L.C. Rietveld
Please Note
163 records found
1
Assessing natural organic matter (NOM) characteristics in South African surface waters using fluorescence-based surrogate tools
Biodegradability and treatment optimization perspectives
Impact of ionic strength and surface charge on ceramic membrane fouling by oil-in-water emulsions
A quantitative analysis using DLVO and XDLVO models
Large amounts of oily wastewater, which can be defined as produced water, are generated in oilfields. Ultrafiltration (UF) serves as an effective and economical method to purify produced water. Unfortunately, membrane fouling during produced water treatment is severe. In this paper, the effects of the ionic strength (1, 20, and 100 mM) as well as different surfactants on the membrane fouling are investigated. Four surfactants, including SDS (anionic), APG (non-ionic), CTAB (cationic) and DDAPS (zwitterionic), were selected for this study. The Derjaguin-Landau-Verwey-Overbeek (DLVO) and extended DLVO (XDLVO) models were used to quantify interactions between the membrane-oil droplet and deposited oil layer-oil droplet surfaces and to compare these interactions with the fouling experiments. The (X)DLVO interaction energies of the membrane-oil droplet exhibited a strong agreement with the fouling tendencies at 1 mM salinity. The SiC-deposited (B20) membrane showed less reversible and irreversible membrane fouling than the Al2O3 (B0) membrane when filtering negatively charged O/W emulsions stabilized with SDS, APG, or DDAPS. The DLVO model predicted a higher fouling tendency at higher salinity levels during the filtration of SDS, APG, or DDAPS-stabilized O/W emulsions and a decreased fouling tendency for CTAB-stabilized emulsion with the B20 membrane. However, at higher salinity levels, the XDLVO energy barrier was affected by both the repulsive electrostatic double layer (EL) interaction and attractive Lewis acid-base (AB) interaction. By comparing both experiments and (X)DLVO modeling, this study improves the fundamental understanding of the effect of ionic strength and surfactant types on reversible and irreversible fouling of the Al2O3 and SiC-coated membranes fouling by O/W emulsions.
Fouling remains a critical challenge for ceramic ultrafiltration membranes, limiting their long-term performance for water treatment. Fenton-like reactions have been widely used for fouling removal due to the formation of strong radicals. Integrating these reactions into backwash offers a promising strategy for fouling control. However, it has been unclear how Fenton-like backwash is influenced by operational parameters and fouling structures. Here we reveal the key factors influencing Fenton-like backwash by systematically studying its performance under varying conditions, such as backwash pressure (0.3–1 bar), duration (18–36 min), fouling structure (caused by 1–5 mM Ca) and the long-term operation, to provide an effective and practical cleaning. CuFe2O4 was grown on ceramic ultrafiltration membranes due to its stability and high catalytic efficiency in activating Fenton-like reactions. We found that Fenton-like backwash achieved the highest cleaning efficacy of approximately 70 % over three cycles at a low backwash pressure of 0.3 bar, while hydraulic backwash remained ineffective under all conditions. Backwash pressure, rather than duration, was identified as the dominant factor governing the Fenton-like cleaning, due to its impact on the residence time of Fenton-like agents (H2O2). The presence of a high Ca concentration (3 and 5 mM) altered the fouling behaviour, and reduced the cleaning efficacy of Fenton-like backwash. This reduction was attributed to the formation of rigid alginate clusters that were resistant to Fenton-like reactions. The contribution of •OH to the enhanced Fenton-like backwash was confirmed by the quenching experiments. Furthermore, the CuFe2O4-coated membranes exhibited stable flux recovery (83 %–94 %) in the long-term treatment of a concentrated alginate (800 mg/L), showed low or negligible leaching in hash environments (30 mM H2O2, 0.1 % NaClO or 10 mM NaOH), and maintained comparable performance after 96 h aging by 30 mM H2O2. This study clarifies the factors governing Fenton-like backwash, and demonstrates that a robust and effective strategy for fouling removal can be achieved by coupling this cleaning method with catalytic ceramic membranes.
Mitigating NOM competition against micropollutant adsorption through staged dosing of activated carbon
Loading redistribution of NOM competitors?
Powdered activated carbon (PAC) adsorption is widely applied for the removal of organic micropollutants in drinking water treatment. However, conventional single-dose PAC application requires high dosages to overcome competitive adsorption from natural organic matter (NOM). This study evaluates a multi-stage PAC dosing strategy to mitigate NOM competition and enhance the removal efficiency of representative odorous micropollutants. Experiments with NOM-rich surface water showed that multi-stage dosing increased adsorption capacity and achieved up to 48% PAC savings at an 80% micropollutant removal benchmark, compared to single-stage application. In contrast, no improvement was observed in NOM-free water. Two-stage PAC dosing considerably improved the removal of weakly adsorbing compounds such as 2-methylisoborneol (MIB) and 2-ethyl-5,5-dimethyl-1,3-dioxane (EDD), while incremental gains were observed for strongly adsorbing micropollutants (e.g., 2-butyl-5,5-dimethyl-1,3-dioxane) with three- or four-stage configurations. Mechanistic analysis indicated that early-stage PAC doses preferentially adsorbed competitive NOM components, preserving high-affinity sites for micropollutants in later stages. PACs enriched in narrow mesopores outperformed microporous PACs in the staged dosing configuration. The proposed strategy, as compared to existing designs summarized from the literature, requires minimal infrastructural modifications and offers a cost-effective, scalable approach for improving micropollutant removal under NOM-rich conditions.
During the extraction of fossil fuels, a complex waste stream is produced simultaneously, also known as produced water (PW). Membrane filtration is a promising technology that can successfully enable the treatment and reuse of PW. Silicon carbide (SiC) membranes are preferred for PW treatment, due to their low (ir)reversible fouling compared to other ceramic membranes. However, full SiC membrane is expensive and thus economically less feasible. Therefore, we established a method for coating SiC on alumina (Al2O3) ultrafiltration membranes, based on low-pressure chemical vapor deposition at 860 °C. In the presented study the fouling resistance and behavior of these novel membranes, with various pore sizes and under different operating conditions, including flux and crossflow velocity, were evaluated. We also used Al2O3 membranes and SiC-coated Al2O3 membranes in constant flux mode to treat real oilfield PW with high salinity (142 mS/cm) and COD (22670 mg/L). Additionally, the fouling mechanisms in the SiC-coated and Al2O3 membranes were analyzed with the help of Focused Ion Beam-Scanning Electron Microscopy imaging. The major findings were that pore blockage served as the initial (irreversible) fouling mechanism and that the (reversible) cake layer, a mixture of organic and inorganic components, dominated the rest of the filtration cycle, where the SiC coated membrane performed better than the original alumina membrane. In addition, it was found that the application of the SiC coating, and the selection of the appropriate pore size (62 nm) and crossflow velocity (0.8 m/s) increased the fouling mitigation, potentially advancing the utilization of ultrafiltration in treating saline PW for reuse purposes.
Monitored natural attenuation is commonly used to manage petroleum hydrocarbon-contaminated groundwater. However, it requires periodic, costly grab sampling. We propose a cost-effective, real-time groundwater monitoring proof-of-concept machine learning (ML) framework using in-situ sensors—pH, dissolved oxygen, electrical conductivity, and redox potential—to detect benzene, ethylbenzene, and xylenes (BEX). We built upon the established correlations between hydrocarbon concentrations and in-situ water quality parameters (iWQPs). Due to limited field data, we validated the framework using datasets at virtual wells within a simulated aquifer from our previously developed reactive transport model. In this application, we detected the spreading of pollution downstream of the established pollution plume. The used framework is a binary classification system that flags contamination at virtual downstream wells. We compared five ML classifiers, i.e. Logistic Regression, Random Forest, XGBoost, Multi-layer Perceptron, and Support Vector Classifier, for early warning when BEX reached or exceeded the regulatory threshold of 5 μg/L. The models were trained on virtual wells at and near the source zone and predicted contamination before BEX reached the threshold at downstream virtual wells. This reflects the spatial variability in flow and reaction dynamics that altered BEX-iWQP relationships. Scenario analyses revealed the ML models' sensitivity to aquifer properties, i.e., hydraulic conductivity, electrical conductivity, and electron acceptor availability. We also assessed the impact of sensor noise and seasonal fluctuations on iWQPs. We found that even moderate levels of noise (10–20 %) can significantly affect model accuracy, particularly when the noise was introduced into the test data. Therefore, we recommended to combine hardware stabilization with adaptive smoothing techniques. With these approaches, our proposed framework remains promising for providing early warnings of plume migration toward sensitive receptors.
Beyond activated carbon properties and hydrophobicity
Data-driven assessment of organic micro-pollutant treatability and mechanistic insights
Activated carbon (AC) is widely used for organic micro-pollutants (OMPs) removal, yet adsorbability evaluation remains challenging due to molecular diversity and adsorbent heterogeneity, especially given the limitations of traditional assessment metrics such as hydrophobicity (logD). This study proposed a machine learning (ML)-driven assessment strategy by aligning the adsorbability of various AC adsorbents with a hypothetical “Standard AC” to evaluate the adsorbabilities across 56 OMPs. XGBoost, RF, and ET models achieved high prediction accuracy on the test set (R2 = 0.88–0.98, RMSE = 0.17–0.38, MAE = 0.13–0.27), and were further validated against a published experimental dataset. Interpretable ML analysis identified a logD threshold of ≈ 2, at which the dominant adsorption mechanisms transitioned from hydrophobic interactions for OMPs with higher hydrophobicity to π-π interactions, hydrogen bonding, and pore-filling for those with lower hydrophobicity. Adsorbability increased with molecular weight, as flexible molecules (rotatable bond ratio > 0.012) overcame steric hindrance in micropores, enhancing pore-filling efficiency through improved accessibility. By introducing a standardized, data-driven adsorbability reference and elucidating the intrinsic interplay between molecular properties and adsorption mechanisms, this study offers a robust framework for knowledge-informed treatability evaluation and a practical benchmark to guide adsorption process design.
(Im)mobilization of iron, manganese, and arsenic during managed aquifer recharge in Bangladesh
Push-pull tests under oxidative and reductive conditions
Evaluation of membrane fouling at constant flux and constant transmembrane pressure conditions
Implications for membrane modification
Membrane modification is commonly applied in water purification and wastewater treatment to reduce fouling of membranes. However, the influence of fouling test methods on evaluating pristine and modified membranes is often overlooked. This study investigates fouling behavior of alumina and SiC-deposited alumina membranes during oil-in-water emulsion filtration under both constant flux and constant transmembrane pressure conditions. Threshold flux was first determined using flux-stepping experiments, with the 90-min SiC-deposited membrane showing the highest value at 95 L m− 2 h− 1. In single-cycle constant flux tests, fouling trends aligned with threshold flux data. However, when backwash was included, fouling characteristics shifted and depended on the permeate flux. Enhanced hydrophilicity and surface charge improved backwash efficiency in modified membranes. Yet, extensive modification negatively affected performance due to significant permeance loss (>57 %). Under constant pressure, fouling was dominated by internal pore blocking, and backwash efficiency was solely linked to membrane permeance, regardless of surface properties. Thus, constant flux filtration with backwash best reflects operational conditions and is recommended for evaluating membrane modifications.
Ceramic membrane filtration for oily wastewater treatment
Basics, membrane fouling and fouling control
Membrane technology presents an effective solution for treating oily wastewater, a significant environmental hazard stemming from industries such as food processing, metalworking, and oil extraction. Compared to polymeric membranes, ceramic ones exhibit superior mechanical, chemical, and thermal stability, enabling more effective oil removal and easier cleaning. Despite their advantages, membrane fouling remains a challenge, impacting the efficiency of oily wastewater treatment. This review explores oily wastewater characteristics and ceramic membrane applications in treatment processes. It examines the factors influencing ceramic membrane fouling, including wastewater properties (e.g., oil concentration, pH), membrane characteristics (e.g., surface hydrophilicity, charge), and operational parameters (e.g., cross-flow velocity, permeate flux). Strategies to mitigate fouling, such as pretreatment, backpulsing/backwashing for sustained operation, and chemical cleaning for fouling removal, are discussed. By using pretreatment, membrane fouling can be reduced. Backpulsing/backwashing is effective to maintain a long-term operation. Chemical cleaning is effective in removing irreversible fouling and restoring the performance of the ceramic membranes. Moreover, membrane modification techniques that enhance performance are highlighted. Ultimately, the review identifies that effective fouling control is crucial for optimizing ceramic membrane use in oily wastewater treatment, underscoring the need for ongoing research in this area.
Ceramic nanofiltration (NF) is a promising alternative for direct surface water treatment, but is hampered for full-scale applications by fouling and a lack of eco-friendly cleaning regimes. In this work, an innovative reactive pre-coat layer, consisting of an iron oxychloride catalyst, was constructed on top of commercial ceramic NF membranes, for segregating a large-sized colloid fraction in canal water and Fenton cleaning with a hydrogen peroxide (H2O2) solution. The large-sized colloids (3−30 μm) were identified as dominant substances fouling the TiO2 separation layer of the pristine membranes, leading to a fast increase in their filtration resistance, in contrast to the small-sized colloids (<0.04 μm) and natural organic matter (NOM). As a consequence, the catalyst pre-coat layer with a pore size of 0.1–0.5 μm was able to segregate the large-sized colloids from the TiO2 separation layer during direct filtration of the raw water. Moreover, filtration under an acceptable flux of around 23 L m−2 h−1 did not cause pore clogging in the catalyst pre-coat. In addition, Fenton oxidation initiated by the catalytic pre-coat efficiently restored the filtration resistance, whereas sole H2O2 flush of the pristine membrane was not effective. In the meantime, the TiO2 separation layer of the membrane exerted a high NOM rejection of approximately 90%, measured as dissolved organic carbon, while the catalyst pre-coat on the membrane remained active in Fenton cleaning, over five one-day cycles. The findings of this work may provide guidance on the structural and functional design of a catalytic pre-coat layer for a dual purpose of foulant segregation and oxidative removal, particularly in response to key fouling-causing substances, during membrane-based treatment of real water matrices.
Long-term consumption of groundwater containing elevated levels of arsenic (As) can have severe health consequences, including cancer. To effectively remove As, conventional treatment technologies require expensive chemical oxidants to oxidise neutral arsenite (As(III)) in groundwater to negatively charged arsenate (As(V)), which is more easily removed. Rapid sand filter beds used in conventional aeration-filtration to treat anaerobic groundwater can naturally oxidise As(III) through biological processes but require an additional step to remove the generated As(V), adding complexity and cost. This study introduces a novel approach where As(V), produced through biological As(III) oxidation in a sand filter, is effectively removed within the same filter by embedding and operating an iron electrocoagulation (FeEC) system inside the filter. Operating FeEC within the biological filter achieved higher As(III) removal (81 %) compared to operating FeEC in the filter supernatant (67 %). This performance was similar to an analogous embedded-FeEC system treating As(V)-contaminated water (85 %), confirming the benefits of incorporating FeEC in a biological bed for comparable As(III) and As(V) removal. However, operating FeEC in the sand matrix consumed more energy (14 Wh/m3) compared to FeEC operated in a water matrix (7 Wh/m3). The efficiency of As removal increased and energy requirements decreased in such embedded-FeEC systems by deep-bed infiltration of Fe(III)-precipitates, which can be controlled by adjusting flow rate and pH. This study is one of the first to demonstrate the feasibility of embedding FeEC systems in sand filters for groundwater arsenic removal. Such systems capitalise on biological As(III) oxidation in aeration-filtration, effectively eliminating As(V) within the same setup without the need for chemicals or major modifications.
A large decrease in permeability is often observed during the filtration of nano-sized colloids, while fouling is widely regarded as the main explanation for this phenomenon. The osmotic pressure or concentration polarization (CP) of colloids can also contribute to the flux decline. However, the contribution of CP to flux loss cannot be determined by the traditional CP model. In this study, the effect of fouling and CP/osmotic pressure on flux was distinguished. The CP values of polyethylene glycol (PEG) and silica-colloids were determined by the osmotic pressures near the membrane surface and in the feed. The CP induced by colloids accounted for 43–95% of the flux loss in our experiments. Silica exhibited higher CP values (127–460), compared to 7–71 for PEG. This was attributed to the slower back diffusion caused by the larger colloids, as evidenced by the diffusion coefficients of 4.30 × 10−11 m2/s for silica (10 nm) and 1.45 × 10−10 m2/s for PEG (2.9 nm). Although the CP was mitigated by increasing the cross-flow velocity, CP values of 31 and 250 were observed for PEG and silica at high Reynolds number of 7317, respectively. The experimentally obtained CP values were also compared with those calculated by the film diffusion model.
Worldwide, a considerable amount of oily wastewater is generated, with oil droplets from 2 to 200 nm that are difficult to separate because of their size and colloidal stability. This study presents a novel approach for effectively separating microemulsions via cubic silicon carbide (3C-SiC)-coated alumina (Al 2O 3) membranes fabricated based on low pressure chemical vapor deposition (LPCVD). SiC was deposited at a relatively low temperature at 860 °C on 100 nm Al 2O 3 membranes using two precursors: SiH 2Cl 2 and C 2H 2. With the increase in deposition time, up to 25 min, the pore size decreased from 41 nm to 33 nm, which is a smaller pore size of a SiC membrane than previously used for oil/water separation. The polycrystalline 3C-SiC-coated membranes showed improved hydrophilicity (water contact angle of 15°) and highly negatively charged surfaces (−65 mV). Microemulsion filtration experiments were carried out at a constant permeate flux (80 Lm −2 h −1) for six cycles with varying deposition time, pH, surfactant types, and pore sizes. The fouling of the SiC-coated membrane was, compared to the Al 2O 3 membrane, effectively mitigated due to the enhanced electrostatic repulsion and hydrophilicity. Surfactant adsorption mainly occurred when the surface charge of the microemulsion and the membranes were opposite. Therefore, the surface charge of the alumina membrane changed from positive to negative when soaked in negatively charged microemulsions, whereas SiC-coated membranes remained negatively charged regardless of surfactant type. The membrane fouling was alleviated when the membrane and oil droplets had the same charge. Lastly, the 62 nm SiC-coated membrane with 20 min coating time was the best choice for the filtration of the microemulsion, because of the high rejection of the oil droplets and low fouling tendency.