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1.
J Hazard Mater ; 445: 130511, 2023 Mar 05.
Article in English | MEDLINE | ID: mdl-36463737

ABSTRACT

In the current scenario of global change, heavy metal pollution is of major concern because of its associated toxic effects and the persistence of these pollutants in the environment. This study is the first to evaluate the changes in heavy metal concentrations worldwide in brown algae over the last 90 years (>15,700 data across the globe reported from 1933 to 2020). The study findings revealed significant decreases in the concentrations of Cd, Co, Cr, Cu, Fe, Hg, Mn, Pb and Zn of around 60-84% (ca. 2% annual) in brown algae tissues. The decreases were consistent across the different families considered (Dictyotaceae, Fucaceae, Laminariaceae, Sargassaceae and Others), and began between 1970 and 1990. In addition, strong relationships between these trends and pH, SST and heat content were detected. Although the observed metal declines could be partially explained by these strong correlations, or by adaptions in the algae, other evidences suggest an actual reduction in metal concentrations in oceans because of the implementation of environmental policies. In any case, this study shows a reduction in metal concentrations in brown algae over the last 50 years, which is important in itself, as brown algae form the basis of many marine food webs and are therefore potential distributors of pollutants.


Subject(s)
Mercury , Metals, Heavy , Phaeophyceae , Water Pollutants, Chemical , Humans , Environmental Monitoring , Water Pollutants, Chemical/analysis , Metals, Heavy/analysis , Phaeophyceae/chemistry
2.
Sci Total Environ ; 780: 146379, 2021 Aug 01.
Article in English | MEDLINE | ID: mdl-33773349

ABSTRACT

The role of mangroves in sequestering metal and nutrients in sediment has been described in the past, but knowledge gaps still exist on storage capacity and recycling fluxes of elements in plant biomass, notably concerning their magnitude in root uptake and loss by litterfall. This study addresses the storage and transport pathways of 16 elements, classified as macro-nutrients (Ca, Mg, Na, K), micro-nutrients (Fe, Mn, Ni, Co, Cu, Cr, Zn, Mo), and potential toxicants (Al, Cd, Sn, Pb) in the world's largest mangroves, the Sundarbans. Elemental concentrations in plant organs were generally lower than in the sediment. The stock of macro and micro-nutrients in plant biomass varied from 60 to 2717 and 0.003 to 37.7 Mg ha-1 respectively, with highest values observed for Na and lowest for Cd. The Avicennia species exhibited the maximal accumulation of all elements. Translocation of major elements to different plant organs increased with increasing their concentrations in the sediment. Elemental loss via litterfall indicated that Sundarbans mangrove could act as a source, particularly of Mn, to the Bay of Bengal. Moreover, belowground uptake of the 16 elements showed 2-3 fold higher fluxes than their loss via litterfall. There was a significant retention of some trace elements (notably Mo, Cd, and Sn) in plant biomass, which might allow one to use these mangroves for phytoremediation and restoration purposes. We conclude that mangroves efficiently store and remobilize major and trace elements from the sediments by root uptake and recycle back to sediment surface via litterfall.


Subject(s)
Avicennia , Metals, Heavy , Trace Elements , Water Pollutants, Chemical , Environmental Monitoring , Geologic Sediments , Metals, Heavy/analysis , Trace Elements/analysis , Water Pollutants, Chemical/analysis , Wetlands
3.
Sci Total Environ ; 775: 145804, 2021 Jun 25.
Article in English | MEDLINE | ID: mdl-33631561

ABSTRACT

The seasonal and spatial variability of the CO2 system parameters and CO2 air-sea exchange were studied in the Northeast Atlantic Ocean between the northwest African coastal upwelling and the oligotrophic open-ocean waters of the North Atlantic subtropical gyre. Data was collected aboard a volunteer observing ship from February 2019 to February 2020. The seasonal and spatial variability of CO2 fugacity in seawater (fCO2,sw) was strongly driven by the seasonal temperature variation, which increased with latitude and was lower throughout the year in coastal regions where the upwelling and offshore transport was more intense. The thermal to biological effect ratio (T/B) was approximately 2, with minimum values along the African coastline related to higher biological activity in the upwelled waters. The fCO2,sw increased from winter to summer by 11.84 ± 0.28 µatm°C-1 on the inter-island routes and by 11.71 ± 0.25 µatm°C-1 along the northwest African continental shelf. The seasonality of total inorganic carbon normalized to constant salinity of 36.7 (NCT) was studied throughout the region. The effect of biological processes and calcification/dissolution on NCT between February and October represented >90% of the reduction of inorganic carbon while air-sea exchange described <6%. The seasonality of air-sea CO2 exchange was controlled by temperature. The surface waters of the entire region acted as a CO2 sink during the cold months and as a CO2 source during the warm months. The Canary basin acted as a net sink of -0.26 ± 0.04 molC m-2 yr-1. The northwest African continental shelf behaved as a stronger sink at -0.48 ± 0.09 molC m-2 yr-1. The calculated average CO2 flux for the entire area was -2.65 ± 0.44 TgCO2 yr-1 (-0.72 ± 0.12 TgC yr-1).

4.
Clin Exp Immunol ; 204(1): 78-95, 2021 04.
Article in English | MEDLINE | ID: mdl-33306195

ABSTRACT

Immune checkpoint therapy to reverse natural killer (NK) and T cell exhaustion has emerged as a promising treatment in various cancers. While anti-programmed cell death 1 (PD-1) pembrolizumab has recently gained Food and Drug Administration (FDA) approval for use in recurrent or metastatic cervical cancer, other checkpoint molecules, such as T cell immunoreceptor with immunoglobulin (Ig) and immunoreceptor tyrosine-based inhibition motif (ITIM) domains (TIGIT) and T cell immunoglobulin and mucin-domain containing-3 (Tim-3), have yet to be fully explored in this disease. We report expression of TIGIT, Tim-3 and PD-1 on subsets of peripheral blood NK (CD56dim/neg CD16bright/dim/neg and CD56bright CD16dim/neg ) and T cells. The percentages of these cells were increased in women with cervical cancer and pre-malignant lesions. PD-1+ NK and T cells were likely to co-express TIGIT and/or Tim-3. These cells, with an apparently 'exhausted' phenotype, were augmented in patients. A subset of cells were also natural killer group 2 member D (NKG2D)- and DNAX accessory molecule 1 (DNAM-1)-positive. PD-1int and PD-1high T cells were notably increased in cervical cancer. Soluble programmed cell death ligand 1 (PD-L1) was higher in cancer patient blood versus healthy donors and we observed a positive correlation between sPD-L1 and PD-1+ T cells in women with low-grade lesions. Within the cancer group, there were no significant correlations between sPD-L1 levels and cervical cancer stage. However, when comparing cancer versus healthy donors, we observed an inverse association between sPD-L1 and total T cells and a correlation between sPD-L1 and CD56dim NK cells. Our results may show an overview of the immune response towards pre-cancerous lesions and cervical cancer, perhaps giving an early clue as to whom to administer blocking therapies. The increase of multiple checkpoint markers may aid in identifying patients uniquely responsive to combined antibody therapies.


Subject(s)
B7-H1 Antigen/metabolism , Killer Cells, Natural/metabolism , Programmed Cell Death 1 Receptor/metabolism , T-Lymphocytes/metabolism , Uterine Cervical Neoplasms/metabolism , Adult , Antigens, Differentiation, T-Lymphocyte/metabolism , CD56 Antigen/metabolism , Female , Flow Cytometry/methods , Hepatitis A Virus Cellular Receptor 2/metabolism , Humans , Killer Cells, Natural/immunology , Middle Aged , NK Cell Lectin-Like Receptor Subfamily K/metabolism , Receptors, Immunologic/metabolism , T-Lymphocytes/immunology , Uterine Cervical Neoplasms/immunology , Uterine Cervical Neoplasms/pathology , Young Adult
5.
Appl Ergon ; 88: 103161, 2020 Oct.
Article in English | MEDLINE | ID: mdl-32678779

ABSTRACT

Laparoscopic surgery techniques are customarily used in non-invasive procedures. That said traditional surgical instruments and devices used by surgeons suffer from certain ergonomic deficiencies that may lead to physical complaints in upper limbs and back and general discomfort that may, in turn, affect the surgeon's skills during surgery. A novel design of the laparoscopic gripper handle is presented and compared with one of the most used instruments in this field in an attempt to overcome this problem. The assessment of the ergonomic feature of the novel design was performed by using time-frequency analysis of the surface electromyography (sEMG) signal during dynamic activities. Singular Spectrum Analysis (SSA) was used to decompose the sEMG signal and extract the median frequency of each muscle to assess muscle fatigue. The results reveal that using the proposed ergonomic grip reduces the mean values of the muscle activity during each of the proposed tasks. The novel design also improves the ease of use in laparoscopic surgery as it minimises high-pressure contact areas, reduces large amplitude movements and promotes a neutral position of the hand, wrist and forearm. Furthermore, the SSA method for time-frequency analysis provides a powerful tool to analyse a prescribed activity in ergonomic terms. The proposed methodology to assess muscle activity during surgery activities may be useful in the selection of surgical instruments when programming extended procedures, as it provides an additional selection criterion based on the surgeon's biomechanics and the proposed activity.


Subject(s)
Equipment Design , Ergonomics , Laparoscopy/instrumentation , Adult , Biomechanical Phenomena , Electromyography , Female , Forearm/physiology , Hand/physiology , Hand Strength/physiology , Humans , Male , Muscle Fatigue/physiology , Surgeons , Wrist/physiology , Young Adult
6.
J Nucl Cardiol ; 24(5): 1674-1679, 2017 10.
Article in English | MEDLINE | ID: mdl-27506703

ABSTRACT

BACKGROUND: While 18F-fluorodeoxyglucose and 18F-sodium fluoride with positron emission tomography relate with inflammation and calcification, their role in the assessment of patients with Takayasu arteritis has not yet been studied. METHODS: We present 5 patients with suspected active metabolic disease who underwent PET with 18F-fluorodeoxyglucose and 18F-sodium fluoride in order to explore the locations and correlations of 18F-fluorodeoxyglucose and 18F-sodium fluoride uptakes. Diagnosis of metabolic active disease was based on 18F-fluorodeoxyglucose uptake. RESULTS: We studied 3 female patients and 2 male patients. Median age was 29 years (min: 19 max: 63). In areas with atherosclerotic plaques, we found a negative correlation between 18F-sodium fluoride and 18F-fluorodeoxyglucose uptakes (r = -0.78) (P = .001). Meanwhile, in areas with only metabolic active disease, we found a positive correlation between 18F-sodium fluoride and 18F-fluorodeoxyglucose uptakes (r = 0.94) (P = .019). CONCLUSIONS: In Takayasu arteritis, 18F-sodium fluoride uptake can document different stages of metabolic disease, even in the absence of active metabolic disease or symptoms.


Subject(s)
Fluorine Radioisotopes/pharmacokinetics , Positron-Emission Tomography , Sodium Fluoride/pharmacokinetics , Takayasu Arteritis/diagnostic imaging , Adult , Aorta/diagnostic imaging , Calcinosis/diagnostic imaging , Female , Fluorodeoxyglucose F18/pharmacokinetics , Humans , Inflammation , Male , Middle Aged , Young Adult
7.
Environ Sci Pollut Res Int ; 23(21): 22136-22150, 2016 Nov.
Article in English | MEDLINE | ID: mdl-27543131

ABSTRACT

Although the industrial use of nanoparticles has increased over the past decade, the knowledge about their interaction with benthic phototrophic microorganisms in the environment is still limited. This study aims to characterize the toxic effect of ionic Ag+ and Ag nanoparticles (citrate-coated silver nanoparticles, AgNPs) in a wide concentration range (from 1 to 1000 µg L-1) and duration of exposure (2, 5 and 14 days) on three biofilm-forming benthic microorganisms: diatom Nitzschia palea, green algae Uronema confervicolum and cyanobacteria Leptolyngbya sp. Ag+ has a significant effect on the growth of all three species at low concentrations (1-10 µg L-1), whereas the inhibitory effect of AgNPs was only observed at 1000 µg L-1 and solely after 2 days of exposure. The inhibitory effect of both Ag+ and AgNPs decreased in the course of the experiments from 2 to 14 days, which can be explained by the progressive excretion of the exopolysaccharides and dissolved organic carbon by the microorganisms, thus allowing them to alleviate the toxic effects of aqueous silver. The lower impact of AgNPs on cells compared to Ag+ can be explained in terms of availability, internalization, reactive oxygen species production, dissolved silver concentration and agglomeration of AgNPs. The duration of exposure to Ag+ and AgNPs stress is a fundamental parameter controlling the bioaccumulation and detoxification in benthic phototrophic microorganisms.


Subject(s)
Biofilms/drug effects , Chlorophyta/drug effects , Cyanobacteria/drug effects , Diatoms/drug effects , Metal Nanoparticles/toxicity , Silver/toxicity , Water Pollutants, Chemical/toxicity , Biofilms/growth & development , Chlorophyta/physiology , Cyanobacteria/physiology , Diatoms/physiology , Time Factors
8.
J Appl Microbiol ; 121(4): 1130-43, 2016 Oct.
Article in English | MEDLINE | ID: mdl-27426967

ABSTRACT

AIM: The occurrence of virulence markers, serotypes and invasive ability were investigated in Shiga toxin-producing Escherichia coli (STEC) isolated from faecal samples of healthy dairy cattle at Rio de Janeiro State, Brazil. METHODS AND RESULTS: From 1562 stx-positive faecal samples, 105 STEC strains were isolated by immuno-magnetic separation (IMS) or plating onto MacConkey agar (MC) followed by colony hybridisation. Fifty (47·6%) strains belonged to nine serotypes (O8:H19, O22:H8, O22:H16, O74:H42, O113:H21, O141:H21, O157:H7, O171:H2 and ONT:H21). The prevalent serotypes were O157:H7 (12·4%), O113:H21 (6·7%) and O8:H19 (5·7%). Virulence genes were identified by polymerase chain reaction (PCR). E-hlyA (77·1%) was the more prevalent virulence marker, followed by espP (64·8%), saa (39%), eae (24·8%) and astA (21·9%). All O157:H7 strains carried the γ (gamma) variant of the locus of enterocyte effacement (LEE) genes and the stx2c gene, while the stx1/stx2 genotype prevailed among the eae-negative strains. None of the eae-positive STEC produced the localized adherence (LA) phenotype in HEp-2 or Caco-2 cells. However, intimate attachment (judged by the fluorescent actin staining test) was detected in some eae-positive strains, both in HEp-2 (23·1%) and in Caco-2 cells (11·5%). Most strains (87·5%) showed 'peripheral association' (PA) adherence phenotype to undifferentiated Caco-2 cells. Twenty-five (92·6%) of 27 strains invaded Caco-2 cells. The highest average value of invasion (9·6%) was observed among the eae-negative bovine strains from serotypes described in human disease. CONCLUSION: Healthy dairy cattle is a reservoir of STEC carrying virulence genes and properties associated with human disease. SIGNIFICANCE AND IMPACT OF THE STUDY: Although reports of human disease associated with STEC are scarce in Brazil, the colonization of the animal reservoir by potentially pathogenic strains offers a significant risk to our population.


Subject(s)
Cattle/microbiology , Disease Reservoirs/microbiology , Shiga-Toxigenic Escherichia coli/isolation & purification , Animals , Brazil , Caco-2 Cells , Escherichia coli Proteins/genetics , Escherichia coli Proteins/metabolism , Feces/microbiology , Humans , Polymerase Chain Reaction , Serotyping , Shiga Toxin/metabolism , Shiga-Toxigenic Escherichia coli/classification , Shiga-Toxigenic Escherichia coli/genetics , Shiga-Toxigenic Escherichia coli/physiology , Virulence/genetics , Virulence Factors/genetics , Virulence Factors/metabolism
9.
J Healthc Eng ; 20162016.
Article in English | MEDLINE | ID: mdl-27372383

ABSTRACT

An estimation of the water used for human consumption in hospitals is essential to determine possible savings and to fix criteria to improve the design of new water consumption models. The present work reports on cold water for human consumption (CWHC) in hospitals in Spain and determines the possible savings. In the period of 2005-2012, 80 Eco-Management and Audit Schemes (EMAS) from 20 hospitals were analysed. The results conclude that the average annual consumption of CWHC is 1.59 m(3)/m(2) (with a standard deviation of 0.48 m(3)/m(2)), 195.85 m(3)/bed (standard deviation 70.07 m(3)/bed), or 53.69 m(3)/worker (standard deviation 16.64 m(3)/worker). The results demonstrate the possibility of saving 5,600,000 m(3) of water per year. Assuming the cost of water as approximately 1.22 €/m(3), annual savings are estimated as 6,832,000 €. Furthermore, 2,912 MWh of energy could be saved, and the emission of 22,400 annual tonnes of CO2 into the atmosphere could be avoided.


Subject(s)
Conservation of Energy Resources , Hospitals , Water , Humans , Management Audit/organization & administration , Spain
10.
Environ Monit Assess ; 187(5): 270, 2015 May.
Article in English | MEDLINE | ID: mdl-25893759

ABSTRACT

Atmospheric inputs to forest ecosystems vary considerably over small spatial scales due to subtle changes in relief and vegetation structure. Relationships between throughfall fluxes (ions that pass through the canopy in water), topographic and canopy characteristics derived from sub-meter resolution light detection and ranging (LiDAR), and field measurements were compared to test the potential utility of LiDAR in empirical models of atmospheric deposition. From October 2012 to May 2013, we measured bulk (primarily wet) deposition and sulfate-S, chloride (Cl(-)), and nitrate-N fluxes beneath eight clusters of Douglas fir trees differing in size and canopy exposure in the Santa Cruz Mountains, California. For all trees sampled, LiDAR data were used to derive canopy surface height, tree height, slope, and canopy curvature, while tree height, diameter (DBH), and leaf area index were measured in the field. Wet season throughfall fluxes to Douglas fir clusters ranged from 1.4 to 3.8 kg S ha(-1), 17-54 kg Cl(-) ha(-1), and 0.2-4 kg N ha(-1). Throughfall S and Cl(-) fluxes were highest under clusters with large trees at topographically exposed sites; net fluxes were 2-18-fold greater underneath exposed/large clusters than all other clusters. LiDAR indices of canopy curvature and height were positively correlated with net sulfate-S fluxes, indicating that small-scale canopy surface features captured by LiDAR influence fog and dry deposition. Although tree diameter was more strongly correlated with net sulfate-S throughfall flux, our data suggest that LiDAR data can be related to empirical measurements of throughfall fluxes to generate robust high-resolution models of atmospheric deposition.


Subject(s)
Ecosystem , Environmental Monitoring/methods , Forests , Pseudotsuga/growth & development , Remote Sensing Technology , California , Light , Models, Theoretical , Plant Leaves/chemistry , Seasons , Trees/chemistry , Water/analysis
11.
Opt Express ; 23(6): 7366-84, 2015 Mar 23.
Article in English | MEDLINE | ID: mdl-25837079

ABSTRACT

Circular scan Spectral-Domain Optic Coherence Tomography imaging (SD-OCT) is one of the best tools for diagnosis of retinal diseases. This technique provides more comprehensive detail of the retinal morphology and layers around the optic disc nerve head (ONH). Since manual labelling of the retinal layers can be tedious and time consuming, accurate and robust automated segmentation methods are needed to provide the thickness evaluation of these layers in retinal disorder assessments such as glaucoma. The proposed method serves this purpose by performing the segmentation of retinal layers boundaries in circular SD-OCT scans acquired around the ONH. The layers are detected by adapting a graph cut segmentation technique that includes a kernel-induced space and a continuous multiplier based max-flow algorithm. Results from scan images acquired with Spectralis (Heidelberg Engineering, Germany) prove that the proposed method is robust and efficient in detecting the retinal layers boundaries in images. With a mean root-mean-square error (RMSE) of 0.0835 ± 0.0495 and an average Dice coefficient of 0.9468 ± 0.0705 pixels for the retinal nerve fibre layer thickness, the proposed method demonstrated effective agreement with manual annotations.

12.
J Colloid Interface Sci ; 435: 59-66, 2014 Dec 01.
Article in English | MEDLINE | ID: mdl-25218048

ABSTRACT

The adsorption of Zn onto the humic and illuvial horizons of the podzol soil in the presence of soil bacteria was studied using a batch-reactor technique as a function of the pH (from 2 to 9) and the Zn concentration in solution (from 0.076mM to 0.760mM). Exopolysaccharides-forming aerobic heterotrophs Pseudomonas aureofaciens were added at 0.1 and 1.0gwetL(-1) concentrations to two different soil horizons, and Zn adsorption was monitored as a function of the pH and the dissolved-Zn concentration. The pH-dependent adsorption edge demonstrated more efficient Zn adsorption by the humic horizon than the mineral horizon at otherwise similar soil concentrations. The Zn adsorption onto the EPS-poor strain was on slightly lower than that onto EPS-rich bacteria. Similar differences in the adsorption capacities between the soil and bacteria were also detected by "langmuirian" constant-pH experiments conducted in soil-Zn and bacteria-Zn binary systems. The addition of 0.1gwetL(-1)P. aureofaciens to a soil-bacteria system (4gdryL(-1)soil) resulted in statistically significant decrease in the adsorption yield, which was detectable from both the pH-dependent adsorption edge and the constant-pH isotherm experiments. Increasing the amount of added bacteria to 1gwetL(-1) further decreased the overall adsorption in the full range of the pH. This decrease was maximal for the EPS-rich bacteria and minimal for the EPS-poor bacteria (a factor of 2.8 and 2.2 at pH=6.9, respectively). These observations in binary and ternary systems were further rationalized by linear-programming modeling of surface equilibria that revealed the systematic differences in the number of binding sites and the surface-adsorption constant of zinc onto the two soil horizons with and without bacteria. The main finding of this work is that the adsorption of Zn onto the humic soil-bacteria system is lower than that in pure, bacteria-free soil systems. This difference is statistically significant (p<0.05). As such, EPS-rich bacteria are capable of efficiently shielding the soil particles from heavy-metal adsorption. The removal efficiency of heavy metals in an abiotic organic-rich soil system should therefore be significantly higher than that in the presence of bacteria. This effect can be explained by the shielding of strongly bound metal sites on the organic-rich soil particles by inert bacterial exopolysaccharides.

13.
Environ Sci Technol ; 48(14): 7933-41, 2014 Jul 15.
Article in English | MEDLINE | ID: mdl-24941285

ABSTRACT

The role played by the natural organic ligands excreted by the green algae Dunaliella tertiolecta on the Fe(II) oxidation rate constants was studied at different stages of growth. The concentration of dissolved organic carbon increased from 2.1 to 7.1 mg L(-1) over time of culture. The oxidation kinetics of Fe(II) was studied at nanomolar levels and under different physicochemical conditions of pH (7.2-8.2), temperature (5-35 °C), salinity (10-37), and dissolved organic carbon produced by cells (2.1-7.1 mg L(-1)). The experimental rate always decreased in the presence of organic exudates with respect to that in the control seawater. The Fe(II) oxidation rate constant was also studied in the context of Marcus theory, where ΔG° was 39.31-51.48 kJ mol(-1). A kinetic modeling approach was applied for computing the equilibrium and rate constants for Fe(II) and exudates present in solution, the Fe(II) speciation, and the contribution of each Fe(II) species to the overall oxidation rate constant. The best fit model took into account two acidity equilibrium constants for the Fe(II) complexing ligands with pKa,1=9.45 and pKa,2=4.9. The Fe(II) complexing constants were KFe(II)-LH=3×10(10) and KFe(II)-L=10(7), and the corresponding computed oxidation rates were 68±2 and 36±8 M(-1) min(-1), respectively.


Subject(s)
Chlorophyta/metabolism , Ferrous Compounds/metabolism , Iron/metabolism , Organic Chemicals/metabolism , Plant Exudates/metabolism , Seawater/chemistry , Ferrous Compounds/chemistry , Hydrogen-Ion Concentration , Iron/chemistry , Kinetics , Models, Chemical , Oxidation-Reduction , Salinity , Solutions , Temperature
14.
Sci Rep ; 4: 4050, 2014 Feb 13.
Article in English | MEDLINE | ID: mdl-24522173

ABSTRACT

Electronic orderings of charges, orbitals and spins are observed in many strongly correlated electron materials, and revealing their dynamics is a critical step toward undertsanding the underlying physics of important emergent phenomena. Here we use time-resolved resonant soft x-ray scattering spectroscopy to probe the dynamics of antiferromagnetic spin ordering in the manganite Pr0.7Ca0.3MnO3 following ultrafast photo-exitation. Our studies reveal a glass-like recovery of the spin ordering and a crossover in the dimensionality of the restoring interaction from quasi-1D at low pump fluence to 3D at high pump fluence. This behavior arises from the metastable state created by photo-excitation, a state characterized by spin disordered metallic droplets within the larger charge- and spin-ordered insulating domains. Comparison with time-resolved resistivity measurements suggests that the collapse of spin ordering is correlated with the insulator-to-metal transition, but the recovery of the insulating phase does not depend on the re-establishment of the spin ordering.

15.
J Colloid Interface Sci ; 415: 169-78, 2014 Feb 01.
Article in English | MEDLINE | ID: mdl-24267345

ABSTRACT

This study quantifies the adsorption of heavy metals on 4 typical moss species used for environmental monitoring in the moss bag technique. The adsorption of Cu(2+), Cd(2+), Ni(2+), Pb(2+) and Zn(2+) onto Hypnum sp., Sphagnum sp., Pseudoscleropodium purum and Brachytecium rutabulum has been investigated using a batch reactor in a wide range of pH (1.3-11.0) and metal concentrations in solution (1.6µM-3.8mM). A Linear Programming Model (LPM) was applied for the experimental data to derive equilibrium constants and the number of surface binding sites. The surface acid-base titration performed for 4 mosses at a pH range of 3-10 in 0.1M NaNO3 demonstrated that Sphagnum sp. is the most efficient adsorbent as it has the maximal number of proton-binding sites on the surface (0.65mmol g(-1)). The pKa computed for all the moss species suggested the presence of 5 major functional groups: phosphodiester, carboxyl, phosphoryl, amine and polyphenols. The results of pH-edge experiments demonstrated that B. rutabulum exhibits the highest percentage of metal adsorption and has the highest number of available sites for most of the metals studied. However, according to the results of the constant pH "Langmuirian" isotherm, Sphagnum sp. can be considered as the strongest adsorbent, although the relative difference from other mosses is within 20%. The LPM was found to satisfactorily fit the experimental data in the full range of the studied solution parameters. The results of this study demonstrate a rather similar pattern of five metal adsorptions on mosses, both as a function of pH and as a metal concentration, which is further corroborated by similar values of adsorption constants. Therefore, despite the species and geographic differences between the mosses, a universal adsorption edge and constant pH adsorption isotherm can be recommended for 4 studied mosses. The quantitative comparison of metal adsorption with other common natural organic and inorganic materials demonstrates that mosses are among the most efficient natural adsorbents of heavy metals.


Subject(s)
Bryophyta/chemistry , Environmental Monitoring/methods , Metals, Heavy/chemistry , Adsorption , Binding Sites , Bryophyta/physiology , Humans , Hydrogen-Ion Concentration , Kinetics , Models, Statistical , Protons , Species Specificity , Thermodynamics , Titrimetry
16.
Anal Bioanal Chem ; 406(5): 1567-71, 2014 Feb.
Article in English | MEDLINE | ID: mdl-24343454

ABSTRACT

The present paper describes a method based on the extraction of analytes by multiple hollow fibre liquid-phase microextraction and detection by ion-trap mass spectrometry and electron capture detectors after gas chromatographic separation. The limits of detection are in the range of 0.13-0.67 µg kg(-1), five orders of magnitude lower than those reached with the European Commission Official method of analysis, with three orders of magnitude of linear range (from the quantification limits to 400 µg kg(-1) for all the analytes) and recoveries in fortified olive oils in the range of 78-104 %. The main advantages of the analytical method are the absence of sample carryover (due to the disposable nature of the membranes), high enrichment factors in the range of 79-488, high throughput and low cost. The repeatability of the analytical method ranged from 8 to 15 % for all the analytes, showing a good performance.


Subject(s)
Liquid Phase Microextraction/instrumentation , Plant Oils/chemistry , Solvents/analysis , Chromatography, High Pressure Liquid , Gas Chromatography-Mass Spectrometry , Halogenation , Limit of Detection , Liquid Phase Microextraction/methods , Membranes, Artificial , Olive Oil , Reproducibility of Results
17.
Nano Lett ; 14(2): 774-82, 2014 Feb 12.
Article in English | MEDLINE | ID: mdl-24372258

ABSTRACT

A liquid metal filament supported on a dielectric substrate was directed to fragment into an ordered, mesoscale particle ensemble. Imposing an undulated surface perturbation on the filament forced the development of a single unstable mode from the otherwise disperse, multimodal Rayleigh-Plateau instability. The imposed mode paved the way for a hierarchical spatial fragmentation of the filament into particles, previously seen only at much larger scales. Ultimately, nanoparticle radius control is demonstrated using a micrometer scale switch.

18.
Sci Rep ; 3: 2299, 2013.
Article in English | MEDLINE | ID: mdl-23903555

ABSTRACT

Resonant elastic x-ray scattering (REXS) is an exquisite element-sensitive tool for the study of subtle charge, orbital, and spin superlattice orders driven by the valence electrons, which therefore escape detection in conventional x-ray diffraction (XRD). Although the power of REXS has been demonstrated by numerous studies of complex oxides performed in the soft x-ray regime, the cross section and photon wavelength of the material-specific elemental absorption edges ultimately set the limit to the smallest superlattice amplitude and periodicity one can probe. Here we show--with simulations and REXS on Mn-substituted Sr3Ru2O7--that these limitations can be overcome by performing resonant scattering experiments at the absorption edge of a suitably-chosen, dilute impurity. This establishes that--in analogy with impurity-based methods used in electron-spin-resonance, nuclear-magnetic resonance, and Mössbauer spectroscopy--randomly distributed impurities can serve as a non-invasive, but now momentum-dependent probe, greatly extending the applicability of resonant x-ray scattering techniques.


Subject(s)
Metals/chemistry , Models, Chemical , X-Ray Diffraction/methods , Computer Simulation , Electrons , Scattering, Radiation
19.
Sci Rep ; 3: 1140, 2013.
Article in English | MEDLINE | ID: mdl-23355953

ABSTRACT

The shallow submarine eruption which took place in October 10(th) 2011, 1.8 km south of the island of El Hierro (Canary Islands) allowed the study of the abrupt changes in the physical-chemical properties of seawater caused by volcanic discharges. In order to monitor the evolution of these changes, seven oceanographic surveys were carried out over six months (November 2011-April 2012) from the beginning of the eruptive stage to the post-eruptive phase. Here, we present dramatic changes in the water column chemistry including large decreases in pH, striking effects on the carbonate system, decreases in the oxygen concentrations and enrichment of Fe(II) and nutrients. Our findings highlight that the same volcano which was responsible for the creation of a highly corrosive environment, affecting marine biota, has also provided the nutrients required for the rapid recuperation of the marine ecosystem.

20.
Phys Rev Lett ; 108(23): 237202, 2012 Jun 08.
Article in English | MEDLINE | ID: mdl-23003984

ABSTRACT

The nature of the ferromagnetic, charge, orbital, and antiferromagnetic order in La0.35Pr0.275Ca0.375MnO3 on the nano- and microscale was investigated by photoemission electron microscopy (PEEM) and resonant elastic soft x-ray scattering (RSXS). The structure of the ferromagnetic domains around the Curie temperature T(C) indicates that they nucleate under a high degree of lattice strain, which is brought about by the charge, orbital, and antiferromagnetic order. The combined temperature-dependent PEEM and RSXS measurements suggest that the lattice distortions associated with charge and orbital order are glassy in nature and that phase separation is driven by the interplay between it and the more itinerant charge carriers associated with ferromagnetic metallic order, even well below T(C).

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