Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L⁻¹ range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17β-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L⁻¹ and 100 μg L⁻¹) and at varying ozone dosages (0-30 mg L⁻¹). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and E1 have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of E1, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages.     

Assessment of human exposure to benzene through foods from the Belgian market

Benzene is a volatile organic compound known to be carcinogenic to humans (Group 1) and may be present in food. In the present study, 455 food samples from the Belgian market were analyzed for benzene contents and some possible sources of its occurrence in the foodstuffs were evaluated. Benzene was found above the level of detection in 58% of analyzed samples with the highest contents found in processed foods such as smoked and canned fish, and foods which contained these as ingredients (up to 76.21 μg kg⁻¹). Unprocessed foods such as raw meat, fish, and eggs contained much lower concentrations of benzene. Using the benzene concentrations in food, a quantitative dietary exposure assessment of benzene intake was conducted on a national representative sample of the Belgian population over 15 years of age. The mean benzene intake for all foods was 0.020 μg kg bw d⁻¹ according to a probabilistic analysis. These values are below the minimum risk level for oral chronic exposure to benzene (0.5 μg kg bw d⁻¹).     

Evaluation of the effect of different treatment methods on sugarcane vinasse remediation

Abstract

Sugarcane vinasse is a by-product obtained during ethanol production in sugar-ethanol plants. For each 1?L of ethanol produced approximately 11?L of vinasse are generated. As this residue is obtained in high amounts, it is used as fertilizer in sugarcane crops. However, despite being rich in nutrients, sugarcane vinasse is approximately one hundred times more polluting than domestic sewage, making it an environmental problem. Thus, the aim of the present study was to propose a treatment sequence for sugarcane vinasse and evaluate the possibility of energetic use of the generated sludge in the coagulation/flocculation stage. pH, conductivity, turbidity and decreases in UV/Vis absorption spectra were determined for each treatment step. In addition, the upper calorific value of the generated sludge was also determined, while ash (adsorption treatment) and catalyst (heterogeneous photocatalysis) characterizations were also carried out. At the end of the treatment, initial vinasse turbidity was reduced by 100% and pH and conductivity values were stabilized. The sludge presented a higher calorific value of approximately 3,000?kcal kg^?1 and the ash and catalyst displayed favorable characteristics to be applied to the sugarcane vinasse treatment stages.     

Respiration induced by substrate and bacteria diversity after application of diuron,hexazinone, and sulfometuron-methyl alone and in mixture

Abstract

After application, herbicides often reach the soil and affect non-target soil microorganisms, decreasing their population, diversity or affecting metabolic activity. Therefore, laboratory studies were performed to evaluate the effects of diuron, hexazinone and sulfometuron-methyl alone and mixed upon carbon transformation by soil microorganisms in clayey and sandy soils and the effect on bacterial diversity and structure. Control treatment without herbicide application was also performed. Sub-samples from the control and herbicide treatments (10?g – in triplicate) were collected before herbicide application and 7, 14, 28 and 42?days after treatment (DAT), then 1?mL of ¹⁴C-glucose solution was applied. The released ¹⁴CO₂ was trapped in 2?M NaOH solution and the radioactivity was analyzed by liquid scintillation counting (LSC), 12?h after glucose application. The effect of herbicides on bacterial diversity was evaluated by T-RFLP. The experiment was conducted in a complete randomized design. Hexazinone did not affect ¹⁴CO₂ evolution. Diuron showed a greater ¹⁴CO₂ evolution in sandy and clayey soil, while sulfometuron-methyl led to an increase in sandy soil, at 42 DAT. A greater evolution of carbon was observed in the treatment with herbicide mixture in sandy soil, compared with the same treatment in clayey soil or control. However, the herbicide mixture application did not affect the soil biological activity measured by the respiration rate induced by substrate. On the other hand, the herbicide mixtures affected the bacterial diversity in both soils, being the strongest effect to diuron and sulfometuron-methyl in clayey soil and hexazinone in sandy soil.     

Determination of pharmaceuticals, personal care products, and pesticides in surface and treated waters: method development and survey

Water is fundamental to the existence of life since it is essential to a series of activities, such as agriculture, power generation, and public and industrial supplies. The residual water generated by these activities is released into the environment, reaches the water systems, and becomes a potential risk to nontarget organisms. This paper reports the development and validation of a quantitative method, based on solid-phase extraction and liquid chromatography tandem mass spectrometry, for the simultaneous analysis of 18 pharmaceuticals and personal care products (PPCPs) and 33 pesticides in surface and drinking waters. The accuracy of the method was determined by calculating the recoveries, which ranged from 70 to 120 % for most pesticides and PPCPs, whereas limits of quantification ranged from 0.8 to 40 ng/L. After the validation step, the method was applied to drinking and surface waters. Pesticides and PPCPs were found in concentrations lower than 135.5 ng/L. The evaluation of different water sources with regard to contamination by pesticides and PPCPs has been quite poor in southern Brazil.     

Leaf morphoanatomy of species tolerant to excess iron and evaluation of their phytoextraction potential

Setaria parviflora (Poir.) Kerguélen and Paspalum urvillei Steudel are grasses that grow naturally in a soil with high iron contents. This study aimed to characterize morphoanatomically and histochemically the iron phytotoxicity on leaves and evaluate the phytoextraction potential of these grasses. Saplings were cultivated in hydroponic solution with and without excess Fe-EDTA. Regarding measurements taken on leaves, reduction was observed among treatments of Fe-EDTA on height values of abaxial epidermis and bundle sheath in both species. As for iron histolocalization, stronger reaction was observed in leaves of S. parviflora, in comparison with P. urvillei. Anatomical damage, such as protoplast retraction, irregular xylem, changes in cell volume, and cell collapse, and visual symptoms, like leaf bronzing, chlorosis, and necrosis, were similar in both species when exposed to excess iron; however, P. urvillei showed more severe damage. This species accumulated more iron in shoots than S. parviflora and therefore is more favorable for use in phytoextraction. The root system of both species accumulated higher iron concentrations in relation to shoots.     

Pristine aquatic systems in a Long Term Ecological Research (LTER) site of the Brazilian Cerrado

The maintenance of limnological monitoring programs in the Cerrado Domain is crucial as a provision of useful information about temporal variations in land use and their respective water quality responses, considering its importance as water source for different Brazilian hydrographic basins. The purpose of this research was to describe limnological variables of low-order lotic systems located in the Cerrado Long Term Ecological Research (LTER) site (Environmental Protection Area (APA) Gama and Cabeça de Veado, Federal District of Brazil). Altogether, nine different streams were considered in this study. Samplings were conducted between 2010 and 2012, concentrated in the dry and rainy seasons. The sampling sites were generally characterized by low nutrient concentrations (e.g., medians, TP?=?14.8 μg L^?1, TN?=?20.0 μg L^?1, NO₃?=?13.8 μg L^?1) and slightly acidic waters (median, pH?=?5.3), with quite low electrical conductivity values (median?=?6.4 μS cm^?1). However, water quality degradation as a response to diffuse pollution was reported in some sampling points (e.g., Onça and Gama streams), expressed by relatively higher N and P concentrations, which were probably highlighted by the good water quality of the data set as whole. Although there was a trend to higher values of nitrogen forms during the dry season, significant statistical differences between the seasonal periods were reported only for the variables temperature and dissolved silica, which were higher in the dry and rainy season, respectively. The streams located in the preserved areas inside the ecological stations of APA Gama and Cabeça de Veado can still be considered good examples of reference lotic systems in the Cerrado Domain; notwithstanding, this study reported incipient signs of water quality degradation which cannot be overlooked in future limnological monitoring.     

Three-dimensional data interpolation for environmental purpose: lead in contaminated soils in southern Brazil

Monitoring of heavy metal contamination plume in soils can be helpful in establishing strategies to minimize its hazardous impacts to the environment. The objective of this study was to apply a new approach of visualization, based on tridimensional (3D) images, of pseudo-total (extracted with concentrated acids) and exchangeable (extracted with 0.5 mol L^?1 Ca(NO₃)₂) lead (Pb) concentrations in soils of a mining and metallurgy area to determine the spatial distribution of this pollutant and to estimate the most contaminated soil volumes. Tridimensional images were obtained after interpolation of Pb concentrations of 171 soil samples (57 points × 3 depths) with regularized spline with tension in a 3D function version. The tridimensional visualization showed great potential of use in environmental studies and allowed to determine the spatial 3D distribution of Pb contamination plume in the area and to establish relationships with soil characteristics, landscape, and pollution sources. The most contaminated soil volumes (10,001 to 52,000 mg Pb kg^?1) occurred near the metallurgy factory. The main contamination sources were attributed to atmospheric emissions of particulate Pb through chimneys. The large soil volume estimated to be removed to industrial landfills or co-processing evidenced the difficulties related to this practice as a remediation strategy.     

A review on human attitudes towards reptiles in Brazil

For many millennia humans and reptiles have interacted, but the attitude of humans towards these animals has depended on culture, environment, and personal experience. At least 719 reptile species are known to occur in Brazil and about 11% of this fauna has been exploited for many different purposes, including bushmeat, leather, ornamental and magic/religious uses, and as folk medicines. Brazil can therefore serve as an interesting case study for better understanding reptile use by human societies, and the present paper catalogues some of the reptile species being used in Brazil and discusses implications for their conservation. A literature review indicated that 81 reptile species are culturally important in this country, with 47 (58%) species having multiple uses, 54 being used for medicinal purposes, 38 as food, 28 for ornamental or decorative purposes, 20 used in magic/religious practices, 18 as pets, and 40 are commonly killed when they come into contact with humans. Regarding their conservation status, 30 (37.5%) are included on State's Red List, Brazilian Red List or the IUCN Red List. There are many forms of interaction between reptiles and humans in Brazil-although most of them are quite negative in terms of wildlife conservation-which reinforces the importance of understanding such uses and interactions in the context of protecting reptiles in Brazil. A better understanding of the cultural, social, and traditional roles of these reptiles is fundamental to establishing management plans for their sustainable use.