Associations between redox‐sensitive trace metals and microbial communities in a Proterozoic ocean analogue

Constraints on Precambrian ocean chemistry are dependent upon sediment geochemistry. However, diagenesis and metamorphism can destroy primary biosignatures, making it difficult to consider biology when interpreting geochemical data. Modern analogues for ancient ecosystems can be useful tools for identifying how sediment geochemistry records an active biosphere. The Middle Island Sinkhole (MIS) in Lake Huron is an analogue for shallow Proterozoic waters due to its low oxygen water chemistry and microbial communities that exhibit diverse metabolic functions at the sediment–water interface. This study uses sediment trace metal contents and microbial abundances in MIS sediments and an oxygenated Lake Huron control site (LH) to infer mechanisms for trace metal burial. The adsorption of trace metals to Mn‐oxyhydroxides is a critical burial pathway for metals in oxic LH sediments, but not for the MIS mat and sediments, consistent with conventional understanding of Mn cycling. Micronutrient trace metals (e.g., Zn) are associated with organic matter regardless of oxygen and sulfide availability. Although U and V are conventionally considered to be organically complexed in suboxic and anoxic conditions, U and organic covary in oxic LH sediments, and Mn‐oxyhydroxide cycling dominates V deposition in the anoxic MIS sediments. Significant correlations between Mo and organic matter across all redox regimes have major implications for our interpretations of Mo isotope systematics in the geologic record. Finally, while microbial groups vary between the sampling locales (e.g., the cyanobacteria in the MIS microbial mat are not present in LH sediments), LH and MIS ultimately have similar relationships between microbial assemblages and metal burial, making it difficult to link trace metal burial to microbial metabolisms. Together, these results indicate that bulk sediment trace metal composition does not capture microbiological processes; more robust trace metal geochemistry such as isotopes and speciation may be critical for understanding the intersections between microbiology and sediment geochemistry.     

The cell wall in plant cell response to trace metals: polysaccharide remodeling and its role in defense strategy

This review paper is focused predominantly on the role of the cell wall in the defense response of plants to trace metals. It is generally known that this compartment accumulates toxic divalent and trivalent metal cations both during their uptake by the cell from the environment and at the final stage of their sequestration from the protoplast. However, from results obtained in recent years, our understanding of the role played by the cell wall in plant defense response to toxic metals has markedly altered. It has been shown that this compartment may function not only as a sink for toxic trace metal accumulation, but that it is also actively modified under trace metal stress. These modifications lead to an increase in the capacity of the cell wall to accumulate trace metals and a decrease of its permeability for trace metal migration into the protoplast. One of the most striking alterations is the enhancement of the level of low-methylesterified pectins: the polysaccharides able to bind divalent and trivalent metal ions. This review paper will present the most recent results, especially those that are concerned with polysaccharide level, composition and distribution under trace metal stress, and describe in detail the polysaccharides responsible for metal binding and immobilization in different groups of plants (algae and higher plants). The review also contains information related to the entry pathways of trace metals into the cell wall and their detection methods.     

Application of the multisubstrate testing method to the characterization of marine microbial fouling communities on metals and alloys

The functional state of marine micro fouling communities of corroding metal plates was analyzed using a modified method of multisubstrate testing. Qualitative and quantitative differences were found in the substrate utilization spectra of the fouling micro flora that were dependent on the type of metal surface and the place of sample exposure. The activity of substrate consumption by fouling micro flora can be used as a criterion for estimating the intensity of corrosion processes on metal surfaces and as a clustering and classification criterion.     

Effect of genetically modified poplars on soil microbial communities during the phytoremediation of waste mine tailings

The application of transgenic plants to clean up environmental pollution caused by the wastes of heavy metal mining is a promising method for removing metal pollutants from soils. However, the effect of using genetically modified organisms for phytoremediation is a poorly researched topic in terms of microbial community structures, despite the important role of microorganisms in the health of soil. In this study, a comparative analysis of the bacterial and archaeal communities found in the rhizosphere of genetically modified (GM) versus wild-type (WT) poplar was conducted on trees at different growth stages (i.e., the rhizospheres of 1.5-, 2.5-, and 3-year-old poplars) that were cultivated on contaminated soils together with nonplanted control soil. Based on the results of DNA pyrosequencing, poplar type and growth stages were associated with directional changes in the structure of the microbial community. The rate of change was faster in GM poplars than in WT poplars, but the microbial communities were identical in the 3-year-old poplars. This phenomenon may arise because of a higher rate and greater extent of metal accumulation in GM poplars than in naturally occurring plants, which resulted in greater changes in soil environments and hence the microbial habitat.     

Lack of correlation between trace metal staining and trace metal content of the rat hippocampus following colchicine microinjection

Summary Following the intrahippocampal injection of colchicine, the trace metal staining with Timm's method is shown to change in the hippocampus. The histochemical examinations were supplemented with atomic absorption spectrophotometric measurement of the trace metals (Zn, Fe, Cu). It was found that intrahippocampal colchicine treatment induces the temporary disappearance of the trace metal staining of the pyramidal cells of the regio superior, while there is a considerable reduction in the staining in the granular cells of the area dentata and in their mossy fibre terminals. Simultaneously, in contrast with the histochemical results, quantitative studies on the trace metal levels showed that colchicine does not lead to evacuation of the trace metals from the hippocampal formation. The combined atomic absorption and trace metal staining investigations prove that there is no correlation between the trace metal staining and the quantitative amounts of the trace metals.Supported by the Scientific Research Council, Ministry of Health, Hungary (4-12-0303-01-0/K)     

Impacts of Yellow River Irrigation Practices on Trace Metals in Surface Water: A Case Study of the Henan-Liaocheng Irrigation Area,China

Large-scale irrigation practices may disturb local hydrologic cycles and distribute trace metals throughout the environment. Reported here is the spatial pattern of trace metals and associated health risks in an agricultural area of China, which has a long history of irrigation with water from the Yellow River. Multivariate statistical analyses and a risk-assessment model were employed to interpret the environmental data. It indicated that Zn, Se, B, Ba, Fe, Mn, Mo, Ni, V, Al, Li, Sr, Be, Cd, Cr, Cu, and Pb were all detected in the surface waters. Compared to drinking water guidelines, the primary trace metal pollution components (Al, Fe, Se, B, Mn, and Zn) exceeded drinking water standards by 40.7%, 14.8%, 29.6%, 25.9%, 11.1%, and 14.8%, respectively. Except for one site that exhibited anomalous metal concentrations, landscape features of trace metals identified a uniform distribution of trace metals for all sample sites. The calculated mean value of Hazard Quotients (HQs) exceeded the USEPA's recommendations by a factor of 2.9 times the threshold value. Primary sources of trace metals were associated with natural deposition, industrial and agrochemical processes, and a mixed source of both geogenic and anthropogenic origins.     

Enzyme inactivation by metal-catalyzed oxidation of coenzyme Q1.

Ubiquinol-1 in aerated aqueous solution inactivates several enzymes--alanine aminotransferase, alkaline phosphatase, Na+/K(+)-ATPase, creatine kinase and glutamine synthetase--but not isocitrate dehydrogenase and malate dehydrogenase. Ubiquinone-1 and/or H2O2 do not affect the activity of alkaline phosphatase and glutamine synthetase chosen as model enzymes. Dioxygen and transition metal ions, even if in trace amounts, are essential for the enzyme inactivation, which indeed does not occur under argon atmosphere or in the presence of metal chelators. Supplementation with redox-active metal ions (Fe3+ or Cu2+), moreover, potentiates alkaline phosphatase inactivation. Since catalase and peroxidase protect while superoxide dismutase does not, hydrogen peroxide rather than superoxide anion seems to be involved in the inactivation mechanism through which oxygen active species (hydroxyl radical or any other equivalent species) are produced via a modified Haber-Weiss cycle, triggered by metal-catalyzed oxidation of ubiquinol-1. The lack of efficiency of radical scavengers and the almost complete protection afforded by enzyme substrates and metal cofactors indicate a 'site-specific' radical attack as responsible for the oxidative damage.     

Millimeter‐scale resolution of trace metal distributions in microbial mats from a hypersaline environment in Baja California,Mexico

Microbial mats from two ponds with different salinities from the saltern of Guerrero Negro (Mexico) points toward millimeter‐scale coherent variations in trace metal (Me) concentrations (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn). Total, HCl‐leachable and pyrite‐associated Me showed a trend of increasing concentrations with increasing depth suggesting gradual addition of reactive Me probably as a result of metal sulfide precipitation at depth. The trends in Me profiles can be ascribed to the establishment and maintenance of microzones that promote geochemical processes, bacterial population distributions, and differential mass transport within the mats. Degrees of trace metal pyritization (1 ± 1% for Zn to 24 ± 7% for Cd) as well as metals associated with the pyrite fraction (<1.4–36 ± 18 nmol g^?1 for Zn and Mn, respectively) were low, as expected from a reactive Fe‐limited system like Guerrero Negro. Calculated enrichment factors showed that Ni (2.6 ± 2.1), Co (5.5 ± 4.0), Pb (9.4 ± 7.4), and Cd (57 ± 39) were, on average, enriched in the microbial mats of Guerrero Negro. Natural enrichments of Cd, Pb, and Co in sediments along the coast of Baja California and metabolical requirements of Co and Ni by the predominant cyanobacteria in the Guerrero Negro mats may explain these enrichments. Metal characteristics in microbial mats could be advantageously used as biosignatures to identify their presence in the geological record or in other planetary systems.     

TRACE METAL CYCLING IN TROPICAL-SUBTROPICAL ESTUARIES DOMINATED BY THE SEAGRASS THALASSIA TESTUDINUM

The present study was designed to determine the uptake and release rates of various trace metal cations by turtle grass and its community in order to provide the coefficients of our previously described computer model intended to simulate trace metal cycling in subtropical and tropical estuaries. The site of uptake in Thalassia was also examined.     

Trace metals in barnacles:the significance of trophic transfer

Barnacles have very high accumulated trace metal body concentrations that vary with local trace metal bioavailabilities and represent integrated measures of the supply of bioavailable metals. Pioneering work in Chinese waters in Hong Kong highlighted the potential value of barnacles (particularly Balanus amphitrite) as trace metal biomonitors in coastal waters, identifying differences in local trace metal bioavailabilities over space and time. Work in Hong Kong has also shown that although barnacles have very high rates of trace metal uptake from solution, they also have very high trace metal assimilation efficiencies from the diet. High assimilation efficiencies coupled with high ingestion rates ensure that trophic uptake is by far the dominant trace metal uptake route in barnacles, as verified for cadmium and zinc. Kinetic modelling has shown that low efflux rate constants and high uptake rates from the diet combine to bring about accumulated trace metal concentrations in barnacles that are amongst the     

Trace metals in barnacles: the significance of trophic transfer

Barnacles have very high accumulated trace metal body concentrations that vary with local trace metal bioavailabilities and represent integrated measures of the supply of bioavailable metals. Pioneering work in Chinese waters in Hong Kong highlighted the potential value of barnacles (particularly Balanus amphitrite) as trace metal biomonitors in coastal waters,identifying differences in local trace metal bioavailabilities over space and time. Work in Hong Kong has also shown that although barnacles have very high rates of trace metal uptake from solution, they also have very high trace metal assimilation efficiencies from the diet. High assimilation efficiencies coupled with high ingestion rates ensure that trophic uptake is by far the dominant trace metal uptake route in barnacles, as verified for cadmium and zinc. Kinetic modelling has shown that low efflux rate constants and high uptake rates from the diet combine to bring about accumulated trace metal concentrations in barnacles that are amongst the highest known in marine invertebrates.     

Bioavailability of trace metals to aquatic microorganisms: importance of chemical, biological and physical processes on biouptake

An important challenge in environmental biogeochemistry is the determination of the bioavailability of toxic and essential trace compounds in natural media. For trace metals, it is now clear that chemical speciation must be taken into account when predicting bioavailability. Over the past 20 years, equilibrium models (free ion activity model (FIAM), biotic ligand model (BLM)) have been increasingly developed to describe metal bioavailability in environmental systems, despite the fact that environmental systems are always dynamic and rarely at equilibrium. In these simple (relatively successful) models, any reduction in the available, reactive species of the metal due to competition, complexation or other reactions will reduce metal bioaccumulation and thus biological effects. Recently, it has become clear that biological, physical and chemical reactions occurring in the immediate proximity of the biological surface also play an important role in controlling trace metal bioavailability through shifts in the limiting biouptake fluxes. Indeed, for microorganisms, examples of biological (transport across membrane), chemical (dissociation kinetics of metal complexes) and physical (diffusion) limitation can be demonstrated. Furthermore, the organism can employ a number of biological internalization strategies to get around limitations that are imposed on it by the physicochemistry of the medium. The use of a single transport site by several metals or the use of several transport sites by a single metal further complicates the prediction of uptake or effects using the simple chemical models. Finally, once inside the microorganism the cell is able to employ a large number of strategies including complexation, compartmentalization, efflux or the production of extracellular ligands to minimize or optimize the reactivity of the metal. The prediction of trace metal bioavailability will thus require multidisciplinary advances in our understanding of the reactions occurring at and near the biological interface. By taking into account medium constraints and biological adaptability, future bioavailability modeling will certainly become more robust.     

Minerals in the rhizosphere: overlooked mediators of soil nitrogen availability to plants and microbes

Non-native earthworms are a continued source of environmental change in the northeastern United States that may affect trace metals in the plant-soil system, with largely unknown effects. We assessed earthworm impacts on exchangeable and strong acid extractable (total) concentrations and pools of Al, Fe, Cu, Zn, Mo, Pb in non-point source polluted, forest soil horizons (Organic, A, and B) and foliar metals concentrations in young (<?3 years) Acer saccharum and Polystichum acrostichoides at four proximal forests in the Finger Lakes Region of New York. We observed decreasing total trace metal Organic horizon pools and increasing total trace metal A horizon concentrations as a function of increasing earthworm biomass. Earthworms had limited effects on exchangeable concentrations in A and B horizons and total metal concentrations in the B horizon. Foliar trace metal concentrations in Acer were better explained by earthworm biomass than soil concentrations but foliar concentrations for Polystichum were poorly predicted by both earthworm biomass and soil metal concentrations. Our results suggest that earthworms can affect trace metal uptake by some plants, but not by increasing soil trace metal exchangeability or from changing soil properties (pH, %SOM, or cation exchange capacity). Instead, non-native earthworms may indirectly alter understory plant uptake of trace metals.     

Trace metals in barnacles: the significance of trophic transfer

Barnacles have very high accumulated trace metal body concentrations that vary with local trace metal bioavailabilities and represent integrated measures of the supply of bioavailable metals. Pioneering work in Chinese waters in Hong Kong highlighted the potential value of barnacles (particularlyBalanus amphitrite) as trace metal biomonitors in coastal waters, identifying differences in local trace metal bioavailabilities over space and time. Work in Hong Kong has also shown that although barnacles have very high rates of trace metal uptake from solution, they also have very high trace metal assimilation efficiencies from the diet. High assimilation efficiencies coupled with high ingestion rates ensure that trophic uptake is by far the dominant trace metal uptake route in barnacles, as verified for cadmium and zinc. Kinetic modelling has shown that low efflux rate constants and high uptake rates from the diet combine to bring about accumulated trace metal concentrations in barnacles that are amongst the highest known in marine invertebrates.     

A Trace Metal Survey of Non-Occupationally Exposed Gauteng Residents

Specific reference values for background levels of body burden of trace metals are not available for South Africa. Currently, laboratories measuring trace metal levels in workers use internationaly established values for comparison. A preliminary cross-sectional survey of 107 non-occupationally exposed volunteers of both genders and all races provided blood and urine samples. The samples were collected with consideration for possible routes of contamination. Seven metals were measured in blood and ten in urine. Reference ranges for a Gauteng population were then calculated using the central 95% of data to provide lower and upper limits, which were then compared to international limits. The trace metal levels described had both lower and higher reference ranges in blood and urine compared to international studies. This reflects the differences in the environments. Statistically significant differences in metal levels were observed by gender. The differences in detected trace metal levels in our sample as compared to other published data demonstrate the need for the establishment of local reference values for laboratories. The establishment of local 95% reference ranges would also allow South Africa to determine its exposure levels compared to those internationally. This would assist with establishing pollution control priorities.     

Models of regulation and accumulation of trace metals in marine invertebrates

1. General principles governing trace metal uptake and accumulation in marine invertebrates are identified.2. Key determinants of trace metal body concentrations are bioavailability from seawater and from food. However, the nature of the trace metal (essential vs non-essential, chemical properties, etc.) and the physiological state of the organism, strongly influence subsequent handling, distribution, tissue accumulation and excretion.3. The roles of metal-binding proteins (metallothioneins, transferrin-like proteins, etc.) and haemolymph cellular elements in metal transport and storage are described.4. Uptake of many trace metals from seawater generally conforms to Fick's Law of Diffusion, but is also influenced by non-specific binding to ligands in body fluids and cells, potential differences across body surfaces and, in some instances, by active transport processes involving ionic pumps and pinocytosis.5. Potential mechanisms underlying regulation of whole organism and tissue metal loads are outlined and compared with accumulation strategies. The significance of trace metal levels is discussed with regard to the well-being of marine invertebrates and their use in biomonitoring studies of trace metal pollution.     

Trace metal optimization in CHO cell culture through statistical design of experiments

A majority of the biotherapeutics industry today relies on the manufacturing of monoclonal antibodies from Chinese hamster ovary (CHO) cells, yet challenges remain with maintaining consistent product quality from high-producing cell lines. Previous studies report the impact of individual trace metal supplemental on CHO cells, and thus, the combinatorial effects of these metals could be leveraged to improve bioprocesses further. A three-level factorial experimental design was performed in fed-batch shake flasks to evaluate the impact of time wise addition of individual or combined trace metals (zinc and copper) on CHO cell culture performance. Correlations among each factor (experimental parameters) and response variables (changes in cell culture performance) were examined based on their significance and goodness of fit to a partial least square's regression model. The model indicated that zinc concentration and time of addition counter-influence peak viable cell density and antibody production. Meanwhile, early copper supplementation influenced late-stage ROS activity in a dose-dependent manner likely by alleviating cellular oxidative stress. Regression coefficients indicated that combined metal addition had less significant impact on titer and specific productivity compared to zinc addition alone, although titer increased the most under combined metal addition. Glycan analysis showed that combined metal addition reduced galactosylation to a greater extent than single metals when supplemented during the early growth phase. A validation experiment was performed to confirm the validity of the regression model by testing an optimized setpoint of metal supplement time and concentration to improve protein productivity.     

Electrochemical analysis of copper ion using a Gly–Gly–His tripeptide modified poly(3-thiopheneacetic acid) biosensor

A novel biosensor harnessing a conducting polymer functionalized with a copper ion specific peptide proved to be highly effective for electrochemical analysis of copper ions. The developed sensor comprised a transducer based on a conducting polymer (poly(3-thiopheneacetic acid)) electrode and a probe (tripeptide, Gly–Gly–His) selectively cognitive of copper ions. For functionalization of the electrode, the carboxylic group of the polymer was covalently coupled with the amine group of the tripeptide, and its structural features were confirmed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection infrared (ATR-IR) spectroscopy. The peptide modified polythiophene biosensor was used for the electrochemical analysis of various trace metal ions by square wave voltammetry. The electrode was found to be highly sensitive and selective to Cu²⁺ in the range of 0.02–20 μM with almost no cross binding to other metal ions such as Ni²⁺ and Pb²⁺. Furthermore, the developed sensor exhibited a high stability and reproducibility despite the repeated use of the sensor electrode and probe. With the advent of more diverse affinity bioprobes specific towards a broad range of analytes, the demonstrated strategy harnessing peptide modified polythiophene biosensor is likely to provide an excellent platform for the selective determination of trace amount of analytes whose detection is otherwise cumbersome.     

Trace element uptake by L-cells as a function of trace elements in a synthetic growth medium

The concentration of trace elements in L-cells has been studied as a function of the trace metal content of the growth medium. Cells were cultured in synthetic media which contained varying trace amounts of the elements manganese, iron, cobalt, copper, zinc and molybdenum. The cellular concentration of the elements potassium, iron, copper and zinc were then determined. It was found that the cell accumulates trace metals at a different rate than they are made available. Deficiencies in zinc could be “induced” in the cell by increasing the concentration of iron, manganese and cobalt; cellular iron deficiencies were observed at larger medium concentrations of zinc, manganese, copper and cobalt. Trace metal uptake by the cell was seen to parallel the utilization by multicellular organisms.