Degradation of cytostatics methotrexate and cytarabine through physico-chemical and advanced oxidative processes: influence of pH and combined processes on the treatment efficiency.

Environmental release of wastewater that contains cytostatic drugs can cause genotoxic impact, since these drugs act directly on the genetic material of aquatic organisms. Thus, the aim of this study was to evaluate the removal of the cytostatic drugs cytarabine (CTR) and methotrexate (MTX) using different physico-chemical methods individually (i.e. US, O3, H2O2 and UV) and combined (i.e. O3/US, US/H2O2, O3/H2O2 and O3/US/H2O2) under different pH conditions (4, 7 and 10). In the degradation tests, the efficiency of the methods applied was found to be dependent on the pH of the solution, with the degradation of CTR being better at pH 4 and MTX at pH 7 and pH 10. The US, H2O2 and US + H2O2 methods were the least efficient in degrading CTR and MTX under the pH conditions tested. The highest MTX degradation rate after 16 min of treatment at pH 7 was achieved by the O3 + H2O2 method (97.05% - C/C0 = 0.0295). For CTR, the highest degradation rate after 16 min of treatment was achieved by the O3 process (99.70% - C/C0 = 0.0030) at pH 4. In conclusion, most of the treatment methods tested for the degradation of CTR and MTX are effective. Notably, ozonolysis is an efficient process applied alone. Also, in combination with other methods (US + O3, O3 + H2O2 and O3 + H2O2 + US) it increases the degradation performance, showing a rapid removal rate of 70-94% in less than 4 min of treatment.

Petroleum-contaminated soil: using sonolysis to improve mineralization and biodegradation potential of Fenton reaction and ozonolysis process.

The degradation efficiency of the Fenton reaction or ozonolysis (O3) to treat soil contaminated by crude petroleum was studied in association with the sonolysis process. To quantify oxidation efficiency, total organic carbon (TOC) and chemical oxygen demand (COD) were measured, while biochemical oxygen demand (BOD5) was measured to estimate biodegradation potential. TOC removal efficiency ranged from 9 to 52% to the Fenton reaction without sonolysis, and 18% and 78% with sonolysis for reagent concentrations of 1% H2O2-100 mM Fe2+ and 20% H2O2-1 mM Fe2+, respectively. For ozonolysis (after 10 and 60 min of treatment), the reduction in TOC ranged from 9 to 43% without sonolysis and 15 to 61% with sonolysis. The Fenton reaction without sonolysis increased the biodegradability in relation to the non-oxidized sample by 6% (1% H2O2-100 mM Fe2+) and 26% (20% H2O2-1 mM Fe2+), and with sonolysis the corresponding values were 13% and 42%, respectively. The biodegradation potential under ozonolysis without sonolysis increased from 0.18 (10 min of treatment) to 0.38 (30 min of treatment), and with sonolysis these values were 0.26 and 0.58, respectively. Optimization of the remediation processes is essential to determine sequential treatment order and efficiency.

Using basic parameters to evaluate adsorption potential of alternative materials: example of amoxicillin adsorption by activated carbon produced from termite bio-waste.

The minimum set of parameters that can be used to assess the adsorption capacity of activated carbon (AC) produced from termite bio-waste was determined. Three types of AC were prepared: AC600 at 600 °C, MAC600 at the same temperature and impregnated with FeCl3, and AC800 at 800 °C. The influence of the solution pH on the adsorption, adsorption kinetics, isotherms and thermodynamic parameters was considered to characterize the amoxicillin (AMX) adsorption process. The AC materials had surface areas (m2 g-1) of approximately 248.8 for AC600, 501.6 for AC800 and 269.5 for MAC600, with point of zero charge (pHPZC) values of 8.3, 7.5 and 1.7, respectively. A time period of 30 min was chosen for the adsorption kinetics, which was best represented by the pseudo-first-order model for AC600, the intraparticle diffusion model for AC800 and the pseudo-second-order model for MAC600. Regarding the isotherms, a maximum adsorption of 23.4 mg g-1 was found for AC800. In general, the thermodynamic parameters demonstrated a non-spontaneous process. It seems that the medium conditions, the adsorbate and adsorbent characteristics, and the Gibbs free energy are the most important parameters to be considered in a preliminary assessment of the adsorption efficiency of specific adsorbent/adsorbate pairs.

Comparing different methods for fast screening of microbiological quality of beach sand aimed at rapid-response remediation.

There is scientific evidence that beach sands are a significant contributor to the pathogen load to which visitors are exposed. To develop beach quality guidelines all beach zones must be included in microbiological evaluations, but monitoring methods for beach sand quality are relatively longstanding, expensive, laborious and require moderate laboratory infrastructure. This paper aimed to evaluate the microorganism activity in different beach zones applying and comparing a classical method of membrane filtration (MF) with two colorimetric screening methods based on fluorescein (FDA) and tetrazolium (TTC) salt biotransformation to evaluate a new rapid and low-cost method for beach sand microbiological contamination assessments. The colorimetric results can help beach managers to evaluate rapidly and at low cost the microbiological quality of different beach zones in order to decide whether remedial actions need to be adopted to prevent exposure of the public to microbes due to beach sand and/or water contamination.

Ecotoxicity assessment of particulate matter emitted from heavy-duty diesel-powered vehicles: influence of leaching conditions.

Concerns regarding the environmental impact of diesel exhaust particulate matter (DPM) have increased in recent years. Following emission to the atmosphere, these fine materials can sorb many contaminants at their surface, which can subsequently be released, for instance, due to physicochemical environmental changes. The desorption of contaminants from particulate matter will increase the environmental pollution and can promote ecotoxicological effects. In this context, the objective of this study was to assess the aquatic ecotoxicity profile of extracts of DPM obtained at two different pH values. Thus, after collecting particulate matter from the diesel exhaust of heavy engines, extracts were obtained with pure water (at pH 2.00 and 5.00) and with a mixture of three organic solvents (dichloromethane, n-hexane, and acetone). To assess the environmental impact of DPM, the exhaust extracts were used in a battery of aquatic bioassays including key organisms of the food chain: bacteria (Aliivibrio fischeri), algae (Scenedesmus subspicatus), daphnids (Daphnia magna), and fishes (Danio rerio). The aqueous leachate at natural pH (2.0) and solvent extracts were extremely ecotoxic, while the aqueous leachate at pH = 5.0 showed the lowest ecotoxicity. The global ranking of sensitivity for the biotests tested was daphnids > algae > bacteria > fishes. Thus, the use of this bioassay battery could improve our understanding of the impact of DPM on aquatic environments, which is dependent on the pH of the leaching process.

Genotoxicity assessment of particulate matter emitted from heavy-duty diesel-powered vehicles using the in vivo Vicia faba L. micronucleus test.

Diesel exhaust particulate matter (PM) can have an impact on the environment due to its chemical constitution. A large number of substances such as organic compounds, sulfates, nitrogen derivatives and metals are adsorbed to the particles and desorption of these contaminants could promote genotoxic effects. The objective of this study was to assess the in vivo genotoxicity profile of diesel exhaust PM from heavy-duty engines. Extracts were obtained through leaching with pure water and chemical extraction using three organic solvents (dichloromethane, hexane, and acetone). The in vivo Vicia faba micronucleus test (ISO 29200 protocol) was used to assess the environmental impact of the samples collected from diesel exhaust PM. The solid diesel PM (soot) dissolved in water, and the different extracts, showed positive results for micronucleus formation. After the addition of EDTA, the aqueous extracts did not show a genotoxic effect. The absence of metals in the organic solvent extract indicated that organic compounds also had a genotoxic effect, which was not observed for a similar sample cleaned in a C18 column. Thus, considering the ecological importance of higher plants in relation to ecosystems (in contrast to Salmonella spp., which are commonly used in mutagenicity studies), the Vicia micronucleus test was demonstrated to be appropriate for complementing prokaryotic or in vitro tests on diesel exhaust particulate matter included in risk assessments.

Abandoned coal mining sites: using ecotoxicological tests to support an industrial organic sludge amendment.

The different stages involved in coal mining-related activities result in a degraded landscape and sites associated with large amounts of dumped waste material. Remediation of these contaminated soils can be carried out by application of industrial organic sludge if the concerns regarding the potential negative environmental impacts of this experimental practice are properly addressed. In this context, the objective of this study was to use ecotoxicological tests to determine the quantity of organic industrial sludge that is required as a soil amendment to restore soil production while avoiding environmental impact. Chemical analysis of the solids (industrial sludge and soil) and their leachates was carried out as well as a battery of ecotoxicity tests on enzymes (hydrolytic activity), bacteria, algae, daphnids, earthworms, and higher plants, according to standardized methodologies. Solid and leachate samples of coal-contaminated soil were more toxic than those of industrial sludge towards enzyme activity, bacteria, algae, daphnids, and earthworms. In the case of the higher plants (lettuce, corn, wild cabbage, and Surinam cherry) the industrial sludge was more toxic than the coal-contaminated soil, and a soil/sludge mixture (66:34% dry weight basis) had a stimulatory effect on the Surinam cherry biomass. The ecotoxicological assessment of the coal-contaminated soil remediation using sludge as an amendment is very important to determine application rates that could promote a stimulatory effect on agronomic species without negatively affecting the environment.

Incorporation of gypsum waste in ceramic block production: Proposal for a minimal battery of tests to evaluate technical and environmental viability of this recycling process.

Civil engineering-related construction and demolition debris is an important source of waste disposed of in municipal solid waste landfills. After clay materials, gypsum waste is the second largest contributor to the residential construction waste stream. As demand for sustainable building practices grows, interest in recovering gypsum waste from construction and demolition debris is increasing, but there is a lack of standardized tests to evaluate the technical and environmental viability of this solid waste recycling process. By recycling gypsum waste, natural deposits of gypsum might be conserved and high amounts of the waste by-product could be reused in the civil construction industry. In this context, this paper investigates a physical property (i.e., resistance to axial compression), the chemical composition and the ecotoxicological potential of ceramic blocks constructed with different proportions of clay, cement and gypsum waste, and assesses the feasibility of using a minimal battery of tests to evaluate the viability of this recycling process. Consideration of the results for the resistance to axial compression tests together with production costs revealed that the best formulation was 35% of plastic clay, 35% of non-plastic clay, 10% of Portland cement and 20% of gypsum waste, which showed a mean resistance of 4.64MPa. Energy dispersive X-ray spectrometry showed calcium and sulfur to be the main elements, while quartz, gypsum, ettringite and nacrite were the main crystalline compounds found in this formulation. Ecotoxicity tests showed that leachate from this formulation is weakly toxic toward daphnids and bacteria (EC(20%)=69.0 and 75.0, respectively), while for algae and fish the leachate samples were not toxic at the EC(50%) level. Overall, these results show that the addition of 20% of gypsum waste to the ceramic blocks could provide a viable substitute for clay in the ceramics industry and the tests applied in this study proved to be a useful tool for the technical and environmental evaluation of this recycling process, bacterial and daphnid tests being more sensitive than algae and fish tests.

Environmental impact of industrial sludge stabilization/solidification products: chemical or ecotoxicological hazard evaluation?

Nowadays, the classification of industrial solid wastes is not based on risk analysis, thus the aim of this study was to compare the toxicity classifications based on the chemical and ecotoxicological characterization of four industrial sludges submitted to a two-step stabilization/solidification (S/S) processes. To classify S/S products as hazardous or non-hazardous, values cited in Brazilian chemical waste regulations were adopted and compared to the results obtained with a battery of biotests (bacteria, alga and daphnids) which were carried out with soluble and leaching fractions. In some cases the hazardous potential of industrial sludge was underestimated, since the S/S products obtained from the metal-mechanics and automotive sludges were chemically classified as non-hazardous (but non-inert) when the ecotoxicity tests showed toxicity values for leaching and soluble fractions. In other cases, the environmental impact was overestimated, since the S/S products of the textile sludges were chemically classified as non-inert (but non-hazardous) while ecotoxicity tests did not reveal any effects on bacteria, daphnids and algae. From the results of the chemical and ecotoxicological analyses we concluded that: (i) current regulations related to solid waste classification based on leachability and solubility tests do not ensure reliable results with respect to environmental protection; (ii) the two-step process was very effective in terms of metal immobilization, even at higher metal-concentrations. Considering that S/S products will be subject to environmental conditions, it is of great interest to test the ecotoxicity potential of the contaminants release from these products with a view to avoiding environmental impact given the unreliability of ecotoxicological estimations originating from chemical analysis.

Terrestrial short-term ecotoxicity of a green formicide.

When ants become annoying, large quantities of formicide are applied to terrestrial ecosystems in tropical regions, but awareness of the health and environmental impacts related to the use of synthetic pesticides has been increasing. The use of green pesticides to combat target organisms could reduce these impacts. In this regard, terrestrial ecotoxicity tests with higher plants (Brassica olaracea, Lactuca sativa and Mucuna aterrima), annelids (Eisenia foetida), Collembola (Folsomia candida) and soil enzyme activity analysis (diacetate fluorescein hydrolysis) were used to evaluate short-term terrestrial ecotoxicity of a green pesticide prepared from naturally-occurring organic compounds. At the highest formicide concentration tested in these experiments (i.e., 50 g kg(-1) soil) no toxicity toward terrestrial organisms was observed. The lack of short-term terrestrial ecotoxicity suggest that this green formicide can be classed as an environmentally friendly product as compared to the ecotoxicity of the most commonly used commercialized formicides.

Physico-chemical, microbiological and ecotoxicological evaluation of a septic tank/Fenton reaction combination for the treatment of hospital wastewaters.

Hospital wastewater is considered a complex mixture populated with pathogenic microorganisms. The genetic constitution of these microorganisms can be changed through the direct and indirect effects of hospital wastewater constituents, leading to the appearance of antibiotic multi-resistant bacteria. To avoid environmental contamination hospital wastewaters must be treated. The objective of this study was to evaluate the efficiency of hospital wastewater treated by a combined process of biological degradation (septic tank) and the Fenton reaction. Thus, after septic tank biodegradation, batch Fenton reaction experiments were performed in a laboratory-scale reactor and the effectiveness of this sequential treatment was evaluated by a physico-chemical/microbiological time-course analysis of COD, BOD(5), and thermotolerant and total coliforms. The results showed that after 120min of Fenton treatment BOD(5) and COD values decreased by 90.6% and 91.0%, respectively. The BOD(5)/COD ratio changed from 0.46 to 0.48 after 120min of treatment. Bacterial removal efficiency reached 100%, while biotests carried out with Scenedesmus subspicatus and Daphnia magna showed a significant decrease in the ecotoxicity of hospital wastewater after the sequential treatment. The use of this combined system would ensure that neither multi-resistant bacteria nor ecotoxic substances are released to the environment through hospital wastewater discharge.

Small hazardous waste generators in developing countries: use of stabilization/solidification process as an economic tool for metal wastewater treatment and appropriate sludge disposal.

The aim of this study was to propose a profitable destination for an industrial sludge that can cover the wastewater treatment costs of small waste generators. Optimized stabilization/solidification technology was used to treat hazardous waste from an electroplating industry that is currently released untreated to the environment. The stabilized/solidified (S/S) waste product was used as a raw material to build concrete blocks, to be sold as pavement blocks or used in roadbeds and/or parking lots. The quality of the blocks containing a mixture of cement, lime, clay and waste was evaluated by means of leaching and solubility tests according to the current Brazilian waste regulations. Results showed very low metal leachability and solubility of the block constituents, indicating a low environmental impact. Concerning economic benefits from the S/S process and reuse of the resultant product, the cost of untreated heavy metal-containing sludge disposal to landfill is usually on the order of US$ 150-200 per tonne of waste, while 1tonne of concrete roadbed blocks (with 25% of S/S waste constitution) has a value of around US$ 100. The results of this work showed that the cement, clay and lime-based process of stabilization/solidification of hazardous waste sludge is sufficiently effective and economically viable to stimulate the treatment of wastewater from small industrial waste generators.

Ecotoxicological evaluation of the short term effects of fresh and stabilized textile sludges before application in forest soil restoration.

The short term (eco)toxicity potential of fresh and stabilized textile sludges, as well as the short term (eco)toxicity of leachates obtained from both fresh and stabilized textile sludges, was evaluated by a battery of toxicity tests carried out with bacteria, algae, daphnids, fish, earthworms, and higher plants. The (eco)toxicological results showed that, after 120 d of stabilization, the experimental loading ratio of 25% sludge:75% soil (v/v) (equivalent to 64.4 ton/ha) did not significantly increase toxicity effects and increased significantly the biomass yield for earthworms and higher plants. The rank of biological sensitivity endpoints was: Algae approximately Plant biomass > Plant germination approximately Daphnids > Bacteria approximately Fish > Annelids. The lack of short term toxicity effects and the stimulant effect observed with higher plants and earthworms are good indications of the fertilizer/conditioner potential of this industrial waste, which after stabilization can be used in the restoration of a non-productive forest soil.

Biomass growth, micronucleus induction, and antioxidant stress enzyme responses in Vicia faba exposed to cadmium in solution.

Biomass growth, micronucleus induction, and antioxidative stress enzymes (superoxide dismutase, peroxidase, glutathione reductase, and catalase) were investigated simultaneously in the Vicia faba plant exposed to cadmium in solution. The biomass lowest-observed-effect concentration (LOEC) value was 2,000 microM Cd2+. In the shoots, enzymic activities increased without concentration-response relationships. In the roots, after an initial increase, activities of all enzymes showed negative concentration-response relationships. A significant increase in micronucleus induction was observed at 20 microM Cd2+. Regarding sensitivity, our results showed that biomass endpoint was less sensitive than micronucleus induction, which was less sensitive than antioxidative enzyme activities. The increase of antioxidant stress enzyme activities in response to cadmium exposure may be taken as evidence for an enhanced detoxification capacity of V. faba plants toward reactive oxygen species (and derivatives) that might be generated in the stressed plants. Concomitant micronucleus induction may be also interpreted as a consequence of oxidative stress, upholding the view that cadmium-induced DNA damage is, to some extent, via generation of reactive (intermediate) oxygen species.