The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer

Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.     

Monitoring of toxicity during degradation of selected pesticides using ionizing radiation

The optimization of experimental conditions for radiolytic removal of organic pollutants from water and waste with the use of ionizing radiation via controlling the concentration of target compound(s) requires also monitoring the toxicity changes during the process. Commonly used herbicides 2,4-D and dicamba were shown to increase toxicity measured with the Microtox test at low irradiation doses resulting from formation of more toxic transient products, which can be decomposed at larger doses. The changes of toxicity were examined with respect to dose magnitude and the presence of commonly occurring scavengers of radiation.     

Prediction of ozone concentration in ambient air using multivariate methods

Multivariate statistical methods including pattern recognition (Principal Component Analysis--PCA) and modeling (Multiple Linear Regression--MLR, Partial Least Squares--PLS, as well as Principal Component Regression--PCR) methods were carried out to evaluate the state of ambient air in Miskolc (second largest city in Hungary). Samples were taken from near the ground at a place with an extremely heavy traffic. Although PCA is not able to determine the significance of variables, it can uncover their similarities and classify the cases. PCA revealed that it is worth to separate day and night data because different factors influence the ozone concentrations during all day. Ozone concentration was modeled by MLR and PCR with the same efficiency if the conditions of meteorological parameters were not changed (i.e. morning and afternoon). Without night data, PCR and PLS suggest that the main process is not a photochemical but a chemical one.     

Emission rates and comparative chemical composition from selected in-use diesel and gasoline-fueled vehicles

Emission samples for toxicity testing and detailed chemical characterization were collected from a variety of gasoline- and diesel-fueled in-use vehicles operated on the Unified Driving Cycle on a chassis dynamometer. Gasoline vehicles included normal particle mass (particulate matter [PM]) emitters (tested at 72 and 30 degrees F), "black" and "white" smokers, and a new-technology vehicle (tested at 72 degrees F). Diesel vehicles included current-technology vehicles (tested at 72 and 30 degrees F) and a high PM emitter. Total PM emission rates ranged from below 3 mg/mi up to more than 700 mg/mi for the white smoker gasoline vehicle. Emission rates of organic and elemental carbon (OC/EC), elements (metals and associated analytes), ions, and a variety of particulate and semi-volatile organic compounds (polycyclic aromatic hydrocarbons [PAH], nitro-PAH, oxy-PAH, hopanes, and steranes) are reported for these vehicles. Speciated organic analysis also was conducted on the fuels and lube oils obtained from these vehicles after the emissions testing. The compositions of emissions were highly dependent on the fuel type (gasoline vs. diesel), the state of vehicle maintenance (low, average, or high emitters; white or black smokers), and ambient conditions (i.e., temperature) of the vehicles. Fuel and oil analyses from these vehicles showed that oil served as a repository for combustion byproducts (e.g., PAH), and oil-burning gasoline vehicles emitted PAH in higher concentrations than did other vehicles. These PAH emissions matched the PAH compositions observed in oil.     

Application and evaluation of two air quality models for particulate matter for a southeastern U.S. episode

The Models-3 Community Multiscale Air Quality (CMAQ) Modeling System and the Particulate Matter Comprehensive Air Quality Model with extensions (PMCAMx) were applied to simulate the period June 29-July 10, 1999, of the Southern Oxidants Study episode with two nested horizontal grid sizes: a coarse resolution of 32 km and a fine resolution of 8 km. The predicted spatial variations of ozone (O3), particulate matter with an aerodynamic diameter less than or equal to 2.5 microm (PM2.5), and particulate matter with an aerodynamic diameter less than or equal to 10 microm (PM10) by both models are similar in rural areas but differ from one another significantly over some urban/suburban areas in the eastern and southern United States, where PMCAMx tends to predict higher values of O3 and PM than CMAQ. Both models tend to predict O3 values that are higher than those observed. For observed O3 values above 60 ppb, O3 performance meets the U.S. Environmental Protection Agency's criteria for CMAQ with both grids and for PMCAMx with the fine grid only. It becomes unsatisfactory for PMCAMx and marginally satisfactory for CMAQ for observed O3 values above 40 ppb. Both models predict similar amounts of sulfate (SO4(2-)) and organic matter, and both predict SO4(2-) to be the largest contributor to PM2.5. PMCAMx generally predicts higher amounts of ammonium (NH4+), nitrate (NO3-), and black carbon (BC) than does CMAQ. PM performance for CMAQ is generally consistent with that of other PM models, whereas PMCAMx predicts higher concentrations of NO3-, NH4+, and BC than observed, which degrades its performance. For PM10 and PM2.5 predictions over the southeastern U.S. domain, the ranges of mean normalized gross errors (MNGEs) and mean normalized bias are 37-43% and -33-4% for CMAQ and 50-59% and 7-30% for PMCAMx. Both models predict the largest MNGEs for NO3- (98-104% for CMAQ 138-338% for PMCAMx). The inaccurate NO3- predictions by both models may be caused by the inaccuracies in the ammonia emission inventory and the uncertainties in the gas/particle partitioning under some conditions. In addition to these uncertainties, the significant PM overpredictions by PMCAMx may be attributed to the lack of wet removal for PM and a likely underprediction in the vertical mixing during the daytime.     

The dissipation,distribution and fate of a branched 14C-nonylphenol isomer in lake water/sediment systems

A single tertiary isomer which is believed to be one of the major branched isomers of the isomeric nonylphenol was synthesized for use in investigations on its metabolism and estrogenicity in aquatic organisms. The physico-chemical properties of the isomer were determined to enable the prediction of its behaviour in aquatic environments. From laboratory investigations on its dissipation and distribution in lake water, which are reported in this paper, it was found that it had a half-life of dissipation of 38.1 days and 20.1 days in an open lake water and in an open lake water/ sediment system, respectively, and to be rapidly partitioned in to sediment giving a high concentration factor of 1.76 after 28 days with an initial dose concentration of 2.52 ppm. The main dissipation route was found to occur through volatilization and co-distillation. The isomer was, however, found to be resistant to biodegradation in both the lake water and sediment, showing only a slight 9% loss (after 56 days) and 4.2% loss (after 28 days), of the 14C-residues in lake water and lake water/sediment systems, respectively, by microbial activity. Transformation to other more polar metabolites possibly by hydroxylation was also found to be minimal in both lake water and sediment samples after 14 days by HPLC analysis. After 7 days, only 2.25 and 7.4% transformation to a more polar metabolite was detected in lake water and sediment samples, respectively.     

Volatile metabolites from indoor molds grown on media containing wood constituents

Since volatile mold metabolites are used for the detection of mold growth in buildings, it was interesting to determine whether different indoor mold species show different affinity for the major components of wood, a common building material. Growth and volatile metabolites were studied when Aspergillus versicolor, Penicillium chrysogenum, and P. palitans were grown on laboratory substrates containing the major wood constituents cellulose, xylan and lignin. Microbial volatile organic compounds (MVOCs) were characterized by thermal desorption/gas chromatography/mass spectroscopy. Growth and volatile metabolites varied considerably and there appeared to be complementary substrate specificities for P. chrysogenum, and P. palitans grown on cellulose and xylan. The failure of A. versicolor to produce characteristic MVOCs when grown on media containing wood constituents suggests that systems using volatile metabolites to detect microbial growth in buildings may be fundamentally unreliable for the detection of this species.     

Influence of ageing on zinc bioavailability in soils

Currently, soil quality criteria or soil risk assessments of metals are based on laboratory toxicity tests which are carried out in soils freshly spiked with metal salts. With these data, species sensitivity distributions are fitted, from which hazardous concentrations and predicted no effect concentrations are derived. However, due to long-term processes, called ageing, soil metal availability decreases with time. Here we show that pH is the most important parameter determining the effect of ageing on zinc partitioning in soils, with the effect of ageing becoming more important with increasing pH. Furthermore, zinc bioavailability, expressed as the internal zinc concentrations in red clover (Trifolium pratense) is closely related to pore water zinc concentration. In addition, there is a clear dose-response relationship between the survival of the earthworm Eisenia fetida and the calcium chloride-extracted zinc fraction. These results indicate that zinc partitioning can be used to predict zinc bioavailability to terrestrial organisms. However, the use of spiked soils in toxicity assays can result in an over-estimation of the effects of zinc, especially at a high pH.     

Relationship between volatile organohalogen compounds in drinking water and human urine in Poland

Selected volatile organohalogen compounds (VOX) were investigated in urine samples from people living in different areas of the Gdańsk-Sopot-Gdynia TriCity (Poland). The analytes were isolated and preconcentrated using the so-called thin layer headspace technique with autogenous generation of the liquid sorbent. Final gas chromatographic determination was carried out by direct aqueous injection with electron capture detection. Analyte concentrations in drinking water ranged from not detected to approximately 8 microg/l (chloroform), depending on the source of drinking water in a given part of the TriCity (underground, surface or mixed). The corresponding urine levels were typically lower by about an order of magnitude. VOX levels in urine of people living in the parts of the TriCity supplied with drinking water containing elevated levels of the analytes were higher than the levels in urine of people whose drinking water originated from deep underground wells. The linear correlation coefficients for the relationships between total VOX and chloroform levels in drinking water and in urine were r2=0.65 and 0.88, respectively. The fraction of VOX excreted with urine in unchanged form did not exceed 20%.     

Surface Consolidation of Pentelic Marble: Criteria for the selection of methods and materials - The Acropolis case (6 pp)

Goal and Scope In order to realize surface consolidation of Pentelic marble on the Acropolis monuments, we have collected the criteria that have to be fulfilled by the methods and materials without side effects on the marbles (and other stones). When the existing methods and materials did not satisfy the requirements (criteria), we invented new ones.Methods The criteria were collected from the literature, by thermodynamic and kinetic viewpoints, by laboratory experiments and in situ observations on monuments, both in Greece and in several countries in which the various methods and materials were applied. Concerning our method of ‘Inversion of sulfation’, performed by spraying a K2CO3 solution, its concentration and its temperature were controlled in order to have a total inversion (certified by liquid crystals) of gypsum back to CaCO3. For the new material of ours, ‘Reinforced Lime’, in order to eliminate the disadvantages of plain lime (low carbonation rate, low mechanical properties of CaCO3 formed, lack of carbonation in the bulk of lime), measurements of the rate of carbonation were performed in plain lime and in lime with a different CaCO3 concentration beforehand as well as in a different CO2 environments, using DTG and XRD to measure the rate of carbonation. The detachment (kg/cm2) of marble specimens stuck by lime in each case was also measured. A microscope was also used to measure the dimensions of the grain in each case as well as ammonium citrate and thymolphthalein to certify the depth of carbonation in each case. Part of the work was communicated in an international congress.Results A table with the criteria of the selection of the methods and materials for the consolidation of Pentelic marble surfaces (and other stones) was established. None of the employed methods and materials fulfilled the criteria. Only the ‘Inversion of gypsum ‘ and the ‘Reinforced Lime’ were adopted and applied to the Acropolis monuments and to other monuments in Greece and in several other countries.Recommendation and Outlook All criteria must be used for the selection of methods and materials for the consolidation of the monument surfaces. This is why we have already studied with the same procedures, methods and materials for restoration, surface cleaning and protection.