草酸改性零价铁活化过硫酸盐降解地下水中2,4-DNT的研究

2,4-二硝基甲苯(2,4-DNT)作为重要的化工原料,由于储存和生产过程中的“跑冒滴漏”,已然成为地下水中常见有毒有害污染物之一,对人体健康和生态环境安全造成极大威胁. 以草酸与商品零价铁为原料,通过球磨法制备草酸化零价铁(OA-ZVIbm),并研究其活化过硫酸盐(PS)降解2,4-DNT的性能. 采用扫描电子显微镜(SEM)、X射线衍射(XRD)和傅里叶变换红外光谱(FT-IR)对活化剂进行表征,并考察活化剂和PS投加量、溶液初始pH及无机阴离子对2,4-DNT降解效果的影响. 结果表明:①通过球磨改性,零价铁表面氧化层被草酸亚铁壳层代替,加速铁核腐蚀生成Fe2+催化PS. ②在pH=7、0.2 g/L OA-ZVIbm和5 mmol/L PS的条件下,4.0 h内对50 mg/L 2,4-DNT降解率达到87.6%,降解过程符合准一级动力学方程. ③2,4-DNT降解率随OA-ZVIbm和PS投加量增加以及溶液初始pH的降低增加,但高浓度PS会抑制2,4-DNT的降解;NO₃?、CO₃2?、Cl?和SO₄2?通过淬灭自由基或者与亚铁离子发生共沉淀,对降解产生不同程度的抑制效果. ④自由基淬灭试验表明,体系中同时产生SO₄? ?、·OH和1O₂,但SO₄? ?在降解过程中起主导作用. ⑤降解中间产物鉴定表明,通过脱硝和氧化反应,2,4-DNT被降解成包括间苯二酚、丙二酸在内的毒性较小分子,可生化性显著提高. 研究显示,OA-ZVIbm能够高效活化PS,实现对地下水2,4-DNT的显著降解,具有一定的应用前景.      

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.     

Enhancing anoxic denitrification of low C/N ratio wastewater with novel ZVI composite carriers

External organic carbon sources are needed to provide electron donors for the denitrification of wastewater with a low COD/NO₃^--N（C/N） ratio, increasing the treatment cost. The economic strategy is to enhance the bioactivity and/or biodiversity of denitrifiers to efficiently utilize organic substances in wastewater. In this study, novel zero-valent iron（ZVI） composite carriers were prepared and implemented in a suspended carrier biofilm reactor to enhance the bioactivity an...     

Novel eco-friendly spherical porous adsorbent fabricated from Pickering middle internal phase emulsions for removal of Pb(II) and Cd (II)

Spherical porous materials prepared from the emulsion template used in the water treat-ment have displayed a vast prospect,as the high surface area,abundant porous structure,convenient operation and excellent adsorption performance.But the tedious fabrication process,high consumption of organic solvent and surfactant limited the application widely.Herein,a facile and eco-friendly spherical porous adsorbent (SPA) is fabricated from the green surfactant-free (corn oil)-in-water Pickering medium internal phase emulsions (Pick-ering MIPEs) via the convenient ion crosslinking procedure.The Pickering MIPEs synergis-tically stabilized with the semi-coke (SC),which is the natural particle produced from the shale oil distillation,and sodium alginate (SA) has excellent storage and anti-coalescence stability.The as-prepared porous adsorbent possessed the abundant pore structure,which provided favorable conditions for effective mass transfer in adsorption,and could be tuned by varying the SA dosage.The saturation adsorption capacities of Pb(Ⅱ) and Cd(Ⅱ) can be achieved with 460.54 and 278.77 mg/g within 45 min at 25℃,respectively.Overall,this study supplied a viable and eco-friendly route for fabricating the spherical porous adsorbent with a tunable porous structure for heavy metal ion wastewater.     

Wall losses of oxygenated volatile organic compounds from oxidation of toluene: Effects of chamber volume and relative humidity

Vapor wall losses can affect the yields of secondary organic aerosol. The effects of surface-to-volume (S/V) ratio and relative humidity (RH) on the vapor-wall interactions were investigated in this study. The oxygenated volatile organic compounds (OVOCs) were generated from toluene-H₂O₂ irradiations. The average gas to wall loss rate constant (k_gw) of OVOCs in a 400 L reactor (S/V = 7.5 m⁻¹) is 2.47 (2.41 under humid conditions) times higher than that in a 5000 L reactor (S/V = 3.6 m⁻¹) under dry conditions. In contrast, the average desorption rate constant (k_wg) of OVOCs in 400 L reactor is only 1.37 (1.20 under humid conditions) times higher than that in 5000 L reactor under dry conditions. It shows that increasing the S/V ratio can promote the wall losses of OVOCs. By contrast, the RH effect on k_gw is not prominent. The average k_gw value under humid conditions is almost the same as under dry conditions in the 400 L (5000 L) reactor. However, increasing RH can decrease the desorption rates. The average k_wg value under dry conditions is 1.45 (1.27) times higher than that under humid conditions in the 400 L (5000 L) reactor. The high RH can increase the partitioning equilibrium timescales and enhance the wall losses of OVOCs.     

休渔期和捕捞作业期黄、渤海区沿海中心渔港表层海水重金属分布及生态风险评估

为了弄清休渔期和捕捞作业期黄、渤海区沿海中心渔港表层海水重金属污染水平,本研究于2020年5月和10月在黄、渤海区沿海11个中心渔港采集水样,分析了Cu、Zn、Pb、Cd、Hg和As 6种重金属的浓度及污染特征,探讨了其主要来源,并评估了其生态风险。结果表明,休渔期Cu、Zn、Pb、Cd、Hg和As的浓度范围分别为1.26～4.46 μg/L、4.10～22.72 μg/L、1.18～16.76 μg/L、0.54～7.80 μg/L、0.02～0.08 μg/L和0.02～0.86 μg/L;捕捞作业期分别为0.60～4.62 μg/L、4.92～10.61 μg/L、0.16～2.95 μg/L、0.14～2.95 μg/L、0.03～0.11 μg/L和0.16～1.37 μg/L,休渔期和捕捞作业期各渔港的Cu、Zn、Pb、Cd、Hg和As浓度均值满足《海水水质标准》（GB 3097－1997）四类标准;黄海沿海中心渔港表层海水重金属浓度略低于渤海地区,与我国东海地区和南海地区相比,黄、渤海区Cu、Pb和Cd浓度处于较高水平,Zn和Hg浓度处于中等水平,As浓度处于较低水平。分析发现,休渔期和捕捞作业期Zn和As来自陆源,Cu来自陆源和船舶防污漆,表层海水Pb与大气沉降和燃料尾气有关。沿海中心渔港表层海水重金属综合污染指数均处于自然本底范围,且生态风险指数（ERI）值（0.84～1.45）也都属于生态低风险和无风险类别,但Cu、Zn、Pb和Cd的危害系数（HQi）大于1,属于潜在关注指标,应予以关注。     

地质高背景区富Se耕地可利用性研究及区划建议

为了促进土地质量地球化学调查成果服务于特色土地资源开发,实现地质高背景区富Se资源的安全利用,以重庆市黔江区五里镇为研究对象,通过评价土壤-农作物的富Se水平及重金属含量,开展地质高背景区富Se耕地区划及可利用性方法研究,以期提高富Se资源利用效率,为地质高背景区富Se资源的安全利用提供思路.结果表明,研究区土壤及农作物中Se含量丰富,具备开发富Se资源的潜力,但部分样品存在Cd超标的问题.土壤pH是影响农作物Se和Cd含量的关键因素,碱性条件下有利于富Se资源安全利用.A～E(A表示可利用富硒耕地,B表示农作物不富硒但农作物安全,C表示农作物富硒但农作物不安全,D表示农作物不富硒且农作物不安全,E表示土壤硒含量小于富硒阈值且土壤重金属不超标)类耕地面积分别为0.72、0.75、0.28、0.13和0.56 km²,建议在A类耕地分布区开展安全富Se资源开发,在C和D类耕地分布区开展土壤酸化调理及作物低累积品种等农艺措施,降低农作物重金属超标风险,并加强全区耕地保护力度,防止新增污染物输入.