Multimedia Fate Model Research Articles

Per- and polyfluoroalkyl substances in soil and sediments: Occurrence, fate, remediation and future outlook

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are contaminants of great concern due to their wide-spread occurrence and persistence in the environments (i.e., in water, soil and sediment) and potential toxicology even at very low concentration. The main focus of this review is on the PFASs in soil and sediments. More specifically, this review systematically examines the occurrence and toxicological effects with associated risks, fate (i.e., PFASs adsorption by soil and sediment, transportation and transformation, and bioaccumulation), and remediation practices of PFASs in soil and sediment. Various models and equations such as fugacity-based multimedia fate and hydrodynamic models are used to study the fate, transport, and transformation of PFASs. Among different remediation practices, sorption is the dominant process for the removal of PFASs from soil and sediments. Results also indicate that PFASs adsorption onto activated carbon decrease with the increase of carbon chain length in the PFASs. The longer-chain PFASs have larger partition coefficient values than shorter-chained PFASs. Sorption of PFASs to soil and sediments are mainly governed by different electrostatic interactions, hydrogen bonds formation, hydrophobic interactions, organic content in soil and sediments, and ligand exchange. Other technology such as thermal treatment might be potential in the removal of PAFSs, but need further study to elucidate a conclusion. Finally, the associated challenges and future outlook have been included.

Screening-Level Estimates of Environmental Release Rates, Predicted Exposures, and Toxic Pressures of Currently Used Chemicals.

We describe a procedure to quantify emissions of chemicals for environmental protection, assessment, and management purposes. The procedure uses production and use volumes from registration dossiers and combines these with Specific Environmental Release Category data. The procedure was applied in a case study. Emission estimations were made for chemicals registered under the European Union chemicals regulations for industrial chemicals (Registration, Evaluation, Authorisation and Restriction of Chemicals [REACH]) and for the active ingredients of medicines and crop protection products. Emissions themselves cannot be validated. Instead, emission estimates were followed by multimedia fate modeling and mixture toxic pressure modeling to arrive at predicted environmental concentrations (PECs) and toxic pressures for a typical European water body at steady state, which were compared with other such data. The results show that screening‐level assessments could be performed, and yielded estimates of emissions, PECs, and mixture toxic pressures of chemicals used in Europe. Steady‐state PECs agreed fairly well with measured concentrations. The mixture toxic pressure at steady state suggests the presence of effects in aquatic species assemblages, whereby few compounds dominate the predicted impact. The study shows that our screening‐level emission estimation procedure is sufficiently accurate and precise to serve as a basis for assessment of chemical pollution in aquatic ecosystems at the scale of river catchments. Given a recognized societal need to develop methods for realistic, cumulative exposures, the emission assessment procedure can assist in the prioritization of chemicals in safety policies (such as the European Union REACH regulation), where “possibility to be used safely” needs to be demonstrated, and environmental quality policies (such as the European Union Water Framework Directive), where “good environmental quality” needs to be reached. Environ Toxicol Chem 2020;39:1839–1851. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

New Data Set of Polychlorinated Dibenzo-p-dioxin and Dibenzofuran Half-Lives: Natural Attenuation and Rhizoremediation Using Several Common Plant Species in a Weathered Contaminated Soil.

In this paper, a new data set of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) half-lives (HLs) in soil is presented. Data are derived from a greenhouse experiment performed with an aged contaminated soil under semi-field conditions, obtained from a National Relevance Site (SIN) located in Northern Italy (SIN Brescia-Caffaro). Ten different treatments (combination of seven plant species with different soil conditions) were considered together with the respective controls (soil without plants). The ability of the plants to stimulate the biodegradation of these compounds was evaluated by measuring the PCDD/F concentration reduction in soil over a period of 18 months. The formation of new bound residues was excluded by using roots as a passive sampler of bioaccessible concentrations. The best treatment which significantly reduced PCDD/F concentrations in soil was the one with Festuca arundinacea (about 11–24% reduction, depending on the congener). These decreases reflected in HLs ranging from 2.5 to 5.8 years. Simulations performed with a dynamic air-vegetation-soil model (SoilPlusVeg) confirmed that these HLs were substantially due to biodegradation rather than other loss processes. Because no coherent PCDD/F degradation HL data sets are currently available for soil, they could substantially improve the predictions of soil remediation time, long-range transport, and food chain transfer of these chemicals using multimedia fate models.

Chemical fate of persistent organic pollutants in the arctic: Evaluation of simplebox

Persistent organic pollutants (POPs) are of great concern for decades due to their persistence, bioaccumulation and long-range transport potential. Multimedia fate models are useful scientific and decision-support tools for predicting the chemical fate in the environment. The SimpleBox multimedia fate model (v4.0) was used in this study to estimate the impact of POP emissions from the European and North American mainland on POP contamination in the Arctic. The purpose of the study was to evaluate the performance of SimpleBox by comparing estimations to measurements. Model performance for the air compartment was reasonable as estimated concentrations were generally within a factor of five of measured concentrations. SimpleBox suggested higher POP concentrations in Arctic oceans than in temperate oceans, contrary to the few measured data. Discrepancies between estimations and measurements may be attributed to the variability in emission estimates and degradation rates of POPs, representativeness of monitoring data, and a missing snow and ice environmental compartment in SimpleBox. Emission rates and degradation rate constants were the most influential input parameters in SimpleBox based on sensitivity analysis. Suggestions for improvements of SimpleBox refining POP risk assessment are provided.

Modelling peak exposure of pesticides in terrestrial and aquatic ecosystems: importance of dissolved organic carbon and vertical particle movement in soil

ABSTRACTIn the present work, an existing vegetation/air/litter/soil model (SoilPlusVeg) was modified to improve organic chemical fate description in terrestrial/aquatic ecosystems accounting for horizontal and vertical particulate organic carbon (POC) transport in soil. The model was applied to simulate the fate of three pesticides (terbuthylazine, chlorpyrifos and etofenprox), characterized by increasing hydrophobicity (log KOW from about 3 to 7), in the soil compartment and more specifically, their movement towards surface and groundwater through infiltration and runoff processes. The aim was to evaluate the role of dissolved organic carbon (DOC) and POC in the soil in influencing the peak exposure of pesticides in terrestrial/aquatic ecosystems. Simulation results showed that while terbuthylazine and chlorpyrifos dominated the free water phase (CW-FREE) of soil, etofenprox was mainly present in soil porewater as POC associated chemical. This resulted in an increase of this highly hydrophobic chemical movement towards groundwater and surface water, up to a factor of 40. The present work highlighted the importance of DOC and POC as an enhancer of mobility in the water of poor or very little mobile chemicals. Further studies are necessary to evaluate the bioavailability change with time and parameterize this process in multimedia fate models.

Multimedia fate modeling of antibiotic sulfamethoxazole, lincomycin, and florfenicol in a seasonally ice-covered river receiving WWTP effluents.

As a result of the widespread use of antibiotics, a large amount of excretions from human and animals, containing antibiotic residues, is discharged into aquatic environments, leading to potential adverse effects on the ecosystems' health. These residues' impact on seasonally ice-covered rivers remains under investigated. To understand the environmental fate of antibiotics with high-detection frequencies and concentration levels, sulfamethoxazole, lincomycin, and florfenicol were used as models in the present study. A Level IV fugacity model was established and applied to a seasonally ice-covered river receiving municipal wastewater treatment plant (WWTP) effluents, the Songhua River in Northeast China. Model validation and sensitivity analysis suggested that the fugacity model could successfully simulate the monitoring concentration within an average difference of one logarithmic unit. The advection process played a major role in the transport and attenuation of the antibiotics in the ice-covered river receiving WWTP effluents. The scenario simulation indicated that increasing the targeted antibiotic concentrations in WWTP effluents to μgL-1 could keep the targeted antibiotic concentrations higher than 10ngL-1 in the receiving river from the WWTP discharge source to 25km downstream. This finding also demonstrates that the depth of water and ice, as well as flow velocity, play key roles in the fate of antibiotics in the ice-covered river receiving WWTP effluents. To our best knowledge, this is the first major study to combine experimental investigation with modeling to explore the environmental behaviors and fate of antibiotics in such a river.

Analysis of environmental behaviour of sulfa-drugs in the Lake Biwa and Yodo River Basin by using Multimedia Models

This study focuses on some sulfa-drugs that have been heavily used in livestock husbandry and emitted into the Lake Biwa and Yodo River Basin. Emissions of sulfa-drugs were estimated using the national statistical data on veterinary drug usage and livestock excrement in Japan. One-box and distributional type multimedia fate models were utilized with the estimated emissions in order to simulate the behaviour of sulfa-drugs in four environmental media (atmosphere, soil, water and sediment) in the study period from 2005 to 2015 in the basin. Based on the calculated results, sulfa-drugs emitted to the soil media were efficiently transported to water, which resulted in the largest amount in water among the environmental media and high concentrations in and around areas with large farmland proportion.

Improving the SoilPlusVeg model to evaluate rhizoremediation and PCB fate in contaminated soils

Tools to predict environmental fate processes during remediation of persistent organic pollutants (POPs) in soil are desperately needed since they can elucidate the overall behavior of the chemical and help to improve the remediation process. A dynamic multimedia fate model (SoilPlusVeg) was further developed and improved to account for rhizoremediation processes. The resulting model was used to predict Polychlorinated Biphenyl (PCB) fate in a highly contaminated agricultural field (1089 ng/g d.w.) treated with tall fescue (Festuca arundinacea), a promising plant species for the remediation of contaminated soils. The model simulations allowed to calculate the rhizoremediation time (about 90 years), given the available rhizoremediation half-lives and the levels and fingerprints of the PCB congeners, to reach the legal threshold, to show the relevance of the loss processes from soil (in order of importance: degradation, infiltration, volatilization, etc.) and their dependence on meteorological and environmental dynamics (temperature, rainfall, DOC concentrations). The simulations showed that the effective persistence of PCBs in soil is deeply influenced by the seasonal variability. The model also allowed to evaluate the role of DOC as a possible enhancer of PCB degradation as a microorganism “spoon feeder” of PCBs in the soil solution. Additionally, we preliminary predicted how the contribution of PCB metabolites could modify the PCB fingerprint and their final total concentrations. This shows that the SoilPlusVeg model could be used in selecting the best choices for a sustainable rhizoremediation of a POP contaminated site.

Modeling the Time-Variant Dietary Exposure of PCBs in China over the Period 1930 to 2100.

This study aimed for the first time to reconstruct historical exposure profiles for PCBs to the Chinese population, by examining the combined effect of changing temporal emissions and dietary transition. A long-term (1930-2100) dynamic simulation of human exposure using realistic emission scenarios, including primary emissions, unintentional emissions, and emissions from e-waste, combined with dietary transition trends was conducted by a multimedia fate model (BETR-Global) linked to a bioaccumulation model (ACC-HUMAN). The model predicted an approximate 30-year delay of peak body burden for PCB-153 in a 30-year-old Chinese female, compared to their European counterpart. This was mainly attributed to a combination of change in diet and divergent emission patterns in China. A fish-based diet was predicted to result in up to 8 times higher body burden than a vegetable-based diet (2010-2100). During the production period, a worst-case scenario assuming only consumption of imported food from a region with more extensive production and usage of PCBs would result in up to 4 times higher body burden compared to consumption of only locally produced food. However, such differences gradually diminished after cessation of production. Therefore, emission reductions in China alone may not be sufficient to protect human health from PCB-like chemicals, particularly during the period of mass production. The results from this study illustrate that human exposure is also likely to be dictated by inflows of PCBs via the environment, waste, and food.

Multimedia fate modeling of perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS) in the shallow lake Chaohu, China

Freshwater shallow lake ecosystems provide valuable ecological services to human beings. However, these systems are subject to severe contamination from anthropogenic sources. Per- and polyfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS), are among the contaminants that have received substantial attention, primarily due to abundant applications, environment persistence, and potential threats to ecological and human health. Understanding the environmental behavior of these contaminants in shallow freshwater lake environments using a modeling approach is therefore critical. Here, we characterize the fate, transport and transformation of both PFOA and PFOS in the fifth largest freshwater lake in China (Chaohu) during a two-year period (2013–2015) using a fugacity-based multimedia fate model. A reasonable agreement between the measured and modeled concentrations in various compartments confirms the model's reliability. The model successfully quantifies the environmental processes and identifies the major sources and input pathways of PFOA and PFOS to the Chaohu water body. Sensitivity analysis reveals the critical role of nonlinear Freundlich sorption, which contributes to a variable fraction of the model true uncertainty in different compartments (8.1%–93.6%). Through additional model scenario analyses, we further elucidate the importance of nonlinear Freundlich sorption that is essential for the reliable model performance. We also reveal the distinct composition of emission sources for the two contaminants, as the major sources are indirect soil volatilization and direct release from human activities for PFOA and PFOS, respectively. The present study is expected to provide implications for local management of PFASs pollution in Lake Chaohu and to contribute to developing a general model framework for the evaluation of PFASs in shallow lakes.

Multimedia fate modeling and risk assessment of antibiotics in a water-scarce megacity

As a result of the widespread use of antibiotics, a large amount of excretion from human and animals containing antibiotic residues was discharged into the environment with wastewaters and manures, leading to potential adverse effects on ecosystem health. To understand the environmental fate of antibiotics, a dynamic level IV fugacity model was established here by introducing the novel process of nondiffusive wastewater irrigation from water to soil, and applied to a large-scale water-scarce region, the megacity Beijing. Furthermore, a Monte-Carlo based risk assessment approach was employed to evaluate the potential risks posed by antibiotics in water, sediment and soil, combined with the soil-water equilibrium partitioning method. Model validation, sensitivity and uncertainty analysis suggests that the fugacity model can successfully simulate the reported concentration data within an average difference of 0.2 logarithmic units. Results showed that more than one hundred tonnes of antibiotics were estimated to be discharged into the environment of Beijing in 2013, and, resulted in high antibiotics levels and posed high potential risks on the aquatic environment. On the other hand, although wastewater irrigation increased the antibiotics concentrations in soil and even dominated the total transfer fluxes, the overall risk levels of antibiotics in the soil were acceptable.

Multiscale Spatial Modeling of Human Exposure from Local Sources to Global Intake.

Exposure studies, used in human health risk and impact assessments of chemicals, are largely performed locally or regionally. It is usually not known how global impacts resulting from exposure to point source emissions compare to local impacts. To address this problem, we introduce Pangea, an innovative multiscale, spatial multimedia fate and exposure assessment model. We study local to global population exposure associated with emissions from 126 point sources matching locations of waste-to-energy plants across France. Results for three chemicals with distinct physicochemical properties are expressed as the evolution of the population intake fraction through inhalation and ingestion as a function of the distance from sources. For substances with atmospheric half-lives longer than a week, less than 20% of the global population intake through inhalation (median of 126 emission scenarios) can occur within a 100 km radius from the source. This suggests that, by neglecting distant low-level exposure, local assessments might only account for fractions of global cumulative intakes. We also study ∼10 000 emission locations covering France more densely to determine per chemical and exposure route which locations minimize global intakes. Maps of global intake fractions associated with each emission location show clear patterns associated with population and agriculture production densities.

Developing a Black Carbon-Substituted Multimedia Model for Simulating the PAH Distributions in Urban Environments

A multimedia fugacity model with spatially resolved environmental phases at an urban scale was developed. In this model, the key parameter, organic matter, was replaced with black carbon (BC) and applied to simulate the distributions of phenanthrene (Phe), pyrene (Pyr) and benzo[α]pyrene (BaP) in Nanjing, China. Based on the estimated emissions and measured inflows of air and water, the Phe, Pyr and BaP concentrations in different environment media were calculated under steady-state assumptions. The original model (OC-Model), BC-inclusive model (dual C-Model) and improved model (BC-Model) were validated by comparing observed and predicted Phe, Pyr and BaP concentrations. Our results suggested that lighter polycyclic aromatic hydrocarbons (PAHs) were more affected by BC substitution than their heavier counterparts. We advocate the utilization of sorption with BC in future multimedia fate models for lighter PAHs based on the comparison of the calculated and observed values from measured and published sources. The spatial distributions of the Phe, Pyr and BaP concentrations in all phases were rationally mapped based on the calculated concentrations from the BC-Model, indicating that soil was the dominant sink of PAHs in terrestrial systems, while sediment was the dominant sink of PAHs in aquatic systems.

Developing and applying a site-specific multimedia fate model to address ecological risk of oxytetracycline discharged with aquaculture effluent in coastal waters off Jangheung, Korea

The overuse of oxytetracycline (OTC) in aquaculture has become a problem because of its chronic toxic effects on marine ecosystems. The present study assessed the ecological risk of OTC in the coastal waters near the Jangheung Flatfish Farm using a site-specific multimedia fate model to analyze exposure. Before the model was applied, its performance was validated by comparing it with field data. The coastal waters in the testbed were sampled and analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) followed by solid-phase extraction (SPE). The concentrations of OTC measured varied from 7.05 to 95.39ng/L. The results of validating the models showed that the site-specific multimedia fate model performed better (root mean square error (RMSE): 24.217, index of agreement (IOA): 0.739) than conventional fugacity approaches. This result demonstrated the utility of this model in supporting effective future management of aquaculture effluent. The results of probabilistic risk assessment indicated that OTC from aquaculture effluent did not cause adverse effects, even in a maximum-use scenario.

Assessing the Risk of Engineered Nanomaterials in the Environment: Development and Application of the nanoFate Model.

We developed a dynamic multimedia fate and transport model (nanoFate) to predict the time-dependent accumulation of metallic engineered nanomaterials (ENMs) across environmental media. nanoFate considers a wider range of processes and environmental subcompartments than most previous models and considers ENM releases to compartments (e.g., urban, agriculture) in a manner that reflects their different patterns of use and disposal. As an example, we simulated ten years of release of nano CeO2, CuO, TiO2, and ZnO in the San Francisco Bay area. Results show that even soluble metal oxide ENMs may accumulate as nanoparticles in the environment in sufficient concentrations to exceed the minimum toxic threshold in freshwater and some soils, though this is more likely with high-production ENMs such as TiO2 and ZnO. Fluctuations in weather and release scenario may lead to circumstances where predicted ENM concentrations approach acute toxic concentrations. The fate of these ENMs is to mostly remain either aggregated or dissolved in agricultural lands receiving biosolids and in freshwater or marine sediments. Comparison to previous studies indicates the importance of some key model aspects including climatic and temporal variations, how ENMs may be released into the environment, and the effect of compartment composition on predicted concentrations.

Significance of metabolites in the environmental risk assessment of pharmaceuticals consumed by human

The purpose of this study is to demonstrate the significance of metabolites to the ERA of human pharmaceuticals. The predicted exposure concentrations (PECs) in surface water were estimated for a total of 24 selected active pharmaceutical ingredients (APIs) and their metabolites using a life cycle based emission estimation model combined with a multimedia fate model with Monte-Carlo calculations. With the eco-toxicity data, the hazard quotients (HQs) of the metabolites were compared with those of individual parents alone.The results showed that PEC or toxicity or both of the metabolites was predicted to be higher than that of their parent APIs, which resulted in a total of 18 metabolites (from 12 parents) that have greater HQs than their parents. This result clearly demonstrated that some metabolites may potentially pose greater risk than their parent APIs in the water environment. Therefore, significance of metabolites should be carefully evaluated for monitoring strategy, priority setting, and scoping of the environmental risk assessment of APIs. The method used in the present work may serve as a pragmatic approach for the purpose of preliminary screening or priority setting of environmental risk posed by both APIs and their metabolites.

Long-Term Temporal Trends of Polychlorinated Biphenyls and Their Controlling Sources in China.

Polychlorinated biphenyls (PCBs) are industrial organic contaminants identified as persistent, bioaccumulative, toxic (PBT), and subject to long-range transport (LRT) with global scale significance. This study focuses on a reconstruction and prediction for China of long-term emission trends of intentionally and unintentionally produced (UP) ∑7PCBs (UP-PCBs, from the manufacture of steel, cement and sinter iron) and their re-emissions from secondary sources (e.g., soils and vegetation) using a dynamic fate model (BETR-Global). Contemporary emission estimates combined with predictions from the multimedia fate model suggest that primary sources still dominate, although unintentional sources are predicted to become a main contributor from 2035 for PCB-28. Imported e-waste is predicted to play an increasing role until 2020-2030 on a national scale due to the decline of intentionally produced (IP) emissions. Hypothetical emission scenarios suggest that China could become a potential source to neighboring regions with a net output of ∼0.4 t year-1 by around 2050. However, future emission scenarios and hence model results will be dictated by the efficiency of control measures.

Diabetes in pregnancy: Impact on fetal and childhood health

Improved understanding of ecological risk associated with Arctic shipping would help advance effective oil spill prevention, control, and mitigation strategies. Ecological risk assessment involves analysis of a release (oil), its fate, and dispersion, and the exposure and intake of the contaminant to different receptors. Exposure analysis is a key step of the detailed ecological risk assessment, which involves the evaluation of the concentration and persistence of released pollutants in the media of contact. In the present study, a multimedia fate and transport model is presented, which is developed using a fugacity-based approach. This model considers four media: air, water, sediment, and ice. The output of the model is the concentration of oil (surrogate hydrocarbons-naphthalene) in these four media, which constitutes the potential exposure to receptors. The concentration profiles can subsequently be used to estimate ecological risk thereby providing guidance to policies for Arctic shipping operations, ship design, and ecological response measures.

Dynamic fugacity model for accidental oil release during Arctic shipping

Improved understanding of ecological risk associated with Arctic shipping would help advance effective oil spill prevention, control, and mitigation strategies. Ecological risk assessment involves analysis of a release (oil), its fate, and dispersion, and the exposure and intake of the contaminant to different receptors. Exposure analysis is a key step of the detailed ecological risk assessment, which involves the evaluation of the concentration and persistence of released pollutants in the media of contact. In the present study, a multimedia fate and transport model is presented, which is developed using a fugacity-based approach. This model considers four media: air, water, sediment, and ice. The output of the model is the concentration of oil (surrogate hydrocarbons-naphthalene) in these four media, which constitutes the potential exposure to receptors. The concentration profiles can subsequently be used to estimate ecological risk thereby providing guidance to policies for Arctic shipping operations, ship design, and ecological response measures.

A Multimedia Fate Model to Support Chemical Management in China: A Case Study for Selected Trace Organics

SESAMe v3.3, a spatially explicit multimedia fate model for China, is a tool suggested to support quantitative risk assessment for national scale chemical management. The key advantage over the previous version SESAMe v3.0 is consideration of spatially varied environmental pH. We evaluate the model performance using estimates of emission from total industry usage of three UV filters (benzophenone-3, octocrylene, and octyl methoxycinnamate) and three antimicrobials (triclosan, triclocarban, and climbazole). The model generally performs well for the six case study chemicals as shown by the comparison between predictions and measurements. The importance of accounting for chemical ionization is demonstrated with the fate and partitioning of both triclosan and climbazole sensitivity to environmental pH. The model predicts ionizable chemicals (triclosan, climbazole, benzophenone-3) to primarily partition into soils at steady state, despite hypothetically only being released to freshwaters, as a result of agricultural irrigation by freshwater. However, further model calibration is needed when more field data becomes available for soils and sediments and for larger areas of water. As an example, accounting for the effect of pH in the environmental risk assessment of triclosan, limited freshwater areas (0.03% or ca. 55 km(2)) in mainland China are modeled to exceed its conservative environmental no-effect threshold. SESAMe v3.3 can be used to support the development of chemical risk assessment methodologies with the spatial aspects of the model providing a guide to the identification regions of interest in which to focus monitoring campaigns or develop a refined risk assessment.