麦秸水热炭及其改良产物对水稻产量和稻田氨挥发排放的影响

水热炭的酸性特性及材料吸附性质为其稻田回用及氨挥发损失控制提供了可能.为实现农业废弃物的资源化利用和稻田环境损失控制,本研究以小麦秸秆为原材料,通过土柱模拟试验,考察了麦秸水热炭（WHC）及其水洗改良产物（W-WHC）对水稻产量和稻田氨挥发排放的影响.结果表明,麦秸水热炭及其改良产物稻田回用能够增加水稻产量,低量添加（0.5%）的增产效应高于高量添加（1.5%）处理.低量添加下,WHC和W-WHC处理的水稻产量分别较对照处理（CKU）增加17.16%和20.20%.结果同时表明,除W-WHC低量添加处理的氨挥发损失量与对照相当,水热炭及其改良产物添加均能够减少稻田氨挥发损失.其中,WHC低量添加和W-WHC高量添加处理的稻田氨挥发损失显著低于CKU处理,NH₃挥发累积排放量分别减少31.01%和17.40%.阶段氨挥发损失结果分析表明,水热炭添加对稻田氨挥发损失的控制效应主要集中在蘖肥期和穗肥期,水热炭添加后蘖肥期田面水氮素浓度的变化和穗肥期田面水pH的改变是秸秆水热炭添加后稻田氨挥发控制的主要驱动因素.结果说明,适宜用量下小麦秸秆碳化还田可以在提高作物产量的同时减少稻田氨挥发损失,是一种适于农业副产物资源化利用的良好方式.     

水热炭减少稻田氨挥发损失的效果与机制

作为生物质水热碳化的产物,水热炭因其丰富的孔隙结构和官能团等良好的表面特性,在稻田氨(NH_3)挥发减排方面有着良好的应用前景.本研究将水热炭作为一种土壤调理剂施加到稻田土壤中,通过水稻全生育期土柱试验,考察其对稻田氨挥发的影响.试验通过设置3个处理:CKU(不施加水热炭对照)、SHC(锯末水热炭)和W-SHC(水洗锯末水热炭),研究了不同水热炭对田面水pH、田面水NH_4~+-N浓度、氨挥发排放通量和累积量及单位产量氨挥发排放累积量的影响.其中水热炭和水洗水热炭施加量为0. 5%(质量分数).结果表明,SHC处理显著降低了NH_3挥发累积排放量和单位产量NH_3挥发累积排放量(P 0. 05),相比CKU分别减少了32. 42%和47. 61%. W-SHC处理氨挥发减排效果稍弱,NH_3挥发累积排放量和单位产量NH_3挥发累积排放量相比CKU分别减少了10. 14%和27. 71%.氨挥发减排可能与水热炭的施用导致的田面水pH变化和NH_4~+-N浓度的降低有关.与CKU相比,SHC和W-SHC处理均降低了田面水pH和NH_4~+-N浓度,且在水稻基肥期(BF)和蘖肥期(SF1)影响较明显.土壤脲酶活性受到水热炭施加的显著抑制(P 0. 05),同时土壤氨氧化基因(AOA和AOB)丰度也显著增加(P 0. 05),导致土壤氨氧化作用增强,这对于田面水NH_4~+-N浓度有削减作用.本研究将为实现稻田氨挥发减排背景下的水热炭农业环境应用提供理论和数据支持.     

水热碳化与干法碳化对剩余污泥的处理比较

污泥碳化为当前剩余污泥的妥善处置提供了新方法,由此转化产生的污泥炭可作为土壤修复和改良剂进行资源化利用。为探讨不同的碳化方法对污泥炭特性的影响,分别采用了干法碳化和湿法碳化(水热碳化)对生活污水处理厂的剩余污泥进行处理。结果表明,碳化处理后C、O元素的质量分数均下降,N元素的质量分数则有所增加。与干法碳化相比,水热碳化保留了较多的有机碳。干法碳化后的污泥炭较原污泥呈现弱碱化,而水热碳化则显示酸化趋势。此外,与干法碳化相比,水热碳化在富集有效营养元素(磷、氮)和固定重金属浸出风险上均表现出明显的优势。这些结果预示着水热碳化法在污泥资源化处理方面的巨大潜能。     

催化剂在生物质水热碳化过程中的应用研究进展

在追求废弃物资源化利用的过程中,生物质转化技术受到广泛关注。水热碳化法目前被认为是将高含水率生物质转化为生物炭的最有效技术之一,其与传统的热解炭相比,获得的水热炭具有灰分低、热值高、比表面积大、吸附能力强等特点。然而,生物质原料的差异需要更高的能耗优化,以此提高水热炭产率和性能。添加催化剂可以克服这一问题,对提高原料的反应速率及水热炭热稳定性具有重要意义,但少有文献归纳总结催化剂在生物质水热碳化过程中的应用。将催化剂分为盐类、酸类、金属氧化物、沸石和组合催化5种类型,探讨添加催化剂对水热炭产率和理化性质的影响,分析各类催化剂的催化反应机理,总结其在水热碳化中的催化特点,并讨论了催化剂在生物质水热碳化中未来重点研究方向。     

大粒径厨余垃圾水热碳化制备炭燃料

开展了不同温度条件（150～300℃）下大粒径（>2 cm）厨余垃圾水热碳化实验,研究了水热炭的理化性质、燃烧特性和关键元素迁移规律.实验结果表明,当水热温度过低,厨余垃圾颗粒尺寸影响水热碳化效果;大粒径厨余垃圾碳化需更高的水热温度;水热温度250～300℃产生的水热炭具有高热值(24.48～26.9 MJ·kg^-1)、高燃料比（0.44～0.56）、高含碳量（59.6%～65.6%）和低含灰量（8.51%～4.35%）的特点.随着水热温度提高,水热炭中碳含量升高、灰含量下降;水热炭的着火温度、燃烬温度、挥发分释放特性指数VI、可燃性指数CI和综合燃烧特性指数CP均上升,提高了燃烧稳定性;同时水热炭中K、Na浓度降低,有利于降低水热炭燃烧结焦;N、S在水热炭中分布比例下降,这将减少水热炭燃烧的烟气污染物排放.因此,水热碳化能实现大粒径厨余垃圾的燃料化利用.     

改性城市污泥水热炭对铜和镉的吸附实验

水热碳化作为废弃生物质资源化利用的新兴工艺技术,可弥补我国城市污泥资源化处理方式的不足。实验研究了反应温度和时间对污泥水热产物性质的影响,并探究了水热炭通过KOH改性后对溶液重金属的吸附性能。结果表明:提高温度和延长时间有利于提升水热炭稳定程度与吸附性能;综合考量吸附效果与制备成本,确定水热碳化反应温度220℃和反应时间1 h为最佳反应条件;水热炭活化后对溶液中铜和镉的吸附性能良好,饱和吸附量分别达到49. 89,52. 04 mg/g,吸附过程可用Lagergren伪二级动力学模型和Langmuir/Freundlich吸附等温模型进行较好地拟合。     

生物炭添加对半干旱地区土壤温室气体排放的影响

为确定生物炭添加对半干旱地区农田土壤温室气体释放的影响,采用小区定位试验,利用锯末(J)和槐树皮(H)及3种添加比例(1%、3%、5%,质量百分比),研究了生物炭添加6个月内表层土壤CO2、CH4和N2O等3种温室气体排放的动态变化.结果表明,与对照相比,各处理土壤CO2排放通量随生物炭的添加呈现增加的趋势,锯末和槐树皮等两种生物炭处理的土壤CO2平均排放通量分别增加了1.89%和3.34%,但差异不显著.CH4排放随着生物炭添加量的增加而降低,各生物炭处理的土壤表层CH4排放量平均降幅分别为:J1:1.17%、J3:2.55%、J5:4.32%、H1:2.35%、H3:5.83%、H5:7.32%.其中,锯末生物炭仅在5%添加量时较对照差异显著(P0.05),而槐树皮生物炭处理在3%和5%的添加量与对照差异均达显著水平(P0.05).生物炭对N2O的排放影响没有明显规律性.研究表明,生物炭在短期内对半干旱地区农田土壤CO2和N2O的排放没有显著影响,而对CH4排放则影响显著(P0.05).就生物炭类型而言,槐树皮生物炭在抑制CH4排放方面优于锯末生物炭,差异显著(P=0.048).     

有机改良剂及生物炭对离子型稀土矿尾砂地生态修复的改良探究

选取有机改良剂稻草、锯末、城市污泥、鸡粪及麻杆生物炭进行单施或配施,通过室内杂交狼尾草和红麻盆栽实验,探讨有机改良剂及同时生物炭对离子型稀土矿尾砂地土壤的改良效果.结果表明:①单施4种有机改良剂均能显著提高杂交狼尾草生物量,其中鸡粪处理效果最好;但鸡粪处理中实验前后土壤中有机质亏损高达73.8%,其改良效果持久性较低;而锯末处理中有机质仅亏损16.0%,改良效果持久性更佳.②相对于单施鸡粪,配施麻杆生物炭或锯末均显著增加红麻生物量,显著提高土壤中有机质的含量及土壤持水性,减缓了营养元素的流失;且明显改善有机质亏损,尤其配施锯末后土壤有机质亏损降至45.4%,提高了改良效果持久性.因此,鸡粪配比麻杆生物炭或锯末处理改良长效性较好,环境风险低,可应用于稀土尾砂地基质改良,加快植被复垦.     

生物炭负载氮还田对水稻生长、根系形态及氮素利用的影响

建立连接富营养化水体养分与农田养分的枢纽是减少农田养分投入、缓解水体富营养化的难点.为探明生物炭材料负载氮还田的可行性,开展了基于溶液氮及生物炭负载氮两种氮源添加方式的水稻根箱试验.结果表明,生物炭负载氮添加方式分别较溶液氮添加方式降低了水稻地上部分生物量及氮累积16%及14%,提高了生物量根冠比25%～27%,降低了氮利用效率.不定根的根长及体积是两种氮源添加方式在水稻地下部分差异的体现,地下部分生物量及氮累积与土壤铵态氮含量呈正相关关系,而地上部分氮累积与根尖数呈负相关关系.生物炭负载氮完全替代化学肥料施用农田会影响水稻生物量及氮素利用.但生物炭负载氮与普通化学肥料共同施用,水稻并不会显现利用偏好.生物炭负载氮对水稻氮素利用无不良影响,且能有效提高土壤矿质态氮固持量.因此,生物炭可以作为载体实现水体到农田土壤的氮素迁移,鉴于化肥氮替代比例对作物生长的影响,适宜替代比例还需进一步研究确定.     

两种土壤增效剂对稻田氨挥发排放的影响

硝化抑制剂和生物炭是农田土壤管理常用的土壤增效剂.其中,硝化抑制剂可以增加作物产量提高氮素利用率,而生物炭是生物质资源利用的一种新方式,且具有一定的吸附特性.以减少稻田氨挥发带来的氮素损失及环境污染问题为目的,在原状土柱模拟试验条件下,以单施化肥处理(CN)为对照,研究了生物炭(B)添加、硝化抑制剂(CP)添加及复合添加处理(BCP)对田面水p H、田面水铵态氮浓度、水稻产量及氨挥发损失的影响.结果表明,两种增效剂施用对水稻产量无显著影响,硝化抑制剂添加有增加水稻产量的趋势.两种土壤增效剂添加均显著增加了稻田氨挥发损失,损失量占施氮量的25%～35%.其中,肥期(施肥后7 d内)氨挥发损失占总损失的86%～91%,是氨挥发损失的主要时期.与CN处理相比,CP处理明显提高了田面水NH_4~+-N浓度和氨挥发损失,基肥期、穗肥期和非肥期增加效应明显,氨挥发增幅分别为138%、48%和78%,全生育期氨挥发总损失量增加59%.生物炭添加对稻田氨挥发损失也有明显的促进效应,且具有阶段性特征,前期(基肥期和蘖肥期)的增加效应高于后期(穗肥期和穗肥后),田面水NH_4~+-N浓度和p H也表现出相同的趋势.两者配施添加处理显现出了正交互作用,氨挥发损失量大于单施处理,与化肥处理差异显著.结果说明,生物炭添加不能解决硝化抑制剂添加引起的铵态氮浓度升高和氨挥发损失增加的问题,对于硝化抑制剂添加引起的氨挥发损失增加的问题需要继续研究.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

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.