不同来源生物炭对砷在土壤中吸附与解吸的影响

采用OECD Guideline 106批平衡方法研究了由凋落松针、玉米秸秆、牛粪制备的3种生物炭对As(Ⅴ)在棕壤中的吸附和解吸特性的影响.结果表明：3种生物炭的添加量为0.5%时,对As(Ⅴ)在土壤中的吸附量大小顺序为牛粪炭处理＞松针炭处理＞玉米秸秆炭处理,这与生物炭的基本性质密切相关;等温吸附曲线能用Langmuir方程进行很好的拟合(R² =0.997);与对照相比,生物炭处理对砷的吸附容量(lgK_f 为1.99～2.10)和吸附强度(1/N 为0413～0.449)降低,生物炭对As(Ⅴ)的主要吸附机制为物理吸附;生物炭处理对As(Ⅴ)解吸率大小顺序为：玉米秸秆炭处理＞松针炭处理＞牛粪炭处理,解吸率在14.5%～18.7%.添加3种来源生物炭降低了棕壤对As(Ⅴ)的吸附,这可能会导致砷的有效性增强,更易被生物吸收,进而增强土壤中砷的毒性.     

Microwave treated Salvadora oleoides as an eco-friendly biosorbent for the removal of toxic methyl violet dye from aqueous solution—A green approach

In the present study, microwave treated Salvadora oleoides (MW-SO) has been investigated as a potential biosorbent for the removal of toxic methyl violet dye. A batch adsorption method was experimented for biosorptive removal of toxic methyl violet dye from the aqueous solution. The effect of various operating variables, viz., adsorbent dosage, pH, contact time and temperature on the removal of the dye was studied and it was found that nearly 99% removal of the dye was possible under optimum conditions. Kinetic study revealed that a pseudo-second-order mechanism was predominant and the overall process of the dye adsorption involved more than one step. Hence, in order to investigate the rate determining step, intra-particle diffusion model was applied. Adsorption equilibrium study was made by analyzing Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) adsorption isotherm models and the biosorption data was found to be best represented by the Langmuir model. The biosorption efficiency of MW-SO was also compared with unmodified material, Salvadora oleoides (SO). It was found that the sorption capacity (q_max) increased from 58.5 mg/g to 219.7 mg/g on MW treatment. Determination of thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) confirmed the spontaneous, endothermic and feasible nature of the adsorption process. The preparation of MW-SO did not require any additional chemical treatment and a high percentage removal of methyl violet dye was obtained in much lesser time. Thus, it is in agreement with the principles of green chemistry. The results of the present research work suggest that MW-SO can be used as an environmentally friendly and economical alternative biosorbent for the removal of methyl violet dye from aqueous solutions.     

Microwave-assisted preparation of bagasse and rice straw for the removal of emulsified oil from wastewater

The present study was carried out to examine modified bagasse and rice straw as absorbents for the removal of emulsified oil by a microwave-assisted technique. The raw adsorbents were chemically modified with sodium hydroxide and surfactant solution for better adsorption of oil. The surface modification was confirmed through Fourier transform infrared (FTIR) spectroscopy and scanning electron microscope (SEM) analysis. Batch studies were performed to identify the influence of contact time, pH, dosage, speed, and temperature on the percentage of removal of emulsified oil from the wastewater. A maximum oil removal of 98.07% and 98.72% was achieved in microwave-assisted bagasse and rice straw at 313 K. The obtained data were compared with isotherm and kinetic models to understand the mechanism behind the adsorption. From the Langmuir isotherm model, a maximum adsorption capacity of 192.58 and 276.82 mg/g was observed for modified bagasse and rice straw. The oil-loaded raw and microwave-assisted adsorbents can act as a potential energy source for renewable energy.     

不同炭化温度制备的蚕丝被废弃物生物炭对重金属Cd2+的吸附性能

以蚕丝被废弃物为原料,在300、500和700 ℃高温缺氧条件下热解炭化制备成3种生物炭(BC300、BC500和BC700).利用扫描电镜(SEM)、傅里叶红外光谱仪(FT-IR)、X-射线衍射仪(XRD)、比表面积分析仪等对其理化性质进行表征,并研究了不同温度下制备的生物炭对溶液中Cd²⁺的吸附特性.结果表明: 随着炭化温度上升,BET比表面积、pH、灰分均增大,生物炭表面形态结构越来越不规则.XRD结果显示:不同温度下获得的生物炭中均含有一定量的方解石,FT-IR光谱图上的峰主要为-OH和方解石典型的吸收峰;pH对生物炭吸附Cd²⁺的影响不大;Langmuir方程能更好地拟合3种生物炭对Cd²⁺的吸附等温过程,其最大吸附量分别为25.61、52.41和91.07 mg·g^-1.3种生物炭对Cd²⁺吸附过程均更符合准二级动力学方程,且BC700对Cd²⁺的吸附效果最佳.进一步研究离子浓度及阳离子共存对BC700吸附Cd²⁺的影响,结果显示: NaCl浓度越高,对Cd²⁺的吸附抑制越明显;共存阳离子中,Ca²⁺和Mg²⁺对Cd²⁺的吸附抑制更明显,而K⁺几乎无影响.因此,以蚕丝被废弃物制备的生物炭作为去除水体中Cd²⁺的吸附剂具有较强的应用潜力.     

Monitoring the Changes of Chemical Properties of Rice Straw–Derived Biochars Modified by Different Oxidizing Agents and Their Adsorptive Performance for Organics

Biochar derived from agricultural biomass waste is increasingly recognized as a multifunctional material for various applications according to its characteristics. In this study, rice straw–derived biochars were produced at different temperatures (550, 650, 750°C), then they were modified by using different oxidizing agents, including KOH, HNO₃, H₂SO₄, H₂O₂, and KMnO_4. The influence of carbonization temperature and the oxidizing agent's nature on the surface chemistry was investigated. Fourier transform infrared (FTIR) analysis detected lactone, carbonyl, quinone or conjugated quinone, carboxyl-carbonate structure, and alcohol groups in most of the oxidized samples. Modified biochars have low pH values compared with their parent biochars. This is due to the fact that most treatments of biochar increase the acidic functional groups on the surface. Modified biochars presented greater capacities for adsorption of organic species of different molecular sizes such as iodine, phenol, and methylene blue from solutions. Such behavior proves that the most important surface properties of these biochars affecting their solution adsorption behavior are their acidity/alkalinity and hydrophilicity.     

Yield and size of oyster mushroom grown on rice/wheat straw basal substrate supplemented with cotton seed hull

Oyster mushroom (Pleurotus ostreatus) was cultivated on rice straw basal substrate, wheat straw basal substrate, cotton seed hull basal substrate, and wheat straw or rice straw supplemented with different proportions (15%, 30%, and 45% in rice straw substrate, 20%, 30%, and 40% in wheat straw substrate) of cotton seed hull to find a cost effective substrate. The effect of autoclaved sterilized and non-sterilized substrate on growth and yield of oyster mushroom was also examined. Results indicated that for both sterilized substrate and non-sterilized substrate, oyster mushroom on rice straw and wheat basal substrate have faster mycelial growth rate, comparatively poor surface mycelial density, shorter total colonization period and days from bag opening to primordia formation, lower yield and biological efficiency, lower mushroom weight, longer stipe length and smaller cap diameter than that on cotton seed hull basal substrate. The addition of cotton seed hull to rice straw and wheat straw substrate slowed spawn running, primordial development and fruit body formation. However, increasing the amount of cotton seed hull can increase the uniformity and white of mycelium, yield and biological efficiency, and increase mushroom weight, enlarge cap diameter and shorten stipe length. Compared to the sterilized substrate, the non-sterilized substrate had comparatively higher mycelial growth rate, shorter total colonization period and days from bag opening to primordia formation. However, the non-sterilized substrate did not gave significantly higher mushroom yield and biological efficiency than the sterilized substrate, but some undesirable characteristics, i.e. smaller mushroom cap diameter and relatively long stipe length.     

The role of Bh4 in parallel evolution of hull colour in domesticated and weedy rice

The two independent domestication events in the genus Oryza that led to African and Asian rice offer an extremely useful system for studying the genetic basis of parallel evolution. This system is also characterized by parallel de‐domestication events, with two genetically distinct weedy rice biotypes in the US derived from the Asian domesticate. One important trait that has been altered by rice domestication and de‐domestication is hull colour. The wild progenitors of the two cultivated rice species have predominantly black‐coloured hulls, as does one of the two U.S. weed biotypes; both cultivated species and one of the US weedy biotypes are characterized by straw‐coloured hulls. Using Black hull 4 (Bh4) as a hull colour candidate gene, we examined DNA sequence variation at this locus to study the parallel evolution of hull colour variation in the domesticated and weedy rice system. We find that independent Bh4‐coding mutations have arisen in African and Asian rice that are correlated with the straw hull phenotype, suggesting that the same gene is responsible for parallel trait evolution. For the U.S. weeds, Bh4 haplotype sequences support current hypotheses on the phylogenetic relationship between the two biotypes and domesticated Asian rice; straw hull weeds are most similar to indica crops, and black hull weeds are most similar to aus crops. Tests for selection indicate that Asian crops and straw hull weeds deviate from neutrality at this gene, suggesting possible selection on Bh4 during both rice domestication and de‐domestication.     

Removal of ammonium from aqueous solutions using alkali-modified biochars

Biochars converted from agricultural residuals can effectively remove ammonium from water. This work further improved the sorption ability of biochars to aqueous ammonium through alkali modification. Three modified biochars were prepared from agricultural residuals pre-treated with NaOH solution through low-temperature (300 °C) slow pyrolysis. The modified biochars effectively removed ammonium ions from water under various conditions with relatively fast adsorption kinetics (reached equilibrium within 10 h) and extremely high adsorption capacity (>200 mg/g). The Langmuir maximum capacity of the three modified biochars were between 313.9 and 518.9 mg/g, higher than many other ammonium adsorbents. Although the sorption of ammonium onto the modified biochar was affected by pH and temperature, it was high under all of the tested conditions. Findings from this work indicated that alkali-modified biochars can be used as an alternative adsorbent for the removal of ammonium from wastewater.     

Pyrolysis temperature and steam activation effects on sorption of phosphate on pine sawdust biochars in aqueous solutions

Biochar can be used as an adsorbent for phosphate removal in aquatic environments to treat eutrophication problems. Designing biochars that have large phosphate adsorption capacity through altering pyrolysis conditions and applying activation techniques will improve phosphate removal efficiency. In this study, four pine sawdust biochars were produced at 300 and 550 °C with and without steam activation. Batch sorption experiments including isotherm and kinetic studies were conducted to understand how phosphate removal capabilities and adsorption mechanisms of biochars were affected by pyrolysis temperature and steam activation. Our results showed that the steam activation and pyrolysis temperature did not affect phosphate adsorption by the biochars. The four biochars removed <4% of phosphate from the aqueous solution, which were not affected by the pH of the solution and biochar application rate. The repulsion forces between biochar surfaces and phosphate ions were likely the cause of the low adsorption.     

Preparation and Characterization of Biochars from Eichornia crassipes for Cadmium Removal in Aqueous Solutions

The study investigated the preparation and characterization of biochars from water hyacinth at 300°C to 700°C for cadmium (Cd) removal from aqueous solutions. The adsorption process was dominated by oxygen-containing functional groups with irregular surfaces via esterification reactions. Furthermore, the mineral components in the biochars also contributed to Cd absorption through precipitation. Parameters such as the effects of solution pH, contact time, and initial concentration were studied. The optimum pH value was observed at 5.0, in which nearly 90% of Cd was removed. The maximum Cd adsorption capacities based on the Langmuir isotherm were calculated at 49.837, 36.899, and 25.826 mg g⁻¹. The adsorption processes of the biochars followed the pseudo-second-order kinetics, with the equilibrium achieved around 5 h. The biochar from E. crassipes is a promising adsorbent for the treatment of wastewater, which can in turn convert one environmental problem to a new cleaning Technology.     

Basic dye adsorption onto an agro-based waste material--sesame hull (Sesamum indicum L.)

The aim of this project was to establish an economical and environmentally benign biotechnology for removing methylene blue (MB) from wastewater. The adsorption process of MB onto abandoned sesame hull (Sesamum indicum L.) (SH) was investigated in a batch system. The results showed that a wide range of pH (3.54-10.50) was favorable for the adsorption of MB onto SH. The Langmuir model displayed the best fit for the isothermal data. The exothermic adsorption process fits a pseudo-second-order kinetic model. The maximum monolayer adsorption capacity (359.88 mg g(-1)) was higher than most previously investigated low-cost bioadsorbents (e.g., peanut hull, wheat straw, etc.). This study indicated that sesame hull is a promising, unconventional, affordable and environmentally friendly bio-measure that is easily deployed for removing high levels of MB from wastewater.     

Cellulase Production in Semisolid Cultures of Trichoderma viride

Cellulase was produced by Trichoderma viride in semisolid cultures of rice bran, rice straw and rice hulls. T. viride QM 9414 generally produced higher cellulolytic activity on CM-cellulose (C_x activity) using rice bran-rice hull mixture (2:1 w/w) as substrate compared to strains ITCC 1433 and D 4014. It showed higher C_x activity on rice bran-rice straw mixtures than on rice bran-rice hull mixtures. Maximal extraction of the enzyme from mold bran was obtained with 0.05 m sodium citrate buffer, pH 3.5.     

Biochar derived from anaerobically digested sugar beet tailings: characterization and phosphate removal potential

Two biochars were produced from anaerobically digested and undigested sugar beet tailings through slow-pyrolysis at 600 °C. The digested sugar beet tailing biochar (DSTC) and raw sugar beet tailing biochar (STC) yields were around 45.5% and 36.3% of initial dry weight, respectively. Compared to STC, DSTC had similar pH and surface functional groups, but higher surface area, and its surface was less negatively charged. SEM-EDS and XRD analyses showed that colloidal and nano-sized periclase (MgO) was presented on the surface of DSTC. Laboratory adsorption experiments were conducted to assess the phosphate removal ability of the two biochars, an activated carbon (AC), and three Fe-modified biochar/AC adsorbents. The DSTC showed the highest phosphate removal ability with a removal rate around 73%. Our results suggest that anaerobically digested sugar beet tailings can be used as feedstock materials to produce high quality biochars, which could be used as adsorbents to reclaim phosphate.     

Influence of NH3/CO2 Modification on the Characteristic of Biochar and the CO2 Capture

This paper was aimed to study the influence of modification of biochar on the performance of CO₂ adsorption. Biochar, obtained from cotton stalk pyrolysis in a fixed bed reactor, was modified with ammonia and CO₂. The physicochemical properties of biochars were characterized by the Fourier transform infrared spectroscopy and automatic adsorption equipment (Micromeritics, ASAP 2020, USA). CO₂ adsorption of biochar was performed in thermogravimetric analyzer. The results showed that the surface area of char was increased significantly by CO₂ modification, while N-contained compound on char surface was enriched obviously by NH₃ modification. CO₂ adsorption of biochar increased greatly with CO₂ and NH₃ modification. CO₂ adsorption was mainly attributed to physical adsorption at 20 °C, and the adsorption quantity (maximum = 99 mg/g) was proportional to the micropore volume of the char. However, at 120 °C, molecular thermal motion increase, chemical adsorption start to play a dominated role, and the adsorption was directly proportional to the N content of this char.     

纤维素高效降解菌YN1的筛选及其降解特性

为了获得降解天然纤维素的微生物菌株,并用于农田秸秆腐熟及竹林地稻壳促腐。从牛羊粪堆肥中筛选出一株纤维素降解菌YN1,对其进行了形态和系统发育分析;测定了YN1的液、固体发酵酶活;进行了YN1对纤维素的失重测定;对YN1在纤维素表面上的定殖及其对纤维素的降解进行了电镜观察。经菌株形态分析和ITS基因序列分析,将YN1鉴定为曲霉(Aspergillussp.);在YN1菌株的液体发酵培养第3天,内切酶、外切酶、β-糖苷酶和总纤维素酶活性都达到最大值,分别为95.7、14.6、20.5和26.6U/mL,固体发酵培养第5d各酶活均达到峰值,依次为1192.2、100.6、136.9和210.7U/g;在失重测定中,YN1在7d内可降解41.87%的秸秆,31.59%的稻壳;在扫描电镜下可明显观察到YN1对滤纸、秸秆和稻壳的降解。YN1可有效降解天然纤维素,对农田秸秆腐熟及竹林地稻壳促腐具有较好的应用前景。     

Enhanced saccharification of rice straw using hypochlorite-hydrogen peroxide

Rice straw is a lignocellulosic biomass, and has been recognized as a renewable organic substance and alternative energy source. In this study, rice straw was pretreated with hypochlorite-hydrogen peroxide (Ox-B) solution. The optimal pretreatment conditions were determined via response surface methodology, and the pretreated rice straw was hydrolyzed with exo-glucanase, endoglucanase, hemicellulase, and β-glucosidase Accellerase 1000? (endo-glucanase equivalent activity of 1,250 carboxy methyl cellulose (CMC) U/g of rice straw pretreated for 24 h). The optimal conditions were as follows: 60 min pretreatment using Ox-B solution containing 0.6% hypochlorite and 25% hydrogen peroxide for 1 g of rice straw in a total reaction volume of 240 mL. Under these conditions, 406.8 mg of d-glucose and 224.0 mg of d-xylose were obtained from 1 g of rice straw. The fermentation of enzymatic hydrolysates containing 8.14 g/L d-glucose and 4.49 g/L d-xylose with Pichia stipitis generated 3.65 g/L of ethanol with a corresponding yield of 0.37 g/g. The maximum possible ethanol conversion rate is 72.54%.     

Efficiency of different types of biochars to mitigate Cd stress and growth of sunflower (Helianthus; L.) in wastewater irrigated agricultural soil

Cadmium contamination in croplands is recognized one of the major threat, seriously affecting soil health and sustainable agriculture around the globe. Cd mobility in wastewater irrigated soils can be curtailed through eco-friendly and cost effective organic soil amendments (biochars) that eventually minimizes its translocation from soil to plant. This study explored the possible effects of various types of plants straw biochar as soil amendments on cadmium (Cd) phytoavailability in wastewater degraded soil and its subsequent accumulation in sunflower tissues. The studied biochars including rice straw (RS), wheat straw (WS), acacia (AC) and sugarcane bagasse (SB) to wastewater irrigated soil containing Cd. Sunflower plant was grown as a test plant and Cd accumulation was recorded in its tissues, antioxidant enzymatic activity chlorophyll contents, plant biomass, yield and soil properties (pH, NPK, OM and Soluble Cd) were also examined. Results revealed that addition of biochar significantly minimized Cd mobility in soil by 53.4%, 44%, 41% and 36% when RS, WS, AC and SB were added at 2% over control. Comparing the control soil, biochar amended soil effectively reduced Cd uptake via plants shoots by 71.7%, 60.6%, 59% and 36.6%, when RS, WS, AC and SB. Among all the biochar, rice husk induced biochar significantly reduced oxidative stress and reduced SOD, POD and CAT activity by 49%, 40.5% and 46.5% respectively over control. In addition, NPK were significantly increased among all the added biochars in soil–plant system as well as improved chlorophyll contents relative to non-bioachar amended soil. Thus, among all the amendments, rice husk and wheat straw biochar performed well and might be considered the suitable approach for sunflower growth in polluted soil.     

Functional Groups Determine Biochar Properties (pH and EC) as Studied by Two-Dimensional 13C NMR Correlation Spectroscopy

While the properties of biochar are closely related to its functional groups, it is unclear under what conditions biochar develops its properties. In this study, two-dimensional (2D) ¹³C nuclear magnetic resonance (NMR) correlation spectroscopy was for the first time applied to investigate the development of functional groups and establish their relationship with biochar properties. The results showed that the agricultural biomass carbonized to biochars was a dehydroxylation/dehydrogenation and aromatization process, mainly involving the cleavage of O-alkylated carbons and anomeric O-C-O carbons in addition to the production of fused-ring aromatic structures and aromatic C-O groups. With increasing charring temperature, the mass cleavage of O-alkylated groups and anomeric O-C-O carbons occurred prior to the production of fused-ring aromatic structures. The regression analysis between functional groups and biochar properties (pH and electrical conductivity) further demonstrated that the pH and electrical conductivity of rice straw derived biochars were mainly determined by fused-ring aromatic structures and anomeric O-C-O carbons, but the pH of rice bran derived biochars was determined by both fused-ring aromatic structures and aliphatic O-alkylated (HCOH) carbons. In summary, this work suggests a novel tool for characterising the development of functional groups in biochars.     

不同有机肥对土壤镉锌生物有效性的影响

在南方典型稻田设置连续4年施用猪粪、鸡粪、稻草的定位试验,监测施用不同有机肥条件下土壤及水稻植株镉(Cd)、锌(Zn)含量的变化,研究有机肥对土壤Cd、Zn活性及其交互作用的影响.结果表明: 施用有机肥(猪粪、鸡粪、稻草)对土壤全Cd、有效态Cd含量及Cd活性皆无显著影响,但有增加土壤Cd全量的趋势,且显著增加土壤全Zn、有效态Zn含量及Zn活性.施用猪粪、鸡粪、稻草皆可降低稻米Cd含量,降Cd效果为猪粪>鸡粪>稻草,猪粪处理水稻稻米、茎、叶Cd含量分别比对照下降37.5%、44.0%、36.4%;鸡粪处理水稻米、茎、叶Cd含量分别比对照下降22.5%、33.8%、22.7%;而稻草处理水稻米Cd含量比对照下降7.5%,但茎、叶Cd含量比对照分别增加8.2%、22.7%;施用猪粪、鸡粪降低稻米Cd含量主要是降低了水稻植株对土壤Cd的富集,而施用稻草则主要是降低了水稻茎Cd向稻米的转运.施用有机肥还增加了水稻茎Zn含量,施用猪粪、鸡粪、稻草的水稻茎Zn含量比单施化肥分别增加53.4%、41.2%、13.9%,但对水稻稻米、叶Zn含量无显著影响.Zn、Cd在土壤、植株茎中皆表现出显著的拮抗作用,土壤及水稻茎Zn含量的增加显著抑制了水稻米、茎、叶对Cd的吸收积累,且随土壤有效态Zn/Cd含量比值的增加,Zn、Cd竞争土壤吸附不是抑制水稻吸收积累Cd的主控因子,而Zn、Cd竞争吸收才是影响水稻吸收积累Cd的主控因子.     

Production of granular activated carbons from select agricultural by-products and evaluation of their physical,chemical and adsorption properties

Representative samples of soft, low density, group 1 (rice straw, rice hulls, sugarcane bagasse) and hard, high density, group 2 agricultural by-products (pecan shells) were converted into granular activated carbons (GACs). GACs were produced from group 1 and 2 materials by physical activation or from group 2 materials by chemical activation. Carbons were evaluated for their physical (hardness, bulk density), chemical (ash, conductivity, pH), surface (total surface area), and adsorption properties (molasses color removal, sugar decolorization) and compared with two commercial reference carbons. The results show that the type of by-product, binder, and activation method determine the properties of GACs. Regardless of the binder, sugarcane bagasse showed a better potential than rice straw or rice hulls as precursor of GACs with the desirable properties of a sugar decolorizing carbon. Pecan shells produced GACs that were closest to the reference carbons in terms of all the properties investigated.