烘箱法测定水和废水中总铬

针对标准法测定总铬存在的诸多不足,提出了烘箱法测定总铬的新方法。改进法制作的校准曲线相关系数γ0.999,相对标准偏差RSD0.88%,加标回收率为98.3%~101.7%,均优于标准法。     

Variation of grain Cd and Zn concentrations of 110 hybrid rice cultivars grown in a low-Cd paddy soil

Enhanced Cd uptake and Zn depletion in rice grains and high potential for food Cd exposure by the high-yielding hybrid cultivars of China had been addressed. A field experiment was conducted in 2006 to determine the di erence in grain Cd and Zn between cultivars. Total 110 cultivars including super rice and common hybrid rice cultivars were grown on a single paddy soil (Entic Haplaquept) with a neutral reaction and low total Cd content. Grain Cd and Zn concentrations were determined with graphite atomic adsorption spectrophotometer (GFAAS) and flame atomic adsorption spectrophotometer (AAS) respectively.Wide variation of Cd content in grain was found in a range of 0.004–0.057 mg/kg, while the Zn content in a range of 10.25–30.06 mg/kg among the cultivars. Higher Cd but lower Zn concentration in grains of super rice cultivars was observed compared to the common hybrid ones. A highly significant positive linear correlation of grain Cd/Zn with grain Cd was found for super rice and common hybrid cultivars, meanwhile much higher slope for these hybrid cultivars than the reported non-hybrid cultivars was also observed. Using the limit value of the Chinese chemical guidelines for foods (MOHC and SSC, 2005), calculated potential risk of food Cd exposure with “Zn hungry” through diet intake was prominent with all the studied 110 hybrid rice cultivars, possessing high potential health problems for rice production in South China using the super rice cultivars. Breeding of genotypes of rice cultivars with low grain Cd and low Cd/Zn ratio is needed for rice production in acidic red soils where Cd bioavailability is prevalently high.     

Synthesis, characterization, and adsorption performance of Pb（Ⅱ）-imprinted polymer in nano-TiO2 matrix

Surface ion-imprinted in combination with sol-gel process was applied to synthesis a new Pb(II)-imprinted polymer for selective separation and enrichment of trace Pb(II) from aqueous solution. The prepared material was characterized by using the infrared spectra, X-ray di ractometer, and scanning electron microscopy. The batch experiments were conducted to study the optimal adsorption condition of adsorption trace Pb(II) from aqueous solutions on Pb(II)-imprinted polymer. The equilibrium was achieved in approximately 4.0 h, and the experimental kinetic data were fitted the pseudo second-order model better. The maximum adsorption capacity was 22.7 mg/g, and the Langmuir equation fitted the adsorption isotherm data. The results of selectivity experiment showed that selectively adsorbed rate of Pb(II) on Pb(II)-imprinted polymer was higher than all other studied ions. Desorption conditions of the adsorbed Pb(II) from the Pb(II)-imprinted polymer were also studied in batch experiments. The prepared Pb(II)-imprinted polymer was shown to be promising for the separation and enrichment of trace Pb(II) from water samples. The adsorption and desorption mechanisms were proposed.     

三株溶藻菌对水华鱼腥藻抗氧化酶活性的影响

研究了三株溶藻菌L7,L8和L18的溶藻活性代谢产物对水华鱼腥藻（Anabaena flos—aquae）超氧化物歧化酶（Superoxide dismutase,SOD）比活性、过氧化氢酶（Catalase,CAT）比活性和膜脂过氧化产物丙二醛（Malondialdehyde,MDA）浓度的影响,试图从藻类的抗氧化酶系的变化揭示溶藻活性代谢产物的溶藻机制。在L7,L8和L18的溶藻活性代谢产物胁迫下,水华鱼腥藻的SOD比活性显著升高,MDA浓度急剧上升。加入L18的溶藻活性代谢产物后,水华鱼腥藻的CAT比活性显著高于空白组,L7和L8的溶藻活性代谢产物对水华鱼腥藻的CAT比活性无显著影响。     

Cu~(2+)/吡啶/H_2O_2对直接大红4BE的快速脱色研究

为了明确影响Cu2+/吡啶/H2O2对模拟染料(DR4BE)废水脱色的主要因素,采用动力学分析、正交和Box-Behnken实验设计研究了不同溶液pH、Cu2+、吡啶、H2O2浓度及Cu2+、吡啶和H2O2组合对初始脱色速率常数和最终脱色率的影响.同时,采用自由基抑制、H2O2催化分解实验探索了Cu2+/吡啶/H2O2对染料的脱色机理.结果发现,Cu2+/吡啶/H2O2能有效使DR4BE快速脱色,脱色效率远高于Cu2+/H2O2;pH是影响初始脱色速率最重要的因素,吡啶、Cu2+及pH是影响最终脱色率最重要的因素;溶液pH在7.0左右时有利于该脱色过程的快速进行.Cu2+与吡啶的交互作用相对较强,吡啶、Cu2+与H2O2的交互作用相对较弱.羟基自由基氧化是Cu2+/吡啶/H2O2对染料DR4BE初始快速脱色的主要机理.研究结果还表明,Cu2+/吡啶/H2O2体系可用于中性条件下染料废水的快速脱色处理.     

沈阳地区水环境和生物样品中全氟化合物的污染分布特征

采用高效液相色谱/电喷雾负电离源串联质谱法对沈阳市各类水环境和生物样品中全氟化合物(PFCs)进行测定,研究了PFCs的河流分布及季节分布特征.同时,对通过饮用水及家禽和鱼摄入全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)的人体健康风险进行了评价.结果表明,沈阳市各类水环境样品中总PFCs浓度范围为nd～6.01ng·L-1,平均浓度为5.23ng·L-1.PFOS和PFOA是沈阳地区所有水环境样品中最主要的PFCs污染物,浓度范围分别为nd～2.83ng·L-1和nd～5.71ng·L-1,平均浓度分别为1.11和2.13ng·L-1.细河的PFOS含量最高,约为浑河PFOS含量的2倍,蒲河PFOS含量的3倍.一些PFCs化合物之间呈正相关关系,说明其可能具有相同的来源.PFOS与PFOA之间无相关关系,由此推断沈阳水体中二者具有不同来源.浑河流经沈阳市时,PFOS和PFOA浓度升高.流经沈阳市区后,PFOS和全氟己烷磺酸钾(PFHxS)浓度明显升高.细河中PFHxS也有检出,表明沈阳市是周边水体中PFOS及PFHxS的主要污染来源.丰水期地表水中PFOS和PFOA浓度与枯水期相比没有明显差异,但丰水期水中PFCs组成更为丰富,出现了大量全氟庚酸(PFHpA).沈阳地区自来水中PFOS和PFOA浓度平均值分别为0.39和0.85ng·L-1,最高浓度分别为1.16和2.55ng·L-1,均低于美国饮用水健康参考值.沈阳生物样品中PFOS和全氟十一酸(PFUnDA)是最普遍的化合物.总PFCs平均含量在鱼样品中为6.59ng.g-1(以干重计),鸡和鸭血清样品中分别为1.65和0.69ng·mL-1,鸡和鸭肝脏样品中分别为0.41和1.68ng.g-1(以干重计),与文献报道相比处于较低水平.     

A comparative investigation of NdSrCu_(1-x) Co_x O_(4-δ) and Sm_(1.8) Ce_(0.2) Cu_(1-x) Co_x O_(4-δ) (x:0–0.4) for NO decomposition

A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ (x: 0–0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu 1-x Co x O 4-δ catalysts were of oxygen vacancies whereas the Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level, the oxygen vacancy density of NdSrCu 1-x Co x O 4-δ decreased while the over-stoichiometric oxygen amount of Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO 3.702 catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr -1 , and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO 3.702 NdSrCu 0.8 Co 0.2 O 3.736 NdSrCu 0.6 Co 0.4 O 3.789 Sm 1.8 Ce 0.2 Cu 0.6 Co 0.4 O 4.187 Sm 1.8 Ce 0.2 Cu 0.8 Co 0.2 O 4.104 Sm 1.8 Ce 0.2 CuO 4.045 , in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu 3+ /Cu 2+ redox ability of NdSrCu 1-x Co x O 4-δ account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.     

基于不同土壤数据单元法的DNDC模型对太湖地区水稻土CH4排放模拟研究

利用农业土壤痕量气体排放模型DNDC(DeNitrification-DeComposition),以整个太湖地区37个县234万hm2水稻土为例,分析了3种不同土壤数据单元法对CH4排放模拟的影响.其中,1∶5万图斑单元法土壤属性来自1∶5万土壤数据库,图斑为最小模拟单元;1∶5万"县级"单元法土壤属性也取自1∶5万土壤数据库,"县"为最小模拟单元;1∶1 400万"县级"单元法土壤属性取自国内同类研究使用最多的1∶1 400万土壤图和《中国土种志》,"县"为最小模拟单元.结果表明,虽然1∶5万图斑单元法大多数县的CH4排放量都在1∶5万"县级"单元法最大与最小值范围之间,但整个地区总排放量(以C计,下同)相差达到1 680 Gg;而1∶1 400万"县级"单元法CH4排放量与1∶5万图斑单元法相比,尽管整个地区总排放量只相差180 Gg,但各"县级"单元之间的估算差异却很大,这一方面说明了土壤数据的详细程度是保证地球生物化学模型模拟精度的重要因子,另一方面也说明在区域CH4排放量估算模拟中使用更详细的土壤资料是非常必要的.     

提高海水中硫化物测定回收率的探讨

通过对测定海水中硫化物的分析方法进行改进和优化处理,解决了一直困扰海水中硫化物测定的回收率偏低和相对标准偏差较大的问题,经过反复实验,硫化物的回收率可提高到90%以上,相对标准偏差为2.6%.     

基于批式呼吸计量法的溶解性COD组分划分

利用批式好氧呼吸计量法结合溶解性慢速水解COD(S_H)水解动力学拟合提出了溶解性COD(SCOD)的组分划分方案.上海2个污水处理厂进水的SCOD组分划分结果表明,A厂沉砂池出水(典型生活污水)的SCOD中含有43.5%～58.6% S_H、 21.8%～35.2%易生物降解COD(S_S)和15.4%～30.9%溶解性惰性COD(S_I); B厂沉砂池出水(长距离输送的合流制污水)SCOD中含有34.5%～45.2% S_H、 29.3%～37.7% S_S和25.6%～31.2% S_I. 9组不同水样的试验拟合结果表明,一级动力学能够很好地描述S_H的水解过程,A厂和B厂进水S_H的水解速率常数分别为28.00～39.77 d^-1和26.48～29.52 d^-1.该组分划分方案能够实现S_S积分区域的理论划分,并消除溶解性微生物产物对S_I测定的影响.