Acute toxicity of copper oxide nanoparticles to Daphnia magna under different test conditions

The acute toxicity of monodispersed 6 nm and <100 nm poly-dispersed copper oxide nanoparticles toward Daphnia magna was assessed using 48 h immobilization tests. CuSO₄ was used as a reference. Four different exposure conditions were tested, to study whether the toxicity of the nanoparticle suspensions changed in a way similar to what is known for dissolved Cu: first in ISO standard test conditions (pH 7.8), second with slight acidity (pH 6.5), third in the presence of citric acid, and fourth in the presence of humic acid. For all four exposure conditions, the toxicity of Cu employed in the three forms followed the same sequence, i.e., CuSO₄ > monodispersed 6 nm CuO ? poly-dispersed CuO. The toxicity of all Cu forms decreased from pH 6.5, ? pH 7.8, > pH 7.8 + citric acid, to ? pH 7.8 + humic acid. This pattern is in agreement with concentrations of Cu²⁺ calculated using the equilibrium model MINTEQ. These findings show that the acute toxicity of copper oxide nanoparticles is governed by test water composition and the chemical species Cu²⁺.     

Copper sulphate use in South African traditional medicine

Copper (Cu) is an essential element to humans; however, exposure to elevated concentrations through occupational hazard and/or environmental means may be detrimental. This paper provides results of a cross-sectional study aimed to determine the prevalence of copper sulphate (CuSO₄) use in South African traditional medicine by traditional health practitioners (THPs) and details the use thereof. A total of 201 THPs were enrolled from two main municipal areas of KwaZulu-Natal (South Africa). Information on demographic characteristics of THPs, reasons for using or not using CuSO₄ as well as administration methods and age groups of recipients were collected. Of the 201 THPs interviewed, 145 (72 %) use CuSO₄ for healing purposes. The use of CuSO₄ was strongly associated with gender (p = 0.009) where the proportion of CuSO₄ users was higher for female than male THPs. CuSO₄ was reportedly administered to individuals of all ages, including infants and children. The main routes of administration were enema (n = 110; 76 %), oral (n = 40; 28 %) and use in bath (n = 40; 28 %). The reasons cited for use are diverse and included skin rashes (n = 43; 30 %), aches, pains and swelling (n = 38; 28 %) as well as sexually transmitted diseases (n = 28; 19 %). This study identified a high prevalence of THPs using CuSO₄ for healing purposes. These findings support the need to regulate South African traditional medicine to safeguard the user.     

老化过程中铜形态变化的X射线吸收精细结构谱的(XAFS)初步研究

利用X射线吸收精细结构谱(XAFS)对老化过程中土壤中铜的分子形态进行初步表征。以硫酸铜、氧化铜和硫化铜的X射线吸收扩展边结构(EXAFS)谱为参比,对土壤样品中Cu的EXAFS谱进行拟合,得到不同老化阶段与参比物质相对应的结合态Cu的百分含量,并与连续提取法表征进行比较。XAFS分析结果表明,老化阶段土壤样品中铜的主要结合形态是CuSO_4,同时还有部分CuS,基本不含有CuO。随着时间的推移,土壤中CuSO_4百分含量呈现出下降的趋势,CuS百分含量呈现出上升的趋势。这与连续提取法研究结果中其可交换态的百分比下降,残渣态上升的趋势相似。     

Carbon nanotubes and Cu–Zn nanoparticles synthesis using hyperaccumulator plants

This article reports a novel way to synthesize carbon nanotubes and Cu/ZnO nanoparticles using metal hyperaccumulator plants. Metal hyperaccumulator plants are traditionally used for phytoremediation to clean soil polluted by toxic metals. However, the transfer of toxic metals in plant shoots and leaves is an environmental issue because animals and other living organisms feeding on plants will transfer the metals to the ecosystem. Therefore, we suggest that hyperaccumulator plants could be used to synthesize nanoparticles. Here, Brassica juncea L., a Cu-hyperaccumulator plant, was collected around a copper mine and used as a raw chemical to produce carbon nanotubes and Cu/ZnO nanoparticles. The chlorophyll in shoots of B. juncea plants was ethanol extracted to yield chlorophyllin. Cu and Zn were extracted by HNO₃ to form Cu/Zn(NO₃)₂. The chlorophyllin reacted with Cu/Zn(NO₃)₂ to form Cu/Zn chlorophyllin. Cu/ZnO nanoparticles were synthesized by direct precipitation of Cu/Zn chlorophyllin with NaOH and ethanol. The vascular bundles in B. juncea plants, which have been purified and carbonized by HNO₃, were rapidly heated to about 400°C and then they were cooled to room temperature to obtain carbon nanotubes. Results indicate that the outer diameter of carbon nanotubes was around 80 nm. Cu/ZnO nanoparticles have a Cu_0.05Zn_0.95O composition, and had a diameter of about 97 nm. Our study not only inspires the search for a new strategy on the synthesis of nanostructure from renewable natural products, but also breaks through the traditional and limited ideas about the reuse of metals by hyperaccumulator plants.     

Efficient oxidation of sulfides into sulfoxides catalyzed by a chitosan–Schiff base complex of Cu(II) supported on supramagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles

Sulfoxides are versatile synthetic intermediates for the preparation of biological products. Therefore, there is a need for efficient methods to oxidize sulfides into sulfoxides. Such oxidation may be catalyzed by magnetic nanocatalysts due to their good stability, easy synthesis, high surface area, low toxicity and easy separation by magnetic forces. Here we prepared a nanocatalyst by immobilization of the chitosan–Schiff base complex on supramagnetic Fe₃O₄ nanoparticles. The chitosan–Schiff base complex has been previously prepared by functionalization of chitosan with 5-bromosalicylaldehyde and metalation with copper(II) acetate. The catalyst was characterized by Fourier transform infrared, powder X-ray diffraction, transmission electron microscope, scanning electron microscopy, energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Results show that the Fe₃O₄ nanoparticles and nanocatalyst were spherical in shape with an average size of 20 nm. Upon the covalently anchoring of chitosan–Schiff base Cu complex on the magnetic Fe₃O₄ nanoparticles, the average size increased to 60 nm. The prepared Fe₃O₄–chitosan–Schiff base Cu complex catalyzed very efficiently the oxidation of sulfides to sulfoxides with 100 % selectivity in all cases under green reaction conditions and excellent yields. Additionally, ease of recovery and reusability up to four cycles without noticeable loss of catalytic activity make the present protocol beneficial from industrial and environmental viewpoint.     

Determination of types of interactions exhibited by binary mixtures of heavy metals tested against the hermit crab,Clibanarius africanus

Single and joint action toxicity of heavy metal compounds (ZnCO₃, CuSO₄ and CdSO₄) were carried out against the hermit crab, Clibanarius africanus in laboratory bioassays. On the basis of 96?h LC₅₀ values, CuSO₄ (96?h LC₅₀?=?0.03?mM) was found to be the most toxic followed by CdSO₄ and ZnCO₃ (96?h LC₅₀?=?0.24?mM) in decreasing order of toxicity. The evaluation of the metal compounds in mixtures of ZnCO₃–CuSO₄, ZnCO₃–CdSO₄ and CdSO₄–CuSO₄ in pre-defined molar ratios revealed that interactions between Zn–Cu and Zn–Cd test mixtures were in conformity with the models of antagonism (reduction in toxicity of constituent metals). The synergistic ratios (S.R.s) and relationship between observed/predicted 96?h LC₅₀ values (relative toxic unit, RTU) were consistently below 1, indicating antagonistic interactions. Analysis using isobolograms also indicated the interactions between the mixture components to be antagonistic. However, with regards to CdSO₄–CuSO₄ test mixtures, the interactions between these metals were mainly in conformity with the model of synergism. The S.R. and RTU values were largely above 1, indicating synergistic interactions. The importance of the joint action evaluations for the management and protection of aquatic ecosystems, particularly in the setting up of water quality criteria was discussed.     

Copper recovery from waste printed circuit boards concentrated metal scraps by electrolysis

Copper recovery is the core of waste printed circuit boards (WPCBs) treatment. In this study, we proposed a feasible and efficient way to recover copper from WPCBs concentrated metal scraps by direct electrolysis and factors that affect copper recovery rate and purity, mainly CuSO₄·5H₂O concentration, NaCl concentration, H₂SO₄ concentration and current density, were discussed in detail. The results indicated that copper recovery rate increased first with the increase of CuSO₄·5H₂O, NaCl, H₂SO₄ and current density and then decreased with further increasing these conditions. NaCl, H₂SO₄ and current density also showed a similar impact on copper purity, which also increased first and then decreased. Copper purity increased with the increase of CuSO₄·5H₂O. When the concentration of CuSO₄·5H₂O, NaCl and H₂SO₄ was respectively 90, 40 and 118 g/L and current density was 80 mA/cm², copper recovery rate and purity was up to 97.32% and 99.86%, respectively. Thus, electrolysis proposes a feasible and prospective approach for waste printed circuit boards recycle, even for e-waste, though more researches are needed for industrial application.

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Voltammetric analysis of metallothioneins and copper (II) in fish for water biomonitoring studies

An major research area in environmental chemistry is the development of methods for the analysis of biomarkers. Metallothioneins are used as biomarkers in studies of heavy metals exposure in water, because metallothioneins are synthesized and accumulated when organisms are exposed to toxic concentrations of pollutants. In this work, simple and sensitive voltammetric methods were developed for metallothionein and copper (II) determinations in fish liver Lepomis gibbosus. Both analytical methodologies were optimized and applied to samples extracted from individuals previously submitted to sub-lethal toxicological trials with copper sulphate (CuSO₄) and cadmium chloride (CdCl₂). The obtained results showed that both methods are very precise, sensitive, and involve simple sample preparation processes. Moreover, metallothioneins showed better correlation with the toxic exposure than Cu²⁺. To the best of our knowledge, this is the first time that hepatic metallothioneins and Cu²⁺ contents are voltammetrically determined in order to be compared in their function as heavy metal biological indicators.     

Sequential extraction of copper from soils and relationships with copper in maize

We studied copper uptake by maize grown on soils that have been contaminated with CuSO₄. In soil the total copper level ranged from 24 to 135 mg kg^–1. The copper distribution in soil fractions was assessed by sequential extraction, showing that anthropogenic copper is mainly concentrated in oxides fractions. The copper concentration of maize at the maturity stage reached values from 36.3 to 65.9 mg kg^–1 compared to copper levels usually found in non-contaminated crops (5–30 mg kg^–1). Here we demonstrate that copper can be accumulated by maize and that copper concentration in maize can be predicted by equations including copper concentration of soil fractions.     

Biofabrication of calcium phosphate nanoparticles using the plant Mimusops elengi

Nanoparticles are now widely applied in products. The synthesis of nanomaterials using biological materials is an emerging field, notably for medical applications because biologically derived compounds can be safe. For instance, calcium phosphate is a natural biomineral that possesses an excellent biocompatibility due to its chemical similarity to human hard tissue such as bone and teeth. Here, we synthesized calcium phosphate nanoparticles by using bark extract of Spanish cherry (Mimusops elengi). Calcium phosphate nanoparticles showed an absorbance at 275 nm by UV–visible analysis and particle size of 25 nm by nanoparticle tracking and analysis. Fourier transform infrared spectroscopy revealed the presence of aromatic amines as a capping and reducing agent. Transmission electron microscopy showed the presence of polydispersed spherical nanoparticles with an average size of 50 nm. Measurements of zeta potential revealed the stability of the synthesized calcium phosphate nanoparticles. These particles demonstrated antibacterial activity against Streptococcus mutans, Staphylococcus aureus and Escherichia coli. We conclude that the synthesis of calcium phosphate nanoparticles by using a M. elengi is easy, eco-friendly and scalable.     

Removal of toluene from air streams by cobalt-copper bimetallic catalysts supported on sepiolite

Abstract

Oxidative removal of toluene using copper and cobalt bimetallic catalysts with varying molar ratios supported on sepiolite was investigated. The catalysts prepared by a deposition precipitation method and were characterized using X-ray diffraction, nitrogen adsorption-desorption, field emission scanning electron microscopy, H₂-temperature-programmed reduction, transmission electron microscope, and inductive coupled plasma atomic emission spectroscopy. The species supported on sepiolite are Co₃O₄, CuO, and CuCo₂O₄. The activities of the tested catalysts increased in the order 0Co-4Cu/Sep <1Co-3Cu/Sep <4Co-0Cu/Sep <1Co-1Cu/Sep <3Co-1Cu/Sep. The latter exhibiting 90% toluene oxidative degradation at 288?°C within 15?h, having high selectivity towards CO₂, and being stable at 300?°C up to 15?h. In conclusion, this study showed that sepiolite has excellent properties as a support.     

Variation in trace element mobility and nitrogen metabolism of Verbascum olympicum Boiss. under copper stress

The aim of this study was to evaluate the effects of copper (Cu) stress on accumulation and transport of trace elements, nitrogen assimilation, and growth parameters of Verbascum olympicum. Eight-week-old seedlings were grown in Hoagland's solution and exposed to 0, 50, 250, or 500?µM CuSO₄ for seven days in laboratory conditions. Bioaccumulation of trace elements (boron, bismuth, cobalt, Cu, iron, lithium, manganese, molybdenum, nickel, lead, zinc) in the roots and leaves was determined by inductively coupled plasma–mass spectrometry after one, three, and seven days. Chlorophyll content, nitrate reductase, and glutamine synthetase activities, soluble protein content, and biomass were determined. Copper accumulated in the roots and leaves (up to 19609.8 and 256.2?mg?kg^?1 dry weight, respectively). Other trace elements accumulated to higher levels in the roots of Cu-treated plants compared with those of control plants. High Cu concentrations decreased nitrogen-assimilatory enzyme activities. Compared with control plants, those treated with high Cu concentrations showed lower chlorophyll contents, total protein contents, and biomass. Nitrogen assimilation and growth parameters of V. olympicum were negatively affected by Cu treatment but mineral nutrition was not severely disrupted. The results support the suitability of V. olympicum as a candidate for phytoremediation of Cu-contaminated soils.     

Improved Cu and Zn sorption on oxidized wheat lignocellulose

We studied the effect an oxidizing treatment of a lignocellulosic substrate, extracted from wheat bran, on the sorption of Cu and Zn. Oxidizing agents, such as potassium permanganate (KMnO₄) or sodium periodate (NaIO₄), creates oxygenated functions, e.g. alcohol and carboxylic acid, which increase the density of functional sites and the binding capacity of lignocellulose towards copper and zinc. We found that the treatment with KMnO₄ is the most efficient, with an increase of about 30–40% metal ion binding, compared to 15–25% using NaIO₄. The investigation of the oxidation process shows that the efficiency of KMnO₄ can be attributed to its affinity towards insaturated double bonds of lignin entities. Oxidized lignocellulose is thus a promising, efficient, and cheap biomaterial for the decontamination of wastewater.     

Comparative effects of indole derivatives as antifouling agents on the growth of two marine diatom species

Antifouling agents, used to prevent biofouling, need to be assessed for their impacts on marine organisms and environment before the application. Diatoms are one of the main components of fouling biofilms, which play important roles in the formation of biofouling. Particularly, diatoms are also the important ingredients of primary production and present interest as ecotoxicological models in marine environment. In this study, two benthic diatoms Nitzschia closterium f. minutissima and Navicula climacospheniae, widely distributed in fouling biofilm, were used as models for screening the activities of potential antifoulants. Nine indole derivatives were tested and CuSO₄ was used as a reference. Indole derivatives showed significant anti-algal activities and the EC₅₀ values of most indole derivatives were lower than that of CuSO₄. Halogen substituent enhanced the anti-algal activities of compounds, and the most efficient compounds for N. closterium f. minutissima were gramine and 7-chloroindole with the EC₅₀ values of 1.94 and 2.1?mg/L, while for N. climacospheniae, 7-chloroindole and 6-bromoindole were the most efficient and the EC₅₀ values were 3.91 and 4.25?mg/L, respectively. In conclusion, indole derivatives would be one of the promising candidates as antifoulants and our results strengthened the need to perform antifouling activity assays and environment-friendly evaluations.     

Cu和Pb对赤潮异弯藻(Heterosigma akashiwo)生长的影响

以添加了不同浓度的CuSO_4和Pb(NO_3)_2混合液的f/2培养基培养赤潮异弯藻,通过分析藻的最大生长密度、生长周期及比生长率这3个参数与Cu和Pb之间的相关关系,讨论2种重金属对赤潮异弯藻生长的影响以及2种重金属之间的互作效应。结果表明,Cu为0～0.02 mg·L~(-1)或Pb为0～0.32 mg·L~(-1)时,对赤潮异弯藻生长有促进作用;当Pb浓度不同的条件下,Cu浓度达到0.5～2.5 mg·L~(-1)时,赤潮异弯藻生长受到明显抑制,甚至无法生长;在Cu浓度不同的条件下,Pb在1～9 mg·L~(-1)范围内,随着浓度的增加,对赤潮异弯藻生长抑制作用逐步增强。在Cu浓度为0～2.5 mg·L~(-1)或Pb浓度为1～9 mg·L~(-1)及两者互作条件下,赤潮异弯藻最大生长密度和生长周期都受到显著影响(P0.01)。另外,Cu和Pb对赤潮异弯藻比生长率无显著影响,两者相互作用不明显。结合湛江海域已报道的这2种重金属实际含量,进一步评估了海区中重金属的潜在生态效应。     

Imprinted polymer particles for preconcentration of copper from water and biological samples

Imprinted polymer particles have been developed as a novel adsorbent for the adsorption of copper from aqueous solution. This method has received much attention in various fields because of their high selectivity for template molecules. In this work, separation of copper from water and biological samples by batch solid phase extraction based on molecular imprinting technique is presented. Copper-imprinted polymer was prepared by free radical solution polymerization in a glass tube containing CuSO₄, morin, 4-vinylpyridine as a functional monomer, ethyleneglycoldimethacrylate as a cross-linking monomer, 2,2′- azobisisobutyronitrile as an initiator. The polymer block obtained was ground and sieved, and the Cu-morin complex was removed from polymer particles. The synthesized polymer particles both prior to and after leaching have been characterized by IR and X-ray diffraction studies. The effect of different parameters, such as pH, adsorption and desorption time, type and least amount of the eluent for elution of the complex from polymer were evaluated. The limit of detection of the proposed method was 0.12 μg L⁻¹. The method was applied to the recovery and determination of copper in water and biological real samples.     

Effects of metal ions on Mg2+-ATPase activity in plasma membranes isolated from the rat uterus

In this study, we investigated the in vitro effects of metal ions on Mg²⁺-ATPase activity in isolated membranes from rat uterus. The effects of increasing concentrations of metal salts (CrCl₂, CuSO₄, HgCl₂ and ZnSO₄) show sigmoidal and almost complete inhibition relative to the control enzyme activity. According to the IC₅₀, the ATPase possesses greater sensibility to $ {\text{Zn}}^{{{\text{2}} + }} > {\text{Cu}}^{{{\text{2}} + }} \cong {\text{Cr}}^{{{\text{3}} + }} \cong {\text{Hg}}^{{{\text{2}} + }} ,$ {\text{Zn}}^{{{\text{2}} + }} > {\text{Cu}}^{{{\text{2}} + }} \cong {\text{Cr}}^{{{\text{3}} + }} \cong {\text{Hg}}^{{{\text{2}} + }} , while other metal salts exhibit the following inhibition: CdCl₂ 55%, CsCl 64.5% and SrCl₂ 58%. Here we demonstrated that the physico-chemical properties of these metals are of importance in defining possible mechanisms of binding and decrease of enzyme activity.     

High reduction of 4-nitrophenol using reduced graphene oxide/Ag synthesized with tyrosine

There is a demand for the development of environmental friendly methods for the synthesis of graphene composites. Reduced graphene oxide/silver (RGO/Ag) nanocomposites are very good catalysts. Here, we propose a simple, green method for the synthesis of RGO/Ag nanocomposite using the amino acid tyrosine as bioreductant and stabilizing agent. RGO/Ag nanocomposite was characterized by using various analytical techniques and studied for its catalytic degradation of 4-nitrophenol. Results of attenuated total reflectance Fourier transform infrared spectroscopy and Zeta potential at ?55 mV reveal the surface capping of tyrosine onto the reduced graphene oxide nanosheets. RGO/Ag nanocomposites show excellent catalytic reduction of 4-nitrophenol with NaBH₄, when compared to actual individual silver nanoparticles.     

The toxicity of heavy metals to embryos of the American oyster Crassostrea virginica

The acute toxicity of 11 heavy metals to embryos of the American oyster Crassostrea virginica was studied and the concentrations at which 50% of the embryos did not develop were determined. The most toxic metals and their LC₅₀ values were mercury (0.0056 ppm), silver (0.0058 ppm), copper (0.103 ppm) and zinc (0.31 ppm). Those metals that were not as toxic and their LC₅₀ values were nickel (1.18 ppm), lead (2.45 ppm) and cadmium (3.80 ppm). Those metals that were relatively non-toxic and their LC₅₀ values were arsenic (7.5 ppm), chromium (10.3 ppm) and manganese (16.0 ppm). Aluminum was non-toxic at 7.5 ppm, the highest concentration tested.     

Large-scale synthesis and antibacterial activity of fungal-derived silver nanoparticles

There is a demand for environmentally friendly processes to synthesize nanoparticles. Here, we synthesized silver nanoparticles using encapsulated biomass beads of Phoma exigua var. exigua. Nanoparticles were characterized by nanoparticle tracking and analysis (NTA), Fourier-transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and zeta potential. Results of NTA show that nanoparticle size was homogenous. Concerning nanoparticle stability, zeta potential decreased with batch number. Silver nanoparticles exhibited an antibacterial activity against Escherichia coli and Staphylococcus aureus. Overall, the encapsulation of fungal biomass by calcium alginate for the batch synthesis of silver nanoparticles was easy, cost-effective, eco-friendly and suitable for the large-scale synthesis of silver nanoparticles. We have also demonstrated the reusability of the fungal biomass during biosynthesis of silver nanoparticles using the sodium alginate encapsulation method.