Arsenic occurrence in Brazil and human exposure

Environmental exposure to arsenic (As) in terms of public health is receiving increasing attention worldwide following cases of mass contamination in different parts of the world. However, there is a scarcity of data available on As geochemistry in Brazilian territory, despite the known occurrence of As in some of the more severely polluted areas of Brazil. The purpose of this paper is to discuss existing data on As distribution in Brazil based on recent investigations in three contaminated areas as well as results from the literature. To date, integrated studies on environmental and anthropogenic sources of As contamination have been carried out only in three areas in Brazil: (1) the Southeastern region, known as the Iron Quadrangle, where As was released into the drainage systems, soils and atmosphere as a result of gold mining; (2) the Ribeira Valley, where As occurs in Pb-Zn mine wastes and naturally in As-rich rocks and soils; (3) the Amazon region, including the Santana area, where As is associated with manganese ores mined over the last 50 years. Toxicological studies revealed that the populations were not exposed to elevated levels of As, with the As concentrations in surface water in these areas rarely exceeding 10 microg/L. Deep weathering of bedrocks along with formation of Fe/Al-enriched soils and sediments function as a chemical barrier that prevents the release of As into the water. In addition, the tropical climate results in high rates of precipitation in the northern and southeastern regions and, hence, the As contents of drinking water is diluted. Severe cases of human As exposure related to non-point pollution sources have not been reported in Brazil. However, increasing awareness of the adverse health effects of As will eventually lead to a more complete picture of the distribution of As in Brazil.     

An integrated assessment of estrogenic contamination and biological effects in the aquatic environment of The Netherlands

An extensive study was carried out in the Netherlands on the occurrence of a number of estrogenic compounds in surface water, sediment, biota, wastewater, rainwater and on the associated effects in fish. Compounds investigated included natural and synthetic hormones, phthalates, alkylphenol(ethoxylate)s and bisphenol-A. The results showed that almost all selected (xeno-)estrogens were present at low concentrations in the aquatic environment. Locally, they were found at higher levels. Hormones and nonylphenol(ethoxylate)s were present in concentrations that are reportedly high enough to cause estrogenic effects in fish. Field surveys did not disclose significant estrogenic effects in male flounder (Platichthys flesus) in the open sea and in Dutch estuaries. Minor to moderate estrogenic effects were observed in bream (Abramis brama) in major inland surface waters such as lowland rivers and a harbor area. The prevalence of feminizing effects in male fish is largest in small regional surface waters that are strongly influenced by sources of potential hormone-disrupting compounds. High concentrations of plasma vitellogenin and an increased prevalence of ovotestes occurred in wild male bream in a small river receiving a considerable load of effluent from a large sewage treatment plant. After employing in vitro and in vivo bioassays, both in situ and in the laboratory, we conclude that in this case hormones (especially 17 alpha-ethynylestradiol) and possibly also nonylphenol(ethoxylate)s are primarily responsible for these effects.     

Estimation of uncertainty arising from different soil sampling devices: the use of variogram parameters

In the frame of the international SOILSAMP project, funded and coordinated by the National Environmental Protection Agency of Italy (APAT), uncertainties due to field soil sampling were assessed. Three different sampling devices were applied in an agricultural area using the same sampling protocol. Cr, Sc and Zn mass fractions in the collected soil samples were measured by k(0)-instrumental neutron activation analysis (k(0)-INAA). For each element-device combination the experimental variograms were calculated using geostatistical tools. The variogram parameters were used to estimate the standard uncertainty arising from sampling. The sampling component represents the dominant contribution of the measurement uncertainty with a sampling uncertainty to measurement uncertainty ratio ranging between 0.6 and 0.9. The approach based on the use of variogram parameters leads to uncertainty values of the sampling component in agreement with those estimated by replicate sampling approach.     

Growth response to ozone of annual species from Mediterranean pastures

Ozone (O3) phytotoxicity has been reported on a wide range of plant species. However, scarce information has been provided regarding the sensitivity of semi-natural grassland species, especially those from dehesa Mediterranean grasslands, in spite of their great biological diversity and the high O3 levels recorded in the region. A screening study was carried out in open-top chambers (OTCs) to assess the O3-sensitivity of representative therophytes of these ecosystems based on the response of selected growth-related parameters. Three O3 treatments and 3 OTCs per treatment were used. Legume species were very sensitive to O3, because 78% of the tested species showed detrimental effects on their total biomass relative growth rate (RGR) following their exposure to O3. The Trifolium genus was particularly sensitive showing O3-induced adverse effects on most of the assessed parameters. Gramineae plants were less sensitive than Leguminosae species because detrimental effects on total biomass RGR were only observed in 14% of the assessed species. No relationship was found between relative growth rates when growing in clean air and O3 susceptibility. The implications of these effects on the performance of dehesa acidic grasslands and on the definition of ozone critical levels for the protection of semi-natural vegetation are discussed.     

Dissipation of DDT in a heavily contaminated soil in Mato Grosso, Brazil

After the prohibition of organochlorine-pesticide use in Brazil for controlling insect vector diseases, Mato Grosso State gathered the exceeding DDT and stored it irregularly in an open air area that belongs to the National Health Foundation, causing soil contamination. This study aimed to evaluate the contamination level and dissipation of p,p'-DDT and p,p'-DDE in this area. For that, surface soil samples were collected on 19 September 2000, 15 December 2000, 4 April 2001 and soil samples 30-40 cm; 60-70 cm and 90-100 cm deep were taken from five points in the studied area on 17 July 2001. The contaminants were determined by a small scale method which consists on extraction and clean-up steps combined into one step by transferring soil samples mixed with neutral alumina to a chromatographic column prepacked with neutral alumina and elution with hexane:dichloromethane (7:3 v:v). The eluate was concentrated and the analytes were quantified by gas chromatography with an electron-capture detector. p,p'-DDT at surface soil ranged from 3,800 to 7,300 mg kg(-1). 30-40 cm deep soil sample concentrations varied from 0.036 to 440 mg kg(-1) while 90-100 cm deep samples varied from 0.069 to 180 mg kg(-1). Volatilization is probably the main dissipation process. The p,p'-DDT is moving slowly downward in the soil profile, however, the levels of this contaminant are high enough to present risk to underground waters.     

Precipitation chemistry in the coast of the Metropolitan Region of Rio de Janeiro, Brazil

Precipitation chemistry was studied in the Metropolitan Region of Rio de Janeiro (MRRJ). This study reveals that rainwater in the MRRJ is affected by emissions of air pollutants and provides essential data for future estimates of regional biogeochemical cycles and the impacts of acid deposition on tropical ecosystems. The volume-weighted mean (VWM) pH was 4.77, varying from 3.50 to 6.85. Sea-salt aerosols were the dominant sources of the Na+, Cl- and Mg2+. Excess SO4(2-), Ca2+ and K+ comprised 82, 91, and 87% of their total VWM concentrations, respectively. There were very strong correlations (r > 0.75, P > 0.01) for NO3- and H+, NO3- and excess(exc-)SO4(2-), NH4+ and exc-K+, and exc-SO4(2-) and exc-Ca2+, suggesting causal relationships between these ion pairs. The VWM concentrations of all major ions, except H+, were higher in the dry season, with dry to wet VWM concentration ratios varying from 1.1 (NH4+) to 4.7 (for total K+).     

Trace elements in muscle of three fish species from Todos os Santos Bay,Bahia State,Brazil

In this study, an analysis was performed on the concentrations of the trace elements Al, As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn in muscle of two carnivorous and one planktivorous fish species collected at Todos os Santos Bay (BTS). The accumulation order of the trace elements in Lutjanus analis was Al >Zn >Fe >Cr >Ba >Ni. In Cetengraulis edentulus, the order was Al >Fe >Zn >Cr >Ni >Mn >As. In the species Diapterus rhombeus, the order was Al >Fe >Zn >Cr >Ni >Mn >Cd. To determine the risk related to the consumption of fish, toxicity guidelines were used as standard references. It was observed that the species C. edentulus contained concentrations of As exceeding WHO limits, but these concentrations were acceptable according to the Agência Nacional de Vigilância Sanitária (ANVISA) guidelines. Cd levels were found only in D. rhombeus and in low concentrations according to the determinations of WHO and ANVISA. Pb levels were not detected in any of the three fish species. The analyzed elements did not differ statistically according to the species and feeding habits. The results point to possible risks of human contamination by As related to the consumption of the fish species C. edentulus from the BTS.     

Chitosan Functionalization with Amino Acids Yields to Higher Copper Ions Adsorption Capacity

Chitosan (Chi) beads were conjugated with three different amino acids [namely, glutamic acid (GLU), methionine (MET), and taurine (TAU)] aiming to increase the divalent copper ions uptake in aqueous media. Scanning Electron Microscopy evidenced the development of a large porous structure after amino acid functionalization, associated with the increase in a number of amino groups in the polymer backbone. X-Ray Photoelectron Spectroscopy and Fourier-Transform Infrared Spectra analyses were also employed to assess the conjugation of these three different amino acids in chitosan backbone. Adsorption experiments were conducted in a batch process, at 298 K, and kinetic data indicated a slightly better fitting for the pseudo-first-order model when compared to pseudo-second order. Intraparticle diffusion model suggested a three-step mechanism for Cu(II) adsorption kinetics, limited by the third step, the intraparticle diffusion. The isotherm data fitting to the traditional Langmuir and Freundlich models indicated a better fit for the former case. The amino acid conjugation resulted in the increase of the maximum adsorption capacity for Cu(II) from 1.30 mmol g^?1 prior to amino acid conjugation to values as high as 2.31 mmol g^?1, 2.40 mmol g^?1 and 2.68 mmol g^?1 for Chi–TAU, Chi–GLU, and Chi–MET, respectively. These results are attributed to the introduction of additional amino groups and new carboxylate and amino acid residues into the chitosan backbone, which might also be explored for amino acid demanding applications.     

Ethical considerations when conservation research involves people

Social science is becoming increasingly important in conservation, with more studies involving methodologies that collect data from and about people. Conservation science is a normative and applied discipline designed to support and inform management and practice. Poor research practice risks harming participants and, researchers, and can leave negative legacies. Often, those at the forefront of field-based research are early-career researchers, many of whom enter their first research experience ill-prepared for the ethical conundrums they may face. We draw on our own experiences as early-career researchers to illuminate how ethical challenges arise during conservation research that involves human participants. Specifically, we considered ethical review procedures, conflicts of values, and power relations, and devised broad recommendations on how to navigate ethical challenges when they arise during research. In particular, we recommend researchers apply reflexivity (i.e., thinking that allows researchers to recognize the effect researchers have on the research) to help navigate ethical challenges and encourage greater engagement with ethical review processes and the development of ethical guidelines for conservation research that involves human participants. Such guidelines must be accompanied by the integration of rigorous ethical training into conservation education. We believe our experiences are not uncommon and can be avoided and hope to spark discussion to contribute to a more socially just conservation.     

2,4-dichlorophenoxyacetic acid (2,4-D) micropollutant herbicide removing from water using granular and powdered activated carbons: a comparison applied for water treatment and health safety

Abstract

Activated carbons are well-known porous materials as an effective adsorbent used for the removal of emerging contaminants, such as herbicides, which are increasingly present in water bodies. Most water treatment plants, specially in Brazil, are unable to completely remove such contaminants by the conventional process and advanced treatment using activated carbons is required. The aim of this paper was to verify the influence of the activated carbons granulometry and specific surface area on the 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide removal efficiency using distilled-deionized water and filtered water collected from a conventional Water Treatment Plant. Commercial activated carbons samples used in this work were obtained from two different manufacturers. Activated carbons were analyzed by the specific surface area, pore size and volume distribution, nuclear magnetic resonance, infrared and x-ray spectroscopy, moisture, volatile matter and ash contents. Batch adsorption isotherms experiments were used and performed by Langmuir and Freundlich models. Granular and powdered activated carbons removed over 99% of 2,4-D in distilled water and near to 99% using filtered water. The activated carbons evaluated in this work presented high performance and played a key role in water treatment by removing 2,4-D herbicide, ensuring the protection of human health and the ecosystem.