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.     

Geographical scenario uncertainty in generic fate and exposure factors of toxic pollutants for life-cycle impact assessment

In environmental life-cycle assessments (LCA), fate and exposure factors account for the general fate and exposure properties of chemicals under generic environmental conditions by means of 'evaluative' multi-media fate and exposure box models. To assess the effect of using different generic environmental conditions, fate and exposure factors of chemicals emitted under typical conditions of (1).Western Europe, (2). Australia and (3). the United States of America were compared with the multi-media fate and exposure box model USES-LCA. Comparing the results of the three evaluative environments, it was found that the uncertainty in fate and exposure factors for ecosystems and humans due to choice of an evaluative environment, as represented by the ratio of the 97.5th and 50th percentile, is between a factor 2 and 10. Particularly, fate and exposure factors of emissions causing effects in fresh water ecosystems and effects on human health have relatively high uncertainty. This uncertainty is mainly caused by the continental difference in the average soil erosion rate, the dimensions of the fresh water and agricultural soil compartment, and the fraction of drinking water coming from ground water.     

Comparison of toxicological impacts of integrated and chemical pest management in Mediterranean greenhouses

The goal of this paper is to assess the relative impacts of pest-control methods in greenhouses, based on current LCA tools. As a case study, the relative impacts of two tomato production methods, chemical pest management (CPM) and integrated pest management (IPM), are assessed. The amount of the active ingredients applied, the fate of the ingredients in the various greenhouse and environmental compartments, the human exposure routes via the various compartments and the inherent toxicity of the ingredients were taken into account in the relative impact calculations. To assess the importance of model selection in the assessment, pesticide-specific fate and exposure factors for humans and aquatic and terrestrial ecosystems, used to aggregate pesticide emissions, were calculated with two different models: (1) the USES-LCA model, adapted in order to calculate the pesticide transfer from greenhouse air and soil to fruits, and (2) the empirical model critical surface time (CST). Impact scores have in general shown a higher level of potential contamination in greenhouses treated with CPM compared to IPM (a factor of 1.4 to 2.3). Relative impacts have been shown highly dependent on the selection of specific pesticides and crop stage development at the moment of pesticide application. This means that both CPM and IPM could be improved by a careful selection of pesticides. In order to improve the relative impact calculations, future research in pesticide transfer to food will be necessary.     

Human intake fractions of pesticides via greenhouse tomato consumption: comparing model estimates with measurements for Captan

Human intake due to pesticide residues in food commodities can be much higher than those related to water consumption and air inhalation, stressing the importance to correctly estimate pesticide uptake into plants and predict subsequent intake by humans. We calculated the human intake fraction of captan via tomato consumption taking into account the time between pesticide application and harvest, the time between harvest and consumption, the absorption of spray deposit on plant surfaces, transfer properties through the cuticle, degradation inside the plant and loss due to food processing. Human population intake fractions due to ingestion were calculated for complete, washed and peeled tomatoes. The calculated intake fractions were compared with measurements derived from an experimental setup in a Mediterranean greenhouse. The fraction of captan applied in the greenhouse as plant treatment that eventually is ingested by the human population is on average 10(-2)-10(-5), depending on the time between pesticide application and ingestion of tomatoes and the processing step considered. Model and experimentally derived intake fractions deviated less than a factor of 2 for complete and washed tomatoes and a factor of 3 for peeled tomatoes. Intake fractions due to air inhalation and consumption of drinking water are expected to be significantly lower (5-9 orders of magnitude) than those induced by the intake of tomatoes in this case study.     

Substituent effects on azo dye oxidation by the FeIII-EDTA-H2O2 system

Toxicity potentials are scaling factors used in life cycle assessment (LCA) indicating their relative importance in terms of potential toxic impacts. This paper presents the results of an uncertainty assessment of toxicity potentials for 181 substances that were calculated with the global nested multi-media fate, exposure and effects model USES-LCA. The variance in toxicity potentials resulting from choices in the modelling procedure was quantified by means of scenario analysis. A first scenario analysis showed to what extent potential impacts in the relatively short term are obscured by the inclusion of impacts on the very long term. Toxicity potentials representing potential impacts over time horizons of 20, 100 and 500 years were compared with toxicity potentials representing potential impacts over an infinite time horizon. Time horizon dependent differences up to 6.5 orders of magnitude were found for metal toxicity potentials, while for toxicity potentials of organic substances under study, differences remain within 0.5 orders of magnitude. The second scenario analysis addressed to what extent potential impacts on the continental scale are obscured by the inclusion of impacts on the global scale. Exclusion of potential impacts on the global scale changed the toxicity potentials of metals and volatile persistent halogenated organics up to 2.3 orders of magnitude. These scenario analyses also provide the basis for determining exports to future generations and outside the emission area.     

Evaluating multimedia/multipathway model intake fraction estimates using POP emission and monitoring data

This paper presents a structured evaluation of a novel multimedia chemical fate and multi-pathway human exposure model for Western Europe, IMPACT 2002, using data for PCDD/F congeners. PCDD/F congeners provide an illustration of the potential use of POPs (Persistent Organic Pollutant) data for the evaluation of such models. Based on available emission estimates, model predictions with and without spatial resolution are evaluated at three different stages against monitored data: at environmental contamination levels, food exposure concentration, and in terms of human intake fractions (iF): the fraction of an emission that is taken in by the population. The iF is approximately 3.5.10(-3) for emissions of dioxin in Western Europe. This iF compares well to the traditional non-spatial multi-media/-pathway model predictions of 3.9.10(-3) for the same region and to 2.10(-3) for the USA. Approximately 95% of the intake from Western European emissions occurs within the same region, 5% being transferred out of the region in terms of food contaminants and atmospheric advective transport.     

Spatial variance in multimedia mass balance models: comparison of LOTOS-EUROS and SimpleBox for PCB-153

The aim of this study was to determine whether nested generic box models can be used to predict spatial variance. An inter-comparison study was performed for the nested box model SimpleBox, and the spatially resolved model LOTOS-EUROS, using PCB-153 emissions in Europe as an example. We compared the two models concerning (1) average environmental concentrations, (2) spatial concentration variances, (3) spatial concentration patterns (maps), and (4) agreement with measured concentrations for the air and soil compartments. In SimpleBox, the spatial concentration variances and patterns were calculated subsequently for each separate grid cell surrounded by a regional and a continental shell with homogeneous, averaged circumstances. Average European PCB-153 concentrations calculated by LOTOS-EUROS and SimpleBox for the period 1981-2000 agree well for the air and soil compartments. Moreover, the predicted concentrations of both models are in line with the measured PCB-153 concentrations in Europe during that period. For PCB-153, the prediction of spatial concentration variances with the nested multimedia fate model SimpleBox performs adequately in most cases, except for the lower concentration boundary in the air compartment. It is concluded that SimpleBox can be used to predict the spatial maximum and average concentrations of PCB-153 in the air and soil compartments. The proposed method has to be tested systematically for different types of compounds, emission scenarios, environmental compartments and spatial scales in order to allow conclusions about the general applicability of the method.     

Calculation of environmental concentration and comparison of output for existing chemicals using regional multimedia modeling

The environmental fate of 40 existing chemicals is discussed using the EUSES multimedia distribution and risk assessment model with site-specific parameter setting in an urban area of Japan including a highly industrial region. There has been a strong need to assess the environmental fate of a huge number of existing chemicals. Data on the emission amounts of chemicals are essential for such prediction, and PRTR surveys may yield this data. The study delivered the following results: (1) Volatile compounds with large amounts of emission showed higher predicted concentrations in air, and the concentrations of several compounds agreed well with averaged monitoring data within an order of magnitude. (2) A close relationship was found between the concentration of water and that of sediment, suggesting that the fate of chemicals in sediment essentially depended on the water environment. (3) A group of volatile solvents had high mass distribution ratio to air. Some compounds having high solubility in water were also included in that group due to the high ratio of air emission. Highly hydrophobic compounds with logK(OW) larger than 6.0 showed a high distribution ratio to soil and sediment. (4) Volatile compounds were mostly taken through air. The exposure through fish is a dominant pathway for highly hydrophobic compounds. (5) Exposure ratio could be gathered from physicochemical properties. The exposure from fish intake was roughly estimated by logK(OW), whereas exposure from air and water intake was difficult to estimate simply by vapor pressure and solubility in water, respectively.     

An environmental fate, exposure and risk assessment of ethylene oxide from diffuse emissions

Ethylene oxide (EO) is mainly used as a chemical intermediate and as a fumigant and sterilizing agent. Through its manufacturing and intended uses, EO may be released into the environment. Therefore, an assessment of the environmental significance of those potential emissions was conducted. Data were collected describing pertinent physical properties, degradation and other loss mechanisms that control the fate of EO in the environment. Available aquatic and terrestrial ecotoxicity data were assembled and used as the basis of calculating critical toxicity values to characterize hazard. Environmental compartment concentrations of EO were calculated using Level III fugacity-based modeling. Six scenarios were developed to account for different climatic conditions in various portions of the US. Finally, potential regional-scale risks to aquatic and terrestrial wildlife were determined. In the conceptual model that was developed in this assessment, EO diffuses into air, partitions between environmental compartments, is transported out of the different compartments via advection, and undergoes abiotic and biological degradation within each compartment. All known emissions within the continental USA were assumed to enter a modeled region roughly the size of the State of Ohio. Organisms (receptors) were assumed to dwell in both terrestrial and aquatic compartments. Receptors were assumed to include small mammals, soil invertebrates, water column (pelagic) organisms, and sediment benthos. The goal of this assessment was to characterize any potential adverse risks to terrestrial and aquatic wildlife populations. Hazard Quotients (HQ) were calculated by dividing predicted concentrations of EO in air, water, sediment, and soil by their critical toxicity values. Maximum calculated HQ values in air were 1.52x10(-7), in water were 1.17x10(-5), in sediment were 2.25x10(-4), and in soil were 1.37x10(-5). The results of this assessment suggest that EO as currently manufactured and used does not pose adverse risks to aquatic or terrestrial wildlife. In all cases, the HQ values were much less than the maximum desired HQ value of 1.0 (4,400-6,600,000 times), indicating that the potential for diffuse emissions of EO to pose adverse environmental risks is quite low.     

Uncertainty analysis using a fugacity-based multimedia mass-balance model: Application of the updated EQC model to decamethylcyclopentasiloxane (D5)

The EQuilibrium Criterion (EQC) model developed and published in 1996 was recently revised to include improved treatment of input partitioning and reactivity data, temperature dependence and an easier sensitivity and uncertainty analysis. This New EQC model was used to evaluate the multimedia, fugacity-based fate of decamethylcyclopentasiloxane (D5; CAS No. 541-02-6) in the environment over a temperature range of 1–25 °C. In addition, Monte Carlo uncertainty analysis was used to quantitatively determine the influence of temperature and input partitioning and reactivity data on the behavior of D5 under various emission scenarios. Results indicated that emission mode was the most influential factor determining the fate and distribution of D5 in the model environment. When emitted to air and soil, D5 partitioned to and remained in the air compartment where rates of removal from degradation and advection processes were relatively rapid. In contrast, D5 emitted to water resulted in a substantial mass fraction of D5 being accumulated in the sediment compartment, where rates of removal from degradation and advection processes were slow. The mass distributions and fate of D5 in the model environment were strongly influenced by multiple input parameters, including temperature, the mode of emission (especially emission rate to water), K_OC and half-life in air. As temperature decreased from 25 °C to 1 °C, K_OC and half-life in air became increasingly more influential such that the mass distribution of D5 increased in air and decreased in sediment, resulting in decreased overall persistence.     

Priority assessment of toxic substances in life cycle assessment. Part II: assessing parameter uncertainty and human variability in the calculation of toxicity potentials

Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. This paper presents the results of an uncertainty assessment of toxicity potentials that were calculated with the global nested multi-media fate, exposure and effects model USES-LCA. The variance in toxicity potentials resulting from input parameter uncertainties and human variability was quantified by means of Monte Carlo analysis with Latin Hypercube sampling (LHS). For Atrazine, 2,3,7,8-TCDD and Lead, variation, expressed by the ratio of the 97.5%-ile and the 2.5%-ile, ranges from about 1.5 to 6 orders of magnitude. The major part of this variation originates from a limited set of substance-specific input parameters, i.e. parameters that describe transport mechanisms, substance degradation, indirect exposure routes and no-effect concentrations. Considerable correlations were found between the toxicity potentials of one substance, in particular within one impact category. The uncertainties and correlations reported in the present study may have a significant impact on the outcome of LCA case studies.     

Multimedia fate of petroleum hydrocarbons in the soil: Oil matrix of constructed biopiles

A dynamic multimedia fugacity model was used to evaluate the partitioning and fate of petroleum hydrocarbon fractions and aromatic indicator compounds within the soil: oil matrix of three biopiles. Each biopile was characterised by four compartments: air, water, soil solids and non-aqueous phase liquid (NAPL). Equilibrium partitioning in biopile A and B suggested that most fractions resided in the NAPL, with the exception of the aromatic fraction with an equivalent carbon number from 5 to 7 (EC₅₋₇). In Biopile C, which had the highest soil organic carbon content (13%), the soil solids were the most important compartment for both light aliphatic fractions (EC₅₋₆ and EC₆₋₈) and aromatic fractions, excluding the EC₁₆₋₂₁ and EC₂₁₋₃₅. Our starting hypothesis was that hydrocarbons do not degrade within the NAPL. This was supported by the agreement between predicted and measured hydrocarbon concentrations in Biopile B when the degradation rate constant in NAPL was set to zero. In all scenarios, biodegradation in soil was predicted as the dominant removal process for all fractions, except for the aliphatic EC₅₋₆ which was predominantly lost via volatilization. The absence of an explicit NAPL phase in the model yielded a similar prediction of total petroleum hydrocarbon (TPH) behaviour; however the predicted concentrations in the air and water phases were significantly increased with consequent changes in potential mobility. Further comparisons between predictions and measured data, particularly concentrations in the soil mobile phases, are required to ascertain the true value of including an explicit NAPL in models of this kind.     

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.     

Carbon deposition in soil rhizosphere following amendments with compost and its soluble fractions, as evaluated by combined soil-plant rhizobox and reporter gene systems

We determined the organic carbon released by roots of maize plants (Zea mays L.) when grown in soils amended with compost and its soluble fractions. In rhizobox systems, soil and roots are separated from the soil of a lower compartment by a nylon membrane. Treatments are applied to the upper compartment, while in the lower compartment luminescent biosensors measure the bioavailable organic carbon released by roots (rhizodeposition). The rhizobox-plants systems were amended with a compost (COM), its water extract (TEA), the hydrophobic (HoDOM) and hydrophilic (HiDOM) fractions of the dissolved organic matter (DOM) extracted from the compost. After root development, the lower untreated compartments were sampled and sliced into thin layers. The bioavailable organic carbon in each layer was assessed with the lux-marked biosensor Pseudomonas fluorescens 10586 pUCD607, and compared with total organic carbon (TOC) analyses. The TOC values ranged between 8.4 and 9.6 g kg(-1) and did not show any significant differences between bulk and rhizosphere soil samples in any treatment. Conversely, the biosensor detected significant differences in available C compounds for rhizosphere soils amended with various organic materials. Concentrations of available organic compounds in the first 2 mm of soil rhizosphere were 1.69 (control), 1.09 (COM), 2.87 (HiDOM), 4.73 (HoDOM) and 2.14 (TEA)micromol Cg(-1) soil g(-1) roots. The applied rhizobox-biosensor integrated method was successful in detecting and quantifying effects of organic amendments on organic carbon released by maize plant roots. This approach may become important in assessing the carbon cycle in agricultural soils and soil-atmosphere compartments.     

Modelling the fate of persistent organic pollutants in Europe: parameterisation of a gridded distribution model

A regionally segmented multimedia fate model for the European continent is described together with an illustrative steady-state case study examining the fate of gamma-HCH (lindane) based on 1998 emission data. The study builds on the regionally segmented BETR North America model structure and describes the regional segmentation and parameterisation for Europe. The European continent is described by a 5 degrees x5 degrees grid, leading to 50 regions together with four perimetric boxes representing regions buffering the European environment. Each zone comprises seven compartments including; upper and lower atmosphere, soil, vegetation, fresh water and sediment and coastal water. Inter-regions flows of air and water are described, exploiting information originating from GIS databases and other georeferenced data. The model is primarily designed to describe the fate of Persistent Organic Pollutants (POPs) within the European environment by examining chemical partitioning and degradation in each region, and inter-region transport either under steady-state conditions or fully dynamically. A test case scenario is presented which examines the fate of estimated spatially resolved atmospheric emissions of lindane throughout Europe within the lower atmosphere and surface soil compartments. In accordance with the predominant wind direction in Europe, the model predicts high concentrations close to the major sources as well as towards Central and Northeast regions. Elevated soil concentrations in Scandinavian soils provide further evidence of the potential of increased scavenging by forests and subsequent accumulation by organic-rich terrestrial surfaces. Initial model predictions have revealed a factor of 5-10 underestimation of lindane concentrations in the atmosphere. This is explained by an underestimation of source strength and/or an underestimation of European background levels. The model presented can further be used to predict deposition fluxes and chemical inventories, and it can also be adapted to provide characteristic travel distances and overall environmental persistence, which can be compared with other long-range transport prediction methods.     

Congener-specific intake fractions for PCDDs/DFs and Co-PCBs: modeling and validation

Intake fractions (iFs) for emissions to air, water, and soil for 17 PCDDs/DFs and 12 Co-PCBs were calculated with a level III multimedia model and a food-chain exposure model in succession. The two integrated models were tested by comparing the predicted and measured concentrations in the environment and by comparing intakes through food. Measurement-based iFs were also calculated and compared with the model-based iFs. The air concentrations predicted by the fate model were close to the median of the observed concentrations, whereas the predicted soil and water concentrations were one-third to one-tenth the observed concentrations. This difference was large in case of PCDDs and Co-PCBs, which was explained by the past pollution such as commercial PCB products and PCDD impurities in chloronitrofen (CNP) and pentachlorophenol (PCP). For fish, the predicted and observed exposures agreed well each other. For meat and milk, the predicted exposures were about 10 times the observed exposures for PCDDs/DFs, whereas the predicted and observed values agreed well for Co-PCBs. When the model was modified to consider feeding of fish meal to livestock and geographic bias in feed-grass production, the predicted congener profile was comparable to the measured profile. The comparison also suggested that chickens should be modeled separately from other terrestrial livestock. The model-based iFs for air emission of OCDD and 2378-TCDD were 0.001% and 0.1%, respectively. The iFs of most Co-PCBs were higher than those of PCDDs/DFs. These iF differences suggest the importance of the fate factor in assessing emissions of the 29 congeners.     

Quantifying the global fractionation of polychlorinated biphenyls

Due to the wide range of their physical-chemical properties, polychlorinated biphenyls (PCBs) have played an important role in the derivation of the global fractionation hypothesis, which predicts changes in the composition of persistent organic pollutant mixtures with latitude. Recent historical emission estimates, the derivation of an internally consistent property data set, in combination with a zonally averaged global fate and transport model, allow a quantitative investigation of the compositional shifts PCBs experience as a function of environmental compartment, latitude and time. Model simulations reproduce the higher relative abundance of lighter PCB congeners with increasing latitude, observed in air and soil, and quantify the relative importance of partitioning, persistence and emissions in establishing PCB patterns. Compositional variations consistent with global fractionation, as well as inverted concentration profiles with higher levels in the Arctic than at lower latitudes, are consistent with only minor fractions of the global PCB inventory being transferred northward.     

Hazardous air pollutants in industrial area of Mumbai - India

Hazardous Air Pollutants (HAPs) have a potential to be distributed into different component of environment with varying persistence. In the current study fourteen HAPs have been quantified in the air using TO-17 method in an industrial area of Mumbai. The distribution of these HAPs in different environmental compartments have been calculated using multi media mass balance model, TaPL3, along with long range transport potential and persistence. Results show that most of the target compounds partition mostly in air. Phenol and trifluralin, partition predominantly into soil while ethyl benzene and xylene partition predominantly into vegetation compartment. Naphthalene has the highest persistence followed by ethyl benzene, xylene and 1,1,1 trihloro ethane. Long range transport potential is maximum for 1,1,1 trichloroethane. Assessment of human health risk in terms of non-carcinogenic hazard and carcinogenic risk due to exposure to HAPs. have been estimated for industrial workers and residents in the study area considering all possible exposure routes using the output from TaPL3 model. The overall carcinogenic risk for residents and workers are estimated as high as unity along with very high hazard potential.     

An assessment of the environmental fate and exposure of benzene and the chlorobenzenes in Canada

Systematic modelling of the fate of benzene and the chlorobenzenes is presented which follows a four-stage process of chemical classification, quantifying discharge rates and environmental concentrations, evaluative assessment of fate and regional mass balance modelling has been carried out for the southern Ontario region. The EQC model was applied to determine the principal transport and transformation processes experienced by this group of chemicals, which vary considerably in volatility and hydrophobicity. Observed environmental concentrations are in satisfactory agreement with the predictions of the steady state Level III ChemCAN model of chemical fate. A multiple pathway human exposure model which estimates intake of contaminants by residents of southern Ontario has been developed and applied to these chemicals. A novel method of deducing maximum tolerable environmental concentrations is presented. Results suggest that benzene and 1,4-dichlorobenzene are present in the environment at levels sufficient to cause exposures near allowable daily intake (ADI) levels for the general population, but the other substances are present at levels which result in exposure ranging from 1/10 to 1/1000 of the ADI.