类-Fenton体系对水中17β-雌二醇的光降解

以250W照明金属卤化物灯为光源研究了水中17β雌二醇(E2)在类Fenton体系中的光降解。结果表明,Fe(Ⅲ)/H2O2体系能有效地光降解E2。pH3～6范围内,E2光降解率及反应初始速率随酸度的增大而增大;H2O2初始浓度越大,E2降解率及反应初始速率越大;E2初始浓度越低,E2降解率越高,反应初始速率越低。     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, α-thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Distribution of pesticides and heavy metals in trophic chain

Determination of triazines herbicides (atrazine and simazine) by high performance liquid chromatography (HPLC) in samples of trophic chain were worked out. Determination limits of 0.5 μg g⁻¹ for atrazine, 0.8 μg g⁻¹ for simazine with pesticides recovery of 70–77% in trophic chain samples were obtained. The content of simazine in soils was in range 1.72–57.89 μg g⁻¹, in grass 5–88 μg g⁻¹, in milk 2.32–15.29 μg g⁻¹, in cereals 10.98–387 μg g⁻¹, in eggs 30.14–59.48 μg g⁻¹, for fruits: 2.45–6.19 μg g⁻¹. The content of atrazine in soils was in range 0.69–19.59 μg g⁻¹, in grass 7.85–23.85 μg g⁻¹, in cereals 1.88–43.08 μg g⁻¹. Cadmium, lead and zinc were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) in the same samples as atrazine and simazine. Determination limits for cadmium 5 × 10⁻³ μg g⁻¹, for lead 1 × 10⁻² μg g⁻¹, and for zinc 0.2 × 10⁻³ μg g⁻¹, were obtained. The content of cadmium in soil was in range 0.13–5.89 μg g⁻¹, in grass 114–627.72 × 10⁻³ μg g⁻¹, in milk 8.88–61.88 × 10⁻³ μg g⁻¹, in cereals 0.20–0.31 μg g⁻¹, in eggs 0.11–0.15 μg g⁻¹, in fruits 0.23–0.59 μg g⁻¹. The content of lead in soils was in range 0.57–151.50 μg g⁻¹, in grass 0.16–136.57 μg g⁻¹, in milk 1.16–3.74 μg g⁻¹, in cereals 1.05–5.47 μg g⁻¹, in eggs 5.79–55.87 μg g⁻¹, in fruits 21.00–87.36 μg g⁻¹. Zinc content in soil was in range 9.15–424.5 μg g⁻¹, in grass 35.20–55.87 μg g⁻¹, in milk 20.00–34.38 μg g⁻¹, in cereals 14.94–28.78 μg g⁻¹, in eggs 15.67–32.01 μg g⁻¹, in fruits 14.94–18.88 μg g⁻¹.

Described below extraction and mineralization methods for particular trophic chains allowed to determine of atrazine, simazine, cadmium, lead and zinc with good repeatability and precision. Emphasis was focused on liquid–liquid extraction and solid-phase extraction of atrazine and simazine from analysed materials, as well as, on monitoring the content of herbicides and metals in soil and along trophic chain. Higher concentration of pesticides in samples from west region of Poland in comparison to that of east region is likely related to common applying them in Western Europe in relation to East Europe. The content of metals strongly depends on samples origin (industry area, vicinity of motorways).     

超声萃取-高效液相色谱法测定土壤中苯并[a]芘研究

采用超声萃取-高效液相色谱荧光检测法对土壤中苯并[a]芘含量进行定性、定量分析.土壤样品用正己烷/二氯甲烷(1+1)超声萃取,萃取液经硅胶柱或佛罗里硅土柱净化浓缩定容,乙腈-水为流动相,线性梯度洗脱,流速为1.0 mL/min,荧光检测器激发波长为280 nm,发射波长为420 nm,外标法峰面积定量.结果显示:该方法检出限低,苯并[a]芘的检出限为0.15μg/kg.这种方法具有很好的精密度,相对标准偏差为3.9%~8.4%.实际水样加标回收率范围在72.5%~85.8%.能够满足土壤的监测要求.     

地面水中酚类污染物的树脂吸附富集反相高压液相色谱测定

以乙腈－水－醋酸（３１：６８：１,Ｖ／Ｖ／Ｖ）为流动相的反相ＨＰＬＣ－ＵＶ法,可以方便地对水中酚类进行直接分离和分析。采用树脂吸附法为ＨＰＬＣ的预富集步骤,选用国产吸附树脂ＧＤＸ－５０２为富集剂,二氧六环为洗脱剂,可以定量测定水中μｇ／Ｌ级以下的多种酚。在实验条件下,９种一元酚的平均变异系数为２．４％,其中８种酚的富集回收率大于９０％。用本法测得的地面水的总酚含量与４－氨基安替比林法具有可比性。     

大气过氧化氢及有机过氧化物的测定

采用ＨＰＬＣ柱后衍生荧光法测定了５、６月份中关村地区大气中的Ｈ２Ｏ２和有机过氧化物,除Ｈ２Ｏ２外,共测出了７种以上有机过氧化物。有３种通过ＨＰＬＣ色谱保留时间得到了鉴定。分别是甲基过氧化氢,羟甲基过氧化氢和乙基过氧化氢。     

高压液相色谱法测定废水中的苯胺和硝基苯胺

建立了MicroPAKCN-10柱和69%正己烷加30%二氯甲烷加1%异丙醇为流动相,用紫外鉴定器在254nm处检测的液相色谱系统,并用该系统测试了染料厂废水。方法检出限为:苯胺7.16ng,邻硝基苯胺1.52ng,间硝基苯胺2.48ng,对硝基苯胺5.39ng。回收率为80%~99%,变异系数在1.82%~9.96%之间。      

道路交通中苯并(a)芘的高效液相色谱快速测定

用超细玻璃纤维滤膜采集杭州市某道路上机动车排放的苯并（ａ）芘,经超声萃取,高速离心后直接进ＨＰＬＣ分析。在选定的色谱条件下,苯并（ａ）芘与其他多环芳烃完全分离,绝对进样量在０．８～０．０２ ｎｇ时线性良好,相关系数为０．９９９７９,最小检出量０．８ ｐｇ,加标回收率８７．５％～９３．８％。     

电解催化降解有机物机理的高效液相色谱研究(Ⅱ)--动力学解析

苯酚与HO·作用的产物有两种 ,据此求解了苯酚在电解催化系统中随时间变化的动力学方程 ,根据动力学方程对在不同时间体系的高效液相色谱分析结果进行了最小二乘法拟合 ,表明苯酚的变化规律基本符合竞争连续反应模型。两种途径的表观一级反应速率常数分别为 :0 .0 82 2min- 1 和 0 .1 1 1 9min- 1 (对苯二酚途径 )、0 .0 0 75min- 1 和 0 .0 51 8min- 1 (邻苯二酚途径 )。由这些参数计算可知 ,有 97.2 8%的苯酚通过对苯二酚中间产物而得以氧化 ,只有 2 .72 %的苯酚通过邻苯二酚。对实验及拟合结果的进一步分析表明 ,苯酚在阳极附近被HO·氧化降解是非常快的 ,对苯二酚和邻苯二酚基本没有积累 ,平均只有 5 .45 %的对苯二酚和 35 .0 7%的邻苯二酚扩散到体相中去 ,而其他部分都连续地在阳极附近氧化掉了。这可能是有机污染物在电解催化氧化系统内降解过程的共同规律。