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.     

Histopathological changes in the earthworm Eisenia andrei associated with the exposure to metals and radionuclides

Earthworms were exposed for 56 d to a contaminated soil, from an abandoned uranium mine, and to the natural reference soil LUFA 2.2. Histological changes in earthworm’s body wall (epidermis, circular and longitudinal muscles) and gastrointestinal tract (chloragogenous tissue and intestinal epithelium) were assessed, after 0, 14 and 56 d of exposure. Results have shown alterations in all the studied tissues after 14 d of exposure (except for the intestinal epithelium), yet more severe effects were registered after 56 d of exposure. Herein we report histopathological alterations as a good biomarker for the evaluation of soil quality. We also demonstrate that morphological changes in the body wall and gastrointestinal tract, are important endpoints that could be added to earthworm’s standardized tests, for the evaluation of soil toxicity, as part of the risk assessment of contaminated areas.     

Occupational exposure to formaldehyde in an institute of morphology in Brazil: a comparison of area and personal sampling

Background, aims, and scope

Formaldehyde (FA) is a harmful chemical, which is classified as carcinogenic to humans (Group 1) by the International Agency for Research on Cancer. Solutions of FA that are used to preserve cadavers in research and education morphological institutes represent a risk to occupational health of professionals and students. During the dissection of cadavers in the anatomy laboratories, FA vapors are emitted, resulting in the exposure of students and their instructors to elevated levels of FA. The World Health Organization recommends an air quality guideline value of 0.1 mg m^?3 for exposure to FA. The limit of occupational exposure adopted by the Brazilian legislation (2.3 mg m^?3) is markedly higher than those adopted by institutions of other countries around the world. The purpose of this study was to determine the levels of personal exposure and the area concentration of FA in the morphology department of the Federal Fluminense University, Brazil, and investigate and compare the relationship between them.

Methods

Four rooms distributed in the three floors of the Morphology Department were evaluated: the embalming laboratory, the anatomy laboratories, the corridor of the teachers?? rooms, and the entrance hall. Thirty-six samples in total were collected in the second semester of 2010 and first semester of 2011. The air sampling and FA analysis were performed according to the EPA TO-11A Protocol, using a diffusive sampling device for carbonyl compounds. Personal samples were collected from monitors using a sampling device pinned on each person??s lapel. The samples were analyzed using rapid resolution liquid chromatography with UV-DAD detection at 360 nm.

Results and discussion

The concentrations of FA ranged from 0.20 and 0.18 mg m^?3 in the corridor between the teachers?? rooms, 0.03 to 0.37 mg m^?3 in the entrance hall, 0.22 to 2.07 mg m^?3 in the anatomy laboratory, 2.21 to 2.52 mg m^?3, in the embalming room. The levels found in the corridor between the teachers?? rooms and in the entrance hall were lower than in other compartments because of their large distances to the sources of FA and better ventilation. The other rooms presented higher levels of FA because of the activities carried there (embalming and dissection procedures). Even in the rooms that showed the lowest levels of FA, the values found were higher than those established by all international guideline limits, except the Brazilian legislation limit, although, the concentration level in the embalming room was even greater than the Brazilian guideline. These concentrations are 100?C1,000-fold higher than those reported in an FA outdoor study. The exposure levels of monitors and students ranged from 1.89 to 4.82 mg m^?3, indicating that current practices at the Morphology Department at the university would represent a health risk. The simultaneous monitoring of area concentrations and personal exposure showed that the characteristics of classes and of cadavers?? parts, the number of students in the room and even the activities of the monitors influence the FA concentrations.

Conclusion

This study revealed that the concentration of FA was low in the ventilated areas of the Morphology Department, and that the personal exposure when the person was close to the cadavers during the dissection procedure was higher than the mean FA concentration. This should be considered in the risk assessment of FA during these activities without effective protection equipment. It is suggested that the Brazilian legislation of exposure to formaldehyde requires an urgent update considering international legislation.     

Solid-phase fluorescence spectroscopy to characterize organic wastes

The production of solid organic waste (SOW) such as sewage sludge (SS) or municipal solid waste (MSW) has been continuously increasing in Europe since the beginning of the 1990'. Today, the European Union encourages the stabilization of these wastes using biologic processes such as anaerobic digestion and/or composting to produce bio-energy and organic fertilizers. However, the design and management of such biologic processes require knowledge about the quantity and quality of the organic matter (OM) contained in the SOW. The current methods to characterize SOW are tedious, time-consuming and often insufficiently informative. In this paper, we assess the potential of solid-phase fluorescence (SPF) spectroscopy to quickly provide a relevant characterization of SOW. First, we tested well known model compounds (tryptophan, bovine serum albumin, lignin and humic acid) and biologic matrix (Escherichia coli) in three dimensional solid-phase fluorescence (3D-SPF) spectroscopy. We recorded fluorescence spectra from proteinaceous samples but we could not record the fluorescence emitted by lignin and humic acid powders. For SOW samples, fluorescence spectra were successfully recorded for MSW and most of its sub-components (foods, cardboard) but impossible for SS, sludge compost (SC) and ligno-cellulosic wastes. Based on visual observations and additional assays, we concluded that the presence of highly light-absorptive chemical structures in such dark-colored samples was responsible for this limitation. For such samples, i.e. lignin, humic acid, SS, SC and ligno-cellulosic wastes, we show that laser induced fluorescence (LIF) spectroscopy enables the acquisition of 2D fluorescence spectra.     

Phenol electrooxidation on Fe-Co3O4 thin film electrodes in alkaline medium

Fe-Co₃O₄ thin film with different amounts of Fe have been used for the electro-oxidation of phenol in alkaline medium at room temperature. The electrodes were prepared by coating stainless steel supports with successive layers of the oxides, obtained by thermal decomposition at 673 K. The electrolysis was carried out at constant potential and the phenol disappearance, during the electrolysis, was monitored by UV-Vis absorbance measurements between 250 and 500 nm. After 3 h of electrolysis, the intermediates were identified by comparing the HPLC data and UV-Vis spectra to those from pure standards. The results indicate that the same oxidation products are formed on the different prepared electrodes, namely the decomposition products of phenol such as benzoquinone, hydroquinone and cathecol in basic medium. Simulated results show clearly the decrease of the amount of phenolic species with the electrolysis time. An enhancement of the phenol removal is observed with the presence of iron in the oxide. Under the operating conditions, around 30% of the initial phenol has been removed at ca. 3 h and the complete degradation is obtained after 54 h of electrolysis, when Fe-Co₃O₄ thin film with 10% of Fe is used as anode.     

Kinetic analysis of constructed systems for the recovery of contaminated areas by acid mine drainage

INTRODUCTION: Flowing of the acid mine drainage may contaminate the adjacent water bodies causing substantial changes in the aquatic ecosystem. This aspect is the most relevant problem in the southern of Santa Catarina once the contaminated areas are inserted in the watershed of the Araranguá, Urussanga, and Tubar?o rivers, increasing the need for recovery studies. These areas are between Criciúma, I?ara, Urussanga, Siderópolis, Lauro Müller, Orleans, and Alfredo Wagner towns where a conservation unit exist called the Environmental Preservation Area of Baleia Franca. Aiming to compare the kinetics of the ash derived from burning coal and to neutralize acid mine drainage, different neutralizer, limestone, fly, and bottom ash, was mounted on a pilot scale experiment. DISCUSSION: The transport parameters showed the same order of infiltration and dispersion: fly ash < bottom ash < limestone. The order of measured alkalinity was: limestone < fly ash < bottom ash, with pH values of 9.34, 12.07, and 12.25, respectively. The limestone kinetics of acidic drainage neutralization was first order with reaction rate constant k?=?0.0963 min(-1), bottom ash was 3/4 with k?=?0.0723 mol(1/4) L(-1/4) min(-1), and the fly ash had higher order kinetics, 4/3, with reaction rate constant k?=?27.122 L(1/3) mol(-1/3) min(-1). However, by mathematical modeling, it was found that due to a combination of transport and kinetics, only limestone treatment reached a pH above 6 within 5 years, corresponding to the ideal as planned.     

Median lethal concentration of formaldehyde and its genotoxic potential in bullfrog tadpoles (Lithobates catesbeianus)

In order to avoid that contaminated frog farms animals escaping in the environment and become potential vector of emergent diseases, studies with disinfection protocol are strictly necessary. The formaldehyde is one of the compounds tested in fungal disinfection protocols and also used in aquaculture. This study aimed to determine the median lethal concentration (LC_50–96h) of formaldehyde in bullfrog tadpoles and to evaluate the possible genotoxic effects in acute exposition. Accordingly, the animals were exposed to formaldehyde in the concentrations of 6, 9, 12, 15, and 18 mg L^?1, and after 96 h blood samples were drawn for the micronucleus (MN) test. The LC_50–96h was 10.53 mg L^?1, and the MN frequency increased in proportion to the formaldehyde concentrations, with an estimated frequency in the negative control being 1.35 MN/individual. We concluded that formaldehyde is genotoxic to tadpoles of bullfrogs in the tested concentrations, and the choice of this chemical should be contemplated before its use in animals in captivity.     

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.     

Mercury bioaccumulation and decontamination kinetics in the edible cockle Cerastoderma edule

Mercury bioaccumulation and decontamination kinetics in the edible cockle Cerastoderma edule were studied through a mesocosms experiment after a medium-term exposure to the metal.The results revealed that the bivalve presented distinct bioaccumulation kinetics according to the different tissues. While the gills showed a linear accumulation pattern, the digestive gland and the entire organism presented a saturation model, with higher accumulation during the first 7d of exposure and lower during the rest of the time. In addition, the bioaccumulation rate was not proportional to the Hg concentration, since the organisms under lower contamination presented higher bioconcentration factors than the ones under higher contamination. Gills were the tissues with higher mercury accumulation capability.Concerning the decontamination phase, C. edule lost approximately 80% of the mercury after 24 h exposure in clean seawater. Nevertheless, never reached the original condition, showing in the final (20 d detox), Hg levels (>0.5 ppm) higher than those allowed by the legislation regulating human food consumption. This represents a matter of concern for Human health.     

Particle emission from heavy-duty engine fuelled with blended diesel and biodiesel

In this study, particulate matter (PM) were characterized from a place impacted by heavy-duty vehicles (Bus Station) fuelled with diesel/biodiesel fuel blend (B3) in the city of Londrina, Brazil. Sixteen priority polycyclic aromatic hydrocarbons (PAH) concentrations were analyzed in the samples by their association with atmospheric PM, mass size distributions and major ions (fluorite, chloride, bromide, nitrate, phosphate, sulfate, nitrite, oxalate; fumarate, formate, succinate and acetate; lithium, sodium, potassium, magnesium, calcium and ammonium). Results indicate that major ions represented 21.2% particulate matter mass. Nitrate, sulfate, and ammonium, respectively, presented the highest concentration levels, indicating that biodiesel may also be a significant source for these ions, especially nitrate. Dibenzo[a,h]anthracene and indeno[1,2,3,-cd]pyrene were the main PAH found, and a higher fraction of PAH particles was found in diameters lower than 0.25 μm in Londrina bus station. The fine and ultrafine particles were dominant among the PM evaluated, suggesting that biodiesel decreases the total PAH emission. However, it does also increase the fraction of fine and ultrafine particles when compared to diesel.