From ideal reactor concepts to reality:The novel drum reactor for photocatalytic wastewater treatment

This article reports the development of a novel drum photocatalytic reactor for treating dye effluent streams. The parameters for operation including drum rotation speed, light source distance, catalyst loading and H2O2 doping have been investigated using methylene blue as a model pollutant. Effluent can be generated by a number of domestic and industrial sources, including pharmaceutical, oil and gas, agricultural, food and chemical sectors. The work reported here proposes the application of semiconductor photocatalysis as a final polishing step for the removal of hydrocarbons from effluents sources, initial studies have proved effective in removing residual hydrocarbons from the effluent.

Remediation of oily wastewater from an interceptor tank using a novel photocatalytic drum reactor

A novel photocatalytic reactor has been developed to remediate oily wastewaters. In the first instance degradation rates of model organic compounds, methylene blue (MB) and 4-c hlorophenol (4-CP) were determined. The experimental set-up investigated a 1:10 w/v catalyst to organic solution volume, 30 g catalyst, 300 mls MB (10 μM) or 4-CP (100 μM). The catalyst investigated was a pellet catalyst to improve separation of the remediated volume from the catalyst following treatment. MB concentration decreased by 93% after 15 mins irradiation whilst 4-CP concentration decreased by 94% following 90 mins irradiation. Oily waste water (OWW) from an interceptor tank typically containing diesel oils was obtained from Sureclean, an environmental clean-up company. The OWW was treated using the same conditions as MB and 4-CP, the model organic compounds. Levels of total organic carbon (TOC) and total petroleum hydrocarbon (TPH) were used to monitor the efficacy of the photocatalytic reactor. TOC reduced by 45% following two 90 mins treatment cycles. TPH reduced by 45% following 90 mins irradiation and by a further 25% during a second stage of treatment. This reactor can be used as a polishing technique assembled within a wastewater treatment plant. Allowing for more than one pass through the reactor improves its efficiency. 

Activity and coke formation of nickel and nickel carbide in dry reforming: A deactivation scheme from density functional theory

Dry reforming is a promising reaction to utilise the greenhouse gases CO2 and CH4. Nickel-based catalysts are the most popular catalysts for the reaction, and the coke formation on the catalysts is the main obstacle to the commercialisation of dry reforming. In this study, the whole reaction network of dry reformation on both flat and stepped nickel catalysts (Ni(111) and Ni(211)) as well as nickel carbide (flat: Ni3C(001); stepped: Ni3C(111)) is investigated using density functional theory calculations. The overall reaction energy profiles in the free energy landscape are obtained, and kinetic analyses are utilised to evaluate the activity of the four surfaces. By careful examination of our results, we find the following regarding the activity: (i) flat surfaces are more active than stepped surfaces for the dry reforming and (ii) metallic nickel catalysts are more active than those of nickel carbide, and therefore, the phase transformation from nickel to nickel carbide will reduce the activity. With respect to the coke formation, the following is found: (i) the coke formation probability can be measured by the rate ratio of CH oxidation pathway to C oxidation pathway (r(CH)/r(C)) and the barrier of CO dissociation, (ii) on Ni(111), the coke is unlikely to form, and (iii) the coke formations on the stepped surfaces of both nickel and nickel carbide can readily occur. A deactivation scheme, using which experimental results can be rationalised, is proposed. 

Efficacy of instant hand sanitizers against foodborne pathogens compared to hand washing with soap and water in food preparation settings: a systematic review

Hands can be a vector for transmitting pathogenic microorganisms to foodstuffs and drinks, and to the mouths of susceptible hosts. Hand washing is the primary barrier to prevent transmission of enteric pathogens via cross contamination from infected persons. Conventional hand washing involves the use of warm water, soap and friction to remove dirt and microorganisms. Over recent years there has been an increasing availability of hand sanitizing products for use when water and soap are unavailable. The aim of this systematic review was to collate scientific information on the efficacy of hand sanitizers compared to hand washing with soap and water for the removal of foodborne pathogens from the hands of food handlers. An extensive literature search was carried out using three electronic databases - Web of Science, Scopus and PubMed. Twenty-eight scientific publications were ultimately included in the review. Analysis of the literature showed various limitations in the scientific information due to the absence of a standardized protocol to evaluate efficacy of hand products, and variation in experimental conditions applied in different studies. Despite the existence of conflicting results, scientific evidence seems to support the historical scepticism about the use of water-less hand sanitizers in food preparation settings. Water and soap appear to achieve greater removal of soil and microorganisms than water-less products from hands. None of the hand sanitizers tested in the literature seemed to achieve complete inactivation or removal of all foodborne pathogens tested, and the presence of food debris significantly affected inactivation rates of hand products.

Co-tape casting fabrication, field assistant sintering and evaluation of a coke resistant La0.2Sr0.7TiO3-Ni/YSZ functional gradient anode supported solid oxide fuel cell

The ability to directly utilize hydrocarbons and other renewable liquid fuels is one of the most important issues affecting the large scale deployment of solid oxide fuel cells (SOFCs). Herein we designed La_0.2Sr_0.7TiO₃-Ni/YSZ functional gradient anode (FGA) supported SOFCs, prepared with a co-tape casting method and sintered using the field assisted sintering technique (FAST). Through SEM observations, it was confirmed that the FGA structure was achieved and well maintained after the FAST process. Distortion and delamination which usually results after conventional sintering was successfully avoided. The La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs showed a maximum power density of 600mWcm^-2 at 750°C, and was stable for 70h in CH₄. No carbon deposition was detected using Raman spectroscopy. These results confirm the potential coke resistance of La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs.

Biological phosphorus removal during high-rate, low-temperature, anaerobic digestion of wastewater.

We report, for the first time, extensive biologically-mediated phosphate removal from wastewater during high-rate anaerobic digestion (AD). A hybrid sludge bed/fixed-film (packed pumice stone) reactor was employed for low-temperature (12°C) anaerobic treatment of synthetic sewage wastewater. Successful phosphate removal from the wastewater (up to 78% of influent phosphate) was observed, mediated by biofilms in the reactor. Scanning electron microscopy and energy dispersive X-ray analysis revealed the accumulation of elemental phosphorus (~2%) within the sludge bed and fixed-film biofilms. 4’, 6-diamidino-2-phenylindole (DAPI) staining indicated phosphorus accumulation was biological in nature and mediated through the formation of intracellular inorganic polyphosphate (polyP) granules within these biofilms. DAPI staining further indicated that polyP accumulation was rarely associated with free cells. Efficient and consistent chemical oxygen demand (COD) removal was recorded, throughout the 732-day trial, at applied organic loading rates between 0.4-1.5 kg COD m-3 d-1 and hydraulic retention times of 8-24 hours, while phosphate removal efficiency ranged from 28-78% on average per phase. Analysis of protein hydrolysis kinetics and the methanogenic activity profiles of the biomass revealed the development, at 12˚C, of active hydrolytic and methanogenic populations. Temporal microbial changes were monitored using Illumina Miseq analysis of bacterial and archaeal 16S rRNA gene sequences. The dominant bacterial phyla present in the biomass at the conclusion of the trial were the Proteobacteria and Firmicutes and the dominant archaeal genus was Methanosaeta. Trichococcus and Flavobacterium populations, previously associated with low temperature protein degradation, developed in the reactor biomass. The presence of previously characterised polyphosphate accumulating organisms (PAOs) such as Rhodocyclus, Chromatiales, Actinobacter and Acinetobacter was recorded at low numbers. However, it is unknown as yet if these were responsible for the luxury polyP uptake observed in this system. The possibility of efficient phosphate removal and recovery from wastewater during AD would represent a major advance in the scope for widespread application of anaerobic wastewater treatment technologies.

Design, production and characterisation of granular adsorbent material for arsenic removal from contaminated wastewater

The objective of this research was to design granulated iron oxide for the adsorption of heavy metals from wastewater. Polyvinyl acetate (PVAc) was chosen as a suitable binder; as it is water insoluble. Initial experiments on selection of suitable solvent of the polymer were carried out using three solvents namely; methanol, acetone and toluene. Based on the initial tests on product yield and mechanical strength, acetone was selected as the solvent for the polyvinyl acetate binder. Design of experiment was then used to investigate the influence of granulation process variables; impeller speed, binder concentration and liquid to solid ratio on the properties of the granular materials. The response variables in the study were granules mean size, stability in water and granule strength. The results showed that the combination of high impeller speed and high binder concentration favour the formation of strong and stable granules. Results also showed that leaching of the binder into the simulated was water was negligible. Trial adsorption experiments carried out using the strongest and most stable iron oxide granules produced in this work showed removal efficiency of around 70% of synthetic arsenic solutions with initial concentration of 1000 ppb.

Fungal contamination in two Portuguese wastewater treatment plants

The presence of filamentous fungi was detected in wastewater and air collected at wastewater treatment plants (WWTP) from several European countries. The aim of the present study was to assess fungal contamination in two WWTP operating in Lisbon. In addition, particulate matter (PM) contamination data was analyzed. To apply conventional methods, air samples from the two plants were collected through impaction using an air sampler with a velocity air rate of 140 L/min. Surfaces samples were collected by swabbing the surfaces of the same indoor sites. All collected samples were incubated at 27°C for 5 to 7 d. After lab processing and incubation of collected samples, quantitative and qualitative results were obtained with identification of the isolated fungal species. For molecular methods, air samples of 250 L were also collected using the impinger method at 300 L/min airflow rate. Samples were collected into 10 ml sterile phosphate-buffered saline with 0.05% Triton X-100, and the collection liquid was subsequently used for DNA extraction. Molecular identification of Aspergillus fumigatus and Stachybotrys chartarum was achieved by real-time polymerase chain reaction (RT-PCR) using the Rotor-Gene 6000 qPCR Detection System (Corbett). Assessment of PM was also conducted with portable direct-reading equipment (Lighthouse, model 3016 IAQ). Particles concentration measurement was performed at five different sizes: PM0.5, PM1, PM2.5, PM5, and PM10. Sixteen different fungal species were detected in indoor air in a total of 5400 isolates in both plants. Penicillium sp. was the most frequently isolated fungal genus (58.9%), followed by Aspergillus sp. (21.2%) and Acremonium sp. (8.2%), in the total underground area. In a partially underground plant, Penicillium sp. (39.5%) was also the most frequently isolated, also followed by Aspergillus sp. (38.7%) and Acremonium sp. (9.7%). Using RT-PCR, only A. fumigatus was detected in air samples collected, and only from partial underground plant. Stachybotrys chartarum was not detected in any of the samples analyzed. The distribution of particle sizes showed the same tendency in both plants; however, the partially underground plant presented higher levels of contamination, except for PM2.5. Fungal contamination assessment is crucial to evaluating the potential health risks to exposed workers in these settings. In order to achieve an evaluation of potential health risks to exposed workers, it is essential to combine conventional and molecular methods for fungal detection. Protective measures to minimize worker exposure to fungi need to be adopted since wastewater is the predominant internal fungal source in this setting.

An uncertainty and sensitivity analysis applied to the prioritisation of pharmaceuticals as surface water contaminants from wastewater treatment plant direct emissions

In this study, the concentration probability distributions of 82 pharmaceutical compounds detected in the effluents of 179 European wastewater treatment plants were computed and inserted into a multimedia fate model. The comparative ecotoxicological impact of the direct emission of these compounds from wastewater treatment plants on freshwater ecosystems, based on a potentially affected fraction (PAF) of species approach, was assessed to rank compounds based on priority. As many pharmaceuticals are acids or bases, the multimedia fate model accounts for regressions to estimate pH-dependent fate parameters. An uncertainty analysis was performed by means of Monte Carlo analysis, which included the uncertainty of fate and ecotoxicity model input variables, as well as the spatial variability of landscape characteristics on the European continental scale. Several pharmaceutical compounds were identified as being of greatest concern, including 7 analgesics/anti-inflammatories, 3 β-blockers, 3 psychiatric drugs, and 1 each of 6 other therapeutic classes. The fate and impact modelling relied extensively on estimated data, given that most of these compounds have little or no experimental fate or ecotoxicity data available, as well as a limited reported occurrence in effluents. The contribution of estimated model input variables to the variance of freshwater ecotoxicity impact, as well as the lack of experimental abiotic degradation data for most compounds, helped in establishing priorities for further testing. Generally, the effluent concentration and the ecotoxicity effect factor were the model input variables with the most significant effect on the uncertainty of output results.

Sustainability and economic evaluation of microalgae grown in brewery wastewater

This article evaluates the sustainability and economic potential of microalgae grown in brewery wastewater for biodiesel and biomass production. Three sustainability and two economic indicators were considered in the evaluation within a life cycle perspective. For the production system the most efficient process units were selected. Results show that harvesting and oil separation are the main process bottlenecks. Microalgae with higher lipid content and productivity are desirable for biodiesel production, although comparable to other biofuel’s feedstock concerning sustainability. However, improvements are still needed to reach the performance level of fossil diesel. Profitability reaches a limit for larger cultivation areas, being higher when extracted biomass is sold together with microalgae oil, in which case the influence of lipid content and areal productivity is smaller. The values of oil and/or biomass prices calculated to ensure that the process is economically sound are still very high compared with other fuel options, especially biodiesel.

Sustainability Evaluation of Biodiesel Produced from Microalgae Chlamydomonas sp Grown in Brewery Wastewater

This study performs a sustainability evaluation of biodiesel from microalga Chlamydomonas sp. grown in 20 % (v/v) of brewery’s wastewater, blended with pentose sugars (xylose, arabinose or ribose resulting from the hydrolysis of brewer’s spent grains (BSG). The life cycle steps considered for the study are: microalgae cultivation, biomass processing and lipids extraction at the brewery site, and its conversion to biodiesel at a dedicated external biofuel’s plant. Three sustainability indicators (LCEE, FER and GW) were considered and calculated using experimental data. Literature data was used, whenever necessary, to complement life cycle data, thus allowing a more accurate sustainability evaluation. A comparative analysis of the biodiesel life cycle steps was also conducted, with the main goal of identifying which steps need to be improved. Results show that biomass processing, especially cell harvesting, microalgae cultivation, and lipids extraction are the main process bottlenecks. It is also analysed the influence on the microalgae biodiesel sustainability of adding each pentose sugar to the cultivation media, concluding that it strongly influences the biomass and lipid productivity. In particular, the addition of xylose is preferable in terms of lipid productivity, but from a sustainability point of view, ribose is the best, though the difference from xylose is not significant. Nevertheless, culture without pentose addition presents the best sustainability results.

The removal of xenobiotic compounds from wastewater through the use of biological processes and advanced oxidation technologies

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química e Bioquímica pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Micropollutant bioremoval in wastewater treatment systems: from microbial population structure to function

Dissertation presented to obtain the Ph.D degree in Biology

Microbiology of membrane bioreactors for wastewater treatment: a molecular approach

Dissertation presented to obtain the Ph.D degree in Engineering and Technology Sciences, Biotechnology.

Monitoring and modelling of membrane bioreactors for wastewater treatment incorporating 2D fluorescence spectroscopy

Dissertação para obtenção do Grau de Doutor em Engenharia Química e Bioquímica, Especialidade em Engenharia Bioquímica