generation atomic fluorescence spectrometry (HG AFS). The determination of Sb(III) and Sb(V) was based on the efficiency of hydride generation employing NaBH₄, with and without a previous KI reduction, using proportional equations corresponding to the two different measurement conditions. The extraction efficiency of total antimony and the stability of Sb(III) and Sb(V) in different extraction media (nitric, sulfuric, hydrochloric, acetic acid, methanol and ethanol) were evaluated. Results demonstrated that, based on the extraction yield and the stability of extracts, 0.5 mol L^− 1 H₂SO₄ proved to be the best extracting solution for the speciation analysis of antimony in mushroom samples. The limits of detection of the developed methodology were 0.6 and 1.1 ng g^− 1 for Sb(III) and Sb(V), respectively. The relative standard derivation was 3.8% (14.7 ng g^− 1) for Sb(V) and 5.1% (4.6 ng g^− 1) for Sb(III). The recovery values obtained for Sb(III) and Sb(V) varied from 94 to 106% and from 98 to 105%, respectively. The method has been applied to determine Sb(III), Sb(V) and total Sb in five different mushroom samples; the Sb(III) content varied from 4.6 to 11.4 ng g^− 1 and Sb(V) from 14.7 to 21.2 ng g^− 1. The accuracy of the method was confirmed by the analysis of a certified reference material of tomato leaves.     

Ion-chromatographic determination of divalent metal ions (Co, Ni, Cu, Zn, Cd) using EDTA as complexing agent

Summary Metal ions, such as cobalt, nickel, copper, zinc and cadmium, were separated as the anionic metal-EDTA complexes using an ion-chromatograph equipped with anion separator system. The separated complex anions in the eluent (3×10^–3 M NaHCO₃/2.4×10^–3 M Na₂CO₃) were detected by conductivity measurement. When 100 l of the sample solution containing 10^–4 M EDTA was introduced into the analytical system, up to 5.0 ppm of metal ions were determined. The method was applied to the determination of metal ions in plating solution and waste water samples. When the sample solution was introduced into the system, a chromatogram of anions in the sample was obtained. Then the sample solution with EDTA was introduced and a chromatogram of anions and metal-EDTA complexes was obtained. The metals were determined from the difference of the former and the latter chromatograms.

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Ionen-chromatographische Bestimmung von zweiwertigen Metallionen (Co, Ni, Cu, Zn, Cd) mit Hilfe von EDTA als Komplexierungsmittel

Zusammenfassung Die Metallionen wurden als anionische Metall-EDTA-Komplexe getrennt, wobei ein Ionenchromatograph mit Anionenseparatorsystem benutzt wurde. Die getrennten Anionenkomplex-Ionen wurden im Eluat (3 · 10^–3 M NaHCO₃/2,4 · 10^–3 M Na₂CO₃) durch Leitfä-higkeitsmessung erfaßt. In 100 l Probelösung mit 10^–4 M EDTA konnten 5,0 ppm Metall bestimmt werden. Das Verfahren wurde auf galvanische Lösungen und Abwasser angewendet. Bei Einführung der Probelösung in das System erhält man ein Chromatogramm der vorhandenen Anionen. Wenn dann Probe + EDTA injiziert wird, ergibt sich ein Chromatogramm der Anionen und Metall-EDTA-Komplexe. Die Metallgehalte resultieren aus der Differenz.

     

Extraction systems of flame atomic absorption determination of trace impurities in high purity nickel salts

Summary Different extraction sytems including long chain quaternary alkylammonium salts and APDC were investigated in order to determine the optimal conditions for extraction separation and preconcentration of traces of Ag, Bi, Cd, Cu, Fe, Mo, Pb, Sb and Zn from high purity NiSO₄·6H₂O, NiCl₂·6H₂O, Ni(OOCCH₃)₂·4H₂O and Ni(NO)₃)₂·6 H₂O. Best results for multielement preconcentration were found with the extraction system HCl-trioctylmethylammonium chloride-0,002 mol/l APDC/MIBK. The proposed method permits the flame atomic absorption determination of 5·10^–6%, Ag, Cd, Cu and Zn, 1·10^–5% Bi, Fe, Pb and 5·10^–5% Mo and Sb with good accuracy and precision.     

Determination of metals, metalloids and non-volatile ions in airborne particulate matter by a new two-step sequential leaching procedure Part A: Experimental design and optimisation

The optimisation of a micro-analytical two-step sequential leaching procedure for the determination of non-volatile ions (NO₃⁻, SO₄²⁻, Cl⁻, Na⁺, Mg²⁺, NH₄⁺ and Ca²⁺) and of 17 elements (Al, As, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, S, Se, V, Zn, Sb, Si and Ti) in two fractions—extract and residue—on the same sample of air particulate matter is described. The two-step method was tested on the SRM NIST 1648 for equivalence with two reference methods, the EMEP procedure for ions extraction and the EN 12341 standard for the elemental determination of the PM₁₀ and is suitable for application to small sample amounts (less than 1 mg of particulate matter is needed), i.e. those collected by daily low volume filter-sampling. Performance times of the procedure were optimised to meet the target of routine application for large scale monitoring samples. A single ultrasonic-assisted extraction of air particulate matter is performed in 0.01 M acetate buffer at pH 4.5, followed by IC ions analysis and ICP-OES elemental analysis of the extract and by ICP-OES elemental analysis of the mineralized residue after dissolution by microwave-assisted digestion with a HNO₃/H₂O₂ mixture. Using a pH buffered extracting solvent was preferred to water or diluted acid solutions to improve the reproducibility of metals extraction with respect to existing leaching methods; the influence of pH, nature and concentration of the buffer solution and extraction time on analytes concentration in the extract is discussed. Values of ions extraction and elements recoveries resulted fairly equivalent with those obtained by the reference methods. The study was also extended to some non-certified elements (Mg, S, Sb, Si and Ti) for their environmental significance. Elements recoveries were obtained as sum of the extract and residue fractions and were comparable with those obtained by direct dissolution. Standard deviations were within 10% for almost all detected ions and elements.     

Comparison of metal analysis in sediments using EDXRF and ICP-OES with the HCl and Tessie extraction methods

The work presents an investigation on metal availability in sediments during 13 months using the dispersive-energy X-ray fluorescence (EDXRF) and atomic emission spectrometry with induced argon plasma (ICP-OES) techniques and single extraction (0.1 mol l⁻¹ HCl) and Tessie’s sequential speciation methods. The EDXRF technique could yield essentially the same profile as ICP-OES for the seasonal variation of metals in sediments, but in a more practical way. The sequential extraction procedure (SEP) was more efficient in metal dissolution than single extraction. The Pb, Ni, Al, Cr, and Fe elements were less efficiently extracted with single extraction in relation to sequential extraction. For Co both methodologies were equivalent, but for Cu and Mn the extraction was higher with single extraction. Single extraction does not mobilize Pb, Ni, Al, Cr, and Fe adsorbed on oxides and bound to organic matter. However for Cu and Mn, not only extracted these metals from the four fractions, but it also dissolved part of the fifth fraction (residual). Principal Component Analysis discriminated seasonal variations in the content of several metals, mainly Fe, Co, Ni, and Zn. The mobility of metallic ions in the sediments is conditioned to the seasonal flow of organic and inorganic material coming from the river or by the erosion of adjacent soils.     

Determination of methylmercury in marine sediment samples: Method validation and occurrence data

The determination of methylmercury (MeHg) in sediment samples is a difficult task due to the extremely low MeHg/THg (total mercury) ratio and species interconversion. Here, we present the method validation of a cost-effective fit-for-purpose analytical procedure for the measurement of MeHg in sediments, which is based on aqueous phase ethylation, followed by purge and trap and hyphenated gas chromatography–pyrolysis–atomic fluorescence spectrometry (GC–Py–AFS) separation and detection. Four different extraction techniques, namely acid and alkaline leaching followed by solvent extraction and evaporation, microwave-assisted extraction with 2-mercaptoethanol, and acid leaching, solvent extraction and back extraction into sodium thiosulfate, were examined regarding their potential to selectively extract MeHg from estuarine sediment IAEA-405 certified reference material (CRM). The procedure based on acid leaching with HNO₃/CuSO₄, solvent extraction and back extraction into Na₂S₂O₃ yielded the highest extraction recovery, i.e., 94 ± 3% and offered the possibility to perform the extraction of a large number of samples in a short time, by eliminating the evaporation step. The artifact formation of MeHg was evaluated by high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC–ICP–MS), using isotopically enriched Me²⁰¹Hg and ²⁰²Hg and it was found to be nonexistent. A full validation approach in line with ISO 17025 and Eurachem guidelines was followed. With this in mind, blanks, selectivity, working range (1–800 pg), linearity (0.9995), recovery (94–96%), repeatability (3%), intermediate precision (4%), limit of detection (0.45 pg) and limit of quantification (0.85 pg) were systematically assessed with CRM IAEA-405. The uncertainty budget was calculated and the major contribution to the combined uncertainty (16.24%, k = 2) was found to arise from the uncertainty associated with recovery (74.1%). Demonstration of traceability of measurement results is also presented. The validated measurement procedure was applied to the determination of MeHg incurred in sediments from a highly polluted and scarcely studied area in the Caribbean region.     

Development and validation of a simple solid‐phase extraction method coupled with liquid chromatography–triple quadrupole tandem mass spectrometry for simultaneous determination of lincomycin,tylosin A and tylosin B in royal jelly

We have developed an analytical method for the determination of lincomycin, tylosin A and tylosin B residues in royal jelly using liquid chromatography–triple quadrupole tandem mass spectrometry analysis. For extraction and purification, we employed 1% trifluoroacetic acid and 0.1 m Na₂EDTA solutions along with an Oasis HLB cartridge. The target antibiotics were well separated in a Kinetex EVO C₁₈ reversed‐phase analytical column using a combination of 0.1% formate acid in ultrapure water (A) and acetonitrile (B) as the mobile phase. Good linearity was achieved over the tested concentration range (5–50 μg/kg) in matrix‐matched standard calibration. The coefficients of determination (R²) were 0.9933, 0.9933 and 0.996, for tylosin A, tylosin B and lincomycin, respectively. Fortified royal jelly spiked with three different concentrations of the tested antibiotics (5, 10 and 20 μg/kg) yielded recoveries in the range 80.94–109.26% with relative standard deviations ≤4%. The proposed method was applied to monitor 11 brand of royal jelly collected from domestic markets and an imported brand from New Zealand; all the samples tested negative for lincomycin, tylosin A and tylosin B residues. In conclusion, 1% trifluoroacetic acid and 0.1 m Na₂EDTA aqueous solvents combined with solid‐phase extraction could effectively complete the sample preparation process for royal jelly before analysis. The developed approach can be applied for a routine analysis of lincomycin, tylosin A and tylosin B residues in royal jelly.     

Speciation of dissolved inorganic antimony in natural waters using liquid phase semi-microextraction combined with electrothermal atomic absorption spectrometry

Liquid-liquid extraction preconcentration technique which allows the achievement of extremely high ratio between the aqueous and organic phase was specified as semi-microextraction. A modified highly effective liquid phase semi-microextraction (LSME) procedure was developed for preconcentration and determination of ultra trace levels of inorganic antimony species in environmental waters using electrothermal atomic absorption spectrometry (ETAAS) for quantification. Antimony(III) species were selectively extracted as dithiocarbamate complexes from 100 mL aqueous phase into 250 μL xylene at pH range of 5-8. Total Sb was determined using the same extraction system over a sample acidity range of pH 0-1.2 without the need for pre-reduction of Sb(V) to Sb(III). The concentration of Sb(V) was obtained as the difference between that of total antimony and Sb(III). With an 8 min extraction an enrichment factor of 400 was achieved. The limit of detection (3 s) was 2 ng L⁻¹ Sb. The method was not affected by the presence of up to 0.01% humic acid, 0.025 mol L⁻¹ EDTA, 0.01 mol L⁻¹ tartaric acid and 0.001 mol L⁻¹ F⁻. Recoveries of spiked Sb(III) and Sb(V) in river, tap, and sea water samples ranged from 93 to 108%. The results for total antimony concentration in the river water reference material SLRS-5 were in good agreement with the information value. The procedure was applied to the determination and quantification of dissolved antimony species in natural waters.     

Determination of total Sb,Se, Te,and Bi and evaluation of their inorganic species in garlic by hydride-generation–atomic-fluorescence spectrometry

A sensitive and simple analytical method has been developed for determination of Sb(III), Sb(V), Se(IV), Se(VI), Te(IV), Te(VI), and Bi(III) in garlic samples by using hydride-generation–atomic-fluorescence spectrometry (HG–AFS). The method is based on a single extraction of the inorganic species by sonication at room temperature with 1 mol L⁻¹ H₂SO₄ and washing of the solid phase with 0.1% (w/v) EDTA, followed by measurement of the corresponding hydrides generated under two different experimental conditions directly and after a pre-reduction step. The limit of detection of the method was 0.7 ng g⁻¹ for Sb(III), 1.0 ng g⁻¹ for Sb(V), 1.3 ng g⁻¹ for Se(IV), 1.0 ng g⁻¹ for Se(VI), 1.1 ng g⁻¹ for Te(IV), 0.5 ng g⁻¹ for Te(VI), and 0.9 ng g⁻¹ for Bi(III), in all cases expressed in terms of sample dry weight.     

Development of analytical method for determination of Sb(V), Sb(III) and TMSb(V) in occupationally exposed human urine samples by HPLC-HG-AFS

In the present paper, we develop a methodology for antimony speciation in occupationally exposed human urine samples by high-performance liquid chromatography with hydride generation atomic fluorescence spectrometry (HPLC-HG-AFS). The methodology was applied to the determination of Sb(V), Sb(III) and (CH₃)₃SbCl₂ (TMSb(V)). Retention time of Sb(V), Sb(III) and TMSb(V) species were 0.88, 2.00 and 3.61 and the detection limits were 0.18, 0.19 and 0.12 μg L^− 1, for 100 μL loop injection respectively which is considered useful for elevated/occupationally exposed urine samples. Studies on the stability of antimony species in urine samples on the function of the elapsed time of preservation (4 °C) and storage (− 70 °C) were performed. Results revealed that antimony species are highly unstable at − 70 °C, probably due to co-precipitation reaction. In this kind of matrix transformation during preservation time may occur, such as oxidation of Sb(III) to Sb(V) and transformation into species that do not elute from the column. EDTA shows that it is able to stabilize Sb(III) for more than one week of preservation time at 4 °C avoiding co-precipitation during storage at − 70 °C. Finally the methodology was applied to occupationally exposed human urine samples. 25% of specimens present antimony levels (Sb(V)) of more than 5 μg L^− 1.     

Determination of pharmaceuticals in soils and sediments by pressurized liquid extraction and liquid chromatography tandem mass spectrometry

The present work describes the development of a sensitive analytical method based on pressurized liquid extraction (PLE) and pre-concentration by solid-phase extraction (SPE), followed by liquid chromatography–electrospray tandem mass spectrometry (LC–ESI-MS/MS) for the determination of seventeen pharmaceuticals in soils and sediments. The method is based on sample homogenisation using Na₂–EDTA washed sand and extraction with water at 90 °C. Special emphasis was placed on the optimization of the extraction procedure to develop a green method that reduces, at a maximum, the use of organic solvents in order to eliminate matrix components during the clean-up. The proposed method was linear in a concentration range from 0.3 to 333 ng g⁻¹, with correlation coefficients higher than 0.993. Method detection (MDLs) and quantification (MQLs) limits ranged from 0.1 to 6.8 ng g⁻¹ and from 0.25 to 23 ng g⁻¹, respectively. Absolute recoveries were analyte dependent, varying between 50% and 105% at the MQL level, except for fenofibrate (40%) and diclofenac (34%). The intra-day and inter-day precision was given by RSD values from 0.7% to 7.9% and from 1.6% to 14.5%, respectively. Acetaminophen, carbamazepine, ciprofloxacin, clofibric acid, codeine, diazepam, fenofibrate, metropolol, ofloxacin and propanolol were detected at concentrations from MDL to 35.62 ng g⁻¹ in soils and sediments from marsh areas. Due to the low recoveries, results for fenofibrate and diclofenac can only be considered as semi-quantitative. The method was fully suitable for the other 15 pharmaceuticals.