Lethal and Sublethal Toxicity of Thiamethoxam and Clothianidin Commercial Formulations to Soil Invertebrates in a Natural Soil.

The use of neonicotinoids in agriculture is a critical environmental protection issue. Although there has been considerable research on pollinator exposure and aquatic toxicological effects, few studies have investigated the chronic impacts on soil-dwelling species. Given the application of neonicotinoids into soil systems, there is the potential for risk to soil invertebrates. The toxicity of 2 commercial formulations containing the active ingredients (a.i.) thiamethoxam (Actara® 240SC) or clothianidin (Titan™) was investigated using 3 soil invertebrate species: Oppia nitens, Eisenia andrei, and Folsomia candida. No adverse effects were observed for O. nitens at the highest tested concentrations (≥92 mg a.i./kg dry soil) after a 28-d exposure. Exposure to clothianidin resulted in a 28-d median inhibitory concentration (IC50) of 0.069 (95% confidence limits: 0.039-0.12) mg/kg dry soil for F. candida, and a 56-d IC50 of 0.26 (0.22-3.2) mg a.i./kg dry soil for E. andrei. Exposure to thiamethoxam was less toxic, with IC50s of 0.36 (0.19-0.66) and 3.0 (2.2-4.0) mg a.i./kg dry soil for F. candida and E. andrei reproduction, respectively. The observed toxicity for F. candida adult survival and reproduction and for E. andrei reproduction occurred at environmentally relevant concentrations. However, because clothianidin is a degradation product of thiamethoxam, and detection of clothianidin rose to levels of concern in the thiamethoxam-amended soils over time, the observed toxicity may be partly attributed to the presence of clothianidin. Environ Toxicol Chem 2019;38:2111-2120. © 2019 Crown in the right of Canada. Published by Wiley Periodicals Inc. on behalf of SETAC.

The ecotoxicity of zinc and zinc-containing substances in soil with consideration of metal-moiety approaches and organometal complexes.

Within Canada, screening-level assessments for chemical substances are required to determine whether the substances pose a risk to human health and/or the environment, and as appropriate, risk management strategies. In response to the volume of metal and metal-containing substances, process efficiencies were introduced using a metal-moiety approach, whereby substances that contain a common metal moiety are assessed simultaneously as a group, with the moiety of concern consisting of the metal ion. However, for certain subgroups, such as organometals or organic metal salts, the organic moiety or parent substance may be of concern, rather than simply the metal ion. To further investigate the need for such additional consideration, certain substances were evaluated: zinc (Zn)-containing inorganic (Zn chloride [ZnCl2] and Zn oxide) and organic (organometal: Zn diethyldithiocarbamate [Zn(DDC)2 ] and organic metal salts (Zn stearate [ZnSt] and 4-chloro-2-nitrobenzenediazonium tetrachlorozincate [BCNZ]). The toxicity of the substances were assessed using plant (Trifolium pratense and Elymus lanceolatus) and soil invertebrate (Folsomia candida and Eisenia andrei) tests in a sandy soil. Effect measures were determined based on total metal and total parent analyses (for organic substances). In general, the inorganic Zn substances were less toxic than the organometals and organic metal salts, with 50% effective concentrations ranging from 11 to >5194 mg Zn kg-1 dry soil. The data demonstrate the necessity for alternate approaches in the assessment of organo-metal complexes, with the organic moieties or parent substances warranting consideration rather than the metal ion alone. In this instance, the organometals and organic metal salts were significantly more toxic than other test substances despite their low total Zn content. Environ Toxicol Chem 2017;36:3324-3332. © 2017 Crown in the Right of Canada. Published by Wiley Periodicals Inc. on behalf of SETAC.

A comparison of the effects of silver nanoparticles and silver nitrate on a suite of soil dwelling organisms in two field soils.

Nanomaterials are increasingly used in a wide range of products, leading to growing concern of their environmental fate. In order to understand the fate and effects of silver nanoparticles in the soil environment, a suite of toxicity tests including: plant growth with Elymus lanceolatus (northern wheatgrass) and Trifolium pratense (red clover); collembolan survival and reproduction (Folsomia candida); and earthworm avoidance, survival and reproduction (Eisenia andrei) was conducted. The effect of silver nanoparticles (AgNP) was compared with the effect of ionic silver (as AgNO3) in two agricultural field soils (a sandy loam and a silt loam). Lethal (LC50) or sub lethal (IC50) effect levels are presented for all endpoints and demonstrate that in most cases AgNO3 (i.e. ionic silver) was found to be more toxic than the AgNP across test species. The difference in effects observed between the two forms of silver varied based on test species, endpoint and soil type. In tests that were conducted across different soil types, organisms in the sandier soil had a greater response to the Ag (ionic and nano) than those in soil with a high silt content. Earthworms (avoidance behavior and reproduction) were the most sensitive to both AgNP and AgNO3, while plant emergence was the least sensitive endpoint to both forms of Ag. The use of a test battery approach using natural field soils demonstrates the need to better quantify the dissolution and transformation products of nanomaterials in order to understand the fate and effects of these materials in the soil environment.

Estimation of the bioaccumulation potential of a nonchlorinated bisphenol and an ionogenic xanthene dye to Eisenia andrei in field-collected soils, in conjunction with predictive in silico profiling.

In silico-based model predictions, originating from structural and mechanistic (e.g., transport, bioavailability, reactivity, and binding potential) profiling, were compared against laboratory-derived data to estimate the bioaccumulation potential in earthworms of 2 organic substances (1 neutral, 1 ionogenic) known to primarily partition to soil. Two compounds representative of specific classes of chemicals were evaluated: a nonchlorinated bisphenol containing an -OH group (4,4'-methylenebis[2,6-di-tert-butylphenol] [Binox]), and an ionogenic xanthene dye (2',4',5',7'-tetrabromo-4,5,6,7-tetrachloro-3',6'-dihydroxy-, disodium salt [Phloxine B]). Soil bioaccumulation studies were conducted using Eisenia andrei and 2 field-collected soils (a clay loam and a sandy soil). In general, the in silico structural and mechanistic profiling was consistent with the observed soil bioaccumulation tests. Binox did not bioaccumulate to a significant extent in E. andrei in either soil type; however, Phloxine B not only accumulated within tissue, but was not depurated from the earthworms during the course of the elimination phase. Structural and mechanistic profiling demonstrated the binding and reactivity potential of Phloxine B; this would not be accounted for using traditional bioaccumulation metrics, which are founded on passive-based diffusion mechanisms. This illustrates the importance of profiling for reactive ionogenic substances; even limited bioavailability combined with reactivity can result in exposures to a hazardous substance not predictable by traditional in silico modeling methods.

Ecotoxicity of xanthene dyes and a non-chlorinated bisphenol in soil.

Soil eco-toxicity testing was conducted in support of Canada's Chemical Management Plan (CMP) to fill data gaps for organic chemicals known to primarily partition to soil, and of which the persistence and inherent toxicity are uncertain. Two compounds representative of specific classes of chemicals: non-chlorinated bisphenols containing an -OH group (4,4'-methylenebis(2,6-di-tert-butylphenol (Binox)) and xanthene dyes (2',4',5',7'-tetrabromo-4,5,6,7-tetrachloro-3',6'-dihydroxy-, disodium salt (Phloxine B), 2',4',5',7'-tetrabromofluorescein (TBF), 4',5'-dibromofluorescein (DBF), and 4,5,6,7-tetrachlorofluorescein (TCF)) were evaluated. The effect of these substances on plant growth (Elymus lanceolatus and Trifolium pratense) and soil invertebrate survival and reproduction (Folsomia candida and Eisenia andrei) were assessed using a field-collected sandy soil. Binox was persistent throughout testing (up to 63 d) with an average recovery of 77±2.9% at test end. Binox was not toxic to plants (IC50s>1076 mg kg(-1)) or E. andrei (IC50s>2651 mg kg(-1)); however, a significant reduction in F. candida adult survival and reproduction (IC50=89 (44-149) mg kg(-1)) was evident. Phloxine B was also persistent throughout testing, with an average recovery of 82±3.0% at test end. Phloxine B was significantly more toxic than Binox, with significant reductions in plant root growth (IC50s ≥ 11 mg kg(-1)) and invertebrate reproduction (IC50s ≥ 22 mg kg(-1)). DBF toxicity was not significantly different from that of Phloxine B for plant root growth (IC50s ≥ 30 mg kg(-1)), but was significantly less toxic for shoot growth (IC50s ≥ 1758 mg kg(-1)), and invertebrate adult survival (IC50s ≥ 2291 mg kg(-1)) and reproduction (IC50s ≥ 451 mg kg(-1)). A comparison between all four xanthene dyes was completed using F. candida, with the degree of toxicity in the order of Phloxine B ≥ TBF∼DBF>TCF. The results from these studies will contribute to data gaps for poorly understood chemicals (and chemical groupings) under review for environmental risk assessments, and will aid in the validation of model predictions used to characterize the fate and effects of these substances in soil environments.

Ecotoxicity of siloxane D5 in soil.

Decamethylcyclopentasiloxane (D5) is a cyclic volatile methyl siloxane (cVMS) commonly found in commercially available products. D5 is expected to enter the terrestrial environment through the deposit of biosolids from sewage treatment plants onto agricultural fields for nutrient enrichment. Little to no information currently exists as to the risks of D5 to the terrestrial environment. In order to evaluate the potential risk to terrestrial organisms, the toxicity of a D5 contaminated biosolid in an agricultural soil was assessed with a battery of standardized soil toxicity tests. D5 was spiked into a surrogate biosolid and then mixed with a sandy loam soil to create test concentrations ranging from 0 to 4074 mg kg(-1). Plant (Hordeum vulgare (barley) and Trifolium pratense (red clover)) and soil invertebrates (Eisenia andrei (earthworm) and Folsomia candida (springtail)) toxicity tests were completed to assess for lethal and sub-lethal effects. Plant testing evaluated the effects on seedling emergence, shoot and root length, and shoot and root dry mass. Invertebrate test endpoints included adult lethality, juvenile production, and individual juvenile dry mass (earthworms only). Soil samples were collected over time to confirm test concentrations and evaluate the loss of chemical over the duration of a test. The toxicity of the D5 was species and endpoint dependent, such that no significant adverse effects were observed for T. pratense or E. andrei test endpoints, however, toxicity was observed for H. vulgare plant growth and F. candida survival and reproduction. Chemical losses of up to 50% were observed throughout the tests, most significantly at high concentrations.