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One of the most important breakthroughs in oceanography in the last 30 years was the discovery that iron (Fe) controls biological production as a micronutrient, and our understanding of Fe and nutrient biogeochemical dynamics in the ocean has significantly advanced. In this review, we looked back both previous and updated knowledge of the natural Fe supply processes and nutrient dynamics in the subarctic Pacific and its impact on biological production. Although atmospheric dust has been considered to be the most important source of Fe affecting biological production in the subarctic Pacific, other oceanic sources of Fe have been discovered. We propose a coherent explanation for the biological response in subarctic Pacific high nutrient low chlorophyll (HNLC) waters that incorporates knowledge of both the atmospheric Fe supplies and the oceanic Fe supplies. Finally, we extract future directions for Fe oceanographic research in the subarctic Pacific and summarize the uncertain issues identified thus far.

Iron (Fe) is well known as a limiting factor to control primary productivity especially in high-nutrient and low chlorophyll area such as the subarctic Pacific. The solubility of Fe is believed to be controlled by its complexation with natural organic ligands, while the distribution of organic ligands is poorly understood. Here, we report that dissolved (

Aerosols and clouds play important roles in the Arctic climate. Conversely, aerosol emissions and cloud formation are affected by changes in the Arctic climate. This paper reviews studies of aerosols and clouds performed during the Arctic Challenge for Sustainability (ArCS) project carried out by the National Institute of Polar Research (NIPR) in Japan and collaborating institutions. The ArCS project included intensive studies of black carbon aerosols (BC). We installed Continuous Soot Monitoring System (COSMOS) instruments to measure atmospheric BC at four locations in the Arctic, establishing the Arctic BC COSMOS Measurement Network (ABCM-net). We also measured BC concentrations in snowpack in extensive areas of the Arctic and showed that previous studies have greatly overestimated BC in snowpack. We developed and improved new aerosol models that achieved better agreements with measurements of BC in the Arctic atmosphere, snowpack, and falling snow. We made new estimates of radiative forcing of BC in the Arctic atmosphere and snow/ice surfaces that lower their albedo. In addition to these researches on BC, we made accurate measurements of ice nucleating particles (INPs) at Ny-Alesund, Svalbard, showing that their concentrations increased in summer as a result of dust particle emissions from glacial outwash sediments. This high ice nucleating ability was likely due to the presence of organic substances mixed with the dust particles. We also made continuous cloud radar measurements and the first continuous in-situ measurements of cloud microphysical properties in the Arctic at Ny-Alesund. Results from these cloud measurements and their relationship with aerosols are described.

The toxicity and bioavailability of Cu in seawater were estimated using its chemical speciation. In this study, the concentrations and conditional stability constants (K'CuL) of Cu complexes with Cu-binding organic ligands (L) in seawater were determined using the reverse titration–competitive ligand exchange–adsorptive cathodic stripping voltammetry method. The concentrations of strong and weak ligands (L1 and L2, respectively) were determined using reverse titration via the addition of Cu to seawater samples to achieve ligand saturation. Our results revealed that the reverse titration method can be successfully used for the detection of high concentrations of L2. Using the reverse titration method, we detected L2 concentrations that exceeded 80 and 120 nM in seawater samples from the subtropical western North Pacific Ocean and Otsuchi Bay Japan, respectively. The K′CuL1 and K′CuL2 values obtained using the reverse titration method were comparable with those obtained using the forward titration method. Therefore, the reverse titration method can be used to determine the chemical speciation of Cu in the ocean and coastal regions as supplement to the more conventional forward titration method.

Distributions of trace metals (Mn, Fe, Ni, Zn and Cd) in the western Arctic Ocean (Chukchi Sea and Canada Basin) in September 2012 were investigated to elucidate the mechanisms behind the transport of these metals from the Chukchi Shelf to the Canada Basin. Filtered (, Deep Sea Research Part I: Oceanographic Research Papers, 116, pp.236-252; 2016

Total dissolved zinc (Zn) and its speciation was investigated by cathodic stripping voltammetry (CSV) in the western North Pacific and its marginal seas, the Sea of Okhotsk and the Sea of Japan (East Sea). In these high latitude areas, Zn complexing ligands in most samples were saturated with zinc because of the high dissolved Zn concentration. Relatively high total ligand concentrations (C L ) and relatively low conditional stability constants ( K Z n L , Z n 2 + ′ ) have been obtained in the surface waters of the Sea of Okhotsk (C L = 2.6 nM, log K Z n L , Z n 2 + ′ = 9.5) and the Sea of Japan (East Sea) (C L = 1.3 nM, log K Z n L , Z n 2 + ′ = 9.1) compared with those in the open ocean (subtropical and subarctic North Pacific, C L = 0.2–1.2 nM, log K ' Z n L , Z n 2 + = 9.1–10.8). The fraction of Zn labile in the deep waters of the Sea of Okhotsk was relatively small (34–38%, > 1479 m), which might indicate the presence of high concentrations of Zn complexing ligands in deep waters of the Sea of Okhotsk. In the western North Pacific, positive relationships were obtained between total ligand and chlorophyll a concentrations, suggesting that Zn complexing ligands in the surface water might be derived from bacteria and phytoplankton in the western North Pacific. However, relatively high concentrations of the ligands exist in low chlorophyll- a surface water in the Sea of Okhotsk and the Sea of Japan (East Sea), implying that Zn complexed ligands in those marginal seas have a different origin.

With the common goal of more accurately and consistently quantifying ambient concentrations of free metal ions and natural organic ligands in aquatic ecosystems, researchers from 15 laboratories that routinely analyze trace metal speciation participated in an intercomparison of statistical methods used to model the most widely-obtained type of experimental dataset, the complexometric titration. All were asked to apply statistical techniques that they felt comfortable using to model synthetic titration curves that are typical of those obtained by applying state-of-the-art electrochemical methods – anodic stripping voltammetry (ASV) and competitive ligand equilibration/adsorptive cathodic stripping voltammetry (CLE-ACSV) – to the analysis of natural waters. Herein, we compare our estimates for parameters describing the natural ligands, examine the accuracy of inferred ambient free metal ion concentrations ([Mf]), and evaluate the influence of the various methods and assumptions used in analyzing the data on these results. The ASV- type titrations were designed to test each participants’ ability to correctly describe the natural ligands present in a sample when provided with data free of measurement error, i.e., random noise. For the three virtual samples containing just one natural ligand, all participants were able to correctly identify the number of ligand classes present and accurately estimate their parameter values. For the four virtual samples containing two or three ligand classes, a few participants detected too few or too many classes and consequently reported inaccurate “measurements” of ambient [Mf]. Since the problematic results arose from human error rather than any specific method of analyzing the data, we recommend that analysts should make a practice of using one’s parameter estimates to generate simulated (back-calculated) titration curves for comparison to the original data. The root-mean squared difference between the fitted observations and simulated curves should be comparable to the expected error of the analytical method and upon visual inspection the distribution of residuals should be unskewed. Modeling the synthetic, CLE-ACSV-type titration dataset proved to be more challenging. The participants were provided with five distinct titration curves generated at different levels of competing ligand added (analytical windows) to the virtual sample. Random measurement error was also incorporated. Comparison of the submitted results was complicated by the differing interpretations of our task. Most adopted the provided “true” instrumental sensitivity in modeling the CLE- ACSV curves, but several estimated sensitivities using internal calibration, exactly as is required for actual samples. Since the fitted sensitivities were biased low, systematic biases in inferred ambient [Mf] and in estimated weak ligand (L2) concentrations resulted from their use. The main distinction between the mathematical approaches taken by participants lies in their choice of the speciation model equation/function, with its implicit definition of independent and dependent variables. In “direct modeling”, the dependent variable is the measured [Mf] (or Ip) and the total metal concentration ([M]T) considered independent. In other, much more widely used methods of analyzing titration data – classical linearization, best known as van den Berg/Ružić, and isotherm fitting by nonlinear regression, best known as the Langmuir or Gerringa methods – [Mf] is defined as independent and the dependent variable derived from a calculation that involves both [M]T and [Mf]. Close inspection of the biases and variability in the estimates of ligand parameters and in predictions of ambient [Mf] revealed that the best results were obtained by the first approach. Linear regression of transformed data yielded the largest bias and greatest variability, while non-linear isotherm fitting generated results with mean bias comparable to direct modeling, but also with greater variability. Participants that performed a unified analysis of ACSV titration curves at multiple detection windows for a sample improved their results regardless of the basic mathematical approach taken. Overall, the three most accurate sets of results were obtained using automated-unified analysis while the single most accurate set of results combined simultaneous calibration and parameter estimation. We therefore recommend that where sample volume and time permit, titration experiments for all natural water samples be designed to include two or more detection windows, especially for coastal and estuarine waters. It is vital that even more practical experimental designs for multi-window titrations be developed. In addition, while nearly every mathematical approach can prove to be adequate for some datasets, matrix-based equilibrium models are most naturally suited to the task for all datasets and can most easily handle the challenges encountered in this work, i.e., the cases where the added ligand in ACSV became titrated. The ProMCC program (Omanović et al., this issue) as well as the Excel Add-in based KINETEQL Multiwindow Solver spreadsheet (Hudson, 2014) have this capability and have been made available for public use as a result of this intercalibration exercise.

The distributions of dissolved iron (Fe), Fe(II) and Fe(III)-binding organic ligands were investigated in the upper 1000 m of the eastern tropical South Pacific from January to March 2010, during an El Nino event. Dissolved Fe concentrations were exceedingly low in surface waters, showed minima near the chlorophyll maxima, and increased below that depth. High rates of nitrogen fixation have been inferred for this region from models, but our data suggest that surface Fe is frequently too low to support diazotrophs. Dissolved Fe and organic Fe(III) ligand concentrations at mid-depth were elevated in the nearshore stations, where virtually all dissolved Fe(III) was bound to these ligands. Subsurface Fe(II) maxima were observed in the secondary nitrite maxima of the oxygen minimum zone (OMZ), comprising 8 to 68% of dissolved Fe. Dissolved Fe concentrations displayed local maxima coinciding with the maxima in Fe(II) and nitrite. We propose that this zone, the most reducing part of the OMZ, plays an important role in Fe transport in the upper 400 m of the water column.

Copper (Cu) complexation and distribution were characterized using competitive ligand exchange adsorptive cathodic stripping voltammetry and isotope dilution inductively coupled plasma mass spectrometry along two transects (20°S and 10°S) in the eastern tropical South Pacific. In the southern and westernmost stations, Cu showed upper water column depletion to values as low as ∼ 0.26 nmol L−1, the lowest concentrations ever reported. However, Cu levels were much higher within the secondary nitrite maxima of the oxygen minimum zone (OMZ) in the northern (10°S) transect. The enrichment of Cu in the reducing conditions of the OMZ has not been reported before and probably reflects remineralization and offshore transport from the shelf. Free [Cu2+] was typically low throughout the water column, ranging from about 3.15 × 10−15 mol L−1 to 1.34 × 10−13 mol L−1, and depth profiles exhibited similar features to those for dissolved Cu, though they showed more variability near the surface. Offshore and beyond the influence of the OMZ, the lowest dissolved and free [Cu2+] was within the primary nitrite maxima (PNM), where ammonia oxidation and nitrate reduction rates are important. This finding is of interest because the two competing explanations for the PNM—iron limitation of diatoms and high rates of ammonia oxidation relative to nitrite oxidation—have high Cu requirements. The low concentrations of free Cu2+ measured here could impose significant constraints on the rates of these processes.

We use the NASA GEOS-5 transport model with tagged tracers to investigate the contributions of different regional sources of CO and black carbon (BC) to their concentrations in the Western Arctic (i.e., 50–90° N and 190–320° E) in spring and summer 2008. The model is evaluated by comparing the results with airborne measurements of CO and BC from the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) field campaigns to demonstrate the strengths and limitations of our simulations. We also examine the reliability of tagged CO tracers in characterizing air mass origins using the measured fossil fuel tracer of dichloromethane and the biomass burning tracer of acetonitrile. Our tagged CO simulations suggest that most of the enhanced CO concentrations (above background level from CH4 production) observed during April originate from Asian anthropogenic emissions. Boreal biomass burning emissions and Asian anthropogenic emissions are of similar importance in July domain wise, although the biomass burning CO fraction is much larger in the area of the ARCTAS field experiments. The fraction of CO from Asian anthropogenic emissions is larger in spring than in summer. European sources make up no more than 10% of CO levels in the campaign domain during either period. Comparisons of CO concentrations along the flight tracks with regional averages from GEOS-5 show that the along-track measurements are representative of the concentrations within the large domain of the Western Arctic in April but not in July.

The concentration of iron(II) (Fe(II)) in seawater was investigated throughout the water column in the Arabian Sea and western tropical Indian Ocean including the oxygen minimum zone (OMZ) as part of the 2009 Japanese GEOTRACES cruise using a luminol-chemiluminescence detection based flow injection analysis technique. A novel modification was the adjustment of the sample pH to 7.2 with a 3-(N-morpholino) propanesulfonic acid (MOPS) buffer to minimize Fe(II) oxidation during sampling. At stations in the Arabian Sea OMZ, Fe(II) had subsurface maxima in the oxygen-deficient and high nitrite layers; fully 7–29% of total dissolved Fe existed as Fe(II) in these samples. Subsurface Fe(II) maxima were not observed in stations south of the oxygen minimum zone. Within the OMZ, the distribution of Fe(II) resembled previous data obtained during the 2004 southwest monsoon, indicating that the Fe(II) maxima are seasonally and interannually persistent feature. These results confirm the close relationship between Fe(II) and the secondary nitrite maxima and suggest that the rich microbial community within this feature is closely involved with Fe redox cycling. Fe(II) concentrations near the seafloor were elevated in locations underlying the OMZ but nowhere else, possibly reflecting inputs from reducing sediments. To the south, a clear maximum in dissolved Fe from the Rodriguez Triple Junction hydrothermal system showed no evidence of Fe(II). The center location of the Rodriguez Triple Junction is 25° 35′S, 70° 00′E ( Gamo et al., 2001 ), more than 800 km southwest of station ER10 (the closest station), so hydrothermally-derived Fe(II) was probably oxidized.

Measurements of ambient OH and HO2 radicals were performed by laser induced fluorescence (LIF) during CAREBeijing2006 (Campaigns of Air Quality Research in Beijing and Surrounding Region 2006) at the suburban site Yufa in the south of Beijing in summer 2006. On most days, local air chemistry was influenced by aged air pollution that was advected by a slow, almost stagnant wind from southern regions. Observed daily concentration maxima were in the range of (4–17) × 106 cm−3 for OH and (2–24) × 108 cm−3 for HO2 (including an estimated interference of 25% from RO2). During daytime, OH reactivities were generally high (10–30 s−1) and mainly contributed by observed VOCs and their calculated oxidation products. The comparison of modelled and measured HOx concentrations reveals a systematic underprediction of OH as a function of NO. A large discrepancy of a factor 2.6 is found at the lowest NO concentration encountered (0.1 ppb), whereas the discrepancy becomes insignificant above 1 ppb NO. This study extends similar observations from the Pearl-River Delta (PRD) in South China to a more urban environment. The OH discrepancy at Yufa can be resolved, if NO-independent additional OH recycling is assumed in the model. The postulated Leuven Isoprene Mechanism (LIM) has the potential to explain the gap between modelled and measured OH at Beijing taking into account conservative error estimates, but lacks experimental confirmation. This and the hereby unresolved discrepancy at PRD suggest that other VOCs besides isoprene might be involved in the required, additional OH recycling. Fast primary production of ROx radicals up to 7 ppb h−1 was determined at Beijing which was dominated by the photolysis of O3, HONO, HCHO, and dicarbonyls. For a special case, 20 August, when the plume of Beijing city was encountered, a missing primary HOx source (about 3 ppb h−1) was determined under high NOx conditions similar to other urban areas like Mexico City. CAREBeijing2006 emphasizes the important role of OVOCs as a radical source and sink, and the need for further investigation of the chemical degradation of VOCs in order to better understand radical chemistry in VOC-rich air.

The spatial distribution of dissolved organic carbon (DOC) concentrations and the optical properties of dissolved organic matter (DOM) determined by ultraviolet-visible absorbance and fluorescence spectroscopy were measured in surface waters of the southern Chukchi Sea, western Arctic Ocean, during the early summer of 2013. Neither the DOC concentration nor the optical parameters of the DOM correlated with salinity. Principal component analysis using the DOM optical parameters clearly separated the DOM sources. A significant linear relationship was evident between the DOC and the principal component score for specific water masses, indicating that a high DOC level was related to a terrigenous source, whereas a low DOC level was related to a marine source. Relationships between the DOC and the principal component scores of the surface waters of the southern Chukchi Sea implied that the major factor controlling the distribution of DOC concentrations was the mixing of plural water masses rather than local production and degradation.

The influence of organic ligands on natural phytoplankton growth was investigated in high-nitrate low-chlorophyll (HNLC) waters and during a phytoplankton bloom induced by a mesoscale iron enrichment experiment (SEEDS II) in the western subarctic Pacific. The growth responses of the phytoplankton in the treatments with iron complexed with model ligand were compared with those with inorganic iron or a control. Desferrioxamine B and protoporphyrin IX were used as models for hydroxamate-type siderophore and tetrapyrrole-type cell breakdown ligand, respectively. In the HNLC water, iron associated with protoporphyrin IX especially stimulated smaller phytoplankton (

Black carbon (BC) aerosols alter the radiation budget both directly (by absorbing solar visible radiation) and indirectly (by acting as cloud condensation nuclei) and cause adverse health effects. The absorbing efficiency and direct radiative effect of BC strongly depend on its mass concentration (MBC) and type of emission source. In the present study, we report measurements of MBC at the Research Center for Advanced Science and Technology (RCAST), located at the center of the urban boundary of Tokyo, using an EC-OC analyzer from 2003 to 2005 and a filter-based Continuous Soot Monitoring System (COSMOS) during 2007–2010. The results indicate that MBC have decreased significantly from 2.6 μg m−3 to 0.5 μg m−3 (∼80% reduction) between 2003 and 2010. Vehicular emissions are the dominant source of BC in Tokyo, and the observed reduction in MBC is mainly attributed to the stringent regulations of particulate matter exhaust from vehicles imposed by the Japanese government. In addition, this observation is also supported from emission estimates using diurnal-weekly variations of MBC in Tokyo and explains the observed reduction to within about 20%. This is the first clear evidence of a significant reduction in BC emissions in Tokyo and shows that measures taken to reduce BC emissions from traffic sources have a strong effect on air quality in a mega-city and also reduce the climate impact of traffic emissions. We highlight the importance of long-term and reliable measurements in detecting BC trends and for the validation and regulation of emission control measures in mega-cities.

Characterization of the speciation of iron and copper is an important objective of the GEOTRACES Science Plan. To incorporate speciation measurements into such a multinational program, standard practices must be adopted that allow data from multiple labs to be synthesized. Competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) is the primary technique employed for measuring metal-binding ligands and determining metal speciation in seawater. The determination of concentrations and conditional stability constants of metal-binding ligands is particularly challenging, as results can be influenced both by experimental conditions and interpretation of titration data. Here, we report an investigation between four laboratories to study the speciation of iron and copper using CLE-ACSV. Samples were collected on the GEOTRACES II intercomparison cruise in the North Pacific Ocean in May 2009 at 30° N, 140° W. This intercomparison was carried out shipboard and included an assessment of the viability of sample preservation by freezing. Results showed that consensus values could be obtained between different labs, but that some existing practices were problematic and require further attention in future work. A series of recommendations emerged from this study that will be useful in implementing multi-investigator programs like GEOTRACES.

The chemical speciation of dissolved Fe was investigated in the Pacific Ocean to elucidate the regional variability of organic ligands. The concentration and conditional stability constants ( K′ Fe′L , with respect to inorganic Fe) of organic ligands were analyzed by a Competitive Ligand Equilibration-Adsorptive Cathodic Stripping Voltammetric (CLE-ACSV) method using 2-(2-thiazolylazo)- p -cresol (TAC). In the surface waters of the Pacific Ocean, a low concentration of dissolved Fe was observed (0.20 ± 0.14 nM, n = 8) with an excess of organic ligands (0.27 ± 0.14 Eq of nM Fe, n = 7); thus, most of the dissolved Fe was estimated to be complexed with these ligands. A 2D cross-section diagram along 160°W and 170°W showed a roughly increasing trend in the concentration of organic ligands toward the north of the deep waters, suggesting the accumulation of ligands in the biogeochemical cycle of deep water. In the equatorial Pacific and central subtropical North Pacific, the concentration of organic ligands was observed to exceed that of dissolved Fe throughout the water column. On the contrary, the concentration of dissolved Fe at depths ranging from 1000 to 3000 m was higher than that of organic ligands in the western North Pacific, suggesting that the excess dissolved Fe can exist as colloidal Fe and/or organic/inorganic complexes with the ligands that were not detectable by our method. A greater concentration of excess dissolved Fe relative to the concentration of organic ligands was also observed in the deep (below 1000 m) waters of the subtropical South Pacific. These differences regarding the saturation state of organic ligands ([L]/[D–Fe]) between the surface and deep waters probably reflect different sink and source mechanisms of organic ligands within the water column. The extent of the organic complexation of Fe varies with the biogeochemical processes in the ocean interior and plays a key role in oceanic Fe cycling.

Ambient OH and HO2 concentrations were measured by laser induced fluorescence (LIF) during the PRIDE-PRD2006 (Program of Regional Integrated Experiments of Air Quality over the Pearl River Delta, 2006) campaign at a rural site downwind of the megacity of Guangzhou in Southern China. The observed OH concentrations reached daily peak values of (15–26) × 106 cm−3 which are among the highest values so far reported for urban and suburban areas. The observed OH shows a consistent high correlation with j(O1D) over a broad range of NOx conditions. The correlation cannot be reproduced by model simulations, indicating that OH stabilizing processes are missing in current models. The observed OH exhibited a weak dependence on NOx in contrast to model predictions. While modelled and measured OH agree well at NO mixing ratios above 1 ppb, a continuously increasing underprediction of the observed OH is found towards lower NO concentrations, reaching a factor of 8 at 0.02 ppb NO. A dependence of the modelled-to-measured OH ratio on isoprene cannot be concluded from the PRD data. However, the magnitude of the ratio fits into the isoprene dependent trend that was reported from other campaigns in forested regions. Hofzumahaus et al. (2009) proposed an unknown OH recycling process without NO, in order to explain the high OH levels at PRD in the presence of high VOC reactivity and low NO. Taking a recently discovered interference in the LIF measurement of HO2 into account, the need for an additional HO2 → OH recycling process persists, but the required source strength may be up to 20% larger than previously determined. Recently postulated isoprene mechanisms by Lelieveld et al. (2008) and Peeters and Müller (2010) lead to significant enhancements of OH expected for PRD, but an underprediction of the observed OH by a factor of two remains at low NO (0.1–0.2 ppb). If the photolysis of hydroperoxy aldehydes from isoprene is as efficient as proposed by Peeters and Müller (2010), the corresponding OH formation at PRD would be more important than the primary OH production from ozone and HONO. While the new isoprene mechanisms need to be confirmed by laboratory experiments, there is probably need for other, so far unidentified chemical processes to explain entirely the high OH levels observed in Southern China.

Both organic carbon (OC) and elemental carbon (EC) were measured during PRIDE-PRD 2006 summer campaign by using a semi-continuous thermal-optical carbon analyzer at a rural site, Back Garden (BG), which is located 50 km to the northwest of Guangzhou City. Together with the online EC/OC analyzer, various kinds of instruments related to aerosol chemical properties were employed here, which provided a good opportunity to check data quality. The concentrations of OC correlated well with the mass of organic matter (OM) and water soluble organic carbon (WSOC), implying the reliability of the data measured in this campaign. The average OC concentrations in fine particle for three typical periods during the campaign (local emission influence, typhoon and precipitation and normal days) were 28.1 μgC m−3, 4.0 μgC m−3 and 5.7 μgC m−3, respectively; and EC were 11.6 μgC m−3, 1.8 μgC m−3, and 3.3 μgC m−3, respectively. The diurnal patterns of EC and OC during the campaign were higher at night and in early morning than daytime, which was probably caused by the primary emission and accumulation in the occurrence of low boundary layer. Compared with the constant diurnal enhancement ratios of EC, the enhancement ratio of OC (OC versus (CO-CObackground)) kept in a relative high level in the afternoon, with a similar diurnal profile to oxygenated organic aerosol (OOA), due to the strong photochemical formation of OC. Here, a modified EC tracer method was used to estimate the formation of secondary organic carbon (SOC). These results showed that the average SOC concentration (normal days) at BG site was about 2.0 ± 2.3 μgC m−3, and the SOC fraction in OC could reach up to 80% with the average of 47%. The modified approach in this study proved to be effective and reliable for SOC estimation based on good correlations between estimated SOC versus OOA or WSOC, and estimated POC versus hydrocarbon-like organic aerosol (HOA).

We use ozone and carbon monoxide measurements from the Tropospheric Emission Spectrometer (TES), model estimates of Ozone, CO, and ozone pre-cursors from the Real-time Air Quality Modeling System (RAQMS), and data from the NASA DC8 aircraft to characterize the source and dynamical evolution of ozone and CO in Asian wildfire plumes during the spring ARCTAS campaign 2008. On the 19 April, NASA DC8 O3 and aerosol Differential Absorption Lidar (DIAL) observed two biomass burning plumes originating from North-Western Asia (Kazakhstan) and South-Eastern Asia (Thailand) that advected eastward over the Pacific reaching North America in 10 to 12 days. Using both TES observations and RAQMS chemical analyses, we track the wildfire plumes from their source to the ARCTAS DC8 platform. In addition to photochemical production due to ozone pre-cursors, we find that exchange between the stratosphere and the troposphere is a major factor influencing O3 concentrations for both plumes. For example, the Kazakhstan and Siberian plumes at 55 degrees North is a region of significant springtime stratospheric/tropospheric exchange. Stratospheric air influences the Thailand plume after it is lofted to high altitudes via the Himalayas. Using comparisons of the model to the aircraft and satellite measurements, we estimate that the Kazakhstan plume is responsible for increases of O3 and CO mixing ratios by approximately 6.4 ppbv and 38 ppbv in the lower troposphere (height of 2 to 6 km), and the Thailand plume is responsible for increases of O3 and CO mixing ratios of approximately 11 ppbv and 71 ppbv in the upper troposphere (height of 8 to 12 km) respectively. However, there are significant sources of uncertainty in these estimates that point to the need for future improvements in both model and satellite observations. For example, it is challenging to characterize the fraction of air parcels from the stratosphere versus those from the fire because of the low sensitivity of the TES CO estimates used to mark stratospheric air versus air parcels affected by the smoke plume. Model transport uncertainties, such as too much dispersion, results in a broad plume structure from the Kazakhstan fires that is approximately 2 km lower than the plume observed by aircraft. Consequently, the model and TES data do not capture the photochemical production of ozone in the Kazakhstan plume that is apparent in the aircraft in situ data. However, ozone and CO distributions from TES and RAQMS model estimates of the Thailand plume are within the uncertainties of the TES data. Therefore, the RAQMS model is better able to characterize the emissions from this fire, the mixing of ozone from the stratosphere to the plume, and the photochemical production and transport of ozone and ozone pre-cursors as the plume moves across the Pacific.

In order to characterize the features of particulate pollution in the Pearl River Delta (PRD) in the summer, continuous measurements of particle number size distributions and chemical compositions were simultaneously performed at Guangzhou urban site (GZ) and Back-garden downwind regional site (BG) in July 2006. Particle number concentration from 20 nm to 10 μm at BG was (1.7±0.8)×104 cm−3, about 40% lower than that at GZ, (2.9±1.1)×104 cm−3. The total particle volume concentration at BG was 94±34 μm3 cm−3, similar to that at GZ, 96±43 μm3 cm−3. More 20–100 nm particles, significantly affected by the traffic emissions, were observed at GZ, while 100–660 nm particle number concentrations were similar at both sites as they are more regional. PM2.5 values were similar at GZ (69±43 μg m−3) and BG (69±58 μg m−3) with R2 of 0.71 for the daily average PM2.5 at these two sites, indicating the fine particulate pollution in the PRD region to be regional. Two kinds of pollution episodes, the accumulation pollution episode and the regional transport pollution episode, were observed. Fine particles over 100 nm dominated both number and volume concentrations of total particles during the late periods of these pollution episodes. Accumulation and secondary transformation are the main reasons for the nighttime accumulation pollution episode. SO42−, NO3− accounted for about 60% in 100–660 nm particle mass and PM2.5 increase. When south or southeast wind prevailed in the PRD region, regional transport of pollutants took place. Regional transport contributed about 30% to fine particulate pollution at BG during a regional transport case. Secondary transformation played an important role during regional transport, causing higher increase rates of secondary ions in PM1.0 than other species and shifting the peaks of sulfate and ammonium mass size distributions to larger sizes. SO42−, NO3−, and NH4+ accounted for about 70% and 40% of PM1.0 and PM2.5, respectively.

In situ measurements of the mass concentration of black carbon (BC) and mixing ratios of carbon monoxide (CO) and carbon dioxide (CO2) were made at Guangzhou, an urban measurement site in the Pearl River Delta (PRD), China, in July 2006. The average ± standard deviation (SD) concentrations of BC, CO, and CO2 were 4.7± 2.3 μgC m−3, 798± 459 ppbv, and 400± 13 ppmv, respectively. The trends of these species were mainly controlled by synoptic-scale changes in meteorology during the campaign. Based on back trajectories, data are analyzed separately for two different air mass types representing northerly and southerly flows. The northerly air masses, which constituted ~25% of the campaign, originated mostly in the PRD and hence represent observations on regional scales. On the other hand, during southerly flow (~75%), the measurements were influenced by dilution due to cleaner marine air. The diurnal patterns of BC, CO, and CO2 exhibited peak concentrations during the morning and evening hours coinciding with rush-hour traffic. The ratios of OC/BC were lower during the morning hour peaks in the concentrations of primary pollutants due to their fresh emissions mainly from vehicular traffic in Guangzhou. The diurnal variations of BC observed in southerly air masses tended to follow the traffic patterns of heavy-duty vehicles (HDV) in Guangzhou, while the roles of other sources need to be investigated. The slopes of ΔBC/ΔCO, ΔBC/ΔCO2, and ΔCO/ΔCO2 observed during northerly flows were 0.0045 μgC m−3/ppbv, 0.13 μgC m−3/ppmv, and 49.4 ppbv/ppmv, respectively, agreeing reasonably with their respective emission ratios derived from regional emission inventories.

The aim of this study was to evaluate the effect of additional polymethyl methacrylate (PMMA) fillers on the physical properties of experimental resin composites. PMMA particles (d=30 µm) were added to an experimental methacrylate-based resin composite in five concentrations of 0, 2.0, 4.8, 9.1, and 23.1 wt%. Properties such as contact angle, water sorption and compressive strength were measured and the fractured specimens were observed with a scanning electron microscope. The results showed that a small amount (2 wt%) of additional PMMA fillers inhibited the crack propagation and enhanced compressive strengths of the resin composites, without a significant change in water contact angle of surface or increased water sorption. However, in higher portions, the mechanical properties were not improved as a debonding at the interface between untreated fillers and the matrix, or failure within the organic filler could reduce the compressive yield strength of the composite.

A patch of water in the western subarctic gyre (low iron concentration, After the iron fertilization, we observed a significant increase in dissolved iron (1.38 nM at 5 m depth) at the center of the patch (D1). Dissolved iron concentrations subsequently decreased to an ambient level (~0.08 nM) on D16–D17, despite the second iron fertilization made on D6. During the 4-day incubations of the shipboard culture experiments, excess DFB-inoculated treatment inhibited the phytoplankton growth compared to the controls for D2, D7 and D11 patch water. This indicated that available iron existed in the iron-fertilized patch at least until D11. Moreover, iron-inoculated treatments induced growth of large-sized phytoplankton with an accompanying silicate decrease for D7, D11 and D17 patch water, but not for D23 patch water. These results indicated that large diatoms, which can respond to additional iron inoculation, existed in the iron-fertilized patch in evolution and early termination phase of the iron-induced bloom (at least until D17); however, there was no significant amount of large diatoms, which could rapidly respond to iron, in late termination phase (D23) of the iron-induced phytoplankton bloom.

A mesoscale iron-enrichment study (SEEDS II) was carried out in the western subarctic Pacific in the summer of 2004. The iron patch was traced for 26 days, which included observations of the development and the decline of the bloom by mapping with sulfur hexafluoride. The experiment was conducted at almost the same location and the same season as SEEDS (previous iron-enrichment experiment). However, the results were very different between SEEDS and SEEDS II. A high accumulation of phytoplankton biomass (∼18 mg chl m−3) was characteristic of SEEDS. In contrast, in SEEDS II, the surface chlorophyll-a accumulation was lower, 0.8 to 2.48 mg m−3, with no prominent diatom bloom. Photosynthetic competence in terms of Fv/Fm for the total phytoplankton community in the surface waters increased after the iron enrichments and returned to the ambient level by day 20. These results suggest that the photosynthetic physiology of the phytoplankton assemblage was improved by the iron enrichments and returned to an iron-stressed condition during the declining phase of the bloom. Pico-phytoplankton (

The Sulu Sea is a deep ocean basin that is isolated from the surrounding ocean by chains of islands and shallow sills less than 420 m in depth. Vertical distributions of dissolved ( ( K Fe 3 + L cond ) varied by two orders of magnitude, with values of 1022.3–1024.1; no significant difference was found between the Sulu Sea and its adjacent seas. This study found that measured [D-Fe] was higher than [LT]; excess [D-Fe] can exist as colloidal Fe and/or organic/inorganic complexes with weak ligands that were not detectable in this study. The presence of excess [D-Fe] for [LT] also was observed in adjacent waters, indicating that high temperatures in the deep water did not characterize excess [D-Fe] in the Sulu Sea. The chemical speciation of iron based on the thermodynamic equilibrium shows that iron exists as organically bound (>99%) in the surface water. The extent of organic complexation of dissolved iron at 500 m is lower (43–92%), suggesting the importance of iron dissolution process from particles in deep waters and the possible existence of colloidal iron or weak ligands. These results suggest that the vertical distributions of [D-Fe] and [LT] in the Sulu Sea and Celebes Sea differ from those obtained for other open and coastal seas. Geological features such as those near islands and deep basins in the Sulu Sea and Celebes Sea seem to influence the dynamics of iron strongly.

保育学科は教育課程の性格上、幼児教育に携わるものを育てる目的学科である。当然のこととして学生は幼稚園教諭や保育士になることを目指して入学するものと思われる。しかし、2年間の学生生活の中でその意識や願望は変化し、卒業時まで初期の動機を持ちつづけることも変化の多い青年期おいては課題のひとつといえる。入学時から卒業までの専門職への意識の変化を見ることを目的として調査を企画したが、本報告では入学時での意識調査の結果のみを報告する。

According to ocean-color remote sensing data, a low phytoplankton biomass exists in the central parts of the Sulu and Celebes seas, whereas higher concentrations of chlorophyll a are observed in the waters near the Sulu Archipelago, which separates these water bodies. These high-chlorophyll a waters have lower temperatures than those of surrounding waters, indicating vertical mixing of nutrient-rich subsurface water that is attributable to the topographical features of the Sulu Ridge. Differences in photosynthetic parameters, primary productivity and the phytoplankton community structure between the high-chlorophyll area near the Sulu Archipelago and the oligotrophic basin area in the Philippine, Sulu and Celebes seas were investigated in November 2002 during the R.V. Hakuho-Maru KH-02-4 cruise. Entrainment of subsurface water and vertical mixing by intense tidal flow from the Sulu Archipelago to the Celebes Sea created a low-temperature, high-nutrient condition at the southeastern edge of the Sulu Ridge. Chlorophyll a concentrations greater than 2 μg l−1 were observed at stations 5–15 km offshore at the edge of the Sulu Ridge. This high-chlorophyll tongue in the Celebes Sea showed high primary productivity: it was 1.6–18 times higher than those measured in oligotrophic central basin regions of the Philippine, Sulu, and Celebes seas. Microscopic observation of these high-chlorophyll waters showed the dominance of chain-forming large centric diatoms. Extension of high-chlorophyll waters was not observed at the Sulu Sea side, where the surface water salinity was lower than in the Celebes Sea and consequently prevented intrusion of the Celebes Sea water into the surface layer. Occasional extensions of productive, chlorophyll-rich surface water from the archipelagic zone to the surrounding basin area seems to be an important factor causing spatiotemporal variability in the phytoplankton biomass in the southern Sulu Sea and the western Celebes Sea.

Anthropogenic pollution and wildfires are main producers of carbon monoxide (CO) and black carbon (BC) in the Northern Hemisphere. High concentrations of these compounds are transported into the Arctic troposphere, influencing the ecosystem in high northern latitudes and the global climate. The global chemical transport model MOZART-4 is used to quantify the seasonal evolution of the contribution of CO and BC from different source regions in spring and summer 2008 by tagging their emissions. Aircraft observations from the POLARCAT experiments, in particular NASA ARCTAS, NOAA ARCPAC, POLARCAT-France, DLR GRACE and YAK-AEROSIB, as well as the NSF START08/preHIPPO experiments during Spring-Summer 2008 are combined to quantify the representation of simulated tracer characteristics in anthropogenic and fire plumes. In general, the model reproduces CO and BC well. Based on aircraft measurements and FLEXPART back-trajectories, the altitude contribution of emissions coming from different source regions is well captured in the model. Uncertainties of the MOZART-4 model are identified by comparing the data with model results on the flight tracks and using MOPITT satellite observations. Anthropogenic emissions are underestimated by about 10% in high northern latitudes in spring, and shortcomings exist in simulating fire plumes. The remote impact of East-Siberian fire emissions is underestimated for spring, whereas the impact of Southeast Asian fire emissions to mid-latitude CO values is overestimated by the model. In summer, mid-latitude CO values agree well between model and observations, whereas summer high latitude East-Siberian fire emissions in the model are overestimated by 20% in comparison to observations in the region. On the other hand, CO concentrations are underestimated by about 30% over Alaska and Canada at altitudes above 4 km. BC values are overestimated by the model at altitudes above 4 km in summer. Based on MOZART-4, with tagged CO and BC tracers, anthropogenic emissions of Asia, Europe and the US have the largest contribution to the CO and BC in mid- and high latitudes in spring and summer. Southeast Asian, Chinese and Indian fires have a large impact on CO pollution in spring in low latitudes with a maximum between 20° and 30°, whereas Siberian fires contribute largely to the pollution in high latitudes, up to 10% in spring and up to 30% in summer. The largest contributions to BC values in high latitudes are from anthropogenic emissions (about 70%). CO and BC have larger mass loadings in April than in July, as a result of photochemistry and dynamics.

We evaluated error prevention education by clarifying the association between dispensing error factors and behavioral characteristics of pharmacists. The subjects were 98 pharmacists (27 men and 71 women) with a mean age of 29.7 years who gave informed consent for participation in our survey. Between November 2001 and January 2002, a questionnaire survey on dispensing errors was performed using the "Tokyo University Egogram, New Version" for the assessment of behavioral characteristics and the "Safety Behavior Questionnaire" for the assessment of error factors. An association was observed between the incidence of dispensing errors and behavioral characteristics. There was also an association between error contents and behavioral characteristics as well as error factors. With more experience, errors associated with becoming accustomed increased, suggesting that error prevention education is necessary not only for newly qualified pharmacists but also for managers.

In order to supplement our lectures on the community health care system and the role of community pharmacists, we created hypertexts linked to 300 or more Web sites related to community health care including such subject areas as community pharmacies, pharmaceutical associations and prefectural governments and then used these resources to teach undergraduate students and assessed the efficacy of this method.The subjects consisted of undergraduate at our university (265 in 1999, 297 in 2000). Before and after reading the hypertexts, they performed a subjective self-estimation of the efficacy of learning about pharmacies and pharmacists using a questionnaire graded from -2 to + 2 points. In the analysis, the subjects were separated into two groups, those who had experienced an externship at a community pharmacy and those without any externship experience. The scores before and after reading the hypertext material were compared in each group and interindividually, and significance was assessed using the Wilcoxon signed-ranks test (P

The location and magnitude of oceanic iron sources remain uncertain owing to a scarcity of data, particularly in the Arctic Ocean. The formation of cold, dense water in the subsurface layer of the western Arctic Ocean is a key process in the lateral transport of iron, macronutrients and other chemical constituents. Here, we present iron, humic-like fluorescent dissolved organic matter and nutrient concentration data in waters above the continental slope and shelf and along two transects across the shelf–basin interface in the western Arctic Ocean. We detected high concentrations in shelf bottom waters and in a plume that extended in the subsurface cold dense water of the halocline layer in slope and basin regions. At σθ = 26.5, dissolved Fe, humic-like fluorescence intensity and nutrient maxima coincided with N* minima (large negative values of N* indicate significant denitrification within shelf sediments). These results suggest that these constituents are supplied from the shelf sediments and then transported laterally to basin regions. Humic dissolved organic matter probably plays the most important role in the subsurface maxima and lateral transport of dissolved Fe in the halocline layer as natural Fe-binding organic ligand.

An airborne instrument for fast-response, high-precision measurement of tropospheric carbon monoxide (CO) was developed using a vacuum ultraviolet (VUV) resonance fluorescence technique. The excitation radiation is obtained by a DC discharge CO resonance lamp combined with an optical filter for the CO fourth positive band emission around 150 nm. The optical filter consists of a VUV monochromator and a crystalline quartz window (

Vertical profiles of HNO 3 , N 2 O, O 3 , and the aerosol extinction coefficient at 780 nm were observed by the Improved Limb Atmospheric Spectrometer (ILAS) on board the Advanced Earth Observing Satellite (ADEOS) during the Arctic winter of 1996-1997. Irreversible redistribution of HNO 3 is evaluated using HNO 3 -N 2 O and HNO 3 -O 3 correlations. Denitrification and nitrification started to be observed just after the Arctic vortex cooled to below the ice frost point (T ICE ) on February 10. Trajectory analyses show that denitrification occurred only in air masses, which were once cooled to near T ICE and were kept at temperatures below the nitric acid trihydrate saturation threshold continuously for more than 4 days. Such a temperature history provides the necessary conditions for nucleation and growth of particles causing denitrification. The average extent of denitrification at 19 km reached 43% at the center of the vortex, suggesting that stratospheric ozone could be affected by denitrification deep inside the vortex. Denitrification (>2 ppbv) and nitrification (> 1 ppbv) covered 40±10% and 35±10% of the vortex area, respectively. Redistributed numbers of HNO 3 molecules at each altitude were calculated by integrating the area-weighted changes in the HNO 3 concentration. The decreases in total HNO 3 concentration at 17-21 km in late February and early March agreed with the increases at 12-15 km to within 25%, confirming conservation of HNO 3 during sedimentation and evaporation of HNO 3 -containing polar stratospheric cloud particles.

A facile ‘one-pot’ synthesis for poly(γ-methyl-l-glutamate) (PMLG) membranes is reported. Despite having an α-helical secondary structure, as demonstrated via IR, these membranes did not show enantioselective behavior in pressure driven permeation of Trp. Therefore, the transesterification of PMLG with Igepal and Brij® 30 is introduced in a next step and the resulting polymers are characterized by means of IR and NMR. Supported membranes made from these materials show permselectivity towards d-Trp under a pressure gradient, but the enantiomeric excess of the permeate phase declines as a function of time. In order to realize a constant enantioselectivity, electrodialysis is demonstrated to be a suitable membrane process. Moreover, the obtained permeation rates of Ac-Trp are among the best ever reported for solid enantioselective membranes and approximate those realized with liquid membranes.

Molecularly imprinted polymeric membranes with tetrapeptide residue H-Asp(OcHex)-Asp(OcHex)-Asp(OcHex)-Asp(OcHex)-CH2- (DDDD) or H-Glu(OBzl)-Glu(OBzl)-Glu(OBzl)-Glu(OBzl)-C H2- (EEEE) were prepared during membrane preparation (casting) processing in the presence of print molecules. The Boc-L-Trp imprinted polymeric membranes thus obtained showed adsorption selectivity toward Ac-L-Trp from its racemic mixtures. From adsorption isotherms of Ac-Trp, the chiral recognition site, that had been formed by the presence of print molecules in the membrane preparation process, exclusively recognized Ac-L-Trp that possessed the same configuration of the print molecule. The affinity constants between chiral recognition sites in the membrane and Ac-L-Trp was determined to be 1.00 × 104 mol−1 dm3 and 1.08 × 104 mol−1 dm3 for the DDDD and EEEE membranes, respectively. Enantioselective electrodialysis could be attained by applying an optimum potential difference to give permselectivity, with a value close to its adsorption selectivity.

Carbon graphite was expected to show affinity toward aromatics by using π–electron interaction. Novel membranes for pervaporation were prepared from carbon graphite (CG) and nylon 6 (N6). The composite membranes showed permselectivity toward benzene from benzene–cyclohexane mixtures. Benzene was permeated in preference to cyclohexane from benzene–cyclohexane mixtures and separation factor toward benzene reached to 435 at the weight fraction of benzene in feed of 0.1. From the sorption experiments, it was made clear that the introduction of CG into N6 enhances the solubility selectivity toward benzene and, as a result, benzene was preferentially permeated through the CG–N6 composite membranes.

Airborne observations of NO during the Subsonics Assessment Ozone and Nitrogen Oxides Experiment (SONEX) reveal episodes of high NOx in the upper troposphere believed to be associated with lightning. Linkage to specific periods of lightning activity is possible through back trajectories and data from the National Lightning Detection Network. Lagrangian model calculations are used to explore the evolution of these high NOx plumes over the 1–2 days between their introduction and subsequent sampling by NASA's DC-8 aircraft. Simulations include expected changes in HNO3, H2O2, CH3OOH, HO2, and OH. Depending on the time of injection and dilution rate, initial NOx concentrations are estimated to range from 1 to 7 ppbv. Similar to many previous studies, simulated HNO3 concentrations tend to be greater than observations. Several possible explanations for this difference are explored. H2O2 observations are shown to be consistent with removal in convective activity. While it is possible that upper tropospheric CH3OOH is enhanced by convection, simulations show such increases in CH3OOH can be short-lived (e.g.