Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.     

Estimation of soil adsorption coefficients of organic compounds by HPLC screening using the second generation of the European reference soil set

The European reference soil set was introduced as common basis for a better comparability of soil sorption data measured within the framework of chemical testing of environmental chemicals. The success of the EUROSOILS, as the set is commonly called, convinced the European Commission's Joint Research Centre to evaluate the possibility of producing a remake of these unique and new type of reference materials maintaining the principal sorption-controlling properties of the soils. In this paper the recently proposed second generation of the EUROSOILS is used to evaluate a HPLC-screening technique for the estimation of soil adsorption coefficients of organic chemicals. It could be shown that the derived correlations between HPLC capacity factors of the test substances and the respective soil adsorption coefficients resulting from batch experiments with the second version of the EUROSOILS agreed with those derived for the first generation of reference soils at a different occasion.     

Bioconcentration of superlipophilic persistent chemicals

According to present understanding, persistent superlipophilic chemicals — such as octachlorodibenzo-p-dioxin, octachlorodibenzofuran, Mirex etc — with log K_ow > 6 and cross sections > 9.5 Å, bioconcentrate in aquatic organisms only little from ambient water. The most convincing argument against it is that in bioconcentration experiments with superlipophilic chemicals amounts applied exceeded water solubility by several orders of magnitude. This paper describes various methods for determining bioconcentration factors (BCF) of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin, BCF values evaluated by these methods match well with those calculated by QSARs for fish and mussels based on log K_ow and water solubility. As expected, these BCF values exceed previous values by several orders of magnitude. For BCF evaluation of superlipophilic chemicals in aquatic organisms we recommend:

1. flow-through systems, kinetic method (OECD guideline No. 305 E)
2. ambient concentrations < water solubility
3. during the uptake and especially during the elimination phase no toxic effects of the test organisms should occur.

     

The effect of wind direction on the observed size distribution of particle adsorbed polycyclic aromatic hydrocarbons on an inner city sampling site

An investigation of the variability in the size distribution of particle adsorbed polycyclic aromatic hydrocarbons (PAHs) on an inner city sampling site showed differences depending on the wind direction. Particle size distributions of PAHs from outdoor air sampling were measured in Munich from 1994 to 1997. The sampling site is located northeast of a crossing with heavy traffic and southwest of a large inner city park. Depending on the wind direction, three different size distributions of particle adsorbed PAHs were observed. The maximum PAH concentration on very small particles (geometric mean diameter 75 nm) was observed with wind from west to southwest coming directly from the crossing area or the roads with heavy traffic. The maximum PAH concentration on particles with geometric mean diameter of 260 nm was found on days with wind from the built-up area north of the sampling site. On particles with geometric mean diameter of 920 nm the maximum PAH concentration was found on days with main wind directions from northeast to east. On these days the wind is blowing from the direction of the city park nearby. The distribution of particle adsorbed PAHs within different particle size classes is substantially influenced by the distance of the sampling site from strong sources of PAH loaded particulate matter.     

Oxidant denuder sampling for analysis of polycyclic aromatic hydrocarbons and their oxygenated derivates in ambient aerosol: evaluation of sampling artefact

The concentrations of some polycyclic aromatic hydrocarbons (PAH) and oxygenated PAH (O-PAH) can be changed by oxidation reactions during sampling. This can lead to an over- or underestimation of the corresponding adverse health effects. The aim of this study was the evaluation of these sampling artefacts. The potential of using an oxidant denuder was shown by parallel low-volume sampling with and without MnO₂ ozone denuder. Twenty-three PAH and 11 O-PAH in ambient air were analysed, both in the vapour and particulate phase. The denuder was proven to be highly efficient for stripping ozone from air while causing no significant particle losses. In general, the concentrations of 5- to 7-ring PAH, which are predominantly associated with particles, were underestimated in non-denuded samples. The highest losses due to reaction with ozone and other atmospheric oxidants were observed for benzo[a]pyrene and perylene. Concurrently, the concentrations of most of the mainly particle-associated 4- to 5-ring O-PAH were higher in the non-denuded samples. The denuder did not only remove ozone, moreover other gaseous species such as more volatile PAH and O-PAH were partially oxidized on the catalytic surface, too. Degradation of PAH and concurrent degradation/formation reactions of O-PAH occurred. The corresponding reactivities of selected PAH and O-PAH are discussed.     

Persistence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in Ya-Er Lake area, China

The concentrations of polychlorinaxed dibenzo-p-dioxins and dibenzofurans (PCDD/F) in surface sediment, soil, human hair, and fish muscle from Ya-Er Lake area, China, were analyzed. The results showed that there were very high concentrations of PCDD/F existing in these samples. The results also indicated that Ya-Er Lake, which received a large amount of waste water from a nearby chloroalkali plant, was heavily polluted by PCDD/F. The present study demonstrated that those congeners, which possess at least three chlorine atoms in the lateral position with a fourth chlorine atom in the neighborhood bond of the third single chlorine atom, such as 1,2,7,8-TCDF and 2,3,6,7-TCDF, were very resistant to biodegradation due to the "neighbor effect" of every two chlorine atoms. The present study suggested that human hair may be a suitable alternative bioindicator for detecting PCDD/F exposure.     

Accumulation and partition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in the muscle and liver of fish

The present study monitored fish from sites contaminated for many years, and the data reflected the results of actual, long-term environmental exposure. The sum concentrations and TEQs of PCDD/F in the muscle of common carp (Cyprinus carpio (linnaeus)) and big head (Aristichthys nobilis) from the different site of a heavily polluted lake in China are decreased with decrease of PCDD/F concentration in sediment and water. Concentration in fish can be highly variable, but the concentration is comparable in muscle between different species of fish if the concentrations are normalized by lipid content. PCDD/F accumulate in certain tissues with the highest proportions found in the liver of fish. The concentrations and TEQs in livers were also decreased with concentrations of sediments and water. The concentrations of PCDD/F in muscle are significantly correlated with those in liver. BCFs of 2,3,7,8-substituted PCDD/F calculated directly from water were consistent with that calculated indirectly from sediment. PCDD/F concentrations in sediment are much higher than that in water, therefore the measurement is much easier and the results are more accurate. Estimated BCFs for superhydrophobic chemicals derived from sediment may also serve as acceptable surrogates for "true" bioaccumulation potential.     

Changes in PCDD/PCDF formation processes during instationary phases of combustor operation--exemplified by the use of Cl4DD isomer patterns

In this paper results of various measurement campaigns at different municipal waste incineration (MWI) plants concerning the change of the PCDD/PCDF isomer distribution in the crude gas during transiently impaired combustion conditions are presented. The focus is on the Cl4DD isomer distributions exemplarily for all other homologue groups to demonstrate the change in PCDD/PCDF formation mechanism at transient combustion conditions. Additionally to crude gas samples, at one plant filter and boiler ash were investigated simultaneously to determine if there is any difference in the isomer distribution between the matrices. For the ash from an electrostatic precipitator (ESP ash), the boiler ash and the corresponding crude gas sample, nearly identical changes in the Cl4DD isomer distribution under transient combustion conditions in relation to the normal operation process could be detected. By comparing the Cl4DD isomer distributions from different incineration plants (two municipal waste incinerators and one little incinerator burning wood chips for heating domestic household) under transient combustion conditions, in all cases the 1,3,6,8- and 1,3,7,9-Cl4DD were dominating the isomer distribution, whereas under normal operation other isomers were predominant. Obviously PCDD/PCDF formation mechanisms under transient combustion conditions are independent from the type of incinerator and of the burned fuel, respectively. Data sets were analyzed with respect to the possible reaction mechanism via chlorophenols and a good correlation of 2,4,6-trichlorophenol during the second phase of a start-up process and during a CO experiment was found. To get more detailed information about possible formation mechanisms, at one plant the dependence of the PCDD/PCDF isomer distribution on the different matrices was studied. Separate analysis of fly ash collected at the boiler exit, subsequent gas phase, ESP ash and boiler ash under normal operation conditions showed that, apart from the fly ash, the Cl4DD isomer distributions are nearly the same in the different matrices. Surprisingly, the Cl4DD isomer distribution of the fly ash was more similar to the distributions found under transient combustion conditions.     

Immissionsbelastungen im Umfeld des Flughafens München

The airborne immissions in the eastern surroundings to the new Munich airport have been investigated by means of different analytical methods between 1992 and 1995. For a detection of environmental impacts, bioindicators were applied to determine the pollution by PAH and to quantify the pollution by photooxidants. In addition, the PAH content in the upper soil layer was determined. During high pressure weather periods in summer the actual air pollution was investigated in the course of seven measuring campaigns. The PAH pollution of the soil is typical for rural background sites with highest concentrations in the close vicinity of busy roads, and exhibits no temporary trend. The actual input of PAH does not differ from the typical situation of rural regions in Bavaria at any measuring sites at all. Road traffic can be identified as the main PAH source in summer, whereas the considerably higher pollution in winter can be related to domestic heating. The pollution by photooxidants was found to be rather homogeneous throughout the eastern surroundings to the airport, being lowest at the sites directly influenced by road traffic. The pollution by volatile hydrocarbons at a busy road junction in the city of Erding is considerably higher than in the rural vicinity of the airport. The concentrations exhibit distinct daily courses which, among other things, can be related to atmospheric photooxidation. The hydroperoxides as secondary air pollutants exhibit an inverse course similar to that of ozone, with maximum values in the afternoon.     

Kinetics of nitromusk compounds degradation in water by ultraviolet radiation and hydrogen peroxide

The photodegradation of five representative nitromusk compounds in water has been performed in a stirred batch photoreactor with a UV low-pressure immersed mercury lamp, at constant temperature and different doses of hydrogen peroxide. The rate constants have been calculated on the basis of experimental data and a postulated first-order kinetic model. The rate constants, at 298 K and a dose of 1.1746 μmol l⁻¹ H₂O₂ ranges from 0.3567 × 10⁻³ s⁻¹ for musk tibetene, to 1.785 × 10⁻³ s⁻¹ for musk ambrette.