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Antibiotics are commonly released into paddy fields as mixtures via human activities. However, the simultaneous extraction and detection of these chemicals from multiple media are technically challenging due to their different physicochemical properties, resulting in unclear patterns of their transport in the soil-rice system. In this study, a "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method was developed for the simultaneous analysis of 4 tetracyclines (TCs) and 4 fluoroquinolones (FQs) in the soil and rice tissues from a local poultry farm, and thereby the distribution patterns of the target antibiotics in the soil-rice system and their risk levels to the soil were analyzed. After parameter optimization, the calibration range used for the target antibiotics was 0.1-50 μg/L and each calibration curve was linear with a coefficient of determination (R 2  > 0.995); The QuEChERS method achieved satisfactory recovery rates (70.3-124.6%) along with sensitive detection limits (0.005-0.21 ng/g) for TCs and FQs in the soil, root, stem, leaf, and grain. Among the 8 antibiotics, enrofloxacin (ENX), ciprofloxacin (CIP), oxytetracycline (OTC), and doxycycline (DOX) were detected around a poultry farm. The four antibiotics in the collected paddy soils around the poultry farm ranged from 7.1 ng/g to 395.5 ng/g. Notably, ENX and DOX had higher ecological risks (risk quotient values >1) than CIP and OTC in soil. ENX, CIP, and DOX were highly enriched in rice roots with concentrations up to 471.9, 857.3, and 547.4 ng/g, respectively, which were also detected in rice aboveground tissues. The findings may provide both technical and practical guidance for the understanding of antibiotic environmental behavior and risks., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Novel metal-organic framework MIL-101(Cr)-NH 2 functionalised hydrophilic polydopamine-modified Fe 3 O 4 magnetic nanoparticles (Fe 3 O 4 @PDA@MIL-101(Cr)-NH 2 ) were synthesised and used as magnetic solid-phase extraction (MSPE) adsorbents for extracting tetracyclines (TCs) from milk samples. The integrated Fe 3 O 4 @PDA@MIL-101(Cr)-NH 2 exhibited convenient magnetic separation and exceptional multi-target binding capabilities. Furthermore, the PDA coating significantly enhanced the hydrophilicity and extraction efficiency of the material, thereby facilitating the extraction of trace TCs. Various factors affecting MSPE, such as adsorbent dosage, extraction time, pH value, and desorption conditions, were optimised. The developed MSPE method coupled with high-performance liquid chromatography demonstrated good linearity (R 2  ≥ 0.9989), acceptable accuracy (82.2%-106.1%), good repeatability (intra-day precision of 0.8%-4.7% and inter-day precision of 1.1%-4.5%), low limits of detection (2.18-6.25 μg L -1 ), and low limits of quantification (6.54-18.75 μg L -1 ) in TCs detection. The approach was successfully used for the quantification of trace TCs in real milk samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Based on novel phosphorus-doped carbon dots (PCDs), a simple, quick, and accurate fluorescence probe for sarecycline (SAR) determination has been created. The PCDs were prepared in just five minutes using green, straightforward one-step microwave pyrolysis. To create the PCD probe, sodium phosphate monobasic was utilized as a phosphorus dopant and citric acid as a carbon supply. The proposed synthesis method was energy efficient and yielded CDs with a narrow particle size distribution. Based on inner-filter effect mechanism, the generated PCDs were used as nano-probe for SAR determination. The fluorescence quenching intensity showed a strong linear relationship with SAR concentration in the 3-90-μM range with a detection limit of 0.88 μM. Because there is no surface alteration of the CDs or creation of a covalent bond between SAR and PCDs, the developed approach is quick, easy, inexpensive, and requires less time. The new probe's enhanced sensitivity, broad linear range, and acceptable selectivity made it suitable for SAR measurement in pharmaceutical formulations and spiked human plasma. Most importantly, the Green Analytical Procedure Index (GAPI) and Analytical GREEnness (AGREE) assessments showed that the suggested method was environmentally friendly., (© 2024 John Wiley & Sons Ltd.)

The traditional preparation method of ratiometric probes faces challenges such as cumbersome preparation and low sensitivity. Thus, there is an urgent need to provide a simple method of preparing a highly sensitive ratiometric probe. Here, Eu 3+ -doped zinc-based organic framework (Eu/Zn-MOF) was prepared through hydrothermal method for the detection of tetracycline analogs (TCs). Under the same excitation conditions, the probe can simultaneously display valuable fluorescence and second-order scattering signals. The developed probe enabled specific identification and fast detection (1 min) of TCs, including tetracycline, oxytetracycline, doxycycline, and chlortetracycline. The linear detection ranges of tetracycline, oxytetracycline, doxycycline and chlortetracycline were respectively 100 nM - 200 μM, 100 nM - 200 μM, 98 nM - 195 μM, and 97 nM - 291 μM, and the corresponding detection limits were respectively 15.79 nM, 20.83 nM, 15.31 nM, and 28.30 nM. The developed sensor was successfully applied to detect TCs in real samples, and the recovery rate was from 92.54 % to 109.69 % and the relative standard deviation was from 0.04 % to 2.97 %. Moreover, the heterometallic Eu/Zn-MOF was designed as a ratiometric neuron for Boolean logic computing and information encryption based on the specific identification of TCs. As a proof of concept, molecular steganography was successfully employed to encode, store, and conceal information by transforming the specific identification patterns of Eu/Zn-MOF into binary strings. This study is anticipated to advance the application of metal-organic frameworks in logic detection and information security, and bridging the gap between molecular sensors and the realm of information., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This work presents the development, synthesis, and application of a layered double hydroxide (LDH) coupled to magnetic particles for the removal of antibiotics as tetracyclines (TC´s): tetracycline (TC), chlortetracycline (CT), oxytetracycline (OT), and doxycycline (DT) from milk samples. The LDH synthesis conditions, reaction time (30-90 min), molar ratios Mg 2+ /Al 3+ (7:1-1:7), interlayer anion (NO 3 - , Cl - , CO 3 2- , and dodecyl sulphate (DS - )) were evaluated. Under synthesis conditions (reaction time of 30 min, Mg 2+ /Al 3+ molar ratio of 7:1, and DS - as interlayer anion), the LDH was coupled in a magnetic solid phase microextraction (MSPμE) methodology. At the optimal extraction conditions (pH 6, 5 min of contact time, 10 mg of adsorbent), a removal percentage of 99.0 % was obtained for each tetracycline. FTIR, TGA, SEM, and adsorption isotherms were employed to characterize the optimal adsorbent. Each experiment was corroborated by large-volume sample stacking capillary electrophoresis (LVSS-CE). The adsorbent was applied directly to positive milk samples (previously tested) for TC´s removal., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Sensor array methods have received much attention in recent years. In this study, a colorimetric sensor array consisting of three kinds of steel slag-based composites (including porphyrin-functionalized non-magnetic steel slag (NMSS-Por), alkali-excited steel slag (A-SS), and platinum modified steel slag (ALANH-Pt)) was developed for the detection and recognition of tetracycline antibiotics (TCs) such as tetracycline (TC), oxytetracycline (OTC) and doxycycline (DOX). Linear discriminant analysis (LDA) and hierarchical cluster analysis (HCA) showed that the colorimetric sensor array has excellent recognition ability for TCs. The detection limits of this sensor array for TC, OTC, and DOX were 0.059 μM, 0.111 μM and 0.118 μM, respectively, which provided higher sensitivity compared to the colorimetric sensors composed of a single steel slag-based composite material. At the same time, the array sensor has anti-interference ability, and this study provides a new application route for steel slag.

Three-dimensional sponge-architecture covalent organic frameworks (COFs)-aerogel was successfully designed and synthesized via a freeze-drying template approach, and utilized as an efficient sorbent in solid-phase extraction (SPE). A method for selective enrichment of pharmaceutical contaminants including tetracycline, chlortetracycline, methacycline and oxytetracycline in the environment and food samples was proposed by combining with high performance liquid chromatography (HPLC). To understand the adsorption mechanism, selectivity test and molecular dynamics (MD) simulated calculation were both carried out. The experimental and in-silico results demonstrated that the COFs-aerogel possessed high selectivity for contaminants with H bond acceptors/donors and good efficiency with maximum adsorption capacity up to 294.1 mg/g. The SPE-based HPLC method worked well in the range of 8-1000 ng/mL, with the need of little dose of adsorbent and sample volume while no need of spectrometer, outgoing the reported adsorbents. Under the optimized conditions, the intra-day and inter-day relative standard deviations (RSD) of repeatability were within 2.78-6.29 % and 2.44-8.42 % (n = 5). The results meet the current detection requirement for practical applications, and could be extended for further design of promising adsorbents., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Tetracyclines are widely used in Chinese apiculture. However, limited information is available on the presence of tetracycline residues in honey and the sources, degradation patterns, and associated health risks of these compounds. In this study, the presence of tetracyclines in honey samples across China was investigated over a four-year period. Additionally, the risks of dietary intake, as well as the sources and degradation patterns of tetracyclines in honey, were assessed. The three-dimensional spatial distributions (floral region, geographical region and entomological origin) of tetracyclines contamination varied significantly. Tetracycline residues in honey posed a moderate risk to children aged 3-10 years in Northwest China. Source analysis indicated that colony migration serves as the primary source of tetracyclines in honey. Based on the degradation patterns of tetracyclines in honey within colonies and during storage, oxytetracycline is more readily degraded than other tetracyclines. The main degradation products of tetracyclines are epimers and dehydration products, and the effects of these products on human health and the environment should be further evaluated in future studies. This comprehensive investigation provides valuable insights into the safe use and regulation of tetracyclines in Chinese apiculture., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Excess use of tetracyclines poses significant health risks arising from animal-derived foods, meaning simple and sensitive methods to detect tetracyclines would be beneficial given current laboratory methods are complex and expensive. Herein, we describe an asynchronous response fluorescence sensor constructed based on Zn-based metal-organic framework and Ru(bpy) 3 2+ (denoted as Ru@Zn-BTEC) for the qualitative and quantitative detection of tetracyclines in foods. Under excitation at 365 nm, the sensor emitted red fluorescence at 609 nm. When tetracyclines were present, these molecules aggregated in the Ru@Zn-BTEC framework, causing green fluorescence emission at 528 nm. The developed sensing system accurately distinguished the different categories of tetracyclines with a classifier accuracy of 94 %. The Ru@Zn-BTEC sensor demonstrated a detection limit of 0.012 μM and satisfactory recovery (87.81 %-113.84 %) for tetracyclines in food samples. This work provides a pathway for constructing asynchronous response fluorescence sensors for food analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

A method utilizing liquid-liquid extraction (LLE) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed and validated according to the Commission Implementing Regulation (CIR) EU 2021/808 for quantifying four tetracyclines (TCs) in potatoes and soil. The method demonstrated recovery values ranging from 70 to 121% and precision (repeatability and within-laboratory reproducibility), with coefficient of variation (CV) values below 18% for all TCs in both matrices. The limits of quantification (LOQs) for the TCs ranged from 0.90 to 1.87 μg/kg in potatoes and from 0.68 to 1.25 μg/kg in soil. The decision limit (CCα) and detection capability (CCβ) ranged from 10.4 to 12.3 μg/kg and 11.9 to 14.3 μg/kg, respectively. Analysis of 538 potato and soil samples from Egyptian farms revealed a 13.2% occurrence of TC residues, with a higher frequency in soil (19.33%) than in potatoes (7.06%). Target hazard quotient (THQ) values indicated that TC residues in potatoes do not pose a health risk to Egyptian consumers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

The misuse of tetracyclines in livestock production poses significant health risks. Thus, establishing convenient detection methods to replace complex laboratory tests for food safety is crucial. In this study, a heterostructure Zn-BTC/IRMOF-3 (denoted as ZBI) asynchronous response fluorescence sensor was developed for the qualitative and quantitative detection of tetracyclines in foods. The ZBI solution exhibited blue fluorescence under UV excitation; upon the introduction of tetracyclines, ZBI selectively recognized the tetracycline molecules through electron transfer, π-π stacking, and chelation, resulting in blue fluorescence quenching and green fluorescence enhancement. The ZBI sensor for tetracycline detection achieved recovery rates ranging from 93.91 to 111.91% in food samples, with a detection limit of as low as 0.086 μmol/L. Lastly, a portable sensing device using support vector classifier was constructed for detecting tetracyclines in real-life scenarios. Our findings introduce a new approach for fabricating fluorescence sensors and offer a novel method for detecting tetracyclines., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Due to the serious detrimental impact on human health, antibiotic pollution particularly tetracyclines residues has become a serious problem. Herein, a multiple response fluorescent probe consisted of dual-emission carbon dots and Eu 3+ (D-CDs@Eu 3+ ) is designed for the determination and discrimination of tetracyclines (TCs). Specifically, the carboxyl and amidogen group of dual-emission carbon dots (D-CDs) can coordinate with Eu 3+ to form the D-CDs@Eu 3+ . Upon adding TCs, the fluorescence intensities of D-CDs at 405 nm and 495 nm are quenched due to inner filter effect (IFE) and the localization of fluorescence resonance energy transfer (L-FRET) between the D-CDs@Eu 3+ and TC. Simultaneously, the D-CDs@Eu 3+ may chelate with TCs to enhance the occurrence of antenna effect, while the characteristic peaks of Eu 3+ at 590 nm and 615 nm are enhanced. On these bases, the TCs detection is achieved with low detection limits from 46.7 to 72.0 nM. Additionally, through the distinct efficiencies of L-FRET, the discrimination of TCs is achieved. Moreover, a novel centrifugated lateral flow assay strips (CLFASs) device is developed by integrating the D-CDs@Eu 3+ , lateral flow assay strips and smartphone using RGB variations for TCs detection, achieving remarkable recoveries (98.6-103.7 %) in real samples. Therefore, this CLFASs device provides a reliable approach for the TCs detection, demonstrating potential applications., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

We investigated the potential accumulation of tetracyclines (TCs) such as chlortetracycline (CTC), oxytetracycline (OTC) and doxycycline (DC), and fluoroquinolones (FQs) like enrofloxacin (ENR) and ciprofloxacin (CIP) in chicken litter and agricultural soils fertilized over short-term to long-term (<1-30 yrs) with chicken litter in a poultry hub for the first time from Tamil Nadu, India. CTC, OTC, DC, CIP, and ENR were detected in 46-92 % of the selected chicken litter samples, with mean levels ranging from 2.90 to 23.30 μg kg -1 . Higher concentrations of TCs and FQs were observed in freshly collected chicken litter from poultry sheds than in those stockpiled in cultivated lands. CTC was the prevalent antibiotic in chicken litter. The overall occurrence, as well as the ecological risks of TCs and FQs, changed over a 30-yr period. The accumulation of veterinary antibiotics (VAs) (in μg kg -1 ) in short-term (>1 yr) to medium-term (1-3 yrs) chicken litter-fertilized soils reached a maximum of 11.60 for CTC, 6.50 for OTC, 0.80 for DC, 3.70 for CIP, and 3.60 for ENR, but decreased in long-term (10-30 yrs) fertilized soils. Ecological risk assessment revealed a Risk Quotient (RQ) of ≤0.10 for CTC, OTC, and DC in all soils, while an average risk (RQ >0.10-<1.0) was evident with CIP and ENR in short-term and medium-term fertilized soils. Antibiotic resistance genes (ARGs), including tetA, tetB, qnrA, qnrB and qnrS were detected in most of the chicken litter samples and litter-fertilized soils. Thus, it is critical to develop and adopt effective mitigation strategies before applying chicken litter in farmlands to decrease VAs and ARGs, reducing their associated risks to public health and ecosystems in India considering 'One Health' approach. Future investigations on the occurrence of other VAs and ARGs in soils fertilized with poultry litter at regional scale are required for effective risk mitigation of the widely used VAs., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Dr. Saranya Kuppusamy reports financial support was provided by India Ministry of Science & Technology Department of Science and Technology., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: The AnticFast® Beta-lactams & Tetracyclines Combo Test Kit is a qualitative two-step (2 min + 5 min) rapid lateral flow assay to detect β-lactam (penicillins and cefalosporins) and tetracycline antibiotic residues in raw commingled cows' milk., Objective: The method performance was evaluated according to Commission Implementing Regulation 2021/808 and Community Reference Laboratories Residues Guidelines for the Validation of Screening Methods for Residues of Veterinary Medicines and submitted for AOAC Performance Tested MethodsSM certification., Methods: The AnticFast Beta-lactams & Tetracyclines Combo Test Kit was evaluated for detection capability (CCβ), selectivity, false-positive results, repeatability, robustness, suitability for various milk types and milk compositions, milks from various species, and test kit consistency and stability. Samples included milks spiked at concentrations bracketing the EU maximum residue limits (MRLs) for β-lactams and tetracyclines as well as bulk farm and tanker milks., Results: The AnticFast Beta-lactams & Tetracyclines Combo Test Kit is specific for the detection of residues of β-lactams and tetracyclines in milk and does not detect residues from other antibiotic families. Interference was seen with clavulanic acid, a β-lactamase inhibitor, which was expected. The test can detect (minimum a 95% detection) all residues of β-lactams (penicillins and cepfalosporins) and tetracyclines (parent drugs and their 4-epimers) present on the EU-MRL list for milk at their respective MRL except for desfuroylceftiofur and cefalexin, with a 95% detection only above the MRL. No false positives were detected in 599 blank samples (out of 305 farm and 301 tanker load samples) tested on both channels. Five real positives were detected and confirmed on the tetracycline channel for the farm milk samples, and two positives were detected and confirmed on the β-lactam channel for the tanker samples. Robustness testing indicated that the detection in high-protein raw cows' milk and heat-treated milk types (UHT, sterilized, and reconstituted milk powder) may be slightly hampered. For substances with a detection capability well below the MRL, this interference does not cause problems since detection at MRL remains guaranteed, but care should be taken for substances with a CCβ at or near their MRL. Diminished sample flow was seen for high-fat raw cows' milk and for all other cows' milk types other than raw milk and blank ewes' milk, so sample flow should always be verified for these milk types., Conclusions: Results of this validation show that the AnticFast Beta-lactams & Tetracyclines Combo Test Kit is a reliable test for rapid screening of raw cows' milk for residues of β-lactam and tetracycline antibiotics., Highlights: The AnticFast Beta-lactams & Tetracyclines Combo Test Kit is an easy, reliable, robust, and highly specific test for screening of β-lactam (penicillins and cefalosporins) and tetracycline antibiotic residues in milk with incubation at room temperature. In raw cows' milk, all tetracyclines are detected below 10 µg/kg., (© The Author(s) 2024. Published by Oxford University Press on behalf of AOAC INTERNATIONAL. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

The overuse and misuse of tetracycline (TCs) antibiotics, including tetracycline (TTC), oxytetracycline (OTC), doxycycline (DC), and chlortetracycline (CTC), pose a serious threat to human health. However, current rapid sensing platforms for tetracyclines can only quantify the total amount of TCs mixture, lacking real-time identification of individual components. To address this challenge, we integrated a deep learning strategy with fluorescence and colorimetry-based multi-mode logic gates in our self-designed smartphone-integrated toolbox for the real-time identification of natural TCs. Our ratiometric fluorescent probe (CD-Au NCs@ZIF-8) encapsulated carbon dots and Au NCs in ZIF-8 to prevent false negative or positive results. Additionally, our independently developed WeChat app enabled linear quantification of the four natural TCs using the fluorescence channels. The colorimetric channels were also utilized as outputs of logic gates to achieve real-time identification of the four individual natural tetracyclines. We anticipate this strategy could provide a new perspective for effective control of antibiotics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Tetracycline antibiotics (TCs) are extensively used in clinical medicine, animal husbandry, and aquaculture because of their cost-effectiveness and high antibacterial efficacy. However, the presence of TCs residues in the environment poses risks to humans. In this study, an inner filter effect (IFE) fluorescent probe, 2,2'-(ethane-1,2-diylbis((2-((2-methylquinolin-8-yl)amino)-2-oxoethyl)azanediyl))diacetic acid (MQDA), was developed for the rapid detection of Eu 3+ within 30 s. And its complex [MQDA-Eu 3+ ] was successfully used for the detection of TCs. Upon coordination of a carboxyl of MQDA with Eu 3+ to form a [MQDA-Eu 3+ ] complex, the carboxyl served as an antenna ligand for the effective detection of Eu 3+ to intensify the emission intensity of MQDA via "antenna effect", the process was the energy absorbed by TCs via UV excitation was effectively transferred to Eu 3+ . Fluorescence quenching of the [MQDA-Eu 3+ ] complex was caused by the IFE in multicolor fluorescence systems. The limits of detection of [MQDA-Eu 3+ ] for oxytetracycline, chlorotetracycline hydrochloride, and tetracycline were 0.80, 0.93, and 1.7 μM in DMSO/HEPES (7:3, v/v, pH = 7.0), respectively. [MQDA-Eu 3+ ] demonstrated sensitive detection of TCs in environmental and food samples with satisfactory recoveries and exhibited excellent imaging capabilities for TCs in living cells and zebrafish with low cytotoxicity. The proposed approach demonstrated considerable potential for the quantitative detection of TCs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The abuse and irrational use of tetracyclines (TCs) in human medicine and animal husbandry has become a serious concern, affecting the ecological environment and human health. The aim of this study was to develop a sensitive and selective method using fully automatic solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry for the determination of twelve TCs in water. Four isotope-labeled internal standards for TCs were used to correct matrix effects. Several parameters affecting extraction efficiency were systematically optimized, and the optimum experimental conditions found were 1.0 L water sample with 0.5 g/L Na 2 EDTA (pH 3.0) extracted and enriched by CNW HLB cartridge and eluted by 4 mL of acetone:methanol ( v / v , 1:1). The enrichment factors were up to 798-1059 but only requiring about 60 min per six samples. Under the optimized conditions, the linearity of the method ranged from 0.2 to 100 μg/L for 12 TCs, the detection limits were as low as 0.01-0.15 ng/L, and the recoveries were in the range of 70%-118%, with relative standard deviations less than 15%. The developed method can be successfully utilized for the determination of 12 TCs in pure water, tap water, river water, and mariculture seawater. In summary, three and six TCs were detected in river water and mariculture seawater, respectively, with total concentrations of 0.074-0.520 ng/L (mean 0.248 ng/L) and 0.792-58.369 ng/L (12.629 ng/L), respectively. Tetracycline (TC) and oxytetracycline (OTC) were the dominant TCs in river water, while doxytetracycline (DXC) and OTC were dominant in mariculture seawater.

Tetracyclines are a group of antibiotic substances largely administered through medicated feed to control diseases in food-producing animals. Fine dosing of antibiotics contained in medicated feed is crucial for the success of the treatment as well as minimising potential threats such as the spread of antimicrobial resistance and the transfer of antibiotic residues in food. A rapid analytical method based on HPLC with diode array detection (HPLC-DAD) was developed to quantify oxytetracycline, chlortetracycline and doxycycline in medicated feed. The reported method underwent in-house validation and was found to be suitable for the quantification of three target tetracyclines within the concentration range of 40-1000 mg kg -1 in official routine analysis. The method was applied to 103 official samples in the framework of the Italian National Plan on animal feed during the years 2021-2023 and nine non-compliant concentrations were identified in swine and fish feed samples.

In this work, a colorimetric/fluorescent dual-signal mode sensor is proposed for the sensitive, selective and accurate detection and removal of tetracycline antibiotics (TCs). A triple-metal MOF of NiCoFe is successfully synthesized and controllable adjusted the shape of the hollow structure for the first time, and then modified with TCs aptamer. The as-prepared triple-atom MOF (apt-NiCoFe-MOF-74) exhibits well-defined hollow morphology, high crystallinity, and high surface areas endow their alluring adsorption and removal performances for TCs. More attractively, this triple-metal MOF show a good peroxidase-like activity and strong fluorescence property at 540 nm of apt-NiCoFe-MOF-74 when excitation wavelength was 370 nm. Inspire by this, a dual-signal output biosensor is constructed and the linear absorbance response is well correlated with wide range and low LOD for TCs. The biosensor provided an universal method with satisfactory sensitivity and accuracy for TCs analysis in real food samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Unmodified hairy basil seed mucilage (Ocimum basilicum L.), with attractive features as structural functionality and adsorption capacity, was employed as a green biosorbent for dispersive solid phase extraction and enrichment of oxytetracycline, tetracycline, and doxycycline before quantitation by HPLC-UV for the first time. Hairy basil crushed seed increased the contacting surface area and was completely dispersed in the sample solution to extract tetracyclines under acidic condition with the assistance of ultrasonic waves. The analytes in the extraction phase were separated on a C 18 column under isocratic condition with a mobile phase consisted of acetonitrile and trifluoroacetic acid. Influence of chemical and physical variables on the extraction efficiency of the developed method was investigated and optimized systematically. Under the optimal condition of all experimental parameters, good linear ranges were obtained at 15.0-500 μg L -1 for tetracyclines with determination coefficients more than 0.9994. Limits of detection (LODs) and limits of quantitation (LOQs) ranged 5.0-7.0 and 15.0 μg L -1 , respectively. Relative standard deviations (RSDs) of the proposed method at 100 and 300 μg L -1 for TCs were less than 13 % and 10 %, respectively with percentage TC recoveries from spiked standard ranging 83.1-109.9 %. This simple, reliable, cost-effective, and environmentally friendly method was successfully applied for the analysis of tetracycline residues in milk. The greenness of the proposed method was assessed using the Analytical Eco-Scale and AGREE protocol., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Tetracyclines are among the most commonly used antibiotics for the treatment of bacterial infections and the improvement of agricultural growth and feed efficiency. All compounds in the group of tetracyclines (tetracycline, chlorotetracycline, doxycycline, and oxytetracycline) are excreted in an unchanged form in urine at a rate of more than 70%. They enter the aquatic environment in altered and unaltered forms which affect aquatic micro- and macroorganisms. This study reviews the occurrence, fate, and removal techniques of tetracycline contamination in Europe. The average level of tetracycline contamination in water ranged from 0 to 20 ng/L. However, data regarding environmental contamination by tetracyclines are still insufficient. Despite the constant presence and impact of tetracyclines in the environment, there are no legal restrictions regarding the discharge of tetracyclines into the aquatic environment. To address these challenges, various removal techniques, including advanced oxidation, adsorption, and UV treatment, are being critically evaluated and compared. The summarized data contributes to a better understanding of the current state of Europe's waters and provides insight into potential strategies for future environmental management and policy development. Further research on the pollution and effects of tetracyclines in aquatic environments is therefore required., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This work presents a multisyringe flow injection analysis (MSFIA) system for the automatic extraction and determination of tetracyclines in wastewater samples. The sample was adjusted with Na 2 EDTA buffer before solid-phase extraction with an Oasis HLB column used for the analyte preconcentration. The europium (Eu 3+ )-based and citrate-mediated method (using Tris-HCl buffer) was selected for the fluorimetric analysis (λ exc/em  = 400/612 nm). For fluorescence detection, a low-cost system consisting of an USB 2000 CCD detector and a 3D-printed support that holds a LED light source was used. Under optimized conditions, the proposed method provided low limits of detection (9.4 μg L -1 ) and quantification (31 μg L -1 ), and good values for intra-day (<4 %) and inter-day precisions (<6 %). Recoveries of spiked TCs in wastewater samples ranged from 87 to 106 %. The results of this work were in good agreement with the measurements obtained by liquid chromatography coupled to a fluorescence detector., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Iron-natural phenolic microparticles were developed as absorbents for dispersive micro solid phase extraction (D-μSPE) synergistic with hydrophobic ionic liquid (IL) for dispersive liquid-liquid microextraction (DLLME) to enrich tetracycline residues, including tetracycline, doxycycline, oxytetracycline and chlortetracycline. In situ iron microparticles synthesized from betel nut natural reagent were employed as an adsorbent for D-μSPE. The hydrophobic IL [Hmim][PF 6 ] was synergistically utilized as an extraction solvent to extract and accumulate adsorbents bound with tetracyclines before quantitation by HPLC-UV. The synergistic combination of DLLME with D-μSPE provided excellent extraction recovery compared with individual extraction. The developed method was successfully applied to enrich and determine tetracycline residues in honey samples, with recoveries ranging from 80.0 to 121.5% and providing high enrichment factors ranging from 61 to 197. This alternative method is simple and rapid, with high extraction efficiency and a high enrichment factor and is also environmentally friendly for the analysis of tetracyclines., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In the present study, a highly efficient analytical method based on preconcentration of tetracyclines (TCs) in water and milk samples using a magnetic molecularly imprinted polymer (Fe 3 O 4 /SiO 2 /MIP) synthesized by means of a novel semi-covalent synthesis for TCs and determination by HPLC-DAD was proposed. Fe 3 O 4 /SiO 2 /MIP showed specific superficial area of 216.0 m 2 /g, superior to Fe 3 O 4 /SiO 2 /NIP (non-imprinted material) (103.6 m 2 /g). Using the Fe 3 O 4 /SiO 2 /MIP, the magnetic dispersive solid phase extraction (MDSPE) for four TCs (chlortetracycline, doxycycline, oxytetracycline, and tetracycline) was based on the preconcentration of 40.0 mL of sample (pH 4.0) vortex-assisted with 10 mg of Fe 3 O 4 /SiO 2 /MIP during 60 s. The method presented a limit of detection (LOD) in the range 0.26-0.60 µg/L, and preconcentration factor in the range 52.3-87.4-fold for the TCs. The method was applied to determine TCs in samples of lake water and cow milk with recovery results ranging from 96.0 to 102.0 %., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

China is one of the major global consumers of veterinary antibiotics. Insufficient recognition of emissions and environmental contamination hamper global efforts to prevent antibiotic resistance development. This pioneering study combined empirical data and modeling approaches to predict total 2010-2020 emissions of 80 veterinary antibiotics ranging from 23,110 to 40,850 tonnes/year, after 36-50% antibiotic removal by manure treatment. Following an initial increase of 10% from 2010 to 2015, emissions declined thereafter by 43%. While 85% of emissions discharged into soils, approximately 56%, 23%, and 18% of environmental residue were ultimately distributed in soils, freshwaters, and seawaters under steady-state conditions. In 2020, 657 (319-1470) tonnes entered the ocean from inland freshwaters. Median ∑antibiotics concentrations were estimated at 4.7 × 10 3 ng/L in freshwaters and 2.9 ng/g in soils, with tetracyclines and sulfonamides as the predominant components. We identified 44 veterinary antibiotics potentially posing high risks of resistance development in freshwaters, with seven exhibiting high risks in >10% of Chinese freshwater areas. Tetracyclines were the category with the most antibiotics exhibiting elevated risks; however, sulfamethylthiazole demonstrated the highest individual compound risk. The Haihe River Basin displayed the highest susceptibility overall. The findings offer valuable support for control of veterinary antibiotic contamination in China.

Although the sorption of antibiotics in soil has been extensively studied, their spatial distribution patterns and sorption mechanisms still need to be clarified, which hinders the assessment of antibiotic resistance risk. In this study, machine learning was employed to develop the models for predicting the soil sorption behavior of three classes of antibiotics (sulfonamides, tetracyclines, and fluoroquinolones) in 255 soils with 2203 data points. The optimal independent models obtained an accurate predictive performance with R 2 of 0.942 to 0.977 and RMSE of 0.051 to 0.210 on test sets compared to combined models. Besides, a global map of the antibiotic sorption capacity of soil predicted with the optimal models revealed that the sorption potential of fluoroquinolones was the highest, followed by tetracyclines and sulfonamides. Additionally, 14.3% of regions had higher antibiotic sorption potential, mainly in East and South Asia, Central Siberia, Western Europe, South America, and Central North America. Moreover, a risk index calculated with the antibiotic sorption capacity of soil and population density indicated that about 3.6% of soils worldwide have a high risk of resistance, especially in South and East Asia with high population densities. This work has significant implications for assessing the antibiotic contamination potential and resistance risk., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Metal-organic frameworks (MOFs) were promising adsorbents for removing antibiotics, but the inherent poor recyclability of MOF powders limits further application. Moreover, the dominant adsorption mechanisms and their quantitative assessment are less studied. Here, ultrahigh adsorption capacities of 821.51 and 931.87 mg g -1 for tetracycline (TC) and oxytetracycline (OTC), respectively, were realised by a novel adsorbents (biochar loaded with MIL-88B(Fe), denoted as BC@MIL-88B(Fe)), which were further immobilised in a 3D porous gelatin (GA) substrate. The obtained BCM/GA 200 showed superior adsorption performance under wide pH ranges and under the interference of humic acid. Moreover, it can survive >8 cycles and even maintain high adsorption efficiency in different actual water samples. Notably, BCM/GA 200 can selectively remove tetracyclines in a multivariate system containing other kinds of antibiotics and from a dynamic adsorption system. Most importantly, the results of X-ray photoelectron spectroscopy, 2D Fourier transform infrared correlation spectroscopy (2D-FTIR-COS) and density functional theory techniques revealed that (1) for TC adsorption, at pH < 4.0, the contribution of complexation was 25 %-45 %, whereas pore filling and hydrogen bonding accounted for 39 %-72 % of the total uptake. At 4.0 < pH < 10.0, the contribution of complexation increased to 60 %-82 %, whereas electrostatic attraction and π-π interaction were 4 %-13 % and 2 %-10 %, respectively. (2) For OTC adsorption, complexation was dominant at 3.0 < pH < 10.0, accounting for 55 %-86 % of the total uptake, and electrostatic attraction and π-π interactions caused 3 %-10 % and 3 %-15 %, respectively. (3) At pH > 10.0, pore filling dominated TC and OTC adsorption. Finally, the reaction sequences of the main adsorption mechanisms were also probed by 2D-FTIR-COS. This work solves the poor recyclability of MOF powders and provides a mechanistic insight into antibiotic removal by MOFs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The study assessed the occurrence of legally-monitored heavy metals and unmonitored antimicrobials in sludge from small, medium, large and very large municipal wastewater treatment plants (WWTPs), and the predicted environmental risk and risk of resistance selection associated with sludge administration to soil. The temporal variations of the studied compounds in sludge and associated risks to soil were determined by sampling over a year. Although the highest concentrations of heavy metals were noted in sludge from the largest WWTP, i.e. from 1.50 mg/kg (mean 1.61 mg/kg) for Cd to 2188 mg/kg (mean 1332 mg/kg) for Zn, the obtained values only reached a few percent of the legal limits. The same WWTP also demonstrated lower concentrations of antimicrobials compared to the smaller ones. The highest concentrations of antimicrobials, ranging from 24.04 μg/kg for trimethoprim to 900.24 μg/kg for tetracycline, were found in the small and medium WWTPs. However, due to lack of regulations at the national and EU levels, the results cannot be compared with legal limits. Principal Component Analysis (PCA), cluster and heatmap analysis separated samples according to WWTP size. Small WWTP demonstrated correlation with antimicrobials (tetracycline, trimethoprim, clindamycin, ciprofloxacin and ofloxacin), while the large and very large WWTP revealed correlations with heavy metals (Cu and Cr). The obtained environmental risk quotients confirmed that the heavy metals did not present a threat, measured either as individual risk quotients (RQ env ), cumulative risk (RQ cumulative ) or risk of mixture of heavy metals (RQ mix-metals ). In the case of antimicrobials, only tetracycline demonstrated moderate RQ env , RQ cumulative and RQ mix-antimicrobials in the small WWTP sludge, with values of 0.1 to 1. Our findings highlight the importance of monitoring sewage sludge before soil application, especially from small WWTPs, to reduce the potential environmental impact of antimicrobials. They also confirm our previous data regarding the environmental risk associated with various toxic compounds, including emerging contaminants, in the sludge from small WWTPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The widespread utilization of tetracyclines (TCs) in agriculture and medicine has led to the borderless spread of tetracycline resistance in humans, animals, and the environment, posing huge risks to both the ecosystem and human society. Changes in the functional group modifications resulted in a higher bacteriostatic efficacy of the new generation of TCs, but their effect on the emergence and evolution of antibiotic resistance genes (ARGs) is not yet known. To this end, four TCs from three generations were chosen to compare their structural effects on influencing the evolution of ARGs in soil microbial communities. The findings revealed that low-generation TCs, such as tetracycline and oxytetracycline, exhibited a greater propensity to stimulate the production and proliferation of ARGs than did high-generation tigecycline. Molecular docking analysis demonstrated that modifications of the D-ring functional group determined the binding capacity of TCs to the substrate-binding pocket of transcriptional regulators and efflux pumps mainly involved in drug resistance. This can be further evidenced by reverse transcription-quantitative polymerase chain reaction quantification and intracellular antibiotic accumulation assessment. This study sheds light on the mechanism of the structural effect of antibiotic-induced ARG production from the perspective of compound-protein binding, therefore providing theoretical support for controlling the dissemination of antibiotic resistance.

Tetracyclines (TCs) are a group of broad-spectrum antibiotics against multiplying microorganisms yet with several adverse effects on humans. Since all types of TCs have the similar chemical skeleton and mechanism of action, quantification of total amount of TCs in the environment was of particular importance. To date, dozens of fluorescent probes have been reported for TCs detection, but only very few of them enabled detection of total TCs. In this study, we report a novel supramolecular sensor constructed by human serum albumin as the recognition moiety and a flavonol fluorophore as the indicator. Under the 370 nm UV excitation, this sensor exhibits the rapid response (5 s), acceptable sensitivity (limit of detection ∼ 0.58 μM), long dynamic detection range (0-20 μM), prominent specificity, and excellent anti-interference properties for analysis of total TCs. The mechanism was carefully validated using 1 H NMR, fluorescence titration experiments, molecular docking, and mass spectrometry. We expect this work can inspire more sensor design for TCs quantification., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The environmental issue of lead (Pb), cadmium (Cd), and tetracycline (TC) contamination in cereal crops has become a growing concern worldwide. An in-depth understanding of this issue would be of importance to promote effective management strategies for heavy metals and antibiotics worldwide. The present study was conducted to assess the toxic effects of heavy metals (Cd, Pb) and antibiotics (TC) on Triticum aestivum (T. aestivum, common wheat) based on studies conducted in the past 22 years. Data pertaining to the growth and development of T. aestivum were extracted and analyzed from 89 publications spanning from 2000 to 2022. Our results showed that Pb, Cd and TC significantly reduced growth and development by 11 %, 9 %, and 5 %, respectively. Additionally, significant accumulation of Cd (42 %) and Pb (17 %) was observed in T. aestivum samples, although there was little change in TC accumulation, which showed limited absorption, accumulation, and translocation of TC in wheat plants. Pb had the greatest impact on the yield of T. aestivum, followed by Cd, while TC had no apparent effect. Furthermore, exposure to Cd, Pb and TC reduced the photosynthetic rate due to chlorophyll reduction, with Cd having the most pronounced effect (58 %), followed by Pb (37 %) and TC (8 %). Cd exposure also significantly enhanced gaseous exchange (37 %) compared to TC and Pb, which reduced gaseous exchange by 4 % and 10 %, respectively. However, the treatments with TC (>50-100 mgL -1 ), Pb (>1000-2000 mg L -1 ) and Cd (>500-1000 mg L -1 ) increased the defense system of T. aestivum samples by 38 %, 15 %, and 11 %, respectively. The obtained findings have significant implications for risk assessment, pollution prevention, and remediation strategies to address soil contamination from Pb, Cd and TC in farmland., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Antibiotics have attracted global attention due to the ecological risks to environment. In this paper, solid-phase extraction and ultra-performance liquid chromatography triple quadrupole mass spectrometry (LC-MS/MS) were utilized to analyze the fugitive characteristics of 10 antibiotics of sulfonamides (sulfadiazine, sulfamethazine, sulfadimidine, sulfathiazole, sulfapyridine, sulfamethoxazole) and tetracyclines (tetracycline, oxytetracycline, chlortetracycline and doxycycline) in the coastal waters and surfece sediments of the Yangtze River Estuary and the ecological risks of antibiotics in water were estimated using ecological risk assessment method. The results have showed that 7 of the 10 antibiotics were detected in the water, with total concentrations ranging from 0.652 to 434.47 ng/L. 8 antibiotics were detected in the sediment, with total concentrations ranging from 0.091 to 499.23 ng/g. The main antibiotic species detected in the sediment and water varied seasonally. Higher concentrations in spatially distributed areas where rivers meet and where human activities have a more significant impact. The ecological risks were found to be higher in spring and autumn than those in winter and summer. Spatial variation in individual microbial communities was not evident in the sediments. The relationship between antibiotics and microorganisms in the environment was predominantly positive. Physical and chemical factors were significantly correlated for both antibiotics and microbial communities. This study can provide research ideas for other types of antibiotics and provide a basis for the prevention of antimicrobial resistance (AMR)., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Antibiotics have been heavily used over the past decades, resulting in their frequent detections in rivers and increasing ecological risks. Recognizing characteristics of antibiotic ecological risks (AERs) and making effective strategies to mitigate the AERs are essential to ensure the safety of aquatic ecosystem and public health. In this study, an integrated technological framework has been proposed toward identifying management options for reducing AERs by jointly utilizing multimedia fugacity modelling and ecotoxicological risk assessment, and applied to characterize the AERs in a peri-urban river in Beijing. Specifically, a level III fugacity model has been successfully established to simulate the fate of antibiotics in the environment, and the manageable parameters have been screened out via sensitivity analysis of the model. Then the validated fugacity model has been used for scenario modellings to optimize mitigation strategies of AERs. Results show most of the antibiotics considered are frequently detected in the river, and pose medium or high risks to aquatic organisms. Relatively, the macrolides and fluoroquinolones present higher ecotoxicological risks than sulfonamides and tetracyclines. Furthermore, the mixture risk quotient and predictive equation of concentration addition suggest joint and synergistic/antagonistic effects of AERs for multiple or binary antibiotics in the environment. Largely, the concentrations of antibiotics in the river are determined by the source emissions into water and soil. Scenario modellings show the improvement of antibiotic removal rates would be considered preferentially to mitigate the AERs. Also, controlling human consumption is conducive to reducing the risks posed by tetracyclines, macrolides and trimethoprim, while controlling animal consumption would benefit the reduction for sulfonamides. Overall, the joint strategy presents the greatest reduction of AERs by reducing antibiotic consumption and together improving sewage treatment rate and antibiotic removal rate. The study provides us a useful guideline to make ecological risk-based mitigation strategy for reducing AERs in environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

A magnetic adsorbent based on a C-nanofiber (Fe 3 O 4 @C-NFs) nanocomposite was synthesized using a simple one-pot co-precipitation method. The characterized results showed that the obtained C-nanofiber-coated magnetic nanoparticles had many attractive features such as a large specific surface area and a highly interwoven and branched mesoporous structure, as well as distinguished magnetism. The nanocomposite was then used as an adsorbent in the magnetic solid phase extraction (MSPE) of four typical tetracyclines (oxytetracycline, tetracycline, chlortetracycline, and doxycycline) in aquatic products. The TCs in the extract were determined using ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Experimental variables of MSPE, including the sorbent amount, pH condition, adsorption and desorption time, and desorption solvent, were investigated and optimized systematically. The method validation indicated that the developed method showed good linearity (R 2 > 0.995) in the range of 1.0-200 ng/mL. The average recoveries at the spiked levels ranged from 90.7% to 102.7% with intra-day and inter-day relative standard deviations (RSDs, n = 6) ranging from 3.72% to 8.17% and 4.20% to 9.69%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) for the four kinds of TCs were 0.7 μg/kg and 2.0 μg/kg, respectively. Finally, MSPE based on C-nanofiber-coated magnetic nanoparticles was successfully applied to TC analysis in real aquatic products (grass carp, large yellow croaker, snakehead, mandarin fish, Penaeus vannamei, swimming crab, etc.). Compared with traditional extraction methods, the proposed method for TC analysis in aquatic products is more sensitive, effective, recyclable, and environmentally friendly.

Copper (Cu) and tetracyclines (TCs) often coexist in agricultural soils because of the use of manures on farmland; however, the influence of Cu on the bioavailability of TCs is still unclear, especially for cases with aging Cu. The freely dissolved concentrations (FDCs) of TCs are believed to be directly related to their bioavailability. In the present study, the FDCs of TCs were determined using organic-diffusive gradients in thin films (o-DGT), and the influence of Cu on the FDCs of TCs in soils was evaluated. The results showed that the FDCs of tetracycline (TC), oxytetracycline (OTC), and chlortetracycline (CTC) were 0.11-0.93, 0.28-1.02, and 0.24-0.53 μg/kg in the CK groups (no Cu added) and accounted for 0.09-0.58, 0.10-1.40, and 0.05-1.19‰ of their total concentrations which ranged from 0.2 to 10.0 mg/kg for TC, OTC, and CTC, respectively. The co-contamination of Cu reduced the FDCs of TCs in most cases, and aging increased the influence of Cu. The presence of Cu resulted in a decrease in the TC FDC by 35.48-95.04% in aged soils and 3.42-87.19% in newly prepared soils. FTIR analysis revealed that aging facilitated the bonding of Cu to soil particles via Cu-O, and Cu bonded to groups such as hydroxyl groups (-OH) in TCs. Our results suggested that the presence of Cu might reduce the bioavailability of TCs, and aging would enhance these effects. This is helpful for the bioavailability analysis of TCs under co-contamination of heavy metals., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Compared with antibody, the recognition spectrum of a receptor is broader, and its recognition ability can be improved using simple mutagenesis technique. Compared with conventional immunoassay, the magnetic bead based immunoassay is simpler and can be recycled. Compared with colorimetric and luminescent immunoassays, fluoroimmunoassay is simpler because it does not require a substrate. So a method combines these merits is desirable. In this study, two amino acids in the binding pocket of a natural Escherichia coli TetR protein were mutated to produce a mutant, and the molecular docking showed the binding energies and the numbers of contact acid for 10 tetracyclines all increased. The mutant was coupled with Fe 3 O 4 to synthesize a magnetic complex, and a fluorescent tracer was synthesized by coupling quantum dot and minocycline with bovine serum albumin. Under the assistance of 96-well bottom magnet, a semi-homogeneous method based on the two materials was developed on conventional microplate for determination of the 10 tetracyclines in milk. Results showed once assay was finished within 20 min, the limits of detection (drug concentration showing 10% inhibition) for the 10 drugs were in the range of 0.32-0.94 ng/mL, and the magnetic complex could be regenerated for 6 times. Furthermore, the sensitivities were improved for 4-6 folds in comparison with the use of natural TetR. Therefore, this method is simple, sensitive, time-saving and recyclable, and it can be used for routine screening of the 10 tetracyclines in milk., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Antibiotics such as tetracyclines (TCs) have become a major threat to ecosystem safety and human health, as their abuse has caused the occurrence and proliferation of antibiotic-resistant bacteria and genes. Currently, there is still a lack of convenient in situ methods for the detection and monitoring of TC pollution in actual water systems. This research reports a paper chip based on the complexation of iron-based metal organic frameworks (Fe-MOFs) and TCs for rapid and in situ visual detection of representative oxytetracycline (OTC) pollution in water environments. The optimized complexation sample NH 2 -MIL-101(Fe)- 350 obtained by calcination at 350 °C exhibited the highest catalytic activity and was then used for paper chip fabrication by printing and surface modification. Notably, the paper chip demonstrated a detection limit as low as 17.11 nmol L -1 and good practicability in reclaimed water, aquaculture wastewater, and surface water systems, with OTC recovery rates of 90.6-111.4%. More importantly, the presence of dissolved oxygen (9.13-12.7 mg L -1 ), chemical oxygen demand (0.52-12.1 mg L -1 ), humic acid (< 10 mg L -1 ), Ca 2+ , Cl - , and HPO 4 2- (< 0.5 mol L -1 ) had negligible interference on the detection of TCs by the paper chip. Therefore, this work has developed a promising method for rapid and in situ visual monitoring of TC pollution in actual water environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Two PPG 1000 based temperature-sensitive magnetic ionic liquid were synthesized and characterized. The temperature-sensitive magnetic ionic liquid aqueous biphasic system combined with HPLC was applied for the continuous enrichment and trace analysis of tetracycline antibiotics (TC) in bovine milk for the first time. High enrichment factors were achieved and the detection was highly sensitive. The trace analysis of TC was rapid, free of organic solvent, recyclable and magnetically assisted for phase separation. Under optimum conditions, wide linear ranges of 0.25-300 ng/mL for all TC, high enrichment factors of 217.7-231.4, good precisions with relative standard deviation in the range of 0.74-3.97%, very low limits of detection of 0.031-0.067 ng/mL, limits of quantification of 0.103-0.223 ng/mL, and good recoveries of 94.28-99.76% were acquired for the proposed analytical method. Real milk analysis was satisfactory. This developed analytical method is showing great potential for trace analysis of targeted analytes in foods and drinks., (The Authors. Published by Elsevier Inc. and Fass Inc. on behalf of the American Dairy Science Association®. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).)

Tetracyclines (TC) is a typical broad-spectrum antimicrobial agent, and excessive use of TC can lead to a large accumulation of residual tetracycline in water. DOM is organic substances that can pass through the 0.45 μm filter. While dissolved organic matter (DOM) is one of the most significant substances in water, which has an important effect on water treatment. In this study, ultraviolet and visible spectrophotometry (UV-Vis) is applied to explore DOM to the effect of the electrochemical degradation. Three-dimension excitation emission matrix fluorescence spectroscopy (3D-EEM) is used to identify the component variation of DOM after the electrochemical oxidation (EO). Liquid chromatograph mass spectrometer (LC-MS) is used to confirm the degradation pathway of TC whether spontaneous or electrochemical oxidation. High performance liquid chromatography (HPLC) suggests the ROS production by DOM in the electrochemical oxidation under different conditions. Results show that DOM can promote the degradation of TC in the electrochemical oxidation. Tailwater DOM containssubstances can produce persistent free radicals, which can promote the degradation under light and dark conditions, natural source DOM can produce more free radicals under light. Therefore, TC wastewater should be added tailwater to promote the degradation of TC before the further water treatment. Otherwise, TC can be degraded to differentpathways (light, electricity, and degrade spontaneously). This study provides a significant idea for practical water treatment of tetracyclines, and promotes the practical application of electrochemical technology., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The aim of this study was to investigate the transfer of residues of five β-lactam antibiotics (ampicillin, penicillin G, cloxacillin, dicloxacillin and cephalexin) and two tetracyclines (tetracycline and oxytetracycline) in the processing of cheese and whey powder, evaluating the effect of the processes and the final concentration in each product generated. Raw milk was fortified at two concentration levels with the seven antibiotics. The first concentration level (C1) was chosen according to the maximum residue limit (MRL) of each antibiotic (ampicillin and penicillin G: 4 µg kg -1 ; cloxacillin and dicloxacillin: 30 µg kg -1 ; cephalexin, tetracycline and oxytetracycline: 100 µg kg -1 ). The second concentration level (C2) was spiked as follows according to each antibiotic: 0.5 MRL (cloxacillin, dicloxacillin, cephalexin), 0.1 MRL (tetracycline and oxytetracycline) and 3 MRL (ampicillin and penicillin G). The antibiotics were analyzed by LC-MS/MS. No ampicillin or penicillin G residues were found in cheese or whey powder, although they were detected in whey at concentrations similar to those added to raw milk. Cephalexin was mostly distributed in whey between 82% and 96%, being the antibiotic that presented the highest concentration in whey powder (784 ± 98 µg kg -1 ) when milk was spiked at the MRL. The whey distribution of cloxacillin and dicloxacillin ranged from 57% to 59% for cloxacillin and from 46% to 48% for dicloxacillin, and both concentrated in whey powder. Tetracyclines were the antibiotics that concentrated in cheese, with retentions between 75% and 80% for oxytetracycline and between 83% and 87% for tetracycline. The distribution of antibiotics in the dissimilar stages of the cheese and whey powder production processes, as well as their concentration in the final products, depend on each type of antibiotic. Knowledge of the transfer of antibiotic residues during the process and final disposal is an input for the risk assessment of their consumption.

Misuse and overuse of tetracycline antibiotics (TCs) brings serious issues to ecological environment, food safety and human health. It is urgent to develop unique platform for high efficient identification and removal of TCs. In the present investigation, an effective and simple fluorescence sensor array was constructed based on the interaction between metal ions (Eu 3+ and Al 3+ ) and antibiotics. Benefiting from the different affinities between the ions and TCs, the sensor array can identify TCs from other antibiotics, which also can further differentiating four kinds of TCs (OTC, CTC, TC and DOX) from each other via linear discriminant analysis (LDA) technique. Meanwhile, the sensor array performed well in quantitative analysis of single TC antibiotic and differentiation of TCs mixtures. More interestingly, Eu 3+ and Al 3+ -doped sodium alginate/polyvinyl alcohol hydrogel beads (SA/Eu/PVA and SA/Al/PVA) were further constructed, which can not only identify the TCs but simultaneously remove the antibiotics with high efficiency. The investigation provided an instructive way for rapid detection and environment protection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Tetracycline antibiotics (TCs), one of the important antibiotic groups, have been widely used in human and veterinary medicines. Their residues in foodstuff, soil and sewage have caused serious threats to food safety, ecological environment and human health. Here, we reviewed the potential harms of TCs residues to foodstuff, environment and human beings, discussed the luminescence and aptamer sensors based analytical determination, adsorptive removal, and degradation strategies of TCs residues from a recent 5-year period. The advantages and intrinsic limitations of these strategies have been compared and discussed, the potential challenges and opportunities in TCs residues degradation have also been deliberated and explored., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Tetracycline antibiotics are used extensively in veterinary medicine, but the majority of the administrated dose is eliminated unmodified from the animal through various excretion routes including urine, faeces and milk. In dairy animals, limits on residues secreted in milk are strictly controlled by legislation. Tetracyclines (TCs) have metal chelation properties and form strong complexes with iron ions under acidic conditions. In this study, we exploit this property as a strategy for low cost, rapid electrochemical detection of TC residues. TC-Fe(III) complexes in a ratio of 2:1 were created in acidic conditions (pH 2.0) and electrochemically measured on plasma-treated gold electrodes modified with electrodeposited gold nanostructures. DPV measurements showed a reduction peak for the TC-Fe(III) complex that was observed at 50 mV (vs. Ag/AgCl QRE). The limit of detection in buffer media was calculated to be 345 nM and was responsive to increasing TC concentrations up to 2 mM, added to 1 mM FeCl3. Whole milk samples were processed to remove proteins and then spiked with tetracycline and Fe(III) to explore the specificity and sensitivity in a complex matrix with minimal sample preparation, under these conditions the LoD was 931 nM. These results demonstrate a route towards an easy-to-use sensor system for identification of TC in milk samples taking advantage of the metal chelating properties of this antibiotic class., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2023 Raykova et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Veterinary antibiotics (VAs) are emerging contaminants in soils as they may pose high risks to the ecosystem and human health. Identifying VAs accumulation in soils is essential for assessing their potential risks. Therefore, we investigated the distribution of VAs in soils from vegetable fields and evaluated their potential ecological and antimicrobial resistance risks in the Chongqing region of the Three Gorges Reservoir area, China. Results indicated that twenty-six species of VAs, including nine sulfonamides (SAs), seven quinolones (QNs), four tetracyclines (TCs), four macrolides (MLs), and two other species of VAs were detected in soils, with their accumulative levels ranging from 1.4 to 3145.7 μg kg -1 . TCs and QNs were the dominant VAs species in soils with high detection frequencies (100% TCs and 80.6% for QNs) and accumulative concentration (up to 1195 μg kg -1 for TCs and up to 485 μg kg -1 for QNs). Risk assessment indices showed that VAs (specifically SAs, TCs, and QNs) in most vegetable soils would pose a medium to high risk to the ecosystem and antimicrobial resistance. Mixture of VAs posed a higher risk to soil organisms, antimicrobial resistance, and plants than to aquatic organisms. Modeling analysis indicated that socioeconomic conditions, farmers' education levels, agricultural practices, and soil properties were the main factors governing VAs accumulation and environmental risks. Farmers with a high educational level owned large-scale farms and were more willing to use organic fertilizers for vegetable production, which eventually led to high VAs accumulation in vegetable soil. These findings would provide a reference for sustainable agricultural and environmental production under the current scenario of chemical fertilizer substitution by organic products and green agricultural development., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

The concern over antibiotic pollution from animal husbandry has significantly increased over recent years. However, few studies on output and environmental risk of veterinary antibiotics (VAs) throughout different exposure matrices from small-scale livestock farms (SSLFs) have been explored. This study explored the output and environmental risk of three classes of VAs (sulfonamides (SAs), tetracyclines (TCs), fluoroquinolones (FQs)) in three different types of environmental media (manure, soil, and plants/vegetables) derived from four livestock feedlots in the Hexi Corridor of Northwest China. Following, a risk assessment was conducted to identify the hazardous potential of these VAs on the ecological health of the surrounding environment. A total of 108 soil, 36 manure, 12 plants/vegetables, and 15 animal product samples were collected from the animal feedlots for analysis. The results showed that each of the three groups of VAs were detected in the soil, manure and plant samples derived from all four feedlots in varying levels. In the soil samples, the detection rate of SAs (68%) was higher than the TCs (57%) and the FQs (27%). The total concentration of VAs ranged from not detected (n.d.) to 275 ng/g, while chlortetracycline (CTC) was the most abundant (275 ng/g) of the VAs in soil samples. The SAs had the highest detection rate (100%), followed by TCs (89%), and FQs (78%) in manure samples. The total concentration of VAs residues ranged from n. d. to 105 ng/g, of which CTC was as high as 91 ng/g in manures. In the plant/vegetable samples, the TCs had the highest detection rate (58%), while sulfamethazine (SDM) was the most abundant (32 ng/g). The total concentration of the VAs ranged from n. d. to 65 ng/g in the plant/vegetable samples. The target VAs were not detected in animal products. Measurements of the composition of VAs in soil samples at different vertical depths as well as horizontal distances from the manure accumulation sites showed that VAs were partially retained in the soil of the feedlots and were distributed into the surrounding environment both horizontally and vertically. It is suspected that the detected VAs could be accumulated in agricultural soils since they could be found in most of the sampled manures and soils in SSLFs. These results highlighted the necessity of considering SSLF practices to mange the accumulation and disposal of manure mitigating and controlling VA pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

This is the first comprehensive report on antibiotics in the Huai River, a major Chinese river. To illuminate the concentrations, prioritization, spatial distributions, sources, and ecological risks of antibiotics, surface water samples were collected and three types of most widely used antibiotics (16 sulfonamides, 8 tetracyclines, and 14 quinolones) were analyzed. The results indicated that concentrations of ∑quinolones (86 ± 31 ng/L) > ∑tetracyclines (20 ± 13 ng/L) > ∑sulfonamides (11 ± 3.7 ng/L). Oxolinic acid (OXA), cinoxacin(CINX), norfloxacin (NFX), and methacycline (MTC) were the priority antibiotics with mean concentrations > or close to 10 ng/L, however, they were rarely included as target compounds in most previous Chinese investigations. Different spatial distributions of antibiotics were discovered across three reaches separated by two sluices, demonstrating that the sluices may impact antibiotic dissemination. According to the results of the source analysis, the aquaculture industry was the major source of observed antibiotics (49%), followed by livestock & poultry farming (26%) and mixed sources (25%). Because commercial fishing in the Huai River has been prohibited, the aquaculture industry will expand in the next years, and antibiotic contamination caused by the aquaculture industry deserves more attention. The risk quotients were calculated by comparing observed antibiotics to predicted no-effect concentrations, and the results showed that observed antibiotics posed negligible or low integrated risks for Green algae, and medium or low integrated risks for Daphnia magna., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Antibiotics have been widely detected in the water environment and thus pose a potential threat to human health. Although antibiotics have health-promoting properties, whether and how they affect health at environmental concentrations remains uncharacterised. We detected antibiotics in surface water and groundwater in China. Sulfonamides (851 ng/L) and tetracyclines (1322 ng/L) showed the highest concentrations in surface water, while the highest concentration of sulfonamides detected in groundwater was 250 ng/L. We analysed the distribution of four classes of antibiotics (sulfonamides, tetracyclines, macrolides, and quinolones) and evaluated the associated health risks in the surface water of seven cities. We found that antibiotic pollution caused health risks to the 0-3-months age group, but not to other age groups. We further demonstrated that simulated long-term exposure to environmental concentrations of antibiotics had concentration-dependent toxic effects on L-02 hepatocytes, affected cell proliferation, and induced oxidative damage and DNA damage. Chronic exposure to mixed sulfonamides affected growth, caused liver damage, and reduced the abundance of intestinal flora in mice. Under exposure to antibiotics, the abundance of Helicobacter pylori in the gut flora significantly increased and posed a health risk to humans. These results indicated that exposure to antibiotics at environmental concentrations can cause oxidative damage and inflammation both in vitro and in vivo. These findings add to the body of basic data on the distribution of antibiotics in the water environment, and provide a scientific basis for the evaluation of antibiotic toxicity., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Qiaoyuan Yang reports financial support was provided by National Natural Science Foundation of China, Natural Science Foundation of Guangdong Province., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

This study was carried out to validate the liquid scintillation counter method (Charm II) for the detection of tetracyclines, beta-lactams, and sulfonamides (Sulfa drugs) in a range of Aquaculture Products. This method of validation followed primary validation performed in Belgium and was therefore transferred to Nigeria but further validation was required, and this was performed according to the European Commission Decision 2002/657/EC. Method performance was based on the detection capability (CCβ), specificity (cross-reactivity), robustness, repeatability, and reproducibility for the detection of antimicrobial residues. Seafood and aquaculture samples used for the validation process included tilapia (Oreochromis niloctus), catfish (Siluriformes), African threadfin (Galeoides decadactylus), common carp (Cyprinus carpio), and shrimps (penaeidae). These were spiked with varying concentrations of tetracyclines, beta-lactams, and sulfonamides standards to determine the validation parameters. Results of the validation showed tetracyclines had detection capabilities of 50 µg/kg, while beta-lactams and sulphonamides had detection capabilities of 25 µg/kg. The relative standard deviation for both repeatability and reproducibility studies ranged between 1.36% and 10.50%. Results of this study are suitable and comparable to the initial validation reports from the primary validation ofCharm II tests forthedetection ofantimicrobial residues inarange ofaquaculture fish conducted in Belgium. The results also prove the specificity, ruggedness, and reliability of the radio receptor assay tests for detection of the various antimicrobials in aquaculture products. This could be used in seafood/aquaculture products monitoring in Nigeria., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Inc. All rights reserved.)

Tetracyclines are a class of antibiotics with a similar four-ringed structure. Due to this structural similarity, they are not easily differentiated from each other. We recently selected aptamers using oxytetracycline as a target and focused on an aptamer named OTC5, which has similar affinities for oxytetracycline (OTC), tetracycline (TC), and doxycycline (DOX). Tetracyclines exhibit an intrinsic fluorescence that is enhanced upon aptamer binding, allowing convenient binding assays and label-free detection. In this study, we analyzed the top 100 sequences from the previous selection library. Three other sequences were found to differentiate between different tetracyclines (OTC, DOX, and TC) by the selective enhancement of their intrinsic fluorescence. Among them, the OTC43 aptamer was more selective for OTC with a limit of detection (LOD) of 0.7 nM OTC, OTC22 was more selective for DOX (LOD 0.4 nM), and OTC2 was more selective for TC (0.3 nM). Using these three aptamers to form a sensor array, principal component analysis was able to discriminate between the three tetracyclines from each other and from the other molecules. This group of aptamers could be useful as probes for the detection of tetracycline antibiotics.

To understand the fate of antibiotics in the aquatic environment, we need to evaluate to which extent the following processes contribute to the overall antibiotic attenuation: adsorption to river sediment, biodegradation, hydrolysis and photodegradation. A laboratory scale mesocosm experiment was conducted in 10 L reactors filled with river sediment and water. The reactors were spiked with four classes of antibiotics (fluoroquinolones, macrolides, sulfonamides, tetracyclines), as well as clindamycin and trimethoprim. The experimental-set-up was designed to study the attenuation processes in parallel in one mesocosm experiment, hence also considering synergetic effects. Our results showed that antibiotics belonging to the same class exhibited similar behavior. Adsorption was the main attenuation process for the fluoroquinolones and tetracyclines (44.4 to 80.0 %). For the sulfonamides, biodegradation was the most frequent process (50.2 to 65.1 %). Hydrolysis appeared to be significant only for tetracyclines (12.6 to 41.8 %). Photodegradation through visible light played a minor role for most of the antibiotics - fluoroquinolones, sulfonamides, and trimethoprim (0.7 to 24.7 %). The macrolides were the only class of antibiotics not affected by the studied processes and they persisted in the water phase. Based on our results, we propose to class the antibiotics in three groups according to their persistence in the water phase. Fluoroquinolones and tetracyclines were non-persistent (half-lives shorter than 11 d). Chlorotetracycline, sulfapyridine and trimethoprim showed a moderate persistence (half-lives between 12 and 35 d). Due to half-lives longer than 36 d sulfonamides and clindamycin were classified as persistent., Competing Interests: Declaration of competing interest The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results. Declaration of interests Ewa Borowska reports financial support was provided by Baden-Württemberg Foundation., (Copyright © 2023 Elsevier B.V. All rights reserved.)