Calculation of environmental concentration and comparison of output for existing chemicals using regional multimedia modeling

The environmental fate of 40 existing chemicals is discussed using the EUSES multimedia distribution and risk assessment model with site-specific parameter setting in an urban area of Japan including a highly industrial region. There has been a strong need to assess the environmental fate of a huge number of existing chemicals. Data on the emission amounts of chemicals are essential for such prediction, and PRTR surveys may yield this data. The study delivered the following results: (1) Volatile compounds with large amounts of emission showed higher predicted concentrations in air, and the concentrations of several compounds agreed well with averaged monitoring data within an order of magnitude. (2) A close relationship was found between the concentration of water and that of sediment, suggesting that the fate of chemicals in sediment essentially depended on the water environment. (3) A group of volatile solvents had high mass distribution ratio to air. Some compounds having high solubility in water were also included in that group due to the high ratio of air emission. Highly hydrophobic compounds with logK(OW) larger than 6.0 showed a high distribution ratio to soil and sediment. (4) Volatile compounds were mostly taken through air. The exposure through fish is a dominant pathway for highly hydrophobic compounds. (5) Exposure ratio could be gathered from physicochemical properties. The exposure from fish intake was roughly estimated by logK(OW), whereas exposure from air and water intake was difficult to estimate simply by vapor pressure and solubility in water, respectively.     

Emission and fate assessment of methyl tertiary butyl ether in the Boston area airshed using a simple multimedia box model: comparison with urban air measurements

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 microg/m3 MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 microg/m3 and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (*OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

De novo formation characteristics of dioxins in the dry zone of an iron ore sintering bed

The objectives of this work are to understand the details of the mechanism of dioxin formation in the part of a sintering bed termed the dry zone, and to obtain ideas on how to prevent their formation. Sinter mixtures of various composition types were heated in a packed bed reactor, and dioxins in the outlet gas and in the sinter mixture residue were measured. The dioxin formation potential of a simple sinter mixture composed of iron ore, coke and limestone was markedly lower than that of fly ash from a municipal solid waste incinerator (MSWI). In consideration of this result, a series of experiments were conducted using a sinter mixture impregnated with CuCl2. Experimental results showed that dioxin formation was temperature-dependent in the range of 300-550 degrees C, with the maximum observed at around 300 degrees C, which was quite similar to that of fly ash from the MSWI. The homologue distribution of PCDD/Fs in gas and solid reflected the possible difference in carbonaceous materials in coke and activated coke. Gaseous hydrogen chloride acted as a chlorinating reagent for dioxin formation.     

Formation characteristics of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and coplanar PCBs in fly ash from a gasification–melting process of municipal solid waste

PCDDs/DF and Co-PCB (dioxin) formations were studied with ash from a newly developed gasification and melting process for municipal solid waste. Ash samples were heated in a laboratory-scale fixed-bed reactor. Emphasis was placed on the effects of the type and composition of ash, temperatures, gas residence time, and gaseous organic precursors. Investigations using macroscopic and homologue distribution analyses led to the following conclusion. The ash from the gasification–melting process had the ability to generate dioxins in flue gas. A possible carbon source is unburned carbon in the ash samples, although this was very low (less than 0.01%). An experimental result that the level of dioxins generated from preheated fly ash obtained from a conventional incinerator was much lower than that from nonheated fly ash supported this conclusion. Dioxin concentrations obviously showed temperature dependence and peaked at 350°C. Dioxins formed in a gasification–melting process ash were readily desorbed from the surface, probably because of the low carbon content of the ash. There was no experimental evidence that gaseous organic precursors fed to the reactor generated dioxins. Therefore, an organic precursor was not essential for the formation of dioxins. A good linear relationship obtained between PCDDs/DFs and gas residence time also supported the assumption. Received: February 14, 2000 / Accepted: June 30, 2000     

Catalyst durability in steam reforming of thermally decomposed waste wood

Thermal gasification and reforming technologies applicable over a wide temperature range were investigated for high efficiency and for the calorific value of the gas evolved from organic waste such as woody debris. The durability of the reforming catalyst and the availability of catalyst regeneration were investigated using laboratory-scale catalytic reformers and a gasifier. Commercial Ni-based catalyst and calcined limestone (CaO) were applied to the reforming reaction. The results of woody waste gasification and reforming revealed the hydrogen concentration produced to be sustained at a high catalyst temperature of 1123 K, which prevented the catalyst from deactivating. The results also indicated that catalyst regeneration by air oxidation at the same temperature would be effective for enhancing catalytic activity.     

Effects of pH on the water solubility and 1-octanol-water partition coefficient of 2,4,6-tribromophenol

2,4,6-Tribromophenol (TBP) is expected to exist in both ionic and non-ionic forms in the environment due to ionisation of the phenolic group at near neutral pH. In this study, the water solubility (Sw) and 1-octanol-water partition coefficient (Kow) of aqueous solutions of TBP at various pH values were measured using the shake flask method. The ionisation resulted in increasing Sw and decreasing Kow by two to three orders of magnitude. From the experimental results, the environmental partitioning characteristics of TBP and the effect of pH on partitioning were discussed through a comparison with the properties of tetrabromobisphenol A (TBBP-A), which has two phenolic groups. Furthermore, the pH dependence of Sw and Kow was represented using a Henderson-Hasselbalch type model and the validity of the model was evaluated. The model was found to be highly useful for predicting the pH dependence within the range of pH 3 to 9.     

Characterization of semi-volatile organic compounds emitted during heating of nitrogen-containing plastics at low temperature

Because of recent volume increases, appropriate management of plastic recycling, which generates various organic compounds, is required to ensure the chemical safety of the processes. The processing temperature and resin type are the important factors determining both the efficiency of the processes and the emission of chemicals. Therefore, we studied the thermal degradation of various plastics at various temperatures from 70 to 300 °C under oxygen-present conditions to identify the semi-volatile organic compounds (SVOCs) emitted and to understand their thermal behaviors. The plastics examined were nitrogen-containing resins, such as polyamide 6, polyurethane, melamine formaldehyde, urea formaldehyde and acrylonitrile-butadiene-styrene. Major commodity plastics were also investigated for comparison. In total, more than 500 SVOCs were detected as emissions from plastics. While various nitrogen-containing SVOCs were detected from nitrogen-containing resins, the major commodity plastics released only these, which possibly were included as additives. These results indicate that the nitrogen atoms in the SVOCs emitted originated from the resins and additives, and not from ambient air at low temperature. As a result of the detection of raw materials, degradation chemicals and by-products of the polymers in the emissions, we found that the variation in chemical species is dependent on the resins. Additives were also emitted from all the resins, meaning that these chemicals were also released to the environment at the temperature examined. In most cases, the numbers and concentrations of SVOCs increased with increasing heating temperature. The variation of thermal behaviors of SVOCs was related to the origins and chemical species of SVOCs.     

Physicochemical properties of selected polybrominated diphenyl ethers and extension of the UNIFAC model to brominated aromatic compounds

The aqueous solubilities (S(w)) at various temperatures from 283 K to 308 K and 1-octanol/water partition coefficients (K(ow)) for four polybrominated diphenyl ethers (PBDEs: 4,4'-dibromodiphenyl ether (BDE-15), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153)) were measured by the generator column method. The S(w) and K(ow) data revealed the effect of bromine substitution and basic structure on S(w) and K(ow). To estimate the infinite dilution activity coefficients (gamma(i)(w,infinity)) of the PBDEs in water from the S(w) data, enthalpies of fusion and melting points for those compounds were measured with a differential scanning calorimeter. Henry's Law constants (H(w)) of the PBDEs were derived from the determined gamma(i)(w,infinity) and literature vapor pressure data. Some physicochemical characteristics of PBDEs were also suggested by comparing the present property data with that of polychlorinated dibenzo-p-dioxins, brominated phenols and brominated benzenes in past studies. Furthermore, in order to represent different phase equilibria including solubility and partition equilibrium for other brominated aromatic compounds using the UNIFAC model, a pair of UNIFAC group interaction parameters between the bromine and water group were determined from the S(w) and K(ow) data of PBDEs and brominated benzenes. The ability of the determined parameters to represent both properties of brominated aromatics was evaluated.