Stabilisation of PFAS in soils: Long-term effectiveness of carbon-based soil amendments.

Immobilisation/stabilisation is one of the most developed and studied approaches for treating soils contaminated with per- and poly-fluoroalkyl substances (PFAS). However, its application has been inhibited by insufficient understanding of the effectiveness of added soil sorbents over time. Herein, we present results on the effectiveness of select carbon-based sorbents, over 4 years (longevity) and multiple laboratory leaching conditions (durability). Standard batch leaching tests simulating aggressive, worst-case scenario conditions for leaching (i.e., shaking for 24-48 h at high liquid/solid ratios) were employed to test longevity and durability of stabilisation in clay-loam and sandy-loam soils historically contaminated with PFAS (2 and 14 mg/kg ∑28 PFAS). The different sorbents, which were applied at 1-6% (w/w), reduced leaching of PFAS from the soils to varying degrees. Among the 5 sorbents tested, initial assessments completed 1 week after treatment revealed that 2 powdered activated carbon (PAC) sorbents and 1 biochar were able to reduce leaching of PFAS in the soil by at least 95%. Four years after treatment, the performance of the PAC sorbents did not significantly change, whilst colloidal AC improved and was able to reduce leaching of PFAS by at least 94%. The AC-treated soils also appeared to be durable and achieved at least 95% reduction in PFAS leaching under repetitive leaching events (5 times extraction) and with minimal effect of pH (pH 4-10.5). In contrast, the biochars were affected by aging and were at least 22% less effective in reducing PFAS leaching across a range of leaching conditions. Sorbent performance was generally consistent with the sorbent's physical and chemical characteristics. Overall, the AC sorbents used in this study appeared to be better than the biochars in stabilising PFAS in the long term.

Enhancing the phosphorus content of layered double hydroxide fertilizers by intercalating polymeric phosphate instead of orthophosphate: A feasibility study.

HYPOTHESIS: Layered double hydroxide (LDH) loaded with orthophosphate (PO4) are suggested as slow-release P fertilizers. However, PO4-LDHs have a low maximal P content, related to high charge HPO42-/PO43- anions occupying the anion exchange capacity (AEC) of LDHs. We postulate that the P content of LDHs can be enhanced by exchanging them with polymeric-P (i.e. trimetaphosphate, P3O9), which has a lower molar charge/P ratio than its monomer. EXPERIMENTS: Adsorption capacities were compared between PO4 and P3O9 for as-synthesized and calcined MgAl LDHs with Mg/Al ratio of 2, 3, or 4; the P-LDHs were characterized (XRD, FTIR). Dialysis and soil incubation experiments were performed with PO4-LDHs, P3O9-LDHs, and corresponding soluble fertilizers to compare their P release and P solubility (CaCl2 extract). FINDINGS: The P adsorption capacities were 1.25-1.60 fold larger for P3O9 compared to PO4, yet the high theoretical P contents with P3O9 were not achieved (incomplete loading, P3O9 depolymerization). P3O9-Mg3Al released polymeric-P whereas P3O9-Mg2Al released depolymerized PO4, and P release from P3O9-LDHs was slower than that of PO4-LDHs. With soil incubation, soluble P from P3O9-LDH was initially lower but later converged to that of PO4-LDH as result of continued hydrolysis, yet did not exceed that of the soluble P3O9 and PO4 fertilizers.

Increasing ionic strength and valency of cations enhance sorption through hydrophobic interactions of PFAS with soil surfaces.

The effect of soluble cations on sorption in soils of a range of anionic PFAS is not well studied. We investigated the role of three common cations (Na+, Ca2+, and Mg2+) at varying solution concentrations on the sorption coefficients (Kd) of 18 anionic PFAS in two contrasting soils. The effective charge of the soil suspension (Zeta potential) became less negative as the concentration of these cations increased in the soil solutions. Perfluorinated compounds showed greater sorption than polyfluorinated compounds, with sulfonates of comparable chain lengths showing higher sorption than the carboxylates. We observed that the Kd values of several PFAS in the two soils were positively correlated with the concentration of cations in solution, especially in the presence of polyvalent cations (Ca2+and Mg2+). The changes in sorption with cation concentration were more prominent for long-chain PFAS, with C > 10 PFAS being completely removed from solution at higher cation concentrations. The emerging PFAS (replacement compounds GenX and ADONA) showed negligible or little sorption (Kd < 0.6 L/kg). While several mechanisms contribute towards sorption of PFAS in the presence of cations, we conclude that the primary effect of cations is through screening of negative charges on head groups of PFAS and reorientation of molecules at the interface between organic matter surfaces and soil solution as well as charge neutralisation at soil solid surface. Screening of negative charges allows for greater hydrophobic interaction between hydrophobic tails of PFAS and soil surfaces resulting in greater sorption. Increasing cation concentrations in soil solutions could thus reduce mobility of PFAS through a soil profile.

Layered Double Hydroxides as Slow-Release Fertilizer Compounds for the Micronutrient Molybdenum.

Molybdenum (Mo) is an essential plant micronutrient. Despite low plant Mo requirements, deficiencies are not uncommon and soluble Mo fertilizers are often applied. However, soluble Mo may result in poor Mo use efficiency due to strong sorption (acid weathered soils) or leaching (lighter-textured soils). Here, ZnAl layered double hydroxides (LDHs), loaded with molybdate (MoO4), were examined for their potential as slow-release Mo compounds. Chloride-exchanged LDHs with varying Zn/Al ratios (2, 3, and 4) were exchanged with MoO4. Zn2Al LDH indicated MoO4 intercalation, whereas Zn3Al and Zn4Al LDHs bound MoO4 merely on edge sites. Short-term Mo-LDH incubation identified sulfate, carbonate, and phosphate as the most competitive anions for MoO4 exchange. Long-term Mo-LDH incubation in simulated pH-neutral soil solutions demonstrated slow Mo release from Zn2Al LDH (half-life of 35 h), with a total Mo desorption of up to 85%. For Zn3Al and Zn4Al LDHs, Mo desorption was limited to <20%. Finally, several macronutrient fertilizers were tested as possible carriers for Mo-LDH fertilizer compounds.

Author Correction: Improving the efficacy of selenium fertilizers for wheat biofortification.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Mineralisation and release of 14C-graphene oxide (GO) in soils.

Graphene-based nanomaterials (GNMs) have been touted as miracle materials due to their extraordinary properties that can benefit many industries, including in agriculture and for environmental remediation. While improvement in nutrient delivery and the ability to adsorb environmental contaminants have been demonstrated, what happens to GNMs in soil is a question that has not been addressed. The main aim of this study was to investigate their degradation in soil to have a better understanding of their environmental fate. Using radioisotope techniques, this study assessed the potential mineralisation and release of graphene oxide (GO), one of the most commonly used forms of graphene. Results revealed that the conversion of GO to carbon dioxide was negligible (<2%) in microbially-active soils. GO remaining in soil was also not readily released by water extractions. The lack of mineralisation and release is indicative of GO's high (bio)degradation stability which is likely due to its limited availability resulting from its rapid homo/hetero-aggregation. Over-all, the results provide new and important information on the environmental fate of graphene nanomaterials applied to soils.

Improving the efficacy of selenium fertilizers for wheat biofortification.

Increasing the selenium (Se) concentration of staple crops by fertilization is a valuable pathway to increase Se in the human diet, thus preventing Se deficiency. A pot trial was set up to investigate whether the application of 3.33 µg kg-1 of Se (equivalent to 10 g ha-1) to wheat can be made more efficient by its co-application with macronutrient carriers, either to the soil or to the leaves. In the soil, Se was applied either on its own (selenate only) or as a granular, Se-enriched macronutrient fertilizer supplying nitrogen, phosphorus, potassium or sulfur. Selenium was also applied to leaves at head emergence with, or without, 2% w/v N fertilizers. With grain Se concentrations varying from 0.13-0.84 mg kg-1, soil application of selenate-only was 2-15 times more effective than granular Se-enriched macronutrient fertilizers in raising grain Se concentrations. Co-application of foliar Se with an N carrier doubled the Se concentration in wheat grains compared to the application of foliar Se on its own, the majority of which was in the highly bioavailable selenomethionine fraction. Results from this study demonstrate the possibility of improving the efficacy of Se fertilizers, which could enrich crops with Se without additional application costs in the field.

Colloidal nitrogen is an important and highly-mobile form of nitrogen discharging into the Great Barrier Reef lagoon.

Soil-borne colloids have been linked to long-distance transport of radionuclides, metal(loid)s and nutrients. Colloid-associated nitrogen (N) will have different mechanisms of biogeochemical cycling and potential for water-borne transport over longer distances compared to dissolved N. The role that colloids play in the supply and mobility of N within catchments discharging into the Great Barrier Reef (GBR) lagoon is unexplored. Here, we examine water-dispersible clay (WDC) from soil samples collected from gullies and agricultural drains within three different land uses (sugarcane, non-agricultural land and grazing) within the Townsville area. The proportion of soil N associated with WDC was inversely correlated with total soil N, with up to 45% of the total soil N being colloid-associated in low N gully soils. Within the <0.45 µm fraction of the WDC, only 17-25% of the N was truly dissolved (<3 kDa) at the gully sites compared to 58% in the sugarcane sites. Our results demonstrate the importance of colloidal N and the inaccuracy of assuming N < 0.45 µm is dissolved in the sampled areas, as well as providing an alternate explanation for the large amounts of what has previously been defined as dissolved inorganic N in runoff from non-fertilized grazing land. In particular, they describe why non-fertilized land uses can contribute significant N < 0.45 µm, and why catchment models of nutrient export based on soil N concentrations can over-estimate loads of particulate nitrogen derived from monitoring data (N > 0.45 µm). The findings suggest that managing soil erosion may also contribute to managing N < 0.45 µm.

Limited Dissolved Phosphorus Runoff Losses from Layered Double Hydroxide and Struvite Fertilizers in a Rainfall Simulation Study.

The enrichment of P in surface waters has been linked to P runoff from agricultural fields amended with fertilizers. Novel slow-release mineral fertilizers, such as struvite and P-exchanged layered double hydroxides (LDHs), have received increasing attention for P recycling from waste streams, and these fertilizers may potentially reduce the risk of runoff losses. Here, a rainfall simulation experiment was performed to evaluate P runoff associated with the application of recycled slow-release fertilizers relative to that of a soluble fertilizer. Monoammonium phosphate (MAP), struvite, and LDH granular fertilizers were broadcasted at equal total P doses on soil packed in trays (5% slope) and covered with perennial ryegrass ( L.). Four rainfall simulation events of 30 min were performed at 1, 5, 15, and 30 d after the fertilizer application. Runoff water from the trays was collected, filtered, and analyzed for dissolved P. For the MAP treatment, P runoff losses were high in the first two rain events and leveled off in later rain events. In total, 42% of the applied P in the MAP treatment was lost due to runoff. In the slow-release fertilizer treatments, P runoff losses were limited to 1.9 (struvite) and 2.4% (LDH) of the applied doses and were more similar over the different rain events. The use of these novel P fertilizer forms could be beneficial in areas with a high risk of surface water eutrophication and a history of intensive fertilization.

Genetic mapping of quantitative trait loci for tuber-cadmium and zinc concentration in potato reveals associations with maturity and both overlapping and independent components of genetic control.

KEY MESSAGE: Cd is a toxic metal, whilst Zn is an essential for plant and human health. Both can accumulate in potato tubers. We examine the genetic control of this process. The aim of this study was to map quantitative trait loci (QTLs) influencing tuber concentrations of cadmium (Cd) and zinc (Zn). We developed a segregating population comprising 188 F1 progeny derived from crossing two tetraploid cultivars exhibiting divergent tuber-Cd-accumulation phenotypes. These progeny were genotyped using the SolCap 8303 SNP array, and evaluated for Cd, Zn, and maturity-related traits. Linkage and QTL mapping were performed using TetraploidSNPMap software, which incorporates all allele dosage information. The final genetic map comprised 3755 SNP markers with average marker density of 2.94 per cM. Tuber-Cd and Zn concentrations were measured in the segregating population over 2 years. QTL mapping identified four loci for tuber-Cd concentration on chromosomes 3, 5, 6, and 7, which explained genetic variance ranging from 5 to 33%, and five loci for tuber-Zn concentration on chromosome 1, 3, 5, and, 6 explaining from 5 to 38% of genetic variance. Among the QTL identified for tuber-Cd concentration, three loci coincided with tuber-Zn concentration. The largest effect QTL for both tuber-Cd and Zn concentration coincided with the maturity locus on chromosome 5 where earliness was associated with increased tuber concentration of both metals. Coincident minor-effect QTL for Cd and Zn sharing the same direction of effect was also found on chromosomes 3 and 6, and these were unrelated to maturity The results indicate partially overlapping genetic control of tuber-Cd and Zn concentration in the cross, involving both maturity-related and non-maturity-related mechanisms.

Soil ecological criteria for nickel as a function of soil properties.

Scientific information for the chemistry and ecotoxicology of metals in soils has been obtained in the research conducted in recent years. However, the latest "science" obtained from this research has not yet been translated into "regulations" in China. In the present study, the predicted no effect concentrations (PNECs) for Ni which denoted as soil ecological criteria for Ni were derived based on the effects of soil properties on bioavailability/ecotoxicity of Ni, incorporating the differences in species sensitivity as well as in laboratory and field conditions. First, collected all ecotoxicity data of Ni from bioassays in Chinese soils and filtered with given criteria to obtain reliable data. Second, corrected the compiled data with either aging factor or leaching and aging factors simultaneously to eliminate the discrepancy caused by difference between laboratory and realistic field conditions. Prior to being put into a species sensitivity distribution (SSD) method to fit SSD curves, the corrected Ni ecotoxicity data were normalized with Ni ecotoxicity predictive models to modify the variation in Ni ecotoxicity caused by different soil properties. Then, the hazardous concentration for x% of the species (HCx) was figured out from the Ni SSD curve and the ecological criterion of Ni (PNEC) was set equal to HCx. Finally, predictive models for HCx were developed by quantifying the relationship between the Ni HCx and soil properties. Soil pH was the major factor controlling the values of HCx for Ni, with HC5 varying from 6.5 mg/kg in an acidic soil (pH 5.0) to 218.8 mg/kg in an alkaline soil (pH 8.5). The predictive models with parameters of soil pH and organic carbon (%) could calculate HCx with determination coefficients (R2) of 0.90-0.95. When soil cation exchange capacity was taken into account the third parameter, the predictive models could predict HCx more accurate with R2 values of 0.94-0.99.

Graphene Oxide: A New Carrier for Slow Release of Plant Micronutrients.

The environmental problems and low efficiency associated with conventional fertilizers provides an impetus to develop advanced fertilizers with slower release and better performances. Here, we report of development of a new carrier platform based on graphene oxide (GO) sheets that can provide a high loading of plant micronutrients with controllable slow release. To prove this concept, two micronutrients, zinc (Zn) and copper (Cu), were used to load on GO sheets and hence formulate GO-based micronutrients fertilizer. The chemical composition and successful loading of both nutrients on GO sheets were confirmed by X-ray photoelectron spectroscopy, thermogravimetric analysis, and X-ray diffraction (XRD). The prepared Zn-graphene oxide (Zn-GO) and Cu-graphene oxide (Cu-GO) fertilizers showed a biphasic dissolution behavior compared to that of commercial zinc sulfate and copper sulfate fertilizer granules, displaying desirable fast and slow micronutrient release. A visualization method and chemical analysis were used to assess the release and diffusion of Cu and Zn in soil from GO-based fertilizers compared with commercial soluble fertilizers to demonstrate the advantages of GO carriers and show their capability to be used as a generic platform for macro- and micronutrients delivery. A pot trial demonstrated that Zn and Cu uptake by wheat was higher when using GO-based fertilizers compared to that when using standard zinc or copper salts. This is the first report on the agronomic performance of GO-based slow-release fertilizer.

Cadmium uptake and partitioning in potato (Solanum tuberosum L.) cultivars with different tuber-Cd concentration.

Potatoes grown in soil with high Cd concentrations can accumulate high levels of Cd in the tubers. Although there is significant environmental variation involved in the trait of crop uptake of Cd, there are also distinctive cultivar differences. In order to understand this differential Cd accumulation mechanism, two potato cultivars were chosen that accumulate high and low levels of Cd in tubers. The patterns of Cd concentration, Cd content and dry weight accumulation of the two cultivars were examined at different stages of plant growth. The data suggest that differences in total Cd uptake and in Cd partitioning among organs are the mechanisms governing differential Cd-tuber accumulation in the two cultivars. The low tuber-Cd accumulator exhibited lower root-to-shoot and shoot-to-tuber translocation driven by higher root and shoot biomass that retained more Cd in roots and shoots, respectively, reducing its movement to the tubers. Higher remobilization and more efficient tuber loading was observed in the high tuber-Cd accumulator, indicating that remobilization of Cd from leaves to tubers was a major factor, not only in tuber-Cd loading, but also in the establishment of differential tuber-Cd levels. Regardless of cultivar differences, the concentration of Cd in the tuber was very low compared to that in other organs suggesting that, despite its high phloem mobility, Cd tends to be sequestered in the shoots.

Validation of site-specific soil Ni toxicity thresholds with independent ecotoxicity and biogeochemistry data for elevated soil Ni.

The Existing Substances Regulation Risk Assessments by the European Union (EU RA) generated new toxicity data for soil organisms exposed to Ni added to sixteen field-collected soils with low background concentration of metals and varying physico-chemical soil characteristics. Using only effective cation exchange capacity (eCEC) as a bioavailability correction, chronic toxicity of Ni in soils with a wide range of characteristics could be predicted within a factor of two. The objective of the present study was to determine whether this was also the case for three independent data sets of Ni toxicity thresholds. Two of the data sets were from Community Based Risk Assessments in Port Colborne ON, and Sudbury ON (Canada) for soils containing elevated concentrations of Ni, Co and Cu arising from many decades of Ni mining, smelting and refining. The third data set was the Metals in Asia study of soluble Ni added to field soils in China. These data yielded 72 leached and aged EC10/NOEC values for soil Ni, for arthropods, higher plants and woodlot structure and function. These were reduced to nine most sensitive single or geometric mean species/function endpoints, none of which were lower than the HC5 predicted for a soil with an eCEC of 20 cmol/kg. Most of these leached and aged EC10/NOEC values were from soils co-contaminated with Cu, in some cases at its median HC5 as predicted by the EU RA from soil characteristics. We conclude that the EU RA is protective of Ni toxicity to higher-tier ecological endpoints, including in mixture with Cu, before the assessment factor of 2 is applied. We suggest that for prospective risk assessment, the bioavailability based PNEC (HC5/2) be used as a conservative screen, but for retrospective and site-specific risk assessment, the bioavailability based HC5 is sufficient.

Agronomic Effectiveness of Granulated and Powdered P-Exchanged Mg-Al LDH Relative to Struvite and MAP.

Layered double hydroxides (LDHs) used to recover P from wastewater have recently been proposed as new slow-release fertilizers. Here, the use of P-exchanged Mg-Al LDHs as powdered or granulated fertilizer is explored and compared with monoammonium phosphate (MAP), a fully water-soluble fertilizer, and with struvite, a recycled phosphate fertilizer with lower solubility. First, these three fertilizers were compared in a 100-day incubation experiment using P diffusion visualization and chemical analysis to assess P release from either granules or powdered fertilizer in three different soils. By the end of the incubation, 74-90% of P remained within the LDH granule, confirming a slow release. Second, a pot experiment was performed with wheat (Triticum aestivum) in an acid and a calcareous soil. The granular treatment resulted in a considerably higher P uptake for MAP compared to LDH and struvite. For the powder treatments, the P uptake was less than for granular MAP and was largely unaffected by the chemical form. The LDHs and struvite showed a lower agronomic effectiveness than granular MAP, but the benefits of their use in P recycling, potential residual value, and environmental benefits may render these slow-release fertilizers attractive.

Fate of radiolabeled C60 fullerenes in aged soils.

Fullerenes (e.g. C60, C70, etc.) present in soil may undergo changes in its retention with aging. In this study, the partitioning behavior of (14C)-C60 aged up to 12 weeks was investigated in biosolids-amended soil. Spiked samples were subjected to sequential partitioning using water, methanol, and toluene followed by total combustion of solids; the distribution of 14C across solvents and matrices were used to provide insights on C60 behavior. In most samples, 14C only partitioned in toluene with the remaining (non-extractable) activity detected in the solid phase. In all biosolids-amended soil samples, an increase in non-extractable 14C were observed for those exposed to light (vs dark) with the greatest difference observed in biosolids + sand samples. Possible processes that contribute to the observed 14C distribution, i.e. retention and potential transformation of C60, were discussed. Over-all, results suggest that environmental exposure to C60 and potentially transformed C60 species, as a result of their release from soils, is likely to be low.

Rapid prediction of total petroleum hydrocarbons in soil using a hand-held mid-infrared field instrument.

This manuscript reports on the performance of a hand-held diffuse reflectance (mid)-infrared Fourier transform (DRIFT) spectrometer for the prediction of total petroleum hydrocarbons (TPH) in three different diesel-contaminated soils. These soils include: a carbonate dominated clay, a kaolinite dominated clay and a loam from Padova Italy, north Western Australia and southern Nigeria, respectively. Soils were analysed for TPH concentration using a standard laboratory methods and scanned in DRIFT mode with the hand-held spectrometer to determine TPH calibration models. Successful partial least square regression (PLSR) predictions, with coefficient of determination (R(2)) ~0.99 and root mean square error (RMSE) <200mg/kg, were obtained for the low range TPH concentrations of 0 to ~3,000mg/kg. These predictions were carried out using a set of independent samples for each soil type. Prediction models were also tested for the full concentration range (0-60,000mg/kg) for each soil type model with R(2) and RMSE values of ~0.99 and <1,255mg/kg, respectively. Furthermore, a number of intermediate concentration range models were also generated for each soil type with similar R(2) values of ~0.99 and RMSE values <800mg/kg. This study shows the capability of using a portable mid-infrared (MIR) DRIFT spectrometer for predicting TPH in a variety of soil types and the potential for being a rapid in-field screening method for TPH concentration levels at common regulatory thresholds. A novel hand-held mid-infrared instrument can accurately detect TPH across different soil types and concentrations, which paves the way for a variety of applications in the field.

Quantifying the Sensitivity of Soil Microbial Communities to Silver Sulfide Nanoparticles Using Metagenome Sequencing.

Soils are a sink for sulfidised-silver nanoparticles (Ag2S-NPs), yet there are limited ecotoxicity data for their effects on microbial communities. Conventional toxicity tests typically target a single test species or function, which does not reflect the broader community response. Using a combination of quantitative PCR, 16S rRNA amplicon sequencing and species sensitivity distribution (SSD) methods, we have developed a new approach to calculate silver-based NP toxicity thresholds (HCx, hazardous concentrations) that are protective of specific members (operational taxonomic units, OTUs) of the soil microbial community. At the HC20 (80% of species protected), soil OTUs were significantly less sensitive to Ag2S-NPs compared to AgNPs and Ag+ (5.9, 1.4 and 1.4 mg Ag kg-1, respectively). However at more conservative HC values, there were no significant differences. These trends in OTU responses matched with those seen in a specific microbial function (rate of nitrification) and amoA-bacteria gene abundance. This study provides a novel molecular-based framework for quantifying the effect of a toxicant on whole soil microbial communities while still determining sensitive genera/species. Methods and results described here provide a benchmark for microbial community ecotoxicological studies and we recommend that future revisions of Soil Quality Guidelines for AgNPs and other such toxicants consider this approach.

Aseptic hydroponics to assess rhamnolipid-Cd and rhamnolipid-Zn bioavailability for sunflower (Helianthus annuus): a phytoextraction mechanism study.

The availability of cadmium (Cd) and zinc (Zn) to sunflower (Helianthus annuus) was investigated in rhamnolipid- and ethylenediaminetetraacetic acid (EDTA)-buffered solutions in order to evaluate the influence of aqueous speciation of the metals on their uptake by the plant, in relation to predictions of uptake by the free ion activity model (FIAM). Free metal ion activity was estimated using the chemical equilibrium program MINTEQ or measured by Donnan dialysis. The uptake of Cd followed the FIAM for the EDTA-buffered solution at EDTA concentrations below 0.4 µM; for the rhamnolipid-buffered solution, the uptake of both metals in roots was not markedly affected by increasing rhamnolipid concentrations in solution. This suggests rhamnolipid enhanced metal accumulation in plant roots (per unit free metal in solution) possibly through formation and uptake of lipophilic complexes. The addition of normal Ca concentrations (low millimetre range) to the rhamnolipid uptake solutions reduced Cd accumulation in shoots by inhibiting Cd translocation, whereas it significantly increased Zn accumulation in shoots. This study confirms that although rhamnolipid could enhance accumulation of Cd in plants roots at low Ca supply, it is not suitable for Cd phytoextraction in contaminated soil environments where Ca concentrations in soil solution are orders of magnitude greater than those of Cd.

Symbiosis between nitrogen-fixing bacteria and Medicago truncatula is not significantly affected by silver and silver sulfide nanomaterials.

Silver (Ag) engineered nanomaterials (ENMs) are being released into waste streams and are being discharged, largely as Ag2S aged-ENMs (a-ENMs), into agroecosystems receiving biosolids amendments. Recent research has demonstrated that biosolids containing an environmentally relevant mixture of ZnO, TiO2, and Ag ENMs and their transformation products, including Ag2S a-ENMs, disrupted the symbiosis between nitrogen-fixing bacteria and legumes. However, this study was unable to unequivocally determine which ENM or combination of ENMs and a-ENMs was responsible for the observed inhibition. Here, we examined further the effects of polyvinylpyrollidone (PVP) coated pristine Ag ENMs (PVP-Ag), Ag2S a-ENMs, and soluble Ag (as AgSO4) at 1, 10, and 100 mg Ag kg(-1) on the symbiosis between the legume Medicago truncatula and the nitrogen-fixing bacterium, Sinorhizobium melliloti in biosolids-amended soil. Nodulation frequency, nodule function, glutathione reductase production, and biomass were not significantly affected by any of the Ag treatments, even at 100 mg kg(-1), a concentration analogous to a worst-case scenario resulting from long-term, repeated biosolids amendments. Our results provide additional evidence that the disruption of the symbiosis between nitrogen-fixing bacteria and legumes in response to a mixture of ENMs in biosolids-amended soil reported previously may not be attributable to Ag ENMs or their transformation end-products. We anticipate these findings will provide clarity to regulators and industry regarding potential unintended consequences to terrestrial ecosystems resulting from of the use of Ag ENMs in consumer products.