(Appendix 1) Age, Ge/Si ratio, aluminium and opal contents in ODP Sites 175-1081 and 175-1084

As a result of both culture and sediment core studies, the ratio of germanium (Ge) to silicon (Si) in diatom shells has been proposed as a proxy for monitoring whole-ocean changes in seawater Ge/Si, a ratio affected by changes in continental weathering. However, because of the difficulties of extracting and cleaning diatom frustules from deep-sea sediments, only samples from highly pure diatom oozes in the Antarctic region have been previously analyzed. Here we present data on diatom Ge/Si ratios, (Ge/Si)opal, for the time interval between 3.1 and 1.9 Ma from a mid-latitude, coastal upwelling area where significant terrigenous sediment input complicated the sample processing and analyses. In general, our (Ge/Si)opal values show the same decreasing trend after 2.6 Ma than previously measured in Antarctic sediments (Shemesh et al., 1989. Paleoceanography 4, 221-231), but with a noisier background that may reflect the local imprint of proximal continental input superimposed upon global changes in the ocean reservoir. The time of initiation of large-scale North Hemisphere glaciation at ~2.6 Ma is characterized by a declining pattern of diatom Ge/Si ratios, which could have resulted from a global increase in the input of riverine Si due to enhanced silica weathering and/or equatorward (northward) intrusions of subantarctic waters enriched in silica. High (Ge/Si)opal ratios are associated with high opal contents from the same sediment samples and with warm climate as indicated by depleted benthic foraminiferal d18O values from the North and Equatorial Atlantic. Cold periods signified by enriched benthic d18O values, on the contrary, are associated with lower (Ge/Si)opal ratios. We interpret diatom Ge/Si values to reflect the prevailing weathering state on the continents, with greater chemical weathering during warm and wet periods of the Pliocene and less during cooler and drier intervals.

Synergistic effects of pCO2 and iron availability on nutrient consumption ratio of the Bering Sea phytoplankton community

Little is known concerning the effect of CO2 on phytoplankton ecophysiological processes under nutrient and trace element-limited conditions, because most CO2 manipulation experiments have been conducted under elements-replete conditions. To investigate the effects of CO2 and iron availability on phytoplankton ecophysiology, we conducted an experiment in September 2009 using a phytoplankton community in the iron limited, high-nutrient, low-chlorophyll (HNLC) region of the Bering Sea basin . Carbonate chemistry was controlled by the bubbling of the several levels of CO2 concentration (180, 380, 600, and 1000 ppm) controlled air, and two iron conditions were established, one with and one without the addition of inorganic iron. We demonstrated that in the iron-limited control conditions, the specific growth rate and the maximum photochemical quantum efficiency (Fv/Fm) of photosystem (PS) II decreased with increasing CO2 levels, suggesting a further decrease in iron bioavailability under the high-CO2 conditions. In addition, biogenic silica to particulate nitrogen and biogenic silica to particulate organic carbon ratios increased from 2.65 to 3.75 and 0.39 to 0.50, respectively, with an increase in the CO2 level in the iron-limited controls. By contrast, the specific growth rate, Fv/Fm values and elemental compositions in the iron-added treatments did not change in response to the CO2 variations, indicating that the addition of iron canceled out the effect of the modulation of iron bioavailability due to the change in carbonate chemistry. Our results suggest that high-CO2 conditions can alter the biogeochemical cycling of nutrients through decreasing iron bioavailability in the iron-limited HNLC regions in the future.

Surface in situ measurements of atmospheric CO, CH4, and CO2 combined with selected meteorological measurements at the University of Wollongong, Australia

Wollongong, Australia is an urban site at the intersection of anthropogenic, biomass burning, biogenic and marine sources of atmospheric trace gases. The location offers a valuable opportunity to study drivers of atmospheric composition in the Southern Hemisphere. Here, a record of surface carbon monoxide (CO), methane (CH4) and carbon dioxide (CO2) was measured with an in situ Fourier transform infrared trace gas analyser between April 2011 and August 2014. Clean air was found to arrive at Wollongong in approximately 10% of air masses. Biomass burning influence was evident in the average annual cycle of clean air CO during austral spring. A significant negative short-term trend was found in clean air CO (-1.5 nmol/mol/a), driven by a reduction in northern Australian biomass burning. Significant short-term positive trends in clean air CH4 (5.4 nmol/mol/a) and CO2 (1.9 ?mol/mol/a) were consistent with the long-term global average trends. Polluted Wollongong air was investigated using wind-direction/wind-speed clustering, which revealed major influence from local urban and industrial sources from the south. High values of CH4, with anthropogenic DCH4/DCO2 enhancement ratio signatures, originated from the northwest, in the direction of local coal mining. A pollution climatology was developed for the region using back trajectory analysis and DO3/DCO enhancement ratios. Ozone production environments in austral spring and summer were associated with anticyclonic meteorology on the east coast of Australia, while ozone depletion environments in autumn and winter were associated with continental transport, or fast moving trajectories from southern latitudes. This implies the need to consider meteorological conditions when developing policies for controlling air quality.