Impact of Cleaning on Membrane Performance during Surface Water Treatment: A Hybrid Process with Biological Ion Exchange and Gravity-Driven Membranes.

In this study, the hybrid biological ion exchange (BIEX) resin and gravity-driven membrane (GDM) process was employed for the treatment of coloured and turbid river water. The primary objective was to investigate the impact of both physical and chemical cleaning methods on ceramic and polymeric membranes in terms of their stabilised flux, flux recovery after physical/chemical cleaning, and permeate quality. To address these objectives, two types of MF and UF membranes were utilised (M1 = polymeric MF, M2 = polymeric UF, M3 = ceramic UF, and M4 = lab-made ceramic MF). Throughout the extended operation, the resin functioned initially in the primary ion exchange (IEX) region (NOM displacement with pre-charged chloride) and progressed to a secondary IEX stage (NOM displacement with bicarbonate and sulphate), while membrane flux remained stable. Subsequently, physical cleaning involved air/water backwash with two different flows and pressures, and chemical cleaning utilised NaOH at concentrations of 20 and 40 mM, as well as NaOCl at concentrations of 250 and 500 mg Cl2/L. These processes were carried out to assess flux recovery and identify fouling reversibility. The results indicate an endpoint of 1728 bed volumes (BVs) for the primary IEX region, while the secondary IEX continued up to 6528 BV. At the end of the operation, DOC and UVA254 removal in the effluent of the BIEX columns were 68% and 81%, respectively, compared to influent water. This was followed by 30% and 57% DOC and UVA254 removal using M4 (ceramic MF). The stabilised flux remained approximately 3.8-5.2 LMH both before and after the cleaning process, suggesting that membrane materials do not play a pivotal role. The mean stabilised flux of polymeric membranes increased after cleaning, whereas that of the ceramics decreased. Enhanced air-water backwash flow and pressure resulted in an increased removal of hydraulic reversible fouling, which was identified as the dominant fouling type. Ceramic membranes exhibited a higher removal of reversible hydraulic fouling than polymeric membranes. Chemical cleaning had a low impact on flux recovery; therefore, we recommend solely employing physical cleaning.

Modeling the fate of viruses in aquifers: Multi-kinetics reactive transport, risk assessment, and governing parameters.

The transport of viruses in groundwater is a complex process controlled by both hydrodynamic and reaction parameters. Characterizing the transport of viruses in groundwater is of crucial importance for investigating health risks associated with groundwater consumption from private individual or residential pumping wells. Setback distances between septic systems, which are the source of viruses, and pumping wells must be designed to offer sufficient groundwater travel times to allow the viral load to degrade sufficiently to be acceptable for community health needs. This study consists of developing numerical simulations for the reactive transport of viruses in the subsurface. These simulations are validated using published results of laboratory and field experiments on virus transport in the subsurface and applying previously developed analytical solutions. The numerical model is then exploited to investigate the sensitivity of the fate of viruses in saturated porous media to hydraulic parameters and the coefficients of kinetic reactions. This sensitivity analysis provides valuable insights into the prevailing factors governing health risks caused by contaminated water in private wells in rural residential contexts. The simulations of virus transport are converted into health risk predictions through dose-response relationships. Risk predictions for a wide range of input parameters are compared with the international regulatory health risk target of a maximum of 10-4 infections/person/year and a 30 m setback distance to identify critical subsurface contexts that should be the focus of regulators.

Effects of weathering on the properties and fate of secondary microplastics from a polystyrene single-use cup.

In this work, we probed the changes to some physicochemical properties of polystyrene microplastics generated from a disposable cup as a result of UV-weathering, using a range of spectroscopy, microscopy, and profilometry techniques. Thereafter, we aimed to understand how these physicochemical changes affect the microplastic transport potential and contaminant sorption ability in model freshwaters. Exposure to UV led to measured changes in microplastic hydrophobicity (20-23 % decrease), density (3% increase), carbonyl index (up to 746 % increase), and microscale roughness (24-86 % increase). The settling velocity of the microplastics increased by 53 % after weathering which suggests that UV aging can increase microplastic deposition to sediments. This impact of aging was greater than the effect of the water temperature. Weathered microplastics exhibited reduced sorption capacity (up to 52 % decrease) to a model hydrophobic contaminant (triclosan) compared to unaged ones. The adsorption of triclosan to both microplastics was slightly reversible with notable desorption hysteresis. These combined effects of weathering could potentially increase the transport potential while decreasing the contaminant transport abilities of microplastics. This work provides new insights on the sorption capacity and mobility of a secondary microplastic, advances our knowledge about their risks in aquatic environments, and the need to use environmentally relevant microplastics.

Weathering pathways and protocols for environmentally relevant microplastics and nanoplastics: What are we missing?

To date, most studies of microplastics have been carried out with pristine particles. However, most plastics in the environment will be aged to some extent; hence, understanding the effects of weathering and accurately mimicking weathering processes are crucial. By using microplastics that lack environmental relevance, we are unable to fully assess the risks associated with microplastic pollution in the environment. Emerging studies advocate for harmonization of experimental methods, however, the subject of reliable weathering protocols for realistic assessment has not been addressed. In this work, we critically analysed the current knowledge regarding protocols used for generating environmentally relevant microplastics and leachates for effects studies. We present the expected and overlooked weathering pathways that plastics will undergo throughout their lifecycle. International standard weathering protocols developed for polymers were critically analysed for their appropriateness for use in microplastics research. We show that most studies using weathered microplastics involve sorption experiments followed by toxicity assays. The most frequently reported weathered plastic types in the literature are polystyrene>polyethylene>polypropylene>polyvinyl chloride, which does not reflect the global plastic production and plastic types detected globally. Only ~10% of published effect studies have used aged microplastics and of these, only 12 use aged nanoplastics. This highlights the need to embrace the use of environmentally relevant microplastics and to pay critical attention to the appropriateness of the weathering methods adopted moving forward. We advocate for quality reporting of weathering protocols and characterisation for harmonization and reproducibility across different research efforts.

Impact of media coating on simultaneous manganese removal and remineralization of soft water via calcite contactor.

The aim of this study was to investigate the negative impact of a newly-formed manganese (Mn)-layer on calcite dissolution in the long-term operation of a calcite contactor. Simultaneous removal of Mn and remineralization of soft water in an up-flow calcite contactor was conducted and led to a progressive loading of Mn into the calcite matrix. The calcite contactor demonstrated high Mn removal; however, the hardness release decreased from 32 to 20 mg CaCO3 L-1 after 600 h of operation on a high Mn concentration (5 mg L-1) feed. For an elevated Mn concentration (i.e. 5 mg Mn L-1) in the feed water, the coated layer was mainly composed of Mn which inhibits the mass transfer from the calcite core to the liquid phase. The superficial layer was identified as 5.2% Mn oxides (MnOx) by X-ray photoelectron spectroscopy (XPS). Therefore, it is postulated that Mn removal starts with an ion exchange sorption reaction between soluble Mn2+ from aqueous phase and Ca2+ from the CaCO3 matrix which is followed by a slow recrystallization of MnCO3 into MnO2. On the other hand, when the Mn content in the feed water was lower (i.e. 0.5 mg Mn L-1), a considerably lower amount of MnOx was detected on the coated media. For all the examined conditions, the formation of this coating improved Mn removal due to the autocatalytic nature of the adsorption/oxidation of dissolved manganese by MnOx. A mechanistic model based on calcite dissolution and the progressive formation of a MnO2 layer was implemented in PHREEQC software to predict the reduction in hardness release expected in long-term operation. The model was calibrated with experimental data and resulted in realistic breakthrough curves. In order to accurately predict the pH of the effluent stream, a slow-rate recrystallization of MnCO3 into MnO2 was implemented (compared to the fast precipitation of MnO2 or the absence of MnO2 formation).

Separation and Analysis of Microplastics and Nanoplastics in Complex Environmental Samples.

The vast amount of plastic waste emitted into the environment and the increasing concern of potential harm to wildlife has made microplastic and nanoplastic pollution a growing environmental concern. Plastic pollution has the potential to cause both physical and chemical harm to wildlife directly or via sorption, concentration, and transfer of other environmental contaminants to the wildlife that ingest plastic. Small particles of plastic pollution, termed microplastics (>100 nm and <5 mm) or nanoplastics (<100 nm), can form through fragmentation of larger pieces of plastic. These small particles are especially concerning because of their high specific surface area for sorption of contaminants as well as their potential to translocate in the bodies of organisms. These same small particles are challenging to separate and identify in environmental samples because their size makes handling and observation difficult. As a result, our understanding of the environmental prevalence of nanoplastics and microplastics is limited. Generally, the smaller the size of the plastic particle, the more difficult it is to separate from environmental samples. Currently employed passive density and size separation techniques to isolate plastics from environmental samples are not well suited to separate microplastics and nanoplastics. Passive flotation is hindered by the low buoyancy of small particles as well as the difficulty of handling small particles on the surface of flotation media. Here we suggest exploring alternative techniques borrowed from other fields of research to improve separation of the smallest plastic particles. These techniques include adapting active density separation (centrifugation) from cell biology and taking advantage of surface-interaction-based separations from analytical chemistry. Furthermore, plastic pollution is often challenging to quantify in complex matrices such as biological tissues and wastewater. Biological and wastewater samples are important matrices that represent key points in the fate and sources of plastic pollution, respectively. In both kinds of samples, protocols need to be optimized to increase throughput, reduce contamination potential, and avoid destruction of plastics during sample processing. To this end, we recommend adapting digestion protocols to match the expected composition of the nonplastic material as well as taking measures to reduce and account for contamination. Once separated, plastics in an environmental sample should ideally be characterized both visually and chemically. With existing techniques, microplastics and nanoplastics are difficult to characterize or even detect. Their low mass and small size provide limited signal for visual, vibrational spectroscopic, and mass spectrometric analyses. Each of these techniques involves trade-offs in throughput, spatial resolution, and sensitivity. To accurately identify and completely quantify microplastics and nanoplastics in environmental samples, multiple analytical techniques applied in tandem are likely to be required.

Steel slag filter design criteria for phosphorus removal from wastewater in decentralized applications.

The objective of this project was to develop a novel phosphorus removal system using steel slag filters applicable in decentralized applications and to propose design criteria about maintenance needs. Slag exhaustion functions were measured on 2-3 mm, 3-5 mm, 5-10 mm and 16-23 mm slag. Three steel slag columns with particle size of 2-3 mm, 3-5 mm and 5-10 mm were fed with the effluent of an aerated lagoon during 589 days. A barrel reactor test was fed during 365 days with the effluent of an attached growth aerated biological reactor. The o-PO4 concentration at the effluent of the 2-3 mm and 3-5 mm columns and barrel reactor test was between 0.04 and 0.3 mg P/L. Particulate phosphorus, however, was removed by about 50%. The P-Hydroslag model implemented in PHREEQC was successfully calibrated with data from the column test, and validated with data from the barrel reactor test. The calibrated model was used to simulate long-term operation of a slag barrel reactor with two parallel streams of five replaceable steel slag barrels, with total hydraulic retention time of voids of 15 h. The system longevity was strongly influenced by the influent alkalinity. The simulated longevity was 7 years with an influent alkalinity of 50 mg CaCO3/L and 2 years with an influent of 210 mg CaCO3/L. The alkalinity of the steel slag filter influent was influenced by the type of aquifer supplying drinking water, the presence of nitrification activity and by the CO2 concentration in the enriched air of the upstream biological process. Simulated scenarios with partial barrel replacement (e. g. barrels 1 and 2 out of 5 replaced at frequency of 0.5, 1, 1.5, 2, 2.5, 3, 3.5 or 4 years) increased the system longevity up to 14 years while slightly increasing the number of barrels needed.

Development and modelling of a steel slag filter effluent neutralization process with CO2-enriched air from an upstream bioprocess.

The main objective of this project was to develop a steel slag filter effluent neutralization process by acidification with CO2-enriched air coming from a bioprocess. Sub-objectives were to evaluate the neutralization capacity of different configurations of neutralization units in lab-scale conditions and to propose a design model of steel slag effluent neutralization. Two lab-scale column neutralization units fed with two different types of influent were operated at hydraulic retention time of 10 h. Tested variables were mode of flow (saturated or percolating), type of media (none, gravel, Bionest and AnoxKaldnes K3), type of air (ambient or CO2-enriched) and airflow rate. One neutralization field test (saturated and no media, 2000-5000 ppm CO2, sequential feeding, hydraulic retention time of 7.8 h) was conducted for 7 days. Lab-scale and field-scale tests resulted in effluent pH of 7.5-9.5 when the aeration rate was sufficiently high. A model was implemented in the PHREEQC software and was based on the carbonate system, CO2 transfer and calcite precipitation; and was calibrated on ambient air lab tests. The model was validated with CO2-enriched air lab and field tests, providing satisfactory validation results over a wide range of CO2 concentrations. The flow mode had a major impact on CO2 transfer and hydraulic efficiency, while the type of media had little influence. The flow mode also had a major impact on the calcite surface concentration in the reactor: it was constant in saturated mode and was increasing in percolating mode. Predictions could be made for different steel slag effluent pH and different operation conditions (hydraulic retention time, CO2 concentration, media and mode of flow). The pH of the steel slag filter effluent and the CO2 concentration of the enriched air were factors that influenced most the effluent pH of the neutralization process. An increased concentration in CO2 in the enriched air reduced calcite precipitation and clogging risks. Stoichiometric calculations showed that a typical domestic septic tank effluent with 300 mg/L of biodegradable COD provides enough biological CO2 for neutralization of a steel slag effluent with pH of 10.5-11.5. A saturated neutralization reactor with no media operated at hydraulic retention time of 10 h and a concentration of 2000 ppm in CO2 enriched air is recommended for full-scale applications.

Numerical simulations with the P-Hydroslag model to predict phosphorus removal by steel slag filters.

The first version of the P-Hydroslag model for numerical simulations of steel slag filters is presented. This model main original feature is the implementation of slag exhaustion behavior, crystal growth and crystal size effect on crystal solubility, and crystal accumulation effect on slag dissolution. The model includes four mineral phases: calcite, monetite, homogeneous hydroxyapatite (constant size and solubility) and heterogeneous hydroxyapatite (increasing size and decreasing solubility). In the proposed model, slag behavior is represented by CaO dissolution kinetic rate and exhaustion equations; while slag dissolution is limited by a diffusion rate through a crystal layer. An experimental test for measurement of exhaustion equations is provided. The model was calibrated with an experimental program made of three phases. Firstly, batch tests with 300 g slag sample in synthetic solutions were conducted for the determination of exhaustion equation. Secondly, a slag filter column test fed with synthetic solution was run for 623 days, divided into 9 cells and sampled at the end of the experiment. Finally, the column was dismantled, sampled and analyzed with XRD, TEM and SEM. Experimental column curves for pH, oPO4, Ca and inorganic carbon were well predicted by the model. Crystal sizes measured by XRD and TEM validated the hypothesis for homogeneous precipitation while SEM observations validated the thin crystal layer hypothesis. A preliminary validation of the model resulted in successful predictions of a steel slag filter longevity fed with real wastewater.

Phosphorus removal by steel slag filters: modeling dissolution and precipitation kinetics to predict longevity.

This article presents an original numerical model suitable for longevity prediction of alkaline steel slag filters used for phosphorus removal. The model includes kinetic rates for slag dissolution, hydroxyapatite and monetite precipitation and for the transformation of monetite into hydroxyapatite. The model includes equations for slag exhaustion. Short-term batch tests using slag and continuous pH monitoring were conducted. The model parameters were calibrated on these batch tests and experimental results were correctly reproduced. The model was then transposed to long-term continuous flow simulations using the software PHREEQC. Column simulations were run to test the effect of influent P concentration, influent inorganic C concentration and void hydraulic retention time on filter longevity and P retention capacity. High influent concentration of P and inorganic C, and low hydraulic retention time of voids reduced the filter longevity. The model provided realistic P breakthrough at the column outlet. Results were comparable to previous column experiments with the same slag regarding longevity and P retention capacity. A filter design methodology based on a simple batch test and numerical simulations is proposed.

Removal of phosphorus, fluoride and metals from a gypsum mining leachate using steel slag filters.

The objective of this work was to evaluate the capacity of steel slag filters to treat a gypsum mining leachate containing 11-107 mg P/L ortho-phosphates, 9-37 mg/L fluoride, 0.24-0.83 mg/L manganese, 0.20-3.3 zinc and 1.7-8.2 mg/L aluminum. Column tests fed with reconstituted leachates were conducted for 145-222 days and sampled twice a week. Two types of electric arc furnace (EAF) slags and three filter sequences were tested. The voids hydraulic retention time (HRT(v)) of columns ranged between 4.3 and 19.2 h. Precipitates of contaminants present in columns were sampled and analyzed with X-ray diffraction at the end of tests. The best removal efficiencies over a period of 179 days were obtained with sequential filters that were composed of Fort Smith EAF slag operated at a total HRT(v) of 34 h which removed 99.9% of phosphorus, 85.3% of fluoride, 98.0% of manganese and 99.3% of zinc. Mean concentration at this system's effluent was 0.04 mg P/L ortho-phosphates, 4 mg/L fluoride, 0.02 mg/L manganese, 0.02 zinc and 0.5 mg/L aluminum. Thus, slag filters are promising passive and economical systems for the remediation of mining effluents. Phosphorus was removed by the formation of apatite (hydroxyapatite, Ca(5)(PO(4))(3)OH or fluoroapatite, Ca(5)(PO(4))(3)F) as confirmed by visual and X-ray diffraction analyses. The growth rate of apatite was favored by a high phosphorus concentration. Calcite crystals were present in columns and appeared to be competing for calcium and volume needed for apatite formation. The calcite crystal growth rate was higher than that of apatite crystals. Fluoride was removed by precipitation of fluoroapatite and its removal was favored by a high ratio of phosphorus to fluoride in the wastewater.

Model of phosphorus precipitation and crystal formation in electric arc furnace steel slag filters.

The objective of this study was to develop a phosphorus retention mechanisms model based on precipitation and crystallization in electric arc furnace slag filters. Three slag columns were fed during 30 to 630 days with a reconstituted mining effluent at different void hydraulic retention times. Precipitates formed in columns were characterized by X-ray diffraction and transmission electronic microscopy. The proposed model is expressed in the following steps: (1) the rate limiting dissolution of slag is represented by the dissolution of CaO, (2) a high pH in the slag filter results in phosphorus precipitation and crystal growth, (3) crystal retention takes place by filtration, settling and growth densification, (4) the decrease in available reaction volume is caused by crystal and other particulate matter accumulation (and decrease in available reaction time), and (5) the pH decreases in the filter over time if the reaction time is too low (which results in a reduced removal efficiency). Crystal organization in a slag filter determines its phosphorus retention capacity. Supersaturation and water velocity affect crystal organization. A compact crystal organization enhances the phosphorus retention capacity of the filter. A new approach to define filter performance is proposed: saturation retention capacity is expressed in units of mg P/mL voids.