Ice sheet and precession controlled subarctic Pacific productivity and upwelling over the last 550,000 years.

The polar oceans play a vital role in regulating atmospheric CO2 concentrations (pCO2) during the Pleistocene glacial cycles. However, despite being the largest modern reservoir of respired carbon, the impact of the subarctic Pacific remains poorly understood due to limited records. Here, we present high-resolution, 230Th-normalized export productivity records from the subarctic northwestern Pacific covering the last five glacial cycles. Our records display pronounced, glacial-interglacial cyclicity superimposed with precessional-driven variability, with warm interglacial climate and high boreal summer insolation providing favorable conditions to sustain upwelling of nutrient-rich subsurface waters and hence increased export productivity. Our transient model simulations consistently show that ice sheets and to a lesser degree, precession are the main drivers that control the strength and latitudinal position of the westerlies. Enhanced upwelling of nutrient/carbon-rich water caused by the intensification and poleward migration of the northern westerlies during warmer climate intervals would have led to the release of previously sequestered CO2 from the subarctic Pacific to the atmosphere. Our results also highlight the significant role of the subarctic Pacific in modulating pCO2 changes during the Pleistocene climate cycles, especially on precession timescale ( ~ 20 kyr).

Fabrication of polyamide nanofiltration membrane with tannic acid/poly(sodium 4-styrenesulfonate) network-like interlayer for enhanced desalination performance.

The traditional polyamide composite nanofiltration membranes have high selectivity and low water permeance, so it is necessary to find strategies to raise the permeance. Herein, a novel polyamide nanofiltration membranes with high permeance were fabricated by coating a loose hydrophilic network-like interlayer, where tannic acid (TA) with pentapophenol arm structure binds to poly(4-styrenesulfonate) (PSS) polymer through hydrogen and ionic interactions. The effects of the network-like TA/PSS interlayer on surface morphology, surface hydrophobicity, and the interfacial polymerization mechanism were investigated. The outcomes demonstrated that the TA/PSS interlayer can offer a favorable environment for interfacial polymerization, enhance the hydrophilicity of the substrate membrane, and delay the release of piperazine (PIP). The optimized TFC-2 presents pure water flux of 22.7 ± 2.8 L m-2 h-1 bar-1, Na2SO4 rejection of 97.1 ± 0.5 %, and PA layer thickness of about 38.9 ± 2.5 nm. This provides new strategies for seeking to prepare simple interlayers to obtain high-performance nanofiltration membranes.

Quantitative source apportionment of heavy metals in sediments from the Bohai Sea, China.

In this study, the sources of nine heavy metals (Cd, As, Hg, Cu, Pb, Ni, Cr, Zn, and Co) in the sediments of the Bohai Sea were quantitatively identified through a positive factor matrix to provide better advice for marine and coastal management. In Bohai Sea sediments, most metals fell below detectable contamination levels, including As, Cu, Pb, Ni, Cr, Zn, and Co. Unfortunately, Bohai Sea sediments were moderately to significantly enrich with Cd and Hg, posing potentially adverse ecological risks to aquatic ecosystems. Our modeled results showed three factors representing natural, anthropogenic, and atmospheric deposition sources. Enriched Cd and Hg were likely derived from anthropogenic activities through river runoff and atmospheric deposition due to adjacent Zn smelting and chlor-alkali production, respectively. The other metals were mainly derived from natural sources.

Regional background determination and pollution assessment of heavy metals in the semi-closed Bohai Sea sediments.

Background metal concentrations are important in assessing pollution level of marine sediments; however, they can be significantly altered by local depositional environments, resulting in significant errors in regional pollution assessment. This study was based on the investigation of the background levels of heavy metals in the Bohai Sea sediments using sediment core, 2-sigma outlier, and regression methods. We also estimate the ecological risks of heavy metals for surface sediments collected from the Bohai Sea using the three methods mentioned above. Ecological risks of heavy metals calculated using the regression method show wide disparities and significant differences from those calculated using the sediment core and 2-sigma methods, indicating that the regression method is not suitable for the Bohai Sea, likely as a result of its complex sources. Conversely, the estimated ecological risks using the sediment core method are moderate, and most heavy metals, except for Hg and Cd, have negligible contamination.

Tubular palladium-based catalysts enhancing direct ethanol electrooxidation.

Direct ethanol fuel cell (DEFC) has the advantages of high power density, high energy conversion efficiency and environmental friendliness, but its commercialization is restricted by factors such as insufficient activity and low anti-poisoning ability of anode catalyst for incomplete oxidation of ethanol. It is of great significance to design and prepare anode catalyst with high activity and high anti-poisoning ability that can be recycled. In this work, tubular palladium-based (Pd-based) catalysts with abundant lattice defect sites were prepared by simple and reproducible electro-displacement reactions using Cu nanowires as sacrificial template. Pd is the main catalytic element which provides adsorption sites for ethanol oxidation. Ag and Cu introduced facilitates the formation of hydroxyl groups to oxidize toxicity intermediates, and changes the d-band center position of Pd, so as to adjust the adsorption and desorption of ethanol and its intermediates on the Pd surface. At the same time, Au introduced with high potential maintains the stability of the catalyst structure. The tubular structure exposes more active sites, improves the atomic utilization rate and enhances the ability of the catalyst resisting dissolution and aggregation. The series of PdAuAgCu tubular catalysts with outer layer dendrites were prepared by electro-displacement reactions using the mixture (ethylene glycol : ultra-pure water = 3 : 1) as the reaction solvent and fivefold twinned Cu nanowires as sacrificial template. The performance evaluation of ethanol electrocatalytic oxidation showed that the Pd17Au40Ag11Cu32 tubular catalysts were prepared at 120 °C and 10 mM CTAB had excellent overall performance, with a peak mass activity of 6335 mA mgPd-1, which was 9.6 times of Pd/C (JM). The residual current density after the stability test of 3000 s was 249 mA mgPd-1, which was 3.3 times of Pd/C (JM).

Biodiversity and oil degradation capacity of oil-degrading bacteria isolated from deep-sea hydrothermal sediments of the South Mid-Atlantic Ridge.

Studies have reported that various hydrocarbons and hydrocarbon-degrading bacteria are found in global deep-sea hydrothermal regions. However, little is known about degradation characteristics of culturable hydrocarbon-degrading bacteria from these regions. We speculate that these bacteria can be used as resources for the bioremediation of oil pollution. In this study, six oil-degrading consortia were obtained from the hydrothermal region of the Southern Mid-Atlantic Ridge through room-temperature enrichment experiments. The dominant oil-degrading bacteria belonged to Nitratireductor, Pseudonocardia, Brevundimonas and Acinetobacter. More varieties of hydrocarbon-degrading bacteria were obtained from sediments (preserved at 4 °C) near hydrothermal vents. Most strains had the ability to degrade high molecular weight petroleum components. In addition, Pseudonocardia was shown to exhibit a high degradation ability for phytane and pristine for the first time. This study may provide new insights into the community structure and biodiversity of culturable oil-degrading bacteria in deep-sea hydrothermal regions.

Distribution and assessment of heavy metal contents in surface sediments of the western Sunda Shelf.

The heavy metal contents (Cr, Cu, Zn, Cd, Pb, Hg, and As) of 88 surface sediment samples from the western Sunda Shelf were analyzed to determine their spatial distribution patterns and contamination status. The results demonstrated that high enrichment regions of heavy metals were focused in the Kelantan, Pahang, and Ambat river estuaries, and deep water regions of the study area. These high enrichment regions were mainly controlled by riverine inputs and their hydrodynamic conditions. The enrichment factor (EF), geoaccumulation index (Igeo), and potential ecological risk index (PERI) were used to assess heavy metal accumulation. The results indicated that the study area was not significantly contaminated overall at the time of the study; however, Cd, As, and Hg were at levels corresponding to moderate contamination at many stations located in the Pahang River estuary, Kelantan River estuary, and north-eastern region of the study area, primarily because of anthropogenic activities.

Reconstruction and evaluation of oil-degrading consortia isolated from sediments of hydrothermal vents in the South Mid-Atlantic Ridge.

In this study, sediments were collected from two different sites in the deep-sea hydrothermal region of the South Atlantic Ocean. Two microbial enrichment cultures (H7S and H11S), which were enriched from the sediments collected at two sample sites, could effectively degrade petroleum hydrocarbons. The bacterial diversity was analyzed by high-throughput sequencing method. The petroleum degradation ability were evaluated by gas chromatography-mass spectrometry and gravimetric analysis. We found that the dominant oil-degrading bacteria of enrichment cultures from the deep-sea hydrothermal area belonged to the genera Pseudomonas, Nitratireductor, Acinetobacter, and Brevundimonas. After a 14-day degradation experiment, the enrichment culture H11S, which was obtained near a hydrothermal vent, exhibited a higher degradation efficiency for alkanes (95%) and polycyclic aromatic hydrocarbons (88%) than the enrichment culture H7S. Interestingly, pristane and phytane as biomarkers were degraded up to 90% and 91% respectively by the enrichment culture H11S, and six culturable oil-degrading bacterial strains were isolated. Acinetobacter junii strain H11S-25, Nitratireductor sp. strain H11S-31 and Pseudomonas sp. strain H11S-28 were used at a density ratio of 95:4:1 to construct high-efficiency oil-degrading consortium H. After a three-day biodegradation experiment, consortium H showed high degradation efficiencies of 74.2% and 65.7% for total alkanes and PAHs, respectively. The degradation efficiency of biomarkers such as pristane and high-molecular-weight polycyclic aromatic hydrocarbons (such as CHR) reached 84.5% and 80.48%, respectively. The findings of this study indicate that the microorganisms in the deep-sea hydrothermal area are potential resources for degrading petroleum hydrocarbons. Consortium H, which was artificially constructed, showed a highly efficient oil-degrading capacity and has significant application prospects in oil pollution bioremediation.

Lead isotopes in the Central Yellow Sea Mud: Evidence of atmospheric deposition and its implication for regional energy consumption shift.

Anthropogenic activities have increased lead (Pb) emissions and impacted their spatiotemporal distributions in coastal seas. To quantify the increasing variability of Pb and identify the specific origins and their corresponding magnitudes, Pb and Pb isotopes are investigated in a well-placed sediment core covering the period of 1928-2008 in the Central Yellow Sea Mud (CYSM). The concentration of Pb varied from 27.17 µg/g to 37.30 µg/g upwardly along the core, with pronounced anthropogenic disturbance since the late 1960s. The Pb input history of the CYSM experienced five stages according to industrialization levels and Pb contamination, with relative pristine stages from 1928 to 1969 and human activity-impacted stages from 1969 to 2008. The 206Pb/207Pb ratio demonstrated an overall decreasing profile while the 208Pb/206Pb ratio displayed the reverse trend upwardly along the core, possibly due to the atmospheric delivery of anthropogenic Pb emissions from northern China. Furthermore, 208Pb/206Pb vs. 206Pb/207Pb shows certain linearity between natural sediment sources and anthropogenic emissions of Pb (atmospheric deposition); thus, atmospheric inputs account for 34-43% of the Pb in the sediment since Pb enrichment using the two-endmember mixing model. Moreover, the steep decrease in 206Pb/207Pb and rapid increase in 208Pb/206Pb since the 1970s suggest the introduction of leaded gasoline and the increasing proportionate consumption of gasoline relative to total energy consumption. The continuously decreasing 206Pb/207Pb ratio and increasing 208Pb/206Pb ratio since 2000 are the combined results of coal consumption, nonferrous smelting, and residual Pb contamination from leaded gasoline, which is quite distinctive from cases in North America and Europe. The relatively high 206Pb/207Pb and low 208Pb/206Pb ratios before 1969 represent the natural Pb isotopic signatures. Hence, Pb input is significantly affected by regional energy consumption and restructuring, and the Pb isotopic ratios may be a potential proxy for the shift in energy consumption.

Distribution and assessment of heavy metals in surface sediments from the Bohai Sea of China.

In this study, we analyzed heavy metals in 404 surface sediment samples from the Bohai Sea to measure contamination status and distribution. We found Zn levels to be the highest, whereas Hg concentrations were the lowest of measured heavy metals. We found that the samples containing the most heavy metals were those collected from Fuzhou Bay, Jinzhou Bay, central Bohai Sea mud area, and the Yellow River Delta. Further analyses suggest that these heavy metals in surface sediments in the Jinzhou Bay and Fuzhou Bay pose a serious ecological risk, with substantial Cd and Hg accumulation in the Jinzhou Bay and Yellow River Delta regions being indicative of intense human activities.

Distribution, sources and chemical screening-level assessment of toxic metals in the northern Bay of Bengal, Bangladesh.

The present study aims to examine the distribution, sources and potential risks of toxic metals in the northern Bay of Bengal, Bangladesh. We found Cu, Pb, Zn and Hg exhibited similar spatial distribution pattern. Influenced by the Ganges-Brahmaputra River and the Karnafuli River, there were higher concentrations of these metals associated with the finer sediment and higher TOC in the northeastern portion of the study area. Moreover, coal transportation was assumed to account for the distinctive spatial distribution of As with higher concentration down the Port of Chittagong in the eastern boundary. Chemical-screening level assessment demonstrated the majority of the metals exceeded the threshold effect values, indicating certain possibility of adverse effect. The concentrations of Ni were higher than the possible hazardous values, suggesting high possibility of harmful consequences. The uncontaminated sediments mainly distributed in northwestern and the central portions affected by the delta erosion and marine transported sediments.

Well-dispersed TiO2 nanoparticles anchored on Fe3O4 magnetic nanosheets for efficient arsenic removal.

Magnetic iron-titanium binary oxide as an effective adsorbent for arsenic contaminant is a challenge primarily because of their bulk structure and agglomeration effect. Herein, a novel and uniform sandwich-like magnetic Fe3O4@TiO2 sheets were synthesized by utilizing a facile strategy involving amorphous-to-crystalline transformation and reduction in H2, to achieve dispersed anatase TiO2 nanoparticles with a small size of ∼8 nm anchored on Fe3O4 sheets. The resultant Fe3O4@TiO2 sheets nanocomposite possessing a high specific surface area of ∼89.4 m2 g-1 and available magnetic susceptibility of ∼20.0 emu g-1, significantly enhanced the photocatalytic oxidation property of arsenite and considerable adsorption capability for arsenic removal. The adsorption capacities of As(V) and As(III) with UV-assisted from adsorption experimental results were 36.36 and 30.96 mg g-1, respectively, while the residual concentrations for both As(V) and As(III) were lower than the strict limit of 10 µg L-1. Adsorption equilibriums were almost reached within 45 min. In addition, the adsorbent exhibited excellent stability over a broad pH range of 3-9 and still maintained great removal efficiency after five time regeneration cycles. Furthermore, except for silicate and phosphate, the extremely weak inhibiting influences of common co-existing ions in arsenic removal process, demonstrated that the developed magnetic Fe3O4@TiO2 sheets with unique nanostructure could be a promising efficient adsorbent for arsenic removal.

Self-recoverable Pd-Ru/TiO2 nanocatalysts with ultrastability towards ethanol electrooxidation.

Self-recoverable Pd-Ru/TiO2 nanocatalysts have been prepared by electrochemical stripping of Pd-Ru/TiO2 precursors. For the ethanol oxidation reaction (EOR), these Pd-Ru/TiO2 nanocatalysts are used as an anode catalyst. The characterization of catalysts via chronoamperometry has been repeated 15 times. After 15 stability tests, the Pd1Ru0.69/TiO2 nanocatalysts still achieve a factor of 9.4 enhancement at the residual current density (309.42 mA mgPd-1) for the EOR over commercial Pd/C catalysts (33.01 mA mgPd-1). From the 5th to 15th test, when each 10 000 s stability test is performed in a fresh ethanol electrolyte, the initial and residual current density of the catalysts could recover to the original or even better value in a few hours before performing another 10 000 s stability test. Herein, these Pd-Ru/TiO2 nanocatalysts with ultrastability towards ethanol electrooxidation are self-recoverable. Density functional theory calculations reveal that the introduction of oxophilic metal Ru and a TiO2 support into Pd-based catalysts and the synergistic effects between Ru and TiO2 have led to the ultrastability towards the EOR. The introduction of oxophilic metal Ru and a TiO2 support into catalysts can reduce the adsorption energy of OHads on the Pd-Ru/TiO2 nanocatalysts, and it will inhibit the COads produced and adsorbed on the Pd surface.

Colorimetric Biosensor for Detection of Cancer Biomarker by Au Nanoparticle-Decorated Bi2Se3 Nanosheets.

The colorimetric biosensors have attracted intensive interest; however, their relatively low sensitivity limits their applications in clinic detection. Herein, we develop an effective colorimetric biosensor based on highly catalytic active Au nanoparticle-decorated Bi2Se3 (Au/Bi2Se3) nanosheets. Au/Bi2Se3 nanosheets are facilely synthesized by simply sonicating Au precursor with the as-synthesized Bi2Se3 nanosheets in aqueous solution. Because of the low redox potential and typical topological insulating properties, Bi2Se3 nanosheets is capable of providing and accumulating electrons on its surface. Such unique properties of Bi2Se3 nanosheets contribute to strong synergistic catalytic effects with Au nanoparticles, particularly when Au/Bi2Se3 nanosheets are utilized for catalyzing the reduction of 4-nitrophenol (4-NP) by NaBH4 (K = 386.67 s-1g-1). The excellent catalytic activity of Au/Bi2Se3 nanosheets can be "switched off" upon treatment of antibody of cancer biomarker such as anticarcinoembryonic antibody (anti-CEA). Addition of the corresponding antigen such as cancer biomarker carcinoembryonic antibody (CEA) can successively help "switch on" the catalytic activity of Au/Bi2Se3 nanosheets, where the resuming degree however depends on the antigen concentration. This cancer biomarker depended catalytic behavior therefore allows Au/Bi2Se3 nanosheets to be employed as a colorimetric sensor for detection of a particular cancer biomarker, for the reduction of 4-nitrophenol (4-NP) by NaBH4 itself involves apparent color change. The sensor shows high sensitivity and selectivity for the cancer biomarker, even for a concentration as low as 160 pg/mL for CEA, which fully satisfies the requirement for real clinical applications. The developed colorimetric sensor shows good generality for detection of different types of cancer biomarkers, such as α-fetoprotein (AFP) and prostate-specific antigen (PSA). Furthermore, real clinic sample analyzing result shows that the prepared biosensor is efficient for detection of CEA, providing an alternative method in cancer diagnosis.

Seaweed-Derived Route to Fe2O3 Hollow Nanoparticles/N-Doped Graphene Aerogels with High Lithium Ion Storage Performance.

We developed a nanoscale Kirkendall effect assisted method for simple and scalable synthesis of three-dimensional (3D) Fe2O3 hollow nanoparticles (NPs)/graphene aerogel through the use of waste seaweed biomass as new precursors. The Fe2O3 hollow nanoparticles with an average shell thickness of ∼6 nm are distributed on 3D graphene aerogel, and also act as spacers to make the separation of the neighboring graphene nanosheets. The graphene-Fe2O3 aerogels exhibit high rate capability (550 mA h g(-1) at 5 A g(-1)) and excellent cyclic stability (729 mA h g(-1) at 0.1 A g(-1) for 300 cycles), outperforming all of the reported Fe2O3/graphene hybrid electrodes, due to the hollow structure of the active Fe2O3 NPs and the unique structure of the 3D graphene aerogel framework. The present work represents an important step toward high-level control of high-performance 3D graphene-Fe-based NPs aerogels for maximizing lithium storage with new horizons for important fundamental and technological applications.

Direct solvothermal growth, crystal structures, and optical properties of one-dimensional lanthanide selenidoarsenate(v) polymers [Ln(dien)2(micro3-AsSe4)] (Ln = Nd, Sm): the first example of an AsSe4(3-) anion acting as a ligand to a lanthanide complex.

Two novel lanthanide selenidoarsenates(v) [Ln(dien)2(micro(3)-AsSe(4))] (Ln = Nd 1, Sm 2, dien = diethylenetriamine) were synthesized by the reactions of As(2)O(3) and Se with Nd(2)O(3) or Sm(2)O(3) in dien under solvothermal conditions. 1 and 2 are in the orthorhombic crystal system with Iba2 and Pbca space groups, respectively. The [AsSe(4)](3-) anion acts as a tridentate micro(3)-AsSe(4) ligand to bridge the lanthanide [Ln(dien)2](3+) complexes leading to one-dimensional neutral [Ln(dien)(2)(micro(3)-AsSe(4))](infinity) chains. The chains contact through hydrogen bonding to form network structures. The lanthanide center lies within a nine-coordinated environment involving six N atoms of two dien ligands and three Se atoms of two different tetrahedral [AsSe(4)](3-) anions forming a distorted monocapped square antiprism. The novel coordination polymers [Nd(dien)2(micro(3)-AsSe(4))](infinity) and [Sm(dien)2(micro(3)-AsSe(4))](infinity) are the first examples of solvothermally synthesized selenidoarsenates with [AsSe(4)](3-) anion acting as a ligand in lanthanide complexes. The band gaps of 2.11 eV for 1, and 2.18 eV for 2 have been derived from optical absorption spectra. TG-DSC curves show that two compounds remove coordinated dien ligands in a single step.