大气降尘中水溶性有机物组成与含量的研究

本文为了研究各个地区大气降尘中水溶性有机物的组成与含量,从离地表２０ 米处的电网绝缘子表面采集九个大气降尘样品,对其水溶性部分用有机溶剂进行有机物的分离萃取,求出有机物的含量,采用ＸＲＰＤ 进行物相鉴定,确定有机物的组成可分为有机酸、有机酸钾盐、有机碱·盐酸盐加合物,尿素与尿素·硝酸盐加合物等四类,并对其影响ＣａＳＯ４·２Ｈ２Ｏ 的溶解度进行一系列实验,结果表明这四类有机物对ＣａＳＯ４·２Ｈ２Ｏ 溶解度的提高均有显著影响,可提高４０ ％ － ６０ ％ ,与实际降尘样品中其溶解度平均提高５０ ％ 左右相一致。由于大气降尘中普遍存在来自土壤与燃煤飞灰所排放的ＣａＳＯ４·２Ｈ２Ｏ,研究有机物的组成与含量,这对了解局部地区环境酸化（ 湿沉降） 有其重要性。     

氟里昂替代品降解产物三氟乙酸的环境影响

氟里昂替代品在大气中的降解反应将产生大量的三氟乙酸,其在大气中可与ＯＨ 自由基反应生成三氟甲烷和二氧化碳,主要的去除机制是沉降和雨除,并在地面水中累积;本文还对其在地表水中的积累预测和背景值监测做了描述     

德国科学家长期测量大气中羟基自由基

据最新报道，德国尤利希研究中心和德国气象服务中心的科学家弗朗茨·罗勒等已在德国南部地区测量大气中羟基自由基浓度长达5年。并发现99％羟基浓度波动是由于太阳辐射，羟基浓度与太阳辐射的变化存在线性关系。这一结果的公布颇受关注的原因是，羟基自由基是清除大气污染物的主要组分，对其存在状况的测量，对了解大气自净有重要意义。     

汽车尾气中NOx再燃烧过程的动力学

为了阐明汽车尾气中ＮＯｘ再燃烧的动力学进程,以甲醛和ＮＯ２作为探针分子,通过ＦＴ－ＩＲ跟踪研究了反应体系不听民 ＨＣＯ自由基与ＮＯ２反应的动力学。结果表明,反应的主要产物中包括ＣＯ、ＣＯ２、ＮＯ、ＨＯＮＯ和Ｈ２Ｏ等分子,经长时间的反应,当体系中的ＮＯ２基本耗尽时,才有少量的Ｎ２Ｏ生成,这些产物分子分别是在几个不同的途径的连串反应在形成的。从体系中ＣＯ和ＣＯ２的生成量,测定了主反应的歧化反应速率比,     

全球大气氧化性研究的回顾与展望

大气氧化性(AOC)是大气氧化的主要驱动力，表现为大气通过氧化反应清除痕量气体并形成二次污染物，是决定大气自净能力的关键因素。羟基自由基(HO·)作为大气氧化过程中的主要参与者，控制多种痕量气体的去除率以及在大气的滞留时间，对全球空气质量和气候有着深远影响。梳理分析了大气HO·的作用机制与环境效应，回顾了大气HO·的研究历史与研究方法，探讨了O₃对大气HO·的影响以及HO·来源的时空分异，预测HO·变化趋势的不确定性，阐述了相关大气污染治理技术和政策，最后提出了当前AOC研究中仍待解决的问题和未来的研究方向，以期为深入探索AOC与二次污染物内在联系提供参考。     

简讯

德囯科学家长期测量大气中羟基自由基据最新报道,德国尤利希研究中心和德国气象服务中心的科学家弗朗茨·罗勒等已在德国南部地区测量大气中羟基自由基浓度长达5年。并发现99%羟基浓度波动是由于太阳辐射,羟基浓度与太阳辐射的变化存在线性关系。这一结果的公布颇受关注的原因是,羟基自由基是清除大气污染物的主要组分,对其存在状况的测量,对了解大气自净有重要意义。以色列水资源管理着重开源当前,许多干旱国家面临水资源短缺的危机。以色列的水资源管理经验可供借鉴。尽管以色列人口不断增长,农业生产不断扩大,海水倒灌,地下水盐碱化,工业…     

高架源大气SO2水平扩散参数的遥测研究

应用加拿大ＣＯＳＰＥＶ Ｖ型相关光谱仪遥测高架源烟羽ＳＯ２浓度剖面，测定烟羽高度处的风向，对Ｅｕｌｅｒｉａｎ平均剖面数据处理及计算σｙ进行了探讨，并用以验证Ｂｒｉｇｇｓ模式，为实测大气扩散参数提供了新的科学方法。     

有机物对水中微量铀测量的影响

通过多年的实验分析和经验积累,使用GB 6768—86中的液体激光荧光法,对紫外脉冲荧光微量铀分析仪和激光荧光微量铀分析仪两种仪器的测量数据进行比较,结果样品分析数据的差异非常明显,最大的有10倍之差。通过比较,选择最佳的制样条件、设备及荧光剂,肯定了激光铀分析仪的优势。激光具有能量高、单色性好的特点,使用激光荧光微量铀分析仪可直接测量,简化操作。水样样品不需预处理,减少了铀的污染和损失,加大了干扰的允许量。在紫外光照射下,产生的荧光物质比较复杂,带来测量结果的偏离。而使用紫外脉冲荧光微量铀分析仪,对有机物高的样品,须进行去除有机物的处理,增加了铀的污染和损失。     

用大气复合源模拟法优化监测站位

采用对大气复合源模拟来分析ＳＯ２在市区的浓度分布，并对模拟结果与历史监测资料作相关分析，从而建立模拟值与实测值之间的直线回归方程。进而对模拟结果进行三测点优化组合，从而达到监测站位优化的目的。     

GIS技术在城区大气降尘污染分区评价中的应用

应用地理信息系统（ＧＩＳ）技术分析了焦作市城区大气降尘污染状况。根据１９９５年城区降尘实测数据,绘制了降尘量等值线图,分析了城区降尘污染持的空间分布特征,引入降尘污染指数,将降尘污染程度做了六级划分,并利用ＡＲＣ／ＩＮＦＯ软件进行图像处理,生成拓扑关系,从而对焦作城区降尘污染程度进行了分区和评价。     

Fluorescence spectroscopy of aromatic species produced in rich premixed ethylene flames

The fluorescence spectra of the condensed species (CS) collected in the soot inception region of a rich premixed laminar ethylene/oxygen flame have been measured by excitation in the UV at 266 and 355 nm excitation wavelength. The contribution of the most abundant polycyclic aromatic hydrocarbons (PAH) to the CS fluorescence has been evaluated in order to attribute the CS fluorescence at different emission wavelengths to specific aromatic structures. The fluorescence peaks detected in the UV region of the CS fluorescence spectrum was found to be mainly due to a typical PAH like fluorene, that is, the most fluorescent one among the PAH analyzed in the CS by chromatographic analysis. The CS exhibited the larger emission in the visible where the PAH contribution has been shown to be negligible and other fluorescing aromatic species, not identified by chromatographic analysis of the CS, have to be considered responsible for the visible fluorescence. Laser induced fluorescence (LIF) flame measurements excited at 266 nm and detected at two selected wavelengths (310 and 410 nm) have been performed along the flame axis and compared with the CS fluorescence intensity. The LIF and CS fluorescence signals show quite similar axial trends demonstrating that the LIF signals are related to CS fluorescence. In particular, the LIF fluorescence signals detected in the UV could be attributed to the PAH fluorescence whereas the unidentified species contained in the CS can be followed by LIF detection in the visible region.     

Direct measurement of NO2 in the marine atmosphere by laser-induced fluorescence technique

A simple and compact instrument for NO₂ measurement by laser-induced fluorescence (LIF) technique with a pulsed solid state laser and a multi-pass excitation system was developed and optimized for several conditions. As a result of laboratory experiment, the limit of detection (LOD) reached 94 pptv for 60 s integration. It was thought that an LIF instrument with this LOD value would be capable of quantifying sub-ppbv NO₂ in unpolluted marine atmosphere. As the second step, a field test of the instrument was conducted in the marine atmosphere at Cape Hedo, Okinawa Island, Japan, in summer 1999. Intercomparison between the LIF instrument and a chemiluminescence detector with a photolytic converter (PLC-CL) was also made in this test. Consequently, the LIF instrument was shown to be of practical use for measuring NO₂ in clean maritime air.     

Kinetic studies of the reaction of hydroxyl radicals with trichloroethylene and tetrachloroethylene

Rate coefficients are reported for the gas-phase reaction of the hydroxyl radical (OH) with C2HCl3 (k(1)) and C2Cl4 (k2) over an extended temperature range at 740+/-10 Torr in a He bath gas. These absolute rate measurements were accomplished using a laser photolysis/laser-induced fluorescence (LP/LIF) technique under slow flow conditions. The simple Arrhenius equation adequately describes the low temperature data for k1 (<650 K) and the entire data set for k2 and is given by (in units of cm3 molecule(-1) s(-1)): k1(291 - 650 K) = (9.73+/-1.15) x 10(-13) exp (158.7+/-44.0)/T, k2(293 - 720 K ) = (1.53+/-0.14) x 10(-12) exp (-688.2+/-67.5)/T. Error limits are 2sigma values. The room temperature values for k1 and k2 are within +/-2sigma of previous data using different techniques. The Arrhenius activation energies for k1 and k2 are a factor of 2-3 lower than previously reported values. The experimental measurements for both k1 and k2 in conjunction with transition state and variation transition state theory calculations infer an OH addition mechanism. The lack of a measurable kinetic isotope effect for k1 is consistent with this mechanism. Insight into the subsequent reactions of the chemically activated intermediate are presented in the form of potential energy diagrams derived from ab initio calculations.     

LP/LIF study of the formation and consumption of mercury (I) chloride: kinetics of mercury chlorination

The laser photolysis/laser induced fluorescence (LP/LIF) technique has been applied to studies of gas-phase mercury (Hg) chlorination. Mercury (I) chloride (HgCl) was been detected via LIF at 272 nm from reactions of elemental Hg with Cl atoms generated from the 193 nm photolysis of carbon tetrachloride. While the formation of HgCl was too fast to be observed on millisecond time scales, the kinetics of the consumption of HgCl have been determined at temperatures characteristic of post-combustion conditions. Rate coefficients and Arrhenius parameters for the reaction of HgCl with Cl2, HCl and Cl atoms were determined. The reaction of HgCl with Cl2 was the fastest reaction studied, while the reaction of HgCl with HCl was the only reaction to show any measurable temperature dependence. Estimates of the rate coefficient for the reaction Hg + Cl --> HgCl were determined using a modeling approach. Comparisons of these new measurements with model predictions are discussed.     

OH and HO2 measurements in a forested region of north-western Greece

Boundary layer concentrations of hydroxyl (OH) and hydroperoxyl (HO₂) radicals were measured at 1180 m elevation in a mountainous, forested region of north-western Greece during the AEROsols formation from BIogenic organic Carbon (AEROBIC) field campaign held in July–August 1997. In situ measurements of OH radicals were made by laser-induced fluorescence (LIF) at low pressure, exciting in the (0, 0) band of the A–X system at 308 nm. HO₂ radicals were monitored by chemical titration to OH upon the addition of NO, with subsequent detection by LIF. The instrument was calibrated regularly during the field campaign, and demonstrated a sensitivity towards OH and HO₂ of 5.2×10⁵ and 2.4×10⁶ molecule cm⁻³, respectively, for a signal integration period of 2.5 min and a signal-to-noise ratio of 1. Diurnal cycles of OH and HO₂ were measured on 10 days within a small clearing of a forest of Greek Fir (Abies Borisi-Regis). In total 4165 OH data points and 1501 HO₂ data points were collected at 30 s intervals. Noon-time OH and HO₂ concentrations were between 4–12×10⁶ and 0.4–9×10⁸ molecule cm⁻³, respectively. The performance of the instrument is evaluated, and the data are interpreted in terms of correlations with controlling variables. A significant correlation (r²=0.66) is observed between the OH concentration and the rate of photolysis of ozone, J(O¹D). However, OH persisted into the early evening when J(O¹D) had fallen to very low values, consistent with the modelling study presented in the following paper (Carslaw et al., 2001, OH and HO₂ radical chemistry in a forest region of north-western Greece. Atmospheric Environment 35, 4725–4737) that predicts a significant radical source from the ozonolysis of biogenic alkenes. Normalisation of the OH concentrations for variations in J(O¹D) revealed a bell-shaped dependence of OH upon NO_x (NO+NO₂), which peaked at [NO_x] ∼1.75 ppbv. The diurnal variation of HO₂ was found to be less correlated with J(O¹D) compared to OH.     

Monitoring of fuel consumption and aromatics formation in a kerosene spray flame as characterized by fluorescence spectroscopy

The large presence of aromatic compounds in distillate fossil fuels should allow, in line of principle, to follow the fuel consumption and/or the presence of unburned fuel in a high temperature environment like a burner or the exhaust of combustion systems by exploiting the high fluorescence emission of aromatic fuel components. To this aim an UV-excited fluorescence source has to be used since the aromatic fuel components are strongly fluorescing in the UV region of the emission spectrum.

In this work UV-excited laser induced fluorescence (LIF) diagnostics was applied to spray flames of kerosene in order to follow the fuel consumption and the formation of aromatic species. A strong UV signal was detected in the spray region of the flame that presented a shape similar to that found in the LIF spectra preliminary measured on the cold spray and in the room-temperature fluorescence of fuel solutions.

The decrease of UV signal along the spray flame region was associated to the consumption of the fuel, but more difficult seems to be the attribution of a broad visible emission, that is present downstream of the flame.

The visible emission feature could be assigned to flame-formed PAH species contained in the high molecular weight species, hypothesizing that their fluorescence spectra are shifted toward the visible for effect of the high temperature flame environment.     

Analysis of exhausts emitted by i.c. engines and stationary burners, by means of u.v. extinction and fluorescence spectroscopy

Optical investigations of the exhausts emitted by internal combustion (i.c.) engines and a stationary burner were performed, in order to assess their relative role as sources of organic matter to the atmosphere. Extinction spectra of air-diluted exhausts in the 200-400 nm u.v. band reveal the expected existence of gaseous trace-species (NO, NO2 and SO2) and carbonaceous particulate matter (soot). In addition, after subtracting the absorption contribution from known species, a strong residual absorption band remains below 250 nm, which is attributed to organic aromatic matter, involving no more than two aromatic rings. A set of ex situ extinction and laser induced fluorescence (LIF) experiments were carried out on condensed combustion-water samples. Extinction measurements from the water samples show absorption spectra similar to those observed from air-diluted samples, which are attributed to low volatility organic compounds, as they are trapped in the condensed phase. Combining the indications of extinction data for both air-diluted and condensed samples, it is suggested that the absorbing species might be molecular clusters of one/two aromatic rings. LIF spectra from condensed samples evidence two fluorescence bands, centered above 300 and 400 nm, respectively, whose intensities correlate with the combustion regimes. Analogous optical analysis on rain samples, collected in an urban area, showed that rain absorption and fluorescence spectra are similar to those found in condensed exhaust samples, which is consistent with the prevailing contribution of i.c. engines to the urban air pollution. The combined experimental data suggest that the absorbing and fluorescent species trapped in the condensed samples are organic (aromatic) compounds, involving mostly one two aromatic rings structural units, since they do not absorb above 250 nm. The overall molecular weight of the trapped material is likely heavy as they show low volatility.     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

Investigations into a novel method for atmospheric polycyclic aromatic hydrocarbon monitoring

A novel analytical method for atmospheric polycyclic aromatic hydrocarbons (PAHs) was developed based on laser induced fluorescence (LIF) of samples on quartz multi-channel polydimethylsiloxane traps. A tunable dye laser with a frequency doubling crystal provided the excitation radiation, and a double monochromator with a photomultiplier tube detected emitted fluorescence. The method allowed for the rapid (<5 min), cost effective analysis of samples. Those yielding interesting results could be further analysed by direct thermal desorption-gas chromatography–mass spectrometry (TD–GC–MS, with limits of detection of ～0.3 ng m^?3), as photodegradation was minimal (<10% over 5 min irradiation). Small amounts of naphthalene photodegradation products identified by TD–GC–MS after >15 min irradiation, included phenol, benzyl alcohol and phthalic anhydride. Without any signal optimization, a LIF detection limit of ～1 μg m^?3 was established for naphthalene using a diffusion tube (diffusion rate of 2 ng s^?1) and 292 nm excitation.     

Laser induced fluorescence instrument for NO2 measurements: Observations at a central Italy background site

A laser induced fluorescence (LIF) instrument has been developed to measure tropospheric NO₂ with low detection limit. The instrument design, development and first measurements are reported. There are also details of the temporal gate system built for the fluorescence acquisition. The instrument is able to make fast measurements (up to 4 Hz) and shows a limit of detection of 10 pptv/60 s. Continuous observations (2 weeks in summer 2007) in a small town in central Italy were used to test the performance of the instrument and to study the photochemistry of ozone in a background site. LIF and a commercial chemiluminescence (CL) instrument simultaneous observations of NO₂ show a good linearity (LIF = 1.02 CL + 0.6 (ppb), R² = 0.98) but there is a bias of the commercial instrument of about 0.60 ppbv on average. The overestimation of the CL system is probably due to conversion of NO_y species into NO by the molybdenum converter used in the CL instrument to detect NO₂. Analysis of 1 s data is used to test the instrument response and the coupling between nitrogen oxides and ozone.