G. Yu. Pavlova

Catchment areas on volcanic territories in different regions are of great interest since they are enriched with nutrients that contribute significantly to coastal ecosystems. The Kamchatka Peninsula is one of the most active volcanic regions of the world; however, to date, the chemistry of its river waters and the state of its coastal ecosystems remain understudied in connection with volcanism. The two rivers under study are the largest in this region. The Kamchatka River, unlike the Penzhina River, drains volcanic territories, including the areas of the most active volcanoes of the Klyuchevskaya group of volcanoes and the Shiveluch Volcano. The mouth of the Kamchatka River has been shown to have DIP and DIN concentrations of 2.79–3.87 and 10.0–23.8 µM, respectively, during different seasons, which are comparable to rivers in urbanized areas with sewerage and agricultural sources of nutrients. It has been established that volcanoes form high concentrations of nutrients in the catchment area of the Kamchatka River. The Penzhina River has had very low DIP and DIN concentrations of 0.2–0.8 and 0.17–0.35 µM, respectively, near the mouth during different seasons, but high concentrations of DOC, at 5.9 mg/L in spring, which may be due to seasonal thawing of permafrost. During the period of increasing river discharge, seasonal phytoplankton blooms occur in spring and summer in bays of the same name, as shown using satellite data. The biomass of zooplankton in Penzhina Bay is at a level of 100 mg/L, while in Kamchatka Gulf, it exceeds 2000 mg/L. Thus, the biomass of zooplankton in the receiving basin, which is influenced by the runoff of the Kamchatka River with a volcanic catchment area in eastern Kamchatka, is 20 times higher than in the basin, which has a small nutrient flux with the river runoff in northwestern Kamchatka. This study demonstrates the connection between nutrient fluxes from a catchment area and the formation of seasonal phytoplankton blooms and high zooplankton biomass in the coastal area. We also study seasonal, year-to-year, and climatic variability of water discharges and hydrometeorological conditions to understand how nutrient fluxes can change in the foreseeable future and influence coastal ecosystems.

Nutrient fluxes with river runoff can largely determine the state of coastal water ecosystems. The Vilyuchinskaya and Avachinskaya Bays of Kamchatka Peninsula were surveyed on 4–5 July 2022, just after the peak of the spring–summer flood of the Vilyucha and Avacha Rivers associated with the snow melting in volcanic areas. Additionally, water sampling was performed in river water in December 2022, in the period of winter low water. A general undersaturation of CO₂ of surface waters was observed in the Vilyuchinskaya and Avachinskaya Bays. Strong supersaturation of CO₂ of the near-bottom waters was observed, due to microbial destruction of organic matter, especially in Avachinskaya Bay. This organic matter was formed as a result of photosynthesis in the water column, which subsequently gravitated to the bottom and concentrated in specific bottom depressions in the studied bays. In these depressions, black sediments were found, in which sulfate reduction occurred. The porewater of sediments had a very high concentration of organic carbon, dissolved and organic nitrogen, and phosphates, as well as CO₂ partial pressure. The source of nutrients for the studied bays is tephra (volcanic suspended particles), which covers all the watersheds, including the soil and snow, as a result of volcanic activity in the study region. Based on the calculated nutrient fluxes in river runoff for the summer and winter seasons and the DIN/DIP ratios in river, sea, and pore waters, the causes of phytoplankton blooms, including the occurrence of red tides, are discussed. The maximum flux of nutrients and, accordingly, phytoplankton blooms should be expected in the years with the highest volcanic activity and high summer air temperatures, since the melting of nutrient-rich snow and ice will be maximum. This will determine the flux of nutrients in the river runoff of the Kamchatka Peninsula and contribute to phytoplankton blooms.

Hydrological conditions are an important factor for aquatic ecosystems. Their contribution to stimulating phytoplankton bloom in eutrophic estuaries is not quite clear. We present the results of an outbreak of a phytoplankton bloom event observed in the eutrophic Razdolnaya R. estuary in 2022 from January 22 to February 23, when the estuary was covered by ice. The bloom spreads over 21 km from the river mouth bar to upstream in the near-bottom layer below the halocline. The Chl-a concentration in the bloom area increased from 15 to 100 μg/L, and the dissolved oxygen concentration from 350 to 567 μmol/kg at a rate of 11 μmol/(kg day) over the study period, while the CO₂ partial pressure was reduced to 108 µatm in the most oxygen-supersaturated waters. The Thalassiosira nordenskioeldii Cleve sea diatom was the dominant phytoplankton species in the bloom area. The opposite trend was observed near the boundary of the saline water wedge penetration over 29 km from the river mouth bar to upstream where the dissolved oxygen concentration decreased from 140 to 53 μmol/kg over a month, and partial pressure of CO₂ reached 4454 μatm. We also present the results obtained in February 2016 before and after a snowfall, when the ability of PAR to penetrate through the ice was impeded by a layer of snow. After the snowfall, photosynthesis in the under-ice water stopped and the oxygen concentration decreased to almost zero due to the microbiological destruction of the phytoplankton biomass. As such, the main effect of phytoplankton bloom is the formation of superoxia/hypoxia (depending on the light conditions), during the period of maximum ice thickness and minimum river discharge. Thus, this study demonstrates that the eutrophication in the future could lead to unstable ecosystems and large synoptic variations of dissolved oxygen and CO₂ partial pressure of the estuaries.

In this study, we investigated the carbonate system in sediments and water columns from five stations in the Sea of Japan (East Sea) (JES) during the R/V Hakuho Maru KH-10-2 research cruise in the summer of 2010. The total alkalinity (TA) and pH were measured. Adopting a saturation degree of 91% and 80% for the lysocline depth and calcite compensation depth (CCD), respectively, we found that those depths corresponded to 1360 and 1980 m. A comparison of the calcite saturation depths, lysocline depths, and CCD depths obtained for 1999 and 2010 suggests that acidification of the interior of the JES occurred. Sediment cores were retrieved using a multi-corer. In the sediment cores, a sharp decrease in the pH by 0.3–0.4 pH units was observed in the subsurface horizons (0–10 cm) compared with the pH of the seawater from the bottom horizons. The TA in the porewaters was significantly higher than that in the overlying seawater. The anaerobic degradation of organic matter is probably the main cause for the increasing TA in the sediments. The porewaters were significantly undersaturated with calcite and aragonite, except in that from the shallowest station, where the sediments below 7.5 cm were saturated, and even supersaturated, with calcite and aragonite. A linear correlation between the dissolved inorganic carbon and the TA for sediments with a slope of 0.9993 was found, despite there being potentially different ways for the diagenesis of the organic matter to occur. The diagenesis of organic matter in the top sediments of the JES forms gradients of TA and CO₂* concentrations on the interface of “bottom water–sediments”. Averaged fluxes of TA and dissolved inorganic carbon (DIC) from the sediments to the bottom waters estimated by means of Fickian diffusion were calculated as 44 and 89 mmol/(m² year) for TA and DIC, respectively.

The relevance of the research consists in studying hydrochemical river discharge as one of the main indicators of the ecological state of water objects.The main aim of the research is to obtain new knowledge on hydrochemical discharge of the rivers at southern Khabarovsk region, which are required for objective assessment of the ecological status of the region and for carrying out effective water protection measures.Objects of the research are the Amur River and seven lesser streams: Bikin, Khor, Podkhorenok, Bira, Kiya, Malaya Chirka, 2-aya Sedmaya. Methods. Concentration of major anions (Cl–, SO42–) wеrе аnаlyzеd by ion chromаtogrаphy (Shimаdzu LC‒10А); mаjor cаtions (Nа+, K+, Cа2+, Mg2+), trace elements and rare earth elements ‒ with ICP‒MS (Agilent, 7500с) method. The hydrocarbonate ion (HCO3-) concentration was taken as the total alkalinity. It wаs аnаlyzеd by dirеct titrаtion by Bruyеvich mеthod. Thе totаl minеrаlizаtion (∑i) is thе sum of concеntrаtions of mаjor rivеr wаtеr еlеmеnts. Results. In July 2011 Amur River and seven lesser streams (Bikin, Khor, Podkhorenok, Bira, Kiya, Malaya Chirka, 2-aya Sedmaya, located at southern part of Khabarovsk region, were sampled and analyzed for their major elements, trace elements and rare earth elements. During summer flood river waters are low-mineralizated, ∑i does not exceed 50 mg/l. Ca2+ is the predominant cation and HCO3– is the major counter-ion for cations in all samples. High concentrations of dissolved Al, Fe и Pb were found in the surface waters of all the rivers studied. In the Malaya Chirka River there are high concentrations of dissolved Co, Cu, Mn and extremely high Cd, exceeding the average global concentrations in 40 times. The concentration of the other trace elements in the studied rivers is general corresponded to their average global concentrations and is a characteristic of the natural regional background during summer floods. A regional level of total concentrations of soluble forms of rare earth elements (1,44–5,44 µg/l) was established. The distribution and level of rare earth elements concentrations in the studied river waters reflect the overall composition of the watershed rocks. The calculated total daily fluxes of major elements, trace elements and rare earth elements, supplied by the Bira, Kiya, Podhorenok, Bikin, Khor and Amur rivers, equal to 61894, 377 and 2,21 t/day, respectively. Актуальность: изучение гидрохимического стока рек как одного из основных индикаторов экологического состояния водных объектов. Цель: получение новых знаний о гидрохимическом стоке рек юга Хабаровского края, которые необходимы для объективной оценки экологического состояния поверхностных вод края и проведения эффективных водоохранных мероприятий. Объекты: р. Амур и семь рек бассейна р. Уссури (одного из наиболее значимых притоков Амура): Бикин, Хор, Подхоренок, Бира, Кия, Малая Чирка и 2-ая Седьмая. Методы. Концентрaции мaкро-aнионов (Cl–, SO42–) измерялись методом ионно-обменной хромaтогрaфии; макро-катионов (Nа+, K+, Cа2+, Mg2+), микроэлементов и редкоземельных элементов ‒ методом ICP‒MS (Agilent, 7500с). В качестве концентрации гидрокарбонатного иона (HCO3–) принималась величина щелочности. Результаты. В июле 2011 г. проведены комплексные гидрохимические исследования в р. Амур и семи реках бассейна р. Уссури (одного из наиболее значимых притоков Амура): Бикин, Хор, Подхоренок, Бира, Кия, Малая Чирка и 2-ая Седьмая. В пробах речной воды были определены параметры основного солевого состава, микроэлементов и редкоземельных элементов. В период высокого расхода воды в высоко увлажненных южных районах Хабаровского края речные воды очень схожи по типу и величине минерализации: среди катионов доминирует Ca2+, основным противо-анионом является HCO3–; воды ультрапресные, ∑i не превышает 50 мг/л. В поверхностных водах всех исследованных рек обнаружены высокие концентрации растворенных форм Al, Fe и Pb. В р. Малая Чирка ‒ высокие концентрации растворенных Co, Cu, Mn и экстремально высокие Cd, превышающие средние глобальные концентрации в 40 раз. Содержание остальных микроэлементов в исследуемых реках в целом соответствовало их средним глобальным концентрациям и является характеристикой природного регионального фона в период летних паводков. Установлен региональный уровень суммарных концентраций растворимых форм редкоземельных элементов...

Chemical water parameters in the Partizanskaya River estuary were measured on July 18–19, 2012 in conditions of low water discharge (20.1 m3 /s). In these conditions, the cline of salt water at the bottom penetrated up to 11 km upstream from the river mouth and the fresh river water passed the estuarine zone of mixing in approximately 2 days. Salt composition of the mixed water in the estuary had conservative dependence on salinity. By dynamical signs, the estuary could be divided into two zones: i) zone of active exchange between the surface freshwater layer and the bottom salted layer on the distance 5.5 km from the river mouth to the first sandy riverbank that the fresh river water passed in 12 hours, and ii) the upper part of the estuary with limited water exchange. The complex of water environments in the estuary, as good water transparency, strong stratification, and high concentrations of terrestrial nutrients, was favorable for phytoplankton blooming, so the chlorophyll concentration in the estuarine waters exceeded 40 μg/L. Destruction of autochthonous organic matter caused anomalies in distribution of carbonate and nutrient parameters and was accompanied by hypoxia in the bottom layer with the dissolved oxygen content lowering to 61 μM/kg.

Seasonal hydrochemical studies of the basic salt composition of water in the Partizanskaya R. estuary (Nakhodka Bay, the Sea of Japan), carried out in 2012, showed no within-year changes in the ratio of major ions, and hence the type of mineralization, in the river against a background of a pronounced seasonal variation of total mineralization. The mixing of river and sea water in the estuary is shown to be of a conservative character.

The complex study of the river water and pore solutions from the bottom sediments in the lower reaches of the Razdol’naya River was conducted in February 2010. The major ion composition of the waters...

In 2000, the Carbon Dioxide in the Ocean working group of the North Pacific Marine Science Organization (PICES) performed an international experiment on the intercalibration of the measurements of the total alkalinity in seawater using certified reference materials (CRM). Taking part in this experiment, Russian specialists presented the method by Bruevich. The results of the intercalibration showed that the alkalinity values obtained by Bruevich’s method using modern burettes, an Na₂CO₃ reactant of high purity as a standard to ascertain the acid titre, and corrections for the acid density and for the weights of the acid and seawater samples in vacuum are in agreement with the standard within ±1 μ M/kg.