Toxicity Of Cu Research Articles

Organic matter mitigates biotic impact of copper in fruit orchard soil

Inorganic copper (Cu) fungicides and bactericides are widely used to control disease in fruit and vegetable crops and has led to widespread accumulation of the metal in soil beyond regulatory thresholds. We aimed to elucidate the impacts of Cu on soil health within cherry orchard soils in New Zealand, focusing on three biological indicators: earthworm behaviour, soil respiration, and plant growth. We sampled soils from four blocks of different ages within a single orchard, varying in amounts of accumulated soil Cu (7 - 263 mg kg-1) but also in Soil Organic Matter (SOM) content (3 - 10 %). Experimental work was designed to isolate the impacts of both Cu and SOM on three critical biological descriptors: earthworm behaviour, soil respiration and root growth. Soils were amended to standardise both variables in laboratory and glasshouse experiments. The results demonstrated a pronounced inhibition of soil respiration and root development, as well as adverse effects on earthworm behaviour, with increasing Cu concentrations. SOM played a mitigating role, reducing the bioavailability and toxicity of Cu to soil organisms. However, the buffering capacity of SOM is limited and long-term reliance on SOM to mitigate Cu toxicity is not sustainable. Currently Cu continues to accumulate in most orchard soils. This study highlights the importance of assessing Cu bioavailability and soil health in the context of orchard management.

Extracellular Acidosis, Cysteine, and Glutathione Enhance the Toxic Effect of Copper Ions in Cultures of Cerebellar Granule Neurons.

We studied the effect of extracellular acidosis, cysteine, glutathione, and iron ions (Fe3+) on the neurocytotoxic effect of copper ions (Cu2+) in vitro. At acidic pH of the culture medium (pH 6.8), the toxic effect of copper on cultured neurons significantly increased in comparison with that at neutral pH 7.3. In the presence of 25 μM Cu2+ in the culture medium at pH 7.3 and 6.8, the neuronal survival was 89±2 and 63±4%, respectively. In the presence of glutathione or cysteine (1 μM) in the culture medium, even 0.5 μM Cu2+ caused 100% death of cultured neurons, while the presence of Fe3+ (10-50 μM) had no effect on the toxicity of Cu2+. In general, acidosis or the presence of glutathione or cysteine increases the cytotoxicity of copper ions.

Bioaccumulation of heavy metals in water and mollusks in the Karnafully estuary: Potential human health risk and environmental contamination

This study investigates the bioaccumulation of heavy metals lead (Pb), cadmium (Cd), copper (Cu), and chromium (Cr) in water and mollusks across the Karnafully River estuaryof Bangladesh. Samples were collected from six different sites encompassing diverse ecological conditions over three seasons: monsoon, post-monsoon, and winter. Six mollusk species were analyzed using atomic absorption spectrophotometry to quantify metal concentrations in both tissues and shells. These species are Neritina violocea, Neritina sulculosa, Telescopium telescopium, Cerithida ecingulata, Corbicula fluminea, and Bellamya bengalesis. The Chaktai canal site had the highest concentration of Cu (13.99±0.92 mg/kg) from the mussel species B. Bengalesis during monsoon season, which was higher than the tolerable limit for human. The the lowest concentration of Cu (1.13±0.76 mg/kg) from the composite mussel species N. sulculosa were fround from the 15 No. Jetty site in winter.. The highest concentration of Cr was found at the Marine Academy site (0.54±0.24 mg/kg) during the post-monsoon period from the mussel species N. violocea, while the lowest concentration was found near the Karnafully Bridge (0.05±0.02 mg/kg) during the monsoon from the mussel species Cerithidea cingulata. The highest concentration of Cd was observed in the Chaktai canal site (0.77±0.04 mg/kg) during the winter from the B. bengalesis, and the lowest concentration was recorded in the Karnafully Bridge (0.33±0.06 mg/kg) site during the winter season from the Cerithidae cingulata species. The highest amount of Pb was found in Chaktai canal site (0.32±0.06 mg/kg) during the monsoon season in B. bengalesis fuana. The lowest amount was found in Karnafully Bridge (0.09±0.02 mg/kg) in the Cerithidae cingulate species at the same time. The results suggested that the possibility of the occurrence of acute toxicities of Cu, Cr, Cd and Pb was unlikely except for the mussel of T. telescopium in the Marine Academy that indicates heavy metals presence at the Marine Academy site. The study revealed that the average concentrations of the heavy metals were in the order of Cu>Cd>Cr>Pb in the monsoon, postmonsoon, and winter seasons. The principal Component Analysis (PCA) highlighted distinct seasonal patterns in metal accumulation, underscoring the need for seasonal-specific monitoring and management strategies in estuarine ecosystems.

Comparative Transcriptome Analysis of the Hepatopancreas from Macrobrachium rosenbergii Exposed to the Heavy Metal Copper.

The contamination of aquatic ecosystems by the heavy metal copper (Cu) is an important environmental issue and poses significant risks to the physiological functions of aquatic organisms. Macrobrachium rosenbergii is one of the most important freshwater-cultured prawns in the world. The hepatopancreas of crustaceans is a key organ for immune defense, heavy metal accumulation, and detoxification, playing a pivotal role in toxicological research. However, research on the molecular response of the hepatopancreas in M. rosenbergii to Cu exposure is still lacking. In this study, the transcriptomic response in the hepatopancreas of M. rosenbergii was studied after Cu exposure for 3 and 48 h. Compared with the control group, 11,164 (7288 up-regulated and 3876 down-regulated genes) and 10,937 (6630 up-regulated and 4307 down-regulated genes) differentially expressed genes (DEGs) were identified after 3 and 48 h exposure, respectively. Most of these DEGs were up-regulated, implying that gene expressions were largely induced by Cu. Functional enrichment analysis of these DEGs revealed that immunity, copper homeostasis, detoxification, DNA damage repair, and apoptosis were differentially regulated by Cu. Seven genes involved in immunity, detoxification, and metabolism were selected for validation by qRT-PCR, and the results confirmed the reliability of RNA-Seq. All these findings suggest that M. rosenbergii attempts to resist the toxicity of Cu by up-regulating the expression of genes related to immunity, metabolism, and detoxification. However, with the excessive accumulation of reactive oxygen species (ROS), the antioxidant enzyme system was destroyed. As a result, DNA damage repair and the cellular stress response were inhibited, thereby exacerbating cell damage. In order to maintain the normal function of the hepatopancreas, M. rosenbergii removes damaged cells by activating the apoptosis mechanism. Our study not only facilitates an understanding of the molecular response mechanisms of M. rosenbergii underlying Cu toxicity effects but also helps us to identify potential biomarkers associated with the stress response in other crustaceans.

Investigating the Combined Toxicity of Cu(II) and Carbon Monoxide (CO); Cellular CO Delivery Using a Cu(II) Flavonolato Complex.

Carbon monoxide (CO) delivery molecules are of significant current interest as potential therapeutics, including for anticancer applications. A recent approach toward generating new types of materials-based anticancer agents involves combining the Fenton reactivity of a redox active metal ion with CO delivery. However, small molecule examples of these types of entities have not been systematically studied to evaluate the combined effect on cellular toxicity. Herein we describe a Cu(II) flavonolato complex which produces anticancer effects through a combination of copper-mediated reactive oxygen species (ROS) generation and light-induced flavonol CO release. Confocal microscopy studies provide evidence of enhanced flavonol uptake in the copper flavonolato system relative to the free flavonol, which leads to an increased amount of CO delivery within cells. Importantly, this work demonstrates that a metal flavonolato species can be used to produce enhanced toxicity effects resulting from both metal ion-induced Fenton reactivity and increased cellular uptake of a flavonol CO donor.

Antagonistic Effect of Zinc Oxide Nanoparticles Dietary Supplementation Against Chronic Copper Waterborne Exposure on Growth, Behavioral, Biochemical, and Gene Expression Alterations of African Catfish, Clarias gariepinus (Burchell, 1822).

The harmful impact of waterborne copper (Cu) as a common abiotic stressor in aquatic environments has gained much more interest. The present study aimed to investigate the utilization of zinc oxide nanoparticles (ZnONPs) dietary supplementation to mitigate the chronic toxicity of Cu in African catfish (Clarias gariepinus). Two hundred and forty fish (92.94 ± 0.13 g) were assigned into six groups for 60 days. Control (C), ZnONPs20, and ZnONPs30 groups were fed on basal diets fortified with 0, 20, and 30 mg kg-1 ZnONPs without Cu exposure. Cu, Cu + ZnONPs20, and Cu + ZnONPs30 groups were exposed to Cu at a dose of 10mg L-1 and fed on basal diets fortified with 0, 20, and 30 mg kg-1 ZnONPs, respectively. The results revealed that the Cu-exposed fish experienced abnormal clinical signs and behavioral changes. The growth indices and acetylcholine esterase activity were significantly decreased (P < 0.05) in the Cu group. Meanwhile, hepatorenal and serum stress indices (P < 0.05) were significantly elevated with chronic Cu exposure. In addition, a higher expression of stress (P < 0.05) (heat shock protein 60 and hypoxia-inducible factor-1 alpha) and apoptotic-related genes (C/EBP homologous protein, caspase-3, and Bcl-2 Associated X-protein) with down-regulation (P < 0.05) of the anti-apoptotic-related genes (B-cell lymphoma 2 and proliferating cell nuclear antigen) was noticed in the Cu-exposed fish. Histopathological alterations in the gills, liver, kidney, and spleen were markedly reported in the Cu-exposed group. The dietary supplementation with ZnONPs significantly alleviated the negative impacts of chronic waterborne-Cu exposure on growth performance, physiological changes, gene expression, and tissue architecture, especially at 30 mg kg-1 diet level. In particular, the inclusion of ZnONPs at the 30 mg kg-1 diet level produced better outcomes than the 20 mg kg-1 diet. Overall, ZnONPs could be added as a feed supplement in the C. gariepinus diet to boost the fish's health and productivity and alleviate the stress condition brought on by Cu exposure.

Evaluation of short-term copper toxicity in a co-culture of Synechococcus sp., Chaetoceros gracilis and Pleurochrisys cf. roscoffensis exposed to changes in temperature and salinity levels

Metals such as copper (Cu) enter marine environments from natural and anthropogenic sources, causing changes in the biodiversity of marine microalgae and cyanobacteria. Cu plays a dual role as either a micronutrient or toxicant depending on the environmental concentration. Many studies have summarized the potential of Cu to become more toxic to microalgae under environmental stress (for instance climate change).Most of the data available on Cu toxicity concerning microalgae and cyanobacteria have been produced using single-species laboratory tests, and there is still a significant gap in the information concerning the behavior of a group of algae exposed to environmental stressors. Thus, the objective of this study was to evaluate the toxicity of Cu at two concentrations (C1 = 2 μg L−1 and C2 = 5 μg L−1) in multispecies bioassays using three phytoplankton species (one cyanobacteria, Synechococcus sp., and two microalgae, Chaetoceros gracilis and Pleurochrisys cf. roscoffensis). Combinations of two temperatures (20 and 23 °C) and two salinities (33 and 36 PSU), were applied in a 96 h study using flow cytometry analysis (FCM). Algal growth and reactive oxygen species (ROS) production by 2′7′-dichlorofluorescein (DCFH) were monitored by FCM. The results indicated that Synechococcus sp. was more sensitive than C. gracilis and P. roscoffensis to Cu stress at a temperature 23 °C and salinity of 36 PSU under both concentrations of Cu. Chlorophyll a fluorescence showed a significant decrease (p < 0.05) in Synechococcus sp. under 5 μg L−1 of Cu in the combined treatment of 20 °C and 33 PSU; however, there was a significant increase in P. roscoffensis in all combinations at C2 = 5 μg L−1 compared to the control with no Cu, indicating a potential hormetic response to Cu for P. roscoffensis. ROS levels were triggered in a combination of 23 °C and 33 PSU and 5 μg L−1 of Cu, which was higher than all the other combinations studied. Our study resulted in data concerning the potential impacts caused by possible future climate change scenarios in aquatic habitats chronically exposed to metals.

Protective Effects of Sanyar Prebiotic on Immunity and Tissue Changes of Common Carp (Cyprinus carpio) Exposed to CuSO4 Stress

Prebiotics, as feed additives, can activate the antioxidant and immune systems of fish and significantly improve the survival of aquaculture animals in stressful conditions. The exposure of fish to copper sulfate leads to oxidative stress, suppression of the immune system, and destruction of vital body tissues. This study aimed to investigate the protective effects of Sanyar prebiotic on the immunity and tissue changes of common carp (Cyprinus carpio) exposed to CuSO4 stress. Two hundred common carp fish with an average weight of 12.33 ± 0.93 g were stocked in four treatments (triplicates) for 60 days. The experimental treatments contained Sanyar commercial prebiotics in 100 g of food, which included P1 (1 ml prebiotic liquid), P2 (0.1 g prebiotic powder), P3 (0.5 ml liquid and 0.05 g powder), and treatment C (control treatment without any additives). At the end of the experimental period, the fish were exposed to acute toxicity of Cu (0.1 m/l) for 96 hours. Gill, kidney, and liver tissue samples were collected and evaluated after 96 hours. According to the results obtained, there were significant differences in specific growth rate (SGR) and final weight ( p &lt; 0.05). The lowest feed conversion ratio (FCR) was observed in the Sanyar treatments (1.56 ± 0.37), which had a significant difference from the control treatment (1.85 ± 0.35) ( p &lt; 0.05). The results showed that immunity indices such as lysozyme, cortisol, and ACH50 increased in the experimental treatments compared to the control treatment ( p &lt; 0.05). The highest and lowest lysozyme activities were observed in P2 (16.35 ± 0.57) and control treatments (13.15 ± 1.00), respectively ( p &lt; 0.05). Generally, no significant difference was observed between growth and nutrition indices in Sanyar treatments ( p &lt; 0.05). Symptoms of kidney, liver, and gill tissue damage were reported from mild (hyperemia and infiltration of inflammatory cells) to severe (hemorrhage and necrosis). The lowest severity of tissue damage was observed in the treatments fed with Sanyar food supplement. In general, the results of this study showed that the addition of Sanyar prebiotic to the diet of common carp improves the growth indicators and immune response and can also be beneficial in increasing fish resistance to copper toxicity.

Effective disposal of hazardous waste from non-ferrous waste recycling through thermal treatment

Hazardous wastes containing non-ferrous metals have significant value in recycling. However, the recycling process generates leaching residues (HWLR) with high levels of heavy metals, posing a risk to the environment. Based on the component characteristics of HWLR, silica residue (SR), and silicon tetrachloride cracking slag (STCS), the feasibility of co-thermal treatment for the efficient disposal of HWLR, SR and STCS was verified in this study. According to the SiO2–Na2O–CaO ternary system diagram, the melting point of the system decreases gradually with the appropriate increase in SiO2 content when the CaO/Na2O ratio in the system was determined to be about 2.33. When the theoretical liquid phase content of the mixed system of 100%, the thermal treatment temperature could be lowered to 1100 °C, which is significantly below the melting points of HWLR, SR, and STCS individually. The experimental results confirmed that thermal treatment at temperatures above 1000 °C effectively eliminated the leaching toxicity of Cu, Ni, Zn, Cr, Cd, and Pb in the mixed samples of HWLR, SR, and STCS, which can mainly be attributed to the formation of a glass network structure during the thermal treatment process. This study demonstrated that low-temperature melting treatments could efficiently and thoroughly solidify heavy metals in HWLR, SR, and STCS.

MitomiR-1736-3p regulates copper-induced mitochondrial pathway apoptosis by inhibiting AATF in chicken hepatocytes

Copper (Cu) is a toxic heavy metal pollutant. The hepatic toxicity of Cu has attracted widespread attention from researchers. However, its underlying mechanism remains elusive. Mitochondrial microRNAs (mitomiRs) are considered important factors in regulating mitochondrial and cellular functions, and their roles have been implicated in the mechanisms of metal toxicity. Therefore, this research revealed the changes in the mitomiRs expression profile of chicken liver after Cu exposure. It was ultimately determined that mitomiR-1736-3p can be involved in Cu-induced chicken liver damage by targeting AATF. In particular, our investigations have uncovered that exposure to Cu can trigger heightened levels of apoptosis in the hepatic tissue of chickens and primary chicken embryo hepatocytes (CEHs). It is noteworthy that we found upregulation of miR-1736-3p expression can exacerbate Cu-induced cell apoptosis, while inhibition of miR-1736-3p can effectively reduce apoptosis occurrence. Subsequently, we found that Cu-induced cell apoptosis could be restored by overexpressing AATF, while silencing AATF exacerbated the level of apoptosis. Fascinatingly, this change in apoptotic level is directly influenced by AATF on Bax and Bak1, rather than on p53 and Bcl-2. Overall, these findings suggest that the mitomiR-1736-3p/AATF axis mediates the mitochondrial pathway of cell apoptosis potentially involved in Cu-induced chicken liver toxicity.

Geochemical dynamics of Cu(II) in contrasting cocoa soils: Kinetics and isotherm modeling

Understanding copper (Cu) dynamics in cocoa soils can help predict the fate, mobility, and toxicity, which is crucial for sustaining soil functionality, as well as the quality and health safety of cocoa products. Herein, the study investigated sorption-desorption characteristics of Cu(II) in six cocoa soils of varying weathering by kinetics, isothermal, and pH effect experiments in a batch system. Equilibrium sorption increased in the order of Fluvisol < Lixisol < Luvisol < Acrisol = Ferralsol = Nitisol. Kinetics data fitted well to pseudo-second-order and Elovich models. Cu(II) sorption was dominated by outer-sphere and inner-sphere complexations at low and high pH, respectively. The sorption data fitted well with Freundlich and Langmuir's models. Sorption maximum increased in the order of Nitisol (0.91 mg g−1) < Ferralsol (1.21 mg g−1) < Acrisol (1.29 mg g−1) < Lixisol (1.61 mg g−1) < Luvisol (1.68 mg g−1) < Fluvisol (2.01 mg g−1). The binding energy values obtained showed the highest interaction between Cu(II) and soil matrix in Fluvisol and the least in Ferralsol and Nitisol. The desorption studies consistent with the hysteresis index indicated high sorption irreversibility and less Cu(II) mobilization in Fluvisol, Lixisol, Luvisol, and Acrisol vis-à-vis Nitisol and Ferralsol. Nitisol and Ferralsol may promote the possible toxicity of Cu(II) to the soil ecosystem. The study contributes to the sensitivity of Cu(II) mobility and toxicity to the degree of soil weathering; thus, management of heavy metals in cocoa soils should be dependent on soil type.

Metal Accumulation and Tolerance of Energy Willow to Copper and Nickel under Simulated Drought Conditions

The aim of this study was to determine the effect of drought on the accumulation and tolerance of energy willow (Salix viminalis L. var. ‘Gigantea’) to copper (Cu) and nickel (Ni) in the context of phytoremediation potential of the plant and biomass production under adverse water conditions. Drought was simulated with polyethylene glycol (PEG-6000. 5%), and metals were added at a concentration of 1 mM. Plants were cultivated in greenhouse conditions for 21 days according to the experimental variants: control, Cu, Ni, PEG, PEG + Cu and PEG + Ni. The results indicate high toxicity of Cu (chlorosis, necrosis, decrease in biomass, plant dehydration, increase in the content of proline and phenolic compounds), and PEG + Cu co-treatment increased the toxicity of the metal. Ni applied at the same concentration did not cause toxicity symptoms. The willow exhibits the ability to accumulate Ni, and mutual application of PEG + Ni increased Ni uptake to new shoots. Cu caused elevated accumulation of proline and phenolics in leaves accompanied with a decreased carbon and nitrogen content in roots in favor of young shoots. Both metals and drought led to disruption in the content of mineral nutrients (Ca, Mg, Fe). Due to high tolerance to Ni and drought, S. viminalis var. ‘Gigantea’ bears high potential for biomass production on Ni-polluted sites with accompanying metal uptake increased under water deficit.

Acute Toxicity of Copper to Three Species of Pacific Salmon Fry in Water with Low Hardness and Low Dissolved Organic Carbon.

Proposed development of a mine within Alaska's Bristol Bay watershed (USA) has raised concerns about the potential impact of copper (Cu) on Pacific salmon (Oncorhynchus spp.). We conducted 96-h flow-through bioassays using low-hardness and low dissolved organic carbon water to determine the acute lethal toxicity of Cu to sockeye (Oncorhynchus nerka), Chinook (Oncorhynchus tshawytscha), and coho salmon (Oncorhynchus kisutch) fry. We aimed to determine Cu toxicity under field-relevant water quality conditions and to assess three methods of calculating ambient Cu criteria: the biotic ligand model (BLM), a multiple linear regression model endorsed by the US Environmental Protection Agency, and the hardness-based model currently used by the State of Alaska. The criteria generated by all models were below 20% lethal Cu concentrations by factors ranging from 2.2 to 54.3, indicating that all criteria would be protective against mortality. The multiple linear regression-based criteria were the most conservative and were comparable to BLM-based criteria. The median lethal concentrations (LC50s) for sockeye, Chinook, and coho were 35.2, 23.9, and 6.3 µg Cu/L, respectively. We also used the BLM to predict LC50s for each species. Model predictions differed from empirical LC50s by factors of 0.7 for sockeye and Chinook salmon, and 1.1 for coho salmon. These differences fell within the acceptable range of ±2, indicating the model's accuracy. We calculated critical lethal Cu accumulation values for each species to account for differing water chemistry in each bioassay; the present study revealed that coho salmon were most sensitive to Cu, followed by sockeye and Chinook salmon. Our findings underscore the importance of considering site- and species-specific factors when modeling Cu toxicity. The empirical data we present may enhance Cu risk assessments for Pacific salmon. Environ Toxicol Chem 2023;42:2440-2452. © 2023 SETAC.

Discriminating Susceptibility of Xanthine Oxidoreductase Family to Metals.

The xanthine oxidoreductase (XOR) family are metal-containing enzymes that use the molybdenum cofactor (Moco), 2Fe-2S clusters, and flavin adenine dinucleotide (FAD) for their catalytic activity. This large molybdoenzyme family includes xanthine, aldehyde, and CO dehydrogenases. XORs are widely distributed from bacteria to humans due to their key roles in the catabolism of purines, aldehydes, drugs, and xenobiotics, as well as interconversions between CO and CO2. Assessing the effect of excess metals on the Rubrivivax gelatinosus bacterium, we found that exposure to copper (Cu) or cadmium (Cd) caused a dramatic decrease in the activity of a high-molecular-weight soluble complex exhibiting nitroblue tetrazolium reductase activity. Mass spectrometry and genetic analyses showed that the complex corresponds to a putative CO dehydrogenase (pCOD). Using mutants that accumulate either Cu+ or Cd2+ in the cytoplasm, we show that Cu+ or Cd2+ is a potent inhibitor of XORs (pCOD and the xanthine dehydrogenase [XDH]) in vivo. This is the first in vivo demonstration that Cu+ affects Moco-containing enzymes. The specific inhibitory effect of these compounds on the XOR activity is further supported in vitro by direct addition of competing metals to protein extracts. Moreover, emphasis is given on the inhibitory effect of Cu on bovine XOR, showing that the XOR family could be a common target of Cu. Given the conservation of XOR structure and function across the tree of life, we anticipate that our findings could be transferable to other XORs and organisms. IMPORTANCE The high toxicity of Cu, Cd, Pb, As, and other metals arises from their ability to cross membranes and target metalloenzymes in the cytoplasm. Identifying these targets provides insights into the toxicity mechanisms. The vulnerability of metalloenzymes arises from the accessibility of their cofactors to ions. Accordingly, many enzymes whose cofactors are solvent exposed are likely to be targets of competing metals. Here, we describe for the first time, with in vivo and in vitro experiments, a direct effect of excess Cu on the xanthine oxidoreductase family (XOR/XDH/pCOD). We show that toxic metal affects these Moco enzymes, and we suggest that access to the Moco center by Cu ions could explain the Cu inhibition of XORs in living organisms. Human XOR activity is associated with hyperuricemia, xanthinuria, gout arthritis, and other diseases. Our findings in vivo highlight XOR as a Cu target and thus support the potential use of Cu in metal-based therapeutics against these diseases.

ʟ-glutamic acid modulates antioxidant defense systems and nutrient homeostasis in lentil (Lens culinaris Medik.) under copper toxicity.

Copper (Cu), an essential micronutrient, can generate reactive oxygen species (ROS) at its supra-optimal level in living cells as a transition metal, thus producing oxidative stress in plants. Therefore, protecting plants from Cu-induced oxidative stress via the exogenous application of chemical substances, particularly L-glutamic acid (L-Glu), could be a viable strategy for mitigating the toxicity of Cu. The aim of our present study was to investigate how ʟ-Glu protects lentil seedlings from oxidative stress produced by toxic Cu and allows them to survive under Cu toxicity. The results exhibited that when lentil seedlings were exposed to excessive Cu, their growth was inhibited and their biomass decreased due to an increase in Cu accumulation and translocation to the root, shoot, and leaves. Exposure to toxic Cu also depleted photosynthetic pigments, imbalanced water content, and other essential nutrients, increased oxidative stress, and reduced enzymatic and non-enzymatic antioxidants. However, pre-treatment of ʟ-Glu improved the phenotypic appearance of lentil seedlings, which was distinctly evidenced by higher biomass production, maintenance of water balance, and an increase in photosynthetic pigments when exposed to toxic Cu. ʟ-Glu also protected the seedlings from Cu-induced oxidative stress by reducing the oxidative stress marker, specifically by the efficient action of enzymatic and non-enzymatic antioxidants, particularly ascorbate, catalase, monodehydroascorbate, and glutathione peroxidase and maintaining redox balance. Furthermore, ʟ-Glu assisted in maintaining the homeostasis of Cu and other nutrient in the roots, shoots, and leaves of lentil. Collectively, our results provide evidence of the mechanism of ʟ-Glu-mediated protective role in lentil against Cu toxicity, thus proposed as a potential chemical for managing Cu toxicity not only in lentil but also other plants.

Influence of Fe2O3 and bacterial biofilms on Cu(II) distribution in a simulated aqueous solution: A feasibility study to sediments in the Pearl River Estuary (PR China)

This study investigated physico-chemical interactions among Cu(II), biogenic materials, and Fe2O3 in a continuous-flow biofilm reactor system under a well-controlled environment. The effects of Fe2O3 and bacterial biofilms on the distribution of Cu(II) in a simulated aquatic environment were studied. To control biological and abiotic elements in the marine environment, a biofilm reactor was designed to understand the metal speciation of Cu(II) and its distribution. The reactor consisted of a biofilm chamber equipped with glass slides for biofilms attachment. Due to its ability to grow as biofilm in the medium, Pseudomonas atlantica was cultivated to adsorb trace Cu(II) to attached and suspended cells. It was found that biofilms with 170–285 mequiv chemical oxygen demand (COD) concentration/m2 of total oxidizable materials accelerated the Cu(II) adsorption to the surface of the reactor significantly by a factor of five. A significant inhibition to the bacterial growth took place (p ≤ 0.05; t-test) when Cu(II) concentration was higher than 0.5 mg/L. In the absence of Cu(II), bacterial cells grew normally to 0.075 of optical density (OD). However, at the Cu(II) concentration of 0.2 mg/L, the cells grew to a lower OD of 0.58. The presence of glycine and EDTA substantially reduced the toxicity of Cu(II) on bacterial growth (p ≤ 0.05; paired t-test). Their complexation with Cu(II) rendered the metal ions less available to bacterial cells. This implies that the Fe2O3 and bacterial biofilm affected Cu(II) distribution and speciation in the aquatic environment.

Polystyrene microplastics enhanced copper-induced acute immunotoxicity in red swamp crayfish (Procambarus clarkii)

Microplastic pollution has attracted a lot of attention in recent years. Not only can it be ingested by animals, but it can easily become a carrier of other pollutants, forming a composite pollutant with potentially toxic effects on organisms. We investigated the effect of Cu on the accumulation of polystyrene microplastics (PS) in the gills of Procambarus clarkii and whether PS exacerbated the immune toxicity of Cu to P. clarkii were exposed to Cu, PS and PS+Cu for 48 h, the accumulation of PS in gill and hepatopancreas immune and antioxidant indices were analyzed. The objective was to investigate the toxic effects of Ps and Cu compound pollutants on P. clarkii and whether the accumulated pollutants would cause food safety problems. The results showed that microplastic particles adhered to each other and aggregated in the PS+Cu group, and the number of microplastic particles in gill in the PS+Cu group was significantly lower than that in the PS group. Compared with the other two treatment groups, SOD, CAT, GPx activities and MDA content increased significantly in the PS+Cu group and were relatively delayed. At 12 h, 24 h, 36 h and 48 h, the SOD mRNA expression levels in the PS+Cu group were all significantly lower than those in the Cu group (P < 0.05). At 24 h and 48 h, CAT mRNA expression in the PS+Cu group was significantly higher than that in the Cu group (P < 0.05). Crustin 4 mRNA expressions in the PS+Cu group was significantly higher than that in the Cu group at 12 h and 36 h (P < 0.05). The results demonstrate that the PS and Cu compound reduced the accumulation of microplastic particles in the gill. PS particles delayed Cu entry into P. clarkii for a short time (12 h) and reduced the toxic effect, but with the increase of exposure time (24 h and 48 h), the toxic effect of PS and Cu complexes on P. clarkii increases, and the large accumulation of PS and Cu complexes may cause food safety problems.

Seasonal dissolved copper speciation in the Strait of Georgia, British Columbia, Canada

The Strait of Georgia (SoG) is a semi-enclosed, urban basin with seasonally dependent estuarine water circulation, dominantly influenced by Northeast Pacific waters and the Fraser River. To establish a baseline and understand the fate and potential toxicity of Cu in the SoG, we determined seasonal and spatial depth profiles of dissolved Cu (dCu) speciation, leading to estimates of the free hydrated copper (Cu2+) concentrations, as a proxy for Cu toxicity. The concentration of dCu was largely controlled by conservative mixing of the ocean and freshwater endmembers in the SoG. In all samples, ligand concentrations exceeded dCu, by a ratio greater than 1.5, resulting in the complexation of 99.98% of the dCu by strong binding organic ligands. The concentrations of Cu2+ were less than 10-13.2 M, significantly lower than the well-established Cu toxicity threshold (10-12 M Cu2+) for microorganisms. Our results indicate that ambient Cu-binding ligands effectively buffer Cu2+ concentrations within the Strait of Georgia, posing no threat to marine life. In almost 90% of the samples, the ligands were best classified as a single ligand class, with a logKCuL,Cu2+cond between 12.5 and 14.1. The concentrations of these single class ligands were greatest in warm, low salinity, nutrient depleted waters, suggesting that either terrestrially sourced ligands dominate dCu speciation in the SoG, or freshwater sources in the SoG establish the conditions that promote the production of Cu binding ligands in its surface waters. The remaining 10% of the samples were from the euphotic zone, where we detected a stronger ligand class, L1, of logKCuL1,Cu2+cond between 13.5 and 14.3, and a weaker ligand class, L2, of logKCuL2,Cu2+cond between 11.5 and 12.3. In these surface samples, logKCuL1,Cu2+cond and logKCuL2,Cu2+cond were positively correlated with temperature, while L2 concentrations were positively correlated with chromophoric dissolved organic matter of terrestrial origin. This study is the first to perform hierarchal clustering of a trace metal speciation dataset and enabled the distinction of 6 clusters across season, depth, and region of the SoG, highlighting the influence of freshwater and open ocean ligand sources, conservative mixing dynamics, and particulate Cu concentrations on dCu speciation within estuarine basins.

Association of copper exposure with prevalence of chronic kidney disease in older adults

Metal exposure is suspected to be associated with the risk of chronic kidney disease (CKD). Copper (Cu) is an essential yet toxic trace element in humans. Epidemiological evidence on the association of Cu exposure with CKD remains inconsistent. This study aims to investigate the association of blood Cu and its co-exposure to other metals with CKD. A cross-sectional study was conducted among 3285 older participants in Zhejiang, China. The whole blood levels of Cu as well as other 10 metals were measured using the inductively coupled plasma mass spectrometry (ICP-MS). CKD events were defined as the presence of albuminuria or estimated glomerular filtration rate (eGFR)<60mL/min/1.73m2. Multivariable logistic regression and linear regression models were applied to assess the association of Cu with kidney function. The Bayesian kernel machine regression (BKMR) was used to examine the association of metal interactions with CKD. In logistic models, we found a dose-dependent positive association between blood Cu and the prevalence of CKD. Compared to the lowest quartile of blood Cu, the odds ratio (OR) of CKD in the highest quartile was 1.65 (95% confidence interval, CI: 1.25, 2.17), and the β of eGFR was-1.74 (95% CI:-3.15,-0.34) after adjusting for multiple covariates. The positive linear dose-response association was found between blood Cu and the OR of CKD, and negative linear association was found between Cu and the β of eGFR. The positive association between blood Cu and CKD risk was stronger at lower level of manganese (Mn) in the BKMR model. The whole blood level of Cu was remarkably associated with the risk of CKD and showed positive dose-response relationships in the older Chinese population. The toxicity of Cu on kidney function could be antagonized by the exposure of Mn. These findings shed new light on the potential role of Cu in kidney health.

Development of a Site-Specific Guideline Value for Copper and Aquatic Life in Tropical Freshwaters of Low Hardness.

Copper (Cu) is a contaminant of potential concern for a uranium mine whose receiving waters are in the World Heritage-listed Kakadu National Park in northern Australia. The physicochemical characteristics of the freshwaters in this region enhance metal bioavailability and toxicity. Seven tropical species were used to assess the chronic toxicity of Cu in extremely soft freshwater from a creek upstream of the mine. Sensitivity to Cu was as follows: Moinodaphnia macleayi > Chlorella sp. > Velesunio sp. > Hydra viridissima > Amerianna cumingi > Lemna aequinoctialis > Mogurnda mogurnda. The 10% effect concentrations (EC10s) ranged from 1.0 µg/L Cu for the cladoceran Moinodaphnia macleayi to 9.6 µg/L for the fish M. mogurnda. The EC50s ranged from 6.6 µg/L Cu for the mussel Velesunio sp. to 22.5 µg/L Cu for M. mogurnda. Geochemical modeling predicted Cu to be strongly bound to fulvic acid (80%-99%) and of low bioavailability (0.02%-11.5%) under these conditions. Protective concentrations (PCs) were derived from a species sensitivity distribution for the local biota. The 99% PC (PC99), PC95, PC90, and PC80 values were 0.5, 0.8, 1.0, and 1.5 µg/L Cu, respectively. These threshold values suggest that the current Australian and New Zealand default national 99% protection guideline value for Cu (1.0 µg/L) would not provide adequate protection in freshwaters of low hardness, particularly for this area of high conservation value. The continuous criterion concentration predicted by the Cu biotic ligand model for conditions of low pH (6.1), low dissolved organic carbon (2.5 mg/L), low hardness (3.3 mg/L), and 27 °C was 0.48 µg/L Cu, comparable with the PC99. Consideration of the natural water quality conditions of a site is paramount for protective water quality guidelines. Environ Toxicol Chem 2022;41:2808-2821. © 2022 Commonwealth of Australia. Environmental Toxicology and Chemistry © 2022 SETAC.