4种重金属离子对间接火焰原子吸收光谱法测定铝的干扰

空气-乙炔间接火焰原子吸收法是我国目前运用较多且易于推广的铝检测方法,研究了Mg2+、Ca2+、Zn2+和Ni2+4种离子对此法测定0.40 mg/L Al3+的干扰情况。得出如下结论:(1)在±5%误差范围内,15.10 mg/L Mg2+、105.00mg/L Ca2+、0.23 mg/L Zn2+、0.88 mg/L Ni2+对0.40 mg/L Al3+无干扰。(2)本方法虽然操作复杂,但成本较低、灵敏度高,检测的浓度范围宽、稳定性好,加标回收率为96%~99%,检出限为0.04 mg/L,适宜测定范围为0.05~100.00 mg/L,适用于饮用水、河水及地下水中Al3+的测定。     

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in seven different marine bird species from Iceland

Data on distribution, concentration and trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) is scarce in biota from the sub-Arctic region of the Atlantic. The present study is an investigation on PBDE and HBCD concentrations in eggs from seven marine bird species from Iceland, i.e. common eider (Somateria mollissima), arctic tern (Sterna paradisaea), guillemot (Uria aalge), fulmar (Fulmarus glacialis), lesser black-backed gull (Larus fuscus), great black-backed gull (Larus marinus) and great skua (Stercorarius skua). Concentrations of sum PBDEs ranged from 44 ng g⁻¹ fat in eider eggs to 2400 ng g⁻¹ fat in great skua eggs. The contribution of different PBDE congeners to the sum concentration differed between species. Concentration of HBCDs (sum of α−,β⁻ and γ−HBCD) ranged from 1.3 ng g⁻¹ fat in arctic tern eggs to 41 ng g⁻¹ fat in great black-backed gull. PCA on PBDE and HBCD shows different trends between the two BFR groups, further indicating different sources/usage. Investigations on any potential health or population effects of environmental pollutants on the great skua are advised since both the PBDE and HBCD concentrations are high.     

酸化油渣与膨胀型阻燃剂协效阻燃环氧树脂

餐厨垃圾生产柴油中产生酸化油渣固废(AR)。采用红外光谱(FTIR)法对AR进行分析,认为AR具有较好的阻燃成炭性能。将AR与多聚磷酸铵/三聚氰胺/季戊四醇(APP/MEL/PER)膨胀阻燃体系(IFR)复配,协效阻燃环氧树脂(EP),用极限氧指数法(LOI)、垂直燃烧法(UL94)对其阻燃性能进行了检测,并通过对燃烧残渣的分析讨论了阻燃机理。结果表明,当APP/MEL/PER/AR质量分数为25%,其中AR的质量分数为2%~6%时,阻燃EP的LOI达到30%,具有良好的阻燃性能,并降低了阻燃剂及阻燃材料总体成本。研究成果对餐厨垃圾能源化起到积极推动作用。     

Detailed analysis of polybrominated biphenyl congeners in bird eggs from Norway

Individual eggs of six species of birds from Norway representing different food chains were analysed for residues of polybrominated biphenyls (PBBs). In all species, the residue pattern was dominated by hexaBBs. The dominating congeners were PBB 153, PBB 154, and PBB 155. Whereas PBB 153 is present in technical hexabromobiphenyl, PBB 154 and PBB 155 are formed by the reductive debromination of decabromobiphenyl. This was evidenced by the detection of several heptaBBs and octaBBs all of which are typical degradation intermediates of PBB 209. Hepta- and octaBBs were more than one order of magnitude less abundant than the hexaBBs. The second most prevailing homologue group was pentaBBs. The most relevant pentabrominated isomers were PBB 99 and PBB 101. Concentrations of the three hexaBBs - PBB 153, PBB 154, and PBB 155 - amounted to 1.3-13 ng/g wet weight or 3-23% of the contamination with polybrominated diphenyl ethers.     

Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

Self-ignition and explosion during discharge of high-pressure hydrogen

The phenomenon of self-ignition and explosion during discharge of high-pressure hydrogen was investigated. To clarify the ignition conditions of high-pressure hydrogen jets, rapid discharge of the high-pressure hydrogen was examined experimentally. A diaphragm was used to allow rapid discharge of the high-pressure hydrogen. The burst pressure was varied from 4 to 30 MPa. The downstream geometry of the diaphragm was a flange and extension pipes, with the pipe length varying from 3 to 300 mm. The diameter of the nozzle was 5 or 10 mm. When short pipes were used, the hydrogen jet did not ignite. However, the hydrogen jet showed an increasing tendency to ignite in the pipe as the length of the pipe became longer. At higher burst pressures, a diffusion jet flame was formed from the pipe. The blast wave from the fireball formed on self-ignition of the hydrogen jet resulted in an extremely rapid pressure rise.     

处理日本遗弃在华化学武器专用透气防毒服的研究

本文针对日本遗弃在华化学武器的性质和特点,根据销毁工程对个人防护装备的需求．通过对目前国内外主要透气防毒材料的比较分析,提出了专用透气防毒服内外层纺织材料的技术性能指标和要求．为专用透气防毒服的研制做了前期技术准备。     

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. ∑PBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n = 42) ranged from 80 to 25 720 ng g⁻¹ lw, (overall mean 2403 ± 5406 ng g⁻¹ lw). By age, mean ∑PBDE concentrations were: 3645 ± 7388, 2945 ± 5995, 1385 ± 1265, and 326 ± 193 ng g⁻¹ lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n = 12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g⁻¹ lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.     

流动注射在线离子交换微柱富集-火焰原子吸收法测定环境样品中的铜、铅和镉

本文用流动注射在线阳离子交换树脂预富集-火焰原子吸收法测定了标准参考物(头发GBW09 101和桃叶GBW08501)及水样中的微量铜、铅和镉.对铜、铅和镉测定灵敏度分别提高27.0 ,37.5和27.5倍;回收率分别为93.7-109.9%,88.9-101.4%,84.7-103.0% ;分析速度为30次·h-1.对0.05μg·ml-1Cu2+,0.2μg·ml-1 Pb2+,0.02μg·ml-1Cd2+溶液,其测定相对标准偏差(n ＝11)分别为2.74%,1.05%和2.97%.     

Application of multiwalled carbon nanotubes treated by potassium permanganate for determination of trace cadmium prior to flame atomic absorption spectrometry

In this study we investigated the enrichment ability of oxidized multiwalled carbon nanotubes (MWCNTs) and established a new method for the determination of trace cadmium in environment with flame atomic absorption spectrometry.The MWCNTs were oxidized by potassium permanganate under appropriate conditions before use as preconcentration packing.Parameters influencing the recoveries of target analytes were optimized.Under optimal conditions,the target analyte exhibited a good linearity (R~2=0.9992) over the concentration range 0.5-50 ng/ml.The detection limit and precision of the proposed method were 0.15 ng/ml and 2.06%, respectively.The proposed method was applied to the determination of cadmium in real-world environmental samples and the recoveries were in the range of 91.3%-108.0%.All these experimental results indicated that this new procedure could be applied to the determination of trace cadmium in environmental waters.