Humic Acid Aggregates Research Articles

Abiotic reversible self-assembly of fulvic and humic acid aggregates in low electrolytic conductivity solutions by dynamic light scattering and zeta potential investigation

The aggregation of humic substances and their interaction with filtration media (membranes, soils) has implications for our understanding of membrane fouling during water treatment, the facilitated transport of contaminants, and the transport of organic matter through the microbial loop. To investigate the aggregation of fulvic and humic acids in low electrolytic conductivity solutions, laboratory studies of simulated environmental water samples as well as actual environmental water samples were examined. Intensity-, volume-, and number-based particle size distributions (PSDs) were obtained by dynamic light scattering. Aggregates were categorized into three ranges, i.e., 10–100nm, 100–1000nm, and >1μm. Individual biomacromolecules and the aggregates between 10nm and 1μm were presumed to be precursors for the formation of a large 5-μm-sized-particle. The self-assembly of the large-in-volume, few-in-number, 5-μm-sized particle was observed in real-time and occurred in unfiltered samples and in samples filtered (0.45μm) at a nominal size one order of magnitude smaller. The supramicrometer-sized particle formed, dissipated, and spontaneously re-formed over turbulent/quiescent cycles in the presence of sodium azide indicating reversible abiotic self-assembly. Zeta potential analyses demonstrated that colloidal stability increased as concentration increased. DLS studies of the environmental water samples were comparable to those of the simulated laboratory samples. The operational range of the instrumentation used in these experiments was 0.6nm–6μm; therefore, aggregates larger than 6μm may exist in these solutions.

Alkaline hydrolysis of vinclozolin: Effect of humic acids aggregates in water

The influence of natural organic substances as humate colloidal aggregates in water solutions upon the chemical stability of vinclozolin has been investigated in basic media. A large inhibition (9 times-fold) has been observed and it has been rationalized in terms of a micellar pseudophase model. The observed behaviour could increase significantly the half-life of this fungicide. Moreover, these experimental results have been compared with the corresponding ones of other substances in these natural colloidal aggregates.

Interaction of humic acids with soil minerals: adsorption and surface aggregation induced by Ca2+

Environmental context Humic acids, important components of natural organic matter in soils, sediments and aquatic media, can interact with the surface of minerals affecting key environmental processes. In the presence of calcium, humic acids can also interact among themselves leading to molecular aggregates. We demonstrate that a solid mineral surface facilitates the formation of humic acid aggregates, and thus surface aggregation occurs under conditions where normal aggregation in solution does not occur. Abstract Humic acids (HAs) interact with the surface of mineral particles leading to the formation of clay–humic complexes that affect the transport of nutrients and contaminants in the environment, soil structure, soil erosion and carbon sequestration by soils. The interaction is influenced by the presence of multivalent ions, such as Ca2+, which enhances the uptake of HAs by the particles. This article reports the effects of Ca2+ on the interaction between a HA and a soil clay fraction, both obtained from the same soil sample. The study was performed by using zeta potential measurements, HA adsorption isotherms, Ca2+ adsorption isotherms and microscopy. The results show that at low HA concentrations and low Ca2+ concentrations HA adsorption takes place, but that at high concentrations surface aggregation and precipitation also takes place, a process that is seldom reported or analysed in the literature. HA adsorption isotherms only give the overall HA uptake by the solid but they do not allow differentiation of HA adsorption from surface aggregation. However, HA adsorption v. Ca2+ concentration plots and Ca2+ adsorption isotherms at different HA concentrations can distinguish these two processes quite clearly. In addition, surface aggregation could be undoubtedly observed with optical microscopy. Surface aggregation starts to take place at a 0.7mM Ca2+ concentration, which is lower than the Ca2+ concentration needed to start HA aggregation in solution. This indicates that the surface of soil minerals acts as a nucleation centre for HA aggregation.

The role of humic acid in stabilizing fullerene (C60) suspensions

Natural organic matter (NOM) has a profound effect on the colloidal stability of discharged C60 nanoparticles in the water environment, which influences the environmental behaviors and risks of C60 and therefore merits more specific studies. This study investigates the effects of humic acid (HA), as a model NOM, on the aqueous stabilization of C60 powder and the colloidal stability of a previously suspended C60 suspension (aqu/nC60) with variations of pH values and ionic strengths. Our results reveal that HA could disperse C60 powder in water to some degree, but was unable to stably suspend them. The aqu/nC60 could remain stable at pH>4 but was destabilized at lower pH values. However, the colloidal stability of aqu/nC60 in the presence of HA was insensitive to pH 3–11, owing to the adsorption of HA onto nC60 and the increased electrosteric repulsions among nC60 aggregates. The colloidal stability of aqu/nC60, with and without HA, decreased as we increased the valence and concentration of the added cations. HA was found to mitigate the destabilization effect of Na+ on the colloidal stability of aqu/nC60 by increasing the critical coagulation concentration (CCC) of Na+, while HA lowered the CCCs of Ca2+ and La3+ probably by the bridging effect of nC60 with HA aggregates formed through the intermolecular bridging of the HA macromolecules via cation complexation at high concentrations of cations with high valences.

Effects of UV radiation on humic acid coagulation characteristics in drinking water treatment processes

Abstract Humic acid (HA) commonly exists in natural waters and drinking water treatment processes. The effects of UV light radiation on the coagulation of HA were investigated in this paper. It was determined that UV light radiation could effectively improve the removal of HA at pH above 6.0. The concentration of residual HA in the coagulated water was in the range of 1.5–3.0 mg/L, which was significantly lower compared to that without pretreatment. However, in waters tested with pH below 5.5, the UV light radiation showed an adverse effect on HA removal using coagulation, which might be connected to its high oxidation function under acidic conditions. The zeta potential of the HA solution with UV light radiation was approximately 10 mv higher compared to that without pretreatment at pH above 6.0; while its apparent diameters and heights increased from less than 130 nm and 0.5–3.5 nm to 100–240 nm and 1.0–4.5 nm respectively, after 2.0 h of UV light radiation as the aggregation of HA. The compressed double electric layer caused by the formation of positive charged sites after UV light radiation was considered to be the primary factor that led to the enhanced removal of HA in the following coagulation process.

Molecular-size-distribution-dependent aggregation of humic substances by Na(I), Ag(I), Ca(II), and Eu(III)

Molecular-size-distribution (MSD)-dependent aggregation of Fluka and International Humic Substance Society humic acids (HAs) in the presence of Na(I), Ca(II), Ag(I), and Eu(III) were studied using high-performance size-exclusion chromatography. Larger molecular size fractions (>8000Da) rich in aliphatic carbons were observed to aggregate in the presence of Na(I) and Ca(II), whereas both large and small molecular size fractions concurrently aggregated in the presence of Ag(I) and Eu(III). In view of the non-specific binding of Na(I) and Ca(II) with HAs, the electric-field screening effect is probably the main cause of HA aggregation by Na(I) and Ca(II), preserving the intrinsic hydrophobicity of the HAs. Reduced surface charges and the hydrophobic heterogeneities of different MSD fractions of HAs by direct binding of Ag(I) and Eu(III) are postulated to induce insignificant dependence of aggregation on the different MSD fractions.

Coagulation Kinetics of Humic Aggregates in Mono- and Di-Valent Electrolyte Solutions

Coagulation behaviors of humic acids (HAs) aggregates in electrolyte solutions at different pHs, valences and concentrations of electrolyte cations were investigated using dynamic light scattering technique in combination of other analytical tools. For monovalent electrolyte sodium chloride (NaCl) solution, at its low concentrations the average hydrodynamic radius (<Rh>) of aggregates kept nearly constant. However, at high NaCl concentrations, <Rh> could be scaled to the time t as <Rh> ∝ t(a), suggesting a diffusion-limited colloid aggregation (DLCA). The coagulation value of NaCl in a buffer at pH 7.1 was calculated to be in a range of 61.3-84.4 mM. Divalent cation Mg(2+) was far more effective in enhancing the HA coagulation, as evidenced by a lower coagulation value (between 1.0 and 1.7 mM) and a more rapid coagulation rate. Such an enhancement could be explained by the combined effects of electrostatic repulsion, complexation and bridging. The highest coagulation rate (d<Rh>/dt) and coagulation value at different pHs followed the order of: acidic > neutral > alkaline, and alkaline > neutral > acidic, respectively. Such a difference was associated with the extent of hydrogen bond and electrostatic repulsion at different protonation/deprotonation states of carboxyl and phenolic -OH groups. Transmission electron microscopic imaging reveals that HA was predominantly globular aggregates with a rough periphery at pH 5.26, and was changed to smooth spherical particles at pH 10.00. These results are useful for better understanding the coagulation behaviors of HAs in both natural and engineered aqueous systems.

Soil humic acid aggregation by dynamic light scattering and laser Doppler electrophoresis

AbstractHumic acids (HAs), similar to other fractions of humic substances (HSs), have a large number of reactive functional groups enabling them to aggregate in solutions. Regardless of the origin of humic acid (aqueous or soil), this aggregation process is dependent on environmental conditions and strongly influences the mobility of soluble ionic and molecular pollutants. The aim of this work was to monitor the aggregation process of two humic acids isolated from different mineral soils (IHSS Elliot soil HA standard and Rendzic Leptosol HA) in the 2–11 pH range. Changes in aggregate size in HA sols were followed up using dynamic light scattering (DLS), while zeta potential (ZP) measurements in the same pH range were performed applying laser Doppler electrophoresis (LDE) technique. The effect of HA sol concentration and soil source on aggregation was examined as well. Besides, HA samples were characterized using Fourier transform infrared (FT‐IR) spectroscopy. By inspecting HA‐particle‐size dependence on pH, it can be concluded that both HAs in corresponding sols behave as molecular aggregates or supramolecular structures, formed from small individual moieties (sizes &lt; 10 nm) at higher pH values. The ZP vs. pH curve for both HAs revealed the ZP minimum in the 5–7 pH range, caused most likely by dissociation of acidic functional groups prevailing at lower pH values and deaggregation predominating over dissociation at higher pH values.

Aggregation kinetics of humic acids in the presence of calcium ions

The aggregation kinetics of a humic acid (HA) sample as a function of Ca2+ concentration at pH 5, 7 and 9 was investigated. UV–VIS spectroscopy was employed to quantify the progress of the aggregation reaction, and electrophoresis was used to evaluate the zeta potential of the HA molecules. The aggregation rate increases significantly by increasing Ca2+ concentration at all investigated pH, being higher at pH 9 than at pH 5 and 7. An aggregation mechanism is proposed, which consists of at least two steps: a rapid binding of Ca2+ to humic molecules, followed by a slower process where HA molecules approach each other and become aggregated. This aggregation is possible because Ca2+ binding decreases the zeta potential of HA from −37mV to −15mV and because it is able to form bridges between HA molecules. There is no molecular fractionation up to 60% of aggregation. Above this value, HA aggregates become enriched with more aromatic HA molecules. The fast aggregation of HA in the presence of calcium ions implies that aggregates may temporarily trap, protect and transport pollutants in the environment.

Characterization of cake layer structure on the microfiltration membrane permeability by iron pre-coagulation

A cake layer is formed by coagulation aggregates under certain transmembrane pressure in the coagulation-microfiltration (MF) process. The characteristics of humic acid aggregates coagulated by different iron-based coagulants, such as charge, size, fractal dimension and compressibility, have an effect on the cake layer structure. At the optimum iron dose of 0.6 to 0.8 mmol/L for ferric chloride (FC) and polymer ferric sulfate (PFS) pre-coagulation, at the point of charge neutralization for near zero zeta potential, the aggregate particles produced possess the greatest size and highest fractal dimension, which contributes to the cake layer being most loose with high porosity and low compressibility. Thus the membrane filterability is better. At a low or high iron dose of FC and PFS, a high negative or positive zeta potential with high charge repulsion results in so many small aggregate particles and low fractal dimension that the cake layer is compact with low porosity and high compressibility. Therefore the membrane fouling is accelerated and MF permeability becomes worse. The variation of cake layer structure as measured by scanning electric microscopy corresponds with the fact that the smaller the coagulation flocs size and fractal dimension are, the lower the porosity and the tighter the cake layer conformation. This also explains the MF membrane flux variation visually and accurately.

Effect of Hydrodynamic Operations, Salinity, and Heavy Metals on HA Removal by Microfiltration Ceramic Tubular Membrane

The removal of humic acids (HA) using ceramic tubular microfiltration membrane operated under various conditions including trans-membrane pressures, cross flow velocities, humic acids concentrations in the presence of different heavy metals, and high NaCl content (10000-35000 mg/L) has been investigated. It was found that HA retention increases sharply in the presence of heavy metals ions and at high salinity levels, while trans-membrane pressure has little effect on HA retention. It was also found that the effect of solution environmental on HA retention should reflect alterations in solute charge and in an extent of aggregation HA macromolecules. The fouling by HA was found to be a critical factor in microfiltration with ceramic membrane. Fouling was more severe at high concentrations of NaCl and heavy metals in the feed due to the tighter packing of the HA aggregates in the fouling layer formed on the membrane surface. These results provide an important insight into ceramic membrane fouling with HA at high salinity conditions relevant to the treatment of brackish and seawater.

Humic acid characteristics and effects on the reactivity of nano-scale zero-valent iron particles during nitrate reduction

ABSTRACT Humic acid (HA) comprises a significant fraction of natural organic matter (NOM), greatly influencing the performance of water and wastewater treatment processes. HA is expected to significantly affect the reactivity of nano-scale zero-valent iron (NZVI), which is receiving increasing attention due to its high reactivity. The effects of HA on nitrate reduction by NZVI were investigated to evaluate the potential of NZVI in practical applications. HA was characterized to identify the mechanism whereby HA affects. Nitrate reduction was enhanced at low HA concentration, but inhibited as HA concentration increased. HA decreased to reach a plateau and considerable amount of Fe3+ was detected when HA was present in dissolved phase. The increase in the degree of condensation of HA was verified by UV–vis spectroscopy, fluorescence spectroscopy, and size exclusion chromatography. Fourier transform infrared spectra confirmed that the Fe3+–HA complexes were formed in both the dissolved and solid fractions, without coexisting metal ions. The HA aggregation on NZVI and discrete HA macroaggregates were observed by transmission electron microscopy. The results suggest that HA induces complex effects on NZVI reactivity by improving iron dissolution, inhibiting readsorption of released iron, enhancing electron transfer, and inhibiting nitrate mass transfer via forming HA accumulation. It indicates that the clogging by aggregated NOM should be considered when NZVI is used for groundwater treatment or in combination with porous materials.

Interaction of Cocos nucifera cream casein with humic acid suspensions

Two caseins labelled as CaSMG (casein without fats) and CaMG (casein with fats) were extracted from coconut cream. Both caseins were used as coagulants for the aggregation of humic acid (HA) particles in synthetic water at pH = 6 during the jar-test essays. The optimum dosage of CaMG or CaSMG and the residual turbidities of treated water obtained depend on the type of used casein (CaMG or CaSMG) and the concentration of particles in solution. The optimal doses of CaMG and CaSMG are respectively 280 and 180 mg/L for solution S(1) (HA aqueous solution at 15 mg/L), and then 340 and 240 mg/L for solution S(2) (HA aqueous solution at 25 mg/L). The residual turbidities of treated water are respectively 6.88 and 3.85 NTU for solution S(1) and 4.52 and 2.53 NTU for solution S(2). The collected sediment volumes are respectively 1.2 and 1.5 mL for solutions S(1) and S(2). The electrophoretic mobility measurement and transmission electron microscopy images of flocs formed during the flocculation essays suggest that both caseins operate through both mechanisms (charge neutralisation and bridging process mechanism), this last one seems to be predominant. The aggregates formed are the large clusters and result from adsorption of HA particles by the casein molecules.

Determination of trace metals accumulated and internalized by marine phytoplankton; interferences with colloidal organic matter

In the present work, we study the effects that aggregation of humic acids in seawater, and its adsorption to surfaces, can have on the determination of Cu and Pb accumulation by phytoplankton within the context of metal bioavailability studies, using the diatom Thalassiosira weissflogii. Two methods commonly used for collection of algae to analyse metal content, filtration and centrifugation, were compared, and a procedure to differentiate the metal internalized by the alga from that adsorbed to cell walls-washing with 0.01 M ethylenediaminetetraacetic acid (EDTA)- was optimized for its use in seawater and in the presence of humic acids. The present results highlight the possibility of obtaining biased results if filtration is used to isolate the algae, and show that centrifugation is a more suitable procedure minimizing contribution of particulate and colloidal forms of metals to the measured cellular and intracellular metal contents. Thus a combination of centrifugation to isolate the algae from the medium with a 10 minutes washing with a washing agent composed of EDTA 0.01 M at pH 8 and NaCl and KCl to 0.5 M ionic strength is recommended to extract metals adsorbed to the surfaces of marine phytoplankton for a seawater containing humic substances. The importance of discriminating between internalized metal and total cellular metal in bioavailability studies is noted, given the different effects of humic substances on metal accumulation in the different cellular pools.

Synergistic effect of coupling zero-valent iron with iron oxide-coated sand in columns for chromate and arsenate removal from groundwater: Influences of humic acid and the reactive media configuration

A column study was conducted using a combination of zero-valent iron (Fe 0) and iron oxide-coated sand (IOCS) for removing Cr(VI) and As(V) from groundwater. The removal efficiency and mechanism of Cr(VI) and As(V), the effects of humic acid (HA), and the various configurations of Fe 0 and IOCS were investigated. The results showed that the use of an Fe 0 and IOCS mixture in a completely mixed configuration can achieve the highest removal of both Cr(VI) and As(V), whilst the effects of HA were marginal in using these reactive materials. The solid phase analysis revealed the occurrence of the synergistic effect in these reactive materials as Fe 2+ can be adsorbed onto the IOCS and transform the iron oxides to magnetite, providing more reactive surface area for Cr(VI) reduction and reducing the passivation on the Fe 0. As(V) can then be removed by adsorption onto these iron corrosion products. HA can be adsorbed onto the IOCS so that the impacts of the deposition of HA aggregates on the Fe 0 surface can be reduced, thus enhancing the Fe 0 corrosion.

The role of humic acid aggregation on the kinetics of photosensitized singlet oxygen production and decay

The effect of humic acid (HA) aggregate formation on the photosensitized generation and subsequent quenching of singlet molecular oxygen O(2)(a(1)Δ(g)) was investigated. Time-resolved O(2)(a(1)Δ(g)) phosphorescence traces were obtained from (a) bulk samples of HA dispersions and (b) microscope-based experiments performed upon irradiation of a single HA aggregate. In the bulk experiments, the dependence of the O(2)(a(1)Δ(g)) lifetime on the HA concentration yields a critical concentration for the formation of micrometric HA aggregates of 0.58 g L(-1). This value is consistent with that obtained using pyrene as a fluorescent probe (0.38 g L(-1)). Microscope-based experiments were also performed with HA samples containing added singlet oxygen sensitizers; either the hydrophobic meso-tetraphenylporphyrin (TPP) or the hydrophilic 5,10,15,20-tetrakis(N-methyl-4-pyridyl)-21H,23H-porphine (TMPyP). Singlet oxygen phosphorescence could only be detected upon irradiation of TMPyP, a molecule which localizes on the exterior part of the HA aggregates. The inability to detect O(2)(a(1)Δ(g)) phosphorescence from HA samples containing TPP is consistent with the model that the O(2)(a(1)Δ(g)) produced in the interior of the aggregate was completely quenched by the high local concentration of HA reactive groups in this environment.

Aggregation Kinetics of Citrate and Polyvinylpyrrolidone Coated Silver Nanoparticles in Monovalent and Divalent Electrolyte Solutions

The aggregation kinetics of silver nanoparticles (AgNPs) that were coated with two commonly used capping agents-citrate and polyvinylpyrrolidone (PVP)--were investigated. Time-resolved dynamic light scattering (DLS) was employed to measure the aggregation kinetics of the AgNPs over a range of monovalent and divalent electrolyte concentrations. The aggregation behavior of citrate-coated AgNPs in NaCl was in excellent agreement with the predictions based on Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, and the Hamaker constant of citrate-coated AgNPs in aqueous solutions was derived to be 3.7 × 10(-20) J. Divalent electrolytes were more efficient in destabilizing the citrate-coated AgNPs, as indicated by the considerably lower critical coagulation concentrations (2.1 mM CaCl(2) and 2.7 mM MgCl(2) vs 47.6 mM NaCl). The PVP-coated AgNPs were significantly more stable than citrate-coated AgNPs in both NaCl and CaCl(2), which is likely due to steric repulsion imparted by the large, noncharged polymers. The addition of humic acid resulted in the adsorption of the macromolecules on both citrate- and PVP-coated AgNPs. The adsorption of humic acid induced additional electrosteric repulsion that elevated the stability of both nanoparticles in suspensions containing NaCl or low concentrations of CaCl(2). Conversely, enhanced aggregation occurred for both nanoparticles at high CaCl(2) concentrations due to interparticle bridging by humic acid aggregates.

Influences of redox transformation, metal complexation and aggregation of fulvic acid and humic acid on Cr(VI) and As(V) removal by zero-valent iron

This study investigated the removal kinetics and mechanisms of Cr(VI) and As(V) by Fe(0) in the presence of fulvic acid (FA) and humic acid (HA) by means of batch experiments. The focus was on the involvements of FA and HA in redox reactions, metal complexation, and iron corrosion product aggregation in the removal of Cr(VI) and As(V) removal by Fe(0). Synthetic groundwater was used as the background electrolyte to simulate typical groundwater. The results showed faster Cr(VI) removal in the presence of HA compared to FA. Fluorescence spectroscopy revealed that no redox reaction occurred in the FA and HA. The results of the speciation modeling indicate that the free Fe(II) concentration was higher in the presence of HA, resulting in a higher removal rate of Cr(VI). However, the removal of As(V) was inhibited in the HA solution. Speciation modeling showed that the concentration of dissolved metal-natural organic matter (metal-NOM) complexes significantly affected the aggregation of the iron corrosion products which in turn affected the removal of As(V). The aggregation was found to be induced by gel-bridging of metal-NOM with the iron corrosion products. The effects of metal-NOM on the aggregation of the iron corrosion products were further confirmed by TEM studies. Larger sizes of iron corrosion products were formed in the FA solution compared to HA solution. This study can shed light on understanding the relationships between the properties of NOM (especially the content of metal-binding sites) and the removal of Cr(VI) and As(V) by Fe(0).

Effect of metal ions on humic acid fouling of hollow fiber ultrafiltration membrane

Ultrafiltration using a hollow fiber membrane is increasingly used in water treatment for the removal of particles, turbidity and microorganisms to meet stringent water quality requirements. Fouling by natural organic matter (e.g. humic acid and fulvic acid) is a critical problem in membrane processes. In this work, experiments were performed to evaluate the effects of metal ions on humic acid fouling of a hollow fiber ultrafiltration membrane. Fouling was severe in the presence of metal ions, especially at high concentration of Ca 2+ or Fe 3+. The accelerated fouling is considered to be due to the formation of intermolecular crosslinking between humic acid molecules, because the humic acid aggregate size increased in the presence of Ca 2+. Addition of ethylendiaminetetraacetic acid (EDTA) decomposed the aggregates and prevented metal ion-induced acceleration of fouling. Scanning electron micrograph images clearly revealed deposition of humic acid on the membrane after filtration, and that the presence of metal ions increased humic acid deposition, which led to accelerated fouling.

Influences of Humic Acid on Cr(VI) Removal by Zero-Valent Iron From Groundwater with Various Constituents: Implication for Long-Term PRB Performance

A 9-month-long continuous flow column study was carried out to investigate Cr(VI) removal by Fe0 with the presence of humic acid. The study focused on the influences of humic acid promoted dissolved iron release and humic acid aggregation in Fe0 columns receiving synthetic Cr(VI) contaminated groundwater containing various components such as bicarbonate and Ca. The effects of humic acid varied significantly depending on the presence of Ca. In Ca-free columns, the presence of humic acid promoted the release of dissolved iron in the forms of soluble Fe-humic acid complexes and stabilized fine Fe (hydr)oxide colloids. As a result, the precipitation of iron corrosion products was suppressed and the accumulation of secondary minerals on Fe0 surfaces was diminished, and a slight increase in Cr(VI) removal capacity by 18% was record compared with that of humic acid-free column. In contrast, in the presence of Ca, as evidenced by the SEM and FTIR results, humic acid greatly co-aggregated with Fe (hydr)oxides and deposited on Fe0 surfaces. This largely inhibited electron transfer from Fe0 surfaces to Cr(VI) and reduced the drainable porosity of the Fe0 matrix, resulting in a significant decrease in Cr(VI) removal capacity of Fe0. The Cr(VI) removal capacity was decreased by 24.4% and 42.7% in humic acid and Ca receiving columns, with and without bicarbonate respectively, compared with that of Ca and humic acid-free column. This study yields new considerations for the performance prediction and design of Fe0 PRBs in the environments rich in natural organic matter (NOM).