ABSTRACT The emissions of CH4 and CO2, the primary greenhouse gases, have a significant impact on radiative forcing. This study investigated these gases along the Cananéia-Iguape estuarine system on the southern coast of the State of São Paulo, Brazil, which is a mangrove region characterized by low anthropogenic impact and a sparse population. As such, this area provides an ideal location for identifying natural emissions and background concentrations. The data for this study were collected using a portable gas analyzer (LGR-ICOSTM GLA131), known for its high sensitivity and precision in detecting gases, mounted on a research boat. The results obtained were promising for both gases. A small variability in CH4 concentrations was observed along the route, ranging from 1.84 ppm to 1.95 ppm, while CO2, showed greater variation in values obtained during routes, ranging from approximately 411 ppm to 575 ppm. This study underscores the importance of investigating areas with minimal environmental impact. Together with future analyses, this research should help improve Greenhouse Gas (GHG) inventories in Brazil by providing valuable baseline data for comparisons with more impacted areas. CH CO2 CO forcing CananéiaIguape Cananéia Iguape Paulo population such LGRICOSTM LGR ICOSTM GLA131, GLA131 GLA , GLA131) boat route 184 1 84 1.8 195 95 1.9 routes 41 57 analyses GHG (GHG GLA13 18 8 1. 19 9 4 5 GLA1

Abstract The Cananéia-Iguape estuarine-lagoon complex (CIELC), located in the State of São Paulo, Brazil, is considered an area of the Biosphere Reserve. However, an artificial channel built in the northern sector of the system (Iguape) has promoted an unnatural input of fresh water into the system, leading to enhanced drainage of terrestrial material into the estuary and influencing silicon biogeochemistry within the complex. This study used the distribution of different fractions of silicon along the system as a proxy for the freshwater input. The samples were collected during August, 2012 (winter) and February 2013 (summer) and analyzed for dissolved silicate, biogenic silica, and lithogenic silica. Dissolved silicate reached values above 200 µmol L -1 in the two seasonal periods, indicating the constant supply of terrestrial material in the northern sector of the system associated with fresh water. Southward, where the system is more preserved (Cananéia-Ararapira), the concentration decreased dramatically. Lithogenic silica (LSi) reached extremely high values of ~700 µmol L -1. Biogenic silica (BSi) showed concentrations up to 120 µmol L -1 with distribution more dependent on assimilation processes and the nature of the biological communities than on the source of fresh water. The availability of different forms of Si revealed remineralization, deposition, adsorption, and uptake mechanisms with different dynamics in the northern and southern sectors of the system, evidencing the environmental impact by the Valo Grande Channel. CananéiaIguape Cananéia Iguape estuarinelagoon estuarine lagoon CIELC, CIELC , (CIELC) Paulo Brazil Reserve However (Iguape August 201 winter (winter summer (summer 20 1 - periods Southward CananéiaArarapira, CananéiaArarapira Ararapira (Cananéia-Ararapira) dramatically LSi (LSi 700 ~70 1. BSi (BSi 12 remineralization deposition adsorption Channel (CIELC 2 (Cananéia-Ararapira 70 ~7 7 ~

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. understanding water places landsea land sea production sedimentwater CananéiaIguape Cananéia Iguape EstuarineLagoon Estuarine Lagoon CIELC (CIELC Coast zones programs O TCO2 TCO year compared (LS (HS expected CO 04 0 4 −0. 32 3 2 −3. m2h1 mh m 2h 1 h m−2h− 01 0. 15 5 1. respectively 2287 228 7 −228. 5448 544 8 544. 2058 205 −205. 41735 173 4,173. 252 25 −25. 296 29 6 29. releaser consumer However observed conditions −0 −3 m2h m−2h 22 −228 54 20 −205 4173 17 4,173 −25 − −22 −20 417 4,17 −2 41 4,1 4,

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. CananéiaIguape Cananéia Iguape EstuarineLagoon Estuarine Lagoon (CIELC ecosystem channel 16 ago (REE sources levels subjected ∑REE 142 14 2 14. 28 1 - depositionaltextural depositional textural contamination REEAl Al HfAl Hf (Ce 3 + 4 Eu (Eu sectors Abundance area

Abstract The construction of a data bank concerning metal and metalloid content of bioindicator fish from coastal areas is very important as it can help environmental managers in decision making. In natural conditions, the concentration of elements can be influenced by abiotic parameters such as water salinity. In this study, catfish Cathorops spixii were evaluated concerning the total arsenic (As) concentration in the muscle tissues of individuals subjected to different abiotic conditions in the Cananéia-Iguape Estuarine-Lagoon Complex (CIELC), which was recently included on the Ramsar list of wetlands of international importance. Seventy-four catfish were seasonally caught in the northern and southern regions of the CIELC and their hydrochemical parameters were obtained. C. spixii from the southern, best preserved, area showed arsenic concentrations around ten times higher than the maximum limit established for fish intended for human consumption. However, these high concentrations of arsenic could be associated with the abiotic parameters of the water, such as salinity variations, in this area. making study As (As CananéiaIguape Cananéia Iguape EstuarineLagoon Estuarine Lagoon CIELC, , (CIELC) importance Seventyfour Seventy four obtained C preserved consumption However variations (CIELC

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. VARIATION BIOAVAILABILITY CananéiaIguape Cananéia EstuarineLagoon Estuarine Lagoon CIELC. CIELC . (CIELC) 2019, 2019 (2019 2021 2022 1 ranges 14.8827.05 14882705 14.88 27.05 14 88 27 05 (14.88-27.0 ºC, ºC , ºC) 7.168.40 716840 7.16 8.40 7 16 8 40 (7.16-8.40 0.2011.28 0201128 0.20 11.28 0 20 11 28 (0.20-11.2 L1 L L-1 0.0532.09 0053209 0.05 32.09 32 09 (0.05-32.09 hydrodynamics influence S 30 values year textures acidification (acidification environment system (CIELC 201 (201 202 8827 14.8827.0 1488270 1488 14.8 2705 27.0 2 (14.88-27. 168 7.168.4 71684 716 7.1 840 8.4 4 (7.16-8.4 2011 0.2011.2 020112 020 0.2 1128 11.2 (0.20-11. L- 0532 0.0532.0 005320 005 0.0 3209 32.0 (0.05-32.0 (20 882 14.8827. 148827 148 14. 270 27. (14.88-27 7.168. 7168 71 7. 84 8. (7.16-8. 0.2011. 02011 02 0. 112 11. (0.20-11 053 0.0532. 00532 00 320 32. (0.05-32. (2 14.8827 14882 (14.88-2 7.168 (7.16-8 0.2011 0201 (0.20-1 0.0532 0053 (0.05-32 ( 14.882 (14.88- (7.16- 0.201 (0.20- 0.053 (0.05-3 (14.88 (7.16 (0.20 (0.05- (14.8 (7.1 (0.2 (0.05 (14. (7. (0. (0.0 (14 (7 (0 (1

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. decades changes erosion rivers estuaries context preservation understanding CananéiaIguape Iguape EstuarineLagoon Estuarine Lagoon CIELC, , (CIELC) statuses photopigments Meanwhile temperature salinity pH oxygen nutrients domain concentrations chlorophyllb chlorophyll b creek 675.32 67532 675 32 (675.3 m2 m 2 m- d1 d 1 d-1 chlorophylla 98.40 9840 98 40 (98.4 2018 rates 1161.20 116120 1161 20 (1161.2 83.27 8327 83 27 (83.2 d1. . 2019 451.24 45124 451 24 (451.2 stratification Channel <100 100 (<10 ultraoligotrophic ultra oligotrophic conditions variation (CIELC 675.3 6753 67 3 (675. d- 98.4 984 9 4 (98. 201 1161.2 11612 116 (1161. 83.2 832 8 (83. 451.2 4512 45 (451. <10 10 (<1 675. 6 (675 98. (98 1161. 11 (1161 83. (83 451. (451 <1 (< (67 (9 (116 (8 (45 < ( (6 (11 (4 (1

Abstract: The human impact on estuarine regions results in an increasing concentration of trace elements in the environment, exposing aquatic organisms. In this study, Zn, Co, Cr, and As were determined in the muscle tissue of some fish species from Santos-São Vicente (SSV), a recognized polluted region, and in the Cananeia estuary (CAN). Genotoxicity was also determined for the evaluation of the chronic effect on ichthyofauna, to enlarge the bank of environmental data regarding the effects of pollution, and to suggest other fish bioindicator species that may contribute to monitoring programs. The obtained data showed a similar profile of an accumulation of Co and Zn in Micropogonias furnieri and Chaetodipterus faber, where: Santos Bay > CAN > inner area of SSV. A low frequency of micronucleus was observed. However, in general, fish from the inner area of the SSV estuary presented more nuclear abnormalities than fish from Santos Bay and CAN. In the inner area of SSV, Centropomus paralelus and Diapterus rhomneus showed more changes than other fish species. It was possible to consider that the habits of each species, contributed to a different profile of trace element accumulation, followed by the chemical components in the organism offering different vulnerability.

Os sistemas estuarinos desempenham um importante papel na retenção de elementos traços devido à afinidade destes com algumas partículas dissolvidas em água. Nesse trabalho, apresenta-se o uso de um sensor voltamétrico para monitorar as concentrações de Zn (II), Cd(II) e Pb (II) na região do Sistema Estuarino Lagunar de Cananéia-Iguape (estado de São Paulo). No setor sul, (Cananéia) obteve-se menores valores de concentração, e no setor norte (Iguape) os valores foram maiores devido às atividades antrópicas, com ênfase à introdução prévia de resíduos de mineração e insumos de efluentes agrícolas, industriais e domésticos. O método proposto é viável, barato e rápido, e permite a determinação dos íons metálicos simultaneamente. Além disso, o dispositivo portátil é simples e pode ser facilmente utilizado para medições de campo a bordo de navios oceanográficos.

Estuarine systems play an important role in the retention of toxic trace elements owing to the affinity of these elements with particles dissolved in water. This work presents the use of a voltammetric sensor to monitor heavy metal (Zn (II), Cd(II) and Pb (II)) concentrations in the Cananéia-Iguape Estuarine-Lagoon region (São Paulo State, Brazil). Lower concentrations were found in the Southern estuarine system (Cananéia City) and increased concentrations observed in the Northern sector (Iguape City) were promoted by anthropogenic activities, with particular influence from the historical introduction of mining wastes and inputs from agricultural, industrial and domestic effluents. The proposed method is reliable, inexpensive and fast, can simultaneously provide information on the concentration of these metallic ions and can be easily used for field measurements aboard oceanographic ships.

Os níveis de mercúrio (Hg) total em cabelos estão diretamente relacionados à alimentação, particularmente ao consumo de peixes por populações costeiras com grande representação caiçara. No presente estudo foram avaliados os níveis de mercúrio total em cabelos de crianças com idade entre 4 e 12 anos, pertencente a três escolas públicas da cidade de Cananéia, São Paulo, Brasil. Os resultados obtidos (mediana e intervalo) para mercúrio total foram de: 0,04mg.kg-1 (0,01-0,77mg.kg-1), 0,39mg.kg-1 (< 0,01-3,33mg.kg-1) e 0,39mg.kg-1 (< 0,01-2,81mg.kg-1) considerando as escolas ES1, ES2 e ES3, respectivamente. Em geral, os valores encontrados estiveram bem abaixo do valor preconizado pela Organização Mundial da Saúde para uma população adulta não exposta ao mercúrio (2,0mg.kg-1). Os baixos valores observados e a inexistência de valores de referência para mercúrio total em cabelos de crianças brasileiras possibilitam a consideração desses valores como possível referência nacional em cabelos de populações costeiras, uma vez que foram obtidos em região de baixo impacto ambiental.

Mercury (Hg) levels in hair are directly related to eating habits, especially fish consumption by coastal populations with a large contingent of traditional fishing families. This study assessed total Hg levels in children's hair. The study group was selected from three public elementary schools in Cananéia, São Paulo State, Brazil (ages 4 to 12 years). The results (median and range) for total Hg levels in children's hair were: 0.04mg.kg-1 (0.01-0.77mg.kg-1), 0.39mg.kg-1 (< 0.01-3.33mg.kg-1), and 0.39mg.kg-1 (< 0.01-2.81mg.kg-1) for schools ES1, ES2, and ES3, respectively. The values were well below the level set by World Health Organization for an adult population unexposed to Hg (2.0mg.kg-1). However, since there are no existing reference values for total Hg in children's hair, these results can be used as a contribution to establishing reference values for total hair Hg in Brazilian children living in coastal areas.

Os níveis de mercúrio (Hg) total em cabelos estão diretamente relacionados à alimentação, particularmente ao consumo de peixes por populações costeiras com grande representação caiçara. No presente estudo foram avaliados os níveis de mercúrio total em cabelos de crianças com idade entre 4 e 12 anos, pertencente a três escolas públicas da cidade de Cananéia, São Paulo, Brasil. Os resultados obtidos (mediana e intervalo) para mercúrio total foram de: 0,04mg.kg-1 (0,01-0,77mg.kg-1), 0,39mg.kg-1 (< 0,01-3,33mg.kg-1) e 0,39mg.kg-1 (< 0,01-2,81mg.kg-1) considerando as escolas ES1, ES2 e ES3, respectivamente. Em geral, os valores encontrados estiveram bem abaixo do valor preconizado pela Organização Mundial da Saúde para uma população adulta não exposta ao mercúrio (2,0mg.kg-1). Os baixos valores observados e a inexistência de valores de referência para mercúrio total em cabelos de crianças brasileiras possibilitam a consideração desses valores como possível referência nacional em cabelos de populações costeiras, uma vez que foram obtidos em região de baixo impacto ambiental.

Mercury (Hg) levels in hair are directly related to eating habits, especially fish consumption by coastal populations with a large contingent of traditional fishing families. This study assessed total Hg levels in children's hair. The study group was selected from three public elementary schools in Cananéia, São Paulo State, Brazil (ages 4 to 12 years). The results (median and range) for total Hg levels in children's hair were: 0.04mg.kg-1 (0.01-0.77mg.kg-1), 0.39mg.kg-1 (< 0.01-3.33mg.kg-1), and 0.39mg.kg-1 (< 0.01-2.81mg.kg-1) for schools ES1, ES2, and ES3, respectively. The values were well below the level set by World Health Organization for an adult population unexposed to Hg (2.0mg.kg-1). However, since there are no existing reference values for total Hg in children's hair, these results can be used as a contribution to establishing reference values for total hair Hg in Brazilian children living in coastal areas.

A toxicidade do efluente líquido do "Dutos e Terminais Centro-Oeste São Paulo" (DTCS) terminal marítimo de petróleo da PETROBRAS, em São Sebastião (SP, Brasil), cujo principal componente é a água de produção, foi avaliada através de testes de toxicidade com a diatomácea Skeletonema costatum. Amostras de dois efluentes (A e B), previamente tratados pela PETROBRAS, foram utilizadas nos experimentos. As duas amostras apresentaram alta salinidade (A=67‰; B=62‰) e baixo valor de pH (6,2), enquanto que as suas concentrações de sulfetos, fenóis e hidrocarbonetos de petróleo dissolvidos/dispersos, bem como os seus valores de DBO e DQO, foram bastante distintos. Nos experimentos de toxicidade, os frascos experimentais, em triplicata, para cada tratamento foram expostos à radiação luminosa fluorescente de 266 µm² S-1 e mantidas em um ciclo luz/escuro de 10 h/14 h, a uma temperatura de 24 :t 2ºC. Os valores de CE50 não puderam ser determinados com precisão para o efluente A: após 60 h e 132 h do início dos experimentos esses valores estavam abaixo de 3% e entre 3-6% da concentração de efluente, respectivamente. Foi observado sinergismo entre a toxicidade e a salinidade do efluente sobre o crescimento de S. costatum. O efluente B apresentou uma toxicidade mais elevada: os valores de CEso foram 0,17% e 0,40% da concentração do efluente, após 48 h e 96 h, respectivamente. Estes resultados evidenciaram claramente os efeitos deletérios dos compostos orgânicos residuais contidos no efluente líquido do DTCS, sobre S. costatum. Pode-se concluir que a disposição do efluente nas águas do canal de São Sebastião poderá ser prejudicial à biota local.

The liquid effluent from an oil maritime terminal, with produced water as the main component, had its toxicity evaluated through toxicity tests with the diatom Skeletonema costatum. Two previously treated effluent samples (effluents A and B), were provided by PETROBRAS for the experiments. Both samples presented high salinity (67‰ for effluent A and 62‰ for effluent B) and low pH values (6.2), whereas total sulphide, phenol and nutrient content, dissolved/dispersed petroleum hydrocarbon concentration, BOD and COD values were quite different from each other. During the toxicity experiment, three replicate flasks with samples for each treatment were exposed to a light radiation of 266µE m² S-1 and maintained under a 10 h/14 h lightldark cycle, at a temperature of 24 :t 2ºC. The EC50 values could not be accurately estimated for effluent A: 60 h and 132 h after starting the experiment they were below 3% and between 3-6% effluent concentration, respectively. Synergistic effects between effluent toxicity and salinity on the growth of S. costatum were detected. The effluent B showed higher toxicity: the EC5O values were 0.17% and 0.40% of effluent concentrations, after 48 h and 96 h, respectively. These results evidenced the deleterious effects of residual organic compounds contained in the aqueous effluents from the oil terminal under the present pretreatment on S. costatum. In the light of the present data, the direct disposal ofthese effluents into São Sebastião Channel waters might be very hazardous to its indigenous biota.