High-throughput analytical methodology of monoalkyl phthalate esters and the composite risk assessment with their parent phthalate esters in aquatic organisms and seawater.

A sensitive, robust, and highly efficient analytical methodology involving solid phase extraction coupled to ultra-high performance liquid chromatography tandem mass spectrometry was successfully established to detect 13 monoalkyl phthalate esters (MPAEs) in aquatic organisms and seawater. After the organisms were preprocessed using enzymatic deconjugation with ß-glucuronidase, extraction, purification, and qualitative and quantitative optimization procedures were performed. Under optimal conditions, the limits of detection varied from 0.07 to 0.88 µg/kg (wet weight) and 0.04-1.96 ng/L in organisms and seawater, respectively. Collectively, MPAEs achieved acceptable recovery values (91.0-102.7%) with relative standard deviations less than 10.4% and matrix effects ranging from 0.93 to 1.07 in the above matrix. Furthermore, MPAEs and phthalate esters were detected by the developed methodology and gas chromatography-triple quadrupole tandem mass spectrometer in practical samples, respectively. Mono-n-butyl phthalate and mono-iso-butyl phthalate were the most predominant congeners, accounting for 24.8-35.2% in aquatic organisms and seawater. Comprehensive health and ecological risks were higher after the MPAEs were incorporated than when phthalate esters were considered separately, and greater than their risk threshold. Therefore, the risks caused by substances and their metabolites in multiple media, with analogous structure-activity relationships, should be considered to ensure the safety of aquatic organisms and consumers.

A novel sample preparation method based on polarity grouping for comprehensive determination of 315 pesticides and other contaminants in wolfberry by liquid chromatography-tandem mass spectrometry.

A novel sample preparation method based on polarity grouping was developed for the comprehensive determination of 315 undesirable low-weight organic pollutants ranging from polar to weakly polar in wolfberry. The method involves the swelling of the sample in ammonium acetate buffer, two-phase extraction, three-phase extraction, and dispersive solid phase extraction (D-SPE) with the assistance of low-temperature centrifugation and analysis by ultrahigh performance liquid chromatography coupled with electrospray ionization tandem mass (UHPLC-ESI-MS-MS) by using the multiple reaction monitoring mode. The recoveries of the analytes with wide range of polarity were satisfactory. The matrix-fortified standard calibration curves were compared for quantification. The results of linearity were satisfactory with linear regression coefficients (R) ranging from 0.9901 to 1.000. The limits of quantification ranged from 1 µg/kg to 10.0 µg/kg, indicating the compliance of products with legal tolerances. The average recoveries for spiked wolfberry were in the range of 69.3 %-145.2 % with RSD values of 0.2 %-28.6 %. The inter-day precision was in the range of 0.2 %-27.0 %. For over 90 % of the analytes, the recoveries were 70 %-120 % with RSD values below 20 %. The application of this method in routine monitoring programs would imply a drastic reduction of both effort and time.

Transcriptome sequencing and metabolite analysis reveal the single and combined effects of microplastics and di-(2-ethylhexyl) phthalate on Peneaus vannamei.

Due to the rising usage of plastics, plastic debris are present throughout marine ecosystems and detrimentally affects marine biota. Additionally, plastics likely result in elusive toxicity effects due to addition of plasticizers. The aim of the present study was to reveal the potential effects and mechanism of microplastics (MPs), di-(2-ethylhexyl) phthalate (DEHP) and copollution of MPs and DEHP (MPs-DEHP) on Peneaus vannamei (P. vannamei) juveniles regarding oxidative stress, transcriptomics and metabolomics. MPs, DEHP and MPs-DEHP significantly induced the activities of superoxide dismutase (SOD) and catalase (CAT); MPs and DEHP have an antagonistic effect for malondialdehyde (MDA); suggesting that disorders of the antioxidant defence systems. 13, 133 and 58 differentially expressed genes and 21, 82 and 39 differentially expressed metabolites were responsible for the distinction of MPs, DEHP and MPs-DEHP groups, respectively. The combination of transcriptomic and metabolomic analyses showed that MPs, DEHP and MPs-DEHP exposure disturbed amino acid and lipid metabolism, and further induced inflammatory responses and dysfunction of purine metabolism. Furthermore, the presence of MPs might alleviate the biotoxicity of DEHP in P. vannamei. These findings provide new insights into the single and combined toxicological effects of MPs and additives for marine biota.

Development and application of tricolor ratiometric fluorescence sensor based on molecularly imprinted nanoparticles for visual detection of dibutyl phthalate in seawater and fish samples.

A tricolor ratiometric fluorescence sensor was fabricated by mixing blue- and red-emission molecularly imprinted quantum dots (MIP-QDs) with green-emission quantum dots at the optimal ratio. The MIP-QDs were synthesized by coating CdSe/ZnS QDs in polymer by inverse microemulsion method. Compared with single-emission or dual-emission sensors, the tricolor ratiometric fluorescence sensor provided a wider range of color variations for visual DBP detection. The ratio fluorescence value I530/(I450 + I630) of the tricolor ratiometric fluorescence sensor linearly changed within the concentration of 2.0-20.0 × 103 µg/L DBP. The correlation coefficient was 0.9910, and the limits of detection were 1.0 µg/kg and 0.65 µg/L in fish and seawater, respectively. Meanwhile, the fluorescence color gradually changed from purple to plum to pink to salmon to yellowish green and finally to green. The recoveries of DBP in fish and seawater were 84.3 %-91.4 % and 88.3 %-110.3 %, respectively. Moreover, no obvious differences were observed between the detection results of the tricolor ratiometric fluorescence sensor and gas chromatography-tandem mass spectrometry. The tricolor ratiometric fluorescence sensor constructed herein provides an ideal choice for rapid and intuitive DBP detection in environmental and aquatic products.

Organophosphate esters in the mariculture ecosystem: Environmental occurrence and risk assessments.

Most investigations on organophosphate esters (OPEs) are conducted predominantly in a separate biological or abiotic medium, and few joint analyses have been performed in the mariculture ecosystem based on yearly sampling. Herein, we investigated the occurrence, load estimation, phase distribution, source diagnostics, and risks of 20 OPEs in seawater, sediment, and aquaculture organisms from a typical mariculture area in China. The total of these OPEs (∑OPEs) ranged within 3.97-1068 ng/L, 0.39-65.5 ng/g (dw), and 4.09-16.3 ng/g (ww) in seawater, sediment and organisms, respectively. Chlorinated OPEs were the predominant congeners detected in seawater, whereas alkyl-OPEs were the leading contributors in sediment and biological samples. Seasonal variations of ∑OPEs in seawater were more distinct than those in sedimentary environments. Load estimation indicated that approximately 70% of the OPEs in the study area existed in the water bodies. Source identification performed using the U.S. EPA positive matrix factorization indicated that polyurethane foam/plastics and hydraulic oil made the greatest contributions in seawater, whereas chemical production was the predominant source in sediment. Indices of ecological and health risks of OPEs were lower than their risk threshold, indicating that the OPEs detected in this study posed a low risk to the aquatic environment and human health.

Highly selective molecularly imprinted-electrochemiluminescence sensor based on perovskite/Ru(bpy)32+ for simazine detection in aquatic products.

A novel molecularly imprinted electrochemiluminescence (MIECL) sensor based on the luminescence of molecularly imprinted polymer-perovskite (MIP-CsPbBr3) layer and Ru(bpy)32+ was fabricated for simazine detection. MIP-CsPbBr3 layers were immobilized onto the surface of glassy carbon electrode as the capture and signal amplification probe, and Ru(bpy)32+ and co-reactant tripropylamine exhibited stronger electrochemiluminescence (ECL) emission. Under optimal conditions, the ECL signal of the MIECL sensor was linearly quenched, with the logarithm of simazine concentration ranging from 0.1 µg/L to 500.0 µg/L, correlation coefficient of 0.9947, and limit of detection of 0.06 µg/L. The practicality of the developed MIECL sensor method for simazine determination in aquatic samples was validated. Excellent recoveries of 86.5 %-103.9 % with relative standard deviation below 1.6 % were obtained for fish and shrimp samples at three different spiked concentrations. The MIECL sensor exhibited excellent selectivity, sensitivity, reproducibility, accuracy, and precision for simazine determination in actual aquatic samples.

A generic and rapid analytical method for comprehensive determination of veterinary drugs and other contaminants in raw honey.

A generic, rapid, simple and low-cost analytical method for simultaneously screening and confirming 400 veterinary drugs and other contaminants in raw honey was developed. The method was based on one-step extraction and ultra-high performance liquid chromatography coupled with electrospray ionization and tandem mass spectrometry. A well-designed extraction method results in the complete precipitation of proteins and separation of analytes from carbohydrates and reduces the time and cost of analysis by covering polar to non-polar analytes. Optimized pretreatment processes lead to no significant interference on analysis from complicated sample matrix. Competent linearity was found for all of target compounds with linear regression coefficients (R) higher than 0.99. Detection limits ranged from 0.05 µg/kg to 10 µg/kg. Average recovery rates spiked in raw honey and ranged from 57.3% to 139.8%, and associated relative standard deviation values ranged from 0.4% to 25.2% under selected conditions. The extraction sensitivity, linearity, recovery, and precision of the method were validated. The results clearly demonstrated the feasibility of using this approach in raw honey purchase. The application of this method, which improved efficiency and the coverage of residues, may considerably reduce effort and time in routine monitoring programs.

Ultrasensitive electrochemiluminescence sensor based on perovskite quantum dots coated with molecularly imprinted polymer for prometryn determination.

A highly effective molecularly imprinted electrochemiluminescence sensor was constructed for prometryn determination in environmental and biological samples by using perovskite quantum dots coated with a molecularly imprinted silica layer (MIP/CsPbBr3-QDs) as the recognition and response element. MIP/CsPbBr3-QDs were immobilized on a glassy carbon electrode (GCE) through electropolymerization, and the electrochemiluminescence (ECL) response of MIP/CsPbBr3-QDs could be motivated under the condition of H2O2 as co-reactant. ECL signal was selectively quenched with prometryn by hindering electron transfer and directly proportional to the logarithm of prometryn concentration (0.10-500.0 µg/L) with a correlation coefficient of 0.9960. Limits of detection in fish and seawater samples were 0.010 µg/kg and 0.050 µg/L, respectively. Excellent recoveries of 88.0%-106.0% were acquired for fish and seawater samples with a relative standard deviation below 4.2%. The constructed MIECL sensor based on MIP/CsPbBr3-QDs showed good stability, accuracy, and precision for sensitive detection of prometryn in aquaculture products and environmental samples.

Probing the contamination characteristics, mobility, and risk assessments of typical plastic additive-phthalate esters from a typical coastal aquaculture area, China.

Contamination characteristics, equilibrium partitioning and risk assessment of phthalate esters (PAEs) were investigated in seawater, sediment and biological samples collected from the Xiangshan Bay area during an annual investigation between January and November 2019. PAE concentrations detected in the mariculture environment in surface seawater, sediment, and biological samples were 172-3365 ng/L, 190-2430 µg/kg (dry weight [dw]), and 820-4926 µg/kg (dw), respectively. The dominant congeners in different media included di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), and di(2-ethylhexyl) phthalate (DEHP). The inner bay and the bay mouth were the gathering area of PAEs and heavily influenced by the mariculture activities, river inputs, and anthropogenic activities. The bioaccumulation of PAEs demonstrated benthic feeding fishes with relatively high trophic levels concentrated high levels of phthalates. The mobility of PAEs in sediment-seawater showed that the transfer tendency of low-molecular weight species was from the sediment to the water, which was in contrast with those of high-molecular weight PAEs. DEHP, DiBP and DnBP had various degrees of ecological risks in the aquatic environment, whereas only the DiBP posed potential risks in sediments. The current assessment of carcinogenic and noncarcinogenic risks posed by fish consumption were within acceptable limits for humans.

A comprehensive study of the effects of phthalates on marine mussels: Bioconcentration, enzymatic activities and metabolomics.

In this study, marine mussels (Mytilus coruscus) were exposed to three typical PAEs (dimethyl phthalate [DMP], dibutyl phthalate [DBP] and di(2-ethylhexyl) phthalate [DEHP]) at a range of doses for different times to investigate the ecotoxicological effects. The accumulation of the three PAE congeners in M. coruscus exhibited the following trend: DEHP > DBP > DMP. The antioxidant response of mussel gonadal tissue was enhanced with increasing concentrations of PAEs. For the DBP and DEHP treatment groups, glutathione (GSH) worked in concert with antioxidant enzymes to protect cells against reactive oxygen species (ROS), while GSH played a prominent antioxidant role in the DMP-treated group. The metabolomics results revealed that PAE exposure disrupted the metabolic balance of mussels. Overall, PAEs affect the amino acid metabolism, lipid metabolism, energy metabolism, osmoregulation and nerve activities of mussels. Our results provide further insight into the toxicological effects of PAEs on marine organisms.

Comparative evaluation of high-density polyethylene and polystyrene microplastics pollutants: Uptake, elimination and effects in mussel.

The high-density polyethylene (HDPE) and the polystyrene (PS), which are typical microplastic contaminants, are frequently detected in the environment and have potential hazard to environmental health. In this study, the accumulation, elimination, tissue distribution and potential effects of the HDPE and the PS in the mussels (Mytilus galloprovincialis) were evaluated. The HDPE and the PS were found in various tissues (digestive gland > gill > gonad ≈ muscle) with no difference in distribution patterns. The accumulation of the HDPE and the PS rapidly increased in the first 48 h exposure, and the accumulation of HDPE was higher than that of PS. After 144 h of elimination, most of the HDPE and the PS were cleared by mussels. In addition, the activities of superoxide dismutase (SOD), catalase (CAT) and the content of oxidized glutathione considerably increased, indicating that the HDPE and the PS induced oxidative stress and prevented oxidative damage in elimination. The metabolomic analysis suggested that exposure to HDPE and PS induced alterations in the metabolic profiles of mussel. Differential metabolites were involved in energy metabolism, lipid metabolism, tricarboxylic acid cycle and neurotoxic response., and Meanwhile, the PS had a lower effect on mussel metabolism during elimination, but the effect of HDPE was increased. Overall, this study elucidated that the HDPE and the PS caused adverse effects on the mussels and provided insights toward understanding the hazard of different microplastics on aquatic organisms.

Contaminant occurrence, mobility and ecological risk assessment of phthalate esters in the sediment-water system of the Hangzhou Bay.

The pollution characteristics, spatiotemporal variation, sediment-water partitioning, and potential ecological risk assessment of phthalate esters (PAEs) in the sediment-seawater system of the Hangzhou Bay (HZB) in summer and autumn were researched. The sum of the concentrations of the 10 PAEs in seawater ranges from 7305 ng/L to 22,861 ng/L in summer and from 8100 ng/L to 33,329 ng/L in autumn, with mean values of 15,567 ± 4390 and 17,884 ± 6850 ng/L, respectively. The Σ16PAEs in the sediments are between 118 and 5888 µg/kg and 145 and 4746 µg/kg in summer and autumn, respectively. The level of PAEs in seawater varies with the seasons, but it is relatively stable in the sediments. Di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DnBP), and diisobutyl phthalate (DiBP) are the predominant PAE congeners in the HZB. The DnBP and DiBP concentrations in seawater are greater than the DEHP concentration, which is the opposite in the sediments. The sediment-seawater equilibrium distribution study indicates that the PAEs with medium molecular weights, such as DiBP, butyl benzyl phthalate, and DnBP, are near dynamic equilibrium in the sediment-seawater system; PAEs with high molecular weights (e.g., di-n-octyl phthalate and DEHP) tend to transfer from water to the sediments; and PAEs with low molecular weights (e.g., dimethyl phthalate, diethyl phthalate, and diamyl phthalate) tend to spread to seawater. The risk assessment results in seawater indicate that DEHP and DiBP might pose high potential risks to sensitive organisms, and DnBP might exhibit medium ecological risks. In the sediment, DiBP might display a high potential risk to fish, and the potential risk of DEHP is high in several sites.

Aquaculture-derived distribution, partitioning, migration, and transformation of atrazine and its metabolites in seawater, sediment, and organisms from a typical semi-closed mariculture bay.

Atrazine (ATR) is one of the most commonly used herbicides that could directly impair the growth and health of organisms in mariculture areas and adversely affect human health through the food chain. This study investigated the contaminant occurrence, migration, and transformation of ATR and three of its chlorinated metabolites, namely deethylatrazine (DEA), deisopropylatrazine (DIA), and didealkylatrazine (DDA), in surface seawater, sediment, and aquatic organisms from the Xiangshan Harbor. ATR was detected in all samples, while DIA and DDA were only respectively detected in aquatic and seawater samples. The distribution of ATR and its metabolites presented different patterns depending on the geographic location and showed a higher level in the aquaculture area than that in the non-aquaculture area. The bioaccumulation of ATR in aquaculture organisms showed that benthic organisms, such as Ditrema, and Sinonovacula constricta (Sin), had increased levels. The ecological risks indicated that ATR posed medium or high risks to algae in the water phase of the study area. The microcosm experiment showed that the main fate of ATR in the simulated microenvironment was sedimentation, which followed the first-order kinetic equation. The ATR in the sediment could be enriched 3-5 times in Sin, and its major metabolites were DEA and DIA.

A novel sample-preparation method for the generic and rapid determination of pesticides and mycotoxins in tea by ultra-performance liquid chromatography-tandem mass spectrometry.

A rapid, simple, and generic analytical method for the simultaneous determination of 140 undesirable low-weight pesticides and mycotoxins from different chemical classes in black tea was developed. The method involved swelling the sample in ammonium acetate buffer, extraction with acetonitrile-dimethyl sulfoxide, cleanup by dual dispersive solid-phase extraction (D-SPE) with the assistance of low-temperature centrifugation, and analysis by ultraperformance liquid chromatography coupled with electrospray ionization tandem mass spectrometry using multiple reaction monitoring mode. The interferences in the extract were eliminated by the combination of dual d-SPE using only C18 sorbent and anhydrous magnesium sulfate, which maintained the chromatographic column under the ideal condition for a long time and enabled satisfactory recoveries of hydrophobic and hydrophilic analytes simultaneously. Matrix-matched calibration curves were obtained for most target compounds with linear regression coefficients above 0.9900. The limits of quantification (LOQs) ranged within 0.5-10.0 µg/kg, which were usually sufficient to verify the compliance of products with legal tolerances. Satisfactory recoveries of 64.5%-138.1% were obtained in black ta samples with the relative standard deviation (RSD) values between 1.8 and 25.9%. The inter-day precision ranged within 2.2%-24.9%. For over 90% of the analytes, the recoveries were between 70% and 120%, with RSD values below 15.0%. The application of this method in routine monitoring programs can drastically reduce effort and time.

Pollution characteristics, spatial variation, and potential risks of phthalate esters in the water-sediment system of the Yangtze River estuary and its adjacent East China Sea.

Spatiotemporal variability in seawater, spatial variation in sediment, pollution characteristics, and risks related to 16 phthalate esters (PAEs) were investigated in the Yangtze River estuary and its adjacent East China Sea. The total concentrations of ΣPAEs in surface water were 0.588-17.7 µg L-1 in summer, 2.63-22.9 µg L-1 in winter, and 1.93-20.7 µg L-1 in spring, with average values of 2.05, 10.2, and 4.89 µg L-1, respectively. PAE concentrations exhibited notable seasonal variations with the highest value in winter and the lowest value in summer. The seasonal variation in PAE concentrations may be influenced by runoff and diluted water from the Yangtze River. The chemical composition of PAEs showed that di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), and di(2-ethylhexyl) phthalate (DEHP) had significantly higher (p < 0.05) concentrations than the other congeners and were the most abundant PAE species in sediment and seawater in all three seasons. In addition, DnBP and DiBP were the two main congeners in seawater, and DEHP concentrations were higher in sediment than in seawater. DEHP had higher potential risks to sensitive organisms in water environment than DnBP and DiBP, and DiBP and DnBP which presented high levels of risk in sedimentary environment. DMP and DEP in watery and sedimentary environments and DEHP in sedimentary environment showed no or low risks to sensitive organisms.

Generic and rapid determination of low molecular weight organic chemical contaminants in protein powder by using ultra-performance liquid chromatography-tandem mass spectrometry.

A rapid, simple, and generic analytical method that could simultaneously determine 291 undesirable low molecular weight chemical contaminants from different drug families in protein powder, such as veterinary drugs and pesticides, etc, had been developed. This method comprised the extraction with acetonitrile-dimethyl sulfoxide (DMSO), clean-up through dispersive solid phase extraction (D-SPE) and low temperature filtration, and analysis by ultra-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry at multiple-reaction monitoring mode. Acetonitrile-DMSO was more generic than acetonitrile or methanol for the extraction of large-scale organic chemical contaminants with different polarities in protein powder. Most interferences in the extract were eliminated by the combination of D-SPE and low temperature filtration, which simultaneously provided satisfactory recoveries of both hydrophobic and hydrophilic analytes. In particular, besides the purification function, the sorbent of D-SPE also played an important role in grinding samples to improve extraction efficiency during homogenization. This streamlined approach allowed the processes of extraction and the main purification were carried out in one-step, and dramatically reduced sample preparation turnaround times and solvent consumption. For quantification, matrix-fortified calibration curves showed competent linearity for most of the target compounds with linear regression coefficients (r) higher than 0.9900, except for two analytes. The limits of quantification ranged from 0.1 µg/kg to 50 µg/kg, which was usually sufficient to verify the compliance of products with legal tolerances. The average recoveries for spiked protein powder ranged from 65.6% to 142.2% with associated RSD values between 0.5% and 28.5%. For over 90% of the analytes, the recoveries were between 70% and 120% with RSD values in the range of 1%-15%. Applying this method in routine monitoring programs would drastically reduce both effort and time.

Phthalic acid esters in the sea-surface microlayer, seawater and sediments of the East China Sea: Spatiotemporal variation and ecological risk assessment.

The spatial and temporal distribution, congener profiles and ecological risk of phthalic acid esters (PAEs) were investigated in the seawater and sediment samples from the East China Sea in spring and autumn. The average concentrations of ΣPAEs in water samples were 3.16 ± 2.16 µg L-1 in autumn and 1.63 ± 1.20 µg L-1 in spring. The ΣPAEs in sediment was much higher than that in seawater, with an average value of 7.36 ± 6.70 mg kg-1 (dw). PAEs levels in the sea-surface microlayer (SML) in spring were 3.61 ± 3.36 µg L-1, indicating that the PAEs were noticeably concentrated in the SML, with an average enrichment factor of 2.10. Among the 16 PAE congeners, di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), and di(2-ethylhexyl) phthalate (DEHP) were the preponderant PAEs in both sediment and seawater samples. Additionally, PAE concentrations in autumn were higher than those in spring, and this difference resulted mainly from the terrigenous input and marine transportation. The horizontal distributions of PAEs showed an opposite distribution pattern to salinity and temperature, a pattern which might be influenced by the inputs of fresh water. The vertical distributions of ΣPAEs were characterized by high concentrations in the surface waters, with a slight decrease with depth, and then an increase close to the seabed. The results of ecological risk in the water-phase showed that the level of potential risk followed the order of DEHP > DiBP and DnBP > DMP and DEP, which posed a high (DEHP), medium (DiBP and DnBP) and low (DMP and DEP) risk to the sensitive organisms, respectively. For the sediment-phase, DiBP and DnBP represented a high risk to the sensitive organisms, whereas DMP, DEP and DEHP had only a low risk.

Effective removal matrix interferences by a modified QuEChERS based on the molecularly imprinted polymers for determination of 84 polychlorinated biphenyls and organochlorine pesticides in shellfish samples.

A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure combined with GC-MS/MS detection approach using a dynamic multiple reaction monitoring (DMRM) mode was successfully applied for the simultaneous analysis of 84 polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in shellfish samples. The novel molecular imprinted polymers (MIPs) were synthesized by precipitation polymerization and characterized by Scanning electron microscopy, Brunauer-Emmett-Teller, Fourier transform infrared spectra and adsorption experiment. The MIPs exhibited good adsorption capability to pigment coextractives in shellfish samples without the loss of analytes compared with other sorbents. Under optimal conditions, spiked experiments in sinonovacula, mussel, and clam at 10.0-100.0 µg/kg concentrations showed excellent recoveries ranging from 70% to 120% for all analytes with the relative standard deviations of <10%. The developed method showed good linearity with the correlation coefficient above 0.9980, and the limits of quantification were in the range of 0.01-9.02 µg/kg. The developed QuEChERS procedure combined with GC-MS/MS was successfully applied to 84 PCBs and OCPs residues detection in shellfish samples.

Development and application of fluorescence sensor and test strip based on molecularly imprinted quantum dots for the selective and sensitive detection of propanil in fish and seawater samples.

Molecularly imprinted quantum dots (MIP-QDs) were successfully synthesized via reversed-phase microemulsion and used as the specific recognition element and signal probe of a fluorescence sensor or test strip to achieve the highly sensitive detection of propanil. The physical-chemical characteristics and excellent selectivity of MIP-QDs were elucidated. Under optimized parameters, the MIP-QDs had good linearity at the propanil concentration range of 1.0 µg/L to 20.0 × 103 µg/L by fluorescence quenching. The developed MIP-QD-based fluorescence sensor showed good recoveries ranging from 87.2 % to 112.2 %, and the relative standard deviation was below 6.0 % for the fish and seawater samples. In addition, the limits of detection (LODs) for fish and seawater were 0.42 µg/kg and 0.38 µg/L, respectively. The fluorescence test strip developed on the basis of the MIP-QDs also displayed satisfactory recoveries of 90.1 %-111.1 %, and the LOD for propanil in the seawater sample was 0.6 µg/L. The proposed fluorescence sensor and test strip were successfully used in propanil determination in environment and aquatic products.

Development and application of a novel fluorescent nanosensor based on FeSe quantum dots embedded silica molecularly imprinted polymer for the rapid optosensing of cyfluthrin.

A novel molecularly imprinted silica layer appended to FeSe quantum dots (MIP-FeSe-QDs) was fabricated and utilized as a recognition element to develop a selective and sensitive fluorescent nanosensor for cyfluthrin (CYF) determination. The MIP-FeSe-QDs were characterized by fluorescence spectrometry, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. Excellent selectivity and high sensitivity of MIP-FeSe-QDs to CYF molecules were observed based on the fluorescence quenching of FeSe-QDs. Under optimal conditions, a good linear relationship was found between fluorescence quenching effect and increased CYF concentration within 0.010-0.20mg/L, with a correlation coefficient of 0.9911. The practicality of the developed sensor method for CYF detection in fish and sediment samples was further validated. Good recoveries ranging from 88.0% to 113.9% with<6.8% relative standard deviations were obtained. The detection limits of CYF in sediment and fish samples were 1.3 and 1.0µg/kg, respectively. This study established a novel, rapid fluorescent nanosensor detection method based on MIP-QDs for successfully analyzing CYF in fish and sediment samples.