兼氧条件下厨余垃圾发酵液作碳源的反硝化性能

在兼氧条件下,利用厨余垃圾厌氧发酵液调节反硝化系统的碳氮比（COD/TN,C/N）,并考察了其脱氮性能.结果表明,不同C/N条件下,反应系统均未出现有机物的积累,但高C/N条件下的亚硝酸盐最大积累浓度和积累速率高于低C/N;随着进水C/N的增大,反应整体脱氮率和反硝化速率不断增大,当C/N为13时,反硝化速率达到了最大值,为9.79mg/（gVSS·h）,其脱氮率超过95%;相同C/N条件下,反硝化速率和最大亚硝酸盐积累浓度均与进水硝酸盐浓度成正比.此外,实验结果表明,兼氧条件下的反硝化过程虽不易出现COD残留,但去除单位氮所需的有机物更多,且整体反硝化速率以及亚硝酸盐还原速率均低于厌氧条件.     

Assessment and prediction of the effect of ageing on the adsorption of nonylphenol in black carbon-sediment systems

Black carbon (BC) is a promising sediment amendment, as proven by its considerable adsorption capacity for hydrophobic organic pollutants and accessibility, but its reliability when used for the removal of pollutants in natural sediments still needs to be evaluated. For example, the ageing process, resulting in changing of surface physicochemical properties of BC, will decrease the adsorption capacity and performance of BC when applied to sediment pollution control. In this study, how the ageing process and BC proportion affect the adsorption capacity of BC-sediment systems was modelled and quantitatively investigated to predict their adsorption capacity under different ageing times and BC additions. The results showed that the ageing process decreased the adsorption capacity of both BC-sediment systems, due to the blockage of the non-linear adsorption sites of BC. The adsorption capacity of rice straw black carbon (RC)-sediment systems was higher than that of fly ash black carbon (FC)-sediment systems, indicating that RC is more efficient than FC for nonylphenol (NP) pollution control in sediment. The newly established model for the prediction of adsorption capacity fits the experimental data appropriately and yields acceptable predictions, especially when based on parameters from the Freundlich model. However, to fully reflect the influence of the ageing process on BC-sediment systems and make more precise predictions, it is recommended that future work considering more factors and conditions, such as modelling of the correlation between the adsorption capacity and the pore volume or specific surface area of BC, be applied to build an accurate and sound model.     

Effects of chemical modification on physicochemical properties and adsorption behavior of sludge-based activated carbon

This study aimed to explore the adsorption performance of sludge-based activated carbon (SBC) towards dissolved organic matters (DOMs) removal from sewage, and investigated the modification effect of different types of chemicals on the structure of synthesized SBC. Waste activated sludge (WAS) was used as a carbon source, and HCl, HNO₃, and NaOH were used as different types of chemicals to modify the SBC. With the aid of chemical activation, the modified SBC showed higher adsorption performances on DOMs removal with maximum adsorption of 29.05 mg/g and second-order constant (k) of 0.1367 (L/mol/sec) due to the surface elution of ash and minerals by chemicals. The surface elemental composition of MSBC suggested that the content of C-C and C-O functional groups on the surface of modified sludge-based activated carbon (MSBC) played an important role on the adsorption capacities of MSBC towards DOMs removal in sewage. Additionally, the residual molecular weight of DOMs in sewage was investigated using a 3-dimension fluorescence excitation-emission matrix (3D-EEM) and high-performance size exclusion chromatography (HP-SEC). Results showed that the chemical modification significantly improved the adsorption capacity of MSBC on humic acids (HA) and aromatic proteins (APN), and both of NaOH-MSBC and HCl-MSBC were effective for a wide range of different AMW DOMs removal from sewage, while the HNO₃-MSBC exhibited poorly on AMW organics of 2,617 Da and 409 Da due to the reducing content of macropore. In brief, this study provides reference values for the impact of the chemicals of the activation stage before the SBCs application.     

生物炭负载P掺杂g-C3N4复合光催化剂制备及其对萘光催化降解机制

采用农业资源废弃物玉米秸秆为生物质原材料,双氰胺为前驱物,（NH₄）₂HPO₄为磷源,通过高温煅烧和浸渍法成功制备了可循环使用的生物炭负载P掺杂g-C₃N₄复合光催化剂,并采用X射线衍射（XRD）、红外光谱（FTIR）、扫描电子显微镜（SEM）、紫外可见漫反射（UV-vis DRS）和光致发光光谱（PL）等手段对所制备样品的化学结构、表观形貌和光学特性进行了表征.结果表明,成功将P元素引入g-C₃N₄结构中,可有效改变其能带结构,降低其光生载流子复合几率;此外,生物炭作为载体,具有较好的稳定性和特殊的光电性能,不仅有利于g-C₃N₄的光电荷分离,还可提高其对可见光的响应能力.选取多环芳烃萘作为研究对象来探究不同种类光催化剂的光催化性能及对萘的去除效率.结果表明,质量比为1：1的生物炭负载P掺杂g-C₃N₄对萘表现出了最优的光催化性能,去除率为76.41%,一级动力学反应速率常数为0.0084 min^-1,是纯g-C₃N₄的3.1倍.此外,通过自由基捕获实验提出了光催化降解萘的可能机理.     

MnFe2O4@HTC活化过硫酸盐体系除藻效能与机制

采用水热法和共沉淀法将MnFe₂O₄负载在水热炭（HTC）表面制备磁性MnFe₂O₄@HTC复合催化剂.采用SEM、XRD、BET、FTIR、XPS对催化剂进行表征,通过考察MnFe₂O₄/HTC负载比、过硫酸钠（PS）投加量、初始pH和不同化学体系对除藻效果的影响,探究无供氧条件下MnFe₂O₄@HTC活化PS体系除藻的效能.基于自由基屏蔽实验和XPS分析对MnFe₂O₄@HTC活化PS体系反应机制进行研究验证.结果表明,当初始藻浓度为1.4×10⁹个·L^-1（OD₆₈₀=0.14）,催化剂投加量为0.2 g·L^-1,PS投加量为0.4 g·L^-1,pH为6时,降解30 min,该体系除藻率可达到99%.在该体系中,MnFe₂O₄@HTC材料可将藻细胞吸附在材料表面,通过Mn、Fe的价态循环和HTC的协同效应反应催化PS产生空穴、¹O₂、·O₂^-、SO₄^-·和·OH多种氧化物质,使藻细胞破裂死亡.     

Catalytic fast pyrolysis of walnut shell for alkylphenols production with nitrogen-doped activated carbon catalyst

• N-doped activated carbon was prepared for catalytic pyrolysis of walnut shell. • Alkylphenols were selectively produced from catalytic pyrolysis process. • The alkylphenols yield increased by 8.5 times under the optimal conditions. • Formation mechanism of alkylphenols was proposed. Alkylphenols are a group of valuable phenolic compounds that can be derived from lignocellulosic biomass. In this study, three activated carbons (ACs) were prepared for catalytic fast pyrolysis (CFP) of walnut shell to produce alkylphenols, including nitrogen-doped walnut shell-derived activated carbon (N/WSAC), nitrogen-doped rice husk-derived activated carbon (N/RHAC) and walnut shell-derived activated carbon (WSAC). Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments were carried out to reveal the influences of AC type, pyrolytic temperature, and AC-to-walnut shell (AC-to-WS) ratio on the product distributions. Results showed that with nitrogen doping, the N/WSAC possessed stronger capability than WSAC toward the alkylphenols production, and moreover, the N/WSAC also exhibited better effects than N/RHAC to prepare alkylphenols. Under the catalysis of N/WSAC, yields of alkylphenols were significantly increased, especially phenol, cresol and 4-ethylphenol. As the increase of pyrolytic temperature, the alkylphenols yield first increased and then decreased, while high selectivity could be obtained at low pyrolytic temperatures. Such a trend was also observed as the AC-to-WS ratio continuously increased. The alkylphenols production achieved a maximal yield of 44.19 mg/g with the corresponding selectivity of 34.7% at the pyrolytic temperature of 400°C and AC-to-WS ratio of 3, compared with those of only 4.67 mg/g and 6.1% without catalyst. In addition, the possible formation mechanism of alkylphenols was also proposed with the catalysis of N/WSAC.     

Influence of pore structure on biologically activated carbon performance and biofilm microbial characteristics

• Pore structure affects biologically activated carbon performance. • Pore structure determines organic matter (OM) removal mechanism. • Microbial community structure is related to pore structure and OM removal. Optimizing the characteristics of granular activated carbon (GAC) can improve the performance of biologically activated carbon (BAC) filters, and iodine value has always been the principal index for GAC selection. However, in this study, among three types of GAC treating the same humic acid-contaminated water, one had an iodine value 35% lower than the other two, but the dissolved organic carbon removal efficiency of its BAC was less than 5% away from the others. Iodine value was found to influence the removal of different organic fractions instead of the total removal efficiency. Based on the removal and biological characteristics, two possible mechanisms of organic matter removal during steady-state were suggested. For GAC with poor micropore volume and iodine value, high molecular weight substances (3500–9000 Da) were removed mainly through degradation by microorganisms, and the biodegraded organics (soluble microbial by-products,<3500 Da) were released because of the low adsorption capacity of activated carbon. For GAC with higher micropore volume and iodine value, organics with low molecular weight (<3500 Da) were more easily removed, first being adsorbed by micropores and then biodegraded by the biofilm. The biomass was determined by the pore volume with pore diameters greater than 100 μm, but did not correspond to the removal efficiency. Nevertheless, the microbial community structure was coordinate with both the pore structure and the organic removal characteristics. The findings provide a theoretical basis for selecting GAC for the BAC process based on its pore structure.     

梵净山不同森林植被生物量、净生产量、碳储量及空间分布特征

为做好梵净山国家级自然保护区森林植被保护,摸清自然保护区森林植被资源家底,采用2016年第四次森林资源规划设计调查数据及变更至2019年的森林资源数据,计算和分析保护区内森林植被生物量、净生产量、碳储量。梵净山8种森林类型的总生物量为443.72×10⁴t,总碳储量为219.80×10⁴t,总生长量为29.75×10⁴t·a^?1,总凋落量为18.65×10⁴t·a^?1,总净生产量为48.40×10⁴t·a^?1,总生物量、总碳储量较大的是栎林,较小的是铁杉林,桦木林、阔叶混交林、马尾松林、软阔林、杉木林和硬阔林居中;平均碳密度为48.86 t·hm^?2,依次为:桦木林>阔叶混交林>栎林>硬阔林>软阔林>马尾松林>杉木林>铁杉林;总生长量、年凋落量、净生产量较高的是栎林、硬阔林,较低的是马尾松林、阔叶混交林和铁杉林,3种森林类型合计比例不到10%;在龄组中的分配依次为:中龄林>近熟林>成熟林>幼龄林>过熟林。在不同海拔中,梵净山森林植被生物量、碳储量、生长量、凋落量和净生产量主要分布在海拔1201—1800 m,其分布比例分别为50.39%、50.38%、49.21%、50.08%和49.54%;在不同坡向中,梵净山森林植被生物量、碳储量、生长量、凋落量和净生产量主要分布在南坡和北坡,二者合计比例大于60%。     

基于DNDC模型评估水位变化对滨海湿地净生态系统CO2交换的影响

水位是影响滨海湿地生态系统蓝碳功能的重要因素。气候变化引起的海平面上升以及极端气候事件的频发,可能加快水位的变化,从而改变生态系统碳交换的过程。然而,滨海湿地碳汇功能响应水位变化的机制尚不清楚。为了评估水位对滨海湿地净生态系统CO₂交换(NEE)特征的影响,以及验证DNDC(denitrification-decomposition)模型对模拟预测滨海湿地生态系统碳交换的适用性,该研究设计了野外水位控制试验(自然水位,地下20 cm水位、地表10 cm水位),并利用DNDC模型模拟和预测水位变化对滨海湿地NEE的影响。结果表明:(1)不同水位处理之间NEE差异显著,地表10 cm水位处理促进CO₂吸收,地下20 cm水位则抑制CO₂吸收;(2)经过校准和验证的DNDC模型可以准确模拟水位变化对黄河三角洲湿地NEE的影响,NEE模拟值的日动态与田间观测结果显著相关(R²>0.6);(3)通过改变气候、土壤和田间管理等输入参数对DNDC模型进行灵敏度检验,生态系统碳交换过程对日均温、降雨和水位改变的响应最为显著,其中,水位对NEE的影响主要作用于土壤呼吸(Rs)。未来气候情境下,不同水位变化下的生态系统碳交换过程随年份增长呈现不同的规律,因此未来的模拟研究应关注DNDC中水文模块和植被演替过程的完善。该研究可为预测水文变化情境下滨海湿地碳汇功能的未来发展以及政策制定提供参考。     

水处理用活性炭改性研究

利用锆和氯化十六烷基三甲铵共同改性活性炭,制备一种新型去除污水中硝酸盐和磷酸盐的水处理吸附剂,并考察吸附剂加量、反应温度、pH值、共存阴离子等影响因素对吸附效果的影响。结果表明:锆-氯化十六烷基三甲铵改性活性炭(Zr-CTAC-AC)吸附剂适用于硝酸盐和磷酸盐浓度在100mg/L以下的污水,随着Zr-CTAC-AC加量的增加,硝酸盐、磷酸盐去除率逐渐增加,单位吸附量逐渐下降,Zr-CTAC-AC加量为8g/L时,硝酸盐去除率为79%,Zr-CTAC-AC加量为4.0g/L时,磷酸盐去除率可达91%,但应在较低的pH值范围内使用;反应温度对Zr-CTAC-AC的吸附效果影响不大;共存Cl-、HCO3^-和SO4^2-可使硝酸盐的吸附率降低,但对磷酸盐吸附率影响较小;1mol/L NaCl溶液可使吸附到Zr-CTAC-AC表面的硝酸盐90.9%左右被解吸出来,1mol/L NaOH溶液可使吸附到Zr-CTAC-AC表面的磷酸盐78.4%左右被解吸出来。Zr-CTAC-AC能够有效去除污水中硝酸盐和磷酸盐,制备方法简单,且可循环利用,处理成本低。