Humic Acid Solution Research Articles

Fabrication of CoFe2O4/Mn3O4 decorated ultrathin graphitic carbon nitride nanosheets membrane for persistent organic pollutants removal: Synergistic performance and mechanisms

Integration of sulfate radicals-based advanced oxidation processes (SR-AOPs) with separation membranes has enthralled considerable attentions because it can remove persistent toxic micropollutants in a low-energy and cost-effective manner. However, fabrication of such an integrated membrane simultaneously with excellent self-cleaning property, catalytic capability and long-term durability remains a challenge. Herein, for the first time, CoFe2O4 (CFO) and Mn3O4 (MO) nanoparticles were anchored on ultrathin graphitic carbon nitride (UCN) nanosheets via a solvothermal method to prepare heterogeneous Fenton-like catalysts (MO/CFOUCN). Systematic characterizations demonstrated the successful preparation of powder catalysts with favorable degradation ability. Notably, the optimal composite catalyst possessed satisfactory degradation (94.5 %) and kinetic rate (0.1367 min−1) for norfloxacin (NOR) within 30 min. Thereafter, an integrated MO/CFO/UCN@P membrane was fabricated by vacuum-assisted filtration of the catalyst on a supporting membrane surface. It was interestingly found that, benefiting from the synergistic effect of in-situ oxidation and membrane filtration, activating peroxymonosulfate (PMS) endowed the membrane with high removal rates (over 91.8 % for tetracycline, bisphenol A, humic acid (HA)) and high permeation flux (332.7 L·m−2·h−1) driven solely by gravity. Significantly, the membrane achieved a flux recovery rate of 91.9 % with the assistance of PMS after filtering HA solution. Furthermore, quenching experiments and electron paramagnetic resonance (EPR) tests confirmed that both radical and nonradical pathways contributed to the mineralization of NOR. Based on the detection of intermediates in the degradation process, potential NOR degradation pathways were proposed. Overall, this study provided new ideas about integrating Fenton-like catalysts with membrane technology for removal of persistent organic pollutants.

Changes in soil organic carbon and its fractions under grassland reclamation in alpine-cold soils, China

Grasslands are the main land use types in China, but their reclamation into croplands can influence the terrestrial carbon and, consequently, impact the global carbon balance. The long-term reclamation of alpine-cold grasslands to croplands are expected to decrease the soil organic carbon (SOC) and its fractions. Here, we conducted an in situ systematic study to measure the SOC and its fraction in soils sampled in an alpine-cold grassland with a gradient of cultivation history from 0 to 40 years. The SOC and its fractions significantly decreased after reclamation (P < 0.05), and the changes in the 0–20 cm soil layer were the greatest among the three sampling depths. After 40 years of reclamation, the SOC content and storage at 0–20 cm decreased by 74 and 60%, respectively. The decreases in the soil labile carbon fractions were more rapid and apparent than the SOC, especially the particular organic carbon (POC), which decreased by 82%. The soil humus carbon fractions also decreased, particularly the humic acid carbon (HAC), which decreased by 81%. The reduction rates of SOC and its fractions gradually decreased with an increase in the cultivation history. Besides, the ratios of the optical densities or absorbances of humic acid (HA) and fulvic acid (FA) solutions at 465 and 665 nm (E<sub>4</sub>/E<sub>6</sub> ratios) and the hue coefficient (Δlog K values), which is the logarithm disparity between the 400 and 600 nm absorbance of the HA (FA) substance, in the solution gradually decreased, indicating that the quality of the soil humus decreased. The reclamation significantly decreased the SOC and its fractions in the alpine-cold soils, which should not be underestimated in the impact on the terrestrial carbon cycles and balance in the long run.

Insight into the Mechanism of Humic Acid’s Dissolution Capacity for Lignin in the Biomass Substrates

The poor solubility of lignin in most solvents causes the biggest challenges in lignin valorization to improve overall biorefinery economics. In this work, humic acid (HA), a natural surfactant, was investigated with respect to its ability to assist in biomass delignification. After obtaining a baseline level of delignification using standard HA, a mechanism of action was proposed in which the lignin removal was driven by hydrophobic interactions. To explore this hypothesis, HA was modified in two ways. One batch was sulfonated to increase HA hydrophilicity, while the other was esterified to increase HA hydrophobicity. Treatment of the same substrates with the modified HA materials revealed that elevated hydrophobicity provided a further increase in the level of delignification. It was found that the solubility of lignin in the HA solution was increased with the enhancement of HA hydrophobicity from 12.2% (S-HA) to 16.8% (E-HA). Therefore, the initial hypothesis was confirmed that HA-derived delignification improvements appear to be a function of hydrophobic interactions. These results should aid further investigation into choosing surfactants (ideally those that are biobased) for utility in biorefinery processes.

Impacts of Calcium Addition on Humic Acid Fouling and the Related Mechanism in Ultrafiltration Process for Water Treatment.

Humic acid (HA) is a major natural organic pollutant widely coexisting with calcium ions (Ca2+) in natural water and wastewater bodies, and the coagulation-ultrafiltration process is the most typical solution for surface water treatment. However, little is known about the influences of Ca2+ on HA fouling in the ultrafiltration process. This study explored the roles of Ca2+ addition in HA fouling and the potential of Ca2+ addition for fouling mitigation in the coagulation-ultrafiltration process. It was found that the filtration flux of HA solution rose when Ca2+ concentration increased from 0 to 5.0 mM, corresponding to the reduction of the hydraulic filtration resistance. However, the proportion and contribution of each resistance component in the total hydraulic filtration resistance have different variation trends with Ca2+ concentration. An increase in Ca2+ addition (0 to 5.0 mM) weakened the role of internal blocking resistance (9.02% to 4.81%) and concentration polarization resistance (50.73% to 32.17%) in the total hydraulic resistance but enhanced membrane surface deposit resistance (33.93% to 44.32%). A series of characterizations and thermodynamic analyses consistently suggest that the enlarged particle size caused by the Ca2+ bridging effect was the main reason for the decreased filtration resistance of the HA solution. This work revealed the impacts of Ca2+ on HA fouling and demonstrated the feasibility to mitigate fouling by adding Ca2+ in the ultrafiltration process to treat HA pollutants.

Active binding sites for ofloxacin resulted from adsorptive fractionation of humic acid on kaolinite

The adsorptive fractionation of humic acid (HA) at the interface between minerals and water can significantly affect the fate of pollutants in water-soil environment. However, the adsorptive fractionation behavior of HA on kaolinite and its effect on the migration of fluoroquinolones (FQs) have not been fully understood. In this study, fluorescence and infrared spectroscopy, combined with two-dimensional correlation analyses, were used to explore the adsorptive fractionation of humic acid (HA) and its effects on ofloxacin adsorption on kaolinite. The results indicated that humic-like, rather than reduced quinone-like and tyrosine-like, was the main adsorptive fractionation component and preferentially bound to the Al–O sites of kaolinite. The adsorption mechanisms of humic-like and tyrosine-like mainly include hydrogen bonds between acidic functional groups and the Si–O or Al–O groups of kaolinite, n-π electron donor-acceptor interaction and electrostatic attraction. At pH 7.0, with addition of 4.0 and 16.0 mg C/L HA in solution, the adsorptive fractionation of HA on kaolinite led to increases in ofloxacin (in zwitterionic form) adsorption capacity by 1.46 and 3.35 mg/g, respectively. The interactions between ofloxacin and the humic-like were mainly hydrogen bonds and electrostatic attraction. Therefore, the influence of adsorptive fractionation of dissolved organic matter on minerals should be considered in estimating FQs environmental behaviors.

Effects of Heating on the Binding of Rare Earth Elements to Humic Acids

In deep underground environments, temperature is one of the key factors affecting the geochemistry behaviors of rare earth elements (REE) in organic-rich fluid. However, the influence of temperature on the interaction between humic acids (HA) and REE is not well known. In the present study, the influence of temperature on the HA–REE-binding behavior was evaluated based on heating experiments of REE-doped HA solution. Lignite-extracted HA and REE-binding experiments were conducted over a temperature range of 20 to 200 °C to quantify HA–REE complexation and the influence of temperature on HA binding sites. Results showed that increasing temperature and decreasing [REE]/[HA] ratio cause an increase of Kd value (the partition coefficient of REE between HA and aqueous solution). During heating KdREE KdREE patterns gradually change from middle REE-enriched-type (M-type) at 20 °C to light and middle REE-enriched-type (L-M-type) at 50 and 100 °C, and to light REE-enriched-type (L-type) at 150 °C and 200 °C. The increase of REE bonded with HA and modifications of KdREE patterns during the thermal treatment may be attributed to the increase of REE-binding sites, especially carboxylic sites, as a consequent of HA decomposition. This study provides a glimpse into the HA–REE-binding behaviors in the deep underground environment, which may shed light on the geochemical characteristics of REE in some organic-bearing rocks, and their changes during the coalification process.

Mineralize complex organic contaminants using only oxygen on dense copper atoms embedded in the walls of carbon nanotubes

In this study, a novel catalytic air oxidation (CAO) process is proposed based on a facilely synthesized nanocomposite catalyst. The catalyst was prepared using Cu single atoms (CuSA) embedded on multiwalled carbon nanotubes (CNTs), denoted as CNTs@CuSA, with mass ratio of CuSA up to 10.02 %. Humic acid (HA) and other typical refractory contaminents were used to investigate the ability of CNTs@CuSA in CAO. The catalysts were pre-excited to cross the energy barrier at 120 °C for 10 min, and then used to catalyze the oxidation of HA at 90 °C in 50 min. The CNTs@CuSA with CuSA mass ratio 8.39 % showed a superior catalytic activity, and 99 % of HA in solution was degraded with 98 % of organic carbon mineralization. Aberration-corrected transmission electron microscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations were applied to detect the mechanism. The results showed that the Cu-N coordination sites on CNT walls and the confinement effect of CNTs activated O2 to produce ·OH radicals, with a high activation efficiency. Moreover, this catalyst remained active after multiple cycles. This result provides a new catalyst to support low-temperature catalytic air oxidation for organic wastewater treatment.

Enhanced permeate flux by air micro-nano bubbles via reducing apparent viscosity during ultrafiltration process.

Micro-nano bubbles (MNBs) play important roles in the reduction of membrane fouling during membrane separation; however, such improvements are always attributed to the reduced concentration polarization on the surface of membranes and little attention has been paid on the variations of physicochemical properties of the feed caused by MNBs. In this study, the separation efficiencies of the feed containing humic acid (HA), bovine serum albumin (BSA), sodium alginate (SA) or dyes can be improved by MNBs during ultrafiltration, and the normalized fluxes can be maximally increased to 139% and 127% in the dead-end and cross-flow modes, respectively in the treatment of HA solution. We further reveal that the decreased apparent viscosity of the feed in the presence of MNBs is the key factor that enhances the normalized flux during ultrafiltration. This study gives new insight on the importance of MNBs in membrane separation and provides valuable clues for other chemical processes.

Development of High Flux Nanocomposite Polyphenylsulfone/Oxidized Multiwalled Carbon Nanotubes Membranes for Ultrafiltration Using the Systems with Critical Solution Temperatures.

The study deals with the investigation of the effect of the modification of polyphenylsulfone (PPSU) flat sheet membranes for ultrafiltration using oxidized multiwalled carbon nanotubes (O-MWCNT) in order to enhance membrane permeability and antifouling performance. The effect of O-MWCNT loading to the PPSU-polyethylene glycol (PEG-20,000, Mn = 20,000 g·mol−1)-polyvinylpyrrolidone (PVP K-30, Mn = 40,000 g·mol−1)-N-methy-2-pyrrolidinone (NMP) colloid systems on the phase state and viscosity was studied. It was found that PPSU-PEG-20,000-PVP K-30-O-MWCNT-NMP colloid systems feature a gel point (T = 35–37 °C) and demixing temperature (T = 127–129 °C) at which two bulk phases are formed and a polymer system delaminates. According to the study of the phase state and viscosity of these colloid systems, a method for the preparation of high flux PPSU membranes is proposed which includes processing of the casting solution at the temperature higher than gel point (40 °C) and using a coagulation bath temperature lower than gel point (25 °C) or lower than demixing temperature (40 °C and 70 °C). Membrane structure, topology and hydrophilic-hydrophobic balance were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle measurements. The effect of coagulation bath temperature and O-MWCNT concentration on the membrane separation and antifouling performance in ultrafiltration of human serum albumin and humic acids solutions was studied. It was found that the modification of PPSU ultrafiltration membranes by O-MWCNTs yielded the formation of a thinner selective layer and hydrophilization of the membrane surface (water contact angle decreased from 53–56° for the reference PPSU membrane down to 33° for the nanocomposite membrane with the addition of 0.19 wt.% O-MWCNT). These changes resulted in the increase in membrane flux (from 203–605 L·m−2·h−1 at transmembrane pressure of 0.1 MPa for the reference membrane up to 512–983 L·m−2·h−1 for nanocomposite membrane with the addition of 0.19 wt.% O-MWCNT depending on coagulation bath temperature) which significantly surpasses the performance of PPSU ultrafiltration membranes reported to date while maintaining a high level of human serum albumin rejection (83–92%). It was revealed that nanocomposite membrane demonstrated better antifouling performance (the flux recovery ratio increased from 47% for the reference PPSU membrane up to 62% for the nanocomposite membrane) and higher total organic carbon removal compared to the reference PPSU membrane in humic acids solution ultrafiltration.

Low-temperature degradation of humic acid via titanium zirconium oxide@copper single-atom activating oxygen: Mechanism and pathways

Humic acid (HA), a refractory organic pollutant, has always been a key obstackle in wastewater treatment (such as biochemical landfill leachate). And catalytic air oxidation is one of the most promising methods to degrade HA efficiently and economically. In this study, a novel high-loading Cu single-atom catalyst (TiZrO4@CuSA) was facilely synthesized using isovolume vacuum impregnation and co-calcination method, and then used to accelerate the oxidation of HA at low temperatures. The TiZrO4@5%CuSA catalytic system showed a superior performance, and 91 % of HA was degraded and 90 % of organic carbon was removed from HA solution within 10 min at 90 °C. Aberration-corrected electron microscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations were applied to reveal the catalytic mechanism of TiZrO 4@5%CuSA. The active center of Cu single-atom co-catalyst with Cu − O coordination sites can quickly transfer electrons to O2 in the water to form O2.−, exhibiting high activation efficiency. Gas chromatography (GC), liquid chromatograph-mass spectrometer (LC-MS), liquid chromatography-organic carbon detection (LC-OCD), and Fourier-transform infrared spectroscopy (FT-IR) spectroscopy provided the results of intermediate products, including 3-phenoxy-benzaldehy, phenylglyoxal, ethanol, acetic acid, butyric acid, and valeric acid, and thus a catalytic degradation pathway of HA was speculated. Based on the new catalyst, a new process can be conceived for efficient and economic removal of HA from HA-containing wastewater.

Durable superhydrophobic polyvinylidene fluoride membranes via facile spray-coating for effective membrane distillation

Membrane wetting and fouling substantially limits application and deployment of membrane distillation process. Designing high-performance superhydrophobic membranes offers an effective solution to solve the challenge. In this work, a highly durable superhydrophobic surface (water contact angle of 170.8 ± 1.3°) was constructed via a facile and rapid spray-coating of extremely hydrophobic SiO2 nanoparticles onto a porous polyvinylidene fluoride (PVDF) substrate for membrane distillation. The superhydrophobic membrane coated by fluorinated SiO2 nanoparticles exhibited a superior physicochemical stability in a wide range of extreme environments (i.e., NaOH, HCl, hot water, rust water, humic acid solution, ultrasonication, and high-speed water scouring). During 8-h continuous membrane distillation desalination experiment, the coated superhydrophobic membrane experienced a consistently stable water vapor flux (ca. 19.1 kg·m−2·h−1) and desalination efficiency (99.99 %). Additionally, such a stable superhydrophobicity endowed the spray-coated PVDF membrane to overcome membrane wetting and fouling during membrane distillation of highly saline solutions containing foulants (i.e., humic acid and rust). Results reported in this study provides a useful concept and strategy in facile construction of robust superhydrophobic membranes via spray-coating for effective membrane distillation.

Improvement in anti‐biofouling property of polyamide thin‐film composite membranes by using copper nanoparticles

AbstractMembrane biofouling is a major problem of the membrane process owing to microbial growth and biofilm on the membrane surface. In this work, a thin‐film composite polyamide membrane was modified with poly(ethylene glycol) and copper nanoparticles. Results demonstrated that surface modification induced changes in membrane‐surface characteristics and enhanced filtration property. The membrane surfaces became more hydrophilic (decreased water contact angle from around 48° to 28°) and had better antibacterial properties than the original ones. The separation property of modified membranes improved, increasing the membrane flux (up to 40%) and antifouling property simultaneously. In particular, the maintained flux ratio (anti‐biofouling property) significantly increased after 4 days of immersing the membranes in Escherichia coli bacterial solution. The membranes were then used for filtration tests with different foulants, such as humic acid and bovine serum albumin solutions.

Confining Nano-Fe3O4 in the Superhydrophilic Membrane Skin Layer to Minimize Internal Fouling.

Membrane surface fouling is often reversible as it can be mitigated by enhancing the crossflow shear force. However, membrane internal fouling is often irreversible and thus more challenging. In this study, we developed a new superhydrophilic poly(vinylidene fluoride) (P-PVDF) membrane confined with nano-Fe3O4 in the top skin layer via reverse filtration to reduce internal fouling. The surface of the P-PVDF membrane confined with nano-Fe3O4 had superwetting properties (water contact angle reaching 0° within 1 s), increased roughness (from 182 to 239 nm), and enhanced water affinity. The Fe3O4@P-PVDF membrane surface showed a thicker and enhanced hydration layer, which prevented foulants from approaching membrane surfaces and pores, thereby improving the rejection. For example, when 50 ppm humic acid (HA) solution was used as the feed, the removal efficiency of the Fe3O4@P-PVDF membrane was ∼67%, while the HA removal of the P-PVDF membrane was only ∼20%. The results from the resistance-in-series model showed that nanoconfinement of Fe3O4 in the top skin layer of the membrane allowed foulants to accumulate on the membrane surface (i.e., surface fouling) rather than within the internal pores (i.e., internal fouling). The filtration results under crossflow fouling and cleaning confirmed that the Fe3O4@P-PVDF membrane had higher surface fouling but it was much more reversible and much lower internal fouling compared with the control membrane. Our fouling analysis offers new insights into mass transfer mechanisms of the membrane with a nanoconfinement-enhanced hydration layer. This study provides an effective strategy to develop membranes with low internal fouling propensities.

Reduction and Elimination of Humic Acid Fouling in Air Sparged Membrane Distillation Using Nanocarbon Immobilized Membrane.

In this paper, we present the treatment of humic acid solution via carbon nanotube immobilized membrane (CNIM) distillation assisted by air sparging (AS). Carbon nanotubes offer excellent hydrophobicity to the modified membrane surface and actively transport water vapor molecules through the membrane to generate higher vapor flux and better rejection of humic acid. The introduction of air sparging in the membrane distillation (MD) system has changed the humic substance fouling by changing the colloidal behavior of the deposits. This modified MD system can sustain a higher run time of separation and has enhanced the evaporation efficiency by 20% more than the regular membrane distillation. The air sparging has reduced the deposition by 30% in weight and offered lesser fouling of membrane surface even after a longer operating cycle. The water vapor flux increased with temperature and decreased as the volumetric concentrating factor (VCF) increased. The mass transfer coefficient was found to be the highest for the air sparged—carbon nanotube immobilized membrane (AS-CNIM) integrated membrane distillation. While the highest change in mass transfer coefficient (MTC) was found for polytetrafluoroethylene (PTFE) membrane with air sparging at 70 °C.

A Hydrogen Bonds-Crosslinked Hydrogels With Self-Healing and Adhesive Properties for Hemostatic.

Hydrogels with adhesive properties have the potential for rapid haemostasis and wound healing in uncontrolled non-pressurized surface bleeding. Herein, a typical hydrogen bond-crosslinked hydrogel with the above functions was constructed by directly mixing solutions of humic acid (HA) and polyvinylpyrrolidone (PVP), in which the HA worked as a crosslinking agent to form hydrogen bonds with the PVP. By altering the concentration of HA, a cluster of stable and uniform hydrogels were prepared within 10 s. The dynamic and reversible nature of the hydrogen bonds gave the HA/PVP complex (HPC) hydrogels injectability and good flexibility, as well as a self-healing ability. Moreover, the numerous functional groups in the hydrogels enhanced the cohesion strength and interaction on the interface between the hydrogel and the substrate, endowing them with good adhesion properties. The unique chemical composition and cross-linking mechanism gave the HPC hydrogel good biocompatibility. Taking advantage of all these features, the HPC hydrogels obtained in this work were broadly applied as haemostatic agents and showed a good therapeutic effect. This work might lead to an improvement in the development of multifunctional non-covalent hydrogels for application to biomaterials.

Species-dependent interaction of Gd-based contrast agents with humic substances

In this study, model experiments regarding species-dependent differences in the interaction of gadolinium-based contrast agents (GBCAs) with humic acids as potential binding partners in the aquatic environment are conducted. For this, the Gd content of different weight fractions obtained via ultracentrifugation of incubation solutions of humic acids with a linear (gadodiamide) and a macrocyclic GBCA (gadobutrol) were analyzed via inductively coupled plasma-mass spectrometry (ICP-MS). This enabled the fractionation of Gd-humic acid adducts and intact GBCAs, since Gd bound to macromolecules would be present in the macromolecular fraction of the filter residue while the low molecular weight Gd species can pass the filter with the filtrate. The Gd concentration in the different weight fractions was determined and a different reaction behavior for the examined GBCAs was observed. 73% of the total Gd amount was present in the macromolecular fraction of the linear GBCA compared to 0.41% in case of the macrocyclic GBCA. Speciation analysis of the macromolecular fractions by size exclusion chromatography-UV-ICP-MS confirmed that Gd-humic acid adducts were formed in case of the linear gadodiamide, but not with the macrocyclic gadobutrol. The findings of this study suggest that humic substance was able to react with the linear GBCA while the macrocyclic GBCA remained stable. Since free Gd ions are toxic, the question remains whether the humic acid bound Gd can be remobilized or if subsequent reactions with other molecules can take place. Furthermore, the persistence of macrocyclic GBCAs towards the humic substances indicates the potential accumulation of these compounds in the environment. However, more experiments regarding other binding partners and long term studies are needed to assess their ultimate fate after their release into the environment.

Catalyst-Free Periodate Activation by Solar Irradiation for Bacterial Disinfection: Performance and Mechanisms.

Periodate (PI)-based advanced oxidation process has recently attracted great attention in the water treatment processes. In this study, solar irradiation was used for PI activation to disinfect waterborne bacteria. The PI/solar irradiation system could inactivate Escherichia coli below the limit of detection (LOD, 10 CFU mL-1) with initial concentrations of 1 × 106, 1 × 107, and 1 × 108 CFU mL-1 within 20, 40, and 100 min, respectively. •O2- and •OH radicals contributed to the bacterial disinfection. These reactive radicals could attack and penetrate the cell membrane, thereby increasing the amount of intracellular reactive oxygen species and destroying the intracellular defense system. The damage of the cell membrane caused the leakage of intracellular K+ and DNA (that could be eventually degraded). Excellent bacterial disinfection performance in PI/solar irradiation systems was achieved in a wide range of solution pH (3-9), with coexisting humic acid (0.1-10 mg L-1) and broad solution ionic strengths (15-600 mM). The PI/solar irradiation system could also efficiently inactivate Gram-positive Bacillus subtilis. Moreover, PI activated by natural sunlight irradiation could inactivate 1 × 107 CFU mL-1 viable E. coli below the LOD in the river and sea waters with a working volume of 1 L in 40 and 50 min, respectively. Clearly, the PI/solar system could be potentially applied to disinfect bacteria in water.

The Influence of Organic Matter Origin on the Chlorine Bulk Decay Coefficient in Reclaimed Water

Using reclaimed water has been increasing to manage water shortages arising due to climate change. Research has been conducted on reclaimed water production, but few studies have investigated the pipe network and supply of reclaimed water. Reclaimed water contains greater amounts of organic matter, nutrients, and ionic substances compared to tap water. Therefore, it is highly likely to cause problems, such as water pollution due to microbial propagation in pipes, and leakage due to pipe corrosion, which interfere with water supply system operations. This study investigated the residual chlorine decay characteristics of chlorine disinfectants applied to a control biofilm in reclaimed water pipe networks. The bulk decay coefficient was compared between reclaimed water and a humic acid solution, and the origin of organic matter was analyzed using fluorescence excitation-emission matrices. The experimental results show that residual chlorine was consumed because protein and amino acid-based organic matter reacted more rapidly with chlorine than natural organic matter, such as humic acid. Moreover, chlorine bulk decay occurred rapidly in reclaimed water when total organic carbon was 3 mg/L or higher. These results confirm that removing organic matter during reclaimed water treatment may affect the management of the pipe network system.

Study on the Flocculation Performance of a Cationic Starch‐Based Flocculant on Humic Substances in Textile Dyeing Wastewater

AbstractDissolved organic matter is one of the difficult problems in the treatment of textile dyeing wastewater, among which humic substances are the most harmful to the environment and human health. Herein, cationic starch‐based flocculants are prepared by free radical polymerization of corn starch (St) and methacryloyloxyethyl trimethyl ammonium chloride (DMC) in a redox‐initiated system of ammonium persulfate and sodium bisulfite. Corn starch‐graft‐poly(methacryloyloxyethyl trimethyl ammonium chloride) is denoted as St‐g‐PDMC. The St‐g‐PDMC is comprehensively characterized in terms of structural (element analysis, Fourier transform infrared, X‐ray diffraction, proton nuclear magnetic resonance spectroscopy), morphological (scanning electron microscopy), and thermal (differential scanning calorimetry) properties. Humic acid (HA) solution is selected to simulate negatively charged dissolved organic matter. The flocculation performance and mechanism of St‐g‐PDMC, cationic polyacrylamide (CPAM), and polymerized aluminum chloride (PAC) are systematically investigated. The experimental results show that St‐g‐PDMC functions mainly through the electric neutralization and bridging effect as the flocculation mechanism, CPAM using its own structure and the colloid formed by PAC through hydrolysis is more in line with the bonded bridging and net roll sweep trapping. The combined formulation of St‐g‐PDMC and PAC shows advantages over a single flocculant in the treatment of textile dyeing wastewater, and its cost is evaluated.

Cyclic voltammetric determination of calcium in water in the presence of natural organic matter (humic acid) and Cu (II) at gold electrode's surface

Calcium and copper are essential for many physiological functions, including enzyme activation and reactive oxygen blockages. However, elevated levels of these metals (separately, synergetically or antagonistically) may result in disorders such as cancer, bone loss, and cardiovascular failure. Foods and water remain the major dietary sources of these metals. Thus, monitoring their levels in foods, water and drinks has become a matter of necessity. This paper reports for the first time the determination of calcium in water in the presence of humic acid (HA) and copper (II) ion (Cu2+) using cyclic voltammetry. The voltammogram displayed a large oxidative potential difference between the two metals (copper existed as a doublet low field while calcium showed a high field potential), enabling a reliable quantification. The detection limits (LODs) of calcium in the copper-free and copper-containing HA solutions are 6.91 × 10−4 and 2.89 × 10−3 mol/L, respectively, suggesting a potential for monitoring calcium in drinking water, soft drinks, wine and dairy products. Also, an LOD of 2.56 × 10−3 mol/L was obtained for Cu2+, implying the potential for simultaneous determination of both metals in aqueous fluids with high degree of reliability.