An overview on exploration and environmental impact of unconventional gas sources and treatment options for produced water.

Rising global energy demands associated to unbalanced allocation of water resources highlight the importance of water management solutions for the gas industry. Advanced drilling, completion and stimulation techniques for gas extraction, allow more economical access to unconventional gas reserves. This stimulated a shale gas revolution, besides tight gas and coalbed methane, also causing escalating water handling challenges in order to avoid a major impact on the environment. Hydraulic fracturing allied to horizontal drilling is gaining higher relevance in the exploration of unconventional gas reserves, but a large amount of wastewater (known as "produced water") is generated. Its variable chemical composition and flow rates, together with more severe regulations and public concern, have promoted the development of solutions for the treatment and reuse of such produced water. This work intends to provide an overview on the exploration and subsequent environmental implications of unconventional gas sources, as well as the technologies for treatment of produced water, describing the main results and drawbacks, together with some cost estimates. In particular, the growing volumes of produced water from shale gas plays are creating an interesting market opportunity for water technology and service providers. Membrane-based technologies (membrane distillation, forward osmosis, membrane bioreactors and pervaporation) and advanced oxidation processes (ozonation, Fenton, photocatalysis) are claimed to be adequate treatment solutions.

Heterogeneous photosensitization for water reuse in cellars: evaluation of silica, spongin, and chitosan as carrier material.

Photosensitization, a powerful oxidation reaction, offers significant potential for wastewater treatment in the context of industrial process water reuse. This environmentally friendly process can be crucial in reducing water consumption and industrial pollution. The ultimate goal is to complete process water reuse, creating a closed-loop system that preserves the inherent value of water resources. The photosensitized oxidation reaction hinges on three essential components: the photosensitizer, visible light, and oxygen. In this study, we assess the performance of three distinct materials-silica, chitosan, and spongin-as carrier materials for incorporating the phthalocyanine photosensitizer (ZnPcS4) in the heterogenous photosensitization process. Among the three materials under study, chitosan emerged as the standout performer in reactor hydrodynamic performance. In the photooxidation process, the photosensitizer ZnPcS4 exhibited notable efficacy, resulting in a significant reduction of approximately 20 to 30% in the remaining COD concentration of the cellar wastewater. Chitosan demonstrated exceptional hydrodynamic characteristics and displayed a favorable response to pH adjustments within the range of 8 to 10, outperforming the other two carrier materials. To further enhance the efficiency of continuous operation, exploring methods for mitigating photosensitizer bleaching within the reaction medium and investigating the impact of different pH values on the process optimization would be prudent.

Advanced oxidation processes for treatment of effluents from a detergent industry.

Ozonation, catalytic ozonation, Fenton's and heterogeneous Fenton-like processes were investigated as possible pretreatments of a low biodegradable and highly toxic wastewater produced by a detergent industry. The presence of a Mn-Ce-O catalyst in ozonation enhances the biodegradability and improves the degradation at low pH values. However, a high content of carbonyl compounds adsorbed on the recovered solid indicates some limitations for real-scale application. A commercial Fe2O3-MnOx catalyst shows higher activity as well as higher stability concerning carbon adsorption, but the leaching of metals is larger than for Mn-Ce-O. Regarding the heterogeneous Fenton-like route with an Fe-Ce-O catalyst, even though a high activity and stability are attained, the intermediates are less biodegradable than the original compounds, indicating that the resulting effluent cannot be conducted to an activated sludge post-treatment. The highest enhancement of effluent biodegradability is obtained with the classic homogeneous Fenton's process, with the BOD5/COD ratio increasing from 0.32 to 0.80. This process was scaled up and the treated effluent is now safely directed to a municipal wastewater treatment plant.

Adopting strategies to improve the efficiency of ozonation in the real-scale treatment of olive oil mill wastewaters.

In this experimental work the ozone action on the depuration of olive oil mill wastewater is studied for different operational conditions based on an actual industrial treatment plant. It was verified that the application of a Mn-Ce-O catalyst prepared at the laboratory, with a Mn/Ce molar proportion of 70/30, enhances the depuration efficiency and the effluent biodegradability. Ozonation operation at the natural pH of the effluent is recommended. Moreover, the integration of the Fenton process as a pretreatment improves the final chemical oxygen demand removal and enables a totally biodegradable effluent to be obtained, as confirmed by respirometric techniques.

Ozonation and UV254nm radiation for the removal of microorganisms and antibiotic resistance genes from urban wastewater.

Conventional wastewater treatment has a limited capacity to reduce antibiotic resistant bacteria and genes (ARB&ARG). Tertiary treatment processes are promising solutions, although the transitory inactivation of bacteria may select ARB&ARG. This study aimed at assessing the potential of ozonation and UV254nm radiation to inactivate cultivable fungal and bacterial populations, and the selected genes 16S rRNA (common to all bacteria), intI1 (common in Gram-negative bacteria) and the ARG vanA, blaTEM, sul1 and qnrS. The abundance of the different microbiological parameters per volume of wastewater was reduced by ∼2 log units for cultivable fungi and 16S rRNA and intI1 genes, by∼3-4 log units, for total heterotrophs, enterobacteria and enterococci, and to values close or below the limits of quantification for ARG, for both processes, after a contact time of 30min. Yet, most of the cultivable populations, the 16S rRNA and intI1 genes as well as the ARG, except qnrS after ozonation, reached pre-treatment levels after 3days storage, suggesting a transitory rather than permanent microbial inactivation. Noticeably, normalization per 16S rRNA gene evidenced an increase of the ARG and intI1 prevalence, mainly after UV254nm treatment. The results suggest that these tertiary treatments may be selecting for ARB&ARG populations.

Integration of traditional systems and advanced oxidation process technologies for the industrial treatment of olive mill wastewaters.

A complete industrial treatment system (involving the integration of coagulation/flocculation and Fenton processes) to depurate real wastewaters coming from two-phase olive oil production mills has been studied. The experimental results indicated that at the end of this combined strategy, involving a primary physical separation stage followed by Fenton's chemical oxidation, chemical oxygen demand (COD) is reduced up to 90% and total polyphenols' concentration is decreased up to 92%. The treated stream biodegradability (BOD5/COD) reached 0.52 and the Total Suspended Solids (TSSs) and Total Dissolved Solids (TDSs) decreased up to 95% and 69%, respectively. Fenton's procedure was optimized bearing in mind the pH adjustment step, different procedures for hydrogen peroxide addition and the use of coagulants instead of the chemical precipitation (by raising pH) to promote iron sludge settling. Our results demonstrated that pH (3.0 ± 0.1) control during the oxidation reaction improves the oxidation efficiency. Moreover, the final NaOH addition is essential to a better sludge formation and consequent precipitation of the residual iron removing also some organic matter.

Fenton's treatment as an effective treatment for elderberry effluents: economical evaluation.

The utilization of Fenton's oxidation for the depuration of elderberry juice wastewater was studied. The aim was to select the adequate cost-effective operating conditions suitable to lead to an effluent within the legal thresholds to be discharged into the natural water courses. The treatment efficacy was assessed by chemical oxygen demand (COD), colour, phenolic content and total solids removal besides its ability to improve biodegradability (biochemical oxygen demand (BOD5)/COD). Moreover, the costs of the applied reactants were also considered. Fenton's reaction was able to abate at least 70% of COD (corresponding to a final value below 150 mg O2 L(-1)). Besides, total phenolic content degradation was always achieved. Within these conditions, the resulting effluent is able to be directly discharged into the natural hydric channels. Fenton oxidation could be successfully applied as a single treatment method with a reactant cost of 4.38 €â€…m(-3) ([Fe(2+)] = 20 mmol L(-1), [H2O2] = 100 mmol L(-1), pH = 3 and 4 h of oxidation procedure).

Photocatalytic ozonation of urban wastewater and surface water using immobilized TiO2 with LEDs: Micropollutants, antibiotic resistance genes and estrogenic activity.

Photocatalytic ozonation was employed for the first time in continuous mode with TiO2-coated glass Raschig rings and light emitting diodes (LEDs) to treat urban wastewater as well as surface water collected from the supply area of a drinking water treatment plant (DWTP). Different levels of contamination and types of contaminants were considered in this work, including chemical priority substances (PSs) and contaminants of emerging concern (CECs), as well as potential human opportunistic antibiotic resistant bacteria and their genes (ARB&ARG). Photocatalytic ozonation was more effective than single ozonation (or even than TiO2 catalytic ozonation) in the degradation of typical reaction by-products (such as oxalic acid), and more effective than photocatalysis to remove the parent micropollutants determined in urban wastewater. In fact, only fluoxetine, clarithromycin, erythromycin and 17-alpha-ethinylestradiol (EE2) were detected after photocatalytic ozonation, by using solid-phase extraction (SPE) pre-concentration and LC-MS/MS analysis. In surface water, this treatment allowed the removal of all determined micropollutants to levels below the limit of detection (0.01-0.20 ng L(-1)). The efficiency of this process was then assessed based on the capacity to remove different groups of cultivable microorganisms and housekeeping (16S rRNA) and antibiotic resistance or related genes (intI1, blaTEM, qnrS, sul1). Photocatalytic ozonation was observed to efficiently remove microorganisms and ARGs. Although after storage total heterotrophic and ARB (to ciprofloxacin, gentamicin, meropenem), fungi, and the genes 16S rRNA and intI1, increased to values close to the pre-treatment levels, the ARGs (blaTEM, qnrS and sul1) were reduced to levels below/close to the quantification limit even after 3-days storage of treated surface water or wastewater. Yeast estrogen screen (YES), thiazolyl blue tetrazolium reduction (MTT) and lactate dehydrogenase (LDH) assays were also performed before and after photocatalytic ozonation to evaluate the potential estrogenic activity, the cellular metabolic activity and the cell viability. Compounds with estrogenic effects and significant differences concerning cell viability were not observed in any case. A slight cytotoxicity was only detected for Caco-2 and hCMEC/D3 cell lines after treatment of the urban wastewater, but not for L929 fibroblasts.