Constructed wetlands as nature-based solutions in managing per-and poly-fluoroalkyl substances (PFAS): Evidence, mechanisms, and modelling.

Per- 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 This study carried out a systematic literature review, supplemented by unpublished experimental data, demonstrating the promise of CWs for PFAS removal from the influents of varying sources and characteristics.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.

The role of concentrations gradients on phosphorus and iron dynamics from chemically-dosed horizontal flow wetlands for tertiary sewage treatment.

This study examined the dynamics of iron (Fe) and phosphorus (P) transformations from the surface sludge accumulated in tertiary horizontal flow (HF) treatment wetlands (TW) chemically dosed for P removal. Site surveys showed P was stored in HF TW with and without artificial aeration on average, with instances of P release in the non-aerated site. Controlled experiments revealed storing TW surface sludge for over 24 hours resulted in limited oxygen and nitrate concentrations, resulting in both P and Fe release. The rate of P release increased with increasing water-sludge P concentration gradients, and the reaction could take as little as 10 minutes. Convection had no impact on P transformation rates. The findings suggest mitigation strategies could include the manipulation of the biogeochemical environment by managing oxygen and nitrate concentrations within the wetlands. A better understanding of links between Fe, P, and nitrate is needed to test proactive mitigation strategies for small wastewater treatment plants.

Impacts of coagulation-flocculation treatment on the size distribution and bioavailability of trace metals (Cu, Pb, Ni, Zn) in municipal wastewater.

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.

Distribution of trace metals (Cu, Pb, Ni, Zn) between particulate, colloidal and truly dissolved fractions in wastewater treatment.

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.

Mercury and antimony in wastewater: fate and treatment.

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.

Nitrous oxide emissions and dissolved oxygen profiling in a full-scale nitrifying activated sludge treatment plant.

This paper reports findings from online, continuous monitoring of dissolved and gaseous nitrous oxide (N2O), combined with dissolved oxygen (DO) and ammonia loading, in a full-scale nitrifying activated sludge plant. The study was conducted over eight weeks, at a 210,000 population equivalent sewage treatment works in the UK. Results showed diurnal variability in the gaseous and dissolved N2O emissions, with hourly averages ranging from 0 to 0.00009 kgN2O-N/h for dissolved and 0.00077-0.0027 kgN2O-N/h for gaseous nitrous oxide emissions respectively, per ammonia loading, depending on the time of day. Similarly, the spatial variability was high, with the highest emissions recorded immediately after the anoxic zone and in the final pass of the aeration lane, where ammonia concentrations were typically below 0.5 mg/L. Emissions were shown to be negatively correlated to dissolved oxygen, which fluctuated between 0.5 and 2.5 mgO2/L, at the control set point of 1.5 mgO2/L. The resulting dynamic DO conditions are known to favour N2O production, both by autotrophic and heterotrophic processes in mixed cultures. Average mass emissions from the lane were greater in the gaseous (0.036% of the influent total nitrogen) than in the dissolved (0.01% of the influent total nitrogen) phase, and followed the same diurnal and spatial patterns. Nitrous oxide emissions corresponded to over 34,000 carbon dioxide equivalents/year, adding 13% to the carbon footprint associated with the energy requirements of the monitored lane. A clearer understanding of emissions obtained from real-time data can help towards finding the right balance between improving operational efficiency and saving energy, without increasing N2O emissions.

Performance of pilot-scale constructed wetlands for secondary treatment of chromium-bearing tannery wastewaters.

Tannery operations consist of converting raw animal skins into leather through a series of complex water- and chemically-intensive batch processes. Even when conventional primary treatment is supplemented with chemicals, the wastewater requires some form of biological treatment to enable the safe disposal to the natural environment. Thus, there is a need for the adoption of low cost, reliable, and easy-to-operate alternative secondary treatment processes. This paper reports the findings of two pilot-scale wetlands for the secondary treatment of primary effluents from a full tannery operation in terms of resilience (i.e., ability to produce consistent effluent quality in spite of variable influent loads) and reliability (i.e., ability to cope with sporadic shock loads) when treating this hazardous effluent. Areal mass removal rates of 77.1 g COD/m2/d, 11 g TSS/m2/d, and 53 mg Cr/m2/d were achieved with a simple gravity-flow horizontal subsurface flow unit operating at hydraulic loading rates of as much as 10 cm/d. Based on the findings, a full-scale wetland was sized to treat all the effluent from the tannery requiring 68% more land than would have been assumed based on literature values. Constructed wetlands can offer treatment plant resilience for minimum operational input and reliable effluent quality when biologically treating primary effluents from tannery operations.

Clogging in subsurface-flow treatment wetlands: measurement, modeling and management.

This paper reviews the state of the art in measuring, modeling, and managing clogging in subsurface-flow treatment wetlands. Methods for measuring in situ hydraulic conductivity in treatment wetlands are now available, which provide valuable insight into assessing and evaluating the extent of clogging. These results, paired with the information from more traditional approaches (e.g., tracer testing and composition of the clog matter) are being incorporated into the latest treatment wetland models. Recent finite element analysis models can now simulate clogging development in subsurface-flow treatment wetlands with reasonable accuracy. Various management strategies have been developed to extend the life of clogged treatment wetlands, including gravel excavation and/or washing, chemical treatment, and application of earthworms. These strategies are compared and available cost information is reported.

A review of the impact and potential of intermittent aeration on continuous flow nitrifying activated sludge.

Intermittent aeration of activated sludge plants (ASPs) is a potential strategy that may help deliver reduced operational costs while providing an adequate effluent quality. This review paper critically assesses the implications of temporary turning aeration offin continuous flow nitrifying ASPs, including impact on dissolved oxygen concentrations, process biology and operational parameters. The potential savings and pitfalls of the approach are further illustrated through an example scenario. Findings from this review indicate rapid dissolved oxygen depletion times of 1-60 minutes and a significant reduction of nitrification rates from 0.12 to less than 0.04 g NH4-N/g VSS/d. Further negative impacts include a potential increase in nitrous oxide emissions from 0.07% to 27% N2O-N per mole of NH4-N oxidized; enhanced filamentous bacteria growth; a noticeable increase in effluent turbidity developing within one hour of air supply interruption; and, if no mechanical mixing is in place, risk of mixed liquor suspended solids settling in the bioreactor within short times (23-53 min). However, the potential savings in terms of aeration costs could amount to 33%-45% if instrumentation adequacy and impact on process biology and carbon equivalent emissions are excluded from the economic analysis. Further research on the areas of nitrous oxide emissions and the use of hybrid systems to provide resilience and robustness to the intermittent operation of continuous flow nitrifying ASPs is recommended.

Chromium fate in constructed wetlands treating tannery wastewaters.

Nine experimental wetlands were built to determine chromium partitioning inside systems treating tannery wastewaters. Results showed 5-day biochemical oxygen demand and chromium removals of 95 to 99% and 90 to 99%, respectively. The majority of chromium was found in association with media (96 to 98%), followed by effluents (2.9 to 3.9%), and the least was found in plant parts (0.1%). Chemical speciation modeling of solutions and scanning electron microscope analysis suggest two potential chromium removal mechanisms--sorption/coprecipitation with iron hydroxides or oxyhydroxides and biomass sorption. The release of the majority of chromium in the iron- and organic-bound phases during sequential extractions supports the proposed dominant removal mechanisms. The use of a mixture of peat and gravel resulted in lower removal efficiencies and stronger partitioning in organic phases during sequential extractions. Chromium was efficiently removed by wetlands, retained through chemical and biological processes. Future research will focus on further exploring removal mechanisms and proposing management strategies for the chromium-containing wetland media.