Development, validation, and implementation of an ultratrace analysis method for the determination of moenomycin A, in aquatic animal products.

Moenomycin A, an antimicrobial growth promoter widely used as an additive in aquaculture feedstuffs, has been restricted for use in the European Union and China due to its potential risk of promoting resistant strains of pathogenic bacteria and causing residues in aquatic animal products. Although methods for analyzing moenomycin A in feedstuffs have been developed, no established method exists for aquatic matrices. In this study, we present, for the first time, a sensitive and validated high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for the determination of moenomycin A in aquatic animal products. Samples were extracted using methanol and purified with the QuEChERS method employing C18 sorbent. The aliquot was dried under a nitrogen stream, reconstituted with methanol-water solvent, and analyzed by HPLC-MS/MS. The developed method exhibited good linearity (r2 > 0.995) over a wide concentration range (1-100 µg/L) and a low limit of detection (1 µg/kg). Average recoveries ranged between 70 and 110% at spiked concentrations of 1, 50, and 100 µg/kg, with associated intra- and inter-day relative standard deviations of 1.25 to 7.32% (n = 6) and 2.91 to 10.08% (n = 3), for different representative aquatic animal production, respectively. To the best of our knowledge, this is the first reported HPLC-MS/MS method for the quantification of moenomycin A in aquatic animal products. The new approach was effectively employed in the analysis of moenomycin A across various aquatic samples.

Determination of earthy-musty odors in tap water by gas chromatography‒mass spectrometry with silica solid-phase extraction.

This research aimed to develop an effective method for detecting semivolatile earthy-musty odors without using the conventional sample processing equipment used for volatile compounds. The concurrent isolation of 2-methylisoborneol (2-MIB), trans-1,10-dimethyl-trans-9-decalol (geosmin, GSM), 2-isopropyl-3-methoxy pyrazine (IPMP), and 2-isobutyl-3-methoxy pyrazine (IBMP) in tap water was successfully achieved by employing a combination of n-hexane liquid‒liquid extraction (LLE) and silica solid-phase extraction (SPE) techniques. Gas chromatography-mass spectrometry (GC-MS) was utilized for the identification of these targets, with the inclusion of borneol (BN) as an internal reference. This robust method was optimized and validated. It was found that the method showed good linearity in the range of 0.5-100 ng/mL and produced good recoveries (84.6 %-103 %) with satisfactory relative standard deviations (1.50 %-10.1 %). The determined limits of detection (LODs) for the group of four substances were found to vary from 0.3 to 0.9 ng/L, whereas the limits of quantitation (LOQs) exhibited variations between 1 and 3 ng/L. The subsequent implementation of this methodology to evaluate the four previously described off-flavor chemicals in tap water resulted in satisfactory results.

Characteristics of arsenic speciation in mainly cultured shellfish from Sanmen Bay, Zhejiang Province, China.

Sanmen Bay plays a crucial role in economic shellfish aquaculture in China, yet few studies exist on the arsenic speciation of shellfish from this area. In this study, arsenic speciation of 11 cultured shellfish species from Sanmen Bay were analyzed by HPLC/ICP-MS. The results showed that organic arsenic particularly AsB, was the dominant arsenic species, constituting 21 %-71 % of the total arsenic. Conversely, the levels of inorganic arsenic were relatively low, ranging from 0.007 to 0.093 mg/kg, only accounted for 0.2 %-5.7 % of the total arsenic. There was no significant level correlation between inorganic arsenic and total arsenic in Sanmen Bay shellfish, so the concentration of inorganic arsenic did not increase with the total arsenic. Overall, the present study firstly revealed the arsenic speciation of shellfish from Sanmen Bay and also suggested that the proportion of inorganic arsenic should be considered in the revision of arsenic limit values.

A baseline study on the distribution characteristics and health risk assessment of cadmium in edible tissues of the swimming crabs (Portunus trituberculatus) from Shanghai, China.

This study analyzed the cadmium accumulation differences in edible tissues of the swimming crabs (Portunus trituberculatus) from Shanghai markets, which were mostly caught in the East China Sea, and the human health risk of cadmium from crabs consumption was evaluated. A total of 78 swimming crabs were collected, and the white meat and brown meat were separated for the cadmium analysis by Inductively coupled plasma mass spectrometry. The results revealed that there was difference in cadmium content in brown meat (1.260-16.303 mg/kg) and white meat (0.005-0.542 mg/kg). Furthermore, pollution index (Pi) results showed that only the claw muscle was at low contamination levels, while other edible tissues had varying degrees of contamination. Based on the health risk assessment by estimated daily intake (EDI), target hazard quotient (THQ) and target cancer risk (TCR), the consumption of the swimming crabs in Shanghai is considered safe, however, the accumulation of cadmium in the brown meat of swimming crabs deserves further attention and evaluation.

Highly Sensitive Determination of Antibiotic Residues in Aquatic Products by High-Performance Liquid Chromatography-Tandem Mass Spectrometry.

Antibiotic drug residues are crucial to ensure food safety and minimize risk to human health. Herein, a sensitive high-performance liquid chromatography−tandem mass spectrometry (HPLC−MS/MS) method was developed and validated for the determination of antibiotic residues (mainly amphenicols) consisting of chloramphenicol (CAP), thiamphenicol (TAP), florfenicol (FF), and florfenicol amine (FFA) in aquatic products. Amphenicols were well separated on a Kinetex F5 (100 mm × 3.0 mm, 2.6 µm) chromatographic column with the mobile phases of 1 mM ammonium acetate aqueous solution and methanol solution and measured after positive and negative electrospray ionizations using four internal standards. To our knowledge, it was the first time to report the good performance of F5 column and four internal standards for the determination of amphenicols. The established method featured a good linear relationship between chromatographic peak area ratios and the concentrations of amphenicols (R2 > 0.992), a wide and low detection matrix-based range of 0.01−5 µg/L, a low detection limit of 0.01 µg/kg, etc. The spiked assays evidenced the accuracy and reliability of the developed method with the recoveries between 84.0 and 105%, the intraday relative standard deviations (RSDs) over the range of 0.769−13.7%, and the interday RSDs over the range of 0.582−13.3%. Finally, the proposed method was applied to investigate amphenicol residues in various aquatic products, including fish, shrimp, crab, shellfish, and other aquatic species.

Identification of 2,2',4,5,5'-Pentachlorobiphenyl (PCB101) metabolites and their transmission characteristics in silver crucian carp (Carassius auratus gibelio).

Polychlorinated biphenyls (PCBs) have been attracting global concern due to their persistence and toxicity. However, the study on the metabolites of PCBs in freshwater fish is limited. In this study, the metabolites of 2,2',4,5,5'-Pentachlorobiphenyl (PCB101) in silver crucian carp (Carassius auratus gibelio) were identified for the first time. After intraperitoneal injection of PCB101 (2 mg/kg), the results showed that it could be metabolized to at least three types of metabolites, including hydroxylated (OH-), methoxylated (MeO-) and methyl sulfonated (MeSO2-) PCB101. The OH- metabolites identified in most tissues were 3-OH-PCB101and 4-OH-PCB101, such as liver, gallbladder, blood and muscle. MeSO2- metabolites identified in gallbladder, blood and brain were 3-MeSO2-PCB101 and 4-MeSO2-PCB101. Meanwhile, the MeO- metabolite identified in liver, gallbladder, blood and spleen of silver crucian carp was 4-MeO-PCB101. The investigation of the types and structures of PCB101 and its metabolites, as well as the tissue distribution and accumulation characteristics in silver crucian carp are beneficial to understand the transformation and metabolic mechanisms of PCBs in aquatic organisms. It is of great significance to identify potential pollution hazards of precursor compounds and their metabolites on aquatic products and ensure the quality and safety of aquatic products.

Simulation experiment on OH-PCB being ingested through daily diet: Accumulation, transformation and distribution of hydroxylated-2, 2', 4, 5, 5'-pentachlorobiphenyl (OH-PCB101) in mice.

Animals exposure to polychlorinated biphenyls (PCBs) may result in retention of hydroxylated PCBs (OH-PCBs). OH-PCBs can be accumulated in animals, including humans, through the transmission of food chain. However, there are few studies on the accumulation and metabolism of OH-PCBs exposed to the body through daily diet. Therefore, this study was conducted to investigate the fate of OH-PCBs after being ingested through dietary intake. By adding 3-OH-PCB101 and 4-OH-PCB101 to the edible tissue of crucian carp, which were used as raw materials to prepare mouse feed, with an exposure concentration of 2.5 µg/kg ww. The exposure experiment lasted for a total of 80 days. The blood, feces and 11 tissues of mice at different times were analyzed qualitatively and quantitatively. It was found that major OH-PCB101 were accumulated in intestine or excreted with feces. A small part was accumulated in heart, lung and spleen. For the first time that the conversion from OH-PCB101 to PCB101 in mice was discovered, which shows from another perspective that persistent organic pollutants are difficult to be completely degraded in the environment. 4-MeO-PCB101, 3-MeSO2-PCB101, and 4-MeSO2-PCB101 were also found in various tissues. The results of this study show that after OH-PCBs accumulated in animals re-enter the organism through the food chain, they can be metabolized again and may be reversely transformed into the parent compounds. The present research shed new light on simulating the metabolic transformation process of OH-PCBs exposed to mammals through ingestion of fish. Available data show that second-generation persistent organic pollutants in the environment still need to be continuously concerned.

Fate of sulfamethoxazole and potential formation of haloacetic acids during chlorine disinfection process in aquaculture water.

There exist two common processes in fishery culture, i.e. antibiotic addition to reduce disease in fishery, and chlorination disinfection to inhibit infectious pathogenic microorganisms. However, antibiotic residues might play important reverse side roles for both aquaculture water pollution and potential formation of chlorination side products. Herein, the transformation behaviour, intermediates analyses and conversion pathway of antibiotic sulfamethoxazole (SMX), and potential generation of halogenated acetic acids (HAAs) in the process of chlorination in fishery water were examined, and the results revealed that the decomposing of SMX satisfied a pseudo first-order kinetic equation. Both the addition of available chlorine and high temperature had affirmative influences on the decontamination of SMX and production of HAAs, and the near-neutral pHs promoted the removal of SMX and generation of HAAs. Br- was favorable for the removal of SMX and yields of brominated acetic acids (Br-AAs). Based on the identified intermediate products, the transformation path of SMX in chlorination process was propounded, to wit, the C-S and S-N bonds in the SMX molecules were firstly cracked, and the primeval intermediate groups are then transformed to form chloroanilines, chlorophenols, etc., and subsequently, chlorophenols were chlorinated and ring-opened to generate toxic HAAs. This study might be meaningful to evaluate the effective removal of sulfonamide antibiotic residues and the potential generation of halogenated DBPs (H-DBPs) when chlorinated in aquaculture water.

An Effective and Efficient Sample Preparation Method for 2-Methyl-Isoborneol and Geosmin in Fish and Their Analysis by Gas Chromatography-Mass Spectrometry.

The intensive aquaculture strategy and recirculating aquaculture system often lead to the production of off-flavor compounds such as 2-methyl-isoborneol (2-MIB) and Geosmin (GSM). The regular purge and trap extraction followed by analysis with gas chromatography-mass spectrometry (GC-MS) usually involve a complicated assembly of facilities, more working space, long sample preparation time, and headspace solid-phase microextraction (SPME). In this work, a method with easier sample preparation, fewer and simplified facilities, and without SPME on GC-MS analysis is developed for the determination of 2-MIB and GSM in fish samples. Unlike previous methods, solvent extract from samples, QuEChERS-based cleanup, and solid-phase extraction for concentration are applied. The LOD (S/N > 3) and LOQ (S/N > 10) of this method were validated at 0.6 µg/kg and 1.0 µg/kg for both 2-MIB and GSM, which are under the sensory limit (1 µg/kg). Application of this method for incurred fish samples demonstrated acceptable analytical performance. This method is suitable for large-scale determination of 2-MIB and GSM in fish samples, owing to the use of simple facility and easy-to-operate procedure, rapid sample preparation, and shorter time for GC-MS analysis without SPME.

Determination of 8 biogenic amines in aquatic products and their derived products by high-performance liquid chromatography-tandem mass spectrometry without derivatization.

A method for the determination of 8 biogenic amines in aquatic products and their derived products was established by HPLC-MS/MS without derivatization. The samples were extracted by 5% perchloric acid solution. N-hexane was used to clean the extract. The analytes were separated by a column of ACQUITY UPLC HSS T3 (100 mm × 2.1 mm, 1.8 µm), and gradient eluted with a mixed solution of (0.5% formic acid) and acetonitrile. Good linearity was obtained with correlation coefficients (R2) >0.99. This method achieved higher sensitivity (from 0.1 mg/kg for tyramine, 2-phenylethylamine and tryptamine to 1.0 mg/kg for spermidine, spermine, cadaverin, histamine and putrescine). The average recoveries were demonstrated in the range of 70.9%-113.1%, with relative standard deviations (RSDs) from 0.33% to 10.81%. This method was suitable for the detection of BAs in aquatic products and their products.

Dehydrogenation of methylcyclohexane over Pt-based catalysts supported on functional granular activated carbon.

Herein, we developed the dehydrogenation of methylcyclohexane over Pt-based catalysts supported on functional granular activated carbon. Sulphuric acid, hydrogen peroxide, nitric acid and aminopropyl triethoxy silane were adopted to modify the granular activated carbon. The structural characterizations suggested that the carbon materials had a large surface area, abundant pore structure, and a high number of oxygen-containing functional groups, which influenced the Pt-based catalysts on the particle size, dispersion and dehydrogenation activity. The hydrogen temperature-programmed reduction technique was utilized to investigate the interaction between the active component Pt and the various functionalized granular activated carbon materials. The CO pulse technique revealed the particle sizes and dispersion of the as-prepared Pt-based catalysts. Finally, the Pt-based catalysts were successfully applied to study their catalytic activity in the dehydrogenation reaction of methylcyclohexane. The results showed that the Pt-based catalyst over granular activated carbon functionalized with sulphuric acid groups had a higher conversion of methylcyclohexane (63%) and a larger hydrogen evolution rate (741.1 mmol gPt -1 min-1) than the other resulting Pt-based catalysts at 300 °C.

Characterization of the complete mitochondrial DNA sequence of the Lagocephalus gloveri (Tetraodontidae, Tetraodontiformes).

The complete mitochondrial genome of Lagocephalus gloveri is reported in the present study, which is 16,446 bp in length. It consists of 13 protein-coding genes, two ribosomal RNA genes, 22 transfer RNA genes and a non-coding control region. The overall base composition of the genome is 27.58% for A, 25.07% for T, 30.83% for C and 16.52% for G. The phylogenetic tree, which is based on 12 protein coding gene sequences, suggested that L. gloveri was closest to L. lagocephalus. This study could give impetus to studies focused on population structure and molecular evolution of L. gloveri.

Characterization of the complete mitochondrial DNA sequence of the Lagocephalus guentheri (Tetraodontidae, Tetraodontiformes).

The complete mitochondrial genome of Lagocephalus guentheri was reported in the present study, which was 16,461 bp in length. It consists of 13 protein-coding genes, two ribosomal RNA genes, 22 transfer RNA genes and a non-coding control region. The overall base composition of the genome is 27.54% for A, 24.80% for T, 31.23% for C and 16.43% for G. The phylogenetic tree, which is based on 12 protein-coding gene sequences, suggested that L. guentheri was closest to L. spadiceus. This study could give impetus to studies focused on population structure and molecular evolution of L. guentheri.

Simultaneous determination of ten aminoglycoside antibiotics in aquatic feeds by high-performance liquid chromatography quadrupole-orbitrap mass spectrometry with pass-through cleanup.

A simple and sensitive method has been established based on pass-through cleanup and high-performance liquid chromatography quadrupole-orbitrap mass spectrometry (HPLC-Q/Orbitrap MS) for the simultaneous determination of ten aminoglycosides (AGs) in aquatic feeds. The extraction solution and cleanup procedure had been optimized, and good sensitivity, accuracy, and precision were obtained. The calibration curves of AGs were linearity (R2 > 0.99) in the range of 2.0 to 200 µg/L (or 5.0 to 500 µg/L). The limits of detection of AGs were between 10 and 25 µg/kg. The recoveries of AGs ranged from 74.9% to 94.3%, and the intraday and interday relative standard deviations were less than 15%. Finally, this method was successfully applied to determine ten AGs in 30 aquatic feed samples. It might be the first time to use pass-through cleanup approach combined with HPLC-Q/Orbitrap MS method for AGs determination in aquatic feed samples.