A highly efficient and selective rapid detection method applied to the detection of amide herbicides in fish serum.

Misuse of amide herbicides in the fisheries environment can pose unpredictable harm to aquatic products and ultimately human health. Thus, the development of a real-time, rapid on-site detection method is crucial. This study proposes for the first time, a paper-based visual detection method for amide herbicides in fish serum, by coating the molecularly imprinted polymer layer onto quantum dots, prepared fluorescent sensing materials (QDs@MIPs) for the detection of amide herbicides in aquatic products. These materials specifically cause fluorescence quenching in the presence of amide herbicides resulting in a color change. For practical application, this research designed a rapid test strip based on QDs@MIPs, meanwhile, incorporate a smartphone or a fluorescence spectrophotometer for qualitative and quantitative measurements, the limit of detection ranges of 0.061-0.500 µM. The method can be used for on-site evaluation of aquatic products, providing new technology for monitoring the safety of aquatic products.

Toxic Effects of Arsenic on Four Freshwater Aquatic Species and Its Transformation Metabolism in Crucian Carp (Carassius auratus).

Inorganic arsenic is a well-known carcinogen that is much more toxic than its organic counterpart. While much is known about the accumulation and transformation of arsenic in marine organisms, little is known regarding these processes in freshwater aquatic species. In this study, the acute toxicity and toxicological effects of inorganic arsenic on four freshwater organisms (Cyprinus carpio, Misgurnus anguillicaudatus, Pseudorasbora parva, Eriocheir sinensis) commonly found in rice-fish farming systems were investigated. The organisms exhibited different levels of sensitivity to inorganic arsenic, with crustaceans being more sensitive than fish. Fish were found to be more tolerant to As(V) than As(III). The study also investigated the accumulation, transformation, and release of inorganic arsenic in crucian carp, an omnivorous species with high environmental tolerance. The fish accumulated As(III) rapidly in various tissues, and were able to transport it to other tissues through gills, intestines, and skin. The accumulated As(III) was converted into less toxic forms, such as monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), via methylation. The fish also converted As(III) into arsenate (AsV) via enzymatic and oxidative reactions. After the transferal to clean water, the forms of arsenic in the various tissues decreased rapidly, but the rates of excretion of the four forms of arsenic were not the same among the different tissues. Our results suggest that crucian carp can reduce the environmental toxicity of As(III) at certain concentrations by transforming it into less toxic forms within their bodies.

Carbon Nanotube-Supported Dummy Template Molecularly Imprinted Polymers for Selective Adsorption of Amide Herbicides in Aquatic Products.

In this study, a carbon nanotube (CNTs)-supported dummy template molecularly imprinted polymer (DMIPs) material was synthesized and utilized for the detection of amide herbicides in aquatic products via matrix solid-phase dispersion technology (MSPD). The DMIPs material was characterized, and its adsorption kinetics and isotherm were determined, the adsorption model was established, and the selective adsorption coefficient was calculated. The extract parameters of the method were optimized and successfully employed for the separation, analysis and detection of real samples, with satisfactory detection limits and linear ranges obtained. By comparing with other methods, the CNTs@DMIPs combined with MSPD technology established in our study can effectively solve false negative problems caused by insufficient destructive force, using dummy template molecules can also address the issue of false positives caused by template molecule leakage in molecular imprinting. Overall, the method is appropriate for the separation and detection of endogenous substances from highly viscous and poorly dispersed samples and is used as a routine detection tool in the aquaculture industry.

Application of solid-phase extraction: High-resolution mass spectrometry analysis strategy in the characterization and quantification of amide herbicides in aquatic products.

In this study, we developed a new method combining thin-layer ultrasonic extraction, efficient SPE purification, ultra-performance liquid chromatography separation, and high-resolution mass spectrometry characterization for seven amide herbicides in fishery products. In sample preparation, to rapidly increase the contact area between the fish meat and the extractant, the fish meat was smeared on a glass slide. This process resulted in quickly reaching the extraction equilibrium and relatively high extraction efficiency. In data analysis, a strategy for characterization and qualitative analysis was constructed by analyzing the fragmentation of amide herbicides using product ion scans. Isomeric pretilachlor and butachlor were separated chromatographically, while the coeluting isomers, alachlor and acetochlor, could be separated by differences in the fragmentation of their selected precursor ions. This method overcame the challenge of poor dispersion in the extractant caused by the high viscosity of fish meat, and the challenge of separation and characterization for isomers. Compared with other methods, the extraction efficiency was improved and the amide herbicides in aquatic products was characterized and quantified rapidly and accurately. Moreover, the qualitative information was much greater and provided an additional strategy for analytes identification. This rapid and accurate method will benefit workers involved in monitoring fishery.

Toward Reduced Interface Contact Resistance: Controllable Surface Energy of Sb2Te3 Films via Tuning the Crystallization and Orientation.

The electrical contact resistance between a metal and semiconductor is one of the keys to improving the output performance of thin-film thermoelectric devices. Herein, we reduced the interface contact resistance by controlling the surface energy of a Sb2Te3 semiconductor via tuning of the crystallization and orientation, preparing an intrinsically compact and flat Sb2Te3 film with high surface energy and low roughness, which can give rise to a low average specific contact resistivity (8.2 × 10-6 Ω cm2) with a Ni/Cu metal. The improvement in interface electrical properties is due to the increase in the surface energy and decrease in the surface roughness of the semiconductor surface, which lead to a transformation from three-dimensional island-shaped nucleation to two-dimensional layered nucleation for surface-attached metal films, forming a longitudinally tight connection contact with a low resistance. This approach allows the resistivity to become close to the fundamental theoretically calculated limit. Our work provides a new idea for reducing the contact resistivity of thin-film thermoelectric devices, which is conducive to supporting the development of thermoelectric semiconductor planarization.

Selective magnetic solid-phase extraction of amide herbicides from fish samples coupled with ultra-high-performance liquid chromatography with tandem mass spectrometry.

An efficient magnetic dummy template molecularly imprinted polymer nanocomposite was prepared using multi-walled carbon nanotubes as a support and metolachlor deschloro as a dummy template. The obtained nanocomposites were characterized using Fourier transform infrared spectroscopy, vibrating sample magnetometry, scanning electron microscopy, and transmission electron microscopy. The adsorption performance of the obtained nanocomposites was evaluated through binding experiments, including static adsorption, kinetic adsorption, and selective recognition studies. The obtained nanocomposites were successfully applied as selective sorbents for the magnetic solid-phase extraction of seven amide herbicides (alachlor, acetochlor, pretilachlor, butachlor, metolachlor, diethatyl ethyl, and dimethachlor) coupled with liquid chromatography-tandem mass spectrometry from fish samples. Under the optimized conditions, the limit of detection was 0.01-0.1 µg/kg. The obtained recoveries of the amide herbicides from the fish samples were in the range of 88.0 to 102.1% with a relative standard deviation of less than 7.5%. This method, which eliminated the effect of template leakage on qualitative and quantitative analysis was found to be superior to the methods reported in the literature. The results indicated that it could be successfully applied to analyze amide herbicides in fish samples with satisfactory recoveries.

Preparation of porous carbon-based molecularly imprinted polymers for separation of triazine herbicides in corn.

A synthesis route of using cellulose as the precursor to prepare porous carbon (PC) had been established in this study. The as-prepared PC was introduced as carriers in the synthesis process of porous carbon-molecularly imprinted polymers (PC-MIPs), which greatly improved the absorption capacity of MIPs. Triazine pesticides in corn were extracted with matrix solid-phase dispersion (MSPD) using the PC-MIPs as dispersants and determined by ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Under the optimal MSPD condition for extracting six kinds of triazines (simazine, terbutryn, simetryne, prometryne, ametryn, and atrazine), the detection limits were 0.005-0.02 ng g-1, while the precisions were 1.2-5.9%, and the recoveries were 92.6-104.7%. The method has been extensively applied to analyze various corn samples. Atrazine residue (1.2 µg kg-1) was detected in one corn sample, which was lower than the maximum residual limit indicated by the Chinese stated standards (50 µg kg-1).

Determination of sulfonamide antibiotics in fish and shrimp samples based on magnetic carbon nanotube dummy molecularly imprinted polymer extraction followed by UPLC-MS/MS.

In this study, a novel purification method using magnetic solid-phase extraction (MSPE) based on magnetic carbon nanotube dummy molecularly imprinted polymer (MCNTMIP) nanocomposite was investigated for separation and enrichment of sulfonamide antibiotics (SAs) in fish and shrimp samples. The MCNTMIP nanocomposite was successfully synthesized by applying carbon nanotubes as supporting template, methacrylic acid as functional monomer, sulfabenzamide as the dummy template for SAs, and ethylene glycol dimethacrylate as crosslinking agent, then was characterized by Fourier-transform infrared spectrometry and vibrating sample magnetometry. The adsorption performance of MCNTMIP was evaluated by binding experiments, including static adsorption, kinetic adsorption, and selectivity recognition study. The results confirmed that an imprinted polymer layer was successfully constructed on the surface of the MCNTMIP and this sorbent has advantages of simple magnetic separation, specific molecular recognition, and high adsorption capacity. Combined with ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS), we developed a rapid, sensitive, efficient MSPE method for detecting SAs analytes. Under the optimal conditions, the limits of detection were low to 0.1 µg/kg, and the recoveries of SAs analytes were ranged between 90.2 and 99.9%. In addition, the precision values were ranged between 0.5 and 9.1%. This method was successfully applied to analyze SAs in fish and shrimp samples with satisfactory recoveries.

Distribution, contents and health risk assessment of heavy metal(loid)s in fish from different water bodies in Northeast China.

This study aimed at investigating the accumulation and potential risks of eight metal(loid)s in fish from natural and culturing water samples in Northeast China. Chromium (Cr), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), cadmium (Cd), lead (Pb) and mercury (Hg) contents in 16 fish species (155 samples) and sediments of their habitats were analyzed. In general, the concentrations of these eight metal(loid)s in most fish samples are lower than the guideline levels and legal limits, and the Pb and Hg level in 0.65% of samples were exceeded the quality standards in China. The Cr, As, Cd and Pb levels in most fish samples are less than those reported in previous studies. Nonetheless, Hg levels in these fish samples are significantly higher than those reported in previous studies conducted in other regions. Different from the wild fish, significant positive correlations are found between Cr, Ni, As and Cd concentrations in cultured fish and those in pond sediment (P < 0.05), which might be due to the closed static water environment and concentrated feeding operations. Cu, Zn, As and Hg concentrations differed significantly among wild species, while Cu and Zn concentrations differed significantly among cultured species (P < 0.05), which might be because of the different feeding and foraging habitats. The target hazard quotients (THQs) at high exposure levels of target metal(loid)s in the studied fish were below 1 (except for Hg), and the carcinogenic risk indices of Cr, As, and Cd were less than 10-4. The levels of metal(loid)s (except for Hg) in the studied fishes fell within an acceptable range, but more attention should be paid to the potential carcinogenic risks.

Adsorption characteristics of metal-organic framework MIL-101(Cr) towards sulfamethoxazole and its persulfate oxidation regeneration.

A metal-organic framework, MIL-101(Cr), was used to adsorb sulfamethoxazole (SMZ) in water and activated persulfate (PS) oxidation was investigated to regenerate SMZ-saturated MIL-101(Cr). Adsorption and oxidation were combined in this study. MIL-101(Cr) was characterized by SEM, BET, XPS and FT-IR analyses. Effects of various operating parameters on adsorption efficiency were studied. The dosages of persulfate for SMZ desorption and oxidation were investigated. The results showed that the recommended pH was 6-8 for SMZ adsorption and optimum MIL-101(Cr) dosage was 0.1 g L-1. SMZ adsorption by MIL-101(Cr) was a spontaneous process and nearly exothermic. Saturation adsorption capacity was achieved in 180 s and the adsorption followed the pseudo-second-order model. The maximum adsorption amount of MIL-101(Cr) to SMZ was 181.82 mg g-1 (Langmuir). MIL-101(Cr) also showed good adsorption capacities for sulfachloropyridazine (SCP), sulfamonomethoxine (SMM), and sulfadimethoxine (SDM). Persulfate was helpful for SMZ desorption from the surface of saturated MIL-101(Cr) and sufficient persulfate could simultaneously oxidize the SMZ. XPS analysis showed that the structure of MIL-101(Cr) was stable after the persulfate oxidation process. Regenerated MIL-101(Cr) had the same level of adsorption capacity as fresh MIL-101(Cr). An adsorption-oxidation combined process may be set up based on the results. This study provides basic data for the deep treatment of organic micropollutants in urban water bodies.

Preparation of magnetic molecularly imprinted polymers by atom transfer radical polymerization for the rapid extraction of avermectin from fish samples.

A novel and highly efficient approach to obtain magnetic molecularly imprinted polymers is described to detect avermectin in fish samples. The magnetic molecularly imprinted polymers were synthesized by surface imprinting polymerization using magnetic multiwalled carbon nanotubes as the support materials, atom transfer radical polymerization as the polymerization method, avermectin as template, acrylamide as functional monomer, and ethylene glycol dimethacrylate as crosslinker. The characteristics of the magnetic molecularly imprinted polymers were assessed by using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, vibrating sample magnetometry, X-ray diffraction, and thermogravimetric analysis. The binding characteristics of magnetic molecularly imprinted polymers were researched through isothermal adsorption experiment, kinetics adsorption experiment, and the selectivity experiment. Coupled with ultra high performance liquid chromatography and tandem mass spectrometry, the extraction conditions of the magnetic molecularly imprinted polymers as adsorbents for avermectin were investigated in detail. The recovery of avermectin was 84.2-97.0%, and the limit of detection was 0.075 µg/kg. Relative standard deviations of intra- and inter-day precisions were in the range of 1.7-2.9% and 3.4-5.6%, respectively. The results demonstrated that the extraction method not only has high selectivity and accuracy, but also is convenient for the determination of avermectin in fish samples.

Heavy Metal Levels in Fish from Heilongjiang River and Potential Health Risk Assessment.

Concentrations of Cu, Zn, Cr, As, Cd, Pb and Hg were determined in 153 samples covering 18 fish species collected from Heilongjiang River, China, and the potential health risks to local residents through fish consumption were estimated. Results revealed that all metals were detected with Cd and Pb having considerably lower detection rate. There were 28.6 % of Lethenteron camtschaticum samples exceeding the limit of inorganic As content established by Chinese legislation. Metal bioaccumulation in fish were poorly correlated with fish sizes, and generally tended to increase with trophic levels. The hazard quotient values of all fish species were far below 1 for general population and fishermen. The carcinogenic risk of As in L. camtschaticum for the local fishermen exceeded the acceptable level of 10(-4) rise in cancer rates, but was considered safe given the migratory habits of the fish.

Trace elements in farmed fish (Cyprinus carpio, Ctenopharyngodon idella and Oncorhynchus mykiss) from Beijing: implication from feed.

Concentrations of 30 trace elements, Li, V, Cr, Mn, Fe, Ni, Cu, Mo, Zn, Se, Sr, Co, Al, Ti, As, Cs, Sc, Te, Ba, Ga, Pb, Sn, Cd, Sb, Ag, Tm, TI, Be, Hg and U in major cultured freshwater fish species (common carp-Cyprinus carpio, grass carp-Ctenopharyngodon idella and rainbow trout-Oncorhynchus mykiss) with the corresponding feed from 23 fish farms in Beijing, China, were investigated. The results revealed that Fe, Zn, Cu, Mn, Sr, Se were the major accumulated essential elements and Al, Ti were the major accumulated non-essential elements, while Mo, Co, Ga, Sn, Cd, Sb, Ag, Tm, U, TI, Be, Te, Pb and Hg were hardly detectable. Contents of investigated trace elements were close to or much lower than those in fish from other areas in China. Correlation analysis suggested that the elemental concentrations in those fish species were relatively constant and did not vary much with the fish feed. In comparison with the limits for aquafeeds and fish established by Chinese legislation, Cd in 37.5% of rainbow trout feeds and As in 20% of rainbow trout samples exceeded the maximum limit, assuming that inorganic As accounts for 10% of total As. Further health risk assessment showed that fish consumption would not pose risks to consumers as far as non-essential element contaminants are concerned. However, the carcinogenic risk of As in rainbow trout for the inhabitants in Beijing exceeded the acceptable level of 10(-)(4), to which more attention should be paid.

Heavy metals in sea cucumber juveniles from coastal areas of Bohai and Yellow seas, north China.

The study was undertaken to assess the contents of heavy metals (Cu, Zn, Cr, Pb, Cd, As and Hg) in sea cucumber (Apostichopus japonicus) juveniles from coastal areas of Bohai and Yellow seas in northern China. Sea cucumber juveniles were collected from twenty commercial hatcheries distributed in five coastal cities. The mean concentrations obtained for heavy metals in mg/kg were as follows: Cu (0.179), Zn (2.634), Cr (0.108), Pb (0.065), Cd (0.161), As (0.372), Hg (0.034). All the mean concentrations were below the maximum residual limits set by Chinese legislation, but As in 10 % samples exceeded the safety threshold. Significant differences in contents of Cr, Pb and Hg were found among the five investigated areas. Overall, the heavy metal levels in sea cucumber juveniles were relatively low and more attention should be paid to toxic metals Pb, Cd, As and Hg in future routine monitoring program.

[Effects of salinity on haematological biochemistrical indices and liver tissue in juvenile Oncorhynchus keta].

In order to simulate the catadromous migration environment of the juvenile salmon (Oncorhynchus keta), five experimental groups containing different salinities (0, 5, 10, 15 and 20) were set up. The juvenile salmons with average body mass of (26.57 +/- 6.32) g and average full length of (14.44 +/- 1.05) cm were cultured for 130 days, and then the haematological biochemistrical indices was analyzed and the structure of liver tissue was observed to investigate the changes in physiological indices during the catadromous migration of juvenile salmon. The results showed that serum osmolality and the concentration of Na+, Cl- illustrated the same tendency with water salinity variation. Specifically, the serum Na+, C- and Mg2+ levels in the salinities of 15, 20 were significantly different from those in the salinity 5 and the freshwater and serum K+ in different salinities were all obviously lower than that in the freshwater. Also, the blood glucose level in salinity 10 was significantly higher than that in salinity 5 and 20, whereas total serum protein (TP), albumin (ALB) and globulin (GLB) levels all declined with the increase of salinity and the serum TP and GLB content in the freshwater group was remarkably higher than those in the salinity 15 and 20. There also existed an obvious discrepancy on total bile acids in freshwater group and the other salinity groups. The alanine aminotransferase (ALT) activity and aspartate aminotransferase (AST) activity in fresh water group were far different from those of the high salinity groups. Furthermore, in the low salinities (0 and 5), the liver cells of juvenile chum salmon partly broke down, and liver tissue was serious vacuolization. Collectively, the growth and survival rate had no significant difference in all groups and according to the physiological and biochemical indices, the appropriated salinity for juvenile chum salmon ranged from 10 to 20 during the catadromous migration.