Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation

In the present study, selected advanced oxidation processes (AOPs)—namely, photo-Fenton (with Fe²⁺, Fe³⁺, and potassium ferrioxalate—FeOx—as iron sources), solar photo-Fenton, Fenton, and UV/H₂O₂—were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H₂O₂ process were most efficient for mineralizing MTX, with 77, 82, and 90 % of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe³⁺:MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10⁴ M^–1, indicating high MTX affinity for Fe³⁺. Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H₂O₂ process is usually slower than the photo-Fenton process, but, in this study, the UV/H₂O₂ process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H₂O₂ or by UV/H₂O₂/FeOx at the concentrations tested.     

The efficiency of electrocoagulation in treating wastewater from a dairy industry,Part I: Iron electrodes

Iron electrodes were used for electrocoagulation (EC) treatment of wastewater from a dairy plant. Electrolysis time, pH, current density and distance between electrodes were considered to assess the removal efficiency of chemical oxygen demand (COD), total solids (TS) and their fractions and turbidity. Samples were collected from the effluent of a dairy plant using a sampling methodology proportional to the flow. The treatments were applied according to design factorial of half fraction with two levels of treatments and three repetitions at the central point. The optimization of parameters for treating dairy industry effluent by electrocoagulation using iron electrodes showed that electric current application for 15 minutes, an initial sample pH close to neutral (pH 7.0) and a current density of 50 A ^{. m?2} resulted in a significant reduction in COD by 58 %; removal of turbidity, suspended solids and volatile suspended solids by 95 %; and a final treated effluent pH of approximately 9.5. Negative consequences of the type of electrode used were the emergence of an undesirable color and an increase in the proportion of dissolved solids in the treated effluent.     

Production and partial characterization of bioemulsifier from a chromium-resistant actinobacteria

Surface-active compounds such as synthetic emulsifiers have been used for several decades, both for the degradation of hydrocarbons and increasing desorption of soil-bound metals. However, due to their high toxicity, low degradability, and production costs unaffordable for use in larger ecosystems, synthetic emulsifiers have been gradually replaced by those derived from natural sources such as plants or microbes. In previous studies, the bacterium Streptomyces sp. MC1 has shown the ability to reduce and/or accumulate Cr(VI), a highly promising advance in the development of methods for environmental clean-up of sites contaminated with chromium. Here, new studies on the production of emulsifier from this strain are presented. The cultivation factors that have a significant influence on emulsifier biosynthesis, as well as the interactions among them, were studied by factorial design. Based upon optimization studies, maximum bioemulsifier production was detected in the culture medium having an initial pH of 8 with phosphate 2.0 g L^?1 and Ca⁺² 1.0 g L^?1 added, with an emulsification index about 3.5 times greater compared to the basal value. Interestingly, in the presence of 5.0 g L^?1 Cr(VI), Streptomyces sp. MC1 retained about 65% of its emulsifier production ability. Partially purified emulsifier presented high thermo-stability and partial water solubility. These findings could have promising future prospects for the remediation of organic- and metal-contaminated sites.     

Extractability and mobility of mercury from agricultural soils surrounding industrial and mining contaminated areas

This study focussed on a comparison of the extractability of mercury in soils with two different contamination sources (a chlor-alkali plant and mining activities) and on the evaluation of the influence of specific soil properties on the behaviour of the contaminant. The method applied here did not target the identification of individual species, but instead provided information concerning the mobility of mercury species in soil. Mercury fractions were classified as mobile, semi-mobile and non-mobile. The fractionation study revealed that in all samples mercury was mainly present in the semi-mobile phase (between 63% and 97%). The highest mercury mobility (2.7 mg kg(-1)) was found in soils from the industrial area. Mining soils exhibited higher percentage of non-mobile mercury, up to 35%, due to their elevated sulfur content. Results of factor analysis indicate that the presence of mercury in the mobile phase could be related to manganese and aluminium soil contents. A positive relation between mercury in the semi-mobile fraction and the aluminium content was also observed. By contrary, organic matter and sulfur contents contributed to mercury retention in the soil matrix reducing the mobility of the metal. Despite known limitations of sequential extraction procedures, the methodology applied in this study for the fractionation of mercury in contaminated soil samples provided relevant information on mercury's relative mobility.     

Assessment of DNA damage in Brazilian workers occupationally exposed to pesticides: a study from Central Brazil

We evaluated 41 rural workers occupationally exposed to pesticides and 32 subjects as a control group, using the micronucleus (MN) and the comet assay. For the comet assay, we evaluated the peripheral blood, and for the MN, we sampled cells from the oral epithelium. Damage to DNA was measured by tail length, % DNA in tail (% tail), olive tail moment (OTM), and tail moment (TM). The exposed group presented an 8× increase in MN frequency, when compared to the control group (p <0.05). When we contrasted the MN frequencies between the individuals that use and do not use personal protective equipment, we found a mean of 7.5 MN (57 % variance) and 12.1 MN (130 % variance), respectively. The binucleated cells were 0.04 and 0.005, in the exposed and control groups, respectively, indicating 8× increase in the number of binucleated cells, when comparing the groups (p <0.05). In the comet assay, we demonstrated statistically significant differences in three parameters (% DNA, OTM, and TM) indicating that the rural workers presented high levels of genomic damages. Our results indicate that occupational exposure to pesticides could cause genome damage in somatic cells, representing a potential health risk to Brazilian rural workers that deal constantly with agrochemicals without adequate personal protection equipment.     

Core–shell magnetite-silica dithiocarbamate-derivatised particles achieve the Water Framework Directive quality criteria for mercury in surface waters

The sorption capacity of nanoporous titanosilicate Engelhard titanosilicate number 4 (ETS-4) and silica-coated magnetite particles derivatised with dithiocarbamate groups towards Hg(II) was evaluated and compared in spiked ultra-pure and spiked surface-river water, for different batch factors. In the former, and using a batch factor of 100 m³/kg and an initial Hg(II) concentrations matching the maximum allowed concentration in an effluent discharge, both materials achieve Hg(II) uptake efficiencies in excess of 99 % and a residual metal concentration lower than the guideline value for drinking water quality. For the surface-river water and the same initial concentration, the Hg(II) uptake efficiency of magnetite particles is outstanding, achieving the quality criteria established by the Water Framework Directive (concerning Hg concentration in surface waters) using a batch factor of 50 m³/kg, while the efficiency of ETS-4 is significantly inferior. The dissimilar sorbents’ Hg(II) removal efficiency is attributed to different uptake mechanisms. This study also highlights the importance of assessing the effective capacity of the sorbents under realistic conditions in order to achieve trustable results.     

The efficiency of electrocoagulation in treating wastewater from a dairy industry, part I: iron electrodes

Iron electrodes were used for electrocoagulation (EC) treatment of wastewater from a dairy plant. Electrolysis time, pH, current density and distance between electrodes were considered to assess the removal efficiency of chemical oxygen demand (COD), total solids (TS) and their fractions and turbidity. Samples were collected from the effluent of a dairy plant using a sampling methodology proportional to the flow. The treatments were applied according to design factorial of half fraction with two levels of treatments and three repetitions at the central point. The optimization of parameters for treating dairy industry effluent by electrocoagulation using iron electrodes showed that electric current application for 15 minutes, an initial sample pH close to neutral (pH 7.0) and a current density of 50 A (.)(m-2) resulted in a significant reduction in COD by 58 %; removal of turbidity, suspended solids and volatile suspended solids by 95 %; and a final treated effluent pH of approximately 9.5. Negative consequences of the type of electrode used were the emergence of an undesirable color and an increase in the proportion of dissolved solids in the treated effluent.     

Large-scale spatial pollution patterns around the North Sea indicated by coastal bird eggs within an EcoQO programme

To categorize the marine environmental health status, the Oslo and Paris commissions have recently formulated Ecological Quality Objectives (EcoQOs) for many ecological features including the contamination of coastal bird eggs with mercury and organochlorines. In this study, we describe spatial and temporal patterns of egg contamination around the North Sea and compared them to the EcoQOs. Concentrations of mercury, polychlorinated biphenyl (??PCB) congeners, dichlorodiphenyltrichloroethane (??DDT) and derivatives, hexachlorobenzene (HCB) and hexachlorocyclohexane (??HCH) isomers were analysed in two tern species (Sterna hirundo and Sterna paradisaea) and Oystercatcher (Haematopus ostralegus) eggs collected between 2008 and 2010 in a total of 21 sites in seven countries surrounding the North Sea. Hg, ??PCB and HCB were highest in the southern sites, while ??DDT and ??HCH concentrations were greatest in eggs from the western North Sea and the Elbe estuary. There were rarely any consistent decreases over time for any compounds. In the terns, Hg, HCB and ??HCH increased at most sites, ??PCB and ??DDT in Sweden and Norway. In the Oystercatcher, HCB and ??HCH increased at more than the half of the sites, ??PCB, ??DDT and Hg at several German sites. In the terns, Hg, ??PCB and ??DDT exceeded the EcoQO in all, HCB in most years and sites. At most sites, ??HCH fulfilled the EcoQO in some study years. In the Oystercatcher, Hg, ??PCB and ??DDT exceeded the EcoQO in all or most years and sites. HCB and ??HCH fulfilled the EcoQO in some or all years at most sites. The EcoQO was exceeded most frequently in estuaries. We conclude that EcoQOs are suitable for drawing contamination patterns of the coastal North Sea in an easily understandable manner, offering the opportunity to harmonize the EcoQOs with coordinated environmental monitoring programmes.     

Determinants of dioxins and furans in blood of non-occupationally exposed populations living near Portuguese solid waste incinerators

Biomonitoring of dioxin body burden, as evaluated by PCDD/F levels in blood, has been carried out in a total of 138 adults from general population living in the vicinity of solid waste incinerators in Portugal. Measurements were performed included in cross-sectional surveys within two Environmental Health Surveillance Programs launched in response to ecotoxicological concern in relation to solid waste incinerators near Lisbon and in Madeira Island. Overall conclusion from first published results is indicative that dioxin exposure of global populations cannot be related to the emissions of these facilities, meaning that dioxin sources control seems to be effective in relation to both incinerators. Main objective of present work was to investigate potential determinants of dioxin levels in the studied populations. Findings from this investigation also suggest that incineration does not impact on dioxin blood levels of nearby residents. Follow-up of a small group of individuals (22) from Lisbon gives preliminary indication on temporal control effectiveness of the Lisbon facility. Regarding comparison between PCDD/F levels from Lisbon and Madeira communities, individuals from Lisbon show higher median PCDD/F levels, likely to be better explained by more highly polluted areas in Lisbon than by eventual differences in dietary habits of the studied groups. In fact, analysis performed on the diet of both groups (not detailed in the present study) does not show a statistically significant difference in relation to any of the most relevant foodstuffs in the context of dioxin exposure. Comparison between Lisbon and Madeira in relation to pattern of the single congeners for PCDD/Fs shows a very similar profile. The highest contributions to the PCDD/Fs toxicity came from 12378-PCDD, 23478-PCDF, Hexa-CDD, 2378-TCDD and Hexa-CDF.     

Biomonitoring of PCDD/Fs in populations living near portuguese solid waste incinerators: levels in human milk

In the context of two Environmental Health Surveillance Programs, launched in response to public and scientific concern in relation to waste incinerators located near Lisbon and in Madeira Island, two human biomonitoring projects have been started in Portugal, focussed in dioxins and dioxin-like compounds in human milk. Results from the undertaken studies have already provided data on the extent and pattern of dioxin body burden of both studied groups as well as a preliminary temporal trend of dioxin levels for the population residing near Lisbon incinerator. The present paper investigates difference between exposed and non-exposed subjects under study and, from a preventive perspective, possible covariates of the dioxin levels in human milk. Emissions from both incinerators appear to be well controlled as there is no increase of human body burden of dioxins as measured in human milk of individuals living near these facilities. Concerning other determinants of dioxin levels, results suggest confirmation of previously found significant age-dependent trend towards higher levels of dioxins in aged subjects. On the contrary, association between mother's levels of dioxins and parity lost significance. Apart from the issue of incineration, the general conclusion for the general population is that living in Lisbon as compared to Madeira results in higher milk dioxin levels and possible health risks. The profile of the single congeners for PCDD/Fs in human milk from Madeira and Lisbon shows similar contributions for 12378-PCDD, 23478-PCDF, 123678-HCDD and 2378-TCDD, that account altogether for about 84% of the total identified dioxin body burden in the studied groups.