Weathering alters the profile of trace metals and organic compounds in leachates and bioavailability extracts from microplastics of trail running shoes.

Microplastics (MPs) from rubber outsoles of trail running shoes may contribute significantly to contamination in protected areas. In the natural environment, weathering processes can damage MP molecular structure and alter the mobility of inorganic and organic compounds used as additives in rubber. In this study, we characterised changes in the surface morphology, functional groups, and thermal stability of MPs weathered on and below the soil surface over 12 weeks, and analysed inorganic and organic additives in leachates (0.01M CaCl2) and bioaccessibility extracts (ethyl acetate). Weathering conditions included UVC irradiation at 25 °C and 80% soil moisture. Microplastics on the soil surface exhibited cracking, fragmentation, and increased extractability of zinc, sulphur, titanium and fatty acids. Microplastics below the soil surface were not significantly physically or chemically altered, however zinc leachability increased following extended weathering by up to 155%. Bioaccessibility of thiol, aromatic and cyclic organic additives decreased from both surface and sub-surface MPs over the 12 week weathering period, but there was evidence of an increase in transformation by-products. Microplastic toxicity may be significantly altered by environmental conditions and MP weathering. It is critical ecotoxicological studies use weathered MPs to assess impacts on rare and endemic species found in protected spaces.

Microplastic pollution on hiking and running trails in Australian protected environments.

Microplastics (MPs) are ubiquitous worldwide, present even in remote areas of the natural environment. Hiking and trail running are a source of MPs on recreational trails in protected environments, which are characterised by high biodiversity and natural, ecological or cultural significance. Our understanding of the risks of microplastic pollution is impeded however by a lack of information on MPs present in the soil environment in such areas. This study characterised the quantity and physicochemical characteristics of MPs in two conservation areas in south-eastern Australia: 1) the adjacent Duval Nature Reserve and Dumaresq Dam Reserve, and 2) the Washpool and Gibraltar Range National Parks. We measured atmospheric deposition over a six-month period in the Reserves, and baseline amounts of MPs on recreational trails in the Reserves and National Parks. Atmospheric deposition averaged 17.4 MPs m-2 day-1 and was dominated by fibres, comprising 84 % of MPs. Microplastics detected on trail surfaces ranged from 162.5 ± 41.6 MPs/linear metre to 168.7 ± 18.5 MPs/linear metre and exhibited a very wide range of physical and chemical characteristics. The majority of MPs on the trail surfaces comprised polyurethane, polyethylene terephthalate and polystyrene, and 47-71 % were fibres. Microplastics were attributed to clothing, footwear, litter, and diffuse sources. Minimising and preventing MP pollution, however, is complex given there are multiple direct and diffuse sources, and several factors influencing increased MP deposition and retention in the environment.

Trail running events contribute microplastic pollution to conservation and wilderness areas.

Clothing and footwear designed for trail running shed microplastics (MPs) during use. Trail running events may therefore present a significant source of MP pollution in conservation and wilderness areas. Microplastics may present long-term risks to biodiversity and endemic plant and animal species in such areas. In this study, we used a before-after-control-impact approach to quantify and characterise MP emissions from clothing and shoe outsoles during trail running events. Microplastic deposition on trail surfaces was assessed using both a controlled study and during two public trail running events in New South Wales, Australia (the Duval Dam Buster and the Washpool World Heritage Trail Race). Microplastics were present on trails after all events and included fibres and rubber fragments. Microplastic counts varied considerably depending on trail surface hardness and gradient, and clothing and footwear properties. The controlled study showed running tights (leggings) and shoes with soft rubber outsoles produced more MPs than shirts and hard rubbers. In the trail running events, abrasive wear to shoe outsoles produced an average of 0.3 ± 0.1 to 0.9 ± 0.2 MPs/linear metre/runner, and clothing produced 0.7 ± 0.3 to 2.0 ± 0.3 fibres/linear metre/runner, with fibres accounting for 63-69% of MPs. Microplastic deposition from both footwear and clothing was higher on sloped and rock trail surfaces than flat and soil surfaces. Laser Direct Infrared (LDIR) Imaging indicated the main types of MPs present on trails were polyurethane, polyethylene terephthalate and polyamide. Trail running is increasing in popularity and large-scale events may cause a rapid and significant input of MPs in protected areas. Land managers, event coordinators and outdoor apparel manufacturers could mitigate MP impacts however, by diverting foot traffic around ecologically sensitive areas, capping participant numbers, and developing abrasion resistant clothing and footwear.

Arsenic and cadmium leaching in co-contaminated agronomic soil and the influence of high rainfall and amendments.

Arsenic (As) and cadmium (Cd) co-contaminate agricultural systems worldwide and threaten water resources, food security and human health. This column leaching study examined As and Cd mobility in an acidic sandy loam Alfisol soil collected from the dry zone of Sri Lankafor four co-contaminant concentration combinations (spiked and 1 year aged As at 20 & 100 mg kg-1 with co-added Cd at 3 & 20 mg kg-1) i, and under the influence of high rainfall (RF), phosphorus fertilizer (P) and lime amendments. In almost all treatments a synergistic co-contaminant adsorption effect was evident which reduced leaching of both elements, significantly in the higher spiked soil concentration treatments. The magnitude of leaching decrease varied with treatment but was greater for As due to its weaker retention in the soil. The co-sorbing effects, evident even under RF, were attributed to electrostatic sorption interactions, the formation of ternary bridging complexes and surface precipitation at higher concentrations. Liming significantly retarded mobilisation of both elements in all treatments, whereas P enhanced As leaching but suppressed Cd leaching, and both amendments moderated co-contaminant effects. An antagonistic effect of Cd on As sorption was evident in two treatments which showed increased As leaching with added Cd: the RF low spike concentration treatment, accredited to washout of stable As-Cd soluble complexes; the P high concentration treatment considered due to P disruption of As-Cd bridging complexes. This work is important for effective risk mitigation in these widely occurring co-contaminated agronomic systems, and demonstrates a strong system effect on synergistic or antagonistic co-contaminant interactions.

Antimony and arsenic particle size distribution in a mining contaminated freshwater river: Implications for sediment quality assessment and quantifying dispersion.

Assessments of antimony (Sb) and arsenic (As) contamination in sediments are reported on a wide range of different particle size fractions, including <63 µm, < 180 µm and <2 mm. Guidelines vary between jurisdictions which limits comparative assessment between contamination events and complicates ecotoxicity assessment, and almost no information exists on Sb size distribution in contaminated sediments. This study quantified and compared the size distribution of Sb and As in 11 sediments (and 2 floodplain soils) collected along 320 km of waterway contaminated by historic mining activity. Sediment particle size distribution was the primary determinant of total metalloid load in size fractions across the varying substrates of the waterway. Minerals and sorption complexes influenced metalloid particle distribution but relative importance depended on location. Arsenic concentrations were greatest in the fine <63 µm fraction across all the different river environments (7.3-189 mg kg-1, or 1-26% of total sample As), attributed to fine-grained primary arsenopyrite and/or sorption of As(V) to fine solid-phases. The Sb particle size concentrations were greatest in mid-size fractions (205-903 mg kg-1) in the upper catchment and up to 100 km downstream to the mid-catchment as a result of remnant Sb minerals. Antimony concentrations in the lower catchment were greatest in the <63 µm fraction (8.8-12.1 mg kg-1), reflecting the increasing importance of sorption for Sb particle associations. This work demonstrates the importance of particle size analysed for assessment of sediment quality, and provides support for analysis of at least the <250 µm fraction for Sb and As when comparing pollutant distribution in events impacted by primary contamination. Analysis of the <63 µm fraction, however, provides good representation in well-dispersed contaminated sediments.

Examining sampling protocols for microplastics on recreational trails.

Hiking and trail running are increasingly popular and could present a significant source of microplastics on recreational trails in nature reserves, wilderness areas and conservation areas. Deposition may be concentrated on trail surfaces, however sampling techniques for microplastics on soil or rock surfaces have not yet been developed. In this study, sampling strategies were evaluated for microplastics on three types of recreational trail surfaces - asphalt, compacted soil, and a loose overlay of soil. We spiked trail surfaces with pink rubber microplastics and collected samples using a handheld vacuum, manual sweeping, and gel lifter tape. Spiked and in situ microplastics were extracted from soil samples using density separation (NaI, ρ = 1.6 g cm-3) with organic matter digestion (30% H2O2), then visualised and counted using stereomicroscopy. The gel lifter tape yielded the highest recovery of spiked and counts of in situ microplastics on asphalt (118% ± 15%, 3183 ± 830 microplastics per 40 cm2) and compacted soil (127% ± 7%, 333 ± 106 microplastics per 40 cm2). Sweeping produced quantitative recovery for spiked microplastics on compacted soil (88% ± 13%) but yielded significantly fewer in situ microplastics (148 ± 40 microplastics per 40 cm2) than the tape. Sweeping was the only technique to achieve quantitative recovery of spiked microplastics in the loose overlay of soil (110% ± 14%) when soil carbon was 0.8% ± 0.3%, however increasing soil carbon was associated with reduced microplastic recovery. Preliminary assessment indicated quantification of microplastics smaller than 100 µm was not possible with any of the methods tested. Sweeping and the gel lifter tape were both effective for evaluating microplastic deposition and spatial distribution on recreational trails, depending on the properties of the trail.

Sensitivity of Freshwater Australian Bass (Macquaria novemaculeata) and Silver Perch (Bidyanus bidyanus) to Waterborne Antimony: Exposure-Dose-Response Characteristics and Ion Homeostasis.

We conducted acute toxicity studies using semi-static protocols to examine the lethal responses of Australian bass and silver perch exposed to antimony (Sb) oxidation states in Sb(III) (10.5-30.5 mg L-1) and Sb(V) (95.9-258.7 mg L-1). Bioavailability and the effects of Sb on body ion regulation (Na, Ca, Mg, and K) were also investigated. Antimony species-specific effects were observed with exposure to both Sb oxidation states. Median lethal concentrations (LC50s) for Sb(III) were 13.6 and 18 mg L-1 for Australian bass and silver perch, respectively, and the LC50 for Sb(V) in Australian bass was 165.3 mg L-1. The LC50 could not be calculated for silver perch exposed to Sb(V) as the maximum exposure concentrations produced 40% mortality but a larger-than value of > 258.7 mg L-1 was estimated. Relative median potency values derived from the LC50s were 0.1 Sb(III) and 12.2 and 16.6 Sb(V) for Australian bass and silver perch, respectively, demonstrating greater toxicity of Sb(III) to both fish species. Antimony uptake in fish was observed. Median critical body residue (CBR50) values of 77.7 and 26.6 mg kg-1 for Sb(III) were estimated for Australian bass and silver perch, respectively, and 628.1 mg kg-1 for Sb(V) in Australian bass. Bioconcentration factors (BCFs) for both Sb(III) and Sb(V) did not change with exposure but the greater BCFs for fish exposed to Sb(III) indicate that it is more bioavailable than Sb(V) in acute exposure. No effects on whole-body Na, Ca, Mg, or K ions were observed with fish exposure to either Sb species.

Transformation of Calcium Phosphates in Alkaline Vertisols by Acidified Incubation.

Acid-soluble soil phosphorus (P) is a potential resource in P-limited agricultural systems that may become critical as global P sources decrease in the future. The fate of P in three alkaline Vertisols, a major agricultural soil type, after acidic incubation was investigated using synchrotron-based K-edge X-ray absorption near-edge structure (XANES) spectroscopy, geochemical modeling, wet chemistry soil extraction, and a P sorption index. Increases in labile P generally coincided with decreased stability and dissolution of calcium phosphate (CaP) minerals. However, only a minor proportion of the CaP dissolved in each soil was labile. In two moderate-P soils (800 mg P kg-1), XANES indicated that approximately 160 mg kg-1 was repartitioned to sorbed phases at pH 5.1 of one soil and at pH 4.4 of the second; however, only 40 and 28% were labile, respectively. In a high-P soil (8900 mg P kg-1), XANES indicated a decrease in P of 1170 mg kg-1 from CaP minerals at pH 3.8, of which approximately only 33% was labile. Phosphorus mobilized by agricultural practices without concurrent uptake by plants may be repartitioned to sorbed forms that are not as plant-available as prior to acidification.

The impact of carbon addition on the organisation of rhizosheath of chickpea.

Spatio-temporal development of the rhizosheath during root elongation has the potential to modify the function of the rhizosphere under abiotic stress. We quantified the impact of carbon (i.e. glucose) addition on the development and function of rhizosheath of drought tolerant and sensitive chickpea (Cicer arietinum L.) by integrating soil pore volume obtained from X-ray microtomography (µCT), soil physical and microbial respiration measures, and measurements of root traits. Structural equation modelling indicated the feedback mechanisms between added carbon, root traits, pore geometry, and soil functions differed between the cultivars in a fashion congruent with the concept of soil as a self-organising system that interacts with an introduced root system. The drought tolerant cultivar partitioned more photosynthetically fixed carbon to the roots, had more root hairs and more porous rhizosheath, as compared with the sensitive cultivar.

Plant roots redesign the rhizosphere to alter the three-dimensional physical architecture and water dynamics.

The mechanisms controlling the genesis of rhizosheaths are not well understood, despite their importance in controlling the flux of nutrients and water from soil to root. Here, we examine the development of rhizosheaths from drought-tolerant and drought-sensitive chickpea varieties; focusing on the three-dimensional characterization of the pore volume (> 16 µm voxel spatial resolution) obtained from X-ray microtomography, along with the characterization of mucilage and root hairs, and water sorption. We observe that drought-tolerant plants generate a larger diameter root, and a greater and more porous mass of rhizosheath, which also has a significantly increased water sorptivity, as compared with bulk soil. Using lattice Boltzmann simulations of soil permeability, we find that the root activity of both cultivars creates an anisotropic structure in the rhizosphere, in that its ability to conduct water in the radial direction is significantly higher than in the axial direction, especially in the drought-tolerant cultivar. We suggest that significant differences in rhizosheath architectures are sourced not only by changes in structure of the volumes, but also from root mucilage, and further suggest that breeding for rhizosheath architectures and function may be a potential future avenue for better designing crops in a changing environment.

Evaluation of amendments to reduce arsenic and antimony leaching from co-contaminated soils.

Co-contamination of soils with arsenic (As) and antimony (Sb) presents unique challenges for risk management. In this study a sequence of leaching experiments evaluated zero valent iron powder, ferrihydrite, ferric chloride, aluminium and manganese oxides, and kaolinite for As and Sb immobilisation in co-contaminated soils. Iron based amendments were most effective for the reduction of As and Sb in leachate in a column leaching study. Over 48 h zero valent iron powder and ferrihydrite applied at 3% (w/w dry weight) were most efficient, decreasing total As and Sb leachate concentrations by more than 80%. Careful moderation of pH (to > 2.5 but < âˆ¼6) with lime was required for effective co-immobilisation of both metalloids using ferric chloride. In a subsequent batch study with pH optimised for maximum sorption using 2% lime, ferric chloride (3%) added to two co-contaminated soils decreased As and Sb in solution after 7 days by at least 79%. Ferrihydrite (3%) and iron powder (3%) were less effective. Ferrihydrite (3%) was then used in a 12-week larger scale Cynodon dactylon plant experiment that also considered plant bioavailability. Porewater As and Sb decreased by up to 90% but over the 12 week trial period no significant change in shoot or root metalloid concentrations was observed. The study demonstrates that iron-based amendments can be extremely effective for co-immobilisation of As and Sb in contaminated soils, but for large scale application amendment feasibility considerations and site specific pH moderation are essential.

XANES Demonstrates the Release of Calcium Phosphates from Alkaline Vertisols to Moderately Acidified Solution.

Calcium phosphate (CaP) minerals may comprise the main phosphorus (P) reserve in alkaline soils, with solubility dependent on pH and the concentration of Ca and/or P in solution. Combining several techniques in a novel way, we studied these phenomena by progressively depleting P from suspensions of two soils (low P) using an anion-exchange membrane (AEM) and from a third soil (high P) with AEM together with a cation-exchange membrane. Depletions commenced on untreated soil, then continued as pH was manipulated and maintained at three constant pH levels: the initial pH (pHi) and pH 6.5 and 5.5. Bulk P K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the main forms of inorganic P in each soil were apatite, a second more soluble CaP mineral, and smectite-sorbed P. With moderate depletion of P at pHi or pH 6.5, CaP minerals became more prominent in the spectra compared to sorbed species. The more soluble CaP minerals were depleted at pH 6.5, and all CaP minerals were exhausted at pH 5.5, showing that the CaP species present in these alkaline soils are soluble with decreases of pH in the range achievable by rhizosphere acidification.