Characterisation and fingerprinting of PCBs in flue gas and ash from waste incineration and in technical mixtures

Congener patterns of mono- to deca-chlorinated biphenyls (PC1-10B) were evaluated in (a) waste incineration flue gases collected in the post-combustion zone of a laboratory-scale fluidized-bed reactor, (b) ashes from two different MSW incineration plants, and (c) published data of eight Aroclor formulations. The congener patterns of the flue gases, ashes, and Aroclor mixtures clearly differed from each other, likely reflecting differences in formation pathways. The flue gas congener patterns were largely dominated by the least chlorinated congeners, whereas the ashes displayed more evenly distributed patterns. The most abundant congeners indicated a preference for 3,3',4,4'-oriented substitution, which may be related to de novo-type formation involving perylene. Principal component analysis confirmed that congener patterns differed among the three matrices and also distinguished flue gases collected at 200 °C from those collected at 300 °C and 450 °C. This distinction could be partly explained by the degree of chlorination, although the substitution status of the ortho-position, and substitution in the 3,3',4,4'-positions also seemed to be influential. Injecting biphenyl into the post-combustion zone of the reactor did not alter the patterns, indicating that availability of the backbone structure is not a limiting factor for PCB formation.     

Formation and chlorination of polychlorinated naphthalenes (PCNs) in the post-combustion zone during MSW combustion

Non- to octa-chlorinated naphthalenes (PCNs) were analyzed in flue gas samples collected simultaneously at three different temperatures (450 degrees C, 300 degrees C and 200 degrees C, respectively) in the post-combustion zone during waste combustion experiments using a laboratory-scale fluidized-bed reactor. PCN homologue profiles in all samples were dominated by the lower chlorinated homologues (mono- to triCN), with successive reductions in abundance with each additional degree of chlorination. The isomer distribution patterns reflected ortho-directionality behavior of the first chlorine substituent, and the beta-positions, i.e. the 2,3,6,7-substitution sites, seemed to be favored for chlorination. Injection of naphthalene into the post-combustion zone resulted in increased PCN levels at 200 degrees C, demonstrating the occurrence of chlorination reactions in the post-combustion zone. However, the increases were restricted to the least-chlorinated homologue (monoCN), probably because there was insufficient residence time for further chlorination. In addition, an episode of poor combustion (manifested by high CO levels) was accompanied by extensive formation of 1,8-diCN, 1,2,3- and 1,2,8-triCN; congeners with substitution patterns that are not thermodynamically favorable. These are believed to be products of PAH breakdown reactions and/or chlorophenol condensation. Overall, PCN formation is likely to occur via more than one pathway, including chlorination of naphthalene that is already present, de novo synthesis from PAHs and, possibly, chlorophenol condensation.     

Calculation of σz and H for an Observed Vertical Profile of Concentration

ABSTRACT

In the present work, nitrous oxide emissions were estimated [mg/L] by the use of lysimeters under the closed chamber technique for a six month period. The lysimeters were classified by the type of irrigation used: one for drinking water, and the other for treated wastewater. Each lysimeter had two different types of soil (sand and clay), based on the types of soil in Chihuahua City, Mexico. An additional classification based on the depth was done (reticular and vadose zone). Each zone collected gas by the use of a closed chamber technique, allowing the samples to be taken for subsequent quantification and analysis by gas chromatography. A statistical analysis of variance (ANOVA) and principal components analysis (PCA) were conducted to identify the most influential variables or parameters in the formation of nitrous oxide. The variables that were considered for analysis were total Kjeldahl nitrogen (TKN), ammoniacal nitrogen (NH3-N), nitrate nitrogen (NO3-N), and nitrite nitrogen (NO2-N), along with meteorological parameters. In total, 58944 mg/L of N2O were emitted during the measurement period. The results showed that concentration emissions of N2O where the type of soil is sandy were smaller than those of clay soil, while the mean concentration in the vadose zone was higher than those in the reticular zone, regardless the type of soil. The parameters that showed greater influence in the N2O emissions were NO2-N and NO3-N concentrations. Temperature also played an important role in the emissions (the highest emissions were emitted during the cold months). Furthermore, denitrification appeared to be the dominant process in the production of nitrous oxide in soils.

Implications: Nitrous oxide (N₂O) emissions produced in lysimeters with two types of soil (sand and clay) at two different depths (vadose and reticular zones) using treated waste water showed that the higher emissions of N₂O are derived from clay soils in vadose zone; it could be due to the formation of clogging that favors the formation of anoxic conditions for the denitrification process. The parameters that showed more influence in the N₂O emissions were nitrite (NO₂-N) and nitrate (NO₃-N) concentrations along with the temperature.     

Prediction of the bioconcentration factor of PCBs in fish using the molecular connectivity index and fragment constant models.

Models based on molecular connectivity index (MCI) and fragment constant (FC) method were developed for prediction of the bioconcentration factor (BCF) for polychlorobiphenyls (PCBs) in fish. The mean residuals for the MCI and FC models were 0.195 and 0.223 log units, respectively. The two models were then compared in terms of their mean residuals. In addition to the chlorine atom substitution number, other important structural features exhibiting a significant influence on the BCFs of PCB congeners were discussed and incorporated to the models. These features include the degree of the ortho-substitution, the presence of chlorine pairs in the three- and five- positions, and the crowding of chlorine atoms on the phenyl ring.     

酚类化合物对硝化颗粒污泥活性抑制的定量结构 活性相关研究

测定了酚类化合物对硝化颗粒污泥活性抑制的logIC₅₀值，以量子化学参数为自变量，应用偏最小二乘法（PLS），建立了酚类化合物对硝化颗粒污泥活性抑制的定量结构活性相关（QSAR）模型。模型所提取的PLS主成分所能解释的因变量总方差的比例Q²_cum为0.820，表明模型具有较好的稳定性和预测能力。模型的结果表明，影响酚类化合物对硝化颗粒污泥活性抑制的主要因素是logkow、CCR和E_homo，酚类化合物对硝化颗粒污泥活性抑制的logIC₅₀随着分子logkow的增大而减小，随着E_homo和CCR的增大而增大。     

Comparative aryl hydrocarbon hydroxylase induction activities of commercial PCBs in Wistar rats and rat hepatoma H-4-II E cells in culture

The activities of several commercial PCB mixtures as inducers of microsomal aryl hydroarbon hydroxylase (AHH) and ethoxyresorufin 0-deethylase (EROD) in male Wistar rats and rat hepatoma cells were dependent on the chlorine content (and congener distribution) of the mixtures. The was a correlation between the $\text{in vivo}$ and $\text{in vitro}$ induction potencies of these mixtures; the most active mixtures, Aroclors 1242, 1248 and 1254 contained 42–54% by weight of Cl whereas formulations with higher or lower (Aroclors 1221 and 1268 respectively) chlorine content exhibited lower activities. This corresponds with studies reported for PCB isomers and congeners in which the most active compounds are tetra-hexachlorobiphenyls.