A Comparison between Four Analytical Methods for the Measurement of Fe(II) at Nanomolar Concentrations in Coastal Seawater

Dissolved Fe(II) in seawater is deemed an important micronutrient for microbial organisms, but its analysis is challenging due to its transient nature. We conducted a series of Fe(II) method comparison experiments, where spikes of 5 to 31 nM Fe(II) were added to manipulated seawaters with varying dissolved oxygen (37 to 156 μM) concentrations. The observed Fe(II) concentrations from four analytical methods were compared: spectrophotometry with ferrozine, stripping voltammetry, and flow injection analysis using luminol (with, and without, a pre-concentration column). Direct comparisons between the different methods were undertaken from the derived apparent Fe(II) oxidation rate constant (k1). Whilst the two luminol based methods produced the most similar concentrations throughout the experiments, k1 was still subject to a 20–30% discrepancy between them. Contributing factors may have included uncertainty in the calibration curves, and different responses to interferences from Co(II) and humic/fulvic organic material. The difference in measured Fe(II) concentrations between the luminol and ferrozine methods, from 10 min–2 h after the Fe(II) spikes were added, was always relatively large in absolute terms (>4 nM) and relative to the spike added (>20% of the initial Fe(II) concentration). k1 derived from ferrozine observed Fe(II) concentrations was 3–80%, and 4–16%, of that derived from luminol observed Fe(II) with, and without, pre-concentration respectively. The poorest comparability of k1 was found after humic/fulvic material was added to raise dissolved organic carbon to 120 μM. A luminol method without pre-concentration then observed Fe(II) to fall below the detection limit (<0.49 nM) within 10 min of a 17 nM Fe(II) spike addition, yet other methods still observed Fe(II) concentrations of 2.7 to 3.7 nM 30 min later. k1 also diverged accordingly with the ferrozine derived value 4% of that derived from luminol without pre-concentration. These apparent inconsistencies suggest that some inter-dataset differences in measured Fe(II) oxidation rates in natural waters may be attributable to differences in the analytical methods used rather than arising solely from substantial shifts in Fe(II) speciation

Isotopic signature of dissolved iron delivered to the Southern Ocean from hydrothermal vents in the East Scotia Sea

It has recently been demonstrated that hydrothermal vents are an important source of dissolved Fe (dFe) to the Southern Ocean. The isotopic composition (?56Fe) of dFe in vent fluids appears to be distinct from other sources of dFe to the deep ocean, but the evolution of ?56Fe during mixing between vent fluids and seawater is poorly constrained. Here we present the evolution of ?56Fe for dFe in hydrothermal fluids and dispersing plumes from two sites in the East Scotia Sea. We show that ?56Fe values in the buoyant plume are distinctly lower (as low as ?1.19 ‰) than the hydrothermal fluids (?0.29 ‰), attributed to (i) precipitation of Fe-sulfides in the early stages of mixing, and (ii) partial oxidation of Fe(II) to Fe(III), > 55 % of which subsequently precipitates as Fe-oxyhydroxides. By contrast, the ?56Fe signature of stabilized dFe in the neutrally buoyant plume is ?0.3 to ?0.5 ‰. This cannot be explained by continued dilution of the buoyant plume with background seawater; rather, we suggest that isotope fractionation of dFe occurs during plume dilution due to Fe ligand complexation and exchange with labile particulate Fe. The ?56Fe signature of stabilized hydrothermal dFe in the East Scotia Sea is distinct from background seawater and may be used to quantify the hydrothermal dFe input to the ocean interior

A First Global Oceanic Compilation of Observational Dissolved Aluminum Data With Regional Statistical Data Treatment

Large national and international observational efforts over recent decades have provided extensive and invaluable datasets of a range of ocean variables. Compiled large datasets, structured, or unstructured, are a powerful tool that allow scientists to access and synthesize data collected over large spatial and temporal scales. The data treatment approaches for any element in the ocean could lead to new global perspectives of their distribution patterns and to a better understanding of large-scale oceanic processes and their impact on other biogeochemical cycles, which may not be evident otherwise. Ocean chemistry Big Data analysis may not just be limited to distribution patterns, but may be used to assess how sampling efforts and analytical methodologies can be improved. Furthermore, a systematic global scale assessment of data is important to evaluate the gaps in knowledge and to provide avenues for future research. In this context, here we provide an extensive compilation of oceanic aluminum (Al) concentration data from global ocean basins, including data available in the GEOTRACES Intermediate Data product (Schlitzer et al., 2018), but also thus far unpublished data

A meta-analytic review of stand-alone interventions to improve body image

Objective Numerous stand-alone interventions to improve body image have been developed. The present review used meta-analysis to estimate the effectiveness of such interventions, and to identify the specific change techniques that lead to improvement in body image. Methods The inclusion criteria were that (a) the intervention was stand-alone (i.e., solely focused on improving body image), (b) a control group was used, (c) participants were randomly assigned to conditions, and (d) at least one pretest and one posttest measure of body image was taken. Effect sizes were meta-analysed and moderator analyses were conducted. A taxonomy of 48 change techniques used in interventions targeted at body image was developed; all interventions were coded using this taxonomy. Results The literature search identified 62 tests of interventions (N = 3,846). Interventions produced a small-to-medium improvement in body image (d+ = 0.38), a small-to-medium reduction in beauty ideal internalisation (d+ = -0.37), and a large reduction in social comparison tendencies (d+ = -0.72). However, the effect size for body image was inflated by bias both within and across studies, and was reliable but of small magnitude once corrections for bias were applied. Effect sizes for the other outcomes were no longer reliable once corrections for bias were applied. Several features of the sample, intervention, and methodology moderated intervention effects. Twelve change techniques were associated with improvements in body image, and three techniques were contra-indicated. Conclusions The findings show that interventions engender only small improvements in body image, and underline the need for large-scale, high-quality trials in this area. The review identifies effective techniques that could be deployed in future interventions

Effects of Voice Pitch on Social Perceptions Vary With Relational Mobility and Homicide Rate

Fundamental frequency ( fo) is the most perceptually salient vocal acoustic parameter, yet little is known about how its perceptual influence varies across societies. We examined how fo affects key social perceptions and how socioecological variables modulate these effects in 2,647 adult listeners sampled from 44 locations across 22 nations. Low male fo increased men’s perceptions of formidability and prestige, especially in societies with higher homicide rates and greater relational mobility in which male intrasexual competition may be more intense and rapid identification of high-status competitors may be exigent. High female fo increased women’s perceptions of flirtatiousness where relational mobility was lower and threats to mating relationships may be greater. These results indicate that the influence of fo on social perceptions depends on socioecological variables, including those related to competition for status and mates

Rad3ATR Decorates Critical Chromosomal Domains with γH2A to Protect Genome Integrity during S-Phase in Fission Yeast

Schizosaccharomyces pombe Rad3 checkpoint kinase and its human ortholog ATR are essential for maintaining genome integrity in cells treated with genotoxins that damage DNA or arrest replication forks. Rad3 and ATR also function during unperturbed growth, although the events triggering their activation and their critical functions are largely unknown. Here, we use ChIP-on-chip analysis to map genomic loci decorated by phosphorylated histone H2A (γH2A), a Rad3 substrate that establishes a chromatin-based recruitment platform for Crb2 and Brc1 DNA repair/checkpoint proteins. Unexpectedly, γH2A marks a diverse array of genomic features during S-phase, including natural replication fork barriers and a fork breakage site, retrotransposons, heterochromatin in the centromeres and telomeres, and ribosomal RNA (rDNA) repeats. γH2A formation at the centromeres and telomeres is associated with heterochromatin establishment by Clr4 histone methyltransferase. We show that γH2A domains recruit Brc1, a factor involved in repair of damaged replication forks. Brc1 C-terminal BRCT domain binding to γH2A is crucial in the absence of Rqh1Sgs1, a RecQ DNA helicase required for rDNA maintenance whose human homologs are mutated in patients with Werner, Bloom, and Rothmund–Thomson syndromes that are characterized by cancer-predisposition or accelerated aging. We conclude that Rad3 phosphorylates histone H2A to mobilize Brc1 to critical genomic domains during S-phase, and this pathway functions in parallel with Rqh1 DNA helicase in maintaining genome integrity

Iron isotopes in seawater:method development and results from the Atlantic ocean

The analysis of the iron (Fe) isotopic composition of seawater can provide unique information about Fe sources to seawater, and Fe cycling within the oceans, which are important for understanding global climate because of the links between the marine carbon and iron cycles. The low dissolved Fe (dFe) concentrations found in seawater mean that analyses of the iron isotopic composition of seawater is an analytical challenge. This thesis describes the development methods for accurate and precise analysis of Fe isotopes in seawater with concentrations as low as ~0.4 nM Fe, and the results of iron isotope analysis of seawater samples from within the oxygen minimum zone (OMZ) of the tropical Atlantic Ocean, and the dissolved phase of hydrothermal plumes in the Southern Ocean.Briefly, Fe is preconcentrated from seawater using NTA resin and is then purified by anion exchange chromatography. Iron isotope ratios are determined by high resolution multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS, Thermo Fisher Neptune) and mass bias effects are corrected using a double-spike technique. The Fe isotope spike consists of 47 % of 57Fe, 53 % of 58Fe, and a small amount (&lt; 0.5 %) of 54Fe, which allows precise measurement of a wide range of sample to spike mixing ratios. Isotope ratios are expressed in delta notation (?56Fe), relative to 54Fe and relative to IRMM-14. The precision of the MC-ICPMS measurements is δ56Fe ~ 0.06 ‰ (2 SD), based on replicate analyses of two different iron isotope standards.The iron isotopic composition of dissolved Fe (δ56FedFe) was measured in seawater samples collected along an E-W transect along ~12 °N in the tropical Atlantic Ocean (GEOTRACES section GA06), extending from the Senegalese shelf towards the open ocean in order to assess the behaviour of dFe in the OMZ. Bottom waters within the OMZ have elevated dFe concentrations and low δ56Fe signatures, as low as ~ -0.3 ‰, which suggests that dFe is principally derived from sediment pore waters that have undergone dissimilatory iron reduction. Towards the open ocean, δ56FedFe values within the OMZ increase, due to formation of iron ligands and/or mixing with adjacent water masses. Dissolved aluminium concentrations in surface waters at the open ocean stations are very high (up to 27 nM), indicating significant supply from atmospheric dust, and the surface waters have high δ56Fe values (up to +0.5 ‰), much higher than bulk silicate Earth, indicating that Fe isotopes are fractionated during dust dissolution.Analyses of the Fe isotopic composition of dFe in hydrothermal plumes from 3 sites in the East Scotia Sea reveal that during the early stages of mixing between hydrothermal fluids and seawater, Fe isotopes are significantly fractionated from the vent fluid; the δ56FedFe value in the plume is as low as -1.2 ‰, compared to vent fluid values of -0.64 to +0.28 ‰. As the plume continues to mix with seawater, δ56FedFe values increase, converging to values of between -0.6 to -0.3 ‰. This strongly suggests that dFe is stabilised by the formation of colloidal Fe-(oxy)hydroxides and Fe-L in the distal parts of the plume. This stabilised dFe is likely to be transported long distances away from its source, contributing to the deep ocean dFe budget.<br/

Behaviour of chromium and chromium isotopes during estuarine mixing in the Beaulieu Estuary, UK

Rivers are the principal source of chromium (Cr) to seawater and the Cr isotopic signatures of ancient marine sediments are widely considered to provide a record of the presence or absence of oxidative weathering processes on land. This assumes, however, that the Cr value of river water is faithfully transferred to the oceans and is not modified in the estuarine mixing zone. To test this assumption we have determined the concentration and Cr values of inorganic Cr (Cr(III) + Cr(VI)), and also Cr speciation for water samples collected within the estuarine mixing zone of the Beaulieu River, UK. The Cr values of dissolved inorganic Cr ranged from −0.59 to 1.68‰, Cr(VI) concentrations from 0.39 to 1.83 nmol kg−1 and Cr(III) concentrations from 0.11 to 3.21 nmol kg−1. Both Cr(VI) concentrations and Cr values increased linearly as a function of salinity, while Cr(III) concentrations decreased linearly with salinity. Thus Cr, Cr(III) and Cr(VI) all showed conservative behaviour in the estuarine mixing zone, and the Cr signature of Beaulieu River water was modified only by mixing between the river and seawater endmembers. The calculated average Cr value of the river water endmember (−0.39 ± 0.08‰) was, however, lower than the range that has been observed in other rivers, which we attribute to input of organically-bound Cr(III) released by anoxic weathering processes. This is supported by the fact that Cr recovered by UV irradiation was found to have low Cr values (−0.11 to −0.75‰). While input of Cr from anoxic weathering processes is unlikely to be an important source of Cr to the oceans today, this suggests that processes other than oxidative weathering may have an influence on the Cr values of estuarine and coastal waters on the local scale. The Cr value of the coastal seawater endmember (1.6 ± 0.4‰) was also higher than the range observed in the deep open ocean, due to in situ biogeochemical cycling of Cr. These factors need to be considered in the interpretation of marine sedimentary Cr records

Atmospheric deposition fluxes over the Atlantic Ocean : a GEOTRACES case study

CITATION: Barraqueta, J., et al. 2019. Atmospheric deposition fluxes over the Atlantic Ocean : a GEOTRACES case study. Biogeosciences, 16:1525–1542. doi:10.5194/bg-16-1525-2019The original publication is available at https://www.biogeosciences.net/Atmospheric deposition is an important source of micronutrients to the ocean, but atmospheric deposition fluxes remain poorly constrained in most ocean regions due to the limited number of field observations of wet and dry atmospheric inputs. Here we present the distribution of dissolved aluminium (dAl), as a tracer of atmospheric inputs, in surface waters of the Atlantic Ocean along GEOTRACES sections GA01, GA06, GA08, and GA10. We used the surface mixed-layer concentrations of dAl to calculate atmospheric deposition fluxes using a simple steady state model. We have optimized the Al fractional aerosol solubility, the dAl residence time within the surface mixed layer and the depth of the surface mixed layer for each separate cruise to calculate the atmospheric deposition fluxes. We calculated the lowest deposition fluxes of 0.15±0.1 and 0.27±0.13 g m−2 yr−1 for the South and North Atlantic Ocean (>40∘ S and >40∘ N) respectively, and the highest fluxes of 1.8 and 3.09 g m−2 yr−1 for the south-east Atlantic and tropical Atlantic Ocean, respectively. Overall, our estimations are comparable to atmospheric dust deposition model estimates and reported field-based atmospheric deposition estimates. We note that our estimates diverge from atmospheric dust deposition model flux estimates in regions influenced by riverine Al inputs and in upwelling regions. As dAl is a key trace element in the GEOTRACES programme, the approach presented in this study allows calculations of atmospheric deposition fluxes at high spatial resolution for remote ocean regions.Department of Scientific Politics of the Basque GovernmentGEOMAR Helmholtz Center for Ocean Research Kielhttps://bg.copernicus.org/articles/16/1525/2019/Publisher’s versio