Joseph Hawthorne

Multiwalled Carbon Nanotubes and C60 Fullerenes Differentially Impact the Accumulation of Weathered Pesticides in Four Agricultural Plants

The effect of multiwalled carbon nanotubes (MWCNT) or C60 fullerenes on the uptake of weathered chlordane or DDx (DDT + metabolites) by Cucurbita pepo (zucchini), Zea mays (corn), Solanum lycopersicum (tomato), and Glycine max (soybean) was investigated. The plants were grown in 50 g of soil with weathered chlordane (2150 ng/g) and DDx (118 ng/g) that was amended with 0, 500, 1000, or 5000 mg/kg MWCNT or C60. After 28 d, the root and shoot content of chlordane components and DDx was determined by GC-MS. Zucchini and tomato growth were unaffected by carbon nanomaterial coexposure, although C60 at 500 mg/kg reduced corn and soybean biomass by 36.5-45.0%. Total chlordane content ranged from 1490 (tomato) to 4780 (zucchini) ng; DDx amounts ranged from 77.8 (corn) to 395 ng (zucchini). MWCNT coexposure decreased chlordane and DDx accumulation 21-80% across all crops, depending on species and nanotube concentration. Conversely, C60 had species- and contaminant-specific effects on pesticide uptake, ranging from complete suppression of DDx uptake (corn/tomato) to 34.9% increases in chlordane accumulation (tomato/soybean). The data show that pesticide accumulation varies greatly with crop species and carbon nanomaterial type/concentration. These findings have implications for food safety and for the use of engineered nanomaterials in agriculture.

Particle-Size Dependent Accumulation and Trophic Transfer of Cerium Oxide through a Terrestrial Food Chain

The accumulation and trophic transfer of nanoparticle (NP) or bulk CeO2 through a terrestrial food chain was evaluated. Zucchini (Cucurbita pepo L.) was planted in soil with 0 or 1228 μg/g bulk or NP CeO2. After 28 d, zucchini tissue Ce content was determined by ICP-MS. Leaf tissue from each treatment was used to feed crickets (Acheta domesticus). After 14 d, crickets were analyzed for Ce content or were fed to wolf spiders (family Lycosidae). NP CeO2 significantly suppressed flower mass relative to control and bulk treatments. The Ce content of zucchini was significantly greater when exposure was in the NP form. The flowers, leaves, stems, and roots of zucchini exposed to bulk CeO2 contained 93.3, 707, 331, and 119,000 ng/g, respectively; NP-exposed plants contained 153, 1510, 479, and 567 000 ng/g, respectively. Crickets fed NP CeO2-exposed zucchini leaves contained significantly more Ce (33.6 ng/g) than did control or bulk-exposed insects (15.0-15.2 ng/g). Feces from control, bulk, and NP-exposed crickets contained Ce at 248, 393, and 1010 ng/g, respectively. Spiders that consumed crickets from control or bulk treatments contained nonquantifiable Ce; NP-exposed spiders contained Ce at 5.49 ng/g. These findings show that NP CeO2 accumulates in zucchini at greater levels than equivalent bulk materials and that this greater NP intake results in trophic transfer and possible food chain contamination.

Accumulation and phytotoxicity of engineered nanoparticles to Cucurbita pepo.

The effect of bulk and engineered nanoparticle (NP) Ag, Au, Cu, Si, and C at 250 and 750 mg/L on zucchini biomass, transpiration, and element content was determined. The pH of bulk and NP solutions prior to plant growth frequently differed. Nanoparticle Cu solution pH was significantly higher than bulk Cu, whereas for Ag and C, the NPs had significantly lower pH. Plants were unaffected by Au, regardless of particle size or concentration. NP Ag reduced plant biomass and transpiration by 49–91% compared to equivalent bulk Ag. NP Si at 750 mg/L reduced plant growth and transpiration by 30–51% relative to bulk Si. Bulk and NP Cu were phytotoxic but much of the effect was alleviated by humic acid. The shoot Ag and Cu content did not differ based on particle size or concentration. The accumulation of bulk Au was greater than the NP, but humic acid increased the accumulation of NP and bulk Au by 5.6-fold and 80%, respectively. The uptake of NP Si was 5.6–6.5-fold greater than observed with the bulk element. These findings show that the NPs may have unique phytotoxicity or accumulation patterns and that solution properties can significantly impact particle fate and effects.

Impact of non-functionalized and amino-functionalized multiwall carbon nanotubes on pesticide uptake by lettuce (Lactuca sativa L.)

Abstract The effect of non-functionalized and amino-functionalized multiwall carbon nanotube (CNT) exposure, as well as the impact of CNT presence on coexistent pesticide accumulation, was investigated in lettuce (Lactuca sativa L.). Lettuce seeds were sown directly into CNT-amended vermiculite (1000 mg L−1) to monitor phytotoxicity during germination and growth. During growth, lettuce seedlings were subsequently exposed to chlordane (cis-chlordane [CS], trans-chlordane [TC] and trans-nonachlor [TN]) and p,p′-DDE (all at 100 ng/L) in the irrigation solution for a 19-d growth period. CNT exposure did not significantly influence seed germination (82–96%) or plant growth. Similarly, pesticide exposure had no impact on plant growth, total pigment production or tissue lipid peroxidation. After 19 d, the root content of total chlordane and p,p′-DDE was 390 and 73.8 µg g−1, respectively; in plants not exposed to CNTs, the shoot levels were 1.58 and 0.40 µg g−1, respectively. The presence and type of CNT significantly influenced pesticide availability to lettuce seedlings. Non-functionalized CNT decreased the root and shoot pesticide content by 88% and 78%, respectively, but amino-functionalized CNT effects were significantly more modest, with decreases of 57% in the roots and 23% in the shoots, respectively. The presence of humic acid completely reversed the reduced accumulation of pesticides induced by amino-functionalized CNT, likely due to strong competition over adsorption sites on the nanomaterial (NM). These findings have implications for food safety and for the use of engineered NMs in agriculture, especially with leafy vegetables.

Terrestrial Trophic Transfer of Bulk and Nanoparticle La2O3 Does Not Depend on Particle Size

The bioaccumulation and trophic transfer of bulk and nanoparticle (NP) La2O3 from soil through a terrestrial food chain was determined. To investigate the impact of growth conditions, lettuce (Lactuca sativa) was grown in 350 or 1200 g of bulk/NP amended soil. Leaf tissues were fed to crickets (Acheta domesticus) or darkling beetles (Tenebrionoidea); select crickets were fed to mantises. In the small pot (350 g), La2O3 exposure reduced plant biomass by 23-30% and La tissue content did not differ with particle size. In the large pot (1200 g), biomass was unaffected by exposure and La content in the tissues were significantly greater with bulk particle treatment. Darkling beetles exposed to bulk and NP La2O3-contaminated lettuce contained La at 0.18 and 0.08 mg/kg; respectively (significantly different, P < 0.05). Crickets fed bulk or NP La2O3-exposed lettuce contained 0.53 and 0.33 mg/kg, respectively (significantly different, P < 0.05) with 48 h of depuration. After 7 d of depuration, La content did not differ with particle size, indicating that 48 h may be insufficient to void the digestive system. Mantises that consumed crickets from bulk and NP-exposed treatments contained La at 0.05-0.060 mg/kg (statistically equivalent). These results demonstrate that although La does trophically transfer, biomagnification does not occur and NP levels are equivalent or less than the bulk metal.

Weathering in soil increases nanoparticle CuO bioaccumulation within a terrestrial food chain

Abstract This study evaluates the bioaccumulation of unweathered (U) and weathered (W) CuO in NP, bulk and ionic form (0–400 mg/kg) by lettuce exposed for 70 d in soil co-contaminated with field incurred chlordane. To evaluate CuO trophic transfer, leaves were fed to crickets (Acheta domestica) for 15 d, followed by insect feeding to lizards (Anolis carolinensis). Upon weathering, the root Cu content of the NP treatment increased 214% (327 ± 59.1 mg/kg) over unaged treatment. Cu root content decreased in bulk and ionic treatments from 70–130 mg/kg to 13–26 mg/kg upon aging in soil. Micro X-ray fluorescence (μ-XRF) analysis of W-NP-exposed roots showed a homogenous distribution of Cu (and Ca) in the tissues. Additionally, micro X-ray absorption near-edge (μ-XANES) analysis of W-NP-exposed roots showed near complete transformation of CuO to Cu (I)-sulfur and oxide complexes in the tissues, whereas in unweathered treatment, most root Cu remained as CuO. The expression level of nine genes involved in Cu transport shows that the mechanisms of CuO NPs (and bulk) response/accumulation are different than ionic Cu. The chlordane accumulation by lettuce upon co-exposure to CuO NPs significantly increased upon weathering. Conversely, bulk and ionic exposures decreased pesticide accumulation by plant upon weathering. The Cu cricket fecal content from U-NP-exposed insects was significantly greater than the bulk or ion treatments, suggesting a higher initial NP accumulation followed by significantly greater elimination during depuration. In the lizard, Cu content in the intestine, body and head did not differ as a function of weathering. This study demonstrates that CuO NPs may undergo transformation processes in soil upon weathering that subsequently impact NPs availability in terrestrial food chains.

Molecular Response of Crop Plants to Engineered Nanomaterials

Functional toxicology has enabled the identification of genes involved in conferring tolerance and sensitivity to engineered nanomaterial (ENM) exposure in the model plant Arabidopsis thaliana (L.) Heynh. Several genes were found to be involved in metabolic functions, stress response, transport, protein synthesis, and DNA repair. Consequently, analysis of physiological parameters, metal content (through ICP-MS quantification), and gene expression (by RT-qPCR) of A. thaliana orthologue genes were performed across different plant species of agronomic interest to highlight putative biomarkers of exposure and effect related to ENMs. This approach led to the identification of molecular markers in Solanum lycopersicum L. and Cucurbita pepo L. (tomato and zucchini) that might not only indicate exposure to ENMs (CuO, CeO2, and La2O3) but also provide mechanistic insight into response to these materials. Through Gene Ontology (GO) analysis, the target genes were mapped in complex interatomic networks representing molecular pathways, cellular components, and biological processes involved in ENM response. The transcriptional response of 38 (out of 204) candidate genes studied varied according to particle type, size, and plant species. Importantly, some of the genes studied showed potential as biomarkers of ENM exposure and effect and may be useful for risk assessment in foods and in the environment.

Inheritance Profile of Weathered Chlordane and P,P′-DDTs Accumulation by cucurbita pepo hybrids

Cucurbita pepo ssp pepo (zucchini) accumulates significant levels of persistent organic pollutants in its roots, followed by unexpectedly high contaminant translocation to the stems. Most other plant species, including the closely related C. pepo ssp ovifera (squash), do not have this ability. To investigate the mechanism of contaminant accumulation, two cultivars each of parental zucchini and squash, as well as previously created first filial (F1) hybrids and F1 backcrosses (BC) of those parental cultivars, were grown under field conditions in a soil contaminated with weathered chlordane (2.29 μg/g) and DDX residues (0.30 μg/g; sum of DDT, DDE, DDD). The parental zucchini had stem-to-soil bioconcentration factors (BCF, contaminant ratio of stem to soil) for chlordane and DDX of 6.23 and 3.10; these values were 2.2 and 3.7 times greater than the squash, respectively. Chlordane and DDX translocation factors, the ratio of contaminant content in the stems to that in the root, were 2.1 and 3.2 times greater for zucchini than for squash. The parental zucchini and squash also differed significantly in chlordane component ratios (relative amounts of trans-nonachlor [TN], cis-chlordane [CC], trans-chlordane [TC]) and enantiomer fractions for the chiral CC and TC. Hybridization of the parental squash and zucchini resulted in significant differences in contaminant uptake. For both the three separate component ratios (CR) and two sets of enantiomer fraction (EF) values, subspecies specific differences in the parental generation became statistically equivalent in the F1 hybrid zucchini and squash. When backcrossed (BC) with the original parental plants, the zucchini and squash F1 BC cultivars reverted to the statistically distinct CR and EF patterns. This pattern of trait segregation upon hybridization suggests either single gene or single locus control for persistent organic pollutant (POP) uptake ability by C. pepo ssp pepo.

Nanoparticle Ag CO-exposure reduces the accumulation of weathered persistent pesticides by earthworms.

Although the use of engineered nanomaterials continues to increase, how these materials interact with coexisting contaminants in the environment is largely unknown. The effect of silver (Ag) in bulk, ionic, and nanoparticle (NP; bare and polyvinyl pyrrolidone-coated) forms at 3 concentrations (0 mg/kg, 500 mg/kg, 1000 mg/kg, 2000 mg/kg; ion at 69 mg/kg, 138 mg/kg, 276 mg/kg) on the accumulation of field-weathered chlordane and dichlorodiphenyldichloroethylene + metabolites (DDX) by Eisenia fetida (earthworm) was investigated. Earthworm biomass and survival were unaffected by treatment. At the 500 mg/kg and 1000 mg/kg exposure levels, NP-exposed earthworms contained significantly greater Ag (194-245%) than did the bulk exposed organisms; NP size or coating had no impact on element content. Generally, exposure to Ag of any type or at any concentration significantly reduced pesticide accumulation, although reductions for DDX (35.1%; 8.9-47.0%) were more modest than those for chlordane (79.0%; 17.4-92.9%). For DDX, the reduction in pesticide accumulation was not significantly affected by Ag type or concentration. For chlordane, the 3 NP exposures suppressed chlordane accumulation significantly more than did bulk exposure; earthworms exposed to bulk Ag contained 1170 ng/g chlordane, but levels in the NP-exposed earthworms were 279 ng/g. At the 500 mg/kg exposure, the smallest coated NPs exerted the greatest suppression in chlordane accumulation; at the 2 higher concentrations, chlordane uptake was unaffected by NP size or coating. The findings show that in exposed earthworms Ag particle size does significantly impact accumulation of the element itself, as well as that of coexisting weathered pesticides. The implications of these findings with regard to NP exposure and risk are unknown but are the topic of current investigation. Environ Toxicol Chem 2017;36:1864-1871.

Endophyte-enhanced phytoremediation of DDE-contaminated using Cucurbita pepo: A field trial

ABSTRACT Although the use of the pesticide 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane (DDT) was banned from the mid-1970s, its most abundant and recalcitrant degradation product, 2,2-bis(p-chlorophenyl)-1,1-dichloro-ethylene (DDE), is still present in terrestrial and aquatic ecosystems worldwide. Zucchini (Cucurbita pepo ssp. pepo) has been shown to accumulate high concentrations of DDE and was proposed for phytoremediation of contaminated soils. We performed a field trial covering a full plant life cycle. C. pepo plants inoculated with the plant growth-promoting endophytic strains Sphingomonas taxi UH1, Methylobacterium radiotolerans UH1, Enterobacter aerogenes UH1, or a consortium combining these 3 strains were grown on a DDE-contaminated field for 100 days. The effects of these inoculations were examined at both the plant level, by evaluating plant weight and plant DDE-content, and at the level of the cultivable and total endophytic communities. Inoculating plants with S. taxi UH1, M. radiotolerans UH1, and the consortium increased plant weight. No significant effects of the inoculations were observed on DDE-concentrations in plant tissues. However, the amount of DDE accumulated by C. pepo plants per growing season was significantly higher for plants that were inoculated with the consortium of the 3 strains. Therefore, inoculation of C. pepo with DDE-degrading endophytes might be promising for phytoremediation applications.