Priority assessment of toxic substances in life cycle assessment. Part I: calculation of toxicity potentials for 181 substances with the nested multi-media fate, exposure and effects model USES-LCA

Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. In most cases, toxicity potentials are calculated with multi-media fate models. Until now, unrealistic system settings were used for these calculations. The present paper outlines an improved model to calculate toxicity potentials: the global nested multi-media fate, exposure and effects model USES-LCA. It is based on the Uniform System for the Evaluation of Substances 2.0 (USES 2.0). USES-LCA was used to calculate for 181 substances toxicity potentials for the six impact categories freshwater aquatic ecotoxicity, marine aquatic ecotoxicity, freshwater sediment ecotoxicity, marine sediment ecotoxicity, terrestrial ecotoxicity and human toxicity, after initial emission to the compartments air, freshwater, seawater, industrial soil and agricultural soil, respectively. Differences of several orders of magnitude were found between the new toxicity potentials and those calculated previously.     

TiO2 photocatalytic degradation of PCBs in soil-water systems containing fluoro surfactant

Titanium dioxide-mediated photodegradation of Polychlorinated biphenyls (PCBs) in soil/aqueous systems with added fluorinated surfactant was investigated. PCBs can bind tightly to organic matter in the soil, especially in aged, contaminated soil. Experiments showed an effective PCB photocatalytic degradation in mixed systems of soil/clay with anionic fluorinated surfactant FC-143 and TiO2. The FC-143 surfactant is stable in this photochemical process. PCB degradation rates in samples followed the order: spiked clay > spiked soil > Hudson River bank soil. The results suggest that anionic fluorinated surfactant may form semimicelles and/or admicelles on the surface of positively charged TiO2. The hydrophobic surface of TiO2 can provide a nonpolar phase that acts as a partioning medium for hydrophobic PCBs. Therefore, PCBs in soil can be released to the semimicelle and/or admicelle on the TiO2 surface and are effectively photodegraded in a dispersion containing anionic fluorinated surfactant. The combination of surfactant extraction and photooxidation forms the basis for a novel two-stage process for the removal and destruction of PCBs from soil.     

Ground discarded tires remove naphthalene, toluene, and mercury from water

Ground discarded tires adsorb naphthalene, toluene, and mercury ions (Hg2+) from aqueous solutions. Their sorption properties and kinetics were determined by batch equilibration techniques at 20 degrees C. The isotherms were linear for naphthalene and toluene and their sorption coefficients were about 1340 and 255 (ml/g), respectively. Sorption of the organic compounds by the ground rubber particles was relatively fast (within 30 min). However, the mercury isotherms were non-linear, and its sorption was slow as compared to the sorption of the organics. The rubber particles had a strong affinity for Hg2+. These results show that ground discarded tires are effective in removing organic compounds and Hg2+ from wastewater and other contaminated environments. In addition it would be a useful, environmentally friendly use of discarded tires (one tire per year per capita is discarded in the United States).     

Replacement of H2O2 by O2 in Fenton and photo-Fenton reactions

The consumption of oxygen during the degradation of aniline by Fenton and photo-Fenton reactions is studied. The effect that parameters like aniline, Fe(II) and H2O2 initial concentration, pH, temperature and O2 flow rate have on the ratio O2 consumed/H2O2 consumed is examined. The determination of those combinations of experimental conditions for which an effective partial replacement of H2O2 by O2 as electron acceptor takes place is investigated. The results show that this replacement takes place in a variable extent, but the presence of H2O2 is necessary along the reaction, and the maximum consumption of O2 only takes place when the ratio amount of aniline mineralized vs. initial aniline concentration is minimal.     

Microbial degradation of phthalic acid esters under anaerobic digestion of sludge

The microbial degradation by anaerobic sludge of three phthalates, priority pollutants, listed by both China National Environmental Monitoring Center and the U.S.EPA, namely, dimethyl (DMP), di-n-butyl (DBP) and di-n-octyl (DOP) phthalates was investigated. The experimental results indicated that the biodegradation rate and the biodegradability of three phthalates under anaerobic conditions appeared to be related to the length of the alkyl-side chains. More than 90% of DMP and DBP with the short alkyl-side chain phthalates can be degraded, whereas the DOP degradation appeared to be relatively slow under the same experimental conditions. The quantity of methane produced was measured and the results showed that both the ester groups and the phthalate ring were mineralized at a significant rate. The kinetics study demonstrated that the biodegradation of three phthalates conformed to the first-order model with respect to their concentrations.     

Development of a sample equilibration system for the TEOM continuous PM monitor

In recent years, scientific discussion has included the influence of thermodynamic conditions (e.g., temperature, relative humidity, and filter face velocity) on PM retention efficiency of filter-based samplers and monitors. Method-associated thermodynamic conditions can, in some instances, dramatically influence the presence of particle-bound water and other light-molecular-weight chemical components such as particulate nitrates and certain organic compounds. The measurement of fine particle mass presents a new challenge for all PM measurement methods, since a relatively greater fraction of the mass is semi-volatile. The tapered element oscillating microbalance (TEOM) continuous PM monitor is a U.S. Environmental Protection Agency (EPA) PM10 equivalent method (EQPM-1090079). Several hundred of these monitors are deployed throughout the United States. The TEOM monitor has the unique characteristic of providing direct PM mass measurement without the calibration uncertainty inherent in mass surrogate methods. In addition, it provides high-precision, near-real-time continuous data automatically. Much attention has been given to semi-volatile species retention of the TEOM method.     

Comparison of particulate mass, chemical species for urban, suburban and rural areas in central Taiwan, Taichung

Aerosol samples for PM2.5, PM(2.5-10) and TSP were collected from June to September 1998 and from February to March 1999 in central Taiwan. Ion chromatography was used to analyze the acidic anions: sulfate, nitrate and chloride in the Universal samples. The ratios of fine particle concentrations to coarse particle concentrations displayed that the fine particle concentrations are almost greater than that of coarse particle concentrations in Taichung area. The average concentrations of PM2.5, PM(2.5-10) and TSP in urban sites are higher than in suburban and rural sites at both daytime and night-time. Chloride dominated in the coarse mode in daytime and in fine mode in night-time. Nitrate can be found in both the coarse and fine modes. Sulfate dominated in fine mode in both daytime and night-time.     

The photocatalytic disinfection of urban waste waters

In this paper we present the results of the photocatalytic disinfection of urban waste water. Two microbial groups, total coliforms and Streptococcus faecalis, have been used as indexes to test disinfection efficiencies. Different experimental parameters have been checked, such as the effect of TiO2, solar or UV-lamp light and pH. Disinfection of water samples has been achieved employing both UV-lamp and solar light in agreement with data shown by other authors. The higher disinfection rates obtained employing an UV-lamp may be explained by the stronger incident light intensity. Nevertheless no consistent differences have been found between TiO2-photocatalysis and direct solar or UV-lamp light irradiation at natural sample pH (7.8). At pH 5 the presence of TiO2 increases the relative inactivation rate compared with the absence of the catalyst. After the photocatalytic bacterial inactivation, the later bacterial reappearance was checked for total coliforms at natural pH and pH 5, with and without TiO2. Two h after the photocatalytic treatment, CFU increment was almost nill. But 24 and 48 h later an important bacterial CFU increment was observed. This CFU increment is slower after irradiation with TiO2 at pH 5 in non-air-purged samples.     

Photooxidation mechanism of nitrogen-containing compounds at TiO2/H2O interfaces: an experimental and theoretical examination of hydrazine derivatives

The photocatalytic oxidation of oxalyldihydrazide, N,N'-bis(hydrazocarbonyl)hydrazide, N,N'-bis(ethoxycarbonyl)hydrazide, malonyldihydrazide, N-malonyl-bis[(N'-ethoxycarbonyl)hydrazide] was examined in aqueous TiO2 dispersions under UV illumination. The photomineralization of nitrogen and carbon atoms in the substrates into N2 gas, NH4+ (and/or NO3-) ions, and CO2 gas was determined by HPLC and GC analysis. The formation of carboxylic acid intermediates also occurred in the photooxidation process. The photocatalytic mechanism is discussed on the basis of the experimental results, and with molecular orbital (MO) simulation of frontier electron density and point charge. Substrate carbonyl groups readily adsorb on the TiO2 surface, and the bonds between carbonyl group carbon atoms and adjacent hydrazo group nitrogen atoms are cleaved predominantly in the initial photooxidation process. The hydrazo groups were photoconverted mainly into N2 gas (in mineralization yields above 70%) and partially to NH4 ions (below 10%). The formation of NO3- ions was scarcely recognized.     

Monitoring, modelling and environmental exposure assessment of industrial chemicals in the aquatic environment

Monitoring and laboratory data play integral roles alongside fate and exposure models in comprehensive risk assessments. The principle in the European Union Technical Guidance Documents for risk assessment is that measured data may take precedence over model results but only after they are judged to be of adequate reliability and to be representative of the particular environmental compartments to which they are applied. In practice, laboratory and field data are used to provide parameters for the models, while monitoring data are used to validate the models' predictions. Thus, comprehensive risk assessments require the integration of laboratory and monitoring data with the model predictions. However, this interplay is often overlooked. Discrepancies between the results of models and monitoring should be investigated in terms of the representativeness of both. Certainly, in the context of the EU risk assessment of existing chemicals, the specific requirements for monitoring data have not been adequately addressed. The resources required for environmental monitoring, both in terms of manpower and equipment, can be very significant. The design of monitoring programmes to optimise the use of resources and the use of models as a cost-effective alternative are increasing in importance. Generic considerations and criteria for the design of new monitoring programmes to generate representative quality data for the aquatic compartment are outlined and the criteria for the use of existing data are discussed. In particular, there is a need to improve the accessibility to data sets, to standardise the data sets, to promote communication and harmonisation of programmes and to incorporate the flexibility to change monitoring protocols to amend the chemicals under investigation in line with changing needs and priorities.