Development of a precolumn derivatization method for the determination of free amines in wastewater by high-performance liquid chromatography via fluorescent detection with 9-(2-hydroxyethyl)acridone

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with fluorescence detection has been developed. 9-(2-Hydroxyethyl)acridone reacts with coupling agent N,N-carbonyldiimidazole at ambient temperature to form activated amide intermediate 9-(2-acridone)oxyethylcarbonylimidazole (AOCD). The amide intermediate (AOCD) preferably reacts with amino compounds under mild reactions in the presence of 4-(dimethylamino)pyridine (base catalyst) in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum lambda(ex) 404 mn and an emission maximum at lambda(em) 440 nm. The labeled derivatives exhibit high stability under reversed-phase conditions. The fluorescence intensities of derivatives in various solvents or at different temperatures were investigated. The method, in conjunction with a gradient elution, offers a baseline resolution of the common amine derivatives on a reversed-phase C-18 column. The LC separation for the derivatized amines shows good reproducibility with acetonitrile-water including 2.5% DMF as mobile phase. The relative standard deviations (n = 6) for each amine derivative are <4.5%. The detection limits (at a signal-to-noise ratio of 3) per injection were 0.16-12.8 ng/mL. Further research for the field of application, based on the AOCD amide intermediate as derivatization reagent, for the determination of free amines in real water samples is achieved.

Analysis of aromatic amines by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence derivatization reagent, has been developed for the analysis of aromatic amines. Taking five monocyclic aromatic amines (o-toluidine, aniline, 3,4-dimethylaniline, N-ethyl-p-toluidine, and p-phenylenediamine) as testing compounds, derivatization conditions such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration have been investigated. By a one-step procedure, CEOC reacts readily with the aromatic amines to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. This derivatization reaction could be finished within 20 min even at room temperature. The peak shapes of the derivatized aromatic amines can be improved greatly without any addition of competition amines into the mobile phase. Furthermore, this method can offer excellent quantitative precision with high tolerance of the matrix of samples. (C) 2003 Elsevier B.V. All rights reserved.

Determination of peptides and amino acids from wool and beer with sensitive fluorescent reagent 2-(9-carbazole)-ethyl chloroformate by reverse phase high-performance liquid chromotography and liquid chromotography mass spectrometry

A new method for the sensitive determination of amino acids and peptides using the tagging reagent 2-(9-carbazole)-ethyl chloroformate (CEOC) with fluorescence (FL) detection has been developed. Identification of derivatives was carried out by liquid chromotography mass spectrometry. The chromophore in the 2-(9-fluorenyl)-ethyl chloroformate (FMOC) reagent was replaced by carbazole, which resulted in a sensitive fluorescence lerivatizing agent CEOC. CEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. Studies on derivatization demonstrate excellent derivative yields over the pH range 8.8-10.0. Maximal yields close to 100% are observed with three- to fourfold molar reagent excess. Derivatives exhibit strong fluorescence and allow direct injection of the reaction mixture with no significant disturbance from the major fluorescent reagent degradation by-products, such as 2(9-carbazole)-ethanol and bis-(2-(9-carbazole)-ethyl) carbonate. In addition, the detection responses for CEOC derivatives are compared to those obtained with FMOC. The ratios AC(CEOC)/AC(FMOC) = 1.00-1.82 for fluorescence (FL) response and AC'(CEOC)/AC'(FMOC) = 1.00-1.21 for ultraviolet (UV) response are observed (here, AC and AC' are, respectively, FL and UV F response). Separation of the derivatized peptides and amino acids has been optimized on a Hypersil BDS C18 column. Excellent linear responses are observed. This method was used successfully to analyze protein hydrolysates from wool and from direct-derivatized beer. (C) 2003 Elsevier Science (USA). All rights reserved.

科尔沁沙地69种植物种子重量比较研究

研究了科尔沁沙地 6 9种植物的繁殖体 (30种为种子 ,39种为果实 )重量。结果表明 :1 )传播体为果实的植物可分为 4个组别 (即果实单粒重 <0 .1mg、0 .1～ 0 .9999mg、1～ 9.9999mg、1 0～ 99.9999mg) ;黄蒿 (Artemisiasco paria)果实 (0 .0 5 1 7mg)和小香蒲 (Typhaminima)果实 (0 .0 6 82mg)最轻 ,苍耳 (Xanthiumsibiricum)单个果实 (77.894 3mg)最重 ;2 )传播体为种子的植物可分为 3个组别 (即种子单粒重 0 .1～ 0 .9999mg、1～ 9.9999mg、1 0～ 99.9999mg) ;马齿苋 (Portulacaoleracea)种子 (0 .1 5 1 4mg)最轻 ,苦参 (Sophoraflavescens)种子 (4 6 .781 6mg)最重 ;3)黄蒿、马齿苋、轮叶沙参 (Adenophoratetraphylla)、碱地肤 (Kochiasieversiana)、狼尾花 (Lysimachiabarystachys)、灰绿藜 (Chenopodiumglaucum)、刺沙蓬 (Salsolaruthenica)、菟丝子 (Cuscutachinensis)、大籽蒿 (Artemisiasieversiana)、狗尾草 (Setariaviridis)、野古草 (Arundinellahirta)等植物所以广泛分布可能是因为它们繁殖体轻 (<1mg)且具有持久土壤种子库 ;4 )流沙上的先锋植物或沙生演替系列前期植物沙蓬 (Agriphyllumsquarrosum)、差巴嘎蒿 (Artemisiahalodendron)、乌丹蒿 (Artemisiawudanica)、狗尾草、雾冰藜 (Bassia

辽河油田超稠油废水潜流湿地处理系统研究

首次以经过驯化的芦苇湿地为介质处理超稠油废水.在辽河油田进行的中试研究表明,即使超稠油废水的BOD5/COD仅为0.06,潜流湿地系统也具有很好的净化效果,当系统的水力负荷为2cm/d时,主要污染物的去除率为石油类91.83%,COD 83.16%,BOD5 90.66%,TN 89.37%;出水平均浓度为:石油类 2.26mg/L,COD 77.34mg/L,BOD5 3.13mg/L,TN 1.66mg/L.中试研究还表明,该系统出水水质稳定、耐冲击负荷强,是一种经济有效的超稠油废水处理新技术.对系统内外芦苇的生长量、纤维素、木质素、戊糖及纤维素的长宽比的研究表明,超稠油废水对芦苇材质无明显影响,可回收用于造纸等.

辽河油田石油污染土壤的2阶段生物修复

建立了污染土壤预制床处理工程 ,对不同类型原油污染土壤分别进行堆腐处理 ,历时 2个阶段 ,共运行2 1 0d .当稀油、稠油、特稠油和高凝油污染土壤中石油烃总量 (TPH)为 2 5 8～ 77 2 g·kg- 1时 ,经过 5 3d(为第 1阶段 )的运行 ,TPH去除率 3 8 3 7%～ 5 6 74 % .第 2年 (为第 2阶段 )继续处理 1 5 6d ,TPH降解率达到 66 5 9%～80 96% .连续运行结果表明 ,污染土壤中易分解的石油烃污染物大部分在第 1阶段得到降解 ,第二阶段降解率明显降低

侵蚀泥沙、有机质和全氮富集规律研究

在自然降雨下 ,研究降雨、坡度、耕作和施肥对侵蚀泥沙、有机质和全N富集率的影响 ,分析土壤和泥沙颗粒组成、富集与泥沙有机质和全N富集的关系 ,揭示土壤有机质和全N在泥沙中的富集规律 .结果表明 ,泥沙粘粒的富集导致有机质和全N的富集 ,泥沙粘粒、有机质和全N富集率分别平均为 1.77、2 .0 9和 1.61.土壤侵蚀模数与泥沙有机质和全N富集率呈显著的负相关关系 ,降雨、坡度、施肥和耕作措施对泥沙有机质富集作用的影响是通过减少土壤侵蚀模数来实现的 ,减少土壤侵蚀的措施可增加泥沙有机质和全N的富集 .

沈阳市城区土壤和灰尘中铅的分布特征

对沈阳市城市土壤和灰尘中铅的分布特征进行了研究.结果表明,沈阳市区土壤中全铅含量为26~2910.60mg/kg,平均为199.72mg/kg,是对照(33.30mg/kg)的6倍,是沈阳市土壤背景值(22.15mg/kg)的9倍;沈阳市区灰尘中铅浓度范围为19.58~2809.90mg/kg,平均为220.06mg/kg,是对照(37.97mg/kg)的5.8倍;沈阳市土壤和灰尘中铅分布空间差异大,局部污染比较严重,灰尘中铅与土壤中铅的分布规律趋于一致,铁西区铅浓度最高,其次是和平区、皇姑区和于洪区的交界处以及大东工业区;土壤和灰尘中铅含量与距污染源的距离成反比,与距地表的距离也成反比.

沈阳市郊不同年限蔬菜温室土壤有效态微量元素分布特征

对沈阳市郊大民屯镇不同使用年限蔬菜温室77个样点土壤有效态微量元素的分布特征进行调查研究的结果表明,土壤有效态Fe、Mn、Cu、Zn含量分别为8.57～60.30mgkg-1、2.69～22.43mgkg-1、0.64～7.52mgkg-1和0.56～9.29mgkg-1,变异系数为50%左右;随着温室使用年限的增加,土壤有效态Fe、Mn、Cu、Zn含量总体上呈增加的趋势;使用年限较短的蔬菜温室,土壤微量元素缺乏的可能性较大,而使用年限较长的蔬菜温室,土壤Cu和Zn超量的风险则相对较高。由于温室管理个体的差异,一些使用年限相对较长的温室通过置换土壤、施加腐熟牛粪、厩肥、作物秸秆以及其他有机物料等措施,也可使土壤中微量元素保持在较适宜的状态。温室土壤微量元素有效态含量与土壤pH呈极显著负相关关系(P<0.01),与土壤有机C含量呈极显著正相关关系(P<0.01)。

施氮及灌溉方式对玉米地土壤硝化潜势及微生物量碳的影响

研究了不同施氮量及灌溉方式下玉米地土壤的微生物量碳及硝化潜势。结果表明:未施氮肥条件下,喷灌比漫灌土壤平均硝化潜势低0.57~4.77 mg/(kg.d);不同时期喷灌施肥土壤平均硝化潜势变化量为2.18~4.77 mg/(kg.d),幅度较小;而漫灌施肥土壤硝化潜势的变化量为-0.57~28.4 mg/(kg.d),幅度较大。土壤微生物量碳的变化受施肥与灌溉方式的影响,9月份土壤微生物量碳均低于7月份,未施氮肥条件下,喷灌下降9.05 mg/kg,变化幅度较小;而漫灌下降176.52 mg/kg,变化幅度较大。施氮肥均降低土壤微生物碳量;不同时期漫灌施肥与漫灌未施肥、喷灌施肥与喷灌未施肥相比分别降低土壤平均微生物量碳108.78~0.57 mg/kg,58.82~86.71 mg/kg。

抑制剂及其组合对尿素~(15)N在小麦土壤系统中的行为和归宿的影响

应用加有脲酶抑制剂 (HQ)、硝化抑制剂 (DCD)及其组合的标记尿素进行春小麦盆栽试验 .结果表明 ,在生长季节结束时 ,小麦回收 ,土壤残留和损失的肥料N各占施入N量的 1 7.65～ 2 3.69%、43.72～ 56.32 %和 1 9.99～ 36.77% .其中 ,与单施尿素相比 ,两种抑制剂配合使用处理的肥料N总回收率高 1 6.78% ,小麦回收高 5.96% .施用氮肥对籽粒贡献最大 ,占吸收肥料N量 43.3～ 62 .0 % .