Evaluation of thermal reaction for two azo compounds by using 20-L apparatus and calorimetry

Azo compounds are widely involved in the industrial processes of dyes, pigments, initiators, and blowing agents. Unfortunately, these compounds have a bivalent unstable –NN– composition, which can be readily broken when the ambient temperature is elevated. Self-accelerating decomposition might cause a runaway reaction and lead to a fire, explosion, or leakage when the cooling system fails or other events occur. This study investigated the explosion properties, thermal stability parameters, and thermal hazard and mechanism of 2,2′–azobisisobutyronitrile (AIBN) and 2,2′–azobis–2–methylbutyronitrile (AMBN). We used a 20-L apparatus, vent sizing package 2, synchronous thermal analysis, and differential scanning calorimetry under explosive, adiabatic, and dynamic conditions to acquire the explosive curves, thermal curves, and thermodynamic parameters of the substances. Moreover, the differential isoconversional method (Friedman method) and ASTM E698 equation were employed to obtain the apparent activation energy E_a. All the experimental results revealed that AIBN is more dangerous than AMBN. The E_a of AIBN was lower than that of AMBN. The results can be used to construct an azo compound thermal hazard database for use for searches and reference examples by industry and related research areas.     

Fuzzy experts on recreational vessels, a risk modelling approach for marine invasions

Understanding risks from the human-mediated spread of non-indigenous species (NIS) is a critical component of marine biosecurity management programmes. Recreational boating is well-recognised as a NIS pathway, especially at a regional scale. Assessment of risks from this pathway is therefore desirable for coastal environments where recreational boating occurs. However, formal or quantitative risk assessment for the recreational vessel pathway is often hampered by lack of data, hence often relies on expert opinion. The use of expert opinion itself is sometimes limited by its inherent vagueness, which can be an important source of uncertainty that reduces the validity and applicability of the assessment. Fuzzy logic, specifically interval type-2 fuzzy logic, is able to model and propagate this type of uncertainty, and is a useful technique in risk assessment where expert opinion is relied upon. The present paper describes the implementation of a NIS fuzzy expert system (FES) for assessing the risk of invasion in marine environments via recreational vessels. The FES was based on expert opinion gathered through systematic elicitation exercises, designed to acknowledge important uncertainty sources (e.g., underspecificity and ambiguity). The FES, using interval type-2 fuzzy logic, calculated an invasion risk value (integrating NIS infection and detection probabilities) for a range of invasion scenarios. These scenarios were defined by all possible combinations of two vessel types (moored and trailered), five vessel components (hull, deck, internal spaces, anchor, fishing gear), two infection modes (fouling, water/sediment retention) and six frequently visited marine habitats (marina, mooring, farm, ramp, wharf, anchorage). Although invasion risk values determined using the FES approach was scenario-specific, general patterns were identified. Moored vessels consistently showed higher invasion risk values than trailered vessels. Invasion risk values were higher for anchorages, moorings and wharves. Similarly, hull-fouling was revealed as the highest infection risk mode after pooling results across all habitats. The NIS fuzzy expert system presented here appears as a valuable prioritising and decision-making tool for NIS research, prevention and control activities. Its easy implementation and wide applicability should encourage the development and application of this type of system as an integral part of biosecurity, and other environmental management plans.     

308 nm光作用下α-Fe2O3表面HNO3的光解

采用紫外可见光谱(UV-Vis)、傅立叶变换红外光谱(FTIR)及离子色谱(IC)技术对HNO3在α-Fe2O3表面暗反应和308nm下光解反应进行了研究.考察了时间、HNO3浓度、相对湿度(RH)等条件对反应的影响.结果表明,随着HNO3浓度、光照时间的增加,HNO3在气相与α-Fe2O3表面光解产物浓度均呈指数增加;HNO3在α-Fe2O3表面光解产生的NO2、NO分别为气相产生的3.27及3.87倍,而无论气相还是表面光解的NO2浓度均约为NO的2倍.随着RH的增加,HNO3光解产生的HONO的浓度随之呈指数增大,其产率从RH 20%时的0.023增加到90%时的0.087.α-Fe2O3的表面效应在HNO3的表面光解反应中起主导作用.     

长期暴露下纳米TiO2对厌氧颗粒污泥体系稳定性的影响

以厌氧颗粒污泥为研究对象,通过静态试验和连续流厌氧反应器,重点研究了长期暴露下纳米TiO_2在对厌氧产甲烷体系的影响及其在颗粒污泥中的归趋.结果表明,短期急性暴露于150 mg·g-1(以VSS计)的纳米TiO_2尽管会暂时减缓产甲烷速率,但产酸阶段及产甲烷阶段代谢产物总量不会明显受到影响,纳米TiO_2对厌氧颗粒污泥具有较低的急性毒性.反应器运行结果表明,纳米TiO_2的长期暴露可导致挥发性脂肪酸(VFAs)积累及生物气产量降低,产酸菌比产甲烷菌对纳米TiO_2的累积效应更加敏感,纳米TiO_2抑制机制可归因于"物理遮蔽"作用.出水中TiO_2的平均含量只有0.632 mg·L~(-1),绝大多数纳米TiO_2都被截留在了反应器中.FISH检测表明,厌氧颗粒污泥微生物的菌群结构有所变化,纳米TiO_2在反应器内的积累使得甲烷八叠球菌的丰度大幅增加了115.6%,其优势地位明显增强.长短期暴露试验的结果对比也说明,用短期暴露试验来说明纳米颗粒对厌氧体系的长期累积效应具有一定局限性,纳米TiO_2对厌氧颗粒污泥中微生物的负面影响需要较长时间的积累才会显现.本研究结果可为厌氧污水处理体系中纳米颗粒的潜在生态风险评价提供理论支持和参考依据.     

高铁酸钾对水中藻类及其次生嗅味污染物二甲基三硫醚同步去除研究

模拟高藻期碱性水源水,采用高铁酸钾对水中以颤藻和二甲基三硫醚为代表的藻类及微量嗅味污染物进行同步控制研究.在高铁酸钾与聚合氯化铁(PFC)单独混凝对藻类的控制效果对比的基础上,展开了高铁酸钾与高锰酸钾预氧化-PFC联用方法对藻类及嗅味污染物的控制效果对比,探讨了pH、预氧化时间和浊度等条件对控制效果的影响.结果表明,PFC单独混凝除藻率最高为90.6%,以Fe计的等量投加条件下,高铁酸钾控藻效果较PFC混凝好,除藻率可达92.4%.高锰酸钾对PFC具有强化混凝效果,可明显提高除藻率(94.5%).高铁酸钾较高锰酸钾预氧化对二甲基三硫醚的去除效果理想,且氧化时间大大缩短,高铁酸钾氧化时间1 min可去除92.5%二甲基三硫醚,高于高锰酸钾预氧化10 min后达到的去除率(74.6%).     

厌氧条件下砂壤水稻土N2、N2O、NO、CO2和CH4排放特征

了解厌氧条件土壤反硝化气体(N2、N2O和NO)、CO2和CH4排放特征,是认识反硝化过程机制的基础,并有助于制定合理的温室气体减排措施.定量反硝化产物组成,可为氮转化过程模型研发制定正确的关键过程参数选取方法或参数化方案.本研究选取质地相同(砂壤土)的两个水稻土为研究对象,通过添加KNO3和葡萄糖的混合溶液,将培养土壤的初始NO-3和DOC含量分别调节到50 mg·kg-1和300 mg·kg-1,采用氦环境培养-气体及碳氮底物直接同步测定方法,研究完全厌氧条件下土壤N2、N2O、NO、CO2和CH4的排放特征,并获得反硝化气态产物中各组分的比率.结果表明,在整个培养过程中,两个供试土壤的N2、N2O和NO累积排放量分别为6~8、20和15~18 mg·kg-1,这些气体排放量测定结果可回收土壤NO-3变化量的95%~98%,反硝化气态产物以N2O和NO为主,其中3种组分的比率分别为15%~19%(N2)、47%~49%(N2O)和34%~36%(NO);但反硝化气体产物组成的逐日动态均显现为从以NO为主逐渐过渡到以N2O为主,最后才发展到以N2为主.以上结果说明,反硝化气体产物组成是随反硝化进程而变化的,在以气体产物组成比率作为关键参数计算各种反硝化气体产生率或排放率的模型中,很有必要重视这一点.     

常规施肥条件下农田不同途径氮素损失的原位研究:以长江中下游地区夏玉米季为例

为了解农田常规施肥条件下的不同途径氮素损失特征,本文通过田间原位试验同步研究了长江中下游地区夏玉米生长季氮肥施用后的农田N2O排放、NH3挥发、氮渗漏和地表径流的变化.结果表明,在复合肥为基肥,尿素为追肥,基追肥氮素水平均为150 kg·hm-2的条件下,整个玉米生长季N2O排放系数为3.3%,NH3挥发损失率为10.2%,氮渗漏和地表径流损失率分别为11.2%和5.1%.此外,基肥施用以氮素渗漏损失为主,而追肥氮素损失以氨挥发和渗漏为主,表明不同途径化肥氮素损失主要受氮肥品种影响,玉米季追肥可改用低氨挥发氮肥品种以减少氮素损失.     

不同部位玉米秸秆对两种质地黑土CO2排放和微生物量的影响

秸秆还田后作物残体的分解是农田生态系统碳循环及养分周转平衡的一个至关重要环节.为了探索秸秆化学性质和土壤质地对黑土区土壤CO2排放和微生物量的影响,本文通过室内恒温培养实验研究了添加不同植株部位玉米秸秆(根、茎下部、茎顶部、叶)进入黑土区两种质地土壤(砂壤土和黏壤土)后的CO2排放、微生物量,并分析了它们与秸秆C/N、木质素含量的关系.结果表明,添加不同部位秸秆一致增加土壤CO2排放量,激发效应值介于216.53~335.17μmol·g-1,黏壤土大于砂壤土.激发效应值与木质素/N之间的线性回归关系明显好于激发效应与木质素含量、C/N、含氮量之间的线性关系.添加秸秆增加MBC和MBN含量,降低MBC/MBN,微生物群落氮固持的速率高于碳固持.添加秸秆后,砂壤土微生物量增加的幅度大于黏壤土,总溶解性氮含量小于黏壤土.结果说明,秸秆的木质素和氮含量均会对它的分解和CO2排放产生影响,木质素/N比木质素含量、C/N等更好地说明秸秆分解和CO2排放的差异;与黏壤土相比,在砂壤土中实施秸秆还田可以取得更好的土壤碳固存、微生物量和氮素保持效果.     

β-In2S3的制备及其太阳光下降解土霉素

利用水热反应法制备β-In2S3纳米颗粒光催化剂,并利用SEM、TEM和XRD等对其进行分析表征;采用土霉素溶液模拟四环素类抗生素废水,探讨In2S3对土霉素的降解效果.结果表明,β-In2S3为立方相纳米颗粒结构,该纳米颗粒由纳米片组成,直径约15~30 nm.以太阳光为辐射光源,In2S3对土霉素具有良好的光催化降解效果,在4 h内对初始浓度为30 mg·L-1的土霉素降解率可达98%以上.降解土霉素后的催化剂在无水乙醇中清洗并烘干,经4次循环利用后,β-In2S3的降解能力仍能达到85%以上,表明β-In2S3光催化剂具有良好的稳定性以及光催化活性.     

石墨烯凝胶电极的制备及电吸附Pb2+的性能

电吸附去除水中重金属离子具有吸附容量高和电极可再生的优点.本文采用高温水热法还原氧化石墨烯(GO)得到石墨烯水凝胶(GS)并经压片制得GS电极.本文对GS电极的电化学性能进行了测试,考察了GS电极电吸附Pb~(2+)的动力学和热力学特性,以及电极的脱附和循环使用情况.结果表明,GS电极的电化学性能优异,其单位质量比电容高达200.4 F·g~(-1)(1 A·g~(-1));提高电压有利于GS电极电吸附Pb~(2+),电压为-1.2 V时,GS电极对Pb~(2+)的去除率达96.4%;GS电极电吸附Pb~(2+)的饱和吸附量达461.20 mg·g~(-1),是不加电时饱和吸附量的2倍;施加反向电压可以实现Pb~(2+)的脱附和电极再生,电吸附-脱附15次后,电极对Pb~(2+)的去除率保持在95%以上.