Cocktail Effect Research Articles

Surprising cocktail effect in high entropy alloys on catalyzing magnesium hydride for solid-state hydrogen storage

Magnesium hydride (MgH2) attracts wide interests as a promising hydrogen energy carrier, but its commercial application is hampered by the high operating temperatures and slow dehydrogenation kinetics. Herein, CrMnFeCoNi and CrFeCoNi high-entropy alloys (HEAs) were adopted to boost the hydrogen storage performance of MgH2. It was demonstrated that the morphology of catalysts and addition of Mn had a great impact on the performance of HEAs catalysts. In particular, the Mn containing HEAs nanosheets presented the best performance. The MgH2-CrMnFeCoNi composite could release 6.5 wt% H2 in 10 min at 300 °C and started to absorb H2 at 40 °C. Moreover, kinetic analysis revealed that the rate control model in dehydrogenation process of HEA-4 modified MgH2 changed from permeation model of MgH2 to diffusion. In addition, 97% hydrogen storage volume could be maintained after 20 cycles at 300 °C, showing a good cycling performance. Microstructure analysis showed that the CrMnFeCoNi nanosheets were uniform dispersed over the surface of MgH2, bringing numerous heterogeneous activation sites to speed up the dispersal of hydrogen. Besides, the cocktail effect of HEAs exerted synergic action between Cr, Mn, Fe, Co and Ni elements to improve the overall catalytic efficiency. Therefore, the de/rehydrogeantion performance of the MgH2-CrMnFeCoNi composite was surprisingly accelerated.

Ultrathin wavy nanowires of high-entropy alloy as cocktail solution in methanol oxidation reaction

High entropy alloys (HEAs) with adjustable composition and diverse surface active sites show good catalytic performance of methanol oxidation reaction (MOR). However, the synthesis and morphology control of HEA remains a challenge. Herein, we use a fast co-reduction method to synthesize a series of ultrathin wavy nanowires (WNWs) with an average diameter of 3–5 ​nm, including Pt-based and Pd-based binary alloys, and HEA with different pairs of immiscible elements. The catalytic properties of PtPdAgCuNi WNWs show that the mass activity and stability of PtPdAgCuNi WNWs is higher than Pt and Pd WNWs. Meanwhile we explored the cocktail effect among high entropy alloy elements through annealing. The cocktail effect among the metal elements in PtPdAgCuNi WNWs provided more active sites with increased metal-metal interactions, thus improving the catalytic efficiency.

Refractory high-entropy alloys: A focused review of preparation methods and properties

• We reviewed the preparation methods of RHEAs, including metallurgical smelting, powder metallurgy, magnetron sputtering and additive manufacturing technology. • The microstructure and phase transformation process of RHEAs were analyzed. • The mechanical properties and main strengthening and toughening mechanisms of RHEAs, such as solid solution strengthening, precipitation strengthening and the transformation-induced plastic (TRIP) were discussed. • The properties of RHEAs, including high strength, oxidation resistance, corrosion resistance and wear resistance were reviewed. • We particularly focus on the generation of the ideal room temperature toughness of brittle BCC-structure RHEAs to achieve the combination of high strength and high toughness as engineering materials. In recent years, high-entropy alloys (HEAs) have become prominent metallic materials due to their unique design strategies and excellent mechanical properties. The HEAs-inherent high-entropy, lattice-distortion, sluggish-diffusion, and cocktail effects make HEAs maintain high strength, oxidation resistance, corrosion resistance, wear resistance, and other excellent comprehensive properties, showing stronger competitiveness relative to traditional alloys. Refractory high-entropy alloys (RHEAs) are considered as a new kind of high-temperature materials with great application prospects due to their excellent mechanical properties and have the potential to replace nickel-based superalloy as the next generation of high-temperature materials. We reviewed the research status and preparation methods of RHEAs in recent years, including the metallurgical smelting, powder metallurgy, magnetron sputtering, and additive manufacturing technologies. The microstructure and phase-transformation process of RHEAs were analyzed. The mechanical properties and main strengthening and toughening mechanisms of RHEAs, such as solid-solution strengthening, precipitation strengthening, and the transformation-induced plasticity (TRIP), were discussed, and the deformation mechanism of RHEAs was revealed. The properties of RHEAs, including high strength, oxidation resistance, corrosion and wear resistance were reviewed. RHEAs will meet the huge market demand in the engineering materials field, but there are still many challenges, such as the trade-off between high strength and high ductility, structural design, and performance optimization of RHEAs with brittle BCC structures. We believe that this combination of knowledge may shape the future of RHEAs and break through the mutually exclusive conundrum of high strength and high toughness for RHEAs.

OVERVIEW OF THE HIGH-ENTROPY ALLOYS CONCEPT

The article presents a review of the results of research on high-entropy alloys, describing the principles of their formation, the basic concepts and properties of high-entropy alloys. The existing categories of the entropic alloys are listed. The effects resulting from the formation of high-entropy alloys are described: high entropy, lattice distortion, sluggish diffusion and cocktail effects. It is noted that the traditional thermodynamic representations for multicomponent alloys require additions. It is also noted that the application of Hume-Rothery rules to predict the phase composition of high-entropy alloys shows some difficulties, since it is difficult to select a large number of elements having the same type of lattice and valence. The results of the analysis of a number of parameters and conditions which, according to the researchers' opinion, affect the structural state created by high-entropy alloys, taking into account which could allow to correctly predict the formation of structures in high-entropy. Analysis of the literature data has shown that at present there is no universal parameter that could allow the correct prediction of the formation of structures in multicomponent alloys systems. Methods for the preparation of powders of high entropy alloys are presented. The results of frequently used methods of obtaining coatings on the basis of high-entropy alloys, such as laser cladding, magnetron sputtering, electrochemical deposition and thermal spraying are reviewed. Disadvantages of obtaining coatings methods are described.

Synergy of cations in high entropy oxide lithium ion battery anode

High entropy oxides (HEOs) with chemically disordered multi-cation structure attract intensive interest as negative electrode materials for battery applications. The outstanding electrochemical performance has been attributed to the high-entropy stabilization and the so-called ‘cocktail effect’. However, the configurational entropy of the HEO, which is thermodynamically only metastable at room-temperature, is insufficient to drive the structural reversibility during conversion-type battery reaction, and the ‘cocktail effect’ has not been explained thus far. This work unveils the multi-cations synergy of the HEO Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O at atomic and nanoscale during electrochemical reaction and explains the ‘cocktail effect’. The more electronegative elements form an electrochemically inert 3-dimensional metallic nano-network enabling electron transport. The electrochemical inactive cation stabilizes an oxide nanophase, which is semi-coherent with the metallic phase and accommodates Li+ ions. This self-assembled nanostructure enables stable cycling of micron-sized particles, which bypasses the need for nanoscale pre-modification required for conventional metal oxides in battery applications. This demonstrates elemental diversity is the key for optimizing multi-cation electrode materials.

Contamination of Baby Foods by Plastic Additives: A Pilot Screening Study

Despite the fact that food production and processing may involve various appliances and materials containing plastic additives (PAs), potential food contamination by a variety of PAs has not been sufficiently investigated, particularly in baby foods. In this study, we screened for a total of 245 legacy and emerging PAs in representative baby foods (n = 70), including formulas, cereals, vegetable/fruit purees, and meat products. Total concentrations of ΣPAs ranged from 3.86 to 9580 ng/g (median of 194 ng/g), and 47 PAs were detected in >50% of the samples, among which 16 were detected for the first time in baby foods. Non-phthalate ester plasticizers exhibited the highest abundances (median of 52.7 ng/g), followed by phthalate esters (46.1 ng/g), organophosphate esters (8.20 ng/g), synthetic antioxidants (8.15 ng/g), ultraviolet stabilizers (1.56 ng/g), bisphenols (0.51 ng/g), and parabens (0.04 ng/g). Food categories and the types of packaging materials appeared to influence the levels and compositional profiles of PA contamination. The estimation of daily intake suggested a low risk of dietary exposure. However, the high complexity of PAs detected in baby foods raises concern about the exposure to an increasing list of industrial chemicals, due to potential cocktail effects, limited knowledge of biological effects of emerging substances, and exposure from additional sources.

Moisissures dans l’environnement et impacts sur la santé humaine

AbstractExposure to ubiquitous molds in our environment is inevitable in many circumstances: at hospital, at work, at home… and can be responsible for infection and allergy depending on different underlying risk factors.In hospitals, exposure of immunosuppressed patients to filamentous micromycetes such as Aspergillus and mucorales can result in lifethreatening invasive aspergillosis and mucormycosis. Prevention of these infections relies on two possible strategies: chemoprophylaxis and environmental prevention with air treatment and associated measures that allow a « protected area ». At work and at home, recurrent exposure to molds can result in chronic infection or immunoallergic disease. Beside molds, combination of exposure to other microorganisms (such as yeasts, Pneumocystis, bacteria and viruses) as well as to chemical compounds, what we call the exposome, can induce synergistic effects on health (or cocktail effects).Monitoring of the environmental fungal biocontamination is an essential tool for protected areas in hospitals and is also pertinent, using different techniques, to evaluate the fungal risk at home and at work.

Cocktail effects of emerging contaminants on zebrafish: Nanoplastics and the pharmaceutical diphenhydramine

Nanoplastics (NPLs) became ubiquitous in the environment, from the air we breathe to the food we eat. One of the main concerns about the NPLs risks is their role as carrier of other environmental contaminants, potentially increasing their uptake, bioaccumulation and toxicity to the organisms. Therefore, the main aim of this study was to understand how the presence of polystyrene NPLs (∅ 44 nm) will influence the toxicity (synergism, additivity or antagonism) of the antihistamine diphenhydramine (DPH), towards zebrafish (Danio rerio) embryos, when in dual mixtures. After 96 hours (h) exposure, at the organismal level, NPLs (0.015 or 1.5 mg/L) + DPH (10 mg/L) induced embryo mortality (90%) and malformations (100%) and decreased hatching (80%) and heartbeat rates (60%). After 120 h exposure, NPLs (0.015 or 1.5 mg/L) + DPH (0.01 mg/L) decreased larvae swimming distance (30–40%). At the biochemical level, increased glutathione S-transferases (55–122%) and cholinesterase (182–343%) activities were found after 96 h exposure to NPLs (0.015 or 1.5 mg/L) + DPH (0.01 mg/L). However, catalase (CAT) activity remained similar to the control group in the mixtures, inhibiting the effects detected after the exposure to 1.5 mg/L NPLs alone (increased 230% of CAT activity). In general, the effects of dual combination – NPLs + DPH (even at concentrations as low as 10 μg/L of DPH) – were more harmful than the correspondent individual exposures, showing the synergistic interactions of the dual mixture and answering to the main question of this work. The obtained results, namely the altered toxicity patterns of NPLs + DPH compared with the individual exposures, show the importance of an environmental risk assessment considering NPLs as a co-contaminant due to the potential NPLs role as vector for other contaminants.

Nonphthalate Plasticizers in House Dust from Multiple Countries: An Increasing Threat to Humans.

Along with the restrictions of phthalate esters (PAEs), a variety of nonphthalate plasticizers (NPPs) have been increasingly used for industrial needs. Knowledge remains limited on the environmental occurrences, fate, and human exposure risks of many emerging NPPs. In this study, we investigated a suite of 45 NPPs along with the major PAEs in house dust from five regions in the Asia-Pacific region and the United States. The findings clearly demonstrated ubiquitous occurrences of many NPPs in the home environment, particularly acetyl tributyl citrate (ATBC), tricapryl trimellitate (TCTM), trioctyl trimellitate (TOTM), glycerol monooleate (GMO), methyl oleate (MO), and diisobutyl adipate (DiBA). The median total concentrations of NPPs ranged from 17.8 to 252 μg/g in the study regions, while the mean ratios of ΣNPPs to ΣPAEs ranged from 0.19 (Hanoi) to 0.72 (Adelaide). Spatial differences were observed not only for the chemical abundances but also for the composition profiles and the hazard quotient (HQ) prioritization of individual chemicals. Although the current exposure may unlikely cause significant health risks according to the HQ estimation, potential exposure risks cannot be overlooked, due to the lack of appropriate toxic threshold data, the existence of additional exposure pathways, and possible cocktail effects from coexisting NPPs and PAEs.

Cocktail effect and synergistic mechanism of two components of Perilla frutescens essential oil, perillaldehyde and carvone, against Tribolium castaneum

Tribolium castaneum (Herbst) is one of the most harmful insects in stored products. The objective of the current study was to search for active constituents of Perilla frutescens (L.) Britt. essential oils from three localities against T. castaneum, as well as to investigate the optimal formula of active constituents and their synergistic mechanism. A total of 38 constituents were identified from the three essential oils by gas chromatography-mass spectrometry (GC-MS) according to the mass spectra and retention index values, and the relative contents of the individual components were determined by the peak normalization method. The following major compounds were identified: perillaldehyde, (R)-(-)-carvone, 2-furyl methyl ketone, d-limonene, and β-caryophyllene. Contact toxicity was assessed by topical application under room temperature, and the insects were reared in a dark incubator for 24 h at approximately 30 °C and 75 % humidity. Of these compounds, perillaldehyde (LD50 =7.71 μg/adult) and R-(-)-carvone (LD50 =10.93 μg/adult) displayed the most significant contact activities against T. castaneum. Synergistic interactions between perillaldehyde and R-(-)-carvone were evaluated using Wadley's model. All nine tested formulas displayed synergistic effects against T. castaneum, and a 1:4 (v:v) mixture exhibited an intense cocktail effect by dramatically reducing the LD50 to 2.73 μg/adult. The results of the RNA-Seq and qRT-PCR analyses suggested that the synergistic effect could be attributed to a reduced capacity for detoxification and elimination of xenobiotics. Three cytochrome P450 genes (CYP6BQ11, CYP6BQ7, and CYP6BK5) in phase I and two multidrug resistance protein genes (MRP4a and MRPX4) in phase III of the detoxification process may play essential roles. These findings provide a basis for the development of novel natural insecticides for the control of storage pests.

Metabolism of benzo[a]pyrene after low-dose subchronic exposure to an industrial mixture of carcinogenic polycyclic aromatic hydrocarbons in rats: a cocktail effect study.

Polycyclic aromatic hydrocarbons (PAHs) are interesting environmental pollutants for understanding cocktail effects. High-molecular-weight-PAHs (HMW-PAHs) are classified as probable or possible carcinogens; only benzo[a]pyrene (B[a]P) is a certain carcinogen in humans. Their toxicity depends on their metabolic activation. While 3-hydroxybenzo[a]pyrene (3-OHB[a]P) represents its detoxification pathway, trans-anti-7,8,9,10-tetrahydroxy-7,8,9,10-tetrahydrobenzo[a]pyrene (tetrol-B[a]P) represents the carcinogenicity pathway. The objective was to study the metabolism of B[a]P and HMW-PAHs during chronic low-dose exposure to B[a]P or a PAH mixture. Rats were exposed orally 5 times/week for 10weeks to low-levels of B[a]P (0.02 and 0.2mg.kg-1.d-1) or to an industrial mixture extracted from coal tar pitch (CTP) adjusted to 0.2mg.kg-1.d-1 B[a]P. Urinary levels of monohydroxy-, diol-, and tetrol-PAH were measured during weeks 1 and 10 by HPLC-fluorescence and GC‒MS/MS. After 1 week, the percentages of B[a]P eliminated as 3-OHB[a]P and tetrol-B[a]P were not different depending on the dose of B[a]P, whereas they were reduced by half in the CTP group. Repeated exposure led to an increase in the percentages of the 2 metabolites for the 0.02-B[a]P group. Moreover, the percentage of B[a]P eliminated as 3-OHB[a]P was equal in the 0.2-B[a]P and CTP groups, whereas it remained halved for tetrol-B[a]P in the CTP group. The percent elimination of HMW-PAH metabolites did not vary between weeks 1 and 10. Thus, dose, duration of exposure and chemical composition of the mixture have a major influence on PAH metabolism that goes beyond a simple additive effect. This work contributes to the reflection on determination of limit values and risk assessments in a context of poly-exposures.

Prenatal and current phthalate exposure and cognitive development in 7-year-old children from the Odense child cohort

BackgroundPhthalates are endocrine disrupters used in a variety of consumer products. Human studies suggest an association between phthalate exposure and cognitive development but adverse effects of the recently introduced phthalate substitutes have only been sparsely studied. ObjectivesTo investigate associations between prenatal and concurrent exposure to phthalates and IQ in 7-year-old children from the Odense Child Cohort. MethodsPregnant women from the Odense Child Cohort had phthalate metabolites measured in urine samples during 3rd trimester in 2010 to 2012. In addition, phthalates were also measured in urine samples from their offspring at age 7 years. IQ was assessed at age 7 years using four subtests from Wechsler Intelligence Scale for Children. The total study population consisted of 585 mother-child pairs with available prenatal urinary phthalate metabolites concentrations and IQ data at age 7 years. A subset of those (N = 274) had urinary phthalate metabolites measured in child urine at age 7 years. Phthalate concentrations were grouped into tertiles and associations with IQ were investigated using multiple linear regression adjusting for sex, maternal education and maternal/child BMI. ResultsUrinary phthalate metabolite concentrations both in pregnant women and children were generally lower compared to previous cohorts. Children with high prenatal urinary concentrations of MEP and metabolites of DEHP (∑DEHPm)(3rd tertile) had −3.1 (95% CI: −5.5, −0.6) (MEP) and − 3.0 (−5.5, −0.6) (∑DEHPm) IQ points at age 7 years compared to children with low concentrations (1st tertile). High concurrent urinary phthalate concentrations of MCPP, ∑DnHxPm, ∑DiDPm and ∑DiNPm in the 3rd tertile was associated with −3.7 (−7.2, −0.2), −4.4 (−7.9, −0.9), −3.7 (−7.2, −0.2) and − 5.6 (−9.1, −2.2) IQ points, respectively, compared to those with the lowest concentrations (1st tertile). ConclusionWe found significant inverse associations between some prenatal and concurrent urinary phthalate concentrations and IQ at age 7 years in this low exposed population. This suggests that exposure to phthalates both prenatally and during early childhood could be hazardous to child neurodevelopment, however, large-scale prospective studies assessing phthalate exposure through multiple urine samples, and possibly investigating cocktail effects of the chemicals as well as long term follow-up are warranted.

Research Progress of High Entropy Materials as Water Electrolysis Catalysts in Recent Years

Hydrogen energy has drawn considerable attention in recent years, among which the efficient production of hydrogen energy from water electrolysis has become a hot research topic in this field. The oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in water electrolysis are the core of the catalytic efficiency. High entropy materials have excellent combinatorial properties due to their "cocktail effect", high entropy effect, slow diffusion effect, and lattice distortion effect. They have outstanding catalytic effect in the process of water electrolysis, and thus become a hot research topic in recent years. This review combines the two hot topics by introducing the up-to-date research progress of high entropy materials in catalyzing water electrolysis. First, evaluation indexes of electrocatalytic performance are explained. Second, this review demonstrates specific materials from the classification of high entropy alloys, high entropy oxides and nitrided high entropy materials, which includes the structure of the materials and their specific catalytic performance. Finally, it summarizes the research progress of high entropy materials in water electrolysis catalysis as well as gives an outlook on the future design direction of the materials.

Designing strategies and enhancing mechanism for multicomponent high-entropy catalysts.

High-entropy materials (HEMs) are new-fashioned functional materials in the field of catalysis owing to their large designing space, tunable electronic structure, interesting "cocktail effect", and entropy stabilization effect. Many effective strategies have been developed to design advanced catalysts for various important reactions. Herein, we firstly review effective strategies developed so far for optimizing HEM-based catalysts and the underlying mechanism revealed by both theoretical simulations and experimental aspects. In light of this overview, we subsequently present some perspectives about the development of HEM-based catalysts and provide some serviceable guidelines and/or inspiration for further studying multicomponent catalysts.

Corrosion-Resistant and High-Entropic Non-Noble-Metal Electrodes for Oxygen Evolution in Acidic Media.

To realize a sustainable hydrogen economy, corrosion-resistant non-noble-metal catalysts are needed to replace noble-metal-based catalysts. The combination of passivation elements and catalytically active elements is crucial for simultaneously achieving high corrosion resistance and high catalytic activity. Herein, the self-selection/reconstruction characteristics of multi-element (nonary) alloys that can automatically redistribute suitable elements and rearrange surface structures under the target reaction conditions during the oxygen evolution reaction are investigated. The following synergetic effect (i.e., cocktail effect), among the elements Ti, Zr, Nb, and Mo, significantly contributes to passivation, whereas Cr, Co, Ni, Mn, and Fe enhance the catalytic activity. According to the practical water electrolysis experiments, the self-selected/reconstructed multi-element alloy demonstrates high performance under a similar condition with proton exchange membrane (PEM)-type water electrolysis without obvious degradation during stability tests. This verifies the resistance of the alloy to corrosion when used as an electrode under a practical PEM electrolysis condition.

A Lightweight AlTiVNb High-Entropy Alloy Film with High Strength-Ductility Synergy and Corrosion Resistance.

The simultaneous improvement of mechanical and corrosion resistance is of great significance for engineering applications. In this work, a novel lightweight amorphous structure AlTiVNb high-entropy alloy (HEA) film was fabricated by magnetron sputtering. The compression test of the AlTiVNb HEA film nanopillar exhibits a high compressive strength of up to 3.6 GPa and deformability approaching 58%. The high strength is affected by the disordered state, the nanostructure, and the lattice distortion effect, while the high ductility comes from the ductile shear band and the island structure. In addition, the AlTiVNb HEA film shows a current density of 4.90 × 10-8 A/cm2 and a potential of -0.234 V in the 3.5% NaCl solution, comparable to that of the 316L stainless steel. The chemical disorder state, cocktail effect, and homogeneous amorphous structure contribute to excellent corrosion resistance. This finding offers new insights into high-performance HEA films with robust mechanical and anticorrosion performances for microelectronic devices and mechanical metamaterials.

Recent progress in oxidation behavior of high-entropy alloys: A review

Recent advancements in high-entropy alloys (HEAs) and high-entropy materials (HEMs) show promising potential for different fields of applications. The emergence of HEAs and HEMs has gained significant interest for their exciting nature and properties. As they consist of five or more elements in considerable amounts, properties vary depending on the synergistic effect of combinations of elements. By selecting proper elements and manufacturing methods, better properties can be tuned. Although many unique behaviors of HEAs and HEMs are reported due to their mixing entropy, sluggish diffusion, severe lattice distortion, and multi-metallic cocktail effects, it is necessary to summarize the data to map their feasibility and potential. For example, the combined properties of high thermal stability, thermal fatigue, creep resistance, higher stiffness, and better corrosion resistance for elevated-temperature environments in aerospace applications are pursued. Moreover, gaining the environmental compatibility and longevity of service-life-oxidation behavior of these materials is one of the crucial aspects and, hence, has been recently explored. Therefore, this Research Update aims at summarizing the recent developments and findings in oxidation behavior and highlighting the challenges and controversies for future research perspectives, particularly, on the sustainability for different applications. Moreover, besides the bulk structure, the performance of the HEAs/HEMs coatings is also reviewed.

Microstructure and Hydrogen Permeability of Nb-Ni-Ti-Zr-Co High Entropy Alloys.

Hydrogen separation membranes are one of the most promising technologies for hydrogen purification. The development of high-entropy alloys (HEAs) for hydrogen separation membranes is driven by a "cocktail effect" of elements with different hydrogen affinities to prevent hydride formation and retain high permeability due to the single-phase BCC structure. In this paper, equimolar and non-equimolar Nb-Ni-Ti-Zr-Co high entropy alloys were fabricated by arc melting. The microstructure and phase composition of the alloys were analyzed by scanning electron microscopy and X-ray diffraction, respectively. The hydrogen permeation experiments were performed at 300-500 °C and a hydrogen pressure of 4 bar. In order to estimate the effect of composition and lattice structure on hydrogen location and diffusivity in Nb-Ni-Ti-Zr-Co alloy, ab initio calculations of hydrogen binding energy were performed using virtual crystal approximation. It was found that Nb-enriched and near equimolar BCC phases were formed in Nb20Ni20Ti20Zr20Co20 HEA while Nb-enriched BCC and B2-Ni(Ti, Zr) were formed in Nb40Ni25Ti18Zr12Co5 alloy. Hydrogen permeability tests showed that Nb20Ni20Ti20Zr20Co20 HEA shows lower activation energy and higher permeability at lower temperatures as well as higher resistance to hydrogen embrittlement compared to Nb40Ni25Ti18Zr12Co5 alloy. The effect of composition, microstructure and hydrogen binding energies on permeability of the fabricated alloys was discussed.

Residues of pesticides and veterinary drugs in diets of dairy cattle from conventional and organic farms in Austria

Modern agriculture depends highly on pesticides and pharmaceutical preparations, so controlling exposure to these substances in the feed and food chain is essential. This article presents the first study on residues of a broad spectrum of pesticides and veterinary drugs in the diets of dairy cattle. One hundred and two representative samples of the complete diets, including basal feed rations and additional fed concentrate, were collected in three Austrian provinces (Styria, Lower and Upper Austria) in 2019 and 2020. The samples were tested for >700 pesticides, veterinary drugs and related metabolites using a validated method based on liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI–MS/MS). In total, 16 residues (13 pesticides and three veterinary drug residues) were detected. > 90% of the diets contained pesticide residues and <10% veterinary drug residues, whereas banned pesticides were not found. The most frequent pesticide residues were fluopyram (62%), piperonyl butoxide (39%) and diethyltoluamide (35%). The following pesticides exceed the default EU maximum residue level (MRL) (10 μg kg−1) for products exclusively used for animal feed production: Benzovindiflupyr (proportion of samples > MRLs: 1%), bixafen (2%), fluopyram (6%), ipconazole (1%) and tebuconazole (3%). Three residues (dinitrocarbanilide, monensin and nicarbazin) of veterinary drugs were identified, all below the MRLs. Over 60% of the evaluated samples contained mixtures of two to six residues/sample. Only one pesticide (diethyltoluamide) presented a significant difference among regions, with higher concentrations in Upper Austria. Brewery's spent grains were the dietary ingredient that showed the strongest correlation to pesticide residues. These findings evidence the realistic scenario of highly occurrent low doses of pesticides cocktails in the feed/food chain, which may affect the animal, human and environmental health. Since the risk assessments are based on single pesticides, the potential synergistic effect of co-occurring chemicals (“cocktail effect”) requires further investigations.

Novel (Sm0.2Lu0.2Yb0.2Y0.2Dy0.2)3TaO7 high-entropy ceramic for thermal barrier coatings

A novel (Sm0.2Lu0.2Dy0.2Yb0.2Y0.2)3TaO7 (SLT-5RE0.2) oxide with a single-fluorite structure was synthesized via an optimized sol-gel and sintering method, and its crystal structure, mechanical and thermophysical properties were investigated. The results indicate that the calcined nanoscale powder is of high crystallinity, and bulk sample is of a uniform elemental distribution. Compared to YSZ (6–8 wt.% Y2O3 partially stabilized by ZrO2), SLT-5RE0.2 exhibits lower Young's modulus, less mean acoustic velocity, and higher Vickers microhardness. Owing to the strengthened anharmonic vibration and phonon scattering, SLT-5RE0.2 exhibits low thermal conductivity (1.107 W K−1·m−1, 900 °C). The high thermal expansion coefficient (11.3 × 10−6 K−1, 1200 °C) of SLT-5RE0.2 ceramic can be ascribed to the reduced lattice energy and ionic spacing as well as the cocktail effect of high-entropy ceramics. The excellent mechanical and thermophysical properties, and excellent phase steadiness during the whole testing temperature cope, indicate that SLT-5RE0.2 high-entropy ceramic can be a candidate material for thermal barrier coatings.