大气中苯乙烯的气相色谱法测定

采用活性炭管吸附大气中基苯乙烯，以二硫化碳洗脱，以溴水加成后，用气相色谱电子捕获器测定苯乙烯的二溴加成物。本方法适合于检测多种污染物共存的大气中痕量苯乙烯。其线性范围为０．０１５－０．７４ｎｇ，最低检出浓度为０．００１ｍｇ／ｍ＾３；重现性实验的变异系数为２．３％：当活性炭管吸附苯乙烯在２．９μｇ时，回收率为９０％，吸附苯乙烯０．２９μｇ时，回收率为７２％。     

萃取分光光度法测定工业废气中的游离溴

用萃取分光光度法测定工业废气中的游离溴，并对样品的采集与保存，萃取条件的选择进行了研究。结果表明，当溴的含量在１８．０－４５０．０μｇ／ｍＬ范围同时，吸光度与浓度具有良好的线性关系，方法的采样效率大于９９％，精密度和准确度较好当采集气体为１００Ｌ时，最低检出肖度为０．１４ｍｇ／ｍ＾３。     

Bioindication of volatile elements emission by the Puyehue-Cordón Caulle (North Patagonia) volcanic event in 2011

The emission of volatile pollutants from the volcanic eruption of the Puyehue-Cordón Caulle complex (North Patagonia Andean Range) that started in June 4th, 2011, was investigated by bioindication means with the epyphytic fruticose lichen Usnea sp. The elemental composition of pooled samples made up with 10 lichen thalli were analysed by Instrumental Neutron Activation Analysis. Eleven sampling sites were selected within the impacted region at different distance from the volcanic source. Five sites were selected as they were already sampled in a previous study prior to the eruption. Two other new sampling sites were selected from outside the impacted zone to provide non-impacted baseline sites.The elements associated with the lichen incorporation of particulate matter (PM) of geological origin were identified by linear correlation with a geochemical tracer (Sm concentrations). The elements associated with PM uptake were Ce, Eu, Fe, Hf, La, Lu, Na, Nd, Sb, Sc, Se, Ta, Tb, Th, U, and Yb. Arsenic and Cs concentrations showed contributions exceeding the PM fraction in sites near the volcanic centre, also higher than the baseline concentrations, which could be associated with permanent emissions from the geothermal system of the Puyehue-Cordón Caulle complex. The lichen concentrations of Ba, Ca, Co, Hg, K, Rb, Sr, and Zn were not associated with the PM, not showing higher concentrations in the sites nearby the volcanic source or respect to the baseline values either. Therefore, there is no indication of the emission of volatile forms of these elements in the lichen records. The lichen records only identified Br volatile emissions associated with the Puyehue-Cordón Caulle complex eruption in 2011.     

Formation and speciation of disinfection byproducts during chlor(am)ination of aquarium seawater

The chemistry associated with the disinfection of aquarium seawater is more complicated than that of freshwater, therefore limited information is available on the formation and speciation of disinfection byproducts(DBPs) in marine aquaria. In this study, the effects of organic precursors, bromide(Br-) and pre-ozonation on the formation and speciation of several typical classes of DBPs, including trihalomethanes(THM4), haloacetic acids(HAAs),iodinated trihalomethanes(I-THMs), and haloacetamides(HAc Ams), were investigated during the chlorination/chloramination of aquarium seawater. Results indicate that with an increase in dissolved organic carbon concentration from 4.5 to 9.4 mg/L, the concentrations of THM4 and HAAs increased by 3.2–7.8 times under chlorination and by 1.1–2.3 times under chloramination. An increase in Br-concentration from 3 to 68 mg/L generally enhanced the formation of THM4, I-THMs and HAc Ams and increased the bromine substitution factors of all studied DBPs as well, whereas it impacted insignificantly on the yield of HAAs. Pre-ozonation with 1 mg/L O3 dose substantially reduced the formation of all studied DBPs in the subsequent chlorination and I-THMs in the subsequent chloramination. Because chloramination produces much lower amounts of DBPs than chlorination, it tends to be more suitable for disinfection of aquarium seawater.     

Characteristics of molecular weight distribution of dissolved organic matter in bromide-containing water and disinfection by-product formation properties during treatment processes

The characteristics of dissolved organic matter (DOM) and bromide ion concentration have a significant influence on the formation of disinfection by-products (DBPs). In order to identify the main DBP precursors, DOM was divided into five fractions based on molecular weight (MW), trihalomethane formation potential and haloacetic acid formation potential were determined for fractions, and the change in contents of different fractions and total DBPs during treatment processes (pre-chlorination, coagulation, sand filtration, disinfection) were studied. Moreover, the relationship between bromide concentration and DBP generation characteristics in processes was also analyzed. The results showed that the main DBP precursors were the fraction with MW < 1 kDa and fraction with MW 3−10 kDa, and the DBP''s generation ability of lower molecular weight DOM (< 10 kDa) was higher than that of higher molecular weight DOM. During different processes, pre-chlorination and disinfection had limited effect on removing organics but could alter the MW distribution, and coagulation and filtration could effectively remove organics with higher MW. For DBPs, trihalomethanes (THMs) were mainly generated in pre-chlorination and disinfection, while haloacetic acids (HAAs) were mostly generated during pre-chlorination; coagulation and sand filtration had little effect on THMs but resulted in a slight removal of HAAs. In addition, the results of ANOVA tests suggested that molecular sizes and treatment processes have significant influence on DBP formation. With increasing bromide concentration, the brominated DBPs significantly increased, but the bromine incorporation factor in the processes was basically consistent at each concentration.     

Analysis of mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/PXDFs) in soil by gas chromatography tandem mass spectrometry (GC-MS/MS)

Mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/PXDFs, X = Br, Cl) are formed through combustion processes, and may be more toxic than their corresponding chlorinated and brominated analogues. With 4600 potential congeners, limited analytical standards, and complex environmental matrices, PXDD/PXDFs present a significant analytical challenge. Gas chromatography tandem mass spectrometry (GC-MS/MS) offers both selectivity and sensitivity through multiple reaction monitoring of unique transitions in a novel approach to PXDD/PXDF congener identification. Method validation was performed through analysis of soil samples obtained from a recycling plant fire. Of the PXDD/PXDFs examined, monobromo-dichlorodibenzofuran was the most prevalent, ranging in concentration from 8.6 ng g⁻¹ to 180 ng g⁻¹. Dibromo-dichlorodibenzo-p-dioxin, a compound of toxicological concern, ranged from 0.41 ng g⁻¹ to 10 ng g⁻¹. Concentrations of PXDD/PXDFs were between 6% and 10% that of the corresponding polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs), with the exception of dibromo-dichlorodibenzo-p-dioxin concentrations, which were 36% that of tetrachlorodibenzo-p-dioxins. Higher levels of polybrominated PXDD/PXDFs may indicate a significant bromine source was present during combustion.     

甲基橙分光光度法测定环境空气及工业废气中游离溴

以０．００５‰甲基橙溶液富集吸收,用分光光度法测定环境空气和工业废气中的游离溴,并对样品的采集、保存和最佳测定条件进行了研究。结果表明,方法的采样效率〉９７％,线性良好,精密度和准确度均较高,方法灵敏,按２０Ｌ采样体积计,方法的最低检出浓度为０．０２５ｍｇ／ｍ＾３。     

Bromine in waste incineration partitioning and influence on metal volatilisation

INTENTION, GOAL, SCOPE, BACKGROUND: The halogen bromine is far less abundant than chlorine, but it can be found at high concentrations in special materials like flame retarded plastics. The fate and effects of Br in waste incineration are not well understood. It may have similar implications like Cl for the volatilisation of heavy metals and the formation of low volatile organic compounds. Due to its lower oxidation potential, there is a risk of formation of elementary Br2 in the offgas. OBJECTIVE: Co-combustion tests of different types of Br containing plastic waste materials (up to 22%) and MSW in the TAMARA pilot plant for waste incineration were conducted to investigate the Br partitioning and the influence of Br on metal volatilisation. METHODS: The Br inventory of the fuel mix was elevated to approx. 1 wt-%. All input and output mass flows of the furnace have been sampled and the partitioning of Cl, Br, S, and a number of heavy metals, has been calculated on the basis of closed mass balances. RESULTS AND DISCUSSION: Organically-bound Br was typically released to more than 90% into the raw gas. Elementary Br2 was detected at high Br levels. Its presence was always analysed when all SO2 in the raw gas was oxidised to SO3. Br enhances the volatilisation of metals like K, Zn, Cd, Sn, Sb, and Pb out of the fuel bed principally in the same way as Cl. The tests gave strong indication that the promoting influence of the halogens on metal volatilisation is more pronounced than that of the fuel bed temperature. The volatilised metals are condensated on the fly ashes and are discharged along with the filter ashes. CONCLUSIONS: As long as a surplus of SO2 is present in the raw gas no Br2 is formed. Although the halogen induced transfer out of the fuel bed causes high concentrations of volatile metals in the filter ashes, a recovery is not economically feasible for the time being. The volatilisation gives no rise to metal emission problems as long as efficient dedusting is achieved. RECOMMENDATION AND OUTLOOK: If there is a risk of Br2 formation, in wet scrubbing a reducing agent has to be added to the neutral scrubber for efficient abatement. Filter ashes should be disposed of in a way that enables access for recovery in the future. The exact volatilisation characteristics of the various metals have to be studied in future using specifically tailored experiments.     

Behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes

We investigated the thermal properties and behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes containing polybrominated flame retardants. The thermal properties of the phenolic laminate wastes were measured with a thermogravimeter and a conduction-type scanning calorimeter (TG-CSC). The weight loss of the wastes on thermal decomposition was mainly in three phases between 40°C and 600°C. The enthalpy (ΔH) of the thermal decomposition was 104 cal/g. The material balance of the decomposition components was measured with batch-type thermal decomposition equipment. The ratios of carbon residue, liquid, and gas on decomposition at 800°C in a vacuum were 37 wt. %, 48 wt. %, and 15 wt. %, respectively. The bromine contents in the carbon residue and liquid were less than 0.02 wt. % and 10 wt. %, respectively. These results are useful both in the carbonization process of these wastes and in the application of carbon residue as carbon materials. Received: August 11, 2000 / Accepted: March 7, 2001     

Influence of bromine on metal volatilization in waste combustion

Co-combustion tests of municipal solid waste and bromine-containing waste plastics have been performed in the TAMARA test incinerator in order to investigate the fate of bromine in waste combustion. HBr is the main bromine combustion product. Approximately 50% of the bromine inventory stays in the grate ashes, which is much more than is found for chlorine. The percentage of bromine transferred into the fly ash also exceeds that of chlorine. There is a strong indication that bromine has a promoting effect upon the volatility of most of the heavy metals that are typically mobilized by chlorine. Received: February 2, 2000 / Accepted: March 3, 2000