Preparation and Properties of a Chitosan–Hyaluronic Acid-Polypyrrole Conductive Hydrogel Catalyzed by Laccase

Electro conductive hydrogels, consisting of chitosan (CS), hyaluronic acid (HA), and polypyrrole (PPy), were prepared via an in situ enzymic polymerization of pyrrole in the CS–HA hydrogel, using laccase as the catalyst. This CS–HA–PPy composite hydrogel showed good conductivity. The chemical structure and morphology of this conductive hydrogel were studied by Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction technique. For CS–HA–PPy and CH–HA hydrogel, the temperature at which fastest decomposition occurred was 260 and 244 °C, respectively. That means the thermal stability of CS–HA–PPy is better than CS–HA hydrogel. The conductive hydrogel also showed excellent swelling and deswelling behaviors.     

Study of the organic matter evolution during municipal solid waste composting aimed at identifying suitable parameters for the evaluation of compost maturity

In this work the composting process of municipal solid wastes was studied in order to characterize the transformations of organic matter, particularly humic acid (HA). A composting process, lasting three months, was monitored by chemical methods; the following parameters were measured: water-soluble carbon concentration (WSC) and humic substances content (humic and fulvic acid (FA)). The effects of humification on the molecular structure of humic acid (HA) were also evaluated by Fourier transform infrared (FT-IR) and (13)C NMR spectroscopy. WSC concentration rapidly increased reaching a maximum at day-14 of the composting process and then declined. The humic and fulvic acid content (HA and FA, respectively) slightly increased during the process. The FT-IR and (13)C NMR spectra of HA indicate a high rate of change in structure during composting. The groups containing aromatic and carboxylic C increased, while polysaccharides and other aliphatic structures degraded during composting, resulting in HA structures of higher aromaticity. Therefore, spectrometric measurements could provide information significantly correlated to conventional chemical parameters of compost maturity.     

Characterization and removal of dissolved organic matter (DOM) from landfill leachate rejected by nanofiltration

Dissolved organic matter (DOM) from wastewater rejected by nanofiltration from a landfill leachate treatment plant was fractionated into humic acid (HA), fulvic acid (FA) and hydrophilic (HyI) fractions. It was found that humic substances (HA and FA) composed 75% of the total dissolved organic carbon (DOC) concentration of the DOM, with an average molecular weight of about 1000 Da. Elemental analysis, infrared spectroscopy, UV-visible spectroscopy and acid-base titration observations showed that the HA and FA of the DOM exhibited lower fractions of condensed aromatic functional groups but larger fractions of acidic groups compared with other aquatic DOMs. The properties of HA and FA were similar, but HA exhibited more complete humification, while the HyI fraction had more acidic groups. An aminated polymeric adsorbent NDA-8 was used to adsorb the DOM in the wastewater along with primary coagulation. Results of bench-scale experiments indicated that the treatment process could effectively remove the DOM and heavy metals while desorption liquid was 10 times more condensed than raw wastewater. Results of desorption and reproducibility tests consolidated the strong application potential of this treatment process as an advanced landfill leachate treatment technology.     

Enhancement of Sedimentation Velocity of Heavy Metals Loaded Hydroxyapatite Using Chitosan Extracted from Shrimp Waste

In this study, synthesize hydroxyapatite (HA) suspensions sedimentation was used after usual terms as support for adsorption of heavy metals ions. Thus, the effectiveness of chitosan, produced from shrimp waste, in the flocculation of turbid suspensions resulting from the treatment of water contaminated with heavy metals was studied by adsorption on HA. Different particles sizes of HA were mainly controlled in this work (an average of granule size ranging from 1.6 to 63 μm). The results of Cu²⁺ and Zn²⁺ adsorption on HA showed relatively fast kinetics, with removal extent of 88–95 % by varying the initial total metal concentration. High removal rates were obtained for Cu²⁺. Chitosan was found to be able to eliminate by flocculation more than 98 % of turbid suspensions generated by metals adsorption on HA after only 30 min of sedimentation. Effects of pH and dose of chitosan on the coagulation–flocculation process were also studied. The optimal dose of chitosan was found between 0.2 and 2 mg/L which corresponds to an optimal pH ranging from 6 to 7.     

Characterization of humic and fulvic acids extracted from landfill by elemental composition, 13C CP/MAS NMR and TMAH-Py-GC/MS

Humic acid (HA) and fulvic acid (FA) extracted from landfills at different landfill ages were characterized by elemental composition, (13)C CP/MAS NMR, and TMAH-Py-GC/MS. The elemental composition analysis revealed high O/C and low H/C ratios in the FA, indicating a high proportion of O-alkyl and carboxylic acids in the FA. The analytical results of (13)C CP/MAS NMR suggested that there were more oxygenated aliphatic carbons and fewer aromatic carbons in FA than in HA. The Py-GC/MS products showed that the HA and FA extracted from the refuse in the landfill were mainly composed of various lignin-derived compounds. Oxidized aromatic acid derivatives originated from the oxidation of side-chains of lignin-like compounds, and this process played a significant role in the process of HA and FA formation in the landfill. All of the results demonstrated that the degree of humification increased with landfill age.     

Fluorescence excitation-emission matrix combined with regional integration analysis to characterize the composition and transformation of humic and fulvic acids from landfill at different stabilization stages

Fluorescence excitation-emission matrix spectroscopy (EEMs) combined with fluorescence regional integration (FRI) analysis was used to investigate the composition and transformation of humic acid (HA) and fulvic acid (FA) from landfill. The EEMs of HAs at different landfill ages were characterized by two typical fluorescence chromophores with Ex/Em pairs at Ex = 420-470 nm/Em = 490-530 nm and Ex = 345-375 nm/Em = 450-465 nm. EEMs of FA were featured by other two distinctly different fluorophores with Ex/Em pairs at Ex = 315-335 nm/Em = 420-440 nm and Ex = 255-275 nm/Em = 425-455 nm. The results show that HA extracted from the refuse disposed in the year of 1989 was formed by connecting small-condensed aromatic structures with protein-like chains. Compared with HA extracted from the refuse disposed in the year of 1992, HA extracted from the refuse of 1996 had a higher fluorescence intensity and lower r_(B,A) (the ratio of the fluorescence intensities of peak B and peak A) value. It contained low molar mass components, low aromatic condensation degree, and more easily oxidized substituents. This indicates that the landfill time strongly affects the EEMs characteristics of HA, and that the humification degree of HA increases with the landfill time. A red shift to a longer wavelength region and an increase of fluorescence intensity were observed when the concentration of HA was increased, suggesting that concentration had a great influence on the fluorescence characteristics of HAs. pH (2-12) also had significant effects on the fluorescence intensity, although it exerted no effect on the peak position of fluorescence of HA and FA. The results of FRI show that increasing concentration lead to more interactions among various structure components and that small molecular weight units tend to aggregate or be masked into more complicated and larger structures. The pH influence on the fluorescence intensity of HA seems mainly through molecular configuration, while the fluorescence intensity change with pH may be due to various substituents of FA.     

催化臭氧氧化对生化尾水中典型有机物的去除特性

系统深入地分析了Fe-Ce/AC催化臭氧氧化对化工园区污水厂生化尾水中典型有机物的去除特性。与单独臭氧氧化相比,催化臭氧氧化可将TOC去除率从7.89%大幅提升至17.54%。120 min时UV_(254)和特征紫外吸光度(SUVA)的去除率分别高达66.80%和59.73%,证明了催化臭氧氧化可有效去除含共轭结构或芳环结构的不饱和有机物。催化臭氧氧化对生化尾水中腐殖酸类(HA)、溶解性微生物产物类(SMP)和疏水性腐殖酸类(HOA)3种荧光组分的去除过程均符合一级动力学模型,且由一级动力学速率常数可知,与生化尾水色度直接相关的HA和HOA被优先去除。40 min时HA、SMP和HOA的去除率即高达95.24%、93.21%和92.96%。     

羟胺强化Fenton反应降解水中氯酚

针对传统Fenton体系Fe（Ⅲ）累积和pH适用范围过窄等缺点,采用羟胺（HA）强化的HA-Fenton体系,以对氯苯酚（4-CP）为目标污染物进行降解实验,考察了Fe（Ⅱ）投加量、H2O2投加量、HA投加量和溶液pH等工艺条件对4-CP去除率的影响。实验结果表明：HA-Fenton体系适用于酸性和弱酸性条件,最佳pH范围为3.0~4.0;在溶液pH为3.0、Fe（Ⅱ）投加量为5.0 μmol/L、H2O2投加量为0.4 mmol/L、HA投加量为0.20 mmol/L的最适条件下,反应10 min, 4-CP去除率达64.25 %。     

Poly(vinyl alcohol-co-lactic acid)/Hydroxyapatite Composites: Synthesis and Characterization

There is a wide range of applications where calcium phosphate and hydroxyapatite (HA) are used as biomaterials, e.g. as synthetic bone grafts, coating on metal prostheses (like hip endoprostheses or dental implants) and drug carriers. In the study, the design and synthesis of composites based on poly(vinyl alcohol-co-lactic acid)/hydroxyapatite (PVA-co-LA/HA) with potential for biomedical applications, they are presented. The hydroxyapatite particles were surface-grafted with l(+)-lactic acid in the presence of manganese acetate as catalyst, resulting in modified hydroxyapatite (HA_m) with improved capacity of bonding, respectively for the preparation of the composite based on PVA-co-LA/HA_m. FT-IR spectra further confirmed the existence of PLA polymer on the surface of HA particles. In synthesis of PVA-co-LA copolymer the different molar ratios PVA/LA (2/1, 1/1, 1/2), toluene/water: 1/2 (as azeotrope solvent mixture) and manganese acetate as catalyst, were used. The composite materials were synthesized in situ with 10 wt% HA, and respectively HA_m (reported to PVA and lactic acid components). The composite materials were characterized by FTIR spectroscopy, thermal analyses (DSC, DTG), ¹H-NMR spectroscopy, particle size distribution and zeta potential.     

Carbon speciation in municipal solid waste incinerator (MSWI) bottom ash in relation to facilitated metal leaching

The release of inorganic and organic contaminants from municipal solid waste incinerator (MSWI) bottom ash is controlled to a large extent by the release of dissolved organic carbon (DOC), and in particular by the reactive humic (HA) and fulvic acids (FA) subfractions of DOC. The properties of organic matter contributing to the release of DOC, HA and FA are, therefore, important for environmental risk assessment. In this study we have quantitatively measured the carbon speciation, and its relation with the leaching of Cu, in three fresh and carbonated MSWI bottom ash samples. Results show that up to only 25% of loss on ignition (LOI) consists of organic carbon (OC), while about 17% of OC in the three samples consists of HA and FA. Up to 50% of DOC in MSWI bottom ash leachates was identified as fulvic acid (FA). This value is substantially higher than previously estimated for these MSWI bottom ash samples and is consistent with the higher recovery of the new method that was applied. The results of this study imply that methods focusing on specific carbon fractions are more appropriate for assessment of environmentally relevant organic carbon species than the measurement of LOI.     

Modification of soil humic matter after 4 years of compost application

Two soil plots, 1 ha each, were amended yearly for 4 years, respectively, with 35.8 and 71.6 Mg ha(-1) yr(-1) of mature compost (CM) obtained from food and vegetable residues. The compost, amended soils, and a control soil plot after 4 years (S4), were analyzed for humin (HUC), humic acid (HAC), fulvic acid (FAC), and non-humic carbon (NHC) content. Compared to S4, the amended soil contained more humified C (HAC, FAC and HUC) and less NHC. Further evidence of the effect of compost on soil organic matter was obtained by the analysis of the humic acid (HA) fractions isolated from both the compost and the soils. These were characterized by elemental analyses and Diffuse Reflectance Infrared Fourier Transformed spectroscopy. The HAs isolated from CM and from S4 were significantly different. The HAs isolated from the amended plots were more similar to HA isolated from CM than to HA isolated from S4. The experimental data of this work indicate that the compost application may affect significantly the soil organic matter composition, and that the approach used in this work allows one to trace the fate of compost organic matter in soil.     

Evolution of organic matter fractions after application of co-compost of sewage sludge with pruning waste to four Mediterranean agricultural soils. A soil microcosm experiment

The effect of co-compost application from sewage sludge and pruning waste, on quality and quantity of soil organic carbon (SOC) in four Mediterranean agricultural soils (South Spain), was studied in soil microcosm conditions. Control soil samples (no co-compost addition) and soils treated with co-composts to a rate equivalent of 140 Mg ha^?1 were incubated for 90 days at two temperatures: 5 and 35 °C. The significances of incubation temperature and the addition of co-compost, on the evolution of the different fractions of SOC, were studied using a 2³ factorial design. The co-compost amendment increased the amounts of humic fractions: humic acids (HA) (1.9 times), fulvic acids (FA) (3.3 times), humin (1.5 times), as well as the free organic matter (1.4 times) and free lipids (21.8 times). Incubation of the soils enhanced its biological activity mainly in the amended soils and at 35 °C, leading to progressive SOC mineralization and humification, concomitant to the preferential accumulation of HA. The incubation results show large differences depending on temperature and soil types. This fact allows us to select suitable organic amendment for the soil when a rapid increase in nutrients through mineralization is preferred, or in cases intending the stabilization and preservation of the SOC through a process of humification. In soils with HA of more than 5 E₄/E₆ ratio, the incubation temperature increased rates of mineralization and humification, whereas lower temperatures limited the extent of both processes. In these soils the addition of co-compost in spring or summer is the most recommendable. In soils with HA of lower E₄/E₆ ratio (<5), the higher temperature favoured mineralization but not humification, whereas the low temperature maintained the SOC levels and even increased the HA/FA ratio. In these soils the moment of addition of organic amendment should be decided depending on the effect intended. On the other hand, the lower the SOC content in the original soil, the greater are the changes observed in the SOC after amendment with co-compost. The results suggest that proper recommendations for optimum organic matter evolution after soil amendment is possible after considering a small set of characteristics of soil and the corresponding soil organic matter fractions, in particular HA.     

Fabrication of Nano Zero valent Iron/Biopolymer Composite with Antibacterial Properties for Simultaneous Removal of Nitrate and Humic Acid: Kinetics and Isotherm Studies

Journal of Polymers and the Environment - This investigation compared the adsorption behavior of humic acid (HA) on cellulose, chitosan and nano zerovalent iron/chitosan (nZVI/chitosan). Results...     

Molecular Structure and Crystallization Dynamics of Poly(3-hydroxyl alkanoate) with Medium-Chain Length Biosynthesized from <Emphasis Type="Italic">Pseudomonas putida</Emphasis>

The molecular structure of poly(3-hydroxyalkanoate) (P3HA) with medium-chain length, biosynthesized from Psuedomonas putida (P. putida), was investigated by thermal analysis, X-ray diffraction, and infrared spectrum. Cultivation in a medium of nonanoic acid and a mixed substrate of nonanoic acid and glycerin as carbon sources provided P3HA with monomer units of 7 and 9 carbons (P3HA_n) and 5, 6, 7, 8, 9, and 10 carbons (P3HA_mix). Since these P3HA has comparatively long side chains, the crystallinity was as low as about 10%. It was suggested that the hydrogen bonding plays an important role in constructing the crystal. The lamellar thickness was 1.20 nm, estimated from the melting temperature depression. This lamellar thickness corresponds to two repeating units. Crystallinity depending on time was observed by the CO stretching mode in the infrared spectrum, and then Avrami’s theory was applied to analyze the crystallization mechanism. The crystallization rate of P3HA_n was very low, on the order of a few hours. An Avrami exponent of 1.45 was estimated from the slope of the Avrami plot. This shows that the conformational arrangement is presumably promoted along the chain axis. The slow crystallization is attributed to the long side chain, which prevents aggregation of the polymer chains.     

Simultaneous Determination and Optimization of Titan Yellow and Reactive Blue 4 Dyes Removal Using Chitosan@hydroxyapatite Nanocomposites

Journal of Polymers and the Environment - Chitosan (CS) and hydroxyapatite (HA) nanocomposites have been prepared and used for the simultaneous removal of Titan Yellow (TY) and Reactive Blue 4 (RB...     

Influence of treatment techniques on Cu leaching and different organic fractions in MSWI bottom ash leachate

The leaching of heavy metals, such as copper, from municipal solid waste incinerator (MSWI) bottom ash is of concern in many countries and may inhibit the beneficial reuse of this secondary material. Previous studies have focused on the role of dissolved organic carbon (DOC) on the leaching of copper. Recently, a study of the Energy Research Centre of The Netherlands (ECN) showed fulvic acid-type components to exist in the MSWI bottom ash leachates and to be likely responsible for the generally observed enhanced copper leaching. These findings were verified for a MSWI bottom ash (slashed circle 0.1-2 mm) fraction from an incinerator in Flanders. The filtered leachates were subjected to the IHSS fractionation procedure to identify and quantify the fractions of humic acid (HA), fulvic acid (FA) and hydrophilic organic carbon (Hi). The possible complexation of fulvic acid with other heavy metals (e.g., lead) was also investigated. The identified role of fulvic acids in the leaching of copper and other heavy metals can be used in the development of techniques to improve the environmental quality of MSWI bottom ash. Thermal treatment and extraction with a 0.2 M ammonium-citrate solution were optimized to reduce the leaching of copper and other heavy metals. The effect of these techniques on the different fractions of organic matter (HA, FA, Hi) was studied. However, due to the obvious drawbacks of the two techniques, research is focused on finding other (new) techniques to treat MSWI bottom ash. In view of this, particle size-based separation was performed to evaluate its effect on heavy metal leaching and on HA, FA and Hi in MSWI bottom ash leachates.     

Assessment of chemical and biochemical stabilization of organic C in soils from the long-term experiments at Rothamsted (UK)

Biological and chemical stabilization of organic C was assessed in soils sampled from the long-term experiments at Rothamsted (UK), representing a wide range of carbon inputs and managements by extracting labile, non-humified organic matter (NH) and humic substances (HS). Four sequentially extracted humic substances fractions of soil organic matter (SOM) were extracted and characterized before and after a 215-day laboratory incubation at 25 degrees C from two arable soils, a woodland soil and an occasionally stubbed soil. The fractions corresponded to biochemically stabilised SOM extracted in 0.5M NaOH (free fulvic acids (FA) and humic acids (HA)) and chemically plus biochemically stabilised SOM extracted from the residue with 0.1M Na4P2O7 plus 0.1M NaOH (bound FA and HA). Our aim was to investigate the effects of chemical and biochemical stabilization on carbon sequestration. The non-humic to humic (NH/H) C ratio separated the soils into two distinct groups: arable soils (unless fertilised with farmyard manure) had an NH/H C ratio between 1.05 and 0.71, about twice that of the other soils (0.51-0.26). During incubation a slow, but detectable, decrease in the NH/H C ratio occurred in soils of C input equivalent or lower to 4Mgha(-1)y(-1), whereas the ratio remained practically constant in the other soils. Before incubation the free to bound humic C ratio increased linearly (R2=0.91) with C inputs in the soils from the Broadbalk experiment and decreased during incubation, showing that biochemical stabilization is less effective than chemical stabilization in preserving humic C. Changes in delta13C and delta15N after incubation were confined to the free FA fractions. The delta13C of free FA increased by 1.48 and 0.80 per thousand, respectively, in the stubbed and woodland soils, indicating a progressive biological transformation. On the contrary, a decrease was observed for the bound FA of both soils. Concomitantly, a Deltadelta15N of up to +3.52 per thousand was measured after incubation in the free FA fraction and a -2.58 Deltadelta15N in the bound FA. These changes, which occurred during soil incubation in the absence of C inputs, indicate that free FA fractions were utilised by soil microorganisms, and bound FA were decomposed and replaced, in part, by newly synthesized FA. The 13CPMAS-TOSS NMR spectra of free HA extracted before and after 215 days of incubation were mostly unchanged. In contrast, changes were evident in bound HA and showed an increase in aromatic C after incubation.     

Alum-based sludge (AbS) recycling for turbidity removal in drinking water treatment: an insight into statistical,technical, and health-related standpoints

This study aimed to evaluate the feasibility of recycling alum-based sludge (AbS) generated from drinking water treatment facility for turbidity removal. A response surface methodology (RSM)-based modeling and factor analysis were first implemented for assessing the optimal conditions of four independent factors, such as initial turbidity concentration, humic acid (HA) concentration, pH, and AbS dose on the water turbidity removal via the use of AbS as a coagulant agent. The optimum values of the four main variables were determined as initial turbidity concentration?=?59.65 NTU, pH?=?5.56, AbS dose?=?19.71 g/L, and HA concentration?=?12.28 mg/L, and at the optimum conditions, the percentage of turbidity removal was obtained as 94.81 (±?1.01)% for real water. At the optimum conditions of AbS usage as a coagulant for real water samples, monitoring of water quality parameters of the process indicated no health-related concerns in terms of hardness (all types), alkalinity, pH, residual aluminum, and even bacteriological (fecal and total coliforms) contamination. The results indicated a potential for AbS recycling in the treatment plant as a coagulant agent, although some requirements should be fulfilled before full-scale application.     

Ion exchange resin for PFAS removal and pilot test comparison to GAC

Amec Foster Wheeler and Emerging Compounds Treatment Technologies, Inc. tested pilot‐scale ex situ treatment technologies for treatment of poly‐ and perfluorinated alkyl substances (PFAS) in groundwater. The pilot test compared ion exchange resin to granular activated carbon (GAC) and evaluated in‐place regeneration of the resin to restore PFAS removal capacity. During the pilot test, both resin and GAC removed perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) below U.S. Environmental Protection Agency (USEPA) health advisories (HAs) of 0.070 micrograms per liter (μg/L) combined. Compared at a common empty bed contact time (EBCT) of five minutes, the resin treated over eight times as many bed volumes (BVs) of groundwater as GAC before PFOS exceeded the USEPA HA and six times as many BVs for PFOA. On a mass‐to‐mass basis, resin removed over four times as much total PFAS per gram as GAC before breakthrough was observed at the USEPA HA. A solution of organic solvent and brine was used to regenerate the resin in the lead vessel, which had treated water up to the point of PFOS and PFOA breakthrough exceeding the USEPA HAs. The pilot test demonstrated successful in‐place regeneration of the resin to near‐virgin conditions. The regenerated resin was then used to treat the contaminated groundwater up to the same breakthrough point. Compared to the virgin resin loading cycles, PFAS removal results for the regenerated resin were consistent with virgin resin.     

Functional changes in culturable microbial communities during a co-composting process: Carbon source utilization and co-metabolism

Microbial communities in sewage sludge and green waste co-composting were investigated using culture-dependent methods and community level physiological profiles (CLPP) with Biolog Microplate. Different microbial groups characterized each stage of composting. Bacterial densities were high from beginning to end of composting, whereas actinomycete densities increased only after bio-oxidation phase i.e. after 40 days. Fungal populations become particularly high during the last stage of decomposition. Cluster analyses of metabolic profiles revealed a similar separation between two groups of composts at 67 days for bacteria and fungi. Principal component analysis (PCA) applied to bacterial and fungal CLPP data showed a chronological distribution of composts with two phases. The first one (before 67 days), where the composts were characterized by the rapid decomposition of non-humic biodegradable organic matter, was significantly correlated to the decrease of C, C/N, organic matter (OM), fulvic acid (FA), respiration, cellulase, protease, phenoloxidase, alkaline and acid phosphatases activities. The second phase corresponding to the formation of polycondensed humic-like substances was significantly correlated to humic acid (HA) content, pH and HA/FA. The influent substrates selected on both factorial maps showed that microbial communities could adapt their metabolic capacities to the particular environment. The first phase seems to be focused on easily degradable substrate utilization whereas the maturation phase appears as multiple metabolisms, which induce the release of metabolites and their polymerization leading to humification processes.