Chapter three: methodology of exposure modeling

In this chapter, the concept of exposure assessment and its evolution is introduced, and evaluated by critically appraising the pertinent literature as it applies to exposures to Particulate Matter (PM). Exposure measurement or estimation methodologies and models are reviewed. Three exposure/measurement methodologies are assessed. Estimation methods focus on source evaluation and attribution, sources include those outdoors and indoors as well as in occupational and in-transit environments. Fate and transport models and their inputs are addressed to estimate concentrations outdoors and indoors; source attribution techniques help focus on the contributing sources. Activity pattern techniques are also reviewed and their use in exposure models to estimate inhalation exposure to PM is presented. Deterministic, regression and other stochastic models of exposure to PM are reviewed and evaluated. Strengths, limitations, assumptions and affirmations of the use of exposure assessment as an integral component of risk assessment and risk management are discussed in the conclusions and discussions section of this work.     

Distribution and levels of eight toxaphene congeners in different tissues of marine mammals, birds and cod livers

Levels and distribution of eight compounds of technical toxaphene (CTTs) were determined in different marine species (seals, cetaceans, birds, and fish). The eight CTTs included six commercially available and two chlorobornanes prepared in our lab. These congeners were present in all investigated samples. In agreement with earlier studies, the octachlorobornane B8-1413 (P-26) and the nonachlorobornane B9-1679 (P-50) were the most abundant congeners in most of the samples. In seal blubber, B8-1413 (P-26) and B9-1679 (P-50) contributed with up to approximately 80% (Weddell seal) to the sum of the eight CTTs. In seals from the northern hemisphere the nonachlorobornane was more abundant while in those from the southern hemisphere (Antarctic and Namibia), the octachlorobornane B8-1413 (P-26) usually appeared at higher concentrations. Depending on the species the contribution of the other congeners varied significantly. B9-1025 (P-62) ranged from 2-20%, B8-1412 was found at 4-25% with highest contribution in birds, and B8-2229 (P-44) was found at 5-15%. The remaining three congeners B7-1453, B8-1414 (P-40), and B8-1945 (P-41) were lower abundant except B8-1414 (P-40) which was found at high contribution in liver and kidney of birds. The sum of the eight CTTs ranged from 4 microg/kg to 1.4 mg/kg, depending on the species and region. In most of the seal blubber samples, PCBs and DDT were more abundant (factor 2-20) but Antarctic Weddell seals showed higher CTT levels than PCBs and DDT.     

Relationship between release of nitric oxide and CO2 and their dependence on oxidation reduction potential in wastewater treatment

Nitric oxide (NO) is an intermediate of denitrification process and can be produced by denitrifiers, nitrifiers and other bacteria. In our experiments we measured the dynamic flow of NO depending on oxidation reduction potential (ORP). Different ORP-ranges were related to various carbon loading stages in the wastewater treatment pilot plant. Nitrification and denitrification were achieved by a sequence of aeration and non-aeration periods. Our measurements show that different carbon loading conditions (low feed, balanced and overloaded conditions) did not change the range of the mixing ratio of NO emissions when the aeration conditions like air-flow and temperature were kept constant. Minimum and maximum NO mixing ratios were 34.7 and 91.8 ppbv; 52.3 and 91.3 ppbv; 57.6 and 109 ppbv for low feed, balanced and overloaded conditions, respectively. The curve of the NO graph relied on nitrification/denitrification dynamics. The dependence of NO release on different ORP and CO2-release during the various conditions are shown. Longer aeration times resulted in an increased release of gaseous NO. The net-release of NO g(-1) nitrogen removed was between 0.014% and 0.028%. The NO fluxes to the air were observed between 8.3 and 14.9 mg m(-2) d(-1) NO. The major release occurred during high aeration periods whereas the concentration of dissolved [NOaq] in the wastewater was less than 0.05% of the gaseous release due to very low solubility of the NO.     

Reactive transport modeling of processes controlling the distribution and natural attenuation of phenolic compounds in a deep sandstone aquifer

Reactive solute transport modeling was utilized to evaluate the potential for natural attenuation of a contaminant plume containing phenolic compounds at a chemical producer in the West Midlands, UK. The reactive transport simulations consider microbially mediated biodegradation of the phenolic compounds (phenols, cresols, and xylenols) by multiple electron acceptors. Inorganic reactions including hydrolysis, aqueous complexation, dissolution of primary minerals, formation of secondary mineral phases, and ion exchange are considered. One-dimensional (1D) and three-dimensional (3D) simulations were conducted. Mass balance calculations indicate that biodegradation in the saturated zone has degraded approximately 1-5% of the organic contaminant plume over a time period of 47 years. Simulations indicate that denitrification is the most significant degradation process, accounting for approximately 50% of the organic contaminant removal, followed by sulfate reduction and fermentation reactions, each contributing 15-20%. Aerobic respiration accounts for less than 10% of the observed contaminant removal in the saturated zone. Although concentrations of Fe(III) and Mn(IV) mineral phases are high in the aquifer sediment, reductive dissolution is limited, producing only 5% of the observed mass loss. Mass balance calculations suggest that no more than 20-25% of the observed total inorganic carbon (TIC) was generated from biodegradation reactions in the saturated zone. Simulations indicate that aerobic biodegradation in the unsaturated zone, before the contaminant entered the aquifer, may have produced the majority of the TIC observed in the plume. Because long-term degradation is limited to processes within the saturated zone, use of observed TIC concentrations to predict the future natural attenuation may overestimate contaminant degradation by a factor of 4-5.     

Environmental effects of one thousand years of copper production at Falun, central Sweden

Copper production in Falun, central Sweden, has emitted sulfur dioxide (SO2) and metals to the air during at least 1000 years. Emissions peaked in the 17th century when Falun produced 2/3 of the world's copper supply. This area offers unique opportunities to study long-term effects of acid deposition and metal pollution, including recovery following the three centuries of decreasing SO2 and metal deposition. Here we present a 1000-yr perspective on local emissions of SO2, estimated air concentrations and dry deposition of SO2, as well as results on acidification and metal pollution of soils and lakes. Despite a long period when deposition of SO2 exceeded the critical load, soil acidification is limited to the most heavily polluted area 12 km NW and SE from the mine. According to diatom analyses of take sediments, only 8 of 14 lakes have become acidified (0.4-0.8 pH units). None of these lakes show recovery from acidification, probably due to large amounts of sulfate still accumulated in the soils and changes in land use.     

Decrease of PCDD/F levels in human blood from Germany over the past ten years (1989-1998)

744 whole blood samples of normal subjects from Germany collected in 1989-1998 have been analyzed for polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) by capillary gas chromatography/high resolution mass spectrometry. Over the examined time period a continuous decrease of the PCDD/F concentrations in human blood was observed. The mean levels found were 43.7 pg I-TEq/g (lipid basis) in 1989 and 20.7 pg I-TEq/g (lipid basis) in 1996/98 [median: 42.2 and 19.4]. The reduction to about the half was found for most congeners. Each one-year subset of the collective and the entire collective shows a positive correlation of the PCDD/F blood levels with age for most of the congeners, the sum values and the calculated toxicity equivalents. For statistical evaluation a multiplicative model was used: Concentration = A x Age(B). The correlation is mostly pronounced for lower chlorinated PCDD and for 2,3,4,7,8-PentaCDF. The PCDD/F concentrations in human blood in relation to the year of examination and the age of the subjects can be described by a linear model: I-TEq [pg/g (lipid basis)] = 6176 - 3.097 x Year + 0.6482 x Age or by a multiplicative model: I-TEq [pg/g(lipid basis)] = 10(89.08-0.04415 x Year + 0.008468 x Age).     

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.     

The use of Littorina littorea for tributyltin (TBT) effect monitoring - Results from the German TBT survey 1994/1995 and laboratory experiments

Field investigations and laboratory experiments were performed to test the applicability of the intersex phenomenon in Littorina littorea for biological TBT-effect monitoring and to give further insights into toxicological aspects of intersex development. The intensity of the phenomenon is correlated with the degree of TBT contamination in the environment. Statistically highly significant correlations of biological indices and TBT concentrations in tissue and sediment exist. Intersex can be induced only in juvenile and sexually immature females and its intensity depends on the ontogenetic stage of development during TBT exposure. For the first time, malformations in male periwinkles closely related to the TBT contamination can be described; the reduction of male mamilliform penial glands shows highly significant correlations to TBT concentrations in tissues. The intersex phenomenon in Littorina littorea is proposed for a biological TBT-effect monitoring in those areas where the dogwhelk Nucella lapillus, as the more sensitive species in European surveys, is absent. The intersex index (ISI) as the mean value of the intersex stages in a sample should be used as the most sensitive biological parameter for the assessment of the TBT contamination in Littorina littorea.     

Modelling stomatal responses of spring wheat (Triticum aestivum L. cv. Turbo) to ozone and different levels of water supply

Spring wheat (Triticum aestivum L. cv. Turbo) was exposed to different levels of ozone and water supply in open-top chambers in 1991. Air was charcoal filtered (CF), non-filtered (NF) and CF plus proportional addition of ambient or twice ambient ozone (CF1, CF2). Seasonal means of O(3), taken over 24 h, were 2.3, 20.6, 17.3, and 34.5 nl litre(-1) for CF, NF, CF1 and CF2 treatments, respectively. A split-plot design was used to obtain two levels of water supply: one-half of the pots was irrigated sufficiently not to show any symptoms of drought stress; the others were exposed to low water supply and received 50% of these amounts. Using a steady-state porometer approximately 800 measurements of stomatal conductance (g(s)) were made on flag leaves from 68 to 106 days after sowing. The measurements yielded only small differences of maximum conductance between the two levels of water supply. Therefore, low water supply did not protect wheat plants against ozone injury via reduced stomatal uptake in this experiment. To describe the effects of environmental variables on the stomatal behaviour, boundary-line analysis and non-linear regression analysis were used. Besides microclimatic parameters, the ozone dose of flag leaves was introduced as an independent variable affecting stomatal aperture. A well-defined boundary line for ozone dose was found, suggesting that increasing ozone dose caused stomatal closure in wheat flag leaves. But at high ozone doses, co-acting senescence seems also responsible for the decrease in stomatal conductance. A multiplicative boundary-line model was used to predict stomatal conductance from combinations of environmental variables. In the test carried out with the measurements of stomatal conductance, the model accounted only for 40% of the variation of g(s). Generalized stomatal response patterns of the herbaceous growth form, the dependence of the variables' age and ozone dose and the lack of an important factor influencing stomatal response (water status of the plant) in the model, are suggested as explanations of the poor results of the test.     

Uptake and metabolism of 2,4,6-trinitrotoluene in higher plants

The fate of the explosive 2,4,6-TNT in plants is of major interest. Therefore, a method was developed to analyse TNT and derivatives in plant tissue. The method was utilized to investigate the uptake and metabolism of TNT inMedicago sativa andAllium schoenoprasum grown in hydroponic cultures containing TNT levels of 0.1 to 10 mg/1. Detectable concentrations of nitrotoluenes were significantly higher inAllium schoenoprasum than inMedicago sativa. The uptake of TNT in plants was directly related to the initial TNT level. The principal nitroaromatic components in roots and shoots of both plant species were identified as 4-ADNT and 2-ADNT in equal amounts, with substantially less TNT.