Environmental assessment of 5-ethylidene-2-norbornene using modeled and measured fate and effects results

Several predictive models were used to assess aquatic exposure, persistence (P) and potential for long-range transport (LRT) of 5-ethylidene-2-norbornene (ENB). Such estimations are components of the assessment process for persistent, bioaccumulative and toxic (PBT) substances, which are also referred to as persistent organic pollutants (POPs). An ecological exposure assessment for ENB from manufacturing activities was conducted based on physical/chemical properties, monitoring data, and degradation, transport and distribution estimates. Based on the results of several model predictions, chronic exposure of aquatic organisms is not expected, due to the anticipated residence time of ENB in aquatic ecosystems. These modeled results consistently predict ENB does not present the potential to persist in the environment. Volatilization from water to the air is calculated to occur at a relatively rapid rate for ENB based on its Henry's Law constant. Once in the air, ENB is expected to degrade rapidly due to oxidation by hydroxyl radicals and ozone based on calculated atmospheric half-lives of 57 and 27 min, respectively. Additionally, ENB is not predicted to undergo long-range transport based on the short atmospheric half-life due to oxidation by hydroxyl radicals and ozone. Additionally, based on predicted exposure from site-specific emission using the EPA model EFAST, ENB is not expected to reach concentrations of concern for chronic aquatic toxicity endpoints.     

Comparison of two methods for obtaining degradation half-lives

Given the paucity of experimental degradation half-life data for most organic chemicals, there is a compelling incentive to use available estimation software when undertaking assessments of chemical persistence and mass balance modeling studies. In this study, half-life data obtained from estimation software for a set of 233 organic chemicals in air, water, soil and sediments were shown to differ significantly from half-life data listed in handbooks. It is suggested that the widely available and used estimation software, EPIWIN (Estimations Program's Interface for Windows), overestimates the reactivity of persistent organic pollutants (POPs). Reasons for this overestimation are explored. It is concluded that the maximum "default half-life values" used by the EPIWIN software are too short for estimating half-lives of highly persistent chemicals such as PCBs. There is a need for estimation software such as EPIWIN to be more thoroughly calibrated against experimental derived half-life data for a wide range of chemicals, including potential POPs, thus improving their reliability.     

Chemical fate,latitudinal distribution and long-range transport of cyclic volatile methylsiloxanes in the global environment: A modeling assessment

Cyclic volatile methylsiloxanes (cVMS) such as octamethycyclotetrasiloxane (D4), decamethycyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are widely used as intermediates in the synthesis of high-molecular weight silicone polymers or as ingredients in the formulation of personal care products. The global environmental fate, latitudinal distribution, and long range transport of those cVMS were analyzed by two multimedia chemical fate models using the best available physicochemical properties as inputs and known persistent organic pollutants (POPs) and highly persistent volatile organic chemicals (“fliers”) as reference. The global transport and accumulation characteristics of cVMS differ from those of typical POPs in three significant ways. First, a large fraction of the released cVMS tends to become airborne and is removed from the global environment by degradation in air, whereas known POPs have a tendency to be distributed and persistent in all media. Secondly, although cVMS can travel a substantial distance in the atmosphere, they have little potential for deposition to surface media in remote regions. This contrasts with a deposition potential of known POPs that exceeds that of cVMS by 4–5 orders of magnitude. Thirdly, cVMS have short global residence times with the majority of the global mass removed within 3 months of the end of release. Global residence times of POPs on the other hand are in years. The persistent fliers resemble the cVMS with respect to the first two attributes, but their global residence times are more like those of the POPs.     

Long-range transport and global fractionation of POPs: insights from multimedia modeling studies

The long-range transport of persistent organic pollutants (POPs) is investigated with two multimedia box models of the global system. ChemRange is a purely evaluative, one-dimensional steady-state (level III) model; CliMoChem is a two-dimensional model with different temperatures, land/water ratios and vegetation types in different latitudinal zones. Model results are presented for three case studies: (i) the effect of atmospheric aerosol particles on the long-range transport of POPs, (ii) the effect of oceanic deposition on the long-range transport of different PCB congeners, (iii) the global fractionation of different PCB congeners. The model results for these case studies show: (i) the low atmospheric half-lives estimated for several organochlorine pesticides are likely to be inconsistent with the observed long-range transport of these compounds; (ii) export to the deep sea reduces the potential for long-range transport of highly hydrophobic compounds (but does not remove these chemicals from the biosphere); (iii) there are different meanings of the term global fractionation that refer to different aspects of the fractionation process and need to be distinguished. The case-study results further indicate that the influences of varying environmental conditions on the physicochemical properties and the degradation rate constants of POPs need to be determined.     

Identification of substances with potential for long-range transport as possible substances of very high concern

According to the European legislation, REACH, organic compounds are considered as substances of very high concern (SVHC) if they are persistent, bioaccumulative and toxic (PBT). A substance's long-range transport potential (LRTP) may also pose a risk to remote regions. This is, however, not yet explicitly included. For identification of compounds, which are not PBT according to REACH criteria, but show LRTP, we investigated 22,438 compounds from the Canadian Domestic Substance List (CDSL). The CDSL was searched for organic, neutral compounds. Substance properties were estimated with EPI Suite v4.00. Next, the substance list was edited in two ways: (1) The half-life criterion in air for LRTP as defined in the Stockholm Convention was applied. (2) For all compounds, indicators for persistence and LRTP were calculated with the multimedia model ELPOS v2.2. Applying the half-life criterion, we identified 594 substances, which are prone to LRT but are not PBT (non-PBT-L substances). In contrast, investigations with ELPOS lead to a shorter list of 188 substances, which are non-PBT-L substances. Finally, the list was compared with potential Arctic contaminants identified in previous literature. Our results show that there is a large number of organic chemicals which would not be considered as SVHC since they are not, at the same time, persistent, bioaccumulative and toxic according to REACH criteria. Nevertheless, they show LRTP according to different screening approaches and thus a potential hazard to remote regions.     

The spatial scale of organic chemicals in multimedia fate modeling. Recent developments and significance for chemical assessment

In the last years, the spatial range (SR) or characteristic travel distance (CTD) of organic chemicals has found increasing scientific interest as an indicator of the long-range transport (LRT) potential and, in combination with persistence, as a kind of 'hazard' indicator on the exposure level. This development coincides with European debates about more effective and more preventive approaches to the chemicals assessment, and about an international, legally-binding instrument for the phase out of persistent organic pollutants (POPs). Persistence and LRT potential are important issues in these debates. Here, the development of the concept of assessing the spatial scale from early ideas in the 1970s and 1980s to recent studies in the field of multimedia fate and transport modeling is summarized. Different approaches to the modeling of environmental transport (advective and dispersive) and different methods for quantifying the SR or CTD are compared. Relationships between SR or CTD and different persistence measures are analyzed. Comparison of these relationships shows that conclusions for chemical assessment should be based on an evaluation of different persistence and spatial scale measures. The use of SR or CTD and persistence as hazard indicators in the chemicals assessment is illustrated.     

Energy transfer and kinetics in mechanochemistry

Mechanochemistry (MC) exerts extraordinary degradation and decomposition effects on many chlorinated, brominated, and even fluorinated persistent organic pollutants (POPs). However, its application is still limited by inadequate study of its reaction kinetic aspects. In the present work, the ball motion and energy transfer in planetary ball mill are investigated in some detail. Almost all milling parameters are summarised in a single factor—total effective impact energy. Furthermore, the MC kinetic between calcium oxide/Al and hexachlorobenzene is well established and modelled. The results indicate that total effective impact energy and reagent ratio are the two factors sufficient for describing the MC degradation degree of POPs. The reaction rate constant only depends on the chemical properties of reactants, so it could be used as an important index to appraise the quality of MC additives. This model successfully predicts the reaction rate for different operating conditions, indicating that it could be suitably applied for conducting MC reactions in other reactors.

     

Polychlorinated Biphenyls (PCBs) in Mussels along the Chilean Coast

- DOI: http://dx.doi.org/10.1065/espr2006.01.011 Goal, Scope and Background Chile signed the Stockholm Convention, which establishes measures to reduce or eliminate Persistent Organic Pollutants (POPs) release into the environment, including the prohibition of their use and reduction of secondary products release, as well as management related with waste treatment. Among POPs, PCBs are a family of 209 compounds that differ in chlorine level and position. These substances present a wide variability in their physicochemical properties such as vapor pressure, water solubility and partition coefficients that determine their behavior and mobility within the different environmental compartments. In Chile, as in other countries, the use of these compounds were and continue to occur in diverse industrial applications such as dielectric fluid in transformers and condensers, with a use in Chile of approximately 550,000 L. A sampling of bivalves was performed during the years 2000-2002 in order to obtain information on the spatial distribution of the PCB levels for the length of the long Chilean coast (180–540 South latitude, 4,200 km), contributing in this way to a better understanding of the PCB trend and eventual fractionation along latitudinal gradients in Chile, using as the bivalve Perumytilus purpuratus ('Chorito Maico') bioindicator. Methods The marine bivalves Perumytilus purpuratus were collected in 16 localities in northern and southern Chile. All samples were lyophilized, and PCBs (51 congeners) were extracted in a Soxhlet system (24 h) with n-hexane. Samples were cleaned in florisil and analyzed by GC-ECD. Blanks, certified reference materials and standards were processed along with the samples. Results and Discussion The results obtained for P. purpuratus indicate a congeneric distribution profile associated to a latitudinal gradient, and the statistical analysis of the congeneric composition of the PCBs indicated five groups in relation to the molecular weight (number of chlorines), where the lighter congeners were observed in areas corresponding to high latitudes with total PCB values of 298 ng/g dry weight. Conclusion P. purpuratus turns out to be a good bioindicator of PCB levels in the coastal areas of Chile due to its wide distribution. The highest concentrations and the more volatile congeners were found in southern Chile, which could be the result of processes of long-range transport or illegal discharge occurring in such remote areas. These results confirm previous data from the International Mussel Watch project ten years ago. Recommendation and Outlook Future studies are needed to confirm our findings utilizing another environmental matrix such as soil/sediments and air samples.     

Current issues and uncertainties in the measurement and modelling of air-vegetation exchange and within-plant processing of POPs

Air-vegetation exchange of POPs is an important process controlling the entry of POPs into terrestrial food chains, and may also have a significant effect on the global movement of these compounds. Many factors affect the air-vegetation transfer including: the physicochemical properties of the compounds of interest; environmental factors such as temperature, wind speed, humidity and light conditions; and plant characteristics such as functional type, leaf surface area, cuticular structure, and leaf longevity. The purpose of this review is to quantify the effects these differences might have on air/plant exchange of POPs, and to point out the major gaps in the knowledge of this subject that require further research. Uptake mechanisms are complicated, with the role of each factor in controlling partitioning, fate and behaviour process still not fully understood. Consequently, current models of air-vegetation exchange do not incorporate variability in these factors, with the exception of temperature. These models instead rely on using average values for a number of environmental factors (e.g. plant lipid content, surface area), ignoring the large variations in these values. The available models suggest that boundary layer conductance is of key importance in the uptake of POPs, although large uncertainties in the cuticular pathway prevents confirmation of this with any degree of certainty, and experimental data seems to show plant-side resistance to be important. Models are usually based on the assumption that POP uptake occurs through the lipophilic cuticle which covers aerial surfaces of plants. However, some authors have recently attached greater importance to the stomatal route of entry into the leaf for gas phase compounds. There is a need for greater mechanistic understanding of air-plant exchange and the 'scaling' of factors affecting it. The review also suggests a number of key variables that researchers should measure in their experiments to allow comparisons to be made between studies in order to improve our understanding of what causes any differences in measured data between sites.     

Relationship of approaches and a tiered methodology for screening chemicals in the context of long-range transport.

In many national and international initiatives, where thousands of chemicals are screened, the ability of a chemical to be transported over long distances is an important criterion in determining whether environmental concern is warranted. Preliminary screening can be conducted using: (1) effective travel distance (ETD); (2) characteristic travel distance (CTD); and/or (3) the degradation half-life in air. The CTD is the distance traveled before the concentration of a chemical in air is reduced by a factor of 50%, for example. Differences in the distance traveled associated with the environmental release medium of a chemical are taken into account the ETD measure. The ETD can be defined as the distance traveled before the concentration in a stated medium (air, water, soil or sediment) is reduced to a specified level for a given mass release rate to air, to water and/or to soil. However, despite their merits, the use of multimedia screening measures like the ETD and CTD remains inhibited by both the limited availability of degradation data (particularly for soils and sediments) and release pattern information. Preliminary screening in terms of the atmospheric degradation half-life is commonly the only practical option. In this paper, straightforward guidelines based on partitioning coefficients (Henry's law constant and octanol water partitioning coefficient) are proposed to reduce the degradation data requirements of multimedia measures like the ETD and CTD. The values used in the guidelines reflect a quantifiable trade-off between data acquisition requirements and uncertainty. The relationship of the potential screening options (using all degradation data versus using only data identified as required in the CTD and ETD approaches; screening in terms of the degradation half-life in air versus the CTD versus the ETD) is derived and the consequences of the differences are illustrated. A three-tiered screening methodology is then proposed. This tiered methodology will result in significant savings in time and money in national and international screening initiatives.     

The maximum reservoir capacity of soils for persistent organic pollutants: implications for global cycling

The concept of maximum reservoir capacity (MRC), the ratio of the capacities of the surface soil and of the atmospheric mixed layer (AML) to hold chemical under equilibrium conditions, is applied to selected persistent organic pollutants (POPs) in the surface 'skin' (1 mm) of soils. MRC is calculated as a function of soil organic matter (SOM) content and temperature-dependent K(OA) and mapped globally for selected PCB congeners (PCB-28; -153; -180) and HCB, to identify regions with a higher tendency to retain POPs. It is shown to vary over many orders of magnitude, between compounds, locations and time (seasonally/diurnally). The MRC approach emphasises the very large capacity of soils as a storage compartment for POPs. The theoretical MRC concept is compared to reality and its implications for the global cycling of POPs are discussed. Sharp gradients in soil MRC can exist in mountainous areas and between the land and ocean. Exchanges between oceans and land masses via the atmosphere is likely to be an important driver to the global cycling of these compounds, and net ocean-land transfers could occur in some areas.     

Contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs): Application to Southeastern France

A modeling approach has been developed to estimate the contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs). It combines an Eulerian chemical transport model for atmospheric processes (Polair3D/Polyphemus) with a fate and transport model for soil and vegetation (Ourson). These two models were specifically adapted for POPs. Results are presented for benzo(a)pyrene (BaP). As expected no accumulation of BaP in leaf vegetables appears during the growth period for each harvest over the 10 years simulated. For BaP and leaf vegetables, this contamination depends primarily on direct atmospheric deposition without chemical transfer from the soil to the plant. These modeling results are compared to available data.