Occurrence and mobility of thiolated arsenic in legacy mine tailings.

We studied the occurrence of dissolved thiolated Arsenic (As) in legacy tailings systems in Ontario and Nova Scotia, Canada, and used aqueous and mineralogical speciation analyses to assess its governing geochemical controls. Surface-accessible and inundated tailings in Cobalt, Ontario, contained ∼1 wt-% As mainly hosted in secondary arsenate minerals (erythrite, yukonite, and others) and traces of primary sulfide minerals (cobaltite, gersdorffite and others). Significant fractions of thiolated As (up to 5.9 % of total dissolved As) were detected in aqueous porewater and surface water samples from these sites, comprising mostly monothioarsenate, and smaller amounts of di- and tri-thioarsenates as well as methylated thioarsenates. Tailings at the Goldenville and Montague sites in Nova Scotia contained less (<0.5 wt-%) As, hosted mostly in arsenopyrite and As-bearing pyrite, than the Cobalt sites, but exhibited higher proportions of dissolved thiolated As (up to 17.3 % of total dissolved As, mostly mono- and di-thioarsenate and traces of tri-thioarsenate). Dissolved thiolated As was most abundant in sub-oxic porewaters and inundated tailings samples across the studied sites, and its concentrations were strongly related to the prevailing redox conditions and porewater hydrochemistry, and to a lesser extent, the As-bearing mineralogy. Our novel results demonstrate that thiolated As species play an important role in the cycling of As in mine waste systems and surrounding environments, and should be considered in mine waste management strategies for high-As sites.

Elucidating the relationship between PFOA and PFOS destruction, particle size and electron generation in amended media commonly found in soils.

Ball milling has emerged as a promising destructive technique for treating per- and polyfluoroalkyl substances (PFAS)-impacted soils. Environmental media properties such as reactive species generated upon ball milling and particle size are postulated to influence the effectiveness of the technology. In this study, four media types amended with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were planetary ball milled to investigate destruction, fluoride recovery without additional co-milling reagents and the relationship between PFOA and PFOS destruction, particle size during milling, and electron generation. Silica sand, nepheline syenite sand, calcite and marble were sieved to achieve similar initial particle sizes (6/35 distribution), amended with PFOA and PFOS, and milled for 4 h. Particle size analysis was conducted throughout milling and 2,2-diphenyl-1-picrylhydrazyl (DPPH•) was used as a radical scavenger to assess electron generation from the four media types. Particle size reduction was observed to be positively correlated to PFOA and PFOS destruction and DPPH• neutralization (demonstrating electron generation by milling) in silica sand and nepheline syenite sand. Milling of a fine fraction (< 500 µm) of silica sand revealed less destruction compared to the 6/35 distribution suggesting the ability to fracture grains in silicate media is integral to PFOA and PFOS destruction. DPPH• neutralization was demonstrated in all four amended media types, confirming silicate sands and calcium carbonates generate electrons as a reactive species during ball milling. Fluoride loss as a function of milling time was observed in all amended media types. A sodium fluoride (NaF) spiked was used to quantify fluoride loss in the media independent of PFAS. A method was developed using the NaF-amended media fluoride concentrations to estimate the total fluorine liberated from PFOA and PFOS by ball milling. Estimates produced suggest complete recovery of theoretical fluorine yield is obtained. Data from this study was used to propose a reductive destruction mechanism for PFOA and PFOS.

Peaks, pores, and dragon eggs: Uncovering and quantifying the heterogeneity of treatment wetland biofilm matrices.

Biofilms serve to house diverse microbial communities, which are responsible for the majority of wastewater constituent degradation and transformation in treatment wetlands (TWs). TW biofilm has been generally conceptualized as a relatively uniform film covering available surfaces. However, no studies attaining direct visual 3D representations of biofilm morphology have been conducted. This study focuses on imaging the morphology of detached, gravel-associated, and rhizospheric (Phalaris arundinacea) biofilms from subsurface TW mesocosms. Images obtained through both traditional light microscopy, environmental scanning electron microscopy (E-SEM) and Wet-SEM revealed that TW biofilms are structurally heterogeneous ranging from corrugated films to clusters of aggregates. Features such as water channels and pores were observed suggesting that pollutant transport inside biofilms is complex, and that the interfacial surface area between water and biofilm is much larger than previously understood. Biofilm thickness generally ranged between 170 and 240 µm, with internal biofilm porosities estimated as 34 ± 10 %, reaching a maximum of 50 %. Internal biofilm matrix pore diameters ranged from 1 to 205.2 µm, with a distribution that favored pores and channels smaller than 10 µm, and a mean equivalent spherical diameter of 8.6 µm. Based on the large variation in pore and channel sizes it is expected that a variety of flow regimes and therefore pollutant dynamics are likely to occur inside TW biofilm matrices. Based on the visual evidence and analysis, a new conceptual model was created to reflect the microscale TW biofilm dynamics and morphology. This new conceptual model will serve to inform future biokinetic modelling, microscale hydrology, microbial community assessment, and pollutant treatment studies.

Retention of PFOS and PFOA Mixtures by Trapped Gas Bubbles in Porous Media.

The transport of per- and polyfluoroalkyl substances (PFAS) in soil and groundwater is important for site investigation, risk characterization, and remediation planning. The adsorption of PFAS at air-water interfaces has been shown to significantly contribute to PFAS retention, with subsequent effects on concentrations and the time scales of transport. In this study, column experiments were conducted to investigate the transport of perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and 6:2 fluorotelomer sulfonate (6:2 FTS) individually and in binary mixtures in the presence of a trapped gas phase, using clean sands to isolate adsorption to air-water interfaces. Consistent with previous studies, the transport of PFOS, PFOA, and 6:2 FTS was retarded by adsorption at the air-water interface, with greater retention of PFOS due to its higher affinity for the air-water interface. Chromatographic separation occurred in the experiments using binary mixtures of PFOS and PFOA, with greater retention at lower influent concentrations. The mixture experiments also showed enhanced breakthrough of PFOA in the presence of PFOS, where effluent concentrations of PFOA were temporarily greater than the influent concentration prior to the breakthrough of PFOS. This enhanced breakthrough was attributed to competition between PFOS and PFOA for adsorption to the air-water interface.

Use of a horizontal ball mill to remediate per- and polyfluoroalkyl substances in soil.

There is a need for destructive technologies for per- and polyfluoroalkyl substances (PFAS) in soil. While planetary ball mill have been shown successful degradation of PFAS, there are issues surrounding scale up (maximum size is typically 0.5 L cylinders). While having lower energy outputs, horizontal ball mills, for which scale up is not a limiting factor, already exist at commercial/industrial sizes from the mining, metallurgic and agricultural industries, which could be re-purposed. This study evaluated the effectiveness of horizontal ball mills in degrading perfluorooctanesulfonate (PFOS), 6:2 fluorotelomer sulfonate (6:2 FTSA), and aqueous film forming foam (AFFF) spiked on nepheline syenite sand. Horizontal ball milling was also applied to two different soil types (sand dominant and clay dominant) collected from a firefighting training area (FFTA). Liquid chromatography tandem mass spectrometry was used to track 21 target PFAS throughout the milling process. High-resolution accurate mass spectrometry was also used to identify the presence and degradation of 19 non-target fluorotelomer substances, including 6:2 fluorotelomer sulfonamido betaine (FtSaB), 7:3 fluorotelomer betaine (FtB), and 6:2 fluorotelomer thioether amido sulfonate (FtTAoS). In the presence of potassium hydroxide (KOH), used as a co-milling reagent, PFOS, 6:2 FTSA, and the non-target fluorotelomer substances in the AFFF were found to undergo upwards of 81%, 97%, and 100% degradation, respectively. Despite the inherent added complexity associated with field soils, better PFAS degradation was observed on the FFTA soils over the spiked NSS, and more specifically, on the FFTA clay over the FFTA sand. These results held through scale-up, going from the 1 L to the 25 L cylinders. The results of this study support further scale-up in preparation for on-site pilot tests.

Silver nanomaterials released from commercial textiles have minimal impacts on soil microbial communities at environmentally relevant concentrations.

Silver nanomaterials (Ag NMs) have been used in a variety of commercial products to take advantage of their antimicrobial properties. However, there are concerns that these AgNMs can be released during/after use and enter wastewater streams, potentially impacting aquatic systems or accumulating in wastewater biosolids. Biosolids, which are a residual of wastewater treatment processes, have been found to contain AgNMs and are frequently used as agricultural fertilizer. Since the function of soil microbial communities is imperative to nutrient cycling and agricultural productivity, it is important to characterize and assess the effects that silver nanomaterials could have in agricultural soils. In this study agricultural soil was amended with pristine engineered (PVP-coated or uncoated AgNMs), aged silver (sulphidized or released from textiles) nanomaterials, and ionic silver to determine the fate and toxicity over the course of three months. Exposures were carried out at various environmentally relevant concentrations (1 and 10 mg Ag/kg soil) representing between 30 to over 800 years of equivalent biosolid loadings. Over thirteen different methodologies and measures were used throughout this study to assess for potential effects of the silver nanomaterials on soil, including microbial community composition, average well colour development (AWCD) and enzymatic activity. Overall, the AgNM exposures did not exhibit significant toxic effects to the soil microbial communities in terms of density, activity, function and diversity. However, the positive ionic silver treatment (100 mg Ag/kg soil) resulted in suppression to microbial activity while also resulting in significantly higher populations of Frankia alni (nitrogen-fixer) and Arenimonas malthae (phytopathogen) as compared to the negative control (p < 0.05, Tukey HSD) which warrants further investigation.

A group-contribution model for predicting the physicochemical behavior of PFAS components for understanding environmental fate.

The factors controlling per- and polyfluoroalkyl substances (PFAS) environmental fate remains the subject of considerable debate and study. As surfactants, PFAS readily partition to interfaces, a property that controls their transport and fate. A group contribution model is developed to predict the extent to which PFAS partitions to the air-water interface. Langmuir adsorption and Szyszkowski equation parameters were fitted to literature air-water surface tension data for a range of PFAS and conventional hydrocarbon surfactants. This approach enabled the prediction of the impact of the hydrophilic head group, and other molecular components, on PFAS interfacial partitioning in instances when PFAS data are unavailable but analogous hydrocarbon surfactant data are available. The model was extended to predict a range of parameters (i.e., solubility, critical micelle concentration (CMC), KD, Koc and Kow) that are used to predict PFAS environmental fate, including long-range PFAS transport and in multimedia models. Model predictions were consistent with laboratory and field derived parameters reported in the literature. Additionally, the proposed model can predict the impact of pH and speciation on the extent of PFAS interfacial partitioning, a potentially important feature for understanding the behaviors of some ionizable PFAS, such as fluorinated carboxylic acids. The proposed model provides a conceptually straightforward method to predict a wide range of environmental fate parameters for a wide range of PFAS. As such, the model is a powerful tool that can be used to determine parameters needed to predict PFAS environmental fate.

Mechanochemical remediation of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) amended sand and aqueous film-forming foam (AFFF) impacted soil by planetary ball milling.

Per- and polyfluoroalkyl substances (PFAS) are manmade, fluorinated organic chemicals which have been identified as persistent organic pollutants. PFAS have surface active properties that have made them suitable for applications in oil- and water-resistant products, as well as many firefighting foams. No on-site remediation strategies exist to treat PFAS impacted soils. Mechanochemical remediation of PFOS- and PFOA-amended sand via a planetary ball mill was studied. The effect of sand mass, KOH as a co-milling reagent, and water saturation on the degradation of PFOA and PFOS was evaluated. By 4 h of milling concentrations were reduced by up to 98% for PFOS-amended dry sand and 99% for PFOA-amended dry sand without the addition of a co-milling reagent. Water saturation was determined to be a significant hindrance on the mechanochemical destruction of PFOS and PFOA. A maximum of 89% of fluoride was recovered from PFOS-amended sand when KOH was used as a co-milling reagent. It is hypothesized that reactive particles generated from the fracture of sand grains react with PFAS molecules to initiate destruction, which can result in full defluorination. Milling experiments were also conducted on soils from a Canadian firefighting training area (FFTA), demonstrating that PFOS concentrations can be reduced by up to 96% in site soils. For the first time, ball milling for the remediation of PFAS in environmental media has been demonstrated using amended sand and legacy soils from a FFTA.

Remediation of PFAS-Contaminated Soil and Granular Activated Carbon by Smoldering Combustion.

This study explored smoldering combustion for remediating polyfluoroalkyl substance (PFAS)-impacted granular activated carbon (GAC) and PFAS-contaminated soil. GAC, both fresh and PFAS-loaded, was employed as the supplemental fuel supporting smoldering in mixtures with sand (≈175 mg PFAS/kg GAC-sand), with PFAS-spiked, laboratory-constructed soil (≈4 mg PFAS/kg soil), and with a PFAS-impacted field soil (≈0.2 mg PFAS/kg soil). The fate of PFAS and fluorine was quantified with soil and emission analyses, including targeted PFAS and suspect screening as well as hydrogen fluoride and total fluorine. Results demonstrated that exceeding 35 g GAC/kg soil resulted in self-sustained smoldering with temperatures exceeding 900 °C. Post-treatment PFAS concentrations of the treated soil were near (2 experiments) or below (7 experiments) detection limits (0.0004 mg/kg). Further, 44% of the initial PFAS on GAC underwent full destruction, compared to 16% of the PFAS on soil. Less than 1% of the initial PFAS contamination on GAC or soil was emitted as PFAS in the quantifiable analytical suite. Results suggest that the rest were emitted as altered, shorter-chain PFAS and volatile fluorinated compounds, which were scrubbed effectively with GAC. Total organic fluorine analysis proved useful for PFAS-loaded GAC in sand; however, analyzing soils suffered from interference from non-PFAS. Overall, this study demonstrated that smoldering has significant potential as an effective remediation technique for PFAS-impacted soils and PFAS-laden GAC.

Assessing the role of microbial communities in the performance of constructed wetlands used to treat combined sewer overflows.

Combined sewer overflows are contaminated with various micropollutants which pose risk to both environmental and human health. Some micropollutants, such as carbamazepine and sulfamethoxazole, are very persistent and difficult to remove from wastewater. Event loaded vertical-flow constructed wetlands (retention soil filters; RSFs) have proven to be effective in the treatment of combined sewer overflows for a wide range of pollutants. However, little is known about how microbial communities contribute to the treatment efficiency, specifically to the reduction of micropollutants. To the best of our knowledge, this is the first study attempting to close this gap. Microbial communities in pilot-scale RSFs were investigated, which showed explicit grouping of metabolic activity at different filter depths with some differential abundance of identified genera. The highest microbial activity was found in the top layer of 0.75 m deep filters, whereas homogeneous activity dominated in a 0.50 m deep filter, indicating oxygen availability to be a limiting factor of the metabolic activity in RSFs. The removal efficiencies of all investigated organic trace substances were correlated to the utilization of specific carbon sources. Most notable is the correlation between the carbon source glucose-1-phosphate and the removal of metoprolol. The strongest correlations for other substances were the removal of diclofenac to the utilization of the carbohydrate i-erythritole; bisphenol A to carbohydrate α-d-lactose, and 1-H-benzotriazole to carbonic acid D-galacturonic acid. Those results are supported by positive correlations of specific microbial genera with both the utilization of the above mentioned carbon sources and the removal efficiency for the respective micropollutants. Most notable is correlation of Tetrasphaera and the removal of benzotriazole and diclofenac.

Influence of Plant Species on Microbial Activity and Denitrifier Population Development in Vegetated Denitrifying Wood-Chip Bioreactors.

The microbial characteristics of four vegetated and one unplanted wood-chip bioreactors treating greenhouse effluent were investigated in a continuous experiment operated for over 2.5 years. The bioreactors were designed to reduce nitrate concentrations via naturally induced microbial denitrification. The vegetation type and reactor depth were both found to be significant factors in defining the mixed microbial activity. However, a consistent correlation between the abundance of the denitrifying communities and reactor depth could not be found across all reactors. The media samples from the unit planted with Typha angustifolia displayed higher microbial activities compared with the other reactors. This plant's root-associated bacteria also demonstrated the greatest copies of the denitrifying genes nirK and nosZ. The most abundant denitrifier communities and those encoding the nosZ gene were found in the unplanted reactor, followed by the T. angustifolia unit. The T. angustifolia reactor demonstrated greater microbial activity and denitrification capacity at the depth of 20 cm, while the greatest denitrification capacity in the unplanted reactor was found at the depth of 60 cm. These findings indicated the importance of the T. angustifolia rhizosphere to support microbial community establishment and growth in the vicinity of the plant's roots, although those populations may eventually develop in an unplanted environment.

Developing a roadmap to determine per- and polyfluoroalkyl substances-microbial population interactions.

We collected over 40 groundwater samples from a per- and polyfluoroalkyl substances (PFAS) impacted legacy fire fighting training area in Canada to develop an in-depth assessment of the relationship between PFAS and in situ microbial communities. Results suggest differential transport of PFAS of differing chain-length and head group. There is also evidence of PFAS degradation, in particular 6:2 FTS degradation. Although PFAS constituents were not major drivers of microbial community structure, the relative abundance of over one hundred individual genera were significantly associated with PFAS chemistry. For example, lineages within the Oxalobacteraceae family had strong negative correlations with PFAS, whilst the Desulfococcus genus has strong positive correlations. Results also suggest a range of genera may have been stimulated at low to mid-range concentrations (e.g., Gordonia and Acidimicrobium), with some genera potentially inhibited at high PFAS concentrations. Any correlations identified need to be further investigated to determine the underlying reasons for observed associations as this is an open field site with the potential for many confounding factors. Positive correlations may ultimately provide important insights related to development of biodegradation technologies for PFAS impacted sites, while negative correlations further improve our understanding of the potential negative effects of PFAS on ecosystem health.

Microbial community metabolic profiles in saturated constructed wetlands treating iohexol and ibuprofen.

The aim of the present study was to elucidate the microbial community metabolic profiles in saturated constructed wetland (CW) mesocosms planted with five different wetland plant species fed with water individually spiked with 100 µg L-1 ibuprofen or iohexol. Community-level physiological profiling (CLPP) using Biolog Ecoplates was performed and coupled with the assessment of water quality parameters (water temperature, pH, DO and TOC, TN, NH4-N, PO4-P removal efficiency). The microbial community metabolic profiles (microbial activity, richness, and carbon source utilization), as well as the water quality parameters revealed similar trends among the control mesocosms and the mesocosms fed with water spiked with iohexol and ibuprofen. Significant differences were observed between the planted and unplanted mesocosms and between seasons (summer and winter) within each of the feeding lines (control, iohexol or ibuprofen). The microbial community metabolic profiles in the saturated CW were shaped by plant presence and plant species, while no negative impact of iohexol and ibuprofen presence was noticed at the 100 µg L-1. In addition, the microbial activity and richness were generally higher in planted mesocosms than in the unplanted systems in the summer. For the first time, a positive correlation between iohexol removal and the microbial community metabolic profiles (activity, richness and amines and amides utilization in summer, and carbohydrates utilization in winter) in the saturated mesocosms was observed. Putrescine utilization in the summer and d-cellobiose, d,l-alpha-glycerol phosphate in winter were linked with the metabolic processing of iohexol, while glycogen in summer and l-phenylalanine, Glycyl-l-glutamic acid in winter were linked with ibuprofen removal efficiency in the saturated CW.

Interstitial water microbial communities as an indicator of microbial denitrifying capacity in wood-chip bioreactors.

The discharge from food production greenhouses (greenhouse effluent) contains high nutrient and salt concentrations, which, if directly released, can have adverse effects on the environment. Wood-chip bioreactors are increasingly popular passive water treatment systems favoured for their economical denitrification in treating agricultural field tile drainage. Microbial communities are central to denitrification; however little is known about the maturation of microbial communities in wood-chip bioreactors treating greenhouse effluents. In this study, multiple subsurface flow wood-chip bioreactors, each vegetated with a different plant species, together with an unplanted unit, received synthetic greenhouse effluent with elevated nitrate concentrations. The hybrid bioreactors were operated for over 2 years, during which time water samples were collected from the inlet, outlet and within the reactors. The increasing denitrification rate in the bioreactor planted with Typha angustifolia (narrowleaf cattail) correlated with increasing microbial activity and metabolic richness, measured by the carbon utilization patterns in Biolog® EcoPlates. Increased denitrifying gene (nirS) copies (determined by quantitative polymerase chain reaction, qPCR), and near-complete nitrate removal were observed in the T. angustifolia and unplanted reactors after 16 and 23 months of operation respectively. The findings suggested that an acclimation period of at least one year can be expected in unseeded bioreactors planted with T. angustifolia, while bioreactors without vegetation may require a longer time to maximize their denitrification capacity. These results are important for the design and operation of wood-chip bioreactors, which are expected to be more commonly applied in the future.

Modelling the transport of shipborne per- and polyfluoroalkyl substances (PFAS) in the coastal environment.

Per- and polyfluoroalkyl substances (PFAS) are presently essential ingredients in aqueous film forming foam (AFFF) used for fire-fighting, but are also pervasive environmental contaminants. The use and subsequent release and transport of AFFF in the ocean environment from marine vessels has not been studied to date. A numerical model (Delft3D) was rigorously calibrated and validated for the hydrodynamics, and used to predict the transport of PFAS released instantaneously into a large harbour (Halifax Harbour, Nova Scotia) that is representative of coastal environments in eastern Canada and other parts of the world. The numerical model results indicate that PFAS released in the presence of strong winds and waves during a storm will travel up to 31 km in 2 days, approximately 40% farther than PFAS release during a time period dominated by tidal currents with light winds and small waves (<1 m). After a 10 day simulation, PFAS levels from release sites in the Inner Harbour were higher (40-60 µg/L) compared to PFAS levels from the Outer Harbour release site which had decreased to low levels (<1 µg/L) during a non-storm period. Along shorelines within the Harbour, PFAS concentrations remained elevated after 12 h (40-500 µg/L) and 48 h (2-300 µg/L). These concentrations are within the range of PFAS guidance values for recreational water use. The methods described here are relevant to studies of PFAS dispersion and transport in other coastal areas, and could be used to determine best practices for applications of AFFF in the coastal environment.

Estimating the number of airports potentially contaminated with perfluoroalkyl and polyfluoroalkyl substances from aqueous film forming foam: A Canadian example.

Assessing the extent to which emerging contaminants (ECs) such as perfluoroalkyl and polyfluoroalkyl substances (PFAS) have been released into the environment is one of the foundations for developing effective management and remediation strategies for impacted sites. PFAS are known to have caused the contamination of soil, groundwater, and surface water as a result of aqueous film forming foam (AFFF) being accidentally or intentionally released into the environment. To date, the scope of the issue has not been evaluated in Canada. In this study we developed a framework, in the form of a decision tree, to estimate the number of potentially PFAS impacted airport sites in Canada as a result of AFFF releases. The screening process was completed using publicly available resources including airport websites, the Canadian Owners and Pilots Association website, Sky Vector, Transport Safety Board of Canada aviation investigation reports, the Aviation Safety Network website, and Google maps. The methodology presented in this study could be used to identify additional PFAS impacted sites in Canada or other jurisdictions worldwide. 2071 airport/heliport sites in Canada were investigated with indications that 152 (7%) of these sites likely have PFAS contamination as a result of the use of AFFF at firefighter training areas (FFTAs) and/or accidents where fires occurred. In addition, another 268 sites (13%) were identified as possibly impacted with PFASs primarily as a result of the location having the ability to store and dispense petroleum products, and therefore having AFFF systems onsite. Surficial geology was also identified for all sites determined to likely have PFAS contamination. An estimated 42.8% had surficial geology composed of sand, 27% had clay, 19.7% organic-based, with the remaining sites found on cryosols or rock. Methodological validation was also completed. The procedure used in this study successfully predicted occurrences of PFAS contamination at 25 sites where contamination, as a result of AFFF use, was confirmed by Canadian governmental departments. For these 25 sites, the distance from potential release areas to the nearest surface water was calculated. Five of the sites were within 200 meters of surface water, 19 were within one kilometer, and all 25 were within 2.5 kilometers. This suggests that surface water may have been historically impacted by PFAS at as many as 152 to 420 different airport locations in Canada.

Impacts of design configuration and plants on the functionality of the microbial community of mesocosm-scale constructed wetlands treating ibuprofen.

Microbial degradation is an important pathway during the removal of pharmaceuticals in constructed wetlands (CWs). However, the effects of CW design, plant presence, and different plant species on the microbial community in CWs have not been fully explored. This study aims to investigate the microbial community metabolic function of different types of CWs used to treat ibuprofen via community-level physiological profiling (CLPP) analysis. We studied the interactions between three CW designs (unsaturated, saturated and aerated) and six types of mesocosms (one unplanted and five planted, with Juncus, Typha, Berula, Phragmites and Iris) treating synthetic wastewater. Results show that the microbial activity and metabolic richness found in the interstitial water and biofilm of the unsaturated designs were lower than those of the saturated and aerated designs. Compared to other CW designs, the aerated mesocosms had the highest microbial activity and metabolic richness in the interstitial water, but similar levels of biofilm microbial activity and metabolic richness to the saturated mesocosms. In all three designs, biofilm microbial metabolic richness was significantly higher (p < .05) than that of interstitial water. Both the interstitial water and biofilm microbial community metabolic function were influenced by CW design, plant presence and species, but design had a greater influence than plants. Moreover, canonical correlation analysis indicated that biofilm microbial communities in the three designs played a key role in ibuprofen degradation. The important factors identified as influencing ibuprofen removal were microbial AWCD (average well color development), microbial metabolic richness, and the utilization of amino acids and amine/amides. The enzymes associated with co-metabolism of l-arginine, l-phenyloalanine and putrescine may be linked to ibuprofen transformations. These results provide useful information for optimizing the operational parameters of CWs to improve ibuprofen removal.

Functionality of microbial communities in constructed wetlands used for pesticide remediation: Influence of system design and sampling strategy.

The objective of this study was to compare the microbial community metabolic function from both unsaturated and saturated constructed wetland mesocosms (CWs) when treating the pesticide tebuconazole. The comparison was performed for both interstitial water and substrate biofilm by community level physiological profiling (CLPP) via BIOLOG™ EcoPlates. For each CW design (saturated or unsaturated), six mesocosms were established including one unplanted and five planted individually with either Juncus effusus, Typha latifolia, Berula erecta, Phragmites australis or Iris pseudacorus. Microbial activity and metabolic richness of interstitial water from unsaturated CWs were significantly lower than that from saturated CWs. However, in general, the opposite result was observed for biofilm samples. Wetland plants promoted significantly higher biofilm microbial activity and metabolic richness than unplanted CWs in both CW designs. Differences in the microbial community functional profiles between plant species were only found for saturated CWs. Biofilm microbial metabolic richness was generally statistically higher than that of interstitial water in both unsaturated (1.4-24 times higher) and saturated (1.2-1.7 times higher) CWs. Carbon source (guild) utilization patterns were generally different between interstitial water and biofilm samples. Functionality of the biofilm microbial community was positively correlated to the removal of all pollutants (TN, NH4+-N, TP, TOC and tebuconazole) for both unsaturated and saturated CWs, suggesting the biofilm plays a more important role in pollutant removal than the interstitial water microbial community. Thus, merely observing the interstitial water microbial communities may underestimate the role of the microbial community in CW performance. Interestingly, the ability for the biofilm microbial community to utilize amino acids and amines/amides was positively correlated with tebuconazole removal in all system types.

Long-Term Field Study of Microbial Community and Dechlorinating Activity Following Carboxymethyl Cellulose-Stabilized Nanoscale Zero-Valent Iron Injection.

Nanoscale zerovalent iron (nZVI) is an emerging technology for the remediation of contaminated sites. However, there are concerns related to the impact of nZVI on in situ microbial communities. In this study, the microbial community composition at a contaminated site was monitored over two years following the injection of nZVI stabilized with carboxymethyl cellulose (nZVI-CMC). Enhanced dechlorination of chlorinated ethenes to nontoxic ethene was observed long after the expected nZVI oxidation. The abundance of Dehalococcoides (Dhc) and vinyl chloride reductase (vcrA) genes, monitored using qPCR, increased by over an order of magnitude in nZVI-CMC-impacted wells. The entire microbial community was tracked using 16S rRNA gene amplicon pyrosequencing. Following nZVI-CMC injection, a clear shift in microbial community was observed, with most notable increases in the dechlorinating genera Dehalococcoides and Dehalogenimonas. This study suggests that coupled abiotic degradation (i.e., from reaction with nZVI) and biotic degradation fueled by CMC led to the long-term degradation of chlorinated ethenes at this field site. Furthermore, nZVI-CMC addition stimulated dehalogenator growth (e.g., Dehalococcoides) and biotic degradation of chlorinated ethenes.