Coexistence Of Humic Acid Research Articles

Multi-interface interaction mechanism of pulp reject-based flocculants for the removal of antibiotics and its combined pollutants

The efficient removal of antibiotics and its combined pollutants is essential for aquatic environment and human health. In this study, a lignin-based organic flocculant named PRL-VAc-DMC was synthesized using pulp reject as the raw material, with vinyl acetate (VAc) and methacryloxyethyltrimethyl ammonium chloride (DMC) as the grafting monomers. A series of modern characterization methods were used to confirm the successful preparation of PRL-VAc-DMC and elucidate its polymerization mechanism. It was found that the Ph-OH group and its contiguous carbon atoms of lignin served as the primary active sites to react with grafting monomers. Flocculation experiments revealed that PRL-VAc-DMC could react with tetracycline (TC) through π-π* interaction, hydrophobic interaction, hydrogen bonding, and electrostatic attraction. With the coexistence of humic acid (HA) and Kaolin, the aromatic ring, hydroxyl, and amide group of TC could react with the benzene ring, hydroxyl group, and carboxyl group of HA, forming TC@HA@Kaolin complexes with Kaolin particles acting as the hydrophilic shell. The increase in particle size, electronegativity, and hydrophily of TC@HA@Kaolin complexes facilitated their interaction with PRL-VAc-DMC through strong interfacial interactions. Consequently, the presence of HA and Kaolin promoted the removal of TC. The synergistic removal mechanism of TC, HA, and Kaolin by PRL-VAc-DMC was systematically analyzed from the perspective of muti-interface interactions. This paper is of great significance for the comprehensive utilization of pulp reject and provides new insights into the flocculation mechanism at the molecular scale.

Natural mineral colloids facilitated transport of EE2 in saturated porous media: Effects of humic acid and conjugate form

Steroid estrogens have posed significant ecological risks to aquatic organisms due to their potent endocrine-disrupting effects. The role of natural mineral colloids in facilitating the transport of hydrophobic organic pollutants in the environment has been confirmed, but the control mechanisms of colloids on 17α-Ethinylestradiol (EE2) migration in the subsurface environment are often still not well understood. This study combined the batch sorption equilibrium experiments and dynamic transport simulations to reveal the interface interactions and co-transport characteristics between illite colloids and EE2 at both macroscopic and microscopic levels. The existing form changes of EE2 and the influence of coexisting humic acid (HA) during transport in porous media were also specifically investigated. The batch experiments demonstrated that the primary mechanisms governing EE2 sorption onto illite colloids involved surface sorption and hydrogen bonding. The coexistence of HA could load onto the surface of illite colloids, thereby enhancing the colloidal sorption capacity for EE2. Transport experiments demonstrated that the migratory ability of EE2 in silty clay was limited, but illite colloids could significantly promote its penetration, with the peak penetration content (Ct/C0) increasing from 0.64 to 0.77. In the absence of HA, EE2 primarily transported in a dissolved form, accounting for 62.86% of the total concentrations. When HA concentrations were increased to 10 mg/L and 20 mg/L, the proportion of colloidal conjugate EE2 in the effluents reached 52.13% and 54.49%, respectively. The enhanced transport of EE2 by HA was primarily attributed to the improved migration ability of illite colloids and the increased proportion of illite-EE2 conjugate, resulting in a maximum Ct/C0 value of 0.94. The validity of these results was further confirmed by employing calculations based on the Derjaguin–Landau–Verwey–Overbeek and Colloidal Filtration Theory. This study provides new insights of understanding the transport of EE2 in subsurface environment.

Adsorption of typical NDMA precursors by superfine powdered activated carbon: Critical role of particle size reduction

Control of N-nitrosodimethylamine (NDMA) in drinking water could be achieved by removing its precursors as one practical way. Herein, superfine powdered activated carbons with a diameter of about 1 µm (SPACs) were successfully prepared by grinding powdered activated carbon (PAC, D50=24.3 µm) and applied to remove model NDMA precursors, i.e. ranitidine (RAN) and nizatidine (NIZ). Results from grain diameter experiments demonstrated that the absorption velocity increased dramatically with decreasing particle size, and the maximum increase in k2 was 26.8-folds for RAN and 33.4-folds for NIZ. Moreover, kinetic experiments explained that rapid absorption could be attributed to the acceleration of intraparticle diffusion due to the shortening of the diffusion path. Furthermore, performance comparison experiments suggested that the removal of RAN and NIZ (C0=0.5 mg/L) could reach 61.3% and 60%, respectively, within 5 min, when the dosage of SAPC-1.1 (D50=1.1 µm) was merely 5 mg/L, while PAC-24.3 could only eliminate 17.5% and 18.6%. The adsorption isotherm was well defined by Langmuir isotherm model, indicating that the adsorption of RAN/NIZ was a monolayer coverage process. The adsorption of RAN or NIZ by SAPC-1.1 and PAC-24.3 was strongly pH dependent, and high adsorption capacity could be observed under the condition of pH > pka+1. The coexistence of humic acid (HA) had no significant effect on the adsorption performance because RAN/NIZ may be coupled with HA and removed simultaneously. The coexistence of anions had little effect on the adsorption also. This study is expected to provide an alternative strategy for drinking water safety triggered by NDMA.

Modification of the distribution of humic acid complexations by introducing microbubbles to membrane distillation process for effective membrane fouling alleviation

Membrane fouling caused by inorganic ions and natural organic matters (NOMs) has been a severe issue in membrane distillation. Microbubble aeration (MB) is a promising technology to control membrane fouling. In this study, MB aeration was introduced to alleviate humic acid (HA) composited fouling during the treatment of simulative reverse osmosis concentrate (ROC) by vacuum membrane distillation (VMD). The objective of this work was to explore the HA fouling inhibiting effect by MB aeration and discuss its mechanism from the interfacial point of view. The results showed that VMD was effective for treating ROC, followed by a severe membrane fouling aggravated with the addition of 100 mg/L HA in feed solution, resulting in 45.7% decline of membrane flux. Analysis using the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory and zeta potential distribution of charged particles proved the coexistence of HA and inorganic cations (especially Ca2+), resulting in more serious membrane fouling. The introduction of MB aeration exhibited excellent alleviating effect on HA-inorganic salt fouling, with the normalized flux increased from 19.7% to 37.0%. The interfacial properties of MBs played an important role, which altered the zeta potential distributions of charged particles in HA solution, indicating that MBs adhere the HA complexations. Furthermore, this mitigating effect was limited at high inorganic cations concentration. Overall, MBs could change the potential characteristics of HA complexes, which also be used for other similar membrane fouling alleviation.

Humic acid-mediated transport of a typical soil passivation remediation product (chloropyromorphite) in saturated porous media

Conversion of labile Pb species into chloropyromorphite (CPY) using phosphorus-bearing amendments was considered to be an ideal strategy in soil passivation remediation. However, the fate and transport of CPY in the soil are poorly understood. This study aims to fill the knowledge gap by evaluating the fate and transport of CPY under environmentally relevant conditions of humic acid (HA), pH, electrolyte concentration, and species through the saturated sandy medium. Results showed that bare CPY colloids are basically immobile in sandy porous media while the co-existence of HA made the transport of CPY improved by 30%–93.5%. Facilitated transport of CPY was attributed to the increased stability of CPY and the repulsive interaction between CPY particles and sands due to HA adsorption. The mobility of CPY was also increased with increasing pH from 5.0 to 9.0. When the pH was 9 with a 10 mmol/L NaCl background solution, the stronger energy barrier between CPY and sand led to enhanced transport behavior. The divalent Ca2+ had a more dramatic effect than monovalent Na+ on the aggregation and sedimentation of CPY colloids due to its effectivescreening of the surface charge of CPY and bridging interaction with CPY particles. Derjaguin-Landau-Verwey-Overbeek theory and attachment efficiency calculation indicated that high energy barriers were responsible for the high mobility of CPY colloids, while the retention of CPY in sands was mainly caused by secondary energy minimum and physically straining. The findings of this work can help to evaluate the fate of soil passivation remediation products in natural water and soil.

Alkaline aging significantly affects Mn(II) adsorption capacity of polypropylene microplastics in water environments: Critical roles of natural organic matter and colloidal particles

Most microplastic particles may undergo various aging in water environments. In this work, surface physicochemical properties were firstly compared among pristine polypropylene (PP-pris) microplastics, and two aged ones obtained after pretreated with HCl (PP-acid) and NaOH (PP-alka). When compared with PP-pris and PP-acid, PP-alka had a much stronger Mn(II) adsorption capacity. The results regarding the role of natural organic matter and colloidal particle concentrations on adsorption demonstrated that for water solutions either containing kaolin or not, humic acid (HA) had significantly negative influence on Mn(II) adsorption capacity of PP-alka due to their complexation and competition effects, and its negative influence became enhanced with increasing kaolin concentrations. Besides, established conceptual models of adsorption were applied to comprehensively explore adsorption mechanisms of PP-alka for Mn(II) in the coexistence of HA and kaolin. An important suggestion was that in complicated adsorption-reactor system, great numbers of microplastics-kaolin heteroaggregates might be formed via ion bridging of Mn(II) and/or polymer bridging of HA. So these formed aggregates were possible to re-organize themselves, under pre-set vibration-speed conditions, for achieving a more stable structure. As a consequence, Mn(II) adsorption behaviors would be affected by changes in steric-hindrance effects of HA molecules and surface charge distribution of resultant heteroaggregates.

Uranium(VI) reduction at mineral surfaces by Fe(II): Periodic DFT studies of mechanistic aspects and combined action of Fe(II) with humic acid

U(VI) reduction to the less soluble U(IV) species at mineral surfaces emerges as an attractive approach to remediate uranium contamination. Herein, mechanisms for U(VI) reduction by Fe(II) at orthoclase surfaces and impacts for coexistence of humic acid (HA) are addressed by DFT+U calculations. Fe(II) causes dual H-transfers and transforms U(VI) to U(IV) facilely. Fe(II) shows higher reactivity than HA, and its role is further examined by changing the Fe(II) content (n) that decides the extent of U(VI) reduction: U(IV), U(V) and U(VI) dominate respectively for n = 2, 1, and 0. Mechanisms with co-existence of HA are rather distinct: 1) Spectator. Only one of HA and Fe(II) acts as reducing agent. HA greatly alters Fe(II) reactivity, and vice versa. Fe(II) participates in charge transfers and significantly enhances HA reactivity, while replacement by Mg(II) causes adverse effects; 2) Combined action. Both HA and Fe(II) act as reducing agents, and their combined action results in not only U(IV), but also U(III) and U(II) of lower oxidation states, which recently become a focus of synthesis and hence U(VI) is turned into useful materials. Results rationalize experimental observations available, and also provide significantly new insights about U(VI) reduction, and uranium disposal and recycling.

Photolytic Degradation of Tetracycline in the Presence of Ca(II) and/or Humic Acid

Photolytic degradation of tetracycline (TC) was investigated in mono- and binary solute systems of Ca(II) and humic acid (HA) under UVA light emitting diode (UVA-LED) light irradiation. TC photolysis proceeded via pseudo-first-order reaction kinetics. The presence of Ca(II) significantly accelerated the degradation rate constants of TC, with the highest value at 0.0314 ± 0.0019 min−1 when the Ca(II) concentration was 5.0 mM. The promoted degradation was attributed to complexation of TC with Ca(II), which increased the light absorption. Absorbance and fluorescence measurements revealed that the strong complexation between TC and Ca(II) likely occurred via the C11 and C12 oxygen groups in the phenolic-diketone moiety of TC in nearly neutral solutions. The formation of HA-Ca(II) complex was found in the binary solute system of HA and Ca(II). Thus, the promotional effect of Ca(II) on photolysis was diminished by HA addition. The largest reduction of 32.5% in rate constants was observed with the highest Ca(II) concentration. Scavenger studies revealed that TC could undergo direct photolysis and self-sensitization by 1O2. These results suggest that the coexistence of HA and Ca(II) greatly influences the fate of TC in natural waters, which has important implications for understanding the behavior of antibiotics coexisting with other metal species and ligands.

Novel ball-milled biochar-vermiculite nanocomposites effectively adsorb aqueous As(Ⅴ)

Ball milling was used to fabricate a nanocomposite of 20% hickory biochar (600 °C) and 80% expanded vermiculite (20%-BC/VE). This novel composite adsorbent had much higher removal of As(V) from aqueous solutions than ball-milled biochar and expanded vermiculite. Characterization of these adsorbents showed that the enhanced As(V) adsorption was ascribed to much larger surface area and pore volume (2–6 times), notable changes in crystallinity, activation of cations, and increased functional groups in the nanocomposite compared with the ball-milled products of their pristine counterparts. The As(V) adsorption process by the 20%-BC/VE fitted well with the pseudo-second-order kinetic model (R2= 0.990) and Langmuir isotherm model (R2= 0.989) with a maximum adsorption capacity of 20.1 mg g−1. The 20%-BC/VE best performed at pH about 6. The adsorption efficiency was not sensitive to the competition of NO3−, Cl−, SO42−, as well as the coexistence of humic acid. However, the adsorption capacity for As(V) was significantly reduced by coexisting with PO43−. The 20%-BC/VE composite can potentially serve as a superior low-cost adsorbent for As(V) removal in real-world applications.

The fate and toxicity of Pb-based perovskite nanoparticles on soil bacterial community: Impacts of pH, humic acid, and divalent cations

Pb-based perovskite nanoparticles (PbPNPs) are amongst others used within highly efficient solar cells. PbPNPs can be released into the environment during their production, recycling or waste processing. In this study we investigated the fate and toxicity of PbPNPs on soil bacterial community under simulated natural environmental conditions across a range of pH, humic acid, and divalent cation concentrations. Increasing pH decreased PbPNPs-particle aggregation as well as Pb-ion release. The presence of only humic acid (HA) prevented the aggregation of PbPNPs-particles, whereas the presence of only divalent cations promoted the aggregation of PbPNPs-particles. The amount of Pb-ions released from the PbPNPs-particles was reduced in the presence of either HA or the divalent cations. Results of toxicity testing of PbPNPs by determining the metabolic potential of a bacterial community indicated that increasing pH alleviated particle toxicity. The presence of only HA reduced the toxicity of PbPNPs, while the presence of only divalent cations enhanced the particle toxicity. The coexistence of HA and divalent cations enhanced PbPNPs aggregation and reduced toxicity, with both Pb-ions and the interaction between the PbPNPs-particles and bacterial cells contributing to the toxic effects. Our study emphasized that environmental conditions play important roles that influencing the fate and toxicity of PbPNPs.

Adsorption of two antibiotics on biochar prepared in air-containing atmosphere: Influence of biochar porosity and molecular size of antibiotics

The porous biochar was prepared by pyrolysis of wood at 600–800 °C in the air-containing atmosphere, so as to enhance the biochar's capacity for adsorption of antibiotics from water. The analytical results obtained from N2 adsorption/desorption indicated that air addition in pyrolysis atmosphere improved significantly the biochar's porosity, especially the development of mesopores. The mesoporous biochars showed high adsorption of antibiotics, and the highest adsorption was observed on the A1/5C800 biochar prepared at the air/gas ratio of 1/5 and heat treatment temperature (HTT) of 800 °C. The adsorption isotherm data were well fitted to the Langmuir model, and the maximum adsorptions (Qm) of tetracycline and sulfadiazine on the A1/5C800 sample are 163 and 261 mg/g respectively, which are 18.8 and 52.8 folds of those on the microporous NC800 biochar prepared at the same HTT but in total nitrogen atmosphere. The outstanding performance of mesoporous biochar was linked to the utilization of more inner pore surface for adsorption, which favors the adsorption of smaller-sized sulfadiazine molecules. While the stronger interactions between tetracycline and biochar contributed to the relatively higher adsorption of tetracycline on the microporous biochar. The mesoporous biochar retained most of the adsorption capacity (>50%) in a wide pH range (3.5–10) and with the co-existence of humic acid (10 mg/L). In general, this research provides a simple and green method to enhance the biochar's efficiency as an adsorbent for remediation of water contaminated by antibiotics.

Removal of glyphosate and aminomethylphosphonic acid from synthetic water by nanofiltration

ABSTRACTThe removal of glyphosate and aminomethylphosphonic acid (AMPA) with synthetic water was carried out on a lab-scale nanofiltration unit using two membranes, NFX and NFW. The presence of humic acid and some inorganic matters (CaCl2 and NaCl) was tested in the experiment. The results demonstrate that NFX exhibits better separation performance than NFW. The herbicide filtration is found to have little effect on the permeate flux as compared to transmembrane pressure. Intermediate concentrations of NaCl act positively on foulant separation, and an increment of 3.3–5.4 percentage points in foulant rejection is obtained with the addition of 100 mg/L of NaCl. In Contrast, CaCl2 has negative effect on foulant separation during nanofiltration. Humic acid alone shows little influence on the rejection performance, whereas it is slightly improved in the coexistence of humic acid and CaCl2. The nanofiltration technology proves to be a good approach to treat the problem of pesticide micropollution in a one-step process. This work clearly shows that the composition of the water matrices may influence the efficiency of the nanofiltration process in terms of the separation of the micropollutants.

Simultaneous removal of atrazine and copper using polyacrylic acid-functionalized magnetic ordered mesoporous carbon from water: adsorption mechanism

Highly efficient simultaneous removal of atrazine and Cu(II) was accomplished using synthesized polyacrylic acid-functionalized magnetic ordered mesoporous carbon (P-MMC) as compared to magnetic ordered mesoporous carbon (MMC) and ordered mesoporous carbon (OMC). The mutual effects and interactive mechanism of their adsorption onto P-MMC were investigated systematically by binary, preloading and thermodynamic adsorption procedures. In both binary and preloading systems, the adsorption of atrazine was inhibited to some extent by the presence of Cu(II) because of selective recognition and direct competition, but the presence of atrazine had negligible effect on Cu(II) desorption. With the coexistence of humic acid (0–20 mg L−1), both atrazine and Cu(II) sorption increased slightly in sole and binary systems. With the concentration of coexisting NaCl increasing from 0 to 100 mM, the adsorption capacity for Cu(II) slightly decreased, but as for atrazine adsorption, it decreased at first, and then increased slightly in sole and binary systems. P-MMC was applied to treat real environmental samples, and the sorption capacities for atrazine and Cu(II) in real samples were all more than 91.47% and 96.43% of those in lab ultrapure water, respectively. Finally, comprehensively considering the relatively good renewability and the superior behavior in the application to real water samples, P-MMC has potential in removal of atrazine, Cu(II) and possibly other persistent organic pollutants from wastewater.

Cd(II) Sorption on Montmorillonite-Humic acid-Bacteria Composites.

Soil components (e.g., clays, bacteria and humic substances) are known to produce mineral-organic composites in natural systems. Herein, batch sorption isotherms, isothermal titration calorimetry (ITC), and Cd K-edge EXAFS spectroscopy were applied to investigate the binding characteristics of Cd on montmorillonite(Mont)-humic acid(HA)-bacteria composites. Additive sorption and non-additive Cd(II) sorption behaviour is observed for the binary Mont-bacteria and ternary Mont-HA-bacteria composite, respectively. Specifically, in the ternary composite, the coexistence of HA and bacteria inhibits Cd adsorption, suggesting a “blocking effect” between humic acid and bacterial cells. Large positive entropies (68.1 ~ 114.4 J/mol/K), and linear combination fitting of the EXAFS spectra for Cd adsorbed onto Mont-bacteria and Mont-HA-bacteria composites, demonstrate that Cd is mostly bound to bacterial surface functional groups by forming inner-sphere complexes. All our results together support the assertion that there is a degree of site masking in the ternary clay mineral-humic acid-bacteria composite. Because of this, in the ternary composite, Cd preferentially binds to the higher affinity components-i.e., the bacteria.

Adsorption of Arsenate on Iron Oxides as Influenced by Humic Acids.

Humic acid (HA) and iron oxides (FeOs) commonly coexist, and their interactions alter their ability to adsorb pollutants in the environment. The influences of HA on arsenate [As(V)] adsorption on FeOs were investigated on the preformation of complexes and their coexistence with As(V) in solution. The results indicated that HA could be strongly adsorbed on FeOs, and the adsorption capacity (, mg g HA-C) followed the sequence goethite (7.73) > ferrihydrite (3.14) > hematite (2.25) with a desorption rate <1%. The HA adsorbed existed uniformly on the FeOs surfaces in spot form and did not change the x-ray diffraction (XRD) patterns of FeOs. The formation of FeOs-HA complexes altered As(V) adsorption with a reduced adsorption capacity, prolonged reaction kinetics, and enhanced adsorption strength. The As(V) adsorption on both FeOs and FeOs-HA complexes decreased with increasing pH (2.5-9) or decreasing ionic strength (0.2-0 M). The coexistence of HA in solution linearly decreased the As(V) adsorption on FeOs. Thus, our results demonstrated two impact pathways of HA on As(V) adsorption on FeOs: (i) blockage or occupation in the surface sites of FeOs if HA preformed complexes with FeOs and (ii) a competition to the surface sites of FeOs when HA coexisted with As(V) in the solution.

Enhanced PCBs sorption on biochars as affected by environmental factors: Humic acid and metal cations

Biochar plays an important role in the behaviors of organic pollutants in the soil environment. The role of humic acid (HA) and metal cations on the adsorption affinity of polychlorinated biphenyls (PCBs) to the biochars in an aqueous medium and an extracted solution from a PCBs-contaminated soil was studied using batch experiments. Biochars were produced with pine needles and wheat straw at 350 °C and 550 °C under anaerobic condition. The results showed that the biochars had high adsorption affinity for PCBs. Pine needle chars adsorbed less nonplanar PCBs than planar ones due to dispersive interactions and separation. Coexistence of HA and metal cations increased PCBs sorption on the biochars accounted for HA adsorption and cation complexation. The results will aid in a better understanding of biochar sorption mechanism of contaminants in the environment.

Influences of humic acid, bicarbonate and calcium on Cr(VI) reductive removal by zero-valent iron

The influences of various geochemical constituents, such as humic acid, HCO 3 −, and Ca 2+, on Cr(VI) removal by zero-valent iron (Fe 0) were investigated in a batch setting. The collective impacts of humic acid, HCO 3 −, and Ca 2+ on the Cr(VI) reduction process by Fe 0 appeared to significantly differ from their individual impacts. Humic acid introduced a marginal influence on Fe 0 reactivity toward Cr(VI) reduction, whereas HCO 3 − greatly enhanced Cr(VI) removal by maintaining the solution pH near neutral. The Cr(VI) reduction rate constants ( k obs ) were increased by 37.8% and 78.3%, respectively, with 2 mM and 6 mM HCO 3 − in solutions where humic acid and Ca 2+ were absent. Singly present Ca 2+ did not show a significant impact to Cr(VI) reduction. However, probably due to the formation of passivating CaCO 3, further addition of Ca 2+ to HCO 3 − containing solutions resulted in a decrease of k obs compared to solutions containing HCO 3 − alone. Ca 2+ enhanced humic acid adsorption led to a minor decrease of Cr(VI) reduction rates. In Ca 2+-free solutions, humic acid increased the amount of total dissolved iron to 25 mg/l due to the formation of soluble Fe-humate complexes and stably dispersed fine Fe (oxy)hydroxide colloids, which appeared to suppress iron precipitation. In contrast, the coexistence of humic acid and Ca 2+ significantly promoted the aggregation of Fe (oxy)hydroxides, with which humic acid co-aggregated and co-precipitated. These aggregates would progressively be deposited on Fe 0 surfaces and impose long-term impacts on the permeability of PRBs.

Chromium(VI) Reduction Kinetics by Zero-Valent Iron in Moderately Hard Water with Humic Acid: Iron Dissolution and Humic Acid Adsorption

In zerovalent iron treatment systems, the presence of multiple solution components may impose combined effects that differ from corresponding individual effects. The copresence of humic acid and hardness (Ca2+/Mg2+) was found to influence Cr(VI) reduction by Feo and iron dissolution in a way different from their respective presence in batch kinetics experiments with synthetic groundwater at initial pH 6 and 9.5. Cr(VI) reduction rate constants (k(obs)) were slightly inhibited by humic acid adsorption on iron filings (decreases of 7-9% and 10-12% in the presence of humic acid alone and together with hardness, respectively). The total amount of dissolved Fe steadily increased to 25 mg L(-1) in the presence of humic acid alone because the formation of soluble Fe-humate complexes appeared to suppress iron precipitation. Substantial amounts of soluble and colloidal Fe-humate complexes in groundwater may arouse aesthetic and safety concerns in groundwater use. In contrast, the coexistence of humic acid and Ca2+/Mg2+ significantly promoted aggregation of humic acid and metal hydrolyzed species, as indicated by XPS and TEM analyses, which remained nondissolved (>0.45 microm) in solution. These metal-humate aggregates may impose long-term impacts on PRBs in subsurface settings.