Tracking the changes of dissolved organic matter throughout the city water supply system with optical indices.

Dissolved organic matter (DOM) is important in determining the drinking water treatment and the supplied water quality. However, a comprehensive DOM study for the whole water supply system is lacking and the potential effects of secondary water supply are largely unknown. This was studied using dissolved organic carbon (DOC), absorption spectroscopy, and fluorescence excitation-emission matrices-parallel factor analysis (EEM-PARAFAC). Four fluorescent components were identified, including humic-like C1-C2, tryptophan-like C3, and tyrosine-like C4. In the drinking water treatment plants, the advanced treatment using ozone and biological activated carbon (O3-BAC) was more effective in removing DOC than the conventional process, with the removals of C1 and C3 improved by 17.7%-25.1% and 19.2%-27.0%. The absorption coefficient and C1-C4 correlated significantly with DOC in water treatments, suggesting that absorption and fluorescence could effectively track the changes in bulk DOM. DOM generally remained stable in each drinking water distribution system, suggesting the importance of the treated water quality in determining that of the corresponding network. The optical indices changed notably between distribution networks of different treatment plants, which enabled the identification of changing water sources. A comparison of DOM in the direct and secondary water supplies suggested limited impacts of secondary water supply, although the changes in organic carbon and absorption indices were detected in some locations. These results have implications for better understanding the changes of DOM in the whole water supply system to help ensure the supplied water quality.

Unveiling changes in the complexation of dissolved organic matter with Pb(II) by photochemical and microbial degradation using fluorescence EEMs-PARAFAC.

Dissolved organic matter (DOM) is very important in determining the speciation, behaviors, and risk of metal pollutants in aquatic ecosystems. Photochemical and microbial degradation are key processes in the cycling of DOM, yet their effects on the DOM-Pb(II) interaction remain largely unknown. This was studied by examining the complexation of river DOM with Pb(II) after degradation, using fluorescence quenching titration and excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC). Three humic-like and two protein-like components were identified, with strong removals of humic-like components and decreasing average molecular weight and humification degree of DOM by photo- and photo-microbial degradation. The changes in humic-like abundance and structure resulted in notable weakening of their interaction with Pb(II). The tryptophan-like C2 was also mainly removed by photo-degradation, while the tyrosine-like C3 could be either removed or accumulated. The Pb(II)-binding of protein-like components was generally weaker but was enhanced in some degradation groups, which might be related to the lowering competition from humic-like components. The binding parameters correlated significantly with the DOM indices, which were dominated by photo-degradation for humic-like components but by seasonal variations for the tyrosine-like component. These results have implications for understanding the key mechanisms underlying the variability of the DOM-metal interaction in aquatic environments.

Effects of Photodegradation on the Optical Indices of Chromophoric Dissolved Organic Matter from Typical Sources.

Chromophoric dissolved organic matter (CDOM) plays important roles in aquatic environments, and its optical properties provide a series of indices for evaluating the source and composition of dissolved organic matter (DOM). However, little is known about the varying photodegradation of CDOM from different sources and the effects on the optical indices of DOM composition. This was studied for typical natural and anthropogenic sources (plant and leaf litter leachates, the influent and effluent of a wastewater treatment plant, and a river). The CDOM absorption (a280) showed a lower degradability for the plant leachate than other sources, mainly due to its low molecular weight and aromaticity. Four fluorescent components were identified with excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC), namely benzoic acid/monolignol-like C1, humic-like C2 and C3, and tryptophan-like C4. The plant leachate contained mainly C1, which was photodegraded moderately, while other sources had more C2 and C3 with higher photodegradability. C4 was photodegraded in most sources but was photoproduced in the leaf litter leachate. The absorption slope (S275-295) and slope ratio (SR) increased while the humification index (HIX) decreased, suggesting a decreasing molecular weight and humic content by photodegradation. This was consistent with the decreasing %C2 and %C3 but increasing %C4, which indicated preferential removal of humic-like components. The %C1, %C2, biological index (BIX), and fluorescence index (FI) were less affected by photodegradation than other indices for most sources. These results have implications for a better understanding of the photochemistry of CDOM and the applications of optical indices.

Critical evaluation of the interaction between fluorescent dissolved organic matter and Pb(II) under variable environmental conditions.

Dissolved organic matter (DOM) can strongly influence the behavior and risk of metal pollutants in aquatic ecosystems. However, a comprehensive study on the effects of DOM level and environmental factors on the binding of DOM with Pb(II) is lacking. This study examined the DOM-Pb(II) interaction in the river water under variable DOM level, pH, and major ions, using fluorescence excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC). Four humic-like and one protein-like component were identified, and the abundant humic-like components showed higher Pb(II)-binding fractions (f) than the protein-like component. The f of PARAFAC components decreased while the conditional stability constants (logKM) increased for the diluted DOM, indicating the influence of DOM level on its metal binding. The DOM-Pb(II) interaction was sensitive to changes in pH, with generally higher f and lower logKM at the alkaline condition due to changes in the DOM conformation. The addition of major ions significantly decreased the fluorescence quenching by Pb(II), due to competitive effects and potential DOM conformation changes at elevated ions. Overall, our results show that the DOM-Pb(II) complexation is highly dependent on both the DOM properties and environmental factors, which have implications for optimizing the experimental conditions and for comparing the results in different environments.

Comparing the Pb(II) binding with different fluorescent components of dissolved organic matter from typical sources.

Dissolved organic matter (DOM) is important for determining the speciation, environmental behavior, and effects of metal pollutants in aquatic environments. However, little is known about the difference between DOM from natural and anthropogenic sources for binding Pb(II). This study examined the Pb(II) binding with DOM from four typical sources including river, leaf litter leachate, and the influent and effluent of a wastewater treatment plant, using fluorescence quenching titration and excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC). Four humic-like and one protein-like fluorescent components were identified, with much higher protein-like fraction and lower humification degree for the influent than for other sources. In the river water and leaf litter leachate, the abundant humic-like components were quenched by 6-17% while the protein-like component kept stable (2-4%) by the addition of Pb(II). In contrast, the influent DOM showed stronger fluorescence quenching of the protein-like component (46%) with higher conditional stability constant and binding fraction of fluorophore than the humic-like components (15-21%). The effluent DOM displayed weak quenching for all fluorescent components (4-6%) and thus weak complexation with Pb(II), indicating notable changes in the chemical composition and metal-binding affinity of DOM by wastewater treatments. These results demonstrated significant impacts of DOM source and chemical composition on its Pb(II) complexation properties, which have implications for understanding the interactions between DOM and heavy metals.

Monitoring dissolved organic matter in wastewater and drinking water treatments using spectroscopic analysis and ultra-high resolution mass spectrometry.

Dissolved organic matter (DOM) plays a critical role in determining the quality of wastewater and the safety of drinking water. This is the first review to compare two types of popular DOM monitoring techniques, including absorption spectroscopy and fluorescence excitation-emission matrices (EEMs) coupled with parallel factor analysis (PARAFAC) vs. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), for the applications in wastewater and drinking water treatments. The optical techniques provide a series of indices for tracking the quantity and quality of chromophoric and fluorescent DOM, while FT-ICR-MS is capable of identifying thousands of DOM compounds in wastewater and drinking water at the molecule level. Both types of monitoring techniques are increasingly used in studying DOM in wastewater and drinking water treatments. They provide valuable insights into the variability of DOM composition in wastewater and drinking water. The complexity and diversity of DOM highlight the challenges for effective water treatments. Different effects of various treatment processes on DOM are also assessed, which indicates that the information on DOM composition and its removal is key to optimize the treatment processes. Considering notable progress in advanced treatment processes and novel materials for removing DOM, it is important to continuously utilize these powerful monitoring tools for assessing the responses of different DOM constituents to a series of treatment processes, which can achieve an effective removal of DOM and the quality of treated water.

Assessing the priming effect of dissolved organic matter from typical sources using fluorescence EEMs-PARAFAC.

Priming effect (PE) is increasingly recognized as an important mechanism in the microbial degradation of dissolved organic matter (DOM) from freshwater to the ocean. However, potential PE during the mixing of DOM from different sources and the effects on different DOM constituents are still largely unknown. This study examined the PE after adding DOM from typical natural and anthropogenic sources (rainwater, fresh plant, leaf litter, and wastewater) into pre-aged river DOM, using dissolved organic carbon (DOC) measurement, absorption spectroscopy, and fluorescence excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC). The plant-derived DOM had a low humic content and was dominated by benzoic acid-like and tyrosine-like fluorescent components (C4 and C5), which showed a high DOC bioavailability of 80%. DOC in rainwater and wastewater also had high bioavailabilities (45%-50%), while DOM in the leaf litter leachate showed high aromaticity, average molecular weight, and humic content but low DOC bioavailability (12%). There was generally limited PE (<5% of the initial values) on the degradation of DOC and chromophoric DOM (CDOM) for most samples. Two humic-like components (C2 and C3) showed little PE, while the humic-like C1 and C6, tyrosine-like C5, and tryptophan-like C7 showed variable PE after adding rainwater, wastewater, and plant leachate. Overall, the results revealed that the DOM from typical natural and anthropogenic sources had different composition and bioavailability, and their inputs to aquatic environments would result in variable PE on the bulk DOC and different DOM components.

Effects of fish culture on particulate organic matter in a reservoir-type river as revealed by absorption spectroscopy and fluorescence EEM-PARAFAC.

Dam construction and fish culture can change the biogeochemical processes in river, yet their impact on the spectral properties of particulate organic matter (POM) remains to be studied. This was investigated in a reservoir-type river (Minjiang river, SE China) using absorption spectroscopy and fluorescence excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC). Five fluorescent components were identified from POM with PARAFAC. Four components C1-C4 were affected by the seasonal variations of rainfall and runoff, indicating the influences of hydrological condition and terrestrial inputs. The Chlorophyll a concentration (Chl a) correlated significantly with the humic-like C3 (p < 0.05) and the protein-like C4 (p < 0.01), indicating phytoplankton was an important source of C3 and C4. The Chl a and fluorescence intensities of C3-C4 were higher in the fish culture zones than in other areas, and the absorption coefficient a300 and C1-C4 were lower downstream the dam. These results indicated that fish farming in the reservoir probably promoted the production of POM. The a300 and C1 per unit mass of suspended particulate matter (a300/TSM and C1/TSM) correlated significantly with the median particle size (p < 0.01), which might be related to the contribution of micro-phytoplankton. The absorption spectra of POM showed a shoulder peak at ∼280 nm, and its intensity correlated significantly and positively with Chl a (p < 0.01). These results indicated that the peak was probably derived from phytoplankton production. Our results have implications for better understanding the influences of human activities on the dynamics of river POM.

Dual-Emissive Metal-Organic Framework as a Fluorescent "Switch" for Ratiometric Sensing of Hypochlorite and Ascorbic Acid.

The detection of hypochlorite (ClO-) content in tap water is extremely important because excess amounts of hypochlorite can convert into highly toxic species and inadequate amounts of hypochlorite cannot fully kill bacteria and viruses. Although several metal-organic frameworks (MOFs) have been successfully employed as fluorescent sensors for hypochlorite detection, all these sensors are based on single emission that responds to the dose of hypochlorite. Ratiometric sensors are highly desirable, which can improve the sensitivity, accuracy, and reliability via self-calibration. Herein, a nanoscale dual-emission multivariate 5-5-Eu/BPyDC@MOF-253-NH2 was synthesized by sequential mixed-ligand self-assembly and postsynthesis method. Among the two emission bands of 5-5-Eu/BPyDC@MOF-253-NH2, the strong blue emitting derived from ligands is sensitive to hypochlorite, while the red emitting derived from Eu(III) almost keeps invariable. Therefore, 5-5-Eu/BPyDC@MOF-253-NH2 was exploited as a fluorescent ratiometric nanosensor for "on-off" sensing of hypochlorite. Notably, the proposed sensing system showed an excellent performance including fast response (within 15 s), relative high specificity, wide linear range (0.1-30 µM), and low detection limit (0.094 µM). Besides, the suppressed blue emitting was recovered after the addition of ascorbic acid (AA) that consumes ClO- via the redox reaction. Therefore, 5-5-Eu/BPyDC@MOF-253-NH2 was further employed as a fluorescent ratiometric nanosensor for the "on-off-on" sensing of AA. This work represents the first MOF-based fluorescent "switch" for the ratiometric sensing of hypochlorite and the second for ratiometric sensing of AA.

Seasonal changes in the chemical composition and reactivity of dissolved organic matter at the land-ocean interface of a subtropical river.

Dissolved organic matter (DOM) is a critical component in aquatic ecosystems, yet its seasonal variability and reactivity remain not well constrained. These were investigated at the land-ocean interface of a subtropical river (Minjiang River, SE China), using absorption and fluorescence spectroscopy. The annual export flux of dissolved organic carbon (DOC) from the Minjiang River (5.48 × 1010 g year-1) was highest among the rivers adjacent to the Taiwan Strait, with 72% occurring in spring and summer. The freshwater absorption coefficient a280, DOC-specific UV absorbance SUVA254 and humification index HIX were higher, while the spectral slope S275-295 and biological index BIX were lower in summer than in winter. This suggests intensified export of terrestrial aromatic and high molecular weight constituents in the rainy summer season. Six fluorescent components were identified from 428 samples, including humic-like C1-C3, tryptophan-like C4 and C6, and tyrosine-like C5. The freshwater levels of four components (C1, C2, C4, and C6) were lower while that of C5 was higher in the wet season than in the dry season, suggesting contrasting seasonal variations of different constituents. Laboratory experiments were performed to assess the effects of photochemical and microbial degradation on DOM. Photo-degradation removed chromophoric and fluorescent DOM (CDOM and FDOM) effectively, which was stronger (i) for high molecular weight/humic constituents and (ii) during summer under higher solar radiation. Microbial degradation under laboratory controlled conditions generally showed little effect on DOC, and had smaller impact on CDOM and FDOM in winter than in summer. Overall, this study showed notable seasonal changes in the chemical composition and reactivity of DOM at the land-ocean interface, and demonstrated the significant effects of photo-degradation.

Zr-Based Metal-Organic Frameworks with Intrinsic Peroxidase-Like Activity for Ultradeep Oxidative Desulfurization: Mechanism of H2O2 Decomposition.

The restriction of sulfur content in fuels has become increasingly stringent as a result of the growing environmental concerns. Although several MOF-derived materials like POM@MOF composites have shown the ability to catalyze oxidative desulfurization (ODS), their catalytic activities inevitably obstructed by the encapsulated catalytic sites like POM due to the blockage of cavities. Therefore, MOFs with intrinsic and accessible catalytic sites are highly desirable for their applications in ultradeep ODS. Herein, four representative Zr-based MOFs (Zr-MOFs), namely, UiO-66, UiO-67, NU-1000, and MOF-808, were assessed for catalytic ODS. These MOFs were confirmed that they have peroxidase-like activity and can catalyze ODS with H2O2 as oxidant. Among them, MOF-808 showed the highest catalytic activity and it can fully desulfurize dibenzothiophene (DBT) in a model gasoline with a S concentration of 1000 ppm under 40 °C within 5 min. An extremely low apparent Arrhenius activation energy (22.0 KJ·mol-1) and an extraordinarily high TOF value (42.7 h-1) were obtained, ranking MOF-808 among the best catalysts for the catalytic DBT oxidation. Further studies confirmed that the excellent catalytic activity is mainly responsible for the high concentration of the accessible Zr-OH(H2O) catalytic sites decorated in MOF-808. The superoxide radicals (•O2-) and hydroxyl radicals (•OH) were identified and were proved to involve in the DBT oxidation. Besides, the effects of Brönsted and lewis acidity to the catalytic efficiency were also discussed. Based on the experimental results, a plausible mechanism concerning on Zr-OH(H2O) groups promoting the H2O2 decomposion in to both •O2- and •OH was first proposed. Moreover, MOF-808 can be facilely reused for at least eight runs without significant loss of its catalytic activity. By the integration of facile synthesis, high catalytic efficiency, and good stability, MOF-808 thus represents a new benchmark catalyst for catalytic oxidative desulfurization.

[Spatial Distribution and Degradation of CDOM in the Minjiang River in Summer].

The composition, distribution, and degradation of chromophoric dissolved organic matter (CDOM) in the lower reach and estuary of the Minjiang River were analyzed using fluorescence excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC) and microbial and photochemical degradation experiments. The results show that there are three types of fluorescence components in the study area:humic-like, tyrosine-like, and tryptophan-like. The humic-like components are the main components in the river zone, while the protein-like components become dominant with increasing salinity in the estuary. The change of the CDOM abundance shows a notable spatial distribution pattern. The absorption coefficient a(280) of CDOM is lower in the river, increases after entering the urban area, shows a decreasing trend in the suburbs, and rapidly declines in the estuary. A conservative estimate of the contribution of the Fuzhou urban area to the CDOM of the Minjiang River is 8%. The a(280) in the river is susceptible to microbial and photochemical degradation and the degradation percentages are (28±8)% and (44±7)%, respectively. The bioavailability and photochemical reactivity of a(280) are much higher in the river than in the estuary. The humic-like, tyrosine-like, and tryptophan-like components show a higher photochemical reactivity in the river, with degradation percentages of (75±0.5)%, (58±21)%, and (73±3)%, respectively. The fluorescent components are not labile with respect to microbial degradation and humic-like components are accumulated after 28 days of microbial culture.

Encapsulation of Phosphotungstic Acid into Metal-Organic Frameworks with Tunable Window Sizes: Screening of PTA@MOF Catalysts for Efficient Oxidative Desulfurization.

Clean fuels with extremely low sulfur content are highly desirable due to environmental concerns. Herein, three water-stable and eco-friendly metal-organic frameworks with tunable window diameters, denoted as MOF-808X, have been employed as PTA solid supports. An array of PTA@MOF-808X composites were facilely synthesized via the encapsulation strategy. With tunable window sizes and adjustable PTA loading amounts, the obtained PTA@MOF-808X composites were screened for catalytic oxidative desulfurization (ODS) with H2O2 serving as oxidant. The experiments found that 42%PTA@MOF-808A had the highest catalytic ODS activity and could completely remove dibenzothiophene (DBT) in a model fuel with an initial sulfur content of 1000 ppm within 30 min, which falls far below the acceptable limits for fuel standards (10 ppm). Further investigations revealed that this high catalytic activity could be attributed to the cooperative catalysis of metal clusters in the host framework and the guest PTA molecules. Moreover, 42%PTA@MOF-808A could be facilely recovered and reused for at least five runs without loss of catalytic activity. Having a combination of eco-sustainability, high stability, high catalytic activity, and good recyclability, 42%PTA@MOF-808A therefore represents a new benchmark material for catalytic ODS and provides a new perspective for ultradeep desulfurization.

Impacts of global changes on the biogeochemistry and environmental effects of dissolved organic matter at the land-ocean interface: a review.

Dissolved organic matter (DOM) is an important component in the biogeochemistry and ecosystem function of aquatic environments at the highly populated land-ocean interface. The mobilization and transformation of DOM at this critical interface are increasingly affected by a series of notable global changes such as the increasing storm events, intense human activities, and accelerating glacier loss. This review provides an overview of the changes in the quantity and quality of DOM under the influences of multiple global changes. The profound implications of changing DOM for aquatic ecosystem and human society are further discussed, and future research needs are suggested for filling current knowledge gaps. The fluvial export of DOM is strongly intensified during storm events, which is accompanied with notable changes in the chemical composition and reactivity of DOM. Land use not only changes the mobilization of natural DOM source pools within watersheds but also adds DOM of distinct chemical composition and reactivity from anthropogenic sources. Glacier loss brings highly biolabile DOM to downstream water bodies. The changing DOM leads to significant changes in heterotrophic activity, CO2 out gassing, nutrient and pollutant biogeochemistry, and disinfection by-product formation. Further studies on the source, transformations, and downstream effects of storm DOM, temporal variations of DOM and its interactions with other pollutants in human-modified watersheds, photo-degradability of glacier DOM, and potential priming effects, are essential for better understanding the responses and feedbacks of DOM at the land-ocean interface under the impacts of global changes.

Unveiling the transformation and bioavailability of dissolved organic matter in contrasting hydrothermal vents using fluorescence EEM-PARAFAC.

The submarine hydrothermal systems are extreme environments where active cycling of dissolved organic matter (DOM) may occur. However, little is known about the optical properties and bioavailability of hydrothermal DOM, which could provide valuable insights into its transformation processes and biogeochemical reactivity. The quantity, quality, and bioavailability of DOM were investigated for four very different hydrothermal vents east of Taiwan, using dissolved organic carbon (DOC), absorption spectroscopy, and fluorescence excitation-emission matrices-parallel factor analysis (EEM-PARAFAC). The DOC and absorption coefficient a280 were both lower in the two hydrothermal vents off the Orchid Island and on the Green Island than in the surrounding seawater and the two vents off the Kueishantao Island, indicating effective removals of DOM in the former two hydrothermal systems owing to possible adsorption/co-precipitation and thermal degradation respectively. The four hydrothermal DOM showed notable differences in the absorption spectral slope S275-295, humification index HIX, biological index BIX, EEM spectra, and the relative distributions of seven PARAFAC components. The results demonstrated a high diversity of chemical composition and transformation history of DOM under contrasting hydrothermal conditions. The little change in the hydrothermal DOC after 28-day microbial incubations indicated a low bioavailability of the bulk DOM, and different PARAFAC components showed contrasting bioavailability. The results have profound implications for understanding the biogeochemical cycling and environmental effects of hydrothermal DOM in the marine environments.

[Sample pretreatment for the measurement of phthalate esters in complex matrices].

Sample pretreatment methods for the measurement of phthalate esters (PAEs) by gas chromatography-mass spectrometry (GC-MS) in various complex matrices, including sediment, soil, suspended particle matter, urban surface dust, Sinonovacula Constricta, cosmet- ic, leather, plastic and coastal/estuarine seawater, were proposed. The pretreatment which was appropriate for GC-MS detection was focused on the investigation and optimization of oper- ating parameters for the extraction and purification, such as the extraction solvent, the eluant and the adsorbent of solid phase extraction. The results of the study of pretreatment for various complex matrices showed that methylene chloride was the best solvent for the ultrasonic extraction when solid-liquid extraction was used; silica gel was the economical and practical adsorbent for solid-phase extraction for purification; C18 was the most commonly adsorbent for preconcentration of PAE in coastal/estuarine seawater sample; the mixed solution of n-hexane and ethyl acetate with a certain proportion was the suitable SPE eluent. Under the optimized conditions, the spiked recoveries were above 58% and the relative standard deviations (RSDs) were less than 10.5% (n = 6). The detection limits (DL, 3σ) were in the range of 0.3 µg/kg (dibutyl phthalate)--5.2 µg/kg ( diisononyl phthalate) for sediment, and 6 ng/L (dipropyl phthalate)--67 ng/L (diisodecyl phthalate) for costal/estuarine seawater. The pretreatment meth- od for various complex matrices is prominent for the measurement of the 16 PAEs with GC-MS.

[Simultaneous determination of 19 phthalate esters in cosmetics using gas chromatography-mass spectrometry].

A method was developed for the simultaneous determination of 19 phthalate esters (PAEs) at trace level in cosmetics by solid phase extraction (SPE) purification and gas chromatography-mass spectrometry (GC-MS) detection. The PAEs were extracted from cosmetic samples by dichloromethane with ultrasonic-assisted technique, purified by an SPE column packed with silica gel and neutral alumina (2: 3, m/m) with the elution of 20 mL of mixed solvent of ethyl acetate-hexane (8: 2, v/v). Qualitative and quantitative analysis were carried out by GC-MS in full scan and selected ion monitoring modes. The retention time of quantitative ions and the abundance ratio of characteristic ions were applied to rapidly and accurately identify each analyte so as to prevent the occurring of possible mistakes from complex matrix intervention. Under optimized conditions, the average recoveries for a shampoo sample spiked with the standards at 0.1, 0.5, 2.0 microg/g were in the range of 72.2% and 110.9%, and the relative standard deviations (RSDs) for the 19 PAEs were less than 10.3% (n = 6) at the spiked level of 0.1 microg/g. The limits of detection (LODs, as 3 times of standard deviation) were between 0.0065 microg/g (for diisopentyl phthalate) and 0.062 microg/g (for diisobutyl phthalate). The method was successfully applied to the determination of the PAEs in 6 types of cosmetics. It is expected to promote the determination of the PAEs in other cosmetics with different matrices.