Simulating behavior of petroleum compounds during refinery effluent treatment using the SimpleTreat model.

Distribution and elimination of petroleum products can be predicted in aerobic wastewater treatment plants (WWTPs) using models such as multimedia fate model SimpleTreat. An advantage of the SimpleTreat model is that it only requires a few basic properties of a chemical in wastewater to calculate partitioning, biodegradation and ultimately emissions to air, surface water and produced sludge. The SimpleTreat model structure reflects a WWTP scheme. However, refinery WWTPs typically incorporate more advanced treatment processes such as dissolved air flotation (DAF), a process that clarifies wastewaters by the removal of suspended matter such as oil or solids. The objective of this work was to develop a WWTP removal model that includes DAF treatment. To understand how including a DAF in the model affects the predicted concentrations of petroleum constituents in effluent, we replaced the primary sedimentation module in SimpleTreat with a module simulating DAF. Subsequently, we compared results from the WWTP-DAF model with results obtained with the original SimpleTreat model for a library of over 1500 representative hydrocarbon constituents. The increased air-water exchange in a WWTP-DAF unit resulted in higher predicted removal of volatile constituents. Predicted removal with DAF was on average 17% larger than removal with primary sedimentation. We compared modelled results with measured removal data from the literature, which supported that this model refinement continues to improve the technical basis of assessment of petroleum products.

Evolution of the sewage treatment plant model SimpleTreat: use of realistic biodegradability tests in probabilistic model simulations.

Given the large number of chemicals under regulatory scrutiny, models play a crucial role in the screening phase of the environmental risk assessment. The sewage treatment plant (STP) model SimpleTreat 3.1 is routinely applied as part of the European Union System for the Evaluation of Substances to estimate the fate and elimination of organic chemicals discharged via sewage. SimpleTreat estimates tend to be conservative and therefore only useful for lower-tier assessments. A probabilistic version of SimpleTreat was built on the updated version of the model (SimpleTreat 3.2, presented in a parallel article in this issue), embracing likeliest as well as worst-case conditions in a statistically robust way. Probabilistic parameters representing the variability of sewage characteristics, STP design, and operational parameters were based on actual STP conditions for activated sludge plants in Europe. An evaluation study was carried out for 4 chemicals with distinct sorption and biodegradability profiles: tonalide, triclosan, trimethoprim, and linear alkylbenzene sulfonate. Simulations incorporated information on biodegradability simulation studies with activated sludge (OECD 314B and OECD 303A tests). Good agreement for both median values and variability ranges was observed between model estimates and monitoring data. The uncertainty analysis highlighted the importance of refined data on partitioning and biodegradability in activated sludge to achieve realistic estimates. The study indicates that the best strategy to refine the exposure assessment of down-the-drain chemicals is by integrating higher-tier laboratory data with probabilistic STP simulations and, if possible, by comparing them with monitoring data for validation.

Evolution of the sewage treatment plant model SimpleTreat: applicability domain and data requirements.

SimpleTreat 3.1 is the sewage treatment plant (STP) model implemented in the European Union (EU) framework for the environmental risk assessment of chemicals. The model was originally designed for neutral hydrophobic chemicals, whereas many substances currently under regulatory scrutiny, are ionizable at environmental pH. Although the model has been adapted to describe ionization (SimpleTreat 3.1), the fate of organic ions is limited to the unbound aqueous phase, which seriously restricts the applicability domain. New regressions were implemented to estimate the sludge-water partition coefficient normalized to organic carbon (KOC ) of monovalent acids and bases from the octanol-water partition coefficient (KOW ), the dissociation constant (pKa) and the pH. We evaluated the updated model (SimpleTreat 3.2) with 10 test chemicals by comparing predictions with monitoring data collected from the literature. Test chemicals were specifically selected to challenge the applicability domain and to cover a wide range of functionality and physical-chemical properties. Although predicted effluent concentrations are generally conservative, SimpleTreat 3.2 provides reasonable estimates for use in lower-tier risk assessment for neutral and monovalent ionizable chemicals. The accuracy of the new KOC regressions is acceptable for monovalent acid but is lower for bases, for which measured sludge KOC is highly recommended. Measured KOC are also recommended for ionic surfactants and necessary for organic ligands, which may limit the applicability of SimpleTreat using a basic input data set. The conservative nature of model estimates reflects the default worst case, non-numerical parameterization of biodegradation rates and the assumption that biodegradation is limited to the unbound aqueous phase. The potential of refining the description of biodegradation using higher tier simulation tests is explored in a parallel article (Franco et al. this issue).

Field sensitivity distribution of macroinvertebrates for phosphorus in inland waters.

The magnitude of ecological damage caused by elevated phosphorus concentrations (C(P) ) in Dutch inland waters is expressed as the fraction of disappeared macroinvertebrate genera. We used field observations of species occurrence from 1980 to 2005 that were stored in the Limnodata Neerlandica to derive the presence of 867 aquatic macroinvertebrate genera in the water column of freshwater bodies with total phosphorus (P(tot) ) concentrations ranging from 0.001 to 40 mg/L. At concentrations > 0.3 mg/L, which is considered to cause nutrient enrichment of freshwater bodies, the disappeared fraction (DF) of macroinvertebrate genera can be described as a logistic function of the C(P) : DF = 1/(1 + 4.07/C( P)¹·¹¹). The logistic function suggests that half of the macroinvertebrate genera that potentially occur in the freshwater column in the Netherlands would disappear at a C(P) = 3.5 mg/L. This field-based effect expression resembles the cumulative sensitivity distribution function for a toxic substance based on the species sensitivity distribution (SSD) concept and exposure data. Whereas an SSD for a toxic chemical is derived from laboratory sensitivity data for a small number of species, our DF is derived from field observations of many macroinvertebrate genera at numerous C(P) levels. By applying this damage function to measured phosphorus in the rivers Rhine, Meuse, and Scheldt, we found that the observed C(P) values in 1975 imply diversity losses of 15% for the Rhine and Meuse, and 20% for the Scheldt. For 2000, the calculated diversity losses are 3% (Rhine), 6% (Meuse), and 9% (Scheldt). The cumulative genera sensitivity distribution function for phosphorus from national freshwater monitoring data can be applied in various environmental screening systems, such as multistress impact assessment of surface waters, and in life cycle impact assessment of products.

Spatial- and time-explicit human damage modeling of ozone depleting substances in life cycle impact assessment.

Depletion of the stratospheric ozone layer is mainly caused by emissions of persistent halocarbons of anthropogenic origin. The resulting increase of solar ultraviolet radiation at the Earth's surface is associated with increased exposure of humans and increased human health damage. Here we assessed the change in human health damage caused by three types of skin cancer and cataract in terms of (healthy) years of life lost per kiloton emission reduction of an ozone-depleting substance (ODS). This so-called characterization factor is used in Life Cycle Assessments (LCAs). Characterization factors are provided for the emissions of five chlorofluorocarbons, three hydrochlorofluorocarbons, three (bromine-containing) halons, carbon tetrachloride, methyl chloroform, and anthropogenic emissions of methyl bromide. We employed dynamic calculations on a global scale for this purpose, taking physical and social geographic data into account such as skin tones, population density, average age, and life expectancy. When emission rates of all ODSs in 2007 are multiplied by our characterization factors, the resulting number of years of life lost may be a factor of 5 higher than reported previously. This increase is merely explained through the global demographic development until 2100 we took into account.

Normalisation in product life cycle assessment: an LCA of the global and European economic systems in the year 2000.

In the methodological context of the interpretation of environmental life cycle assessment (LCA) results, a normalisation study was performed. 15 impact categories were accounted for, including climate change, acidification, eutrophication, human toxicity, ecotoxicity, depletion of fossil energy resources, and land use. The year 2000 was chosen as a reference year, and information was gathered on two spatial levels: the global and the European level. From the 860 environmental interventions collected, 48 interventions turned out to account for at least 75% of the impact scores of all impact categories. All non-toxicity related, emission dependent impacts are fully dominated by the bulk emissions of only 10 substances or substance groups: CO(2), CH(4), SO(2), NO(x), NH(3), PM(10), NMVOC, and (H)CFCs emissions to air and emissions of N- and P-compounds to fresh water. For the toxicity-related emissions (pesticides, organics, metal compounds and some specific inorganics), the availability of information was still very limited, leading to large uncertainty in the corresponding normalisation factors. Apart from their usefulness as a reference for LCA studies, the results of this study stress the importance of efficient measures to combat bulk emissions and to promote the registration of potentially toxic emissions on a more comprehensive scale.

Uncertainty in msPAF-based ecotoxicological effect factors for freshwater ecosystems in life cycle impact assessment.

Ecotoxicological effect factors are part of the analysis of relative impacts by chemical contaminants on ecosystems. Uncertainty distributions, represented by the 90% confidence interval, belonging to ecotoxicological effect factors for freshwater ecosystems were determined. This study includes 869 high production volume chemicals, related to 7 nonspecific toxic modes of action (TMoAs). The ecotoxicological effect factors are divided into a TMoA-specific part and a chemical-specific part. The 90% confidence interval of the TMoA-specific part of the effect factor ranges from 23 orders of magnitude for acrylate toxicity to 2 orders of magnitude for nonpolar narcosis. The range in the TMoA-specific part of the effect factor is mainly caused by uncertainty in the spread in toxic sensitivity between species (sigma(j)). Average uncertainty in the chemical-specific part of the effect factors depends on the number of species tested and ranges on average from a factor of 5 for more than 3 species tested to a factor of about 1,000 for 2 species tested. Average uncertainty in the ecotoxicological effect factors ranges from a factor of 100 for more than 3 species tested to a factor of nearly 10,000 for 2 species tested. It is recommended that the ecotoxicological effect factor of a chemical is based on toxicity data of at least 4 species.

Time horizon dependent characterization factors for acidification in life-cycle assessment based on forest plant species occurrence in Europe.

This paper describes a new approach in life-cycle impact assessment to derive characterization factors for acidification in European forests. Time horizon dependent characterization factors for acidification were calculated, whereas before only steady-state factors were available. The characterization factors indicate the change in the potential occurrence of plant species due to a change in emission, and they consist of a fate and an effect factor. The fate factor combines the results of an atmospheric deposition model and a dynamic soil acidification model. The change in base saturation in soil due to an atmospheric emission change was derived for 20, 50, 100, and 500 year time horizons. The effect factor was based on a dose-response curve of the potential occurrence of plant species, derived from multiple regression equations per plant species. The results showed that characterization factors for acidification increase up to a factor of 13 from a 20 years to a 500 years time horizon. Characterization factors for ammonia are 4.0-4.3 times greater than those for nitrogen oxides (NO(x)), and characterization factors for sulfur dioxide are 1.4-2.0 times greater than those for NO(x). Aggregation of damage due to acidification with other impact categories on the European scale becomes feasible with the applied approach.

Distribution of PAHs and PCBs to dissolved organic matter: high distribution coefficients with consequences for environmental fate modeling.

Dissolved organic carbon/water distribution coefficients (K(DOC)) were measured for a selection of PCBs with octanol/water partition coefficients (K(OW)) ranging from 10(5.6) to 10(7.5). A solid phase dosing and sampling technique was applied to determine K(DOC) to Aldrich humic acid. This technique is in particular suitable for determining the distribution of very hydrophobic chemicals to complex matrices like humic acids. The K(DOC) values were calculated from the experimental data using a linear model. Determined K(DOC)'s were evaluated in relation to octanol/water partition coefficients of the test compounds, and compared to literature data. Measured K(DOC) values were somewhat higher than literature data, which can probably be attributed to the overestimation of freely dissolved aqueous concentration as a result of incomplete phase separation in other studies, and to the unique character of Aldrich humic acid as a "sorbent" or co-solute or to the fact that Aldrich humic acid is not a typical DOC, and other (adsorption) processes can occur. This study reports DOC distribution coefficients that belong to the highest ones ever measured. In addition, the DOC distribution was discussed in relation to current risk assessment modeling.

Is cumulative fossil energy demand a useful indicator for the environmental performance of products?

The appropriateness of the fossil Cumulative Energy Demand (CED) as an indicator for the environmental performance of products and processes is explored with a regression analysis between the environmental life-cycle impacts and fossil CEDs of 1218 products, divided into the product categories "energy production", "material production", "transport", and "waste treatment". Our results show that, for all product groups but waste treatment, the fossil CED correlates well with most impact categories, such as global warming, resource depletion, acidification, eutrophication, tropospheric ozone formation, ozone depletion, and human toxicity (explained variance between 46% and 100%). We conclude that the use of fossil fuels is an important driver of several environmental impacts and thereby indicative for many environmental problems. It maytherefore serve as a screening indicatorfor environmental performance. However, the usefulness of fossil CED as a stand-alone indicator for environmental impact is limited by the large uncertainty in the product-specific fossil CED-based impact scores (larger than a factor of 10 for the majority of the impact categories; 95% confidence interval). A major reason for this high uncertainty is nonfossil energy related emissions and land use, such as landfill leachates, radionuclide emissions, and land use in agriculture and forestry.

Occurrence of phthalate esters in the environment of The Netherlands.

Overviews of levels of n-dibutylphthalate (DBP) and di(2-ethylhexyl)phthalate (DEHP) found in freshwater, marine water, sediment, and fish in the Netherlands are given. Sampling spanned a 9-month period (all seasons except winter) and allowed assessing whether phthalate levels are season dependent. Results obtained are compared to data reported for other Western European countries and a fugacity-based modeling approach is used to assess whether there is equilibrium among the various compartments. Highest levels of dissolved DBP and DEHP were found in freshwater samples, whereas these compounds were usually below the limit of detection (LOD) in marine water and sediment. Median levels were log-normally distributed; statistical analysis showed that sampling season is not a relevant determinant parameter. Similar results were obtained for the freshwater sediment compartment, with DEHP levels exceeding concentrations of DBP. DBP levels in fish were often below the LOD. Nevertheless, mean values around 1.8 microg kg(-1) wet fish were found for both DEHP and DBP. Fugacity calculations revealed that especially for DEHP there is no equilibrium among the compartments. DEHP emissions are directed to water, whereas the calculations reveal that sediments provide a sink for DEHP and there is net transport to air. Although it has been suggested that water is the primary compartment for DBP, fugacity plots suggest that air is the compartment to which emissions are directed dominantly. The data reported are in line with values found in Western Europe.

Solid phase dosing and sampling technique to determine partition coefficients of hydrophobic chemicals in complex matrixes.

Determination of polymer-water and dissolved organic carbon (DOC)-water distribution coefficients of very hydrophobic chemicals (log K0w > 6) is not straightforward. Poor water solubility of the test compounds complicates the spiking and analysis of actual freely dissolved concentrations. By dosing a system via a PDMS-fiber and monitoring the depletion in the polymer, spiking and analysis of concentrations in the aqueous phase are avoided, and sorption to the polymer and other hydrophobic phases can be determined easily and accurate. In this publication we report the determination of poly(dimethyl-siloxane) (PDMS)-water, and Aldrich humic acid-water distribution coefficients for six PAHs with log K0w values varying from 4.56 to 6.85. The distribution coefficients to a PDMS fiber llog Kf) and the DOC (log KDOC) range from 3.86 to 5.39 and 4.78 to 7.43, respectively. Even for the most hydrophobic compounds, the distribution coefficients show small standard errors (< or = 0.05 log units). Therefore, this method might be applied to determine sorption coefficients of numerous, even more hydrophobic compounds, to humic acids as well as other dissolved hydrophobic matrixes.

Human population intake fractions and environmental fate factors of toxic pollutants in life cycle impact assessment.

The present paper outlines an update of the fate and exposure part of the fate, exposure and effects model USES-LCA. The new fate and exposure module of USES-LCA was applied to calculate human population intake fractions and fate factors of the freshwater, marine and terrestrial environment for 3393 substances, including neutral organics, dissociating organics and inorganics, emitted to 7 different emission compartments. The human population intake fraction is on average 10(-5)-10(-8) for organics and 10(-3)-10(-4) for inorganics, depending on the emission compartment considered. Chemical-specific human population intake fractions can be 1-2.7 orders of magnitude higher or lower compared to the typical estimates. For inorganics, the human population intake fractions highly depend on the assumption that exposure via food products can be modelled with constant bioconcentration factors. The environmental fate factor is on average 10(-11)-10(-18) days m(-3) for organics and 10(-10)-10(-12) days m(-3) for inorganics, depending on the receiving environment and the emission compartment considered. Chemical-specific environmental fate factors can be 1-8 orders of magnitude higher or lower compared to the typical estimates. The largest differences between the new and old version of USES-LCA are found for emissions to air and soil. This is caused by a significant change in the structure of the air and soil compartments in the new version of USES-LCA, i.e. the distinction between rural and urban air, including rain-no rain conditions and including soil depth dependent intermedia transport.

Use of semi-permeable membrane devices and solid-phase extraction for the wide-range screening of microcontaminants in surface water by GC-AED/MS.

An automated GC-MS-based screening method was developed for over 400 industrial, agrochemical and household chemicals. Extracted ion chromatograms were used and the method was aimed at creating a minimum number of false positives. The compound polarity range usually associated with solid-phase extraction was extended to include very apolar, bioaccumulative, compounds by using the complementary semi-permeable membrane device technique. Real-life samples were taken at four locations in the main Dutch river systems and one in an agricultural area. Some 150 compounds were detected in the low-ng/l to low-microg/l range. Next to the target compounds, several brominated and chlorinated non-target compounds were detected by means of GC with atomic emission detection and tentatively identified using mass spectral library searching.