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Per- and polyfluoroalkyl substances (PFAS) are a group of widely used man-made organic chemical substances. PFAS have been used because of their particular physicochemical properties: most are stable at high temperatures, recalcitrant to chemical oxidation and biological degradation, and act as a surfactant. Many PFAS may also be bio-accumulative and toxic and there are concerns around their environmental effect. In this study several treatment technologies for PFAS removal were tested in the laboratory on both groundwater containing PFAS, and firefighting wastewater obtained from a firefighting training site where firefighting foam was applied. The treatment technologies assessed were performance of sorbents, coagulation/flocculation, nanofiltration, foam- and ozo fractionation technologies. In all cases the PFAS removal effectiveness was evaluated. Experiments showed that all sorbents were able to remove PFAS from both groundwater containing PFAS as well as firefighting wastewater, but the latter required sorbent dosages in g/L range. It was therefore concluded that groundwater containing PFAS can be treated with one of the tested sorbents directly, while for firefighting wastewater, typically has higher PFAS concentrations as well as other contaminants, a treatment train approach is likely to be more efficient.

Refinery effluents represent an emission source of hydrocarbons (HCs) and other constituents to the environment. Thus, characterisation of effluent quality in terms of concentrations of key parameters relative to permitted standards is important and for total petroleum hydrocarbons (TPH), the specific composition of the HC mixture can affect its toxicity to aquatic organisms. Therefore, this study was designed to analyse TPH, benzene, toluene, ethyl benzene, xylenes (BTEX), polycyclic aromatic hydrocarbons (PAHs), (bio) chemical oxygen demand, total nitrogen, total suspended solids and selected metals before, and after, treatment steps to demonstrate removal efficiencies across 13 refineries with variable wastewater treatment systems. Final discharge concentrations of the measured parameters were by 97% within the so called Best Available Technique Associated Emission Levels (BAT-AELs). Further, TPH composition was characterised using high-resolution two-dimensional gas chromatography (GCxGC) analysis to understand the mass distribution by carbon number and specific chemical class. Measurements were compared to SimpleTreat model predictions for validation. SimpleTreat successfully predicted the shape of the effluent composition since it is essentially a removal constant applied to the influent composition. The predictions were of similar magnitude as, or were greater than, the effluent concentrations since SimpleTreat is based on typical performance and is intended to be conservative. This was especially true for aromatic constituents. Reduction in potential HC exposures also coincided with a decrease in predicted toxicity using a mechanistic oil toxicity model, PETROTOX. Overall, the results indicate that EU petroleum refineries are likely to achieve a high performance level regarding effluent treatment.

Microbes in aquifers are present suspended in groundwater or attached to the aquifer sediment. Groundwater is often sampled at gasoline ether oxygenate (GEO)-impacted sites to assess the potential biodegradation of organic constituents. However, the distribution of GEO-degrading microorganisms between the groundwater and aquifer sediment must be understood to interpret this potential. In this study, the distribution of ethyl tert-butyl ether (ETBE)-degrading organisms and ETBE biodegradation potential was investigated in laboratory microcosm studies and mixed groundwater-aquifer sediment samples obtained from pumped monitoring wells at ETBE-impacted sites. ETBE biodegradation potential (as determined by quantification of the ethB gene) was detected predominantly in the attached microbial communities and was below detection limit in the groundwater communities. The copy number of ethB genes varied with borehole purge volume at the field sites. Members of the Comamonadaceae and Gammaproteobacteria families were identified as responders for ETBE biodegradation. However, the detection of the ethB gene is a more appropriate function-based indicator of ETBE biodegradation potential than taxonomic analysis of the microbial community. The study shows that a mixed groundwater-aquifer sediment (slurry) sample collected from monitoring wells after minimal purging can be used to assess the aquifer ETBE biodegradation potential at ETBE-release sites using this function-based concept.

Water is used in petroleum oil refineries in significant volumes for cooling, steam generation and processing of raw materials. Effective water management is required at refineries to ensure their efficient and responsible operation with respect to the water environment. However, ascertaining the potential environmental risks associated with discharge of refinery effluents to receiving waters is challenging because of their compositional complexity. Recent European research and regulatory initiatives propose a more holistic approach including biological effect methods to assess complex effluents and surface water quality. The study presented here investigated potential effects of effluent composition, particularly hydrocarbons, on aquatic toxicity and was a component of a larger study assessing contaminant removal during refinery wastewater treatment (Hjort et al 2021). The evaluation of effects utilised a novel combination of mechanistic toxicity modelling based on the exposure composition, measured bioavailable hydrocarbons using biomimetic solid phase microextraction (BE-SPME), and bioassays. The results indicate that in the refinery effluent assessments measured bioavailable hydrocarbons using BE-SPME was correlated with the responses in standard bioassays. It confirms that bioassays are providing relevant data and that BE-SPME measurement, combined with knowledge of other known non-hydrocarbon toxic constituents, provide key tools for toxicity identification. Overall, the results indicate that oil refinery effluents treated in accordance to the EU Industrial Emissions Directive requirements have low to negligible toxicity to aquatic organisms and their receiving environments. Low-cost, animal-free BE-SPME represents a compelling tool for rapid effluent characterization.

Natural source zone depletion (NSZD) encompasses all processes that result in petroleum hydrocarbon light non-aqueous phase liquid (LNAPL) mass loss. Vertical gas transport between the subsurface and atmosphere is a key component of NSZD. Gas exchange with the atmosphere may be restricted at sites with ground cover, which is typical for European fuel retail sites. This raises questions of whether, and to what extent, the generic NSZD conceptual model applies at these sites. Here, we present a study that evaluated how concrete and asphalt pavement affected NSZD processes and data interpretation for three NSZD assessment methods: soil gas concentration gradient, biogenic heat and carbon dioxide traps. All methods demonstrated that NSZD was occurring and NSZD rates were generally within the low end of values reported in the literature for unpaved sites. However, there was considerable variability in the rates, which highlights the need for careful examination of the conceptual site model and potential interferences for each method. The results demonstrate the viability of soil gas and temperature data collected from existing monitoring wells screened into the unsaturated zone without the need for additional, intrusive subsurface installations. The results also provide useful guidance for developing optimal long-term NSZD monitoring approaches, where necessary.

Hazard assessment of refinery effluents is challenging because of their compositional complexity. Therefore, a weight-of-evidence approach using a combination of tools is often required. Previous research has focused on several predictive tools for sophisticated chemical analyses: biomimetic extraction to quantify the potentially bioaccumulative substances, 2-dimensional gas chromatography, modeling approaches to link oil composition to toxicity (PETROTOX), and whole-effluent toxicity assessments using bioassays. The present study investigated the value of these tools by comparing predicted effects to actual effects observed in stream mesocosm toxicity studies with refinery effluents. Three different effluent samples, with and without fortification by neat petroleum substances, were tested in experimental freshwater streams. The results indicate that the biological community shifted at higher exposure levels, consistent with chronic toxicity effects predicted by both modeled toxic units and potentially bioaccumulative substance measurements. The present study has demonstrated the potential of the predictive tools and the robustness of the stream mesocosm design to improve our understanding of the environmental hazards posed by refinery effluents. Environ Toxicol Chem 2019;38:650-659. © 2018 SETAC.

Distribution and elimination of petroleum products can be predicted in aerobic wastewater treatment plants (WWTPs) using models such as multimedia fate model SimpleTreat. An advantage of the SimpleTreat model is that it only requires a few basic properties of a chemical in wastewater to calculate partitioning, biodegradation and ultimately emissions to air, surface water and produced sludge. The SimpleTreat model structure reflects a WWTP scheme. However, refinery WWTPs typically incorporate more advanced treatment processes such as dissolved air flotation (DAF), a process that clarifies wastewaters by the removal of suspended matter such as oil or solids. The objective of this work was to develop a WWTP removal model that includes DAF treatment. To understand how including a DAF in the model affects the predicted concentrations of petroleum constituents in effluent, we replaced the primary sedimentation module in SimpleTreat with a module simulating DAF. Subsequently, we compared results from the WWTP-DAF model with results obtained with the original SimpleTreat model for a library of over 1500 representative hydrocarbon constituents. The increased air-water exchange in a WWTP-DAF unit resulted in higher predicted removal of volatile constituents. Predicted removal with DAF was on average 17% larger than removal with primary sedimentation. We compared modelled results with measured removal data from the literature, which supported that this model refinement continues to improve the technical basis of assessment of petroleum products.

Production of polyhydroxyalkanoate (PHA) biopolymers by mixed microbial cultures concurrent to wastewater treatment is a valorization route for residual organic material. This development has been at pilot scale since 2011 using industrial and municipal organic residuals. Previous experience was the basis for a PHA production demonstration project: PHARIO. PHARIO was centred on processing surplus activated sludge biomass from the Bath full-scale municipal wastewater treatment plant in the Netherlands to produce PHA. Full-scale surplus activated sludge was fed to a pilot facility to produce PHA rich biomass using fermented volatile fatty acid (VFA) rich liquors from industry or primary sludge sources. A PHA rich biomass with on average 0.41 gPHA/gVSS was obtained with reproducible thermal properties and high thermal stability. A routine kilogram scale production was established over 10 months and the polymer material properties and market potential were evaluated. Surplus full-scale activated sludge, over four seasons of operations, was a reliable raw material to consistently and predictably produce commercial quality grades of PHA. Polymer type and properties were systematic functions of the mean co-polymer content. The mean co-polymer content was predictably determined by the fermented feedstock composition. PHARIO polymers were estimated to have a significantly lower environmental impact compared to currently available (bio)plastics.

A process was developed for biological treatment of municipal wastewater for carbon and nitrogen removal while producing added-value polyhydroxyalkanoates (PHAs). The process comprised steps for pre-denitrification, nitrification and post-denitrification and included integrated fixed-film activated sludge (IFAS) with biofilm carrier media to support nitrification. In a pilot-scale demonstration (500-800L), wastewater treatment performance, in line with European standards, were achieved for total chemical oxygen demand (83% removal) and total nitrogen (80% removal) while producing a biomass that was able to accumulate up to 49% PHA of volatile suspended solids with acetic acid or fermented organic residues as substrates. Robust performance in wastewater treatment and enrichment of PHA-producing biomass was demonstrated under realistic conditions including influent variability during 225days of operation. The IFAS system was found to be advantageous since maintaining nitrification on the biofilm allowed for a relatively low (2days) solids retention time (SRT) for the suspended biomass in the bulk phase. Lower SRT has advantages in higher biomass yield and higher active fraction in the biomass which leads to higher PHA productivity and content. The outcomes show that production of added-value biopolymers may be readily integrated with carbon and nitrogen removal from municipal wastewater.

A strategy was evaluated for conditioning activated sludge biomass to a new substrate whereby the polyhydroxyalkanoate (PHA) accumulation capacity of the biomass was enhanced based on a series of aerobic feast–famine acclimation cycles applied prior to PHA accumulation. Different biomass types enriched during the treatment of municipal wastewater at laboratory, pilot, and full scales were exposed to aerobic feast–famine acclimation cycles at different feast-to-famine ratios with an acetate–propionate mixture (laboratory scale), acetate (pilot scale), and fermented waste–sludge centrate (pilot scale). A sevenfold increase in specific PHA storage rates and 20% increase in substrate utilization rates were observed during acclimation cycles (laboratory acetate–propionate). Biomass acclimation led to more than doubling of the specific substrate utilization rates, PHA storage rates, biomass PHA contents, and specific PHA productivities (per initial biomass) during PHA accumulation. The biomass PHA contents were found to increase due to acclimation from 0.19 to 0.34 (laboratory acetate–propionate), 0.39 to 0.46 (pilot acetate) and 0.19 to 0.25 gPHA/gVSS (pilot centrate). A similar bacterial community structure during acclimation indicated that a physiological rather than a genotypic adaptation occurred in the biomass. The physiological state of the biomass at the start of PHA accumulation was deemed significant in the subsequent PHA-accumulation performance. Positive acclimation trends can be monitored by measuring the relative increase in feast substrate utilization or respiration rates with respect to those of the first acclimation cycle.

Aerobic biodegradation of ethyl tert butyl ether (ETBE) in a gasoline-impacted aquifer was investigated in laboratory microcosms containing groundwater and aquifer material from ETBE-impacted and non-impacted locations amended with either ETBE, or ETBE plus methyl tert butyl ether (MTBE). As sole substrate, ETBE was biodegraded (maximum rate of 0.54 day-1) without a lag in ETBE-impacted microcosms but with a lag of up to 66 days in non-impacted microcosms (maximum rate of 0.38 day-1). As co-substrate, ETBE was biodegraded preferentially (maximum rate of 0.25 and 0.99 day-1 in non-impacted and impacted microcosms, respectively) before MTBE (maximum rate of 0.24 and 0.36 day-1 in non-impacted and impacted microcosms, respectively). Further addition of ETBE and MTBE reduced lags and increased biodegradation rates. ethB gene copy numbers increased significantly (>100 fold) after exposure to ETBE, while overall cell numbers remained constant, suggesting that ethB-containing microorganisms come to dominate the microbial communities. Deep sequencing of 16S rRNA genes identified members of the Comamonadaceae family that increased in relative abundance upon exposure to ETBE. This study demonstrates the potential for ETBE biodegradation within the unsaturated and saturated zone, and that ETBE biodegrading capability is rapidly developed and maintained within the aquifer microbial community over extended timescales.

Pilot and prototyping scale investigations were undertaken in order to evaluate the technical feasibility of producing value-added biopolymers (polyhydroxyalkanoates (PHAs)) as a by-product to essential services of wastewater treatment and environmental protection. A commonly asked question concerns PHA quality that may be expected from surplus biomass produced during biological treatment for water quality improvement. This paper summarizes the findings from a collection of investigations. Alongside the summarized technical efforts, attention has been paid to the social and economic networks. Such networks are needed in order to nurture circular economies that would drive value chains in renewable resource processing from contaminated water amelioration into renewable value-added bioplastic products and services. We find commercial promise in the polymer quality and in the process technical feasibility. The next challenge ahead does not reside so much any more in fundamental research and development of the technology but, rather, in social-economic steps that will be necessary to realize first demonstration scale polymer production activities. It is a material supply that will stimulate niche business opportunities that can grow and stimulate technology pull with benefit of real life material product market combinations.

A pilot-scale process was operated over 22 months at the Brussels North Wastewater Treatment Plant (WWTP) in order to evaluate polyhydroxyalkanoate (PHA) production integration with services of municipal wastewater and sludge management. Activated sludge was produced with PHA accumulation potential (PAP) by applying feast-famine selection while treating the readily biodegradable COD from influent wastewater (average removals of 70% COD, 60% CODsol, 24% nitrogen, and 46% phosphorus). The biomass PAP was evaluated to be in excess of 0.4gPHA/gVSS. Batch fermentation of full-scale WWTP sludge at selected temperatures (35, 42 and 55 °C) produced centrate (6-9.4 gCODVFA/L) of consistent VFA composition, with optimal fermentation performance at 42 °C. Centrate was used to accumulate PHA up to 0.39 gPHA/gVSS. The centrate nutrients are a challenge to the accumulation process but producing a biomass with 0.5 gPHA/gVSS is considered to be realistically achievable within the typically available carbon flows at municipal waste management facilities.

The present investigation has focused on generating a surplus denitrifying biomass with high polyhydroxyalkanoate (PHA) producing potential while maintaining water treatment performance in biological nitrogen removal. The motivation for the study was to examine integration of PHA production into the water treatment and residuals management needs at the Suiker Unie sugar beet factory in Groningen, the Netherlands. At the factory, process waters are treated in nitrifying–denitrifying sequencing batch reactors (SBRs) to remove nitrogen found in condensate. Organic slippage (COD) in waters coming from beet washing is the substrate used for denitrification. The full-scale SBR was mimicked at laboratory scale. In two parallel laboratory scale SBRs, a mixed-culture biomass selection strategy of anoxic-feast and aerobic-famine was investigated using the condensate and wash water from Suiker Unie. One laboratory SBR was operated as conventional activated sludge with long solids retention time similar to the full-scale (SRT >16 days) while the other SBR was a hybrid biofilm-activated sludge (IFAS) process with short SRT (4–6 days) for the suspended solids. Both SBRs were found to produce biomass with augmented PHA production potential while sustaining process water treatment for carbon, nitrogen and phosphorus for the factory process waters. PHA producing potential in excess of 60 percent g-PHA/g-VSS was achieved with the lab scale surplus biomass. Surplus biomass of low (4–6 days) and high (>16 days) solids retention time yielded similar results in PHA accumulation potential. However, nitrification performance was found to be more robust for the IFAS SBR. Assessment of the SBR microbial ecology based on 16sDNA and selected PHA synthase genes at full-scale in comparison to biomass from the laboratory scale SBRs suggested that the full-scale process was enriched with a PHA storing microbial community. However, structure–function relationships based on RNA levels for the selected PHA synthases could not be established and, towards this ambition, it is speculated that a wider representation of PHA synthesases would need to be monitored. Additionally at the factory, beet tail press waters coming from the factory beet residuals management activities are available as a carbon source for PHA accumulation. At pilot scale, beet tail press waters were shown to provide a suitable carbon source for mixed culture PHA production in spite of otherwise being of relatively low organic strength (≤10 g-COD/L). A copolymer of 3-hydroxybutyrate with 3-hydroxyvalerate (PHBV with 15% HV on a molar basis) of high thermal stability and high weight average molecular mass (980 kDa) was produced from the beet tail press water. The mixed culture accumulation process sustained PHA storage with parallel biomass growth of PHA storing bacteria suggesting a strategy to further leverage the utilization of surplus functional biomass from biological treatment systems. Integration of PHA production into the existing factory water management by using surplus biomass from condensate water treatment and press waters from beet residuals processing was found to be a feasible strategy for biopolymer production.

Polyhydroxyalkanoates (PHAs) are biodegradable polyesters with comparable properties to some petroleum-based polyolefins. PHA production can be achieved in open, mixed microbial cultures and thereby coupled to wastewater and solid residual treatment. In this context, waste organic matter is utilised as a carbon source in activated sludge biological treatment for biopolymer synthesis. Within the EU project Routes, the feasibility of PHA production has been evaluated in processes for sludge treatment and volatile fatty acid (VFA) production and municipal wastewater treatment. This PHA production process is being investigated in four units: (i) wastewater treatment with enrichment and production of a functional biomass sustaining PHA storage capacity, (ii) acidogenic fermentation of sludge for VFA production, (iii) PHA accumulation from VFA-rich streams, and (iv) PHA recovery and characterisation. Laboratory- and pilot-scale studies demonstrated the feasibility of municipal wastewater and solid waste treatment alongside production of PHA-rich biomass. The PHA storage capacity of biomass selected under feast–famine with municipal wastewater has been increased up to 34% (g PHA g VSS−1) in batch accumulations with acetate during 20 h. VFAs obtained from waste activated sludge fermentation were found to be a suitable feedstock for PHA production.