河南省典型炭素企业VOCs排放特征及臭氧生成潜势分析

挥发性有机物（VOCs）是主要的臭氧前体物之一,控制VOCs排放是打赢“蓝天保卫战”的重要组成部分.研究工业源VOCs排放特征和对O₃生成贡献对制定和修订相关VOCs排放标准、有针对性控制VOCs排放具有重要意义.炭素行业是非金属制品业的重要组成部分,属于高污染行业,对该行业有组织VOCs排放的研究鲜见文献报道.本文选取河南省某典型炭素企业Y炭素厂作为研究对象,通过实地采样分析了不同工序有组织和车间内、外无组织117种VOCs排放特征,计算臭氧生成潜势（OFP）并评估了不同VOCs类别和物种对O₃生成的贡献.研究表明,Y炭素厂排放因子为0.031 g·kg^-1,其中焙烧工序有组织VOCs排放量最大.总有组织排放占比较大的VOCs类别有烯烃（23.56%）、烷烃（21.24%）、芳香烃（18.17%）、卤代烃（15.34%）和含氧化合物（8.95%）等,占比较大的VOCs物种有乙烯（18.2%）、乙烷（11.5%）、苯（8.66%）和 乙炔（7.15%）等.车间内无组织排放占比较大的VOCs物种则为萘和四氯化碳等.总有组织排放的VOCs中,烯烃、芳香烃和含氧化合物的OFP占比较大,分别为71.72%、11.35%、10.05%,其中乙烯、丙烯的OFP占比分别为52.91%和13.98%,是需要重点治理的O₃生成前体物.     

Bayesian model-based cluster analysis for predicting macrofaunal communities

To predict macrofaunal community composition from environmental data a two-step approach is often followed: (1) the water samples are clustered into groups on the basis of the macrofauna data and (2) the groups are related to the environmental data, e.g. by discriminant analysis. For the cluster analysis in step 1 many hard, seemingly arbitrary choices have to be made that nevertheless influence the solution (similarity measure, clustering strategy, number of clusters). The stability of the solution is often of concern, e.g. in clustering by the program. In the discriminant analysis of step 2 it can occur that a water sample is misclassified on the basis of the environmental data but on further inspection happens to be a borderline case in the cluster analysis. One would then rather reclassify such a sample and iterate the two steps. Bayesian latent class analysis is a flexible, extendable model-based cluster analysis approach that recently has gained popularity in the statistical literature and that has the potential to address these problems. It allows the macrofauna and environmental data to be modelled and analyzed in a single integrated analysis. An exciting extension is to incorporate in the analysis prior information on the habitat preferences of the macrofauna taxa such as is available in lists of indicator values. The output of the analysis is not a hard assignment of water samples to clusters but a probabilistic (fuzzy) assignment. The number of clusters is determined on the basis of the Bayes factor. A standard feature of the Bayesian method is to make predictions and to assess their uncertainty. We applied this approach to a data set consisting of 70 water samples, 484 macrofauna taxa and four environmental variables for which previously a five cluster solution had been proposed. The standard for Bayesian estimation, the Gibbs sampler, worked fine on a subset with only 12 selected taxa but did not converge on the full set with 484 taxa. This is due to many configurations in which the assignment probabilities are all very close to either 0 or 1. This convergence problem is comparable with the local optima problem in classical cluster optimization algorithms, including the EM algorithm used in Latent Gold, a Windows program for latent class analysis. The convergence problem needs to be solved before the benefits of Bayesian latent class analysis can come to fruition in this application. We discuss possible solutions.     

农业面源污染对我国农村地表水的影响与对策研究

基于2015—2021年我国农村地表水环境质量监测数据,分析了农村地表水环境质量状况特征;选取农业农村社会经济活动相关参数,与农村地表水中主要超标因子的超标比例进行了相关性分析;以2020年为基准年,对全国31个行政区,涵盖农村地表水水质状况、农业农村活动水平和污染压力、环境容量3个方面的9个指标进行了聚类分析。结果表明,我国农村地表水的变化趋势、季节特点和主要超标因子等表现出明显的农业面源污染特征;乡村人口、农业投入品使用量和经济作物种植比例等参数与主要超标指标具有较强的相关性（R＞0.9）;聚类分析将全国31个行政区划分为7种不同的农业面源污染类型。提出,应根据不同地区农业面源污染特点,因地制宜地推进标准化规模养殖、畜禽粪污资源化利用、化肥减量行动、高效低风险农药推广等农业面源污染治理措施,进一步加大农村生活污水处理设施建设,同时,完善农村环境质量监测网络,加强农业面源污染监测和评估。     

Investigations into the PCDD contamination of topsoil,river sediments and kaolinite clay in Queensland,Australia

Recent findings of elevated PCDDs from an unknown source in the coastal marine environment of Queensland, Australia has instigated further investigations into the distribution of, and environments associated with the PCDD contamination. This study presents data for OCDD concentrations in the coastal, mountainous and inland environment of Queensland. Additionally, full 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofuran (PCDD/F) profiles from different land-use types and environments in the coastal region were analysed. Distinct east–west gradients were detected in topsoil collected from various bushland regions with elevated OCDD concentrations confined to the coastal region. However, PCDD/F results from topsoil and river sediments collected in the Queensland coastal region suggest that elevated OCDD concentrations cannot be attributed to any of the environments, land-use or industry types investigated. PCDD/F congener profiles from select samples were remarkably similar to those previously described in marine sediments collected along the entire Queensland coastline. In addition, kaolinite clay samples from Queensland exhibited elevated OCDD concentrations, and PCDD/F profiles in these samples were similar to those detected in kaolinite clays elsewhere. Natural formation processes have been hypothesised as the source of elevated PCDDs in Queensland and other locations, where similar PCDD/F profiles and the general lack of anthropogenic sources are evident. This study presents additional data supporting this hypothesis and provides further information that may assist in the identification of the processes involved in the natural formation of PCDDs.     

Specific biomagnification of polychlorinated dibenzo-p-dioxins and dibenzofurans in tufted ducks (Aythya fuligula), common cormorants (Phalacrocorax carbo) and their prey from Lake Shinji,Japan

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) were detected in waterfowl such as common cormorants, tufted ducks, and their prey, namely fish and bivalves from Lake Shinji, Japan. The concentration of total PCDDs/DFs-TEQ was found to be higher in the muscle tissues of common cormorants than in those of tufted ducks. The results of hierarchical cluster analysis implied that the residue distribution pattern of PCDD/DF homologues was considerably different between these two species. Furthermore, biomagnification factors (BMFs) were estimated from bivalves as prey to tufted duck muscles as target organs. Despite the highest concentrations of 1,3,6,8- and 1,3,7,9-TeCDD in tufted ducks and their prey, however, the BMFs of these isomers were calculated to be lower than those of the toxic 2,3,7,8-substituted PCDDs/DFs. On the other hand, log BMF of toxic 2,3,7,8-substituted PCDDs/DFs were significantly higher for lower chlorinated isomers than those of the higher chlorinated isomers. The biota-sediment accumulation factors (BSAFs) of PCDDs/DFs were also estimated using shijimi clam and fish samples against sediment from Lake Shinji. The average BSAFs were estimated and ranged from 4.0×10⁻³ to 2.2×10⁻¹ and 2.0×10⁻⁴ to 2.0×10⁻¹ for bivalve and fish samples, respectively. Based on calculated BMFs and BSAFs, the total PCDD/DF-TEQ levels in the tufted duck were estimated to have been lowest (2.0 pg TEQ/g dry weight basis) in 1947 and highest (9.8 pg TEQ/g) in 1971.     

Effects of copper chloride on formation of polychlorinated dibenzo-p-dioxins in model waste incineration

Combustion experiments in a laboratory-scale fluidized-bed reactor were conducted to elucidate the effects of copper chloride as a catalyst on polychlorinated dibenzo-p-dioxins (PCDDs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl₂ · 2H₂O), both of which contained polyvinyl chloride as a chlorine source. Combustion temperature was set to 900 °C, and the amount of air supplied was twice the stoichiometric ratio. The experimental setup was carefully planned to suppress the influences of experimental conditions except the waste composition. Results of these experiments showed that copper chloride in the waste increased the amount of PCDDs formed and made the homologue profile to shift towards the highly chlorinated species. Copper chloride contributes to the PCDDs formation by promoting chlorination, whereby the reaction is important in that organic matter is chlorinated directly by copper compounds. Copper chloride did not exert a great influence on the isomer distribution patterns of PCDDs, while there appeared a significant difference in the case of PCDFs. This points out the difference of the major formation mechanisms between PCDDs and PCDFs. PCDDs are less formed by the catalytic reactions from carbon/polycyclic aromatic hydrocarbons than PCDFs in our experimental conditions.     

实现保定市大气污染防治目标的对策及建议

摘 要:目前,京津冀及周边地区已成为国内大气污染最严重的区域,引起了社会广泛关注。文章在对保定市大气污染现状详细梳理的基础上,分析了保定市在生产、生活过程中造成大气污染的原因,探讨和提出了解决保定市大气污染的对策及实施建议。     

4种甲氧基丙烯酸酯类杀菌剂不同剂型对斑马鱼急性毒性效应

采用半静态法测定了4种甲氧基丙烯酸酯类杀菌剂原药及制剂对斑马鱼(Brachydonio rerio)急性毒性。结果表明,以实测浓度计,250 g·L~(-1)嘧菌酯悬浮剂对斑马鱼的96 h半数致死浓度(LC50)值为0.539 mg·L~(-1),急性毒性为高毒,95%嘧菌酯原药和50%嘧菌酯水分散粒剂对斑马鱼的LC50(96 h)值分别为1.09和1.21 mg·L~(-1),急性毒性均为中毒;98%啶氧菌酯原药和22.5%的啶氧菌酯悬浮剂对斑马鱼的LC50(96 h)值分别为0.0974和0.0972 mg·L~(-1),急性毒性均为剧毒;95%吡唑醚菌酯原药、15%吡唑醚菌酯悬浮剂和250 g·L~(-1)吡唑醚菌酯乳油对斑马鱼的LC50(96 h)值为0.0613、0.0549和0.0487 mg·L~(-1),急性毒性均为剧毒;95%醚菌酯原药和50%醚菌酯水分散粒剂对斑马鱼的LC50(96 h)值分别为0.468和0.702 mg·L~(-1),急性毒性均为高毒。这4种甲氧基丙烯酸酯类杀菌剂对斑马鱼均有较高风险,会对其他水生生物也存在潜在的风险。     

石油炼化无组织VOCs的排放特征及臭氧生成潜力分析

选取我国光化学活跃的珠江三角洲地区(PRD)典型石油炼化工艺的炼油装置、化工装置和污水处理装置,采用离线和在线的多种先进仪器监测其VOCs的无组织排放特征,并采用间、对-二甲苯/苯(X/B)、甲苯/苯(T/B)、乙苯/苯(E/B)比值分析其VOCs的老化特征,采用最大增量反应活性法(MIR)、等效丙烯浓度法和OH自由基反应速率法(L_OH)3种方法综合评价其VOCs的化学反应活性及臭氧生成潜势(OFP).研究发现,炼油装置区和化工装置区总挥发性有机物(TVOC)浓度早晚高,中午低;污水处理区呈双峰趋势.3个装置区无组织排放的VOCs中烷烃浓度均占比最高,同一装置区内的不同装置VOCs排放特征不同.石化企业X/B、T/B和E/B值较城区和郊区的高,化工装置区的压缩碱洗装置区(CAW)T/B值最大.石化企业VOCs的活性较城区和郊区的强,其平均OH消耗速率常数为15.22×10^-12cm³/(mol·s),最大增量反应活性为4.21mol(O₃)/mol(VOC).化工装置区对石化企业OFP总量的贡献最高,为84.83%;其次是污水处理区,12.95%;炼油装置区最低,为2.22%.化工装置区的CAW对石化企业OFP贡献率最高,为34.26%;污水处理区的浮选池(FT)贡献率最低,为0.36%.     

液相色谱-电喷雾质谱法测定污水和污泥中壬基酚聚氧乙烯醚的参数优化

在液相色谱-电喷雾质谱法测定壬基酚聚氧乙烯醚的过程中,对壬基酚聚氧乙烯醚加合离子的形成影响因素进行分析,优化了关键参数,建立了测定污水和污泥中壬基酚聚氧乙烯醚的高分辨高灵敏的液相色谱-电喷雾质谱方法.流动相A为0.1mmol·l~(-1)乙酸钠缓冲液,流动相B为甲醇,各聚合度壬基酚聚氧乙烯醚的加合离子响应值达到最大;锥孔电压没为60V能最大程度上避免[NPnEO+2Na]~(2+)对测定的干扰.NP1EO,NP2EO和NPnEOs(n=3-15)的仪器检出限分别为10pg,1pg和0.1pg.该方法成功用于污水和污泥中壬基酚聚氧乙烯醚的测定.