Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

反硝化菌株DA-1的脱氮研究

菌株DA-1被发现能在好氧和厌氧环境中将硝酸盐转化为气态氮。在以NO3-为唯一氮源的条件下研究了碳源、C/N和pH值对菌株DA-1好氧和厌氧反硝化脱氮的影响。结果表明:同等条件下,48 h内菌株DA-1的厌氧脱氮效率高于好氧脱氮率;菌株DA-1能在好氧和厌氧条件下利用乙酸、柠檬酸以及葡萄糖进行细胞增殖和反硝化。在厌氧条件下,三者作为碳源时的反硝化效率分别为(34.04±0.15)%、(22.72±0.32)%和(11.32±0.06)%,均低于好氧条件下的(25.38±0.14)%、(17.52±0.11)%和(8.06±0.01)%。2种条件下均是乙酸为碳源时反硝化效率最高。而丁二酸仅能在厌氧环境中作为电子供体参与反硝化反应。C/N越高越有利于菌株DA-1的厌氧反硝化,当C/N为10时,反硝化效率最高为(35.06±0.19)%。而在好氧条件下,菌株反硝化效率随着C/N的升高,先升高再降低,当C/N为8时,反硝化效率最高;好氧和厌氧脱氮的最适pH值为7.0。体系偏酸或者偏碱都会造成菌株DA-1脱氮效率的降低并出现亚硝酸盐累积。厌氧环境中pH=5.0时累积的亚硝酸盐浓度高达(8.95±2.05)mg/mL。     

2种生物反硝化法去除地下水中硝酸盐的研究

采用砂柱装置,在实验室研究了自养微生物和异养微生物2种生物反硝化方法对地下水中硝酸盐的去除效果。自养反硝化反应在以硫作为电子供体的硫/石灰石/细沙反应柱中进行,异养反硝化反应在石灰石/细沙反应柱中进行,进水增加乙醇作为外加碳源。实验结果用以比较2种反硝化方法在硝酸盐去除率、微生物反应动力学和反应产物三者的异同。结果表明,自养反硝化反应中NO3--N去除率达95.4%,异养反硝化反应去除率可达99.3%;分别与Monod微生物0级、1/2级和1级反应动力学方程进行拟合,2种反硝化反应均符合1/2级微生物反应动力学,适合用1/2级微生物反应方程描述;在反应结束阶段,自养反硝化主要反应产物SO42-出水浓度低于250mg/L,异养反硝化副产物CH3OO-易成为二次污染源,异养反硝化的反硝化速率明显高于自养反硝化反应。     

金佛山地区地下水硝态氮污染时空变异性研究

根据1976～1977年、2004～2006年和2009年金佛山地区23处地下水排泄点水中硝态氮的质量浓度,采用地球化学、统计学与GIS相结合的方法确定了区内地下水中硝态氮的地球化学背景值,分析了硝态氮污染的时空变异特征.结果表明,区内地下水中硝态氮的地球化学背景值为0.72～2.00 mg.L-1,正异常下限为3.20 mg.L-1;2004～2006年和2009年金佛山自然保护区内地下水硝态氮平均质量浓度为：2.08、2.67、2.59和3.92 mg.L-1;保护区外为：39.08、25.46、17.99和13.73mg.L-1;平均超标率（标准规定NO 3--N≤10 mg.L-1）为：451.64%、478.61%、331.85%和145.67%;最高浓度为：157.58、118.04、63.82和46.18 mg.L-1;最大超标率为：1 475.81%、1 080.39%、538.20%和361.78%.插值分析结果显示,区内地下水中硝态氮高值中心随时间而变化,低值区沿金佛山自然保护区分布.当地合理的环境保护政策和产业结构调整,对环境保护工作起到了积极作用.     

阿替洛尔在硝酸根溶液中的光降解研究

以氙灯为模拟太阳光光源,研究了β阻滞剂阿替洛尔(ATL)在硝酸根溶液中的光解,探讨了硝酸根离子浓度、溶液pH值、碳酸氢根离子浓度和腐殖质浓度对ATL光解的影响.结果表明,ATL在不同浓度硝酸根溶液中的光解反应符合准一级动力学规律,增大硝酸根离子浓度促进了ATL的光降解率,当硝酸根离子浓度由0增至5 mmol.L-1时其速率常数由0.002 26min-1增至0.009 4 min-1;酸性或碱性溶液有利于ATL在硝酸根溶液中的光解,碳酸氢根离子浓度对光解无明显影响,而加入Suwannee富里酸(SRFA)对光解产生抑制作用.采用异丙醇作为羟基自由基分子探针检测到.OH存在于ATL光解过程中.采用SPE-LC-MS方法鉴定了ATL在硝酸根溶液中的主要光解产物,并提出了可能的光解途径.     

稀土钇对蚯蚓的急性毒性及蚓体内蓄积研究

文章以蚯蚓为指示生物,分别采用滤纸接触法和自然土壤法研究了稀土元素钇对蚯蚓的急性毒性效应。结果表明,滤纸接触法测得钇对蚯蚓的半数致死浓度LC50为0.18 g/L;土壤法所测LC50值为1.08 g/kg。可见,稀土钇对蚯蚓具有毒性作用,但属低毒级,并且自然土壤法中蚯蚓的半数致死浓度要低于滤纸接触法中的结果。应用ICP-AES分别研究了2种实验方法中钇在蚯蚓体内的富集情况,发现硝酸钇浓度及染毒时间、蚯蚓的死亡率及速度和钇在蚯蚓体内的富集三者存在显著的相关性。     

Effects of seed aerosols on the growth of secondary organic aerosols from the photooxidation of toluene

Hydroxyl radical （.OH）-initiated photooxidation reaction of toluene was carried out in a self-made smog chamber. Four individual seed aerosols such as ammonium sulfate, ammonium nitrate, sodium silicate and calcium chloride, were introduced into the chamber to assess their influence on the growth of secondary organic aerosols （SOA）. It was found that the low concentration of seed aerosols might lead to high concentration of SOA particles. Seed aerosols would promote rates of SOA formation at the start of the reaction and inhibit its formation rate with prolonging the reaction time. In the case of ca. 9000 pt/cm^3 seed aerosol load, the addition of sodium silicate induced a same effect on the SOA formation as ammonium nitrate. The influence of the four individual seed aerosols on the generation of SOA decreased in the order of calcium chloride〉sodium silicate and ammonium nitrate〉ammonium sulfate.     

Effects of nitrate concentration in interstitial water on the bioremediation of simulated oil-polluted shorelines

Nutrient addition has been proved to be an effective strategy to enhance oil biodegradation in marine shorelines.To determine the optimal range of nutrient concentrations in the bioremediation of oil-polluted beaches,nitrate was added to the simulated shoreline models in the initial concentration of 1,5 and 10 mg/L.Whenever the NO3-N concentration declined to 70% of its original value, additional nutrients were supplemented to maintain a certain range.Results showed adding nutrients increased the oil biodegradation level,the counts of petroleum degrading bacteria(PDB)and heterotrophic bacteria (HB),and the promoted efficiency varied depending on the concentration of nitrate.Oil degradation level in 5 mg/L(NO_3-N)group reached as much as 84.3% accompanied with the consistently highest counts of PDB;while in 1 mg/L group oil removal efficiency was only 35.2%,and the numbers of PDB and HB were relatively low compared to the other groups supplemented with nutrients.Although counts of HB in the 10 mg/L group were remarkable,lower counts of PDB resulted in poorer oil removal efficiency (70.5%) compared to 5 mg/L group.Furthermore,it would need more NO_3-N(0.371 mg)to degrade 1 mg diesel oil in the 10 mg/L group than in the 5 mg/L group(0.197 mg).In conclusion, Nitrate concentration in 5 mg/L is superior to 1 and 10 mg/L in the enhancement of diesel oil biodegradation in simulated shorelines.     

Competition of bloom-forming marine phytoplankton at low nutrient concentrations

Competition of three bloom-forming marine phytoplankton (diatom Skeletonema costatum, and dinoflagellates Prorocentrum minimum and Alexandrium tamarense) was studied through a series of multispecies cultures with di erent nitrate (NaNO3) and phosphate (NaH2PO4) levels and excess silicate to interpret red tide algae succession. S. costatum outgrew the other two dinoflagellates in nitrate and phosphate replete cultures with 10 mol/L Na2SiO3. Under nitrate limited (8.82 mol/L NaNO3) conditions, the growth of S. costatum was also dominant when phosphate concentrations were from 3.6 to 108 mol/L. Cell density of the two dinoflagellates only increased slightly, to less than 400 and 600 cells/mL, respectively. Cell density of S. costatum decreased with time before day 12, and then increased to 4000 cells/mL (1.5 mg/L dry biomass) at NaNO3 concentrations between 88.2 and 882 mol/L with limited phosphate (0.36 mol/L NaH2PO4) levels. In addition, P. minimum grew well with a maximal cell density of 1690–2100 cells/mL (0.5–0.6 mg/L dry biomass). Although S. costatum initially grew fast, its cell density decreased quickly with time later in the growth phase and the two dinoflagellates were dominant under the nitrate-limited and high nitrate conditions with limited phosphate. These results indicated that the diatom was a poor competitor compared to the two dinoflagellates under limited phosphate; however, it grew well under limited nitrate when growth of the dinoflagellates was near detection limits.     

Silver impregnated carbon for adsorption and desorption of elemental mercury vapors

The Hg0 vapor adsorption experimental results on a novel sorbent obtained by impregnating a commercially available activated carbon (Darco G60 from BDH) with silver nitrate were reported. The study was performed by using a fundamental approach, in an apparatus at laboratory scale in which a synthetic flue gas, formed by Hg0 vapors in a nitrogen gas stream, at a given temperature and mercury concentration, was flowed through a fixed bed of adsorbent material. Breakthrough curves and adsorption isotherms were obtained for bed temperatures of 90, 120 and 150°C and for Hg0 concentrations in the gas varying in the range of 0.8–5.0 mg/m3. The experimental gas-solid equilibrium data were used to evaluate the Langmuir parameters and the heat of adsorption. The experimental results showed that silver impregnated carbon was very effective to capture elemental mercury and the amount of mercury adsorbed by the carbon decreased as the bed temperature increased. In addition, to evaluate the possibility of adsorbent recovery, desorption was also studied. Desorption runs showed that both the adsorbing material and the mercury could be easily recovered, since at the end of desorption the residue on solid was almost negligible. The material balance on mercury and the constitutive equations of the adsorption phenomenon were integrated, leading to the evaluation of only one kinetic parameter which fits well both the experimentally determined breakthrough and desorption curves.