Although ultrafiltration (UF) membranes are applicable in wastewater and water treatment, most UF membranes are hydrophobic and susceptible to severe fouling by natural organic matter. In this work, polysulfone (PSf) membrane was blended with silicaluminophosphate (SAPO) nanoparticles, SAPO-34, to study the effect of SAPO-34 incorporation in humic acid (HA) fouling mitigation. The casting solution was prepared by blending 5-20 wt% of SAPO-34 nanoparticles into the mixture of PSf, 1-methyl-2-pyrrolidinone and polyvinyl alcohol at 75 °C. All membrane samples were then prepared using the phase inversion method. Blending SAPO-34 zeolite into PSf membranes caused augmentation in surface hydrophilicity and pore size, leading to higher water permeation. In the HA filtration test, mixed matrix membranes (MMMs) with SAPO-34 zeolite showed reduced HA fouling initiated from pore blocking. The MMM with 20 wt% SAPO-34 loading exhibited the highest increment of water permeation (83%) and maintained about 75% of permeate flux after 2.5 h. However, the SAPO-34 fillers agglomerated in the PSf matrix and induced macrovoid formation on the membrane surface when excessive zeolite was added.
The complex nature of natural organic matter (NOM), and the impact of this matter on drinking water quality have necessitated the characterization studies of NOM. A fluorescence technique for the characterization of NOM in Malaysian river water is reported. Water samples from several river sampling sites were collected and concentrated using a low-pressure reverse osmosis (LPROM). Solid phase extraction (SPE) using C18 extraction cartridges were used to fractionate the water samples into humic and non-humic fractions. To differentiate and classify various types of humic substances, fluorescence was applied in emission, excitation and in synchronous-scan modes. A synchronous spectral profile was found to be able to differentiate humic and fulvic acids better than the emission or excitation spectra. Synchronous excitation spectra showed different spectral patterns for the water samples due to different origin. All water samples showed the presence of both fulvic and humic acids.
The removal of concentrated colour (around 5039 Pt-Co) and chemical oxygen demand (COD; around 4142 mg L-1) from matured landfill leachate through a novel combination of humic acid extraction and coagulation with natural oil palm trunk starch (OPTS) was investigated in this study. Central composite design from response surface methodology of Design Expert-10 software executed the experimental design to correlate experimental factors with desired responses. Analysis of variance developed the quadratic model for four factors (e.g. coagulant dosage, slow mixing speed and time and centrifugation duration) and two responses (% removal of colour, COD). The model confirmed the highest colour (84.96%) and COD (48.84%) removal with a desirability function of 0.836 at the optimum condition of 1.68 g L-1 coagulant dose, 19.11 rpm slow mixing speed, 16.43 minutes for mixing time and 35.75 minutes for centrifugation duration. Better results of correlation coefficient (R2 = 0.98 and 0.96) and predicted R2 (0.94 and 0.84) indicates the model significance. Electron microscopic images display the amalgamation of flocs through bridging. Fourier transforms infrared spectra confirmed the existence of selected organic groups in OPTS, which eventually signifies the applied method.
Tubers of safed musli (Chlorophytum borivilianum) were immersed in three different concentrations of gibberellic acid (GA3) or humic acid (HA) prior to planting. The highest concentration of GA3 (20 mg L(-1)) and all concentrations of HA (5, 10, and 15%) appeared to hasten tuber sprouting and promote uniform sprouting pattern. The use of 20 mg L(-1) GA3 or 15% HA successfully improved sprouting and mean sprouting time. Safed musli growth and development was improved through the increase in the number of leaves, total leaf area, leaf area index, and total fibrous root length. This directly influenced the number of new tubers formed. The use of 20 mg L(-1) GA3 or 15% HA gave similar response with nonsignificant difference among them. However, due to the cost of production, the result from this study suggests that 15% HA should be used to obtain improved sprouting percentage, homogeneous stand establishment, efficient plant growth and development, and increased yield of safed musli.
Production of agriculture and timber commodities leads generation of enormous quantity of wastes. Improper disposal of these agroindustrial wastes pollutes the environment. This problem could be reduced by adding value to them. Therefore, a study was carried out to analyse and compare the nutrients content of RS, RH, SD, and EFB of composts and crude humic substances; furthermore, their effect on growth, dry matter production, and nutrient uptake for Zea mays L., and selected soil chemical properties were evaluated. Standard procedures were used to analyze humic acids (HA), crude fulvic acids (CFA), crude humin (CH), soil, dry matter production and nutrient uptake. Sawdust and RS compost matured at 42 and 47 days, respectively, while RH and EFB composts were less matured at 49th day of composting. Rice straw compost had higher ash, N, P, CEC, HA, K, and Fe contents with lower organic matter, total organic carbon, and C/N and C/P ratios. The HA of sawdust compost showed higher carbon, carboxylic, K, and Ca contents compared to those of RS, RH, and EFB. Crude FA of RS compost showed highest pH, total K, Ca, Mg, and Na contents. Crude humin from RS compost had higher contents of ash, N, P, and CEC. Rice straw was superior in compost, CFA, and CH, while sawdust compost was superior in HA. Application of sawdust compost significantly increased maize plants' diameter, height, dry matter production, N, P, and cations uptake. It also reduced N, P, and K based chemical fertilizer use by 90%. Application of CH and the composts evaluated in this study could be used as an alternative for chemical fertilizers in maize cultivation.
Agricultural waste, such as sago waste (SW), is one of the sources of pollution to streams and rivers in Sarawak, particularly those situated near sago processing plants. In addition, unbalanced and excessive use of chemical fertilizers can cause soil and water pollution. Humic substances can be used as organic fertilizers, which reduce pollution. The objectives of this study were to produce K- and ammonium-based organic fertilizer from composted SW and to determine the efficiency of the organic-based fertilizer produced. Humic substances were isolated using standard procedures. Liquid fertilizers were formulated except for T2 (NPK fertilizer), which was in solid form. There were six treatments with three replications. Organic fertilizers were applied to soil in pots on the 10th day after sowing (DAS), but on the 28th DAS, only plants of T2 were fertilized. The plant samples were harvested on the 57th DAS during the tassel stage. The dry matter of plant parts (leaves, stems, and roots) were determined and analyzed for N, P, and K using standard procedures. Soil of every treatment was also analyzed for exchangeable K, Ca, Mg, and Na, organic matter, organic carbon, available P, pH, total N, P, nitrate and ammonium contents using standard procedures. Treatments with humin (T5 and T6) showed remarkable results on dry matter production; N, P, and K contents; their uptake; as well as their use efficiency by maize. The inclusion of humin might have loosened the soil and increased the soil porosity, hence the better growth of the plants. Humin plus inorganic fertilizer provided additional nutrients for the plants. The addition of inorganic fertilizer into compost is a combination of quick and slow release sources, which supplies N throughout the crop growth period. Common fertilization by surface application of T2 without any additives (acidic and high CEC materials) causes N and K to be easily lost. High Ca in the soil may have reacted with phosphate from fertilizer to form Ca phosphate, an insoluble compound of phosphate that is generally not available to plants, especially roots. Mixing soil with humin produced from composted SW before application of fertilizers (T5 and T6) significantly increased maize dry matter production and nutrient use efficiency. Additionally, this practice does not only improve N, P, and K use efficiency, but it also helps to reduce the use of N-, P-, and K-based fertilizers by 50%.
Due to the 1997/98 haze problem in South-East Asia and the increasing need for sustainable food production and development, the usual management of crop residues (including pineapple wastes) through burning is prohibited. As a result, the need for alternative uses of pineapple wastes in pineapple production has been emphasized. This study investigated an environmentally friendly means of recycling pineapple leaves for agricultural use. Pineapple leaves were shredded and composted in a composting drum for 30 days. Part of the shredded leaves was ashed in a muffle furnace for 4 h. Humic acid (HA), K-fulvate, and K in HA and compost were analyzed using standard procedures. An ash to water ratio of 1:7 was used to extract 0.1 molar (M) KOH from the shredded leaves. The 0.1 M KOH contained 50% K and was able to extract 20% HA from the composted pineapple leaves. Percent K in the fulvate using 0.1 M KOH was 43. Besides serving as a foliar spray (supplement soil application K fertilizers), source of K for freshwater fish (e.g., tilapia), the HA produced can be used as a soil conditioner. Studies show that between 0.05-0.01 g of HA per kg soil retards runoff by 36% in sandy and sandy loam soils. The K-fulvate can be used as a fluid fertilizer. In addition, the pH of 2 of the K-fulvate suggests it could be used to dissolve phosphate rocks, particularly those in the arid regions where high soil pH does not facilitate the dissolution of these important rocks that serve as one of the sources of phosphorus fertilizer in agriculture.
In this paper, ambient total suspended particulates (TSP) with a focus on humic-like substances (HULIS) are characterized based on intensive ground-based field samplings collected in Malaysia during non-haze and haze periods caused by peatland fires on the Indonesian island of Sumatra. Furthermore, concentrations of water-soluble organic carbon (WSOC) and carbon content of HULIS (HULIS-C) were determined, and fluorescence spectra of the HULIS samples were recorded by excitation emission matrix (EEM) fluorescence spectroscopy. The concentrations of WSOC and HULIS-C over the entire period ranged from 4.1 to 24 and 1.3 to 18 μgC m-3, respectively. The concentrations of WSOC and HULIS-C during the peatland fire-induced strong haze periods were over 4.3 and 6.1 times higher, respectively, than the average values recorded during the non-haze periods. Even during the light haze periods, the concentrations of WSOC and HULIS-C were significantly higher than their averages during the non-haze periods. These results indicate that peatland fires induce high concentrations of WSOC, particularly HULIS-C, in ambient TSP at receptor sites. EEM fluorescence spectra identified fulvic-like fluorophores at the highest intensity level in the EEM fluorescence spectra of the haze samples. A peak at excitation/emission (Ex/Em) ≈ (290-330)/(375-425) nm is also observed at high intensity, though this peak is normally associated with marine humic-like fluorophores. It is shown that a peak at Ex/Em ≈ (290-330)/(375-425) nm is not derived from marine sources only; furthermore, peatland fires are shown to be important contributors to HULIS around this peak.
Functional surfaces and polymers with branched structures have a major impact on physicochemical properties and performance of membrane materials. With the aim of greener approach for enhancement of permeation, fouling resistance and detrimental heavy metal ion rejection capacity of polyetherimide membrane, novel grafting of poly (4-styrenesulfonate) brushes on low cost, natural bentonite was carried out via distillation-precipitation polymerisation method and employed as a performance modifier. It has been demonstrated that, modified bentonite clay exhibited significant improvement in the hydrophilicity, porosity, and water uptake capacity with 3 wt. % of additive dosage. SEM and AFM analysis showed the increase in macrovoides and surface roughness with increased additive concentration. Moreover, the inclusion of modified bentonite displayed an increase in permeation rate and high anti-irreversible fouling properties with reversible fouling ratio of 75.6%. The humic acid rejection study revealed that, PEM-3 membrane having rejection efficiency up to 87.6% and foulants can be easily removed by simple hydraulic cleaning. Further, nanocomposite membranes can be significantly employed for the removal of hazardous heavy metal ions with a rejection rate of 80% and its tentative mechanism was discussed. Conspicuously, bentonite clay-bearing poly (4-styrenesulfonate) brushes are having a synergistic effect on physicochemical properties of nanocomposite membrane to enhance the performance in real field applications.
This study examines the influence of humic acids (HA) on adsorption of radium (Ra) ions onto coir pith (CP) in aqueous solution. The adsorption behaviours of Ra ions onto CP under the influence of HA in aqueous solution were investigated in the series of batch mode adsorption experiments. The effects of various experimental conditions such as pH, contact time, adsorbent dosage and initial concentration of Ra ions have been studied. The results revealed that the presence of HA in aqueous solution enhanced the adsorption of Ra ions onto CP. The adsorption results showed that the percentage of Ra adsorbed was increased with an increase in the pH or alkalinity of aqueous solutions. Time dependence of the batch studies showed that a contact time of one day was sufficient to reach equilibrium. The result also showed that there was no significant difference on the effect of adsorbent dose on adsorption of radium onto CP. It was shown that the equilibrium data could be fitted by Freundlich equation.
The removal of impurities from water or wastewater by the membrane filtration process has become more reliable due to good hydraulic performance and high permeate quality. The filterability of the membrane can be improved by having a material with a specific pore structure and good hydrophilic properties. This work aims at preparing a polyvinylidene fluoride (PVDF) membrane incorporated with phospholipid in the form of a 2-methacryloyloxyethyl phosphorylcholine, polymeric additive in the form of polyvinylpyrrolidone, and its combination with inorganic nanosilica from a renewable source derived from bagasse. The resulting membrane morphologies were analyzed by using scanning electron microscopy. Furthermore, atomic force microscopy was performed to analyze the membrane surface roughness. The chemical compositions of the resulting membranes were identified using Fourier transform infrared. A lab-scale cross-flow filtration system module was used to evaluate the membrane's hydraulic and separation performance by the filtration of humic acid (HA) solution as the model contaminant. Results showed that the additives improved the membrane surface hydrophilicity. All modified membranes also showed up to five times higher water permeability than the pristine PVDF, thanks to the improved structure. Additionally, all membrane samples showed HA rejections of 75-90%.
In this study, the antifouling properties of polyethersulfone (PES) membranes blended with different amounts of ZnO nanoparticles and a fixed ratio of N-methyl-2-pyrrolidone (NMP)-acetone mixture as a solvent were investigated. The properties and performance of the fabricated membranes were examined in terms of hydrophilicity, porosity, pore size, surface and cross-section image using scanning electron microscopy (SEM), surface roughness using atomic force microscopy (AFM), pure water flux, and humic acid filtration. Addition of ZnO as expected was found to improve the hydrophilicity as well as to encourage pore formation. However, the agglomeration of ZnO at a higher concentration cannot be avoided even when dissolved in a mixed solvent. The presence of highly volatile acetone contributed to the tight skin layer of the membrane which shows remarkable antifouling ability with the highest flux recovery ratio and negligible irreversible fouling. ZnO NPs in acetone/NMP mixed solvent shows an improvement in flux and rejection, but, the fouling resistance was moderate compared to the pristine membrane.
Natural organic matters (NOMs) have been found to be the major foulant in the application of ultrafiltration (UF) for treating surface water. Against this background, although hydrophilicity has been demonstrated to aid fouling mitigation, other parameters such as membrane surface morphology may contribute equally to improved fouling resistance. In this work, with humic acid solution as the model substance, the effects of titanium dioxides (TiO2) types (PC-20, P25, and X500) on membrane anti-fouling and defouling properties were comparatively analysed. The aims are (1) to determine the correlation between membrane surface morphology and membrane fouling and (2) to investigate the anti-fouling and UV-cleaning abilities of PVDF/TiO2 mixed-matrix membranes with different membrane topographies and surface energy conditions. The mixed-matrix membrane with P25 TiO2 exhibited the most significant UV-defouling ability, with a high irreversible flux recovery ratio (IFRR(UV)) of 16.56 after 6 h of UV irradiation, whereas that with X500 TiO2 exhibited both superior anti-fouling and defouling properties due to its smoother surface and its highly reactive surface layer.
Effect of washing solutions’ pH on removal of radium-226 from radium-contaminated soil using distilled water and humic acid extracted from Malaysian peat soil was studied by a single batch washing method. The study encompassed the extraction of humic acid and the washing of radium-contaminated soil using distilled water and humic acid solutions of varying pH in the range between 3 to 11. Activity of radium-226 was determined by gamma spectrometer. In the pH range studied, the removal of radium-226 was greater when humic acid solutions were used compared to distilled water. Greater removal of radium-226 was obtained using highly basic pH washing solutions compared to neutral and acidic solutions.
Despite recent interest in transforming biomass into bio-oil and syngas, there is inadequate information on the compatibility of byproducts (e.g., biochar) with agriculture and water purification infrastructures. A pyrolysis at 300°C yields efficient production of biochar, and its physicochemical properties can be improved by chemical activation, resulting in a suitable adsorbent for the removal of natural organic matter (NOM), including hydrophobic and hydrophilic substances, such as humic acids (HA) and tannic acids (TA), respectively. In this study, the adsorption affinities of different HA and TA combinations in NOM solutions were evaluated, and higher adsorption affinity of TA onto activated biochar (AB) produced in the laboratory was observed due to its superior chemisorption tendencies and size-exclusion effects compared with that of HA, whereas hydrophobic interactions between adsorbent and adsorbate were deficient. Assessment of the AB role in an adsorption-coagulation hybrid system as nuclei for coagulation in the presence of aluminum sulfate (alum) showed a synergistic effect in a HA-dominated NOM solution. An AB-alum hybrid system with a high proportion of HA in the NOM solution may be applicable as an end-of-pipe solution.
Home composting can be an effective way to reduce the volume of municipal solid waste. The aim of this study is to evaluate the effect of Effective Microorganism™ (EM) for the home scale co-composting of food waste, rice bran and dried leaves. A general consensus is lacking regarding the efficiency of inoculation composting. Home scale composting was carried out with and without EM (control) to identify the roles of EM. The composting parameters for both trials showed a similar trend of changes during the decomposition. As assayed by Fourier Transform Infrared Spectroscopy (FTIR), the functional group of humic acid was initially dominated by aliphatic structure but was dominated by the aromatic in the final compost. The EM compost has a sharper peak of aromatic CC bond presenting a better degree of humification. Compost with EM achieved a slightly higher temperature at the early stage, with foul odour suppressed, enhanced humification process and a greater fat reduction (73%). No significant difference was found for the final composts inoculated with and without EM. The properties included pH (∼7), electric conductivity (∼2), carbon-to-nitrogen ratio (C: N 100%), humic acid content (4.5-4.8%) and pathogen content (no Salmonella, <1000 Most Probable Number/g E. coli). All samples were well matured within 2 months. The potassium and phosphate contents in both cases were similar however the EM compost has a higher nitrogen content (+1.5%). The overall results suggested the positive effect provided by EM notably in odour control and humification.
A new sample pre-treatment technique termed cone-shaped membrane liquid phase microextraction (CSM-LPME) was developed and combined with micro-liquid chromatography (micro-LC) for the determination of selected pesticides in water samples. Four pesticides (hexaconazole, procymidone, quinalphos and vinclozolin) were considered as target analytes. Several important extraction parameters such as types of extraction solvent, agitation rate, pH value, total exposure time and effect of salt and humic acids were optimized. Enrichment factors of > 50 folds were easily achieved within 20 min of extraction. The analytical data demonstrated relative standard deviations for the reproducibility of the optimized CSM-LPME method ranging from 6.3 to 7.5%. The correlation coefficients of the calibration curves were at least 0.9995 across a concentration range of 2-100 microg/L. The detection limits for all the analytes were found to be in the range of 1.1-1.9 microg/L.
Effect of AP+, Ca", Cu" and Fe" on the removal of radium-226 from radium-contaminated soil using humic acid extracted from a Malaysian peat soil was investigated using batch washing method. The concentration of Al,+ Ca", Cu" and Fe" ranged from 0 to 100 ppm. The radioactivity concentration of radium-226 was determined by gamma spectrometer. The removal of radium-226 was enhanced in the presence of AP' with concentration between 20 - 60 ppm. Meanwhile, higher concentration of 80 - 100 ppm did not lead to further increase in the removal of radium-226. The removal of radium-226 was decreased in the presence of Ca" and Cu". In the presence of Fe" with concentration between 20 - 60 ppm, decrease in the removal of radium-226 was also observed. Nevertheless, at concentration between 80 - 100 ppm, the presence of Fe" led to increase in the removal of radium-226.
Nanostructured photoanodes were prepared via a novel combination of titanium dioxide (TiO2) nanoparticles and mesoporous carbon (C). Four different photoanodes were synthesized by sol-gel spin coating onto a glassy substrate of fluorine-doped tin oxide. The photocatalytic activities of TiO2, TiO2/C/TiO2, TiO2/C/C/TiO2, and TiO2/C/TiO2/C/TiO2 photoanodes were evaluated by exposing the synthesized photoanodes to UV-visible light. The photocurrent density observed in these photoanodes confirmed that an additional layer of mesoporous carbon could successfully increase the photocurrent density. The highest photocurrent density of ~1.022 mA cm(-2) at 1 V/saturated calomel electrode was achieved with TiO2/C/C/TiO2 under an illumination intensity of 100 mW cm(-2) from a solar simulator. The highest value of surface roughness was measured for a TiO2/C/C/TiO2 combination owing to the presence of two continuous layers of mesoporous carbon. The resulting films had a thickness ranging from 1.605 µm to 5.165 µm after the calcination process. The presence of double-layer mesoporous carbon resulted in a 20% increase in the photocurrent density compared with the TiO2/C/TiO2 combination when only a single mesoporous carbon layer was employed. The improved performance of these photoanodes can be attributed to the enhanced porosity and increased void space due to the presence of mesoporous carbon. For the first time, it has been demonstrated here that the photoelectrochemical performance of TiO2 can be improved by integrating several layers of mesoporous carbon. Comparison of the rate of removal of humic acid by the prepared photoanodes showed that the highest performance from TiO2/C/C/TiO2 was due to the highest photocurrent density generated. Therefore, this study showed that optimizing the sequence of mesoporous carbon layers can be a viable and inexpensive method for enhanced humic acid removal.
Ultrafiltration grade polysulfone-based mixed matrix membranes (MMMs) incorporated with two-dimensional boron nitride nanosheet (BNNS) was prepared via phase inversion method. The amount of BN incorporated was varied and the influence on membrane morphology, contact angle, surface charge, as well as water permeability and humic acid rejection were investigated. Results revealed that the addition of BN to the membrane matrix resulted in profound increase in water permeability (almost tripled to that of neat PSf) and humic acid rejection due to the increase in pore size and surface negative charge. Beyond the morphological changes imparted by the inclusion of BNNS, we postulated that the presence of BNNS within the membrane matrix also contribute to the enhancement in flux and rejection based on surface-slip and selective interlayer transport. Despite the favourable augmentation of water transport and filtration performance, the MMMs suffered with fouling problem due to the entrapment of foulant within the enlarged pores and the membrane valleys. Its inherent adsorptive character could be a disadvantage when utilized as membrane filler.