Chemical and isotopic compositions of sediments and some minerals from the Derugin Basin, Sea of Okhotsk

The paper reports specific mineralogical and geochemical characteristics of deposits from local depressions of the Derugin Basin. They were formed in an environment with periodic changes from oxic to anoxic conditions and show evidence for presence of hydrogen sulfide in bottom waters. Deposits of this type can be considered as a modern model for ancient ore-bearing black shale associations. Compared with typical metalliferous black shale sequences, which are characterized by high contents of organic matter, the sediments described here are depleted in elements of the organophilic association (Mo, Ni, Cu, Zn, V, and U), but have higher Mn contents.

Otolith microstructure and trace elemental concentrations in juvenile Pacific bluefin tuna (Thunnus orientalis) caught off of Southern California in 2012

We combined longitudinal analyses of otolith microstructure and trace elemental composition in ~ age 1-2 Pacific bluefin tuna (PBT, n = 24) for inferring the arrival of individuals in the California Current Large Marine Ecosystem (CCLME). Element:Ca ratios in transverse otolith sections (9-12 rows, triplicate ablations from coreprimordium to edge, ø50 µm) were quantified for eight elements: Li, Mg, Mn, Co, Cu, Zn, Sr, and Ba, which was followed by microstructure analysis to provide age estimates corresponding to each ablation spot. Age estimates from otoliths ranged from 328 to 498 days post hatch. The combined elemental signatures of four elements (Ba, Mg, Co, Cu) showed a significant increase at the otolith edge in approximately half of the individuals (30-60 days prior to catch). Given the different oceanographic properties of oligotrophic open Pacific vs. high nutrient, upwelling CCLME waters, this signal is consistent with the entry of the fish into the CCLME, which was estimated to occur primarily in July after a transoceanic migration of ~1.5-2.0 months.

Chemical composition and fluxes of deep sea suspended matter within and over the 9°50'N hydrothermal field, EPR

Results of geochemical studies of suspended matter from the water mass over the hydrothermal field at 9°50'N on the East Pacific Rise are reported. The suspended matter was sampled in background waters, in the buoyant plume, and in the near-bottom waters. Contents of Si, Al, P, Corg, Fe, Mn, Cu, Zn, Ni, Co, As, Cr, Cd, Pb, Ag, and Hg were determined. No definite correlations were found between the elements in the background waters. Many of the chemical elements correlated with Fe and associated with its oxyhydroxides in the buoyant plume. In the near-bottom waters trace elements are associated with Fe, Zn, and Cu (probably, with their sulfides formed during mixing of hydrothermal fluids with seawater). Chemical composition of sediment matter precipitated in a sediment trap was similar to the near-bottom suspended matter.

Graphs of experimental results given in concentration of trace metals versus time in days

The impact of CO2 leakage on solubility and distribution of trace metals in seawater and sediment has been studied in lab scale chambers. Seven metals (Al, Cr, Ni, Pb, Cd, Cu, and Zn) were investigated in membrane-filtered seawater samples, and DGT samplers were deployed in water and sediment during the experiment. During the first phase (16 days), "dissolved" (<0.2 µm) concentrations of all elements increased substantially in the water. The increase in dissolved fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb in the CO2 seepage chamber was respectively 5.1, 3.8, 4.5, 3.2, 1.4, 2.3 and 1.3 times higher than the dissolved concentrations of these metals in the control. During the second phase of the experiment (10 days) with the same sediment but replenished seawater, the dissolved fractions of Al, Cr, Cd, and Zn were partly removed from the water column in the CO2 chamber. DNi and DCu still increased but at reduced rates, while DPb increased faster than that was observed during the first phase. DGT-labile fractions (MeDGT) of all metals increased substantially during the first phase of CO2 seepage. DGT-labile fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb were respectively 7.9, 2.0, 3.6, 1.7, 2.1, 1.9 and 2.3 times higher in the CO2 chamber than that of in the control chamber. AlDGT, CrDGT, NiDGT, and PbDGT continued to increase during the second phase of the experiment. There was no change in CdDGT during the second phase, while CuDGT and ZnDGT decreased by 30% and 25%, respectively in the CO2 chamber. In the sediment pore water, DGT labile fractions of all the seven elements increased substantially in the CO2 chamber. Our results show that CO2 leakage affected the solubility, particle reactivity and transformation rates of the studied metals in sediment and at the sediment-water interface. The metal species released due to CO2 acidification may have sufficiently long residence time in the seawater to affect bioavailability and toxicity of the metals to biota.

Chemical analyses and results of sediments from different DSDP Holes from the North Atlantic

Chemical analyses of North Atlantic D.S.D.P. (Deep Sea Drilling Project) sediments indicate that basal sediments generally contain higher concentrations of Fe, Mn, Mg, Pb, and Ni, and similar or lower concentrations of Ti, Al, Cr, Cu, Zn, and Li than the material overlying them. Partition studies on selected samples indicate that the enriched metals in the basal sediments are usually held in a fashion similar to that in basal sediments from the Pacific, other D.S.D.P. sediments, and modern North Atlantic ridge and non-ridge material. Although, on average, chemical differences between basal sediments of varying ages are apparent, normalization of the data indicates that the processes leading to metal enrichment on the crest of the Mid-Atlantic Ridge appear to have been approximately constant in intensity since Cretaceous times. In addition, the bulk composition of detrital sediments also appears to have been relatively constant over the same time period. Paleocene sediments from site 118 are, however, an exception to this rule, there apparently having been an increased detrital influx during this period. The bulk geochemistry, partitioning patterns, and mineralogy of sediments from D.S.D.P. 9A indicates that post-depositional migration of such elements as Mn, Ni, Cu, Zn, and Pb may have occurred. The basement encountered at the base of site 138 is thought to be a basaltic sill, but the overlying basal sediments are geochemically similar to other metalliferous basal sediments from the North Atlantic. These results, as well as those from site 114 where true oceanic basement was encountered, but where there was an estimated 7 m.y. hiatus between basaltic extrusion and basal sediment deposition, indicate that ridge-crest sediments are not necessarily deposited during active volcanism but can be formed after the volcanism has ceased. The predominant processes for metal enrichment in these deposits and those formed in association with other submarine volcanic features is a combination of shallow hydrothermal activity, submarine weathering of basalt, and the formation of ferromanganese oxides which can scavenge metals from seawater. In addition, it seems as though the formation of submarine metalliferous sediments is not restricted to active-ridge areas.

New data on the ophiolitic VMS deposits of Moeche (Cabo Ortegal Complex, NW Spain)

As a result of the variscan collision, several allochtonous complexes were emplaced on the Iberian margin in Devonian times, among them the Cabo Ortegal Complex comprising the Moeche ophiolitic sequence. Copper has been won from several mines (Piquitos I & II, Barqueira, Maruxa) from disseminated ores and thin massive sulphide layers in the Moeche Unit, a strongly deformed meta-volcanic sequence comprising mainly quartz-chlorite schists and mylonites, which defines the top of the ophiolite. The ores were metamorphosed and strongly deformed under brittle conditions (for pyrite), but their textures are often apparently post-deformational, due to very common solution-transfer processes; they are composed mostly of pyrite and chalcopyrite, with minor sphalerite, pyrrhotite, etc., and with traces of native gold and PGE. The geology, mineralogy, and geochemistry of the orebodies relate closely to VMS of the Cu-Zn (Cyprus) type. Fluid inclusion studies allowed an estimation of metamorphic conditions at pressures of 2/2’5 kb and T 325/350ºC. New determinations using the chlorite geothermometer yield temperatures around 320 ºC, corresponding to pressures near 2 kb according to the isochores deduced from the fluid inclusion study, although in the Barqueira mine higher temperatures, up to 350 ºC, are found, corresponding to presssures up to 2’5 kb. Pb isotopic compositions of pyrite point to a double source of Pb, i.e. a main mantle and a subordinate crustal source. The values for 87SR/86Sr in pyrite support this interpretation, but some results suggest later mobilization in an open system, corresponding to solution-transfer. Age determinations of pyrite deduced from the Pb isotope uranogenic graph, ≈ 480 Ma, do not fit with the metamorphic ages published for the Moeche Unit, and might point to the age of Pb extraction from the mantle.

Impact of fire and post-fire management techniques on soil chemical properties

The effects of fire ( Control burned soil) and two emergency stabilisation techniques (grass Seeding and straw Mulching ) on 20 chemical characteristics were evaluated on 0 – 5 cm top-soils sampled 1, 90, 180 and 365 days after an experimental fi re in a steep shrubland of a temperate-humid region (NW Spain). Most part of pH (in H 2 O and KCl) variance was explained by the sampling date. No clear temporal trends were identi fi able for total soil C and N content, likely due to the large SOM pool in these soils; however, changes on soil δ 13 C were explained by the deposition of 13 C-depleted ashes, followed by its progressive erosion, while those on soil δ 15 N were a consequence of fi re induced N outputs. After the fi re, NH 4 + – N, P, Na, K, Mg, Ca, Mn, Cu, Zn and B concentrations increased, while those of NO 3 − – N, Al, Fe and Co did not vary significantly. Despite a significant decline with time, concentrations of Mg, Ca and Mn at the end of the study were still higher than in unburned soil, while those of K, Cu, Zn and B were similar to the pre-fire levels and those of NH 4 + – N, P and Na were below pre-fire values. Mulching and Seeding treatments for burned soil emergency stabilisation had significant effects on soil δ 15 N and extractable K, Mg and Ca, while data were inconclusive for their possible effects on the extractable Al, Fe and Co

Efecto de la adición de una turba comercial en la asimilabilidad de cobre, zinc, hierro, manganeso de un suelo en el que se ha cultivado trigo

Se ha estudiado el efecto de la adición de diferentes cantidades de una turba comercial (con un 80 % de turba rubia y un 20% de turba negra) en la asimilabilidad de los elementos nutritivos en un suelo calcáreo en el que se cultivó trigo. Para ello se determinaron los contenidos en N, P y K, así como las concentraciones totales y potencialmente asimilables para las plantas de los micronutrientes Cu, Zn, Fe y Mn. También se determinó el rendimiento en grano y el índice de cosecha del cultivo de trigo realizado en función del tratamiento de turba aplicado. Los resultados estadísticos no mostraron diferencias significativas entre tratamientos en cuanto a la concentración total de N, K, Cu, Zn, Fe y Mn en el suelo de la rizosfera del cultivo. Sin embargo sí se obtuvieron diferencias significativas (P < 0,05) en las concentraciones de Cu, Zn, Fe y Mn potencialmente disponibles en el suelo, aumentando en general, dichas concentraciones con los incrementos de la dosis de turba. El aumento de la dosis de turba también afectó al valor de pH del suelo, disminuyendo el valor del mismo a medida que aumenta dicha dosis. El mayor rendimiento en grano del cultivo de trigo se obtuvo con el tratamiento con turba que consiguió en el suelo un contenido en materia orgánica del 2,5 %.

Identification of the prooxidant site of human ceruloplasmin: A model for oxidative damage by copper bound to protein surfaces

Free transition metal ions oxidize lipids and lipoproteins in vitro; however, recent evidence suggests that free metal ion-independent mechanisms are more likely in vivo. We have shown previously that human ceruloplasmin (Cp), a serum protein containing seven Cu atoms, induces low density lipoprotein oxidation in vitro and that the activity depends on the presence of a single, chelatable Cu atom. We here use biochemical and molecular approaches to determine the site responsible for Cp prooxidant activity. Experiments with the His-specific reagent diethylpyrocarbonate (DEPC) showed that one or more His residues was specifically required. Quantitative [14C]DEPC binding studies indicated the importance of a single His residue because only one was exposed upon removal of the prooxidant Cu. Plasmin digestion of [14C]DEPC-treated Cp (and N-terminal sequence analysis of the fragments) showed that the critical His was in a 17-kDa region containing four His residues in the second major sequence homology domain of Cp. A full length human Cp cDNA was modified by site-directed mutagenesis to give His-to-Ala substitutions at each of the four positions and was transfected into COS-7 cells, and low density lipoprotein oxidation was measured. The prooxidant site was localized to a region containing His426 because CpH426A almost completely lacked prooxidant activity whereas the other mutants expressed normal activity. These observations support the hypothesis that Cu bound at specific sites on protein surfaces can cause oxidative damage to macromolecules in their environment. Cp may serve as a model protein for understanding mechanisms of oxidant damage by copper-containing (or -binding) proteins such as Cu, Zn superoxide dismutase, and amyloid precursor protein.

Peroxynitrite, the coupling product of nitric oxide and superoxide, activates prostaglandin biosynthesis

Peroxynitrite activates the cyclooxygenase activities of constitutive and inducible prostaglandin endoperoxide synthases by serving as a substrate for the enzymes’ peroxidase activities. Activation of purified enzyme is induced by direct addition of peroxynitrite or by in situ generation of peroxynitrite from NO coupling to superoxide anion. Cu,Zn-superoxide dismutase completely inhibits cyclooxygenase activation in systems where peroxynitrite is generated in situ from superoxide. In the murine macrophage cell line RAW264.7, the lipophilic superoxide dismutase-mimetic agents, Cu(II) (3,5-diisopropylsalicylic acid)2, and Mn(III) tetrakis(1-methyl-4-pyridyl)porphyrin dose-dependently decrease the synthesis of prostaglandins without affecting the levels of NO synthase or prostaglandin endoperoxide synthase or by inhibiting the release of arachidonic acid. These findings support the hypothesis that peroxynitrite is an important modulator of cyclooxygenase activity in inflammatory cells and establish that superoxide anion serves as a biochemical link between NO and prostaglandin biosynthesis.

Chaperone-facilitated copper binding is a property common to several classes of familial amyotrophic lateral sclerosis-linked superoxide dismutase mutants

Mutations in Cu, Zn superoxide dismutase (SOD1) cause the neurodegenerative disease familial amyotrophic lateral sclerosis from an as-yet-unidentified toxic property(ies). Analysis in Saccharomyces cerevisiae of a broad range of human familial amyotrophic lateral sclerosis–linked SOD1 mutants (A4V, G37R, G41D, H46R, H48Q, G85R, G93C, and I113T) reveals one property common to these mutants (including two at residues that coordinate the catalytic copper): Each does indeed bind copper and scavenge oxygen-free radicals in vivo. Neither decreased copper binding nor decreased superoxide scavenging activity is a property shared by all mutants. The demonstration that shows that all mutants tested do bind copper under physiologic conditions supports a mechanism of SOD1 mutant-mediated disease arising from aberrant copper-mediated chemistry catalyzed by less tightly folded (and hence less constrained) mutant enzymes. The mutant enzymes also are shown to acquire the catalytic copper in vivo through the action of CCS, a specific copper chaperone for SOD1, which in turn suggests that a search for inhibitors of this SOD1 copper chaperone may represent a therapeutic avenue.

Periplasmic superoxide dismutase protects Salmonella from products of phagocyte NADPH-oxidase and nitric oxide synthase

Superoxide dismutase (SOD) catalyzes the conversion of superoxide radical to hydrogen peroxide. Periplasmic localization of bacterial Cu,Zn-SOD has suggested a role of this enzyme in defense against extracellular phagocyte-derived reactive oxygen species. Sequence analysis of regions flanking the Salmonella typhimurium sodC gene encoding Cu,Zn-SOD demonstrates significant homology to λ phage proteins, reflecting possible bacteriophage-mediated horizontal gene transfer of this determinant among pathogenic bacteria. Salmonella deficient in Cu,Zn-SOD has reduced survival in macrophages and attenuated virulence in mice, which can be restored by abrogation of either the phagocyte respiratory burst or inducible nitric oxide synthase. Moreover, a sodC mutant is extremely susceptible to the combination of superoxide and nitric oxide. These observations suggest that SOD protects periplasmic or inner membrane targets by diverting superoxide and limiting peroxynitrite formation, and they demonstrate the ability of the respiratory burst and nitric oxide synthase to synergistically kill microbial pathogens in vivo.

Winter Survival of Transgenic Alfalfa Overexpressing Superoxide Dismutase1

To test the hypothesis that enhanced tolerance of oxidative stress would improve winter survival, two clones of alfalfa (Medicago sativa) were transformed with a Mn-superoxide dismutase (Mn-SOD) targeted to the mitochondria or to the chloroplast. Although Mn-SOD activity increased in most primary transgenic plants, both cytosolic and chloroplastic forms of Cu/Zn-SOD had lower activity in the chloroplast SOD transgenic plants than in the nontransgenic plants. In a field trial at Elora, Ontario, Canada, the survival and yield of 33 primary transgenic and control plants were compared. After one winter most transgenic plants had higher survival rates than control plants, with some at 100%. Similarly, some independent transgenic plants had twice the herbage yield of the control plants. Prescreening the transgenic plants for SOD activity, vigor, or freezing tolerance in the greenhouse was not effective in identifying individual transgenic plants with improved field performance. Freezing injury to leaf blades and fibrous roots, measured by electrolyte leakage from greenhouse-grown acclimated plants, indicated that the most tolerant were only 1°C more freezing-tolerant than alfalfa clone N4. There were no differences among transgenic and control plants for tetrazolium staining of field-grown plants at any freezing temperature. Therefore, although many of the transgenic plants had higher winter survival rates and herbage yield, there was no apparent difference in primary freezing injury, and therefore, the trait is not associated with a change in the primary site of freezing injury.

Essential role for mammalian copper transporter Ctr1 in copper homeostasis and embryonic development

The trace metal copper (Cu) plays an essential role in biology as a cofactor for many enzymes that include Cu, Zn superoxide dismutase, cytochrome oxidase, ceruloplasmin, lysyl oxidase, and dopamine β-hydroxylase. Consequently, Cu transport at the cell surface and the delivery of Cu to intracellular compartments are critical events for a wide variety of biological processes. The components that orchestrate intracellular Cu trafficking and their roles in Cu homeostasis have been elucidated by the studies of model microorganisms and by the characterizations of molecular basis of Cu-related genetic diseases, including Menkes disease and Wilson disease. However, little is known about the mechanisms for Cu uptake at the plasma membrane and the consequences of defects in this process in mammals. Here, we show that the mouse Ctr1 gene encodes a component of the Cu transport machinery and that mice heterozygous for Ctr1 exhibit tissue-specific defects in copper accumulation and in the activities of copper-dependent enzymes. Mice completely deficient for Ctr1 exhibit profound growth and developmental defects and die in utero in mid-gestation. These results demonstrate a crucial role for Cu acquisition through the Ctr1 transporter for mammalian Cu homeostasis and embryonic development.

Photosystem I Is an Early Target of Photoinhibition in Barley Illuminated at Chilling Temperatures1

Light-induced damage to photosystem I (PSI) was studied during low-light illumination of barley (Hordeum vulgare L.) at chilling temperatures. A 4-h illumination period induced a significant inactivation of PSI electron transport activity. Flash-induced P700 absorption decay measurements revealed progressive damage to (a) the iron-sulfur clusters FA and FB, (b) the iron-sulfur clusters FA, FB, and FX, and (c) the phylloquinone A1 and the chlorophyll A0 or P700 of the PSI electron acceptor chain. Light-induced PSI damage was also evidenced by partial degradation of the PSI-A and PSI-B proteins and was correlated with the appearance of smaller proteins. Aggravated photodamage was observed upon illumination of barley leaves infiltrated with KCN, which inhibits Cu,Zn-superoxide dismutase and ascorbate peroxidase. This indicates that the photodamage of PSI in barley observed during low-light illumination at chilling temperatures arises because the defense against active oxygen species by active oxygen-scavenging enzymes is insufficient at these specific conditions. The data obtained demonstrate that photoinhibition of PSI at chilling temperatures is an important phenomenon in a cold-tolerant plant species.