Mobility, bioavailability and distribution of Fe and Cu in mangroves (Avicennia schaueriana and Rhizophora mangle) from a semiarid coast in NE Brazil.

Mangroves buffer metals transfer to coastal areas though strong accumulation in sediments making necessary to investigate metals' bioavailability to plants at the rhizosphere. This work evaluates the effect of mangrove root activity, through iron plaque formation, on the mobility of iron and copper its influence on metals' uptake, and translocation through simultaneous histochemical analysis. The Fe2+ and Fe3+ contents in porewaters ranged from 0.02 to 0.11 µM and 1.0 to 18.3 µg.l-1, respectively, whereas Cu concentrations were below the method's detection limit (<0.1 µM). In sediments, metal concentrations ranged from 12,800 to 39,500 µg.g-1 for total Fe and from 10 to 24 µg.g-1 for Cu. In iron plaques, Cu concentrations ranged from 1.0 to 160 µg.g-1, and from 19.4 to 316 µg.g-1 in roots. Fe concentrations were between 605 to 36,000 µg.g-1 in the iron plaques and from 2,100 to 62,400 µg.g-1 in roots. Histochemical characterization showed Fe3+ predominance at the tip of roots and Fe2+ in more internal tissues. A. schaueriana showed significant amounts of Fe in pneumatophores and evident translocation of this metal to leaves and excretion through salt glands. Iron plaques formation was essential to the Fe and Cu regulation and translocation in tissues of mangrove plants.

Non-conservative behavior of organic matter and its interaction with metals in an equatorial estuary, Brazil.

Droughts are becoming more intense and frequent in the Brazilian semiarid because of El Niño and global climate changes. The Jaguaribe River estuary is a semiarid ecosystem that experiences a reduction in freshwater discharges due to droughts and river damming. The decrease in freshwater fluxes has increased metal availability through the water residence time increase in the Jaguaribe River estuary. Then, this study aimed to evaluate the dissolved organic matter quality and its interaction with metals in the Jaguaribe River estuary after a severe drought period. It was performed through carbon analyses, fluorescence spectroscopy, ultrafiltration technique, and determinations of metals by ICP-MS. Optical analysis showed that the dissolved organic carbon (DOC) was preponderantly composed of terrestrial-derived humic compounds, while the low ratio between the particulate organic carbon (POC) and chlorophyll-a indicated that POC was predominantly phytoplankton-derived. DOC and POC presented non-conservative removal during the estuarine mixing. DOM and dissolved elements were mostly distributed within the LMW fraction and presented a low percentage in the colloidal fraction. Li, Rb, Sr, Mo, and U showed conservative behavior, while Cu, Fe, Cr, and V had non-conservative behavior with a significant positive correlation with DOM, suggesting DOM as a relevant driver of metal availability at the Jaguaribe River estuary even during the rainy season.

Trace metal partitioning in the parnaíba delta in dry season, equatorial coast of Brazil.

Trace metal concentrations in the particulate fractions (MP), dissolved fractions (MD) and sediments (MS), such as Ba, Cu, Co, Cr, Pb, Ni and Zn, were determined during the dry season of the largest open sea delta of Americas, the Parnaíba River Delta (Brazil). This study aimed to comprehend the distribution, dynamic changes of metal speciation and environmental quality index of trace metals in the particulate fractions and subsurface sediments in scenario of major marine influence over the delta. The trace metals bound to suspended particulate material (SPM) from weathering the drainage basin exhibited a removal trend under increases in salinity and pH. Desorption influenced the partitioning of BaMP, ZnMP, NiMP, CoMP, CuMP, and the adsorption and precipitation of PbMP and CrMP to the surface sediments. The organic matter contents in the sediments acts as an important geochemical carrier of these contaminants, and the dissolved organic carbon influences the binding of PbMD in the subsurface waters. The geoaccumulation index (Igeo) plays a crucial role in revealing potential contamination with ZnMP contents and weak association to this fraction. These results make possible the assessment of ecological risk by metal contamination and global pollution mitigation in coastal tidal estuaries under intensive physical mixing along the equatorial coast.

Dredging impacts on the toxicity and development of sediment quality values in a semi-arid region (Ceará state, NE Brazil).

Sediment dredging impacts coastal environments by promoting the resuspension of fine particles and remobilization of contaminants that may trigger toxic effects. In this study, we evaluated the sediment quality in harbor areas of Mucuripe bay, a semi-arid ecosystem located in Ceará state (Brazil), which is subject to dredging activities. A sampling survey was conducted right after dredging operations and data compared to another survey performed prior dredging. Sediments were analyzed for fine particles, organic carbon, nutrients, metals, hydrocarbons, and tributyltin (TBT). Toxicity of whole-sediment and liquid phase exposures were also determined. The concentrations of Cd, Cr, Cu, and Zn decreased after dredging, which was confirmed by the geoaccumulation index. Levels of TBT dropped while phosphorus, aliphatic and polycyclic aromatic hydrocarbons increased. Toxic effects persisted, indicating a post-dredging recontamination combined with other sources such as urban runoff, wastewater discharges, harbor activities, and antifouling particles. Data from Mucuripe and Pecém harbors were compiled and site-specific sediment quality values (SQVs) were developed by using multivariate methods. The threshold values proposed by our study were lower and more effective to predict toxicity compared to international guidelines, indicating levels of contamination for this tropical region in which toxic effects may occur. Considering the large geographic area with different sediment characteristics of the Brazilian coast, this study represents a significant contribution to sediment toxicity assessment of dredging activities in semi-arid environments.

Phosphorus and suspended matter retention in mangroves affected by shrimp farm effluents in NE Brazil.

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.

Biomarkers responses of the clam Anomalocardia flexuosa in sediment toxicity bioassays using dredged materials from a semi-arid coastal system.

Few test organisms are employed for sediment toxicity assessments in Tropical regions, including Brazil. We assessed the ability of the clam Anomalocardia flexuosa to respond to contamination in sediment bioassays using dredging materials of a semi-arid region (Ceará State, NE Brazil), with attention to sublethal responses. Sediments were collected during and after dredging (survey 1 and 2, respectively) and animals exposed in laboratory over 28 days, with responses measured at 7 days. Bioaccumulation of contaminants was determined in whole-body soft tissues as a metric of bioavailability, and biomarkers' changes were monitored in terms of enzymes of phase I and II metabolism, acetylcholinesterase (AChE), and antioxidant responses, lipid peroxidation (LPO) and DNA damage (strand breaks). Clams accumulated aliphatic (AHs) and aromatic hydrocarbons (PAHs), and linear alkylbenzenes (LABs) compared to control conditions (day 0), with increased amounts of As, Cd, Cu, and Zn observed in some samples. The enzyme glutathione S-transferase was enhanced in animals exposed to samples, indicating activation of phase II metabolism. Changes observed in glutathione peroxidase (GPx), glutathione reductase (GR), LPO and strand breaks were related to oxidative stress. AChE enzymatic activity also changed, as an indicator of neurotoxicity caused by sediment exposure. The computed integrated biomarker response index (IBR) ranked sites according to the contamination status and proximity to its sources. Correlations found for biomarkers and bioaccumulation of hydrocarbons indicated the influence of harbor activities, effluent discharges, and urban runoff on the sediment pollution of Mucuripe Bay. Data also showed that SQGs are unable to predict bioaccumulation and subchronic effects. Based on our results we consider that biomarkers responses in A. flexuosa are important endpoints to be applied in sediment toxicity bioassays in tropical regions.

Carbon influence on metal distribution in sediment of Amazonian macrotidal estuaries of northeastern Brazil.

The present work aims to observe the spatial distribution of metals associated with carbon forms (fraction < 2 mm) in surface sediments of two macrotidal estuaries, São Marcos Bay and Anil River Estuary, which are located within the transition region between the Amazonian and the semi-arid northeast regions. Grain size, metal content (Al, Fe, Mn, Cu, Pb, Cr, Zn, and Ni), organic matter, and calcium carbonate content were determined. Grain size analyses showed the predominance of the sand-sized fraction < 2 mm due to the local hydrodynamic conditions. Anil River Estuary sediments exhibited high organic matter content due to both the mangrove outwelling and domestic sewage discharge. They also presented high calcium carbonate content as a result of abundant remnants of gastropod shells. Organic matter acted as the primary geochemical carrier for most metals in both estuaries, while calcium carbonate acted as the secondary carrier. Enrichment factors indicated Mn sediment contamination in São Marcos Bay and Fe, Pb, and Zn contamination in the Anil River Estuary. These results also suggest that São Marcos Bay is influenced by harbor activities, mostly ore shipment, whereas Anil River Estuary sediments are enriched in these metals as a result of domestic and hospital effluents reaching the urbanized drainage basin.

Sub-lethal Responses of the Polychaete Armandia agilis in Whole-sediment Toxicity Testing.

The present study assessed biochemical responses as sublethal endpoints in the polychaete Armandia agilis exposed to contaminated sediments to in order to assess its potential use as a test organism. Sediment samples from several locations at a dredging site were obtained and used in whole-sediment exposures. Samples were tested with A. agilis to determine the 10-day toxicity of the 100% sample and the enzymatic activity of catalase (CAT), glutathione-S-transferase (GST) and acetylcholinesterase (AChE) biochemical measurements made in whole-body homogenates of a subset of the surviving organisms. Biochemical responses reported in A. agilis were not statistically different from the reference site sediment, however, the integrated analysis demonstrated that contaminants bound to sediment samples influenced the sublethal effects.

Limnology of the largest multi-use artificial reservoir in NE Brazil: The Castanhão Reservoir, Ceará State.

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.

Phosphorus partitioning in sediments from a tropical reservoir during a strong period of drought.

Monitoring phosphorus (P) concentration in water and sediments in the Castanhão reservoir, under intensive aquaculture, in Northeastern Brazil showed internal process to dominate P cycling following a reduction of reservoir volume due to an extended drought period. A strong negative correlation between soluble reactive phosphorus in surface waters (SRPs) with the reservoir volume results from diminishing dilution capacity; bottom water SRP showed no significant correlation with volume and imply SRP remobilization to surface layers. Total suspended solids (TSS) showed a significant correlation with chlorophyll-a, suggesting change primary productivity following SRP enrichment of surface waters and living cells dominating the TSS. As a result, eutrophication, as established by a trophic state index, was triggered in the reservoir probably enforced by intensive fish farming effluents, whose nutrients accumulated in bottom waters and which became available due to breaking of the thermocline. Since low rainfall periods are typical of the semiarid region and tend to be more frequent and stronger due to climate change, multiple use of reservoirs in NE Brazil should be reevaluated.

Background values for evaluation of heavy metal contamination in sediments in the Parnaíba River Delta estuary, NE/Brazil.

This study establishes regional background levels and upper thresholds (geochemical baseline) for Zn, Cu, Pb, Cr, Mn, and Fe from surface samples and profiles taken in 16 sedimentary environments of the Parnaíba River Delta estuary, NE-Brazil. Three approaches were applied to evaluate metal contamination: normalization to Fe, statistical analysis and sediment quality guidelines or environmental assessment criteria (TEL-PEL). Metal concentrations in sediments ranged from 2.4 to 31 mg Zn kg(-1), 1.5 to 48 mg Cu kg(-1), 1.3 to 28 mg Pb kg(-1), 1.5 to 38 mg Cr kg(-1); 145 to 1,356 mg Mn kg(-1), and 0.3% to 2.5% for Fe. All metals showed positive correlations with the <0.63 µm sediment fraction, indicating a significant association with rich lithogenic sources of iron oxide-hydroxides. Results suggest a low probability of adverse effects to the local aquatic biota. The background values of the area were lower than those reported for other areas of the northeastern coast of Brazil.

Sediment quality assessment in a tropical estuary: the case of Ceará River, Northeastern Brazil.

The present study aimed to assess the sediment quality in a tropical estuary located in the northeast of Brazil under semi-arid conditions and multiple sources of contamination, using both toxicity bioassays and metal distribution. The metal distribution followed a concentration gradient decreasing one order of magnitude from the inner station toward the outer estuary, with amounts in the following order: Fe > Al > Zn > Cr > Pb > Cu. The index of geoaccumulation indicated a metal enrichment in the Ceará river sediment, mainly at inner sites, considered from moderately to strongly contaminated by Al, Cu, Cr and Zn. Sediment samples were considered toxic by means of whole sediment tests with copepods (reproduction) and amphipods (survival), and also elutriate fraction and sediment-water interface with sea urchin embryos (development). Acute and chronic toxicity did not exhibit a significant correlation with metals, emphasizing the influence of other contaminants mainly related to the pollution sources installed in the mid-estuary.

A new protocol to detect light elements in estuarine sediments by X-ray microanalysis (SEM/EDS).

The analytical scanning electron microscope (SEM) has been used to determine the presence and distribution of atomic elements in mineralogy. However, the detection of light elements such as carbon is difficult to obtain with standard energy-dispersive X-ray spectrometry (EDS) and usual proceedings for SEM. This study proposes a new protocol to detect calcium carbonate by SEM/EDS using sediments from the Jaguaribe River estuary, NE Brazil, as a model. Handmade gold mounting discs (Au stubs) were used as sample support and samples were adhered with inexpensive glue (Loctite Super_Bonder) or directly disposed on the Au stubs. CaCO(3) and NaCl for chemical analysis were used as control and counterproof to the carbon adhesive tape. Control salts EDS analyses indicate that the method was efficient to detect light elements. Sediments obtained from different depths in the core sampled at the Jaguaribe River estuary consist of particles and aggregates with diverse morphology that covers a wide range of particle or aggregate size. Morphology and dimensions were similar for all core depths. Analysis of samples disposed on gold mounting disc without glue showed that sediment bulk particles usually presented small particles adhering on the surface. Clay minerals were predominant but silica was also often identified. Calcium was a trace element in a small number of sediment bulk particles. Biological and non-biological calcium carbonates, including nanoparticles, were identified in all core depths. X-ray emitted from Au stub did not interfere in the CaCO(3) EDS analysis. Calcium carbonate particles from sediments were identified using this novel approach.

Mercury degassing from forested and open field soils in Rondônia, Western Amazon, Brazil.

A Teflon dynamic flux chamber was used to characterize Gaseous Elemental Mercury (GEM) flux from forested and open field soils in a highly changing environment in Rondônia State, western Amazon. We simultaneously analyzed meteorological parameters at the soil level relating GEM fluxes to soil temperature, air humidity, soil moisture, solar radiation, and speed and wind direction. We also examined variations of atmospheric GEM concentration. GEM fluxes during the day and night in the open field site were significantly different (17+/-14ngm(-2) h(-1) and 0.9+/-1.9ngm(-2)h(-1), for day and night, respectively), but were similar within the forest site (4.8+/-1.4ngm(-2)h(-1) and 4.4+/-1.8ngm(-2) h(-1) for day and night periods, respectively). A comparison between 24-h periods averages in the two sites showed much larger emission from the open field site. GEM fluxes at the open field site were positively correlated with soil moisture, solar irradiation and soil temperature and inversely correlated with air humidity. At the forest site GEM fluxes showed no correlation with meteorological variables. At the open field site GEM concentrations significantly correlated with GEM flux, at least during the day. At night in the open field site and during the day and night at the forest site no correlation was found between GEM fluxes and GEM concentrations in the ambient air. Higher emissions from the open field site support earlier studies showing larger Hg remobilization following forest conversion to pasture.

Mercury emissions into the Sepetiba Bay basin, SE Brazil

Mercury emissions to soil, waters, and the atmosphere in the Sepetiba Bay basin were estimated by means of emission factors and data base of major industrial and urban sources of Hg. This approach is the most effective in assessing pollutant loads from diffuse sources, as in the case of Hg in the Sepetiba Bay basin. Total Hg emission ranges from 20 to 364 kg yr(-1). A significant fraction of this input is to the atmosphere, ranging from 115 to 149 kg yr(-1) (41 to 58 per cent), mostly due to emissions from iron and steel production and an oil fired power plant. Inputs to soil range from 84 to 215 kg yr(-1) (42 to 59 per cent), mostly from an urban ladfill and from metal manufacturing. Direct inputs to surface water are small (<1.0 kg yr(-1). Estimated total and atmospheric emissions agree with measurements of atmospheric Hg deposition and with preliminary data on fluvial systems.