Soluble Copper Concentrations Research Articles

Impact of HO2 aerosol uptake on radical levels and O3 production during summertime in Beijing

Abstract. The impact of heterogeneous uptake of HO2 on aerosol surfaces on radical concentrations and the O3 production regime in Beijing in summertime was investigated. The uptake coefficient of HO2 onto aerosol surfaces, γHO2, was calculated for the AIRPRO campaign in Beijing, in summer 2017, as a function of measured aerosol soluble copper concentration, [Cu2+]eff, aerosol liquid water content, [ALWC], and particulate matter concentration, [PM]. An average γHO2 across the entire campaign of 0.070±0.035 was calculated, with values ranging from 0.002 to 0.15, and found to be significantly lower than the value of γHO2=0.2, commonly used in modelling studies. Using the calculated γHO2 values for the summer AIRPRO campaign, OH, HO2 and RO2 radical concentrations were modelled using a box model incorporating the Master Chemical Mechanism (v3.3.1), with and without the addition of γHO2, and compared to the measured radical concentrations. The rate of destruction analysis showed the dominant HO2 loss pathway to be HO2 + NO for all NO concentrations across the summer Beijing campaign, with HO2 uptake contributing <0.3 % to the total loss of HO2 on average. This result for Beijing summertime would suggest that under most conditions encountered, HO2 uptake onto aerosol surfaces is not important to consider when investigating increasing O3 production with decreasing [PM] across the North China Plain. At low [NO], however, i.e. <0.1 ppb, which was often encountered in the afternoons, up to 29 % of modelled HO2 loss was due to HO2 uptake on aerosols when calculated γHO2 was included, even with the much lower γHO2 values compared to γHO2= 0.2, a result which agrees with the aerosol-inhibited O3 regime recently proposed by Ivatt et al. (2022). As such it can be concluded that in cleaner environments, away from polluted urban centres where HO2 loss chemistry is not dominated by NO but where aerosol surface area is high still, changes in PM concentration and hence aerosol surface area could still have a significant effect on both overall HO2 concentration and the O3 production regime. Using modelled radical concentrations, the absolute O3 sensitivity to NOx and volatile organic compounds (VOCs) showed that, on average across the summer AIRPRO campaign, the O3 production regime remained VOC-limited, with the exception of a few days in the afternoon when the NO mixing ratio dropped low enough for the O3 regime to shift towards being NOx-limited. The O3 sensitivity to VOCs, the dominant regime during the summer AIRPRO campaign, was observed to decrease and shift towards a NOx-sensitive regime both when NO mixing ratio decreased and with the addition of aerosol uptake. This suggests that if [NOx] continues to decrease in the future, ozone reduction policies focussing solely on NOx reductions may not be as efficient as expected if [PM] and, hence, HO2 uptake to aerosol surfaces continue to decrease. The addition of aerosol uptake into the model, for both the γHO2 calculated from measured data and when using a fixed value of γHO2=0.2, did not have a significant effect on the overall O3 production regime across the campaign. While not important for this campaign, aerosol uptake could be important for areas of lower NO concentration that are already in a NOx-sensitive regime.

The kinetics of copper corrosion in nitric acid

AbstractThe strategy for the permanent disposal of high‐level nuclear waste in Canada involves sealing it in a copper‐coated steel container and burying it in a deep geologic repository. During the early emplacement period, the container could be exposed to warm humid air, which could result in the condensation of nitric acid, produced by the radiolysis of the humid air, on the copper surface. Previous studies have suggested that both nitrate and oxygen reduction will drive copper corrosion, with the nitrate reduction kinetics being dependent on the concentration of soluble copper(I) produced by the anodic dissolution of copper in the reaction with oxygen. This study focused on determining the kinetics of nitrate and oxygen reduction and elucidating the synergistic relationship between the two processes. This was investigated using corrosion potential and polarization measurements in conjunction with scanning electron microscopy and X‐ray photoelectron spectroscopy. Oxygen reduction was shown to be the dominant cathodic reaction with the oxidation of copper(I) to copper(II) by nitrate, promoting the catalytic cycle involving the reaction of copper(II) with copper to reproduce copper(I).

Blended pulp mill, forest humus and mine residual material Technosols for mine reclamation: A growth-chamber study to explore the role of physiochemical properties of substrates and microbial inoculation on plant growth

A growth chamber trial was conducted to investigate the effects of blends of pulp and paper mill residuals and forest humus on soil properties, microbial communities and germination rate and biomass production of annual ryegrass (Lolium multiflorum) in both acid-producing and neutral to mildly alkaline mine tailings in a mine reclamation context. The organic residual amendments improved the nutritional status of the tailings substrates, and increased pH in acid-generating tailings, leading to higher germination rates and improved plant growth. A trace addition (<0.02% of sludge by dry weight) of natural forest floor material as a microbial inoculum to the sludge could increase plant biomass up to four-fold. The effects of sludge application on bioavailability of metals were variable, with the concentration of soluble copper (Cu) and nickel (Ni) increasing in some of the substrates following organic amendments. Addition of paper mill residuals to mine tailings modified the microbial communities observed in the oligotrophic tailings with the majority of DNA sequences in the sludge amended substrates being found to be closely related to heterotrophic bacterial species rather than the chemolithotrophic communities that dominate tailings environments.

Deposition Corrosion of Galvanized Steel in the Presence of Copper

Deposition corrosion, via formation of microgalvanic cells from copper ions (e.g., Cu[I], Cu[II]) on iron or galvanized (zinc-coated) steel pipe, has been linked to disastrous field corrosion failures. Key factors expected to control deposition corrosion, including soluble copper concentration, copper ion speciation, and flow pattern (stagnant versus recirculating), were examined. The mass of copper plating was directly proportional to the soluble copper concentration in solution. The presence of flow, which allowed greater mass transport of reactants to the pipe surface, proved to be crucial to replicating deposition corrosion in the laboratory: tests with flow demonstrated up to 7× more zinc release and 55× more iron release when copper was present than when it was absent, compared to increases of only ≈2× in the same water under stagnant conditions. Scale dissolution, x-ray fluorescence, and scanning electron microscopy were used to characterize copper-rich deposits on the surface of both field and lab...

Responses of Lyngbya wollei to algaecide exposures and a risk characterization associated with their use

To make informed decisions regarding management of noxious algal growths, water resource managers require information on responses of target and non-target species to algaecide exposures. Periodic treatments of Phycomycin®-SCP (sodium carbonate peroxyhydrate) followed by Algimycin®-PWF (gluconate and citrate chelated copper) to control Lyngbya wollei growths for ten years provided an opportunity for a risk evaluation of treated coves in Lay Lake, AL. Abiotic sediment characteristics (acid soluble copper concentrations, acid volatile sulfides, percent organic matter and cation exchange capacity) and survival of Hyalella azteca and Chironomus dilutus were measured in sediment samples from treated and untreated coves to assess the bioavailability of potential copper-residuals. In laboratory studies to seek a more effective approach for managing the growth of Lyngbya, six algaecide treatments consisting of combinations of copper-based algaecides (Cutrine®-Ultra, Clearigate® and Algimycin®- PWF), a hydrogen peroxide based algaecide (Phycomycin®-SCP) and an adjuvant (Cide-Kick II) were assessed for efficacy in controlling L. wollei sampled from Lay Lake. The most efficient algaecide treatment was determined based on post-treatment algal wet weight and visual observations of responses to exposures. To estimate the margin of safety for non-target organisms, Pimephales promelas was exposed to the most efficacious treatment and a treatment of Phycomycin®-SCP followed by Algimycin®-PWF. Results from sediment experiments demonstrated that there were no measureable copper residuals and no adverse effects on H. azteca and C. dilutus from sediments following ten years of copper-based algaecide treatments. Based on the laboratory results, a treatment of Phycomycin®-SCP at 10.1mg H2O2/L followed by Cide-Kick II at 0.2mg/L and Algimycin®- PWF at 0.26mg Cu/L could control the growth of Lyngbya wollei from Lay Lake, AL and enhance the margin of safety for non-target species (e.g. P. promelas).

Influence of chloride on the long-term interaction of copper with deoxygenated neutral aqueous solutions

The evolution of open-circuit potential, soluble copper concentration and impedance during immersion of Cu in deoxygenated neutral borate buffer containing 0.01–1.0 mol l−1 NaCl was monitored for up to 3000 h. The open-circuit potential was found to be close to the CuCl2-/Cu equilibrium potential. No corrosion layer was detected by voltammetric scans and the soluble copper concentration reached a steady state. Experimental data were quantitatively interpreted by a kinetic model featuring CuOH and CuCl intermediates. The process through which the system reached steady state is tentatively related to a reaction that could lead to hydrogen evolution.

Significance of Microbial Communities and Interactions in Safeguarding Reactive Mine Tailings by Ecological Engineering

Pyritic mine tailings (mineral waste generated by metal mining) pose significant risk to the environment as point sources of acidic, metal-rich effluents (acid mine drainage [AMD]). While the accelerated oxidative dissolution of pyrite and other sulfide minerals in tailings by acidophilic chemolithotrophic prokaryotes has been widely reported, other acidophiles (heterotrophic bacteria that catalyze the dissimilatory reduction of iron and sulfur) can reverse the reactions involved in AMD genesis, and these have been implicated in the "natural attenuation" of mine waters. We have investigated whether by manipulating microbial communities in tailings (inoculating with iron- and sulfur-reducing acidophilic bacteria and phototrophic acidophilic microalgae) it is possible to mitigate the impact of the acid-generating and metal-mobilizing chemolithotrophic prokaryotes that are indigenous to tailing deposits. Sixty tailings mesocosms were set up, using five different microbial inoculation variants, and analyzed at regular intervals for changes in physicochemical and microbiological parameters for up to 1 year. Differences between treatment protocols were most apparent between tailings that had been inoculated with acidophilic algae in addition to aerobic and anaerobic heterotrophic bacteria and those that had been inoculated with only pyrite-oxidizing chemolithotrophs; these differences included higher pH values, lower redox potentials, and smaller concentrations of soluble copper and zinc. The results suggest that empirical ecological engineering of tailing lagoons to promote the growth and activities of iron- and sulfate-reducing bacteria could minimize their risk of AMD production and that the heterotrophic populations could be sustained by facilitating the growth of microalgae to provide continuous inputs of organic carbon.

The application of wetland technology for copper removal from distillery wastewater: a case study

The ability of reed beds to remove significant levels of metals from effluent streams is well cited in the literature. Various methods of removal have been postulated and demonstrated including physical methods such as filtration and settlement, precipitation when the metal is present as a salt and adsorption to organic species or take up by macrophytes when the metal is in a soluble or ionic form. Consequently, reed beds have been used in a variety of applications for metal removal in water treatment processes. The distillation process for whisky generates an effluent containing a significant amount of copper which is scoured from the copper stills during the process and cleaning operations. High soluble copper concentrations can breach discharge consents. A horizontal subsurface flow reed bed system has been designed and installed for copper removal at a distillery in Scotland. This paper presents the findings of the literature search, outlines the design of the bed and reviews the performance results.

Effect of copper speciation at different pH on temporal sensory attributes of copper

The effect of copper solubility on temporal characteristics of copper sensation was investigated by evaluating bitterness, astringency, and metallic sensory characteristics of samples containing copper (39.4 and 78.8 μM) at two pH levels (pH 5.5 and pH 7.5) using the time–intensity test. Concentration of soluble copper in samples was measured with atomic absorption spectroscopy after filtering samples through 0.2 μm filter to remove insoluble copper particles. Decrease in copper concentration significantly inhibited metallic flavor. Astringency was not significantly affected by copper concentration, but changed as a function of pH. The level of soluble copper at pH 7.5 decreased by 50% compared to that at pH 5.5. There was a significant positive relationship between soluble copper concentration, overall sensory response, and intensity of metallic flavor. The result suggested that soluble copper species influence the perception of copper sensation by controlling metallic flavor.

Xanthomonas axonopodispv.citri enters the VBNC state after copper treatment and retains its virulence

The most severe form of citrus canker disease is caused by Xanthomonas axonopodis pv. citri (Xac) and affects all types of important citrus crops, reducing fruit yield and quality. Copper-based products are routinely used as a standard control measure for citrus canker. In this work we demonstrate that copper treatment induces the viable but nonculturable (VBNC) state in Xac but does not prevent the development of symptoms in susceptible plants. Short-term exposures to different concentrations of copper solutions were assayed to determine which treatment resulted in Xac nonculturability. Treatment of 10(6) mL(-1) Xac cells for 10 min in a 135-muM CuSO(4) solution (equivalent to three times the free soluble copper concentration applied in one field treatment) resulted in nonculturability. However, 16% of cells were viable based on 5-cyano-2,3-ditolyl tetrazolium chloride staining and 1% were capable of producing canker lesions after infiltrating grapefruit plants. If induction of the VBNC state in Xac cells were to occur under field conditions, this would have to be taken into consideration for an effective control of canker disease.

Effect of Molybdenum and Sulphur on Copper Status and Mohair Quality in Merghoze Goat

This study was made on the effects of a normal diet containing 12.8 mg Cu kg(-1) DM which added gradually molybdenum and sulphur on the copper status and fibre quality in eight 1-year Merghoze goat. One group (n = 4 mean weight 31 +/- 2.0 kg) was treated with Mo and S supplements for 20 weeks, the second group (n = 4 mean weight 32 +/- 2.1 kg) served as controls. In addition of blood sampling for measuring copper status in plasma, the copper content and quality of fleeces were measured every 6 weeks. Mohair measurements were carried out by taking patch samples (10 x 10 cm2) from the mid-side area of the goat. The analytical set consists of plasma copper concentrations (Pl Cu), Trichloroacetic acid soluble copper concentrations (TCA-Cu), and fleece copper content. The results indicated that the addition of 20-30 mg Mo and 2-2.5 g S kg(-1) DM to the normal diet did produce sub clinical copper deficiency in treated goats. One such visual symptom was the loss of fleeces pigmentation and poorer crimp being observed. The Pl Cu minus TCA-Cu plasma became more than 2 microM in the blood of treated goat, indicating that there was a significant thiomolybdate formation in the body. The results showed that there was a significant decrease in Pl Cu (p < 0.05) along with a significant increase in thiomolybdate (MoS) production after 4 months. The sub clinical signs of copper deficiency and mohair quality are likely to be from high molybdenum intake and thiomolybdate formation in the body.

Effects of organic matters coming from Chinese tea on soluble copper release from copper teapot

The morphology and elemental composition of the corrosion products of copper teapot's inner-surface were characterized by the scanning electron microscopy and energy dispersive X-ray surface analysis (SEM/EDS), X-ray powder diffraction (XRD) and X-ray photon spectroscopy (XPS) analysis. It was revealed that Cu, Fe, Ca, P, Si and Al were the main elements of corrosion by-products, and the α-SiO 2, Cu 2O and CaCO 3 as the main mineral components on the inner-surface of copper teapot. The effects of organic matters coming from Chinese tea on soluble copper release from copper teapots in tap water were also investigated. The results showed that the doses of organic matter (as TOC), temperate and stagnation time have significant effects on the concentration of soluble copper released from copper teapots in tap water.

Molecular characterization of mesophilic and thermophilic sulfate reducing microbial communities in expanded granular sludge bed (EGSB) reactors

The microbial communities established in mesophilic and thermophilic expanded granular sludge bed reactors operated with sulfate as the electron acceptor were analyzed using 16S rRNA targeted molecular methods, including denaturing gradient gel electrophoresis, cloning, and phylogenetic analysis. Bacterial and archaeal communities were examined over 450 days of operation treating ethanol (thermophilic reactor) or ethanol and later a simulated semiconductor manufacturing wastewater containing citrate, isopropanol, and polyethylene glycol 300 (mesophilic reactor), with and without the addition of copper(II). Analysis, of PCR-amplified 16S rRNA gene fragments using denaturing gradient gel electrophoresis revealed a defined shift in microbial diversity in both reactors following a change in substrate composition (mesophilic reactor) and in temperature of operation from 30 degrees C to 55 degrees C (thermophilic reactor). The addition of copper(II) to the influent of both reactors did not noticeably affect the composition of the bacterial or archaeal communities, which is in agreement with the very low soluble copper concentrations (3-310 microg l(-1)) present in the reactor contents as a consequence of extensive precipitation of copper with biogenic sulfides. Furthermore, clone library analysis confirmed the phylogenetic diversity of sulfate-reducing consortia in mesophilic and thermophilic sulfidogenic reactors operated with simple substrates.

Lixiviación de concentrados de cobre utilizando NaCI y el cobre soluble aportado por el propio concentrado

Leaching of copper concentrates using cupric chlorocomplexes, generated situ by the reaction between Cu(II), aported by the soluble copper content of the concentrate, and sodium chloride in acid media was studied. The concentrate samples were obtained from mineral processing plants from Antofagasta, Chile. Chemical and mineralogical characterization from original concentrates was made. Typical variables such as chloride concentration, soluble copper concentration, leaching time, solid percentage and temperature were studied. DRX and EDS analyzed some of the residues. The experimental results indicated that it is possible to obtain solutions having high copper content ( 15 to 35 g/l) and 2 to 5 g/l free acid in order to submit this solution directly to a solvent extraction stage. The leaching tests use common reactive and low cost such as sodium chloride and sulfuric acid

Optimization of the aerobic biological treatment of thermophilically treated refractory wastewater

A pilot scale conventional activated sludge was operated for over 600 days to study its effectiveness at further remediating the effluent of an existing industrial site's thermophilic biological treatment stage. During the course of the study, the activated sludge was able to further biodegrade the contaminants in the incoming industrial wastewater in terms of both BOD and nitrogen reductions at varying hydraulic and solids retention times, despite elevated concentrations of soluble copper being present. A limiting hydraulic retention time (HRT) for BOD removal of 1.5 days was observed as well as the loss of nitrification occurred at a solids retention time (SRT) of approximately 6 days. Biokinetic coefficients were determined with the maximum rate of substrate utilization per unit mass of microorganisms, k, of 0.14 mg VSS/(mg sBOD-d) and the Monod half velocity constant, K s, of 9.4 mg sBOD/L. Simultaneous nitrification and denitrification (SND) of the nitrogenous compounds found in this wastewater was observed throughout the majority of the experimentation while the bulk DO in the system was greater than 1 mg/L. The activated sludge was estimated to contain soluble copper on the order of 1 mg/L throughout the course of operation with no apparent detriment to nitrification. Additionally, the activated sludge was able to biologically remove the main solvents found in the influent wastewater. The removals of trace levels of N-nitrosodimethylamine (NDMA) were also observed.

Anaerobic biodegradability and methanogenic toxicity of key constituents in copper chemical mechanical planarization effluents of the semiconductor industry

Copper chemical mechanical planarization (CMP) effluents can account for 30–40% of the water discharge in semiconductor manufacturing. CMP effluents contain high concentrations of soluble copper and a complex mixture of organic constituents. The aim of this study is to perform a preliminary assessment of the treatability of CMP effluents in anaerobic sulfidogenic bioreactors inoculated with anaerobic granular sludge by testing individual compounds expected in the CMP effluents. Of all the compounds tested (copper (II), benzotriazoles, polyethylene glycol ( M n 300), polyethylene glycol ( M n 860) monooleate, perfluoro-1-octane sulfonate, citric acid, oxalic acid and isopropanol) only copper was found to be inhibitory to methanogenic activity at the concentrations tested. Most of the organic compounds tested were biodegradable with the exception of perfluoro-1-octane sulfonate and benzotriazoles under sulfate reducing conditions and with the exception of the same compounds as well as Triton X-100 under methanogenic conditions. The susceptibility of key components in CMP effluents to anaerobic biodegradation combined with their low microbial inhibition suggest that CMP effluents should be amenable to biological treatment in sulfate reducing bioreactors.

Responses of polychaete Hydroides elegans life stages to copper stress

Two experiments were performed to examine the sensitivity of Hydroides elegans to copper stress. The first experiment tested the development of 4 distinct early stages in copper solu- tions from 10 to 250 µg l -1 . Copper significantly reduced survivorship of the newly released oocyte and trochophore stages at concentrations ≥ 10 µg l -1 , and of the 2-cell and blastula stages at ≥ 25 µg l -1 . The EC50 values were 47, 50, 71 and 29 µg Cu l -1 for the newly released oocytes, 2-cell embryos, blastulae and trochophores, respectively. After 2 h into the bioassay, where Isochrysis galbana was used as food for the trochophores, algal sorption resulted in a reduction in copper concentration from 32% in the 10 µg l -1 treatment to 6% in the 250 µg l -1 treatment. Duration of development did not significantly differ among the treatments, except in the oocyte to 2-cell stage where higher copper concentration resulted in longer developmental time. In the second experiment, adult H. elegans were exposed to copper concentrations from 125 to 4000 µg l -1 for 48 h. Significant mortality occurred only at copper concentrations ≥ 500 µg l -1 . This study thus shows that the embryogenesis and larval development of H. elegans are sensitive to copper stress, and that algal sorption can substantially reduce soluble copper concentration and may affect the larval toxicity result.

Gastrointestinal Effects Associated with Soluble and Insoluble Copper in Drinking Water

The aim of this study was to determine whether total copper or soluble copper concentration is associated with gastrointestinal signs and symptoms. Forty-five healthy adult women (18-55 years of age), living in Santiago, Chile, ingested tap water with 5 mg/L of copper containing different ratios of soluble copper (copper sulfate) and insoluble copper (copper oxide) over a 9-week period. Three randomized sequences of the different copper ratios (0:5, 1:4, 2:3, 3:2, and 5:0 mg/L) were followed. Subjects recorded their water consumption and gastrointestinal symptoms daily on a special form. Mean water consumption was similar among groups. Serum copper levels, ceruloplasmin, and activities of liver enzymes were within normal limits. No differences were detected between the means of biochemical parameters at the beginning and at the end of the study. Twenty subjects presented gastrointestinal disturbances at least once during the study, 9 suffered diarrhea (with or without abdominal pain and vomiting), and the other 11 subjects reported abdominal pain, nausea, or vomiting. No differences were found in incidence of abdominal pain, nausea, vomiting, and diarrhea regardless of the ratio of copper sulfate to copper oxide. In conclusion, both copper sulfate (a soluble compound) and copper oxide (an insoluble compound) have comparable effects on the induction of gastrointestinal manifestations, implying that similar levels of ionic copper were present in the stomach.

Role of Temperature and pH in Cu(OH)2 Solubility

The wide variation in reported cupric hydroxide solubility constants is attributed to the age of the solid, kinetic limitations in approaching equilibrium, and transient formation of basic copper nitrate solids. In situations similar to those where cupric hydroxide solubility constants were determined via precipitation in dilute nitrate solutions, copper nitrate solids (gerhadtite) form first followed by a rapid transition to cupric hydroxide and then a slower transition to tenorite. In solutions containing hydroxide and nitrate as the sole anionic constituents, fresh cupric hydroxide solids control soluble copper concentrations for minutes to days depending on pH and temperature. Thus, although a log K of 9.36 ± 0.02 was most consistent with the experimental data for Cu(OH)2 solubility, decreasing log K values from 9.36 [fresh Cu(OH)2] to 7.6 [CuO] can be expected with aging as controlled by temperature, pH, and other factors.

Copper, zinc and haemocyanin concentrations in four caridean decapods (crustacea) : size relationships

The relationships between individual dry weight and bodycontent of the essential metals copper and zinc and of therespiratory pigment haemocyanin have been investigated in fourBritish species of caridean decapod crustaceans, Palaemonelegans, Palaemon longirostris, Palaemonetesvarians and Crangon crangon. Also considered were thebody concentrations of soluble copper and copper associatedwith haemocyanin. These decapods regulate total bodyconcentrations of copper and zinc to approximately constantlevels which can vary interspecifically. An attempt is made tointerpret these regulated concentrations in terms of essentialrequirements for the metals in the physiological functioningof haemocyanin, the body concentration of which variesinterspecifically and intraspecifically with environmentalvariables.