Pore Water Concentrations Research Articles

Influence of chain length on field-measured distributions of PFAS in soil and soil porewater

Soil and porewater concentrations measured for multiple PFAS were compiled from three field studies. The soil:porewater concentration ratios were shown to be functions of molar volume for all three data sets. Remarkable consistency was observed between the three sets of field-based measurements, indicating that PFAS distributions in the three soil systems exhibited similar magnitudes of overall retention. The relative contributions of solid-phase sorption and air-water interfacial adsorption to total retention were examined. The contribution of air-water interfacial adsorption was greater than that of solid-phase sorption for the longer-chain PFAS, whereas it was less than that of solid-phase sorption for the shorter-chain PFAS. These results show that the relative contributions of the two processes can vary as a function of the particular PFAS when the solid-phase sorption functionality deviates from that of air-water interfacial adsorption. This might occur for example when sorption is influenced by addition mechanisms beyond hydrophobic interaction, or when sorption and/or adsorption are nonlinear. Based on the results from all three data sets, soil concentrations are likely to be smaller than porewater concentrations for the shortest-chain PFAS. Conversely, soil concentrations will generally be significantly greater than porewater concentrations for longer-chain PFAS. The results from this study have implications for characterizing and evaluating PFAS distributions in vadose-zone soils.

Releasing mechanism of ammonium during clayey sediments compaction and its impact on groundwater environment

Compaction of clayey aquitard would release pore water containing high levels of ammonium to adjacent aquifers, potentially affecting the concentration of groundwater ammonium. However, the releasing process and impact effect of ammonium within clayey aquitard during compaction remain unknown. Four groups of pre-experiments and two groups of simulation experiments were conducted to reveal the releasing mechanism of ammonium during clayey sediment compaction. (1) The results of Experiment A simulating continuous sedimentation conditions showed that the sediment ammonium transferred into pore water sequentially through desorption of ion exchange form, degradation of organic matter, and simultaneous release of mineral-bound ammonium. The concentration of pore water ammonium was 3.54–8.20 mg N/L, with a significant periodical variation due to sediment ammonium transformation. The lower moisture content (<42.4 %) in the later stage of compaction inhibited the biological transformation of ammonium, and the change in mineral structure caused the isomorphic replacement of K to capture ammonium, resulting in a decrease in ammonium concentration in released pore water. (2) The results of Experiment B simulating artificial compaction conditions (such as land subsidence) showed that the pore water ammonium was primarily caused by desorption of ion exchange form ammonium due to changes in pore structure and moisture content. The ammonium concentration in pore water was 4.72–9.91 mg N/L, with a significant increase in response to a large change in pressure in the short term. (3) The estimate results in the Chen Lake wetland suggested that the contribution of clayey aquitard compaction to groundwater ammonium concentration in the adjacent aquifer would be 2.68–4.29 mg N/L, which accounted for a considerable portion of groundwater ammonium concentration and was far higher than that of advection and diffusion. The findings of this study reveal the releasing mechanism of ammonium during clayey sediments compaction, in which reaction products may affect adjacent aquifers.

Response of dissolved organic matter characteristics to nitrogen addition in a boreal peatland of Northeast China

Boreal peatlands, a crucial stock of dissolved organic matter (DOM), are susceptible to increased reactive nitrogen (N) inputs. However, the response of DOM characteristics to elevated N availability in these ecosystems is still obscure. Here, we investigated the seasonal variability of DOM quantity and characteristics in surface water and soil pore water after 5-year multi-level N addition (0, 3, 6, and 12 g N m−2 year−1) in a permafrost peatland of Northeast China. In this study, we used the excitation-emission matrix fluorescent spectroscopy combined with fluorescence regional integration, parallel factor analysis, and fluorescence parameters to decipher the effects of N addition on DOM composition, origin, and fate. Irrespective of N addition level, increased N availability reduced dissolved organic carbon concentrations in surface water and soil pore water. However, DOM characteristics are more responsive to N addition in soil pore water than in surface water. Nitrogen addition did not affect DOM composition in surface water, but altered the proportions of tyrosine-, tryptophan-, fulvic acid-, and humic-like DOM in soil pore water. Moreover, the changing trends of DOM composition were diverse during the growing season. In addition, compositional transformations of DOM did not change its biogenic signals, freshness, and humification in both surface water and soil pore water across the growing season. Our results suggest that increased N availability reduces DOM quantity and alters DOM chemical composition, which will improve our understanding of soil organic matter dynamics in boreal peatlands.

Rhizosphere processes by the nickel hyperaccumulator Odontarrhena chalcidica suggest Ni mobilization.

Plant Ni uptake in aboveground biomass exceeding concentrations of 1000μgg-1 in dry weight is defined as Ni hyperaccumulation. Whether hyperaccumulators are capable of mobilizing larger Ni pools than non-accumulators is still debated and rhizosphere processes are still largely unknown. The aim of this study was to investigate rhizosphere processes and possible Ni mobilization by the Ni hyperaccumulator Odontarrhena chalcidica and to test Ni uptake in relation to a soil Ni gradient. The Ni hyperaccumulator O. chalcidica was grown in a pot experiment on six soils showing a pseudo-total Ni and labile (DTPA-extractable) Ni gradient and on an additional soil showing high pseudo-total but low labile Ni. Soil pore water was sampled to monitor changes in soil solution ionome, pH, and dissolved organic carbon (DOC) along the experiment. Results showed that Ni and Fe concentrations, pH as well as DOC concentrations in pore water were significantly increased by O. chalcidica compared to unplanted soils. A positive correlation between Ni in shoots and pseudo-total concentrations and pH in soil was observed, although plant Ni concentrations did not clearly show the same linear pattern with soil available Ni. This study shows a clear root-induced Ni and Fe mobilization in the rhizosphere of O. chalcidica and suggests a rhizosphere mechanism based on soil alkalinization and exudation of organic ligands. Furthermore, it was demonstrated that soil pH and pseudo-total Ni are better predictors of Ni plant uptake in O. chalcidica than labile soil Ni. The online version contains supplementary material available at 10.1007/s11104-023-06161-w.

Pre-activated biochar by fertilizers mitigates nutrient leaching and stimulates soil microbial activity

BackgroundPrevious studies have suggested that the targeted application of biochars in agricultural soils may benefit soil health and crop production. Physico-chemical properties of soils after biochar addition have been explored, but less is known about how microbial parameters respond. Therefore, impact of biochar (NB), mineral fertilizer-activated biochar (AB), or mineral fertilizer (MF) application on selected chemical and microbial parameters of lettuce-planted soil was evaluated in a pot experiment.ResultsIn comparison to the control, soil enzymes activities, related to carbon (C), nitrogen (N), and phosphorus (P) cycling, and their content in plant biomass, were significantly increased by the addition of mineral fertilizer with or without biochar (MF, NB + MF). Conversely, microbial respiration (basal and substrate induced) was highly responsive to the activated biochar amendment (AB) as compared to other treatments. N, P, and potassium (K) concentrations in soil pore water were stabilized by the mineral fertilizer-activated biochar, indicating reduced leaching and the likelihood of increased longevity of these nutrients in soils. Enhanced carbon acquisition and mitigated nitrogen acquisition in soil of the most experimental treatments were coupled with higher crop (lettuce) biomass.ConclusionsOur study demonstrates that the application of biochar both with and without mineral fertilizer has the potential to enhance microbial activity and fertility in the tested agricultural soil, but that leaching of fertilizer-borne nutrients may be mitigated by the activation process.Graphical

Has the Rio Doce "time bomb" been defused? Using a weight-of-evidence approach to determine sediment quality.

The Fundão mine tailings dam rupture of 2015, in the Rio Doce basin, Brazil, resulted in the deposition of tailings downstream of the dam. It has yet to be determined if metals associated with the tailings have contributed toxicity to organisms, burying a time bomb that could be ticking. Currently the data on toxicity to benthic and aquatic organisms have not been assessed sufficiently to allow an informed assessment using an approach based on weight-of-evidence. This study was conducted to ascertain if sediments at "hot spots" that received Fundão tailings reflected elevated concentrations of metals and if these concentrations were sufficient to result in toxicity to freshwater organisms. The lines-of-evidence considered included assessing metals concentrations in relation to sediment quality criteria, establishing biogeochemical characterizations, completing an evaluation of potential metal release upon resuspension to provide information on bioavailability, and identifying acute and chronic toxicity effects using sensitive native species for waters (water flea, Daphnia similis) and sediments (burrowing midge larvae, Chironomus sancticaroli). Only porewater concentrations of iron and manganese exceeded Brazilian surface water criteria, whereas most trace elements exhibited no enrichment or elevated environmental indexes. The concentrations of bioavailable metals were assessed to be low, and metal concentrations did not increase in the overlying water upon resuspension; rather, they decreased through time. Toxicity testing in resuspended waters and bulk sediments resulted in no acute or chronic toxicity to either benthic or aquatic species. The low metal bioavailability and absence of toxicity of the tailings-enriched sediments was attributed to the strong binding and rapid removal of potentially toxic metal ions caused by oxyhydroxides and particles in the presence of iron-rich particulates. The findings of these sediment hot-spot studies indicate the Fundão dam release of tailings more than six years ago is not causing the current release of toxic concentrations of metals into the freshwaters of the Rio Doce. Integr Environ Assess Manag 2024;20:148-158. © 2023 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Review of DDT, DDE, DDD, DDMU and DDMS Toxicity Data for Organisms Used in Estuarine and Marine Sediment Toxicity Tests.

The open literature was searched for laboratory toxicity data for marine/estuarine organisms exposed to dichlorodiphenyltrichloroethane (DDT) and its degradation products of dichlorodiphenyldichloroethylene (DDE), dichlorodiphenyldichloroethane (DDD), dichlorodiphenylchloroethylene (DDMU), and dichlorodiphenylchloroethane (DDMS). The goal of the review was to determine water-column toxicity values that could be used for porewater-based assessment of sediment toxicity. Data for individual compounds (and isomers thereof) in this group were very limited; most available data were for mixtures of multiple compounds, some defined and others undefined. Further, the majority of relevant studies involved exposure to spiked or field-contaminated sediment (rather than waterborne exposure), which requires inferring concentration in porewater from bulk sediment. Comparing data on the basis of effect concentrations for water or inferred concentration in sediment pore water, the lower reported effect concentrations were in the range of 0.05 to 0.1µg/L, generally in studies of longer duration and/or evaluating sub-lethal effects. Because field exposures are generally to mixtures of these compounds in varied proportions, additional data on chemical-specific toxicity would aid in pore-water based toxicity assessment for marine/estuarine sediments contaminated with DDT-related chemicals.

Mercury and methylmercury in Hg-contaminated paddy soil and their uptake in rice as regulated by DOM from different agricultural sources.

In this study, from the perspectives of structural and compositional variations of soil-dissolved organic matter (DOM), we explored the effects of agricultural DOM inputs on methylmercury (MeHg) accumulation in the soil and mercury (Hg) bioaccumulation in rice grains. Pot experiments with the addition of DOMs from maize straw (MaS), rape straw (RaS), rice straw (RiS), composted rice straw (CRiS), cow dung (CD), and composted cow dung (CCD) were then conducted. Results showed that, relative to the control, the DOM amendment from each agricultural source elevated MeHg concentrations in the soil, with an increase of 18-227%, but only parts of DOMs elevated total dissolved Hg (DHg) and MeHg (DMeHg) concentrations in pore water. Among all DOM species, RiS, CRiS, and CCD significantly increased total Hg (THg) and MeHg contents in rice grains by 34-64% and 32-118%, respectively. Compared with RiS, THg and MeHg contents in rice grains in the CRiS treatment decreased slightly, which was consistent with the distributions of DHg and DMeHg concentrations in pore water and the aromaticity variation of soil DOM. In contrast, the CCD input significantly enhanced the enrichment of THg and MeHg in rice grains relative to CD because it significantly reduced the humification of soil DOM at all rice-growing stages while increasing the low-molecular-weight fractions in soil DOM. The THg and MeHg contents in the rice grains were significantly lower treated by RaS than those by MaS and RiS, which may be related to the higher sulfur-containing compounds such as sulfate and cysteine in rape straw or its DOM solution. Overall, DOM amendment from different agricultural sources resulted in significantly discriminative effects on the MeHg accumulation in soil and Hg enrichment in rice in the Hg-contaminated paddy field by shaping soil DOM properties.

Trace element, rare earth element and trace carbon compounds in Subglacial Lake Whillans, West Antarctica

Whillans Subglacial Lake (SLW) lies beneath 801 m of ice in the lower portion of the Whillans Ice Stream (WIS) in West Antarctica and is part of an extensive and active subglacial drainage network. Here, the geochemical characterization of SLW rare earth elements (REE), trace elements (TE), free amino acids (FAA), and phenolic compounds (PC) measured in lakewater and sediment porewater are reported. The results show, on average, higher values of REEs in the lakewater than in the porewater, and clear changes in all REE concentrations and select redox sensitive trace element concentrations in porewaters at a depth of ~15 cm in the 38 cm lake sediment core. This is consistent with prior results on the lake sediment redox conditions based on gas chemistry and microbiological data. Low concentrations of vanillyl phenols were measured in the SLW water column with higher concentrations in porewater samples and their concentration profiles in the sediments may also reflect changing redox conditions in the sediments. Vanillin concentrations increased with depth in the sediments as oxygenation decreases, while the concentrations of vanillic acid, the more oxidized component, were higher in the more oxygenated surface sediments. Collectively these results indicate redox changes occurring with the upper 38 cm of sediment in SLW and provide support for the existence of a seawater source, already hypothesized, in the sediments below the lowest measured depth, and of a complex and dynamic geochemical system beneath the West Antarctic Ice Sheet.Our results are the first to detail geochemical properties from an Antarctic subglacial environment using direct sampling technology. Due to their isolation from the wider environment, subglacial lakes represent one of our planets last pristine environments that provide habitats for microbial life and natural biogeochemical cycles but also impact the basal hydrology and can cause ice flow variations.

Model of Activated Carbon Dose and Sediment–Water Diffusion Fluxes of Hydrophobic Organic Chemicals: Implications for Sediment Remediation

Activated carbon (AC) amendment is an effective strategy for remediating contaminated sediment by hydrophobic organic chemicals. Reductions of porewater chemical concentrations have been used for estimating recommended AC dose for effective sediment remediation, but the AC dose may have large uncertainties resulting from site-specific parameters. The present study examined sediment–water diffusion flux as an alternative assessment parameter by correlating diffusion fluxes of organophosphorus flame retardants (OPFRs) and polybrominated diphenyl ethers (PBDEs) with AC doses. AC at doses of 8–36% substantially reduced sediment porewater concentrations and diffusion fluxes of the target chemicals. Diffusion fluxes of OPFRs and PBDEs normalized by their corresponding sediment concentrations significantly correlated with total organic carbon contents (r2 = 0.57–0.93). A model was established to estimate the required AC dose for effective sediment amendment from the diffusion flux and sediment concentration of a target chemical. Using contaminated sediment in a typical e-waste recycling zone, the AC doses (0.1 ± 1.3–12.8 ± 0.3%) required to reduce 90% of diffusion fluxes for tri-n-butyl phosphate and BDE-17 were within the recommended range (1.9 ± 3.6–5.6 ± 8.3%) in lowering porewater concentrations by the same magnitude. This finding suggested the feasibility of the new model in supporting sediment remediation.

Model-based evaluation of reduction strategies for point and nonpoint source Cd pollution in a large river system

Cadmium (Cd) is a toxic trace element that threatens ecosystem and human health worldwide. Quantitative understanding of land-to-river Cd fluxes and riverine Cd loads in response to various watershed management measures is essential for developing effective mitigation strategies for large river systems. However, detailed analyses of watershed Cd dynamics under different management scenarios are lacking. Here, we investigated the effects of four management scenarios by combining point and nonpoint source control measures with a previously developed watershed Cd model that was validated with site-specific measurements. The Soil and Water Assessment Tool-Heavy Metal (SWAT-HM) model was applied to simulate the Xiang River Basin's (XRB, ∼90,000 km2) baseline hydrology, soil erosion, and Cd transport processes in China. Using scenario simulations, we found that smelting emissions reduction was the most influential measure for controlling dissolved Cd (DCd) and particulate Cd (PCd) loads at the basin scale. Elimination of 50% emissions from the smelting sector could significantly (p < 0.05) decrease the monthly mean loads of DCd from 940 to 720 kg and of PCd from 2150 to 1760 kg at the XRB outlet. In contrast, reduction in mining emissions had no influence on the Cd load at the XRB outlet because most mining Cd emissions occurred upstream and midstream of the XRB, and the natural attenuation processes in the river limit the transportation of Cd downstream. The effectiveness of management practices for reducing total Cd (TCd) and DCd loads was not always mutually beneficial. For example, soil erosion control may decrease the PCd flux via erosion but increase the subsurface DCd flux to rivers due to greater lateral flow. In addition, increasing soil pH could be a practical and effective measure to reduce nonpoint DCd and PCd fluxes. Such effects may be caused by the declined upward migration of Cd through soil evaporation owing to the decreased Cd concentration in the soil pore water after pH increases. In conclusion, effective watershed management of Cd pollution in large basins requires an integrated plan that combines multiple mitigation measures; strategic modeling experiments could provide valuable insights into the design of such plans.

Long-term monitoring and modeling of PAHs in capped sediments at the Grand Calumet River

The assessment of a cap for remediation of sediments requires long-term monitoring because of the slow migration of contaminants in porous media. In this study, coring and passive sampling tools were used to assess the transport and degradation of polycyclic aromatic hydrocarbons (PAHs) in an amended cap (sand + Organoclay® PM-199) in the Grand Calumet River (Indiana, USA) during four sampling events from 2012 to 2019. Measurements of three PAHs (phenanthrene (Phe), pyrene (Pyr) and benzo[a]pyrene (BaP), representing low, medium, and high molecular weight compounds, respectively) showed a difference of at least two orders of magnitude between bulk concentrations in the native sediments and the remediation cap. Averages of pore water measurements also showed lower levels in the cap respective to the native sediments by a factor of at least 7 for Phe and 3 for Pyr. In addition, between the baseline (BL), which corresponds to observations from 2012 to 2014, and the measurements in 2019, there was a decrease in depth-averaged pore water concentrations of Phe (C2019/CBL=0.20−0.07+0.12 in sediments and 0.27−0.10+0.15 in cap) and Pyr (C2019/CBL=0.47−0.12+0.16 in sediments and 0.71−0.20+0.28 in the cap). In the case of BaP in pore water, no change was observed in native sediments (C2019/CBL=1.0−0.24+0.32) and there was an increase in the cap (C2019/CBL=2.0−0.54+0.72).Inorganic anions and estimates of pore water velocity along with measurements of PAHs were used to model the fate and transport of contaminants. The modeling suggested that degradation of Phe (t1/2=1.12−0.11+0.16 years) and Pyr (t1/2=5.34−1.8+5.3 years) in the cap is faster than migration, thus the cap is expected to be protective of the sediment-water interface indefinitely for these constituents. No degradation was noted in BaP and the contaminant is expected to reach equilibrium in the capping layer over approximately 100 years if there exists sufficient mass of BaP in the sediments and there is no deposition of clean sediment at the surface.

Long-term environmental impact of an artificial island of solidified dredged marine silt

Marine dredging silt that has been solidified is commonly used as a filler material for inland reclamation and artificial island construction. However, determining the long-term environmental safety of artificial islands made of solidified silt is a challenge. A bridge–tunnel conversion artificial island made of solidified silt was the research location of this study. Laboratory tests were conducted to study the effect of cement content on the pollutant pore-water concentration and hydraulic conductivity of solidified silt. The results showed that after solidification treatment, the heavy-metal concentration in the pore water of dredged silt reduced by 60–85%, whereas the concentration of hydroxide (OH−) ions increased 106–1070 times, and the hydraulic conductivity decreased by approximately three orders of magnitude. On the basis of the test results, the finite-element method was used for simulating the long-term transport of heavy metal nickel (II) (Ni2+) and hydroxide in artificial islands. When the cement content increased from 60 to 100 kg/m3, the nickel (II) concentration in the dam around the solidified silt decreased by approximately 68%, whereas the hydroxide concentration increased approximately tenfold. However, none of them exceeded the seawater water quality standard. This indicates that the long-term environmental safety of the artificial island could be ensured.

Shallow Sediment as a Phosphorus Reservoir in an Oligotrophic Lake

AbstractLake sediment is an important reservoir for storage of phosphorus (P). Skaneateles Lake, a pristine oligotrophic, midsize lake in New York State, USA, is the primary unfiltered water source for the city of Syracuse and nearby communities. We conducted a lake‐wide survey of shallow sediments in Skaneateles Lake to inform understanding of the potential role of sediment in P storage and release into the water column. A total of 103 shallow samples of surface sediments were collected along 17 transects around the lake margin and analyzed for sediment and pore water elemental concentration, grain size, total organic carbon, nitrogen, carbonate content, stable isotopes of carbon, and mineral content. Reduction‐oxidation (redox) processes of Fe‐bound and Mn‐bound P appear to be a primary control of P storage and release. Sediment P concentrations are positively correlated with water depth and negatively correlated with Ca. Grain size and sediment P distributions around the lake are heterogeneous and patchy. Pore water concentrations reveal strong but variable partitioning of P, apparently controlled by sediment redox conditions. Pore water P concentrations (mean 90 μg L−1) are elevated compared with the oligotrophic water column (∼5 μg L−1) and may be an important source of nutrients to the water column of the lake.

Arsenic migration at the sediment-water interface of anthropogenically polluted Lake Yangzong, Southwest China

The lability and controlling factors of arsenic (As) at the sediment-water interface (SWI) are crucial for understanding As behaviors and fates in As-contaminated areas. In this study, we combined high-resolution (5 mm) sampling using diffusive gradients in thin films (DGT) and equilibrium dialysis sampling (HR-Peeper), sequential extraction (BCR), fluorescence signatures, and fluorescence excitation-emission matrices (EEMs)-parallel factor analysis (PARAFAC) to explore the complex mechanisms of As migration in a typical artificially polluted lake, Lake Yangzong (YZ). The study results showed that a high proportion of the reactive As fractions in sediments can resupply pore water in soluble forms during the change from the dry season (winter, oxidizing period) to the rainy season (summer, reductive period). In dry season, the copresence of Fe oxide-As and organic matter (OM)-As complexes was related to the high dissolved As concentration in pore water and limited exchange between the pore water and overlying water. In the rainy season, with the change in redox conditions, the reduction of Fe-Mn oxides and OM degradation by microorganisms resulted in As deposition and exchange with the overlying water. Partial least squares path modelling (PLS-PM) indicated that OM affected the redox and As migration processes through degradation. Based on comprehensive analyses of the As, Fe, Mn, S and OM levels at the SWI, we suggest that the complexation and desorption of dissolved organic matter and Fe oxides play an important role in As cycling. Our findings shed new light on the cascading drivers of As migration and OM features in seasonal lakes and constitute a valuable reference for scenarios with similar conditions.

Climate drivers alter nitrogen availability in surface peat and decouple N2 fixation from CH4 oxidation in the Sphagnum moss microbiome.

Peat mosses (Sphagnum spp.) are keystone species in boreal peatlands, where they dominate net primary productivity and facilitate the accumulation of carbon in thick peat deposits. Sphagnum mosses harbor a diverse assemblage of microbial partners, including N2 -fixing (diazotrophic) and CH4 -oxidizing (methanotrophic) taxa that support ecosystem function by regulating transformations of carbon and nitrogen. Here, we investigate the response of the Sphagnum phytobiome (plant + constituent microbiome + environment) to a gradient of experimental warming (+0°C to +9°C) and elevated CO2 (+500 ppm) in an ombrotrophic peatland in northern Minnesota (USA). By tracking changes in carbon (CH4 , CO2 ) and nitrogen (NH4 -N) cycling from the belowground environment up to Sphagnum and its associated microbiome, we identified a series of cascading impacts to the Sphagnum phytobiome triggered by warming and elevated CO2 . Under ambient CO2 , warming increased plant-available NH4 -N in surface peat, excess N accumulated in Sphagnum tissue, and N2 fixation activity decreased. Elevated CO2 offset the effects of warming, disrupting the accumulation of N in peat and Sphagnum tissue. Methane concentrations in porewater increased with warming irrespective of CO2 treatment, resulting in a ~10× rise in methanotrophic activity within Sphagnum from the +9°C enclosures. Warming's divergent impacts on diazotrophy and methanotrophy caused these processes to become decoupled at warmer temperatures, as evidenced by declining rates of methane-induced N2 fixation and significant losses of keystone microbial taxa. In addition to changes in the Sphagnum microbiome, we observed ~94% mortality of Sphagnum between the +0°C and +9°C treatments, possibly due to the interactive effects of warming on N-availability and competition from vascular plant species. Collectively, these results highlight the vulnerability of the Sphagnum phytobiome to rising temperatures and atmospheric CO2 concentrations, with significant implications for carbon and nitrogen cycling in boreal peatlands.

Alum reduced phosphorus release from flooded soils under cold spring weather conditions.

The effectiveness of amendments such as alum [Al2 (SO4 )3 ·18H2 O] in reducing phosphorus (P) loss to floodwater has been reported under summer conditions and laboratory-controlled environments, but not under actual spring weather conditions in cold climate regions with high diurnal temperature variations when potential for P losses is high. The effectiveness of alum in reducing P release under Manitoba spring weather conditions was evaluated in a 42-day experiment using 15-cm soil monoliths from eight agricultural soils, which were unamended or alum-amended (5 Mg ha-1 ) and flooded to a 10-cm head. Dissolved reactive P (DRP) concentrations and pH of porewater and floodwater were determined on flooding day and every 7 days after flooding (DAF). Porewater and floodwater DRP concentrations in unamended soils increased 1.4- to 4.5-fold, and 1.8- to 15.3-fold, respectively, from 7 to 42 DAF. In alum-amended soils, DRP concentrations averaged across soils was 43%-73% (1.0-2.0mg L-1 ) lower in porewater, and 27%-64% (0.1-1.2mg L-1 ) lower in floodwater than unamended soils during the flooding period. The reduction of DRP by alum was more pronounced under high fluctuating diurnal spring air temperature than with controlled air temperature (4°C) in a previous similar study. Acidic pH in porewater and floodwater due to alum did not persist over 7 days. This study showed that alum application is a viable option in reducing P released to floodwater in agricultural soils of cold regions where flooding-induced P loss is prevalent in the spring.

Revising the EPA dilution-attenuation soil screening model for PFAS

Per and polyfluoroalkyl substances (PFAS) have been shown to be ubiquitous in the environment, and one issue of critical concern is the leaching of PFAS from soil to groundwater. The risk posed by contaminants present in soil is often assessed in terms of the anticipated impact to groundwater through the determination of soil screening levels (SSLs). The U.S. Environmental Protection Agency (EPA) established a soil screening model for determining SSLs. However, the model does not consider the unique retention properties of PFAS and, consequently, the SSLs established with the model may not represent the actual levels that are protective of groundwater quality. The objective of this work is to revise the standard EPA SSL model to reflect the unique properties and associated retention behavior of PFAS. Specifically, the distribution parameter used to convert soil porewater concentrations to soil concentrations is revised to account for adsorption at the air-water interface. Example calculations conducted for PFOS and PFOA illustrate the contrasting SSLs obtained with the revised and standard models. A comparison of distribution parameters calculated for a series of PFAS of different chain length shows that the significance of air-water interfacial adsorption can vary greatly as a function of the specific PFAS. Therefore, the difference between SSLs calculated with the revised versus standard models will vary as a function of the specific PFAS, with greater differences typically observed for longer-chain PFAS. It is anticipated that this revised model will be useful for developing improved SSLs that can be used to enhance site investigations and management for PFAS-impacted sites. SynopsisThe widely used EPA SSL model is revised for PFAS applications to account for adsorption at the air-water interface.

Effects of freeze-thaw cycles on methanogenic hydrocarbon degradation: Experiment and modeling

Cold regions are warming much faster than the global average, resulting in more frequent and intense freeze-thaw cycles (FTCs) in soils. In hydrocarbon-contaminated soils, FTCs modify the biogeochemical and physical processes controlling petroleum hydrocarbon (PHC) biodegradation and the associated generation of methane (CH4) and carbon dioxide (CO2). Thus, understanding the effects of FTCs on the biodegradation of PHCs is critical for environmental risk assessment and the design of remediation strategies for contaminated soils in cold regions. In this study, we developed a diffusion-reaction model that accounts for the effects of FTCs on toluene biodegradation, including methanogenic biodegradation. The model is verified against data generated in a 215 day-long batch experiment with soil collected from a PHC contaminated site in Ontario, Canada. The fully saturated soil incubations with six different treatments were exposed to successive 4-week FTCs, with temperatures oscillating between −10 °C and +15 °C, under anoxic conditions to stimulate methanogenic biodegradation. We measured the headspace concentrations and 13C isotope compositions of CH4 and CO2 and analyzed the porewater for pH, acetate, dissolved organic and inorganic carbon, and toluene. The numerical model represents solute diffusion, volatilization, sorption, as well as a reaction network of 13 biogeochemical processes. The model successfully simulates the soil porewater and headspace concentration time series data by representing the temperature dependencies of microbial reaction and gas diffusion rates during FTCs. According to the model results, the observed increases in the headspace concentrations of CH4 and CO2 by 87% and 136%, respectively, following toluene addition are explained by toluene fermentation and subsequent methanogenesis reactions. The experiment and the numerical simulation show that methanogenic degradation is the primary toluene attenuation mechanism under the electron acceptor-limited conditions experienced by the soil samples, representing 74% of the attenuation, with sorption contributing to 11%, and evaporation contributing to 15%. Also, the model-predicted contribution of acetate-based methanogenesis to total produced CH4 agrees with that derived from the 13C isotope data. The freezing-induced soil matrix organic carbon release is considered as an important process causing DOC increase following each freezing period according to the calculations of carbon balance and SUVA index. The simulation results of a no FTC scenario indicate that, in the absence of FTCs, CO2 and CH4 generation would decrease by 29% and 26%, respectively, and that toluene would be biodegraded 23% faster than in the FTC scenario. Because our modeling approach represents the dominant processes controlling PHC biodegradation and the associated CH4 and CO2 fluxes, it can be used to analyze the sensitivity of these processes to FTC frequency and duration driven by temperature fluctuations.

How arsenic contamination influences downslope wetland plant and microbial community structure and function

Mine tailings are prevalent worldwide and can adversely impact adjacent ecosystems, including wetlands. This study investigated the impact of gold (Au) mine tailings contamination on peatland soil and pore water geochemistry, vegetation and microbial communities, and microbial carbon (C) cycling. Maximum arsenic (As) concentrations in peat and pore water reached 20,137 mg kg−1 and 16,730 μg L−1, respectively, but decreased by two orders of magnitude along a 128 m gradient extending from the tailings into the wetland. Carbon and other macronutrient (N, P, K) concentrations in peat and pore water significantly increased with distance from contamination. Relative percent cover and species richness of vascular and non-vascular plants significantly increased with distance into the wetland, with higher non-vascular richness being found at intermediate distances before transitioning to a vascular plant dominated community. Bacterial and archaeal community composition exhibited a decreased proportion of members of the phylum Acidobacteria (notably of the order Acidobacteriales) and increased diversity and richness of methanogens across a larger range of orders farther from the tailings source, an indication of microbial C-cycling potential. Consistent with changes in microbial communities, in vitro microbial CH4 production potential significantly increased with distance from the contaminant source. This study demonstrates both the profound negative impact that metalliferous tailings contamination can have on above and belowground communities in peatlands, and the value of wetland preservation and restoration.