不同裂解条件对生物炭稳定性的影响

在300⁵00℃温度下热裂解水稻秸秆、玉米秸秆制备生物炭,并采用红外光谱(FTIR)和元素分析的方法,以生物炭表面官能团和元素组成为主要考察指标,研究了不同裂解温度、不同保留时间对生物炭稳定性的影响。生物炭红外光谱图结果显示,生物质原材料经过裂解炭化过程,原材料分子结构中所含醚键(C-O-C)、羰基(C=O)等基团消失。随着裂解温度升高,生物炭中甲基(-CH3)和亚甲基(-CH2)也逐渐消失,而芳环结构增加,生物炭芳香化程度增强。延长生物炭制备过程中的保留时间亦有相同结果。生物炭元素组成的结果显示,裂解温度升高及保留时间延长均能使生物炭的H/C比下降,同时裂解温度对生物炭H/C的影响更加显著。相比水稻秸秆生物炭,玉米秸秆生物炭的芳环骨架更加明显,芳香化程度更高。     

不同裂解温度对水稻秸秆制备生物炭及其特性的影响

以农业废弃物水稻秸秆为原料,采用限氧裂解法不同温度(300℃、400℃、500℃、600℃、700℃)下制备生物炭,利用SEM电镜扫描、比表面测定、傅里叶红外光谱、元素分析等现代分析手段对生物炭的结构、形貌、比表面积、孔径、表面官能团和元素含量等理化特性指标进行分析表征.结果表明:随着热解温度的升高,产率和挥发分比例下降,灰分含量升高,p H值增大,含碳量上升,N、H、O含量下降,H/C、O/C、(O+N)/C下降,这表明生物炭芳香性增强,亲水性和极性减弱.生物炭具有丰富的孔隙结构,随着温度升高,孔隙数量增加,孔结构发育更加完全.稻秆生物炭孔结构主要为中孔,且随着热解温度的升高,平均孔径变小,比表面积有所增大,在600℃达到最大.红外光谱结果显示,随着裂解温度升高,水稻秸秆中烷烃基缺失,甲基(—CH3)和亚甲基(—CH2)逐渐消失,而芳香族化合物增加,芳香化程度增强.     

农业废弃物基生物炭对水溶液中镉的吸附效果与机制

以畜禽粪便（牛粪、鸡粪、猪粪）为原料分别在300℃和700℃下制备生物炭,以作物秸秆（小麦秸秆、水稻秸秆、玉米秸秆）为原料分别在300℃和500℃下制备生物炭,利用比表面积和孔径分析仪、扫描电镜、傅里叶红外光谱仪、X射线衍射仪和CHN分析仪等对农业废弃物基生物炭的理化性质、表面结构和元素组成进行表征,研究生物炭理化性质差异和其对镉吸附效果和机制.结果表明,不同农业废弃物基生物炭对Cd²⁺的等温吸附符合Langmiur方程,拟合结果发现随着热解温度的升高,牛粪、鸡粪和猪粪基生物炭对Cd²⁺的最大吸附量分别从83.40、19.65和96.74 mg·g^-1增加至106.54、 268.89和164.53 mg·g^-1;而不同热解温度下制备的秸秆基生物炭对Cd²⁺的最大吸附量差异不显著.农业废弃物基生物炭呈碱性,除牛粪生物炭外,灰分含量随热解温度上升而增加.随着热解温度的上升,生物炭孔隙结构变丰富,含氧官能团增加,出现芳香结构.通过定量分析,发现生物炭Cd²⁺总...     

生物炭对水中五氯酚的吸附性能研究

利用小麦秸秆和花生壳在300,400,600℃条件下制备生物炭,运用元素分析仪、扫描电镜和比表面积仪对生物炭的理化性质进行表征,同时探讨其对水中五氯酚(PCP)的吸附特性.结果表明,随炭化温度升高,生物炭芳香性增加,极性降低.花生壳生物炭对水中PCP的吸附效果优于小麦秸秆生物炭,3种温度制备的生物炭对PCP吸附量表现为400℃>600℃>300℃.随着生物炭添加量增大,水中PCP去除能力由81.79%提高至89.02%,生物炭的吸附量由30.32减小至5.54mg/g.生物炭对PCP的吸附动力学更符合准二级动力学方程,吸附等温线符合Freundlich方程.吸附过程主要受快速反应控制,降低反应温度有利于生物炭对水中PCP的吸附.     

生物炭结构性质对氨氮的吸附特性影响

氨抑制现象在富含有机氮底物的沼气工程中普遍存在,采用生物炭吸附法可固定发酵液中氨氮.为探究生物炭理化结构与氨氮吸附特性之间的相关关系,在不同热解温度(350、450和550℃)下制备以玉米秸秆、稻壳为原料的生物炭,通过元素分析、FTIR和BET等分析生物炭结构及其理化性质,并结合批式吸附实验,研究不同理化性质生物炭对氨氮的吸附特性影响.结果表明随着热解温度的升高,生物炭中碳及灰分含量增多; 450℃制备的玉米秸秆生物炭(CS450)与550℃制备的稻壳生物炭(RH550)对氨氮的吸附分别遵循准二级和准一级动力学模型.Freundlich吸附模型能更好地描述CS450和RH550生物炭对氨氮的等温吸附过程;玉米秸秆炭吸附量与其表面官能团间具有显著相关性;而与稻壳炭的吸附量相关性最显著的为生物炭的比表面积,其次是表面官能团,最后是灰分.其中,RH550吸附性能最好,最大吸附量为12. 16 mg·g~(-1).     

生物炭对三氯生的吸附热动力学研究

以玉米秸秆、皇竹草和花生壳为原料制备成玉米秸秆生物炭(BCcs)、皇竹草生物炭(BCn)、花生壳生物炭(BCps),采用CEC、等电点滴定,表面官能团分析,元素分析、FT-IR、扫描电镜等方法对3种生物炭进行表征,采用单因素静态吸附实验方法考察了生物炭吸附三氯生的主要影响因素.结果表明:CEC和表面官能团数量排序为BCcsBCnBCps,BCcs极性和亲水性更强,孔结构发育更加完善,其次是BCn,BCps的极性和亲水性最弱,孔隙极少.3种生物炭对三氯生的吸附去除率均随着三氯生初始浓度的升高而升高,随着温度的升高而降低,酸性更有利于吸附实验的进行.低离子强度有利于BCcs和BCn吸附三氯生,BCps则相反.在10、25、40℃3种温度下,3种生物炭对三氯生的吸附均更符合准二级反应动力学,Freundilich等温方程和Langmuir等温方程都能描述这3种生物炭对三氯生的吸附行为,吸附反应属于自发、放热反应.吸附机制主要为物理吸附,生物炭与三氯生之间无化学键、配位基交换等强作用力.     

花生壳生物炭的制备、表征及其吸附性能

选择花生壳作为原材料,采用限氧升温炭化法在200、450、700℃温度下制备生物炭,在对其元素组成和表面性质进行分析的基础上,重点考察生物炭对邻苯二甲酸酯的吸附性能。结果表明,花生壳生物炭的元素含量由高到低为COHN,热解温度的升高使碳元素含量显著增高,芳香性增强且极性减弱;花生壳生物炭的比表面积、总孔面积、微孔面积和微孔孔容均随热解温度的升高而增加,平均孔隙宽度随之减小;花生壳生物炭含有丰富的表面官能团,热解温度升高使羟基数量大幅减少,烃基逐渐消失,芳香化程度增强;花生壳生物炭对DEP、DBP的吸附符合Freundlich方程,吸附能力随热解温度的升高而增强,高温生物炭的吸附过程呈现明显的非线性特征。     

不同温度下小麦秸秆生物炭的制备及表征

以小麦秸秆作为生物质原材料,在200、400、600℃温度条件下,采用限氧控温裂解法制备生物炭。采用热重分析、元素分析、红外光谱分析、比表面积分析和扫描电镜分析表征各物质结构特征,并分析不同制备方法对其元素组成、表面结构、表面性质的影响。结果显示:热重、红外光谱分析结果显示小麦秸秆在热解温度升高到350℃时失重率最大,为33.73%,秸秆的热解过程发生化学键的断裂及脂肪性烷基链的消失;小麦秸秆焚烧物的产率、灰分分别为12%、64.78%,灰分较大;生物炭随着碳化温度的升高,其产率降低,灰分含量增大;随着热解温度升高,生物炭逐渐成为"富炭颗粒",其极性降低,芳香性增大,疏水性增强;电镜扫描分析显示随着炭化温度升高,生物炭孔壁逐渐变薄,内部孔结构逐渐增大,甚至出现大量微孔。     

不同裂解温度稻壳生物炭对阿特拉津的吸附行为及机制

为探究不同裂解温度下稻壳生物炭的结构和性质差异及其对阿特拉津（AT）的吸附作用机制和构-效关系,以稻壳为原料在300、500和700℃下制备稻壳生物炭（分别记为RH300、RH500、RH700）,通过电镜扫描、元素分析仪、比表面积分析仪和傅里叶变换红外光谱分析仪等对3种稻壳生物炭进行结构表征分析,并采用批量等温吸附法研究稻壳生物炭对AT的吸附特性.结果表明:裂解温度由300℃升至700℃时,稻壳生物炭中w（C）由48.81%升至64.67%,w（H）、w（N）和w（O）则由3.22%、1.45%和34.66%分别降至0.89%、0.92%和16.29%,原子比H/C、O/C和（O+N）/C值均降低.可见,随着裂解温度升高,稻壳生物炭的芳香性增强,亲水性和极性降低,且比表面积和孔体积增大,平均孔径减小.3种稻壳生物炭对AT的吸附均可用Freundlich和Langmuir两种等温吸附模型进行较好地拟合（R≥0.948,P < 0.01）,吸附作用及非线性程度与生物炭的比表面积（SSA）、芳香性（H/C）、亲水性（O/C）和极性〔（O+N）/C〕呈良好的指数关系,大小表现为RH700 > RH500 > RH300.稻壳生物炭对AT的吸附机制主要包括分配作用和表面吸附,分配作用强度与生物炭的极性和炭化程度有关;而表面吸附作用与AT的分子大小有关,3种稻壳生物炭对AT的表面吸附除表面覆盖外,还存在多层平铺、毛细管现象和孔隙填充等.研究显示,裂解温度是影响生物炭吸附有机污染物的重要因素,在综合考虑成本和制备工艺的同时,适当提高裂解温度可增强生物炭对有机污染物的吸附作用.      

蚯蚓粪便生物炭对水体中雌二醇的吸附

为寻求高效、廉价的E2(雌二醇激素)吸附剂及开拓蚯蚓粪便的资源化利用途径,将蚯蚓粪便在300、500和700 ℃下热解碳化制备生物炭(分别记为BC300、BC500和BC700),对所得生物炭的基本理化性质(包括物质组成、表面官能团、孔隙结构等)进行分析,并将其用于吸附水体中E2,考察生物炭投加量、溶液pH、反应时间及初始ρ(E2)对生物炭吸附性能的影响,并探讨了吸附机理.结果表明:随热解温度的升高,生物炭的H/C(原子比)由0.13降至0.03,O/C(原子比)由0.46降至0.02,芳香性增强,极性降低,逐渐由脂肪炭结构过渡到芳香炭结构;生物炭比表面积由24.33 m2/g增至76.29 m2/g,总孔体积由0.09 cm3/g增至0.19 cm3/g.不同热解温度下制备的生物炭对E2的吸附过程均符合准二级动力学方程,拟合系数大于0.991;Langmuir和Freundlich等温吸附模型均能较好地描述蚯蚓粪便生物炭对E2的吸附过程,Langmuir理论最大吸附量表现为BC700(7.66 mg/g)>BC500(5.23 mg/g)>BC300(3.32 mg/g).随热解温度的升高,O/C和H/C降低,说明碳化程度增强,生物炭吸附E2的分配作用减弱而表面吸附作用增强.研究显示,蚯蚓粪便生物炭对E2的吸附效果随比表面积和孔体积的增加而增强.      

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effects of arsenic on seed germination and physiological activities in wheat seedlings

The effects of arsenic(As)were investigated on seed germination,root and shoot length and their biomass and some other factors to elucidate the toxicity of As.The results showed low concentrations of As(O-1 mg/kg)stimulated seed germination and the growth of root and shoot,however,these factors all decreased gradually at high concentrations of As(5-20 mg/kg).The contents Of O2-,MDA,soluble protein and peroxidase(POD)activity all increased with increasing As concentrations.Soluble sugar content,ascorbate peroxidase(APX),and superoxide dismutase(SOD)activities decreased at low concentrations of As,and increased at high concentrations of As.While acetylsalicylic acid(ASA)and chlorophyll contents,catalase(CAT)activity displayed increasing trend when the concentrations of As was lower than 1 mg/kg,and then decreasing trend.By polyacrylamide gel electrophoresis(PAGE).As induced the expression of POD isozymes of wheat seedlings.As induced the expression of CAT isozymes but inhibited the expression of SOD isozymes of wheat seedlings at concentrations lower than 1 mg/kg.However,As inhibited the expression of CAT isozymes but induced the expression of SOD isozymes at concentrations higher than 5 mg/kg.The results indicated As could exert harmfulness in the early development stage of wheat at inappropriate concentrations.     

Sustainability： A view from the wind-eroded field

This article explores the assessment of sustainability in fields subject to wind erosion. In the first part, simple sustainability audits are examined, as of soil depth and nutrients. Direct measurement of these characteristics has many problems, largely because of huge variability in space and time at all scales. Modelling still has its problems, but it may be possible to overcome many of them soon. It is true that wind erosion preferentially removes soil nutrients, but there are imponderables even here. The nutrient balance in many of these soils includes considerable input from dust. In West Africa, it has been shown that the amounts of calcium and potassium that are added in dust are sufficient to fertilize dispersed crops. In mildly acidic sandy soils, such as those found on the widespread palaeo- aeolian deposits, much of the phosphorus is fixed and unavailable to plants by the time it is removed by wind erosion, so that erosion has no added downside. Most of the nutrients carried by dust have been shown to travel close to the ground （even when they are attached to dust-sized particles）, and so are trapped in nearby fallow strips, and are thus not lost to the farming system. Second, the sustalnabillty of a whole semi-arid farming system is explored. Wind erosion in semi-arid areas （like China, the Sahel and Norflawestern Europe） generally takes place on aeolian deposits of the recent geological past. Most of these soils are deep enough to withstand centuries of wind erosion before they are totally lost to production, and some of these soils have greater fertility at greater depth （so that wind erosion may even improve the soil）. Finally some remarks are made about environmental change in relation to sustainability.     

Bioconcentration kinetics of PCBs in various parts of the lifecycle of the tadpoles Xenopus laevis

Polychlorinated biphenyls （PCBs） in Xenopus laevis have been reported only for a few congeners. Additionally, there is very little information on the ability of Xenopus laevis to bioconcentrate PCBs. To address these issues, the tadpole Xenopus laevis was exposed to Aroclor 1254 mixtures in water at room temperature for 110 d followed by an additional 110 d of nonspiked PCBs in the water for the control group. During the whole process, bioconcentration factors （BCFs） of PCBs ranged from 1180 to 15670. For most PCB congeners, the highest and lowest bioconcentrations of the kinetic curves were found to be remarkably simultaneous, respectively. All 141 PCB congeners under the same experimental conditions had no linear correlation on the lgBCF versus lgKow relationship. The relationship between lgBCFs and lgKow followed a parabolic pattern indicative of selective bioconcentration, suggesting that the kinetic curves of the PCB congeners observed in the lifecycle of the tadpoles may be concentrated due to the amphibian special species and internal metabolism. In contrast, lgBCFs for PCBs were inversely related to lgKow, suggesting that a metabolism of the higher Kow PCB congeners occurred. These results support the author＇s conclusion that the tadpole Xenopus laevis plays major roles in the bioconcentration of PCB congeners, and demonstrated that the exposure kinetic curves of PCB congeners are complex. Besides the amphibian metamorphous development, the lifecycle of the tadpole Xenopus laevis also may be of importance in determining the bioconcentration of PCB congeners.