Global Patterns of Metal and Other Element Enrichment in Bog and Fen Peatlands.

Peatlands are found on all continents, covering 3% of the global land area. However, the spatial extent and causes of metal enrichment in peatlands is understudied and no attempt has been made to evaluate global patterns of metal enrichment in bog and fen peatlands, despite that certain metals and rare earth elements (REE) arise from anthropogenic sources. We analyzed 368 peat cores sampled in 16 countries across five continents and measured metal and other element concentrations at three depths down to 70 cm as well as estimated cumulative atmospheric S deposition (1850-2009) for each site. Sites were assigned to one of three distinct broadly recognized peatland categories (bog, poor fen, and intermediate-to-moderately rich fen) that varied primarily along a pH gradient. Metal concentrations differed among peatland types, with intermediate-to-moderately rich fens demonstrating the highest concentrations of most metals. Median enrichment factors (EFs; a metric comparing natural and anthropogenic metal deposition) for individual metals were similar among bogs and fens (all groups), with metals likely to be influenced by anthropogenic sources (As, Cd, Co, Cu, Hg, Pb, and Sb) demonstrating median enrichment factors (EFs) > 1.5. Additionally, mean EFs were substantially higher than median values, and the positive correlation (< 0.40) with estimated cumulative atmospheric S deposition, confirmed some level of anthropogenic influence of all pollutant metals except for Hg that was unrelated to S deposition. Contrary to expectations, high EFs were not restricted to pollutant metals, with Mn, K and Rb all exhibiting elevated median EFs that were in the same range as pollutant metals likely due to peatland biogeochemical processes leading to enrichment of these nutrients in surface soil horizons. The global patterns of metal enrichment in bogs and fens identified in this study underscore the importance of these peatlands as environmental archives of metal deposition, but also illustrates that biogeochemical processes can enrich metals in surface peat and EFs alone do not necessarily indicate atmospheric contamination.

Variation in carbon and nitrogen concentrations among peatland categories at the global scale.

Peatlands account for 15 to 30% of the world's soil carbon (C) stock and are important controls over global nitrogen (N) cycles. However, C and N concentrations are known to vary among peatlands contributing to the uncertainty of global C inventories, but there are few global studies that relate peatland classification to peat chemistry. We analyzed 436 peat cores sampled in 24 countries across six continents and measured C, N, and organic matter (OM) content at three depths down to 70 cm. Sites were distinguished between northern (387) and tropical (49) peatlands and assigned to one of six distinct broadly recognized peatland categories that vary primarily along a pH gradient. Peat C and N concentrations, OM content, and C:N ratios differed significantly among peatland categories, but few differences in chemistry with depth were found within each category. Across all peatlands C and N concentrations in the 10-20 cm layer, were 440 ± 85.1 g kg-1 and 13.9 ± 7.4 g kg-1, with an average C:N ratio of 30.1 ± 20.8. Among peatland categories, median C concentrations were highest in bogs, poor fens and tropical swamps (446-532 g kg-1) and lowest in intermediate and extremely rich fens (375-414 g kg-1). The C:OM ratio in peat was similar across most peatland categories, except in deeper samples from ombrotrophic tropical peat swamps that were higher than other peatlands categories. Peat N concentrations and C:N ratios varied approximately two-fold among peatland categories and N concentrations tended to be higher (and C:N lower) in intermediate fens compared with other peatland types. This study reports on a unique data set and demonstrates that differences in peat C and OM concentrations among broadly classified peatland categories are predictable, which can aid future studies that use land cover assessments to refine global peatland C and N stocks.

Periostracum of bivalve mollusk shells for sampling engineered metal nanoparticles: A case study of silver-based nanoparticles in Canada's experimental lake.

Given the ability of engineered metal nanoparticles to be transformed in natural waters in unpredictable manners, various sampling methods must be developed. Here, we took a novel approach to collection silver nanoparticles (AgNPs) that involved the use of the intact periostracum, the outer proteinaceous organic layer, of freshwater unionid mussels Pyganodon sp. Eight adult mussels were collected in August 2019 from a small boreal lake (L222) at the International Institute for Sustainable Development - Experimental Lakes Area (northwestern Ontario), which had been dosed with 15 kg of poly(vinylpyrrolidone)-coated silver nanoparticles (PVP-AgNPs) in 2014-2015. Additionally, three adult mussels were collected from a control lake (L375). Numerous silica (SiO2) diatom frustules were adhered to periostracum of all mussels. Intact periostracum promotes the formation of layer composed of diatoms and sand grains. The Ag content in soft tissues and shells of the mussels from L375 was as low as ≤ 0.1 µg/g. In mussels from L222, Ag concentrations in the periostracum of five shells were in detectable amounts (1-4 µg/g); in three shells concentrations were as high as 86, 122, and 494 µg/g. The underlying mineral shell is depleted in Ag (<0.1 µg/g). The Ag content in soft tissue organs (whole body) ranged from 44 to 191 µg/g. AgNPs occur on the surface of both periostracum and diatoms. Single AgNPs (d = 20-60 nm) were partly sulfidized to Ag2S. The observed AgNPs often form aggregates with an average and a maximal size of circa 100 nm and 1.5 µm, respectively. Scraping small fragments of intact periostracum of unionid shell is non-lethal to mussels, and is easy to do under field conditions. This simple sampling protocol could be used to detect metal-based nanoparticles (engineered or accidental) with the use of unionid and dreissenid bivalves.

Pre-exposure to Cu2+ and CuO NPs leads to infection of caged blue mussels, Mytilus edulis L., by pathogenic microalga: Pilot study in the Lower St. Lawrence Estuary (Québec, Canada).

As evidenced from literature, exposure to non-lethal concentrations of dissolved copper (Cu2+) and copper nanoparticles (CuO NPs) promotes blue mussels susceptibility to various bacterial infections. We study whether pre-exposure (3.5 h) with CuSO4 (100 µg Cu L-1) and CuO NPs (1000 µg Cu L-1) will result in infection of M. edulis L. with pathogenic microalga Coccomyxa sp. under field conditions. In May - September 2019, cages were installed in the site Metis-sur-Mer, St. Lawrence Estuary (QC, Canada) where the native mussel population is known to be infected with the pathogen. Untreated and pre-exposed mussels were grown for up to 130 days. Only the mussels pre-exposed to copper were infected by Coccomyxa. This finding allows proposing that occurrences of Coccomyxa-infected mussels worldwide might have an association with water pollution with xenobiotics. Pre-exposure of caged mussels to copper, as a protocol monitoring for other infectious agents, can be recommended to test.

Organic amendments potentially stabilize metals in smelter contaminated Arctic soils: An incubation study.

The long-term emission impacts of the nickel processing industry in the Kola Peninsula, the largest source of sulfur dioxide and heavy metals emissions in Northern Europe, have created vast technogenic barrens near the mineral industry complexes. The pace of rehabilitation using the improved remediation technologies to enhance sustainable environmental management and regional economic development is of crucial social and economic importance. In a 120-day incubation experiment, we evaluated the prospects for the restoration of two soils at different degradation stages via carbon pool regulation comparing to mineral ameliorants - NPK fertilizer, and liming agent. Organic additives used included a humic preparation based on an alkaline brown coal extract, wood-derived biochar, and peat-derived gel, supplied by mycorrhizae fungi. The results demonstrate that the selected organic amendments are suitable for restoration of acidic metal contaminated soils. Specifically, the treatments provided a measurable increase in soil carbon content, a marked decrease in acidity, a decrease in extractable metal contents, together with an enhanced nutrient uptake and vegetative growth. A stabilization effect increased from biochar to peat-gel, liming agent and humic preparation, with an accompanying increase in soil pH. Although biochar showed a reduced ability to metal stabilization, the associated treatments were the most productive. The most effective amendments in multi-metallic contaminated soils need to be able to stabilize bioavailability of metals, adjust pH to the optimum for plant growth, and regulate nutrient consumption.

Blended municipal compost and biosolids materials for mine reclamation: Long-term field studies to explore metal mobility, soil fertility and microbial communities.

Application of stable soil amendments is often the key to successful phytostabilization and rehabilitation of mine tailings, and microbial guilds are primary drivers of many geochemical processes promoted by these amendments. Field studies were set up at a tailings management area near Sudbury, Ontario to examine performance of blends of lime stabilized municipal biosolids and compost at nine different rates over thick (1 m) municipal compost covers planted with agricultural crops. Based on biogeochemical variability of the substrates four and ten years after application of the initial compost cover, the experimental plots could be classified into three categories: "Low" rate (0-100 t ha-1 biosolids), "Medium" rate (200-800 t ha-1), and "High" rate (1600-3200 t ha-1) treatments. The addition of biosolids materials to the thick compost cover at rates higher than 100 t ha-1 significantly reduced C:N ratio of the substrates, available phosphorus, and some of the nutrient cations, while notably increasing inorganic carbon and the potential solubility of Ni and Cu. This suggests that increasing biosolids application rates may not equivalently ameliorate soil quality and geochemical stability. Correspondingly, microbial communities were altered by biosolids additions, further intensifying the negative impacts of biosolids on long-term efficiency of the initial compost cover. Abundance of cellulose, hemicellulose, and lignocellulose decomposers (as key drivers of mineralization and humification) was significantly reduced by "Medium" and "High" rate treatments. Most DNA sequences with high affinity to denitrifiers were detected in "High" rate treatments where geochemical conditions were optimal for higher microbial denitrification activities. These findings have implications for improving the long-term efficiency of reclamation and environmental management programs in mine tailings of northern temperate climates.

First report of signs of infection by Coccomyxa-like algae in wild blue mussels, Mytilus spp., in the Gulf of Maine (USA, Maine).

In August 2019, visual inspection of intertidal zones of the Gulf of Maine (ME, USA) revealed young and adult wild blue mussels, Mytilus spp., in Alley Bay (Jonesport area) with the distinctive L-shaped shell deformity (LSSD) and green spots (GS) in the mantle and adductor muscle. LSSD is a characteristic sign of current or previous mussel infection by photosynthetic unicellular alga from the group Coccomyxa, while GS are algal colonies. Based on these findings, this study represents the first report of infection signs by pathogenic Coccomyxa-like algae in mussels from the coastal waters of the Northeastern United States, providing a base for future large scale monitoring of the alga in the region.

Rhizobioaugmentation of Casuarina glauca with N-fixing actinobacteria Frankia decreases enzymatic activities in wastewater irrigated soil: effects of Frankia on C. glauca growth.

The use of wastewater for irrigation in agroforestry is cost-effective for water management. It is well established that rhizospheric microorganisms such as N2-fixing bacteria are able to modulate rhizobioaugmention and to boost phyoremediation process. To date, no study has been conducted to evaluate biological effects of rhizobioaugmentation in Casuarina glauca trees induced by their symbiont N-fixing actinobacteria of the genus Frankia. The objective of the present study was to evaluate the main effects of rhizobioaugmentation on the biological activity in the C. glauca's rhizosphere and on C. glauca growth in soils irrigated with industrial wastewater. Two Frankia strains (BMG5.22 and BMG5.23) were used in a single or dual inoculations of C. glauca seedlings irrigated with industrial wastewater. Soil enzymes activity related to carbon, phosphorus, sulfur and nitrogen cycling were measured. Results revealed that the BMG5.22 Frankia strain increases significantly the size (dry weight) of C. glauca shoots and roots while dual inoculation increased significantly the root length. Surprisingly, ß-glucosidase (BG), cellobiohydrolase (CBH), ß-N-acetylglucosaminidase (NAGase), aryl sulfatase (AS), acid phosphatase (AP), alkaline phosphatase (AlP), glycine aminopeptidase (GAP), leucine aminopeptidase (LAP), and peroxidase (PER) activity in the rhizosphere decreased significantly in soils treated with the two strains of symbionts. This suggests no positive correlations between enzymatic activity and C. glauca growth.

Practical advice on monitoring of U and Pu with marine bivalve mollusks near the Fukushima Daiichi Nuclear Power Plant.

Following the Fukushima Daiichi nuclear power plant accident in 2011, some marine radionuclide monitoring studies report a lack of evidence for contamination of Japanese coastal waters by U and Pu, or state that marine contamination by them was negligible. Nevertheless, Fukushima-derived U and Pu were reported as associated with Cs-rich microparticles (CsMPs) found in local soil, vegetation, and river/lake sediments. Over time, CsMPs can be transported to the sea via riverine runoff where actinides, as expected, will leach. We recommend establishing a long-term monitoring of U and Pu in the nearshore area of the Fukushima Prefecture using marine bivalve mollusks; shells, byssal threads and soft tissues should all be analyzed. Here, based on results from Th biosorption experiments, we propose that U and Pu could be present at concentrations several times higher in shells with a completely destroyed external shell layer (periostracum) than in shells with intact periostracum.

Shell deformity as a marker for retrospective detection of a pathogenic unicellular alga, Coccomyxa sp., in mytilid mussels: A first case study and research agenda.

An L-shaped shell deformity (LSSD) on the posterior shell edge is known exclusively in wild mytilid mussels infected with photosynthetic Coccomyxa-like algae. LSSD forms due to the appearance of extra shell material; it only occurs if the mussel is heavily infected with the alga. Traditionally, observation of high amount of the green spots (algal colonies) on a large area of host soft tissues (most of the mantle and in adductor muscle) has been used to indicate a high infection rate. We examined 300 Mytilus spp. (100 small, 20-30 mm; 200 large, 40-60 mm) with a high degree of LSSD (parameter "d" > 5 mm) from the Lower St. Lawrence Estuary (Québec, Canada). Green spots were absent in two large mussels, and were only present along the mantle posterior edge in 14 large mussels; other individuals had high infection levels. Our observations suggest that some individuals could be in a state of remission, or, even more optimistically - mussels may be able to resist the pathogen. LSSD is the stable through-time marker for detection of mytilid mussels that are or were infected with Coccomyxa algae, and, thus, may provide information for the study of mussel immunity and control of alga distribution/migration in coastal waters worldwide.

Blended pulp mill, forest humus and mine residual material Technosols for mine reclamation: A growth-chamber study to explore the role of physiochemical properties of substrates and microbial inoculation on plant growth.

A growth chamber trial was conducted to investigate the effects of blends of pulp and paper mill residuals and forest humus on soil properties, microbial communities and germination rate and biomass production of annual ryegrass (Lolium multiflorum) in both acid-producing and neutral to mildly alkaline mine tailings in a mine reclamation context. The organic residual amendments improved the nutritional status of the tailings substrates, and increased pH in acid-generating tailings, leading to higher germination rates and improved plant growth. A trace addition (<0.02% of sludge by dry weight) of natural forest floor material as a microbial inoculum to the sludge could increase plant biomass up to four-fold. The effects of sludge application on bioavailability of metals were variable, with the concentration of soluble copper (Cu) and nickel (Ni) increasing in some of the substrates following organic amendments. Addition of paper mill residuals to mine tailings modified the microbial communities observed in the oligotrophic tailings with the majority of DNA sequences in the sludge amended substrates being found to be closely related to heterotrophic bacterial species rather than the chemolithotrophic communities that dominate tailings environments.

Rates and processes affecting As speciation and mobility in lake sediments during aging.

Sediments from an arsenic (As) contaminated groundwater vent site were used to investigate As(III) binding, transformation and redistribution in native and iron oxide amended lake sediments using aging spiked batch reactions and a sequential extraction procedure that maintains As(V) and As(III) speciation. In the native sediments, fractionation analysis revealed that 10% of the spiked As(III) remained intact after a 32-day aging experiment and was predominantly adsorbed to the strongly sorbed (NH4H2PO4 extractable) and amorphous Fe oxide bound (H3PO4 extractable) fractions. Kinetic modelling of the experimental results allowed identifying the dominant reaction path for depletion of dissolved As(III) to As(III) absorbed on to the solid phase, followed by oxidation in the solid phase. Arsenite was initially adsorbed primarily to the easily exchangeable fraction ((NH4)2SO4 extractable), then rapidly transformed into As(V) and redistributed to the strongly sorbed and amorphous Fe oxide bound fractions. Oxidation of As(III) in recalcitrant fractions was less efficient. The iron oxide amendments illustrated the controls that iron oxides can have on As(III) binding and transformation rates. In goethite amended samples As(III) oxidation was faster and primarily occurred in the strongly sorbed and amorphous Fe oxide bound fractions. In these samples, 19.3µg Mn was redistributed (compared to the native sediment) from the easily exchangeable and crystalline Fe oxide bound fractions to the strongly sorbed and amorphous Fe oxide bound fractions, indicating that goethite may act as a catalyst for Mn(II) oxidation, thereby producing sorbed Mn(III/IV), which then appears to be involved in rapidly oxidizing As(III).

Validation of an updated fractionation and indirect speciation procedure for inorganic arsenic in oxic and suboxic soils and sediments.

A sequential extraction procedure (SEP) for the speciation analysis of As(III) and As(V) in oxic and suboxic soils and sediments was validated using a natural lake sediment and three certified reference materials, as well as spike recoveries of As(III) and As(V). Many of the extraction steps have been previously validated making the procedure useful for comparisons to similar previous SEP studies. The novel aspect of this research is the validation for the SEP to maintain As(III) and As(V) species. The proposed five step extraction procedure includes the extraction agents (NH4)2SO4, NH4H2PO4, H3PO4 + NH2OH·HCl, oxalate + ascorbic acid (heated), and HNO3 + HCl + HF, targeting operationally defined easily exchangeable, strongly sorbed, amorphous Fe oxide bound, crystalline Fe oxide bound, and residual As fractions, respectively. The third extraction step, H3PO4 + NH2OH·HCl, has not been previously validated for fraction selectivity. We present evidence for this extraction step to target As complexed with amorphous Fe oxides when used in the SEP proposed here. All solutions were analyzed on ICP-MS. The greatest concentrations of As were extracted from the amorphous Fe oxide fraction and the dominant species was As(V). Lake sediment materials were found to have higher As(III) concentrations than the soil materials. Because different soils/sediments have different chemical characteristics, maintenance of As species during extractions must be validated for specific soil/sediment types using spiking experiments.

Multi-dimensional water quality assessment of an urban drinking water source elucidated by high resolution underwater towed vehicle mapping.

Spatial surveys of Ramsey Lake, Sudbury, Ontario water quality were conducted using an innovative underwater towed vehicle (UTV) equipped with a multi-parameter probe providing real-time water quality data. The UTV revealed underwater vent sites through high resolution monitoring of different spatial chemical characteristics using common sensors (turbidity, chloride, dissolved oxygen, and oxidation/reduction sensors) that would not be feasible with traditional water sampling methods. Multi-parameter probe vent site identification is supported by elevated alkalinity and silica concentrations at these sites. The identified groundwater vent sites appear to be controlled by bedrock fractures that transport water from different sources with different contaminants of concern. Elevated contaminants, such as, arsenic and nickel and/or nutrient concentrations are evident at the vent sites, illustrating the potential of these sources to degrade water quality.

Radionuclide release from simulated waste material after biogeochemical leaching of uraniferous mineral samples.

Biogeochemical mineral dissolution is a promising method for the released of metals in low-grade host mineralization that contain sulphidic minerals. The application of biogeochemical mineral dissolution to engineered leach heap piles in the Elliot Lake region may be considered as a promising passive technology for the economic recovery of low grade Uranium-bearing ores. In the current investigation, the decrease of radiological activity of uraniferous mineral material after biogeochemical mineral dissolution is quantified by gamma spectroscopy and compared to the results from digestion/ICP-MS analysis of the ore materials to determine if gamma spectroscopy is a simple, viable alternative quantification method for heavy nuclides. The potential release of Uranium (U) and Radium-226 ((226)Ra) to the aqueous environment from samples that have been treated to represent various stages of leaching and passive closure processes are assessed. Dissolution of U from the solid phase has occurred during biogeochemical mineral dissolution in the presence of Acidithiobacillus ferrooxidans, with gamma spectroscopy indicating an 84% decrease in Uranium-235 ((235)U) content, a value in accordance with the data obtained by dissolution chemistry. Gamma spectroscopy data indicate that only 30% of the (226)Ra was removed during the biogeochemical mineral dissolution. Chemical inhibition and passivation treatments of waste materials following the biogeochemical mineral dissolution offer greater protection against residual U and (226)Ra leaching. Pacified samples resist the release of (226)Ra contained in the mineral phase and may offer more protection to the aqueous environment for the long term, compared to untreated or inhibited residues, and should be taken into account for future decommissioning.

X-ray microCT imaging technique reveals corm microstructures of an arctic-boreal cotton-sedge, Eriophorum vaginatum.

X-ray computed tomography (CT), a non-destructive imaging technique, has recently been effectively applied to botanical research. In this study an X-ray microCT technique was developed to allow for anatomical study of the overwintering corms of Eriophorum vaginatum, an ecologically important sedge species in arctic tussock-tundra and boreal peatlands. Using a GE Medical MS8X-130 X-ray microCT scanner, optimal imaging parameters included scanning isolated corms at 80 k Vp and 100 microA with a 3500 ms exposure time and an isotropic voxel size of 10 microm. A Gaussian blur image filter with a blur radius (sigma) of two pixels was applied to the optimal dataset to improve visual detection and contrast of tissues while removing 99.2% of image noise. Using the developed X-ray microCT technique several undocumented anatomical characteristics of the corm were identified including the vascular connection between a parent corm and branching cormel and the 3D shape of sclereid clusters. The 3D structure of sclereid clusters was determined whereby the perimeter of their lance shape is greatly reinforced by sclereids with thicker secondary cell walls as compared to those of the interior of the cluster. The structure of sclereid clusters and their association with leaf traces suggests they may be stabilizing the corm-leaf connection to protect vascular tissues from physical damage. The proposed X-ray microCT technique is an excellent tool for determination of the 3D structure of E. vaginatum corms and may be used to detect alterations in tissue structure and chemistry in response to environmental change in this and other Cyperaceous species.

Effects of estimates from different geochemical models on metal fate predicted by coupled speciation-fate models.

Coupled metal speciation-fate models are an improvement over stand-alone fate-transport models for accurately assessing metal fate and transport. These coupled models estimate fate-controlling partition coefficients using geochemical speciation/complexation models. Commercially available geochemical models are practical options for a two-step, loose coupling with fate-transport models. These models differ in their partitioning estimates because of differences in assumptions, databases, and so on. The present study examines the effects of differences in estimates from geochemical models on estimates of cationic metal fate using two geochemical models: the Windermere humic aqueous model (WHAM) and the minicomputer equilibrium+ model (MINEQL+). The results from each geochemical model were used as input to the fate module of TRANSPEC (a general, coupled metal transport and speciation model). The two versions of the TRANSPEC model were then used to assess the fate of five cationic metals (Cd, Cu, Ni, Pb, and Zn) in Ross Lake (Flin Flon, MB, Canada; alkaline, eutrophic, mine impacted), Kelly Lake (Sudbury, ON, Canada; circumneutral, mesotrophic, mine influenced), and Lake Tantaré (Quebec City, QC, Canada; acidic, oligotrophic, pristine). For relatively soluble metals (Cd, Ni, and Zn), the WHAM and MINEQL+ estimates of speciation/complexation were similar for Ross and Kelly lakes but differed for Lake Tantaré. These differences, however, did not result in significant differences in overall fate estimates. Marked differences were observed between the WHAM and MINEQL+ estimates of partition coefficient, Kd, for more particle-reactive Cu and Pb that translated into the greatest impact on fate in mesotrophic Kelly Lake, in which particle movement is important for fate.