不同结构有机磷在(氢)氧化铝表面的吸附与解吸特征

研究了4种不同分子结构的有机磷[甘油磷酸(GP)、葡萄糖六磷酸(G6P)、三磷酸腺苷(ATP)和肌-肌醇六磷酸(植酸,IHP)]在无定形Al(OH)3、勃姆石和α-Al2O3等3种(氢)氧化铝表面的吸附解吸特征,并探讨了相关机制.结果表明,单位质量(氢)氧化铝对有机磷最大吸附量顺序为:无定形Al(OH)3>勃姆石>α-Al2O3,这与矿物的结晶度和表面异质性有关.除IHP在无定形Al(OH)3上的吸附外,有机磷在(氢)氧化铝表面的吸附密度随相对分子质量增大而减小:GP>G6P>ATP>IHP.而无定形Al(OH)3对最大分子尺寸的IHP吸附量却远大于其他有机磷,这是由于IHP表面络合物转化成了表面沉淀,大大促进了吸附.吸附动力学表明,有机磷吸附起始经历快速吸附阶段,极短时间内达到一定的吸附量,随后是一个较长时间的慢吸附过程,无定形Al(OH)3对有机磷的起始快速吸附密度最大,不同有机磷在铝氧化物表面的起始快速吸附密度与相对分子质量呈反比.KCl和柠檬酸对有机磷的解吸能力取决于磷化合物和勃姆石的表面亲和力.KCl初始解吸率大小顺序是:G6P(10.53%)>GP(6.91%)>ATP(3.06%)>IHP(0.8%).柠檬酸对有机磷的最大解吸率是KCl的4~5倍.KCl对磷的解吸过程经历了几个小时的快速解吸后达到最大解吸率,随后是慢速的扩散再吸附,解吸率反而逐渐下降.对IHP,除扩散再吸附外,表面沉淀也促进了再吸附.因此,有机磷与(氢)氧化铝界面发生较强的专性吸附反应,其分子结构和尺寸以及矿物的结晶度和晶体结构等是影响有机磷的界面反应和环境行为的重要因素.     

湖南地区不同集约化栽培模式下双季稻稻田CH4和N2O的排放规律

采用静态暗箱-气相色谱法研究了湖南双季稻稻田不施氮(NN)、当地常规(FP)、高产高效(YE)、再高产(HY)、再高效(HE)5种不同栽培模式下温室气体(CH4、N2O)的排放规律.结果表明:水稻生长季CH4累积排放量变化为(206.5±37.5) kg· hm-2(FP,早稻)～(490.5±65.7) kg·hm-2(HE,晚稻),N2O-N累积排放量变化为(0.08±0.05) kg·hm-2(NN,早稻)～(0.326±0.15) kg·hm-2(HY,晚稻).不同栽培模式对CH4和N2O的排放都有显著影响(p＜0.05).HE模式CH4排放显著高于其他模式62％～ 87％(p＜0.05),尤其是晚稻季节;除NN模式外,其他4种模式间N2O排放差异不显著.冬季休闲期也是CH4和N2O排放的重要时期,分别占全年排放量的9.7％～19.7％和42％～ 62％.CH4主导了稻田不同栽培模式下的综合温室效应,在各模式中均占95％以上.施氮肥提高了作物产量,降低了温室气体强度(GHGI).在5种模式中,YE和HY模式温室气体强度较小,HY模式下仅为(0.97±0.16) kg·kg-1(以每kg产量排放的CO2当量计).因此,与FP模式相比,YE和HY模式既能提高产量和氮肥利用率,也能减缓温室效应;但HE模式排放的温室气体较高,在实际应用前尚需进一步研究.     

新型材料磁性氧化锆的除氟效能

采用一步共沉淀法制备了磁铁矿纳米颗粒为核和水合氧化锆为壳的磁性氧化锆材料,研究了其除氟性能.结果表明,磁性氧化锆对氟的Langmuir最大吸附量为35. 46 mg·g~(-1),远高于磁铁矿、活性氧化铝和活性炭.磁性氧化锆对氟的吸附过程较快且吸附动力学数据符合准二级动力学模型,吸附过程为吸热反应.磁性氧化锆对氟的吸附量随pH升高而降低. Cl~-、NO_3~-和SO_4~(2-)的共存对磁性氧化锆除氟没有明显影响,而HCO_3~-和CO_3~(2-)明显抑制氟的吸附.磁性氧化锆吸附的氟可通过1mol·L~(-1)NaOH成功脱附,脱附率99. 5%～99. 6%.脱附后的磁性氧化锆经过再生处理可继续使用.磁性氧化锆对实际井水中的氟的去除效果低于纯水,但适当增加投加量仍可以达到饮用水标准对氟浓度的要求.磁性氧化锆制备简单、使用后可从水中磁分离从而可反复使用,因此是一种有较好应用前景的除氟材料.     

Simultaneous removal of CO2, NOx and SOx using single stage absorption column

Capturing flue gases often require multiple stages of scrubbing, increasing the capital and operating costs. So far, no attempt has been made to study the absorption characteristics of all the three gases (NO, SO₂ and CO₂) in a single stage absorption unit at alkaline pH conditions. We have attempted to capture all the three gases with a single wet scrubbing column. The absorption of all three gases with sodium carbonate solution promoted with oxidizers was investigated in a tall absorption column. The absorbance was found to be 100% for CO₂, 30% for NO and 95% for SO₂ respectively. The capture efficiency of sodium carbonate solution was increased by 40% for CO₂ loading, with the addition of oxidizer. Absorption kinetics and reaction pathways of all the three gases were discussed individually in detail.     

Review on heterogeneous oxidation and adsorption for arsenic removal from drinking water

The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite (As(III)) to negatively-charged arsenate (As(V)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal; however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(III) by solid oxidants such as manganese oxide, and the adsorption of As(V) accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(III). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(V). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants (DWTPs). This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.     

The role of metal oxides on oxidant decay and disinfection byproduct formation in drinking waters: Relevance to distribution systems

Maintaining a residual disinfectant/oxidant (e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, such as hypobromous acid (HOBr), can be formed during chlorination of bromide-containing waters. The decay of oxidants and formation of disinfection byproducts (DBPs) due to the interaction between oxidants and selected metal oxides were studied. Selected metal oxides generally enhanced the decay of these halogen-containing oxidants via three pathways: (1) catalytic disproportionation to yield an oxidized form of halogen (i.e., halate) and reduced form (halide for chlorine and bromine or chlorite for chlorine dioxide), (2) oxygen formation, and (3) oxidation of a metal in a reduced form (e.g., cuprous oxide) to a higher oxidation state. Cupric oxide (CuO) and nickel oxide (NiO) showed significantly strong abilities for the first pathway, and oxygen formation was a side reaction. Cuprous oxide can react with oxidants via the third pathway, while goethite was not involved in these reactions. The ability of CuO on catalytic disproportionation of HOBr remained stable up to four cycles. In chlorination process, bromate formation tends to be important (exceeding 10 µg/L) when initial bromide concentration is above 400 µg/L in the presence of dissolved organic matter. Increasing initial bromide concentrations increased the formation of DBPs and calculated cytotoxicity, and the maximum was observed at pH 8.6 during chlorination process. Therefore, the possible disinfectant loss and DBP formation should be carefully considered in drinking water distribution systems.     

NGO/PDA-DAG改性膜制备及抗污染性能研究

以多巴胺（DA）、1,3-二氨基胍盐酸盐（DAG）、氨基化氧化石墨烯（NGO）为改性剂,将氧化沉积和表面接枝法联用于聚偏氟乙烯（PVDF）原膜表面改性,得到NGO/PDA-DAG改性膜,研究改性膜的制备条件及其抗污染性能.结果表明：①改性膜最佳制备条件为DA浓度1.5mg/mL,DA氧化沉积时间4h,DAG质量浓度1wt%,NGO浓度2mg/mL,NGO接枝时间1h;②改性膜的亲水性能改善明显.改性剂向膜面引入了-NH₂、C=N、-OH、C=O等亲水性官能团,使静态接触角由68.7°（原膜）下降到38.7°（改性膜）;③改性膜比原膜具有更高的机械强度.改性层改善了原膜表面应力传递盲区,使改性膜表面粗糙度由原膜的46.5nm下降到18.3nm.改性膜的拉伸强度和杨氏模量分别为22.83和376.25Mpa,比原膜提高了39.72%和13.57%;④改性膜的选择透过性和抗有机污染性能显著提高.与原膜相比,改性膜对牛血清白蛋白（BSA）的截留率提高18.64%、纯水通量恢复率提高34.08%、膜总污染率下降20.67%（可逆污染率提高13.41%、不可逆污染率下降34.08%）;⑤改性膜抗菌性能强,且抗菌效果稳定持久.改性膜连续4次抗菌测试（38℃下接触2h）的平均抗菌率分别为92.3%、88.5%、87.9%、85.6%,能有效防止生物膜污染发生,而原膜无任何抗菌特性.     

河口区养殖塘水-气界面N2O扩散通量比较

以闽江河口区水产养虾塘为研究对象,于2017年6~11月,采用漂浮箱法和扩散模型法同步原位观测了养殖塘N₂O排放通量.结果表明,研究期间悬浮箱法和扩散模型法获得的养殖塘水－气界面N₂O通量变化范围分别为（0.38±0.05）~（20.63±5.63）μg/（m²·h）和（2.77±0.52）~（17.23±2.27）μg/（m²·h）,随时间推移均呈现“增加-降低-增加-降低”的双峰变化特征.两种方法观测的N₂O通量均与水温、水体硝酸盐氮（NO₃^--N）和氨氮（NH₄⁺-N）浓度呈现显著正相关关系（P<0.05）,与水体溶解氧（DO）呈现出显著负相关关系（P<0.05）.悬浮箱法与不同扩散模型法测定的N₂O排放通量大小排序表现为：模型DM_RC01>悬浮箱法>模型DM_CL98>模型DM_W92a>模型DM_MY95>模型DM_CW03>模型DM_LM86.相比其他几种模型方法,模型RC01与悬浮箱法测得的养殖塘水－气界面N₂O通量相关性系数最高.本研究结果初步表明,今后进行东南沿海河口区养殖塘N₂O通量的大尺度观测研究时,可考虑选择RC01模型法来代替悬浮箱法进行测定,进而减小人力及物力的投入.     

催化氧化除氨氮/锰技术在滤池改造中的应用研究

西安市某地下水源水厂石英砂滤池中滤料表面形成的氧化膜催化活性很低,基本不具备去除铁、锰、氨氮的能力,出水安全隐患较高,因此在中试滤柱系统中评价了石英砂滤料除铁（Fe²⁺）、锰（Mn²⁺）、氨氮（NH₄⁺-N）效能,并进行活性滤料的性能优化.在此基础上,在水厂原有石英砂滤池中进行活性滤料的原位制备.结果表明,水厂石英砂滤料基本不具备去除Fe²⁺、Mn²⁺、NH₄⁺-N能力.在中试滤柱系统中,经过3d挂膜,低浓度Fe²⁺、Mn²⁺、NH₄⁺-N的去除率均可达93%以上.在滤池中进行原位改造后,进水NH₄⁺-N浓度为（0.3±0.05） mg/L时,去除率由28%提高到90%,进水Mn²⁺浓度为（0.3±0.05） mg/L时,去除率由50%提高到80%.进一步分析滤料表征发现,改造后滤料形貌和结构均发生了改变.XRD分析结果表明,改造后滤料产生了新峰,证明了滤料具备了活性.改造后可满足案例水厂净水安全的需要,具有较高的实用价值.     

Land Use and Climate Variability Amplify Carbon,Nutrient, and Contaminant Pulses: A Review with Management Implications

Nonpoint source pollution from agriculture and urbanization is increasing globally at the same time climate extremes have increased in frequency and intensity. We review >200 studies of hydrologic and gaseous fluxes and show how the interaction between land use and climate variability alters magnitude and frequency of carbon, nutrient, and greenhouse gas pulses in watersheds. Agricultural and urban watersheds respond similarly to climate variability due to headwater alteration and loss of ecosystem services to buffer runoff and temperature changes. Organic carbon concentrations/exports increase and organic carbon quality changes with runoff. Nitrogen and phosphorus exports increase during floods (sometimes by an order of magnitude) and decrease during droughts. Relationships between annual runoff and nitrogen and phosphorus exports differ across land use. CH₄ and N₂O pulses in riparian zones/floodplains predominantly increase with: flooding, warming, low oxygen, nutrient enrichment, and organic carbon. CH₄, N₂O, and CO₂ pulses in streams/rivers increase due to similar factors but effects of floods are less known compared to base flow/droughts. Emerging questions include: (1) What factors influence lag times of contaminant pulses in response to extreme events? (2) What drives resistance/resilience to hydrologic and gaseous pulses? We conclude with eight recommendations for managing watershed pulses in response to interactive effects of land use and climate change.