Speciation of copper in relation to its bioavailability

Abstract

Copper speciation and bioavailability for Scenedesmus quadricauda has been studied in natural waters and in synthetic culture media. Other elements were studied simultaneously. When phosphorus and nitrogen limitation were excluded by adding these elements, copper was limiting algal growth in some natural waters. In the toxic range, growth inhibition by copper was highly correlated with copper detected by electrochemical methods and with calculated free copper.

Copper was toxic to S. quadricauda when free copper concentrations roughly exceeded 10^?10.5 M, and was limiting for values somewhere lower than 10^?12.5 M. Because we found copper limitation in some natural water samples, free copper concentration in those water samples therefore must have been lower than 10^?12.5 M.

The hypothesis that the free metal concentration rather than the total concentration determines bioavailability was confirmed for copper, cobalt and zinc.     

A natural macroalgae consortium for biosorption of copper from aqueous solution: Optimization,modeling and design studies

In this study, the capacity of a natural macroalgae consortium consisting of Chaetomorpha sp., Polysiphonia sp., Ulva sp. and Cystoseira sp. species for the removal of copper ions from aqueous environment was investigated at different operating conditions, such as solution pH, copper ion concentration and contact time. These environmental parameters affecting the biosorption process were optimized on the basis of batch experiments. The experimentally obtained data for the biosorption of copper ions onto the macroalgae-based biosorbent were modeled using the isotherm models of Freundlich, Langmuir, Sips and Dubinin–Radushkevich and the kinetic models of pseudo-first-order, pseudo-second-order, Elovich and Weber and Morris. The pseudo-first-order and Sips equations were the most suitable models to describe the copper biosorption from aqueous solution. The thermodynamic data revealed the feasibility, spontaneity and physical nature of biosorption process. Based on the data of Sips isotherm model, the biosorption capacity of biosorbent for copper ions was calculated as 105.370 mg g^?1 under the optimum operating conditions. A single-stage batch biosorption system was developed to predict the real-scale-based copper removal performance of biosorbent. The results of this investigation showed the potential utility of macroalgae consortium for the biosorption of copper ions from aqueous medium.     

Evaluation of copper speciation and water quality factors that affect aqueous copper tasting response

This study determined taste thresholds for copper as its speciation was varied among free cupric ion, complexed cupric ion, and precipitated cupric particles. The impact of copper chemistry on taste is important as copper is added to many beverages and can be present in drinking water as a natural mineral or due to corrosion of copper plumbing. A one-of-five test was used to define thresholds with solutions containing 0.025-8 mg/l Cu (from copper sulfate) in distilled or mineralized water of varying pH. The mineralized water was designed to mimic the composition of a typical tap water. Group thresholds for copper in either distilled-deionized water or mineralized water were not significantly different and ranged from 0.4 to 0.8 mg/l Cu. A difference from control test was used to assess the impact of soluble and particulate copper on taste. Soluble copper species, including free cupric ion and complexed copper species, were readily tasted, while particulate copper was poorly tasted.     

Re-evaluating the effects of organic ligands on copper toxicity to barley root elongation in culture solution

Abstract

In the presence of weak ligands, both free ion activity and organic complexes of Cu should b considered when predicting Cu toxicity in aquatic and soil-plant systems. However, there is littl information about the quantitative contribution of Cu that is organically complexed to Cu toxicity. In thi study, a bioassay using barley root elongation in culture solution was used to investigate the effects o organic ligands with different conditional stability constants on Cu toxicity and the quantitativ contribution of the organically complexed Cu to the Cu toxicity. The results indicated that a significan decrease (p<0.05) in Cu toxicity, assessed by barley root elongation, was observed in response to th addition of organic ligands. The decrease differed, to some extent, with different organic ligands o disodium ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), oxalate and malate at low and constant free Cu²⁺ activity. Addition of EDTA or NTA resulted in strong reduction of Cu toxicity while modest reduction of Cu toxicity was observed for the addition of malate as the relatively wea ligand. Furthermore, the results of the present study revealed that the CuNTA^? and CuEDTA^2? complexes were not toxic, while the Cu–malate complexes were mildly toxic to barley root elongation More importantly, it was found that the toxicity of Cu–malate complexes were nearly 0.5-fold less than that of free Cu²⁺ ions.     

Cadmium and copper accumulation in the common mussel Mytilus edulis in the Western Scheldt estuary: a model approach

The Western Scheldt of the Dutch Delta area is severely contaminated with trace metals. Accumulation models of trace metals in the mussel Mytilus edulis are required to predict the biological efficiency of reductions in the metal and organic matter load. Two models are constructed: a black-box model and a physiologically structured model. The black-box model predicts metal accumulation in mussels from uptake and elimination parameters. The physiological model attempts to improve predictions by taking into account the kinetics of individual uptake and elimination routes. These in turn, are taken as depending upon two more general physiological processes, the ventilation rate and the metabolic rate. Metal uptake via food and water are expressed as relative fractions. Metal input is differentiated into particulate adsorbed, and dissolved species.The reliability of the two models is evaluated by comparing predicted concentrations for mussels with measurements. Model predictions for copper deviate less than 100% from measured concentrations, but neither model appears to predict cadmium concentration with sufficient accuracy since deviations of more than 100% occured. The introduction of physiological refinements did not improve performance. Food mediated contributions for cadmium and copper to total body burden had been overestimated in the model by a factor of 100 when compared to literature values. The physiological model did predict that the ratio of food mediated contribution to total body burden is probably different for cadmium and copper and decreases with increasing salinity for both. As yet there are no measurements available to confirm such predictions.We conclude that additional laboratory experiments should be done for a better understanding of why there is poor agreement between the few field observations and the simulations. In these experiments mussels grown under different environmental condition can be tested for their accumulation capacity of trace metals. More field observations are needed.     

鱼体(去鳃)和鱼鳃对不同形态铜的积累特征

在实验室条件下研究实验鱼Ｐａｒａｃｈｅｉｒｏｄｏｎ对人工河水中不同形态的积累特征,对比了鱼体（去鳃）和鱼鳃对铜吸收量的差异,并探讨了鱼对铜的吸收机理。研究结果表明,实验鱼鳃部和体内铜积累量均随水相游离铜浓度增高,暴露时间增长而增加,但鳃部积累浓度较鱼体其余部分高一个数量级,其从水相富集铜的速率显著高于鱼体。     

Mathematical modeling of precipitation and dissolution reactions in microbiological systems

We expand the biogeochemical model CCBATCH to include a precipitation/dissolution sub-model that contains kinetic and equilibrium options. This advancement extends CCBATCH's usefulness to situations in which microbial reactions cause or are affected by formation or dissolution of a solid phase. The kinetic option employs a rate expression that explicitly includes the intrinsic kinetics for reaction ormass-transport control, the differencefrom thermodynamic equilibrium, and the aqueous concentration of the rate-limiting metal or ligand. The equilibrium feature can be used alone, and it also serves as check that the kinetic rate never is too fast and ``overshoots' equilibrium. The features of the expanded CCBATCH are illustrated by an example in which the precipitation of Fe(OH)_{3 (s)} allows the biodegradation of citric acid, even though complexes are strong and not bioavailable. Precipitation releases citrate ligand, and biodegradation of the citrate increases the pH.     

小麦根系三维形态建模及可视化

作物三维形态建模和可视化技术是数字植物研究的重要组成部分,本文旨在构建基于形态特征参数的小麦根系三维形态模型,并实现小麦根系生长的可视化.基于小麦根系生长的可视化技术框架,首先构建了小麦根轴的三维显示模型,包括根轴生长模型、分枝几何模型和根轴曲线模型;然后结合根系拓扑结构,确定相应的图元,利用根系形态模型输出的形态特征参数,对整个小麦根系进行三维重构;最后基于OpenGL图形平台,综合纹理映射、光照渲染、碰撞检测等真实感处理手段,实现了小麦根系生长的三维可视化表达.结果表明：模型输出的根系真实感较强,能较好地实现不同品种、水分和氮素条件下小麦根系的三维可视化表达.研究结果为进一步建立完整的可视化小麦生长系统奠定了技术基础.     

Culturing Selenastrum capricornutum (Chlorophyta) in a synthetic algal nutrient medium with defined mineral particulates

Algal nutrient studies in chemically-defined media typically employ a synthetic chelator to prevent iron hydroxide precipitation. Micronutrient-particulate interactions may, however, significantly affect chemical speciation and hence biovailability of these nutrients in natural waters. A technique is described by which Selenastrum capricornutum Printz (Chlorophyta) may be cultured in a medium where trace metal speciation (except iron) is controlled, not by organic chelation, but by sorption onto titanium dioxide. Application of this culturing protocol in conjunction with results from sorption studies of nutrient ions on mineral particles provides a means of studying biological impacts of sorptive processes in aquatic environments.     

Statistical modeling of nitrogen-dependent modulation of root system architecture in Arabidopsis thaliana

Plant root development is strongly affected by nutrient availability. Despite the importance of structure and function of roots in nutrient acquisition,statistical modeling approaches to evaluate dynamic and temporal modulations of root system architecture in response to nutrient availability have remained as widely open and exploratory areas in root biology. In this study,we developed a statistical modeling approach to investigate modulations of root system architecture in response to nitrogen availability. Mathematical models were designed for quantitative assessment of root growth and root branching phenotypes and their dynamic relationships based on hierarchical con figuration of primary and lateral roots formulating the fishbone-shaped root system architecture in Arabidopsis thaliana. Time-series datasets reporting dynamic changes in root developmental traits on different nitrate or ammonium concentrations were generated for statistical analyses. Regression analyses unraveled key parameters associated with:(i) inhibition of primary root growth under nitrogen limitation or on ammonium;(ii) rapid progression of lateral root emergence in response to ammonium; and(iii) inhibition of lateral root elongation in the presence of excess nitrate or ammonium. This study provides a statistical framework for interpreting dynamic modulation of root system architecture,supported by metaanalysis of datasets displaying morphological responses of roots to diverse nitrogen supplies.     

Chemical reactivity of metallic copper in a model system containing biological metabolites

Chemical reactivity of metallic copper in a model system containing biological metabolites is described. Methionine, methional, and propanal produced ethylene when exposed to metallic copper in the presence of oxygen. It may be that metallic copper in this system serves as the '1 electron reducing agent' in the proposed chemical model system (Kumamoto et al). The requirement for oxygen was verified by removing this electron acceptor and observing the reduced ethylene production. Preliminary studies have shown that other reaction products of the reaction of copper metal with methionine include dimethyl sulfide and dimethyl disulfide or methyl mercaptan or both. These data further suggest that these chemicals are liberated from methionine when copper comes in contact with methionine-containing biological fluids.     

Measuring the bioavailable/toxic concentration of copper in natural water by using anodic stripping voltammetry and Vibrio-qinghaiensis sp.Nov.-Q67 bioassay

Abstract

Bioassays were carried out in the culture media for Vibrio-qinghaiensis sp.Nov.-Q67 and the influences of alkalinity and different concentrations of chloride, ethylene diamine tetraacetic acid (EDTA) and natural derived fulvic acid (FA) on the labile concentration and toxicity of Cu were investigated. The labile concentration of Cu was obtained by differential pulse anodic stripping voltammetry with a double acidification method (DAM-DPASV). Changes in water alkalinity and chloride concentrations did not affect the labile concentration of Cu, but increases of alkalinity and concentrations of chloride reduced the toxicity on Q67. In the presence of EDTA and FA, both labile concentration of Cu and toxicity were reduced. By excluding Cu-carbonate complexes and Cu-chloride from labile concentration, a bioavailable concentration of Cu (or [Cu*]) was obtained and used to predict the acute toxicity of Cu on Q67. For natural waters, the labile concentration of Cu was measured by DAM-DPASV and [Cu*] was calculated by a MINTEQ A2 software based on composition of waters. This procedure was tested for Guanting Reservoir waters by spiking different concentration Cu. The results showed that [Cu*] was a good indicator for Cu toxicity and could be used in field conditions.     

流程化的生态建模方法与科学工作流系统

科学工作流系统是由一系列经过特殊设计的数据分析与管理步骤组成的、按照一定的逻辑组织在一起, 并在给定的运行环境下, 完成特定科学研究的工作流管理系统。科学工作流系统致力于使全世界的科学家可以在一个简单易用的平台上交换思想, 共同设计全球尺度的实验, 共享数据、实验步骤与结果等。每一个科学家可以独立创建自己的工作流, 执行工作流并实时查看结果; 不同科学家之间也可以方便地共享和复用这些工作流。本文以开普勒系统(Kepler system)和生物多样性虚拟实验室(BioVeL)两个项目为例, 介绍了科学工作流的发展历史、背景、现有项目和应用等。以生态位模型工作流为例, 介绍了科学工作流的流程以及特点等。并通过对现有科学工作流的分析, 对其发展方向和存在的问题提出了自己的看法及预期。     

Computational modeling of synchronization process of the circadian timing system of mammals

This paper presents a model for the circadian temporization system of mammals which associates the synchronization dynamics of coupling oscillators to a set of equations able to reproduce the synaptic characteristics of somatodendritic membrane of neurons. The circadian timing system is organized in a way to receive information from the external and internal environments, and its function is the timing organization of physiological and behavioral processes in a circadian pattern. Circadian timing system in mammals is constituted by a group of structures which includes the suprachiasmatic nucleus, the intergeniculate leaflet and the pineal gland. In suprachiasmatic nucleus are found neuron groups working as a biological pacemaker—the so-called biological master clock. By means of numerical simulations using the Kuramoto model, we simulated the dynamics behavior of the biological pacemaker. For this we used a set of 1,000 coupled oscillators with long-range coupling, which were distributed on a 10 × 10 × 10 spherical lattice, and a new method to estimate the order parameter, which characterizes the degree of synchronization of oscillator system. Our model has been able to produce frequency responses in accordance with physiological patterns, and to reproduce two fundamental characteristics of biological rhythms: the endogenous generation and synchronization to the light–dark cycle.     

Speciation of copper(II) in natural waters in the presence of ligands of high and intermediate strength

Abstract

A new procedure is presented for the determination of the ligands of copper(II) in natural waters, based on titration with the metal ion, monitored by measuring the concentration of copper(II) sorbed on the carboxylic resin Amberlite CG 50. The data are treated by the Ruzic linearization method to obtain the concentration of the ligands and the conditional stability constant of the complexes. Ligands with reaction coefficient α_M higher than 0.1 K*w/V are detected, where K* is the ratio of the concentration of sorbed metal to the concentration of free metal in solution, which can be evaluated from the sorption equilibria of copper(II) on Amberlite CG 50, w is the amount of water in the resin phase, and V the volume of the solution phase. Some natural waters at high and low salinity were examined. The ligand concentration determined in these samples ranged from around 50 to 2000 nM, while the original copper concentrations from 11 to 130 nM. The ligand concentration was always much higher than that of copper(II). The conditional stability constants were very high, particularly in low salinity waters, where values as high as K’= 10^15.7 were obtained. In high salinity waters values around 10⁹ were found for the complex formation constant of the ligands titrated with copper(II). The investigation was also extended to a model solution, containing EDTA, obtaining K’ = 10^15.5, in acceptable agreement with that evaluated from the literature values.     

Dynamics of speciation and diversification in a metapopulation

We develop a simple framework for modeling speciation and diversification as a continuous process of accumulation of genetic (or morphological) differences accompanied by species and subpopulation extinction and/or range expansion. This framework can be used to approach a number of questions such as species-area distribution, species-range size distribution, the rate of ecological turnover, asymmetries of range division between sister species, waiting time until speciation and extinction, the relationship between the geographic range size and the probability of speciation, the relationships between subpopulation-level parameters and metapopulation-level parameters, and the effects of taxonomic level on these rates, distributions, and parameters. We illustrate some of these applications using numerical simulations. We develop approximations describing the dependence of the number of different taxonomic units, their average range size, and the rate of their turnover on the system size, the rate of fixation of genetic (or morphological) changes in local demes, and the rate of local extinction and colonization.     

Sorption and precipitation of metals in activated sludge

A conceptual model describing the relative roles of sorption and precipitation processes for metals in solid-solution suspensions is presented. The model performance is demonstrated using experimental data on sorption and precipitation of metals in samples of activated sludge mixed liquor. Based on the experimental results presented here, it appears that, at total metal and mixed liquor suspended solids concentrations and pH values generally encountered in full-scale municipal (or combined municipal/industrial) activated sludge systems, metals are primarily removed by sorption processes.     

NMR and homology modeling studies of copper(II)-halocyanin from Natronobacterium pharaonis bacteria

Halocyanin from the haloalkaliphilic archaean Natronobacterium pharaonis is a peripheral membrane type 1 blue copper protein with a single polypeptide chain of 163 amino acid residues. Halocyanin participates as putative electron carrier protein associated to an electron acceptor role for a terminal oxidase and has the lowest redox potential value reported to date for a BCP. NMR studies and homology modeling calculations were performed to evaluate the electronic properties of Cu(II)-halocyanin from Natronobacterium pharaonis. The copper coordination site properties of Cu(II)-halocyanin are discussed. The ¹H NMR spectra, isotropic chemical shifts and relaxation times for halocyanin are compared with those of other BCPs such as azurin, amicyanin, plastocyanin and stellacyanin. The wild-type Cu(II)-halocyanin presents almost the same ¹H NMR spectra in comparison with Cu(II)-plastocyanin as expected from a similar coordination symmetry. However, minor differences were found. In order to get some insight on these differences, a computational model for Cu(II)-halocyanin from N. pharaonis was built. Model is based on sequential homology of halocyanin with two different families of proteins: plastocyanins and pseudoazurins. Homology modeling was performed using two different structural templates and copper ion was added for further refinement of the coordination site. Proposed structure was in good agreement with NMR experimental information and is the first three-dimensional model reported to date of an halocyanin. Small differences were found in the copper coordination site with respect to other BCP with known structure. This work is also an interesting example of expertise-driven homology modeling across different protein families.     

Short Communication: Carbon source-starvation-induced precipitation of copper by Pseudomonas putida strain S4

Pseudomonas putida strain S4, when starved of carbon source, precipitated Cu2+ in the medium. The precipitate, apart from containing copper, consisted of phosphate and hydroxide residues. While high acid phosphatase activity provided the necessary phosphates for Cu2+-precipitation, hydroxyl residues generated by metal efflux pathway may be used for metal hydroxide precipitation. This phenomenon could be exploited in the biorecovery of copper from different sources.