铈锰改性生物炭对土壤As的固定效应

利用高温热解法在600℃下制备铈锰改性生物炭(modified biochar,MBC),以3种基本性质差异较大的砷(As)污染红壤、黄壤和紫色土为研究对象,探讨了MBC的施用对土壤活性As的影响及固定效应.结果表明:改性生物炭(MBC)的施用导致3种土壤中水溶态As含量显著降低,随着施用量的增加,MBC对As的固定效率不断升高,当添加量为1%～10%时,MBC对3种土壤中活性As的固定效率为:红壤70. 59%～94. 72%,黄壤75. 24%～98. 35%,紫色土为76. 53%～99. 61%,在MBC添加量为10%时,其对3种土壤中有效As的固定效率均达到了95%以上,而未改性生物炭的施用则导致土壤As的活化效应明显.比较而言,MBC对3种土壤中有效As的固定效率大小排序为:紫色土黄壤红壤,MBC的施用导致了土壤中活性态As向稳定态转化,发生了由非专性吸附(F1)、专性吸附态(F2)向结晶水合铁铝氧化物结合态(F4)和残渣态(F5) As的转化过程,使得土壤中As的迁移性能降低,根据扫描电镜(SEM)及X射线衍射分析(XRD)的结果,MBC对As的固定作用与生物炭上铈锰氧化物的成功负载有关.因此,MBC对As污染土壤表现出良好的应用修复潜力.     

The Evaluation of Mesoporous Materials as Catalyst in Fast Pyrolysis of Wheat Straw

In this study, wheat straw was chosen as a biomass sample and the fast pyrolysis of this sample was carried out with or without catalyst at different conditions in a well-swept fixed-bed reactor. Experiments were carried out in a well-swept tubular fixed-bed reactor with a heating rate of 300°C/min, between pyrolysis temperature ranges 300–800°C in the nitrogen atmosphere. The results indicated that a maximum oil yield of 31.9% was obtained at a pyrolysis temperature of 500°C in non-catalytic procedure. Siliceous and Al-MCM-41 materials were evaluated as potential catalysts in the pyrolysis experiments. Mesoporous materials have large pore dimensions with strong acid sites. These acidic sites catalyze some reactions in pyrolysis. The product yields and the quality of bio-oil were influenced with using MCM-41 materials. The bio-oil yield was reduced, whereas the gas yield increased with using a catalyst in the experiments. An increase in the fractions of pure phenol, alkyl phenols, alkenes+alkanes, carbonyls, aromatic, and cyclic compounds and a decrease in the fractions of methoxy phenols, acids+esters, furans, and alcohols were observed in the presence of Al-MCM-41 material. According to all results, the use of Al-MCM-41 materials as catalyst in the pyrolysis can be suggested to obtain both quality fuels and valuable chemicals.     

The Effects of Gas Flow Rate and the Interval Time of Water Supplement on Ethanol Production of Rice Straw by Simultaneous Saccharification and Fermentation

In the present work, characteristics of ethanol production from a single particle composing of pretreated rice straw, cellulase, and β-glucosidase were invesitgated by simultaneous saccharification and fermentation (SSF). The experiment experienced a start-up stage for S. cerevisiae biofilm formation, which was operated at an initial pH value of 4.8 for yeast solution, culture temperature of 30°C, flow rate of 0.8 mL/min for yeast solution, and stably operating stage for ethanol production at a culture temperature of 30°C. Investigations found that the maximal ethanol yield of 9.7 mg/g and the biofilm thickness of 0.37 mm were obtained at 30 mL/min of carrier gas flow rate. Also, the optimal interval time of water supplement was 4 h for SSF. The results show that the appropriate gas flow rate and the interval time of water supplement can keep the high activities of biofilm and enzymes during SSF and result in a high ethanol yield.     

臭氧污染对不同品种小麦干物质与生物量碳积累与分配的影响

近地层臭氧(O3)污染对陆地生态系统及植物生长的危害备受关注.本研究利用开放式臭氧污染(Free-air O3concentration enrichment,O3FACE)研究平台,研究了大气O3浓度增加(比周围大气高50%)对长江三角洲地区5个冬小麦(Tritcium aestivum L.)品种(扬麦15、扬麦16、烟农19、扬幅麦2号和嘉兴002)的干物质与生物量碳的积累与分配以及作物残体C/N比的影响.结果表明,不同品种小麦的干物质积累和分配对O3升高的响应差异明显;O3升高具有降低扬麦15、嘉兴002和增加扬幅麦2号总生物量的趋势,但对扬麦16和烟农19几乎无影响,其中嘉兴002达到显著水平.O3升高显著增加了扬麦15、嘉兴002和显著降低了烟农19和扬幅麦2号的根/冠比,而对品种扬麦16无影响,导致干物质在地上和地下分配呈现品种差异.高O3环境下扬麦15、扬麦16和嘉兴002穗重降低,而烟农19和扬幅麦2号无明显变化;小麦籽粒占穗的比重在高O3条件下嘉兴002、烟农19和扬幅麦2号显著降低8.2%～15.5%,扬麦15呈增加趋势而扬麦16变化不大;表明O3升高将致嘉兴002、烟农19、扬幅麦2号和扬麦16不同程度减产.O3升高导致烟农19和扬幅麦2号秸秆碳量显著增加14.1%～22.9%和C/N比显著降低10.9%～29.1%,JX002秸秆碳量显著减少和C/N比显著增加,扬麦16和扬麦15的秸秆碳量与C/N比则分别呈增加和降低趋势.O3升高显著降低了扬麦16、烟农19和扬幅麦2号品种的根茬碳量和C/N比,对嘉兴002的根茬碳量无显著影响却显著降低了C/N比,但对扬麦15根茬碳数量与质量均影响不大.评价小麦干物质的形成与分配、根茬和秸秆固碳的质与量对O3污染的响应需考虑品种差异影响.     

Role of sorbent surface functionalities and microporosity in 2,2’,4,4’-tetrabromodiphenyl ether sorption onto biochars

The study provides insight into the combined effect of sorbent surface functionalities and microporosity on2,2 ′,4,4 ′-tetrabromodiphenyl ether (BDE-47) sorption onto biochars. A series of biochars prepared underdifferent conditionswere used to test their sorption behaviorswith BDE-47. The extents of sorption behaviorswere parameterized in terms of the single-point adsorption equilibrium constant (Koc ) at three equilibrium concentration (C e ) levels (0.001Sw (solubility), 0.005Sw , and 0.05Sw )whichwasdetermined using the Freundlich model. To elucidate the concentration-dependentdominant mechanisms for BDE-47 sorption onto biochars, K ocwas correlatedwith four major parameters using multiple parameter linear analysis accompaniedwith significance testing. The results indicated that at low concentration (Ce = 0.001Sw ), the surface microporosity term,which represented a pore-filling mechanism, contributed significantly to this relationship,while as concentrationwas increased to higher levels, surface functionality related to surface adsorption began to take thedominant role,whichwas further confirmed by the results of Polanyi-based modeling. Given the above results, adual mode model based on Dubinin-Radushkevich andde Boer-Zwikker equationswas adopted to quantitatively assess the changes of significance of surface adsorption aswell as that of pore fillingwith sorption processdevelopment. In addition, UV spectra of four typical aromatic compoundswhich represented the key structural fragments of biochars before and after interactionswith BDE-47were analyzed todetermine the active functional groups and supply complementary evidence for thedominant interaction force for surface adsorption, based onwhich π-π electron-donor-acceptor interactionwas proposed to contribute greatly to surface adsorption.     

灰分示踪法测定秸秆降解菌降解率方法的建立

建立了用灰分示踪法测定秸秆降解菌对秸秆的降解率的方法,由于灰分是固定存在于秸秆中的,通过定量测定灰分,可准确定量分析秸秆降解菌的降解能力,采用此方法测定了2个秸秆降解菌群对秸秆的降解率,其结果与产糖率法测定结果一致,表明该方法可实现定量准确测定微生物对秸秆的降解率。进一步应用该方法测定了实验室筛出的3个菌株对秸秆的降解率,结果表明:72号菌株为降解能力最高的秸秆降解菌。该方法的建立和应用为秸秆降解菌的筛选及秸秆资源的开发利用提供了实验方法与理论依据。     

氢氧化镧改性介孔稻壳生物炭除磷性能

通过共沉淀法将氢氧化镧固定在高介孔率的稻壳生物炭上,重点研究了生物炭孔结构、溶液pH和共存物质对氢氧化镧改性介孔稻壳生物炭吸附磷酸盐的影响.结果表明,镧负载量与生物炭介孔率呈正相关,生物炭介孔率越高,对磷酸盐的吸附速率越快,镧浸出量越低.吸附过程符合伪二级动力学模型,且受颗粒内扩散控制.Langmuir模型能够较好地描述氢氧化镧改性介孔稻壳生物炭对磷酸盐的吸附过程,理论最大吸附量分别为41.22、43.26和45.62 mg·g^-1,镧利用率较高,P/La量比均大于1.5.此外,氢氧化镧改性介孔稻壳生物炭能在pH 3~9的范围内有效吸附磷酸盐.共存物质影响实验表明,氢氧化镧改性介孔稻壳生物炭对磷酸盐表现出良好的选择吸附性,共存Ca²⁺会强化其对磷酸盐的吸附,而共存Mg²⁺则会抑制吸附过程.     

炭基-Co3O4复合材料活化过一硫酸盐降解阿特拉津

利用水热浸渍法制备了生物炭基-Co₃O₄复合材料（Co-OB）,采用扫描电子显微镜（SEM）、X射线衍射仪（XRD）、傅里叶变换衰减全反射红外光谱仪（ATR-IR）等手段对Co-OB进行表征,并研究了其活化过一硫酸盐（PMS）降解阿特拉津（ATZ）的性能,探究了PMS投加量、腐殖酸（HA）和Cl^-对ATZ降解的影响.结果表明,在Co-OB活化投加量0.025g/L,PMS浓度200μmol/L,ATZ浓度20μmol/L,室温条件下10min内ATZ的去除率为86.3%,与生物炭（OB）和Co₃O₄相比,其去除率为后两者之和的2.2倍.随着PMS浓度增加,ATZ去除率显著提高.Cl^-、HA的存在抑制了ATZ的降解,且随Cl^-、HA浓度增加,抑制程度增大.自由基猝灭实验表明·OH和SO₄·^-是ATZ降解的主要活性物种.通过液相色谱-质谱联用仪（LC-MS）分析出6种中间产物,并推测出ATZ的降解途径.稳定性实验表明Co-OB具有重复使用性及低Co²⁺溶出.     

溶磷微生物改性生物炭吸附重金属的机理研究

利用磷溶菌（PSB）对稻壳（RB）和污泥（SB）生物炭进行不同时间的改性,研究了其对水体中Pb²⁺和Cd²⁺（1000mg/L）的修复机制.主要通过测定改性生物炭的理化特性和重金属含量,并利用结构方程模型研究了微生物改性生物炭对重金属的吸附机理.结果表明,PSB显著改善生物炭的孔径结构、比表面积BET （增加了12.5%~175.0%）和表面官能团.特别是还增加了生物炭中C和P元素的释放,促进了生物炭表面的生物矿化机制.PSB改性显著提高了生物炭对Pb²⁺和Cd²⁺的吸附作用（RB提高：Pb²⁺=9.5%~34.5%,Cd²⁺=34.7%~219.9%,SB提高：Pb²⁺=65.3%~101.3%,Cd²⁺=106.6%~248.6%）.通过Pb和Cd的修复差异,发现不同重金属对微生物的胁迫是导致改性生物炭对重金属的修复反应路径相反的原因.此外,结构方程模型证实6~12h的PSB改性效果最好,且BET不是主要影响因素.不同的生物质炭改性后的修复机制也存在明显差异,孔径结构（R_max²=0.99）是改性RB的主要吸附途径,化学沉淀（R_max²=0.99）是改性SB的主要吸附途径.     

氨氧化过程中稻壳生物炭抑制酸性农田土壤N2O排放

为探明在土壤环境有利于氨氧化作用发生的条件下,稻壳生物炭对酸性农田土壤N₂O排放的影响,将生物炭分别按质量比0%（对照）、2%、5%和10%与土壤充分混匀,开展为期17d的室内静态土壤培养实验,研究土壤N₂O排放速率的日变化以及整个培养期间的N₂O累积排放量.同时,测定了培养终态土壤样品的pH值、NH₄⁺-N、NO₃^--N、NO₂^--N和溶解性有机碳（DOC）含量,分析稻壳生物炭对土壤N₂O排放影响的机理.结果表明,不同稻壳生物炭添加量均显著抑制了酸性农田土壤的N₂O排放（P<0.001）,且以5%和10%处理的抑制作用最明显;与对照处理相比,2%、5%和10%处理的N₂O累积排放量分别减少了87.68%、94.59%和96.90%.培养前后土壤pH值、NH₄⁺-N和NO₃^--N含量的变化表明,稻壳生物炭显著促进了土壤的硝化作用,尤其是5%和10%处理.线性回归分析表明,土壤N₂O排放速率与NO₂^--N含量显著正相关（P<0.01）,且NO₂^--N含量对N₂O排放速率的解释程度为45%.由于稻壳生物炭促进了土壤的硝化作用,使NO₂^-更易转化为NO₃^-,减少了NO₂^-积累,进而减少了通过硝化菌反硝化作用途径产生的N₂O.培养结束时,5%和10%处理的DOC含量显著高于对照处理,但培养过程中,稻壳生物炭并未显著促进土壤有机碳矿化.