Natural concentrations and reference values of heavy metals in sedimentary soils in the Brazilian Amazon

The soils of the Brazilian Amazon exhibit large geochemical diversity reflecting the different soil formation processes in an area covering 49% of the Brazilian territory. Soil contamination by heavy metals is one of the threats to the sustainability of this Biome but establishing quality reference values (QRVs) for the region is a challenging owing to the immense territorial area of the Amazon. This study aimed to determine the natural background of heavy metals in soils from the southwestern Brazilian Amazon in order to propose QRVs for Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, and Zn for alluvial sedimentary soils. One hundred and twenty-eight soil samples were collected at a depth of 0.0–0.2 m in sites with minimal anthropogenic interference. Soil sample digestion was based on the EPA 3051A method and metal concentrations were determined by ICP-OES. QRVs calculated for the southwestern Brazilian Amazon are among the lowest recorded in Brazil (mg kg^?1): Ba (16.5), Cd (0.1), Cr (6.9), Cu (2.8), Fe (15.4), Mn (13.4), Ni (1.7), Pb (4.4), Sb (0.9), and Zn (5.7). The low metal concentration is likely a result of the sedimentary origin of the soils. The results of this study can serve as a basis for defining public policies to investigate the environmental impacts resulting from changes in land use in areas of the Brazilian Amazon.     

Acetamiprid, carbendazim, diuron and thiamethoxam sorption in two Brazilian tropical soils

Sorption of acetamiprid ((E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine), carbendazim (methyl benzimidazol-2-ylcarbamate), diuron (N-(3,4-dichlorophenyl)-N, N-dimethyl urea) and thiamethoxam (3-(2-chloro-thiazol-5-ylmethyl)-5-methyl-[1,3,5]oxadiazinan-4-ylidene-N-nitroamine) was evaluated in two Brazilian tropical soils, Oxisol and Entisol, from Primavera do Leste region, Mato Grosso State, Brazil. To describe the sorption process, batch experiments were carried out. Linear and Freundlich isotherm models were used to calculate the K(d) and K(f) coefficients from experimental data. The K(d) values were utilized to calculate the partition coefficient normalized to soil organic carbon (K(oc)). For the pesticides acetamiprid, carbendazim, diuron and thiamenthoxan the K(oc) (mL g(- 1)) values ranged in both soils from 98 - 3235, 1024 - 2644, 145 - 2631 and 104 - 2877, respectively. From the studied pesticides, only carbendazim presented correlation (r(2) = 0.82 and p < 0.01) with soil organic carbon (OC) content. Acetamiprid and thiamethoxam showed low sorption coefficients, representing a high risk of surface and ground water contamination.     

Marine debris contamination along undeveloped tropical beaches from northeast Brazil

We hypothesize that floating debris leaving polluted coastal bays accumulate on nearby pristine beaches. We examined composition, quantities and distribution of marine debris along approximately 150 km of relatively undeveloped, tropical beaches in Costa do Dendê (Bahia, Brazil). The study site is located south of Salvador City, the largest urban settlement from NE Brazil. Strong spatial variations were observed. Plastics accounted for 76% of the sampled items, followed by styrofoam (14%). Small plastic fragments resultant from the breakdown of larger items are ubiquitous all over the area. Because the dominant littoral drift in Bahia is southward, average beach debris densities (9.1 items/m) along Costa do Dendê were threefold higher than densities previously observed north of Salvador City. River-dominated and stable beaches had higher debris quantities than unstable, erosional beaches. Areas immediately south of the major regional embayments (Camamu and Todos os Santos) were the preferential accumulation sites, indicating that rivers draining populous areas are the major source of debris to the study site. Our results provide baseline information for future assessments. Management actions should focus on input prevention at the hydrographic basin level rather than on cleaning services on beaches.     

Comparison of USEPA digestion methods to heavy metals in soil samples

The use of appropriate analytical methods is of paramount importance for risk assessment and monitoring of potentially toxic metals in soils. In this sense, the objective of this study was to compare the effectiveness of two sample digestion methods, recommended by the Brazilian legislation for the management of contaminated areas (CONAMA 2009), aiming at the determination of environmentally available metal concentrations (USEPA 3050B, USEPA 3051A), as well as a total digestion method (USEPA 3052). Samples from 10 classes of soils were analyzed for Cu, Zn, Cd, Pb, Ni, and Hg. The results showed that the USEPA method 3051A is more efficient than the USEPA method 3050B in the extraction of levels considered environmentally available of Zn, Cu, Cd, Pb, and Ni. Besides providing a higher recovery of these elements, the method requires shorter digestion time, lower consumption of acids, and reduced risk of contamination. The USEPA method 3051A showed greater efficiency in Hg extraction in soils with higher clay content. Therefore, it is suitable for situations where a wide range of soils with different mineralogical characteristics are analyzed or in order to decrease the losses due to volatilization of the element in open systems.     

Spatial distribution and quantification of endocrine-disrupting chemicals in Sado River estuary, Portugal

The important Portuguese Sado River estuary has never been investigated for the presence of potentially endocrine-disrupting chemicals (EDCs), such as natural estrogens (estradiol, estrone), pharmaceutical estrogens (17α-ethynylestradiol), phytoestrogens (daidzein, genistein and biochanin A), or industrial chemicals (4-octylphenol, 4-nonylphenol, and bisphenol A). Thus, the main objective of this study was to evaluate their presence at 13 sampling points distributed between both the industrial and the natural reserve areas of the estuary, zones 1 and 2, respectively. For that, water samples collected in summer and winter were processed by solid phase extraction and analyzed by high-performance liquid chromatography with photodiode array detection and gas chromatography–mass spectroscopy. Results showed that estrone, ethynylestradiol, all the aforementioned phytoestrogens as well as bisphenol A and 4-octylphenol were found in zone 1. In zone 2, neither estrogens nor 4-OP were found. However, in the same zone, daidzein (500 ng/L) and genistein (320 ng/L) attained their highest levels in summer, whereas biochanin A peaked in winter (170 ng/L). Furthermore, bisphenol A was also found in some areas of zone 2, but showed similar concentrations in both surveys (about 220 ng/L). This study demonstrated that the Sado River estuary had low EDCs levels, suggesting that the Sado’s high hydrodynamic activity may be involved in the dilution of local pollution. It was suggested that at the current levels of concentrations, all assayed EDCs are unlikely to individually cause endocrine disruption in local animals. However, under a continuous exposure scenario, an additive and/or synergistic action of the estrogenic chemicals load can not be excluded, and so, continuous monitoring is advisable.     

Evaluation of surface water quality in aquatic bodies under the influence of uranium mining (MG, Brazil)

The quality of the water in a uranium-ore-mining area located in Caldas (Minas Gerais State, Brazil) and in a reservoir (Antas reservoir) that receives the neutralized acid solution leaching from the waste heaps generated by uranium mining was investigated. The samples were collected during four periods (October 2008, January, April and July 2009) from six sampling stations. Physical and chemical analyses were performed on the water samples, and the data obtained were compared with those of the Brazilian Environmental Standards and WHO standard. The water samples obtained from waste rock piles showed high uranium concentrations (5.62 mg L^?1), high manganese values (75 mg L^?1) and low average pH values (3.4). The evaluation of the water quality at the point considered the limit between the Ore Treatment Unit of the Brazilian Nuclear Industries and the environment (Consulta Creek) indicated contamination by fluoride, manganese, uranium and zinc. The Antas reservoir showed seasonal variations in water quality, with mean concentrations for fluoride (0.50 mg L^?1), sulfate (16 mg L^?1) and hardness (20 mg L^?1) which were low in January, evidencing the effect of rainwater flowing into the system. The concentrations for fluoride, sulfate and manganese were close or above to the limits established by current legislation at the point where the treated mining effluent was discharged and downstream from this point. This study demonstrated that the effluent discharged by the UTM affected the quality of the water in the Antas reservoir, and thus the treatments currently used for effluent need to be reviewed.     

Elicitors as alternative strategy to pesticides in grapevine? Current knowledge on their mode of action from controlled conditions to vineyard

Development and optimisation of alternative strategies to reduce the use of classic chemical inputs for protection against diseases in vineyard is becoming a necessity. Among these strategies, one of the most promising consists in the stimulation and/or potentiation of the grapevine defence responses by the means of elicitors. Elicitors are highly diverse molecules both in nature and origins. This review aims at providing an overview of the current knowledge on these molecules and will highlight their potential efficacy from the laboratory in controlled conditions to vineyards. Recent findings and concepts (especially on plant innate immunity) and the new terminology (microbe-associated molecular patterns, effectors, etc.) are also discussed in this context. Other objectives of this review are to highlight the difficulty of transferring elicitors use and results from the controlled conditions to the vineyard, to determine their practical and effective use in viticulture and to propose ideas for improving their efficacy in non-controlled conditions.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Tibouchina pulchra (Cham.) Cogn., a native Atlantic Forest species, as a bio-indicator of ozone: visible injury

Tibouchina pulchra saplings were exposed to carbon filtered air (CF), ambient non-filtered air (NF) and ambient non-filtered air+40 ppb ozone (NF+O3) 8 h per day during two months. The AOT40 values at the end of the experiment were 48, 910 and 12,895 ppb h(-1), respectively, for the three treatments. After 25 days of exposure (AOT40=3871 ppb h(-1)), interveinal red stippling appeared in plants in the NF+O3 chamber. In the NF chamber, symptoms were observed only after 60 days of exposure (AOT40=910 ppb h(-1)). After 60 days, injured leaves per plant corresponded to 19% in NF+O3 and 1% in the NF treatment; and the average leaf area injured was 7% within the NF+O3 and 0.2% within the NF treatment. The extent of leaf area injured (leaf injury index) was mostly explained by the accumulated exposure of ozone (r2=0.89; p<0.05).