Decolourisation and treatment of pulp and paper mill effluent by lignin‐degrading Bacillus sp.

Three lignin‐degrading bacterial strains, identified as Paenibacillus sp., Aneurinibacillus aneurinilyticus and Bacillus sp. have been examined for the treatment of pulp and paper mill effluent. The results of this study revealed that all three bacterial strains effectively reduced colour (39–61%), lignin (28–53%), biochemical oxygen demand (BOD) (65–82%), chemical oxygen demand (COD) (52–78%) and total phenol (64–77%) within six days of incubation. However, the highest reduction in colour (61%), lignin (53%), BOD (82%) and COD (78%) was recorded by Bacillus sp. while, maximum reduction in total phenol (77%) was recorded with Paenibacillus sp. treatment. Significant reduction in colour and lignin content by these bacterial strains was observed after two days of incubation, indicating that bacterium initially utilized growth supportive substrates and subsequently chromophoric compounds thereby reducing lignin content and colour in the effluent. The total ion chromatograph (TIC) of compounds present in the ethyl acetate extract of control and bacterial treated samples revealed the formation of several lignin‐related aromatic compounds. The compounds identified in extracts of treated samples by Paenibacillus sp were t‐cinnamic acid and ferulic acid, while 3‐hydroxy‐4‐methoxyphenol, vanillic acid and vanillin acid by A. aneurinilyticus and gallic acid and ferulic acid by Bacillus sp. respectively indicating the degradation of lignin present in the effluent. The identified compounds obtained after different bacterial treatments were found to be strain‐specific. Among these identified compounds, ferulic acid, vanillic acid and vanillin could have immense value for their use in preservatives and in the food flavour industry. Copyright © 2007 Society of Chemical Industry     

Lignin solvated in zwitterionic Good's buffers displays antibacterial synergy against Staphylococcus aureus

The volume of industrial lignin is expected to increase with the deployment of biorefineries that convert lignocellulosic biomass to renewable chemicals and fuels. Interest in using lignin for value-added biomedical applications requires understanding of its effects on mammalian and microbial cells, which has been impaired by the toxicity of the solvents used to solubilize lignin. In this study, lignin is solvated in zwitterionic Good's buffers compatible with culture media. Up to 100 mg lignin can be solvated in 1 ml of 3-morpholinopropane-1-sulfonic acid (MOPS, pH 7.2) within 60 min at room temperature, whereby MOPS acts as a chaotropic agent. The addition of MOPS-solvated lignin to cultures of Staphylococcus aureus UAMS-1 containing a subinhibitory concentration of tunicamycin reduced growth more than 99% compared to tunicamycin alone, making lignin of interest as an antibiotic adjuvant. This effect of lignin is attributed to damage to the bacterial cell membrane.     

How Well Do MWL and CEL Preparations Represent the Whole Hardwood Lignin?

Hardwood lignin preparations were isolated using classical milled wood lignin (MWL) and cellulolytic enzyme lignin (CEL) protocols. Furthermore, we managed to produce a lignin preparation of a very high yield, above 90%, with high purity and minimal structural degradation. This was achieved by dissolution and regeneration of milled wood prior to enzymatic hydrolysis, along with the use of 80% dioxane for lignin extraction. This preparation (RCEL-80) yield was about 4.5 and 2.5 times higher than the yields of the traditional MWL and CEL preparations, correspondingly, at the same milling time. The preparations obtained were comprehensively analyzed with state-of-the-art quantitative NMR techniques and wet chemistry methods. CELs were representative preparations for hardwood lignins as the S/G ratios in the CELs were equivalent to those in lignin in situ. Degradation of the main lignin subunits was very low. Importantly, the structures of CELs were independent of the preparation yield and were very similar to the structure of the high-yield lignin, RCEL-80. In contrast, the structures of MWLs were noticeably dependent on the preparation yield, especially when the yield was below 15–20% of total wood lignin. In particular, the S/G ratio increased with increasing MWL yield, but was still lower than the S/G ratios of the whole lignins in situ, even at high MWL yields. The amounts of β-O-4 lignin units in MWL were lower than those in the corresponding CEL preparations. It has been concluded that CEL preparations were representative of the whole wood lignin whereas MWLs represent a fraction with a lower S/G ratio.     

Characteristics and Reactivity of Lignin in Acacia and Eucalyptus Woods

The chemical characteristics of lignin, including the Klason lignin content, acid-soluble lignin content, proportion of the aromatic ring types [syringyl ratio = syringyl/(syringyl + guaiacyl)], and proportion of the diastereomeric forms for the β-O-4 structure [erythro ratio = erythro/(erythro + threo)], and pulpability were investigated for 28 wood samples belonging to the genera Acacia and Eucalyptus. Although the lignin characteristics of these 28 woods varied widely, the chemical characteristics of the two genera could be categorized in two clearly distinguished groups on the basis of the syringyl ratio. Clear negative correlations were observed between both the syringyl and erythro ratios and the total lignin content (sum of the Klason and acid-soluble lignin contents) within each genus. In addition, the syringyl ratio correlated positively with the erythro ratio and acid-soluble lignin content, regardless of the genus. The existence of a clear, high correlation between the syringyl and erythro ratios supports the hypothesis that the aromatic ring type (syringyl ratio) is a decisive factor for controlling the diastereomeric forms of the β-O-4 structure (erythro ratio). Each of the wood samples was also subjected to Kraft pulping, and it was demonstrated that the woods with higher syringyl ratios were easier to delignify. This tendency is reasonably attributed to the high reactivity of the erythro-rich and syringyl-rich β-O-4 structures, and the low lignin content of these syringyl-rich woods.     

Comparative study of three lignin fractions isolated from mild ball‐milled Tamarix austromogoliac and Caragana sepium

Six lignin fractions from mild ball‐milled Tamarix austromogoliac (TA) and Caragana sepium (CS) were sequentially isolated with 80% dioxane containing 0.05M HCl at 75°C for 4 h, 50% aqueous ethanol containing 1M triethylamine at 70°C for 4 h, and 8% aqueous NaOH at 45°C for 3 h. The results showed that the successive treatments made it possible to isolate lignin from wood with a high yield and purity, in which 89.4 and 90.6% of the original lignin from TA and CS were released, respectively. The lignin fractions isolated with the three‐step method were analyzed with Fourier transform infrared, ¹H‐ and ¹³C‐NMR, alkaline nitrobenzene oxidation, and gel permeation chromatography. It was found that the three lignin fractions isolated from TA were rich in syringyl units, and the molar ratio of the relatively total moles of vanillin, vanillic acid, and acetovanillin to the relatively total moles of syringaldehyde, syringic acid, and acetosyringone decreased from 1: 2.6 to 1 : 3.2 to 1: 3.6 in the lignin preparations, whereas this ratio in the corresponding lignin fractions isolated from CS was found to be 1.4 : 1, 1.1 : 1, and 1 : 1.4, respectively. More importantly, the results revealed that the sequential extractions of the mild ball‐milled TA and CS with 80% acidic dioxane, 50% alkaline ethanol, and 8% aqueous NaOH under the conditions used did not significantly cleave the β–O‐4 and α–O‐4 linkages in lignin macromolecules. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ozonation,Ozone/UV and UV/H2O2 Degradation of Chlorophenols

The performance of the O₃, O₃/UV and UV/H₂O₂ processes for degradation of six chlorophenols (4-chlorophenol, 2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol) were studied in laboratory reactors. Comparative study showed that chlorophenols can be degraded successfully by all of the methods studied, whilst traditional ozonation at high pH was determined to be the most effective method to treat chlorophenols. Even though the molar absorptivity of chlorophenols is known to be relatively high in the UV-region, the combination of UV-radiation with ozone did not accelerate the degradation of chlorophenols further. The toxicity of degradation products formed during ozonation of chlorophenols has been compared with the toxicity of pure chlorophenols utilizing Daphnia magna 24 hours test. Ozonation of chlorophenols yielded less toxic or even nontoxic products for Daphnia magna compared with parent compounds.     

Biodegradation of chlorophenols using the cell‐free culture broth of Phanerochaete chrysosporium immobilized in polyurethane foam

A cell‐free culture broth of Phanerochaete chrysosporium immobilized in polyurethane foam has been evaluated for the biodegradation of chlorophenols. Lignin peroxidase, manganese peroxidase, and oxalate concentrations in cell‐free culture broth were measured and compared to find the optimum combination of secondary metabolites for the highest biodegradation of chlorophenols. The isozyme distributions and their expression levels were significantly different and changed with increases in the culture time. The oxalate concentration was also found to vary, depending on culture time. Cell‐free broth containing an optimal combination of secondary metabolites showed the greatest biodegradation of 2,4,5‐chlorophenol in the presence of veratryl alcohol and H₂O₂. Phenols with greater numbers of chlorines were degraded more efficiently by this cell‐free culture broth according to the results of biodegradation experiments for five chlorophenols, including 2‐, 4‐, 2,4‐, 2,4,5‐, and pentachlorophenol, as well as phenol. This degradation efficiency correlated well with remaining lignin peroxidase activity during degradation. Cell‐free culture broths may readily be used for biodegradation of highly recalcitrant chemicals since the system would not be affected by the toxicity of the chemicals nor would the adsorption characteristics of the cells be of concern. © 2002 Society of Chemical Industry     

Biodegradation of gelating-g-poly(ethyl acrylate) copolymers. II

Gelatin-g-poly(ethyl acrylate) copolymers were prepared in an aqueous medium using K₂S₂O₈ initiator. Three copolymer samples with grafting efficiencies of 33.3%, 61.0%, and 84.0% were tested for their microbial susceptibility in a synthetic medium with pure cultures of Pseudomonas aeruginosa, Bacillus subtilis, and Serratia marcescens. The percent weight losses were recorded over 6 weeks of incubation period in nitrogen-free and nitrogen-rich media. The relationship between [log (rate)] during the first week of the test period and the composition of grafted samples showed a linear behavior. Pure cultures were more effective than the mixed inoculum, although there was no essential difference in the agressivity of different bacterial stains. Growth–time curves and pH measurement also complement these observations.     

SO_4~(2-)/ZrO_2固体酸催化氧化降解木质素的因素分析

以固体超强酸为催化剂,过氧化氢为氧化剂降解高沸醇竹子木质素。探讨了反应时间、溶剂配比、固体酸用量和反应温度等因素对降解程度的影响。结果表明,当反应时间4h,反应温度80℃,DMF与水的体积比为1∶2,酸加入量为木质素的4%时,在硫酸亚铁促催化的情况下,降解效果最佳。并利用红外光谱和气相色谱-质谱联用对降解产物进行分析。可知,固体酸催化降解木质素可以得到小分子产物,含有明显的醛酸类物质。     

石油污染物的微生物降解研究

从炼油厂污水池底泥中分离出3株石油降解菌。经过摇床培养研究了各菌株及混合菌对石油烃的降解性能,并考察了营养物质、电子受体对石油污染生物降解作用的影响。结果表明,25 d后,3种单菌对石油烃的降解率依次达到87.69%,52.14%,92.02%,混合菌高达93.18%;营养物质、电子受体对石油污染物生物降解影响显著,营养物质N与P适宜比为2∶1(质量比),电子受体H2O2适宜累计添加量为12 000 mg/kg。     

Photooxidation of Some Mono-, Di-, and Tri-chlorophenols in Aqueous Solution by Hydrogen Peroxide/UV Combinations

A number of chlorophenols, namely 2-, 3-, and 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol, have been decomposed in aqueous solution by using hydrogen peroxide as the oxidizing agent under UV radiation emitted by a 400 W high-pressure mercury lamp in a thermostatted Pyrex-glass column photoreactor, and the organic-bound chlorine has been converted into the environmentally harmless inorganic chloride. For H₂O₂/chlorophenol mole ratios between 1: 1 and 16: 1, the photooxidation reaction approached pseudo-first order kinetics, and the rate constants increased with increasing ratio of the oxidant. A theoretical model for the degradation pathway is proposed. The fact that the reaction order was not simply unity could be attributed to the complex reaction sequence processing via a radical mechanism through colored intermediates possibly comprising hydroquinone, catechol and resorcinol.     

Pulping with organic acids: 3-acetic acid pulping of Bagasse

Bagasse was subjected to acetic acid pulping; the effects of the addition of 0.5% H₂SO₄ to the pulping solutions (50, 70 and 90% acetic acid) and varying the liquor ratio, on pulp yield, delignification %, pentosan content and strength properties of the pulps obtained were evaluated. Addition of H₂SO₄ improved the delignification but at the expense of yield and pentosan content. The breaking length and burst deteriorated, whereas the tear was slightly improved. Raising the liquor ratio from 5:1 to 10:1 also reduced the strength properties of the pulps. Delignification of Casuarina was easier than bagasse. IR studies of the acetic acid lignins obtained from both raw materials showed that Casuarina lignins contained more syringyl nuclei than bagasse lignin; the latter resembled softwood lignins. Addition of H₂SO₄ to bagasse changed the syringyl-deficient to guaiacyl-deficient lignin. A relationship was found between the ease of delignification for both raw materials and the relative intensity of the bands corresponding to syringyl groups.     

Properties and thermal degradation study of blend films with poly(4‐vinylpyridine) and lignin

A series of blend films with different ratio of poly(4‐vinylpyridine) (PVP) to lignin were subjected to dynamic DSC and TGA measurement under nitrogen atmosphere at various heating rates. DSC curves showed that the glass transition temperatures of these blends decreased with the increase of lignin content. TGA studies indicated that the lignin content produced obvious effect on the thermal stability of these blends. The kinetic model function of the thermal decomposition of these blends obeyed the Avrami‐Erofeev model equation, g(α) = [‐ln(1‐α)]^1/m. The degradation kinetic parameters were also obtained. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1875–1879, 2005     

Biodegradation of gelatin graft copolymers. IV

Gelatin graft copolymers of different compositions were tested for microbial susceptibility in a synthetic medium with pure cultures of Pseudomonas aeruginosa, Bacillus subtilis, and Serratia marcescens. The percent weight losses were recorded over 6 weeks of incubation period in nitrogen-free and nitrogen-rich media. The relationship between [log(rate)] during the first week of the test period and composition of the grafted samples showed a linear behavior. There was no difference in the aggressivity of these bacterial strains. Nitrogen analysis data and pH measurements of the media seem to reinforce our earlier observations. Soil burial tests also indicate degradation of polymer samples under natural weathering conditions. This article also summarizes the salient features of our series of investigations.     

Oxidation of several chlorophenolic derivatives by UV irradiation and hydroxyl radicals

The oxidation of some chlorophenols: 4‐chlorophenol, 2,4‐dichlorophenol, 2,4,6‐trichlorophenol, 2,3,4,6‐tetrachlorophenol, tetrachlorocatechol (3,4,5,6‐tetrachloro‐2‐hydroxy phenol) and 4‐chloroguaiacol (4‐chloro‐2‐methoxy phenol) has been studied via single photodecomposition produced by polychromatic UV irradiation, oxidation by hydroxyl radicals generated by Fenton's reagent (hydrogen peroxide plus ferrous ions), and degradation by hydroxyl radicals produced by combinations of UV irradiation plus hydrogen peroxide, and UV irradiation plus hydrogen peroxide and ferrous ions (photo‐Fenton system). These organics have been selected as models of chloro‐phenolic derivative pollutants present in wastewaters and groundwaters. The degradation levels obtained in each process are reported. The quantum yields in the single photodecomposition reaction and the rate constants between the chlorophenols and the hydroxyl radicals in the reaction with Fenton's reagent are determined. Finally, the additional contributions to the photodecomposition promoted by the radical reaction in the combined UV/H₂O₂ and photo‐Fenton systems are also evaluated. © 2001 Society of Chemical Industry     

Effects of Solvation and Ionization on 13C NMR Spectra of Lignin Model Compounds,Spruce Milled Wood Lignin and Kraft Lignin

The effects of alkali and polar aprotic solvent on the aromatic carbons signals in ¹³C NMR (Carbon-13 nuclear magnetic resonance) spectra of lignin model compounds and spruce milled wood lignin (MWL) were studied. It was found that in 1 M aqueous NaOH signal shifts of C-1 and C-4 carbon atoms in the aromatic ring were the most noticeable in lignin models with free phenolic hydroxyl groups, which are ionized under the conditions. A similar effect in the spectra of the studied model compounds was observed in 0.5 M aqueous NaOD-deuterated dimethyl sulfoxide (DMSO) mixture (DMSO: water ratio 3:7 v/v). The model data help explaining changes in the ¹³C NMR spectra of MWL and lignin in situ dissolved in spruce kraft black liquor caused by ionization. In the ¹³C NMR spectra of spruce black liquor the signals of phenolic and non-phenolic lignin units are clearly separated and do not overlap with the signals of the carbon atoms of carbohydrates and other aliphatic products of wood degradation. The data obtained are useful in understanding the important role of solvation and ionization processes leading to lignin solubilization.     

Degradation and stabilization of cosmetic polyetherurethane in alcoholic solution

A polyetherurethane (PEU) was synthesized for potential cosmetic applications by coupling poly(tetramethylene oxide) (PTMO, M_n = 2000 g mol^?1) and poly(ethylene oxide) (PEO, M_n = 2000 g mol^?1) with 4,4′‐diphenylmethane diisocyanate (MDI), without using a chain extender. The PEU polymer, synthesized with PEO and PTMO in the ratio of 1:3 by weight, was soluble in ethanol–water mixed solvents. The solution formed a thin film in situ on the skin by coating, which was flexible and elastomeric with appropriate skin adhesiveness. However, PEU was susceptible to degradation when it was exposed to an ethanol–water (80/20 v/v %) mixed solvent and stored in an air‐filled and sealed bottle at 60°C for 4 weeks. These conditions resulted in deterioration of PEU molecular weight (M_n), viscosity, and mechanical properties. Peak analysis of the Fourier transform infrared spectrum of the aged PEU revealed that >97% of the urethane carbonyl bonds remained, whereas ether bonds were significantly reduced (～82% of initial value). The degraded PEU contained ester bonds, which were confirmed by proton and carbon‐13 nuclear magnetic resonance spectroscopy. This observation suggests that oxidative chain cleavage rather than hydrolysis was the dominant reaction in the degradation process. Two approaches were adopted to minimize oxidative degradation of PEU dissolved in an ethanol–water (80/20 v/v %) mixed solvent; they were, applying a nitrogen environment and adding an antioxidant (1.8 wt % dry PEU). The results indicate that reduction of oxidative degradation produced a synergistic effect. Vitamin E was a more effective antioxidant than butylated hydroxytoluene (BHT), which is a typical antioxidant for commercial polyurethanes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2270–2276, 2003     

Batch and continuous studies on treatment of pulp mill wastewater by Aeromonas formicans

Batch and continuous studies have been conducted on the treatment of black liquor from a kraft pulp and paper mill by a bacterial strain, Aeromonas formicans. The results of batch studies revealed that the strain was able to remove 71% and 78% of COD and lignin respectively, while the colour removal efficiency was around 86% in 10 days of retention time. The analysis of lignin degradation products by gas chromatography after 20 days of incubation revealed the formation of some phenolic acids, which were responsible for the decrease in pH during batch studies. The removal efficiencies of COD, colour and lignin obtained in continuous reactor studies were 73, 88 and 77% respectively for an 8 day detention period and these efficiencies were almost the same as obtained in batch studies. © 2001 Society of Chemical Industry     

Parametric Study and Process Evaluation of Fenton Oxidation: Application of Sequential Response Surface Methodology and Adaptive Neuro-Fuzzy Inference System Computing Technique

The Fenton oxidation is rarely used industrially due to its high operating cost, large chemical consumption, excessive sludge production, and operability only within a narrow pH range. Therefore, there is a need to evaluate the Fenton oxidation to maximize its ability to degrade high-strength dye wastewater at reduced operating cost. Optimization tools are among the most commonly used tool to maximize the degradation of pollutants. The current study aims at evaluating the applicability of response surface methodology (RSM) and adaptive neuro-fuzzy inference system (ANFIS) to optimize the degradation of Remazol brilliant blue through the Fenton oxidation. The effects of four operating parameters including dye concentration, retention time, and mass ratios of Dye:Fe²⁺ and H₂O₂:Fe²⁺ were evaluated by applying RSM. According to the RSM results, color and chemical oxygen demand (COD) removal of 99.9% and 84%, respectively, were obtained at 120?min at the COD value of 795?mg/L, mass ratios of Dye:Fe²⁺?=?16, H₂O₂:Fe²⁺?=?15 and pH?=?3. ANFIS was also used to evaluate the most influential operating parameters on the COD removal based on the RSM results. The ANFIS results showed that the mass ratio of H₂O₂:Fe²⁺ had the most significant contribution to the COD removal. High R² values (≥90%) indicated that the predictions of RSM and ANFIS models for COD removal were acceptable. In conclusion, this study demonstrated that RSM and ANFIS were able to determine the most significant operating parameters and optimum ratios of pollutant:oxidant:catalyst, which reduced the operating cost directly.     

酸性助水溶剂脱除木质素机理分析

系统探讨了酸性助水溶剂对甲苯磺酸(p-toluenesulfonic acid,TSA)和马来酸(maleic acid,MA)分离桉木各组分的工艺过程,并对其中木质素脱除机理进行了研究。通过分析对比两种优化后的工艺发现：(1)两种酸性助水溶剂都可以高效脱除木质素,TSA木质素脱除率为67.94%,MA为65.14%;(2)在相同质量分数下,TSA的木质素脱除率比MA更高;(3)在温和条件下,TSA木质素的β-芳醚键含量比MA的高,随着反应条件的加剧,TSA和MA处理后木质素产品中β-芳醚键含量逐渐减少;(4)两种酸性助水溶剂处理后,纤维素保留率都较高,可保持90%以上;但是半纤维素的降解程度随着反应条件的加剧而增加;(5)酸性助水溶剂质量分数越高,在疏水表面的接触角越小,对木质素的助溶作用越明显,脱除木质素效率越高,溶液中木质素聚集体的粒径越小。综上所述,酸性助水溶剂对木质素的脱除基于润湿溶解、木质素芳醚键断裂、半纤维素降解等的综合作用。相关研究可为后续实现温和条件脱木质素工艺优化及机理提供参考。