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Imidacloprid (IDP) is an active ingredient of the Admire brand pesticide used to control the vector (Asian citrus psyllid) that transmits the causative organism Candidatus Liberibacter asiaticus (CLas) for citrus greening or huanglongbing disease. Imidacloprid products are applied via soil drench where citrus roots are mostly concentrated which is between 0 and 60 cm depth. These soil depths exhibit different characteristics that may affect IDP leaching beyond the rooting zone. Representative soil samples were collected from Entisols and Ultisols, which are the dominant soil orders under citrus production in central Florida, at 15 cm increments up to 60 cm to estimate and understand the batch sorption, kinetics, equilibria, and degradation of IDP. Results showed that the equilibrium time for IDP at 0-15 cm depth (10 hours) was 2 times faster than at 15-60 cm (20 hours) for the Entisol. Nevertheless, all depths reached equilibrium within 24 hours for the Entisol. The 0-30 cm depth adsorbed 2 times more IDP than the 30-60 cm depth for both soils. Nevertheless, the adsorption coefficient was approximately ≤ 1 mL g-1 for both soils. The half-life of IDP in both soils ranged from 10 to 17 days. The Entisol showed higher adsorption than the Ultisol at both depths, probably due to relatively lower organic carbon (OC) content in the Ultisol compared to the Entisol. Thus, the Ultisol showed high IDP leaching vulnerability compared to the Entisol. Movement of IDP is affected by the amount of OC in the citrus critical zone., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright: This is an open access article, free of all copyright, and may be freely reproduced, distributed, transmitted, modified, built upon, or otherwise used by anyone for any lawful purpose. The work is made available under the Creative Commons CC0 public domain dedication.)

Per- and polyfluoroalkyl substances (PFAS) are a class of highly persistent contaminants that have been linked to human health effects at low exposure concentrations. Public concerns exist that land-application of biosolids may result in the release of PFAS into terrestrial and aquatic ecosystems. The relative importance of inorganic constituents such as Fe and Al, which are known to impact PFAS retention/release behavior in soils, on PFAS release from wastewater residuals (WWRs, i.e., biosolids and sewage sludges) is not well understood. Here, we examine native concentrations and WWR-water partition coefficients of a range of PFAS in the context of WWRs characteristics including oxalate-extractable Fe and Al, organic matter (OM), dissolved organic carbon, and total protein content. Total PFAS concentrations, which included perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, fluorotelomer sulfonates and some sulfonamides, ranged from ∼480 to 3500 μg PFAS kg -1 dry weight. PFAS WWR-water partition coefficients ranged from ∼10 to 20,000 L kg -1 , consistent with the literature. PFAS partitioning was significantly correlated to oxalate extractable Al and Fe as well as bulk OM and protein content. These results have important implications for wastewater treatment facilities that recycle Al- and Fe-based drinking water treatment residuals in terms of both PFAS retention and loading., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

PFASs are highly persistent in the environment and the potential exists for terrestrial biota to accumulate PFAS, which may result in exposure of higher trophic level organisms to these compounds through consumption. However, trophic transfer of proteinophilic compounds such as PFAS has not been extensively studied and the degree to which plant-accumulated PFAS will be transferred to herbivorous consumers is unclear. Here, we exposed Solanum lycopersicum (tomato) plants to a suite of 7 different PFAS, including 4 carboxylic acids (PFOA, PFHxA, PFHpA and PFDA) and 3 sulfonates (PFBS, PFHxS and PFOS). Exposed leaf tissues were subsequently fed to Manduca sexta (tobacco hornworm) caterpillars. Biomagnification factors (BMFs) were all below 1 and patterns of uptake and elimination were similar between the different PFAS. However, PFOS bioaccumulated in the hornworms to a much higher concentration, with approximately 5-fold higher BMFs and assimilation efficiencies (AEs) than other PFAS tested. AE and BMF, as well as PFAS uptake by the plants, were positively correlated with PFAS carbon chain length for both sulfonates and carboxylic acids, providing evidence that longer chain PFAS may be more efficiently accumulated (or less efficiently eliminated) than shorter-chain PFAS in some contexts., (Copyright © 2022. Published by Elsevier Ltd.)

The long-term effect of heavy metals on soil microbial communities and their function is relatively unknown and little work has been done in field settings. To address this gap, we revisited a field-based experiment, 12 years after the application of copper (Cu) to agricultural soils, with treatment concentrations ranging from 0 to 3310 mg Cu kg -1 soil. We measured the long-term effects of Cu exposure to soils using multiple functionality assessments and environmental DNA-based community analyses. The assessment results revealed that soils that received moderate to high Cu doses had still not recovered functionality 12-years post exposure. However, plots that received doses of 200 mg kg -1 Cu or less appeared to have a functionality index not dissimilar to control plots. Environmental DNA analyses of the microbial communities revealed a high level of beta diversity in low Cu treatment plots, whereas communities within high Cu treatment plots had similar community structures to one another (low beta diversity), indicating that specific Cu-tolerant or dormant taxa are selected for in high-Cu environments. Interestingly, high Cu plots had higher within-sample taxa counts (alpha diversity) compared with controls and low Cu plots. We hypothesise that taxa in high Cu plots activated dormancy mechanisms, such that their genetic signal remained present, whilst the functionality of the soil was reduced. Many species identified in high Cu plots are known to have associated dormancy mechanisms and survive in high stress environments. Understanding how these mechanisms collectively contribute to contaminant outcomes is of great importance for the goals of predicting and managing microbial communities and their function. As we found that Cu concentrations above 200 mg kg -1 can cause significant functionality loss and a selective pressure on microbial communities, it is recommended that Cu concentrations above 200 mg kg -1 are avoided in agricultural soils., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Azithromycin (AZ) and ciprofloxacin (CIP) are commonly prescribed antibiotics frequently detected in municipal biosolids and identified by the USEPA as contaminants of emerging concern. The land application of municipal biosolids is an agronomically beneficial practice but is also a potential pathway of CIP and AZ release into the environment. Understanding retention-release behavior is crucial for assessing the environmental fate of and risks from land-applied biosolids-borne target antibiotics. Here, we used batch equilibrations to assess retention and release of environmentally relevant concentrations of CIP and AZ in ten different biosolids. The biosolids included Class A and Class B materials with a range of physiochemical characteristics (e.g. pH, cation exchange capacity (CEC), organic matter content (OM), and iron (Fe) and aluminum (Al)) expected to influence retention and release of AZ and CIP. Retention was linear (R 2  > 0.99 for AZ and >0.96 for CIP) and sorption coefficients (K d ) ranged from 52 to 370 L kg -1 for AZ and 430-2300 L kg -1 for CIP. Desorption also varied but was highly hysteretic, with hysteresis coefficients (H) ranging 0.01 to 0.15 for AZ and ≤0.01 for CIP, suggesting limited bioaccessibility. The penalized and shrinkage method least absolute shrinkage and selection operator (LASSO) was used to produce models describing AZ and CIP sorption behavior based on any given biosolids physiochemical characteristics. Multiple linear regression analysis linked AZ sorption behavior to total Fe content, likely due to a predisposition of AZ to participate in reactions with in situ Fe species. CIP sorption behavior was linked to oxalate extractable Al and total phosphorus (P) content, suggesting CIP bonding with amorphous forms of Al and a potential relationship between CIP sorption to biosolids and biosolids production processes, as manifested by correlation of CIP sorption with total P content., Competing Interests: Declaration of competing interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Sustainable alternatives to landfill disposal for municipal mixed wastes represents a major challenge to governments and waste management industries. In the state of New South Wales (NSW) Australia, mechanical biological treatment (MBT) is being used to reduce the volume and pathogen content of organic matter isolated from municipal waste. The product of this treatment, a compost-like output (CLO) referred to as mixed waste organic output (MWOO), is being recycled and applied as a soil amendment. However, the presence of contaminants in MWOO including trace organics, trace metals and physical contaminants such as microplastic fragments has raised concerns about potential negative effects on soil health and agriculture following land application. Here, we used multiple lines of evidence to examine the effects of land application of MWOO containing microplastics in three soils to a variety of terrestrial biota. Treatments included unamended soil, MWOO-amended soil and MWOO-amended soil into which additional high-density polyethylene (HDPE), polyethylene terephthalate (PET), or polyvinyl chloride (PVC) microplastics were added. Tests were conducted in soil media that had been incubated for 0, 3 or 9 months. Addition of microplastics had no significant negative effect on wheat seedling emergence, wheat biomass production, earthworm growth, mortality or avoidance behaviour and nematode mortality or reproduction compared to controls. There was also little evidence the microplastics affected microbial community diversity, although measurements of microbial community structure were highly variable with no clear trends., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

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.

The environmental fate and potential impacts of nanopesticides on agroecosystems under realistic agricultural conditions are poorly understood. As a result, the benefits and risks of these novel formulations compared to the conventional products are currently unclear. Here, we examined the effects of repeated realistic exposures of the Cu(OH) 2 nanopesticide, Kocide 3000, on simulated agricultural pastureland in an outdoor mesocosm experiment over 1 year. The Kocide applications were performed alongside three different mineral fertilization levels (Ambient, Low, and High) to assess the environmental impacts of this nanopesticide under low-input or conventional farming scenarios. The effects of Kocide over time were monitored on forage biomass, plant mineral nutrient content, plant-associated non-target microorganisms (i.e., N-fixing bacteria or mycorrhizal fungi) and six soil microbial enzyme activities. We observed that three sequential Kocide applications had no negative effects on forage biomass, root mycorrhizal colonization or soil nitrogen fixation rates. In the Low and High fertilization treatments, we observed a significant increase in aboveground plant biomass after the second Kocide exposure (+14% and +27%, respectively). Soil microbial enzyme activities were significantly reduced in the short-term after the first exposure (day 15) in the Ambient (-28% to -82%) and Low fertilization (-25% to -47%) but not in the High fertilization treatment. However, 2 months later, enzyme activities were similar across treatments and were either unresponsive or responded positively to subsequent Kocide additions. There appeared to be some long-term effects of Kocide exposure, as 6 months after the last Kocide exposure (day 365), both beta-glucosidase (-57% in Ambient and -40% in High fertilization) and phosphatase activities (-47% in Ambient fertilization) were significantly reduced in the mesocosms exposed to the nanopesticide. These results suggest that when used in conventional farming with high fertilization rates, Kocide applications did not lead to marked adverse effects on forage biomass production and key plant-microorganism interactions over a growing season. However, in the context of low-input organic farming for which this nanopesticide is approved, Kocide applications may have some unintended detrimental effects on microbially mediated soil processes involved in carbon and phosphorus cycling.

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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Bioaccumulation of engineered nanomaterials (ENMs) by plants has been demonstrated in numerous studies over the past 5-10 years. However, the overwhelming majority of these studies were conducted using hydroponic systems and the degree to which the addition of the biological and chemical components present in the soil might fundamentally alter the potential of plant bioaccumulation of ENMs is unclear. Here, we used two genotypes of Solanum lycopersicum (tomato), reduced mycorrhizal colonization ( rmc ), a mutant which does not allow arbuscular mycorrhizal fungi (AMF) colonization, and its progenitor, 76R, to examine how colonization by AMF alters trends of gold ENM bioaccumulation from a natural soil. Gold was taken up and bioaccumulated by plants of both genotypes. Gold concentrations were significantly higher in the rmc treatment although this was likely attributable to the large differences in biomass between the 76R and rmc plants. Regardless, there was little evidence that AMF played a significant role in trafficking Au ENMs into the plants. Furthermore, despite very low NH₄NO₃ extractable Au concentrations, Au accumulated at the root-soil interface. Although this observation would seem to suggest that ENMs may have potential to influence this particularly biologically active and important soil compartment, we observed no evidence of this here, as the 76R plants developed a robust AMF symbiosis despite accumulation of Au ENMs at the rhizoplane.

Manufactured nanoparticles (NPs) are increasingly being used for commercial purposes and certain NP types have been shown to have broad spectrum antibacterial activity. In contrast, their activities against fungi and fungi-like oomycetes are less studied. Here, we examined the potential of two types of commercially available Zn NPs (Zn NPs and ZnO NPs) to inhibit spore germination and infectivity on tobacco leaves resulting from exposure to the fungi-like oomycete pathogen Peronospora tabacina ( P. tabacina ). Both types of NPs, as well as ZnCl₂ and bulk ZnO control treatments, inhibited spore germination compared to a blank control. ZnO ENMs were shown to be a much more powerful suppressor of spore germination and infectivity than bulk ZnO. ZnO and Zn NPs significantly inhibited leaf infection at 8 and 10 mg·L -1 , respectively. Both types of NPs were found to provide substantially higher concentration dependent inhibition of spore germination and infectivity than could be readily explained by the presence of dissolved Zn. These results suggest that both NP types have potential for use as economic, low-dose, potentially non-persistent anti-microbial agents against the oomycete P. tabacina .

We investigated effects of Ag2S engineered nanomaterials (ENMs), polyvinylpyrrolidone (PVP) coated Ag ENMs (PVP-Ag), and Ag(+) on arbuscular mycorrhizal fungi (AMF), their colonization of tomato (Solanum lycopersicum), and overall microbial community structure in biosolids-amended soil. Concentration-dependent uptake was measured in all treatments. Plants exposed to 100 mg kg(-1) PVP-Ag ENMs and 100 mg kg(-1) Ag(+) exhibited reduced biomass and greatly reduced mycorrhizal colonization. Bacteria, actinomycetes and fungi were inhibited by all treatment classes, with the largest reductions measured in 100 mg kg(-1) PVP-Ag ENMs and 100 mg kg(-1) Ag(+). Overall, Ag2S ENMs were less toxic to plants, less disruptive to plant-mycorrhizal symbiosis, and less inhibitory to the soil microbial community than PVP-Ag ENMs or Ag(+). However, significant effects were observed at 1 mg kg(-1) Ag2S ENMs, suggesting that the potential exists for microbial communities and the ecosystem services they provide to be disrupted by environmentally relevant concentrations of Ag2S ENMs., (Copyright © 2015 Elsevier Ltd. All rights reserved.)