A Method to Replace NaCl as a Flotation Solution for Extracting MPs in Soil: A Case Study of the Jiaxing Agricultural Soil from China.

Microplastics (MPs) have become an important global issue in recent years. However, MPs in the soil have received far less attention than water. Effective and nondestructive extraction of MPs is important for studying MPs in agricultural soils. This study uses different floatation solutions as experiments and uses MgCl2 as the floatation solution of the density extraction method. Five types of standard MPs (PE, PP, PS, PVC, and PET) are used as the objects of this experiment. The recovery of the two particle sizes was between 90.82% and 109.69%. The extracted standard MPs were then subjected to IR and Raman spectroscopic analysis, and the results showed that Raman spectroscopy was more suitable for the identification of the extracted MPs. Finally, this method collected and verified a vast number of soil samples and further analyzed the abundance and characteristics of the collected MPs.

Chain-locked precursor ion scanning based HPLC-MS/MS for in-depth molecular analysis of lipase-catalyzed transesterification of structured phospholipids containing ω-3 fatty acyl chains.

Lipase-catalyzed transesterification of structured phospholipids (sPLs) is a hot topic, but the structural variation of the fatty acyl chains in intact phospholipids at the molecular level remains unclear to date. The present study explored the detailed characteristics of synthesized phospholipids through high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in precursor ion scan mode. The optimal conditions were in-depth inspected and determined for the reaction system, including phospholipase A1 as catalyst, 15% lipase loading, and 1% water content. The sPLs enriched with EPA/DHA were structurally and quantitatively characterized by focusing on the fragments of m/z 301.6 (eicosapentaenoic acid, EPA) and m/z 327.6 (docosahexaenoic acid, DHA), and the results were statistically analyzed using partial least squares discriminant analysis and clustered heatmap hierarchical clustering analysis. PC 38:6 (18:1/20:5), PC 38:7 (18:2/20:5), PC o-40:6 (o-18:0/22:6), and PE 40:8 (18:2/22:6) etc. were revealed as the main variables that were active in the reaction.

Study on the physicochemical indexes, nutritional quality, and flavor compounds of Trichiurus lepturus from three representative origins for geographical traceability.

Trichiurus lepturus (hairtail) is an important economic component of China's marine fishing industry. However, due to the difficulty in identifying the appearance of hairtail from different geographical distributions, hairtails with geographical indication trademarks were imitated by general varieties. In this study, the texture characteristics, color, basic nutrients, amino acids, mineral, fatty acids, and volatile flavor substances were used as indicators for multivariate statistical analysis to determine whether three origins of hairtails from the habitats of Zhoushan (East China Sea, T.Z), Hainan (South China Sea, T.N), and Qingdao (Yellow Sea, T.Q) in the market could be distinguished. The findings revealed that there were significant differences in amino acids composition, mineral composition, fatty acid composition in lipids, and volatile flavor substances among the hairtails of three origins (P < 0.05), but no differences in color, texture, protein content. T.Z had moisture, crude fat, essential amino acids (EAA), flavor amino acids (FAA), unsaturated fatty acids (UFA), and docosahexaenoic acids and dicosapentaenoic acids (ΣEPA + DHA) contents of 74.33, 5.4%, 58.25 mg⋅g-1, 46.20 mg⋅g-1, 66.84 and 19.38%, respectively, and the contents of volatile alcohols, aldehydes and ketones were 7.44, 5.30, and 5.38%, respectively. T.N contains moisture, crude fat, EAA, FAA, UFA and ΣEPA + DHA as 77.69, 2.38%, 64.76 mg⋅g-1, 52.44 mg⋅g-1, 65.52 and 29.45%, respectively, and the contents of volatile alcohols, aldehydes and ketones as 3.21, 8.92, and 10.98%, respectively. T.Q had the contents of moisture, crude fat, EAA, FAA, UFA, and ΣEPA + DHA 79.69, 1.43%, 60.9 mg⋅g-1, and 49.42 mg⋅g-1, respectively. The contents of unsaturated fatty acid and ΣEPA + DHA were 63.75 and 26.12%, respectively, while the volatile alcohols, aldehydes, and ketones were 5.14, 5.99, and 7.85%, respectively. Partial least squares-discriminant analysis (PLS-DA) multivariate statistical analysis showed that volatile flavor compounds could be used as the most ideal indicators for tracing the source of hairtail. In conclusion, the findings of this study can distinguish the three hairtail origins using some basic indicators, providing ideas for hairtail geographical identification.

Detection of lipidomics characterization of tuna meat during different wet-aging stages using iKnife rapid evaporative ionization mass spectrometry.

As a high-value processed aquatic product, wet-aged tuna has gradually become a popular food, but its lipidomics characteristics during the aging process have not been investigated. Herein, the lipidomics phenotypic data of tuna at different wet-aging stages were acquired using iKnife rapid evaporative ionization mass spectrometry, in which the dominant lipid components, including fatty acid (FA), phosphatidylcholine (PC), phosphatidylethanolamine (PE), and phosphatidylinositol (PI), were structurally identified. Principal component analysis, permutation test, heatmap, and circos plot analysis were performed to characterize lipids in wet-aged tuna, among which FAC18:1, docosahexaenoic acid (DHA), and PIC18:0/22:6 were the most contributing components for determining the wet-aging stage of tuna. The results indicated that iKnife-REIMS is accurate (86.5%), reliable, and could be used in the real-time detection of tuna meat during different wet-aging stages.

Insight into the effect of ultrasound treatment on the rheological properties of myofibrillar proteins based on the changes in their tertiary structure.

This was the first study to perform correlation analysis to determine the relationships between tertiary structural and rheological properties of the myofibrillar proteins (MPs) under ultrasound treatment (UT, frequency 20 kHz, power 500 W, intensity 30 %) for 0, 2, 4, 6, 8, and 10 min. The objectives of this study were to 1) characterize the changes of the small and large deformation rheological properties of MPs based on the tertiary structural changes; 2) determine relationships of rheological property, tertiary structural changes, and UT time. The results showed that UT could enhance the structural rigidity and the resistance of the system to permanent deformation observed in rheological tests. Besides, UT could unfold MPs, expose more hydrophobic amino acid residues to increase the surface hydrophobicity (S0-BPB), destroy disulfide bonds to increase the content of reactive sulfhydryl content (R-SH). The correlation analysis showed that the rheological properties of MPs could be improved by UT with a longer treatment time (0-10 min), while inevitably and significantly changing the tertiary structure of MPs (p < 0.05). These findings suggested that UT might be effective in the food-processing industry to change the structure of proteins and improve rheological properties.

Effect of propiconazole on plastic film microplastic degradation: Focusing on the change in microplastic morphology and heavy metal distribution.

With the rapid increase in the use of plastic films, microplastic (MP) pollution in agricultural soils has become a global environmental problem. Propiconazole is widely used in agriculture and horticulture; however, its role in plastic film degradation remains elusive. Butylene adipate-co-terephthalate (PBAT) and polyethylene (PE) films were used to analyze the effects of propiconazole on plastic film and MP degradation. We identified the surface morphologies of PBAT and PE at different propiconazole concentrations and soil pH values, as well as the adsorption and release characteristics of heavy metals during the degradation process via scanning electron microscopy, Fourier transform infrared spectroscopy and inductively coupled plasma mass spectrometry. Propiconazole accelerated the degradation of MPs, adsorption of heavy metals (Ni and Zn), and release of Sn at low concentrations (≤40 mg/kg); however, these effects were evidently absent at a high concentration (120 mg/kg). Furthermore, MPs were more prone to degradation in acidic or alkaline soils than in neutral soil when they coexisted with propiconazole. Hence, we suggest that PBAT and PE plastic films may not be suitable for application in acidic and alkaline soils with propiconazole, because of shorter rupture time and more heavy metal adsorption. PBAT degraded faster, absorbed and released more heavy metals than PE. Under all tested conditions, the heavy metal contents in MPs gradually approached those in soil, which proves that MPs are carriers of heavy metal pollutants. These results may help in assessing the impact of MPs on soil environments and provide a theoretical basis for the standardized propiconazole and plastic film usage.

Real-time authentication of minced shrimp by rapid evaporative ionization mass spectrometry.

Minced shrimp is popular seafood due to its delicious flavor and nutritional value. However, the biological species of raw material of minced shrimp are not distinguished by naked eyes after processing. Thus, an in situ and real-time minced shrimp authentication method was established using iKnife rapid evaporative ionization mass spectrometry (REIMS) based lipidomics. The samples were analyzed under ambient ionization without any tedious preparation step. Seven economic shrimp samples were tested, whose phenotypes were used to develop a real-time recognition model. A total of 19 fatty acids and 45 phospholipid molecular species were efficiently identified and statistically analyzed by multivariate statistical analysis. The results showed that the seven shrimp species were well distinguished, and the most contributing ions at m/z 255.2, 279.2, 301.2, 327.2, 699.5, 742.5, etc., were revealed by variable importance in projection. The proposed iKnife REIMS showed excellent performance in minced shrimp authentication.

In Situ Quality Assessment of Dried Sea Cucumber (Stichopus japonicus) Oxidation Characteristics during Storage by iKnife Rapid Evaporative Ionization Mass Spectrometry.

Sea cucumber (Stichopus japonicus) is one of the most luxurious and nutritious seafoods in Asia. It is always processed into dried products to prevent autolysis, but its quality is easily destructed during storage. Herein, an extremely simplified workflow was established for real-time and in situ quality assessment of dried sea cucumbers (DSCs) during storage based on the lipid oxidation characteristics using an intelligent surgical knife (iKnife) coupled with rapid evaporative ionization mass spectrometry (REIMS). The lipidomic phenotypes of DSCs at different storage times were acquired successfully, which were then processed by multivariate statistical analysis. The results showed that the discrepancy in the characteristic ions in different DSCs was significant (p < 0.05) with high R2(Y) and Q2 values (0.975 and 0.986, respectively). The receiver operating characteristic curve revealed that the ions of m/z 739.5, m/z 831.5, m/z 847.6, and m/z 859.6 were the most specific and characteristic candidate biomarkers for quality assessment of DSCs during accelerated storage. Finally, this method was validated to be qualified in precision (RSDintraday ≤ 9.65% and RSDinterday ≤ 9.36%). In conclusion, the results showed that the well-established iKnife-REIMS method was high-throughput, rapid, and reliable in the real-time quality assessment of DSCs.

Fast and Specific Screening of EPA/DHA-Enriched Phospholipids in Fish Oil Extracted from Different Species by HILIC-MS.

Eicosapentaenoic acid- and docosahexaenoic acid-enriched phospholipids (PLEPA/DHA) have versatile health-beneficial functions and can be well absorbed in the intestine. Herein, a precursor ion scan-driven hydrophilic interaction chromatography mass spectrometry (PreIS-HILIC-MS) method with the fatty acyl moieties of m/z 301.6 and 327.6 locked was established to specifically and selectively screen PLEPA/DHA in different fish oil samples, including saury, grass carp, hairtail, and yellow croaker. Taking saury oil as an example, a total of 24 PLEPA/DHA were successfully identified and quantified, including 20 PCEPA/DHA and 4 PEEPA/DHA. Finally, this method was validated in terms of sensitivity (limit of detection ≤ 4.15 µg·mL-1), linearity (≥0.9979), precision (RSDintraday ≤ 4.65%), and recovery (≥78.6%). The performance of the PreIS-HILIC-MS method was also compared with that of the traditional full-scan mode, and the former demonstrated its unique superiority in targeted screening of PLEPA/DHA in fish oils.

Lipidomics phenotyping of clam (Corbicula fluminea) through graphene/fibrous silica nanohybrids based solid-phase extraction and HILIC-MS analysis.

Polyunsaturated phospholipids are abundant in clam (Corbicula fluminea) but difficult to be fully extracted. Herein, graphene/fibrous silica (G/KCC-1) nanohybrids were synthesized, characterized, and applied for solid-phase extraction (SPE) of phospholipids in clam. The effectiveness of G/KCC-1 SPE was verified by hydrophilic interaction chromatography mass spectrometry (HILIC-MS) based lipidomics and statistical analysis. The ions of PE 16:0/18:1 (m/z 716.4), PC 16:0/20:5 (m/z 824.6) and etc. were regarded as the main difference among the crude lipids, acetone washed extract, and eluate of G/KCC-1 SPE. Finally, this method was validated in terms of linearity (R2 0.9965 to 0.9981), sensitivity (LOD 0.19-0.51 µg·mL-1 and LOQ 0.48 - 1.47 µg·mL-1), and precision (RSDintra-day ≤ 7.16% and RSDinter-day ≤ 7.30%). In conclusion, the G/KCC-1 SPE and HILIC-MS method was shown to be accurate and efficient in selective extracting and phenotyping phospholipids in C. fluminea.

Real-Time In Situ Screening of Omega-7 Phospholipids in Marine Biological Resources Using an iKnife-Rapid-Evaporative-Ionization-Mass-Spectrometry-Based Lipidomics Phenotype.

Omega-7 (n-7) phospholipids were bioactive substances in marine animals. In this study, a fast lipidomics phenotyping approach for real-time in situ screening of n-7 phospholipids in five kinds of economic seafood, salmon, prawn, bluefin tuna, hairtail, and butterfish, was established using iKnife rapid evaporative ionization mass spectrometry (REIMS). The n-7 phospholipids were structurally characterized and quantitatively analyzed, and the profiles were statistically analyzed by multivariate recognition analysis. It indicated that the difference of n-7 phospholipids in seafood samples was significant (p < 0.05), with R2(cum) and Q2(cum) values of >0.9. The proportion of n-7 phospholipids in salmon was the highest (20.43%), followed by bluefin tuna, prawn, hairtail, and butterfish. The ions of m/z 742.54 (PC 16:1-18:1), 768.55 (PC 16:1-20:2), 697.48 (PE 16:1-18:1), and 699.48 (PE 16:1-18:0) were the main n-7 phospholipids. The effectiveness of iKnife REIMS was further verified by hydrophilic interaction chromatography mass spectrometry and gas chromatography. The results demonstrated that proposed iKnife REIMS was an excellent technique for front-line screening of n-7 phospholipids in a large variety of marine biological resources.

QuEChERS and 96-well plate solid phase extraction for determination of vancomycin and norvancomycin in fish meat by UPLC-MS/MS.

Vancomycin and norvancomycin are glycopeptide antibiotics for gram-positive bacteria infection, but indiscriminately used in aquaculture. In this study, a QuEChERS (quick, easy, cheap, effective, rugged, and safe)/96-well solid-phase extraction (SPE) plate method was used to extract vancomycin and norvancomycin in fish meat samples, and the drugs were further analyzed by ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The parameters, such as the sorbent of cation exchange resin, the proportion of acetonitrile (15%) in extractant, the mobile phase of water (0.1% formic acid)/acetonitrile, were optimized. The method was validated in terms of linearity (0.9990-0.9994), LOD (0.51 µg·kg-1), LOQ (1.73 µg·kg-1), intra-dayprecision (<5.19%), inter-day precision (<6.30%), and recovery (86.7-98.6%). Finally, the method was successfully applied to contaminated and randomly collected samples. The results indicated that the proposed method meet the daily monitoring requirements for vancomycin and norvancomycin.

Untargeted Screening of EPA/DHA Structured Phospholipids in Krill Oil by Chain-Lock-Driven Hydrophilic Interaction Liquid Chromatography Tandem Mass Spectrometry.

Eicosapentaenoic and docosahexaenoic acids structured phospholipids (PLEPA/DHA) have multiple biochemical and pharmacological effects on human health. In this study, EPA and DHA chains were locked under precursor ion scan (PreIS) mode for untargeted screening PLEPA/DHA in krill oil using hydrophilic interaction liquid chromatography tandem mass spectrometry (HILIC-MS/MS). The effect of collision energy and declustering potential on the fragmentation of EPA (m/z 301.2) and DHA (m/z 327.2) chains was studied. A total of 33 PLEPA/DHA were characterized (sn-1/sn-2) and quantified using regression models, including 16 PCEPA/DHA, 11 PEEPA/DHA, and 6 PIEPA/DHA. Afterward, this method was validated in terms of linearity (≥0.9978), sensitivity (LOD ≤ 4.02 µg·L-1), precision (RSDintraday ≤ 4.71%), and recovery (≥78.9%). Finally, the performance of HILIC-PreIS-MS/MS was compared with those of conventional methods, and the results indicated its superiority in selective screening PLEPA/DHA in krill oil.

Microplastic acts as a vector for contaminants: the release behavior of dibutyl phthalate from polyvinyl chloride pipe fragments in water phase.

The pollution of contaminants brought by plastic fragments is worth paying attention in the study of microplastic. The additives, like phthalates (PAEs), introduced during manufacture, are physically dispersed and can easily release into environment. Polyvinyl chloride pipes are widely used in China, and DBP is also a typical kind of additives in PVC materials. Here, the release behavior of DBP from PVC plastic pipe fragments was investigated in water environment under different conditions. Low-density polyethylene (LDPE) passive sampler was used to monitor the contents of DBP. The curve of DBP concentration started from the first increasing stage until a short equilibrium after 45 days' incubation followed by a second increasing part. The release kinetics and the rate-limiting step were discussed. For the whole migration period, the release process was better fitted to pseudo-second order which was participated by both intraparticle and plastic-water film diffusion processes while the two separated parts had different results. Moreover, light, smaller fragments, and higher temperature could all accelerate the release rate and increase the migration amount of DBP. The effect of temperature was the most significant of all, and higher temperature showed more significant effects. Besides, DBP tended to migrate in a long-time continuously. However, the release of additives will be promoted by various physical and chemical processes in nature compared to laboratory tests. Consequently, microplastic (plastic fragments with sizes smaller than 5 mm) with additives acts as a vector for pollutants, and will bring more threat to both environment and organisms.

Characterization of microplastics in environment by thermal gravimetric analysis coupled with Fourier transform infrared spectroscopy.

As a global pollutant, microplastics have attracted attention from the public and researchers. However, the lack of standard and time-saving methods for analysis has become one of the bottlenecks in microplastics research. Here, we demonstrate TGA coupled to FTIR to identify and quantify certain microplastics in environment. Samples were pyrolyzed in TGA and the pyrolysis gases were analyzed by FTIR. Combining TGA and FTIR data adds discriminatory power as temperature profiles and absorption spectra differ among several common plastics. To quantify on a mass basis, we calibrated on characteristic IR peaks at temperatures of maximum weight loss for individual polymers. The method can distinguish PVC, PS and was validated by spiking samples with known quantities of microplastics. The result of field sample experiments showed that TGA-FTIR can be used to identify and quantify PVC and PS in bivalves, seawater and soil. And the method may be applicable to environmental samples.

Development and validation of a universal primer pair for the simultaneous detection of eight animal species.

In the present study, we developed a novel simplex PCR assay for the simultaneous detection of eight animal species, including goat, sheep, deer, buffalo, cattle, yak, pig and camel. A unique pair of universal primers was designed to target mitochondrial DNA variable regions in the eight animal species, generating, 787, 763, 563, 512, 507, 491, 455 and 385bp long fragments for goat, sheep, deer, buffalo, cattle, yak, pig and camel, respectively. The assay showed no cross-reactivity with other common domestic animals, and was validated by sequencing and enzyme digestion. Detection limit for DNA samples from the eight animal species varied between 6 and 20pg in a 20µl PCR mixture. Interestingly, the newly developed method successfully identified 170 commercial meat products, and is simple, fast, sensitive, specific, and cost-effective. Therefore, it could be used for the detection of goat, sheep, deer, buffalo, cattle, yak, pig, and camel species in foodstuffs.

[Rapid screen of 15 basic artificial dyes in fishery products by ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry].

A new method was established for the simultaneous determination of 15 basic artificial dyes in fishery products by ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry (UPLC-Q-TOF MS). The analytes in fishery products were extracted with acetonitrile containing 10% (v/v) acetic acid, then purified by dispersive solid phase extraction with C18-silicone adsorbent. The compounds were separated by a C18 column with acetonitrile and 0.1% (v/v) formic acid-5 mmol/L ammonium acetate solution as the mobile phases, and measured by UPLC-Q-TOF MS with electrospray ionization in positive mode. As a result, the limits of quantification (LOQs, S/N = 10) of the 15 target compounds were 0.1-100 µg/kg in fishery products. The 15 analytes behaved linearly in their respective ranges with the correlation coefficients no less than 0.993. The average recoveries of the 15 analytes spiked at three levels were ranged from 80.60% to 107.37% with the RSDs of 3.33%-6. 69% (n = 6). This method is suitable for routine qualitative and quantitative analyses of the 15 basic artificial dyes in fishery products due to its fastness, simplicity and relatively high sensitivity.

[Rapid screening of 28 acidic artificial dyes in fishery products by ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry].

An analytical method was established for the simultaneous determination of 28 acidic artificial dyes in fishery products by ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry (UPLC-Q-TOF MS). The analytes in fishery products were extracted with ethyl alcohol containing 20% (v/v) ammonia water and 10% (v/v) water. Then the extract solution was purified according to amination adsorbent matrix dispersion method. The compounds were separated by an Eclipse Plus-C18 column with acetonitrile and 0.1% (v/v) formic acid-5 mmol/L ammonium acetate solution as the mobile phases, and measured by UPLC-Q-TOF MS with electrospray ionization in negative mode. As a result, the limits of quantification ( LOQs, S/N = 10) of the target compounds were 20-100 µg/kg in fishery products. The 28 analytes behaved linearly in wide-range with the correlation coefficients more than 0. 991 as well as the relative standard deviations (RSDs) of the peak areas less than 5.61% (n = 6). The average recoveries of the 28 analytes spiked at three levels were ranged from 70. 24% to 106. 47% with RSDs of 5.62%-9.65% (n = 6). This method can be applied to the analysis of the 28 acidic artificial dyes in fishery products due to its fastness, simplicity and relatively high sensitivity.

[Determination of volatile N-nitrosamine compounds in salted aquatic products by gas chromatography-mass spectrometry].

An analytical method was developed for the determination of the extraction of volatile N-nitrosamine compounds including N-nitrosodimethylamine ( NDMA) , N-nitrosodiethylamine (NDEA), N-nitrosodipropylamine (NDPA), N-nitrosodibutylamine (NDBA), N-nitrosopiperidine (NPIP), and N-nitrosopyrrolidine (NPYR) from salted aquatic products by gas chromatography-mass spectrometry (GC-MS). In this experiment, the separation and detection conditions were optimized for different extraction methods, solid-phase extraction columns, and chromatographic columns. The results showed that the linear correlation coefficients (R2) were higher than 0. 999 8 within 10 - 1 000 micro g/L, and the reproducibilities were good with the - relative standard deviations (RSD) less than 8%. The recoveries were 79% - 105%. It is noted that this method for the determination of volatile N-nitrosamine compounds in salted aquatic products was much more sensitivity and with a lower detection limits (0. 05 micro g/kg except NDPA) than the previously reported methods. This proposed method is rapid and convenient for the determination, and easy for the operation. It is appropriate for the determination of volatile N-nitrosamine compounds in various salted aquatic products.

[Determination of dichlorobromomethane in water by headspace-trap gas chromatography/mass spectrometry].

A novel method was developed for the determination of dichlorobromomethane in water using headspace-trap gas chromatography/mass spectrometry (GC/MS). Three parameters of headspace-trap including thermostatic temperature, time and cycle number were optimized by orthogonal experiment analysis. Dichlorobromomethane in water samples was analyzed under the optimized conditions of 70 degrees C and 20 minutes with the cycle number of two. The results showed that the calibration curve was linear in the range of 0.1 - 10.0 microg/L, and the correlation coefficient was 0.999 1. The detection limit was 0.03 microg/L. The average recovery was 83.1% - 111.3% with the relative standard deviation (RSD) not more than 5.2% (n = 6). This method is rapid, sensitive and reproducible for the routine detection of the low concentration of dichlorobromomethane in water.