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Capturing the breadth of chemical exposures in utero is critical in understanding their long-term health effects for mother and child. We explored methodological adaptations in a Non-Targeted Analysis (NTA) pipeline and evaluated the effects on chemical annotation and discovery for maternal and infant exposure. We focus on lesser-known/underreported chemicals in maternal and umbilical cord serum analyzed with liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QTOF/MS). The samples were collected from a demographically diverse cohort of 296 maternal-cord pairs (n = 592) recruited in San Francisco Bay area. We developed and evaluated two data processing pipelines, primarily differing by detection frequency cut-off, to extract chemical features from non-targeted analysis (NTA). We annotated the detected chemical features by matching with EPA CompTox Chemicals Dashboard (n = 860,000 chemicals) and Human Metabolome Database (n = 3140 chemicals) and applied a Kendrick Mass Defect filter to detect homologous series. We collected fragmentation spectra (MS/MS) on a subset of serum samples and matched to an experimental MS/MS database within the MS-Dial website and other experimental MS/MS spectra collected from standards in our lab. We annotated ~72 % of the features (total features = 32,197, levels 1-4). We confirmed 22 compounds with analytical standards, tentatively identified 88 compounds with MS/MS spectra, and annotated 4862 exogenous chemicals with an in-house developed annotation algorithm. We detected 36 chemicals that appear to not have been previously reported in human blood and 9 chemicals that were reported in less than five studies. Our findings underline the importance of NTA in the discovery of lesser-known/unreported chemicals important to characterize human exposures., 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 The Authors. Published by Elsevier B.V. All rights reserved.)

Here, isotopically labeled 68 ZnO NPs (ZnO NPs) and 68 ZnO NPs with a thin 68 Zn 3 (PO 4 ) 2 shell (ZnO_Ph NPs) were foliarly applied (40 μg Zn) to pepper plants ( Capsicum annuum ) to determine the effect of surface chemistry of ZnO NPs on the Zn uptake and systemic translocation to plant organs over 6 weeks. Despite similar dissolution of both Zn-based NPs after 3 weeks, the Zn 3 (PO 4 ) 2 shell on ZnO_Ph NPs (48 ± 12 nm; -18.1 ± 0.6 mV) enabled a leaf uptake of 2.31 ± 0.34 μg of Zn, which is 2.7 times higher than the 0.86 ± 0.18 μg of Zn observed for ZnO NPs (26 ± 8 nm; 14.6 ± 0.4 mV). Further, ZnO_Ph NPs led to higher Zn mobility and phloem loading, while Zn from ZnO NPs was stored in the epidermal tissues, possibly through cell wall immobilization as a storage strategy. These differences led to higher translocation of Zn from the ZnO_Ph NPs within all plant compartments. ZnO_Ph NPs were also more persistent as NPs in the exposed leaf and in the plant stem over time. As a result, the treatment of ZnO_Ph NPs induced significantly higher Zn transport to the fruit than ZnO NPs. As determined by spICP-TOFMS, Zn in the fruit was not in the NP form. These results suggest that the Zn 3 (PO 4 ) 2 shell on ZnO NPs can help promote the transport of Zn to pepper fruits when foliarly applied. This work provides insight into the role of Zn 3 (PO 4 ) 2 on the surface of ZnO NPs in foliar uptake and in planta biodistribution for improving Zn delivery to edible plant parts and ultimately improving the Zn content in food for human consumption.

Background: Nontargeted analysis (NTA) methods identify novel exposures; however, few chemicals have been quantified and interrogated with pregnancy complications., Objectives: We characterized levels of nine exogenous and endogenous chemicals in maternal and cord blood identified, selected, and confirmed in prior NTA steps, including linear and branched isomers perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), monoethylhexyl phthalate, 4-nitrophenol, tetraethylene glycol, tridecanedioic acid, octadecanedioic acid, and deoxycholic acid. We evaluated relationships between maternal and cord levels and between gestational diabetes mellitus (GDM) and hypertensive disorders of pregnancy in a diverse pregnancy cohort in San Francisco., Methods: We collected matched maternal and cord serum samples at delivery from 302 pregnant study participants from the Chemicals in Our Bodies cohort in San Francisco. Chemicals were identified via NTA and quantified using targeted approaches. We calculated distributions and Spearman correlation coefficients testing the relationship of chemicals within and between the maternal and cord blood matrices. We used adjusted logistic regression to calculate the odds of GDM and hypertensive disorders of pregnancy associated with an interquartile range increase in maternal chemical exposures., Results: We detected linear PFOS, PFHxS, octadecanedioic acid, and deoxycholic acid in at least 97% of maternal samples. Correlations ranged between - 0.1 and 0.9. We observed strong correlations between cord and maternal levels of PFHxS, linear PFOS, and branched PFOS ( coefficient = 0.9 , 0.8, and 0.8, respectively). An interquartile range increase in linear and branched PFOS, tridecanedioic acid, octadecanedioic acid, and deoxycholic acid was associated with increased odds ratio (OR) of GDM [ OR = 1.33 (95% CI: 0.89, 2.01), 1.24 (95% CI: 0.86, 1.80), 1.26 (95% CI: 0.93, 1.73), 1.24 (95% CI: 0.86, 1.80), and 1.23 (95% CI: 0.87, 1.75), respectively]. Tridecanedioic acid was positively associated with hypertensive disorders of pregnancy [ OR = 1.28 (95% CI: 0.90, 1.86)]., Discussion: We identified both exogenous and endogenous chemicals seldom quantified in pregnant study participants that were also related to pregnancy complications and demonstrated the utility of NTA to identify chemical exposures of concern. https://doi.org/10.1289/EHP11546.

Finding and quantifying engineered nanomaterials (ENMs) in soil are challenging because of the abundance of natural nanomaterials (NNMs) with the same elemental composition, for example, TiO 2 . Isotopically enriched ENMs may be distinguished from NNMs with the same elemental composition using single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOF-MS) to measure multiple isotopes simultaneously within each ENM and NNM in soil, but the minimum isotope enrichment needed for detection of ENMs in soil is not known. Here, we determined the isotope enrichment needed for 47 Ti-enriched TiO 2 ENMs to be detectable in soil and assessed the effects of weathering on those requirements for less soluble TiO 2 and more soluble CuO ENMs. The isotope-enriched ENMs were dosed into two different soils and were extracted and measured by spICP-TOF-MS after 1, 7, and 30 days. Isotope-enriched ENMs were recovered and detected for all three time points. The 47 Ti-enriched TiO 2 ENMs were detectable in Lufa 2.2 soil at a nominal dosed concentration of 10 mg-TiO 2 kg -1 which is an environmentally relevant concentration in biosolid-amended soils. For distinguishing an ∼70 nm diameter TiO 2 ENM from TiO 2 NNMs in Lufa 2.2 soil, an ∼10 wt % 47 Ti isotope-enrichment was required, and this enrichment requirement increases as the particle size decreases. This study is the first to evaluate the tracking ability of isotope-enriched ENMs at an individual particle level in soil and provides guidance on the isotope enrichment requirements for quantification of ENMs made from Earth-abundant elements in soils.

Identifying engineered nanomaterials (ENMs) made from earth-abundant elements in soils is difficult because soil also contains natural nanomaterials (NNMs) containing similar elements. Here, machine learning models using elemental fingerprints and mass distributions of three TiO 2 ENMs and Ti-based NNMs recovered from three natural soils measured by single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS) was used to identify TiO 2 ENMs in soil. Synthesized TiO 2 ENMs were unassociated with other elements (>98%), while 40% of Ti-based ENM particles recovered from wastewater sludge had distinguishable elemental associations. All Ti-based NNMs extracted from soil had a similar chemical fingerprint despite the soils being from different regions, and >60% of Ti-containing NNMs had no measurable associated elements. A machine learning model best distinguished NNMs and ENMs when differences in Ti-mass distribution existed between them. A trained LR model could classify 100 nm TiO 2 ENMs at concentrations of 150 mg kg -1 or greater. The presence of TiO 2 ENMs in soil could be confirmed using this approach for most ENM-soil combinations, but the absence of a unique chemical fingerprint in a large fraction of both TiO 2 ENMs and Ti-NNMs increases model uncertainty and hinders accurate quantification.

Particle-specific properties, including size and chemical speciation, affect the reactivity of mercury (Hg) in natural systems (e.g., dissolution or methylation). Here, terrestrial, river, and marine sediments were size-fractionated and characterized to correlate particle-specific properties of Hg-bearing solids with their bioavailability potential and measured biomethylation. Marine sediments contained ∼20-50% of the total Hg in the <0.5 μm size fraction, compared to only 0.5 and 3.0% in this size fraction for terrestrial and river sediments, respectively. X-ray absorption spectroscopy (XAS) analysis indicated that metacinnabar (β-HgS) was the main mercury species in a marine sediment, whereas organic Hg-thiol (Hg(SR) 2 ) was the main mercury species in a terrestrial sediment. Single-particle inductively coupled plasma time-of-flight mass spectrometry analysis of the marine sediment suggests that half of the Hg in the <0.5 μm size fraction existed as individual nanoparticles, which were β-HgS based on XAS analyses. Glutathione-extractable mercury was higher for samples containing Hg(SR) 2 species than β-HgS species and correlated well with the amount of Hg biomethylation. This particle-scale understanding of how Hg speciation and particle size affect mercury bioavailability potential helps explain the heterogeneity in Hg methylation in natural sediments.

Here we compared the efficiency of Cu extraction (dissolved + particulate) from two soils dosed with CuO nanoparticles (NPs) at 50 or 250 mg kg -1 by pore water collection, and single- and multi-step soil extraction tests. Pore water collection recovered low levels of Cu (<0.18%, regardless of soil type or Cu dose). Single soil extraction by either CaCl 2 or DI water led to higher Cu recovery than pore water collection, but still <3% of total dose. These methods were useful for assessing the labile Cu ions pool. This fraction is controlled by Cu 2+ dissolved from CuO NPs and it varies with time and soil type. Particulate Cu was poorly retrieved (<0.7%) by pore water extraction and by single-step soil extraction using CaCl 2 solution or water. Multi-step extraction including dispersing and metal-chelating agents allowed for simultaneous characterization of dissolved Cu (total ionic Cu 2+ , 24-49% of dosed Cu), extractable CuO NPs (reversibly attached, 15-26% of dosed Cu), and non-extractable CuO NPs (irreversibly attached, 36-50% of dosed Cu), and it could describe the aging of NPs along 30 d. This method extracted a significantly higher concentration of Cu than pore water collection and was less sensitive to method parameters (e.g. filtration). This multi-step method can reduce pore water extraction-related factors that may confound the interpretation of environmental exposure data in NPs studies, and describe upper limits of both exchangeable Cu 2+ and dispersible CuO NPs in soil that can potentially become bioavailable to plants and organisms and thus provide a sounder basis for risks evaluations., 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.)

Technologies for removal of mercury from produced water and hydrocarbon phases are desired by oil and gas production facilities, oil refineries, and petrochemical plants. Herein, we synthesize and demonstrate the efficacy of an amphiphilic, thiol-abundant (11.8 wt % S, as thiol) polymer nanogel that can remove environmentally relevant mercury species from both produced water and the liquid hydrocarbon. The nanogel disperses in both aqueous and hydrocarbon phases. It has a high sorption affinity for dissolved Hg(II) complexes and Hg-dissolved organic matter complexes found in produced water and elemental (Hg 0 ) and soluble Hg-alkyl thiol species found in hydrocarbons. X-ray absorption spectroscopy analysis indicates that the sorbed mercury is transformed to a surface-bound Hg(SR) 2 species in both water and hydrocarbon regardless of its initial speciation. The nanogel had high affinity to native mercury species present in real produced water (>99.5% removal) and in natural gas condensate (>85% removal) samples, removing majority of the mercury species using only a 50 mg L -1 applied dose. This thiolated amphiphilic polymeric nanogel has significant potential to remove environmentally relevant mercury species from both water and hydrocarbon at low applied doses, outperforming reported sorbents like sulfur-impregnated activated carbons because of the mass of accessible thiol groups in the nanogel.

The effects of a model natural organic matter (NOM) on the transport of Hg(II) into diffusive gradient in thin-film devices (DGTs) was evaluated in order to better understand their ability to measure colloidal Hg species in porewater. The presence of NOM significantly reduced the diffusivity of the Hg(II) species and the reduction was dependent upon NOM to Hg(II) ratio. This relationship was modeled by determining the Hg(II) partition coefficients (K d ) of size fractionated NOM obtained by ultrafiltration and estimating the Hg diffusivity through the DGT for the different NOM size fractions across a range of Hg-NOM ratios. The estimated diffusivities were consistent with experimental observations of uptake into the DGT. Overall, this study indicated that Hg(II) associated with NOM passes into a DGT, however the transport is slowed in accordance with the diffusivity of the NOM to which the Hg(II) is associated. Thus, the Hg-NOM association and complex diffusivities need to be considered when relating DGT uptake to Hg porewater concentration. The results also suggest that Hg(II) associated with colloidal or larger particles of negligible diffusivity are unlikely to contribute significantly to DGT measurements., 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 B.V. All rights reserved.)

The objective of this study is to assess how method parameters impact the extraction of moderately soluble CuO nanoparticles (NPs) from a standard natural soil (LUFA 2.1) suitable for chemical analysis. The extraction procedure is comprised of three steps: (i) preconditioning the soil to increase the sodium adsorption ratio, (ii) extracting colloids/NPs from the soil matrix using sonication and a dispersing agent, and (iii) separating the dissolved and nanoparticulate CuO fractions using cloud point extraction. Method parameters of the extraction procedure, including sonication, number of extraction cycles, and dispersing agent, were adjusted to achieve the highest extraction of CuO NPs, while minimizing dissolution. The maximum recovery of CuO NPs ranged from 31% to 42% for an amended concentration range of 10-250 mg-Cu (kg soil) -1 using a preconditioning step to exchange divalent cations for monovalent ions, 0.2% carboxymethyl cellulose (CMC) 700 kg mol -1 as the dispersing agent, probe sonication for 1 min, 3 extraction cycles, and a 1:10 soil-to-liquid ratio. CuO NPs that are polyvinylpyrrolidone (PVP)-coated with a greater stability against aggregation had significantly higher extractability and dissolution. This procedure is the first to effectively extract moderately soluble NPs from soil and experimentally separate them from their dissolved fraction and can be applied to other moderately soluble metal containing natural, incidental, or engineered NPs in soil.

The application of nanoparticles (NPs) to soils, as either fertilizers or fungicides (e.g., CuO NPs), has been proposed to improve the sustainability of agriculture. The observed effects could result directly from the NP-plant interactions or indirectly through effects on the soil microbiome. The objective of this study was to assess the effects of CuO NPs on the changes in the bacterial community structure and nitrogen-cycling-associated functions in a high pH soil and to correlate these changes with nitrate accumulation, soil parameter changes, and plant growth over 28 days. Triticum aestivum seedlings were exposed to 50 mg/kg CuO NPs, 50 mg/kg CuSO 4 , or 0.5 mg/kg CuSO 4 in a standard soil (Lufa 2.1 soil, pH adjusted to 7.6). While Cu treatments reduced nitrate accumulation in the bulk soil, the effects were opposite in the rhizosphere (the soil influenced by root exudates). While nitrate accumulation in bulk soil negatively correlated with total Cu concentration, part of the nitrate concentration in the rhizosphere was explained by root uptake during plant growth, the rest being modulated by Cu treatments. The abundance of genes involved in the nitrogen cycle in the rhizosphere soil correlated with the ionic copper concentration. The increased nitrate concentration in the rhizosphere correlated with an increase of the gene abundance related to the nitrogen fixation and a decrease of denitrification gene abundance. Microbial diversity in bulk or rhizosphere soil under the different treatments alone could not explain these variations, while differences in the assemblages of bacteria associated with these functional gene abundances gave good insights. This study highlights the complexity of microbial N-related function in the rhizosphere and the need to characterize the rhizosphere soil, plant growth and root activity, NP (bio)transformations, along with microbial networks, to understand the impact of agrochemicals (here CuO NPs) on soil fertility.

Plant nanobiotechnology has the potential to revolutionize agriculture. However, the lack of effective methods to deliver nanoparticles (NPs) to the precise locations in plants where they are needed impedes these technological innovations. Here, model gold nanoparticles (AuNP) were coated with citrate, bovine serum albumin (BSA) as a protein control, or LM6-M, an antibody with an affinity for functional groups unique to stomata on leaf surfaces to deliver the AuNPs to stomata. One-month-old Vicia faba leaves were exposed via drop deposition to aqueous suspensions of LM6-M-coated AuNPs and allowed to air dry. After rinsing, Au distribution on the leaf surface was investigated by enhanced dark-field microscopy and X-ray fluorescence mapping. While citrate-coated AuNPs randomly covered the plant leaves, LM6M-AuNPs strongly adhered to the stomata and remained on the leaf surface after rinsing, and BSA-AuNPs specifically targeted trichome hairs. To the authors' knowledge, this is the first report of active targeting of live leaf structures using NPs coated with molecular recognition molecules. This proof-of-concept study provides a strategy for future targeted nanopesticide delivery research.

Arsenic being a naturally-occurring groundwater contaminant is subject to stringent water quality regulations. Coagulation and adsorption are widely used methods to treat arsenic-contaminated water, however, these treatments have been reported to be less efficient for the removal of arsenite (As(III)) than arsenate (As(V)). In this study, the feasibility of in situ oxidation of As(III) during coagulation was investigated in two systems: Fe(II) or H2O2-assisted oxidative coagulation treatment using ferric chloride as the coagulant. This setup exploits the catalytic property of the fresh formed Fe(III) hydroxide colloids in coagulation suspension to mediate the production of reactive oxidants capable of As(III) oxidation. Fe(II)-assisted coagulation brought about small improvements in As(III) removal compared to treatment with Fe(III) coagulant alone, however, its arsenic removal efficiency is strongly dependent on pH (observed optimal pH = 7-9). Addition of H2O2 together with ferric chloride led to a significant enhancement in arsenic retention at pH 6-8, with final arsenic concentrations well below the U.S.EPA regulatory limit (10 μg/L). H2O2-assisted oxidative coagulation can attain reliable As(III) removal over a broad pH range of 4-9. Radical quenching experiments reveal the participation of superoxide radical in As(III) removal in the oxidative coagulation systems. Phosphate (at > 0.1 mM) strongly suppresses As(III) removal efficiency, whereas carbonate and humic acid pose a minor impact. Overall, the results suggest that a low dose addition of H2O2 along with ferric coagulant is a feasible method for the existing water treatment facilities to achieve improved As(III) removal efficiency., (Copyright © 2016 Elsevier Ltd. All rights reserved.)