Effects of Vibrio vulnificus and Microcystis aeruginosa co-exposures on microplastic accumulation and depuration in the Eastern Oyster (Crassostrea virginica).

Microplastics are ubiquitous in the aquatic environment, and bivalves such as the Eastern oyster (Crassostrea virginica) can accumulate these particles directly from the water column. Bivalves are concurrently exposed to pathogenic and toxin-producing bacteria, including Vibrio spp. and Microcystis spp., which have been shown to adversely impact filtration rates. Exposure to these bacteria could thus affect oysters' ability to accumulate and depurate microplastics. As climate change creates conditions that favor Vibrio spp. and Microcystis spp. growth in estuaries, it is increasingly important to understand how these co-occurring biotic stressors influence microplastic contamination in bivalves. The objective of this study was to examine how co-exposures to Vibrio vulnificus and Microcystis aeruginosa influence microplastic accumulation and depuration in Eastern oysters. Oysters were exposed to nylon microplastics (5000 particles L-1) and either V. vulnificus, M. aeruginosa, or both species (104 colony-forming units or cells mL-1, respectively) and sampled over time up to 96 h. Following exposure, remaining oysters were allowed to depurate in clean seawater and sampled over time for up to 96 h. Microplastic concentrations in oysters were quantified and compared among treatments, and rate constants for uptake (ku) and depuration (kd) were calculated using nonlinear regression and two-compartment kinetic models. Overall, microplastic concentrations in oysters exposed to V. vulnificus (X‾ = 2.885 ± 0.350 (SE) particles g-1 w.w.) and V. vulnificus with M. aeruginosa (X‾ = 3.089 ± 0.481 particles g-1 w.w.) were higher than oysters exposed to M. aeruginosa (X‾ = 1.540 ± 0.235 particles g-1 w.w.) and to microplastics alone (X‾ = 1.599 ± 0.208 particles g-1 w.w.). Characterizing microplastic accumulation and depuration in oysters co-exposed to these biotic stressors is an important first step in understanding how contaminant loads in bivalves can change. With this research, the efficacy of depuration for commonly-consumed seafood species can be estimated.

Where the rubber meets the road: Emerging environmental impacts of tire wear particles and their chemical cocktails.

About 3 billion new tires are produced each year and about 800 million tires become waste annually. Global dependence upon tires produced from natural rubber and petroleum-based compounds represents a persistent and complex environmental problem with only partial and often-times, ineffective solutions. Tire emissions may be in the form of whole tires, tire particles, and chemical compounds, each of which is transported through various atmospheric, terrestrial, and aquatic routes in the natural and built environments. Production and use of tires generates multiple heavy metals, plastics, PAH's, and other compounds that can be toxic alone or as chemical cocktails. Used tires require storage space, are energy intensive to recycle, and generally have few post-wear uses that are not also potential sources of pollutants (e.g., crumb rubber, pavements, burning). Tire particles emitted during use are a major component of microplastics in urban runoff and a source of unique and highly potent toxic substances. Thus, tires represent a ubiquitous and complex pollutant that requires a comprehensive examination to develop effective management and remediation. We approach the issue of tire pollution holistically by examining the life cycle of tires across production, emissions, recycling, and disposal. In this paper, we synthesize recent research and data about the environmental and human health risks associated with the production, use, and disposal of tires and discuss gaps in our knowledge about fate and transport, as well as the toxicology of tire particles and chemical leachates. We examine potential management and remediation approaches for addressing exposure risks across the life cycle of tires. We consider tires as pollutants across three levels: tires in their whole state, as particulates, and as a mixture of chemical cocktails. Finally, we discuss information gaps in our understanding of tires as a pollutant and outline key questions to improve our knowledge and ability to manage and remediate tire pollution.

Biological responses to activated carbon amendments in sediment remediation.

Sorbent amendment with activated carbon (AC) is a novel in situ management strategy for addressing human and ecological health risks posed by hydrophobic organic chemicals (HOCs) in sediments and soils. A large body of literature shows that AC amendments can reduce bioavailability of sediment-associated HOCs by more than 60-90%. Empirically derived biodynamic models can predict bioaccumulation in benthic invertebrates within a factor of 2, allowing for future scenarios under AC amendment to be estimated. Higher AC dose and smaller AC particle size further reduce bioaccumulation of HOCs but may induce stress in some organisms. Adverse ecotoxicity response to AC exposure was observed in one-fifth of 82 tests, including changes in growth, lipid content, behavior, and survival. Negative effects on individual species and benthic communities appear to depend on the characteristics of the sedimentary environment and the AC amendment strategy (e.g., dose and particle size). More research is needed to evaluate reproductive end points, bacterial communities, and plants, and to link species- and community-level responses to amendment. In general, the ability of AC to effectively limit the mobility of HOCs in aquatic environments may outshine potential negative secondary effects, and these outcomes must be held in comparison to traditional remediation approaches.

Evaluation of biochars and activated carbons for in situ remediation of sediments impacted with organics, mercury, and methylmercury.

In situ amendment of activated carbon (AC) to sediments can effectively reduce the bioavailability of hydrophobic organic contaminants. While biochars have been suggested as low-cost and sustainable alternatives to ACs, there are few comparative sorption data especially for mercury (Hg) and methylmercury (MeHg) at the low porewater concentrations in sediments. Here we compare the ability of a wide range of commercially available and laboratory synthesized ACs and biochars to sorb PAHs, PCBs, DDTs, inorganic Hg, and MeHg at environmentally relevant concentrations. Compared to natural organic matter, sorption capacity for most organic compounds was at least 1-2 orders of magnitude higher for unactivated biochars and 3-4 orders of magnitude higher for ACs which translated to sediment porewater PCB concentration reductions of 18-80% for unactivated biochars, and >99% for ACs with 5% by weight amendment to sediment. Steam activated carbons were more effective than biochars in Hg sorption and translated to modeled porewater Hg reduction in the range of 94-98% for sediments with low native Kd and 31-73% for sediments with high native Kd values for Hg. Unactivated biochars were as effective as the steam activated carbons for MeHg sorption. Predicted reductions of porewater MeHg were 73-92% for sediments with low native Kd and 57-86% for sediment with high native K(d). ACs with high surface areas therefore are likely to be effective in reducing porewater concentrations of organics, Hg, and MeHg in impacted sediments. Unactivated biochars had limited effectiveness for organics and Hg but can be considered when MeHg exposure is the primary concern.

Comparison of sedimentary PAHs in the rivers of Ammer (Germany) and Liangtan (China): differences between early- and newly-industrialized countries.

As a proxy to trace the impact of anthropogenic activity, sedimentary polycyclic aromatic hydrocarbons (PAHs) are compared between the early industrialized and newly industrialized countries of Germany and China, respectively. Surface sediment samples in the Ammer River of Germany and the Liangtan River of China were collected to compare concentration levels, distribution patterns, and diagnostic plots of sedimentary PAHs. Total concentrations of 16 PAHs in Ammer sediments were significantly higher by a factor of ~4.5 than those in Liangtan. This contrast agrees with an extensive literature survey of PAH levels found in Chinese versus European sediments. Distribution patterns of PAHs were similar across sites in the Ammer River, whereas they were highly varied in the Liangtan River. Pyrogenic sources dominated in both cases. Strong correlations of the sum of 16 PAHs and PAH groups with TOC contents in the Liangtan River may indicate coemission of PAHs and TOC. Poor correlations of PAHs with TOC in the Ammer River indicate that other factors exert stronger influences. Sedimentary PAHs in the Ammer River are primarily attributed to input of diffuse sources or legacy pollution, while sediments in the Liangtan River are probably affected by ongoing point source emissions. Providing further evidence of a more prolonged anthropogenic influence are the elevated black carbon fractions in sedimentary TOC in the Ammer compared to the Liangtan. This implies that the Liangtan River, like others in newly industrialized regions, still has a chance to avoid legacy pollution of sediment which is widespread in the Ammer River and other European waterways.

Enumeration of microparticles on a gridded filter using a stratified random sampling tool.

Quantifying microplastics and other microparticles is a matter of interest in the field of environmental science. Stereomicroscopy is one of the most common methods to identify and enumerate micro-size particles. However, the process of enumerating an entire environmental sample can be tedious and time-consuming, especially when target particles are abundant. Here we present a method to develop a subsampling strategy and spreadsheet-based tool to speed up the process of microparticle enumeration while maintaining particle count accuracy. We first identified the pattern in which tire road wear particles (TRWPs) from environmental samples were distributed on a filter when vacuum-plated, then used particle abundance within relatively homogeneous subsection arrangements to establish stratified random subsampling schemes. We describe a repeated sampling experiment using count data to test the stratified design and illustrate the relationship between the fraction of the filter counted (sample size) with accuracy and variance in the extrapolated total sample count and the corresponding analyst time savings when applied to analyzing TRWPs isolated from sediments. Based on the results, a particle enumeration tool was created in Microsoft Excel Visual BasicⓇ configured using a 47 mm gridded filter, and the source is available for free modification under the same open license.•Vacuum-plated microparticles are often highly abundant and not homogenously distributed across a filter.•A random sampling selection data tool was created using knowledge of particle distribution.•Method describes how to structure and use partial filter counts to extrapolate for total particle enumeration.

Sorption of organic compounds to fresh and field-aged activated carbons in soils and sediments.

Activated carbon (AC) amendment to polluted sediment or soil is an emerging in situ treatment technique that reduces freely dissolved porewater concentrations and subsequently reduces the ecological and human health risk of hydrophobic organic compounds (HOCs). An important question is the capacity of the amended AC after prolonged exposure in the field. To address this issue, sorption of freshly spiked and native HOCs to AC aged under natural field conditions and fresh AC amendments was compared for one soil and two sediments. After 12-32 months of field aging, all AC amendments demonstrated effectiveness for reducing pore water concentrations of both native (30-95%) and spiked (10-90%) HOCs compared to unamended sediment or soil. Values of K(AC) for field-aged AC were lower than freshly added AC for spiked HOCs up to a factor of 10, while the effect was less for native HOCs. The different behavior in sorbing native HOCs compared to freshly spiked HOCs was attributed to differences in the sorption kinetics and degree of competition for sorption sites between the contaminants and pore-clogging natural organic matter. The implications of these findings are that amended AC can still be effective in sorbing additional HOCs some years following amendment in the field. Thus, a certain level of long-term sustainability of this remediation approach is observed, but conclusions for decade-long periods cannot be drawn solely based on the present study.

Phthalate exposure among U.S. college-aged women: Biomonitoring in an undergraduate student cohort (2016-2017) and trends from the National Health and Examination Survey (NHANES, 2005-2016).

IMPORTANCE: Phthalates are ubiquitous and many are known or suspected human reproductive and endocrine-disrupting toxicants. A data gap exists in reporting on biomonitoring of phthalate biomarkers in college-aged adults. OBJECTIVE: To analyze phthalate exposure in a cross-sectional sample of female college students using urinary phthalate metabolite concentrations and compare to reference populations including college-aged women sampled in the National Health and Nutrition Examination Survey (NHANES). METHODS: Nine monoester phthalate metabolites were analyzed in spot urine collected from 215 female undergraduates (age 18-22, 2016-2017) at a public university in Charleston, SC USA and a subset of participants completed a questionnaire detailing demographics and behaviors including personal care and cosmetic product use (e.g. in the past 6 or 24 hrs). Urine specific gravity was used to assess effect of urine dilution. Phthalate metabolite concentrations were compared to reference populations and the temporal trends of the same age-group in the National Health and Nutrition Examination Survey (NHANES) were analyzed. RESULTS: Total urinary phthalate metabolite concentrations in individuals ranged three orders of magnitude (geometric mean 56.6 ng/mL, IQR 26.6-114 ng/mL). A third of urine samples had relatively high urine specific gravity levels indicating potential dehydration status. All geometric mean concentrations were similar to the U.S. female population in the most recent NHANES cycle (2015-2016) except for MEP and mono-isobutyl phthalate (MiBP). Relatively low MEP and MiBP may be explained by a time trend of declining MEP in the general U.S. population, the sociocultural character of this cohort, and the time of day of spot sampling in evening. NHANES data indicate a significant effect of sample timing on phthalate metabolite concentrations and decline in most, but not all, phthalate metabolites sampled in women aged 18-22 years over the decade (2005-2016). SIGNIFICANCE: This study reports phthalate metabolites in college-aged women, an understudied group, emphasizes the benefit of survey information for interpreting biomonitoring data, and is a useful case study for communicating phthalate chemical exposure risks to college students.

Comprehensive Multi-compartment Sampling for Quantification of Long-Term Accumulation of PAHs in Soils.

Long-term accumulation in the soils of ubiquitous organic pollutants such as many polycyclic aromatic hydrocarbons (PAHs) depends on deposition from the atmosphere, revolatilization, leaching, and degradation processes such as photolysis and biodegradation. Quantifying the phase distribution and fluxes of these compounds across environmental compartments is thus crucial to understand the long-term contaminant fate. The gas-phase exchange between soil and atmosphere follows chemical fugacity gradients that can be approximated by gas-phase concentrations, yet which are difficult to measure directly. Thus, passive sampling, measured sorption isotherms, or empirical relationships to estimate sorption distribution have been combined in this study to determine aqueous (or gas) phase concentrations from measured bulk concentrations in soil solids. All these methods have their strengths and weaknesses but agree within 1 order of magnitude except for ex situ passive samplers employed in soil slurries, which estimated much lower concentrations in soil water and gas likely due to experimental artifacts. In field measurements, PAH concentrations determined in the atmosphere show a pronounced seasonality with some revolatilization during summer and gaseous deposition during winter, but overall dry deposition dominates annual mean fluxes. The characteristic patterns of PAHs in the different phases (gas phase, atmospheric passive samplers, bulk deposition, and soil solids) confirm the expected compound-specific distribution pattern and behavior. Since revolatilization fluxes in summer are only minor and wet and dry deposition is ongoing, our results clearly show that the PAH loads in topsoils will continue to increase.

Field-scale reduction of PCB bioavailability with activated carbon amendment to river sediments.

Remediation of contaminated sediments remains a technological challenge because traditional approaches do not always achieve risk reduction goals for human health and ecosystem protection and can even be destructive for natural resources. Recent work has shown that uptake of persistent organic pollutants such as polychlorinated biphenyls (PCBs) in the food web is strongly influenced by the nature of contaminant binding, especially to black carbon surfaces in sediments. We demonstrate for the first time in a contaminated river that application of activated carbon to sediments in the field reduces biouptake of PCBs in benthic organisms. After treatment with activated carbon applied at a dose similar to the native organic carbon of sediment, bioaccumulation in freshwater oligochaete worms was reduced compared to preamendment conditions by 69 to 99%, and concentrations of PCBs in water at equilibrium with the sediment were reduced by greater than 93% at all treatment sites for up to three years of monitoring. By comparing measured reductions in bioaccumulation of tetra- and penta-chlorinated PCB congeners resulting from field application of activated carbon to a laboratory study where PCBs were preloaded onto activated carbon, it is evident that equilibrium sorption had not been achieved in the field. Although other remedies may be appropriate for some highly contaminated sites, we show through this pilot study that PCB exposure from moderately contaminated river sediments may be managed effectively through activated carbon amendment in sediments.

Impact of trophic levels on partitioning and bioaccumulation of polycyclic aromatic hydrocarbons in particulate organic matter and plankton.

The distribution and bioconcentration of polycyclic aromatic hydrocarbons (PAHs) in water, suspended particulate material (SPM), algae, and zooplankton samples from the Pearl River Delta (PRD), South China, were investigated. The PAHs in the water and SPM samples is significantly associated with chlorophyll a (Chl a), implying the important role of the aquatic productivity on PAH distribution. PAHs in the water or SPM samples were strongly correlated to dissolved organic carbon (DOC) or algal particulate organic carbon (A-POC). Moreover, the log bioconcentration factor (BCF) values (mL g-1) of PAHs in both the algae and zooplankton samples were linearly related to their log octanol-water coefficient (Kow) values. However, the slopes of these relationships were negatively correlated with Chl a, attributing to the difference in the dominant plankton species or the non-equilibrium exchange between air-water-biota. The above results indicate the important role of trophic levels on the distribution and bioaccumulation of PAHs.

Correction: A characterization of personal care product use among undergraduate female college students in South Carolina, USA.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

A characterization of personal care product use among undergraduate female college students in South Carolina, USA.

Some chemicals used in personal care products (PCPs) are associated with endocrine disruption, developmental abnormalities, and reproductive impairment. Previous studies have evaluated product use among various populations; however, information on college women, a population with a unique lifestyle, is scarce. The proportion and frequency of product use were measured using a self-administered survey among 138 female undergraduates. Respondents were predominately Caucasian (80.4%, reflecting the college's student body), and represented all years of study (freshman: 24.6%; sophomore: 30.4%; junior: 18.8%; senior: 26.1%). All respondents reported use of at least two PCPs within 24 h prior to sampling (maximum = 17; median = 8; IQR = 6-11). Compared with studies of pregnant and postpartum women, adult men, and Latina adolescents, college women surveyed reported significantly higher use of deodorant, conditioner, perfume, liquid soap, hand/body lotion, sunscreen, nail polish, eyeshadow, and lip balm (Chi Square, p < 0.05). More study is needed to understand the magnitude and racial disparities of PCP chemical exposure, but given the potential effects on reproduction and fertility, our findings of abundant and frequent product use among these reproductive-aged women highlight opportunities for intervention and information on endocrine disrupting chemical (EDC)-free alternative products and behaviors.

Microplastic and tire wear particle occurrence in fishes from an urban estuary: Influence of feeding characteristics on exposure risk.

The influence of feeding behavior and feeding ecology on microplastic occurrence in fishes in an urbanized estuary was studied by surveying microplastics in the digestive tracts (gut) of five fish species: the planktivorous Bay Anchovy and Atlantic Menhaden, the piscivore Spotted Seatrout, the benthivore Spot and the detritivore/benthivore Striped Mullet. Microplastics were found in 99% of fishes collected with an average of 27 microplastics per individual fish, 6 microplastics per gram of fish, and 21 microplastics per gram of gut, although exposure varied among species. Atlantic Menhaden possessed significantly more microplastic per fish weight than other species, which may be attributed to their regular ingestion of marine snow aggregates. Fibers were the most common type of microplastic in all fishes, and suspected tire wear particles were found in 14% of individuals across all five species, constituting the first evidence of tire wear particle consumption in field-collected organisms.

Wastewater treatment plants as a source of microplastics to an urban estuary: Removal efficiencies and loading per capita over one year.

Wastewater treatment plants serve to collect and treat wastes that are known to include microplastic (MP; synthetic polymer materials <5 mm in size) and other small anthropogenic litter as particles, fibers and microbeads. Here, we determined the microplastic loads and removal efficiencies of three wastewater treatment plants (WWTPs) with different treatment sizes, operations and service compositions discharging to Charleston Harbor, South Carolina, USA over the course of a year. Overall, we found that MP concentrations (counts per L) varied within a factor of 2.5 in influent and 4.8 in effluent at each WWTP, and that neither concentrations nor removal efficiencies demonstrated a seasonal trend. The largest wastewater treatment plant in the study, which also employed primary clarification, had the highest MP removal efficiency of 97.6 ±â€¯1.2%. The other two smaller facilities had average removal efficiencies of 85.2 ±â€¯6.0% and 85.5 ±â€¯9.1%. We demonstrate through source modeling that microplastic fiber loads in influent were consistent with service area populations laundering textiles given previously published rates of microplastic generation in washing machines. Using measured WWTP flow rates and MP counts, we find a combined load of MPs leaving all three WWTPs with discharged effluent totaling 500-1000 million MPs per day. We estimate from this the emission of 0.34-0.68 g MP per capita per year in treated wastewater, which may only account for <0.1% of plastic debris input to this metropolitan area's surface waters on an annual mass basis when land-based (mis)managed plastic waste sources are also considered. However, the potential for sorption of chemicals present in wastewater to microplastics and their small size, which confers immediate bioaccessibility, may present unique toxicological risks for microplastics discharged from WWTPs.

Urinary Phthalate Metabolites in Common Bottlenose Dolphins (Tursiops truncatus) From Sarasota Bay, FL, USA.

Phthalates are chemical additives to common consumer goods including cleaning products, cosmetics, personal care products, and plastic. Because they are not chemically bound to these products and are widely used, the potential for environmental contamination is significant. Phthalates and their metabolites have been associated with endocrine disruption and reproductive impairment, among other adverse health effects, in laboratory animals and human epidemiologic studies. Common bottlenose dolphins (Tursiops truncatus) are vulnerable to environmental pollutants due to their apex position in the food chain, long life spans, and habitat overlap with developed coastal areas. The objective of this study was to quantify phthalate metabolite concentrations in urine collected from bottlenose dolphins in Sarasota Bay, Florida, during May 2016 (n = 7) and May 2017 (n = 10). Screening of nine phthalate monoester metabolites in bottlenose dolphin urine was performed by liquid chromatography tandem mass spectrometry using methods adapted from those used for analyzing human samples. At least one phthalate metabolite was detected in 71% of the dolphins sampled across both years, with the highest concentrations detected for monoethyl phthalate (MEP; GM = 5.4 ng/ml; 95%CI: 1.3-22.0 ng/ml) and mono-(2-ethylhexyl) phthalate (MEHP; GM = 1.9 ng/ml; 95%CI: 1.1-3.2 ng/ml). These data demonstrate exposure to two of the most commonly used phthalates in commercial manufacturing, diethyl phthalate (DEP) and di-2-ethylhexyl phthalate (DEHP). This study establishes methods for urinary detection of phthalate metabolites in marine mammals and provides baseline data to address a significant and growing, yet poorly understood, health threat to marine wildlife.

Toxicity comparison of the shoreline cleaners Accell Clean® and PES-51® in two life stages of the grass shrimp, Palaemonetes pugio.

Oil spills are a significant source of coastal pollution. Shoreline cleaners, used to remove oil from surfaces during spill response and remediation, may also act as toxins. Adult and larval grass shrimp, Palaemonetes pugio, were tested for lethal and sublethal impacts from two shoreline cleaners, Accell Clean SWA® and PES-51®, alone and in combination with crude oil using Chemically Enhanced Water Accommodated Fractions (CEWAFs). Median lethal toxicity values determined for the individual cleaners were similar. However, when tested in mixture with oil as CEWAFs, Accell Clean SWA resulted in greater hydrocarbon concentrations in the water column and greater toxicity than PES-51. Increased glutathione levels were observed for adult shrimp exposed to Accell Clean SWA, and glutathione was elevated in shrimp exposed to both CEWAFs. Larval shrimp development was delayed after exposure to both CEWAFs. These findings may have implications for managing and mitigating oil spills.

Modeling short-term concentration fluctuations of semi-volatile pollutants in the soil-plant-atmosphere system.

Temperature changes can drive cycling of semi-volatile pollutants between different environmental compartments (e.g. atmosphere, soil, plants). To evaluate the impact of daily temperature changes on atmospheric concentration fluctuations we employed a physically based model coupling soil, plants and the atmosphere, which accounts for heat transport, effective gas diffusion, sorption and biodegradation in the soil as well as eddy diffusion and photochemical oxidation in the atmospheric boundary layer of varying heights. The model results suggest that temperature-driven re-volatilization and uptake in soils cannot fully explain significant diurnal concentration fluctuations of atmospheric pollutants as for example observed for polychlorinated biphenyls (PCBs). This holds even for relatively low water contents (high gas diffusivity) and high sorption capacity of the topsoil (high organic carbon content and high pollutant concentration in the topsoil). Observed concentration fluctuations, however, can be easily matched if a rapidly-exchanging environmental compartment, such as a plant layer, is introduced. At elevated temperatures, plants release organic pollutants, which are rapidly distributed in the atmosphere by eddy diffusion. For photosensitive compounds, e.g. some polycyclic aromatic hydrocarbons (PAHs), decreasing atmospheric concentrations would be expected during daytime for the bare soil scenario. This decline is buffered by a plant layer, which acts as a ground-level reservoir. The modeling results emphasize the importance of a rapidly-exchanging compartment above ground to explain short-term atmospheric concentration fluctuations.

Magnetite impregnation effects on the sorbent properties of activated carbons and biochars.

This paper discusses the sorbent properties of magnetic activated carbons and biochars produced by wet impregnation with iron oxides. The sorbents had magnetic susceptibilities consistent with theoretical predictions for carbon-magnetite composites. The high BET surface areas of the activated carbons were preserved in the synthesis, and enhanced for one low surface area biochar by dissolving carbonates. Magnetization decreased the point of zero charge. Organic compound sorption correlated strongly with BET surface areas for the pristine and magnetized materials, while metal cation sorption did not show such a correlation. Strong sorption of the hydrophobic organic contaminant phenanthrene to the activated carbon or biochar surfaces was maintained following magnetite impregnation, while phenol sorption was diminished, probably due to enhanced carbon oxidation. Copper, zinc and lead sorption to the activated carbons and biochars was unchanged or slightly enhanced by the magnetization, and iron oxides also contributed to the composite metal sorption capacity. While a magnetic biochar with 219 ± 3.7 m(2)/g surface area nearly reached the very strong organic pollutant binding capacity of the two magnetic activated carbons, a magnetic biochar with 68 ± 2.8 m(2)/g surface area was the best metal sorbent. Magnetic biochars thus hold promise as more sustainable alternatives to coal-derived magnetic activated carbons.

Modeling long-term uptake and re-volatilization of semi-volatile organic compounds (SVOCs) across the soil-atmosphere interface.

Soil-atmosphere exchange is important for the environmental fate and atmospheric transport of many semi-volatile organic compounds (SVOCs). This study focuses on modeling the vapor phase exchange of semi-volatile hydrophobic organic pollutants between soil and the atmosphere using the multicomponent reactive transport code MIN3P. MIN3P is typically applied to simulate aqueous and vapor phase transport and reaction processes in the subsurface. We extended the code to also include an atmospheric boundary layer where eddy diffusion takes place. The relevant processes and parameters affecting soil-atmosphere exchange were investigated in several 1-D model scenarios and at various time scales (from years to centuries). Phenanthrene was chosen as a model compound, but results apply for other hydrophobic organic compounds as well. Gaseous phenanthrene was assumed to be constantly supplied to the system during a pollution period and a subsequent regulation period (with a 50% decline in the emission rate). Our results indicate that long-term soil-atmosphere exchange of phenanthrene is controlled by the soil compartment - re-volatilization thus depends on soil properties. A sensitivity analysis showed that accumulation and transport in soils in the short term is dominated by diffusion, whereas in the long term groundwater recharge and biodegradation become relevant. As expected, sorption causes retardation and slows down transport and biodegradation. If atmospheric concentration is reduced (e.g. after environmental regulations), re-volatilization from soil to the atmosphere occurs only for a relatively short time period. Therefore, the model results demonstrate that soils generally are sinks for atmospheric pollutants. The atmospheric boundary layer is only relevant for time scales of less than one month. The extended MIN3P code can also be applied to simulate fluctuating concentrations in the atmosphere, for instance due to temperature changes in the topsoil.