Browsing by Author "Campo, Pablo"
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Item Open Access Analytical progress and challenges for the detection of oxygenated polycyclic aromatic hydrocarbon transformation products in aqueous and soil environmental matrices: A review(Taylor and Francis, 2019-01-11) Pulleyblank, Coren; Cipullo, Sabrina; Campo, Pablo; Kelleher, Brian; Coulon, FredericOver the past 20 years, a growing body of research has raised concerns about the toxicity, fate, and transport of oxygenated transformation products of polycyclic aromatic hydrocarbons. Research targeting these diverse compounds in soil and water systems has been challenged by a lack of standard analytical techniques and suitable reference materials. However, recent efforts towards the consolidation of traditional analytical techniques as well as the development of novel approaches to improve sample preparation and hyphenated instrumental techniques show promise. This review discusses progress and challenges for both trends in analytical method development and makes recommendations for supporting oxygenated PAH research.Item Open Access Assessing bioavailability of complex mixtures in contaminated soils: progress made and research needs(Elsevier, 2017-10-17) Cipullo, Sabrina; Prpich, George; Campo, Pablo; Coulon, FredericUnderstanding the distribution, behaviour and interactions of complex chemical mixtures is key for providing the evidence necessary to make informed decisions and implement robust remediation strategies. Much of the current risk assessment frameworks applied to manage land contamination are based on total contaminant concentrations and the exposure assessments embedded within them do not explicitly address the partitioning and bioavailability of chemical mixtures. These oversights may contribute to an overestimation of both the eco-toxicological effects of the fractions and the mobility of contaminants. In turn, this may limit the efficacy of risk frameworks to inform targeted and proportionate remediation strategies. In this review we analyse the science surrounding bioavailability, its regulatory inclusion and the challenges of incorporating bioavailability in decision making process. While a number of physical and chemical techniques have proven to be valuable tools for estimating bioavailability of organic and inorganic contaminants in soils, doubts have been cast on its implementation into risk management soil frameworks mainly due to a general disagreement on the interchangeable use of bioavailability and bioaccessibility, and the associated methods which are still not standardised. This review focuses on the role of biotic and abiotic factors affecting bioavailability along with soil physicochemical properties and contaminant composition. We also included advantages and disadvantages of different extraction techniques and their implications for bioavailability quantitative estimation. In order to move forward the integration of bioavailability into site-specific risk assessments we should (1) account for soil and contaminant physicochemical characteristics and their effect on bioavailability; (2) evaluate receptor's potential exposure and uptake based on mild-extraction; (3) adopt a combined approach where chemical-techniques are used along with biological methods; (4) consider a simplified and cost-effective methodology to apply at regulatory and industry setting; (5) use single-contaminant exposure assessments to inform and predict complex chemical mixture behaviour and bioavailability.Item Open Access Bacterial community legacy effects following the Agia Zoni II oil-spill, Greece(Frontiers Media, 2020-07-17) Thomas, Gareth E.; Cameron, Tom C.; Campo, Pablo; Clark, Dave R.; Coulon, Frederic; Gregson, Benjamin H.; Hepburn, Leanne J.; McGenity, Terry J.; Miliou, Anastasia; Whitby, Corinne; McKew, Boyd A.In September 2017 the Agia Zoni II sank in the Saronic Gulf, Greece, releasing approximately 500 tonnes of heavy fuel oil, contaminating the Salamina and Athens coastlines. Effects of the spill, and remediation efforts, on sediment microbial communities were quantified over the following 7 months. Five days post-spill, the concentration of measured hydrocarbons within surface sediments of contaminated beaches was 1,093–3,773 μg g–1 dry sediment (91% alkanes and 9% polycyclic aromatic hydrocarbons), but measured hydrocarbons decreased rapidly after extensive clean-up operations. Bacterial genera known to contain oil-degrading species increased in abundance, including Alcanivorax, Cycloclasticus, Oleibacter, Oleiphilus, and Thalassolituus, and the species Marinobacter hydrocarbonoclasticus from approximately 0.02 to >32% (collectively) of the total bacterial community. Abundance of genera with known hydrocarbon-degraders then decreased 1 month after clean-up. However, a legacy effect was observed within the bacterial community, whereby Alcanivorax and Cycloclasticus persisted for several months after the oil spill in formerly contaminated sites. This study is the first to evaluate the effect of the Agia Zoni II oil-spill on microbial communities in an oligotrophic sea, where in situ oil-spill studies are rare. The results aid the advancement of post-spill monitoring models, which can predict the capability of environments to naturally attenuate oilItem Open Access Constructed wetlands as nature-based solutions in managing per-and poly-fluoroalkyl substances (PFAS): evidence, mechanisms, and modelling(Elsevier, 2024-05-18) Savvidou, Pinelopi; Dotro, Gabriela; Campo, Pablo; Coulon, Frederic; Lyu, TaoPer- and poly-fluoroalkyl substances (PFAS) have emerged as newly regulated micropollutants, characterised by extreme recalcitrance and environmental toxicity. Constructed wetlands (CWs), as a nature-based solution, have gained widespread application in sustainable water and wastewater treatment and offer multiple environmental and societal benefits. Despite CWs potential, knowledge gaps persist in their PFAS removal capacities, associated mechanisms, and modelling of PFAS fate. This study carried out a systematic literature review, supplemented by unpublished experimental data, demonstrating the promise of CWs for PFAS removal from the influents of varying sources and characteristics. Median removal performances of 64, 46, and 0 % were observed in five free water surface (FWS), four horizontal subsurface flow (HF), and 18 vertical flow (VF) wetlands, respectively. PFAS adsorption by the substrate or plant root/rhizosphere was deemed as a key removal mechanism. Nevertheless, the available dataset resulted unsuitable for a quantitative analysis. Data-driven models, including multiple regression models and machine learning-based Artificial Neural Networks (ANN), were employed to predict PFAS removal. These models showed better predictive performance compared to various mechanistic models, which include two adsorption isotherms. The results affirmed that artificial intelligence is an efficient tool for modelling the removal of emerging contaminants with limited knowledge of chemical properties. In summary, this study consolidated evidence supporting the use of CWs for mitigating new legacy PFAS contaminants. Further research, especially long-term monitoring of full-scale CWs treating real wastewater, is crucial to obtain additional data for model development and validation.Item Open Access COREXIT 9500 enhances oil biodegradation and changes microbial community structure of oil-enriched microcosms(American Society for Microbiology, 2017-03-10) Techtmann, Stephen M.; Zhuang, Mobing; Campo, Pablo; Holder, Edith; Elk, Michael; Hazen, Terry C.; Conmy, Robyn; Santo Domingo, Jorge W.To better understand the impacts of Corexit 9500 on the structure and activity levels of hydrocarbon-degrading microbial communities, we analyzed next-generation 16S rRNA gene sequencing libraries of hydrocarbon enrichments grown at 5 and 25°C using both DNA and RNA extracts as the sequencing templates. Oil biodegradation patterns in both 5 and 25°C enrichments were consistent with those reported in the literature (i.e., aliphatics were degraded faster than aromatics). Slight increases in biodegradation were observed in the presence of Corexit at both temperatures. Differences in community structure were observed between treatment conditions in the DNA-based libraries. The 25°C consortia were dominated by Vibrio, Idiomarina, Marinobacter, Alcanivorax, and Thalassospira species, while the 5°C consortia were dominated by several species of the genera Flavobacterium, Alcanivorax, and Oleispira. Most of these genera have been linked to hydrocarbon degradation and have been observed after oil spills. Colwellia and Cycloclasticus, known aromatic degraders, were also found in these enrichments. The addition of Corexit did not have an effect on the active bacterial community structure of the 5°C consortia, while at 25°C, a decrease in the relative abundance of Marinobacter was observed. At 25°C, Thalassospira, Marinobacter, and Idiomarina were present at higher relative abundances in the RNA than DNA libraries, suggesting that they were active in degradation. Similarly, Oleispira was greatly stimulated by the addition of oil at 5°C.Item Open Access Effects of dispersants and biosurfactants on crude-oil biodegradation and bacterial community succession(MDPI, 2021-06-01) Thomas, Gareth E.; Brant, Jan L.; Campo, Pablo; Clark, Dave R.; Coulon, Frederic; Gregson, Benjamin H.; McGenity, Terry J.; McKew, Boyd A.This study evaluated the effects of three commercial dispersants (Finasol OSR 52, Slickgone NS, Superdispersant 25) and three biosurfactants (rhamnolipid, trehalolipid, sophorolipid) in crude-oil seawater microcosms. We analysed the crucial early bacterial response (1 and 3 days). In contrast, most analyses miss this key period and instead focus on later time points after oil and dispersant addition. By focusing on the early stage, we show that dispersants and biosurfactants, which reduce the interfacial surface tension of oil and water, significantly increase the abundance of hydrocarbon-degrading bacteria, and the rate of hydrocarbon biodegradation, within 24 h. A succession of obligate hydrocarbonoclastic bacteria (OHCB), driven by metabolite niche partitioning, is demonstrated. Importantly, this succession has revealed how the OHCB Oleispira, hitherto considered to be a psychrophile, can dominate in the early stages of oil-spill response (1 and 3 days), outcompeting all other OHCB, at the relatively high temperature of 16 °C. Additionally, we demonstrate how some dispersants or biosurfactants can select for specific bacterial genera, especially the biosurfactant rhamnolipid, which appears to provide an advantageous compatibility with Pseudomonas, a genus in which some species synthesize rhamnolipid in the presence of hydrocarbons.Item Open Access Environmentally friendly synthesized and magnetically recoverable designed ferrite photo-catalysts for wastewater treatment applications(Elsevier, 2019-09-10) Hermosilla, Daphne; Han, Changseok; Nadagouda, Mallikarjuna; Machala, Libor; Gascó, Antonio; Campo, Pablo; Dionysiou, Dionysios D.Fenton processes are promising wastewater treatment alternatives for bio-recalcitrant compounds. Three different methods (i.e., reverse microemulsion, sol-gel, and combustion) were designed to synthesize environmentally friendly ferrites as magnetically recoverable catalysts to be applied for the decomposition of two pharmaceuticals (ciprofloxacin and carbamazepine) that are frequently detected in water bodies. The catalysts were used in a heterogeneous solar photo-Fenton treatment to save the cost of applying high-energy UV radiation sources, and was performed under a slightly basic pH to avoid metal leaching and adding salts for pH adjustment. All the developed catalysts resulted in the effective treatment of ciprofloxacin and carbamazepine in both synthetic and real domestic wastewater. In particular, the sol-gel synthesized ferrite was more magnetic and more suitable for reuse. The degradation pathways of both compounds were elucidated for this treatment. The degradation of ciprofloxacin involved attacks to the quinolone and piperazine rings. The degradation pathway of carbamazepine involved the formation of hydroxyl carbamazepine and dihydroxy carbamazepine before yielding acridine by hydrogen abstraction, decarboxylation, and amine cleavage, which would be further oxidized.Item Open Access Impacts of coagulation-flocculation treatment on the size distribution and bioavailability of trace metals (Cu, Pb, Ni, Zn) in municipal wastewater(Elsevier, 2017-10-25) Hargreaves, Andrew J.; Vale, Peter; Whelan, Jonathan; Alibardi, Luca; Constantino, Carlos; Dotro, Gabriela; Cartmell, Elise; Campo, PabloThis study investigated the impact of coagulation-flocculation treatment on metal form and bioavailability in municipal wastewater. Real humus effluent samples were separated into particulate, colloidal and truly dissolved fractions before and after treatment with either ferric chloride (FeCl3) or the biopolymer Floculan. Results revealed that both reagents effectively (≥48%) eliminated Cu, Pb and Zn from the particulate fraction and removed Cu and Zn from the colloidal fraction in conjunction with colloidal organic carbon (COC). Although organics in the truly dissolved fraction were resistant to removal, Floculan reduced Cu in this fraction by 72% owing to the complexation of free Cu ions to phenol and amino groups along the polymeric chains, revealing an additional removal pathway. In fact, COC removed in the CF process by Floculan was replaced with truly dissolved compounds, input as a result of this reagents organic composition. Floculan, therefore, reduced the soluble concentration of Cu and Zn without changing the DOC concentration, thus reducing the bioavailability of these metals in treated effluent. FeCl3 did not reduce the bioavailability of target metals, thus did not deliver any environmental benefit. This work provides important information for the selection and development of high performance coagulants to improve metal removal.Item Open Access Influence of solids and hydraulic retention times on microbial diversity and removal of estrogens and nonylphenols in a pilot-scale activated sludge plant(Elsevier, 2023-08-30) Mensah, Lawson; Petrie, Bruce; Scrimshaw, Mark; Cartmell, Elise; Fletton, Mandy; Campo, PabloThe removal of EDCs in activated sludge processes can be enhanced by increasing solid and hydraulic retention times (SRT and HRT); it has been suggested that the improvement in removal is due to changes in microbial community structure (MCS). Though the influence of SRT and HRT on chemical removal and MCS has been studied in isolation, their synergistic impact on MCS and the removal of estrogens and nonylphenols in activated sludge remains unknown. Hence, we investigated how both parameters influence MCS in activated sludge processes and their ulterior effect on EDC removal. In our study, an activated sludge pilot-plant was fed with domestic sewage fortified with 100 and 1000 ng/L nonylphenols or 2 and 15 ng/L estrogens and operated at 3, 10 and 27 d SRT (constant HRT) and at 8, 16 and 24 h HRT (constant SRT). The MCS was assessed by phospholipid fatty acids (PLFA) analysis, and the archaeal and bacterial diversities were determined by 16S rRNA analysis. From the PLFA, the microbial abundance ranked as follows: Gram-negative > fungi > Gram-positive > actinomycetes whilst 16S rRNA analysis revealed Proteobacteria > Bacteroidetes > Others. Both PLFA and 16S rRNA analysis detected changes in MCS as SRT and HRT were increased. An SRT increment from 3 to 10 d resulted in higher estrone (E1) removal from 19 to 93% and nonylphenol-4-exthoxylate (NP4EO) from 44 to 73%. These findings demonstrate that EDC-removal in activated sludge plants can be optimised where longer SRT (>10 d) and HRT (>8 h) are suitable. We have also demonstrated that PLFA can be used for routine monitoring of changes in MCS in activated sludge plants.Item Open Access A method for the characterisation of microplastics in sludge(Elsevier, 2019-11-19) Campo, Pablo; Holmes, Anita; Coulon, FredericMicroplastics (MP) have become a concern owing to their increasing detection in the environment and potential impact on ecosystems. One of the main MP reservoirs is sludge generated during wastewater treatment. Estimates suggest that, through sludge settling, treatment processes remove between 80 and 90 % of MP present in wastewater. Nevertheless, reliable measurements of actual plastics loads retained by sludge are still lacking for management purposes. Hence, our goal was to validate a quick method for MP quantitation in sludge. Recovery tests were conducted with red low-density polyethylene (LDPE) fragments whose sizes ranged between 5 to 1 mm, 1 to 0.5 mm and 500 to 150 μm. For each size fraction, either 10 or 100 LDPE fragments were spiked into wet sludge (50 mL). Subsequent LDPE analysis involved steps such as freeze-drying, sieving, Fenton purification, visual shorting and FTIR identification. When expressed as number of fragments, quantitative (i.e. percentage values between 80 and 100) were obtained regardless of size fraction or initial spiked number. In terms of total spiked LDPE weight, however, recoveries consistently exceeded 100 % because LDPE fragments retained other materials. Such residues contributed to an overestimation of MP by weight up to 33 % of the 500−150 μm fraction.Item Open Access Microbial degradation of Cold Lake Blend and Western Canadian select dilbits by freshwater enrichments(Elsevier, 2018-03-21) Deshpande, Ruta S.; Sundaravadivelu, Devi; Techtmann, Stephen; Conmy, Robyn N.; Santo Domingo, Jorge W.; Campo, PabloTreatability experiments were conducted to determine the biodegradation of diluted bitumen (dilbit) at 5 and 25 °C for 72 and 60 days, respectively. Microbial consortia obtained from the Kalamazoo River Enbridge Energy spill site were enriched on dilbit at both 5 (cryo) and 25 (meso) ºC. On every sampling day, triplicates were sacrificed and residual hydrocarbon concentrations (alkanes and polycyclic aromatic hydrocarbons) were determined by GCMS/MS. The composition and relative abundance of different bacterial groups were identified by 16S rRNA gene sequencing analysis. While some physicochemical differences were observed between the two dilbits, their biodegradation profiles were similar. The rates and extent of degradation were greater at 25 °C. Both consortia metabolized 99.9% of alkanes; however, the meso consortium was more effective at removing aromatics than the cryo consortium (97.5 vs 70%). Known hydrocarbon-degrading bacteria were present in both consortia (Pseudomonas, Rhodococcus, Hydrogenophaga, Parvibaculum, Arthrobacter, Acidovorax), although their relative abundances depended on the temperatures at which they were enriched. Regardless of the dilbit type, the microbial community structure significantly changed as a response to the diminishing hydrocarbon load. Our results demonstrate that dilbit can be effectively degraded by autochthonous microbial consortia from sites with recent exposure to dilbit contamination.Item Open Access A novel CuBi2O4/polyaniline composite as an efficient photocatalyst for ammonia degradation(Elsevier, 2022-08-17) Ahmad, Nafees; Anae, Jerry; Khan, Mohammad Zain; Sabir, Suhail; Campo, Pablo; Coulon, FredericA novel polyaniline (PANI) coupled CuBi2O4 photocatalyst was successfully synthesized via in situ polymerization of aniline with pre-synthesized CuBi2O4 composites. The structure and morphology of the synthesized CuBi2O4/PANI composite photocatalyst were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) and the photocatalytic performance were evaluated through degradation process of ammonia in water under visible light irradiation. The resultant CuBi2O4/PANI composite showed exceptional stability as its structure and morphology persisted even after being immersed in water for 2 days. The composite photocatalyst exhibited improved charge transport properties due to the electrical conductivity of the PANI protective layer, leading to enhanced photoelectrochemical activity in water and removal of ammonia. PANI with CuBi2O4 (10% wt) heterostructure was applied for photodegradation of ammonia and exhibited a 96% ammonia removal efficiency (30 mg/l with 0.1 g photocatalyst and 180 min), as compared to PANI (78%) and CuBi2O4 (70%). The degradation was attributed to the efficient charge transfer (e− and h+) and formation of reactive oxygen species upon simulated sunlight exposure. The present work suggests that the CuBi2O4/PANI photocatalyst can be synthesized in a simple process and provides an excellent adsorption capacity, high photocatalytic activity, long term stability, and reusability making it a promising alternative for ammonia removal from wastewater.Item Open Access Recovery of polycyclic aromatic hydrocarbons and their oxygenated derivatives in contaminated soils using aminopropyl silica solid phase extraction(Elsevier, 2020-06-06) Pulleyblank, Coren; Kelleher, Brian; Campo, Pablo; Coulon, FredericThe formation, fate, and toxicology of oxy-, hydroxy-, and carboxy- substituted PAH (OPAH, OHPAH, COOHPAH, respectively) alongside PAH in contaminated soils have received increasing attention over the past two decades; however, there are still to date no standardized methods available for their identification and quantitation in soil. Here we investigated and developed the first method using aminopropylsilica solid phase extraction (SPE) for these compounds. We further investigated the efficacy of the developed method for three soils representing a range of contamination levels and soil textural characteristics and evaluated the impact of different sample preparation steps on the recovery of targeted compounds. Average recovery of PAH, OPAH, and OHPAH standards were 99%, 84%, and 86%, respectively for the SPE method. In contrast, COOHPAH exhibited the lowest recovery (0–82%) and poor inter-batch reproducibility. Soil texture and contamination levels influenced full method efficiency. Specifically, soils with higher proportion of clay contributed to the loss of the higher molecular weight OHPAH prior to SPE. Soil with the highest contamination showed enhanced recovery of some lower-concentration mid weight PAH and OPAH, while the least contaminated soil showed greater sensitivity to evaporative losses during sample preparation. Recommendations for reducing matrix effects as well as the practice of using deuterated PAH surrogate standards for OPAH analysis are further discussed. Quantitation of recovered PAH and oxygenated PAH across the three soils showed high reproducibility (<10% relative standard deviation for a majority of compounds), supporting the use of this method for PAH, OPAH, and OHPAH at contaminated sites.Item Open Access The role of coagulation on the fate of PFAS, brominated flame retardants and other trace contaminants in tertiary wastewater treatment for phosphorus control(Elsevier, 2023-05-15) Zoumpouli, Garyfalia A.; Herron, Dean; Thornton, Arthur; Jefferson, Bruce; Campo, PabloCoagulant dosing to achieve low phosphorus concentrations in wastewater effluents may favour the removal of trace organics such as pharmaceuticals, plasticisers and flame retardants. Nevertheless, the behaviour of trace organics in coagulation processes is currently poorly understood because of the complex interactions between these compounds, the coagulants and dissolved organic matter (DOM). This study assessed the coagulation removal from synthetic secondary effluent of twenty-four compounds including ten PFAS and four brominated flame retardants. Testing involved two coagulants (alum, ferric chloride) and five DOM surrogates (resorcinol, benzoic acid, citric acid, tannic acid, humic acid); DOM surrogates had assorted molecular weights, structures, charges, and hydrophobicity. With coagulant doses of 14 mg Fe/L and 4 mg Al/L, ten trace organics were removed by >30 % in the presence of at least one DOM surrogate. Humic acid effected the highest removals owing to complexation of trace organics and subsequent co-removal by adsorption or sweep floc. For instance, removal extents for three brominated diphenyl ethers were 60 to 75 % with Al and 50 to 88 % with Fe (initial concentration 0.4 to 0.8 ng/L); PFTDA, a long-chain PFAS, was removed by 87 and 91 % with Fe in the presence of tannic or humic acid, respectively (initial concentration 0.03 μg/L). The varying coagulation performance of different treatment works in terms of trace substance removal can be explained because of the site-specific DOM characteristics. Addition of humic acids as complexing agents has the potential to improve the removal of hydrophobic trace substances, including some long-chain PFAS and brominated flame retardants.Item Open Access Treatment options for reclaiming wastewater produced by the pesticide industry(Sciforschen - Open HUB for Science Research, 2017-11-10) Goodwin, Lindsey; Carra, Irene; Campo, Pablo; Soares, AnaThe pesticide production industry generates a high strength wastewater containing a range of toxic pollutants (2,4-dichlorphenoxy acetic acid: 2,4-D; 4-(2,4-dichlorphenox) propionic acid: 2,4-DP; 4-(2,4-dichlorophenox) butyric acid: 2,4-DB; 2,4-dichlorophenol: 2,4-DCP; 2,4,6-trichlorophenol: 2,4,6-TCP; 4-chlororthocresol: PCOC; 4-chloro-2-methyl phenoxyacetic acid: MCPA, 4-(4-chloro-2-methylphenoxy) butyric acid: MCPB and 2-(4-chloro-2-methylphenoxy) propionic acid: MCPP). These pesticides can enter the natural environment and water sources if not removed in a wastewater treatment plant. Treated effluents are regulated by legislation such as the Water Framework Directive (WFD). Most studies found in literature focused on synthetic solutions, synthetic wastewater, at lab-scale or pilot-scale. Although these studies can provide information on the removal mechanisms and provide a comparison between process efficiency, they have limited practical applicability. The process that has been more widely used to treat high strength wastewaters rich in recalcitrant compounds at full-scale, is the combination of biological/granular activated carbon and granular activated carbon/biological processes. The pesticide production wastewater contains a variety of compounds, that can be removed by 80-90% using biological processes (such as membrane bioreactors) and granular activated carbon has been shown to selectively remove the pesticides, potentially creating a high quality effluent. Nevertheless, in order to assert processes design, efficiencies or costs, it is crucial to evaluate these processes experimentally.Item Open Access Visible light-conducting polymer nanocomposites as efficient photocatalysts for the treatment of organic pollutants in wastewater(Elsevier, 2021-07-24) Ahmad, Nafees; Anae, Jerry; Khan, Mohammad Zain; Sabir, Suhail; Yang, Xiao Jin; Thakur, Vijay Kumar; Campo, Pablo; Coulon, FredericThis review compiles recent advances and challenges on photocatalytic treatment of wastewater using nanoparticles, nanocomposites, and polymer nanocomposites as photocatalyst. The review provides an overview of the fundamental principles of photocatalytic treatment along the recent advances on photocatalytic treatment, especially on the modification strategies and operational conditions to enhance treatment efficiency and removal of recalcitrant organic contaminants. The different types of photocatalysts along the key factors influencing their performance are also critically discussed and recommendations for future research are provided.