Understanding Environmental Fate: Soil Variability and Rainfall Influence on Triafamone and Ethoxysulfuron Leaching.

Considering the environmental impact of triafamone and ethoxysulfuron, it is crucial to investigate their leaching behaviour under different geographical conditions. The present study evaluates the effects of application rate, soil properties and rainfall conditions on leaching of these herbicides and their metabolites. Ethoxysulfuron leached up to 50-60 cm with 82.95 to 89.23% detected in leachates while triafamone leached only to 10-20 cm and was < 0.01 µg mL-1 in leachates. Highest leachability was observed in loamy sand followed by sandy loam and clay loam soil. M1 metabolite (N-(2-((4,6-dimethoxy-1,3,5-triazin-2-yl) (hydroxy) methyl) -6-fluorophenyl) -1,1-difluoro-N-methyl methane sulfonamide) was majorly present in 0 to 10 cm soil depth. With increase in rainfall, downward mobility of both parent and M1 increased. Amendment of loamy sand soil with farmyard manure reduced the leachability indicating it could mitigate groundwater pollution. However, the effect of different exogenous OM amendments on leaching behaviour of herbicides needs to be evaluated.

An outbreak of renal failure in asian dogs due to s-triazine adulteration of pet food raw material: Analysis of unique, green kidney stones formed as a result.

Renoliths were removed at necropsy from dogs that had died from acute kidney injury in Asia in 2004 and submitted to our laboratories for analysis including elemental composition, mass spectrometry, and nuclear magnetic resonance spectroscopy. The presence of a mixed s-triazine matrix comprising melamine, cyanuric acid, and ammelide, but no detectable ammeline, was found in the stone samples we analyzed. The unusual and unique green coloration of these stones was determined to be due to the presence of biliverdin. The occurrence of these green stones distinguished the 2004 incident from another incident in 2007 in the USA and other reported cases. The presence of crystals was reported in renal tubules and collecting ducts in both outbreaks, but no stones were reported in the 2007 incident. This difference suggested a variation in the disease process caused by mixed s-triazine ingestion. Careful monitoring of food additives is warranted to prevent future problems in animals and humans.

Effect of crosslinker/porogen ratio on sponge-nested polymer monoliths for solid-phase extraction.

Polymer monoliths can be polymerised within different molds, but limited options are available for the preparation of free-standing polymer monoliths for analytical sample preparation, and in particular, solid-phase extraction (SPE). Commercial melamine-formaldehyde sponges can be used as supports for the preparation of polymer monoliths, due its flexibility, giving various shapes to monoliths. Herein, the crosslinker/porogen ratio of highly porous sponge-nested divinylbenzene (DVB) polymer monoliths has been evaluated. Monoliths prepared using different crosslinker/porogen ratios were applied to the extraction of bisphenol F, bisphenol A, bisphenol AF, and bisphenol B. Monoliths containing 50 wt % DVB and 50 wt % porogens presented the highest recovery of bisphenols. Under the optimised conditions, the developed method showed a linear range between 2.5 µg L-1 and 150 µg L-1 for BPA and BPAF, and between 5 µg L-1 and 150 µg L-1 for BPB and BPF. The limits of detection (LOD, S/N = 3) and limits of quantification (LOQ, S/N = 10) ranged from 0.36 µg L-1 to 1.09 µg L-1, and from 1.20 µg L-1 to 3.65 µg L-1, respectively. The recoveries for spiked bisphenols (10 µg L-1) in tap water and water contained in a polycarbonate containers were between 82 % and 114 %.

Pollution level and ecological risk assessment of triazine herbicides in Laizhou Bay and derivation of seawater quality criteria.

Triazine herbicides are widely used in agriculture and have become common pollutants in marine environments. However, the spatiotemporal distribution characteristics and water quality criteria (WQC) of triazine herbicides are still unclear. This study found that triazine herbicides had a high detection rate of 100 % in surface seawater of Laizhou Bay, China, with average concentrations of 217.61, 225.13, 21.97, and 1296.72 ng/L in March, May, August, and October, respectively. Moreover, estuaries were important sources, and especially the Yellow River estuary exhibited the highest concentrations of 16,115.86 ng/L in October. The 10 triazine herbicides were detected in the sediments of Laizhou Bay, with a concentration ranging from 0.14-1.68 µg/kg. Atrazine and prometryn accounted for 33.41 %-59.10 % and 28.93 %-50.06 % of the total triazine herbicides in the seawater, and prometryn had the highest proportion (63.50 %) in the sediments. Correlation analysis revealed that triazine herbicides led to the loss of plankton biodiversity, which further decreased the dissolved oxygen. In addition, this study collected 45 acute toxicity data and 22 chronic toxicity data of atrazine, 16 acute toxicity data of prometryn, and supplemented with toxicity experiments of prometryn on marine organisms. Based on the toxicity database, the WQCs of atrazine and prometryn were derived using species sensitivity distribution. The overall risk probability of atrazine and prometryn were both less than 1.75 % in the Laizhou Bay, indicating an acceptable risk. This study not only clarified the pollution status and ecological risk of triazine herbicides, but also provided scientific basis for their environmental management standards.

Benzo(b)fluoranthene and benzo(k)fluoranthene removal by microalgae in the presence of triazine herbicides: Matrix solid-phase dispersion and solid-phase extraction (MSPD/SPE) for HPLC-UV analysis of the different culture components.

Over the last decade, human activities in the industrial and agricultural sectors have significantly increased the concentration of persistent and harmful pollutants in aquatic ecosystems. The use of microorganisms is a green strategy for the bio-removal of certain contaminants. However, other pollutants in the same ecosystems can reduce their degrading activity and even affect their survival. Therefore, this study aimed to evaluate the efficiency of benzo(b)fluoranthene (BbF) and benzo(k)fluoranthene (BkF) removal by Selenastrum capricornutum in the presence of triazine herbicides, compounds mainly used in broadleaf weeds. The interest of this work focused on identifying in which of the microalgal components the degrading activity is best evidenced and affected. For this purpose, the use of solid-phase extraction (SPE) and matrix solid-phase dispersion (MSPD) extraction procedures and HPLC-UV analysis allowed the BbF and BkF trace quantification in biomass, liquid medium, and cell lysate separately from cultures exposed to these polycyclic aromatic hydrocarbons (PAHs) alone or with herbicides. The recovery percentages were between 78 and 94 %, good linearity (r2 ≈ 0.99), precision values measured as RSD < 15 %, and limits of detection (LOQs) at levels of ng mL-1 and ng mg-1 were obtained. The individual PAH amounts measured in the components of microalgae cultures show similar removal kinetics (removal percentages: 82-89 %). Likewise, the analysis demonstrated that the removal of PAHs is not affected in the presence of triazine herbicides (atrazine and cyanazine) and with similar removal percentages (79-86 %) compared to those cultures exposed to individual PAHs (74-83 %). These results support the possible real-world applications of PAH removal by extracts from S. capricornutum in aquatic environments contaminated with PAHs and near agriculture areas where triazine herbicides are used.

Melamine-based hyper-cross-linked resin for efficient removal of total petroleum hydrocarbons (C10-C32) from aqueous solutions.

Petroleum hydrocarbons (PHCs) are produced from industrial discharges, storage leakages, accidental spills, and operational failures. The hazardous nature of PHCs causes serious health risks and threatens the entire aquatic habitat. In this research work, the investigation of the removal of total petroleum hydrocarbons (TPHs) from the contaminated water is carried out utilizing a novel hypercross-linked resin, MAICY, which is generated by condensation of commercially available precursors. The chemical structures of MAICY have been examined extensively by FESEM, FT-IR, solid (CP-MAS) 13C-NMR, and TGA. A comprehensive analysis for adsorption parameters of TPHs has been performed, and different models such as Langmuir and Freundlich isotherms have been employed where the Freundlich isotherm was found to be the best fit for removal of THPs (R2= 0.9991). The results revealed that the performance of MAICY for the adsorption of TPHs from contaminated water gives a maximum adsorption capacity (qe) of 146 mg.g-1. The results of various parameters hinted that the contact time (0.25-4 h), the dosage of adsorbent (0.17 g/L), pH (7), and concentration of TPHs (26.5 mg/L) have controlled the overall adsorptive performance. Moreover, the kinetic data of qe(expt.) and qe(calc.) for adsorption of TPHs disclosed the regression values (R2) for pseudo-first order (R2= 0.9921) and pseudo-second order (R2= 0.9891). Additionally, based on CHI factor (X2) error estimations, the data was shown to be more consistent with pseudo-first-order kinetics. Moreover, MAICY demonstrated excellent reusability and recycling properties for up to four consecutive adsorption-desorption cycles.

Label-free direct detection of melamine using functionalized gold nanoparticles-based dual-fluorescence colorimetric nanoswitch sensing platform.

Developing a simple, economical, sensitive, and selective method for label-free direct detection analytes is attractive, especially the strategies that could achieve signal amplification without complicated operations. Herein, a dual-fluorescence colorimetric nanoswitch sensing platform for label-free direct melamine (MEL) detection was established. We first explored the relationship between MEL-induced aggregation of gold nanoparticles (AuNPs) and size and determined the optimal size to be 37 nm. Using surfactant Triton X-100 to modify AuNPs and clarify possible interaction mechanisms to improve detection performance. The dynamic changes of surface plasmon resonance absorption peaks in the dispersed and aggregated states of AuNPs were skillfully utilized to match the emission of multicolor gold nanoclusters to trigger the multi-inner filter effect. Accompanied by the addition of MEL-induced AuNPs to change from dispersed to aggregated state, the fluorescence of green-emitting and red-emitting gradually turned on and turned off, respectively. The fluorescence turn-on mode detection limit was 10 times higher than the colorimetric method and as low as 5.5 ng/mL; the detection took only 10 min. The sensor detected MEL in spiked milk samples with a good recovery in the range of 81.2-111.0 % with a coefficient of variation less than 11.4 % and achieved a good correlation with commercial kits. The proposed sensor integrates numerous merits of label-free, multi-signal readout, self-calibration, simple operations, and economical, which provides a promising tool for convenient on-site detection of MEL.

In vivo tracing of cyromazine and three neonicotinoids in cowpea under field conditions by solid-phase microextraction combined with ultra-performance liquid chromatography-tandem mass spectrometry.

BACKGROUND: Excessive pesticide residues in agricultural products could accumulate in organisms through the food chain, causing potential harm to human health. The investigation of dissipation kinetics and residues of pesticides in crops is crucial for the scientific application of pesticides and the mitigation of their adverse effects on human health. In vivo solid-phase microextraction (in vivo SPME) has unique advantages, but the research on field plants is still lacking and the quantitative correction methods need to be further developed. RESULTS: A method combining in vivo solid-phase microextraction with ultra-performance liquid chromatography-tandem mass spectrometry (in vivo SPME-UPLC-MS/MS) was developed to monitor the presence of acetamiprid, cyromazine, thiamethoxam and imidacloprid in cowpea fruits grown in the field. The sampling rates (Rs) were determined using both in vitro SPME in homogenized cowpea samples and in vivo SPME in intact cowpea fruit samples. The in vivo-Rs values were significantly higher than the in vitro-Rs for the same analyte, which were used for in vivo SPME correction. The accuracy of this method was confirmed by comparison with a QuEChERS-based approach and subsequently applied to trace pesticide residues in field-grown cowpea fruits. The residual concentrations of each pesticide positively correlated with application doses. After 7 days of application at two different doses, all of the pesticides had residual concentrations below China's maximum residue limits. Both experimental data and predictions indicated that a safe preharvest interval for these pesticides is 7 days; however, if the European Union standards are to be met, a safe preharvest interval for cyromazine should be at least 13 days. SIGNIFICANCE: This study highlights the advantages of in vivo SPME for simultaneous analysis and tracking of multiple pesticides in crops under field conditions. This technique is environmentally friendly, minimally invasive, highly sensitive, accurate, rapid, user-friendly, cost-effective, and capable of providing precise and timely data for long-term pesticide surveillance. Consequently, it furnishes valuable insights to guide the safe utilization of pesticides in agricultural production.

A SERS-based point-of-care testing approach for efficient determination of diquat and paraquat residues using a flexible silver flower-coated melamine sponge.

Diquat (DQ) and paraquat (PQ) residues in food are potential hazards to consumers' health. Point-of-care testing (POCT) of them remains challenging. Based on surface-enhanced Raman spectroscopy (SERS) technology, we developed a POCT strategy for DQ and PQ on apple surface and in apple juice. A point-of-use composite was fabricated using a piece of porous melamine sponge (MS) modified with silver nanoflowers (AgNFs), combining the specificity of the SERS fingerprint and the excellent adsorption capacity of MS. Using this dual-functional AgNFs@MS, the on-site determination of the DQ and PQ residues was completed within 3 min without pretreatment. Clear trends were observed between SERS intensity and logarithmic concentrations, with r values from 0.962 to 0.984. The limit of detection of DQ and PQ were 0.14-0.70 ppb in apple juice and on apple surface. This study provides a new point-of-use alternative for rapidly detecting DQ and PQ residues in nonlaboratory settings.

A magnetic imprinted polymer nano-adsorbent with embedded quantum dots and mesoporous carbon for the microextraction of triazine herbicides.

A magnetic molecularly imprinted polymer (MMIP) adsorbent incorporating amino-functionalized magnetite nanoparticles, nitrogen-doped graphene quantum dots and mesoporous carbon (MIP@MPC@N-GQDs@Fe3O4NH2) was fabricated to extract triazine herbicides from fruit juice. The embedded magnetite nanoparticles simplified the isolation of the adsorbent from the sample solution. The N-GQDs and MPC enhanced adsorption by affinity binding with triazines. The MIP layer provided highly specific recognition sites for the selective adsorption of three target triazines. The extracted triazines were determined by high-performance liquid chromatography (HPLC) coupled with diode-array detection (DAD). The developed method exhibited linearity from 1.5 to 100.0 µg L-1 with a detection limit of 0.5 µg L-1. Recoveries from spiked fruit juice samples were in the range of 80.1- 108.4 %, with a relative standard deviation of less than 6.0 %. The developed MMIP adsorbent demonstrated good selectivity, high extraction efficiency, ease of fabrication and use, and good stability.

Melamine sponges incorporated azo-linked porous organic polymer as adsorbent for extraction and determination of six B vitamins using pipette tip micro solid-phase extraction.

A novel azo-linked porous organic polymer (AL-POP) was synthesized from caffeic acid and benzidine via an azo-coupling reaction and characterized by FTIR, SEM-EDS, BET, TGA, XRD and zeta potential analysis. AL-POPs were incorporated into melamine sponges and used for pipette tip micro solid-phase extraction (PT-MSPE) of six types of B vitamins (including thiamine, riboflavin, nicotinamide, pyridoxine, folic acid, and cyanocobalamin). After extraction, the samples were analyzed using high performance liquid chromatography-diode array detection (HPLC-DAD) system. The effect of AL-POP composition on the extraction efficiency (EE) of vitamins was investigated and benzidine to caffeic acid mol ratio of 1.5, 3.35 mmol of NaNO2, and reaction time of 8 h were selected as optimum conditions. The efficiency of the extraction process was improved by optimizing various parameters such as the amount of sorbent, pH and ionic strength of the sample, sample volume, number of sorption and desorption cycles, type of wash solvent, and type and volume of eluent solvent. Linearity (R2≥0.9987), Limit of detection (LOD) (11.88-18.97 ng/mL), limit of quantification (LOQ) (39.62-63.23 ng/mL), and enrichment factor (EF) (1.27-4.31) were obtained using calibration curves plotted under optimum conditions. Recovery values of these six B vitamins in the spiked multivitamin syrup samples varied from 80.01% to 108.35%, with a relative standard deviation (RSD) below 5.44%. Eventually, the optimized method was successfully used to extract and quantify the B vitamins in multivitamin syrup and non-alcoholic beer.

Rapid quantification models for assessing melamine adulteration in sport nutrition supplements via benchtop and portable NIRS instruments.

Sport nutrition supplements (SNS) are vulnerable to adulteration with melamine, artificially augmenting their protein content as determined by conventional assay methodologies. Vibrational spectroscopy techniques are suitable for the detection of adulteration because they allow rapid analysis, require minimal sample preparation, and can perform numerous analyses in a short time. The aim of this study was to develop rapid quantification models for the determination of melamine adulteration in a variety of SNS matrices using NIRS (near-infrared spectroscopy) in combination with multivariate data processing. Moreover, a comparison of benchtop and portable NIR instruments was carried out. Employing a stepwise approach involving OPLS-DA and PLS analysis, matrix discrimination and prediction ability were investigated. The benchtop instrument effectively discriminated among matrices (R2Y = 0.964, Q2 = 0.933), while the portable device, although showing a slightly altered pattern, maintained favorable discrimination capability (R2Y = 0.966, Q2 = 0.931). The quantitative PLS models for each SNS matrix exhibited comparable statistical indicators for both instruments with reasonable errors for melamine content estimation and prediction (RMSEE: 0.3-2.4 %, RMSEP: 0.98-2.99 %). Higher estimation and prediction errors were observed for protein-containing samples in both acquisition modes, probably due to the tendency of protein agglomeration and adhesion to different surfaces, which affects the homogeneity of the powder. Despite data loss due to the narrower spectral range and lower resolution of the portable instrument, all models were found to be suitable for predicting melamine content in sport nutrition supplements.

A facile and intelligent detection method for diclazuril based on a stable dual emissive Eu3+-dopped metal-organic framework.

Diclazuril (DIC) is a broad-spectrum anti-coccidiosis drug of the triazine class, widely used in poultry farming. The overuse of DIC may lead to its accumulation in animal bodies, which may enter the food chain and threaten human health. In this work, we fabricated a stable Eu3+-doped UiO-66 fluorescence sensor (EuUHIPA-30) for the sensitive detection of DIC. Among 20 veterinary drugs, the fluorescence of EuUHIPA-30 selectively responds to DIC, with a low detection limit (0.19 µM) and fast response (10 s). EuUHIPA-30 is recyclable and can detect DIC in chicken and eggs with good recoveries. Moreover, a smartphone-integrated paper-based sensor enables the instrument-free, rapid, visual, and intelligent detection of DIC in chickens and eggs. This work provides a promising candidate for practical fluorescent DIC sensing in animal-derived food to promote food safety.

A nanogold sensor test for tire wear chemicals based on the plasmon ruler approach.

The release of tire wear substances in the environment is raising concerns about potential impacts on aquatic ecosystems. The purpose of this study was to develop a quick and inexpensive screening test for the following tire wear substances: 6-phenylphenyldiamine quinone (6-PPD quinone), hexamethoxymethylmelamine (HMMM), 1-3-diphenylguanidine (1,3-DPG), and melamine. A dual strategy consisting of nanogold (nAu) signal intensity and the plasmonic ruler principle was used based on the spectral shift from the unaggregated free-form nAu from 525 nm to aggregated nAu at higher wavelengths. The shift in resonance corresponded to the relative sizes of the tire wear substances at the surface of nAu: 6-PPD (560 nm), HMMM (590 nm), 1,3-DPG (620 nm), and melamine (660 nm) in a concentration-dependent manner. When present in mixtures, a large indiscriminate band between 550 and 660 nm with a maximum corresponding to the mean intermolecular distance of 0.43 nm from the tested individual substances suggests that all compounds indiscriminately interacted at the surface of nAu. An internal calibration methodology was developed for mixtures and biological extracts from mussels and biofilms and revealed a proportional increase in absorbance at the corresponding resonance line for each test compound. Application of this simple and quick methodology revealed the increased presence of melamine and HMMM compounds in mussels and biofilms collected at urban sites (downstream city, road runoffs), respectively. The data also showed that treated municipal effluent decreased somewhat melamine levels in mussels.

Occurrence and Ecological Risk of Alkylamine Triazines in Chinese Estuarine Sediments: An Emerging Class of Persistent, Mobile, and Toxic Substances.

Identifying persistent, mobile, and toxic (PMT) substances from synthetic chemicals is critical for chemical management and ecological risk assessment. Inspired by the triazine analogues (e.g., atrazine and melamine) in the original European Union's list of PMT substances, the occurrence and compositions of alkylamine triazines (AATs) in the estuarine sediments of main rivers along the eastern coast of China were comprehensively explored by an integrated strategy of target, suspect, and nontarget screening analysis. A total of 44 AATs were identified, of which 23 were confirmed by comparison with authentic standards. Among the remaining tentatively identified analogues, 18 were emerging pollutants not previously reported in the environment. Tri- and di-AATs were the dominant analogues, and varied geographic distributions of AATs were apparent in the investigated regions. Toxic unit calculations indicated that there were acute and chronic risks to algae from AATs on a large geographical scale, with the antifouling biocide cybutryne as a key driver. The assessment of physicochemical properties further revealed that more than half of the AATs could be categorized as potential PMT and very persistent and very mobile substances at the screening level. These results highlight that AATs are a class of PMT substances posing high ecological impacts on the aquatic environment and therefore require more attention.

Rapid detection of melamine by DNA Walker mediated SERS sensing technique based on signal amplification function.

A new method is proposed for detecting typical melamine dopants in food using surface-enhanced Raman scattering (SERS) biosensing technology. Melamine specific aptamer was used as the identification probe, and gold magnets (AuNPs@MNPs) and small gold nanoparticles (AuNPs@MBA) were used as the basis for Raman detection. The Raman signal of the detection system can directly detect melamine quantitatively. Under optimized conditions, the detection of melamine was carried out in the low concentration range of 0.001-500 mg/kg, the enhancement factor (EF) was 2.3 × 107, and the detection limit was 0.001 mg/kg. The method is sensitive and rapid, and can be used for the rapid detection of melamine in the field environment.

Porous poly(bismaleimide-co-divinylbenzene) microspheres as dispersive solid-phase extraction adsorbent coupled to high-performance liquid chromatography for the determination of triazine herbicide residues in vegetable samples.

In this work, monodisperse and nano-porous poly(bismaleimide-co-divinylbenzene) microspheres with large specific surface area (427.6 m2 /g) and rich pore structure were prepared by one-pot self-stable precipitation polymerization of 2,2'-bis[4-(4-maleimidophenoxy) phenyl] propane and divinylbenzene. The prepared poly(bismaleimide-co-divinylbenzene) microspheres were employed as dispersive solid-phase extraction (DSPE) adsorbent for the extraction of triazine herbicides. Under optimized conditions, good linearities were obtained between the peak area and the concentration of triazine herbicides in the range of 1-400 µg/L (R2 ≥ 0.9987) with the limits of detection of 0.12-0.31 µg/L. Triazine herbicides were detected using the described approach in vegetable samples (i.e., cucumber, tomato, and maize) with recoveries of 93.6%-117.3% and relative standard deviations of 0.4%-3.5%. In addition, the recoveries of triazine herbicides remained above 80.7% after being used for nine DSPE cycles, showing excellent reusability of poly(bismaleimide-co-divinylbenzene) microspheres. The adsorption of poly(bismaleimide-co-divinylbenzene) microspheres toward triazine herbicides was a monolayer and chemical adsorption. The adsorption mechanism between triazine herbicides and adsorbents might be a combination of hydrogen bonding, electrostatic interaction, and π-π conjugation. The results confirmed the potential use of the poly(bismaleimide-co-divinylbenzene) microspheres-based DSPE coupled to the high-performance liquid chromatography method for the detection of triazine herbicide residues in vegetable samples.

Mechanistic insight into biotransformation of novel triazine-based flame retardant 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione by human cytochrome P450s.

The escalating focus on the environmental occurrence and toxicology of emerging pollutants underscores the imperative need for a profound exploration of their metabolic transformations mediated by human CYP450 enzymes. Such investigations have the potential to unravel the intricate metabolite profiles, substantially altering the toxicological outcomes. In this study, we integrated the computational simulations with in vitro metabolism experiments to investigate the metabolic activity and mechanism of an emerging pollutant, 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione (TDBP-TAZTO), catalyzed by human CYP450s. The results highlight the important contributions of CYP2E1, 3A4 and 2C9 to the biotransformation of TDBP-TAZTO, leading to the identification of four distinct metabolites. The effective binding conformations governing biotransformation reactions of TDBP-TAZTO within active CYP450s are unveiled. Structural instability of primary hydroxyTDBP-TAZTO products suggests three potential outcomes: (1) generation of an alcohol metabolite through successive debromination and reduction reactions, (2) formation of a dihydroxylated metabolite through secondary hydroxylation by CYP450, and (3) production of an N-dealkylated metabolite via decomposition and isomerization reactions in the aqueous environment. The formation of a desaturated debrominated metabolite may arise from H-abstraction and barrier-free Br release during the primary oxidation, potentially competing with the generation of hydroxyTDBP-TAZTO. These findings provide detailed mechanistic insight into TDBP-TAZTO biotransformation by CYP450s, which can enrich our understanding of the metabolic fate and associated health risk of this chemical.

Mechanistic interpretation of the sorption of terbuthylazine pesticide onto aged microplastics.

Microplastics (MPs) pose a global concern due to their ubiquitous distribution. Once in the environment, they are subject to aging, which changes their chemical-physical properties and ability to interact with organic pollutants, such as pesticides. Therefore, this study investigated the interaction of the hydrophobic herbicide terbuthylazine (TBA), which is widely used in agriculture, with artificially aged polyethylene (PE) MP (PE-MP) to understand how aging affects its sorption. PE was aged by an accelerated weathering process including UV irradiation, hydrogen peroxide, and ultrasonic treatment, and aged particles were characterized in comparison to pristine particles. Sorption kinetics were performed for aged and pristine materials, while further sorption studies with aged PE-MP included determining environmental factors such as pH, temperature, and TBA concentration. Sorption of TBA was found to be significantly lower on aged PE-MP compared to pristine particles because aging led to the formation of oxygen-containing functional groups, resulting in a reduction in hydrophobicity and the formation of negatively charged sites on oxidized surfaces. For pristine PE-MP, sorption kinetics were best described by the pseudo-second-order model, while it was intra-particle diffusion for aged PE-MP as a result of crack and pore formation. Sorption followed a decreasing trend with increasing pH, while it became less favorable at higher temperatures. The isotherm data revealed a complex sorption process on altered, heterogeneous surfaces involving hydrophobic interactions, hydrogen bonding, and π-π interactions, and the process was best described by the Sips adsorption isotherm model. Desorption was found to be low, confirming a strong interaction. However, thermodynamic results imply that increased temperatures, such as those resulting from climate change, could promote the re-release of TBA from aged PE-MP into the environment. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed TBA sorption onto PE.

May 1,3,5-Triazine derivatives be the future of leather tanning? A critical review.

Leather is produced by a multi-step process among which the tanning phase is the most relevant, transforming animal skin collagen into a stable, non-putrescible material used to produce a variety of different goods, for the footwear, automotive, garments, and sports industry. Most of the leather produced today is tanned with chromium (III) salts or alternatively with aldehydes or synthetic tannins, generating high environmental concern. Over the years, high exhaustion tanning systems have been developed to reduce the environmental impact of chromium salts, which nevertheless do not avoid the use of metals. Chrome-free alternatives such as aldehydes and phenol based synthetic tannins, are suffering from Reach restrictions due to their toxicity. Thus, the need for environmentally benign and economically sustainable tanning agents is increasingly urgent. In this review, the synthesis, use and tanning mechanism of a new class of tanning agents, 1,3,5-triazines derivatives, have been reported together with organoleptic, physical mechanical characteristics of tanned leather produced. Additionally environmental performance and economic data available for 1,3,5-triazines have been compared with those of a standard basic chromium sulphate tanning process, evidencing the high potentiality for sustainable, metal, aldehyde, and phenol free leather manufacturing.