Attenuation of wind intensities exacerbates anoxic conditions leading to sulfur plume development off the coast of Peru.

The release of vast quantities of sulfide from the sediment into the water column, known as a sulfidic event, has detrimental consequences on fish catches, including downstream effects on other linked element cycles. Despite being frequent occurrences in marine upwelling regions, our understanding of the factors that moderate sulfidic event formation and termination are still rudimentary. Here, we examined the biogeochemical and hydrodynamic conditions that underpinned the formation/termination of one of the largest sulfur plumes to be reported in the Peruvian upwelling zone. Consistent with previous research, we find that the sulfur-rich plume arose during the austral summer when anoxic conditions (i.e., oxygen and nitrate depletion) prevailed in waters overlying the upper shelf. Furthermore, the shelf sediments were organically charged and characterized by low iron-bound sulfur concentrations, further enabling the diffusion of benthic-generated sulfide into the water column. While these biogeochemical conditions provided a predicate to sulfidic event formation, we highlight that attenuations in local wind intensity served as an event trigger. Namely, interruptions in local wind speed constrained upwelling intensity, causing increased stratification over the upper shelf. Moreover, disturbances in local wind patterns likely placed additional constraints on wind-driven mesoscale eddy propagation, with feedback effects on coastal elemental sulfur plume (ESP) formation. We suggest ESP development occurs as a result of a complex interaction of biogeochemistry with regional hydrodynamics.

Carbon fluxes in a carbonate rock dominated microbasin of the Quadrilátero Ferrífero, Brazil.

This study evaluated carbon dynamics in a carbonate microbasin (Bule stream), located in an important metallogenetic area (QF) in Brazil. River water collections were performed on a base and high flow. The microbasin showed high DIC, with HCO3- being the main component, followed by CO2. The pCO2 showed high values, indicating fluxes in the water → air direction. The degassing was 683.4 mmol m-2 day-1 (average at low flow) and 43.4 mmol m-2 day-1 (average at high flow). The fluvial flow was 9 to 31 kg km-2 day-1 of HCO3- and 1.4 to 0.7 kg km-2 day-1 of CO2, respectively, at the base and high flow. Considering the importance of the lithological unit of the Minas Supergroup for the QF, the total flow of CO2 released by all the basins that compose such units was estimated. The estimated values were 1.3 × 1012 mmol day-1 in low flow and 8.4 × 1010 mmol day-1 in high flow. The data obtained in this study were the first in the QF region. The Bule stream is an environmental protection area, free from contamination, considered a background for other drainage basins inserted in the QF. The results obtained reinforce the importance of hydrographic microbasins influence on the river carbon fluxes in a regional and global context.

Evaluation of the bioaccumulation kinetics of toxic metals in fish (A. brasiliensis) and its application on monitoring of coastal ecosystems.

This study proposes a pro-active approach for evaluations of methylmercury (MeHg), total mercury (THg), arsenic (As), cadmium (Cd) and lead (Pb) in situ bioaccumulation in fish (Atherinella brasiliensis) muscles, using specimens from the external sector of Guanabara Bay as a study case. This approach included an hierarchical sequence: analysis of the pollutants concentrations and their comparison to safety criteria; correlations between specimens concentrations vs length (as a proxy of exposure time); projections of concentrations in key lengths (sexual maturation, asymptotic, length limits for fishing and median of fish population) through polynomial regressions, dose-response analysis (Probit), decreasing curves and incorporation rates (using only three length intervals). The incorporation rates were ascending for MeHg and THg (continued bioaccumulation) and descending for As, Pb and Cd (possible biological dilution). The projections were satisfactory, evidencing their use for an improvement on the risks monitoring of fishing and fish consumption by humans in coastal environments.

Foliar mercury content from tropical trees and its correlation with physiological parameters in situ.

The terrestrial biogeochemical cycle of mercury has been widely studied because, among other causes, it presents a global distribution and harmful biotic interactions. Forested ecosystems shows great concentrations from Hg and Litterfall is known as the major contributor to the fluxes at the soil/air interface, through the superficial adsorption on the leaves and by the gas exchange of the stomatal pores. The understanding of which processes control the stage of Hg cycle in these ecosystems is still not totally clear. The influences of physiological and morphological parameters were tested against the Hg concentrations in the leaves of 14 endemic species of an evergreen tropical forest in south-eastern Brazil, and an exotic species from Platanus genus. Pathways were studied through leaf areas and growing tree parameters, where maximum rate of net photosynthesis (Pnmax), transpiration rate (E), stomatal conductance (Gs) were examined. The results obtained in situ indicated a positive correlation between Pnmax and the Hg concentration; Cedrela fissilis and Croton floribundus were the most sensitive species to the accumulation of Hg and the most photosynthetically active in this study. The primary productivity from Tropical forest should be a proxy of Hg deposition from atmosphere to soil, retained there while forests stand up, representing an environmental service of sequestration of this global pollutant. Therefore, forests and trees with great photosynthetic potential should be considered in predictions, budgets and non-geological soil content regarding the global Hg cycle.

Mercury sequestration by rainforests: The influence of microclimate and different successional stages.

Mercury (Hg) concentrations in tropical forest soils and litter are up to 10 times higher than those from temperate and boreal forests. The majority of Hg that has been stored in tropical soils, as the forest is left intact, could be trapped in deeper layers of soil and only small quantities are exported to water bodies. The quantitative approach to the Hg cycle in tropical forests is uncommon; the South America Atlantic Forest indeed is a hotspot for species conservation and also seems to be for the Hg's cycle. This study reports on a biannual dynamics of Hg through different species assemblage of different successional stages in this biome, based on 24 litter traps used to collect litterfall from 3 different successional stages under a rainforest located at Brazilian Southeast. The mean Hg litterfall flux obtained was 6.1 ± 0.15 µg ha-1 yr-1, while the mean Hg concentration in litter was 57 ± 16 ng g-1 and the accumulation of Hg via litterfall flux was 34.6 ± 1.2 µg m-2 yr-1. These inventories are close to those found for tropical areas in the Amazon, but they were lower than those assessed for Atlantic Forest biome studies. These low concentrations are related to the remoteness of the area from pollution sources and probably to the climatic limitation, due to the altitude effects over the forest's eco-physiology. The mercury fluxes found in each different successional stage, correlated with time variations of global radiation, suggesting a mandatory role of the forest primary production over Hg deposition to the soil.

Carbon accumulation rates recorded in the last 150years in tropical high mountain peatlands of the Atlantic Rainforest, SE - Brazil.

Peatlands are environmental matrices that store large amounts of organic carbon (TOC) and work as records of environmental changes. Recent record of organic carbon accumulated were assessed in two Forest National Parks, Itatiaia and Serra dos Órgãos in the Southeastern of Brazil. Based on organic and inorganic characterization, the cores from peatlands presented a predominance of organic material in an advanced stage of decomposition and those soils were classified as typical Haplosaprists Histosols. The combination of favorable topographic and climatic conditions led to rapid C accumulation across coastal mountain in the tropical peatlands studied, presenting an average accumulation rate of C, in the last century, of 194gCm-2yr-1 about 7 higher times than the rate found in boreal and subarctic peatlands, those higher values may be related to changes in the hydrological cycle occurred since 1950s.

Mercury dilution by autochthonous organic matter in a fertilized mangrove wetland.

A dated sediment core from a highly-fertilized mangrove wetland located in Cubatão (SE Brazil) presented a negative correlation between mercury (Hg) and organic carbon contents. This is an unusual result for a metal with well-known affinity to organic matter. A dilution of Hg concentrations by autochthonous organic matter explained this observation, as revealed by carbon stable isotopes signatures (δ(13)C). Mercury dilution by the predominant mangrove-derived organic matter counterbalanced the positive influences of algal-derived organic matter and clay contents on Hg levels, suggesting that deleterious effects of Hg may be attenuated. Considering the current paradigm on the positive effect of organic matter on Hg concentrations in coastal sediments and the expected increase in mangrove organic matter burial due to natural and anthropogenic stimulations of primary production, predictions on the influences of organic matter on Hg accumulation in mangrove wetlands deserve caution.

Mercury speciation in plankton from the Cabo Frio Bay, SE--Brazil.

Mercury (Hg) is considered a global pollutant, and the scientific community has shown great concern about its toxicity as it may affect the biota of entire systems, through bioaccumulation and bioamplification processes of its organic form, methylmercury (MeHg), along food web. However, few research studies deal with bioaccumulation of Hg from marine primary producers and the first-order consumers. So, this study aims to determine Hg distribution and concentration levels in phytoplankton and zooplankton in the Cabo Frio Bay, Brazil, a site influenced by coastal upwelling. The results from Hg speciation analyses show that inorganic mercury Hg(II) was the predominant specie in plankton from this bay. The annual Hg species distribution in plankton shown mean concentration of 2.00 ± 1.28 ng Hg(II) g(-1) and 0.15 ± 0.08 ng MeHg g(-1) wet weight (phytoplankton) and 2.5 ± 2.03 ng Hg(II) g(-1) and 0.25 ± 0.09 ng MeHg g(-1) wet weight (zooplankton). Therefore, upwelling zones should be considered in the Hg biogeochemical cycle models as a process that enhances Hg(II) bioaccumulation in plankton, raising its bioavailability and shelf deposition.

Carbon, nitrogen, and phosphorus stoichiometry of plankton and the nutrient regime in Cabo Frio Bay, SE Brazil.

This long-term study, performed during the years 2003-2005 and 2008-2009, investigated the carbon (C), nitrogen (N), and phosphorus (P) contents of the phyto- and zooplankton communities and the nutrient regime of Cabo Frio Bay, SE Brazil. The information intends to serve as baseline of the plankton C, N, and P stoichiometry for the calibration of biogeochemical and ecological models in support to future findings related to the local and regional phenomena of climatic change. Cabo Frio Bay is a small semienclosed system set adjacent to a region subject to sporadic coastal upwelling. Zooplankton exhibited average annual C, N, and P contents of 11.6 ± 6.9 %, 2.8 ± 1.8 %, and 0.18 ± 0.08 %, and phytoplankton (>20 µm) 6.8 ± 6.0 %, 1.6 ± 1.5 %, and 0.09 ± 0.08 %, respectively. The C/N/P ratios correspond to the lowest already found to date for a marine environment. The low C contents must have been brought about by a predominance of gelatinous zooplankton, like Doliolids/ Salps and also Pteropods. Average annual nutrient concentrations in the water were 0.21 ± 0.1 µM for phosphate, 0.08 ± 0.1 µM for nitrite, 0.74 ± 1.6 µM for nitrate, and 1.27 ± 1.1 µM for ammonium. N/P ratios were around 8:1 during the first study period and 12:1 during the second. The plankton C/N/P and N/P nutrient ratios and elemental concentrations suggest that the system was oligotrophic and nitrogen limited. The sporadic intrusions of upwelling waters during the first study period had no marked effect upon the systems metabolism, likely due to dilution effects and the short residence times of water of the bay.

Mercury deposition during the previous century in an upwelling region; Cabo Frio, Brazil.

To investigate the upwelling influence on Hg biogeochemical cycles and the sedimentological changes during the previous ≈ 150 years, four sediment box-cores were sampled along an inshore offshore transect on the Southeastern Brazilian continental shelf. Mercury values were found to be relatively low, with means ranging between 8.08 and 30.4 ng g(-1). Mercury fluxes along the sediment cores are directly related to the well documented historical regional activity and global atmospheric deposition. The narrow relationship between mercury and organic carbon suggest that upwelling phenomenon and primary production may play an important role on Hg input and distribution along continental shelf depositional settings.

Combined SEM/AVS and attenuation of concentration models for the assessment of bioavailability and mobility of metals in sediments of Sepetiba Bay (SE Brazil).

This study proposes a new methodology to study contamination, bioavailability and mobility of metals (Cd, Cu, Ni, Pb, and Zn) using chemical and geostatistics approaches in marine sediments of Sepetiba Bay (SE Brazil). The chemical model of SEM (simultaneously extracted metals)/AVS (acid volatile sulfides) ratio uses a technique of cold acid extraction of metals to evaluate their bioavailability, and the geostatistical model of attenuation of concentrations estimates the mobility of metals. By coupling the two it was observed that Sepetiba Port, the urban area of Sepetiba and the riverine discharges may constitute potential sources of metals to Sepetiba Bay. The metals are concentrated in the NE area of the bay, where they tend to have their lowest mobility, as shown by the attenuation model, and are not bioavailable, as they tend to associate with sulfide and organic matter originated in the mangrove forests of nearby Guaratiba area.

Litterfall mercury deposition in Atlantic forest ecosystem from SE-Brazil.

Litterfall is believed to be the major flux of Hg to soils in forested landscapes, yet much less is known about this input on tropical environment. The Hg litterfall flux was measured during one year in Atlantic Forest fragment, located within Rio de Janeiro urban perimeter, in the Southeastern region of Brazil. The results indicated a mean annual Hg concentration of 238 ± 52 ng g(-1) and a total annual Hg deposition of 184 ± 8.2 µg m(-2) y(-1). The negative correlation observed between rain precipitation and Hg concentrations is probably related to the higher photosynthetic activity observed during summer. The total Hg concentration in leaves from the most abundant species varied from 60 to 215 ng g(-1). Hg concentration showed a positive correlation with stomatal and trichomes densities. These characteristics support the hypothesis that Tropical Forest is an efficient mercury sink and litter plays a key role in Hg dynamics.

Recent 137Cs deposition in sediments of Admiralty Bay, Antarctica.

Cesium-137, radium-226 and lead-210 profiles of a 25 cm sediment core give an indication of recent changes in land-ocean interactions at a polar coastal environment (Admiralty Bay, King George Island, Antarctica). The linear sedimentation accumulation rate at the study site calculated from the unsupported (210)Pb profile was 6.7 mm/year from 1965 to 2005. A 3.5-fold increase in (137)Cs concentrations was observed in the top layer of this sediment core. This sharp increase seems to indicate a recent redistribution of fallout radionuclides previously deposited on soil, vegetation and snow. These results imply enhanced land-ocean interactions at this site likely as a result of climate change. Because our results are based on a single core, additional investigations are needed to confirm our observations.

Mercury flux to estuarine sediments, derived from Pb-210 and Cs-137 geochronologies (Guaratuba Bay, Brazil).

A sediment core from Guaratuba Bay was used to indicate possible Hg modifications to this coastal environment brought about by growing agricultural activity. Sedimentation rates were estimated to be 6.1 mm/year and 5.2 mm/year through 210Pb and 137Cs geochronologies, respectively. Mercury concentrations and organic matter ratios in the surface layers are greater than in the older sediments, supporting the hypothesis of anthropogenic enrichment. Results show that the Hg flux has raised more than twofold during the second half of the 20th century. These results point to the need for further studies to substantiate the hypothesis of anthropogenic enrichment and to quantify point sources of Hg to this estuary.

Mercury deposition through litterfall in an Atlantic forest at Ilha Grande, Southeast Brazil.

Atmospheric Hg transfer to the forest soil through litterfall was investigated in a primary rainforest at Ilha Grande (Southeast Brazil) from January to December 1997. Litter mass deposition reached 10.0 t ha (-1)y(-1), with leaves composing 50-84% of the total litter mass. Concentrations of Hg in the total fallen litter varied from 20 to 244 ng g(-1), with higher concentrations during the dry season, between June and August (225+/-17 ng g(-1)), and lower concentrations during the rainy season (99+/-54 ng g(-1)). This seasonal variability was reflected in the Hg flux through litterfall, which corresponded to a Hg input to the forest floor of 122 microg m(-2)y(-1), with average Hg deposition of 16.5+/-1.5 microg m(-2)month(-1) during and just after the dry season (June-September) and 7.0+/-3.6 microg m(-2)month(-1) in the rest of the year. The variability in meteorological conditions (determining atmospheric Hg availability to foliar scavenging) may explain the pulsed pattern of Hg deposition, since litterfall temporal variability was generally unrelated with such deposition, except by a peak in litterfall production in September. Comparisons with regional data on Hg atmospheric deposition show that litterfall promotes Hg deposition at Ilha Grande two to three orders of magnitude higher than open rainfall deposition in non-industrialized areas and approximately two times higher than open rainfall deposition in industrialized areas in Rio de Janeiro State. The observed input suggests that atmospheric Hg transfer through litterfall may explain a larger fraction of the total Hg input to forest soils in Southeast Brazil than those recorded at higher latitudes.

Apparent discrepancy in contamination history of a sub-tropical estuary evaluated through 210Pb profile and chronostratigraphical markers.

Zn and Cd concentrations, stable lead isotopes and 210Pb-derived chronology were determined in a sediment core sampled at Sepetiba Bay (South-eastern Brazil). During the last decades, the bay's watershed has been modified by the increase of industrial activities and human interventions. In particular, Zn and Cd ore treatment plants were built near the coast in 1960 and 1970, respectively, and water has been diverted from the adjacent Paraíba do Sul River watershed since 1950. The core collected at shallow depth near the industrial area exhibits four successive events: (i) at 50 cm depth, a change in the 206Pb/207Pb ratio from about 1.162 to more than 1.18 might be the result of the São Francisco Channel opening and water diversion from Paraíba do Sul river; (ii) at 40 cm depth, Zn concentration starts to increase (up to 0.8 mg g(-1)) (iii) above 30 cm depth, relatively high Cd concentrations (up to 1.6 microg g(-1)) are observed and (iv) at 16 cm depth, change in unsupported 210Pb slope is probably related to a waste dam built to prevent strong metal contamination in the bay. Sediment accumulation rates evaluated by Zn and Cd profiles used as time-markers are higher than those calculated from 210Pb-based chronology models. Using the constant initial concentration (CIC) model both events are supposed to date back to about 1884 and 1902, respectively, while using the constant rate of supply (CRS) model it shifts to about 1925 and 1935. Such discrepancies are probably assigned to the fact that these models do not take into account site-specific local sedimentation dynamics. In the study area, particles deposition seems to be controlled by enrichment with unsupported 210Pb transported by runoff from a mangrove flat bank. Chronology derived from a model that assumes an exponential increase of the initial 210Pb activity fits well with the estimated rates obtained from historical events.

Heavy metal contamination in coastal sediments and soils near the Brazilian Antarctic Station, King George Island.

This paper investigates the natural and anthropogenic processes controlling sediment chemistry in Admiralty Bay, King George Island, Antarctica, emphasizing the area affected by the Brazilian Antarctic Station Comandante Ferraz (Ferraz). Total and bioavailable concentrations of sixteen elements were determined in 32 sediment and 14 soils samples. Factor analysis allowed us to distinguish three groups of samples: (1) Ferraz sediments, with higher content of total trace metals and organic matter; (2) control sediments, with intermediate characteristics; (3) Ferraz soils, with higher bioavailability of most metals due to its oxidizing condition and low organic matter content. Major elements such as Fe, Al, Ca and Ti presented similar levels in all three groups. Enrichment factor calculations showed that paints, sewage and petroleum contamination enhanced metal concentrations in Ferraz surface sediments as follows: B, Mo, and Pb (>90%); V and Zn (70-80%); Ni, Cu, Mg, and Mn (30-40%). Despite evidence of contamination in these sediments, the low bioavailability, probably caused by iron-sulfide, indicates small environmental risks.