三氮的离子色谱法连续测定研究

本文首次提出用电导检测器和紫外检测器串联,对氮的三种形态(N-NO_2~-,N-NO_3~-,N-NH_4~+)进行连续测定;盐酸/甘氨酸作淋洗液,HPIC-CS_5作分离柱,建立了同时测定“三氮”灵敏的色谱方法,方法的线性相关系数大于0.999,各离子的相对标准偏差均小于0.5％,对样品的测定,回收率均在100％％+5％以内,与标准方法比较,结果颇为一致。     

水体中常见无机阴离子对TiO_2薄膜光催化还原Cr(Ⅵ)的影响

选择了5种水体中常见的阴离子(Cl~-,SO_4~(2-),HCO_3~-,NO_3~-以及HPO_4~(2-)/H_2P_4~-),分别考察了其对TiO_2薄膜光催化还原模拟Cr(Ⅵ)废水的影响.从上述离子的光吸收,对·OH的捕获作用以及与Cr(Ⅵ)的竞争吸附三个方面讨论了上述离子影响TiO_2薄膜光催化还原Cr(Ⅵ)速率的原因.结果表明,体系酸性越强,越有利于Cr(Ⅵ)的还原;在pH值约为6时,HCO_3~-,Cl~-和SO_4~(2-)对TiO_2薄膜光催化还原Cr(Ⅵ)具有促进作用,NO_3~-具有抑制作用,H_2PO_4~-/HPO_4~(2-)在低浓度时具有促进作用,而在高浓度时具有抑制作用.造成上述结果的主要原因是Cl~-,SO_4~(2-)和HCO_3~-具有较强的·OH捕获作用和在TiO_2表面较低的吸附能力;H_2PO_4~-/HPO_4~(2-)在TiO_2表面具有较强的吸附能力;NO_3~-对紫外光吸收作用降低了TiO_2表面的紫外光强度以及自身光化学反应产生了·OH.     

固体吸收管携带式采样-离子色谱法测定大气中SO_2和NO_2

本文用简单的携带式采样技术、用浸渍三乙醇胺的分子筛13X装填的固体吸收剂采样管采样、用淋洗液(0.003M NaHCO_3/0.0024M Na_2CO_3)把定量吸附在分子筛上的NO_2和SO_2提取出来。提取液为含NO_2~-、NO_3~-、SO_3~(2-)和SO_4~(2-)的混合液,加入过氧化氢把SO_3~(2-)氧化成SO_4~(2-),继用离子色谱法测定NO_2~-、NO_3~-和SO_4~(2-),以NO_2~-和NO_3~-的离子浓度之和换算出样品中的NO_2浓度。文中讨论了固体吸附剂的制备、影响固体吸附剂吸收效率的因素、固体吸收管的吸收容量以及吸收剂的稳定时间,并与几种液体吸收剂作了对照。     

环形扩散管和滤膜联用采集和测定大气中气固相物质

建立了环形扩散管(annular diffusion denuder)和滤膜连用的采样装器。采用涂渍1％碳酸钠甲醇水溶液和5％亚磷酸甲醇溶液的两段环形扩散管串联分别收集气态HNO_3,HCl,SO_2和NH_3、空气经扩散管后,继而抽入滤膜采样头,用Teflon滤膜采集颗粒物,Nylon滤膜收集由Teflon滤膜上颗粒物挥发产生的气态HNO_3和HCl。样品提取后,用离子色谱法测定SO_4~(2-),NO_3~-和Cl~-;采用流动注射荧光法测定NH_4~+。当采样流速为10L/min,采样24h,环形扩散管对气态硝酸、氯化氢和二氧化硫的检出限(3σ)为0.04—0.09μg/m~3,对氨的检出限为0.12μg/m~3。实验结果表明本法适用于大气和室内空气的采样和测定。     

西南地区降雨对大气中元素的清洗作用

探讨了西南地区城市、郊区和偏远地区降雨对大气中某些元素及SO_4~(2-),NO_3~-,HNO_3等的清洗作用,估算了不同地区元素的清洗削减率。结果表明,降雨时HNO_3和NO_3~-的清洗作用比SO_4~(2-)大,雨水中的S约有83％以SO_4~(2-)状态存在。     

水体中不同形态氮对阿昔洛韦光解的影响

以350 W氙灯为太阳光模拟光源,探讨了水环境中不同形态氮(NO3-、NO_2~-和NH+4)对阿昔洛韦(ACV)光解的影响.结果表明,ACV在不同形态氮离子溶液中的光解符合一级动力学规律,NO_3~-和NO_2~-均促进ACV的光解,NH+4对ACV的光解基本无影响;在NO_3~-、NO_2~-存在下,加入异丙醇作为羟基自由基猝灭剂,显著抑制了ACV的降解,表明NO_3~-、NO_2~-在光照下产生了·OH参与ACV的氧化降解.同时模拟研究了水体处于不同p E值时,水中不同形态氮共存对ACV光解的复合影响.p E值增大,ACV的光解速率先增大后减小;当NO_2~-和NH+4共存时,对ACV的光解主要表现为NO_2~-的影响;当NO_2~-和NO_3~-共存时,两者对ACV的光解存在拮抗作用,说明其对ACV的光解不是简单的叠加.     

天然水中金属形态分析

一、概述 在环境科学研究工作中不仅要求测定各种有害元素的总量,而且进一步要求鉴别、测定和研究其赋存的化学形态,以便为环境生物学、环境地学、环境工程学、环境质量评价等提供可靠有用的资料。 Stumm认为化学形态(Chemical species)指的是某一元素在环境中以某种离子或分子存在的实际形式。例如碘在水溶液中可能以一种或更多种的形式存在,如:I_2、I~-、Ⅰ_3~-、HIO、IO~-、IO_3~-以及离子对、络合物或有机碘化物等。汤鸿霄提出:“所谓形态,实     

离子色谱法检测饮用水中的无机阴离子——美国国家环保局(U.S.EPA)方法300.1简介(上)

1 应用范围该方法适用于检测地表水、地下水和饮用水中的无机阴离子,分为A,B两部分.进样体积的大小取决于样品中阴离子的浓度和检测器的动态范围.(1)A部分:普通阴离子(图1)F~-,CI~-,NO_2~-,Br~-,NO_3~-O,PO_4~3-,SO_4~2-(2)B部分:无机消毒副产物(图2)BrO_3~-,ClO_2~-,ClO_3~-.     

磁性聚吡咯的合成及其快速去除水中硝酸盐

在四氧化三铁表面采用原位化学氧化合成了磁性聚吡咯(Ppy/Fe_3O_4)吸附剂,并用FTIR、XRD、TGA、XPS以及VSM等对材料进行表征.结果表明,聚吡咯成功包覆到Fe_3O_4表面,且具有超顺磁性.吸附实验结果表明,Ppy/Fe_3O_4对水中硝酸盐(NO_3~-)具有较好的吸附性能,在NO_3~-初始浓度为50 mg·L~(-1)条件下,当pH值为4.2时,温度为25℃下吸附剂对NO_3~-的吸附效果最佳,最佳吸附量为37.57 mg·g~(-1),阴离子的存在对NO_3~-吸附具有抑制作用.Ppy/Fe_3O_4对NO_3~-的吸附可以通过Langmuir模型很好地描述,吸附过程服从拟二级动力学,并且吸附速率随着NO_3~-初始浓度的增加而增加.磁性聚吡咯通过表面质子化氮与NO_3~-之间的静电作用而达到去除的目的.吸附饱和的吸附剂可以很好地进行磁性分离,并可以在0.01 mol·L~(-1)的NaCl溶液中进行脱附再生.     

南京北郊冬春季大气颗粒物中含氮无机水溶性离子组分特征

为了解南京北郊大气颗粒物中含氮二次水溶性离子组分特征,2014年冬春两季使用Anderson 9级采样器对南京北郊大气颗粒物进行分级采样,利用离子色谱仪分析得到了各粒径范围颗粒物中的含氮二次无机组分质量浓度,结合能见度、相对湿度、颗粒物浓度等观测数据探讨了不同天气状况下大气颗粒物中含氮二次水溶性离子组分的含量及其粒径分布特征。结果表明:冬季和春季平均PM_(2.5)质量浓度分别达到了80.81μg·m~(-3)和52.57μg·m~(-3),明显超过二类标准限值。PM_(10)中NO_3~-和NH_4~+表现出较好的一致性,相关系数高达0.92,表明两种离子的来源比较相似;NO_2~-与NO_3~-和NH_4~+均呈现明显的负相关关系。就季节平均而言,冬季NO_3~-和NH_4~+质量浓度明显高于春季,尤其在0.43~2.1μm粒径范围内,这与冬季二次细颗粒物污染加剧有关;其他粒径段的浓度值季节差异不明显。不同能见度下,NO_3~-和NH_4~+质量浓度谱均呈三峰分布;当水平能见度3 km时,NO_3~-和NH_4~+最大谱峰大多在9.0~10μm粗粒径段;能见度降至3 km以下时,谱最大峰值出现在1.1~2.1μm粒径段。能见度水平越低,NO_3~-和NH_4~+的质量浓度越高,表明随着NO_3~-和NH_4~+浓度增加气溶胶的消光作用有所增强,从而导致能见度降低。霾天细模态中NH_4~+和NO_3~-的浓度较非霾天明显增加,粗模态无明显变化。NO_2~-作为中间产物其性质极不稳定,谱分布也比较复杂,但任何天气状况下均在粗粒径段出现高峰值。     

不同水力负荷下凤眼莲去除氮、磷效果比较

采用人工模拟方法,研究了不同水力负荷(0.14、0.20、0.33和1.00m3.m-2.d-1)对凤眼莲去除富营养化水体氮、磷效果的影响,试验期间进水TN、NH4+-N、NO3-N、TP平均质量浓度分别为4.85、1.33、2.92和0.50mg.L-1。结果表明,凤眼莲净化系统对富营养化水体具有较好的去除效果,低水力负荷(0.14、0.20m3.m-2.d-1)下,出水TN、NH4+-N和TP均达到了GB3838—2002《地表水环境质量标准》的Ⅳ类水质标准;当水力负荷提高到1.00m3.m-2.d-1后,出水TN、NH4+-N、NO3-N和TP质量浓度明显上升。4种水力负荷下,凤眼莲净化系统对TN和TP去除率分别为84.95%和80.65%、73.87%和73.04%、51.60%和64.05%、30.77%和47.79%,即随水力负荷的提高而降低;相应的TN、TP去除负荷分别为0.58和0.06、0.72和0.07、0.83和0.11、1.47和0.23g.m-2.d-1,即随水力负荷的提高而增加。综合考虑净化效果和污水处理能力,本试验条件下凤眼莲系统的水力负荷宜控制在0.33m3.m-2.d-1。     

有机肥中4类典型兽药抗生素的多残留测定

建立了固相萃取-超高效液相色谱-串联质谱（SPE—UPLC—MS／MS）法同时测定有机肥中7种磺胺类、4种氟喹诺酮类、4种四环素类和3种大环内酯类抗生素残留的方法。采用乙腈和磷酸盐缓冲液（pH=3）的混合液作为有机肥样品的提取溶液,用强阴离子交换柱（SAX）-亲水亲脂平衡萃取柱（HLB）串联进行提取液的富集和纯化。以甲醇-φ=0．1％的甲酸溶液作为流动相,进行液相质谱分析。18种抗生素在5—500μg·kg-1的浓度范围内线性关系良好,决定系数（r2）1〉0．99。以3倍信噪比估算磺胺类、氟喹诺酮类、四环素类和大环内酯类的检测限分别为0．37～4．65、0．43—2．42、0．94～2．78和0．83～4．20μg·kg-1,这4类抗生素50和500μg·kg。2个添加水平的样品平均加标回收率分别为71．6％～94．3％、72．3％～86．7％、71．0％～102．2％和70．7％～93．3％,相对标准偏差在2．1％～11．4％之间。采用所建方法对南京地区市售8种有机肥中18种抗生素含量的测定结果显示,除磺胺类外,其他抗生素均有不同程度的检出。     

不同施肥水平下菜地径流氮磷流失特征

研究施肥对菜地径流氮、磷流失的影响,对控制水体富营养化有重要意义。采用田间小区监测的方法,研究常规施肥、减量施肥1和减量施肥2等三种施肥水平对菜地径流氮磷流失的影响。结果表明,（1）不同施肥水平的径流氮、磷流失浓度均较高,径流TN、NH4＋-N、NO3--N的平均流失质量浓度分别在20.5~34、2.2~2.4、6.3~9.5 mg L-1之间,径流TP、DP的平均流失质量浓度分别在7.7~11.1、2.1~2.4 mg L-1之间,菜地土壤径流氮、磷流失风险较大。（2）减量施肥可明显降低径流TN和NO3--N的流失浓度,与当地常规施肥相比,减施肥料20%和30%可分别降低径流TN流失浓度的40%、32%和NO3--N流失浓度的23%、35%,而减量施肥对径流TP、DP的流失浓度影响不大。（3）不同施肥水平的径流TN、NO3--N流失负荷分别在5.8~7.6、1.6~2.3 kg hm-2之间,与常规施肥相比,减施肥料20%和30%可分别减少TN、NO3--N流失负荷的24%、19%和11%、29%。不同施肥水平的径流TP、DP流失负荷分别在1.7~2.9、2.5~2.7 kg hm-2之间,减量施肥并不能减少径流TP、DP的流失负荷。     

汉沽生物稳定塘净化效果研究

汉沽生物稳定塘建于１９９３年．它由１０级池塘组成,ＡＴ７５ｈｍ２,用于处理城市污水（主要是化工废水）．根据２年试运行期间化学和生物学资料,分析了稳定塘的净化效果．结果表明,该稳定塘净化效能较好．主要污染物ＢＯＤ５、ＣＯＤＣｒ、ＮＨ３Ｎ和ＰＯ４Ｐ的平均去除率分别为８６．２％、７０．１％、６０．３％和６７．５％;平均年去除ＢＯＤ５４２９７．８ｔ、ＣＯＤＣｒ６１７９．８ｔ、ＮＨ３Ｎ１５４．６ｔ和ＰＯ４Ｐ８１．９ｔ．但由于有机物负荷量过高,使出水水质较差．文中提出若干改善出水水质的措施和建议     

Denitrification in nitrate-rich streams: application of N2:Ar and 15N-tracer methods in intact cores.

Rates of benthic denitrification were measured using two techniques, membrane inlet mass spectrometry (MIMS) and isotope ratio mass spectrometry (IRMS), applied to sediment cores from two NO3(-)-rich streams draining agricultural land in the upper Mississippi River Basin. Denitrification was estimated simultaneously from measurements of N2:Ar (MIMS) and 15N[N2] (IRMS) after the addition of low-level 15NO3- tracer (15N:N = 0.03-0.08) in stream water overlying intact sediment cores. Denitrification rates ranged from about 0 to 4400 micromol N x m(-2) x h(-1) in Sugar Creek and from 0 to 1300 micromol N x m(-2) x h(-1) in Iroquois River, the latter of which possesses greater streamflow discharge and a more homogeneous streambed and water column. Within the uncertainties of the two techniques, there is good agreement between the MIMS and IRMS results, which indicates that the production of N2 by the coupled process of nitrification/denitrification was relatively unimportant and surface-water NO3- was the dominant source of NO3- for benthic denitrification in these streams. Variation in stream NO3- concentration (from about 20 micromol/L during low discharge to 1000 micromol/L during high discharge) was a significant control of benthic denitrification rates, judging from the more abundant MIMS data. The interpretation that NO3- concentration directly affects denitrification rate was corroborated by increased rates of denitrification in cores amended with NO3-. Denitrification in Sugar Creek removed < or = 11% per day of the instream NO3- in late spring and removed roughly 15-20% in late summer. The fraction of NO3- removed in Iroquois River was less than that of Sugar Creek. Although benthic denitrification rates were relatively high during periods of high stream flow, when NO3 concentrations were also high, the increase in benthic denitrification could not compensate for the much larger increase in stream NO3- fluxes during high flow. Consequently, fractional NO3- losses were relatively low during high flow.     

一株菲降解菌的分离鉴定及其降解条件研究

以菲为研究对象,从克拉玛依稠油污染土壤中筛选到1株对菲具有较好降解效果的菌株JZ3-21。通过形态观察、生理生化指标及16S rDNA序列分析对该菌株进行了鉴定。该株菌的16S rDNA序列与Pseudomonas属的相似性达99%,结合分离菌株的形态、生理生化特征和16S rDNA基因序列的分析结果,初步鉴定该菌株为恶臭假单胞菌（Pseudomonas putida.）。对其降解条件进行了研究,结果表明：在40℃,pH 8.0,接种量为1.5%的条件下,菌株对初始质量浓度为100 mg.L-1的菲在64 h内的降解率高达94.2%。该菌对高质量浓度菲有较好的耐受性,其最高耐受质量浓度可达2 000 mg.L-1。     

吡虫啉光降解产物中阴离子的毛细管电泳分析

本文建立了吡虫啉光降解产物中无机阴离子的毛细管电泳分析方法,背景电解质采用铬酸钠和十四烷基三甲基溴化铵,２５４ｎｍ紫外间接检测,在选定条件下,光降解产物中各种阴离子在３ｍｉｎ内达到完全分离;     

Quantitative relationships among phytoplankton body size classes and production processes in the North Adriatic frontal region

The variation patterns of phytoplankton standing crop and productivity in the North Adriatic frontal region and the relative importance of pico-, nano-, micro-phytoplankton are shown. Data of standing crop (chlorophyll a - Chl a ) and productivity ( 14 C assimilation) and PAR radiation ( w Em m 2 r s m 1 ) were collected during the four oceanographic cruises of the PRISMA II project. Average standing crop and productivity in the study area were 1.41 - 0.42 r mg r m m 3 Chl a and 1.23 - 0.37 r mg r C r m m 3 r h m 1 ; average assimilation number (P/B) was 0.872 - 0.589 r mg r C (mg-Chl a ) m 1 h m 1 and average photosynthetic efficiency (PE) was 0.020 - 0.054 (mg r C(mg-Chl a ) m 1 r h m 1 ) [ w Em m 2 r s m 1 ] m 1 . Phytoplankton biomass and productivity showed significant patterns of variation with the distance from the coast, with increasing depth and decreasing light intensity. The same patterns were shown by the three phytoplankton size classes. The spatio-temporal variations were significantly larger within the microplankton than within the pico- and nano-plankton size classes. Planktonic guilds were dominated by picoplankton, both as standing crop and productivity, in the northern stations (0.539 - 0.21 r mg r m m 3 Chl a and 0.572 - 0.25 r mg r C r m m 3 r h m 1 ) and in those more offshore, while microplankton was more important in the coastal and southern stations (0.727 - 0.58 r mg r m m 3 Chl a and 0.63 - 0.28 r mg r C r m m 3 r h m 1 ). In relative terms, picoplankton accounts for the 53% and 46% of biomass and primary production, while the microplankton account for the 43.6% and 48%. Assimilation number and photosynthetic efficiency did not show spatio-temporal variations but PE was inversely related with PAR radiation for all the size classes. Data suggest that the spatio-temporal patterns observed in this study are affected by the competitive relationships among body size classes in the phytoplankton guilds.     

Optimum nitrogen use and reduced nitrogen loss for production of rice and wheat in the Yangtse Delta region

A long-term field and lysimeter experiment under different amount of fertilizer-N application was conducted to explore the optimal N application rates for a high productive rice-wheat system and less N leaching loss in the Yangtse Delta region. In this region excessive applications of N fertilizer for the rice-wheat production has resulted in reduced N recovery rates and environment pollution. Initial results of the field experiments showed that the optimal N application rate increased with the yield. On the two major paddy soils (Hydromorphic paddy soil and Gleyed paddy soil) of the region, the optimal N application rate was 225-270 kg N hm(-2) for rice and 180-225 kg N hm(-2) for wheat, separately. This has resulted in the highest number of effective ears and Spikelets per unit area, and hence high yield. Nitrogen leaching in the form of NO(3-)-N occurs mainly in the wheat-growing season and in the ponding and seedling periods of the paddy field. Its concentration in the leachate increased with the N application rate in the lysimeter experiment. When the application rate reached 225 kg N hm(-2), the concentration rose to 5.4-21.3 mgN l(-1) in the leachate during the wheat-growing season. About 60% of the leachate samples determined contained NO(3-)-N beyond the criterion (NO(3-)-N 10 mg l(-1)) for N pollution. In the field experiment, when the N application rate was in the range of 270-315 kg hm(-2), the NO(3-)-N concentration in the leachate during the wheat-growing season ranged from 1.9 to 11.0 mg l(-1). About 20% of the leachate samples reached close to, and 10% exceeded, the criterion for N pollution. Long-term accumulation of NO(3-)-N from leaching will no doubt constitute a potential risk of N contamination of the groundwater in the Yangtse Delta Region.     

Seasonal composition of meroplankton and holoplankton in the Bristol Channel

A decreasing gradation in the plankton standing stock of the Bristol Channel was observed from the seaward section to the inner, less saline, reaches. Two sub-regions of our survey, the North Outer Channel (NOC) and the Inner Channel (IC), represented the extremes of this gradient and were selected for detailed comparison. The integrated zooplankton biomass, over the 307 d sampling period (4 November 1973 to 6 September 1974), was 2 475 mg C m^-3 (266 mg C m^-2 d^-1) in the NOC and 335 mg C m^-3 (20 mg C m^-2 d^-1) in the IC. The omnivorous plankton accounted for 76% of the standing stock in the NOC and 89% in the IC, of which 58 and 23% were meroplankton and 39 and 71% were holoplankton, respectively; the remainder was unassigned. The majority of the meroplankton in both subregions was decapod larvae and adults, whereas the holoplankton biomass was dominated in the NOC by copepods (89%) and in the IC by mysids (57%), mainly Schistomyzis spiritus. Centropages hamatus was the most abundant copepod species in the NOC and accounted for 32% of the total holoplankton omnivore standing stock. In the NOC and IC, the carnivorous plankton accounted for 24 and 11% of the total plankton biomass, respectively. In the two sub-regions, 20 and 21% of the carnivores were meroplanktonic (primarily larvae of sprats and pilchards), while the holoplankton carnivores contributed 75 and 74% to the NOC and IC, respectively (Sagitta elegans, Pleurobrachia pileus). S. elegans dominated the holoplankton carnivore biomass for the majority of the year and accounted for 96% in the NOC and 60% in the IC. The integrated total particulate carbon over the 307 d period was 200 g C m^-3 (6 600 g C m^-2) in the NOC and 838 g C m^-3 (15 084 g C m^-2) in the IC. The annual primary production ranged from 164.9 g C m^-2 yr^-1 in the Outer Channel (North and South) to 6.8 g C m^-2 yr^-1 in the IC. The zooplankton biomass reached a maximum in July. The total particulate carbon (TPC) in July was 400 mg C m^-3 in the NOC of which ca. 78 mg C m^-3 were phytoplankton and ca. 21 mg C m^-3 were zooplankton; these values compare favourably with those found in the adjoining Celtic Sea. In the IC, the TPC was 2 800 mg C m^-3, of which ca. 107 mg C m^-3 were phytoplankton and 2.8 mg C m^-3 were zooplankton. From the low primary production estimates for the IC it can be concluded that the majority of the chlorophyll, like the TPC, was allochthonous in origin. Furthermore it is suggested that zooplankton plays a minor role in this estuarine ecosystem and is not the main consumer of the suspended particulate carbon; the benthic filter-feeding communities are presumed to fulfill this role in the Bristol Channel.