Rapid and long-effective removal of broad-spectrum pollutants from aqueous system by ZVI/oxidants

• The coupling of oxidants with ZVI overcome the impedance of ZVI passive layer. • ZVI/oxidants system achieved fast and long-effective removal of contaminants. • Multiple mechanisms are involved in contaminants removal by ZVI/oxidant system. • ZVI/Oxidants did not change the reducing property of ORP in the fixed-bed system. Zero-valent iron (ZVI) technology has recently gained significant interest in the efficient sequestration of a wide variety of contaminants. However, surface passivation of ZVI because of its intrinsic passive layer would lead to the inferior reactivity of ZVI and its lower efficacy in contaminant removal. Therefore, to activate the ZVI surface cheaply, continuously, and efficiently is an important challenge that ZVI technology must overcome before its wide-scale application. To date, several physical and chemical approaches have been extensively applied to increase the reactivity of the ZVI surface toward the elimination of broad-spectrum pollutants. Nevertheless, these techniques have several limitations such as low efficacy, narrow working pH, eco-toxicity, and high installation cost. The objective of this mini-review paper is to identify the critical role of oxygen in determining the reactivity of ZVI toward contaminant removal. Subsequently, the effect of three typical oxidants (H₂O₂, KMnO₄, and NaClO) on broad-spectrum contaminants removal by ZVI has been documented and discussed. The reaction mechanism and sequestration efficacies of the ZVI/oxidant system were evaluated and reviewed. The technical basis of the ZVI/oxidant approach is based on the half-reaction of the cathodic reduction of the oxidants. The oxidants commonly used in the water treatment industry, i.e., NaClO, O₃, and H₂O₂, can be served as an ideal coupling electron receptor. With the combination of these oxidants, the surface corrosion of ZVI can be continuously driven. The ZVI/oxidants technology has been compared with other conventional technologies and conclusions have been drawn.     

Methodological considerations for nitrogen policies in the Netherlands including a new role for research

The Netherlands has attempted to follow EU guidelines in developing national policies to reduce pollution of groundwater by nitrates originating from (over) fertilized agricultural land. The EU has not been satisfied with these policies and this is resulting in legal conflicts. National policies have focused on nitrogen budgeting and on fertilization rates, over-simplifying the crucial role of soils during the leaching of nitrates to groundwater. As an alternative, a dynamic approach using simulation modeling is introduced as is illustrated for a study area in the Netherlands. A number of considerations for future policy directions are suggested, including requirements for research: (i) promotion of research aimed at improving and maintaining nutrient use efficiency at farm level; (ii) promotion of joint learning experiences between farmers and researchers, where farmers’ organizations could act as “research consortia”; (iii) emphasis on site and time specific management (precision agriculture) in policy development, and provision of site-specific advice via modern information and communication technologies; (iv) clearer guidelines for groundwater monitoring procedures, including additional monitoring at greater depths and consideration of groundwater quality from an appropriate regional perspective; (v) groundwater monitoring should take place at locations selected according to specific hydro-geological characteristics, rather than being executed at random and (vi) clear goals that are defined within existing and future policies at EU and international level, should allow for regional differentiation in indicators; these being the outcome of negotiations between farmers or their representatives, policy makers and researchers.     

Influence of modified biochar supported sulfidation of nano-zero-valent-iron (S-nZVI/BC) on nitrate removal and greenhouse gas emission in constructed wetland

In this study, the biochar (BC) produced from sawdust, sludge, reed and walnut were used to support sulfidation of nano-zero-valent-iron (S-nZVI) to enhance nitrate (${\text{NO}}_3^{-}$-N) removal and investigate the impact on greenhouse gas emissions. Batch experiment results showed the S-nZVI/BC_{sawdust (2:1, 500)}, S-nZVI/BC_{sludge (2:1, 900)}, S-nZVI/BC_{reed (2:1, 700)}, and S-nZVI/BC _{walnut (2:1, 700)} respectively improved ${\text{NO}}_3^{-}$-N removal efficiencies by 22%, 20%, 3% and 0.1%, and the selectivity toward N₂ by 22%, 25%, 22% and 18%. S-nZVI uniformly loaded on BC provided electrons for the conversion of ${\text{NO}}_3^{-}$-N to N₂ through Fe⁰. At the same time, FeS_x layer was formed on the outer layer of ZVI in the sulfidation process to prevent iron oxidation, so as to improve the electrons utilization efficiency After adding four kinds of S-nZVI/BC into constructed wetlands (CWs), the ${\text{NO}}_3^{-}$-N removal efficiencies could reach 100% and the N₂O emission fluxes were reduced by 24.17%-36.63%. And the average removal efficiencies of TN, COD, TP were increased by 21.9%, -16.5%, 44.3%, repectively. The increasing relative abundances of denitrifying bacteria, such as Comamonas and Simplicispira, suggested that S-nZVI/BC could also improve the process of microbial denitrification. In addition, different S-nZVI/BC had different effects on denitrification functional genes (narG, nirk, nirS and nosZ genes), methanotrophs (pmoA) and methanogenesis (mcrA). This research provided an effective method to improve ${\text{NO}}_3^{-}$-N removal and reduce N₂O emission in CWs.     

Determination of nitrogen reduction levels necessary to reach groundwater quality targets in Slovenia

Within a collaborative project between Slovenian Environment Agency （ARSO） and Research Center Jfilich （FZJ）, nitrogen reduction levels necessary to reach groundwater quality targets in Slovenia were assessed. For this purpose the hydrological model GROWA- DENUZ was coupled with agricultural N balances and applied consistently to the whole territory of Slovenia in a spatial resolution of 100 x 100 m. GROWA was used to determine the water balance in Slovenia for the hydrologic period 1971-2000. Simultaneously, the displaceable N load in soft was assessed from agricultural Slovenian N surpluses for 2011 and the atmospheric N deposition. Subsequently, the DENUZ model was used to assess the nitrate degradation in soil and, in combination with the percolation water rates from the GROWA model, to determine nitrate concentration in the leachate. The areas showing predicted nitrate concentrations in the leachate above the EU groundwater quality standard of 50 mg NO3/L have been identified as priority areas for implementing nitrogen reduction measures. For these ＂hot spot＂ areas DENUZ was used in a backward mode to quantify the maximal permissible nitrogen surplus levels in agriculture to guarantee a nitrate concentration in percolation water below 50 mg NO3/L. Model results indicate that additional N reduction measures should be implemented in priority areas rather than area-covering. Research work will directly support the implementation of the European Union Water Framework Directive in Slovenia, e.g., by using the maximal permissible nitrogen surplus levels as a framework for the derivation of regionally adapted and hence effective nitrogen reduction measures.     

硝酸盐和甲烷对覆土中苯系物厌氧氧化的影响

苯系物是填埋场填埋气中恶臭有机气体的重要成分之一,填埋气中的CH4则是重要的温室气体.填埋覆土层中的微生物可以氧化CH4和苯系物,因此,强化微生物的氧化效能有助于削减和控制填埋气的污染.电子受体还原可耦合甲烷和某些有机物的厌氧氧化,从而去除甲烷和有机物.鉴此,本研究通过静态培养试验,分析了电子受体SO2-4共存条件下,NO-3和CH4共存对覆土中苯系物厌氧降解的影响.结果表明不外加NO-3时,苯系物抑制CH4的降解,加入NO-3后,苯系物共存反而有利于CH4的去除;单独添加NO-3或CH4都能促进填埋覆土中苯系物的去除;而同时添加NO-3和CH4能更好地促进苯系物的去除,甲苯、二甲苯和异丙苯的去除率最高可达65%、88%和82%,远高于不添加NO-3和CH4对照处理的53%、76%和31%;NO-3还原与CH4厌氧氧化耦合过程能同步促进苯系物的厌氧氧化.     

Seasonal differences in sources and formation processes of PM2.5 nitrate in an urban environment of North China

Nitrate (NO₃⁻) has been the dominant ion of secondary inorganic aerosols (SIAs) in PM_2.5 in North China. Tracking the formation mechanisms and sources of particulate nitrate are vital to mitigate air pollution. In this study, PM_2.5 samples in winter (January 2020) and in summer (June 2020) were collected in Jiaozuo, China, and water-soluble ions and (δ¹⁵N, δ¹⁸O)-NO₃⁻ were analyzed. The results showed that the increase of NO₃⁻ concentrations was the most remarkable with increasing PM_2.5 pollution level. δ¹⁸O-NO₃⁻ values for winter samples (82.7‰ to 103.9‰) were close to calculated δ¹⁸O-HNO₃ (103‰ ± 0.8‰) values by N₂O₅ pathway, while δ¹⁸O-NO₃⁻ values (67.8‰ to 85.7‰) for summer samples were close to calculated δ¹⁸O-HNO₃ values (61‰ ± 0.8‰) by OH oxidation pathway, suggesting that PM_2.5 nitrate is largely from N₂O₅ pathway in winter, while is largely from OH pathway in summer. Averaged fractional contributions of P_N2O5+H2O were 70% and 39% in winter and summer sampling periods, respectively, those of P_OH were 30% and 61%, respectively. Higher δ¹⁵N-NO₃⁻ values for winter samples (3.0‰ to 14.4‰) than those for summer samples (-3.7‰ to 8.6‰) might be due to more contributions from coal combustion in winter. Coal combustion (31% ± 9%, 25% ± 9% in winter and summer, respectively) and biomass burning (30% ± 12%, 36% ± 12% in winter and summer, respectively) were the main sources using Bayesian mixing model. These results provided clear evidence of particulate nitrate formation and sources under different PM_2.5 levels, and aided in reducing atmospheric nitrate in urban environments.     

Homogeneous and heterogeneous photolysis of nitrate in the atmosphere: state of the science,current research needs,and future prospects

● Recent advances in the photolysis of nitrate/HNO₃ are reviewed. ● Mechanisms and key factors affecting the photolysis of nitrate/HNO₃ are summarized. ● Atmospheric implications and future research recommendations are provided. Nitrate is an important component of atmospheric particulate matter and affects air quality, climate, human health, and the ecosystem. Nitrate was previously considered a permanent sink for nitrogen oxides (NO_x). However, this viewpoint has been challenged in recent years because growing research evidence has shown the transformation of nitrate into NO_x (i.e., renoxification). The photolysis of nitrate/HNO₃, especially in the particulate phase or adsorbed on particles, can be a significant renoxification process in the atmosphere. The formation and photolysis of nitrate in aerosol not only change the diurnal variation of NO_x, but also provide long-distance transport of NO_x in the form of nitrate, which affects local and regional atmospheric chemistry and air quality. This review summarizes recent advances in the fundamental understanding of the photolysis of nitrate/HNO₃ under various atmospheric conditions, with a focus on mechanisms and key factors affecting the process. The atmospheric implications are discussed and future research is recommended.     

饮用水中亚硝酸盐产生的研究

经监测发现,在自来水管中滞留过的水,不同程度地存在亚硝酸盐。本文对自来水中亚硝酸盐产生的原因、程度、变化规律做了初步探索和研究。      

pH值、温度对反硝化的影响

在悬浮污泥系统中,当以挥发性脂肪酸为碳源时,适宜的ｐＨ值是７．５。当ｐＨ偏离这一适宜值时,反硝化速率逐渐降低,亚硝酸盐出现累积。经驯化后,氮去除率会有所改善。随着温度的上升,反硝化速率会平行地提高,温度常数Ｋ_ｔ值是０．０３（１０～３０℃）。本文还讨论了亚硝酸盐积累的原因和避免的方法。     

气态硝酸在钙质山毛榉森林中沉降通量的研究

1987年5月至12月,在联邦德国哥廷根森林中,位于树冠不同高度上完成了气态硝酸浓度分布的测定。同时,还测定了森林中大气扩散参数。用模式计算出气态硝酸的沉降速度和沉降通量。结果表明,气态硝酸沉降通量平均约为26kg HNO₃—N/a·ha,气态硝酸浓度平均约为0.88μgHNO₃—N/m3,夜间浓度下降,43m处(树冠上面)气态硝酸浓度高于33m(树冠中)。在第1至第10个实验里气溶胶中气态硝酸与硝酸盐的比值是0.3,而在第11~14个实验中约为1~3。