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The similarity of the average nitrogen-to-phosphorus ratios (N:P) in marine dissolved-inorganic and particulate-organic matter indicates tight links between those pools in the World Ocean. Here we analyse the sensitivity of marine biogeochemistry to variations in phytoplankton N and P subsistence quotas in an optimality-based ecosystem model coupled to the UVic Earth system model. Our results reveal distinct feedbacks between changes in the N and P quotas, N2 fixation, and denitrification that loosen the coupling between dissolved and particulate N:P. We demonstrate the importance of particulate N:C and P:C for regulating dissolved N:P on the global scale, with oxygen concentration being an important mediator. Our analysis also reveals a potential interdependence between phytoplankton stoichiometry and global equilibrium climate conditions.

We have synthesized several morphologies and crystal structures of MgWO 4 using a one-pot hydrothermal method, producing not only monoclinic stars and large nanoparticles but also triclinic wool balls and sub-10 nm nanoparticles. Herein we describe the importance of reaction parameters in demonstrating morphology control of as-prepared MgWO 4 . Moreover, we correlate structure and composition with the resulting photoluminescence and radioluminescence properties. Specifically, triclinic-phase samples yielded a photoluminescence emission of 421 nm, whereas monoclinic-phase materials gave rise to an emission maximum of 515 nm. The corresponding radioluminescence data were characterized by a broad emission peak, located at 500 nm for all samples. Annealing the wool balls and sub-10 nm particles to transform the crystal structure from a triclinic to a monoclinic phase yielded a radioluminescence (RL) emission signal that was two orders of magnitude greater than that of their unannealed counterparts. Finally, to confirm the practical utility of these materials for biomedical applications, a series of sub-10 nm particles, including as-prepared and annealed samples, were functionalized with biocompatible PEG molecules, and subsequently were found to be readily taken up by various cell lines as well as primary cultured hippocampal neurons with low levels of toxicity, thereby highlighting for the first time the potential of this particular class of metal oxides as viable and readily generated platforms for a range of biomedical applications.

The consideration of marine biogeochemistry is essential for simulating the carbon cycle in an Earth system model. Here we present the implementation and evaluation of a marine biogeochemical model, Model of Oceanic Pelagic Stoichiometry (MOPS) in the Flexible Ocean and Climate Infrastructure (FOCI) climate model. FOCI-MOPS enables the simulation of marine biological processes, the marine carbon, nitrogen and oxygen cycles, air-sea gas exchange of CO2 and O2, and simulations with prescribed atmospheric CO2 or CO2 emissions. A series of experiments covering the historical period (1850–2014) were performed following the DECK (Diagnostic, Evaluation and Characterization of Klima) and CMIP6 (Coupled Model Intercomparison Project 6) protocols. Overall, modelled biogeochemical tracer distributions and fluxes, as well as transient evolution in surface air temperature, air-sea CO2 fluxes, and changes of ocean carbon and heat, are in good agreement with observations. Modelled inorganic and organic tracer distributions are quantitatively evaluated by statistically-derived metrics. Results of the FOCI-MOPS model, also including sea surface temperature, surface pH, oxygen (100–600 m), nitrate (0–100 m), and primary production, are within the range of other CMIP6 model results. Overall, the evaluation of FOCI-MOPS indicates its suitability for Earth climate system simulations.

Nitrogen (N) is one of the crucial limiting nutrients for phytoplankton growth in the ocean. The main source of bioavailable N to the ocean is N2-fixing diazotrophs in the surface layer. Since the global coverage of N2 fixation observations is sparse on temporal and spatial scales, the fundamental processes and mechanisms controlling N2 fixation are not well understood nor constrained. We implement benthic denitrification in the optimality-based plankton ecosystem model (OPEM), which is incorporated into an Earth System Model of intermediate complexity (UVic-ESCM 2.9). Benthic denitrification occurs mostly in coastal upwelling regions and shallow continental shelves, and affects significantly the marine fixed-N budget since it is the largest N-loss process in the global ocean. We carry out model calibration and parameter selection based on observations of Chl, NO3-, PO43-, O2 and N*=NO3--16PO43-. Compared to considering water-column denitrification in suboxic zones as the only N-loss process in the ocean, our new model version simulates a more realistic distribution and higher global rates of N2 fixation, which are supported by independent rate measurements. The optimized cellular N:P ratios of diazotrophs in the model version with benthic denitrification better correspond to independent culture estimates, and result in a closer reproduction of the particulate N:P ratios. Our model results indicate that benthic denitrification plays an important role shaping patterns, rates and even physiological aspects of N2 fixation throughout the global ocean and should be accounted for when understanding and predicting changes to N2 fixation.

The factors that control the distribution of marine diazotrophs and their ability to fix N₂ are not fully elucidated. We discuss insights that can be gained from the emerging picture of a wide geographical distribution of marine diazotrophs and provide a critical assessment of environmental (bottom-up) versus trophic (top-down) controls. Expanding a simplified theoretical framework, we find that selective mortality on non-fixing phytoplankton is identified as a critical process that can broaden the ability of diazotrophs to compete for resources in top-down controlled systems and explain an expanded ecological niche for diazotrophs. Our simplified analysis predicts a larger importance of top-down control on competition patterns as resource levels increase. As selective mortality can control the faster growing phytoplankton, coexistence of the slower growing diazotrophs can be established. However, these predictions require corroboration by experimental and field data, together with the identification of specific traits of organisms and associated trade-offs related to selective top-down control. Elucidation of these factors could greatly improve our predictive capability for patterns and rates of marine N2fixation.

Description of the content of this code and data archive is available in the README.md in the archive.

The development of the dendrite and the axon during neuronal polarization underlies the directed flow of information in the brain. Seminal studies on axon development have dominated the mechanistic analysis of neuronal polarization. These studies, many originating from examinations in cultured hippocampal and cortical neurons in vitro, have established a prevalent view that axon formation precedes and is necessary for neuronal polarization. There is also in vivo evidence supporting this view. Nevertheless, the establishment of bipolar polarity, the leading edge, and apical dendrite development in pyramidal neurons in vivo occur when axon formation is prevented. Furthermore, recent mounting evidence suggest that directed mechanisms might mediate bipolar polarity/leading process and subsequent apical dendrite development. In the presence of spatially directed extracellular cues in the developing brain, these events may operate independently of axon forming events. In this perspective we summarize evidence in support of these evolving views in neuronal polarization and highlight recent findings on dedicated mechanisms acting in apical dendrite development.

The ability of marine diazotrophs to fix dinitrogen gas (N2) is one of the most influential yet enigmatic processes in the ocean. With their activity diazotrophs support biological production by fixing about 100–200 Tg N/year and turning otherwise unavailable dinitrogen into bioavailable nitrogen (N), an essential limiting nutrient. Despite their important role, the factors that control the distribution of diazotrophs and their ability to fix N2 are not fully elucidated. We discuss insights that can be gained from the emerging picture of a wide geographical distribution of marine diazotrophs and provide a critical assessment of environmental (bottom-up) versus trophic (top-down) controls. We expand a simplified theoretical framework to understand how top-down control affects competition for resources that determine ecological niches. Selective mortality, mediated by grazing or viral-lysis, on non-fixing phytoplankton is identified as a critical process that can broaden the ability of diazotrophs to compete for resources in top-down controlled systems and explain an expanded ecological niche for diazotrophs. Our simplified analysis predicts a larger importance of top-down control on competition patterns as resource levels increase. As grazing controls the faster growing phytoplankton, coexistence of the slower growing diazotrophs can be established. However, these predictions require corroboration by experimental and field data, together with the identification of specific traits of organisms and associated trade-offs related to selective top-down control. Elucidation of these factors could greatly improve our predictive capability for patterns and rates of marine N2 fixation. The susceptibility of this key biogeochemical process to future changes may not only be determined by changes in environmental conditions but also via changes in the ecological interactions.

Observational estimates point to pronounced changes of the Southern Ocean carbon uptake in the past decades, but the mechanisms are still not fully understood. In this study we assess physical drivers of the Southern Ocean carbon uptake variability in a suite of global ocean biogeochemistry models with 0.5º, 0.25º and 0.1º horizontal resolution as well as in a 3-member ensemble performed with an Earth System Model (ESM) sharing the same ocean biogeochemistry model. The ocean models show a positive trend of the Southern Ocean CO2 uptake in the past decades, with a weakening of its rate of increase in the 1990s. The 0.1º model exhibits the strongest trend in the Southern Ocean carbon uptake. Different physical drivers of the carbon uptake variability and of its trends (such as changes in stratification, ventilation, overturning circulation, and SST) are analyzed. A particular focus of this study is to assess the role of open-ocean polynyas in driving Southern Ocean carbon uptake. Open-ocean polynyas in the Southern Ocean have pronounced climate fingerprints, such as reduced sea-ice coverage, heat loss by the ocean and enhanced bottom water formation, but their role for the Southern Ocean carbon uptake has been as yet little studied. To this end we analyze conjunctly ESM simulations and an ocean-only sensitivity experiment where open-ocean polynyas are artificially created by perturbing the Antarctic freshwater runoff. We find that enhanced CO2 outgassing takes place during the polynya opening, because old carbon-rich waters come in contact with the atmosphere. The concomitant increased uptake of anthropogenic CO2 partially compensates the CO2 outgassing. When the polynya closes, the ocean CO2 uptake increases significantly, possibly fueled by abundant nutrients and higher alkalinity brought to the surface during the previous convective phase. Our results suggest that open-ocean polynyas could have a significant impact on the Southern Ocean CO2 uptake and could thus modulate its decadal variability.

Forty percent of the plastic produced annually ends up in the ocean. What happens to the plastic after that is poorly understood, though a growing body of data suggests it is rapidly spreading throughout the ocean. The mechanisms of this spread are not straightforward for small, weakly or neutrally buoyant plastic size fractions (the microplastics), in part because they aggregate in marine snow and are consumed by zooplankton. This biological transport pathway is suspected to be a primary surface microplastic removal mechanism, but exactly how it might work in the real ocean is unknown. We search the parameter space of a new microplastic model embedded in an earth system model to show biological uptake significantly shapes global microplastic inventory and distributions, despite its being an apparently inefficient removal pathway.

Uncertainties in projections from Earth system models (ESMs) are associated to a large degree with the imperfect representation of the marine plankton ecosystem, in particular the physiology of primary and secondary producers. Here we describe the implementation of an optimality-based plankton-ecosystem model (OPEM) with variable C:N:P stoichiometry in the University of Victoria ESM (UVic) and the behaviour of two calibrated reference configurations, which differ in the assumed temperature dependence of diazotrophs. Predicted tracer distributions of oxygen and dissolved inorganic nutrients are similar to those of an earlier fixed-stoichiometry model (Keller et al., 2012). Compared to the classic fixed-stoichiometry model, OPEM is closer to recent satellite-based estimates of net community production (NCP), despite overestimating net primary production (NPP), can better reproduce deep-ocean gradients in the NO3:PO43− ratio, and partially explains observed patterns of particulate C:N:P in the surface ocean. Allowing diazotrophs to grow (but not necessarily fix N2) at similar temperatures as other phytoplankton results in a better representation of surface Chl and NPP in the Arctic and Antarctic Oceans. Deficiencies of our calibrated OPEM configurations may serve as a magnifying glass for shortcomings in global biogeochemical models and hence guide future model development. The overestimation of NPP at low latitudes indicates the need for improved representations of temperature effects on biotic processes, as well as phytoplankton community composition, which may be represented by locally-varying parameters based on suitable trade-offs. Discrepancies between observed and predicted vertical gradients in particulate C:N:P ratios suggest the need to include preferential P remineralisation, which could also benefit the representation of N2 fixation. While OPEM yields a much improved distribution of surface N* (NO3− 16·PO43− + 2.9 mmol m−3), it still fails to reproduce observed N* in the Arctic, possibly related to a mis-representation of the phytoplankton community there and the lack of benthic denitrification in the model. Coexisting ordinary and diazotrophic phytoplankton can exert strong control on N* in our simulations, which questions the interpretation of N* as reflecting the balance of N2 fixation and denitrification.

We analyse 400 perturbed-parameter simulations for two configurations of an optimality-based plankton-ecosystem model (OPEM), implemented in the University of Victoria Earth-System Climate Model (UVic-ESCM), using a Latin-Hypercube sampling method for setting up the parameter ensemble. A likelihood-based metric is introduced for model assessment and selection of the model solutions closest to observed distributions of NO3−, PO43−, O2, and surface chlorophyll a concentrations. According to our metric the optimal model solutions comprise low rates of global N2 fixation and denitrification. These two rate estimates turned out to be poorly constrained by the data. For identifying the “best” model solutions we therefore also consider the model’s ability to represent current estimates of water-column denitrification. We employ our ensemble of model solutions in a sensitivity analysis to gain insights into the importance and role of individual model parameters as well as correlations between various biogeochemical processes and tracers, such as POC export and the NO3− inventory. Global O2 varies by a factor of two and NO3− by more than a factor of six among all simulations. Remineralisation rate is the most important parameter for O2, which is also affected by the subsistence N quota of ordinary phytoplankton (QN0,phy) and zooplankton maximum specific ingestion rate. QN0,phy is revealed as a major determinant of the oceanic NO3− pool. This indicates that unraveling the driving forces of variations in phytoplankton physiology and elemental stoichiometry, which are tightly linked via QN0,phy, is a prerequisite for understanding the marine nitrogen inventory.

The development of the apical dendrite from the leading process of the bipolar pyramidal neuron might be directed by spatially organized extrinsic cues acting on localized intrinsic determinants. The extracellular cues regulating apical dendrite polarization remain elusive. We show that leading process and apical dendrite development are directed by class III Semaphorins and mediated by a localized cGMP-synthesizing complex. The scaffolding protein Scribble that associates with the cGMP-synthesizing enzyme soluble guanylate cyclase (sGC) also associates with the Semaphorin3A (Sema3A) co-receptor PlexinA3. Deletion or knockdown of PlexinA3 and Sema3A or disruption of PlexinA3-Scribble association prevents Sema3A-mediated cGMP increase and causes defects in apical dendrite development. These manipulations also impair bipolar polarity and leading process establishment. Local cGMP elevation or sGC expression rescues the effects of PlexinA3 knockdown or PlexinA3-Scribble complex disruption. During neuronal polarization, leading process and apical dendrite development are directed by a scaffold that links Semaphorin cue to cGMP increase.

The current manuscript reports the first bioavailable radiogenic strontium isotope (87Sr/86Sr) data for Chavin de Huantar, a U.N.E.S.C.O. World Heritage site long recognized as one of the most important ceremonial centers of the Andean Formative Period. 87Sr/86Sr ratios were measured in local soil, vegetation, and archaeological and modern fauna from in and around the archaeological site. 87Sr/86Sr signatures from human tooth enamel from five Mariash-Recuay era (1–700 CE) individuals also were generated. Results indicate that 87Sr/86Sr values among soil, plants, and animals are relatively uniform, although the range of 87Sr/86Sr ratios within each category is broad. While in the present study, non-migrants and migrants were distinguishable based on their 87Sr/86Sr values, the wide range of Chavin's bioavailable 87Sr/86Sr signature might hinder the differentiation of local and non-local individuals in subsequent analyses. We caution that future 87Sr/86Sr applications at Chavin should consider both bioavailable 87Sr/86Sr signatures calculated from fauna, plants, and soil along with statistically analyzed human data when investigating evidence for residential mobility in the archaeological record.

Dissolved lead (Pb) concentrations and isotope ratios in seawater of the Western Philippine Sea (WPS) were determined to investigate sources of Pb in the region. Surface seawater concentrations at seven sampling stations ranged from 36.2 to 68.1 pmol kg − 1 . Isotopic composition of surface water, with 206 Pb/ 207 Pb ranging from 1.162 to 1.170, 208 Pb/ 207 Pb ranging from 2.445 to 2.451, and 206 Pb/ 204 Pb ranging from 18.14 to 18.27, reflects Asian anthropogenic aerosols input to the WPS. Shallow water Pb concentrations within the Kuroshio Current domain are about 15 pmol kg − 1 lower than at other sites and, together with a distinct isotopic signature ( 206 Pb/ 207 Pb = 1.167–1.170, 208 Pb/ 207 Pb = 2.447–2.451 and 206 Pb/ 204 Pb = 18.22–18.27), reflect water originating from the Equatorial Pacific that is relatively less impacted by contamination from anthropogenic inputs. An isotopically distinct sub-surface Pb maximum at about 100 to 250 m, representing water originating from the Western North Pacific where anthropogenic Pb deposition is high, was seen at all seven sites. Lead concentrations in deep water in the stations further from shore are typically lower than in the surface layer and ranged from 11.2 to 51.6 pmol kg − 1 . Lead isotopic signatures in deep water at these sites ( 206 Pb/ 207 Pb = 1.162–1.184; 208 Pb/ 207 Pb = 2.448–2.471; 206 Pb/ 204 Pb = 18.13–18.51) are offset from pre-anthropogenic values and suggest that anthropogenic sources have penetrated the deep water column. Elevated concentrations and isotopic signatures observed in the deep water at stations closer to shore, where sediment transport is prevalent, indicate that sedimentary input is a major source of dissolved Pb at these sites. Differences in Pb concentrations and isotopic signatures between samples collected from the Pacific Deep Water (PDW) water-mass during this study and those collected a decade ago suggest that Pb inputs even in deep water change on decadal scales.

Lead concentrations [Pb] and isotope ratios (Pb-206/Pb-207, Pb-208/Pb-207) have been measured in samples of total suspended particulate (TSP) aerosols, seawater, and suspended and sinking particles in the Gulf of Aqaba (GOA), Red Sea. Isotope ratios of Pb in seawater and in the soluble fraction of Pb in atmospheric TSP were similar suggesting that TSP is an important source of Pb in this area. Pb concentrations in seawater measured in this study (max 76.8 pmol kg(-1)) were much lower than those recorded at the same location in 2003-2004 (up to 1000 pmol kg(-1)). Changes in Pb isotope ratios in TSP depositions in these years indicate that leaded gasoline was responsible for the high dissolved Pb in GOA more than a decade ago and that recent regulation reduced Pb contamination. The similarity in Pb isotope ratios in suspended and sinking particles implies close interactions between these two size fractions. This study demonstrates the effect of the phasing out of leaded gasoline on TSP and seawater Pb chemistry in the Northern GOA; the rate of change in dissolved Pb concentrations in the GOA is faster than that reported for the open ocean possibly due to higher particle scavenging and the relatively short residence time of deep water in the Basin.

Atmospheric deposition can be an important source of nutrients and trace metals to oligotrophic alpine lakes, affecting their biogeochemistry. We measured trace metal concentrations and lead (Pb) isotope ratios in lake water, river water, ground water, and aerosol total suspended particles (TSP), as well as nutrient (NO3−, NH4+, PO43−) concentrations in TSP in the Tahoe Basin. The contribution of TSP deposition to the lake trace metal budget was assessed. Our results show seasonality in TSP and associated trace metal concentrations with higher concentrations during Oct – April. However, trace metal solubilities are higher during May – Sept, resulting in a higher contribution of soluble trace metals to the lake water. The source of most of the trace metals in TSP in the Lake Tahoe Basin is mineral dust; however, Zn, Cu, and Cd also have an anthropogenic origin. Among major nutrients, NO3− concentrations are slightly higher during Oct – April, while NH4+ and soluble reactive phosphorus (SRP) are higher during May – Sept. The distributions of trace metal concentrations and Pb isotopic ratios are homogenous throughout the lake water column, suggesting that the residence time of the trace metals in the lake is longer than the lake water mixing time. The contribution of atmospheric TSP deposition to the upper 20 m of lake water trace metal inventory is low, ranging from 0.03% for V to 5.7% for Mn. A triple-isotopes plot of Pb indicates that riverine and groundwater inputs are the major Pb sources, but aerosols still contribute some Pb to the lake. This article is part of a special issue entitled: “Cycles of trace elements and isotopes in the ocean – GEOTRACES and beyond” - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. Gonzalez.

Primary productivity in both the Arctic Ocean and the Gulf of Alaska (GOA) is nitrogen limited in the summer when light limitation is relieved, and stratification in the GOA inhibits nutrient fluxes from deep water sources. Concentrations of nutrients and trace metals in these regions are higher closer to shore, and thus rivers have been attributed as the primary coastal source of nutrients and trace metals. Here we evaluate the role of Submarine Groundwater Discharge (SGD), a previously unquantified source of nutrients and trace metals to the coastal Arctic Ocean and GOA. SGD is an especially enriched in nitrate relative to other nutrients, contributing 1.2 ± 0.4 mol NO 3 day − 1 m − 1 of shoreline of the Arctic Ocean. In the GOA, both SGD-associated nitrate flux (4.3 ± 2.1 NO 3 day − 1 m − 1 of shoreline) and silicate flux (13 ± 6 SiO 4 day − 1 m − 1 of shoreline), are substantial when compared to other external nutrient sources. Conservative extrapolations indicate overall SGD supplies more nitrate (1.5–17.5 times) to the GOA than rivers.

Bioassay incubation experiments conducted with nutrients and local atmospheric aerosol amendments indicate that phosphorus (P) availability limited phytoplankton growth in the low-nutrient low-chlorophyll (LNLC) ocean off Barbados. Atmospheric deposition provides a relatively large influx of new nutrients and trace metals to the surface ocean in this region in comparison to other nutrient sources. However, the impact on native phytoplankton is muted due to the high ratio of nitrogen (N) to P (NO3:SRP > 40) and the low P solubility of these aerosols. Atmospheric deposition induces P limitation in this LNLC region by adding more N and iron (Fe) relative to P. This favors the growth of Prochlorococcus, a genus characterized by low P requirements and highly efficient P acquisition mechanisms. A global three-dimensional marine ecosystem model that includes species-specific phytoplankton elemental quotas/stoichiometry and the atmospheric deposition of N, P, and Fe supports this conclusion. Future increases in aerosol N loading may therefore influence phytoplankton community structure in other LNLC areas, thereby affecting the biological pump and associated carbon sequestration.

Chinese coastal waters support vast fisheries and vital economies, but their productivity is threatened by increasingly frequent harmful algal blooms (HABs). Here we provide direct experimental evidence that atmospheric deposition, along with riverine input, opens new niches for bloom-forming dinoflagellates and diatoms in the East China Sea (ECS) by increasing the ratio of nitrogen to phosphorus (N:P), inducing severe P limitation, and altering trace metal micronutrient inventories. Remote sensing analysis of blooms in the region showed that dinoflagellate blooms were associated with increased aerosol optical thickness and decreased sea surface temperature, whereas diatom blooms were primarily associated with seasonally decreased temperature (e.g., during spring blooms). Bottle incubation experiments revealed that aerosol additions approximating 10 days of strong deposition increased iron availability and intensified P limitation, which together promoted dinoflagellate growth in offshore waters. Diatom growth was correlated with elevated trace metal and nutrient content from aerosols. Aerosols did not induce phytoplankton growth at a station within the Yangtze River plume where light was limiting, consistent with remote sensing observations that aerosol effects are stronger in offshore waters. Eutrophication and trace metal enrichment from Yangtze River discharge together with atmospheric deposition may underlie the transition from diatom-dominated spring blooms toward more frequent spring and summer dinoflagellate blooms that has occurred over the past three decades in the ECS.

This study explores the potential impacts of microbes deposited into the surface seawater of the southeastern Mediterranean Sea (SEMS) along with atmospheric particles on marine autotrophic and heterotrophic production. We compared in situ changes in autotrophic and heterotrophic microbial abundance and production rates before and during an intense dust storm event in early September 2015. Additionally, we measured the activity of microbes associated with atmospheric dry deposition (also referred to as airborne microbes) in sterile SEMS water using the same particles collected during the dust storm. A high diversity of prokaryotes and a low diversity of autotrophic eukaryotic algae were delivered to surface SEMS waters by the storm. Autotrophic airborne microbial abundance and activity were low, contributing ~1% of natural abundance in SEMS water and accounting for 1-4% to primary production. Airborne heterotrophic bacteria comprised 30-50% of the cells and accounted for 13-42% of bacterial production. Our results demonstrate that atmospheric dry deposition may supply not only chemical constitutes but also microbes that can affect ambient microbial populations and their activity in the surface ocean. Airborne microbes may play a greater role in ocean biogeochemistry in the future in light of the expected enhancement of dust storm durations and frequencies due to climate change and desertification processes.

A metal-wire-cutting bended monopole antenna (BMA) fed by mini-coaxial cable jointly with a thin printed ground-line which protrudes from ground-plane to be a balance-feed structure for bandwidth enhancement is proposed. A prototype of the proposed antenna with 40 mm in length, 6 mm in height and 5 mm in width has been fabricated and experimentally investigated. The human's hand effect on impedance bandwidth and radiation characteristics of the proposed antenna is studied. A prototype is designed to cover penta-band: CDMA (824-894 MHz), GSM (880-960 MHz), DCS (1710-1880 MHz), PCS (1850-1990 MHz) and WCDMA (1920-2170 MHz). Experimental results are shown to verify the validity of theoretical work.

A novel flow injection ion chromatograph (FI-IC) system has been developed to fully automate pretreatment procedures for multi-elemental analysis of trace metals in seawater by inductively coupled plasma mass spectrometer (ICPMS). By combining 10-port, 2 position and 3-way valves in the FI-IC manifold, the system effectively increase sample throughput by simultaneously processing three seawater samples online for: sample loading, injection, buffering, preconcentration, matrix removal, metal elution, and sample collection. Forty-two seawater samples can be continuously processed without any manual handing. Each sample pretreatment takes about 10 min by consuming 25 mL of seawater and producing 5 mL of processed concentrated samples for multi-elemental offline analysis by ICPMS. The offline analysis improve analytical precision and significantly increase total numbers of isotopes determined by ICPMS, which include the metals Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V, and Zn. The blank value and detection limits of trace metals using the system with ICPMS analysis all range from 0.1 to 10 parts per trillion (ppt), except Al, Fe, and Zn. The accuracy of the pretreatment system was validated by measuring open-ocean and coastal reference seawater, NASS-5 and CASS-4. Using the system with ICPMS analysis, we have obtained reliable trace metal concentrations in the water columns of the South China Sea. Possessing the features of full automation, high throughput, low blank, and low reagent volume used, the system automates and simplifies rigorous and complicated pretreatment procedures for multi-elemental analysis of trace metals in seawater and effectively enhances analytical capacity for trace metal analysis in environmental and seawater samples.

© 2015 Mackey, Chien, Post, Saito and Paytan. Atmospheric deposition is a major source of trace metals in marine surface waters and supplies vital micronutrients to phytoplankton, yet measured aerosol trace metal solubility values are operationally defined, and there are relatively few multi-element studies on aerosol-metal solubility in seawater. Here we measure the solubility of aluminum (Al), cadmium (Cd), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), and zinc (Zn) from natural aerosol samples in seawater over a 7 days period to (1) evaluate the role of extraction time in trace metal dissolution behavior and (2) explore how the individual dissolution patterns could influence biota. Dissolution behavior occurs over a continuum ranging from rapid dissolution, in which the majority of soluble metal dissolved immediately upon seawater exposure (Cd and Co in our samples), to gradual dissolution, where metals dissolved slowly over time (Zn, Mn, Cu, and Al in our samples). Additionally, dissolution affected by interactions with particles was observed in which a decline in soluble metal concentration over time occurred (Fe and Pb in our samples). Natural variability in aerosol chemistry between samples can cause metals to display different dissolution kinetics in different samples, and this was particularly evident for Ni, for which samples showed a broad range of dissolution rates. The elemental molar ratio of metals in the bulk aerosols was 23,189Fe: 22,651Al: 445Mn: 348Zn: 71Cu: 48Ni: 23Pb: 9Co: 1Cd, whereas the seawater soluble molar ratio after 7 days of leaching was 11Fe: 620Al: 205Mn: 240Zn: 20Cu: 14Ni: 9Pb: 2Co: 1Cd. The different kinetics and ratios of aerosol metal dissolution have implications for phytoplankton nutrition, and highlight the need for unified extraction protocols that simulate aerosol metal dissolution in the surface ocean.

Coastal California is a dynamic upwelling region where nitrogen (N) and iron (Fe) can both limit productivity and influence biogeochemistry over different spatial and temporal scales. With global change, the flux of nitrate from upwelling is expected to increase over the next century, potentially driving additional oceanic regions toward Fe limitation. In this study we explored the effect of changes in Fe/N ratio on native phytoplankton from five currently Fe-replete sites near the major California upwelling centers at Bodega Bay and Monterey Bay using nutrient addition incubation experiments. Despite the high nitrate levels (13–30 μ M) in the upwelled water, phytoplankton at three of the five sites showed increased growth when 10 μ M nitrate was added. None of the sites showed enhanced growth following addition of 10 nM Fe. Nitrate additions favored slow sinking single-celled diatoms over faster sinking chain-forming diatoms, suggesting that future increases in nitrate flux could affect carbon and silicate export and alter grazer populations. In particular, solitary cells of Cylindrotheca were more abundant than the toxin-producing genus Pseudonitzschia following nitrate addition. These responses suggest the biogeochemistry of coastal California could change in response to future increases in nitrate, and multiple stressors like ocean acidification and hypoxia may further result in ecosystem shifts.