Inverse modeling of the 14C bomb pulse in stalagmites to constrain the dynamics of soil carbon cycling at selected European cave sites

The decomposition of soil organic matter (SOM) is temperature dependent, but its response to a future warmer climate remains equivocal. Enhanced rates of decomposition of SOM under increased global temperatures might cause higher CO2 emissions to the atmosphere, and could therefore constitute a strong positive feedback. The magnitude of this feedback however remains poorly understood, primarily because of the difficulty in quantifying the temperature sensitivity of stored, recalcitrant carbon that comprises the bulk (>90%) of SOM in most soils. In this study we investigated the effects of climatic conditions on soil carbon dynamics using the attenuation of the 14C ‘bomb’ pulse as recorded in selected modern European speleothems. These new data were combined with published results to further examine soil carbon dynamics, and to explore the sensitivity of labile and recalcitrant organic matter decomposition to different climatic conditions. Temporal changes in 14C activity inferred from each speleothem was modelled using a three pool soil carbon inverse model (applying a Monte Carlo method) to constrain soil carbon turnover rates at each site. Speleothems from sites that are characterised by semi-arid conditions, sparse vegetation, thin soil cover and high mean annual air temperatures (MAATs), exhibit weak attenuation of atmospheric 14C ‘bomb’ peak (a low damping effect, D in the range: 55–77%) and low modelled mean respired carbon ages (MRCA), indicating that decomposition is dominated by young, recently fixed soil carbon. By contrast, humid and high MAAT sites that are characterised by a thick soil cover and dense, well developed vegetation, display the highest damping effect (D = c. 90%), and the highest MRCA values (in the range from 350 ± 126 years to 571 ± 128 years). This suggests that carbon incorporated into these stalagmites originates predominantly from decomposition of old, recalcitrant organic matter. SOM turnover rates cannot be ascribed to a single climate variable, e.g. (MAAT) but instead reflect a complex interplay of climate (e.g. MAAT and moisture budget) and vegetation development.

The polychaete worm Nereis diversicolor increases mercury lability and methylation in intertidal mudflats

The polychaete worm Nereis diversicolor engineers its environment by creating oxygenated burrows in anoxic intertidal sediments. The authors carried out a laboratory microcosm experiment to test the impact of polychaete burrowing and feeding activity on the lability and methylation of mercury in sediments from the Bay of Fundy, Canada. The concentration of labile inorganic mercury and methylmercury in burrow walls was elevated compared to worm-free sediments. Mucus secretions and organic detritus in worm burrows increased labile mercury concentrations. Worms decreased sulfide concentrations, which increased Hg bioavailability to sulfate-reducing bacteria and increased methylmercury concentrations in burrow linings. Because the walls of polychaete burrows have a greater interaction with organisms, and the overlying water, the concentrations of mercury and methylmercury they contain is more toxicologically relevant to the base of a coastal food web than bulk samples. The authors recommend that researchers examining Hg in marine environments account for sediment dwelling invertebrate activity to more fully assess mercury bioavailability.

Mercury and methylmercury bioaccumulation by polychaete worms is governed by both feeding ecology and mercury bioavailability in coastal mudflats

Polychaete worms are abundant in many mudflats but their importance to coastal food web Hg biomagnification is not known. We sampled sediments and polychaete worms from mudflats in the Bay of Fundy to investigate the bioaccumulation of mercury (Hg) and methylmercury (MeHg) in the coastal invertebrate food web. Hg concentrations in the sediments were low (<20 μg kg−1). Labile Hg (methanol/KOH sediment extraction) in surface sediments (0–1 cm) was positively correlated with Hg bioaccumulation by surface sediment-ingesting polychaetes but, surprisingly, there was a negative correlation between δ15N (i.e. trophic level) and THg bioaccumulation factors in polychaete worms. Worms feeding on deeper sediments contained the greatest MeHg concentrations (69.6 μg kg−1). Polychaetes are an important vector for Hg biomagnification to the coastal avian food web. This research demonstrates that feeding depth and method of feeding are more important than trophic position or sediment Hg concentrations for predicting Hg bioaccumulation.

Soil carbon and litter development along a reconstructed biodiverse forest chronosequence of South-Western Australia

Soil organic matter (SOM) increases with time as landscape is restored. Studying SOM development along restored forest chronosequences would be useful in clarifying some of the uncertainties in quantifying C turnover rates with respect to forest clearance and ensuing restoration. The development of soil organic matter in the mineral soils was studied at four depths in a 16-year-old restored jarrah forest chronosequence. The size-separated SOM fractionation along with δ13C isotopic shift was utilised to resolve the soil C temporal and spatial changes with developing vegetation. The restored forest chronosequence revealed several important insights into how soil C is developing with age. Litter accumulation outpaced the native forest levels in 12 years after restoration. The surface soils, in general, showed increase in total C with age, but this trend was not clearly observed at lower depths. C accumulation was observed with increasing restoration age in all three SOM size-fractions in the surface 0–2 cm depth. These biodiverse forests show a trend towards accumulating C in recalcitrant stable forms, but only in the surface 0–2 cm mineral soil. A significant reverse trend was observed for the moderately labile SOM fraction for lower depths with increasing restoration age. Correlating the soil δ13C with total C concentration revealed the re-establishment of the isotopically depleted labile to enriched refractory C continuum with soil depth for the older restored sites. This implied that from a pedogenic perspective, the restored soils are developing towards the original native soil carbon profile.

Carbon trading for phosphorus gain: the balance between rhizosphere carboxylates and arbuscular mycorrhizal symbiosis in plant phosphorus acquisition

Two key plant adaptations for phosphorus (P) acquisition are carboxylate exudation into the rhizosphere and mycorrhizal symbioses. These target different soil P resources, presumably with different plant carbon costs. We examined the effect of inoculation with arbuscular mycorrhizal fungi (AMF) on amount of rhizosphere carboxylates and plant P uptake for 10 species of low-P adapted Kennedia grown for 23 weeks in low-P sand. Inoculation decreased carboxylates in some species (up to 50%), decreased plant dry weight (21%) and increased plant P content (23%). There was a positive logarithmic relationship between plant P content and the amount of rhizosphere citric acid for inoculated and uninoculated plants. Causality was indicated by experiments using sand where little citric acid was lost from the soil solution over 2 h and citric acid at low concentrations desorbed P into the soil solution. Senesced leaf P concentration was often low and P-resorption efficiencies reached >90%. In conclusion, we propose that mycorrhizally mediated resource partitioning occurred because inoculation reduced rhizosphere carboxylates, but increased plant P uptake. Hence, presumably, the proportion of plant P acquired from strongly sorbed sources decreased with inoculation, while the proportion from labile inorganic P increased. Implications for plant fitness under field conditions now require investigation.

Differential uptake, partitioning and transfer of Cd and Zn in the soil-pea plant-aphid system

The biomagnification of trace metals during transfer from contaminated soil to higher trophic levels may potentially result in the exposure of predatory arthropods to toxic concentrations of these elements. This study examined the transfer of Cd and Zn in a soil−plant−arthropod system grown in series of field plots that had received two annual applications of municipal biosolids with elevated levels of Cd and Zn. Results showed that biosolids amendment significantly increased the concentration of Cd in the soil and the shoots of pea plants and the concentration of Zn in the soil, pea roots, shoots, and pods. In addition, the ratio of Cd to Zn concentration showed that Zn was preferentially transferred compared to Cd through all parts of the system. As a consequence, Zn was biomagnified by the system whereas Cd was biominimized. Cd and Zn are considered to exhibit similar behaviors in biological systems. However, the Cd/Zn ratios demonstrated that in this system, Cd is much less labile in the root−shoot−pod and shoot−aphid pathways than Zn.

SHIMMER (1.0): a novel mathematical model for microbial and biogeochemical dynamics in glacier forefield ecosystems

SHIMMER (Soil biogeocHemIcal Model for Microbial Ecosystem Response) is a new numerical modelling framework designed to simulate microbial dynamics and biogeochemical cycling during initial ecosystem development in glacier forefield soils. However, it is also transferable to other extreme ecosystem types (such as desert soils or the surface of glaciers). The rationale for model development arises from decades of empirical observations in glacier forefields, and enables a quantitative and process focussed approach. Here, we provide a detailed description of SHIMMER, test its performance in two case study forefields: the Damma Glacier (Switzerland) and the Athabasca Glacier (Canada) and analyse sensitivity to identify the most sensitive and unconstrained model parameters. Results show that the accumulation of microbial biomass is highly dependent on variation in microbial growth and death rate constants, Q10 values, the active fraction of microbial biomass and the reactivity of organic matter. The model correctly predicts the rapid accumulation of microbial biomass observed during the initial stages of succession in the forefields of both the case study systems. Primary production is responsible for the initial build-up of labile substrate that subsequently supports heterotrophic growth. However, allochthonous contributions of organic matter, and nitrogen fixation, are important in sustaining this productivity. The development and application of SHIMMER also highlights aspects of these systems that require further empirical research: quantifying nutrient budgets and biogeochemical rates, exploring seasonality and microbial growth and cell death. This will lead to increased understanding of how glacier forefields contribute to global biogeochemical cycling and climate under future ice retreat.

Holocene Climatic Optimum centennial-scale paleoceanography in the NE Aegean (Mediterranean sea)

Combined micropaleontological and geochemical analyses of the high-sedimentation gravity core M-4G provided new centennial-scale paleoceanographic data for sapropel S1 deposition in the NE Aegean Sea during the Holocene Climatic Optimum. Sapropel layer S1a (10.2–8.0 ka) was deposited in dysoxic to oxic bottom waters characterized by a high abundance of benthic foraminiferal species tolerating surface sediment and/or pore water oxygen depletion (e.g., Chilostomella mediterranensis, Globobulimina affinis), and the presence of Uvigerina mediterranea, which thrives in oxic mesotrophic-eutrophic environments. Preservation of organic matter (OM) is inferred based on high organic carbon as well as loliolide and isololiolide contents, while the biomarker record and the abundances of eutrophic planktonic foraminifera document enhanced productivity. High inputs of terrigenous OM are attributed to north Aegean borderland riverine inputs. Both alkenone-based sea surface temperatures (SSTs) and δO18G. bulloides records indicate cooling at 8.2 ka (S1a) and ~7.8 ka (S1 interruption). Sapropelic layer S1b (7.7–6.4 ka) is characterized by rather oxic conditions; abundances of foraminiferal species tolerant to oxygen depletion are very low compared with the U. mediterranea rise. Strongly fluctuating SSTs demonstrate repeated cooling and associated dense water formation, with a major event at 7.4 ka followed by cold spells at 7.0, 6.8, and 6.5 ka. The prominent rise of the carbon preference index within the S1b layer indicates the delivery of less degraded terrestrial OM. The increase of algal biomarkers, labile OM-feeding foraminifera and eutrophic planktonic species pinpoints an enhanced in situ marine productivity, promoted by more efficient vertical convection due to repeated cold events. The associated contributions of labile marine OM along with fresher terrestrial OM inputs after ~7.7 ka imply sources alternative/additional to the north Aegean riverine borderland sources for the influx of organic matter in the south Limnos Basin, plausibly related to the inflow of highly productive Marmara/Black Sea waters.

Direct Observation of Millisecond to Second Motions in Proteins by Dipolar CODEX NMR Spectroscopy

We present a site-resolved study of stow (ms to s) motions in a protein in the solid (microcrystalline) state performed with the use of a modified version of the centerband-only detection of exchange (CODEX) NMR experiment. CODEX was originally based on measuring changes in molecular orientation by means of the chemical shift anisotropy (CSA) tensor, and in our modification, angular reorientations of internuclear vectors are observed. The experiment was applied to the study of stow (15)N-(1)H motions of the SH3 domain of chicken a-spectrin. The protein was perdeuterated with partial back-exchange of protons at labile sites. This allowed indirect (proton) detection of (15)N nuclei and thus a significant enhancement of sensitivity. The diluted proton system also made negligible proton-driven spin diffusion between (15)N nuclei, which interferes with the molecular exchange (motion) and hampers the acquisition of dynamic parameters. The experiment has shown that approximately half of the peaks in the 2D (15)N-(1)H correlation spectrum exhibit exchange in a different extent. The correlation time of the slow motion for most peaks is 1 to 3 s. This is the first NMR study of the internal dynamics of proteins in the solid state on the millisecond to second time scale with site-specific spectral resolution that provides both time-scale and geometry information about molecular motions.

Fenchyl substituted 1,2-dioxetanes as an alternative to adamantyl derivatives for bioanalytical applications

The synthesis and study of the chemiluminescence parameters and thermal stability of 1,2-dioxetanes containing a spirofenchyl substituent are reported. Three fenchyl-substituted 1,2-dioxetanes were synthesized by photooxygenation of the corresponding alkenes, obtained by Barton-Kellogg olefination of the readily available (-)-fenchone. The fenchyl-substituted 1,2-dioxetanes showed thermal stabilities similar to those of the corresponding spiroadamantyl-substituted derivatives, although being slightly more labile with respect to unimolecular decomposition than the latter derivatives, which are widely utilized as labels in a great variety of chemiluminescent immunoassays. Fluoride induced decomposition of one triggerable fenchyl 1,2-dioxetane derivative showed kinetic parameters similar to those of the corresponding adamantyl-substituted derivative. The chemiluminescence quantum yields in the one percent range are also similar to that of other widely utilized chemiluminescence systems as the luminol reaction. These results indicate that fenchyl-substituted 1,2-dioxetanes can potentially be utilized as a cheaper alternative to substitute the corresponding spiroadamantyl derivatives in bioanalytical applications. (C) 2010 Elsevier B.V. All rights reserved.

Trace-metal biogeochemistry in the Mediterranean Thau Lagoon, a shellfish farming area

The present study contributes to the knowledge of the biogeochemistry of Pb, Cd, Cu, and Ni in the Mediterranean Than Lagoon, southern France, which is an important shellfish farming system. The concentrations of the metals were determined in sediment cores and the overlying waters using inductively coupled plasma mass spectrometry. Particular attention was given to the determination of dissolved Cu species because of their dual role as essential nutrient and toxicant to planktonic organisms. Dissolved Cu speciation was determined using the diffusive gradient in thin-film technique (DGT) and competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV). Our data indicated a significant historical contamination of the sediments, which commenced in the second half of the 19th century, with trace metal inputs persisting until the end of the 20th century. In recent years a decrease in metal contamination has become apparent. The maxima observed for Pb, Cd, and Cu profiles probably indicate the occurence of anoxia crises. A strong complexation of the dissolved Cu species was observed in the waters of the Than Lagoon, which reduced the bioavailability of Cu. The dissolved Cu(2+) concentrations were probably too low to cause direct toxic effects on shellfish, but the highest concentration (5.29 pM) observed in this study can potentially influence phytoplankton communities. A comparison between the Cu speciation data indicates that up to 50% of the complexed Cu determined using CLE-ACSV was DGT labile.

Determinação da glico-hemoglobina : relação com a glicemia e aspectos analíticos

A glico-hemoglobina (HbA1c) é um parâmetro importante no controle glicêmico de pacientes diabéticos. Vários estudos clínicos mostraram claramente que a melhora no controle glicêmico está fortemente associada com a diminuição no desenvolvimento e/ou progressão das complicações microvasculares do diabetes. A medida exata e precisa da HbA1c é uma questão importante para os laboratórios clínicos. Vários fatores afetam os resultados e podem levar a resultados errôneos. Este trabalho analisou o efeito de fatores analíticos, estados patológicos e drogas nos resultados de HbA1c. Em um primeiro estudo, demonstramos que a fração lábil de HbA1c contribui significativamente para o resultado final. Quando está fração é separada inadequadamente, há a necessidade de um pré - tratamento na amostra, para evitarmos valores falsamente elevados. O armazenamento das amostras é um fator pré – analítico importante. Amostras mantidas sob refrigeração são estáveis por 10 dias e o armazenamento a longo prazo deve ser feito a – 80oC. No entanto, amostras congeladas a –20oC apresentam uma diminuição significativa nos valores de HbA1c, já nas primeiras 24h de armazenamento. Em um segundo estudo, relatamos que as hemoglobinas anômalas estão associadas com valores muito baixos de HbA1c. Adicionalmente, também demonstramos que a anemia é uma importante fonte de interferência negativa nos resultados. Sugerimos que, para a correta interpretação dos valores de HbA1c, o estado hematológico do paciente seja sempre considerado. Em um terceiro estudo, analisamos o uso crônico de aspirina, vitamina C e vitamina E nos níveis de HbA1c. Houve inexistência de efeito significativo nos resultados de HbA1c, medidos por 3 métodos rotineiramente utilizados pelos laboratórios clínicos, em indivíduos não - diabéticos. O clínico deve conhecer os fatores que afetam a determinação de HbA1c na população atendida e os resultados discordantes com a história clínica do paciente devem ser sempre investigado.

An investigation of Hebbian phase sequences as assembly graphs

Hebb proposed that synapses between neurons that fire synchronously are strengthened, forming cell assemblies and phase sequences. The former, on a shorter scale, are ensembles of synchronized cells that function transiently as a closed processing system; the latter, on a larger scale, correspond to the sequential activation of cell assemblies able to represent percepts and behaviors. Nowadays, the recording of large neuronal populations allows for the detection of multiple cell assemblies. Within Hebb's theory, the next logical step is the analysis of phase sequences. Here we detected phase sequences as consecutive assembly activation patterns, and then analyzed their graph attributes in relation to behavior. We investigated action potentials recorded from the adult rat hippocampus and neocortex before, during and after novel object exploration (experimental periods). Within assembly graphs, each assembly corresponded to a node, and each edge corresponded to the temporal sequence of consecutive node activations. The sum of all assembly activations was proportional to firing rates, but the activity of individual assemblies was not. Assembly repertoire was stable across experimental periods, suggesting that novel experience does not create new assemblies in the adult rat. Assembly graph attributes, on the other hand, varied significantly across behavioral states and experimental periods, and were separable enough to correctly classify experimental periods (Naïve Bayes classifier; maximum AUROCs ranging from 0.55 to 0.99) and behavioral states (waking, slow wave sleep, and rapid eye movement sleep; maximum AUROCs ranging from 0.64 to 0.98). Our findings agree with Hebb's view that assemblies correspond to primitive building blocks of representation, nearly unchanged in the adult, while phase sequences are labile across behavioral states and change after novel experience. The results are compatible with a role for phase sequences in behavior and cognition.

Estudo da labilidade de Cu(II), Cd(II), Mn(II) e Ni(II) em substâncias húmicas aquáticas utilizando-se membranas celulósicas organomodificadas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dynamics and Heterogeneity of Pb(II) Binding by SiO2 Nanoparticles in an Aqueous Dispersion

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)