Soil properties influence the toxicity and availability of Zn from ZnO nanoparticles to earthworms.

To develop models that support site-specific risk assessment for nanoparticles (NPs), a better understanding of how NP transformation processes, bioavailability and toxicity are influenced by soil properties is needed. In this study, the influence of differing soil properties on the bioavailability and toxicity of zinc oxide (ZnO) NPs and ionic Zn to the earthworm Eisenia fetida was investigated. Earthworms were exposed to ZnO_NPs and ionic Zn, between 100 and 4400 mg Zn/kg, in four different natural soils (organic matter content: 1.8-16.7%, soil pH: 5.4-8.3, representing sandy loam to calcareous soils). Survival and reproduction were assessed after 28 and 56 days, respectively. Zn concentrations in soil pore waters were measured while labile concentrations of Zn were measured using an in-situ dynamic speciation technique (diffusive gradient in thin films, DGT). Earthworm Zn tissue concentrations were also measured. Soil properties influenced earthworm reproduction between soil controls, with highest reproductive output in soils with pH values of 6-7. Toxicity was also influenced by soil properties, with EC50s based on total Zn in soil ranging from 694 to >2200 mg Zn/kg for ZnO_NP and 277-734 mg Zn/kg for ionic Zn. Soil pore water and DGT measurements showed good agreement in the relative amount of Zn extracted across the four soils. Earthworms exposed to ZnO_NPs survived higher Zn concentrations in the soils and had higher tissue concentrations compared with ionic Zn exposures, particularly in the high organic content calcareous soil. These higher tissue concentrations in ZnO_NP exposed earthworm could have consequences for the persistence and trophic mobility of Zn in terrestrial systems and need to be further investigated to elucidate if there any longer-term risks associated with sustained input of ZnO_NP to soil.

A Kinetic Approach for Assessing the Uptake of Ag from Pristine and Sulfidized Ag Nanomaterials to Plants.

Nanomaterials (NMs) are thermodynamically unstable by nature, and exposure of soil organisms to NMs in the terrestrial environment cannot be assumed constant. Thus, steady-state conditions may not apply to NMs, and bioaccumulation modeling for uptake should follow a dynamic approach. The one-compartment model allows the uptake and elimination of a chemical to be determined, while also permitting changes in exposure and growth to be taken into account. The aim of the present study was to investigate the accumulation of Ag from different Ag NM types (20 nm Ag0 NMs, 50 nm Ag0 NMs, and 25 nm Ag2 S NMs) in the crop plant wheat (Triticum aestivum). Seeds were emerged in contaminated soils (3 or 10 mg Ag/kg dry soil, nominal) and plants grown for up to 42 d postemergence. Plant roots and shoots were collected after 1, 7, 14, 21, and 42 d postemergence; and total Ag was measured. Soil porewater Ag concentrations were also measured at each sampling time. Using the plant growth rates in the different treatments and the changing porewater concentrations as parameters, the one-compartment model was used to estimate the uptake and elimination of Ag from the plant tissues. The best fit of the model to the data included growth rate and porewater concentration decline, while showing elimination of Ag to be close to zero. Uptake was highest for Ag0 NMs, and size did not influence their uptake rates. Accumulation of Ag from Ag2 S NMs was lower, as reflected by the lower porewater concentrations. Environ Toxicol Chem 2021;40:1861-1872. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Impact of Ag2S NPs on soil bacterial community - A terrestrial mesocosm approach.

Soils might be a final sink for Ag2S nanoparticles (NPs). Still, there are limited data on their effects on soil bacterial communities (SBC). To bridge this gap, we investigated the effects of Ag2S NPs (10 mg kg-1 soil) on the structure and function of SBC in a terrestrial indoor mesocosm, using a multi-species design. During 28 days of exposure, the SBC function-related parameters were analysed in terms of enzymatic activity, community level physiological profile, culture of functional bacterial groups [phosphorous-solubilizing bacteria (P-SB) and heterotrophic bacteria (HB)], and SBC structure was analysed by 16S rRNA gene-targeted denaturing gradient gel electrophoresis. The SBC exposed to Ag2S NPs showed a significative decrease of functional parameters, such as ß-glucosidase activity and L-arginine consumption, and increase of the acid phosphatase activity. At the structural level, significantly lower richness and diversity were detected, but at later exposure times compared to the AgNO3 treatment, likely because of a low dissolution rate of Ag2S NPs. In fact, stronger effects were observed in soils spiked with AgNO3, in both functional and structural parameters. Changes in SBC structure seem to negatively correlate with parameters related to phosphorous (acid phosphatase activity) and carbon cycling (abundance of HB, P-SB, and ß-glucosidase activity). Our results indicate a significant effect of Ag2S NPs on SBC, specifically on parameters related to carbon and phosphorous cycling, at doses as low as 10 mg kg-1 soil. These effects were only observed after 28 days, highlighting the importance of long-term exposure experiments for slowly dissolving NPs.

Extending standard testing period in honeybees to predict lifespan impacts of pesticides and heavy metals using dynamic energy budget modelling.

Concern over reported honeybee (Apis mellifera spp.) losses has highlighted chemical exposure as a risk. Current laboratory oral toxicity tests in A. mellifera spp. use short-term, maximum 96 hour, exposures which may not necessarily account for chronic and cumulative toxicity. Here, we use extended 240 hour (10 day) exposures to examine seven agrochemicals and trace environmental pollutant toxicities for adult honeybees. Data were used to parameterise a dynamic energy budget model (DEBtox) to further examine potential survival effects up to 30 day and 90 day summer and winter worker lifespans. Honeybees were most sensitive to insecticides (clothianidin > dimethoate ≫ tau-fluvalinate), then trace metals/metalloids (cadmium, arsenic), followed by the fungicide propiconazole and herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). LC50s calculated from DEBtox parameters indicated a 27 fold change comparing exposure from 48 to 720 hours (summer worker lifespan) for cadmium, as the most time-dependent chemical as driven by slow toxicokinetics. Clothianidin and dimethoate exhibited more rapid toxicokinetics with 48 to 720 hour LC50s changes of <4 fold. As effects from long-term exposure may exceed those measured in short-term tests, future regulatory tests should extend to 96 hours as standard, with extension to 240 hour exposures further improving realism.

A marriage of convenience; a simple food chain comprised of Lemna minor (L.) and Gammarus pulex (L.) to study the dietary transfer of zinc.

Macrophytes contribute significantly to the cycling of metals in aquatic systems, through accumulation during growth and release during herbivory or decomposition. Accumulation of high levels of metals has been extensively documented in Lemnaceae (duckweeds). However, the degree of trophic transfer of metals from Lemnaceae to secondary consumers remains poorly understood. This study demonstrates that zinc accumulated in Lemna minor is bioavailable to the herbivore consumer Gammarus pulex. Overall, the higher the zinc content of L. minor, the more zinc accumulated in G. pulex. Accumulation in G. pulex was such that mortality occurred when they were fed high zinc-containing L. minor. Yet, the percentage of consumed zinc retained by G. pulex actually decreased with higher zinc concentrations in L. minor. We hypothesise that this decrease reflects internal zinc metabolism, including a shift from soluble to covalently bound zinc in high zinc-containing L. minor. Consistently, relatively more zinc is lost through depuration when G. pulex is fed L. minor with high zinc content. The developed Lemna-Gammarus system is simple, easily manipulated, and sensitive enough for changes in plant zinc metabolism to be reflected in metal accumulation by the herbivore, and therefore suitable to study ecologically relevant metal cycling in aquatic ecosystems.