An asynchronous response fluorescence sensor combines machine learning theory to qualitatively and quantitatively detect tetracyclines.

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)32+ (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.

Comprehensive Assessment of Environmental Emissions, Fate, and Risks of Veterinary Antibiotics in China: An Environmental Fate Modeling Approach.

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 × 103 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.

Tetracyclines contamination in European aquatic environments: A comprehensive review of occurrence, fate, and removal techniques.

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.

Highly efficient removal of tetracyclines from water by a superelastic MOF-based aerogel: Mechanism quantitative analysis and dynamic adsorption.

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/GA200 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/GA200 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.

Prediction of antibiotic sorption in soil with machine learning and analysis of global antibiotic resistance risk.

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 R2 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.

Sensitive dual-signal detection and effective removal of tetracycline antibiotics in honey based on a hollow triple-metal organic framework nanozymes.

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.

Green hairy basil seed mucilage biosorbent for dispersive solid phase extraction enrichment of tetracyclines in bovine milk samples followed by HPLC analysis.

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 C18 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.

The occurrence of heavy metals and antimicrobials in sewage sludge and their predicted risk to soil - Is there anything to fear?

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 (RQenv), cumulative risk (RQcumulative) or risk of mixture of heavy metals (RQmix-metals). In the case of antimicrobials, only tetracycline demonstrated moderate RQenv, RQcumulative and RQmix-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.

D-Ring Modifications of Tetracyclines Determine Their Ability to Induce Resistance Genes in the Environment.

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.

Automated method for the solid phase extraction of tetracyclines in wastewater followed by fluorimetric determination.

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 Na2EDTA buffer before solid-phase extraction with an Oasis HLB column used for the analyte preconcentration. The europium (Eu3+)-based and citrate-mediated method (using Tris-HCl buffer) was selected for the fluorimetric analysis (λexc/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.

One Pot Synthesis of Nanofiber-Coated Magnetic Composites as Magnetic Dispersive Solid-Phase Extraction Adsorbents for Rapid Determination of Tetracyclines in Aquatic Food Products.

A magnetic adsorbent based on a C-nanofiber (Fe3O4@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 (R2 > 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.

Occurrence of sulfonamides and tetracyclines in the coastal areas of the Yangtze River (China) Estuary.

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).

An integrated multimedia fate modeling framework for identifying mitigation strategy of antibiotic ecological risks: A case study in a peri-urban river.

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.

Influence of copper and aging on freely dissolved tetracycline concentration in soil.

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.

Toxic effects of lead (Pb), cadmium (Cd) and tetracycline (TC) on the growth and development of Triticum aestivum: A meta-analysis.

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.

Evolution of a natural TetR protein and development of a Fe3O4 assisted semi-homogeneous fluorescent method for determination of tetracyclines in milk.

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 Fe3O4 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.

Continuous enrichment and trace analysis of tetracyclines in bovine milk using dual-functionalized aqueous biphasic system combined with high-performance liquid chromatography.

Two PPG1000 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.

Fabrication and optimization of paper chips from calcinated Fe-MOFs for rapid and in situ visual detection of tetracyclines in water environments.

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 NH2-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), Ca2+, Cl-, and HPO42- (< 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.

Towards direct detection of tetracycline residues in milk with a gold nanostructured electrode.

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.

Transfer of ß-lactam and tetracycline antibiotics from spiked bovine milk to Dambo-type cheese, whey, and whey powder.

The aim of this study was to investigate the transfer of residues of five ß-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.