大气中痕量氯苯气相色谱分析方法的研究

通过对氯苯在ＴｅｎａｘＧＣ上的富集和热解吸收效果的研究，建立了大气中痕量氯苯的分析方法。该方法操作简便，快速，重现性好，当大气采样量为５Ｌ时，最低检出浓度为０．００１ｍｇ／ｍ＾３。方法可用于大气中痕量氯苯的测定。     

甲基异柳磷和三唑磷对几种淡水鱼的毒性比较

测定了有机磷杀虫剂甲基异柳磷和三唑磷对淡水鲳Ｃｏｌｏｓｓｏｍａ ｂｒａｃｈｙｐｏｍｕｍ尼罗罗非鱼Ｔｉｌａｐｉａ ｎｉｌｏｔｉｃａ和麦穗鱼Ｐｓｅｕｄｏｒａｓｂｏｒａ ｐａｒｖａ的急性毒性。其中甲基异柳磷对三种鱼的９６ｈＬＣ５０分别为１．３４、１．４６和０．１４ｍｇ／Ｌ,三唑磷为０．０６、０．０３５和０．００８ｍｇ／Ｌ,该测定结果表明,在常规用药条件下,甲基异柳磷对鱼类较为安全。     

催化光度法测定水中痕量亚硝酸根

基于亚硝酸根对溴酸钾氧化结果紫而使其褪色的催化作用,建立了灵敏的催化光度测定痕量亚硝酸根的新方法,测定范围为０．０２－０．１６μｇ／ｍＬ,用于水样中亚硝酸根的测定,获得了满意结果。     

吹脱-捕集气相色谱法测定底质中易挥发性有机物

研究并建立了利用吹脱－捕集气相色谱法测定底质中易挥发性有机物的分析方法。该方法对底质中２５种易挥发性有机物进行测定。方法回收率在９６％－１０５％,最低检出浓度在０．３－１４．５μｇ／ｋｇ,变异系数在２．７％－５．３％。     

顶空气相色谱法测定水体中的低分子量胺类

选用在强碱性条件下加入电解质,使水体中的胺类进入气相,顶空进样至气相色谱分析。同时选用ＨＰ－１大口径毛细管柱及ＮＰＤ检测器分析,既保证了各低分子量胺类物质的分离,又保证定量分析的高灵敏度。本方法操作简单,灵敏度高,重复性好、适应范围广,对水中各胺类的最低检出浓度分别为：甲胺０．４μｇ／Ｌ、二甲胺０．４μｇ／Ｌ、三甲胺０．４μｇ／Ｌ、乙胺０．５μｇ／Ｌ。本方法可用于水和废水中低分子量胺类的测定。     

重氮化偶合反应测定亚硝酸盐方法的改进

用Ｈ酸代替α－萘胺或盐酸萘乙二胺作为重氮化合物的偶联试剂测定水中亚硝酸盐，亚硝酸盐在０．０２５￣１．０μｇ／ｍＬ范围内与吸光值呈线性关系。方法的精密度ＣＶ％小于５，样品加标回收率范围在９６．５％￣１０５％之间，结果令人满意。     

杭州市大气总悬浮颗粒物中铵盐的测定与变化规律

了解杭州城区大气中ＴＳＰ铵盐成份的含量与变化，我们在朝晖（居民区）、南星桥（混合区）、和睦小学（工业区）进行了为期１年的大气监测，使用大流量采样仪，每季采样３ｄ，每天连续采样２４ｈ，然后对样品进行ＴＳＰ及其中铵成份分析测定，通过１年的监测分析与研究，初步探索了大气中ＴＳＰ铵离子浓度变化及污染程度。１实验部分１．１采样采样仪器为２Ｃ—１０００Ｇ大流量采样仪，流量１０５０Ｌ／ｍｉｎ，每季采样３ｄ，连续开机２４ｈ为一次。采样滤膜为聚氯乙烯滤膜。１．２测定方法（１）铵离子的测定：ＴＳＰ中的铵离子测定，国…     

废水中对硝基苯酚的极谱测定法

对硝基苯酚在 ０．０１ ｍｏｌ／Ｌ　乙二胺－０．０５ ｍｏｌ／Ｌ 氯化铵介质中于－０． ５５ Ｖ（ｖｓ． ＳＣＥ）处产生一波形好、灵敏度高的导数极谱波,在此实验条件下对硝基苯酚浓度在１．００×１０~－７～５．００×１０~－４ｍｏｌ／Ｌ范围内与导数波峰电流（Ｉｐ）呈良好的线性关系。检测下限为８．０×１０~－８ｍｏｌ／Ｌ。本方法测定废水中对硝基苯酚的含量取得了满意结果。     

华北地区旱田土壤氧化亚氮的排放

在１９９１－１９９３年间用封闭罩测定了对照田、施肥田Ｎ２Ｏ的排放量。结果表明，Ｎ２Ｏ通量显示出时、空变化规律。对照田，施尿素田和施混合肥田（尿素加有机肥）Ｎ２Ｏ排放量分别是１．０３±０．４ｋｇＮ／ｈｍ２ａ；１．９１±０．６ｋｇＮ／ｈｍ２ａ和２．１１±１．０ｋｇＮ／ｈｍ２ａ．尿素和混合肥释放Ｎ２Ｏ系数分别为０．２９％和０．３５％。由土壤含水量，土壤温度和速效氮浓度等土壤变量建立了Ｎ２Ｏ排放的统计模式。     

接种稀释水的空白对BOD5测定的影响

从接种液种类、空白ＢＯＤ５大小、接种液最佳添加范围等方面对ＢＯＤ５测定进行探讨，提出以接纳工业废水的河水作为最佳接种液，雨季时以土壤浸取液更适合。探讨了接种液空白值对ＢＯＤ５标液和工业废水的影响，结果表明，河水空白应控制在０．１－０．８ｍｇ／Ｌ土壤浸取液空白控制在０．０１－０．１０ｍｇ／Ｌ为宜。     

Pyrolysis of tetrabromobisphenol-A containing paper laminated printed circuit boards

Tetrabromobisphenol-A (TBBA) is the most common brominated fire retardant. In this study, a TBBA containing paper laminated printed circuit board (PCB) prepared from novolac was pyrolysed by both TGA and in a quartz glass reactor between 40 and 1,000 degrees C. The products were online detected by MS. It was found that the PCB degraded in three steps. Step one (<270 degrees C) consisted of the evolution of water and CO(2) from the paper laminate. In the second step, between 270 and 370 degrees C, the fire retardant decomposed, releasing HBr and brominated aromatics. In the third step, at temperatures above 370 degrees C, the phenol resin decomposed and char was formed. Compared to pure TBBA, which mainly produces brominated phenols, the brominated products enclosed in the char released HBr during the last degradation step as well as during the second step. Most of the bromine left the resin in the form of HBr, with about 14% of the bromine being fixed in brominated aromatics and less than 2% remaining in the residue.     

Effect of decabromodiphenyl ether and antimony trioxide on controlled pyrolysis of high-impact polystyrene mixed with polyolefins

The controlled pyrolysis of polyethylene/polypropylene/polystyrene mixed with brominated high-impact polystyrene containing decabromodiphenyl ether as a brominated flame-retardant with antimony trioxide as a synergist was performed. The effect of decabromodiphenyl ether and antimony trioxide on the formation of its congeners and their effect on distribution of pyrolysis products were investigated. The controlled pyrolysis significantly affected the decomposition behavior and the formation of products. Analysis with gas chromatograph with electron capture detector confirmed that the bromine content was rich in step 1 (oil 1) liquid products leaving less bromine content in the step 2 (oil 2) liquid products. In the presence of antimony containing samples, the major portion of bromine was observed in the form of antimony bromide and no flame-retardant species were found in oil 1. In the presence of synergist, the step 1 and step 2 oils contain both light and heavy compounds. In the absence of synergist, the heavy compounds in step 1 oil and light compounds in step 2 oils were observed. The presence of antimony bromide was confirmed in the step 1 oils but not in step 2 oils.     

Occurrence and source of brominated organic compounds in surface waters

Monitoring of organic halogen compounds, measured as adsorbable organically bound bromine (AOBr), in an eutrophic lake, which is influenced by treated waste water, revealed repeatedly high concentrations of organobromine compounds in late summer, whereas five times lower values were measured during the rest of the year. It was possible to reproduce the in situ observed AOBr increase in the laboratory. Batch experiments were performed with lake water from two different lakes and an algae culture. It could be shown that the AOBr production is not limited to strong waste water influenced lakes. Furthermore, the AOBr formation requires light and the presence of algae, and thus is most probably biotic in nature. A low content of nutrients favours the formation of organic bromine compounds. To our knowledge this is the first report about the seasonally occurrence of naturally produced organic bromine compounds in lakes/surface waters.     

Behavior of bromide in the photoelectrocatalytic process and bromine generation using nanoporous titanium dioxide thin-film electrodes

In this study, the photoelectrocatalytic behavior of bromide and generation of bromine using TiO2 was investigated in the separate anode and cathode reaction chambers. Our results show that the generation of bromine begins around a flatband potential of -0.34 V vs. standard calomel electrode (SCE) at pH 3.0 under UV illumination and increases with an increase in positive potential, finally reaching a steady-state concentration at 1.0 V vs. SCE. Maximum bromine formation occurs over the range of pH 4-6, decreasing sharply at conditions where the pH>7.     

High bromine oxide concentrations in the semi-polluted boundary layer

Bromine chemistry in the marine boundary layer is recognized to play an important role through catalytic ozone destruction, changes to the atmospheric oxidising capacity (by changing the OH/HO₂ and NO/NO₂ ratio) and oxidation of compounds such as dimethyl sulphide (DMS). However, the chemistry of bromine in polluted environments is not well understood and its effects are thought to be inhibited by reactions involving NO_x (NO₂ & NO). This paper describes long-path Differential Optical Absorption Spectroscopy (DOAS) observations of bromine oxide (BrO) at a semi-polluted coastal site in Roscoff, France. Significant concentrations of BrO (up to 7.5 ± 1.0 pptv) were measured during daytime, indicating the presence of unknown sources or efficient recycling of reactive bromine from bromine nitrate (BrONO₂), which should be the major reservoir for bromine in a high NO_x environment. These measurements indicate that bromine chemistry can play an important role in polluted environments.     

Electrolytic debromination of PBDEs in DE-83 technical decabromodiphenyl ether

Electrochemical debromination of the commercial decabromodiphenyl ether flame retardant DE-83 in partly aqueous tetrahydrofuran (THF) solution gave lower brominated congeners by sequential loss of bromine atoms. Hydrodebromination was most facile for the most heavily brominated congeners. It involves initial electron transfer and proton transfer from water, rather than hydrogen atom abstraction from THF, as shown by experiments with deuterated water. The product distribution from electrolysis involves preferential loss of bromine meta- and para- to the ether linkage, comparable with the products of metabolism of BDE-209 in various organisms. Significantly, the environmentally relevant congeners BDE-47, BDE-99, and BDE-154 were not major products of debromination of BDE-209 by the electron transfer mechanism.     

The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer

Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.     

Birnessite mediated debromination of decabromodiphenyl ether

Decabromodiphenyl ether (BDE-209) is a major component of a commercial flame retardant formulation; however, there is limited information on the fate of BDE-209 in the environment, including metal oxide mediated degradation. Laboratory experiments were conducted to investigate the birnessite (delta-MnO(2))-promoted debromination of BDE-209 in tetrahydrofuran (THF)-water systems as well as catechol solutions. Up to 100% (0.1044 micromol initial charge) of BDE-209 disappeared upon reaction with birnessite in THF/H(2)O (4:6-9:1). The formation of aqueous Br(-) from BDE-209 reduction was determined and up to 16 mole% of initial bromine was released over the course of the reaction indicating approximately 1.7 Br-C bonds were reduced per BDE-209 molecule. The distribution of debrominated congeners, however, indicated a much greater extent of debromination for some products than what was inferred from an average bromine mass balance. The produced congeners varied from tetra- to nona-bromodiphenyl ether, including BDE-47 and -99, during the 24 h reaction. Experiments with deuterated water indicated that water was not the major hydrogen donor in the reduction but rather THF provided the reducing power. This conclusion was supported by the presence of succinic acid, which was produced from oxidation of THF. The reactions with aqueous catechol, rather than THF-water mixtures, were performed to assess the possible role that compounds found in natural environments, such a tannin-like phenols, might have on the chemistry. These experiments indicated that birnessite mediated debromination of BDE-209 might occur in natural settings.     

Synoptic evaluation of regional PM2.5 concentrations

By comparing short-term fluctuations in PM2.5 species concentrations among nearby air quality monitors and among species, it becomes possible to understand the regional and local events leading to higher concentrations. This approach was applied at thirteen sites in the Maryland area for the 2001–2006 timeframe in order to identify and explain the behavior of eighteen different analytes as well as the daily Air Quality Index.Findings included identification of local upwind events such as fireworks displays, construction and demolition, the spatial extent of sulfate, nitrate, and ammonium correlations between ground-level monitors, correlations between some crustal species to indicate similar emissions sources in urban areas, and indicators of particle adsorption as a rate-limiting step for certain species. For example, the bromine behavior suggests that bromine concentrations on particulate matter may be limited by the particle adsorption rate and thus show a dependence on the Air Quality Index measurements.     

Probing the sensitivity of gaseous Br2 production from the oxidation of aqueous bromide-containing aerosols and atmospheric implications

This paper presents a global sensitivity and uncertainty analysis of the bromine chemistry included in the Model of Aqueous, Gaseous and Interfacial Chemistry (MAGIC) in dark and photolytic conditions. Uncertainty ranges are established for input parameters (e.g. chemical rate constants, Henry's law constants, etc.) and are used in conjunction with Latin hypercube sampling and multiple linear regression to conduct a sensitivity analysis that determines the correlation between each input parameter and model output. The contribution of each input parameter to the uncertainty in the model output is calculated by combining results of the sensitivity analysis with input parameters' uncertainty ranges. Model runs are compared using the predicted concentrations of molecular bromine since Br_2(g) has been shown in previous studies to be generated via an interface reaction between O_3(g) and Br_(surface)^? during dark conditions [Hunt et al., 2004]. Formation of molecular bromine from the reaction of ozone with deliquesced NaBr aerosol: evidence for interface chemistry. Journal of Physical Chemistry A 108, 11559–11572]. This study also examines the influence of an interface reaction between OH_(g) and Br_(surface)^? in the production of Br_2(g) under photolytic conditions where OH_(g) is present in significant concentrations. Results indicate that the interface reaction between O_3(g) and Br_(surface)^? is significant and is most responsible for the uncertainty in MAGICs ability to calculate precisely Br_2(g) under dark conditions. However, under photolytic conditions the majority of Br_2(g) is produced from a complex mechanism involving gas-phase chemistry, aqueous-phase chemistry, and mass transport.