In this study, three tertiary solid separation technologies were assessed on their robustness and resilience against an effluent phosphorus target of <0.3 mg P/L at steady state and dynamic conditions. The ballasted flocculation system was found to be very robust at delivering the low P target. Alternatively, cloth filtration provided a more sustainable option for less strict consents of sub 0.5 mg P/L. The effluent from the membrane system was more variable but it was shown to meet the low consents even with increased phosphorus and solids content in the feed. A molar ratio of 1.37 Fe: P was shown to be sufficient to meet the P target at short contact times as with the ballasted flocculation process. It was highlighted that optimisation of up-stream flocculation can be a considerable factor for consistent performance. Overall, the study determined key attributes of the different technologies tested providing valuable insights for technology selection at full scale.
Reactive media present an alternative to gravel in constructed wetlands and have the potential to sustainably and efficiently remove phosphorus from wastewater. In this study, a full-scale steel slag wetland has been operated for its whole lifecycle at which 1.39 mg P/g media were retained. During its lifecycle, this wetland met strict consents below 0.5 mg P/L for the first 6 months and was operated for 266 and 353 days before the effluent phosphorus concentration rose above the typical consents of 1 and 2 mg P/L, respectively. A detailed analysis of the system demonstrated that the performance was directly associated with the release of materials from the media into the water which in turn affected other critical parameters such as pH. Further analysis of the media suggested that greater understanding was needed concerning the role of carbonates and in particular calcite if steel slag is to be effectively managed for use on constructed wetlands. Importantly, controlled release of calcium oxide from the media surface is required by managing the concerns of pH and vanadium release.
Solid and liquid products can form in the gas phase of membrane contactors applied to reactive ternary systems for CO2 absorption, which poses a critical barrier for carbon capture applications. The mechanism initiating these unwanted gas-phase reactions is unclear. This study therefore systematically characterises CO2 absorption in distinct regions of the vapour-liquid equilibrium (VLE) within an illustrative ternary system (CO2-NH3-H2O), to provide an explanation for the formation and mitigation of gas-phase reactions. Unstable CO2 absorption and increased pressure drop indicated product formation from gas-phase reactions, which occurred at high CO2 capture ratios. Temporal analysis of gas-phase composition enabled gas-phase products to be related to the relative reactant composition. This was subsequently correlated to distinct regions of the VLE. Consequently, mitigation strategies can be developed with recognition for where reaction products are least likely to form. Pressurisation was proposed to modify the relative gas-phase ammonia composition to reposition conditions within the VLE. The commensurate increase of CO2 into the solvent shifts the ammonia-ammonium equilibrium towards ammonium to indirectly reduce vapour pressure. This synergistic strategy allows sustained operation of membrane contactors for CO2 separation within reactive ternary systems which are critical to delivering carbon capture economically at scale.
Hollow fibre membrane contactor (HFMC) technology has been developed for CO2 absorption primarily using synthetic gas, which neglects the critical impact that trace contaminants might have on separation efficiency and robustness in industrial gases. This study, therefore, commissioned a demonstration-scale HFMC for CO2 separation at a full-scale anaerobic digester facility to evaluate membrane integrity over six months of operation on real biogas. The CO2 capture efficiency identified using real biogas was benchmarked at comparable conditions on synthetic gas of an equivalent partial pressure, and an equivalent performance identified. Two HFMC were subsequently compared, one with and one without a pre-treatment stage that targeted particulates, volatile organic compounds (VOCs) and humidity. Similar CO2 separation efficiency was again demonstrated, indicating limited impact within the timescale evaluated. However, gas phase pre-treatment is advised in order to ensure robustness in the long term. Over longer-term operation, a decline in CO2 separation efficiency was observed. Membrane autopsy identified shell-side deposition, where the structural morphology and confirmation of amide I and II groups, indicated biofouling. Separation efficiency was reinstated via chemical cleaning, which demonstrated that proactive maintenance could minimise process risk.
The tightening of phosphorus (P) standards has forced the UK water industry to identify options to improve P removal in sewage treatment works. This article presents results of 12-month trials testing three technologies at full-scale: a membrane bioreactor (MBR), a continuous backwash up-flow sand filter (CBUSF) and a high-rate compressible media filter (HRCMF). The aim of the trial was to determine the lowest total phosphorus (TP) concentrations that these systems can consistently achieve under stable operating conditions. MBR is a mature technology combining biological treatment with membrane filtration for solids removal. CBUSF uses granular media deep filtration as removal process while HRCMF uses a synthetic fibre compressible media to retain solids and both technologies are typically applied as tertiary treatments in combination with chemical P removal. The lowest TP effluent concentration was recorded for CBUSF (0.22 mg P/L) while the highest TP removal was recorded for MBR (95 ? 3 %). HRCMF delivered the poorest performance (32 ? 26 % TP removal, 1.7 mg P/L average TP effluent), attributed to limited chemical TP binding and solids removal under the conditions tested. Factors affecting P removal performance during the trial were the identification of the optimal coagulant dose to bind soluble P, the formation of solids that can be removed by the separation unit, insufficient reaction time for the coagulation process and the carryover of coagulant into the final effluent. The trials gave valuable insights to address the implementation of new technologies or upgrade existing assets? performance.
Phosphorus and nutrient recovery from wastewater as mineral salts can support local replenishment of fertilisers and reduce mining, contributing to the circular economy. Wastewater and related streams are rich in nutrients, however; there is need to develop bio-based processes to recover them. This study investigates the fractions of phosphorus (P) used by Brevibacterium antiquum to form struvite biominerals (bio-struvite) in wastewater sludge dewatering liquors. After 72h of incubation, 25.6 mg P/L were recovered as bio-struvite from 12.4 mg P/L organic plus condensed P and 13.2 mg P/L of orthophosphate. The potential of sludge dewatering liquors to recover nutrients as struvite was investigated by characterising ten types of sludge liquors (originating from primary, secondary sludge, feed to anaerobic digester and digestate, from 3 types of wastewater treatment plants) for their P fractions together with other parameters relevant for B. antiquum growth. Results indicated that liquors obtained from primary sludge, feed to anaerobic digesters and digestate were the most suitable to produce biostruvite, as these were found to frequently have a high content of organic and condensed P, between to 276-732 mg P/L. Liquors, from all the investigated sites, presented a higher potential for bio-struvite production than with conventional struvite precipitation. This study demonstrated that B. antiquum could convert organic and condensed P into bio-struvite, and this opens up a completely new way to recover forms of phosphorus that are not typically available for nutrient recovery in a single process.(C) 2020 The Author(s). Published by Elsevier B.V. on behalf of Chinese Society for Environmental Sciences, Harbin Institute of Technology, Chinese Research Academy of Environmental Sciences.
Ballasted flocculation is an efficient high-rate sedimentation process getting more attention as an advanced P removal technology for levels below 0.1 mg/L. The process is well-known yet only very few studies have investigated the interactions, within the matrix of wastewater, of coagulant, polymer and ballast, especially when it comes to polymer doses and types which are, in the industry, rather based on recommendations than scientific evidence. In this work, the impact of anionic and cationic polymers has been investigated on P removal and floc properties. Anionic polymers showed to be superior to cationic ones when it comes to P removal and doses even as low as 0.01 mg/L yield better results than coagulant alone. There appears to be a "best-case" floc size with which very good P removal (>90%) can be achieved and flocs of sufficient strength can be generated.
Carbon dioxide (CO2) enrichment of anaerobic digesters (ADs) without hydrogen addition has been demonstrated to provide a potential solution to manage CO2 streams generated in the water and organic waste sectors, with concomitant increases in methane (CH4) production. This study investigates the CO2 utilization mechanisms, by considering chemical and biological pathways in food waste and sewage sludge ADs. Methanosaetaceae was observed to be the dominant methanogen in sewage sludge ADs (Abundance of 83.8-98.8%) but scarce in food waste units (3.5-5.8%). Methanosarcinaceae was dominant in food waste (14.3-32.4%), likely due to a higher tolerance to the free ammonia nitrogen concentration recorded (885 mg L-1). R-Methanosaetaceae (ratio of Methanosaetaceae fluorescence signal between test and control) of 1.45 and 1.79 were observed for sludge ADs enriched once and periodically with CO2, respectively (p-value < .05), suggesting a higher Methanosaetaceae activity associated with CO2 enrichment. Reduction of CO2 by homoacetogenesis followed by acetoclastic methanogenesis was proposed as a CO2 utilization mechanism, which requires validation by radiolabelling or carbon isotope analysis. [GRAPHICS]
This 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.
Struvite production mediated by bacteria has opened up a new route for phosphorus recovery from wastewater streams but its application to digested sludge dewatering liquors is not yet well understood. This study investigates the growth and biological struvite production of selected bacteria in wastewater liquors with pHs between 5.7 to 9.1. The bacterial growth was assessed through flow cytometry. Bacillus pumilus, Halobacterium salinarum and Brevibacterium antiquum remained viable at pHs between 5.7 to 9.1 but B. antiquum was able to grow at pHs between 7.3 to 7.8. Further analysis allowed the identification of crystals as struvite in tests between pH 7.3 to 8.3. All strains were capable of producing struvite at a range of pHs, but the highest production of 135–198 mg/L was observed for pHs between 7.3 to 8.3. At pHs > 8.3, precipitation of struvite and calcium compounds was observed in inoculated and non-inoculated tests. This study demonstrates that biological struvite production can occur at a wide range of pHs, hence significantly different from chemical struvite precipitation that occurs at pH > 8.3, making it a potentially viable process for phosphorus recovery as struvite from wastewater streams and sludge liquors without strict pH control.
Biological struvite (bio-struvite) production through biomineralization has been suggested as an alternative to chemically derived struvite production to recover phosphorus from wastewater streams. In this study, statistical experimental design techniques were used to find the optimal growth rate (μ) of Brevibacterium antiquum in sludge liquors. Acetate, oleic acid, NaCl, NH4-N, and Ca2+ were shown to affect the growth rate of B. antiquum. The growth rate reached 3.44 1/d when the bacteria were supplemented with 3.0% w/v NaCl and 1124 mg chemical oxygen demand/L as acetate. However, NaCl was found to hinder the biomineralization of bio-struvite. A two-stage experiment demonstrated that bio-struvite was produced in the presence of acetate. Bio-struvite production was confirmed with X-ray spectroscopy and crystal morphology (prismatic, tabular, and twinned crystal habit) through electron microscope analysis. The bio-struvite production was estimated by measuring phosphate content of the recovered precipitates, reaching 9.6 mg P/L as bio-struvite. Overall, these results demonstrated the optimal conditions required to achieve high growth rates as well as bio-struvite production with B. antiquum. The results obtained in this study could be used to develop a process to grow B. antiquum in wastewater streams in mixed cultures and recover phosphorus-rich products such as struvite.
The article “Coagulation–flocculation process with metal salts, synthetic polymers and biopolymers for the removal of trace metals (Cu, Pb, Ni, Zn) from municipal wastewater”, written by Andrew J. Hargreaves, Peter Vale, Jonathan Whelan, Luca Alibardi, Carlos Constantino, Gabriela Dotro, Elise Cartmell and Pablo Campo, was originally published Online First without open access.
Extended Abstract As a consequence of their potential to cause harm, there are strong regulatory drivers that require metals to be removed as part of the wastewater treatment process. Bioavailability-based standards have recently been specified for Cu, Pb, Ni and Zn and are expected to reduce acceptable metal concentrations. In order to comply with these standards, wastewater treatment works may require new treatment types to enhance metal removal and it is, therefore, important to examine potential treatment options. A previous study found that a substantial proportion of Cu, Pb, Ni and Zn in effluent is adsorbed to or complexed with macromolecules (e.g. proteins, polysaccharides, aminosugars, etc.) that are typically present in the colloidal size fraction. Thus technologies capable of removing colloidal particles have good potential to enhance metals removal from wastewater. Coagulation-flocculation (CF) has been shown to effectively remove colloidal particles, however, few studies have comprehensively compared the effectiveness of the three primary coagulants, namely; metal salts, synthetic polymers and biopolymers. The present study investigated the effectiveness of CF at removing trace metals from humus effluent using the following coagulants; ferric chloride (FeCl3), the synthetic polymer polyethyleneimine (PEI), and the biopolymers chitosan and Floculan. Effluent samples were collected from a trickling filter treatment works operating in the UK. Using jar tests, the influence of coagulant dosage and the velocity and time of the slow mixing stage were studied. Chitosan and PEI had a moderate effect on the removal of trace metals (≤ 35%). FeCl3 removed 48% Cu, 56% Pb and 41% Zn at the recommended dose of 0.10 mg/L. At the recommended dose of 0.25 mg/L Floculan removed 77% Cu, 68% Pb and 42% Zn. The elimination of Ni was negligible for Floculan; additionally, Ni concentrations were significantly increased in effluent treated with FeCl3. In fact, a linear relationship between FeCl3 dosage and Ni concentration was observed in treated effluent. Thus, the use of FeCl3 may pose a potential risk to compliance with Environmental Quality Standards for Ni. High turbidity removal achieved in conjunction with negative zeta potentials indicated that charge neutralisation did not play a significant role in the removal of particles from effluent when treated with FeCl3. As such, the sweep flocculation mechanism, which is not influenced by the properties of particles (i.e. negatively charged particles can become entrapped in precipitates), was deduced as the main removal mechanism. Floculan is composed of polymeric chains with cationic charge that neutralise particles, as indicated by data on zeta potential, enabling aggregation and removal through the mechanism of inter-particle bridging. This study was one of the first of its kind to investigate the effectiveness of the CF treatment process for the elimination of trace metals (in the μg/L range) from municipal wastewater. Overall, FeCl3 and Floculan were found to be most effective at removing trace metals.
Carbon dioxide (CO2) injection in anaerobic digestion has recently been proposed as an interesting possibility to boost methane (CH4) recovery from sludge and organic waste by converting a greenhouse gas into a renewable resource. This research assessed the effects of exogenous CO2 injection on performance and process stability of single-phase continuous anaerobic digesters. Two pilot scale reactors treating sewage sludge were operated for 130days. One reactor was periodically injected with CO2 while the other acted as control. Two injection frequencies and injection devices were tested. The results indicated that CO2 enrichment allowed an increase in CH4 production of ca. 12%, with a CH4 production rate of 371±100L/(kgVSfed·d) and a CH4 concentration of ca. 60% when dissolved CO2 levels inside the test reactor were increased up to 1.9-fold. Results also indicated an improvement in process resilience to temporary overloads and no impacts on stability parameters.
Energy consumption of the water sector presents an increasing energy demand, contrary to GHG mitigation aims. As a result, research aimed at capturing emitted CO2 and at developing treatment technologies with a low energy demand and increased renewable energy production has increased, leading to a surge in implementation of anaerobic digestion (AD). Valorization of the biogenic CO2 emitted with biogas AD (estimated at over 1 MtCO(2) per annum for the UK water and organic waste sectors), presents an opportunity to further reduce carbon footprint and support energy supply decarburization. This paper reviews bioconversion of CO2 into CH4 in ADs (without addition of H-2) as a means to valorize CO2 emissions. The review has concluded this to be a promising solution to reduce carbon footprint and uplift renewable energy production. However, in order to increase readiness for implementation (1) the mechanisms of CO2 utilization need to be elucidated, including the sources of additional H-2 needed, (2) studies need to report more thoroughly the conditions of CO2 injection and (3) trials where ADs are integrated with gas to liquid mass transfer technologies need to be performed.
The distribution of Cu, Pb, Ni and Zn between particulate, colloidal and truly dissolved size fractions in wastewater from a trickling filter treatment plant was investigated. Samples of influent, primary effluent, humus effluent, final effluent and sludge holding tank returns were collected and separated into particulate (i.e. > 0.45 μm), colloidal (i.e. 1 kDa to 0.45 μm), and truly dissolved (i.e. < 1 kDa) fractions using membrane filters. In the influent, substantial proportions of Cu (60%), Pb (67%), and Zn (32%) were present in the particulate fraction which was removed in conjunction with suspended particles at the works in subsequent treatment stages. In final effluent, sizeable proportions of Cu (52%), Pb (32%), Ni (44%) and Zn (68%) were found within the colloidal size fraction. Calculated ratios of soluble metal to organic carbon suggest the metal to be adsorbed to or complexed with non-humic macromolecules typically found within the colloidal size range. These findings suggest that technologies capable of removing particles within the colloidal fraction have good potential to enhance metals removal from wastewater.
It is important to understand the fate of Hg and Sb within the wastewater treatment process so as to examine potential treatment options and to ensure compliance with regulatory standards. The fate of Hg and Sb was investigated for an activated sludge process treatment works in the UK. Relatively high crude values (Hg 0.092 μg/L, Sb 1.73 μg/L) were observed at the works, whilst low removal rates within the primary (Hg 52.2 %, Sb 16.3 %) and secondary treatment stages (Hg 29.5 %, Sb −28.9 %) resulted in final effluent concentrations of 0.031 μg/L for Hg and 2.04 μg/L for Sb. Removal of Hg was positively correlated with suspended solids (SS) and chemical oxygen demand (COD) removal, whilst Sb was negatively correlated. Elevated final effluent Sb concentrations compared with crude values were postulated and were suggested to result from Sb present in returned sludge liquors. Kepner Tregoe (KT) analysis was applied to identify suitable treatment technologies. For Hg, chemical techniques (specifically precipitation) were found to be the most suitable whilst for Sb, adsorption (using granulated ferric hydroxide) was deemed most appropriate. Operational solutions, such as lengthening hydraulic retention time, and treatment technologies deployed on sludge liquors were also reviewed but were not feasible for implementation at the works.
Fourteen full-scale wastewater treatment plants (WwTPs) owned and operated by Severn Trent Water, a major UK water utility, were assessed to determine the long-term efficiency of using chemical dosing upstream of biofilm processes followed by horizontal flow wetlands to remove phosphorus and any residual metals. Results showed that the flowsheets used are an effective strategy to remove BOD, solids, ammonia, nitrate, and phosphorus, with all sites meeting their discharge consents for the past 10 years. Wetland removal rates of up to 6.7, 3.8, 0.24, 2.4, and 0.5 mg m(-2) d(-1) were found for solids, nitrate, ammonia, phosphorus, and iron, respectively. Under flooded conditions, settling mechanisms dominated as evidenced by average surface sludge accumulation rates of 2 cm year(-1). Subsurface flow resulted in lower or no sludge accumulation on top of the gravel. The average concentration of P and Fe in the sludge per site was in the range of 17-48 and 9-178 g kg(-1), respectively, much higher than sediment concentrations found in non-dosed wetlands and river sediments. Analysis of suspended, colloidal, and dissolved fractions showed a change in phase for P from particulate to dissolved after the wetland, suggesting release. Phosphorus release was observed under low P conditions in wastewater (< 1 mg L-1) and high sludge P levels, with release rates of 12-52 44 mg m(-2) d(-1) in the field and 44 mg m(-2) d(-1) under laboratory conditions. Iron release was observed under controlled experiments but not detected in the field, indicating additional transformation reactions take place in full-scale wetlands. Further research is required to provide adequate data for modifying the design and improving the operation and maintenance recommendations to ensure wetlands continue to deliver environmental benefit at WwTPs required to remove phosphorus.