Spatiotemporal distribution and ecological risk assessment of pharmaceuticals and personal care products (PPCPs) from Luoma Lake, an important node of the South-to-North Water Diversion Project.

PPCPs (pharmaceuticals and personal care products) are widely found in the environment and can be a risk to human and ecosystem health. In this study, spatiotemporal distribution, critical risk source identification and potential risks of 14 PPCPs found in water collected from sampling points in Luoma Lake and its inflowing rivers in two seasons in 2019 and 2020 were investigated. The PPCPs concentrations ranged from 27.64 ng·L-1 to 613.08 ng·L-1 in December 2019, and from 16.67 ng·L-1 to 3287.41 ng·L-1 in April 2020. Ketoprofen (KPF) dominated the PPCPs with mean concentrations of 125.85 ng·L-1 and 640.26 ng·L-1, respectively. Analysis of sources showed that the pollution in Luoma Lake mostly originated from sewage treatment plant effluents, inflowing rivers and domestic wastewater. Among them, the inflowing rivers contributed the most (82.95%) to the concentration of total PPCPs. The results of ecological risk assessment showed that there was a moderate risk (0.1 < RQs < 1) from carbamazepine (CBZ) in December 2019 and a high risk (RQs > 1) from naproxen (NPX) in April 2020. The results of human risk assessment found that NPX posed a high risk to infant health, and we found that NPX was associated with 83 diseases according to Comparative Toxicogenomics Database. NPX was identified as a substance requiring major attention. The results provide an understanding of the concentrations and ecological risks of PPCPs in Luoma Lake. We believe the data will support environmental departments to develop management strategies and prevent PPCPs pollution.

Non-target screening and risk assessment of organophosphate esters (OPEs) in drinking water resource water, surface water, groundwater, and seawater.

By use of an integrated target, suspect, and non-target screening strategy, we investigated occurrence and spatial distribution of organophosphate esters (OPEs) in four types of water (drinking water resource water, surface water, groundwater, and seawater) collected from Jiangsu Province (China) in 2021 (n = 111). Eighteen out of 23 target OPEs were detectable at least once in these analyzed samples, and the total concentrations (Σ18OPEs) of OPEs in various water samples exhibited a descending order following as: groundwater (67026 ng/L) > surface water (35803 ng/L) > drinking water resource water (21055 ng/L) > seawater (17820 ng/L). The highest concentration detected in groundwater may be ascribed to pollution from surrounding factories. Among the target OPEs, triethyl phosphate (TEP), tris(chloroethyl) phosphate (TCEP), and tris (1-chloro-2-propyl) phosphate (TCIPP) were the most abundant congeners with the average concentrations of 407 ng/L, 143 ng/L, and 475 ng/L, respectively. Besides of 18 target OPEs, we further identified 17 suspect OPEs (3 of them were fully identified by authentic standards) on the basis of in-house suspect screening OPE database, and 2 non-target organophosphates (OPs) on the basis of feature fragments. One of these 2 non-target OPs was fully identified as bis(2-chloroethyl) 2-chloroethylphosphonate (B2CE2CEPP) by matching the retention time and MS/MS data with authentic standard, and the other one was preliminarily identified as 2,4,8,10-tetra-tert-butyl-6-methoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-one (TTBMDBDOPPO). We also observed that B2CE2CEPP shared a similar structure with TCEP, suggesting that they may have similar toxicological characteristics and commercial sources. The ecological and human health risk assessments indicated that all OPEs posed a low or negligible ecological risk to aquatic organisms (algae, crustacean, and fish), and negligible risk to human health except for trimethyl phosphate (TMP) in drinking water resource water.

Suspect Screening of Liquid Crystal Monomers (LCMs) in Sediment Using an Established Database Covering 1173 LCMs.

Recent studies have suggested that liquid crystal monomers (LCMs) are emerging contaminants in the environment, and knowledge of this class of substances is very rare. Here, we reviewed existing LCM-related documents, i.e., publications and patents, and established a database involving 1173 LCMs. These 1173 LCMs were further calculated for their physicochemical properties, i.e., persistence (P), bioaccumulation (B), long-range transport potential (LRTP), and Arctic contamination and bioaccumulation potential (ACBAP). We found that 476 out of them were P&B chemicals (99% of them were halogenated), and 320 of them could have ACBAP properties (67% of them were halogenated). This LCM database was further applied for suspect screening of LCMs in n = 33 sediment samples by use of gas chromatography coupled to quadrupole time-of-flight mass spectrometry (GC-QTOF/MS). We tentatively identified 26 LCM formulas, which could have 43 chemical structures. Two out of these 43 suspect LCM candidates, 1-butoxy-2,3-difluoro-4-(4-propylcyclohexyl) benzene (3cH4OdFP) and 1-ethoxy-2,3-difluoro-4-(4-pentyl cyclohexyl) benzene (5cH2OdFP), were fully confirmed by a comparison of unique GC and MS characteristics with their authentic standards. Overall, our present study expanded the previous LCM database from 362 to 1173, and 1173 LCMs in this database were calculated for their physicochemical properties. Meanwhile, taking n = 33 sediment samples as an exercise, we successfully developed a suspect screening strategy tailored for LCMs, and this strategy could have promising potential to be extended to other environmental matrices.

Enhanced ferrate oxidation of organic pollutants in the presence of Cu(II) Ion.

In this study, we found that the introduction of Cu(II) (several µM, close to the concentration level of some real water/wastewater) in ferrate (Fe(VI)) oxidation can remarkably accelerate the abatement of various organic pollutants under slightly alkaline conditions. The results show that 5 µM sulfamethoxazole (SMX) can be completely degraded by Fe(VI) (50 µM) in the presence of 20 µM Cu(II) within 10 min at pH 8.0, which was 1.65 times higher than that by Fe(VI) alone. High-valent iron intermediates (i.e. Fe(V), Fe(IV)) and Cu(III) were generated as reactive species in the Cu(II)/Fe(VI) system, all of which contributed to the enhanced oxidation of SMX. Common water components, except for HCO3- and humic acid, exhibited no influence on SMX removal. Additionally, the enhanced removal of SMX by Cu(II)/Fe(VI) was also observed in real water with the benefit of total removal of Cu(II) by the ferrate resultant particles. Due to the presence of highly reactive and selective oxidant, the Cu(II)/Fe(VI) system could react readily with organic pollutants containing electron-rich moieties, such as phenol, olefin or amino groups. This study provided a simple, selective, and practical strategy for the abatement of organic pollutants and a simultaneous removal of Cu(II).

[Occurrence Characteristics and Risk Assessment of Antibiotics in the Surface Water of Luoma Lake and Its Main Inflow Rivers].

The concentration levels of 39 antibiotics, including sulfonamides (SAs), quinolones (QUs), tetracyclines (TCs), macrolides (MLs), and penicillins (PLs), in the surface water of Luoma Lake, and its main inflow rivers were analyzed using SPE-UPLC-MS/MS. The contribution rates of pollution of major rivers entering the lake were analyzed, and the potential ecological and health risks of antibiotics were assessed. The results showed that ρ(antibiotics)in 42 sampling sites was between 30.10 ng·L-1 and 582.37 ng·L-1, and a total of four classes of 23 antibiotics were detected. Among them, the average detection concentration of enrofloxacin (ERX) was the highest (88.05 ng·L-1), and the detection rate of lincomycin (LIN) was the highest (100%). The average concentration of antibiotics in the northern region of Luoma Lake was higher than that in the south, and among the two main rivers entering the lake, Yihe River was the main river contributing to the pollution of antibiotics in Luoma Lake, with a contribution rate of 53.91%. The results of risk assessment showed that ERX had the largest risk quotient. For the cumulative risk quotient (RQcum), RQcum of L6, R30, R31, R32, R33, and R42 was between 0.1 and 1, which is considered medium risk, and RQcum of other points was>1, which is considered high risk. The health risk assessment of 11 antibiotics showed that the health risk quotient (RQH) of adults and children ranged from 4.16×10-6 to 2.46×10-3, and there was no health risk to the human body.

Occurrence, distribution, and risk assessment of bisphenol analogues in Luoma Lake and its inflow rivers in Jiangsu Province, China.

Bisphenol analogs (BPs) are widely used in industrial and commercial products and have been detected in surface water, sediment, sewage, and sludge. The presence of BPs in the natural environment poses threats to the aquatic ecosystem and human health. The concentration, distribution, seasonal variation, and risk assessment of BPA and BPA structural analogs including BPB, BPF, BPS, BPZ, BPAF, and BPAP in surface water and sediment during dry season and flood season in Luoma Lake and its inflow rivers in Jiangsu Province, China, were investigated in this study. The detection frequency of BPA and BPF was 100%. Although the use of BPA is restricted, BPA is still the dominant BPs in surface water and sediment. The concentration of BPs in surface water during flood season was higher than that in dry season. The concentrations of BPs in Fangting River, Zhongyun River, and Bulao River were higher than those in Luoma Lake. The average concentrations of BPs in surface water were in the order of BPA > BPF> BPS> BPB > BPZ > BPAF> BPAP. Compared with other studies, the concentration of BPs in Luoma Lake was moderate. There is no significant spatial distribution and difference in seasonal variation of BPs concentration in sediment (p > 0.05). Compared with other studies, the contamination of BPs in sediment of Luoma Lake was relatively low. Risk quotient (RQ) was used to evaluate the ecological risk of BPs in water environment, and the 17ß estradiol equivalent (EEQ) method was used to estimate the estrogenic activity of BPs. The risk assessment showed no high ecological risk (RQ < 1.0) and estrogenic risk (EEQ < 1.0 ng/L) in dry season and flood season. The estimated RQ and EEQt indicated that the ecological and human health impacts were negligible in the short term.

Distribution, abundance, and risk assessment of selected antibiotics in a shallow freshwater body used for drinking water, China.

With rapid improvements in industrialization and urbanization, antibiotics are now extensively used to prevent and treat human and animal diseases and husbandry and aquaculture. Some research has been conducted to assess the environmental distribution and risk level of antibiotics, but their distribution remains largely uncharacterized. Thus, this study investigated the distribution and abundance of 39 antibiotics belonging to five groups, and their associated risks in surface water around Luoma Lake in the north of Jiangsu province, China. Nineteen antibiotics were detected, at a detection frequency (DF) ranging from 2.27% to 100%. The total antibiotics (ΣABs) concentrations ranged from 34.91 to 825.93 ng/L, with a median concentration of 195.45 ng/L. Among these antibiotics, chlortetracycline (DF: 100%; median: 172.02 ng/L) was the dominant antibiotic, accounting for a median percentage of 91.0% of ΣABs concentrations. Spearman rank correlation method found a significant correlation between clindamycin (DF: 72.7%; median: 2.01 ng/L) and lincomycin (DF: 79.5%; median: 4.58 ng/L). The ecological risk quotient (RQ) values for two out of 44 sampling sites were higher than 1, indicating a high risk; 11.4% of the RQ values fell between 0.1 and 1, indicating a medium risk. Moreover, roxithromycin was found to be the dominant contributor to the ecological risk, accounting for a median of 79.7% of ΣABs. However, the total non-carcinogenic (<6.54 × 10-4) and carcinogenic risks (<1.64 × 10-7) of ΣABs were negligible at the detected concentrations.

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation.

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H2O2 oxidation process. The removal rate of TCEP in the UV/H2O2 system was 89.1% with the production of Cl- and PO43- of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H2O2 system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min-1 (R2=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO• and H2O and the oxidation reaction with H2O2 were found during the degradation pathway of 5 mg/L TCEP in the UV/H2O2 system. For the first time, environment risk was estimated via the "ecological structure activity relationships" program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H2O2 system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.

Enhanced Transformation of Emerging Contaminants by Permanganate in the Presence of Redox Mediators.

In this study, a permanganate/redox mediator system for enhanced transformation of a series of emerging contaminants was evaluated. The presence of various redox mediators (i.e., 1-hydroxybenzotriazole, N-hydroxyphthalimide, violuric acid, syringaldehyde, vanillin, 4-hydroxycoumarin, and p-coumaric acid) accelerated the degradation of bisphenol A (BPA) by Mn(VII). Since 1-hydroxybenzotriazole (HBT) exhibited the highest reactive ability, it was selected to further investigate the reaction mechanisms and quantify the effects of important reaction parameters on Mn(VII)/redox-mediator reactions with BPA and bisphenol AF (BPAF). Interestingly, not only HBT accelerated the degradation of BPA, but also BPA enhanced the decay of HBT. Evidence for the in situ formation of HBT· radicals as the active oxidant responsible for accelerated BPA and BPAF degradation was obtained by radical scavenging experiments and 31P NMR spin trapping techniques. The routes for HBT· radical formation involving Mn(VII) and the electron-transfer pathway from BPA/BPAF to HBT· radicals demonstrate that the Mn(VII)/HBT system was driven by the electron-transfer mechanism. Compared to Mn(VII) alone, the presence of HBT totally inhibited self-coupling of BPA and BPAF and promoted ß-scission, hydroxylation, ring opening, and decarboxylation reactions. Moreover, Mn(VII)/HBT is also effective in real waters with the order of river water > wastewater treatment plant (WWTP) effluent > deionized water.

Degradation of tri(2-chloroisopropyl) phosphate by the UV/H2O2 system: Kinetics, mechanisms and toxicity evaluation.

A photodegradation technology based on the combination of ultraviolet radiation with H2O2 (UV/H2O2) for degrading tri(chloroisopropyl) phosphate (TCPP) was developed. In ultrapure water, a pseudo-first order reaction was observed, and the degradation rate constant reached 0.0035 min-1 (R2 = 0.9871) for 5 mg L-1 TCPP using 250 W UV light irradiation with 50 mg L-1 H2O2. In detail, the yield rates of Cl- and PO43- reached 0.19 mg L-1 and 0.58 mg L-1, respectively. The total organic carbon (TOC) removal rate was 43.02%. The pH value of the TCPP solution after the reaction was 3.46. The mass spectrometric detection data showed a partial transformation of TCPP into a series of hydroxylated and dechlorinated products. Based on the luminescent bacteria experimental data, the toxicity of TCPP products increased obviously as the reaction proceeded. In conclusion, degradation of high concentration TCPP in UV/H2O2 systems may result in more toxic substances, but its potential application for real wastewater is promising in the future after appropriate optimization, domestication and evaluation.

[Pollution Characteristics and Health Risk Assessment of VOCs Fugitively Emitted from Typical Brewers].

Food processing plants are an important industrial source of volatile organic compounds (VOCs). Research on the unorganized emissions of VOCs to the surrounding environment from food processing plants is still quite scarce. The purpose of this study was to investigate the concentration characteristics, odor pollution, and health risk of the VOCs fugitively emitted from the brewing industry. The concentration characteristics of VOCs fugitively emitted from a typical vinegar factory and a typical distillery were detected via portable gas chromatography-mass spectrometry. The thresholds of the diluted multiple and sensory methods were also used for analyzing the VOCs. In addition, the assessment of health risk was conducted according to the US EPA evaluation model. The results show that the concentrations of the total VOCs emitted from the vinegar factory and the distillery were 0.968 mg·m-3 and 0.293 mg·m-3, respectively. Ethyl acetate and acetic acid were the main VOCs in the atmosphere of the vinegar plant, accounting for 76.3% and 13.5% of the total VOCs, respectively. The VOCs of the distillery were mainly characterized by ethanol and ethyl acetate, which accounted for 56.3% and 30.4% of the total VOCs, respectively. Oxygen-containing VOCs were the most important component of the studied brewing industry source. The total odor indices of the VOCs emitted from the vinegar factory and the distillery were both higher than 1, which indicates that their unorganized emission of VOCs have odor pollution to the atmosphere. The odor concentrations of the vinegar factory and the distillery were also higher than the standard limit of malodorous pollutants. The results of the health risk assessment show that the carcinogenic risk indices of VOCs were 2.45×10-6 and 5.25×10-6, respectively, which exceeded the suggested risk value by the EPA but were lower than the OSHA and ICRP values.

[Contamination Levels and Ecological Risk Assessment of Phthalate Esters (PAEs) in the Aquatic Environment of Key Areas of Taihu Lake].

To better understand phthalate esters (PAEs) pollution in key areas of Taihu Lake, water and sediment samples were collected for content analysis. The concentrations of ∑PAEs in water samples from wet, dry, and normal seasons ranged 1.6-11.2 µg·L-1 (mean:3.68 µg·L-1), nd-6.21 µg·L-1 (mean:1.3 µg·L-1), and nd-1.72 µg·L-1 (mean:0.48 µg·L-1), respectively. No differences were found between upstream and downstream samples. DEHP was the predominant component in water samples, whereas DBP exceeded the national surface water environmental quality standards. The total PAE concentration in the sediment ranged between 0.74 and 6.90 µg·g-1 (mean:2.64 µg·g-1), with DBP and DEHP the predominant PAEs. The risk quotient (RQ) results showed that DBP and DEHP contributed the most potentially adverse effects to the aquatic environment in the key areas. The contents of PAEs in sediment were all less than the ERLs, thus posing no significant threat to aquatic organisms. The overall level of PAEs in the study area was moderate compared to those in other areas, including rivers, lakes, and estuaries from cities worldwide. Industrial pollution and urban activities are the major sources of PAEs in the aquatic environment of key areas of Taihu Lake.

Analysis of trace-level nitrated polycyclic aromatic hydrocarbons in water samples by solid-phase microextraction with gas chromatography and mass spectrometry.

A solid-phase microextraction coupled with gas chromatography and mass spectrometry method has been developed for the determination of ten nitrated polycyclic aromatic hydrocarbons in water samples. Five different kinds of commerical fibers were used to compare the extraction efficiency, including 65 µm polydimethylsiloxane/divinylbenzene, 100 µm polydimethylsiloxane, 30 µm polydimethylsiloxane, 7 µm polydimethylsiloxane, and 85 µm polyacrylate fibers. Five factors were also selected to optimize conditions, including extraction temperature, time, stirring speed, salt concentration, and headspace volume. Taguchi design was applied to design the experiments and obtain the best parameters. The results show that 65 µm polydimethylsiloxane/divinylbenzene fiber directly immersed into aqueous solution for 35 min at 55°C with a constant stirring rate of 1150 rpm were the optimal conditions. Under these conditions, the limits of quantification were 0.007-0.063 µg/L, and the relative standard deviation based on six replicates ranged from 2.8 to 9.5%. The spiked recoveries ranged from 69.1 to 110.1%. Intra- and inter day relative standard deviations at three concentration levels were less than 12%, and the recoveries were 66.4-111.5%. The proposed method is reliable for analyzing nitrated polycyclic aromatic hydrocarbons in different water samples.

Assessing bioaccessibility and bioavailability of chlorinated organophosphorus flame retardants in sediments.

The distribution of chlorinated organophosphate flame retardants (OPFRs) in sediments has been well documented, but the study about their bioavailability remains lacking. This study investigated the applicability of solid phase microextraction (SPME) fiber and Tenax extraction to predict the bioavailability of two chlorinated OPFRs: tri(2-chloroisopropyl) phosphate and tri(1,3-dichloro-2-isopropyl) phosphate, in sediments. Our results showed that both SPME fiber and Tenax extracted concentrations correlated significantly with the measured concentrations in the aquatic worm (Lumbriculus variegatus). We also measured the Tenax extracted concentrations at 6 and 24 h, and a strong linear relationship between these two time durations was found. In addition, the 6-h Tenax extracted concentrations also significantly correlated with the SPME fiber extracted concentrations, and the Tenax extracted concentrations were much higher than the SPME fiber extracted concentrations. These results demonstrate the efficiency of SPME and Tenax extraction methods to predict the bioavailability of chlorinated OPFRs in sediments, and it was found that the Tenax extraction is more promising than the SPME extraction.

Efficient degradation of Acid Orange 7 in aqueous solution by iron ore tailing Fenton-like process.

An effective method based on iron ore tailing Fenton-like process was studied for removing an azo dye, Acid Orange 7 (AO7) in aqueous solution. Five tailings were characterized by X-ray fluorescence spectroscope (XFS), Brunner-Emmet-Teller (BET) measurement, and Scanning Electron Microscope (SEM). The result of XFS showed that Fe, Si and Ca were the most abundant elements and some toxic heavy metals were also present in the studied tailings. The result of BET analysis indicated that the studied tailings had very low surface areas (0.64-5.68 m(2) g(-1)). The degradation efficiencies of AO7 were positively correlated with the content of iron oxide and cupric oxide, and not related with the BET surface area of the tailings. The co-existing metal elements, particularly Cu, might accelerate the heterogeneous Fenton-like reaction. The effects of other parameters on heterogeneous Fenton-like degradation of AO7 by a converter slag iron tailing (tailing E) which contains highest iron oxide were also investigated. The tailing could be reused 10 times without significant decrease of the catalytic capacity. Very low amount of iron species and almost undetectable toxic elements were leached in the catalytic degradation of AO7 by the tailing E. The reaction products were identified by gas chromatography-mass spectrometry and a possible pathway of AO7 degradation was proposed. This study not only provides an effective method for removing azo dyes in polluted water by employing waste tailings as Fenton-like catalysts, but also uses waste tailings as the secondary resource.

Determination of organophosphorus flame retardants in fish by pressurized liquid extraction using aqueous solutions and solid-phase microextraction coupled with gas chromatography-flame photometric detector.

A novel method was developed for the determination of organophosphorus flame retardants (PFRs) in fish. The method consists of a combination of pressurized liquid extraction (PLE) using aqueous solutions and solid-phase microextraction (SPME), followed by gas chromatography-flame photometric detector (GC-FPD). The experimental parameters that influenced extraction efficiency were systematically evaluated. The optimal responses were observed by extracting 1g of fish meat with the solution of water:acetonitrile (90:10, v/v) at 150°C for 5min and acid-washed silica gel used as lipid sorbent. The obtained extract was then analyzed by SPME coupled with GC-FPD without any additional clean-up steps. Under the optimal conditions, the proposed procedure showed a wide linear range (0.90-5000ngg(-1)) obtained by analyzing the spiked fish samples with increasing concentrations of PFRs and correlation coefficient (R) ranged from 0.9900 to 0.9992. The detection limits (S/N=3) were in the range of 0.010-0.208ngg(-1) with standard deviations (RSDs) ranging from 2.0% to 9.0%. The intra-day and inter-day variations were less than 9.0% and 7.8%, respectively. The proposed method was successfully applied to the determination of PFRs in real fish samples with recoveries varying from 79.8% to 107.3%. The results demonstrate that the proposed method is highly effective for analyzing PFRs in fish samples.

Development of pressurized liquid extraction and solid-phase microextraction combined with gas chromatography and flame photometric detection for the determination of organophosphate esters in sediments.

Organophosphate esters have been extensively used as flame retardants and plasticizers. The analysis of organophosphate esters in the environment is a hot topic because many of them are toxic and persistent. We developed a novel procedure for determining organophosphate esters in sediment. In this work, pressurized liquid extraction and solid-phase microextraction are used for sample preparation to extract and concentrate the analytes, which are then analyzed by gas chromatography with flame photometric detection. The extraction parameters of pressurized liquid extraction were investigated and optimized by orthogonal design and then evaluated by range analysis and analysis of variance. Under the optimal conditions, the proposed procedure showed wide linear ranges (0.90-100 ng/g) with correlation coefficients ranging from 0.9921 to 0.9990. The detection limits of the method were in the range of 0.009-0.280 ng/g with standard deviations ranging from 2.2 to 9.5%. Recoveries of the proposed method ranged from 82.3 to 108.9% with relative standard deviations <8.4%. The obtained method was applied successfully to the determination of organophosphate esters in real sediments with recoveries varying from 79.8 to 107.3%. The proposed method was proved to be simple, easy, and sensitive for analyzing organophosphate esters in sediment samples.

Solid-phase microextraction based on polyaniline doped with perfluorooctanesulfonic acid coupled to HPLC for the quantitative determination of chlorophenols in water samples.

A porous and highly efficient polyaniline-based solid-phase microextraction (SPME) coating was successfully prepared by the electrochemical deposition method. A method based on headspace SPME followed by HPLC was established to rapidly determine trace chlorophenols in water samples. Influential parameters for the SPME, including extraction mode, extraction temperature and time, pH and ionic strength procedures, were investigated intensively. Under the optimized conditions, the proposed method was linear in the range of 0.5-200 µg/L for 4-chlorophenol and 2,4,6-trichlorophenol, 0.2-200 µg/L for 2,4-dichlorophenol and 2-200 µg/L for 2,3,4,6-tetrachlorophenol and pentachlorophenol, with satisfactory correlation coefficients (>0.99). RSDs were <15% (n = 5) and LODs were relatively low (0.10-0.50 µg/L). Compared to commercial 85 µm polyacrylate and 60 µm polydimethylsiloxane/divinylbenzene fibers, the homemade polyaniline fiber showed a higher extraction efficiency. The proposed method has been successfully applied to the determination of chlorophenols in water samples with satisfactory recoveries.

Mixed hemimicelles solid-phase extraction based on ionic liquid-coated Fe3O4/SiO2 nanoparticles for the determination of flavonoids in bio-matrix samples coupled with high performance liquid chromatography.

A novel magnetic solid-phase extraction (MSPE) method based on mixed hemimicelles of room temperature ionic liquids (RTILs) coated Fe3O4/SiO2 nanoparticles (NPs) was developed for simultaneous extraction of trace amounts of flavonoids in bio-matrix samples. A comparative study on the use of RTILs (C16mimBr) and CTAB-coated Fe3O4/SiO2 NPs as sorbents was presented. Owing to bigger adsorption amounts for analytes, RTILs-coated Fe3O4/SiO2 NPs was selected as MSPE materials and three analytes luteolin, quercetin and kaempferol can be quantitatively extracted and simultaneously determined coupled with high performance liquid chromatography (HPLC) in urine samples. No interferences were caused by proteins or endogenous compounds. Good linearity (R(2)>0.9993) for all calibration curves was obtained, and the limits of detection (LOD) for luteolin, quercetin and kaempferol were 0.10 ng/mL, 0.50 ng/mL and 0.20 ng/mL in urine samples, respectively. Satisfactory recoveries (93.5-97.6%, 90.1-95.4% and 93.3-96.6% for luteolin, quercetin and kaempferol) in biological matrices were achieved. It was notable that while using a small amount of Fe3O4/SiO2 NPs (4.0 mg) and C16mimBr (1.0 mg), satisfactory preconcentration factors and extraction recoveries for the three flavonoids were obtained. To the best of our knowledge, this is the first time a mixed hemimicelles MSPE method based on RTILs and Fe3O4/SiO2 NPs magnetic separation has ever been used for pretreatment of complex biological samples.

Determination of organophosphate esters in water samples using an ionic liquid-based sol-gel fiber for headspace solid-phase microextraction coupled to gas chromatography-flame photometric detector.

A simple, low-cost and sensitive method for determining organophosphate esters (OPEs) in water samples has been developed based on headspace solid-phase microextraction (SPME) followed by gas chromatography-flame photometric detector. The ionic liquid (1-allyl-3-methylimidazolium tetrafluoroborate, [AMIM][BF4])-based coating was developed by sol-gel technology and employed for extracting analytes. The prepared coating performed stably at high temperatures (up to 335°C) and with a range of solvents. It can be used at least 200 times without an obvious decrease in extraction efficiency. The extraction capability of the new fiber was much higher than polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polyacrylate (PA) fibers. The experimental parameters that influenced the extraction efficiency, including extraction time, extraction temperature, stirring rate and ionic strength were investigated and optimized. Under the optimal conditions, the method detection limits (S/N=3) were in the range of 0.7-12ngL(-1), and the limits of quantification (S/N=10) were between 1.0 and 28ngL(-1). The repeatability of a single fiber varied from 3.3 to 7.6% (intra-day precision, n=6) and 4.3 to 8.9% (inter-day precision, n=6). The reproducibility of fiber-to-fiber (n=6) was in the range of 3.1-9.4%. The proposed method was applied successfully for the determination of OPEs in lake water, wastewater, sewage treatment plant effluent, and tap water with recoveries varying from 75.2 to 101.8%. The results demonstrate that the proposed method is highly effective for analyzing OPEs in water samples.