不同类型堆肥中腐殖酸与富里酸的光谱特性和分子量分布

以中药渣(HR)、小麦秸秆(WS)和稻壳(RH)为辅料工业化生产的鸡粪堆肥中的腐殖酸(HA)和富里酸(FA)为研究对象,系统对比分析了不同类型堆肥腐殖质(HSs)的光谱特性和分子量分布。结果表明,3类堆肥中HA的芳香性均高于FA,HR和RH堆肥中HA和FA的芳香化程度均高于WS堆肥。三维荧光区域体积积分结果显示,HA的类腐殖质含量(Ⅲ+Ⅴ,86%～91%)高于FA(56%～64%),而FA的类蛋白物质(Ⅰ+Ⅱ,28%～37%)远高于HA(5%～9%),表明HA具有更高的腐殖化程度和分子量特征;其次,RH和WS堆肥中FA分别含有更多的类富里酸和类腐殖酸,而HR堆肥中FA的类络氨酸组分更多。傅里叶红外光谱分析发现,FA比HA含有更多的酰胺和羧酸,其中HR、WS和RH堆肥中FA分别富含芳香族羧酸、酰胺和多糖结构。元素分析结果显示,与FA相比,堆肥HA具有较高的C/N比和较低的O/C比,表明HA具有更多的不饱和结构,而FA具有更多的含氧官能团。添加不同辅料的堆肥中,WS堆肥HSs的脂肪化程度最高。高效体积排阻色谱结果显示,HA比FA具有更宽的高分子量分布(>2×10⁴     

菌渣好氧堆肥过程中腐熟度指标及红外光谱的动态变化

为实现食用菌菌渣的合理处置及资源化利用,以食用菌菌渣、鸡粪和豆渣为原料,共设计3个堆肥处理(菌渣与黄豆渣混堆,C1;菌渣与鸡粪混堆,C2;菌渣直接堆制,C3),通过高温好氧堆肥方式研究堆肥过程中相关腐熟度指标及红外光谱的动态变化。结果表明,堆肥过程中温度变化经历了3个阶段,50℃以上高温持续时间均大于10 d。pH总体呈上升趋势,至堆肥结束达到8.0—9.0之间,符合腐熟堆肥的标准;EC值在1.0—2.5 mS·cm~(-1)范围内浮动,C1处理的EC值大于C3的EC值;C/N总体呈下降趋势,堆肥结束时3种处理的比值均低于20;种子发芽指数(GI)随着堆肥过程逐渐上升,至21d时,3种处理的GI值均超过50%,堆肥结束时,C3的GI值达到72.46%,C1、C2的GI值分别为81.02%和82.36%。堆肥过程中胡敏酸(HA)含量逐渐升高,富里酸(FA)的含量变化不大,3种处理胡敏酸与富里酸的比值(HA/FA)总体呈升高趋势,C1、C2和C3的HA/FA值分别由初始的2.38、2.20和2.28增加到3.92、3.22和3.82。红外光谱数据表明,随着堆肥过程的进行,多糖类物质含量减少,有机物中不饱和结构的多聚化或联合程度增大,芳香结构物质与氨基基团有所增加,说明堆肥过程中有机物质的变化规律先是大分子物质(如蛋白质、多糖类等)被降解,然后是腐殖质类物质的逐渐合成。     

蚯蚓处理对城市生活污泥水溶性有机物结构特性的影响

对蚯蚓处理前后污泥水溶性有机物的量及分子量比例进行了分析,同时采用傅立叶红外光谱(FTIR)和荧光光谱分析技术,研究了水溶性有机物的组成与结构特征变化.结果表明,和对照相比,污泥经蚯蚓处理后,水溶性有机物的含量和小分子有机物的比例增加,小分子物质含量增加12%.红外光谱和荧光光谱的结果表明,污泥经蚯蚓处理后,水溶性有机物中羧基和多糖类物质增加,芳香族类物质的量增多,产生了少量的蛋白质类物质.同时发现,蚯蚓处理使污泥水溶性有机物不饱和结构的多聚化或联合程度变小,水溶性有机物的结构变得更加简单,形成了更多的小分子有机物。     

草炭溶解态有机物质与Cu2+、Cd2+络合稳定性的研究

研究了由草炭提取的胡敏酸(HA)、富里酸(FA)、水溶解态有机物质(WSOM)的基团特征,分子量分布及其与Cu2+、Cd2+两种金属离子之间的络合稳定性。对HA、FA及WSOM的红外光谱研究显示三者的官能团组成相似,只是含量略有不同。固态13C-NMR对HA、FA及WSOM结构特征的描述以及水相凝胶色谱法对三种有机质样品的分子量及分子量分布的测定结果显示HA分子最大且含有大量的长链烷烃,而FA分子小得多,结构以碳水化合物及多糖为主,WSOM的分子量略低于FA,结构与FA相近。离子交换平衡法对三种有机质样品与Cu2+、Cd2+的络合配位数和稳定常数的测定结果显示两种介质条件下络合配位数(x)、络合稳定常数(logk)的次序均为:Cu2+>Cd2+;同一介质条件下,对不同有机质而言均满足:M-HA>M-FA>M-WSOM。     

松花江腐殖酸的提取、表征及与重金属的络合作用

本文提得了第二松花江水及底泥中的黄腐酸(FA)和棕腐酸(HA),测定了总酸性基、羧基、醌基等官能团并进行了元素分析,研究了红外、紫外及荧光光谱,与一般水体腐殖酸的特征相同。 选用凝胶过滤法研究了腐殖酸与汞、镉、锌的络合作用,测定了水及底泥的FA和HA对Zn、Cd、Hg的络合容量,其趋势为Hg>Cd>Zn,计算了条件稳定常数,logA值显示出汞与腐殖酸的稳定性高于汞与水体中除S~(2-)及SH-外的其它配位络合物,合成了腐殖酸汞固体络合物,用红外光谱确定其络合作用,测定了腐殖酸汞在水中的溶解度。     

污泥堆腐过程中腐殖酸组分及结构变化特征

污泥是污水处理过程中的副产物,含有重金属、有机污染物、病原菌和寄生虫卵等有毒有害物质。为了明确堆腐对污泥中腐殖酸的影响,本研究在污泥∶草炭∶稻草=3∶1∶2(干重比)和55%含水量条件下,开展了为期30 d的堆腐试验。采用紫外光谱仪、红外光谱仪等仪器手段,研究了污泥堆腐过程中腐殖酸组成及结构变化。结果表明,污泥堆腐过程中腐殖酸含碳量呈先下降后上升的变化规律,但变幅较小;胡敏酸含碳量由23.5 g·kg~(-1)逐渐增至51.4 g·kg~(-1),增幅为118.9%;而富里酸碳含量则由46.1 g·kg~(-1)逐渐降至20.8 g·kg~(-1),降幅为54.8%。紫外光谱表明,堆腐过程中胡敏酸和富里酸的最大吸收峰位置没有发生明显变化,但峰形变宽,E_(465)/E_(665)值降低;傅立叶变换红外光谱表明,堆腐前后胡敏酸和富里酸特征吸收峰位置比较相近,但某些官能团的强度发生改变,堆腐后胡敏酸和富里酸的芳构化和腐殖化程度提高。     

市政污泥堆肥过程胡敏酸电子转移能力的演变规律

腐殖质作为电子穿梭体在介导有机污染物和重金属降解和转化过程中具有十分重要的作用.本研究通过电化学方法测定了市政污泥堆肥胡敏酸的电子转移能力(electron transfer capability,ETC),并利用三维荧光光谱和紫外-可见光光谱分析探讨堆肥过程胡敏酸化学组成和结构变化对其ETC的影响.结果表明,堆肥胡敏酸的电子接受能力(electron accepting capacity,EAC)和电子供给能力(electron donating capacity,EDC)分别在12.46—18.62μmol e-·g~(-1)C和165.07—257.84μmol e-·g~(-1)C之间,从堆肥初期到堆肥末期,两者均呈现增加的趋势.元素分析结果表明在堆肥前期N、C和H含量下降较快,而S含量在后期下降较快.平行因子分析发现,随着堆肥进行胡敏酸中代表类腐殖质物质的组分1和组分3的含量逐渐升高,而代表类蛋白物质的组分2的含量逐渐减少.胡敏酸HIX、S_R和SUVA_(269)分别从初期的0.523、3.33和1.69变至0.732、2.20和2.39,说明胡敏酸中有机质的腐殖质化程度、分子量和芳香性均随着堆肥腐熟呈现出增大趋势.相关性分析表明,随着堆肥进行胡敏酸中类腐殖质物质增多、类蛋白物质减少,导致胡敏酸分子量、芳香度与腐殖质化程度增大,从而促进了胡敏酸EDC和EAC的增加.     

垃圾渗滤液中有机物分子量的分布及在MBR系统中的变化

利用凝胶层析方法分析了垃圾渗滤液中有机物分子量的分布情况,并考察了利用膜生物反应器(MBR)处理垃圾渗滤液系统中有机污染物分子量的分布以及水溶性腐殖质(AHS)含量的变化．研究发现,垃圾渗滤液中的有机物主要由两部分组成,即分子量大于6000的大分子物质和分子量小于1500的小分子物质．大分子物质主要是水溶性腐殖质,而小分子物质主要由挥发性有机酸及水溶性腐殖质组成．大分子的AHS难以被微生物降解,但能被微滤膜截留．大部分小分子的AHS既难以被微生物降解,又不能被膜截留,是构成MBR处理出水COD的主要成分．     

生活垃圾填埋富里酸电子转移能力与影响因素

为了研究生活垃圾填埋过程中富里酸(fulvic acids,FA)电子转移特征及其影响因素,通过紫外-可见吸收、荧光和红外光谱手段表征FA结构,使用电化学方法测定FA的电子供给能力(electron donating capacity,EDC)和电子接受能力(electron accepting capacity,EAC).结果表明,填埋初期(1—3年)FA分子量和芳香性随填埋深度增加而减小,而填埋中后期(3年)FA分子量和芳香性随填埋深度增加而增加.随着填埋深度的增加FA中羟基和羧基含量先增加后减少,碳水化合物含量持续减少.填埋初期,FA的EAC随着填埋深度的增加而增加,EDC变化趋势不明显;填埋中后期FA的EDC和EAC随填埋深度呈现先增加后减小的趋势.表层填埋垃圾中FA给电子基团起主导作用,而深层填埋垃圾中FA接受电子基团起主导作用.相关性分析显示FA分子量越小、碳水化合物含量越低、羟基含量越高,越利于FA给出电子;而FA分子量越大、羧基含量越高、碳水化合物和脂肪族含量越低,越利于FA得到电子.     

堆肥过程中腐殖质含量变化及其对重金属分配的影响

以H2O和Na4P2O7+NaOH连续浸提污泥堆肥过程中堆体的腐殖酸以及与其结合的重金属,分析腐殖酸及重金属含量随时间的变化规律。结果表明,堆肥过程中重金属主要以胡敏酸(HA)结合态为主,水溶态重金属含量较少,且重金属有效性与迁移性较低;堆肥结束时各水溶态重金属含量减少,HA-Pb、HA-Ni和HA-Cu含量占重金属总量的比例明显升高,与堆肥初始相比分别增加28.00、17.34和1.40百分点,堆肥促进了水溶态重金属向HA结合态转变;HA对几种重金属的固定能力由大到小依次为Cu、Pb、Ni和Zn。     

Scanning Electron Microscopy of Humic Substances Produced During Cellulose Decomposition

Humic substances (HS) produced during the aerobic decomposition of polysaccharides still need to be recognized as such and characterized. Humic (HA) and fulvic (FA) acids extracted at different time intervals during composting of cotton residues from carding, where no decomposition of lignin occurred, were investigated by scanning electron microscopy (SEM) size exclusion chromatography and infrared spectroscopy. Throughout the experiment, fulvic acids possessed a larger number of carboxyl groups but a lower number of weak acidic groups (negatively charged acid groups at pH 11) than humic acids. the number of carboxyl groups increased with time in both fulvic and humic acids, while that of phenolic groups decreased. Infrared spectra showed that the ratio between carboxyl and methyl groups decreased from 8.5 to 4 in FA after 18 days. This change corresponded with the disappearance of flat sheet structures observed by SEM at pH 6. Our results suggest that the shape of humic molecules as observed by SEM reflects the strength of hydrophilic/hydrophobic interactions with the solvent molecules. About 80% of FA molecules had a molecular weight lower than 3500 as deduced from column calibration with HS standards obtained by ultrafiltration. About 40% of humic acids were composed of small molecules; only 20% HA had a molecular weight larger than 45000. Polysaccharide-derived HS may not be limited to the high molecular weight poorly transformed fraction containing bonded polysaccharide structures, but may also consist of low molecular weight components with no structural similarity to the original material.     

不同时期添加蘑菇渣对落叶堆肥过程的影响

研究不同时期添加蘑菇渣对落叶堆肥过程的影响.结果表明:堆肥降温期添加蘑菇渣有利于提高有机质的降解率,堆肥末期各处理有机质降解率分别为15.85%,10.17%,12.90%和15.16%;有利于吸收固定堆肥中的氨,减少氨的挥发,降低堆肥的pH值.在堆肥初始一次性添加蘑菇渣,有利于堆肥总氮的积累,提高堆肥产品中胡敏酸和腐殖质含量,降低堆肥总氮损失率.在堆肥初始和降温期分次添加蘑菇渣有利于堆肥硝态氮的合成,富里酸的分解以及HA/FA的增加.在整个堆肥过程中,各处理HA和HA/FA均呈增加趋势,FA呈降低趋势,较好地反映了落叶堆肥的腐熟程度.在堆肥不同阶段添加蘑菇渣各有其优点,综合后认为在堆肥初始添加蘑菇渣的效果最为理想.     

蚯蚓-稻壳炭联合堆肥对工业污泥中重金属的影响研究

蚯蚓堆肥相关研究多集中在生活污泥方面,对工业污泥的探索较少。该研究以马鞍山某钢铁污水处理站污泥为例,添加不同比例稻壳炭(2%、4%、8%),设置污泥单独堆肥、稻壳炭与污泥堆肥以及蚯蚓-稻壳炭联合污泥堆肥试验,探索蚯蚓与稻壳炭联合堆肥对工业污泥中重金属形态和生物有效性的影响。研究表明,(1)相比污泥单独堆肥,稻壳炭联合污泥堆肥能增加污泥pH、EC、TP和降低TOC、TN,而蚯蚓联合稻壳炭堆肥污泥可增加TN,并进一步增加污泥EC、TP,显著降低污泥的pH、TOC。(2)稻壳炭堆肥中重金属Zn、Cu、Pb、Cd含量因浓缩效应而上升;而蚯蚓联合稻壳炭堆肥,重金属含量显著下降,添加4%稻壳炭时,重金属Zn、Cu、Pb、Cd质量分数达到最小值,分别为856.64、137.10、158.92、15.48mg·kg-1。(3)重金属形态分析表明,随着稻壳炭比例增加,稻壳炭堆肥中重金属Zn、Cu、Pb、Cd的交换态和碳酸盐结合态转化为残渣态及铁锰氧化态的比例增大,添加8%稻壳炭时DTPA提取的有效态重金属质量分数最低,分别为705.72、47.95、50.43、4.47 mg·kg-1;蚯蚓-稻壳炭联合堆肥会使得污泥中重金属交换态、碳酸盐结合态、铁锰结合态和有机结合态均向残渣态转化,添加4%稻壳炭与蚯蚓的协同转化能力最大,Zn、Cu、Pb、Cd有效态重金属质量分数分别为629.84、38.63、36.76、1.63mg·kg-1,说明稻壳炭添加入蚯蚓堆肥可进一步降低工业污泥中重金属有效性,使重金属钝化。本研究可为稻壳炭联合蚯蚓堆肥处理工业污泥提供参考和科学依据。     

交替冻融对东北典型土壤腐殖质的影响

以受季节性冻融过程影响显著的东北地区的黑土、暗棕壤和水稻土为例,采用实验室模拟的方法,研究交替冻融循环过程（分别在-20℃和20℃下处理）对土壤腐殖质的影响。研究表明：交替冻融后,黑土和暗棕壤松结态腐殖质质量分数分别增加了39%和28%,HA/FA分别上升了45%和35%;水稻土松结态腐殖质质量分数和HA/FA分别下降了18%和31%。三维荧光结果进一步验证,黑土、暗棕壤在交替冻融中土壤芳香化程度增高,HA/FA上升,而水稻土则相反。黑土和暗棕壤松结态腐殖质和HA/FA升高,主要是微生物分解作用和土壤大团聚体破坏等原因造成,水稻土松结态腐殖质和HA/FA降低,主要是水稻土的缺氧环境造成。     

新型调理剂CTB-2污泥堆肥的氧气时空变化特征研究

采用新型CTB-2调理剂与城市污泥进行堆肥,研究了堆肥过程中氧气、温度的时空变化特征。结果表明,m（CTB-2调理剂）：m（污泥）=1：2能够有效降低污泥容重,改善堆体结构;堆体能够快速升温至高温期并持续7d以上,最终完成无害化;采用该比例的调理剂能够保证堆体的通风供氧,使堆体各层通风后的氧气体积分数都恢复至19％以上,最低氧气体积分数维持在数17％以上;堆肥过程中堆体的氧气体积分数、耗氧速率和温度都具有明显的层次效应,堆体耗氧速率呈先升高后降低的趋势,堆体通风后的氧气和最低氧气体积分数均随着堆肥的进行而增加。     

城市污泥不同处理处置方式的成本和效益分析--以北京市为例

以北京市为例,估算不同电价及运输距离下填埋、焚烧及堆肥等方式的城市污泥处理处置成本,在此基础上讨论各种处理处置方案的前景,展望北京市污泥处理处置出路。污泥填埋在一定时期内还将是主要处理处置方式,但所占比例将逐渐下降;堆肥是经济上较为可行的处理处置方式,适合大力推广;随着经济实力与技术水平提高,焚烧法可以适用于个别特殊地点。同时,分析了政府补贴对污泥处理处置效益的影响。     

Use of gamma-irradiation pretreatment for enhancement of anaerobic digestibility of sewage sludge

The effects of γ-irradiation pretreatment on anaerobic digestibility of sewage sludge was investigated in this paper. Parameters like solid components, soluble components, and biogas production of anaerobic digestion experiment for sewage sludge were measured. The values of these parameters were compared before and after γ-irradiation pretreatment. Total solid (TS), volatile solid (VS), suspended solid (SS), volatile suspended solid (VSS), and average floc size of samples decreased after γ-irradiation treatment. Besides, floc size distribution of sewage sludge shifted from 80–100 μm to 0–40 μm after γ-irradiation treatment at the doses from 0 to 30 kGy, which indicated the disintegration of sewage sludge. Moreover, microbe cells of sewage sludge were ruptured by γ-irradiation treatment, which resulted in the release of cytoplasm and increase of soluble chemical oxygen demand (SCOD). Both sludge disintegration and microbe cells rupture enhanced the subsequent anaerobic digestion process, which was demonstrated by the increase of accumulated biogas production. Compared with digesters fed with none irradiated sludge, the accumulated biogas production increased 44, 98, and 178 mL for digesters fed sludge irradiated at 2.48, 6.51, and 11.24 kGy, respectively. The results indicated that γ-irradiation pretreatment could effectively enhance anaerobic digestibility of sewage sludge, and correspondingly, could accelerate hydrolysis process, shorten sludge retention time of sludge anaerobic digestion process.     

高温堆肥碳氮循环及腐殖质变化特征研究

堆肥化处理，是指依靠自然界广泛分布的细菌、放线菌、真菌等微生物，对有机物有控制地进行生物降解，使之转化为腐殖质的生物化学处理技术。作者采用畜禽粪便条垛式高温堆肥实验方法，研究了堆肥过程中碳氮循环及腐殖质变化特征。结果表明，堆肥过程中，碳素和氮素变化最大，表现为二者总量的减少，其中以碳素总量减少较多，氮素总量次之，从而导致碳氮质量分数比降低。腐殖酸总量、胡敏酸和富里酸总量均呈下降趋势，但腐殖酸占有机碳的比例以及胡敏酸与富里酸质量分数比却在提高，速效养分含量也在升高，表明堆肥过程是一个有机质数量减少、有机质质量提高的过程。     

Possible solutions for sludge dewatering in China

In China, over 1.43×10⁷ tons of dewatered sewage sludge, with 80% water content, were generated from wastewater treatment plants in 2007. About 60% of the COD removed during the wastewater treatment process becomes concentrated as sludge. Traditional disposal methods used by municipal solid waste treatment facilities, such as landfills, composting, or incineration, are unsuitable for sludge disposal because of its high water content. Disposal of sludge has therefore become a major focus of current environmental protection policies. The present status of sludge treatment and disposal methodology is introduced in this paper. Decreasing the energy consumption of sludge dewatering from 80% to 50% has been a key issue for safe and economic sludge disposal. In an analysis of sludge water distribution, thermal drying and hydrothermal conditioning processes are compared. Although thermal drying could result in an almost dry sludge, the energy consumption needed for this process is extremely high. In comparison, hydrothermal technology could achieve dewatered sewage sludge with a 50%–60% water content, which is suitable for composting, incineration, or landfill. The energy consumption of hydrothermal technology is lower than that required for thermal drying.     

Biodegradation of triclosan and triclocarban in sewage sludge during composting under three ventilation strategies

TCS and TCC can be biodegraded during sewage sludge composting. Ventilation significantly accelerated the biodegradation of TCS and TCC in sludge. Composting can reduce the environmental risk of TCS and TCC in sewage sludge. Triclosan (TCS) and triclocarban (TCC) are widely used in home and personal care products as antimicrobial agents. After these products are used, TCS and TCC enter the terrestrial environment and pose a great risk to humans and animals. In this research, the biodegradation of TCS and TCC was investigated during sewage sludge composting with ventilation rates of 108, 92, and 79 m³/min. TCS and TCC were mainly biodegraded in the mesophilic and thermophilic phases, and the biodegradation rates improved with an increase in ventilation. After sewage sludge was composted for 16 days with forced ventilation (108 m³/min), the concentration of TCS decreased from 497.4 to 214.5 μg/kg, and the concentration of TCC decreased from 823.2 to 172.7 μg/kg. The biodegradation rates of TCS and TCC were 65.2% and 83.1%, respectively. However, after the sewage sludge was stacked for 16 days, the biodegradation rates of TCS and TCC were only 17.0% and 18.2%, respectively. The environmental risks of TCS and TCC in the sewage sludge piles significantly decreased after composting. In the sludge pile with a ventilation rate of 108 m³/min, the RQ values of TCS and TCC decreased from 8.29 and 20.58 to 3.58 and 4.32 after composting for 16 days, respectively. There is still a high risk if the sludge compost is directly used as a culture substrate. Nevertheless, the environmental risk could be decreased distinctly if a reasonable quantity of sludge compost is applied to land to ensure an RQ of<1 for TCS and TCC.