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Summary: Accumulation of toxic ions in plant tissues modulates the levels of primary and secondary metabolites, which may be related to salinity tolerance. In this study two sugarcane clones, CP-4333 (tolerant) and HSF-240 (sensitive), were exposed to salinity levels at the formative stage, and evaluated three times at 10-day intervals. Although net rate of photosynthesis (Pn), leaf area, length and dry weight of shoots were decreased in both clones, the CP-4333 showed less reduction compared to HSF-240. Both clones displayed a general tendency to accumulate Na+ and Cl− and little K+, though CP-4333 accumulated less Na+ and more K+ compared to HSF-240, and thus showed a higher K+:Na+ ratio. The carotenoid (CAR) content remained steady, while total chlorophyll (CHL) was slightly reduced in the tolerant clone and significantly reduced in HSF-240. In contrast, soluble phenolics (PHE), anthocyanins (ANT) and flavones (FLA) levels were 2.5, 2.8 and 3.0 times greater in CP-4333 in comparison with HSF-240. The decrease in Pn and most secondary metabolites demonstrated by the sensitive clone, but not evidenced in the tolerant clones, suggest that the presence of those metabolites is related to increased salt tolerance of sugarcane. The increased synthesis of PHE, ANT and FLA seems to protect sugarcane from ion-induced oxidative stress, probably due to a common structural skeleton, the phenyl group, of those metabolites. CAR, as components of the light harvesting center (LHC) and biosynthesized in chloroplasts, may confer resistance to this organelle. The PHE, ANT and FLA synthesized in the cytosol may protect cells from ion-induced oxidative damage by binding the ions and thereby showing reduced toxicity on cytoplasmic structures. [Copyright &y& Elsevier]

The recent need for remote health wellness monitoring has led to the extensive use of wearable sensors. Owing to their increased use, these sensors are required to exhibit both functionality and safety to the user. A major component in the fabrication of these sensors and their associated circuitry is the use of metallic/organic conductive inks. However, very less is known about the interfacial and molecular interactions of these inks with biological matter as they can result in an inflammatory reaction to the user. Significant efforts are thus needed to explore and improve the bio-acceptability of such conductive ink-based wearable sensors. The present study investigates the biocompatibility of encapsulated and non-encapsulated wearable electrochemical sensors used for sensing uric acid as a biomarker for wound healing fabricated using screen-printing technique. Ionic release of metallic ions was investigated first to understand the susceptibility of the conductive inks towards ionic leaching when in contact with a fluid. Time-lapse investigation using ICPS (inductive couple plasma spectroscopy) shows a high concentration (607.31 ppb) of leached silver (Ag + ) ions from the non-encapsulated sensors. The cell viability data suggests a 2.5-fold improvement in the sensor biocompatibility for an encapsulated sensor. While the carbon ink shows negligible effect on cell viability, the silver ink elicits significant decrease (< 50%) in cell viability at concentrations higher than 2 mg ml -1 . The toxicity pathway of these sensors was further determined to be through the generation of reactive oxygen species resulting in over 20% apoptotic cell death. Our results show that the lower biocompatibility of the non-encapsulated sensor attributes to the higher leaching of Ag + ions from the printed inks which elicits several different inflammatory pathways. This work highlights the importance biocompatibility evaluation of the material used in sensor fabrication to develop safe and sustainable sensors for long-term applications., (© 2022. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

The increasing release of nanomaterials has attracted significant concerns for human and environmental health. Similarly, the dissemination of antimicrobial resistance (AMR) is a global health crisis affecting approximately 700,000 people a year. However, a knowledge gap persists between the spread of AMR and nanomaterials. This study aims to fill this gap by investigating whether and how nanomaterials could directly facilitate the dissemination of AMR through horizontal gene transfer. Our results show that commonly-used nanoparticles (NPs) (Ag, CuO and ZnO NPs) and their ion forms (Ag + , Cu 2+ and Zn 2+ ) at realistic concentrations within aquatic environments can significantly promote the transformation of extracellular antibiotic resistance genes in Acinetobacter baylyi ADP1 by a factor of 11.0-folds, which is comparable to the effects of antibiotics. The enhanced transformation by Ag NPs/Ag + and CuO NPs/Cu 2+ was primarily associated with the overproduction of reactive oxygen species and cell membrane damage. ZnO NPs/Zn 2+ might increase the natural transformation rate by stimulating the stress response and ATP synthesis. All tested NPs/ions resulted in upregulating the competence and SOS response-associated genes. These findings highlight a new concern that nanomaterials can speed up the spread of AMR, which should not be ignored when assessing the holistic risk of nanomaterials., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Background: Asymmetric intracellular and extracellular ionic gradients are critical to the survivability of mammalian cells. Given the importance of manganese (Mn 2+ ), calcium (Ca 2+ ), and bicarbonate (HCO 3 - ) ions, any alteration of the ion-content balance could induce a series of cellular responses. HCO 3 - plays an indispensable role for Mn-mediated Fenton-like reaction, but this is difficult to achieve because bicarbonates are tightly regulated by live cells, and are limited in anticancer efficacy. Methods: A responsive and biodegradable biomineral, Mn-doped calcium carbonate integrated with dexamethasone phosphate (DEX) (Mn:CaCO 3 -DEX), was reported to enable synergistic amplification of tumor oxidative stress, reduce inflammation, and induce Ca-overload cell apoptosis by elevating the intracellular and extracellular ionic gradients. Results: Under the acidic environment in tumor region, the ions (Mn 2+ , CO 3 2- , Ca 2+ ) were released by the degradation of Mn:CaCO 3 -DEX and then escalated oxidative stresses by triggering a HCO 3 - -indispensable Mn-based Fenton-like reaction and breaking Ca 2+ ion homeostasis to cause oxidative stress in cells and calcification. The released anti-inflammatory and antitumor drug, DEX, could alleviate the inflammatory environment. The investigations in vitro and in vivo demonstrated that the synergistic oncotherapy could effectively inhibit the growth of subcutaneous tumors and orthotopic liver tumors. Notably, normal cells showed greater tolerance of the synergistic influences. Conclusion: As an ion drug, Mn:CaCO 3 -DEX is an excellent potential diagnostic agent for precise orthotopic tumor management by the generation in situ of toxic ion and drug pools in the environment of tumor region, with synergistic effects of enhanced chemodynamic therapy, calcification, and anti-inflammation effects., Competing Interests: Competing Interests: The authors have declared that no competing interest exists., (© The author(s).)

The metal/metal alloy-based implants and prostheses are in use for over a century, and the rejections, revisions, and metal particle-based toxicities were reported concurrently. Complications developed due to metal ions, metal debris, and organo-metallic particles in orthopedic patients have been a growing concern in recent years. It was reported that local and systemic toxicity caused by such released products from the implants is one of the major reasons for implant rejection and revision. Even though the description of environmental metal toxicants and safety limits for their exposure to humans were well established in the literature, an effort was not adequately performed in the case of implant-based metal toxicology. Since the metal ion concentration in serum acts as a possible indicator of the systemic toxicity, this review summarizes the reported human serum safe limits, toxic limits, and concentration range (μg/L, ppb, etc.) for mild to severe symptoms of six (cardiac, hepatic, neuro, nephron, dermal and endocrine) systemic toxicities for twelve most commonly used metallic implants. It also covers the widely used metal ion quantification techniques and systemic toxicity treatments reported., Competing Interests: Declaration of Competing Interest The authors report no declarations of interest., (Copyright © 2021. Published by Elsevier B.V.)

Silver nanoparticles (AgNPs) are the most commonly used nanoparticles (NPs) owing to their anti-microbial properties, and the pulmonary system provides a major portal of entry for these NPs used in aerosolized products. AgNPs have the potential to cause pulmonary toxicity, cross the alveolar-capillary barrier, and distribute to remote organs following pulmonary exposure. The mechanism underlying the effects of AgNPs, secondary to lung exposure, on the major organs including liver, spleen, kidney and brain, however, is still not completely understood. The aim of this study was to analyze the organ toxicity and distribution of pulmonary exposure to single dose of 5 mg/kg AgNPs (10 nm) with varying coatings (polyvinylpyrrolidone and citrate), at different time points (1 and 7 days), in Balb/C mice. Silver ions (Ag + ) were used as ionic control. Histological evidence of inflammation was observed in lungs for both types of AgNPs. Markers of inflammation including tumor necrosis factor α (TNF-α) and interleukin 6 (IL-6) were significantly increased in lung, brain and liver in AgNPs exposed animals. Ag + ions caused significant increase of TNF-α and IL-6 in the spleen and kidney. Significant increase of reduced glutathione, nitric oxide, and 8-isoprostane was observed in most of the organs investigated. Furthermore, AgNPs induced DNA damage and apoptosis in the lung, liver and brain. The biodistribution showed that, AgNPs were distributed mainly in the spleen, liver, lung and little in kidney and brain. Comparatively, reduced amount of Ag was detected in most organs 7 days after exposure, except for AgAc in the kidney and brain. In conclusion, pulmonary exposure to AgNPs caused oxidative stress markers, inflammation, DNA damage and biodistribution in remote organs. These findings provide a novel mechanistic insight into the pathophysiological effects and tissue distribution of lung exposure to AgNPs., (Copyright © 2021. Published by Elsevier B.V.)

Textile wastewater contains large quantities of azo dyes mixed with various contaminants especially heavy metal ions. The discharge of effluents containing methyl orange (MO) dye and Cu 2+ ions into water is harmful because they have severe toxic effects to humans and the aquatic ecosystem. The dried algal biomass was used as a sustainable, cost-effective and eco-friendly for the treatment of the textile wastewater. Box-Behnken design (BBD) was used to identify the most significant factors for achieving maximum biosorption of Cu 2+ and MO from aqueous solutions using marine alga Fucus vesiculosus biomass. The experimental results indicated that 3 g/L of F. vesiculosus biomass was capable of removing 92.76% of copper and 50.27% of MO simultaneously from aqueous solution using MO (60 mg/L), copper (200 mg/L) at pH 7 within 60 min with agitation at 200 rpm. The dry biomass was also investigated using SEM, EDS, and FTIR before and after MO and copper biosorption. FTIR, EDS and SEM analyses revealed obvious changes in the characteristics of the algal biomass as a result of the biosorption process. The dry biomass of F. vesiculosus can eliminate MO and copper ions from aquatic effluents in a feasible and efficient method.

Proteases are industrially important catalysts. They belong to a complex family of enzymes that perform highly focused proteolysis functions. Given their potential use, there has been renewed interest in the discovery of proteases with novel properties and a constant thrust to optimize the enzyme production. In the present study, a novel extracellular neutral protease produced from Arthrospira platensis was detected and characterized. Its proteolytic activity was strongly activated by β-mercaptoethanol, 5,5-dithio-bis-(2-nitrobenzoic acid) and highly inhibited by Hg 2+ and Zn 2+ metal ions which support the fact that the studied protease belongs to the cysteine protease family. Using statistical modelling methodology, the logistic model has been selected to predict A. platensis growth-kinetic values. The optimal culture conditions for neutral protease production were found using Box-Behnken Design. The maximum experimental protease activities (159.79 U/mL) was achieved after 13 days of culture in an optimized Zarrouk medium containing 0.625 g/L NaCl, 0.625 g/L K 2 HPO 4 and set on 9.5 initial pH. The extracellular protease of A. platensis can easily be used in the food industry for its important activity at neutral pH and its low production cost since it is a valuation of the residual culture medium after biomass recovery., 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 © 2020 Elsevier B.V. All rights reserved.)

Indirect oxidation induced by reactive free radicals, such as hydroxyl radical (HO), sulfate radical (SO 4 - ) and carbonate radical (CO 3 - ), plays an important or even crucial role in the degradation of micropollutants. Thus, the coadjutant degradation of phenacetin (PNT) by HO, SO 4 - and CO 3 - , as well as the synergistic effect of O 2 on HO and HO 2 were studied through mechanism, kinetics and toxicity evaluation. The results showed that the degradation of PNT was mainly caused by radical adduct formation (RAF) reaction (69% for Г, the same as below) and H atom transfer (HAT) reaction (31%) of HO. For the two inorganic anionic radicals, SO 4 - initiated PNT degradation by sequential radical addition-elimination (SRAE; 55%), HAT (28%) and single electron transfer (SET; 17%) reactions, while only by HAT reaction for CO 3 - . The total initial reaction rate constants of PNT by three radicals were in the order: SO 4 -  > HO > CO 3 - . The kinetics of PNT degradation simulated by Kintecus program showed that UV/persulfate could degrade target compound more effectively than UV/H 2 O 2 in ultrapure water. In the subsequent reaction of PNT with O 2 , HO and HO 2 , the formation of mono/di/tri-hydroxyl substitutions and unsaturated aldehydes/ketones/alcohols were confirmed. The results of toxicity assessment showed that the acute and chronic toxicity of most products to fish increased and to daphnia decreased, and acute toxicity to green algae decreased while chronic toxicity increased., (Copyright © 2020 Elsevier Inc. All rights reserved.)

An increase in the production and usage of gold nanoparticles (AuNPs) triggers the necessity to focus on their impact on ecosystems. Therefore, the purpose of this study was to investigate the acute toxicity of AuNPs and ionic gold (Au (III)) to organisms representing all trophic levels of the aquatic ecosystem, namely producers (duckweed Lemna minor), consumers (crustacean Daphnia magna, embryos of Danio rerio) and decomposers (bacteria Vibrio fischeri). The organisms were exposed according to a standardized protocol for each species and endpoints. The AuNPs (1.16 and 11.6 d.nm) were synthesized using citrate (CIT) and polyvinylpyrrolidone (PVP) as capping agents, respectively. It was found, that Au (III) was significantly more toxic than AuNPs PVP and AuNPs CIT. AuNPs showed significant toxicity only at high concentrations (mg/L), which are not environmentally relevant in the present time, but a cautious approach is advised, due to the possibility of interactions with other contaminants.

The incidence of peri-implant bone loss is high, and is a difficult condition to treat. Previous studies have shown that titanium (Ti) ions released from implants can lead to osteoblast cell damage, but the specific mechanisms have not been elucidated. The present study established a Ti ion damage osteoblast cell model. The levels of mitochondrion‑derived reactive oxygen species (mROS) and autophagy, cell viability and the sirtuin 3 (SIRT3)/superoxide dismutase 2 (SOD2) pathway were examined in this model. It was found that Ti ions decreased osteoblast viability. Moreover, with increased Ti ion concentration, the expression levels of microtubule associated protein 1 light chain 3α (LC3) progressively increased, P62 decreased, autophagic flow increased and mROS levels increased. After the addition of an autophagy inhibitor Bafilomycin A1 and Mito‑TEMPO, a mitochondrial antioxidant, the production of mROS was inhibited, the level of autophagy was decreased and cell activity was improved. In addition, with increased Ti ion concentration, the activity of SOD2 decreased, the acetylation level of SOD2 increased, the SIRT3 mRNA and protein expression levels decreased, and the activity of SIRT3 was significantly decreased. Furthermore, it was demonstrated that SIRT3 overexpression reduced the acetylation of SOD2 and increased the activity of SOD2, as well as reducing the production of mROS and the expression level of LC3, thus increasing cell viability. Therefore, the present results suggested that excessive production of mROS induced by Ti ions led to autophagic cell death of osteoblasts, which is dependent on the SIRT3/SOD2 pathway.

Objective: To evaluate the effects of Cu 2+ and Cd 2+ at different concentrations on superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD) activity in Oncomelania hupensis ., Methods: Cu 2+ - and Cd 2+ -containing solutions were prepared at 7 concentrations, and O. hupensis snails were exposed to the solutions for 24 h, of 15 snails in each concentration. Then, the snail body was collected following removal of the snail shell and homogenated, and the SOD, CAT and POS activities were detected in the supernatants., Results: With the increase of the Cu 2+ concentration, the SOD activity appeared a rise followed by a reduction in O. hupensis snails, and the CTA activity appeared a decline-rise-decline tendency, while the POD activity showed a tendency towards rise followed by decline. With the increase of the Cd 2+ concentration, the SOD activity appeared a rise followed by a reduction in O. hupensis snails, and the CTA activity appeared a decline- rise- decline tendency, while the POD activity showed a decline-rise-decline tendency., Conclusions: Exposure to Cu 2+ and Cd 2+ at high concentrations results in a decline in the activity of SOD, CAT and POD in O. hupensis at the same time.

Objective: To assess the acute toxicity of Cu 2+ , Cd 2+ , Hg 2+ and Pb 2+ to Oncomelania hupensis ., Methods: Cu 2+ , Cd 2+ , Hg 2+ and Pb 2+ solutions were prepared at five concentrations, and 10 snails were exposed to each concentration for 24, 48, 72 h and 96 h. Then, the inhibition of snail activity and snail death was observed, and the half maximal effective concentration (EC 50 ) and median lethal concentrations (LC 50 ) were estimated., Results: The 24, 48, 72 h and 96 h EC50 values of Cu 2+ , Cd 2+ , Hg 2+ and Pb 2+ were 0.74, 0.56, 0.46, 0.37 mg/L, 4.79, 3.52, 1.70, 1.26 mg/L, 1.90, 1.49, 0.83, 0.76 mg/L and 21.40, 9.98, 7.90, 5.42 mg/L for snails, respectively. The 96 h LC 50 values of Cu 2+ , Cd 2+ , Hg 2+ and Pb 2+ were 0.43, 2.96, 1.12 mg/L and 12.22 mg/L for snails, the safe concentrations were 0.004 3, 0.029 6, 0.011 2, 0.122 2 mg/L, respectively., Conclusions: Cu 2+ shows a high acute toxicity to snails, and Cd 2+ and Hg 2+ exhibit a moderate acute toxicity to snails, while Pb 2+ is lowly toxic to snails.

In this study, a biodegradable natural polymer chitosan was modified with salicylaldehyde to prepare salicylaldehyde functionalized chitosan nanoparticles (N-Ch-Sal). The N-Ch-Sal was characterized by atomic force microscopy (AFM), scanning electron microscopy-energy-dispersive X-ray (SEM-EDX), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The salicylaldehyde functionalized chitosan nanoparticles (N-Ch-Sal) (~80 nm) were then used for the adsorption of three heavy metals viz., Cu(II), Cd(II) and Pb(II) ions. The above-mentioned techniques were also employed for evaluation of changes in N-Ch-Sal after metal adsorption. The parameters affecting the adsorption of metal ions including pH, contact time, amount of adsorbent, initial metal ion concentration and the effect of interfering ions, were studied thoroughly and optimized. The concentration of metal ions remaining in the aqueous system after adsorption experiments was analyzed by ICP-MS. At optimal conditions, sorption capacity of Pb(II) ion was found to be highest i.e., 123.67 followed by Cu(II) (84.60) and Cd(II) (63.71 mg/g). The adsorption process followed the pseudo-second-order kinetic model and fitted well with the Langmuir adsorption isotherm. The adsorption method was applied to a real tap water sample for the quantification and removal of Pb(II) ions. The concentration of Pb(II) ions in the tested sample was 4.88 ppb., Competing Interests: Declaration of competing interest Authors declare no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In the present work, we have utilized a simple, no-cost, unmodified eggshell powder as a naked-eye colorimetric detector, which on simple dispersion in aqueous solution of metal ions exhibited characteristic color change from white to pale green, pale blue, yellow, pale yellow, dark yellow, pale pink, blue, and brown for metal ions V 4+ , Cr 3+ , Cr 6+ , Fe 2+ , Fe 3+ , Co 2+ , Cu 2+ , and Ag + , respectively. The effects of various parameters like concentration of metal ions, pH, temperature, and adsorbent dosage were investigated by batch sorption experiments. Also, Freundlich and Langmuir models were used to describe the adsorption isotherm. The eggshell powder before and after adsorption was characterized qualitatively by the naked-eye and quantitatively by diffuse reflectance spectroscopy-UV, Fourier transform infrared, atomic absorption spectroscopy, powder X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, Brunauer-Emmett-Teller, zeta potential, and X-ray photoelectron spectroscopy techniques. In addition, the competitive adsorption of metal ions in mixtures and the recycle experiments were carried out to prove the sustainability of the material. Further, the red, green, and blue alterations were extracted from the colorimetric array and subjected to hierarchical clustering analysis using the Ward method by calculating the Euclidean distance, which displayed facile discrimination of 10 heavy metal ions at 1 mM level. Thus, the unmodified eggshell powder has been proven to be an impressive value-added sustainable material for synergistic metal adsorption and colorimetric naked-eye detection of a series of metal ions with detection limits of 10 -4 M for Fe 3+ , Fe 2+ , and Cu 2+ ; 10 -3 M for Cr 3+ , Cr 6+ , Ag + , and Co 2+ ; and 5 × 10 -3 M for V 4+ .

A present ecological issue causing secondary salinization in different countries is the discharge of effluents by the potash mining industry. In Germany, the River Werra is used as a sink for potash mining discharges containing high concentrations of ions, predominantly Cl - , K + , Na + , and Mg 2+ resulting in a strong decline of the biodiversity and abundance of local species. However, hardly anything is known about the acute and chronic physiological effects of high concentrations and imbalances of ions being prevalent in potash mining effluents in fish. Therefore, the stress response and selected immune and growth parameters were investigated in standardized laboratory experiments. A native freshwater fish species, Rutilus rutilus, was exposed to concentrations of the high currently allowed (HT) and lowered future thresholds (LT) and three different ion solutions (containing high Mg 2+ (Mg), high K + (K) and high Mg 2+ +K + (Mg+K) concentrations) for four different exposure times (24 h, 7 d, 21 d, 8 wk). Tank water (additionally after 9 and 12 h) and plasma cortisol, glucose and protein, hematocrit and hemoglobin were determined after each exposure time. Furthermore, plasma lysozyme and head kidney leucocyte respiratory burst activity (only after 21 d) were evaluated as well as growth parameters. A transient stress response was induced in almost all groups. Tank water cortisol was elevated after 9 h in HT, LT and Mg+K and in HT after 12 h, whereas glucose concentrations increased after 24 h in all exposure groups except K. HT led to enhanced hematocrit and hemoglobin content after 24 h. Plasma protein, immune system and growth were not affected in any group. None of the ion solutions induced acute toxicity but most triggered typical acute stress reactions. Rather the sum of high ion concentrations than single ions challenged the fish. Even though the effects observed in adult roach were only transient and indicate acclimatization under laboratory conditions, adverse effects observed in the river are evident and further research on physiological endpoints including reproductive parameters and impacts on younger life stages seem to be needed to scientifically base protective thresholds., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Rare earth (RE) ions at high concentrations are toxic to many organisms as they induce oxidative stress and cause improper incorporation of the ions into calcium-binding proteins. Although the mechanism of action underlying the toxicity of REs has been identified, intracellular signaling pathways involved in stress responses against RE ions still remain unclear. In Caenorhabditis elegans, cellular responses against heavy metal stresses are primarily regulated by the c-Jun N-terminal kinase (JNK)-like mitogen-activated protein kinase (MAPK) pathway with a minor contribution of the p38-like MAPK pathway. In this study, we found that both JNK- and p38-like MAPK pathways were involved in stress responses against RE. Unlike heavy metal responses, mutations in both the JNK and p38 pathways caused similar hypersensitivity to RE ions. Although the signaling pathways used for these stress responses were found to be similar, the degree of their respective contribution slightly differed between heavy metal and RE ions.

The biotic ligand model (BLM) is proposed as a tool to quantitatively evaluate biological toxicity of metals considering both metal speciation and the influence of environmental conditions. The model assumes that biological sites bind to metals as biotic ligands (BLs) and obtains a series of BLM parameters including conditional binding constants (K). However, developing a BLM for each metal and biology takes a lot of experimentation. In the present study, relationships between metal ionic characters and BLM parameter K were respectively investigated for three terrestrial organisms. The results showed that ionization potential was the most strongly related to log K for barley (R 2  = 0.845, p <  0.01) and earthworm (R 2  = 0.881, p <  0.01), and electronegativity index most significantly related to log K for lettuce (R 2  = 0.835, p <  0.01). Based on these relationships, a set of quantitative ion character-activity relationships (QICARs) were developed for predicting log K of metals. Then the QICAR were coupled with BLM and a novel QICAR-BLM was constructed. Finally, the QICAR-BLM was applied to predict EC 50 of other unknown-toxicity metals for selected species, and compensate for the lack of toxicity data for a large number of metals in soil., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The acute toxicity of divalent mercury ion to Anguilla japonica from seawater and freshwater aquaculture was assessed. In particular, the effects of toxicity on the microstructures of the gill and liver tissues were examined using the hydrostatic method, without feeding, at a water temperature of 20 °C. The median lethal concentrations (LC 50 ) of divalent mercury ion to fishes in seawater and freshwater over various durations were: 24 h = 1.637 and 1.428 mg/L; 48 h = 1.562 and 1.377 mg/L; 72 h = 1.530 and 1.284 mg/L; and 96 h = 1.442 and 1.228 mg/L. The safety mass concentrations were 0.1442 and 0.01228 mg/L, respectively. After exposure to divalent mercury ion, adhesion between the gill lamellae and massive cellular disintegration and necrotic shedding were observed in the gill tissue sections. The liver tissues underwent hyperemia and swelling, with the appearance of blood spots, swelling of the hepatocyte mitochondria, dilation of the rough endoplasmic reticulum, and intercellular inflation.

The acquisition of metal ions such as iron, copper and manganese is essential for the survival of microorganisms as these are constituents of metalloproteins including enzymes, storage proteins, structural elements, transcription factors and antimicrobial factors in various biological processes. However, excess of these metal ions is associated with significant toxicity due to spontaneous redox cycling of ions and obstruction of normal metabolic pathways. To overcome this, microbes have developed a variety of metal regulatory systems allowing them to adapt to the changing biotic and abiotic environments. Multi-copper oxidases (MCOs) such as ceruloplasmins, ferroxidases, laccases and nitrite reductases are such regulatory systems employed by microbes to resist the toxicity of metal ions by controlling their oxidation states under aerobic conditions. MCOs help pathogens survive during an infection by evasion of the toxic environment generated by the host immune system and thus are considered necessary determinants of virulence. This review summarizes the role of MCOs in metal homeostasis under stressful conditions and the extent to which these MCOs contribute to microbial virulence within the host that might prove as an esteemed avenue for the development of novel antimicrobial therapies., (Copyright © 2019 Elsevier GmbH. All rights reserved.)

Although silver nanoparticles are the most widespread product of nanotechnology, the mechanisms underlying AgNP microbial toxicity remain the subject of intense debate. In this study, Bacillus subtilis has been used as model organism to elucidate the molecular interactions between this class of bacteria and different forms of silver such as nanoparticles, nanoparticles functionalized with tetracycline and silver ions. For this purpose, we carried out transmission electron microscopy and MALDI-TOF MS analysis of cells treated with silver nanoparticles (AgNPs, AgNPs functionalized with tetracycline, combination of AgNPs with tetracycline) and silver ions as well as we measured the level of reactive oxygen species. The data demonstrate that B. subtilis exhibits high resistance to silver nanoparticles and this phenomenon is associated with following processes: (I) initiation of endospore formation, (II) reduction of free Ag + released from nanoparticles and (III) modification of the AgNPs surface. However, high silver ions concentration appeared to be very toxic to studied strain of bacterium. MALDI-TOF MS analysis revealed that the spectra of B. subtilis cells treated with silver ions are significantly different from spectra of control cells and cell treated with AgNPs and antibiotic which can suggest that silver ions in the highest degree modify bacterial components., (Copyright © 2018. Published by Elsevier B.V.)

The effect of extracellular polymeric substances (EPS), vital organic matters and nutrient elements in the natural environment, on the behavior and toxicology of silver nanoparticles (AgNPs) and ions remains ambiguous. In this study, the role of EPS on the toxicity of AgNPs and dissolved silver ions (from AgNO 3 ) to a green algae Chlorella vulgaris was investigated. After the removal of EPS, algae accumulated more silver, about 7.41- and 1.25-fold of those in the algae with EPS for AgNPs and AgNO 3 treatments, respectively. The large amount of accumulated silver was bound to the algal cell surface for AgNPs treatment and was internalized in the algae for AgNO 3 treatment, irrespective of the presence of EPS in algae. After exposure to AgNPs, the ruffles in the surfaces of algal cells were filled by AgNPs, and almost invisible. FTIR showed that for both AgNPs and AgNO 3 , the aldehyde groups on the cell surface were oxidized to carboxyl groups by silver ions, irrespective of the presence of EPS in algal cells, indicating that silver ions were released from the oxidization of AgNPs and reacted with algal cells. The content of chlorophyll showed that AgNPs depressed algal growth more remarkably than did AgNO 3 , independent of the presence of EPS in algae, suggesting that AgNPs had greater toxic effects on algae than did silver ions. The findings suggest that the barrier effect of EPS gave nanoparticles an extraordinary edge over ions, but EPS had no discerning effect on the interaction of algal cells with the silver ions released from AgNPs and AgNO 3 , and also on the effect of AgNPs and AgNO 3 on algal growth., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Alzheimer's disease (AD) is the most common cause of dementia in late life. It is difficult to precisely diagnose AD at early stages, making biomarker search essential for further developments. The objective of this study was to identify protein biomarkers associated with aluminum ions toxicity (AD-like toxicity) in a human neuroblastoma cell model, SH-SY5Y and assess potential prevention by NAP (NAPVSIPQ). Complete proteomic techniques were implemented. Four proteins were identified as up-regulated with aluminum ion treatment, CBP80/20-dependent translation initiation factor (CTIF), Early endosome antigen 1 (EEA1), Leucine-rich repeat neuronal protein 4 (LRRN4) and Phosphatidylinositol 3-kinase regulatory subunit beta (PI3KR2). Of these four proteins, EEA1 and PI3KR2 were down-regulated after NAP-induced neuroprotective activity in neuroblastoma cells. Thus, aluminum ions may increase the risk for neurotoxicity in AD, and the use of NAP is suggested as a treatment to provide additional protection against the effects of aluminum ions, via EEA1 and PI3KR2, associated with sorting and processing of the AD amyloid precursor protein (APP) through the endosomal system., (Copyright © 2019. Published by Elsevier Taiwan LLC.)

The reductive detoxification of microbes is of significant importance as toxic high oxidation-state metals are ubiquitous in the environment. As a protective interface, extracellular polymeric substances (EPS) are known to play an important role in reducing the toxicity, the relative contribution of different EPS fractions in the process of microbial reductive detoxification remains not to be understood. In this study, we used toxic gold ions (Au 3+ ) and EPS fractions from Paenibacillus mucilaginosus as an example to quantitatively assess the relative contribution of different EPS fractions in the process of the reductive detoxification. At different concentrations of EPS (300 mg/L to 500 mg/L), B-EPS contributed higher reductive ratio (10.6%±0.6% to 25.9%±0.3%) for reducing the toxicity of Au 3+ , while it was lower (1.7%±0.3% to 5.4%±0.6%) for L-EPS. Confronted with the attack of the Au 3+ ions (0 ppm-180 ppm), sugars in B-EPS had a more positive metabolic response than proteins (secreted sugars/ proteins>1) against the toxicity of Au 3+ . Ultimately, FTIR and electrochemical titration analyses showed that the detoxification process of microbial EPS was mainly mediated by the aldehyde groups of sugars in B-EPS. This study contributed a quantitative understanding for the role of different fractions of EPS in microbial defense against the attack of toxic metal ions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

As nano- and micro-sized plastics accumulate in the environment and the food chain of animals, including humans, it is imperative to assess the effects of nanoplastics in living organisms in a systematic manner, especially because of their ability to adsorb potential toxicants such as pollutants, heavy metals, and organic macromolecules that coexist in the environment. Using the zebrafish embryo as an animal model, we investigated the bioaccumulation and in vivo toxicity of polystyrene (PS) nanoplastics individually or in combination with the Au ion. We showed that smaller PS nanoplastics readily penetrated the chorion and developing embryos and accumulated throughout the whole body, mostly in lipid-rich regions such as in yolk lipids. We also showed that PS nanoplastics induced only marginal effects on the survival, hatching rate, developmental abnormalities, and cell death of zebrafish embryos but that these effects were synergistically exacerbated by the Au ion in a dose- and size-dependent manner. Such exacerbation of toxicity was well correlated with the production of reactive oxygen species and the pro-inflammatory responses synergized by the presence of PS, supporting the combined toxicity of PS and Au ions. The synergistic effect of PS on toxicity appeared to relate to mitochondrial damage as determined by ultrastructural analysis. Taken together, the effects of PS nanoplastics were marginal but could be a trigger for exacerbating the toxicity induced by other toxicants such as metal ions.

Background: Due to the potential advantages of Gadolinium Nanoparticles (NPs) over gadolinium elements, gadolinium based NPs are currently being explored in the field of MRI. Either in elemental form or nanoparticulate form, gadolinium toxicity is believed to occur due to the deposition of gadolinium ion (designated as Gd3+ ion or simply G ion)., Objective: There is a serious lack of literature on the mechanisms of toxicity caused by either gadolinium-based NPs or ions. Breast cancer tumors are often subjected to MRIs, therefore, human breast cancer (MCF-7) cells could serve as an appropriate in vitro model for the study of Gadolinium Oxide (GO) NP and G ion., Methods: Cytotoxicity and oxidative damage was determined by quantifying cell viability, cell membrane damage, and Reactive Oxygen Species (ROS). Intracellular Glutathione (GSH) was measured along with cellular Total Antioxidant Capacity (TAC). Autophagy was determined by using Monodansylcadaverine (MDC) and Lysotracker Red (LTR) dyes in tandem. Mitochondrial Membrane Potential (MMP) was measured by JC-1 fluorescence. Physicochemical properties of GO NPs were characterized by field emission transmission electron microscopy, X-ray diffraction, and energy dispersive spectrum., Results: A time- and concentration-dependent toxicity and oxidative damage was observed due to GO NPs and G ions. Bax/Bcl2 ratios, FITC-7AAD double staining, and cell membrane blebbing in phase-contrast images all suggested different modes of cell death induced by NPs and ions., Conclusion: In summary, cell death induced by GO NPs with high aspect ratio favored apoptosis-independent cell death, whereas G ions favored apoptosis-dependent cell death., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Ionic silver is a potential hazard to aquatic life forms because of the increasing usage of silver based materials. The need for developing a sustainable and ecofriendly process to minimize the toxic effects of the free ions burden is now a scientific consensus. Therefore, we report the latest results in cyanobacterium Leptolyngbya JSC-1 investigating the tolerance towards toxic doses of silver, its extracellular biomineralization and silver nano-deposits formation inside the cells, and speculate about potential environmental impacts. In this study, scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS) analysis reveal the extracellular biomineralization of soluble silver (1-100 μM) into corresponding nanoparticles (50-100 nm in diameter) by JSC-1, while X-ray photoelectron spectroscopy (XPS) examination divulged the presence of both Ag + and Ag 0 in extracellularly biomineralized silver, depicting a mixture of both Ag x O and elemental Ag. The scanning transmission electron microscopy (STEM), EDS and elemental mapping visualized the formation of intracellular silver nanoparticles. Moreover, this feature of silver tolerance in JSC-1 was further exploited and a novel protocol was developed for isolation and maintenance of axenic culture of this filamentous cyanobacterium. Consequently, this capability of silver biomineralization by JSC-1, both extra- and intra-cellularly might be useful for modeling the Ag resistance mechanism in cyanobacteria and also might be a sustainable alternative for heavy metals bioremediation in aquatic environments., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Acetylcholinesterase (AChE; EC 3.1.1.7) is a serine hydrolase, whose main function is to modulate neurotransmission at cholinergic synapses. It is, therefore, the primary target of some pesticides and heavy metals. Its inhibition in aquatic organisms has been used as an indicator of the presence of these pollutants in water bodies. The present study aimed to characterize physicochemical and kinetic parameters of brain AChE in the benthic fish Hoplosternum littorale and to analyze the in vitro effects of pesticides (dichlorvos, diazinon, chlorpyrifos, parathion-methyl, temephos, carbaryl, carbofuran, aldicarb, diflubenzuron, novaluron and pyriproxyfen) and metal ions (As 3+ , Cd 2+ , Cu 2+ , Fe 2+ , Mn 2+ , Mg 2+ , K + , Pb 2+ , Hg 2+ , Zn 2+ ) investigating the potential of this enzyme as environmental biomarker based on current regulations. Specific substrates and inhibitors have indicated AChE to be the predominant cholinesterase (ChE) in the brain of H. littorale. Peak activity was observed at pH 8.0 and 30 °C. The enzymatic activity is otherwise moderately thermostable (≈ 50% activity at 45 °C). The enzyme can reduce the activation energy of acetylthiocholine hydrolysis reaction to 8.34 kcal mol -1 while reaching a rate enhancement of 10 6 . Among the pesticides under study, dichlorvos presented an IC 50 value below the maximum concentrations allowed by legislation. This study presents the first report on the inhibition of brain AChE activity from Siluriformes by the pesticides novaluron and pyriproxyfen. Mercury ion also exerted a strong inhibitory effect on its enzymatic activity. The H. littorale enzyme thus has the potential to function as an in vitro biomarker for the presence of the pesticide dichlorvos as well as mercury in areas of mining and industrial discharge., (Copyright © 2018. Published by Elsevier B.V.)

The study was conducted to determine how aluminum (Al) and selenium (Se) ions alone and in combination affect superoxide dismutase (SOD) activity and to evaluate the distribution of these elements in the blood and the brain of laboratory mice. SOD activity in mouse brain was evaluated after single-time (within 24 h) and repeated (over 14 days) intraperitoneal (IP) injections of SeO 3 2- , Al 3+ , and (SeO 3 2- +Al 3+ ) solutions. The control mice received IP injections of the same volume of saline. Aluminum concentration in mouse blood increased both after single-time and repeated injections of AlCl 3 and the combined (AlCl 3  + Na 2 SeO 3 ) solutions. The concentration of Se increased in blood after single-time and repeated injections of Na 2 SeO 3 and the combined (AlCl 3  + Na 2 SeO 3 ) solutions. After the single-time injection of the experimental solutions, the concentrations of both Al and Se in mouse brain remained at baseline, but after repeated injections of (AlCl 3  + Na 2 SeO 3 ) solutions increased aluminum concentration. A single IP injection of Al did not change SOD activity in mouse brain, while a single injection of Se or the Se + Al mixture decreased it. After 14 days, IP injections of Al or Se alone did not affect SOD activity, while their combination decreased it. Our results showed that Se ions decreased SOD activity in mouse brain after both single-time and repeated IP injections of selenium-containing solutions. The study failed to show a direct or linear effect of increased Al or Se concentrations on SOD activity in mouse brain.

Hydrate formation in seafloor pipelines is considered an economic and flow assurance issue for the oil and gas industries. Ionic liquids (ILs) have been recently used as potential hydrate inhibitors. Although branded as green compounds, their ecotoxicity in case of leakage from pipelines onto the aquatic environment needs more deep evaluations. Here, we investigate the impacts of three ILs previously used as successful thermodynamic hydrate inhibitors namely choline chloride (ChC1), 1-methyl-1-propyl pyrrolidinium triflate (PMPy [triflate]) and tetra-methyl ammonium acetate (TMAA). Mortality (including LC50), teratogenicity, locomotion and neurotoxicity, and hatching rate were utilized to investigate any potential acute toxicity of these ILs on embryonic development of zebrafish. No significant mortality or teratogenic effects were found for all tested compounds in a concentration range between 50 and 200 mg/L. The LC50 was significantly higher than the tested dose >200 mg/L. While, up to 200 mg/L all compound had no impact on the survival rate, ChCl showed a significant effect on neuromuscular development as judged by the increase of spontaneous tail coiling activity (25 VS 4 burst/ minutes of the negative control-treated embryos). Further, apart from PMPy [triflate], ChC1 and TMAA had a significant adverse effect on the hatching rate of the treated embryos at concentrations of 200 mg/L. However, this effect was very mild at lower concentrations (≤100 mg/L). Our data indicate that within the tested concentrations both TMAA and PMPy [triflate] had no or little potential harmful effect on embryonic development of aquatic fauna "green", while ChC1 should be used with caution., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The current study was designed to evaluate genotoxicity of different sizes of iron oxide nanoparticles (IONPs) and ionic iron using coelomocytes of the earthworms Eisenia hortensis. Earthworms were exposed to different series of IONPs and ionic iron concentrations to find the respective LC50 of the chosen chemicals. LC 50 for < 50, <100 nm and the ionic iron of IONPs were 500, 200, 250 µg/mL respectively. Concentrations of LC 50 /2 (250, 100, 125 µg/mL for < 50, <100 nm and the ionic iron respectively) and LC 50 for 48 h were used to perform the comet assay and micronucleus test. Statistically significant (p < 0.05) increase in DNA and chromosomal damage was observed for all sizes of IONPs and ionic iron. In the comet assay system, the greatest genotoxicity was observed in the treatments with < 100 nm IONPs, whereas the greatest numbers of micronuclei and binucleate cells were observed in the treatments with ionic iron. It was concluded that different types of nanoparticles (i.e. sizes, shapes) may have different genotoxic potencies in different assays with E. hortensis earthworms.

Copper oxide (CuO) nanoparticles (NPs) are increasingly investigated, developed and produced for a wide range of industrial and consumer products. Notwithstanding their promising novel applications, concern has been raised that their increased use and disposal could consequently increase their release into marine systems and potentially affect species within. To date the understanding of factors and mechanisms of CuO (nano-) toxicity to marine invertebrates is still limited. Hence, we studied the characteristics and behaviour of two commercially available CuO NPs of similar size, but produced employing distinct synthesis methods, under various environmentally and experimentally relevant conditions. In addition, cell viability and DNA damage, as well as gene expression of detoxification, oxidative stress, inflammatory response, DNA damage repair and cell death mediator markers were studied in primary cultures of hemocytes from the marine clam Ruditapes philippinarum and, where applicable, compared to bulk CuO and ionic Cu (as CuSO 4 ) behaviour and effects. We found that the synthesis method can influence particle characteristics and behaviour, as well as the toxicity of CuO NPs to Ruditapes philippinarum hemocytes. Our results further indicate that under the tested conditions aggregating behaviour influences the toxicity of CuO NPs by influencing their rate of extra- and intracellular dissolution. In addition, gene expression analysis identified similar transcriptional de-regulation for all tested copper treatments for the here measured suite of genes. Finally, our work highlights various differences in the aggregation and dissolution kinetics of CuO particles under environmental (marine) and cell culture exposure conditions that need consideration when extrapolating in vitro findings., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In the present work, lanthanum (III) encapsulated chitosan-montmorillonite composite (La-CS-MMT) was prepared as an adsorbent for the effective removal of phosphate ions from aqueous solution. Characterization of the adsorbent using FT-IR, XRD, SEM with EDX, TGA and DTA techniques were carried out. Batch adsorption experiments were carried out to optimize the effects of various operating parameters viz., shaking time, initial concentration of phosphate ions, dosage, competitor co-existing ions, pH and temperature. Phosphate ions adsorbed effectively on La-CS-MMT composite through hydrogen bonding and by outer-sphere complex formation mechanism. Freundlich isotherm model fit well with the equilibrium isotherm data. The experimental values of ∆G°, ∆S° and ∆H° revealed that the nature of adsorption was feasible, spontaneous and exothermic. The kinetic study was well fitted with pseudo-second-order model. Regeneration study of the spent La-CS-MMT-P composite was carried out upto five cycles and found that about 70% of adsorption efficiency was retained., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The objective of this study was to develop a ratiometric and colorimetric organic sensor for Pb 2+ detection in environmental samples. A new probe 4-phenyl amino thiourea (PAT) was designed and synthesized using hydrazine hydrate and phenyl isothiocyanate as raw materials. After its structure was characterized and confirmed, its UV-vis spectral property was investigated in detail. PAT possesses a specifically real-time, ratiometric and colorimetric response to Pb 2+ in dimethyl formamide (DMF)/H 2 O (v/v = 9:1, pH = 7.0) within 18.0 s. There was little interference in the presence of some other common metal ions, such as Fe 3+ , Cd 2+ , Zn 2+ , Mg 2+ , Cr 3+ , Ca 2+ , Ba 2+ , Sn 2+ , Na + , Mn 2+ , Hg 2+ , and Pb 2+ . Under the optimized conditions (DMF/H 2 O with v/v of 9:1, c PAT = 1.0 × 10 -3 mol·L -1 , pH = 7.0), the present sensor PAT was successfully applied for Pb 2+ determination in environmental water samples with satisfied recoveries (83.0%-106.0%) and analytical precision (≤7.2%). The recognition mechanism was confirmed to form a stable 1:1 six-member ring complex between the target dye and Pb 2+ with a coordination constant of 4.96 × 10 4 .

Field and laboratory studies have shown that mayflies (Ephemeroptera) tend to be relatively sensitive to elevated major ion concentrations, but little is known about how ionic composition influences these responses. The present study evaluated the acute toxicity of major ion salts to the mayfly Neocloeon triangulifer over a range of background water quality conditions. The mayfly was particularly sensitive to Na 2 SO 4 , with the median lethal concentration (LC50) of 1338 mg SO 4 /L being lower than LC50s reported for 7 other species at that hardness. Increasing hardness of the dilution water from 30 to 150 mg/L (as CaCO 3 ) resulted in doubling of LC50s for sodium salts, and an approximately 1.5-fold increase in LC50 for MgSO 4 . Potassium salt toxicity was not strongly influenced by hardness, consistent with findings for other species. When hardness was held constant but the Ca to Mg ratio was manipulated, the ameliorative effect on Na 2 SO 4 and NaCl did not appear as strong as when hardness was varied; but for MgSO 4 the amelioration relative to Ca activity was similar between the 2 experiments. The toxicity of K salts to N. triangulifer was similar to Na salts on a millimolar basis, which contrasts with several other species for which K salts have been much more toxic. In addition, the toxicity of KCl to N. triangulifer was not notably affected by Na concentration, as has been shown for Ceriodaphnia dubia. Finally, plotting LC50s in terms of ion activity (Cl, SO 4 , Na, Mg, or K) over the range of Ca activities in dilution water resulted in significant positive relationships, with comparable slopes to those previously observed for C. dubia over the same range of Ca activities. Environ Toxicol Chem 2018;37:1330-1339. © 2018 SETAC., (© 2018 SETAC.)

Highly efficient removal of metal ion pollutants, such as toxic and nuclear waste-related metal ions, remains a serious task from the biological and environmental standpoint because of their harmful effects on human health and the environment. Recently, highly porous metal-organic frameworks (MOFs), with excellent chemical stability and abundant functional groups, have represented a new addition to the area of capturing various types of hazardous metal ion pollutants. This review focuses on recent progress in reported MOFs and MOF-based composites as superior adsorbents for the efficient removal of toxic and nuclear waste-related metal ions. Aspects related to the interaction mechanisms between metal ions and MOF-based materials are systematically summarized, including macroscopic batch experiments, microscopic spectroscopy analysis, and theoretical calculations. The adsorption properties of various MOF-based materials are assessed and compared with those of other widely used adsorbents. Finally, we propose our personal insights into future research opportunities and challenges in the hope of stimulating more researchers to engage in this new field of MOF-based materials for environmental pollution management.

Crosslinked chitosan beads were grafted with N-vinyl-2-pyrrolidone (NVP) using ammonium persulfate (APS) as free radical initiator. Important variables on graft copolymerization such as temperature, reaction time, concentration of initiator and concentration of monomer were optimized. The results revealed optimum conditions for maximum grafting of NVP on 1g crosslinked chitosan as follows: reaction temperature, 60°C; reaction time, 2h and concentrations of APS and NVP of 2.63×10 -1 M and 26.99×10 -1 M, respectively. The modified chitosan beads were characterized by FTIR spectroscopy, 13 C NMR, SEM and BET to provide evidence of successful crosslinking and grafting reactions. The resulting material (cts(x)-g-PNVP) was evaluated as adsorbent for the removal of Cu(II) ions from aqueous solutions in a batch experiment. The Langmuir and Freundlich adsorption models were also applied to describe the equilibrium isotherms. The results showed that the adsorption of the copper ions onto the beads agreed well with Langmuir model with the maximum capacity (q max ) of 122mgg -1 ., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The bacterium Cupriavidus metallidurans can reduce toxic gold(I/III) complexes and biomineralize them into metallic gold (Au) nanoparticles, thereby mediating the (trans)formation of Au nuggets. In Au-rich soils, most transition metals do not interfere with the resistance of this bacterium to toxic mobile Au complexes and can be removed from the cell by plasmid-encoded metal efflux systems. Copper is a noticeable exception: the presence of Au complexes and Cu ions results in synergistic toxicity, which is accompanied by an increased cytoplasmic Cu content and formation of Au nanoparticles in the periplasm. The periplasmic Cu-oxidase CopA was not essential for formation of the periplasmic Au nanoparticles. As shown with the purified and reconstituted Cu efflux system CupA, Au complexes block Cu-dependent release of phosphate from ATP by CupA, indicating inhibition of Cu transport. Moreover, Cu resistance of Au-inhibited cells was similar to that of mutants carrying deletions in the genes for the Cu-exporting P IB1 -type ATPases. Consequently, Au complexes inhibit export of cytoplasmic Cu ions, leading to an increased cellular Cu content and decreased Cu and Au resistance. Uncovering the biochemical mechanisms of synergistic Au and Cu toxicity in C. metallidurans explains the issues this bacterium has to face in auriferous environments, where it is an important contributor to the environmental Au cycle. IMPORTANCE C. metallidurans lives in metal-rich environments, including auriferous soils that contain a mixture of toxic transition metal cations. We demonstrate here that copper ions and gold complexes exert synergistic toxicity because gold ions inhibit the copper-exporting P-type ATPase CupA, which is central to copper resistance in this bacterium. Such a situation should occur in soils overlying Au deposits, in which Cu/Au ratios usually are ≫1. Appreciating how C. metallidurans solves the problem of living in environments that contain both Au and Cu is a prerequisite to understand the molecular mechanisms underlying gold cycling in the environment, and the significance and opportunities of microbiota for specific targeting to Au in mineral exploration and ore processing., (Copyright © 2017 American Society for Microbiology.)

The potential toxic effects of silver nanoparticles (AgNPs), administered by a single intratracheal instillation (i.t), was assessed in a rat model using commercial physico-chemical characterized nanosilver. Histopathological changes, overall toxic response and oxidative stress (kidney and plasma protein carbonylation), paralleled by ultrastructural observations (TEM), were evaluated to examine renal responses 7 and 28 days after i.t. application of a low AgNP dose (50 µg/rat), compared to an equivalent dose of ionic silver (7 µg AgNO₃/rat). The AgNPs caused moderate renal histopathological and ultrastructural alteration, in a region-specific manner, being the cortex the most affected area. Notably, the bulk AgNO₃, caused similar adverse effects with a slightly more marked extent, also triggering apoptotic phenomena. Specifically, 7 days after exposure to both AgNPs and AgNO₃, dilatation of the intercapillary and peripheral Bowman's space was observed, together with glomerular shrinkage. At day 28, these effects still persisted after both treatments, accompanied by an additional injury involving the vascular component of the mesangium, with interstitial micro-hemorrhages. Neither AgNPs nor AgNO₃ induced oxidative stress effects in kidneys and plasma, at either time point. The AgNP-induced moderate renal effects indicate that, despite their benefits, novel AgNPs employed in consumer products need exhaustive investigation to ensure public health safety., Competing Interests: The authors declare no conflict of interest.

Metal containing engineered nanomaterials (ENMs) are now commonly used in various industrial and commercial applications. Many of these materials can be transformed during waste water treatment and ultimately enter terrestrial ecosystems via agriculturally applied biosolids. It is unclear how agriculturally important soil microbes will be affected by exposure to environmentally relevant, sublethal concentrations of ENMs and their transformation products (i.e., ions, aggregates, etc.). A method was developed, which puts O 2 consumption responses in terms of viability, and tested by examining the toxic effects of Ag + , Zn 2+ , and Ni 2+ ions on the plant growth promoting rhizobacterium (PGPR) Bacillus amyloliquefaciens GB03. The method was then used to examine the toxicity of Ag + , as-synthesized polyvinylpyrrolidone-coated silver ENM (PVP-AgENMs), and 100% sulfidized AgENM on B. amyloliquefaciens GB03, and two additional PGPRs Sinorhizobium meliloti 2011, and Pseudomonas putida UW4. S. meliloti was found to have the highest LC 50 for Ag + and PVP-AgENMs (6.6 and 207 μM, respectively), while B. amyloliquefaciens and P. putida exhibited LC 50 's for Ag + and PVP-AgENMs roughly half those observed for S. meliloti. The authors observed species-specific O 2 consumption responses to ENM and ion exposure. PVP-AgENMs were less toxic than ions on a molar basis, and abiotic dissolution likely explains a significant portion of the observed toxic responses. Our results suggest microbes may exhibit distinct metabolic responses to metal and ENM exposure, even when similar LC 50 's are observed. These findings together illustrate the importance of understanding species-specific toxic responses and the utility of examining O 2 consumption for doing so.

Silver nanomaterials (AgNMs) are widely used in many fields because of their antimicrobial properties. Depending on the shapes and dimensions of the AgNMs, their potential uses and needs vary. Consequently, vast quantities of multi-dimensional AgNMs are being manufactured and released into aquatic ecosystems, where they have toxic effects on aquatic organisms. Therefore, an assessment of the toxicities of each multi-dimensional AgNM on aquatic ecosystems is necessary. In this study, important aquatic model species, Daphnia magna and Daphnia galeata, were used to assess and compare the toxic effects of silver ions (Ag + ions) and multi-dimensional AgNMs, including silver nanoparticles (AgNPs), silver nanowires (AgNWs), and silver nanoplates (AgPLs). The results indicated that Ag + ions were more toxic than AgNMs of different dimensions and sizes, and that AgPLs were the most toxic of the AgNMs. In the case of AgNWs, the longer (20 μm) nanowire was more toxic than the shorter (10 μm) one. In addition, D. galeata was more sensitive than D. magna to both Ag + ions and AgNMs. This study elucidates the dimension-dependent toxicity of and silver ions and nanomaterials in the cladocerans D. magna and D. galeata. Further studies will be necessary to further elucidate the actual risk of multi-dimensional nanomaterials in ecosystems., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Manufactured nanoparticles (NPs) have become emerging pollutants and attracted extensive concern about their potential effects on the marine environment. However, the contribution of particles and their corresponding released ions to the overall toxicity of CuO NPs is poorly understood. In this study, we investigated the toxicological effects of CuO NPs and their corresponding released ions on the hemocytes of Chlamys farreri. Both copper species induced membrane damage, and increased lysosome contents in hemocytes. Based on the integrated biomarker responses method, the relative contributions of particles (NP particle ) and dissolved ions (NP ion ) to the toxicity of CuO NPs after 2h of exposure were 62.07% and 37.93%, respectively, indicating that the particles rather than the dissolved ions were the dominant source of NP toxicity. Transmission/scanning electron microscopy analysis confirmed the greater histopathological effects exerted by particles than Cu ions. Higher reactive oxygen species (ROS) generation induced by NP particle than by NP ion suggested that the intracellular ROS production might be responsible for the NP toxicity. Our findings suggest that particles effects play a key role in risk assessment of CuO NPs on the marine ecosystem., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The presence of heavy metal in food chains due to the rapid industrialization poses a serious threat on the environment. Therefore, detection and monitoring of heavy metals contamination are gaining more attention nowadays. However, the current analytical methods (based on spectroscopy) for the detection of heavy metal contamination are often very expensive, tedious and can only be handled by trained personnel. DNA biosensors, which are based on electrochemical transduction, is a sensitive but inexpensive method of detection. The principles, sensitivity, selectivity and challenges of electrochemical biosensors are discussed in this review. This review also highlights the major advances of DNA-based electrochemical biosensors for the detection of heavy metal ions such as Hg 2+ , Ag + , Cu 2+ and Pb 2+ ., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Background: The widespread application of silver nanoparticles (AgNPs) and silver-containing products has raised public safety concerns about their adverse effects on human health and the environment. To date, in vitro toxic effects of AgNPs and ionic silver (Ag + ) on many somatic cell types are well established. However, no studies have been conducted hitherto to evaluate their effect on cellular transcriptome in embryonic stem cells (ESCs)., Results: The present study characterized transcriptomic changes induced by 5.0 µg/ml AgNPs during spontaneous differentiation of mouse ESCs, and compared them to those induced by Ag + under identical conditions. After 24 h exposure, 101 differentially expressed genes (DEGs) were identified in AgNP-treated cells, whereas 400 genes responded to Ag + . Despite the large differences in the numbers of DEGs, functional annotation and pathway analysis of the regulated genes revealed overall similarities between AgNPs and Ag + . In both cases, most of the functions and pathways impacted fell into two major categories, embryonic development and metabolism. Nevertheless, a number of canonical pathways related to cancer were found for Ag + but not for AgNPs. Conversely, it was noted that several members of the heat shock protein and the metallothionein families were upregulated by AgNPs but not Ag + , suggesting specific oxidative stress effect of AgNPs in ESCs. The effects of AgNPs on oxidative stress and downstream apoptosis were subsequently confirmed by flow cytometry analysis., Conclusions: Taken together, the results presented in the current study demonstrate that both AgNPs and Ag + caused transcriptomic changes that could potentially exert an adverse effect on development. Although transcriptomic responses to AgNPs and Ag + were substantially similar, AgNPs exerted specific effects on ESCs due to their nanosized particulate form.

Aggregation and dissolution of CuO and ZnO nanoparticles (NPs) increased with increasing exposure time (24, 48, and 72 h). Acute toxicity of CuO NPs to Daphnia magna also increased significantly with increasing exposure time (p < 0.05), whereas exposure time did not significantly affect acute toxicity of ZnO NPs. The dissolved Cu concentration of CuO NPs was much lower than the median effective concentration (EC 50 ) value (44 μg L -1 at 72 h), implying that the increase in acute toxicity was caused by particles rather than by dissolved ions. However, the dissolved Zn concentration of ZnO NPs was higher than the EC 50 value (600 μg L -1 at 72 h), suggesting this acute toxicity may be caused by dissolved ions. Moreover, CuO NPs induced greater lipid peroxidation than Cu ions did at an exposure time of 72 h, whereas converse results were observed for ZnO NPs.

Silver nanoparticles (AgNPs) are the dominating nanomaterial in consumer products due to their well-known antibacterial and antifungal properties. To enhance their properties, different surface coatings may be used, which affect physico-chemical properties of AgNPs. Due to their wide application, there has been concern about possible environmental and health consequences. Since plants play a significant role in accumulation and biodistribution of many environmentally released substances, they are also very likely to be influenced by AgNPs. In this study we investigated the toxicity of AgNO 3 and three types of laboratory-synthesized AgNPs with different surface coatings [citrate, polyvinylpyrrolidone (PVP) and cetyltrimethylammonium bromide (CTAB)] on Allium cepa roots. Ionic form of Ag was confirmed to be more toxic than any of the AgNPs applied. All tested AgNPs caused oxidative stress and exhibited toxicity only when applied in higher concentrations. The highest toxicity was recorded for AgNPs-CTAB, which resulted with increased Ag uptake in the roots, consequently leading to strong reduction of the root growth and oxidative damage. The weakest impact was found for AgNPs-citrate, much bigger, negatively charged NPs, which also aggregated to larger particles. Therefore, we can conclude that the toxicity of AgNPs is directly correlated with their size, overall surface charge and/or surface coating., (Copyright © 2016 Elsevier Inc. All rights reserved.)

We have recently shown that the toxicological potential of GaAs and InAs particulates in cells is size- and dissolution-dependent, tending to be more pronounced for nano- vs micron-sized particles. Whether the size-dependent dissolution and shedding of ionic III-V materials also apply to pulmonary exposure is unclear. While it has been demonstrated that micron-sized III-V particles, such as GaAs and InAs, are capable of inducing hazardous pulmonary effects in an occupational setting as well as in animal studies, the effect of submicron particles (e.g., the removal of asperities during processing of semiconductor wafers) is unclear. We used cytokine profiling to compare the pro-inflammatory effects of micron- and nanoscale GaAs and InAs particulates in cells as well as the murine lung 40 h and 21 days after oropharyngeal aspiration. Use of cytokine array technology in macrophage and epithelial cell cultures demonstrated a proportionally higher increase in the levels of matrix metalloproteinase inducer (EMMPRIN), macrophage migration inhibitory factor (MIF), and interleukin 1β (IL-1β) by nanosized (n) GaAs and n-InAs as well as As(III). n-GaAs and n-InAs also triggered higher neutrophil counts in the bronchoalveolar lavage fluid (BALF) of mice than micronscale particles 40 h post-aspiration, along with increased production of EMMPRIN and MIF. In contrast, in animals sacrificed 21 days after exposure, only n-InAs induced fibrotic lung changes as determined by increased lung collagen as well as increased levels of TGF-β1 and PDGF-AA in the BALF. A similar trend was seen for EMMPRIN and matrix metallopeptidase (MMP-9) levels in the BALF. Nano- and micron-GaAs had negligible subacute effects. Importantly, the difference between the 40 h and 21 days data appears to be biopersistence of n-InAs, as demonstrated by ICP-OES analysis of lung tissue. Interestingly, an ionic form of In, InCl 3 , also showed pro-fibrogenic effects due to the formation of insoluble In(OH) 3 nanostructures. All considered, these data indicate that while nanoscale particles exhibit increased pro-inflammatory effects in the lung, most effects are transient, except for n-InAs and insoluble InCl 3 species that are biopersistent and trigger pro-fibrotic effects. These results are of potential importance for the understanding the occupational health effects of III-V particulates.

Large-scale synthesis and release of nanomaterials in environment is a growing concern for human health and ecosystem. Therefore, we have investigated the cytotoxic and genotoxic potential of zinc oxide nanoparticles (ZnO-NPs), zinc oxide bulk (ZnO-Bulk), and zinc ions (Zn 2+ ) in treated roots of Allium cepa, under hydroponic conditions. ZnO-NPs were characterized by UV-visible, XRD, FT-IR spectroscopy and TEM analyses. Bulbs of A. cepa exposed to ZnO-NPs (25.5 nm) for 12 h exhibited significant decrease (23 ± 8.7%) in % mitotic index and increase in chromosomal aberrations (18 ± 7.6%), in a dose-dependent manner. Transmission electron microcopy and FT-IR data suggested surface attachment, internalization and biomolecular intervention of ZnO-NPs in root cells, respectively. The levels of TBARS and antioxidant enzymes were found to be significantly greater in treated root cells vis-à-vis untreated control. Furthermore, dose-dependent increase in ROS production and alterations in ΔΨm were observed in treated roots. FT-IR analysis of root tissues demonstrated symmetric and asymmetric P=O stretching of >PO 2 - at 1240 cm -1 and stretching of C-O ribose at 1060 cm -1 , suggestive of nuclear damage. Overall, the results elucidated A. cepa, as a good model for assessment of cytotoxicity and oxidative DNA damage with ZnO-NPs and Zn 2+ in plants.

Owing to wide range of applications, nanotechnology is growing expeditiously. Likely negative impact of nanoparticles (NPs), which are inevitably released into our surroundings, on living organisms is of growing concern. Findings presented here are outcome of investigations carried out to evaluate the impact of ionic and NP speciation states of silver on light harnessing photosynthetic events in Spirodela polyrhiza fronds. Fronds exposed to ionic speciation state showed significant decline in PS (photosystem) II efficiency (Fv/Fm; variable fluorescence/maximal fluorescence), while those exposed to silver nanoparticles (Ag-NPs) showed marginal decline. Accordingly, decline in amplitude of Chl a fluorescence transients was sharper in fronds treated with Ag + than those treated with Ag-NPs. Of the various phases Chl a fluorescence transient, J-I phase [which reflects reduction of plastoquinone (PQ) pool] was most sensitive to both Ag + and Ag-NPs. Phenomenological yield models, built using Biolyzer software, revealed that fronds exposed to Ag + possessed significantly lower potential to trap and harness absorbed light energy for photochemical reactions than those exposed to Ag-NPs. Accordingly, dissipation of absorbed light energy as heat was significantly higher in fronds exposed to Ag + than those exposed to Ag-NPs. These findings revealed that NP speciation state of silver is significantly less toxic to light harnessing photosynthetic machinery of S. polyrhiza, compared to ionic speciation state.