Impact of forest fire on the mercury stable isotope composition in litter and soil in the Amazon.

Mercury (Hg) emissions from forest fires, especially tropical forests such as the Amazonian forest, were shown to contribute significantly to the atmospheric mercury budget, but new methods are still necessary to improve the traceability and to reduce the great uncertainties related to this emission source. Recent studies have shown that the combustion process can result in Hg stable isotope fractionation that allows tracking coal combustion Hg emissions, as influenced by different factors such as combustion temperature. The main goal of the present study was, therefore, to investigate for the first time the potential of Hg stable isotopes to trace forest fire Hg emissions and pathways. More specifically, small-scale and a large scale prescribed forest fire experiments were conducted in the Brazilian Amazonian forest to study the impact of fire severity on Hg isotopic composition of litter, soil, and ash samples and associated Hg isotope fractionation pathways. In the small-scale experiment, no difference was found in the mercury isotopic composition of the samples collected before and after burning. In contrast, the larger-scale experiment resulted in significant mass dependent fractionation (MDF δ202Hg) in soils and ash suggesting that higher combustion temperature influence Hg isotopic fractionation with the emission of lighter Hg isotopes to the atmosphere and enrichment with heavier Hg in ashes. As for coal combustion, mass independent fractionation was not observed. To our knowledge, these results are the first to highlight the potential of forest fires to cause Hg isotopic fractionation, depending on the fire severity. The results also allowed to establish an isotopic fingerprint for tropical forest fire Hg emissions that corresponds to a mixture of litter and soil Hg isotopic composition (resulting atmospheric δ202Hg, Δ200Hg and Δ199Hg were -1.79 ± 0.24‰, -0.05 ± 0.04‰ and -0.45 ± 0.12‰, respectively).

A simple, green and low-cost agarose-based binding layer for simultaneous determination of cations and anions in aquatic systems using DGT.

The diffusive gradients in thin films (DGT) technique pre-concentrates labile species of trace elements, giving time-integrated in situ information about their labile concentrations. All previous DGT approaches for simultaneous uptake of cations and anions have used the hazardous polyacrylamide reagent to immobilize the binding phase. The present work proposes a diffusive layer of agarose and a mixed binding layer of ZrO2 and Chelex 100 immobilized in an agarose hydrogel to simultaneously determine the labile concentration of cations (Mn, Co, Ni, Cu, Zn and Cd) and anions (V, As, Se, Mo and Sb) in aquatic systems. The use of both layers using agarose instead of carcinogenic polyacrylamide as the hydrogel significantly reduces the costs and simplifies the manufacturing process. The proposed device was evaluated through recovery tests, deployment curves and pH/ionic strength tests. The mixed binding layer was compared with commercially available DGT devices for in situ deployment in river water. The relationships between accumulated mass and time (24 h) was linear (r2 > 0.9) for all analytes. The diffusion coefficients obtained were consistent with the literature, ranging from 3.98 to 8.43 × 10-6 cm2 s-1. Except for Zn at pH 8.0, the obtained values of CDGT/Cbulk were within the range of 1.00 ± 0.2 for the studied range of pH and for most ionic strengths. However, at low ionic strength, the concentrations of Mn, Co, Ni, Zn, V and Mo were underestimated. The concentrations of trace elements determined in river water using the proposed devices agreed with the labile concentrations determined by using commercial devices.

Bioaccumulation and speciation of arsenic in plankton from tropical soda lakes along a salinity gradient.

Uptake and transformation of arsenic (As) by living organisms can alter its distribution and biogeochemical cycles in the environment. Although well known for its toxicity, several aspects of As accumulation and biological transformation by field species are still little explored. In this study, the bioaccumulation and speciation of As in phytoplankton and zooplankton from five soda lakes in the Brazilian Pantanal wetland were studied. Such lakes exhibited contrasting biogeochemical characteristics along an environmental gradient. Additionally, the influence of contrasting climatic events was assessed by collecting samples during an exceptional drought in 2017 and a flood in 2018. Total As (AsTot) content and speciation were determined using spectrometric techniques, while a suspect screening of organoarsenicals in plankton samples was carried out by high-resolution mass spectrometry. Results showed that AsTot content ranged from 16.9 to 62.0 mg kg-1 during the dry period and from 2.4 to 12.3 mg kg-1 during the wet period. The bioconcentration and bioaccumulation factors (BCF and BAF) in phytoplankton and zooplankton were found to be highly dependent on the lake typology, which is influenced by an ongoing evapoconcentration process in the region. Eutrophic and As-enriched lakes exhibited the lowest BCF and BAF values, possibly due to the formation of non-labile As complexes with organic matter or limited uptake of As by plankton caused by high salinity stress. The season played a decisive role in the results, as significantly higher BCF and BAF values were observed during the flooding event when the concentration of dissolved As in water was low. The diversity of As species was found to be dependent on the lake typology and on the resident biological community, cyanobacteria being responsible for a significant portion of As metabolism. Arsenosugars and their degradation products were detected in both phytoplankton and zooplankton, providing evidence for previously reported detoxification pathways. Although no biomagnification pattern was observed, the diet seemed to be an important exposure pathway for zooplankton.

Spatial and seasonal variation of arsenic speciation in Pantanal soda lakes.

The occurrence of high arsenic concentrations (up to 3000 µg L-1) in water of soda lakes of the Pantanal wetland is a remarkable case of natural arsenic contamination in South America. However, little is known about arsenic speciation in this environment, particularly regarding speciation changes related to lake trophic status and seasonal variations. To fill this gap, arsenic speciation analysis was carried out in surface (SW) and subsurface (SSW) waters sampled in five soda lakes with different eutrophication status, in two dry and one wet season. As(V) was the dominant species in these waters, while As(III), DMA, MMA and likely complex organic species were present in lower amounts. The results allow to conclude that the arsenic speciation in SW and SSW varies seasonally according to the regional wet or dry periods and lake water levels. In eutrophic turbid and in oligotrophic vegetated soda lakes, arsenic speciation was also characterized by spatial differences between edge and center or between the SW and SSW. Cyanobacteria or macrophytes/algae are involved in arsenic biotransformation in soda lakes through its metabolic and detoxification processes. Significant variation in surface water arsenic speciation occurs as a result of seasonal primary production fluctuation or water arsenic concentration changes in the soda lakes, increasing organoarsenics in dry periods, whereas in flood periods, As(V) prevails. Spatial distribution of arsenic species is significantly impacted by biogeochemical conditions at the water/sediment interface in soda lakes.

A synthesis of mercury research in the Southern Hemisphere, part 1: Natural processes.

Recent studies demonstrate a short 3-6-month atmospheric lifetime for mercury (Hg). This implies Hg emissions are predominantly deposited within the same hemisphere in which they are emitted, thus placing increasing importance on considering Hg sources, sinks and impacts from a hemispheric perspective. In the absence of comprehensive Hg data from the Southern Hemisphere (SH), estimates and inventories for the SH have been drawn from data collected in the NH, with the assumption that the NH data are broadly applicable. In this paper, we centre the uniqueness of the SH in the context of natural biogeochemical Hg cycling, with focus on the midlatitudes and tropics. Due to its uniqueness, Antarctica warrants an exclusive review of its contribution to the biogeochemical cycling of Hg and is therefore excluded from this review. We identify and describe five key natural differences between the hemispheres that affect the biogeochemical cycling of Hg: biome heterogeneity, vegetation type, ocean area, methylation hotspot zones and occurence of volcanic activities. We review the current state of knowledge of SH Hg cycling within the context of each difference, as well as the key gaps that impede our understanding of natural Hg cycling in the SH. The differences demonstrate the limitations in using NH data to infer Hg processes and emissions in the SH.

A synthesis of mercury research in the Southern Hemisphere, part 2: Anthropogenic perturbations.

Environmental mercury (Hg) contamination is a global concern requiring action at national scales. Scientific understanding and regulatory policies are underpinned by global extrapolation of Northern Hemisphere Hg data, despite historical, political, and socioeconomic differences between the hemispheres that impact Hg sources and sinks. In this paper, we explore the primary anthropogenic perturbations to Hg emission and mobilization processes that differ between hemispheres and synthesize current understanding of the implications for Hg cycling. In the Southern Hemisphere (SH), lower historical production of Hg and other metals implies lower present-day legacy emissions, but the extent of the difference remains uncertain. More use of fire and higher deforestation rates drive re-mobilization of terrestrial Hg, while also removing vegetation that would otherwise provide a sink for atmospheric Hg. Prevalent Hg use in artisanal and small-scale gold mining is a dominant source of Hg inputs to the environment in tropical regions. Meanwhile, coal-fired power stations continue to be a significant Hg emission source and industrial production of non-ferrous metals is a large and growing contributor. Major uncertainties remain, hindering scientific understanding and effective policy formulation, and we argue for an urgent need to prioritize research activities in under-sampled regions of the SH.

In situ arsenic speciation at the soil/water interface of saline-alkaline lakes of the Pantanal, Brazil: A DGT-based approach.

Arsenic (As) is a naturally occurring element in the Earth's crust, exhibiting toxicity towards a wide range of living organisms. Its properties and environmental dynamics are strongly regulated by its speciation, and the species As(III) and As(V) are the most commonly found in environmental systems. Recently, high concentrations of As were found in saline-alkaline lakes of the Pantanal (Brazil), which is the largest wetland area in the world. Therefore, we evaluated As contamination and its redox speciation (As(III) and As(V)) at the soil/water interface of biogeochemically distinct saline-alkaline lakes of Pantanal wetlands (Brazil). Both conventional sampling and in situ diffusive gradients in thin films (DGT) technique were employed. Zirconium oxide and 3-mercaptopropyl were used as ligand phases in DGT to selectively bind As species. High concentrations of total dissolved As in a shallow water table were found (<2337.5 µg L-1), whereas levels in soils were up to 2.4 µg g-1. Distinct scenarios were observed when comparing speciation analysis through spot sampling and DGT. Considering spot sampling, As(V) was the main species detected, whereas As(III) was only detected in only a few samples (<4.2 µg L-1). Conversely, results obtained by DGT showed that labile As(III) dominated arsenic speciation at the soil/water interface with levels up to 203.0 µg L-1. Coupling DGT data and DGT induced fluxes in sediments and soils model allowed obtaining kinetic data, showing that the soil barely participated in the arsenic dynamics on the shore of the lakes, and that this participation depends on the evapoconcentration process occurring in the region. Therefore, soil acts like a nonreactive matrix depending on the natural concentration process. In addition, our results reinforced the different geochemical characteristics of the studied saline-alkaline lakes and highlights the importance of robust passive sampling techniques in the context of metal/metalloid speciation in environmental analysis.

In situ fractionation and redox speciation of arsenic in soda lakes of Nhecolândia (Pantanal, Brazil) using the diffusive gradients in thin films (DGT) technique.

In situ fractionation and redox speciation of As in three different saline-alkaline lakes (green, black and crystalline lakes) in the Pantanal of Nhecolândia (Brazil) were performed by using Diffusive Gradients in Thin films (DGT). The results indicated that As is present mainly in dissolved form. Total As concentration was similar when using different filter membranes, demonstrating that the species adsorbed by DGT devices were <10 kDa. Higher concentrations of labile total As were observed in the center of the lakes, indicating that the nature of the organic matter influences the formation of As complexes. Total As concentrations determined by using ZrO2 DGT were consistent with As concentration in ultrafiltered water samples collected in the black lake. However, part of the data about As(III) obtained in grab samples contrasted with DGT results. The differences observed may indicate that alterations in the species occur during the storage period before analysis by ultrafiltration. As(III) concentrations measured by DGT in the black and crystalline lakes were 1-3 µg L-1 and 4-7 µg L-1, respectively, accounting for only 4%-8% of the total DGT inorganic As. In the green lake, As(III) concentrations were significantly higher at the center (217 µg L-1). Both the phytoplankton community and the dissolved organic carbon influence the As speciation and bioavailability in the lakes of Nhecolândia. The DGT approach used in the present work was able to perform As speciation and demonstrates that in situ sampling analytical techniques are essential in understanding As speciation and its behavior in complex natural aquatic systems.

Preparation of environmental samples for chemical speciation of metal/metalloids: A review of extraction techniques.

Chemical speciation is a relevant topic in environmental chemistry since the (eco)toxicity, bio (geo)chemical cycles, and mobility of a given element depend on its chemical forms (oxidation state, organic ligands, etc.). Maintaining the chemical stability of the species and avoiding equilibrium disruptions during the sample treatment is one of the biggest challenges in chemical speciation, especially in environmental matrices where the level of concomitants/interferents is normally high. To achieve this task, strategies based on chemical properties of the species can be carried out and pre-concentration techniques are often needed due to the low concentration ranges of many species (µg L-1 - ng L-1). Due to the significance of the topic and the lack of reviews dealing with sample preparation of metal (loid)s (usually, sample preparation reviews focus on the total metal content), this work is presented. This review gives an up-to-date overview of the most common sample preparation techniques for environmental samples (water, soil, and sediments), with a focus on speciation of metal/metalloids and determination by spectrometric techniques. Description of the methods is given, and the most recent applications (last 10 years) are presented.

Dissolved arsenic in the upper Paraguay River basin and Pantanal wetlands.

Although high levels of dissolved arsenic were detected in surface and ground waters of Nhecolândia, a sub-region of the vast Pantanal wetlands in Brazil, the possible sources have not been clearly identified and the potential release from the wetland to the draining rivers has not been investigated. In this study we measured the dissolved As content in all the rivers and small streams that supply the southern Pantanal region, as well as in the two main rivers draining the wetland, i.e., the Cuiaba and Paraguay rivers and tributaries. In addition, Arsenic in surface waters, perched water-table, soils and sediments from 3 experimental sites located in the heart of Nhecolândia were compared. On the one hand, the results show the absence of As contamination in rivers that supply the Pantanal floodplain, as well as a lack of significant release from the floodplain to the main drains. The As contents in the rivers are <2 µg L-1, with variations that depend on the lithology and on the geomorphology at the collection point (uplands or floodplain). On the other hand, they confirm the regional extension of As contamination in Nhecolândia's alkaline waters with some values above 3 mg L-1. Arsenic is mainly in the arsenate form, and increases with the evaporation process estimated from sodium ion concentrations. The pH of soil solution and surface water increases rapidly during evapo-concentration up to values above 9 or 10, preventing adsorption processes on oxides and clay minerals and promoting the retention of dissolved arsenic in solution. Solutions from organic soil horizons show higher As contents in relation to Na, attributed to the formation of ternary complex As-(Fe/Al)-OM. In this alkaline pH range, despite high levels of dissolved As, soil horizons and lake sediments in contact with these waters show As values that correspond to uncontaminated environments.

The metagenomic landscape of xenobiotics biodegradation in mangrove sediments.

Metagenomics is a powerful approach to study microorganisms present in any given environment and their potential to maintain and improve ecosystem health without the need of cultivating these microorganisms in the laboratory. In this study, we combined a cultivation-independent metagenomics approach with functional assays to identify the detoxification potential of microbial genes evaluating their potential to contribute to xenobiotics resistance in oil-impacted mangrove sediments. A metagenomic fosmid library containing 12,960 clones from highly contaminated mangrove sediment was used in this study. For assessment of metal resistance, clones were grown in culture medium with increasing concentrations of mercury. The analyses metagenomic library sequences revealed the presence of genes related to heavy metals and antibiotics resistance in the oil-impacted mangrove microbiome. The taxonomic profiling of these sequences suggests that at the genus level, Geobacter was the most abundant genus in our dataset. A functional screening assessment of the metagenomic library successfully detected 24 potential heavy metal tolerant clones, six of which were capable of growing with increased concentrations of mercury. The genetic characterization of selected clones allowed the detection of genes related to detoxification processes, such as chromate transport protein ChrA, haloacid dehalogenase-like hydrolase, lipopolysaccharide transport system, and 3-oxoacyl-[acyl-carrier-protein] reductase. Clones were capable of growing in medium containing increased concentrations of metals and antibiotics, but none manifested strong mercury removal from culture medium characteristic of mercuric reductase activity. These results suggest that resistance to xenobiotic stress varies greatly and that additional studies to elucidate the potential of metal biotransformation need to be carried out with the goal of improving bioremediation application.

Sorption behaviors of antimicrobial and antiparasitic veterinary drugs on subtropical soils.

Brazil is one of the world's largest producers of animal protein, requiring the large-scale use of veterinary drugs. The administration of antimicrobials and antiparasitics is a common practice. However, there is a lack of information on how these drugs impact the environment. Antimicrobials are capable of altering the soil microbial population and are responsible for the development of multidrug-resistant microbial strains. Therefore, it is important to evaluate the fate and transport of these compounds in the environment, and one parameter used for this purpose is the soil-water partition coefficient. In this work, an assessment was made of the soil sorption behaviors of 18 drugs from seven different families, including antimicrobials (sulfonamides, fluoroquinolones, amphenicols, and macrolides) and antiparasitic drugs (milbemycin, avermectins, and benzimidazoles). Seven subtropical soils of different textural classes were tested. The Freundlich sorption coefficients, expressed as µg1-1/n (cm3)1/n g-1, were in the following ranges: 0.45 to 19 (sulfonamides), 72 to 2410 (fluoroquinolones), 9 to 58 (thiabendazole), 0.03 to 0.48 (florfenicol), 105 to 424 (moxidectin), 14 to 184 (avermectins), and 1.5 to 74 (macrolides). The results showed that the drugs belonging to the same family, with chemical structures in common, presented similar behaviors regarding sorption and desorption, for the different soils tested and are generally in agreement with soils from temperate regions. The data set obtained in this work give an overview of the fate of the veterinary drugs in Brazilian subtropical soils with different textures and composition and can be very helpful for exposure risk assessments.

Exposure of Brazilian soil and groundwater to pollution by coccidiostats and antimicrobial agents used as growth promoters.

The World Health Organization has identified antimicrobial resistance as one of the most important threats to global health. Brazil is one of the world's leading meat producers and the Brazilian use of veterinary antimicrobials as therapeutic agents and prophylactic or growth promoters in animal production remains problematic. Many antimicrobials are not completely metabolized and their excretion represents a significant source of environmental exposure. The aim of this work was to estimate the exposure risk of soil and groundwater to pollution by growth promoters (GPs) and anticoccidial additives (AAs) in Brazil by using a method based on a geographical information system (GIS). The principle adopted is that the greater the amount of animals, the greater the quantity of antimicrobials present, and the greater the soil vulnerability to pollution. Our research showed that GPs and AAs are extensively used in the Brazilian animal production system. An analysis of market data showed that zinc bacitracin, monensin, salinomycin, colistin and tylosin are representative GPs and AAs. This study presents a qualitative approach for risk assessment based on worst-case scenarios. First, the probable environmental concentration was estimated using a correlation between the number of heads of the herds of poultry and cattle, and the amounts of drug released. The leaching risk potential was characterized for each compound, as proposed in ISO 15175. The potential of soil pollution was evaluated for each antimicrobial as a function of its binding and dissipation rates. These rates were calculated using georeferenced data of organic carbon, average temperature, water balance and hydro-geological parameters. The consequences were modeled based on Brazilian soil usage. Finally, the risk was calculated by combining the different maps generated using spatial multi-criteria decision analysis. Higher risk was found for the midwest, southeast and south regions of Brazil. Groundwater was found to be more vulnerable than soil.

Mobility of polivinylpyrrolidone coated silver nanoparticles in tropical soils.

Experiments in saturated soil columns were performed to investigate the transport and retention of 25 nm and 75 nm silver nanoparticles stabilized with polyvinylpyrrolidone (PVP-AgNPs) in two Brazilian soils (sandy and sandy-clay). The normalized concentration of the PVP-AgNPs was obtained through a flow injection analysis method based on the surface plasmon ressonance effect of the metallic nanoparticles. The use of the ultraviolet-visible spectroscopy (UV-Vis) allows a rapid and low-cost analysis. The obtained breakthrough curves (BCs) were modeled with a deterministic model of solute transport in steady conditions of water flow and considering two regions of non-physical equilibrium; this model allowed the determination of the hydrodynamic parameters. It was found that the process occurs in condition of non-equilibrium, with a low mass transfer for larger NP, and that the process is predominantly advective and affected by the pore size of the soil packed in the columns. The BCs for PVP-AgNPs obtained by UV-Vis spectroscopy were compared with the BCs obtained by ICP-MS and with BCs of the bromide anion, confirming that the nanoparticles have a low retention and few modifications when transported through the soil column. These PVP-AgNPs are highly mobile and can be transported through the studied tropical soils, representing a potential environmental problem, due to the possibility of these materials reaching groundwater. On the contrary, the conservative behavior of PVP-AgNPs in the studied tropical soils, indicates its potential use as tracers, substituting the bromide anion which has been demonstrated to be not a good tracer in the same conditions.

Proof of concept for a passive sampler for monitoring of gaseous elemental mercury in artisanal gold mining.

Mercury emissions from artisanal gold mining operations occurring in roughly 80 developing countries are a major workplace health hazard for millions of people as well as the largest contributor to global mercury pollution. There are no portable, cheap, and rapid methods able to inform workers or health practitioners of mercury exposure on site in remote locations. In this work, a proof of concept for a miniaturized mercury sampler, prepared by the direct reduction of gold into the porous nanostructures of Vycor glass (PVG), is introduced. Mercury retention on the PVG/Au sampler induces significant color changes, due to the formation of Au-Hg amalgam that affects the surface plasmon resonance characteristics of the material. The color change can potentially be quantified by the analysis of pictures obtained with a cell phone camera rapidly and onsite. Laboratory experiments showed the viability of using PVG/Au as passive sampler for monitoring of Hg°. PVG/Au samplers were then deployed in an artisanal and small-scale gold mining (ASGM) operations in Burkina Faso and it was able to indicate personal mercury exposures. The amount of mercury quantified in the samplers for all miners was higher than the current personal exposure limit set by the US Occupational Safety & Health Administration (OSHA).

Sorption of thiabendazole in sub-tropical Brazilian soils.

Thiabendazole (TBZ) is an ionizable anthelmintic agent that belongs to the class of benzimidazoles. It is widely used in veterinary medicine and as a fungicide in agriculture. Sorption and desorption are important processes influencing transport, transformation, and bioavailability of xenobiotic compounds in soils; data related to sorption capacity are therefore needed for environmental risk assessments. The aim of this work was to assess the sorption potential of TBZ in four Brazilians soils (sandy, sandy-clay, and clay soils), using batch equilibrium experiments at three pH ranges (2.3-3.0, 3.8-4.2, and 5.5-5.7). The Freundlich sorption coefficient (K F) ranged from 9.0 to 58 µg1-1/n  (mL) 1/n  g-1, with higher values generally observed at the lower pH ranges (2.3-3.0 and 3.8-4.2) and for clay soils. The highest organic carbon-normalized sorption coefficients (KOC) obtained at pH 3.8-5.7 (around the natural pH range of 4.1-5.0) for both clay soils and sandy-clay soil were 3255 and 2015 mL g-1, respectively. The highest correlations K F vs SOM (r = 0.70) and K F vs clay content (r = 0.91) were observed at pH 3.8-4.2. Our results suggest that TBZ sorption/desorption is strongly pH dependent and that its mobility could be higher in the studied soils than previously reported in soils from temperate regions.

Fate of ivermectin in the terrestrial and aquatic environment: mobility, degradation, and toxicity towards Daphnia similis.

Ivermectin (IVM) is a broad-spectrum antiparasitic drug that is regularly employed in veterinary medicine. In this work, the sorption and desorption of IVM in two Brazilian soils (N1-sand and S2-clay) as well as its leaching capacity, dissipation under aerobic conditions, and degradation in aqueous solution by photocatalysis with TiO2 in suspension were evaluated. The kinetic sorption curves of IVM were adjusted to a pseudo-second-order model. The sorption and desorption data were well fitted with the Freundlich isotherms in the log form (r > 0.96). The Freundlich sorption coefficient (K F (ads) ) and the Freundlich desorption coefficient (K F (des) ) were 77.7 and 120 µg(1-1/n) (cm(3))(1/n) g(-1) and 74.5 and 138 µg(1-1/n) (cm(3))(1/n) g(-1), for soils N1 and S2, respectively. A greater leaching capacity of IVM was observed for the sandy soil N1 than for the clay soil S2. Under aerobic conditions, the dissipation (DT50) at 19.3 °C was 15.5 days (soil N1) and 11.5 days (soil S2). Photocatalysis with UVC and TiO2 in suspension resulted in the degradation of 98 % of IVM (500 µg L(-1)) in water in 600 s. The toxicity (Daphnia similis) of the solutions submitted to the photocatalytic process was completely eliminated after 10 min.

Litter mercury deposition in the Amazonian rainforest.

The objective of this work was to assess the flux of atmospheric mercury transferred to the soil of the Amazonian rainforest by litterfall. Calculations were based on a large survey of published and unpublished data on litterfall and Hg concentrations in litterfall samples from the Amazonian region. Litterfall based on 65 sites located in the Amazon rainforest averaged 8.15 ± 2.25 Mg ha(-1) y(-1). Average Hg concentrations were calculated from nine datasets for fresh tree leaves and ten datasets for litter, and a median concentration of 60.5 ng Hg g(-1) was considered for Hg deposition in litterfall, which averaged 49 ± 14 µg m(-2) yr(-1). This value was used to estimate that in the Amazonian rainforest, litterfall would be responsible for the annual removing of 268 ± 77 Mg of Hg, approximately 8% of the total atmospheric Hg deposition to land. The impact of the Amazon deforestation on the Hg biogeochemical cycle is also discussed.

Sorption of norfloxacin in soils: analytical method, kinetics and Freundlich isotherms.

Fluoroquinolones are potent antibacterial agents that are active against a wide range of pathogenic organisms and are widely used in veterinary medicine. Fluoroquinolones and their metabolites may reach the soil through animal excreta or manure and may contaminate water and soils. The degree of sorption of these antimicrobials to soils varies widely, as does the mobility of these drugs. In the present study, sorption of norfloxacin in four soils of the state of São Paulo was investigated with batch equilibrium experiments. A strong matrix effect on the chromatographic determination of norfloxacin was verified. Sorption kinetics were best fit by a pseudo second-order model (r>0.99), and sorption/desorption isotherms were well fit by the Freundlich model in log form (r>0.97). Norfloxacin showed high affinity for soil particles, with KF sorption values ranging from 643 to 2410 µg(1-1/n)(cm(3))(1/n)g(-1) and KF desorption values ranging from 686 to 2468 µg(1-1/n)(cm(3))(1/n)g(-1). The high desorption KF values indicate that norfloxacin is highly immobile in the evaluated soils.

Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles.

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO2 immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO2 concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO2 concentration of the coating solution: 10%; Fe(II): 7.0 mg l(-1); solar exposure time: 120 min) were applied to natural water samples spiked with 500 microg l(-1) As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 microg l(-1)) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO2 can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO2 immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.