An overview of TCDD half-life in mammals and its correlation to body weight

Major determinants of TCDD half-life in organisms are lipophilicity, metabolism, and hepatic binding sites. In addition, half-life seems to be empirically correlated to organism body weight. In this paper, this correlation is evaluated by a regression analysis of half-life measures and body weight data selected from the literature. Single exposure studies on laboratory mammals and human half-life data were specifically taken in consideration. The analysis outcome appears to be highly significant probably owing to the stability and generally slow metabolism of the substance in the organisms considered. The effect on half-life of factors other than body weight does not seem to influence significantly data dispersion around the regression line. The potential effects of a dose-dependent excretion cannot be excluded as toxicokinetic studies have been usually carried out at high exposure doses.     

Alumina as a model support in the formation and dechlorination of polychlorinated dibenzo-p-dioxins and dibenzofurans

Alumina was studied as a model matrix for formation and dechlorination reactions of PCDDs and PCDFs. Only small differences in PCDD and PCDF formation were found between de-novo synthesis on alumina and on fly ash. The amounts of PCDDs and PCDFs formed on acidic alumina were much larger than on neutral and alkaline alumina. OCDD and OCDF were rapidly dechlorinated on basic alumina.     

Methodology for estimating soil carbon for the forest carbon budget model of the United States, 2001

The largest carbon (C) pool in United States forests is the soil C pool. We present methodology and soil C pool estimates used in the FORCARB model, which estimates and projects forest carbon budgets for the United States. The methodology balances knowledge, uncertainties, and ease of use. The estimates are calculated using the USDA Natural Resources Conservation Service STATSGO database, with soil dynamics following assumptions based on results of site-specific studies, and area estimates from the USDA Forest Service. Forest Inventory and Analysis data and national-level land cover data sets. Harvesting is assumed to have no effect on soil C. Land use change and forest type transitions affect soil C. We apply the methodology to the southeastern region of the United States as a case study.     

A model for estimating the effects of fluctuations in long term meteorology on observed maximum acid gas levels

A model is proposed to estimate the effect of long term meteorology on maximum daily acid gas levels for each year of 10 years of data for Newcastle, New South Wales, Australia. The model assumes that (1) the probability density functions of both air pollution data and wind speed are lognormally distributed and (2), on average, an inverse relationship exists between air pollution levels and wind speed. Two acid gas monitoring stations in Newcastle and a nearby wind speed station have data which satisfy both these requirements. The maximum acid levels at both stations vary by a factor of about 3–4 over a ten-year period and the model shows that about half of this variation is directly related to fluctuations in the wind speed distribution, leaving the rest of the variation to be explained either by changes in emissions or more meteorological change. It is clear that, if the two prerequisite conditions hold, a significant proportion of the effect of long-term meteorological fluctions on maximum air pollutant levels may be explained by the model to within a reasonable accuracy.     

Effects of copper chloride on formation of polychlorinated dibenzofurans in model waste incineration in a laboratory-scale fluidized-bed reactor

Combustion experiments in a laboratory-scale fluidized-bed reactor have been performed to clarify the effects of copper chloride as a catalyst on polychlorinated dibenzofurans (PCDFs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl2 x 2H2O) as a catalyst, both of which contained polyvinyl chloride (PVC) as a chlorine source. Combustion temperature was set to 900 degrees C, and the amount of air supplied was twice as much as the theoretical amount. The experimental setup had been carefully planned to ensure avoidance of the influences of previous experiments. Results of these present experiments revealed that copper chloride in the waste increased the amount of PCDFs formed and made the homologue profile shifted towards the highly chlorinated species. Copper chloride contributes to PCDFs formation by promoting chlorination via catalytic reactions, whereby the reaction could be important in that organic matters are chlorinated directly by chlorinated compounds related to Deacon reaction such as copper chloride. It was elucidated that characteristic isomer distribution patterns appeared in case the waste contained copper chloride. It is probable in our experiment with copper chloride that PCDFs are mainly formed via catalytic reactions of copper compounds and carbon.     

An evaluation of three empirical air-to-leaf models for polychlorinated dibenzo-p-dioxins and dibenzofurans

Three empirical air-to-leaf models for estimating grass concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (abbreviated dioxins and furans) from air concentrations of these compounds are described and tested against two field data sets. All are empirical in that they are founded on simplistic bioconcentration and related approaches which rely on field data for their parameterization. One of the models, identified as the EPA Model, partitions the total air concentration into vapor and particle phases, and separately models the impact of both. A second model addresses only the vapor phase; grass concentrations are modeled as a function of vapor deposition. For the third model, it is assumed that the grass plants "scavenge" a fixed volume of air of dioxins, and hence grass concentrations are modeled as a simple product of total air concentration and a constant scavenging coefficient. Field data from two sites, a rural and an industrial site in the United Kingdom, included concurrent measurements of dioxins in air and field grass, and dioxin and furan depositions, for one 6-week sampling period. Principal findings include: (1) the EPA Model underpredicted grass concentrations at the rural field site by a factor of 2, while the Scavenging Model underpredicted grass concentrations by a factor of 3.8, and the Vapor Deposition Model significantly underpredicted grass concentrations (by a factor greater than 10), (2) the presence of high soil concentrations for some of the dioxins and furans at the industrial site appears to have caused higher grass concentrations and confounded the air-to-plant modeling exercise, (3) the Scavenging Model could be calibrated to the data set; however, a key premise of this model that vapor and particle phase dioxins equally impact the plants, is not supported by the field data, (4) measured depositions are highly correlated to but systematically lower than modeled depositions, which could be due to modeling assumptions or a systematic measurement bias.     

A model for estimating the potential biomagnification of chemicals in a generic food web: Preliminary development

GOAL, SCOPE AND BACKGROUND: Bioaccumulation and biomagnification of organic pollutants have been increasingly assessed and modeled during the last years. Due to the complexity of these processes and the large variability of food webs, setting generic assessments for these parameters is really difficult. Equilibrium models, based on a compound's lipophylicity, are the main tool in regulatory proposals, such as for identifying Persistent, Bioaccumulative and Toxic Substances (PBTs), although a refinement has been claimed by the scientific community. Toxicokinetic studies offer an alternative for these estimations, where biomagnification is modeled as a succession of bioaccumulation processes, each one regulated by toxicokinetic parameters. METHODS: A review of kinetic models covering species belonging to different trophic levels and with different ecological behavior has been conducted. The results were employed for setting a conceptual model for estimating the biomagnification potential in a generic food web, which was mathematically implemented through system dynamic models developed under data sheet software. Crystal Ball was then employed for allowing Monte Carlo based probabilistic calculations. Bioaccumulation laboratory assays have been performed to estimate toxicokinetic parameters in mussels (Mytilus edulis) with two PAHs (chrysene and benzo[a]pyrene). The contamination was delivered via food. The exposure period lasted more than one month followed then by a depuration phase. The contaminant content was determined on an individual basis on five replicates. RESULTS AND DISCUSSION:. The reviewed information suggested the development of a tiered conceptual biomagnification model, starting with a simplified food chain which can be refined to more realistic and complex models in successive levels. CONCLUSIONS: The mathematical implementation of the conceptual model offers tools for estimating the potential for bioaccumulation and biomagnification of chemicals under very different conditions. The versatility of the model can be used for both comparative estimations and for validating the model. RECOMMENDATIONS AND PERSPECTIVES: Since bioaccumulation and biomagnification processes are crucial elements for a proper risk assessment of chemicals, their estimation by mathematical models has been widely tested. However, inregulatory assessments, too simplistic models are still being used quite often. The biomagnification model presented in this study should be amore accurate alternative to these models. In comparison to other previously published biomagnification models, the present one covers the time variation of bioaccumulation using just a few toxicokinetic parameters.     

Simple model for estimating dry deposition velocity of ozone and its destruction in a polluted nocturnal boundary layer

Determining the destructions of both ozone and odd oxygen, O_x, in the nocturnal boundary layer (NBL) is important to evaluate the regional ozone budget and overnight ozone accumulation. This work develops a simple method to determine the dry deposition velocity of ozone and its destruction at a polluted nocturnal boundary layer. The destruction of O_x can also be determined simultaneously. The method is based on O₃ and NO₂ profiles and their surface measurements. Linkages between the dry deposition velocities of O₃ and NO₂ and between the dry deposition loss of O_x and its chemical loss are constructed and used. Field measurements are made at an agricultural site to demonstrate the application of the model. The model estimated nocturnal O₃ dry deposition velocities from 0.13 to 0.19 cm s^?1, very close to those previously obtained for similar land types. Additionally, dry deposition and chemical reactions account for 60 and 40% of the overall nocturnal ozone loss, respectively; ozone dry deposition accounts for 50% of the overall nocturnal loss of O_x, dry deposition of NO₂ accounts for another 20%, and chemical reactions account for the remaining 30%. The proposed method enables the use of measurements made in typical ozone field studies to evaluate various nocturnal destructions of O₃ and O_x in a polluted environment.     

Applicability of a sharp-interface model for estimating steady-state salinity at pumping wells--validation against sand tank experiments

A numerical sharp-interface model of saltwater and freshwater behavior was validated against experiments conducted in two small scale sand tanks. A simple algorithm was proposed to determine saltwater and freshwater withdrawal rates at a pumping well at which a total pumping rate was specified. Model estimates were compared with transient salinity breakthroughs and steady-state salinities of water extracted from pumping wells in the sand tanks. Experimental scenarios included various combinations of freshwater pumping and injection and saltwater pumping. The corresponding Nash-Sutcliffe model efficiency was 0.95, which showed that the agreement between observations and computed results was satisfactory.     

Analytical protocol for the analysis of polybrominated dibenzo-dioxins and dibenzofurans: Data quality objectives and single-laboratory evaluation

An analytical protocol for the measurement of part per billion and sub-part per billion levels of PBDDs and PBDFs in selected flame retardant chemicals (polybrominated diphenyloxides; PBDPO) was developed. The fractionation/enrichment procedures were optimized to minimize the effects of the PBDPOs upon the ability to recover and measure the PBDD/PBDFs. Results from the method validation show that the current methodology is capable of accuracies ranging from 70% to 150% at the 0.1 to 10 ppb levels while larger sample sizes (from 20–200 mg to 4 g) are necessary in order to meet the EPA target Test Rule limit of quantification (LOQ) requirements.     

Matrix effects on the de novo synthesis of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes

The formation of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes in de novo synthesis experiments have been studied on model fly ashes with a wide range of matrices. The model fly ash consisted of 18 selected matrices with the addition of CuCl(2) x 2H(2)O, activated charcoal and NaCl. The studied matrices were not restricted to the commonly investigated matrices with defined chemical composition (silica gel, alumina, florisil) and industrially produced adsorbents with silicate structures (diatomaceous earths), but also included natural occurring matrices (clays, kaolin, bentonite and feldspars). In addition fly ashes from a hazardous waste incinerator were included in the study for comparison. Differences in the isomer composition (homologue profiles and isomer patterns) of the substances formed by de novo synthesis experiments are discussed in dependence on the chemical composition of the studied matrices. The de novo synthesis experiments on matrices with silicate structures resulted in high concentration of mainly perchlorinated aromatic compounds while for other matrices in particular alkaline matrices a homologue shift to lower chlorinated homologues and lower formation rates were found. The paper discusses the resulting PCDD/PCDF pattern and compares them to the PCDD/PCDF profile found in naturally occurring kaolin and ball clay (illite).     

QSARs for the toxicity of polychlorinated dibenzofurans through DFT-calculated descriptors of polarizabilities, hyperpolarizabilities and hyper-order electric moments

DFT-B3LYP method with 6-31G(**) basis set was employed to fully optimize the electronic structures of 135 polychlorinated dibenzofurans and parent compound, namely dibenzofuran. It was demonstrated that polarizability anisotropy and mean polarizability could change sensitively and systematically with chlorine number and substitution pattern. And new quantitative structure-activity relationships (QSARs) focused on the binding affinities of aryl hydrocarbon receptor (AhR), aryl hydrocarbon hydroxylase (AHH) and 7-ethoxyresorufin O-deethylase (EROD) induction potencies of PCDFs were developed. It was concluded that polarizability anisotropy in conjunction with hyperpolarizabilties and hyper-order electric moments, e.g. octupole moments could well interpret the variation of toxicity of different congeners and dispersion interaction should be the leading form among various interactions. Although the terms of hyperpolarizabilities and hyper-order electric moments were not the same significant ones as polarizability anisotropy, the long-range interactions characterized by them should not be ignored in explaining the toxicity.     

Extraction of polychlorinated dibenzo-p-dioxins and dibenzofurans from solid samples using the Randall technique

This study deals with a new sample extraction technique which minimizes pollution in analytical laboratories whilst reducing sample preparation time and cost. The device uses the Randall technique for solid sample extraction, performed by immersion of the sample in boiling solvent. The fast solubilization operated by the hot solvent leads to a sharp reduction in extraction time. This method was tested for the extraction of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from different solid matrices using toluene as extractant, and compared with the conventional Soxhlet. The reduction in the extraction times (from 48 to 2 h) with an efficiency similar to or higher than that afforded by the conventional Soxhlet technique indicates the suitability of this method.     

Modeling the atmospheric transport and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in North America

The atmospheric fate of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was simulated for the year 2000 in North America using a SMOKE/CMAQ-based chemical transport model that was modified for this purpose. The 1999 USEPA emission inventories of PCDD/Fs and criteria pollutants were used. The 1995 Canadian emission inventory of criteria pollutants and the 1995 Canadian area source emissions for PCDD/Fs were used with the 2000 Canadian point source emissions. Modifications to CMAQ involved coupling it with dual organic matter (OM) absorption and black carbon (BC) adsorption models to calculate PCDD/F gas–particle partitioning. The model satisfactorily reproduced the particle bound fractions at all rural sites for which there were measured data and across the whole domain, the modeled vs. measured differences in particle bound fractions were less than 20% for nearly all congeners. The model predicted ambient air PCDD/F concentrations were also consistent with measurements. Simulated deposition fluxes were within 58% of direct measurements. PCDD/F atmospheric depositions to each of the Great Lakes were estimated for the year 2000. The results indicate that approximately 76% of the total deposition of PCDD/Fs to the Great Lakes (in W-TEQ, or toxic equivalent units as defined by the World Health Organization) is attributed to PCDD/Fs absorbed into OM in aerosol. For all of the lakes, more than 92% of all deposition is particle phase wet deposition and only 5–8% is particle phase dry deposition. Wet deposition from the gas phase is negligible. Of the 17 toxic PCDD/F congeners, the Cl_4–5DD/F compounds contribute approximately 70% to the total atmospheric deposition to the Great Lakes. The seasonal changes in the PCDD/F deposition flux track variations in ambient temperature.     

A study of polychlorinated dibenzo-p-dioxins and dibenzofurans in the atmosphere of Hong Kong

A total of 27 ambient air samples of were collected from six locations in Hong kong during the period of January-August, 2000 and analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). In all sampling locations, higher concentrations of PCDDs/PCDFs, ranging from 0.03 to 0.43 pg I-TEQ/m3 were measured in winter months (January and March) than in the summer months (July and August) of concentrations at 0.018-0.025 pg I-TEQ/m3. These concentrations are similar to annual ranges reported earlier for two Hong Kong urban sites and other urban cities in Asia. Europe, and the United States. Despite significant seasonal variations in ambient air concentrations of PCDD/Fs (expressed in I-TEQ) were observed, the congener profiles of all the samples in this study period were similar, with OCDD, 1,2,3,4,6,7,8-HpCDD, OCDF and 1,2,3,4,6,7,8-HpCDF being the predominant species. However, the homologue profiles for the samples collected at the six locations of this study were found to display significantly different spatial and seasonal trends.     

Simulation of long-term environmental dynamics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans using the dynamic multimedia environmental fate model and its implication to the time trend analysis of dioxins

Long term environmental fate of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were studied using the fugacity-based dynamic multimedia environmental fate model. New formulation about soil wind erosion into air was included into the model. Effect of process assumption, sensitivity analysis for parameters, and tentative validation against the measured sediment core analysis was performed. Mass fluxes between compartments were estimated by the dynamic modeling. From the model estimates, major mass fluxes coming from emission source were shown to go to the soil and water through wet/dry deposition, then go to degradation mainly in the soil and sediment. Major mass fluxes of TCDD and OCDD come from the impurities in CNP (Chlornitrofen) and PCP (Pentachlorophenol) directly into the soil. Consideration about multimedia environmental dynamics using the modeled mass fluxes was shown in the discussion.