EVALUATING DIRECT AND INDIRECT pCO2 MEASUREMENTS IN ESTUARINE ENVIRONMENTS. Estuaries are dynamic systems globally characterized as sources of CO2 to the atmosphere. However, they present large spatial-temporal variability in both pCO2 and FCO2. Increased CO2 emissions turns imperative to obtain continuous and accurate measurements of pCO2 in air and water to monitor FCO2 in these sensitive and complex environments. Currently, direct measurements of pCO2 and estimates of FCO2 in estuarine regions are still scarce and frequently the indirect pCO2 estimates are used that consists of measurements from at least two other parameters of the carbonate system: total alkalinity, dissolved inorganic carbon or pH. In this work, we evaluated recent direct and indirect measurements of pCO2 in the Jaguaribe River estuary-CE. This study provides a critical analysis of the data obtained through the two main methods mostly used to estimate pCO2, presenting the challenges towards greater consistency in obtaining data for a better understanding of the carbonate system in estuarine waters. We highlight the potential for continuous pCO2 measurements and long-term monitoring in coastal environments, contributing to improve knowledge of regional CO2 exchanges and to elucidate the role of estuaries in the global carbon cycle. pCO ENVIRONMENTS CO atmosphere However spatialtemporal spatial temporal FCO environments Currently alkalinity pH work estuaryCE. estuaryCE estuary CE. CE estuary-CE waters longterm long term cycle

Abstract This study compares two mangroves with different land uses in the Jaguaribe River estuary, harboring large shrimp farms, and in the more pristine Pacotí River estuary. Normalized Difference Vegetation Index (NDVI) was used to compare the overall health of the forests. Measures of suspended matter (TSS), total (TP), particulate (PartP) and soluble reactive phosphorus (SRP) in the inflow and outflow waters of tidal channels draining the mangroves were performed during tidal cycles. NDVI varied from 0.65 in the Jaguaribe estuary to 0.85 in the Pacotí, suggesting the impact of shrimp farm effluents on mangrove canopy cover. The shrimp farm influenced site showed 10 times larger absolute ∑P (TP + PartP + SRP) = 1.2-5.2 kg.hr-1) flux than the pristine site (∑P = 0.22 kg.hr-1). Tidal balances showed smaller retentions of the total influx: 28-54%; 44-45%; 38-65% and 8-53% for TSS; TP; SRP; and PartP respectively, in the shrimp farm influenced site to over 93% of the total tidal input of TSS and all P fractions in the pristine mangrove. This suggests that mangrove phosphorus accumulation is decreased in the forest with lower NDVI and limits mangrove’s potential as a natural barrier to the nutrient transport to adjacent estuarine and coastal waters.

Abstract This work reviews the limnology of the largest multi-use reservoir in NE Brazil, the Castanhão Reservoir in Ceará State, during 5 years of an extended drought when the reservoir’s volume decreased from 88% to about 30%. Major physical and chemical parameters of the water column, phytoplankton community, trophic state and sediment geochemistry were monitored, as well as the impact from extensive aquaculture. Water quality of the full reservoir was maintained due to hydrodynamics, which transport nutrients to the hypolimnion of a stratified water column, rendering an oligotrophic state to the reservoir, notwithstanding the large nutrient inputs from aquaculture and irrigated agriculture. However, with the extension of the drought period, the reservoir volume reduced, decreasing water depth leading to breaking of the thermocline due to wind forcing, and mixing the entire water column. This increased turbidity, nutrient availability and primary productivity, also changed phytoplankton functional groups. As a result, at the end of the monitoring period, when the reservoir attained its lowest volume, its trophic state became eutrophic. Under a scenario of climate change, where annual precipitation is decreasing, human uses of reservoirs in the semiarid should be very restricted to maintain water quality proper for human use.

Fluxos de Hg foram determinados entre 2005 e 2009 nas estações seca e chuvosa no estuário do Rio Jaguaribe, que desagua no Oceano Atlântico Equatorial, NE do Brasil. Na estação chuvosa a massa d'água no estuário apresenta um curto tempo de residência no estuário (0,8 dias), quatro vezes menor que na seca (3,1 dias). As concentrações e fluxos de Hg dissolvido (< 0,7 µm) e particulado foram maiores na interface rio/estuário que na estuário/mar, acumulando Hg particulado na região estuarina. A exportação de Hg particulado (1,8 a 12,6 mg s-1) ao oceano ocorreu sob chuva extrema, enquanto a exportação de Hg dissolvido foi quase zero na estação chuvosa e de até 0,45 mg s-1 na seca. Como a lixiviação continental no semiárido é afetada por mudanças climáticas globais e dos usos da terra, um aumento da acumulação de Hg particulado nos estuários e uma maior exportação de Hg dissolvido para o oceano é esperada.

Mercury fluxes were measured during the dry and rainy seasons (2005 to 2009) at the Jaguaribe River estuary, which discharges into the Equatorial Atlantic Ocean in NE Brazil. During rainy periods, the water masses exhibited a short residence time within the estuary (0.8 days). During dry periods, seawater choked the fluvial discharge, resulting in longer residence times (3.1 days). Dissolved (< 0.7 µm) and particulate Hg concentrations and fluxes were greater from the river to the estuary than from the estuary to the sea, producing accumulated particulate Hg in the estuary. Particulate Hg export (1.8 to 12.6 mg s-1) to the ocean occurred during extremely rainy periods, while dissolved Hg export was practically nonexistent during rainy periods and increased up to 0.45 mg s-1 during dry periods. Because continental runoff in semi-arid regions is affected by land use and global climate changes, the increasing accumulation of particulate Hg in the estuaries and increasing export of dissolved Hg to the ocean are expected.

Emission factors of anthropogenic activities and natural processes were used to estimate nutrients and metals loads to the Contas River lower basin, Southern Bahia, Brazil. Among natural sources, emission from soil leaching is larger for N, Cu and Pb. Atmospheric deposition is the major natural source of P, Zn, Cd and Hg. Among anthropogenic sources, agriculture is the major source of N, Cu and P. Urban sources are the major contributors to the other elements. Present anthropogenic land uses are already responsible for 78 and 99% of total N and P loads and about 50% of total Cu and Hg.

O objetivo desse trabalho foi otimizar uma metodologia semi-automática utilizando cartuchos comerciais preenchidos com ouro puro (Tekran Inc.) para a quantificação de mercúrio gasoso elementar em atmosfera tropical. O limite de detecção foi 0,020 ± 0,006 ng de Hg. Isso corresponde a limites de detecção variando entre 0,2 e 0,4 ng m-3, para volumes de amostragem entre 0,1 e 0,05 m³. A similaridade entre os 9 cartuchos foi avaliada. A avaliação do efeito da vazão de amostragem entre 0,4 e 2,0 L min-1 não representou diferença. A capacidade máxima de retenção dos cartuchos (breakthrough) não foi alcançada nos experimentos com vazão de 1 ou 2 L min-1, concentração de Hg de 25 ng m-3 e volume máximo de 150 L. A condensação de água na superfície do ouro mostrou ser um problema, mas isso foi solucionado com o aquecimento do cartucho de amostragem a 60 ºC.

The aim of this study was to optimize a semi-automatic methodology using commercial pure gold cartridges (Tekran Inc.) to quantify gaseous elemental mercury (GEM) in the Amazon atmosphere. The detection limit was 0.020 ± 0.006 ng Hg. This corresponds to detection limits varying from 0.2 to 0.4 ng Hg m-3, for field sample volumes ranging between 0.1 and 0.05 m³. The similarity between the 9 tested cartridges was evaluated. Under sampling flow rates varying between 0.4 and 2.0 L min-1 no difference among cartridges was observed. The maximum retention capacity of the cartridge (breakthrough) was not reached in experiments with flow rates of 1 or 2 L min-1, and with Hg concentration of 25 ng m-3 and maximum air volume of 150 L. Water condensation on the gold surface showed to be a problem, but that was solved by heating the sample cartridge at 60 ºC during sampling.

Este estudo descreve as mudanças na especiação de Hg nas águas da Baía de Sepetiba, SE, Brasil, ao longo do gradiente estuarino, durante eventos de maré em diferentes estações. A avaliação química das águas da baía indicou uma exportação de material particulado em suspensão (MPS) pobre em carbono orgânico para a plataforma continental adjacente, principalmente durante a estação chuvosa e uma importação de MPS oceânico rico em carbono orgânico, provavelmente de origem fitoplanctônica, durante a estação seca. A especiação química do Hg demonstrou que a produção de Hg0 na Baía de Sepetiba pode ser controlada pela produtividade primária, e que a baía atua como produtora e exportadora de formas orgânicas de Hg para as áreas adjacentes, já que as maiores concentrações de Hg não-reativo foram encontradas durante a maré vazante. Não foram observadas correlações significantes entre as concentrações de Hg não-reativo e carbono orgânico dissolvido ou particulado. Em geral, as frações de Hg particulado, Hg não-reativo e Hg reativo representam 55%, 35% e 9,5% do conteúdo total de Hg nas águas da Baía de Sepetiba, respectivamente.

This work describes changes in Hg speciation in water along the transport from Sepetiba Bay, SE Brazil, to the adjacent continental platform during tide events and in different seasons. The chemical evaluation of Sepetiba Bay waters showed that the bay exports suspended particulate material (SPM) impoverish in organic carbon to adjacent continental platform areas, mainly during the wet season and imports SPM enriched in organic carbon from the ocean, probably of phytoplanktonic origin, during the dry season. The chemical speciation of Hg during the study period showed that Hg0 production can be controlled by primary productivity and that the bay acts as a producer and exporter of organic species of Hg to adjacent areas, since the highest non-reactive Hg concentrations were observed during the ebb tide. No significant correlations were found between non-reactive Hg and dissolved or particulate organic matter concentrations. In general the particulate Hg, non-reactive Hg and reactive Hg fractions represents 55%, 35.5% and 9.5% of the total Hg content in Sepetiba Bay waters, respectively.

The monitoring of the pollution status of the Brazilian coast is hampered by the lack of a consistent environmental indicator. We propose Hg as an environmental proxy to anthropogenic pollution of coastal regions due to its absence in the Brazilian geology, its ubiquity in anthropogenic effluents, and its toxicity. Available data suggest Hg "backgrounds" in coastal sediments of 1-10 ng g-1, in the East and 15-30 ng g-1 in the South. We suggest short sediment cores to establish these values estimating a geo-accumulation index to compare all areas. The distribution of index values showed the majority of southern coast at least moderately contaminated whereas many eastern areas are still pristine.

The determination of the physical-chemical mercury speciation in tropical coastal waters using the derivatization technique with CVAFS detection was optimized. This methodology is able to separate the elementary, reactive, organic and total mercury phases with low operational costs. The importance of bromide chloride solution, the diluted aqua regia, used as the oxidative solution, and different compositions of the reductive solution of stannous chloride were tested and the better results for coastal waters are presented. The recuperation of the sum of the different phases ranges from 80 to 94% of the total Hg content in duplicates of different marine samples. The optimized methodology permits important studies on the mercury cycle in the coastal environment.

As concentrações totais de Hg foram medidas em amostras de deposição atmosférica total coletadas em três regiões costeiras do Estado do Rio de Janeiro, sudeste do Brasil entre Outubro de 1998 e Dezembro de 1999. Amostras foram coletadas em Campos dos Goytacazes, área agrícola no norte do estado, em Niterói, região urbanizada e industrializada, e em Itacuruçá, um pólo turístico no litoral sul. As concentrações de Hg em Campos apresentaram uma média de 0,51 ng L-1, variando de 0,07 a 1,01 ng L-1, e mostraram uma tendência sazonal aparentemente afetada pela queima da cana de açúcar no inverno. Em Niterói, foram medidas as maiores concentrações, com média de 0,73 ng L-1 e variando de 0,06 a 2,95 ng L-1, sem padrão de distribuição sazonal definido. Em Itacuruçá, 35% das amostras apresentaram concentrações menores que o limite de detecção do método (<0,02 ng L-1), com média de 0,24 ng L-1 e variando entre <0,02 a 1,04 ng L-1.

Total Hg concentrations were measured in bulk atmospheric deposition from three sampling stations along the Rio de Janeiro State coast, Southeast, Brazil, from October 1998 to December 1999. Samples were collected at Campos dos Goytacazes, an agriculture center at the North coast; Niterói, an industrialized metropolitan area and at Itacuruçá, a tourist town at the South. Concentrations at Campos average 0.51 ng L-1, ranging from 0.07 to 1.01 ng L-1, and showed a seasonal trend, probably affected by burning of sugar cane plantations in winter. At Niterói, concentrations were highest, averaging 0.73 ng L-1 andranging from 0.06 to 2.95 ng L-1. No pattern of temporal variation was observed and concentration peaks are probably related to industrial emissions. At Itacuruçá, Hg concentrations were below the detection limit of the method (0.02 ng L-1) in 35% of the samples, with an average of 0.24 ng L-1 and ranging from <0.02 to 1.04 ng L-1.

As concentrações de Hg total e reativo, de carbono orgânico dissolvido (COD) e carbono orgânico particulado (COP) foram medidas em diferentes massas d'água na Baía de Sepetiba, SE do Brasil, com o objetivo de avaliar mudanças na reatividade do Hg ao longo do gradiente estuarino. As concentrações de Hg reativo foram mais baixas em águas da baía franca (0,09 ± 0,06 ng L-1), seguidas pelas águas influenciadas por rios (0,19 ± 0,06 ng L-1), e pelas de manguezais (0,29 ± 0,02 ng L-1). As concentrações de Hg total foram menores em águas da baía franca (0,38 ± 0,20 ng L-1), seguidas pelas águas de manguezais (0,56 ± 0,01 ng L-1), e foram maiores nas águas influenciadas por rios (0,99 ± 0,29 ng L-1). O percentual de Hg reativo em relação à concentração total foi menor nas águas influenciadas por rios (20,7%), seguidas pelas de águas da baía franca (31,2%), e foram maiores nas águas de manguezais (53,2%). O percentual de Hg reativo em relação à concentração total apresentou significativa correlação inversa com as concentrações de Hg total. Nenhuma correlação significativa foi encontrada entre as concentrações de Hg e a salinidade, o COP e o pH. Entretanto, as concentrações de Hg reativo apresentaram uma correlação positiva, significativa com o COD, mostrando que o controle da reatividade do Hg e, eventualmente, de sua biodisponibilidade na Baía de Sepetiba, deve-se principalmente a formação de complexos com a matéria orgânica dissolvida.

A survey of the reactive and total Hg concentrations in surface waters and of the quantity of particulate organic carbon (POC) and dissolved organic carbon (DOC), were performed along a transect from the major rivers mouths and mangrove dominated areas to the open bay waters of Sepetiba Bay, SE Brazil. The objective of the survey was to evaluate changes in Hg reactivity during the transport along the estuarine gradient. Reactive Hg concentrations were lowest in open bay waters, (0.09 ± 0.06 ng L-1), followed by river influenced waters (0.19 ± 0.06 ng L-1), and mangrove (0.29 ± 0.02 ng L-1). Total Hg concentrations were lowest in open bay (0.38 ± 0.20 ng L-1), followed by mangrove waters (0.56 ± 0.01 ng L-1), and river influenced waters (0.99 ± 0.29 ng L-1). The percentages of reactive Hg relative to the total Hg concentrations were lowest in river influenced waters, (20.7%), followed by open bay waters (31.2%), and mangrove waters (53.2%). The percent of reactive Hg to the total Hg concentrations showed a significant negative correlation with the total Hg concentrations following a potential equation. No relationship between reactive Hg concentrations and POC, salinity or pH were found, however, reactive Hg correlates significantly with DOC, suggesting that organo-complexes, rather than chloro-complexes, are the major controllers of Hg reactivity, and eventually bioavailability in Sepetiba Bay.