Falcon Probe: A High-Pressure and Robust Sampling Interface for Coupling Lossless Liquid Chromatography Injection with In Situ Nanoliter-Scale Sample Pretreatment.

With the increasing demand for trace sample analysis, injecting trace samples into liquid chromatography-mass spectrometry (LC-MS) systems with minimal loss has become a major challenge. Herein, we describe an in situ LC-MS analytical probe, the Falcon probe, which integrates multiple functions of high-pressure sample injection without sample loss, high-efficiency LC separation, and electrospray. The main body of the Falcon probe is made of stainless steel and fabricated by the computer numerical control (CNC) technique, which has ultrahigh mechanical strength. By coupling a nanoliter-scale droplet reactor made of polyether ether ketone (PEEK) material, the Falcon probe-based LC-MS system was capable of operating at mobile-phase pressures up to 800 bar, which is comparable to those of conventional ultraperformance liquid chromatography (UPLC) systems. Using the probe pressing microamount in situ (PPMI) injection approach, the Falcon probe-based LC-MS system showed high separation efficiency and good repeatability with relative standard deviations (RSDs) of retention time and peak area of 1.8% and 9.9%, respectively, in peptide mixture analysis (n = 6). We applied this system to the analysis of a trace amount of 200 pg of HeLa protein digest and successfully identified an average of 766 protein groups (n = 5). By combining in situ sample pretreatment at the nanoliter range, we further applied the present system in single-cell proteomic analysis, and 241 protein groups were identified in single 293 cells, which preliminarily demonstrated its potential in the analysis of trace amounts of samples with complex compositions.

A multiplex approach of MS, 1D-, and 2D-NMR metabolomics in plant ontogeny: A case study on Clusia minor L. organs (leaf, flower, fruit, and seed).

INTRODUCTION: The genus Clusia L. is mostly recognised for the production of prenylated benzophenones and tocotrienol derivatives. OBJECTIVES: The objective of this study was to map metabolome variation within Clusia minor organs at different developmental stages. MATERIAL AND METHODS: In total 15 organs/stages (leaf, flower, fruit, and seed) were analysed by UPLC-MS and 1H- and heteronuclear multiple-bond correlation (HMBC)-NMR-based metabolomics. RESULTS: This work led to the assignment of 46 metabolites, belonging to organic acids(1), sugars(2) phenolic acids(1), flavonoids(3) prenylated xanthones(1) benzophenones(4) and tocotrienols(2). Multivariate data analyses explained the variability and classification of samples, highlighting chemical markers that discriminate each organ/stage. Leaves were found to be rich in 5-hydroxy-8-methyltocotrienol (8.5 µg/mg f.w.), while flowers were abundant in the polyprenylated benzophenone nemorosone with maximum level detected in the fully mature flower bud (43 µg/mg f.w.). Nemorosone and 5-hydroxy tocotrienoloic acid were isolated from FL6 for full structural characterisation. This is the first report of the NMR assignments of 5-hydroxy tocotrienoloic acid, and its maximum level was detected in the mature fruit at 50 µg/mg f.w. Seeds as typical storage organ were rich in sugars and omega-6 fatty acids. CONCLUSION: To the best of our knowledge, this is the first report on a comparative 1D-/2D-NMR approach to assess compositional differences in ontogeny studies compared with LC-MS exemplified by Clusia organs. Results derived from this study provide better understanding of the stages at which maximal production of natural compounds occur and elucidate in which developmental stages the enzymes responsible for the production of such metabolites are preferentially expressed.

Prevalence of selected UV filter compounds in Biscayne National Park.

This research was carried out in order to assess a baseline occurrence in Biscayne National Park, Florida, of four organic contaminants: the UV filters oxybenzone, dioxybenzone, and benzophenone, as well as the topical pain reliever benzocaine. A total of 35 samples were taken from five locations within the park, four near barrier islands, and one at a coral reef. Analyses were carried out using liquid chromatography coupled to high-resolution mass spectrometry. Oxybenzone was detected in 26% of samples from the park at concentrations up to 31 ng/L. Benzophenone was detected in 49% of samples from the park at concentrations up to 131 ng/L. Benzocaine and dioxybenzone were not detected in any of the samples.

Role of soil organic matter on the retention and mobility of common plastic additives, Di(2-ethylhexyl) phthalate, bisphenol A and benzophenone, in soil.

The objectives of this study were to assess the role of soil organic matter on retaining plastic additives, Di(2-ethylhexyl) phthalate (DEHP), Bisphenol A (BPA) and Benzophenone (BP), to postulate the retention mechanisms and mobility in soil. Batch experiments were conducted for red yellow podzolic soil (OM) and soil subjected to high temperature oxidation at 600 °C for 2 h to remove total organic matter (OMR). Pristine soil, which contains organic matter abbreviated as OM (soil with organic matter) whereas total organic matter removed soil is abbreviated as OMR (organic matter removed soil). The pH edge and kinetic experiments were conducted with 20 g/L soil suspension spiked with 10 mg/L of each additive, whereas 1-20 mg/L concentration range was used in isotherm experiments and analyzed using high performance liquid chromatography. DEHP demonstrated the highest retention, 331 and 615.16 mg/kg in OM and OMR soils respectively, at pH 6.6. However, BPA and BP showed highest retentions of 132 and 128 mg/kg, respectively around pH 4.3 in pristine soil. DEHP interaction with soil OM indicated weak physical bonding whereas chemisorption to OMR soil. In the case of BPA, physisorption governed its interaction with both soil organic matter and mineral fraction. Nevertheless, BP demonstrated chemical interactions with OM and minerals. Desorption of DEHP was close to 100% however, BPA and BP were <15%. Overall, DEHP and BPA could be easily released into soil water and possibly be available for plant uptake while, BP is immobilized in soil.

Influence of mobile phase composition on the analytical sensitivity of LC-ESI-MS/MS for the concurrent analysis of bisphenols, parabens, chlorophenols, benzophenones, and alkylphenols.

Phenols are significant environmental endocrine disruptors that can have adverse health effects on exposed individuals. Correlating phenol exposure to potential health implications requires the development of a comprehensive and sensitive analytical method capable of analyzing multiple phenols in a single sample preparation and analytical run. Currently, no such method is available for multiple classes of phenols due to electrospray ionization (ESI) limitations in concurrent ionization and lack of sensitivity to certain phenols, particularly alkylphenols. In this study, we investigated the influence of mobile phase compositions in ESI on concurrent ionization and analytical sensitivity of liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) during the analysis of multiple classes of phenols, and we propose a comprehensive and sensitive analytical method for various classes of phenols (i.e., bisphenols, parabens, benzophenones, chlorophenols, and alkylphenols). The proposed method was affected by 0.5 mM ammonium fluoride under methanol conditions. It enabled the concurrent ionization of all the phenols and significantly improved the analytical sensitivity for bisphenols and alkylphenols, which typically have poor ionization efficiency. This method, combined with a "dilute and shoot" approach, allowed us to simultaneously quantify 38 phenols with good chromatographic behavior and sensitivity. Furthermore, the method was successfully applied to the analysis of 61 urine samples collected from aquatic (swimming) and land (indoor volleyball and outdoor football) athletes.

Layered Double Hydroxide/Graphene Quantum Dots as a New Sorbent for the Dispersive Solid-Phase Microextraction of Selected Benzophenones, Phenols, and Parabens.

In this study, the synthesis of a layered double hydroxide (LDH) composite with graphene quantum dots (GQDs) and its utilization for the development of a dispersive solid-phase extraction procedure are described. To this end, a carbonate-free Mg-Al LDH was synthesized. The development of the composite material made feasible the use of GQDs in a sample preparation procedure, while the incorporation of the GQDs in the LDH structure resulted in an 80% increase in extraction efficiency, compared to the bare LDH. As a proof of concept, the composite material was used for the development of an analytical method for the extraction, and preconcentration, of benzophenones, phenols, and parabens in lake water using high-performance liquid chromatography, coupled to a diode array detector. The analytical method exhibits low limits of quantification (0.10-1.33 µg L-1), good recoveries (92-100%), and satisfactory enrichment factors (169-186). Due to the abovementioned merits, the easy synthesis and simple extraction, the developed method can be used for the routine analysis of the target compounds.

Determination of Benzophenones in Water and Cosmetics Samples: A Comparison of Solid-Phase Extraction and Microextraction by Packed Sorbent Methods.

Benzophenones (BPs) are extensively used in a wide variety of cosmetic products and other materials (e.g., textiles or plastics) to avoid damaging effects of UV radiation. In the present work, we compared two extraction methods for the determination of BPs, namely, 2,4-dihydroxybenzophenone (BP-1), 2-hydroxy-4-methoxybenzophenone (BP-3) and 2,2-dihydroxy-4-methoxybenzophenone (BP-8), in water and cosmetics samples. The following extraction methods were used for the research: solid-phase extraction (SPE) and microextraction by packed sorbent (MEPS), whereas analysis was performed by gas chromatography with mass spectrometric detection. A comparison between the methods indicates that the MEPS technique(s) can be reliably used for analysis of BPs (sunscreen residue) in water samples and cosmetic samples with satisfactory results. This microextraction technique is cheap, easy, quick to implement, and consumes small amounts of solvents. On the other hand, the main advantage of the SPE method are low detection limits for the determination of BPs in water samples, i.e., from 0.034 to 0.067 µg L-1, while, for the MEPS method, LODs were at the level of 1.8-3.2 µg L-1. For both methods, the recoveries of BPs were 96-107% and 44-70% for water and cosmetics samples, respectively. The presented methods are suitable for use in cosmetics quality control and environmental pollution assessment.

Menstrual blood concentrations of parabens and benzophenones and related factors in a sample of Spanish women: An exploratory study.

AIM: To evaluate concentrations of parabens (PBs) and benzophenones (BzPs) in menstrual blood and explore related sociodemographic/lifestyle factors, and to compare between menstrual and peripheral blood concentrations in a subset of samples. MATERIAL AND METHODS: Concentrations of 4 PBs [methyl- (MeP), ethyl- (EtP), propyl- (PrP) and butyl-paraben (BuP)] and 6 BzPs [BzP-1, BzP-2, BzP-3, BzP-6, BzP-8 and 4-OH-BzP] were determined in menstrual blood from 57 women and in both menstrual and peripheral blood samples from 12 women, all healthy Spanish women of reproductive age. Socio-demographic characteristics and lifestyle habits [diet and use of cosmetics and personal care products (PCPs)] were gathered using an online questionnaire. Spearman correlation analysis was performed to examine the relationship between menstrual and peripheral blood concentrations, while multivariable linear regression was used to identify potential explanatory variables for menstrual PB and BzP concentrations. RESULTS: Globally, all menstrual blood samples had detectable levels of ≥3 compounds, and 52.6% of the samples contained ≥6 compounds. MeP, PrP, and BzP-3 were the most frequently detected compounds (detection frequencies >90.0%), with median concentrations of 1.41, 0.63, and 1.70 ng/mL of menstrual blood, respectively. Age, the use of PCPs, and consumption of some food items (meat, pasta, cheese, or dairy products) were related to the menstrual blood concentrations of some PBs/BzPs. Serum:menstrual blood ratios of PBs/BzPs ranged from 1.7 to 3.6, with no inter-matrix correlations. CONCLUSIONS: This study reveals, to our knowledge for the first time, the widespread presence of several PBs and BzPs in intimate contact with gynecological tissues, although their concentrations in menstrual blood were not correlated with those in peripheral blood from the same women. These results shed light on the information provided by the menstrual blood as a potential matrix for characterizing exposure to PBs and BzPs, whose consequences for women's reproductive health need to be addressed.

Dalbergia ecastaphyllum (L.) Taub. and Symphonia globulifera L.f.: The Botanical Sources of Isoflavonoids and Benzophenones in Brazilian Red Propolis.

The Brazilian red propolis (BRP) constitutes an important commercial asset for northeast Brazilian beekeepers. The role of Dalbergia ecastaphyllum (L.) Taub. (Fabaceae) as the main botanical source of this propolis has been previously confirmed. However, in addition to isoflavonoids and other phenolics, which are present in the resin of D. ecastaphyllum, samples of BRP are reported to contain substantial amounts of polyprenylated benzophenones, whose botanical source was unknown. Therefore, field surveys, phytochemical and chromatographic analyses were undertaken to confirm the botanical sources of the red propolis produced in apiaries located in Canavieiras, Bahia, Brazil. The results confirmed D. ecastaphyllum as the botanical source of liquiritigenin (1), isoliquiritigenin (2), formononetin (3), vestitol (4), neovestitol (5), medicarpin (6), and 7-O-neovestitol (7), while Symphonia globulifera L.f. (Clusiaceae) is herein reported for the first time as the botanical source of polyprenylated benzophenones, mainly guttiferone E (8) and oblongifolin B (9), as well as the triterpenoids ß-amyrin (10) and glutinol (11). The chemotaxonomic and economic significance of the occurrence of polyprenylated benzophenones in red propolis is discussed.

Comparative study of ink photoinitiators in food packages using gas chromatography with vacuum ultraviolet detection and gas chromatography with mass spectrometry.

This work focused on the development and validation of the analytical procedure using gas chromatography equipped with vacuum-ultraviolet detection for the specific and sensitive determination of nine photoinitiators in food packages. Subsequently, a comparison of the combination of vacuum ultraviolet spectroscopy with gas chromatography and a developed gas chromatography with mass spectrometry method was performed. The vacuum-ultraviolet spectra of all tested photoinitiators were collected and found to be highly distinct, even for isomers. Under the optimal conditions, the limits of detection for nine photoinitiators ranged from 1 to 5 mg/L using vacuum ultraviolet detection and from 0.15 to 0.5 mg/L using mass spectrometric detection. Both techniques were successfully applied for screening of photoinitiators in seven kinds of food packages and the obtained data showed good agreement (the relative difference was between 3 and 18%). The variability in concentrations found in triplicate samples was assessed to be below 18%. Predominantly benzophenone was found in all analysed samples in the range of 0.31-4.23 mg/kg. It appears to be preferably selected by food packaging manufacturers. This study proposes a new simple and sensitive technique used for analysis of photoinitiators that could be a good alternative to gas chromatography with mass spectrometry.

Isolation and characterization of a novel benzophenone-3-degrading bacterium Methylophilus sp. strain FP-6.

Benzophenone-3 (BP-3) is extensively applied in sunscreens and some other related cosmetic products. It is necessary to efficiently and safely remove BP-3 from environments by application of various treatment technologies. However, to the authors' knowledge, BP-3 biodegradation by a single bacterial strain has not been reported before. In this study, a Gram-negative aerobic bacterium capable of degrading BP-3 as a sole carbon source was isolated from a municipal wastewater treatment plant and classified as Methylophilus sp. FP-6 according to BIOLOG GEN III and 16S rDNA analysis. Methanol was chosen for further experiments as a co-metabolic carbon source to enhance the microbial degradation efficiency of BP-3. Orthogonal and one-way experiments were all performed to investigate the optimal culture conditions for degradation of BP-3 by Methylophilus sp. FP-6. The degradation rate of BP-3 reached about 65% after 8 days of incubation with strain FP-6 under optimal culture conditions. The half-life (t1/2) of BP-3 biodegradation by strain FP-6 was estimated as 2.95 days according to the BP-3 degradation curve. The metabolite intermediates generated during the BP-3 degradation process were analyzed by LC-MS/MS and three metabolite products were identified. According to the analysis of metabolic intermediates, three pathways for degradation of BP-3 by strain FP-6 were proposed. The results from this study gave first insights into the potential of BP-3 biodegradation by a single bacterial strain.

Environmental characterization of 4,4'-dichlorobenzophenone in surface waters from Macao and Hong Kong coastal areas (Pearl River Delta) and its toxicity on two biological models: Artemia salina and Daphnia magna.

The Pearl River Delta (PRD) is one of the areas with higher environmental concentration of organochlorine pesticides (OCPs), being DDT one of the most abundant. In this work, 4,4'-dichlorobenzophenone (4,4'-DCBP), a common metabolite of dicofol (DDT related) and DDT, was quantified in surface waters of Hong Kong and Macao, together with the analysis of physicochemical and nutrients parameters. Hong Kong presented higher 4,4'-DCBP mean levels (12.50 ng/L) than Macao (4.05 ng/L), which may be due to the use of dicofol as a pesticide and DDT as antifouling-paint for ships. The region presented a possible eutrophication state due to the high nutrients' concentration. For the first time, toxicity evaluation of this metabolite in Artemia salina and Daphnia magna was done, in order to compute valid EC50s and theoretically evaluate the risk in the PRD. The toxicity results (EC50 = 0.27 mg/L for A. salina; and EC50 = 0.17 mg/L and LC50 = 0.26 mg/L for D. magna), together with the 4,4'-DCBP levels quantified, indicated a low environmental risk.

Migration Studies of Two Common Components of UV-curing Inks into Food Simulants.

The Rapid Alert System for Food and Feed (RASFF) has reported many cases of different UV curing inks components in foodstuffs during the last few years. These contaminants reach foodstuffs mainly by set-off, their principal migration mechanism from the package. Under this premise, this work has tried to characterize the process of migration of two common UV ink components: a photoinitiator (4-Methylbenzophenone) and a coinitiator (Ethyl-4-(dimethylamino) benzoate), from the most common plastic material used in food packaging low-density polyethylene (LDPE) into six different food simulants. The migration kinetics tests were performed at four different common storage temperatures, obtaining the key migration parameters for both molecules: the coefficients of diffusion and partition. The migration process was highly dependent on the storage conditions, the photoinitiator properties and the pH of the foodstuff.

Identification of intentionally and non-intentionally added substances in plastic packaging materials and their migration into food products.

Plastic materials are widely used in food packaging applications; however, there is increased concern because of the possible release of undesirable components into foodstuffs. Migration of plastic constituents not only has the potential to affect product quality but also constitutes a risk to consumer health. In order to check the safety of food contact materials, analytical methodologies to identify potential migrants are required. In the first part of this work, a GC/MS screening method was developed for the identification of components from plastic packaging materials including intentionally and "non-intentionally added substances" (NIAS) as potential migrants. In the second part of this study, the presence of seven compounds (bis (2-ethylhexyl) phthalate (DEHP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), butylated hydroxytoluene (BHT), acetyl tributyl citrate (ATBC), benzophenone (BP)) previously identified in packaging materials were investigated in food products (corn and potatoes snacks, cookies, and cakes). For this purpose, a suitable extraction method was developed and quantification was performed using GC-MS. The developed method was validated in terms of linearity, recovery, repeatability, and limits of detection and quantification. The spiked recoveries varied between 82.7 and 116.1%, and relative standard deviation (RSD) was in the range of 2.22-15.9%. The plasticizer ATBC was the most detected compound (94% samples), followed by DEP (65%), DEHP (47%), BP (44%), DBP (35%), DIBP (21%), and BHT (12%). Regarding phthalates, DEP and DEHP were the most frequently detected compounds in concentrations up to 1.44 µg g-1. In some samples, only DBP exceeded the European SML of 0.3 mg kg-1 established in Regulation 10/2011. Graphical abstract Chemical migration from plastic packaging into food.

Optimization of solid-phase extraction of parabens and benzophenones in water samples using a combination of Plakett-Burman and Box-Behnken designs.

An automated method for the analysis of methylparaben, propylparaben, benzophenone-3, and benzophenone-4 in water effluents via on-line solid-phase extraction coupled with high-performance liquid chromatography/ultraviolet detection was proposed. The preconcentration parameters were studied using Plackett-Burman and Box-Behnken experimental designs using a C18 sorbent material. The results demonstrated that the eluent volume, composition, and sorbent amount were statistically significant. Optimal conditions for these variables were an eluent volume of 1.55 mL, eluent composition of acetonitrile 100% v/v, and sorbent amount of 100 mg. The eluted sample was analyzed on-line using high-performance liquid chromatography equipped with a reversed-phase C18 column and ultraviolet detection. Separation of the analytes was achieved in 15 min using gradient elution with acetonitrile/water. A simple, sensitive, and rapid analytical method was proposed for personal care compounds without sophisticated or expensive equipment. The limits of detection were 1.20, 1.73, 2.51, and 4.67 µg/L for propylparaben, methylparaben, benzophenone-3, and benzophenone-4, respectively. The analysis time was 48 min, consuming only 1.59 mL of eluent acetonitrile for the solid phase extraction step, with minimal sample handling. The method was applied to the analysis of spiked swimming pool and wastewater, with recoveries between 65-107%. These results indicate the reliability of the flow-based procedure.

Simple method for the determination of personal care product ingredients in lettuce by ultrasound-assisted extraction combined with solid-phase microextraction followed by GC-MS.

A simple method for the simultaneous determination of personal care product ingredients: galaxolide, tonalide, oxybenzone, 4-methylbenzyliden camphor, padimate-o, 2-ethylhexyl methoxycinnamate, octocrylene, triclosan, and methyl triclosan in lettuce by ultrasound-assisted extraction combined with solid-phase microextraction followed by gas chromatography with mass spectrometry was developed. Lettuce was directly extracted by ultrasound-assisted extraction with methanol, this extract was combined with water, extracted by solid-phase microextraction in immersion mode, and analyzed by gas chromatography with mass spectrometry. Good linear relationships (25-250 ng/g, R2  > 0.9702) and low detection limits (1.0-25 ng/g) were obtained for analytes along with acceptable precision for almost all analytes (RSDs < 20%). The validated method was applied for the determination of personal care product ingredients in commercial lettuce and lettuces grown in soil and irrigated with the analytes, identifying the target analytes in leaves and roots of the latter. This procedure is a miniaturized and environmentally friendly proposal which can be a useful tool for quality analysis in lettuce.

Measurement of concentrations of four chemical ultraviolet filters in human breast tissue at serial locations across the breast.

The human population is widely exposed to benzophenone-3 (BP-3), octylmethoxycinnamate (OMC), 4-methylbenzilidenecamphor (4-MBC) and homosalate from their use in consumer goods to absorb ultraviolet (UV) light. Their oestrogenic activity and presence in human milk suggest a potential to influence breast cancer development. In this study, high-performance liquid chromatography-tandem mass spectrometry was used to measure concentrations of these UV filters in human breast tissue from three serial locations across the breast from 40 women undergoing mastectomy for primary breast cancer. One or more of these UV filters were quantifiable in 101 of 120 (84%) of the tissue samples and at least one breast region for 38 of 40 women. BP-3 was measured in 83 of 120 (69%) tissue samples and at least one breast region for 33 of 40 women (range 0-26.0 ng g-1 tissue). OMC was measured in 89 of 120 (74%) tissue samples and at least one breast region for 33 of 40 women (range 0-58.7 ng g-1 tissue). 4-MBC was measured in 15 of 120 (13%) tissue samples and at least one breast region for seven of 40 women (range 0-25.6 ng g-1 tissue). Homosalate was not detected in any sample. Spearman's analyses showed significant positive correlations between concentrations of BP-3 and OMC in each of the three breast regions. For ethical reasons cancerous tissue was not available, but as the location of the cancer was known, Mann-Whitney U-tests investigated any link between chemical concentration and whether a tumour was present in that region or not. For the lateral region, more BP-3 was measured when a tumour was present (P = .007) and for OMC the P value was .061. For seven (of 40) women with measurable 4-MBC, six of seven had measurable 4-MBC at the site of the tumour.

Pollution patterns and underlying relationships of benzophenone-type UV-filters in wastewater treatment plants and their receiving surface water.

The environmental behaviors of emerging pollutants, benzophenone-type UV filters (BP-UV filters) and their derivatives were investigated in four wastewater treatment plants (WWTPs), and their receiving surface waters in Shanghai. The concentration level of selected BP-UV filters in the WWTPs was detected from ngL-1 to µgL-1. BP (621-951ngL-1) and BP-3 (841-1.32 × 103ngL-1) were the most abundant and highest detection frequency individuals among the target BP-UV filters in influents, whereas BP (198-400ngL-1), BP-4 (93.3-288ngL-1) and BP-3 (146-258ngL-1) were predominant in effluents. BP-UV filters cannot be completely removed and the total removal efficiency varied widely (-456% to 100%) during the treatment process. It can be inferred that the usage of BP and BP-3 are higher than other BP-UV filters in the study area. The lowest and highest levels were BP-2 (ND-7.66ngL-1) and BP-3 (68.5-5.01 × 103ng L-1) in the receiving surface water, respectively. Interestingly, the seasonal variation of BP-3 is larger than those of other BP-UV filters in surface water from Shanghai. There is no obvious pollution pattern of BP-UV filters in the surface water from the cosmetic factory area. The correlation analysis of BP-UV filters between WWTPs effluents and nearby downstream water samples suggested that BP-UV filters emitted from some WWTPs might be the main source of receiving surface water. Preliminary risk assessment indicated that the levels of BP-UV filters detected by the effluent posed medium to high risk to fish as well as other aquatic organisms.

Occurrence, distribution and ecological risk of ultraviolet absorbents in water and sediment from Lake Chaohu and its inflowing rivers, China.

The available information is insufficient to enable a reliable understanding of the global distribution and effect of organic ultraviolet absorbents (UVAs) on ecosystems. Little is known about the pollution of China's lakes by these chemicals. We conducted a survey of UVAs in water and sediment from Lake Chaohu and its inflowing rivers. The UVAs were widely present in this area and the concentrations of total 12 UVAs (Σ12 UVAs) ranged between 162 and 587 ng/L in water and 9.70-178 ng/g in sediment. Benzophenone and benzophenone-3 were dominant in water, and benzophenone and octocrylene dominated in sediment. Higher concentrations of benzophenone were detected in the investigated water samples, although the contamination levels of UVAs in this study were comparable to those investigated in other areas. In addition to the inputs from the UVAs used as filters in cosmetics, the discharge from industries using UVAs as stabilizers also contributed much to the pollution in the study waters. Generally, the risk to aquatic organisms from exposure to UVAs in this area was low, but further research is needed to elucidate the fate of UVAs and to understand bioaccumulation and associated risks.

Benzophenone-type UV filters in surface waters: An assessment of profiles and ecological risks in Shanghai, China.

Benzophenone-type UV filters (BP-UV filters) are frequently introduced into aquatic environment from several sources. The occurrence and fate of select BP-UV filters and their metabolites were investigated in this study. All target compounds were detected in water samples, except for 2, 3, 4-trihydroxybenzophenone (2, 3, 4-OH-BP). The concentration reached up 131ngL-1 for 5-benzoyl-4-hydroxy-2-ethoxybenzenesulfonic acid (BP-4), 30.0ngL-1 for 2-hydroxy-4-methoxybenzophenone (BP-3), and mean value of 158ngL-1 for benzophenone (BP). Concentrations of BP-UV filters were not related to recreational waters but with high population frequencies. In addition, five BP-UV filters, namely 2,2',4,4'-tetrahydroxybenzophenone (BP-2), 2,3,4-OH-BP, 2,4-dihydroxybenzophenone (BP-1), 4-hydroxybenzophenone (4-OH-BP) and BP were investigated for probable sources, and found that they originate from BP-3 metabolism. There is a similar source for BP-3, BP-4, BP-1, 4-OH-BP and BP. Environmental risk assessment (ERA) showed that risk quotients (RQs) of BP-4, BP-3 and BP were 2.7, 0.8 and 0.5, respectively.