Nitrogen-based fertilizers are frequently employed in bioremediation to stimulate microbial degradation of hydrocarbon contaminants. At Casey Station, in eastern Antarctica, a urea-based fertilizer was applied to seven engineered biopiles to remediate soils impacted by historic diesel spills. While this treatment enhanced hydrocarbon degradation, it also altered soil chemistry, resulting in elevated concentrations of ammonia and nitrite. If left unmanaged, the reuse of nutrient-enriched soils poses a risk of off-site migration of soluble nitrogen species, potentially impacting adjacent ecosystems. To assess the feasibility of large-scale nutrient removal, we developed and optimized a laboratory-scale soil washing protocol aimed at reducing excess nitrogen in partially remediated soils. Three intensive washing treatments were evaluated, achieving removal of over 60

Microbes in hyper-arid and oligotrophic ecosystems like Antarctica rely on energy from atmospheric trace gas oxidation to support persistence, primary production, and carbon mitigation. Hydrocarbon contamination is common around Antarctic research stations, yet its implications for these critical ecological processes are unknown. Here, we examined the soil microbial communities of Bunger Hills, East Antarctica, including the impact of a 40-year-old legacy petroleum spill. Metagenomic analysis and gas chromatography revealed significant shifts in microbiome composition and function in contaminated soils, including severely reduced hydrogen oxidation rates, and higher (14CO2) carbon fixation rates. We reconstructed 300 microbial genomes across 16 prokaryotic phyla, describing 24 novel candidate species. Our results demonstrate the long-lasting effects of pollutants on polar microbial ecosystems, highlight the role of trace gas scavengers and hydrocarbon degraders in regulating key ecological functions, and advance our understanding of anthropogenic impacts on microbial nutrient and energy acquisition in dry desert environments.

Hydrocarbon contaminated soils resulting from human activities pose a risk to the natural environment, including in the Arctic and Antarctic. Engineered biopiles constructed at Casey Station, Antarctica, have proven to be an effective strategy for remediating hydrocarbon contaminated soils, with active ex-situ remediation resulting in significant reductions in hydrocarbons, even in the extreme Antarctic climate. However, the use of urea-based fertilisers, whilst providing a nitrogen source for bioremediation, has also altered the natural soil chemistry leading to increases in pH, ammonium and nitrite. Monitoring of the urea amended biopiles identified rising levels of nitrite to be of particular interest, which misaligns with the long term goal of reducing contaminant levels and returning soil communities to a ‘healthy’ state.Here, we combine amplicon sequencing, microfluidic qPCR on field samples and laboratory soil microcosms to assess the impact of persistent nitrite accumulation (up to 60 months) on nitrifier abundances observed within the Antarctic biopiles. Differential inhibition of ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) Nitrobacter and Nitrospira in the cold, urea treated, alkaline soils (pH 8.1) was associated with extensive nitrite accumulation (76 ± 57 mg N/kg at 60 months). When the ratio of Nitrospira:AOB dropped below ∼1:1, Nitrobacter was completely inhibited or absent from the biopiles, and nitrite accumulated. Laboratory soil microcosms (incubated at 7 °C and 15 °C for 9 weeks) reproduced the pattern of nitrite accumulation in urea fertilized soil at the lower temperature, consistent with our longer-term observations from the Antarctic biopiles, and with other temperature-controlled microcosm studies. Diammonium phosphate amended soil did not exhibit nitrite accumulation, and could be a suitable alternative biostimulant to avoid excessive nitrite build-up.

Microorganisms comprise the bulk of biodiversity and biomass in Antarctic terrestrial ecosystems. To effectively protect and manage the Antarctic environment from anthropogenic impacts including contamination, the response and recovery of microbial communities should be included in soil remediation efficacy and environmental risk assessments. This is the first investigation into the microbial dynamics associated with large scale bioremediation of hydrocarbon contaminated soil in Antarctica. Over five years of active management, two significant shifts in the microbial community were observed. The initial shift at 12-24 months was significantly correlated with the highest hydrocarbon degradation rates, increased microbial loads, and significant increases in alkB gene abundances. ANCOM analysis identified bacterial genera most likely responsible for the bulk of degradation including Alkanindiges, Arthrobacter, Dietzia and Rhodococcus. The second microbial community shift occurring from 36 to 60 months was associated with further reductions in hydrocarbons and a recovery of amoA nitrification genes, but also increasing pH, accumulation of nitrite and a reduction of oligotrophic bacterial species. Over time, the addition of inorganic fertilisers altered the soil chemistry and led to a disruption of the nitrogen cycle, most likely decoupling ammonia oxidisers from nitrite oxidisers, resulting in nitrite accumulation. The results from this study provide key insights to the long-term management of hydrocarbon bioremediation in Antarctic soils.

This study assesses toxicity of groundwater from remediated fuel spill sites, as the final phase of an environmental risk assessment of contaminated sites at sub-Antarctic Macquarie Island, Tasmania, Australia. To complement previous terrestrial ecotoxicological research, we determine risk to marine environments from residual biodegraded hydrocarbon contaminants in groundwater discharges. Direct toxicity assessments were conducted on 7 composite groundwater test solutions, adjusted to ambient seawater salinity. Eleven native marine invertebrates (from varied taxa: gastropods, bivalves, flatworms, amphipods, copepods, isopods) were exposed and observed for up to 21 d. Lethal time estimates (LT10, LT50) showed sensitivity was time dependent (LT10s = 4-15 d) and variable between species. Three species showed no response to any test solution, and most species did not respond for up to 5 d. Data were interpreted using an expert judgment response matrix with multiple lines of evidence to predict risk. No consistent patterns in the relative toxicity of test solutions, based on polar or nonpolar hydrocarbon concentrations, were identified. Although toxicity was observed in some species, this was only under worst-case conditions of undiluted, continuous, extended exposure. Natural dynamics of the site, including low groundwater discharge rates, high rainfall, and a highly energetic receiving environment, ensure groundwater is rapidly diluted and dispersed. In this context, and based on site conditions at the time of testing, these toxicity assessments provide robust evidence that residual contamination in groundwater at remediated sites at Macquarie Island is unlikely to represent a risk to the adjacent marine communities tested. Integr Environ Assess Manag 2021;17:785-801. © 2020 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

An Antarctic biopile using a composite liner (high-density polyethylene geomembrane (GMB) over a geosynthetic clay liner (GCL)) was constructed on a coarse granular subgrade to contain hydrocarbon-contaminated soil and leachate. The soil was remediated after 4 years and the biopile was decommissioned. The liner was exhumed to assess the properties and performance of the GMB and GCL. There was no significant change in the GMB index properties. Although cobbles and coarse gravel of the subgrade had left indentations in the GMB, implying tensile strains that could impact long-term performance, there were no holes. There was significant variability in the hydration of the GCL (from 10% to 220%) and in the underlying subgrade soil water content (from 5% to 30%). This reflects the complexity of the subgrade and groundwater flow in the Antarctic environment. The exhumed GCL specimens had low hydraulic conductivity (1 x 10(-11) to 7 x 10(-11) m/s) at 13 kPa. Soil samples from below the composite liner showed no detectable hydrocarbons and confirmed no migration through the barrier. It is concluded that the composite barrier contained the leachate and biopile soil over the 4 years in service in the extreme Antarctic conditions.

Hydrocarbon polar metabolites are gaining interest from industry and the remediation community due to their ubiquity and uncertainty around their toxicity. In this study, we used headspace-gas chromatography/mass spectrometry (HS-GC/MS) to characterize polar metabolites present in elutriates derived from uncontaminated, freshly hydrocarbon contaminated and partially remediated Antarctic soils. Elutriates represent the bioavailable fraction and may be used as a proxy for leachate runoff in environmental risk assessments. Control and contaminated soil elutriates were analysed for the presence of 12 aldehydes and two ketones, which cover a broad spectrum of metabolites, ranging from nC2 - nC12 carbon chain length. A total of nine aldehydes were detected in the soil elutriates. Types of aldehydes present in uncontaminated and hydrocarbon contaminated elutriates were similar. Among the polar metabolites measured in elutriates, acetaldehyde was most abundant in partially remediated soils. Microtox assays were used to determine the potential toxicity of elutriates. In addition, three aldehydes that were present at the highest concentrations in the contaminated and partially remediated soil elutriates (acetaldehyde, octanal and undecanal) were tested as single compounds. Contaminated soil elutriates tested were found to be toxic, with partially remediated elutriates less toxic than freshly contaminated elutriates. None of the three aldehydes tested separately were toxic at levels at which they were measured in elutriates. We infer that high levels of acetaldehyde in partially remediated soil due to hydrocarbon degradation highlight the potential of this metabolite as a useful chemical marker for hydrocarbon degradation under certain conditions. Microtox was sensitive to metabolites and provided a useful initial screening tool for elutriates.

A new vapour intrusion contaminant transport model was designed specifically to allow an assessment of the impact of a hydrocarbon fuel spill on air quality in cold region buildings. The model is applied to a recent situation in Antarctica, where a diesel spill impacted the construction of a new building. For the first time, this model allows consideration of the diffusive resistance of different vapour barrier to the transport of hydrocarbons into the building and an assessment of the effectiveness of different products. Site specific indoor air criteria are derived. Five scenarios are modelled at field temperatures: (1) build on current contaminated site; (2) excavate contaminated soil, backfill with clean soil and assess impact of residual contamination; (3) excavate and backfill with remediated (biopile) soil; (4) backfill with remediated soil and assess impact of residual contamination; (5) backfill with remediated soil and assess impact of a potential future fuel spill. Two different vapour barriers, a co-extruded ethylene vinyl alcohol (EVOH) geomembrane (VB1) and a linear low-density (LLDPE) geomembrane (VB2), are investigated for each scenario and compared to a base case with no vapour barrier, providing quantifiable evidence of the benefit of installing an engineered vapour barrier Contaminant concentrations were below regulatory limits for Scenarios (2–5) with VB1 and air exchange in the building. For all scenarios, the EVOH geomembrane (VB1) was consistently superior at reducing vapour transport into the building indoor air space over the LLDPE geomembrane (VB2) and no vapour barrier. The risk mitigation measures developed for this contaminated Antarctic site may be relevant for other buildings in cold regions.

Microorganisms are useful biological indicators of toxicity and play a key role in the functioning of healthy soils. In this study, we investigated the residual toxicity of hydrocarbons in aged contaminated soils and determined the extent of microbial community recovery during in-situ bioremediation at subantarctic Macquarie Island. Previously identified microbial indicators of hydrocarbon toxicity were used to understand interactions between hydrocarbon concentrations, soil physicochemical parameters and the microbial community. Despite the complexity of the field sites, which included active fuel storage areas with high levels of soil heterogeneity, multiple spill events and variable fuel sources, we observed consistent microbial community traits associated with exposure to high concentrations of hydrocarbons. These included; reductions in alpha diversity, inhibition of nitrification potential and a reduction in the ratio of oligotrophic to copiotrophic species. These observed responses and the sensitivity of microbial communities in the field, were comparable to sensitivity estimates obtained in a previous lab-based mesocosm study with hydrocarbon spiked soils. This study provides a valuable and often missing link between the quite disparate conditions of controlled lab-based spiking experiments and the complexity presented by 'real-world' contaminated field sites.

Human activity in the Polar Regions has resulted in petroleum contamination of soils. In this context, subantarctic islands are a unique management challenge for climatic, biological and logistical reasons. In this review we identify the main abiotic factors affecting petroleum-contaminated soils in the subantarctic environment, the primary effects of such contamination on biota, and lessons learned with regards to remediation techniques in this region. The sensitivity of biota to contamination depends on organism life stage, on soil properties, and on the degree of contaminant weathering. Initial studies using species endemic to subantarctic islands suggest that for fresh diesel fuel, sensitivities may range between 103 and 20 000 mg total petroleum hydrocarbons (TPH) kg(-1) soil. Diesel that has undergone a short period of weathering is generally more toxic, with sensitivities ranging between 52 and 13 000 mg TPH kg(-1) soil for an earthworm and a grass respectively (based on EC20 and IC50 values). A sufficient body of data from which to develop remediation targets for existing spills in the region does not yet exist for the region, but there has been a recent increase in research attention to address this data gap. A range of remediation methods have also now been trialled, and techniques such as in-ground aeration and nutrient addition have achieved some success. Passive management techniques such as permeable reactive barriers and phytoremediation are in preliminary stages of investigation for the region and show promise, not least because they cause less collateral disturbance than other methods. Crown Copyright (C) 2017 Published by Elsevier Ltd. All rights reserved.

A reliance on diesel generated power and a history of imperfect fuel management have created a legacy of petroleum hydrocarbon contamination at subantarctic Macquarie Island. Increasing environmental awareness and advances in contaminant characterisation and remediation technology have fostered an impetus to reduce the environmental risk associated with legacy sites. A funnel and gate permeable bio-reactive barrier (PRB) was installed in 2014 to address the migration of Special Antarctic Blend diesel from a spill that occurred in 2002, as well as older spills and residual contaminants in the soil at the Main Power House. The PRB gate comprised of granular activated carbon and natural clinoptilolite zeolite. Petroleum hydrocarbons migrating in the soil water were successfully captured on the reactive materials, with concentrations at the outflow of the barrier recorded as being below reporting limits. The nutrient and iron concentrations delivered to the barrier demonstrated high temporal variability with significant iron precipitation observed across the bed. The surface of the granular activated carbon was largely free from cell attachment while natural zeolite demonstrated patchy biofilm formation after 15 months following PRB installation. This study illustrates the importance of informed material selection at field scale to ensure that adsorption and biodegradation processes are utilised to manage the environmental risk associated with petroleum hydrocarbon spills. This study reports the first installation of a permeable bio-reactive barrier in the subantarctic.

An overview of the design and performance of geosynthetics in composite barrier systems for biopiles used to remediate hydrocarbon-contaminated soil at Casey Station, Antarctica, is presented. Seven instrumented biopiles were constructed over three field seasons. To minimize the risk of hydrocarbon migration to groundwater, composite barrier systems were used (each using different combinations of geosynthetic clay liners (GCLs), high density polyethylene (HDPE) geomembranes (GMB), and geotextiles (GTXs)). One biopile used a co-extruded geomembrane (HDPE with an ethylene vinyl alcohol (EVOH) core). The liner system was subject to a combination of coupled phenomena that could interact and affect the GMB–GCL composite barrier performance. The exposure conditions involved potential freeze–thaw cycling, hydration–desiccation cycles, cation exchange, direct and diffusive exposure to hydrocarbons. The effect of these phenomena was investigated by monitoring GCL and GMB sacrificial coupons. GCL coupons were placed between the main GCL component and the main geomembrane component of the composite liner and GMB coupons placed between the main GMB sheet and the GTX protection layer. Coupons were exhumed from the biopiles each year. The exhumed GCL field moisture content values ranged from 162% to 22%. After three (3) years in the field, GCL coupons that had undergone at least one hydration/desiccation cycle showed no significant change in swell index values or fluid loss values. The measured hydraulic conductivity of exhumed GCL coupons from Biopiles 1 and 2 (3 × 10−11 m s−1) was within the expected range and not significantly different from the values for virgin GCL. GMB coupons exhumed after three years from Biopiles 1 and 2 showed no significant change in oxidative induction time (OIT), melt flow index or tensile properties. Diffusion tests were performed as an index test for establishing the performance of the GMBs as a diffusive barrier to hydrocarbons, with permeation parameters for BTEX contaminants ranging from Pg = 0.9–9.2 × 10−13 m2 s−1 for the exhumed GMB (with values depending on the contaminant and GMB). These values were similar to the parameters obtained for virgin GMBs and there was no significant change with field exposure, with GMBs appearing to be performing well.

The first large-scale remediation of fuel contamination in Antarctica treated 10000L of diesel dispersed in 1700t of soil, and demonstrated the efficacy of on-site bioremediation. The project progressed through initial site assessment and natural attenuation, passive groundwater management, then active remediation and the managed reuse of soil. Monitoring natural attenuation for the first 12years showed contaminant levels in surface soil remained elevated, averaging 5000mg/kg. By contrast, in five years of active remediation (excavation and biopile treatment) contaminant levels decreased by a factor of four. Chemical indicators showed hydrocarbon loss was apportioned to both biodegradation and evaporative processes. Hydrocarbon degradation rates were assessed against biopile soil temperatures, showing a phase of rapid degradation (first 100days above soil temperature threshold of 0°C) followed by slower degradation (beyond 100days above threshold). The biopiles operated successfully within constraints typical of harsh climates and remote sites, including limitations on resources, no external energy inputs and short field seasons. Non-native microorganisms (e.g. inoculations) and other organic materials (e.g. bulking agents) are prohibited in Antarctica making this cold region more challenging for remediation than the Arctic. Biopile operations included an initial fertiliser application, biannual mechanical turning of the soil and minimal leachate recirculation. The biopiles are a practical approach to remediate large quantities of contaminated soil in the Antarctic and already 370t have been reused in a building foundation. The findings presented demonstrate that bioremediation is a viable strategy for Antarctica and other cold regions. Operators can potentially use the modelled relationship between days above 0°C (threshold temperature) and the change in degradation rates to estimate how long it would take to remediate other sites using the biopile technology with similar soil and contaminant types.

A dynamic multi-media model that includes temperature-dependency for partitioning and degradation was developed to predict the behaviour of petroleum hydrocarbons during biopiling at low temperature. The activation energy (Ea) for degradation was derived by fitting the Arrhenius equation to hydrocarbon concentrations from temperature-controlled soil mesocosms contaminated with crude oil and diesel. The model was then applied to field-scale biopiles containing soil contaminated with diesel and kerosene at Casey Station, Antarctica. Temporal changes of total petroleum hydrocarbons (TPH) concentrations were very well described and predictions for individual hydrocarbon fractions were generally acceptable (disparity between measured and predicted concentrations was less than a factor two for most fractions). Biodegradation was predicted to be the dominant loss mechanism for all but the lightest aliphatic fractions, for which volatilisation was most important. Summertime losses were significant, resulting in TPH concentrations which were about 25% of initial concentrations just 1 year after the start of treatment. This contrasts with the slow rates often reported for hydrocarbons in situ and suggests that relatively simple remediation techniques can be effective even in Antarctica.

The management of the soil microbial P pool could improve system sustainability. The long-term impact of inorganic P inputs (0, 40 and 80 kg P2O5 ha-1) and tillage (conventional and ridge tillage) on soil microbial biomass P (SMB-P) was defined in the soybean phase of a 10-yr-old maize-soybean rotation, on a Gleysolic clay-loam. Soil microbial biomass C (SMB-C) and SMB-P were determined four times in the growing season. Yearly applications of 40 kg P2O5 ha-1 increased soil organic carbon level, partly explaining the increase in SMB-P measured at this rate. Results suggest that P-mediated modification of soil microbial community structure also contributed to increase SMB-P at this P rate. The increase of application of P rate (80 kg P2O5 ha-1) produced the largest soybean yield, but generally decreased SMB-P. Our results and those of others suggest that balanced soil fertility (corresponding to fertilizer recommendations in our case) promotes soil microbial development. The use of ridge tillage did not increase the soil organic carbon level, but did increase SMB-P. The SMB-P pool was large (equivalent to 24.4kg P2O5 ha-1) in the 0- to 20-cm soil layer, but unrelated to yield. Improving the ability of crops to access this pool of soil P would increase the value of its management. Key words: Conventional tillage, conservation tillage, P fertilization, soil microbial biomass C, P, and C to P ratio

Summary Environmental concerns currently trigger the development of more sustainable soil fertility management strategies. It appears that effective sustainable practices are those that enhance natural soil processes. Soil processes include the decomposition of residues and mineralization of organic matter, nitrogen fixation, nitrification, nitrate leaching, denitrification and sulfur reduction. Natural soil processes also include less well-understood interactions, namely, those leading to the dissolution of minerals by organic acids, as well as rhizospheric and mycorrhizospheric interactions. Plants, associated with arbuscular mycorrhizal symbionts, supply and distribute carbon and energy, sustaining most of the biotic mechanisms responsible for nutrient release from soil, and maintaining organic pools of nutrients. Among these pools, the microbial biomass and fine roots pools, with their very fast turnover time, are particularly important as they can maintain large amounts of nutrients in very labile form and, therefore, increase soil fertility. Agricultural soil systems are very dynamic and are characterized by large spatial and temporal variations, which are largely driven by plant development. In addition, nutrient dynamics in agricultural soil systems seem particularly influenced by temperature, moisture, and nitrogen and phosphorus fertilization. Nitrogen losses from soil are reduced in systems where nitrogen release corresponds to plant demand. Biological nitrogen fixation is a sound way to input nitrogen in cropping systems. Phosphorus losses can be reduced through increased reliance on the arbuscular mycorrhizal symbiosis of crops. Soils are diverse and complex systems, which, furthermore, respond to increasingly unpredictable climatic variations. Optimal agricultural soil management is a moving target and, hence, a challenging goal that will never be totally reached.