The occurrence of eight organic UV filters (UV-Fs) was assessed in fish from four Iberian river basins. This group of compounds is extensively used in cosmetic products and other industrial goods to avoid the damaging effects of UV radiation, and has been found to be ubiquitous contaminants in the aquatic ecosystem. In particular, fish are considered by the scientific community to be the most feasible organism for contamination monitoring in aquatic ecosystems. Despite that, studies on the bioaccumulation of UV-F are scarce. In this study fish samples from four Iberian river basins under high anthropogenic pressure were analysed by liquid chromatography–tandem mass spectrometry (HPLC–MS/MS). Benzophenone-3 (BP3), ethylhexyl methoxycinnamate (EHMC), 4-methylbenzylidene camphor (4MBC) and octocrylene (OC) were the predominant pollutants in the fish samples, with concentrations in the range of ng/g dry weight (d.w.). The results indicated that most polluted area corresponded to Guadalquivir River basin, where maximum concentrations were found for EHMC (241.7 ng/g d.w.). Sediments from this river basin were also analysed. Lower values were observed in relation to fish for OC and EHMC, ranging from below the limits of detection to 23 ng/g d.w. Accumulation levels of UV-F in the fish were used to calculate biota-sediment accumulation factors (BSAFs). These values were always below 1, in the range of 0.04–0.3, indicating that the target UV-Fs are excreted by fish only to some extent. The fact that the highest concentrations were determined in predators suggests that biomagnification of UV-F may take place along the freshwater food web.
Lagrangian ocean analysis, where virtual parcels of water are tracked through hydrodynamic fields, provides an increasingly popular framework to predict the dispersal of water parcels carrying particles and chemicals. We conduct the first direct test of Lagrangian predictions for emerging contaminants using (1) the latitude, longitude, depth, sampling date, and concentrations of UV filters in raft cultured mussel (Mytilus galloprovincialis) of the estuary Ria de Arousa, Spain (42.5 degrees N, 8.9 degrees W); (2) a hydrodynamic numerical model at 300 m spatial resolution; and (3) a Lagrangian dispersion scheme to trace polluted water parcels back to pollution sources. The expected dispersal distances (mean +/- SD) are 2 +/- 1 km and the expected dispersal times (mean +/- SD) are 6 +/- 2 h. Remarkably, the probability of dispersal of UV filters from potential sources to rafts decreases 5-fold over 5 km. In addition to predicting dispersal pathways and times, this study also provides a framework for quantitative investigations of concentrations of emerging contaminants and source apportionment using turbulent diffusion. In the coastline, the ranges of predicted concentrations of the UV-filters 4-methylbenzylidene-camphor, octocrylene, and benzophenone-4 are 3.2 X 10(-4) to 0.023 ng/mL, 2.3 X 10(-5) to 0.009 ng/mL, and 5.6 X 10(-4) to 0.013 ng/mL, respectively. At the outfalls of urban wastewater treatment plants these respective ranges increase to 8.9 X 10(-4) to 0.07 ng/mL, 6.2 X 10(-5) to 0.027 ng/mL, and 1.6 X 10(-3) to 0.040 ng/mL.
Nowadays, concern over skin cancer has been growing more and more, especially in tropical countries where the incidence of UVA/B radiation is higher. The correct use of sunscreen is the most efficient way to prevent the development of this disease. The ingredients of sunscreen can be organic and/or inorganic sun filters. Inorganic filters present some advantages over organic filters, such as photostability, non-irritability and broad spectrum protection. Nevertheless, inorganic filters have a whitening effect in sunscreen formulations owing to the high refractive index, decreasing their esthetic appeal. Many techniques have been developed to overcome this problem and among them, the use of nanotechnology stands out. The estimated amount of nanomaterial in use must increase from 2000 tons in 2004 to a projected 58000 tons in 2020. In this context, this article aims to analyze critically both the different features of the production of inorganic filters (synthesis routes proposed in recent years) and the permeability, the safety and other characteristics of the new generation of inorganic filters.
The degradation of two of the most frequently used UV-filters was investigated through microcosm studies. Marine sediments sampled from two sites in Italy (La Spezia harbour and Sarno river estuary, S1 and S2 respectively) were used to set up aerobic and anaerobic sets of reactors. The sediments were spiked with a methanol solution of 3-(4-methylbenzylidene)camphor (4-MBC) and 2-ethylhexyl 4-(dimethylamino)benzoate (EH-DPAB), at concentrations of either 25 or 50 mg kg each. Methanol (6.3 g/L) also served as an organic amendment and growth substrate for improving microbial activity. Monitoring of the biotic and abiotic degradation of the selected contaminants over 16 months revealed that 4-MBC biodegradation was very slow and incomplete, whereas over 90% of EH-DPAB was degraded both in the aerobic and the anaerobic reactors by the natural microbial communities of both sediments. Repeated spikes of EH-DPAB were followed by complete decay, characterised by first-order kinetics. The calculated kinetic rate constants under aerobic and anaerobic conditions were similar. In reactors inoculated with the S1 sediment the degradation rate constants progressively increased after each spike, up to the value of 0.039 d . For the S2 sediment the rate constant was around 0.020 d throughout the duration of the experiment. Mass spectrometry analysis of sediment extracts allowed detection of potential transformation products of EH-DPAB and 4-MBC. Moreover, the natural microbial community of the sediments was studied using the CAtalyzed Reporter Deposition Fluorescence In Situ Hybridization (CARD-FISH) both in the initial sediments and after degradation under aerobic and anaerobic conditions.
We performed a trace analytical study covering nine hormonally active UV-filters by LC–MS/MS and GC–MS in river water and biota. Water was analysed at 10 sites above and below wastewater treatment plants in the river Glatt using polar organic chemical integrative samplers (POCIS). Four UV-filters occurred in the following order of decreasing concentrations; benzophenone-4 (BP-4) > benzophenone-3 (BP-3) > 3-(4-methyl)benzylidene-camphor (4-MBC) > 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC). BP-4 ranged from 0.27 to 24.0 μg/POCIS, BP-3, 4-MBC and EHMC up to 0.1 μg/POCIS. Wastewater was the most important source. Levels decreased with higher river water flow. No significant in-stream removal occurred. BP-3, 4-MBC and EHMC were between 6 and 68 ng/L in river water. EHMC was accumulated in biota. In all 48 macroinvertebrate and fish samples from six rivers lipid-weighted EHMC occurred up to 337 ng/g, and up to 701 ng/g in 5 cormorants, suggesting food-chain accumulation. UV-filters are found to be ubiquitous in aquatic systems. Several UV-filters from cosmetics and materials protection occur in rivers and EHMC accumulates in biota.
In this study the bioaccumulation kinetics of organic UV filters, such as 4-MBC, BP-3, BP-4, OC and OD-PABA in wild mussels was investigated. The uptake and accumulation of waterborne 4-MBC, BP-4 and OC was very rapid, and after only 24 h of exposure to 1 μg L , the tissular concentrations were 418, 263 and 327 μg kg d.w., respectively. The kinetics of bioaccumulation of BP-4 and OC significantly fitted to an asymptotic model with BCF values of 905 L kg and 2210 L kg , respectively. Measured bioaccumulation of the hydrophilic chemical BP-4 was much higher than predicted by K -based bioconcentration models, which would lead to a marked underestimation of actual risk. On the other hand, the patterns of uptake found for BP-3 and OD-PABA suggest biotransformation ability of mussels for these two chemicals.
Eight organic UV filters and stabilizers were quantitatively determined in wastewater sludge and effluent, landfill leachate, sediments, and marine and freshwater biota. Crab, prawn and cod from Oslofjord, and perch, whitefish and burbot from Lake Mjøsa were selected in order to evaluate the potential for trophic accumulation. All of the cod livers analysed were contaminated with at least 1 UV filter, and a maximum concentration of almost 12 μg/g wet weight for octocrylene (OC) was measured in one individual. 80% of the cod livers contained OC, and approximately 50% of cod liver and prawn samples contained benzophenone (BP3). Lower concentrations and detection frequencies were observed in freshwater species and the data of most interest is the 4 individual whitefish that contained both BP3 and ethylhexylmethoxycinnamate (EHMC) with maximum concentrations of almost 200 ng/g wet weight. The data shows a difference in the loads of UV filters entering receiving water dependent on the extent of wastewater treatment. Primary screening alone is insufficient for the removal of selected UV filters (BP3, Padimate, EHMC, OC, UV-234, UV-327, UV-328, UV-329). Likely due in part to the hydrophobic nature of the majority of the UV filters studied, particulate loading and organic carbon content appear to be related to concentrations of UV filters in landfill leachate and an order of magnitude difference in these parameters correlates with an order of magnitude difference in the effluent concentrations of selected UV filters ( ). From the data, it is possible that under certain low flow conditions selected organic UV filters may pose a risk to surface waters but under the present conditions the risk is low, but some UV filters will potentially accumulate through the trophic food chain.
Benzophenones and benzotriazoles are widely used as ultraviolet (UV) light filters and stabilizers in cosmetics, skin creams, and body lotions and as corrosion inhibitors in building materials, automobile components, and automotive antifreeze cooling systems. Benzophenones and benzotriazoles have been reported to occur in the environment. Some of these UV filters have been reported to possess significant estrogenic activity. Despite this, very few studies have examined their occurrence and profiles in the environment. In this work, we determined five benzophenone-type UV filters and two benzotriazole-type corrosion inhibitors, namely, 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (24OH-BP), 2,2'-dihydroxy-4-methoxybenzophenone (2,2'OH-4MeO-BP), 2,2',4,4'-tetrahydroxybenzophenone (2,21,4,4'OH-BP), 4-hydroxybenzophenone (4OH-BP), 1H-benzotriazole (1H-BT), and 5-methyl-1H-benzotriazole (5Me-1H-BT), in sediment and sewage sludge samples, using liquid-liquid extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS). In addition, four benzotriazole-type UV stabilizers, namely, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326), 2,4-di-t-butyl-6-(5-chloro-2H-benzotriazole-2yl) phenol (UV-327), 2-(2H-benzotriazole-2yl)-4,6-di-t-pentylphenol (UV-328), and 2-(5-t-butyl-2-hydroxyphenyl) benzotriazole (TBHPBT) were determined by gas chromatography (GC)-mass spectrometry (MS). The limits of quantitation (LOQ) were in the ranges of 0.06-0.33 ng g(-1) dry weight (dw) and 0.1-1.65 ng g(-1) dw for sediment and sludge samples, respectively. Recoveries of target compounds spiked into sample matrices and passed through the entire analytical procedure ranged from 70% to 116% (RSD: 3.32-13.8%) and from 82% to 106% (RSD: 2.89-8.09%) for the compounds analyzed by LC-MS/MS and GC-MS, respectively. The methods were applied to the analysis of sediment samples from the Songhua, Saginaw, and Detroit Rivers; the sum concentrations of target compounds were 3.29-9.93, 5.81-22.5, and 190-389 ng g(-1) dw, respectively. Five sludge samples collected from five wastewater treatment plants in northeastern China contained the sum concentrations of target compounds in the range of 104-6370 ng g(-1) dw. The concentration of UV-328 in sludge was the highest (mean: 1300 ng g(-1) dw) among the target compounds. To our knowledge, this is the first work to report the occurrence of 2OH-4MeO-BP, 2,4OH-BP, 2,2'OH-4MeO-BP, 2,2,4,4'OH-BP, and 4OH-BP in sediment and sludge samples.