Endocrine disrupting activity in sewage sludge: Screening method, microbial succession and cost-effective strategy for detoxification.

Sewage sludge (SS) presents a high agronomic potential due to high concentrations of organic matter and nutrients, encouraging its recycling as a soil conditioner. However, the presence of toxic substances can preclude this use. To enable the safe disposal of this waste in agriculture, SS requires additional detoxification to decrease the environmental risks of this practice. Although some alternatives have been proposed in this sense, little attention is provided to eliminating endocrine-disrupting chemicals (EDCs). To fill this gap, this study aimed to develop effective and low-cost technology to eliminate EDCs from SS. For this, a detoxification process combining microorganisms and biostimulating agents (soil, sugarcane bagasse, and coffee grounds) was performed for 2, 4, and 6 months with aerobic and anaerobic SSs. The (anti-)estrogenic, (anti-)androgenic, retinoic-like, and dioxin-like activities of SSs samples were verified using yeast-based reporter-gene assays to prove the effectiveness of the treatments. A fractionation procedure of samples, dividing the target sample extract into several fractions according to their polarity, was conducted to decrease the matrix complexity and facilitate the identification of EDCs. A decrease in the abundance and microbial diversity of the SS samples was noted along the biostimulation with the predominance of filamentous fungal species over yeasts and gram-positive bacteria and non-fermenting rods over enterobacteria. Among the 9 EDCs quantified by LC-ESI-MS/MS, triclosan and alkylphenols presented the highest concentrations in both SS. Before detoxification, the studied SSs induced significant agonistic activity, especially at the human estrogen receptor α (hERα) and the human aryl hydrocarbon receptor (AhR). The raw anaerobic sludge also activated the androgen (hAR), retinoic acid (RARα), and retinoid X (RXRα) receptors. However, no significant endocrine-disrupting activities were observed after the SS detoxification, showing that the technology applied here efficiently eliminates receptor-mediated toxicity.

Multiresidue determination and predicted risk assessment of contaminants of emerging concern in marine sediments from the vicinities of submarine sewage outfalls.

Submarine sewage outfalls (SSOs) are considered the main input source of contaminants of emerging concern continuously released in coastal areas, with the potential to cause adverse effects for aquatic organisms. This work presents the investigation of nine endocrine disrupting chemicals (EDCs) and 26 pharmaceutically active chemicals (PhACs) in marine sediments within the vicinities of 7 SSOs along the São Paulo State Coast (Brazil). Method optimization for the multi-residue determination by GC-MS/MS and LC-MS/MS using QuEChERS extraction/clean-up are discussed. Results demonstrate the occurrence of EDCs in concentrations ranging from less than method quantification limits (MQL) to 72.5 ng g-1 in sediments. All PhACs were

Photochemical transformation of zearalenone in aqueous solutions under simulated solar irradiation: Kinetics and influence of water constituents.

The presence of estrogenic mycotoxins, such as zearalenone (ZEN), in surface waters is an emerging environmental issue. Little is known about its phototransformation behavior, which may influence its environmental fate. In this context, the phototransformation of ZEN was investigated in pure water, river water and estuarine water using simulated sunlight irradiation. Kinetic studies revealed that two concomitant processes contribute to the fate of ZEN under solar irradiation: photoisomerization and photodegradation. This phototransformation followed a pseudo-first order kinetics. ZEN degrades quickly in natural waters and slowly in deionized water, with half-lives (t1/2) of 28 ± 4 min (estuarine water), 136 ± 21 min (river water) and 1777 ± 412 min (deionized water). The effects of different water constituents on the phototransformation of ZEN in aqueous solution have been assessed (NaCl, Ca2+, Mg2+, Fe3+, NO3- and oxalate ions, synthetic seawater, Fe(III)-oxalate and Mg(II)-oxalate complexes, humic acids, fulvic acids and XAD-4 fraction). In the presence of synthetic seawater salt (t1/2 = 18 ± 5 min) and Fe(III)-oxalate complexes (t1/2 = 61 ± 9 min), the transformation rate increased considerably in relation to other water constituents tested. The solution pH also had a considerable effect in the kinetics with maximum transformation rates occurring around pH 8.5. These results allow us to conclude that phototransformation by solar radiation can be an important degradation pathway of ZEN in natural waters.

Influence on the oxidative potential of a heavy-duty engine particle emission due to selective catalytic reduction system and biodiesel blend.

Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OP(ESR)) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OP(ESR) results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100cm(-1) and 1600cm(-1) indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation.