低NOx环境异戊二烯促进甲苯生成甲基丁烯二醛的模拟实验

在低NO_x浓度条件下开展甲苯和异戊二烯复合体系的烟雾箱模拟实验,使用高时间分辨率的在线质子转移反应飞行时间质谱(PTR-TOF-MS)实时监测混合体系中反应物与产物的浓度变化情况,探究人为源与天然源交汇过程中, 自然源挥发性有机物 (BVOCs)对人为挥发性有机物(AVOCs)化学降解的影响.结果表明,异戊二烯与甲苯竞争OH自由基,从而抑制了甲苯的化学降解,该竞争反应开始得越早,抑制效果越显著.研究还发现异戊二烯会增强甲苯RO₂降解途径产物的产量,生成更多1,4不饱和-二羰基化合物(如丁烯二醛和甲基丁烯二醛)与二羰基化合物(如乙二醛和甲基乙二醛),其中甲基丁烯二醛增量最高可达38.6%.此外,异戊二烯快速氧化生成的RO₂自由基碳数更少,可能与甲苯氧化生成的RO₂自由基发生了快速的交叉反应,有利于甲苯RO自由基的生成及裂解,最终导致甲苯RO₂途径裂解产物的增加.     

Dosing low-level ferrous iron in coagulation enhances the removal of micropollutants, chlorite and chlorate during advanced water treatment

Drinking water utilities are interested in upgrading their treatment facilities to enhance micropollutant removal and byproduct control. Pre-oxidation by chlorine dioxide (ClO₂) followed by coagulation-flocculation-sedimentation and advanced oxidation processes (AOPs) is one of the promising solutions. However, the chlorite (ClO₂^–) formed from the ClO₂ pre-oxidation stage cannot be removed by the conventional coagulation process using aluminum sulfate. ClO₂^– negatively affects the post-UV/chlorine process due to its strong radical scavenging effect, and it also enhances the formation of chlorate (ClO₃^–). In this study, dosing micromolar-level ferrous iron (Fe(II)) into aluminum-based coagulants was proposed to eliminate the ClO₂^– generated from ClO₂ pre-oxidation and benefit the post-UV/chlorine process in radical production and ClO₃^– reduction. Results showed that the addition of 52.1-µmol/L FeSO₄ effectively eliminated the ClO₂^– generated from the pre-oxidation using 1.0 mg/L (14.8 µmol/L) of ClO₂. Reduction of ClO₂^– increased the degradation rate constant of a model micropollutant (carbamazepine) by 55.0% in the post-UV/chlorine process. The enhanced degradation was verified to be attributed to the increased steady-state concentrations of HO^· and ClO^· by Fe(II) addition. Moreover, Fe(II) addition also decreased the ClO₃^– formation by 53.8% in the UV/chlorine process and its impact on the formation of chloro-organic byproducts was rather minor. The findings demonstrated a promising strategy to improve the drinking water quality and safety by adding low-level Fe(II) in coagulation in an advanced drinking water treatment train.     

MoS2 quantum dots based MoS2/HKUST-1 composites for the highly efficient catalytic oxidation of elementary mercury

Due to the ever-tightening regulation on mercury emission in recent decades, there is an urgent need to develop novel materials for the removal of elemental mercury at coal-fired power plants. In this study, a series of MoS₂ quantum dots (QDs)-based MoS₂/HKUST-1 composite materials were prepared. It is found that MoS₂ QDs were encapsulated by HKUST-1 and enhanced the crystallinity and specific surface area of HKUST-1. The MoS₂/HKUST-1 showed excellent performance in catalytic oxidation of Hg⁰ as compared with pristine HKUST-1. It is found that surface layer of lattice oxygens is active and participates in Hg⁰ oxidation, while the consumption of surface oxygens then leads to the formation of oxygen vacancies on the surface. These vacancies are effective in the adsorption and dissociation of O₂, which subsequently participates in the oxidation of Hg⁰. Moreover, the study on the influence of commonly seen gas components, such as SO₂, NO, NH₃ and H₂O, etc., on Hg⁰ oxidation demonstrated that synergistic effects exist among these gas species. It is found that the presence of NO promotes the oxidation of Hg⁰ using oxygen as the oxidant.     

设施农业土壤磷素累积迁移转化及影响因素

为了科学合理施用磷肥,减小对设施农业环境带来的污染风险,以北京市大兴区设施农业集中区为研究对象,通过对不同种植年限设施农业剖面土壤(0～100 cm)磷素含量的测定分析,探究磷素累积与迁移转化特征.结果表明,设施农业表层土壤全磷和有效磷含量变化范围大,显著高于周边粮田土壤,主要跟不同种植年限农户的施磷量相关,随着土层深度的增加,全磷和有效磷含量逐渐减小,呈现表聚特征,其中土壤ω(全磷)范围在0.38～2.58 g·kg^-1,ω(有效磷)范围在1.60～256.00 mg·kg^-1.随着种植年限的增加,土壤全磷和有效磷含量呈现先增加后减小的趋势,在15 a左右达到峰值,随后逐渐减少,趋于稳定,总体处于较高水平.无机磷主要集中在设施农业表层土壤,其中Ca-P占无机磷的比例最大,达到了98.38%,Ca₁₀-P是最主要的Ca-P形态,含量占Ca-P的78.70%,Ca₂-P占比最小,仅占9.50%.不同形态无机磷含量呈现表层土壤富集,向下减少的垂直分布特征;不同土层深度,不同形态无机磷占全磷比例变化存在差...     

节水灌溉和控释肥施用耦合措施对单季稻田CH4和N2O排放的影响

以我国华东地区典型单季稻水稻田(江苏宜兴)的原柱状土为研究对象,通过两年土柱观测试验,研究不同灌溉管理模式(长期淹水CF、间隙灌溉Ⅱ、控制灌溉CI)和氮肥施用(不施氮CK、尿素Urea和控释肥CRF)耦合措施对水稻生长期内CH4和N2O排放和产量的影响,以期优选典型单季稻田减排增效的水肥管理模式.结果表明,两种节水灌溉方式(CI和Ⅱ)均显著影响稻田土壤CH4和N2O排放量及二者的综合温室效应(GWP)和排放强度(GHGI),与CF相比,Ⅱ和CI均显著提高了 N2O排放量(P＜0.05),降低了 CH4排放量(P＜0.05),进而二者的GWP和GHGI分别显著降低28.9％～71.4％和14.3％～70.4％(P＜0.05);两种节水灌溉模式相比,CI较Ⅱ模式呈现较好的CH4减排优势,排放总量降低了 57.7％～91.8％,而二者的N2O排放量无显著性差异(P＞0.05),最终CI对GWP和GHGI的减排效应略优于Ⅱ模式2.0％～56.2％.施用氮肥(Urea和CRF)均显著促进N2O排放18.4％～2547.8％(P＜0.05),其中CRF处理N2O排放量均略高于Urea处理32.7％～78.6％,但无显著性差异(P＞0.05);CH4排放总量对施氮处理的响应随水分管理模式的不同而不同,总体而言,施用CRF较Urea对稻田土壤GWP和GHGI均无显著影响(P＞0.05).相关分析表明,2018年CF模式的Urea处理和Ⅱ模式的Urea、CRF处理中N2O排放通量与田面水NH4+-N浓度分别呈现显著(P＜0.05)和极显著的正相关关系(P＜0.01),而二者在2019年CI模式的CK和CRF处理中呈现相反规律;2018年CI模式下CK、CRF处理的N2O排放通量与田面水NO3--N浓度呈极显著的正相关关系(P＜0.01).节水灌溉和氮肥施用对水稻产量均呈显著影响(P＜0.05),与CF相比,两种节水灌溉模式(Ⅱ、CI)水稻产量均下降了 14.7％～37.7％;CRF处理较Urea处理略提高水稻产量2.5％～7.4％(P＜0.05).综合考虑稻田土壤GWP、GHGI和水稻产量,节水模式与控释肥施用对稻田土壤减排增产的耦合效应仍有待进一步研究.