Speciation of butyltin compounds in marine sediments by preconcentration on C60 and gas chromatography-mass spectrometry

A new method for the speciation of butyltin compounds by solid phase extraction and direct injection using gas chromatography-mass spectrometry (GC/MS) is described. The compounds were complexed with sodium diethyldithiocarbamate and retained on a C60 sorbent column. The neutral chelates of butyltin compounds were eluted with ethyl acetate containing NaBPr4 as derivatising reagent. The main analytical figures of merit of the proposed method for 10 ml of sample are: linear range 0.2-35 ng/g expressed as Sn; limits of detection, 0.07, 0.09 and 0.10 ng/g as Sn for monobutyltin, dibutyltin and tributyltin, respectively. No interferences from metal ions such as Zn2+, Fe3+, Sb3t, Pb2+, Ni2+ and Mn2+ were observed in the determination of organotin compounds. The validation of method was performed out by the analysis of a standard reference sediment (CRM 462). The method was also applied to the determination of butyltin compounds in marine sediment samples.     

A compact portable flow analysis system for the rapid determination of total phosphorus in estuarine and marine waters

The development and evaluation of a portable flow analysis system for the in situ determination of total phosphorus is described. The system has been designed with rapid underway monitoring in mind. The system employs an ultra-violet photo-reactor and thermal heating for peroxodisulfate digestion of total phosphorus to orthophosphate, followed by spectrophotometric detection with a multi-reflective flow cell and low-power light emitting diode using the molybdenum blue method. Reagents are stored under gas pressure and delivered using software controlled miniature solenoid valves. The fully automated system has a throughput of 115 measurements per hour, a detection limit of 1 μg P L⁻¹, and gives a linear response over the calibration range of 0-200 μg P L⁻¹ (r² = 0.9998), with a precision of 4.6% RSD at 100 μg P L⁻¹ (n = 10). Field validation of the instrument and method was performed in Port Philip and Western Port Bays in Victoria, SE Australia, where 2499 analyses were performed over a 25 h period, over a cruise path of 285 km. Good agreement was observed between determinations of samples taken manually and analysed in the laboratory and those measured in situ with the flow analysis system.     

Isotope dilution analysis mass spectrometry for the routine measurement of butyltin compounds in marine environmental and biological samples

The highly qualified primary method of species-specific isotope dilution analysis has been employed in this work to evaluate for the first time the levels of butyltin compounds in the estuary of the river Eo (Northwest Spain) where there is, since many years, a high oyster farming activity. A spike solution containing mono-, di- and tributyltin enriched in ¹¹⁹Sn allowed the simultaneous determination of the three compounds in different marine environmental and biological samples collected in this area (seawater samples, sediments and biological tissues of four different marine species). The results obtained in this work showed toxic TBT levels for many marine species in 45% of the seawater samples analyzed whereas significant organotin concentrations were found to be obtained only in one of the sediments analyzed. On the other hand, TBT levels ranging from 20 to almost 200 ng g^− 1 (dry weight) were obtained in the different biological tissues analyzed demonstrating the bioaccumulation of organotin compounds in certain marine species.     

Variability of butyltin determination in water and sediment samples from european coastal environments

A large amount of data has appeared in the literature within the last few years dealing with the monitoring of butyltin compounds in coastal environments. However, the strategies used strongly differed from one author to another, which led to difficulties in the comparison of contamination levels and the evaluation of long-term trends. In this paper, different causes of pitfalls due to uncontrolled sources of variability are addressed; they involve precautions to be undertaken for the monitoring of butylins in water and sediment, particularly: sample collection; sample pretreatment (filtration/centrifugation, acidification, sieving); sample storage (different methods for storage and drying procedures); variability over the same site; variations over a tidal cycle; and variability due to diffusion (e.g. due to flushing).     

Certification of mono-, di-, and tributyltin compounds in marine sediment certified reference material by species-specific isotope dilution mass spectrometric analysis using synthesized <Superscript>118</Superscript>Sn-labeled butyltins

A new marine sediment reference material (NMIJ CRM 7301-a) for butyltins analysis was prepared and certified by the National Metrological Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). The original material of the sediment was collected at a bay near industrial activities in Japan. The sediment material was air-dried, sieved, homogenized, and packaged into 1,000 glass bottles (60 g each). Certification of NMIJ CRM 7301-a was carried out at NMIJ using two different types of species-specific isotope dilution mass spectrometry: isotope dilution–ethylation–gas chromatography/inductively coupled plasma mass spectrometry (GC/ICPMS) and isotope dilution–ethylation–gas chromatography/mass spectrometry (GC/MS). A mixture of ¹¹⁸Sn-enriched monobutyltin, dibutyltin, and tributyltin was synthesized in our laboratory and was used as a spike for both techniques. Certified values are given for tributyltin (0.044±0.004 mg kg^–1 as Sn), dibutyltin (0.056±0.006 mg kg^–1 as Sn, and monobutyltin (0.058±0.013 mg kg^–1 as Sn), being at lower levels than currently available sediment CRMs for the analysis of organotins.     

Determination of natural and synthetic estrogenic compounds in coastal lagoon waters by HPLC-electrospray-mass spectrometry

A new analytical method was developed for the simultaneous determination of estrogenic compounds of natural (estradiol, estriol, estrone) and synthetic origin, both steroidal (ethinylestradiol, mestranol) and non-steroidal (benzophenone, bisphenol-A, diethylstilbestrol, octylphenol, nonylphenol, nonylphenol monoethoxylate carboxylate), in environmental aqueous samples by high-performance liquid chromatography coupled with ion trap-mass spectrometry via electrospray interface (HPLC-ESI-IT-MS). Quantitative MS detection was performed in the negative mode for all compounds except mestranol and benzophenone, which were detected under positive ion conditions. Very low method detection limits (MDLs), between 0.1 and 2.6?ng/L, were achieved in coastal lagoon water samples, while the developed solid-phase-extraction (SPE) procedure permitted simultaneous recovery of all analytes from spiked water samples with yields >70% (7–11 RSD%), except estriol and benzophenone, which were recovered with 60% (9 RSD%) and 50% (11 RSD%) yields, respectively. The proposed method was applied to the analysis of Venice (Italy) lagoon waters, where average concentrations of selected compounds in the 2.8–33?ng/L concentration range were found.     

Mercury and organotin compounds monitoring in fresh and marine waters across Europe by Chemcatcher passive sampler

Several field trials have been carried out to assess the performance of the passive sampler Chemcatcher as aquatic monitoring technology for inorganic mercury and the organotin pollutants monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) in different types of waters across ten locations in Europe. Two version of the sampler were used. One for mercury that consists on 47?mm Empore? disks of iminodiacetic chelating groups as the receiving phase overlaid by a diffusion membrane of polyethersulphone; and other for organotin compounds comprising a C₁₈ disk and a cellulose acetate membrane. Both membranes were held in a disposable polycarbonate body. The two samplers were calibrated in the laboratory in a previous work to estimate the pollutant concentration. For field sampling, the samplers were deployed for 14 days. In parallel spot samples were periodically collected during the deployment period for comparison purposes. No significant biofouling on the samplers was observed for the locations monitored. In general, water concentrations estimated by Chemcatcher were lower than those found in spot water samples due to the device only collected the soluble bioavailable fraction of target pollutants. However, the pre-concentration capability of Chemcatcher allowed the determination of the tested pollutants at levels where spot sampling fails, even in difficult water bodies such as sewage treatment plants. These advantages lead to consider this emerging methodology as a complementary tool to traditional spot sampling.     

Determination of butyl- and phenyltin compounds in biological material by gas chromatography-flame photometric detection after ethylation with sodium tetraethylborate

A reliable and rapid speciation method for the simultaneous determination of butyl- and phenyltin species in biological samples has been developed. Three extraction procedures are compared: enzymatic hydrolysis and solubilization by ethanoic and hydrochloric acids. Derivatization is performed by the one-step ethylation/extraction procedure using the sodium tetraethylborate reagent directly in the aqueous phase in the presence of an isooctane layer. Analysis is performed using capillary gas chromatography coupled to flame photometric detection. The detection limits are in the range of a few ng(Sn)/g. Analysis of the environmental samples and the certified reference material demonstrates the accuracy of the analytical method.     

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.     

Applicability of solid-phase microextraction combined with gas chromatography atomic emission detection (GC-MIP AED) for the determination of butyltin compounds in sediment samples

The performance of solid-phase microextraction (SPME) applied to the determination of butyltin compounds in sediment samples is systematically evaluated. Matrix effects and influence of blank signals on the detection limits of the method are studied in detail. The interval of linear response is also evaluated in order to assess the applicability of the method to sediments polluted with butyltin compounds over a large range of concentrations. Advantages and drawbacks of including an SPME step, instead of the classic liquid–liquid extraction of the derivatized analytes, in the determination of butyltin compounds in sediment samples are considered in terms of achieved detection limits and experimental effort. Analytes were extracted from the samples by sonication using glacial acetic acid. An aliquot of the centrifuged extract was placed on a vial where compounds were ethylated and concentrated on a PDMS fiber using the headspace mode. Determinations were carried out using GC-MIP AED.     

Optimal conditions and sample storage for the determination of H2O2 in marine waters by the scopoletin-horseradish peroxidase fluorometric method

The conditions presently in use for the fluorometric determination of H₂O₂ in marine waters, by reacting H₂O₂ with scopoletin in the presence of horseradish peroxidase (HRP) and measuring the quenching of the fluorescence intensity of scopoletin, are not the optimal conditions. Under the optimized conditions of a pH of 8.5–9.5, an excitation wavelength of 390 nm and an emission wavelength of 460, the sensitivity of the method can be increased significantly, by up to more than a factor of 3 and the variations in the sensitivity from sample to sample can be significantly reduced. Furthermore, the samples need not be analyzed immediately after sample collection as presently prescribed. After scopoletin and HRP have been added to a sample immediately after sample collection, the sample may be stored at room temperature in the dark for up to four days before the quenched fluorescence intensity of scopoletin is read.     

Dissolved inorganic carbon effect in the determination of arsenic and chromium in mineral waters by inductively coupled plasma-mass spectrometry

The analysis of some Italian mineral waters by ICP-MS has revealed errors in the determination of As and Cr in natural effervescent or carbonated waters due to the presence of dissolved inorganic carbon (DIC). This leads to overestimate As and Cr in 1% (v/v) HNO₃ acidified samples, analysed within 1-2 h after the acidification. The overestimation of As concentration is caused by matrix interferences producing a signal enhancement due to the presence of dissolved inorganic carbon. This effect is analogous to that observed in the presence of organic carbon and occurs at millimolar DIC levels. The overestimation of Cr concentration is due to the ⁴⁰Ar¹²C⁺ species interfering with ⁵²Cr⁺ despite the use of the octopole reaction system. The optimization of the He flow in the collision cell can solve the latter problem, but the required increase in the flow rate decreases the sensitivity of the ICP-MS technique. The observed effects in CO₂ rich mineral waters and artificial NaHCO₃ solutions suggest that 5-10 mM DIC levels may affect the determination of As and Cr concentration in thermal waters, rivers, lakes and groundwaters.     

Determination of dissolved organic nitrogen in natural waters using high-temperature catalytic oxidation

Studies on nitrogen in natural waters have generally focussed on dissolved inorganic nitrogen (DIN), primarily because of relative ease of analysis and the important influence of DIN on water quality. Advances in analytical techniques now permit the systematic study of dissolved organic nitrogen (DON), and this work has shown that DON is quantitatively significant in many waters. This article describes the sampling and analytical protocols required for rapid, precise and reliable determinations of DON, involving high-temperature catalytic oxidation (HTCO), coupled to chemiluminescence detection. This approach simultaneously determines dissolved organic carbon (DOC) and total dissolved nitrogen (TDN), and DON is derived by subtraction of DIN measured by colorimetry. The DON determination is simple to perform, exhibits excellent precision (<1% for C and 1.5% for N) and is applicable to a wide range of natural waters.     

Simultaneous determination of three naturally occurring estrogens in environmental waters by high-performance liquid chromatography

A simple, sensitive and accurate reversed-phase high-performance liquid chromatographic (HPLC) method for simultaneous determination of three naturally occurring estrogenic steroids including estrone (E1), 17β-estradiol (E2) and estriol (E3) in environmental water samples was developed. Analytes were extracted with ethyl acetate solvents and preconcentrated prior to HPLC analysis. Separations were accomplished in <20 min using a reversed-phase C(18) column (4.6×250 mm id, 5 μm) with a gradient elution of mobile phase containing 3.0 mM ammonium acetate/acetonitrile mixtures (flow rate, 1.0 mL/min). UV light absorption responses at 205 nm were linear over a wide concentration range from 100,000 μg/L to the detection limits of 0.96 μg/L E1, 0.64 μg/L E2 and 0.78 μg/L E3. Quantitation was carried out by the peak area method. The relative standard deviation for the analysis of three estrogens was <3.0%. This method was applied for the simultaneous determination of estrogens in environmental water samples collected in Zhejiang, China. The higher concentrations of both E2 and E3 were found in Tang River and West Lake waters, and E1 was detected in lake water only. All three estrogens were below the detection limits in rain waters.     

Uncovering seasonal patterns of 56 pesticides in surface coastal waters of the Ria Formosa lagoon (Portugal), using a GC-MS method

This study describes the simultaneous quantification of 56 pesticides in surface coastal water, supported by the development and validation of a gas chromatography (GC)–ion trap (IT) mass spectrometry (MS) method. Samples (500 mL) were pre-concentrated 2500 times by solid phase extraction (OASISTMHLB). The compounds were identified and quantified, within 35 minutes, by GC tandem mass spectrometry (GC-MS/MS) and GC-MS, respectively. The methodology proved to be highly specific for all target pesticides, with an average linearity of 0.99. Detection limits and recovery rates ranged from 0.4 to 1.3 ng L^?1 and 71% to 120%, respectively. The performance of the method was checked using water samples collected from nine sampling sites along the Ria Formosa Lagoon Natural Park (south of Portugal, n = 54) in each season (2010). The total annual concentrations of all pesticides in each category (fungicides, herbicides and insecticides) were 1.4, 0.6 and 9.0 µg L^?1, respectively. Moreover, 89% of the pesticides tested for were detected, 84% could be quantified and 25% had concentrations above the European recommended levels (2013/39/EU). The highest total loads of pesticides were found in the spring, which is in agreement with their seasonal application. Physicochemical parameters such as, nitrites, nitrates, ammonia and phosphates, also indicate poor water quality, supporting the fact that the Ria Formosa lagoon actually needs an effective monitoring programme for effective preservation of its natural reserve status.     

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.     

Optimization of GC-ICPMS system parameters for the determination of butyltin compounds in Hungarian freshwater origin sediment and mussel samples

The optimization and application of gas chromatograph coupled with inductively coupled plasma mass spectrometer (GC-ICPMS) (equipped with a commercially available interface) for the speciation of butyltin compounds in freshwater origin sediment and mussel samples is described. Optimization focused on the system parameters that have the greatest effect on signal intensity such as plasma power, ion lenses and make up gas flow (in the interface). Xenon (Xe) containing argon gas (Ar) was applied as tuning gas providing continuous Xe signal for the optimization of system parameters. It was found that plasma power and make up gas are interrelated variables and provide a set of paired optimum values at each power settings. The absolute optimum values obtained at 800 W plasma power and 1.2 L min⁻¹ make up gas flow rate when 7 mm sample depth was adjusted. The optimum settings obtained were then checked by means of a test solution (tetraethyltin dissolved in hexane). Same optimum conditions were found when tin (Sn) transient signals were monitored. Detection limits were calculated for the three species using the optimized system parameters. Detection limits are the following: for monobutyltin (MBT) 5.6 ng Sn kg⁻¹, for dibutyltin (DBT) 6.6 ng Sn kg⁻¹ and for tributyltin (TBT) 3.4 ng Sn kg⁻¹ obtained. Determination of the butyltin compounds were carried out by means of species-specific isotope dilution analysis. The spike solution contained all species investigated but with altered isotopic composition. Each species were enriched in their ¹¹⁹Sn isotope. Concentrations found in Hungarian freshwater origin mussel and sediment samples ranged between 19 and 39 ng g⁻¹for MBT, between 1.2 and 6.3 ng g⁻¹ for DBT and between 1.2 and 3.2 ng g⁻¹ for TBT indicated as Sn in dry weight. Validation of the method was done by means of certified reference materials (BCR CRM 646 and 477). Good agreement was found between certified and experimental values. Normalized deviation (E_n) was also computed in order to validate the method used. E_n values obtained ranged between 0.07 and 0.11 for mussel samples and between 0.26 and 0.72 for sediment samples. These values show that isotope dilution-GC-ICPMS methodology is valid for the determination of MBT, DBT and TBT from both types of matrices.     

Determination of cobalt,molybdenum and vanadium in austrian mineral waters by ICP-AES after ion-exchange separation and preconcentration

A method is described for the determination of cobalt, molybdenum and vanadium in mineral water samples by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) after separation of these elements from the matrix by ion exchange. The samples are acidified with concentrated hydrochloric acid (10 ml/l) and the elements are adsorbed as thiocyanate complexes. Elution is performed with a mixture 2M in perchloric acid and 1M in hydrochloric acid and subsequently with 1M hydrochloric acid. After evaporation of the eluates and dissolution of the residue the volume of the measuring solution for ICP-AES is 10 ml. The recoveries for Co, Mo and V at a concentration level of 1 g/1 in mineral waters were approximately 99%. A concentration factor of 100 is achieved by this procedure.     

Single-walled carbon nanotubes as solid-phase microextraction adsorbent for the determination of low-level concentrations of butyltin compounds in seawater

Carbon nanotubes are a kind of new carbon-based nanomaterials, which have drawn great attention in many application fields. The potential of single-walled carbon nanotubes (SWCNTs) as solid-phase microextraction (SPME) adsorbent for the preconcentration of environmental pollutants has been investigated in recent years. In the present study, the feasibility of SWCNTs as SPME adsorbent for the determination of monobutyltin, dibutyltin and tributyltin in seawater samples was studied. To achieve this aim, the potential factors affecting the SPME efficiency, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity were optimized. The developed method showed good performance according to the ICH (International Conference on Harmonization of Technical Requirements for Analytical Methods) criteria. The acquired calibration curves were linear (r ≥ 0.992) over the concentration range from ≤12 to 2000 ng L⁻¹. For all of the analytes, the limit of detection at signal-to-noise ratio of 3 was below 5 ng L⁻¹. Furthermore, in comparison with the commercial carboxen/polydimethylsiloxane fiber, the developed SWCNT fiber showed better thermal stability (over 350 °C) and longer life span (over 150 times). The application of the proposed method in environmental analyses was shown by analyzing seawater samples from the harbors on the Persian Gulf for butyltin residues. Some of the butyltins were detected in the analyzed samples. Results of the present study demonstrate the feasibility of the SWCNTs as SPME adsorbent for the determination of butyltins in seawater samples.     

HPLC-MS/MS multiclass determination of steroid hormones in environmental waters after preconcentration on the carbonaceous sorbent HA-C@silica

In this study, a sensitive and multiclass method has been developed for analysis of three families of steroid hormones, i.e. progestins, oestrogens, androgens, by SPE-HPLC-ESI-MS/MS. The extraction efficiency of thermally condensed humic acids onto silica sorbent (HA-C@silica), here for the first time studied for multiclass enrichment of these sex hormones, was tested in different environmental waters (tap and river water, urban wastewater treatment plant effluent) spiked at the nanograms per litre levels (5–1000 ng L⁻¹). Quantitative adsorption was achieved using 200 mg sorbent for preconcentration of 250–1000 mL sample, at the native pH (pH = 6.5–7.7). Elution was performed by two sequential fractions (methanol followed by acetonitrile), obtaining in all the matrices investigated satisfactory recoveries (71% to 124% for river waters and 71–113% for urban wastewater treatment plant effluent) and RSDs below 15% (n = 3). The high enrichment factors (up to 4000) coupled with high-performance liquid chromatography tandem mass spectrometry quantification (MRM mode) provided low limits of detection and quantification (a few ng L⁻¹), that are suitable for environmental monitoring. Most of the analytes were detected in river water and in wastewater effluent samples (in the ng L⁻¹ concentration range), attesting their environmental diffusion. The proposed method was extended to a fourth class, Glucocorticoids, achieving good results in river samples, by the same SPE cartridge and chromatographic run.