THE ESTUARINE ENVIRONMENT AND pH VARIATION: NATURAL LIMTS AND EXPERIMENTAL OBSERVATION OF THE ACIDIFICATION EFFECT ON PHOSPHORUS BIOAVAILABILITY. This study shows the variation of pH in the Cananéia-Iguape Estuarine-Lagoon Complex (CIELC). Data from 3 years (2019, 2021, 2022) were obtained in 17 points presenting the following ranges: temperature (14.88-27.05 ºC), pH (7.16-8.40) and DIP (0.20-11.28 µmol L-1) along a saline gradient (0.05-32.09) under different hydrodynamics, biogeochemical processes and anthropogenic influence. The pH buffering capacity due to the presence of weak acid salts in saline water (S ≥ 30) was associated to the lowest DIP, decreasing with low salinity values, confirming the direct correlation among salinity and pH. The highest temperatures in the winter of 2021, corroborated with the abnormal climate event in that year. An in vitro experiment showed results of the interaction of PID and sediments with different textures, with and without the presence of the benthic microbiota under a considerable decreasing of the pH (acidification) in relation to the natural condition of this environment. The P sediment flux characterized Iguape sector as a P sink with or without biota, Ararapira sector as a P source with biota and Cananéia, as P source without biota. The salt water buffered the pH and sediment buffered DIP both associated to the biogeochemical and hydrodynamic processes contribute to the homeostasis in the system.

Abstract The Cananéia-Iguape Estuarine-Lagoon Complex (CIELC) is an extremely productive coastal ecosystem. It encloses the Valo Grande channel, built 160 years ago, which introduces water from the Ribeira River directly into the estuarine system, contributing to important biogeochemical changes in the region. Many nutrients arrive at the estuary through this channel, as well as metals and other slightly soluble elements that become part of the sediments. This study aims to evaluate the processes that govern the distribution of rare earth elements (REE) in the sediments of the complex by using fractionation patterns, anomalies, and the geochemical signature of minerals to evaluate sources, natural levels, and the possible anthropogenic forcing to which CIELC is subjected. ∑REE* ranged from 14.2 to 285 mg kg -1 and showed a distribution related to depositional/textural characteristics influenced by the regional and local lithological setting and a possible contamination. The REE/Al ratio indicated enrichment in the sea adjacent to the estuary and at stations in the Ribeira River and Valo Grande. While the Hf/Al ratio indicated natural enrichment related to the presence of heavy minerals in most of these stations, this ratio fails to justify enrichment at some stations in the northern part of the estuary and the Ribeira River. Fractionation patterns and anomalies allowed us to identify the main heavy minerals related to REE enrichment at CIELC. Cerium (Ce) anomalies showed a possible relation with biologically mediated Ce +3 to Ce +4 oxidation processes in the most productive areas of the estuary. Europium (Eu) anomalies were strongly associated with different mineral assemblies in several CIELC sectors. Abundance, fractionation patterns, and REE anomalies corroborate the categorization of CIELC sediments as part of a pristine system in its southern region and as subject to anthropogenic influences in its northern area.

Abstract Over the last decades, regional climate changes, erosion, and heightened agricultural runoffs have increased nutrient and particle input in rivers, unbalancing the biogeochemical cycle of this suspended material along estuaries. In this context, particle fluxes in the euphotic zone, a very productive layer and important to maintain the food chain and estuarine preservation, require better understanding. This study aims to evaluate particle sedimentation fluxes in the photic zone of the Cananéia-Iguape Estuarine-Lagoon Complex (CIELC), considering sectors under different salinities and trophic statuses. A cylindrical sediment trap was installed at the base of the photic layer to measure particle fluxes and photopigments. Meanwhile, water samples were taken to measure temperature, salinity, pH, dissolved oxygen, and nutrients. Valo Grande (a freshwater domain) showed high nutrient concentrations, in which high fluxes of phaeopigments and chlorophyll-b highlighted the contribution of vegetable detritus to particle sinking. In the Batatais mangrove creek, the high fluxes of organic particles (675.32 mg m-2 d-1) and chlorophyll-a (98.40 mg m-2 d-1) evinced a high contribution of microplankton to carbon sinking. During the winter of 2018, flocculation processes were evinced in the flood tide of the Cananéia Bay as an important driver of sedimentation rates, with considerable fluxes of inorganic particles (1161.20 mg m-2 d-1) and chlorophyll-a (83.27 mg m-2 d-1). In the summer of 2019, we observed a lower flux in total particles (451.24 mg m-2 d-1) in a period of haline stratification. In the Ararapira Channel, the lowest organic particle fluxes (<100 mg m-2 d-1) were associated with ultra-oligotrophic conditions, indicating a low influence of microplankton on sinking particles. These findings suggest that freshwater input, tidal variation, and trophic status are relevant controls of sinking particles in different CIELC sectors.

Abstract Estuaries are important features for global biogeochemical understanding, due to their highly coupled interaction between sediment and water. In those places, the land-sea transect sometimes has a gradient of physical and chemical characteristics, influencing the availability of nutrients and consequently primary production. This study aimed to observe the benthic aerobic respiration and sediment-water nutrient fluxes in a freshwater to marine transect in the Cananéia-Iguape Estuarine-Lagoon Complex (CIELC) on the southeastern Brazilian Coast. This area contains the most pristine mangrove at the limit between tropical and subtropical zones, providing an ideal observatory for ecological research programs. Intact sediment cores were incubated in laboratory to determine fluxes of O2, TCO2, and dissolved nutrients. Three different sites with different salinities were sampled during the four seasons of the year. Sediment characteristics of the sites were compared, showing higher organic matter in the lowest saline (LS) site and higher phytopigments in the highest saline (HS) site, as expected. Benthic aerobic respiration, O2 and CO2 fluxes, ranged from −0.4 to −3.2 mmol m−2h−1 and 0.1 to 1.5 mmol m−2h−1, respectively, and exhibited statistically significant variations between seasons and in a salinity gradient. Dissolved inorganic nitrogen and silicate, ranging from −228.7 to 544.8 μmol m−2h−1 and −205.8 to 4,173.5 μmol m−2h−1, respectively, were generally released from the sediment, whereas phosphate ranged from −25.2 to 29.6 μmol m−2h−1 with more variation in time and space. The LS site was characterized as a nitrogen sink and a silicate and phosphate releaser, and the HS site was characterized as a nitrogen producer and a phosphorus consumer. However, seasonal and spatial variations were observed, and the interaction between space and time factors was always highly significant, indicating that the metabolic behavior of the benthic compartment depends on both trophic and physicochemical conditions.