•4MBC induced mortality, malformations and reduced growth in S. senegalensis larvae.•Swimming behaviour was affected by 4MBC at low concentrations.•4MBC caused alterations in AChE and LDH biochemical ...markers.•Assessment of behaviour is recommended in ecotoxicological studies with sole larvae.
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The inclusion of organic UV filters in personal care products (PCPs) has increased in recent years. 4-Methylbenzylidene camphor (4MBC) is one of the most used UV filters, and thus it is commonly found in aquatic ecosystems, with proved negative effects on aquatic organisms. Effects on early life stages of marine vertebrates are largely unknown. Therefore, the main goal of this work was to evaluate 4MBC effects on Senegalese sole (Solea Senegalensis Kaup, 1858) larvae at different levels of biological organization. S. senegalensis were exposed to increasing concentrations of 4MBC from egg stage until 96 h. Mortality, growth, malformations, behaviour and biochemical responses, including enzymatic biomarkers were studied. The exposure to 4MBC until 96 h post-fertilization (hpf) induced mortality and malformations in a dose-response manner. Besides, reduced growth with increasing concentrations was observed. The exposure to 4MBC also caused alterations on behaviour, including overall lower swimming time during light and dark periods. Biomarker alterations caused by 4MBC included imbalance of neurotransmission related endpoints (increased acetylcholinesterase activity) and decreased activity of enzymes related to anaerobic metabolism (lower cellular lactate dehydrogenase activity) at the lower concentrations tested. Furthermore, our results suggest that 4MBC do not induce oxidative stress in S. senegalensis larvae, since catalase and lipid peroxidation levels were not significantly altered by 4MBC.
S. senegalensis revealed to be a good model species for vertebrate animal testing in the marine environment. Sub-lethal concentrations of 4MBC induced toxic effects at all organizational levels. Swimming behaviour was a sensitive endpoint and showed that exposure to 4MBC causes impairment on response to light stimulus which is possibly linked with the observed imbalances on cholinesterase activity in larvae. Conservation concerns along distribution range of S. senegalensis should consider that increasing levels of UV filters in marine environment might have impact on the ecology of the species.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
•UV filters are determined in both the soluble and particulate fractions of seawater.•It is the first time that these compounds are determined in the particulate fraction.•The method has been ...developed and validated obtaining good analytical features.•Real seawater samples of different origin have been successfully analyzed.•The contents of UV filters in the particulate fraction are significant.
An analytical method to determine the total content (i.e., not only in the soluble fraction but also in the particulate one) of eight commonly used UV filters in seawater samples is presented for the first time. Dispersive liquid–liquid microextraction (DLLME) is used as microextraction technique to pre-concentrate the target analytes before their determination by gas chromatography–mass spectrometry (GC–MS). In order to release the UV filters from the suspended particles an ultrasound treatment is performed before DLLME. The ultrasound treatment time was studied in order to achieve a quantitative lixiviation of the target analytes. The type and volume of both disperser and extraction solvent, the sample volume, the pH and the ionic strength involved in the DLLME have been optimized to provide the best enrichment factors. Under the optimized conditions, the method was successfully validated showing good linearity, enrichment factors between 112 and 263 depending on the analyte, limits of detection and quantification in the low ngL−1 range (10–30ngL−1 and 33–99ngL−1, respectively) and good intra- and inter-day repeatability (RSD <15%). No significant matrix effects were found. Finally, the method was satisfactorily applied to the analysis of three seawater samples from different origin. Results showed significant amounts of UV filters in the particulate fraction that would have been ignored if only the soluble fraction had been considered. This fact shows that the UV filters are also accumulated in the suspended particles contained in water, what should be taken into account from an environmental standpoint.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
A green procedure based on reversed-phase liquid chromatography with gradient elution using environmentally friendly solvents, has been developed to determine 18 UV filters, which are most used in ...Europe nowadays as sunscreen in cosmetics. Samples were weighed and dissolved in ethanol. Two aliquots were taken from the initial sample solution to prepare two solutions, so analytes could be determined chromatographically in two groups (the most fat-soluble and the easily water-soluble ones) using a different gradient elution program for each group. The mobile phases were based on mixtures of ethanol and 1% acetic acid or 1% sodium acetate buffer pH 4.75. The same C
18 stationary phase column was employed in both cases. The chromatographic variables such as mobile phase composition, pH, flow rate and temperature were studied and selected in order to achieve total separation of all the peaks involved. The proposed method has been validated by the analysis of 27 commercial sunscreen samples (with different cosmetic forms: cream, lipstick, makeup, sun water, lotion, milk) and two synthetic samples. The method allows any mixture of the 18 UV filters studied to be separated with a good resolution and determined without interference from cosmetic matrices, moreover it does not require the use of highly toxic organic solvents.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
A new, simple, fast and high sensitive analytical method based on dispersive liquid–liquid microextraction (DLLME) followed by gas chromatography–mass spectrometry (GC–MS) for the simultaneous ...determination of nitro musks in surface water and wastewater samples is presented. Different parameters, such as the nature and volume of both the extraction and disperser solvents and the ionic strength and pH of the aqueous donor phase, were optimized. Under the selected conditions (injection of a mixture of 1mL of acetone as disperser solvent and 50μL of chloroform as extraction solvent, no salt addition and no pH adjustment) the figures of merit of the proposed DLLME–GC–MS method were evaluated. High enrichment factors, ranging between 230 and 314 depending on the target analyte, were achieved, which redound to limits of detection in the ngL−1 range (i.e., 4–33ngL−1). The relative standard deviation (RSD) was below 5% for all the target analytes. Finally, the recoveries obtained for different water samples of diverse origin (sea, river, irrigation channel and water treatment plant) ranged between 87 and 116%, thus showing no matrix effects.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
A rapid and sensitive analytical gas chromatography-mass spectrometry (GC-MS) method for perfume analysis to determine the phthalates banned by the European Union Regulation on cosmetic samples is ...presented. This method has been tested in commercial alcoholic perfume samples for the determination of the following seven phthalates: dibutyl phthalate, bis(2-ethylhexyl) phthalate, bis(2-methoxyethyl) phthalate, n-pentyl-isopentylphthalate, di-n-pentyl phthalate, diisopentylphthalate and benzyl butyl phthalate. Sample evaporation and redissolution in ethanol is carried out before GC-MS analysis, with no dilution of the sample. External calibration and standard addition calibration are compared to detect possible matrix effects. External calibration could provide good results in some cases but standard addition calibration is recommended as matrix effects are observed in many cases in the determination of the target phthalates. The accuracy of the method has been proven by the analysis of quality control samples prepared from commercial free phthalate perfumes after spiking with known concentrations of the analytes. Accurate results were obtained with limits of detection in the ng mL super(-1) range and good repeatability (relative standard deviations lower than 6%). The method was satisfactorily applied to the analysis of commercial perfume samples, and the results revealed considerable amounts of dibutyl phthalate and bis(2-ethylhexyl) phthalate in some of the analyzed samples.
A novel arrangement for microporous membrane liquid–liquid extraction from the aqueous donor phase to the organic acceptor phase within a micro-vial, which is compatible with the chromatograph ...autosampler is presented. The device consisted of a stoppered glass micro-vial containing the organic solvent where the septum of the screw stopper was replaced by a sized piece of membrane which is hermetically assembled to the volumetric flask containing the aqueous donor solution. The placement of the membrane in alternative contact with the solutions was achieved by orbital agitation. As a preliminary study, 2-ethylhexyl 4-(dimethylamino)benzoate has been determined (limit of quantification 0.11
μg
L
−1, precision 7.4%). The small quantity of organic solvent used, the achieved sample cleanup, and the minimal handling and risk of cross-contamination are significant operational advantages.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Simultaneous determination of organic UV filters worldwide authorised in sunscreen formulations was performed by HPLC with UV spectrophotometric detection. The filters determined were: ...benzophenone-4, benzophenone-3, butyl methoxydibenzoylmethane, octyl dimethyl PABA, octyl methoxycinnamate, homosalate and octyl salicylate. A C
18 stationary phase and an isocratic mobile phase of ethanol–water–acetic acid (70:29.5:0.5) containing 65.4 m
M of hydroxypropyl-β-cyclodextrin, were used with a flow-rate of 0.6 ml/min. UV measurements were carried out at 313 nm. The time required for the analysis was 20 min and the limits of detection were between 1.5 and 2.3 mg/l. The procedure proposed provides a green analytical method with a basic instrumental configuration, it is fast and accurate and does not involve highly toxic organic solvents.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
A sensitive and selective method to determine disodium phenyl dibenzimidazole tetrasulphonate (PDT) in the urine of sunscreen users, which is suitable for studies on body accumulation/excretion is ...proposed. On-line solid-phase extraction allows the analyte to be retained and subsequentely eluted, using a strong anion exchange (SAX) microcolumn. Standard addition calibration was carried out with only one standard. The wavelengths of excitation and emission were 330 and 454
nm, respectively. The method allows PDT to be determined in both, spiked and unspiked human urine samples, without any pre-treatment. Results obtained for spiked urine samples (40–200
ng
ml
−1) showed the accuracy of the method. The mean relative standard deviations (R.S.D.) of the results was 7%. Five volunteers applied a sunscreen lotion containing 5% PDT and their urinary excretion was controlled from the moment of application until the excreted amounts were no longer detectable. The sensitivity of the proposed method is in the order of 1900
ml
μg
−1 and the detection limit (3
S
y/
x
/
b) is in the order of 5
ng of PDT, which means 10
ng
ml
−1 for a 500
μl injected volume, and this is suitable for the PDT levels found in the urine.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
No previous publications about percutaneous absorption of polyethylene glycol 25
p-aminobenzoic acid (PEG-25 PABA) have been found in the literature and the expected levels to be found in human urine ...after sunscreens use are unknown. The method proposed here is suitable to determine PEG-25 PABA in the urine of sunscreens users in order to carry out studies on body accumulation/excretion. It is based on solid-phase extraction (SPE) with size-exclusion liquid chromatography determination. Solid-phase extraction allows the analyte to be retained and subsequently eluted for a clean-up, using a silica-based cartridge. The size-exclusion liquid chromatography of the eluted allows the rest of matrix interferences to be avoided. Fluorescence intensity was measured at
λ
em
=
350
nm (
λ
exc
=
300
nm). The sensitivity of the proposed method is in the order of 450
±
5
mL
ng
−1 and the detection limit (3
S
y/
x
/b) in the measured solutions is in the order of 13
ng
mL
−1, that is 2.6
ng
mL
−1 in urine samples. The method enables PEG-25 PABA to be determined in both, spiked and unspiked human urine samples. Results obtained for spiked human urine samples (11–100
ng
mL
−1) demonstrated the accuracy of the method. The mean relative standard deviation of the results was in the order of 3–10%. Three volunteers applied a sunscreen lotion containing a 8% PEG-25 PABA sunscreen cream and their urinary excretion was controlled from the moment of application until the excreted amounts were no longer detectable.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
