我国再生锌行业二噁英污染有效控制技术探讨

分析了我国再生锌行业产生二噁英污染的概况,为我国再生锌行业二噁英污染控制提供了基本依据;在对我国再生锌行业二噁英污染节点分析基础上,阐述了我国再生锌行业二噁英污染的控制方法;并提出了再生锌二噁英污染控制的有效技术途径.     

Chemical looping combustion: A new low-dioxin energy conversion technology

Dioxin production is a worldwide concern because of its persistence and carcinogenic, teratogenic, and mutagenic effects. The pyrolysis-chemical looping combustion process of disposing solid waste is an alternative to traditional solid waste incineration developed to reduce the dioxin production. Based on the equilibrium composition of the Deacon reaction, pyrolysis gas oxidized by seven common oxygen carriers, namely, CuO, NiO, CaSO₄, CoO, Fe₂O₃, Mn₃O₄, and FeTiO₃, is studied and compared with the pyrolysis gas directly combusted by air. The result shows that the activity of the Deacon reaction for oxygen carriers is lower than that for air. For four typical oxygen carriers (CuO, NiO, Fe₂O₃, and FeTiO₃), the influences of temperature, pressure, gas composition, and tar on the Deacon reaction are discussed in detail. According to these simulation results, the dioxin production in China, Europe, the United States, and Japan is predicted for solid waste disposal by the pyrolysis-chemical looping combustion process. Thermodynamic analysis results in this paper show that chemical looping combustion can reduce dioxin production in the disposal of solid waste.     

同位素稀释高分辨气相色谱-高分辨质谱法测定氯化石蜡工业品中二噁英

氯化石蜡（CPs）作为一种用途广泛、产量大的有机氯化学工业品,具有组成多样、基质复杂等特点,对其中产生的二噁英（PCDD/Fs）检测是当前工作面临的难题。建立了同位素稀释高分辨气相色谱-高分辨质谱法检测CPs工业品中PCDD/Fs的分析方法。对样品净化过程进行了优化,通过提取溶剂筛选,去除固体CPs中部分基质,建立的双活性炭柱法可高效去除CPs基质。方法采用¹³ C₁₂标记的PCDD/Fs内标物进行定性和定量分析。17种PCDD/Fs同系物的检出限为0.1～3 pg/g,回收率为31.7%～100%。该方法可对高纯度工业品中痕量持久性有机污染物进行高效的定性和定量分析,能够满足国家标准方法对PCDD/Fs检测的要求。     

大体积进样与分流/不分流进样气相色谱/质谱测定二噁英的对比

选取传统分流／不分流进样技术与大体积进样技术,结合气相色谱／质谱测定条件,对二者的测定效果和不同进样量的色谱图进行了分析对比。结果表明,使用大体积的进样测定二噁英,在不影响色谱分离度的同时可以大幅度提高仪器分析的灵敏度,可以代替传统分流／不分流进样。     

Verification results of jet resonance-enhanced multiphoton ionization as a real-time PCDD/F emission monitor

A jet resonance-enhanced multiphoton ionization (REMPI) monitor was tested on a hazardous-waste-fired boiler for its ability to determine concentrations of polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs). Jet REMPI is a real-time instrument capable of highly selective and sensitive (from parts per billion to parts per trillion) detection of a broad range of aromatic compounds, including a number of air toxic compounds. The PCDD/F toxic equivalency (TEQ) value was derived from a predetermined correlation (R ² = 0.74) with monochlorobenzene (MClBz). This relationship was applied to nine subsequent jet REMPI on-line measurements of MClBz and parallel, standard extractive sampling for PCDD/F TEQ. For high waste-firing rates, with a range of PCDD/F TEQ values between 3.9 and 6.0 ng TEQ/m³, the TEQ values predicted by jet REMPI had a relative difference of 26% with the standard EPA Method 23 results. At low waste-firing rates (0.9–1.6 ng TEQ/m³), the relative difference increased to 219%. This limited testing shows that jet REMPI has promise as an on-line diagnostic monitor, providing feedback on the effects on PCDD/F emissions of operating parameter changes such as fuel feed interruptions or air pollution control failures.     

上海市危险废物焚烧行业二噁英排放特征研究

通过对上海市危险废物焚烧行业焚烧炉排放烟气数据的分析,结果表明：不管是医疗废物焚烧炉还是一般危险废物焚烧炉,其二蟋英分布规律大致相同;PCDFs对二曝英的贡献率远高于PCDDs;实测检出的二嚼英异构体中,占二嚼英总量比例较大的依次为1,2,3,4,6,7,8-HpCDF、1,2,3,4,6,7,8-HpCDD和OCDD;I—TEQ贡献最高的二嚼英异构体为2,3,4,7,8-PeCDF,贡献率达31．08％～53．56％。17种二喏英异构体与I—TEQ的相关性分析表明,仅2,3,4,7,8-PeCDF在2类焚烧炉中与I—TEQ均存在相关性,其相关系数分别为0．989和0．998,可以作为潜在的测定指示物。     

垃圾焚烧厂对环境空气中二噁英影响研究

本文通过对垃圾焚烧炉废气和周边环境空气采样,采用同位素稀释-高分辨气相色谱/高分辨质谱(HRGC-HRMS)法分析样品中二噁英浓度。废气样品中二噁英总浓度为0.919~1.152 ng TEQ/m^3,总毒性当量为0.071~0.100 ng TEQ/m^3,环境空气样品中二噁英总浓度为1.194~2.268 pg TEQ/m^3,总毒性当量为0.100~0.200 pg TEQ /m^3。比较废气与环境空气中各PCDD/Fs单体浓度的占比,得出该农村区域范围内环境空气中二噁英污染物主要来源于该垃圾焚烧炉。     

Distribution of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in municipal solid waste incinerators

The stack flue gases and the ashes in different units of two municipal solid waste incinerators (MSWIs) are sampled to investigate the characteristics of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Bottom ashes (BA) exhibited much higher PBDD/F (8.11-52.2 pg TEQ/g) and PBDE contents (20.4-186 ng/g) than those of fly ashes (0.0932-2.02 pg TEQ/g and 0.332-25.5 ng/g), revealing that the PBDD/Fs and PBDEs in the feeding waste may not be completely destroyed. The PBDE concentrations/contents in the stack flue gases (26.1-109 ng/Nm³) and in the BA (20.4-186 ng/g) of the MSWIs could reach three orders higher than those in the atmosphere and reference soils. PBDE contributions to the environment from the stack flue gases or the reutilization of BA of MSWIs should not be ignored from the developing PBDE inventory.     

Fish products available in Polish market – Assessment of the nutritive value and human exposure to dioxins and other contaminants

Chemical analyses were performed on one hundred and twenty of the most popular varieties of fish products (smoked fish, salted fish, and marinated fish) of the fish market in Poland. The contents of the nutritive substances of fish products (protein, micro- and macronutrients, vitamins A₁, D₃, E, and fatty acids) and the chosen contaminant (toxic metals – mercury, cadmium, lead, arsenic; dioxin/furans – PCDDFs; dioxin-like PCB – dl-PCBs; seven congeners of polybrominated diphenyl ethers – PBDEs; organochlorine pesticides – ΣDDT, HCB, ΣHCH and marker polychlorinated biphenyls – PCB₇) levels were determined. It was confirmed that fish products are a good source of digestible proteins, iodine, selenium, and vitamin D₃. The fundamental nutritive benefit of processed fish lies in its highly beneficial fatty acid composition, which is what imparts them healthy nutritive qualities. The high content of long-chain polyunsaturated fatty acids (LC-PUFAs), which is not noted in other food products, is particularly important.The majority of contaminants studied were present in low levels. The possible threats, particularly in the case of pregnant/nursing women and young children, can pose the levels of dioxin/furans (PCDD/Fs) and dioxin-like (dl-PCBs) in smoked Baltic salmon and smoked sprat, elevated in a relation to particular requirements concerning the content of sum of PCDD/Fs and dl-PCBs in fish (8 pg WHO-TEQ g⁻¹).The health benefits and risks stemming from consumption of fish products were determined according to the Provisional Tolerable Weekly Intake (PTWI) for chosen contaminants (Cd, Hg, As, PCDD/Fs + dl-PCB) and the quantity of ingredients that render a fish diet healthy based on data from the EFSA Journal [EFSA (European Food Safety Authority), 2005. Opinion of the scientific panel on contaminants in the food chain on a request from the European Parliament related to the safety assessment of wild and farmed fish. EFSA J. 236, 1–118]. In regard of high content of LC-PUFAa and other nutritive ingredients, fish products available in Polish market may be considered as healthy food.However, many authors point at contaminants (methylmercury, PCDD/Fs) occurring in fish and fish products as on potential health problem, and emphasize that the amount of that hazardous substances should be limited in human diet.     

Serum concentrations of chlorinated dibenzo-p-dioxins and dibenzofurans among former New Zealand trichlorophenol workers

This study examined serum levels of 2,3,7,8-substituted chlorinated dioxins and furans, and 15 PCBs for 346 New Zealand employees who worked at a site that manufactured 2,4,5-trichlorophenol (TCP) and 2,4,5-trichlorophenoxy acetic acid (2,4,5-T). Participants with potential TCP or 2,4,5-T exposures had mean lipid-adjusted 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) levels of 9.9 ng kg⁻¹ lipid compared to 4.9 ng kg⁻¹ for workers with no exposure at the site. Among exposed workers, we found evidence of differences in 2,3,7,8-TCDD levels by department and duties. Workers involved in an accidental release had the highest mean 2,3,7,8-TCDD levels, 37.9 ng kg⁻¹, followed by workers in the trichlorophenol plant, 23.4 ng kg⁻¹. Workers with potential intermittent exposures to 2,3,7,8-TCDD in construction, maintenance, mechanics, and transport had 2,3,7,8-TCDD levels above New Zealand background levels of 3.9 ng kg⁻¹, indicating workplace exposures. Among participants with work history indicating no 2,3,7,8-TCDD exposures, we observed some individuals with 2,3,7,8-TCDD levels above background levels. However, in most cases, these workers reported workplace exposures not recorded on their work histories or held other jobs with the potential for 2,3,7,8-TCDD exposures outside the plant. All other dioxin, furan, and PCB levels were similar among the exposed and unexposed workers.