The Main Features of Phosphorus Transport in World Rivers

Data on the geochemistry of phosphorus in the continental runoff of dissolved and solid substances were systematized and generalized, with a separate consideration of the processes of runoff transformation in river mouth areas. It has been established that atmospheric deposition, which many authors consider to be an important source of phosphorus in river runoff and not associated with mobilization processes in catchments, actually contains phosphorus from soil-plant recycling. This is confirmed by the fact that the input of phosphorus from the atmosphere into catchments exceeds its removal via water runoff. An analysis of the mass ratio of phosphorus in the adsorbed form and in the form of its own minerals was carried out. It was shown that the maximum mass of adsorbed phosphorus is limited by the solubility of its most stable minerals. The minimum concentrations of dissolved mineral and total phosphorus were observed in the rivers of the Arctic and subarctic belts; the maximum concentrations were confined to the most densely populated temperate zone and the zone of dry tropics and subtropics. In the waters of the primary hydrographic network, the phosphorus concentration exhibited direct relationships with the population density in the catchments and the mineralization of the river water and was closely correlated with the nitrogen content. This strongly suggests that economic activity is one of the main factors in the formation of river phosphorus runoff. The generalization of the authors’ and the literature’s data on the behavior of phosphorus at the river–sea mixing zone made it possible to draw a conclusion about the nonconservative distribution of phosphorus, in most cases associated with biological production and destruction processes. The conservative behavior of phosphorus was observed only in heavily polluted river mouths with abnormally high concentrations of this element.

Non-Equilibrium Uranium as an Indicator of Global Climate Variations—The World Ocean and Large Lakes

In natural water, as a rule, there is a violation of radioactive equilibrium in the chain 238U … → 234U → 230Th →. Groundwater usually has a 234U/238U ratio in the range of 0.8–3.0 (by activity). However, in some regions, the 234U/238U ratio reaches >10 and up to 50. Ultrahigh excesses of 234U can be explained by climatic variations. During a cold period, minerals accumulate 234U as a normal component of the radioactive chain, and after the melting of permafrost, it is lost from the mineral lattice faster than 238U due to its higher geochemical mobility. This hypothesis was tested using data on the isotopic composition of uranium in the chemo- and bio-genic formations of the World Ocean and large lakes, which are reservoirs that accumulate continental runoff. The World Ocean has the most significant 234U enrichments in the polar and inland seas during periods of climatic warming in the Late Pleistocene and Holocene. In the bottom sediments of Lake Baikal, the 234U/238U ratio also increases during warm periods and significantly exceeds the 234U excess of the World Ocean. Furthermore, the 234U/238U ratio in the water of Lake Baikal and its tributaries increases from north to south following a decrease in the area of the continuous permafrost and has a seasonal variation with a maximum 234U/238U ratio in summer. The behavior of 234U in large water reservoirs is consistent with the hypothesis about the decisive influence of permafrost degradation on the anomalies in 234U/238U ratios in groundwater.

Carbon Dioxide Flux at the Water–Air Boundary at the Continental Slope in the Kara Sea

The values and direction of carbon dioxide flux in the area of the continental slope in the north of the Kara Sea (St. Anna Trough) are calculated based on field studies in 2020 within the Siberian Arctic Sea Ecosystems program. The existence of a stable frontal zone in this area has been confirmed, which is formed by an alongslope current and limits the northward spread of surface waters freshened by the continental runoff. The simultaneous analysis of the carbonate system in the upper sea layer and the CO2 concentration in the surface air layer shows the CO2 flux with a rate of 0.2 to 22 mmol/m2 day to be directed from the atmosphere into the water in the area of the outer shelf, which is affected by the river runoff, and in the area of the continental slope, which is beyond this effect. The highest rates of CO2 absorption by the sea surface layer are localized above the continental slope. Local processes in the area of the slope frontal zone determine the CO2 emission into the atmosphere with a rate of 0.34 mmol/m2 day.

Argo Float Reveals Biogeochemical Characteristics Along the Freshwater Gradient Off Western Patagonia

The coastal region off Chilean Patagonia has been poorly studied due to the lack of available observations. Here we analyzed, by the very first time, biogeochemical (BGC) data to elucidate the role that biological and physical processes play on nitrate, oxygen, pH and hydrographic variables, along a salinity gradient off central Patagonia. Argo float profiles covering the upper ocean from December 2015 to July 2019 reveal that offshore waters are characterized by low temperatures and high salinities related to high oxygen and medium-high values of pH and nitrate. As the Argo float drifted onshore, freshwater influences the upper 50–100 m with low salinity and high temperature. Waters under the influence of the continental runoff were characterized by medium-to-high oxygen and pH levels, and the lowest nitrate concentrations. Interestingly, oxygen-deficient waters located beneath the freshwater-modified layer showed the lowest pH and highest nitrate. A comprehensive analysis of the temporal and vertical variability of the oxygen:nitrate ratio, in conjunction with biological-related and physical parameters, indicates that the BGC variability seems to be the result of a synergistic interaction between physical and biological processes, where the stratification sets up the environment and promotes the biological response that, in turn, is auto-regulated by modifying the chemical composition in the freshwater-influenced zone. The arrival of future floats with additional sensors (Chlorophyll/Fluorescence, Photosynthetically Active Radiation, Backscatter, etc.) will add new BGC properties that improve our understanding of the coastal marine response to the increasing freshwater input off western Patagonia in the context of climate change.

Estimation of the seasonal input of freshwater in the Kara sea surface layer using hydrochemical proxies

<p>The Kara Sea receives about 55 % of the total continental runoff to the Siberian Arctic. Water of the Yenisei and Ob Rivers with low salinity (mineralization), flowing into the sea, forms a surface desalinated layer. The desalinated layer spreads over the sea area under the influence of hydrological and meteorological factors. Meltwater generated by the melting of marine and riverine ice and precipitation contribute to the formation of a surface desalinated layer along with continental runoff.</p><p>Determining the amount of fresh water is not accurate enough if only the salinity of surface water is considered. It is possible to identify riverine water and meltwater using hydrochemical proxies. The ratio of the major ions in seawater differs from that in riverine and meltwater. River waters are characterized by an increased content of silicate and reduced values of total alkalinity. At the same time, it is possible to identify the waters of the Ob and Yenisei Rivers by the estimated values of the total alkalinity and dissolved inorganic carbon obtained during the research expeditions to the Kara sea from 1993 to 2020.</p><p>The calculation of the parts of waters of different origin is done as a result of solving a system of equations. It includes the salinity and alkalinity values of the observed surface waters and those presumably involved in the mixing process. The salinity and alkalinity values of meltwater are taken as 0 and 134 µM respectively.</p><p>The total contribution of the Ob and Yenisei runoff ranges from 20 to 90% as it approaches the estuarine areas. The correlation coefficient between the proportion of river water and the salinity of the surface layer is quite high, it is equal to -0.9. This characterizes the inverse linear relationship. The separate contribution of the waters of the Yenisei differs from the contribution of the waters of the Ob, which is related to the hydrological conditions of the rivers.</p><p>The contribution of meltwater to the formation of the surface layer of the Kara Sea did not exceed 20%, with the exception of the coastal zone of the Novaya Zemlya. In this coastal zone, meltwater provides the greatest contribution compared to the other sources, which is associated with glacial runoff.</p><p>The work is implemented in the framework of the state assignment of the Shirshov Institute of Oceanology RAS (theme No. 0149-2019-0008), with the support of the Russian Scientific Foundation (project № 19-17-00196) and the grant of President of Russian Federation № MK-860.2020.5.</p>

Projected climate change in the South Asia and northern Indian Ocean by the end of the 21st century as obtained from a Regional Earth System Model

<p>Detailed atmospheric, ocean physical and biogeochemical characteristics for the period 2015-2100 within the South Asia CORDEX domain have been obtained from simulations of the Regional Earth System Model ROM.</p><p>Comparative analysis of average climatic characteristics for the past (1975-2004) and future (2070-2099) climates has been carried out. It shows significant future SST increase, reaching 3ºC on average, over the considered area. The salinity of the ocean's upper layer will decrease by 1 ‰ on average, which indicates a change in the precipitation-evaporation balance in the future climate. The simulated annual MLD will decrease by 5 m in the future. However, this MLD change will be strongly irregular, both in time and space. Simulations also show a widespread decrease of the chlorophyll-a concentration in the surface layer (up to 2 mg Chl m-3) in the future, especially pronounced in the northern and western parts of the Arabian Sea. It is a significant change, given that absolute chlorophyll-a concentration in these areas is typically 3-4 mg Chl m-3 in spring and 5-8 mg Chl m-3 in summer, as obtained for the 1975-2004 model run. The model also shows that the chlorophyll-a concentration at the surface will decrease by 1–2 mg Chl m-3 along the western coast of the Bay of Bengal in the future. The relative decrease in the surface chlorophyll-a concentration will be about 40% in the future climate in the Arabian Sea and the Bay of Bengal.</p><p>The model solution according to the SSP5-8.5 scenario shows a decrease in the amount of precipitation in the future climate (up to 3-4 mm/day) over the northeastern part of India and over Nepal in summer. But over the central part of India, in the Andaman Sea, over Thailand and Myanmar, there will be an increase in the amount of precipitation. The total continental runoff into the Bay of Bengal will increase, but the runoff in the Ganges delta will be greatly weakened. Thus, despite the decrease in the runoff of the Ganges and Brahmaputra rivers, the total continental runoff into the Bay of Bengal turns out to be higher in the future climate (2070-2099) relative to retrospective calculations (1975-2004) due to the runoff of smaller rivers.</p><p> </p><p>Acknowledgements: This work is funded by Russian Science Foundation (RSF, Project 19-47-02015) and Department of Science and Technology (DST, Govt. of India, grant DST/INT/RUS/RSF/P-33/G). The research was performed in the framework of the state assignment of the Ministry of Science and Higher Education of Russia (theme No. 0128-2021-0014). This work used resources of the Deutsches Klimarechenzentrum (DKRZ) granted by its Scientific Steering Committee (WLA) under project ID ba1144.</p>

Low-salinity Mediterranean gypsum deposits: chemical vs biological products

<p>Large deposits of gypsum accumulated in the marginal basins of the Mediterranean Sea during the Messinian Salinity Crisis. These form the marginal portions of the Mediterranean Salt Giant (MSG) that also occupies the deep, central Mediterranean basins. Although the marine, evaporitic origin of the MSG is undisputed, the analysis of gypsum fluid inclusions and of gypsum-bound water (d<sup>18</sup>O<sub>H2O</sub> and dD<sub>H2O</sub>) suggest that marginal basin gypsum formed from low- to moderate-salinity water masses (5 - 60 ‰), rather than from high-salinity brines (130 - 320 ‰), as expected during the evaporation of seawater. We present a new set of water isotope and fluid inclusion salinity data that extends the low salinity signature of gypsum to include five Mediterranean Sea marginal basins: Caltanissetta Basin (Sicily), Sorbas Basin (Spain), Piedmont Basin and Vena del Gesso Basin (northern Italy) and Catanzaro Trough (Southern Italy). With a simple geochemical model we explore the salinity-d<sup>18</sup>O<sub>H2O</sub>-dD<sub>H2O</sub> evaporation path and the <sup>87/86</sup>Sr and d<sup>34</sup>S<sub>SO4</sub> composition of the Mediterranean Sea subject to a variety of evaporation conditions and mixing ratios with continental runoff. This approach suggests that evaporation and mixing with continental runoff - including freshwater transiting via the Paratethys - cannot lead to the observed geochemical signature of MSC gypsum deposits. An alternative process that decouples the saturation state with respect to gypsum from salinity must have been active. We are exploring the possibility that the biogeochemical sulfur cycle leads to spatially and temporally localized gypsum supersaturation conditions via the production of SO<sub>4</sub><sup>2-</sup> by the oxidation and disproportionation of reduced sulfur compounds.</p>

The transient impact of the African monsoon on Plio-Pleistocene Mediterranean sediments

Over the Plio-Pleistocene interval a strong linkage exists between northern African climate changes and the supply of dust over the surrounding oceans and continental runoff towards the Mediterranean Sea. Both these signatures in the sedimentary record are determined by orbital cycles influencing glacial variability on the one hand and northern African monsoon intensity on the other hand. In this paper, we use the intermediate-complexity model CLIMBER-2 to simulate African climate during the Plio-Pleistocene between 3.2 and 2.3 million years ago (Ma) and compare our simulations with existing and new climate reconstructions. The CLIMBER-2 model is externally forced with atmospheric CO2 concentrations, ice sheet topography, and orbital variations, all of which strongly influence climate during the Pliocene and Pleistocene. Our simulations indicate that the records of northern Africa climate oscillate in phase with climatic precession. For the Earth's obliquity cycle, the time lag between the 41 000-year component in insolation forcing and the climatic response increased after inception of Northern Hemisphere (NH) glaciation around 2.8 Ma. To test the outcome of our simulations, we have put emphasis on the comparison between the simulated runoff of grid boxes encompassing the Sahara desert and the Sahel region and the sedimentary records of marine sediment cores from ODP Site 659 (Atlantic Ocean) and ODP Site 967 (Mediterranean). In this study we will show for the first time an extended Ti∕Al record of Site 967 down to 3.2 Ma. This record strongly correlates with runoff in the Sahara and Sahel regions, whereas correlation with the dust record of Site 659 is moderate and slightly improves after NH ice sheet inception. We investigated the transient variability of the individual and combined contributions of the Sahel and Sahara regions and found significant transient behaviour overlapping the inception of NH ice sheets (2.8 Ma) and the Plio-Pleistocene transition (2.6 Ma). Prior to 2.8 Ma, a larger contribution from the Sahara region is required to explain the variability of Mediterranean dust input. After this transition, we found that a more equal contribution of the two regions is required, representing an increased influence of Sahel runoff and wet periods.