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Aquatic humic substances (AHS) are defined as an important components of organic matter, being composed as small molecules in a supramolecular structure and can interact with metallic ions, thereby altering the bioavailability of these species. To better understand this behavior, AHS were extracted and characterized from Negro River, located near Manaus city and Carú River, that is situated in Itacoatiara city, an area experiencing increasing anthropogenic actions; both were characterized as blackwater rivers. The AHS were characterized by 13 C nuclear magnetic ressonance and thermochemolysis GC-MS to obtain structural characteristics. Interaction studies with Cu (II), Al (III), and Fe (III) were investigated using fluorescence spectroscopy applied to parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy with Fourier transform infrared spectroscopy (2D-COS FTIR). The AHS from dry season had more aromatic fractions not derived from lignin and had higher content of alkyls moities from microbial sources and vegetal tissues of autochthonous origin, while AHS isolated in the rainy season showed more metals in its molecular architecture, lignin units, and polysacharide structures. The study showed that AHS composition from rainy season were able to interact with Al (III), Fe (III), and Cu (II). Two fluorescent components were identified as responsible for interaction: C1 (blue-shifted) and C2 (red-shifted). C1 showed higher complexation capacities but with lower complexation stability constants (K ML ranged from 0.3 to 7.9 × 10 5 ) than C2 (K ML ranged from 3.1 to 10.0 × 10 5 ). 2D-COS FTIR showed that the COO - and C-O in phenolic were the most important functional groups for interaction with studied metallic ions., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Tyrosinase (TYR) is an essential oxidase that is responsible for the regulation of multiple physiological processes and diseases. Achieving the trace and reliable detection of TYR in complex biological samples is of great significance for the diagnosis of TYR-related diseases, but which faces a great challenge. In this study, we developed an ingenious and powerful method for the ultrasensitive detection of TYR by click reaction-combined dark-field microscopy. This method begins with the formation of cuprous ions (Cu + ) based on the reduction of copper ions (Cu 2+ ) by ascorbic acid (AA). Subsequently, the formed Cu + can catalyze the crosslinking between azide- and alkyne-functionalized gold nanoparticles, causing a significant red-shift in the scattering spectrum. However, AA can chelate with TYR, which inhibits the generation of Cu + and subsequent click reaction, thus achieving TYR-controlled scattering spectral shift. The proposed sensing platform shows a good linear detection range of 0.01-0.8 U/L with a low detection limit of 0.003 U/L, which is three orders of magnitude lower than the best performance of TYR sensing probes reported to date. Most importantly, the strategy has the ability to reliably and accurately detect TYR in serum sample, suggesting its potential clinical application in diagnosing TYR-related diseases. This visual sensing platform offers promising prospects for future research in enzymatic analysis and biomedical diagnostics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The sensing behavior of 2,5-thienylene-bridged tetrakis(2,6-dichlorophenyl)-[26]hexaphyrin (2) towards various metal ions and anions were investigated by UV-vis and fluorescence spectroscopies. Using this strapped hexaphyrin (2), the molecular sensor displayed highly selective and sensitive colorimetric responses to Cu 2+ and Hg 2+ in MeOH/THF. The spectral changes are distinctive enough in the visible region of the spectrum to enable naked-eye detection. The detection limits of Cu 2+ and Hg 2+ using this chemo-sensor in a mixed MeOH/THF solution were 1.978 and 1.283 μM, respectively, and 1.052 μM for F - in dichloromethane. Chemosensor 2,5-thienylene strapped [26]hexaphyrin (2) shows absorption responses both a 1 : 1 molecular ratio for 2 interacting with Cu 2+ and Hg 2+ and a 1 : 2 ratio between 2 and F - ions., (© 2024 Wiley-VHCA AG, Zurich, Switzerland.)

Cardiomyopathies (CMP) represent a significant health problem as they have a poor long-term prognosis and often require transplantation. Heavy metals are known to have cardiotoxic effects and some of them, such as cadmium (Cd), are found to be elevated in the urine and blood of individuals with heart diseases; nevertheless, direct measurement of metals (e.g. zinc (Zn) which is necessary for normal heart function), in the myocardium of individuals with CMP has not been performed. Here, we aimed to analyze the levels of a group of metals in the myocardium of the left ventricle in individuals with CMP. At the Institute of Pathology, we collected 52 samples of left ventricle post-mortem, out of which 19 subjects had been diagnosed with CMP (mean age: 72 y ± 10), and 33 subjects had not suffered from any heart disease (mean age: 67 y ± 15). We found out that individuals with CMP had a significantly higher concentrations of lead, nickel, manganese and copper than non-CMP subjects (p = 0.002, p < 0.001, p = 0.011, and p = 0.002). Interestingly, zinc was significantly lower in CMP subjects than in n-CMP individuals (p = 0.017). Our results indicated the involvement of an increased lead, nickel, copper and manganese heart load in individuals with CMP coupled with lower concentrations of zinc., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Soil heavy metal pollution is an important issue that affects human health and ecological well-being. In-situ thermal treatment techniques, such as self-sustaining smoldering combustion (SSS), have been widely studied for the treatment of organic pollutants. However, the lack of fuel in heavy metal-contaminated soil has hindered its application. In this study, we used corn straw as fuel to investigate the feasibility of SSS remediation for copper and lead in heavy metal-contaminated soil, as well as to explore the remediation mechanism. The results of the study showed that SSS increased soil pH, electrical conductivity (EC), total phosphorus (TP), total potassium (TK), rapidly available phosphorus (AP), and available potassium (AK), while decreasing total nitrogen (TN), alkali-hydrolyzed nitrogen (AN), and cation exchange capacity (CEC). The oxidation state of copper (Cu) increased from 10% to 21%-40%, and the residual state of lead (Pb) increased from 18% to 51%-73%. The Toxicity characteristic leaching procedure (TCLP) of Cu decreased by a maximum of 81.08%, and the extracted state of Diethylenetriaminepentaacetic acid (DTPA) decreased by 67.63%; the TCLP of Pb decreased by a maximum of 81.87%, and DTPA decreased by a maximum of 85.68%. The study indicates that SSS using corn straw as fuel successfully achieved remediation of heavy metal-contaminated soil. However, SSS does not reduce the content of copper and lead; it only changes their forms in the soil. The main reasons for the fixation of copper and lead during the SSS process are the adsorption of biochar, complexation with -OH functional groups, binding with π electrons, and the formation of crystalline compounds. This research provides a reference for the application of SSS in heavy metal-contaminated soil and has potential practical implications., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Jianhong Huang reports financial support was provided by National Natural Science Foundation of China. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Industrial hemp (Cannabis sativa L.) has great application potential in heavy metal-polluted soils owing to its safe non-food utilization. However, the fate of heavy metals in different varieties of hemp planted in strongly contaminated natural soils remains unknown. Here, we investigated the growth, heavy metal uptake, distribution, and transfer of nine hemp varieties in soils strongly contaminated with Cu, As, Cd, and Pb. Hemp variety and metal type were the main factors affecting the growth and heavy metal uptake in hemp. The nine hemp varieties grew well in the contaminated soils; however, differences existed among the varieties. The biomass of Z3 reached 5669.1 kg hm -1 , whereas that of Yunma No. 1 was only 51.8 % of Z3. The plant height, stalk diameter, and stalk bark thickness of Z3 were greater than those of the other varieties, reaching 168 cm, 9.2 mm, and 0.56 mm, respectively. Permanova's analysis revealed that the total effects of Cu, As, Cd, and Pb on the growth of the nine hemp varieties reached 60 %, with leaf As having the greatest effect, reaching 16 %. , Even in strongly contaminated soils, the nine varieties showed poor Cu, As, Cd, and Pb uptake. Most of the Cu, As, Cd, and Pb were retained in the root, reaching 57.7-72.4, 47.6-64.7, 76.0-92.9, and 70.0-87.8 %, respectively. Overall, the Cu, As, Cd, and Pb uptake of Wanma No.1 was the highest among the nine varieties, whereas that of Guangxi Bama was the lowest. These results indicate that hemp is a viable alternative for phytoattenuation in soils contaminated with heavy metals because of its ability to tolerate and accumulate Cu, As, Cd, and Pb in its roots, and Guangxi Bama is superior to the other varieties considering the safe utilization of hemp products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Soil washing technology plays an important role in the removal of heavy metals, and the efficacy of this process depends on the washing agent used. Due to the difficulty in treating soils contaminated by multiple heavy metals, there is still a need for further exploration of efficient washing agents with low environmental impact. Although single washing agents, such as chelators, can also effectively remove heavy metals from soil, combining efficient washing agents and determining their optimal washing conditions can effectively improve their removal efficiency for multiple heavy metals in soil simultaneously. Based on the previous research, the present study was carried out to combine different types of washing agents to remediate contaminated soils at a commonly e-waste recycling site. The objectives were to investigate their efficient washing conditions and assess the impact of the washing process on the speciation distribution and pollution level associated with heavy metals in soil. The results showed that the combination of HEDP (1-hydroxyethylidene-1,1-diphosphonic acid) and FeCl 3 at a ratio of 6:4 exhibited the most effective removal of Cd, Cu and Ni from the contaminated soil at an e-waste recycling site. Under optimal washing conditions, with a soil-to-liquid ratio of 1:20 and a washing time of 48 h, the removal rates of Cd, Cu and Ni were 96.72%, 69.91% and 76.08%, respectively. It needed to be emphasized that the combination washing agents were able to remove most of the acid-soluble, reducible and oxidizable fractions of heavy metals, and even the removal rates of the stable residual fraction (e.g., of Cd) was at a relatively high level. In addition, the washing process significantly reduced the pollution level associated with heavy metals in soil. This study aid in the development of combined efficient washing agents and explores optimal washing strategies for the remediation of Cd, Cu, and Ni-contaminated soil at e-waste recycling sites. The findings may play a role in enhancing the remediation capabilities for soils contaminated with multiple heavy metals, due to its characteristics of and high-efficiency and environmental friendliness., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Background: In kidney damage, molecular changes can be used as early damage kidney biomarkers, such as Kidney Injury Molecule-1 and Neutrophil gelatinase-associated lipocalin. These biomarkers are associated with toxic metal exposure or disturbed homeostasis of trace elements, which might lead to serious health hazards. This study aimed to evaluate the relationship between exposure to trace elements and early damage kidney biomarkers in a pediatric population., Methods: In Tlaxcala, a cross-sectional study was conducted on 914 healthy individuals. The participants underwent a medical review and a socio-environmental questionnaire. Five early damage kidney biomarkers were determined in the urine with Luminex, and molybdenum, copper, selenium, nickel, and iodine were measured with ICP-Mass., Results: The eGFR showed a median of 103.75 mL/min/1.73 m2. The median levels for molybdenum, copper, selenium, nickel, and iodine were 24.73 ng/mL, 73.35 ng/mL, 4.78 ng/mL, 83.68 ng/mL, and 361.83 ng/mL, respectively. Except for molybdenum and nickel, the other trace elements had significant associations with the eGFR and the early kidney damage biomarkers. Additionally, we report the association of different exposure scenarios with renal parameters., Discussion: and Conclusions. Among the explored metals, exposure to Cu and iodine impairs renal function. In contrast, Se may manifest as a beneficial metal. Interactions of Mo-Se and Mo-Iodine seem to alter the expression of NGAL; Mo-Cu for CLU; Mo-Cu, Mo-Se, and Mo-iodine for Cys-C and a-1MG; and Mo-Cu and Mo-iodine for KIM-1; were noticed. Our study could suggest that trace element interactions were associated with early kidney damage biomarkers., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Dissolved organic matter (DOM), the most active component in interstitial waters, determines the stability of heavy metals and secondary release in sediments. However, little is known about the composition and metal-binding patterns of DOM in interstitial water from oligotrophic lakes affected by different anthropogenic perturbations. Here, 18 interstitial water samples were prepared from sediments in agricultural, residential, tourist, and forest regions in an oligotrophic lake (Shengzhong Lake in Sichuan Province, China) watershed. Interstitial water quality and DOM composition, properties, and Cu(II)- and Pb(II)-binding characteristics were measured via physicochemical analysis, UV-vis spectroscopic, fluorescence excitation-emission matrix-parallel factor analysis (EEM-PARAFAC), and fluorescence titration methods. The DOM, which was produced mainly by microbial activities, had low molecular weights, humification degrees, and aromaticity. Based on EEM-PARAFAC results, the DOM was generally composed of tryptophan- (57.7%), terrestrial humic- (18.7%), microbial humic- (15.6%), and tyrosine-like (8.0%) substances. The DOM in the metal complexes was primarily composed of tryptophan-like substances, which accounted for ~42.6% of the DOM-Cu(II) complexes and ~72.0% of the DOM-Pb(II) complexes; however, microbial humic-like substances primarily contributed to the stability of DOM-Cu(II) (logK Cu = 3.7-4.6) and DOM-Pb(II) (logK Pb = 4.3-4.8). Water quality parameters did not significantly affect the stability of DOM-metal complexes. We demonstrated that the metal-binding patterns of DOM in interstitial water from oligotrophic lakes are highly dependent on microbial DOM composition and are affected by anthropogenic perturbations to a lesser extent., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Glyphosate is a widely used broad-spectrum herbicide in agriculture and horticulture to control a variety of weeds and undesirable plants. However, the excessive use of glyphosate has raised a number of environmental and human health concerns. It is urgent to develop tools to detect glyphosate. Herein, a novel dual-signal probe CCU-Cu 2+ was designed and synthesized on the basis of CCU. CCU exhibited excellent selectivity and great sensitivity for Cu 2+ which were based on both fluorescence "turn-off" reaction and comparative color visualisation methods. Due to the strong chelating ability of glyphosate on Cu 2+ , the CCU-Cu 2+ complex was applied to glyphosate detection in practical samples. The experimental results in vitro showed that the CCU-Cu 2+ complex was highly selective and rapid, with a low detection limit (1.6 μM), and could be recognised by the naked eye in the detection of glyphosate. Based on the excellent properties of the CCU-Cu 2+ complex, we also constructed a smartphone-assisted detection sensing system for glyphosate detection, which has the advantages of precision, sensitivity, and high interference immunity. Moreover, the CCU-Cu 2+ complex was also successfully employed for exogenous glyphosate imaging in living cells. These characteristics demonstrated that CCU-Cu 2+ holds significant potential for detection and imaging of glyphosate in bio-systems.

In the present study, a green and sensitive analytical method for the determination of copper ion at trace levels in apple tea samples was developed. Simultaneous complexation/extraction of the analyte were achieved by spraying-based fine droplet formation liquid-phase microextraction (SFDF-LPME). Copper ion was complexed with a Schiff base chelating agent called as N,N'-Bis(salicylidene)-1,2-phenylenediamine (BSP). Under the optimum conditions, the developed SFDF-LPME-FAAS and FAAS system were assessed with respect to limit of detection (LOD), limit of quantitation (LOQ), linearity and percent relative standard deviation (%RSD). LOD and LOQ values for SFDF-LPME-FAAS method were found to be 6.0 and 19.9 µg/kg, respectively. Enhancement in calibration sensitivity for developed method was found as 23 folds. In addition, accuracy/suitability of the developed SFDF-LPME-FAAS method were confirmed by spiking experiments. Two different apple tea samples were spiked to different concentration values and percent recovery results from 91.1 and 123.8 % proved the accuracy/suitability of the method., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Fluorescent gold nanoclusters (AuNCs) have shown promise as metal ion sensors. Further research into surface ligands is crucial for developing sensors that are both selective and sensitive. Here, we designed simple tripeptides to form fluorescent AuNCs, capitalizing on tyrosine's reduction capability under alkaline conditions. We investigated tyrosine's role in both forming AuNCs and sensing metal ions. Two tripeptides, tyrosine-cysteine-tyrosine (YCY) and serine-cysteine-tyrosine (SCY), were used to form AuNCs. YCY peptides produced AuNCs with blue and red fluorescence, while SCY peptides produced blue-emitting AuNCs. The blue fluorescence of YCY- and SCY-AuNCs was selectively quenched by Fe 3+ and Cu 2+ , whereas red-emitting YCY-AuNC fluorescence remained stable with 13 different metal ions. The number of tyrosine residues influenced the sensor response. DLS measurements revealed different aggregation propensities in the presence of various metal ions, indicating that chelation between the peptide and target ions led to aggregation and fluorescence quenching. Highlighting the innovation of our approach, our study demonstrates the feasibility of the rational design of peptides for the formation of fluorescent AuNCs that serve as highly selective and sensitive surface ligands for metal ion sensing. This method marks an advancement over existing methods due to its dual capability in both synthesizing gold nanoclusters and detecting analytes, specifically Fe 3+ and Cu 2+ .

Conventional monitoring and mapping approaches are laborious, expensive, and time-consuming because they need a large number of data and consequently extensive sampling and experimental operations. Therefore, due to the growing concern about the potential of contamination of soils and agricultural products with heavy metals (HMs), a field experiment was conducted on 77 farm lands in an area of 2300 ha in the southeast of Shiraz (Iran) to investigate the source of metal contamination in the soils and vegetables and to model spatial distribution of HMs (iron, Fe; manganese, Mn; copper, Cu; zinc, Zn; cadmium, Cd; nickel, Ni, and lead, Pb) over the region using geographic information system (GIS) and geostatistical (Ordinary Kriging, OK) approaches and compare the results with deterministic approaches (Inverse Distance Weighting, IDW with different weighting power). Furthermore, some ecological and health risks indices including Pollution index (PI), Nemerow integrated pollution index (NIPI), pollution load index (PLI), degree of contamination (C deg ), modified contamination degree (mCd), PI average and PI vector for soil quality, multi-element contamination (MEC), the probability of toxicity (MERMQ), the potential ecological index (RI), total hazard index (THI) and total carcinogenic risk index (TCR) based on ingestion, inhalation, and dermal exposure pathways for adults and children respectively for analyzing the noncarcinogenic and carcinogenic risks were calculated. Experimental semivariogram of the mentioned HMs were calculated and theoretical models (i.e., exponential, spherical, Gaussian, and linear models) were fitted in order to model their spatial structures and to investigate the most representative models. Moreover, principal component analysis (PCA) and cluster analysis (CA) were used to identify sources of HMs in the soils. Results showed that IDW method was more efficient than the OK approach to estimate the properties and HMs contents in the soils and plants. The estimated daily intake of metals (DIM) values of Pb and Ni exceeded their safe limits. In addition, Cd was the main element responsible for ecological risk. The PI ave and PI vector indices showed that soil quality in the study area is not suitable. According to mCd values, the soils classified as ultra-high contaminated for Cu and Cd, extremely high for Zn and Pb, very high, high, and very low degree of contamination for Ni, Mn, and Fe, respectively. 36, 60, and 4 % of the sampling sites had high, medium, and low risk levels with 49, 21, and 9 % probability of toxicity, respectively. The maximum health risk index (HRI) value of 20.42 with extremely high risk for children was obtained for Ni and the HI for adults and children were 0.22 and 1.55, respectively. The THI values of Pb and Cd were the highest compared to the other HMs studied, revealing a possible non-cancer risk in children associated with exposure to these metals. The routes of exposure with the greatest influence on the THI and TCR indices were in the order of ingestion > inhalation > dermal. Therefore, ingestion, as the main route of exposure, is the route of greatest contribution to health risks. PCA analysis revealed that Fe, Mn, Cu, and Ni may originate from natural sources, while Fe was appeared to be controlled by fertilizer, and Cu primarily coming from pesticide, while Cd and Pb were mainly associated with the anthropogenic contamination, atmospheric depositions, and terrific in the urban soils. While, Zn mainly originated from fertilization. Findings are vital for developing remediation approaches for controlling the contaminants distribution as well as for monitoring and mapping the quality and health of soil resources., Competing Interests: Declaration of competing interest All authors state that there is no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Nitrofurans are important synthetic broad-spectrum antibacterial drugs with the basic structure of 5-nitrofuran. Due to their toxicity, it is essential to develop a sensitive sensor with strong anti-interference capabilities for their detection. In this work, two {P 4 Mo 6 O 31 } 12- -based compounds, [H 4 (HPTTP)] 2 {Cu I [Mo 12 O 24 (OH) 6 (PO 4 ) 3 (HPO 4 )(H 2 PO 4 ) 4 ]}· x H 2 O ( x = 13 for ( 1 ), 7 for ( 2 ); HPTTP = 4,4',4″,4‴-(1 H -pyrrole-2,3,4,5-tetrayl)tetrapyridine), exhibiting similar coordination but distinct stacking modes. Both compounds were synthesized and used for the electrochemical detection of nitrofuran antibiotics. The tetrapyridine-based ligand was generated in situ during assembly, and its potential mechanism was discussed. Composite electrode materials, formed by mixing graphite powder with compounds 1 - 2 and physically grinding them, proved to be highly effective in the electrochemical trace detection of furazolidone (FZD) and furaltadone hydrochloride (FTD·HCl) under optimal conditions. Besides, the possible electrochemical detection mechanisms of two nitro-antibiotics were studied.

The exponential growth of the global population has resulted in a significant surge in the demand for food worldwide. Additionally, the impact of climate change has exacerbated crop losses caused by pests and pathogens. The transportation and utilization of traditional agrochemicals in the soil are highly inefficient, resulting in significant environmental losses and causing severe pollution of both the soil and aquatic ecosystems. Nanotechnology is an emerging field with significant potential for market applications. Among metal-based nanomaterials, copper-based nanomaterials have demonstrated remarkable potential in agriculture, which are anticipated to offer a promising alternative approach for enhancing crop yields and managing diseases, among other benefits. This review firstly performed co-occurrence and clustering analyses of previous studies on copper-based nanomaterials used in agriculture. Then a comprehensive review of the applications of copper-based nanomaterials in agricultural production was summarized. These applications primarily involved in nano-fertilizers, nano-regulators, nano-stimulants, and nano-pesticides for enhancing crop yields, improving crop resistance, promoting crop seed germination, and controlling crop diseases. Besides, the paper concluded the potential impact of copper-based nanomaterials on the soil micro-environment, including soil physicochemical properties, enzyme activities, and microbial communities. Additionally, the potential mechanisms were proposed underlying the interactions between copper-based nanomaterials, pathogenic microorganisms, and crops. Furthermore, the review summarized the factors affecting the application of copper-based nanomaterials, and highlighted the advantages and limitations of employing copper-based nanomaterials in agriculture. Finally, insights into the future research directions of nano-agriculture were put forward. The purpose of this review is to encourage more researches and applications of copper-based nanomaterials in agriculture, offering a novel and sustainable strategy for agricultural development., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Electrochemical sensors offer promising prospects for real-time pollutant monitoring. In this study, copper oxide-dispersed graphitic carbon nanofibers (CuO-CNFs) grown via chemical vapour deposition were employed as a robust platform for detecting a variety of environmental pollutants. This array-based sensor adeptly identifies three different classes of analytes, i. e., antibiotics (chloramphenicol (CP) and tylosin tartrate (TT)), heavy metals (cadmium (Cd) and lead (Pb)), and pesticides (quinalphos (QP) and imidacloprid (IP)). Electron collection is facilitated by a glassy carbon electrode, while various physico-electrochemical methods delve into the properties of CuO-CNFs. The CuO-CNF-modified GCE array rapidly discerns (<15 sec) a broad linear range: 1-20 ppm for CP, 1-13.33 ppm for TT, 0.66-11.66 ppm for Cd, 20-33.33 ppm for Pb, 1.6-11.6 ppm for QP, and 5-25 ppm for IP, boasting quantification limits of 1.0, 1.0, 0.66, 20.0, 1.6, and 5.0 ppm for CP, TT, Cd, Pb, QP, and IP, respectively. Notably, this sensor achieves simultaneous identification of mixed analytes, including CP and TT, Cd and Pb, and QP and IP, within real tap water. Furthermore, the electrochemical sensor exhibits robustness; heightened sensitivity, selectivity, and stability; a swift response; and impressive reproducibility in detecting CP, TT, Cd, Pb, QP, and IP within aqueous samples. Consequently, this array-based electrochemical sensor has emerged as a rapid and simultaneous detection tool for diverse pollutant residues in surface and groundwater samples., (© 2024 ACES and Wiley-VCH GmbH.)

Multiple analytical methodologies allow quantitation of H 2 S and methanethiol (MeSH) in wine, but confirmation that the determined concentrations are related to perceived off-aromas, or "reductive" faults, is yet to be provided. Fifty white wines underwent sensory evaluation and measurement of free and salt-treated H 2 S and MeSH concentrations by gas chromatography with sulfur chemiluminescence detection and/or gas detection tubes. The determined concentrations were compared across techniques and different analysis laboratories. Sulfhydryl off-odors in the wines were best described by boiled and rotten egg and natural gas/sewerage/durian aroma attributes. The wines with the highest ratings for both aromas had high concentrations of free H 2 S, free MeSH, and/or salt-treated MeSH but were unrelated to salt-treated H 2 S. The free sulfhydryl concentrations and their associated aromas appeared to be suppressed by specific Cu fractions in the wines. This study provides evidence of the relevant measures of reductive aroma compounds and their relation to off-odors and Cu fractions.

Engineered nanoparticles (ENPs) have been increasingly used in agricultural operations, leading to an urgent need for robust methods to analyze co-occurring ENPs in plant tissues. In response, this study advanced the simultaneous extraction of coexisting silver, cerium oxide, and copper oxide ENPs in lettuce shoots and roots using macerozyme R-10 and analyzed them by single-particle inductively coupled plasma-mass spectrometry (ICP-MS). Additionally, the standard stock suspensions of the ENPs were stabilized with citrate, and the long-term stability (up to 5 months) was examined for the first time. The method performance results displayed satisfactory accuracies and precisions and achieved low particle concentration and particle size detection limits. Significantly, the oven drying process was proved not to impact the properties of the ENPs; therefore, oven-dried lettuce tissues were used in this study, which markedly expanded the applicability of this method. This robust methodology provides a timely approach to characterize and quantify multiple coexisting ENPs in plants.

Mangroves buffer metals transfer to coastal areas though strong accumulation in sediments making necessary to investigate metals' bioavailability to plants at the rhizosphere. This work evaluates the effect of mangrove root activity, through iron plaque formation, on the mobility of iron and copper its influence on metals' uptake, and translocation through simultaneous histochemical analysis. The Fe2+ and Fe3+ contents in porewaters ranged from 0.02 to 0.11 µM and 1.0 to 18.3 µg.l-1, respectively, whereas Cu concentrations were below the method's detection limit (<0.1 µM). In sediments, metal concentrations ranged from 12,800 to 39,500 µg.g-1 for total Fe and from 10 to 24 µg.g-1 for Cu. In iron plaques, Cu concentrations ranged from 1.0 to 160 µg.g-1, and from 19.4 to 316 µg.g-1 in roots. Fe concentrations were between 605 to 36,000 µg.g-1 in the iron plaques and from 2,100 to 62,400 µg.g-1 in roots. Histochemical characterization showed Fe3+ predominance at the tip of roots and Fe2+ in more internal tissues. A. schaueriana showed significant amounts of Fe in pneumatophores and evident translocation of this metal to leaves and excretion through salt glands. Iron plaques formation was essential to the Fe and Cu regulation and translocation in tissues of mangrove plants.

The speciation, bioaccumulation, and toxicity of the newly deposited atmospheric heavy metals in the soil-earthworm (Eisenia fetida) system were investigated by a fully factorial atmospheric exposure experiment using soils exposed to 0.8-year and 1.8-year atmospheric depositions. The results shown that the newly deposited metals (Cu, Cd, and Pb) primarily accumulated in the topsoil (0-6 cm) and were present as the highly bioavailable speciation. They can migrate further to increase the concentrations of Cu, Cd, and Pb in soil solution of the deeper layer (at 10 cm) by 12 %-436 %. Earthworms tended to preferentially accumulate the newly deposited metals, which contributed 10 %-61 % of Cu, Cd, and Pb in earthworms. Further, for the unpolluted and moderately polluted soils, the newly deposited metals induced the significant oxidative stress in earthworms, resulting in significant increases in antioxidant enzyme activities (SOD, CAT, and GSH-Px). No significant differences were observed in the levels of heavy metals in soil solutions, bioaccumulation, and enzyme activities in earthworms exposed to 0.8-year and 1.8-year depositions, indicating the bioavailability of atmospheric metals deposited into soils was rapidly decreased with time. This study highlights the high bioaccumulation and toxicity of heavy metals to earthworm from the new atmospheric deposition during the earthworm growing period., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Nanostructured metal oxides (NMOs) provide electrical properties such as high surface-to-volume ratio, reaction activity, and good adsorption strength. Furthermore, they serve as a conductive substrate for the immobilization of biomolecules, exhibiting notable biological activity. Capitalizing on these characteristics, they find utility in the development of various electrochemical biosensing devices, elevating the sensitivity and selectivity of such diagnostic platforms. In this review, different types of NMOs, including zinc oxide (ZnO), titanium dioxide (TiO 2 ), iron (II, III) oxide (Fe 3 O 4 ), nickel oxide (NiO), and copper oxide (CuO); their synthesis methods; and how they can be integrated into biosensors used for medical diagnosis are examined. It also includes a detailed table for the last 10 years covering the morphologies, analysis techniques, analytes, and analytical performances of electrochemical biosensors developed for medical diagnosis.

In this study, Cu 2+ modulated silver nanoclusters were constructed for the turn-on, label-free detection of L-histidine. Six Ag NCs protected by oligonucleotides (DNA-Ag NCs) were tested in a series of experiments. Finally, A-DAN-Ag NCs were chosen as the best candidate due to their excellent fluorescent properties. The fluorescence of A-DAN-Ag NCs was quenched using Cu 2+ through energy or electron transfer. However, quenched fluorescence could be restored dramatically in the presence of L-histidine due to Cu 2+ liberation from A-DAN-Ag NCs and because of the chelation between the imidazole group of L-histidine and Cu 2+ . The proposed sensor exhibited high selectivity towards L-histidine over other amino acids, with a limit of detection (LOD) of 0.096 μM ranging from 0 to 8 μM. The proposed sensor succeeded in detecting L-histidine in diluted human urine. Therefore, the sensor has promising practical applications in biological systems.

Histidine plays an essential role in most biological systems. Changes in the homeostasis of histidine and histidine-rich proteins are connected to several diseases. Herein, we report a water-soluble Cu(II) coordination polymer, labeled CuCP, for the fluorimetric detection of histidine and histidine-rich proteins and peptides. Single-crystal structure determination of CuCP revealed a two-dimensional wavy network structure in which a carboxylate group connects the individual Cu(II) dimer unit in a syn-anti conformation. The weakly luminescent and water-soluble CuCP shows turn-on blue emission in the presence of histidine and histidine-rich peptides and proteins. The polymer can also stain histidine-rich proteins via gel electrophoresis. The limits of quantifications for histidine, glycine-histidine, serine-histidine, human serum albumin (HSA), bovine serum albumin, pepsin, trypsin, and lysozyme were found to be 300, 160, 600, 300, 600, 800, 120, and 290 nM, respectively. Utilizing the fluorescence turn-on property of CuCP, we measured HSA quantitatively in the urine samples. We also validated the present urinary HSA measurement assay with existing analytical techniques. Job's plot, 1 H NMR, high-resolution mass spectrometry (HRMS), electron paramagnetic resonance (EPR), fluorescence, and UV-vis studies confirmed the ligand displacement from CuCP in the presence of histidine.

Traditional identification methods based on cholinesterase inhibition are limited to recognizing organic phosphorus and carbamate esters, and their response to sulfonylurea pesticides is weak. Residual sulfonylurea pesticides can pose a threat to human health. So, it is very important to develop an effective, rapid and portable method for sulfonylurea pesticides detection. Herein, we first found that sulfonylurea pesticides have activity-enhancing effects on copper-based nanozymes, and then combined them with the array technology to construct a six-channel sensing array method for selectively identifying sulfonylurea pesticides and detecting total concentration of sulfonylurea pesticides (the limit of detection was 0.03 µg/mL). This method has good selectivity towards sulfonylurea pesticides. In addition, a smartphone-based colorimetric paper sensor analysis method was developed to achieve the on-site detection of the total concentration of sulfonylurea pesticides. And this array can also be used for individual differentiation (1-100 µg/mL). Our work not only investigates the specific responses of copper-based nanozymes to sulfonylurea pesticides, but also develops a simple method that contributes to directly detect sulfonylurea pesticides at the source of pollution, providing insights for further research on sulfonylurea pesticides detection and filling the gap in pesticide residue studies., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Aging is the main risk factor for Alzheimer's disease (AD). AD is linked to alterations in metal homeostasis and changes in stable metal isotopic composition can occur, possibly allowing the latter to serve as relevant biomarkers for potential AD diagnosis. Copper stable isotopes are used to investigate changes in Cu homeostasis associated with various diseases. Prior work has shown that in AD mouse models, the accumulation of 63Cu in the brain is associated with the disease's progression. However, our understanding of how the normal aging process influences the brain's isotopic composition of copper remains limited. In order to determine the utility and predictive power of Cu isotopes in AD diagnostics, we aim-in this study-to develop a baseline trajectory of Cu isotopic composition in the normally aging mouse brain. We determined the copper concentration and isotopic composition in brains of 30 healthy mice (WT) ranging in age from 6 to 12 mo, and further incorporate prior data obtained for 3-mo-old healthy mice; this range approximately equates to 20-50 yr in human equivalency. A significant 65Cu enrichment has been observed in the 12-mo-old mice compared to the youngest group, concomitant with an increase in Cu concentration with age. Meanwhile, literature data for brains of AD mice display an enrichment in 63Cu isotope compared to WT. It is acutely important that this baseline enrichment in 65Cu is fully constrained and normalized against if any coherent diagnostic observations regarding 63Cu enrichment as a biomarker for AD are to be developed., (© The Author(s) 2024. Published by Oxford University Press.)

Hydrazine substituted thienopyrimidine, a new fluorophore, was used to synthesize a novel Schiff base R1 as a chemosensor via the condensation with p-formyltriphenylamine, and the structure was confirmed using nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry (MS) analysis. When treated with Cu 2+ in dimethylsulfoxide (DMSO)/H 2 O buffer, R1 showed a phenomenon of fluorescence quenching, which was reversible with the action of ethylenediaminetetraacetic acid (EDTA). When treated with Fe 3+ in dimethylformamide (DMF)/H 2 O buffer, R1 exhibited the same phenomenon, but fluorescence was recovered with inorganic pyrophosphate (PPi) quantitatively. The complexation ratios for R1-Cu 2+ and R1-Fe 3+ were both 1:2, which were manifested by MS titrations and corresponding Job's plots. The limits of detection of R1 for Cu 2+ and Fe 3+ were 3.11 × 10 -8 and 1.24 × 10 -7  M, respectively. The sensing mechanism of R1 toward Cu 2+ and Fe 3+ was confirmed using density functional theory calculations and electrostatic potential analysis. Test strips of R1 were fabricated successfully for on-site detection of Cu 2+ and Fe 3+ . In addition, R1 was applied to recognize Cu 2+ and Fe 3+ in actual water samples with satisfactory recovery., (© 2024 John Wiley & Sons Ltd.)

Metal clusters have drawn considerable research attention over the years due to their fascinating optical properties. Owing to their appealing photophysical characteristics, these materials have drawn attention as potential candidates for various application in diverse fields, including disease detection, biosensing, chemical sensing, and the fabrication of light-harvesting materials. Presently, there is an increasing research focus on the use of clusters in biomedical research, both as biodetection platform and as bioimaging agents. Of special interest are chiral clusters, which can selectively interact with chiral biomolecules owing to their optical activity. Herein, we showcase the use of a pair of chiroptically active copper clusters for the enantioselective detection of lysine, an amino acid of vast biological relevance. Two techniques are concurrently employed for the detection of lysine at varying concentrations. Circular dichroism serves as a potent tool for detecting lysine at low concentrations, whereas luminescence is effectively employed as a detection method for high analyte concentrations. The combined electronic impact of clusters and lysine resulted in the emergence of an enhanced enantioselective Cotton effect at specific wavelength., (© 2024 Wiley Periodicals LLC.)

Two new Schiff bases were synthesized from 1-(2,4-dihydroxyphenyl)ethanone and pyridine derivatives. Both compounds were characterized using infrared, UV-Vis., 1 H NMR, 13 C NMR and mass spectral studies. Density functional theory (DFT) calculations were performed for both the Schiff bases with 6-31G(d, p) as the basis set. Vibrational frequencies calculated using the theoretical method were in good agreement with the experimental values. Both the Schiff bases were highly fluorescent in nature. The cation-recognizing profile of the compounds was investigated in aqueous methanol medium. The Schiff base 4-(1-(pyridin-4-ylimino)ethyl)benzene-1,3-diol (PYEB) was found to interact with Fe(III) and Cu(II) ions, whereas the Schiff base 4,4'-((pyridine-2,3-diylbis(azanylylidene))bis(ethan-1-yl-1-ylidene))bis(benzene-1,3-diol) (PDEB) was found to detect Cu(II) ions. The mechanism of recognition was established as combined excited state intramolecular proton transfer (ESIPT)-chelation-enhanced fluorescence (CHEF) effect and chelation-enhanced quenching (CHEQ) process for the detection of Fe(III) and Cu(II) ions, respectively. The stability constant of the metal complexes formed during the sensing process was determined. The limit of detection for Fe(III) and Cu(II) ions with respect to Schiff base PYEB was found to be 1.64 × 10 -6 and 2.16 × 10 -7  M, respectively. With respect to Schiff base PDEB, the limit of detection for Cu(II) ion was found to be 4.54 × 10 -4  M. The Cu(II) ion sensing property of the Schiff base PDEB was applied in bioimaging studies for the detection of HeLa cells., (© 2024 John Wiley & Sons Ltd.)

Objectives: Reports of unsafe school drinking water in the United States highlight the importance of ensuring school water is safe for consumption. Our objectives were to describe (1) results from our recent school drinking water sampling of 5 common contaminants, (2) school-level factors associated with exceedances of various water quality standards, and (3) recommendations., Methods: We collected and analyzed drinking water samples from at least 3 sources in 83 schools from a representative sample of California public schools from 2017 through 2022. We used multivariate logistic regression to examine school-level factors associated with lead in drinking water exceedances at the American Academy of Pediatrics (AAP) recommendation level (1 part per billion [ppb]) and state action-level exceedances of other contaminants (lead, copper, arsenic, nitrate, and hexavalent chromium)., Results: No schools had state action-level violations for arsenic or nitrate; however, 4% had ≥1 tap that exceeded either the proposed 10 ppb action level for hexavalent chromium or the 1300 ppb action level for copper. Of first-draw lead samples, 4% of schools had ≥1 tap that exceeded the California action level of 15 ppb, 18% exceeded the US Food and Drug Administration (FDA) bottled water standard of 5 ppb, and 75% exceeded the AAP 1 ppb recommendation. After turning on the tap and flushing water for 45 seconds, 2%, 10%, and 33% of schools exceeded the same standards, respectively. We found no significant differences in demographic characteristics between schools with and without FDA or AAP exceedances., Conclusions: Enforcing stricter lead action levels (<5 ppb) will markedly increase remediation costs. Continued sampling, testing, and remediation efforts are necessary to ensure drinking water meets safety standards in US schools., Competing Interests: Declaration of Conflicting InterestsThe authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Rose tea infusion has gained popularity worldwide due to its health benefits. However, it is known that tea plants can be contaminated with heavy metals including copper. Hence, an accurate and applicable analytical method namely emulsification liquid-liquid microextraction based deep eutectic solvent - flame atomic absorption spectrometry (ELLME-DES-FAAS) was proposed to determine copper at trace levels in rose tea samples. Under the optimum experimental conditions, analytical figures of merit for the developed method were examined, and dynamic range, limit of detection (LOD) and limit of quantification (LOQ) were found to be 5.07-246.61 µg/kg (mass-based) with 0.9992 coefficient of determination, 2.50 µg/kg and 8.32 µg/kg, respectively. A matrix matching calibration strategy was employed to boost recovery results, and the acceptable recovery results were recorded between 95.9 % and 118.4 %. According to recovery results, the developed analytical method can be safely employed to determine the concentration of copper in rose tea samples accurately., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The application of carbon nanoparticles (CNPs) and biochar in agriculture for improving plant health and soil quality and alleviating metal stress offers alternative approaches to meet the ever-increasing demand for food. However, poor understanding of their roles in improving crop production under Cu stress represents a significant obstacle to their wide application in agriculture. To clarify how CNPs and biochar affect corn (Zea mays L.) seed germination, seedling growth, plant health, and nutrient uptake under different Cu stress levels, soil-less Petri-dish and greenhouse soil-based bioassays were conducted. The results revealed that CNPs and biochar stimulated corn seed germination and seedling growth. Besides, they were effective in immobilizing Cu 2+ sorption in sandy soil and alleviating Cu stress for plant growth, as shown by the increased plant height and dry biomass. The plant nutrient uptake efficiency (NUE) was significantly increased by CNPs, with a maximum increase of 63.1% for N and 63.3% for K at the highest Cu 2+ stress level (400 mg Cu 2+ L -1 ). In contrast, non-significant effects on NUE were observed with biochar treatments regardless of Cu stress levels. Interestingly, CNPs significantly increased plant uptake of Cu in the Petri dish test, while biochar inhibited plant uptake of Cu under both experimental conditions. Principle component analysis (PCA) and Pearson correlation analysis indicated that CNPs mitigated Cu stress mainly by elevating antioxidant enzyme activities, enhancing plant photochemical efficiency, and increasing plant uptake of N and K, while biochar was more likely to reduce bioavailability and uptake of Cu in the plant. These findings have great implications for the application of CNPs and biochar as plant growth stimulators and de-toxicity agents in agriculture., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Swine farming produces large quantities of nutrient-rich wastewater, which often contains metals such as Cu and Zn, used as feed additives for pigs. These metals must be removed from the wastewater before discharge but their retention in the biomass can limit its subsequent utilization. Photobioreactors are a very promising alternative for swine wastewater treatment, as the consortium of microalgae and bacteria growing symbiotically in these reactors allows high nutrient and metal removal efficiency at moderate costs. This work studies the mechanisms of removal of Cu(II) and Zn(II) by the two types of microorganisms growing in these photobioreactors. A microalga commonly used in wastewater treatment (Scenedesmus almeriensis) and an activated sludge were kept in contact with synthetic wastewater containing 100 mg/L of Cu and Zn. After 72 h, Scenedesmus almeriensis removed 43% of Cu and 45% of Zn, while activated sludge removed 78% of Cu and 96% of Zn. Single and sequential extractions of the biomasses using different extracting reagents revealed that biosorption on protonable groups is the dominant removal mechanisms. Mild reagents solubilized 69% of Cu and 94% of Zn from the microalgae and 76% of Cu and 93% of Zn from the activated sludge. Low metal concentrations in the oxidizable and residual fractions evidenced minimal bioaccumulation inside the cells. FTIR and ESEM-EDX analysis confirmed biosorption by ion exchange and complexation as the main metal remediation mechanisms. The weak bonds of the biosorbed Cu and Zn ions are beneficial for the valorization of biomass and the obtaining of safe bioproducts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

While zinc protects plants from copper in hydroponics, its behavior in soil remains unclear. We investigated the potential of zinc sulfate to protect ryegrass from copper toxicity in contaminated soil. Twelve soil treatments combined varying levels of copper oxide (CuO) and zinc sulfate (ZnSO 4 ). Increasing CuO significantly stunted ryegrass, but adding ZnSO 4 mitigated the effects at each CuO level. ZnSO 4 had no effect in unpolluted conditions. These results, supported by the Terrestrial Biotic Ligand Model, indicate that zinc competes with copper for binding sites, reducing copper uptake by ryegrass and mitigating its toxicity. Application of zinc sulfate to copper-contaminated soils appears promising for ryegrass growth, although field studies are critical to confirm real-world efficacy., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Marine pollution by trace elements is a global concern due to potential toxicity to species and ecosystems. Copper is a fundamental trace element for many organisms; however, it becomes toxic at certain concentrations. The green turtle (Chelonia mydas) is a good sentinel species, due to its circumglobal distribution, long life cycle, coastal habits when juvenile, and is subject to environmental pollution. Quantifying and comparing copper levels makes it possible to understand the availability of this trace element in nature. During this research, comparisons were made between the levels of copper found in the liver, kidneys, and muscles of 35 turtles, from the United States (Hawaii and Texas), Brazil, and Japan. Copper was found in all specimens. In the liver, animals from Hawaii (91.08 µg g -1 ), Texas (46.11 µg g -1 ), and Japan (65.18 µg g -1 ) had statistically equal means, while those from Brazil (16. 79 µg g -1 ) had the lowest means. For the kidney, copper means were statistically equal for all Hawaii (3.71 µg g -1 ), Texas (4.83 µg g -1 ), Japan (2.47 µg g -1 ), and Brazil (1.89 µg g -1 ). In muscle, the means between Texas (0.75 µg g -1 ) and Japan (0.75 µg g -1 ) were the same, and the mean for Brazil (0.13 µg g -1 ) was the lowest. Among the organs, the highest levels of copper were found in the liver (28.33 µg g -1 ) followed by the kidney (2.25 µg g -1 ) and with the lowest levels in the muscle (0.33 µg g -1 ). This is the first study of copper levels among marine vertebrates in distant parts of the globe using similar comparative filters between different locations. Similar levels in turtles from such distant locations may indicate that there is a pantropical pattern of copper distribution in the biota, and that these animals are subject to the process of bioavailability of this metal in the environment and metabolic regulation., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

A new molecular structure 1 has been developed on naphthalimide motif. The amine and triazole binding groups have been employed at the 4-position of naphthalimide to explore the sensing behavior of molecule 1. Single crystal x-ray diffraction and other spectroscopic techniques confirm the identity of 1. Compound 1 exhibits high selectivity and sensitivity for Cu 2+ ions in CH 3 CN. The binding of Cu 2+ shows ∼ 70-fold enhancement in emission at 520 nm. The binding follows 1:1 interaction and the detection limit is determined to be 6.49 × 10 -7 M. The amine-triazole binding site in 1 also corroborates the detection of F - through a colour change in CH 3 CN. Initially H-bonding and then deprotonation of amine -NH- in the presence of F - are the sequential steps involved in F - recognition with a detection limit of 4.13 × 10 -7 M. Compound 1 is also sensible to CN - like F - ion and they are distinguished by Fe 3+ ion. Cu 2+ -ensemble of 1 fluorimetrically recognizes F - among the tested anions and vice-versa. The collaborative effect of amine and triazole motifs in the binding of both Cu 2+ and F - /CN - has been explained by DFT calculation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The fluorescence detection of ions and pharmaceutical effluents by using organic chemosensors is a valuable surrogate to the currently existing expensive analytical methods. In this regard, the design of multi-functional chemosensors to recognize desirable guests is of utmost importance. In this study, we first show that levofloxacin (LVO) is able to use as a fluorescent chemosensor for the detection of biologically important Cu 2+ (turn-off) and Fe 3+ (turn-on) ions via independent signal outputs in 100% aqueous buffer solutions. Next, using the reciprocal recognition of LVO and Fe 3+ provides a unique emission pattern for the detection of LVO. This approach exhibited a high specificity to LVO among various pharmaceutical samples, namely acetaminophen (AC), azithromycin (AZ), gemifloxacin (GEM) and ciprofloxacin (CIP) and also showed great anti-interference property in urine. The attractive features of this sensing system are availability, easy-to-use, high sensitivity (limit of detection = 18 nM for Cu 2+ , 22 nM for Fe 3+ and 0.12 nM for LVO), rapid response (5 s) with an excellent selectivity., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

As one of the most important industrial enzymes, α-amylase is widely used in food processing, such as starch sugar and fermentation, bringing high added value to industry of more than a trillion dollars. We developed a multi-enzyme system (Glu&Gox@Cu-MOF-74) prepared by embedding α-glucosidase (Glu) and glucose oxidase (Gox) into the biomimetic metal-organic framework Cu-MOF-74 using in situ encapsulation within 15 min at room temperature for efficient and sensitive detection of α-amylase activity. Benefitting from the remarkable peroxidase-mimicking property and rigid skeleton of Cu-MOF-74, the biocatalytic platform exhibited excellent cascade activity and tolerance in various extremely harsh environments compared to natural enzymes. On this basis, a cascade biocatalytic platform was constructed for the detection of α-amylase activity with wide linear range (5-100 U/L) and low limit of detection (1.45 U/L). The colorimetric cascade scheme is important for the sensitive and selective determination of α-amylase in complex fermentation samples, and the detection time is short (∼0.5 h). This work provides new ideas for the detection of α-amylase based on the cascade amplification method., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Innate immune systems alter the concentrations of trace elements in host niches in response to invading pathogens during infection. This work reports the interplay between d-block metal ions and their associated biomolecules using hyphenated elemental techniques to spatially quantify both elemental distributions and the abundance of specific transport proteins. Here, lung tissues were collected for analyses from naïve and Streptococcus pneumoniae-infected mice fed on a zinc-restricted or zinc-supplemented diet. Spatiotemporal distributions of manganese ( 55 Mn), iron ( 56 Fe), copper ( 63 Cu), and zinc ( 66 Zn) were determined by quantitative laser ablation-inductively coupled plasma-mass spectrometry. The murine transport proteins ZIP8 and ZIP14, which are associated with zinc transport, were also imaged by incorporation of immunohistochemistry techniques into the analytical workflow. Collectively, this work demonstrates the potential of a single instrumental platform suitable for multiplex analyses of tissues and labelled antibodies to investigate complex elemental interactions at the host-pathogen interface. Further, these methods have the potential for broad application to investigations of biological pathways where concomitant measurement of elements and biomolecules is crucial to understand the basis of disease and aid in development of new therapeutic approaches., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

In recent years, the rapid development of pig farming has led to a large quantity of heavy metal-polluted wastewater. Thus, it was desirable to develop a simple heavy metal detection method for fast monitoring of the wastewater from the pig farms. Therefore, there was an urgent need to develop a simple method for rapidly detecting heavy metal ions in pig farm wastewater. Herein, a simple electrochemical method for simultaneous detection of Cu 2+ and Zn 2+ was developed and applied to pig farm wastewater. With a glassy carbon electrode and anodic stripping voltammetry, simultaneous detection of Cu 2+ and Zn 2+ in water was achieved without the need for complicated electrode modification. Furthermore, it was found that the addition of Cd 2+ can enhance the response current of the electrode to Zn 2+ , which increased the signal by eight times. After systematic optimization, the limit of detection (LOD) of 9.3 μg/L for Cu 2+ and 45.3 μg/L for Zn 2+ was obtained. Finally, it was successfully applied for the quantification of Cu 2+ and Zn 2+ with high accuracy in pig farm wastewater. This work provided a new and simple solution for fast monitoring of the wastewater from pig farms and demonstrated the potential of electrochemical measurement for application in modern animal husbandry.

Assessing the impact of mining activity on the availability of environmental pollutants is crucial for informing health policies in anticipation of future production scenarios of critical minerals essential for the transition to a net-zero carbon society. However, temporal and spatial monitoring is often sparse, and measurements may not extend far enough back in time. In this study, we utilize variations of chemical elements contained in tree-rings collected in local villages from an area heavily affected by copper mining in the Atacama Desert since the early 20th century to evaluate the temporal distribution of pollutants and their relationship with local drivers. By combining time-varying data on local drivers, such as copper production and the dry tailings deposit area, we show how the surge in copper production during the 1990s, fueled by trade liberalization and increased international demand, led to a significant increment in the availability of metal(loid)s related to mining activities on indigenous lands. Our findings suggest that the environmental legislation in Chile may be underestimating the environmental impact of tailing dams in neighboring populations, affecting the well-being of Indigenous Peoples from the Atacama mining hotspot region. We argue that future changes in production rates driven by international demand could have negative repercussions on the environment and local communities. Therefore, mining emissions and the management of tailing dams should be carefully considered to anticipate their potential negative effects on human and ecosystem health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Transition metal doping is an ideal strategy to construct multifunctional and efficient nanozymes for biosensing. In this work, a metal-doped CoMnO x nanozyme was designed and synthesized by hydrothermal reaction and high-temperature calcination. Based on its oxidase activity, an "on-off-on" smartphone sensing platform was established to detect ziram and Cu 2+ . The obtained flower-shaped CoMnO x could exhibit oxidase-, catalase-, and laccase-like activities. The oxidase activity mechanism of CoMnO x was deeply explored. O 2 molecules adsorbed on the surface of CoMnO x were activated to produce a large amount of O 2 ·- , and then, O 2 ·- could extract acidic hydrogen from TMB to produce blue oxTMB. Meanwhile, TMB was oxidized directly to the blue product oxTMB via the high redox ability of Co species. According to the excellent oxidase-like activity of CoMnO x , a versatile colorimetric detection platform for ziram and Cu 2+ was successfully constructed. The linear detection ranges for ziram and Cu 2+ were 5~280 μM and 80~360 μM, and the detection limits were 1.475 μM and 3.906 μM, respectively. In addition, a portable smartphone platform for ziram and Cu 2+ sensing was established for instant analysis, showing great application promise in the detection of real samples including environmental soil and water.

With the transformation and upgrading of industries, the environmental problems caused by industrial residual contaminated sites are becoming increasingly prominent. Based on actual investigation cases, this study analyzed the soil pollution status of a remaining sites of the copper and zinc rolling industry, and found that the pollutants exceeding the screening values included Cu, Ni, Zn, Pb, total petroleum hydrocarbons and 6 polycyclic aromatic hydrocarbon monomers. Based on traditional analysis methods such as the correlation coefficient and spatial distribution, combined with machine learning methods such as SOM + K-means, it is inferred that the heavy metal Zn/Pb may be mainly related to the production history of zinc rolling. Cu/Ni may be mainly originated from the production history of copper rolling. PAHs are mainly due to the incomplete combustion of fossil fuels in the melting equipment. TPH pollution is speculated to be related to oil leakage during the industrial use period and later period of vehicle parking. The results showed that traditional analysis methods can quickly identify the correlation between site pollutants, while SOM + K-means machine learning methods can further effectively extract complex hidden relationships in data and achieve in-depth mining of site monitoring data., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Environmental contamination is aninsistent concern affecting human health and the ecosystem. Wastewater, containing heavy metals from industrial activities, significantly contributes to escalating water pollution. These metals can bioaccumulate in food chains, posing health risks even at low concentrations. Copper (Cu), an essential micronutrient, becomes toxic at high levels. Activities like mining and fungicide use have led to Copper contamination in soil, water, and sediment beyond safe levels. Copper widely used in industries, demands restraint of heavy metal ion release into wastewater for ecosystem ultrafiltration, membrane filtration, nanofiltration, and reverse osmosis, combat heavy metal pollution, with emphasis on copper.Physical and chemical approaches are efficient, large-scale feasibility may have drawbackssuch as they are costly, result in the production of sludge. In contrast, bioremediation, microbial intervention offers eco-friendly solutions for copper-contaminated soil. Bacteria and fungi facilitate these bioremediation avenues as cost-effective alternatives. This review article emphasizes on physical, chemical, and biological methods for removal of copper from the wastewater as well asdetailing microorganism's mechanisms to mobilize or immobilize copper in wastewater and soil., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The Itezhi-tezhi Dam on the Kafue River in Zambia is a major capture fishery. However, the upstream reaches of the Kafue River receive effluents from copper mines. It was unclear whether fish health in the dam is adversely affected due to the mining effluents. We investigated the health status of fish in Itezhi-tezh Dam using a histology-based fish health assessment protocol with Oreochromis andersonii as a bioindicator. Fish were sampled in the Itezhi-tezh Dam and at a reference site further upstream on the Kafue River before it enters the mining region. Metal bioaccumulation, biometric indices and histological alterations in the gills, gonads, hearts, kidneys and livers were assessed. The findings revealed significantly higher copper and selenium sediment concentrations (p = 0.02843 and p = 0.02107 respectively), bioaccumulation of copper and selenium, and increased histological alterations in the gills, kidneys and livers of fish in the Itezhi-tezhi Dam., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

A field trial was performed to carry out an enhanced phytoremediation technique for multi-metal contaminated copper tailings by Sudan grass (Sorghum Sudanese), ryegrass (Lolium perenne L.), and Bermuda grass (Cynodon dactylon), using conditioner (TH-LZ01) and straw combination into composite amendments as soil amendments, aimed to obtain the maximum of phytoremediation effect. The results showed that compared with untreated herbaceous plants, the application of conditioner and straw planted with herbaceous plants reduced the pH and conductivity and increased the organic matter and water content of the copper tailings to different degrees. With the addition of conditioner and straw, the DTPA-Cd, DTPA-Cu, DTPA-Pb, and DTPA-Zn contents in the copper tailings showed a decreasing trend compared with the untreated group. The herbaceous plants were promoted to reduce the percentage contents of acid soluble fractions Cd, Cu, Pb, and Zn and to increase the percentage contents of reducible, oxidizable, and residual fractions heavy metals (Cd, Cu, Pb, and Zn) in the copper tailings to different degrees. The contents of Cd, Cu, Pb, and Zn in the underground part of herbaceous plants were higher than those in the aboveground part, and the contents of Cd, Cu, Pb, and Zn in the aboveground part and underground part decreased after adding conditioner and straw, which indicated that the conditioner and straw inhibited the transport of heavy metals in the plant. Furthermore, the principal component analysis showed that the application of conditioner and straw with planting ryegrass had more potential for improving the physicochemical properties of copper tailings and reducing heavy metal toxicity, followed by Bermuda grass and Sudan grass., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

This study assessed the phytotoxicity of a mixture of five different trace elements (TEs) frequently found as pollutants in soils: arsenic, cadmium, copper, lead and zinc. On the other hand, the plant response to a magnetite (Fe 3 O 4 ) nanoparticle amendment on this mixture as well as nanomagnetite remediation potential has been tested. Sunflower (Helianthus annuus) plants were grown for 90 days in soil contaminated with the five mentioned TEs at the limit levels of TEs in soils likely to receive sludge established by French legislation. Depending on the conditions, experimental set-ups were amended or not with 1% dry weight nanomagnetite (NPsMagn), citric acid-coated nanomagnetite (NPsMagn@CA) or micro-sized magnetite (μPs) in order to assess the behavior of nanomagnetites in a TEs-contaminated water-soil-plant system under repeated water-deficiency stress. The mixture of TEs did not induce phytotoxicity as estimated by plant growth, pigment content, maximum quantum yield of photosynthesis, oxidative impact and antioxidant response. Furthermore, both nanomagnetites treatments in a TEs-contaminated soil significantly increased biomass production by 64 % compared to control and antioxidant enzyme activities compared to control and TEs-treated plants. NPsMagn and NPsMagn@CA particularly enhance phytoextraction of Cd and Cu, increasing the amounts of TEs in aerial parts from 1.5 to 4.5 times compared to set-ups without nanomagnetites. Based on Cd, Cu, Pb and Zn contents in soil solutions, both nanomagnetites treatments improved TEs phytoextraction without increasing groundwater contamination. On the contrary, nanomagnetites significantly reduce arsenic uptake by plants and solubilization in dissolved phase. Our results show that modifying surface physicochemical properties of NPsMagn with citric acid coating does not improve their effects compared to bare NPsMagn. NPsMagn and NPsMagn@CA also appear to mitigate the effects of drought stress. This work highlights several positive environmental aspects related to the use of nanomagnetites in phytoremediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Zinc (Zn) and copper (Cu) stable isotopic compositions have been analyzed in various species of bivalve mollusks worldwide, but no comprehensive systematic interspecies comparison exists. Thus, we assessed isotope differences between species harvested in emblematic French coastal ecosystems to unveil biologically driven Cu and Zn isotope fractionation patterns. Inter-species isotopic variability of Cu is larger than Zn, with organisms that regulate internal concentrations displaying preferential bioaccumulation of heavy isotopes. The degree of internal isotope fractionation decreases from mussels > clams > oysters, affecting Cu more than Zn. The less pronounced Zn inter-specie variability helps preserve source information more reliably. Spatial analysis of a single oyster species denotes thus an important isotope variability of environmental Zn sources, including natural, anthropogenic and dietary components. Overall, results highlight the importance of considering systematic offset in Cu and Zn isotope values when comparing data from different bivalve species., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Anthropogenic activities have increased the discharge of marine contaminants threatening marine life. Small gulfs, such as the Arabian Gulf, are vulnerable to accumulating potentially toxic elements in marine species due to slow water exchange. The concentration of 21 elements was determined in the tissues of Scomberomorus commerson from Umm Al Quwain (United Arab Emirates) and Bandar Abbas (Iran). Chromium, Copper, and Iron exceeded internationally established maximum permissible limits. Sites could not be distinguished based on Principle Component Analyses of elements. Elevated Cu and Cr in muscle are of concern to marine species as well as humans. Metal Pollution Index showed a significant difference between sites, with 20.34 % and 100 % of individuals suffering high metal toxicity and poor body conditions, respectively. The Arabian Gulf is experiencing an increase in discharge of industrial wastes. Implementation of strict policies to reduce discharge of toxic substances is required to protect marine organisms and humans., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Heavy metals are naturally omnipresent in aquatic systems. Excess amounts of heavy metals can accumulate in organisms of pollution impacted systems and transfer across a food web. Analysing the food web structure and metal contents of the organisms can help unravel the pathways of biomagnification or biodilution and gain insight in trophic linkages. We measured heavy metals and other elements in mussel bank detritus and organisms of the Biesbosch reservoirs (the Netherlands) and linked those to stable isotopic signatures. The heavy metal contents (cadmium, copper, lead, and zinc) were often lowest in benthivorous, omnivorous and piscivorous species (mainly fish); whereas, phosphorus contents were lower in the autotrophs. Mussel bank detritus contained the highest amounts of heavy metals. The heavy metals were negatively correlated with δ 15 N values. For selenium no clear trend was observed. Furthermore, there was a negative correlation between fish length and some heavy metals. Based on all 20 analysed elemental contents, similarities between species became apparent, related to niche or habitat. This study confirms that elemental contents of species can differ between feeding guilds and/or species, which can be attributed to metabolic and physiological processes. The organisms in higher trophic levels have adaptations preventing metal accumulation, resulting in lower contents. Within the fish species biodilution occurs, as most metal contents were lowest in bigger fish. Overall, the metals did not seem to biomagnify, but biodilute in the food web. Metal analyses combined with isotopic signatures could thus provide insights in metal transfer and possible trophic linkages within a system., (© 2024. The Author(s).)