The role of char nutrients in the biodegradation of coexisting dichlobenil and atrazine in a soil by their respective bacterial degraders, DDN and ADP, was evaluated. Under growing conditions, their degradation in soil extract was slow with <40% and <20% degraded within 64 h, respectively. The degradation in extracts and slurries of char-amended solids increased with increasing char content, due to nutritional stimulation on microbial activities. By supplementing soil extract with various major nutrients, the measured degradation demonstrated that P was the exclusive limiting nutrient. The reduction in the degradation of coexisting dichlobenil and atrazine resulted apparently from the competitive utilization of P by DDN and ADP. With a shorter lag phase, ADP commenced growing earlier than DDN with the advantage of utilizing P first in insufficient supply. This resulted in an inhibition on the growth of DDN and thus suppression on dichlobenil degradation. Competitive utilization of char nutrients by bacterial degraders resulted in the preferential biodegradation of atrazine over dichlobenil in a soil containing a wheat-straw-derived char.

To evaluate the influence of surface coatings on nano-fertilizers uptake and their phytotoxicity to crops and its health risk to Chinese adults, trisodium citrate (TC) and polyethylene glycol (PEG) coatings were prepared on the surface of copper oxide nanoparticles (CuO NPs), respectively, with 100 and 500 mg/L of bare CuO NPs, TC-CuO NPs, and PEG-CuO NPs were exposed to soil-grown Ipomoea aquatica Forssk. Combined bio-transmission electron microscopy and micro-CT observed cellular migration of coated CuO NPs in symplastic and apoplastic pathways, as well as nanoparticles transported through vascular tissues to the above-ground parts. Since TC-CuO NPs had less inhibition on vascular phylogeny of I. aquatica roots which was determined by RT-qPCR, their migration in plants was more efficient, thus exhibiting greater phytotoxicity to shoots. Meanwhile, coatings significantly reduced the phytotoxicity of CuO NPs by stimulating plant antioxidant defense. The risk of CuO nano-fertilizers on human dietary safety was evaluated, the HQ > 1 in the 500 mg/L CuO NPs treatment indicated a potential health risk to Chinese adults, which was reduced by the coatings. This work explored for the first time the mechanism of coating effects on nanoparticles migration efficiency and phytotoxicity at the molecular level and demonstrated that the migration of nanoparticles between tissues could have an impact on phytotoxicity. It implied that coating can be tailored to target nanoparticles to specific regions of the plant. In addition, this study highlights the potential health risks associated with the consumption of I. aquatica fertilized with CuO NPs and provides valuable insights into the environmental applications of nano-fertilizers.

Silver nanoparticles (AgNPs) are increasingly used in various commercial products. This increased use raises ecological concerns because of the large release of AgNPs into the environment. Once released, the local water chemistry has the potential to influence the environmental fates and behaviors of AgNPs. The impacts of dissolved oxygen and natural organic matter (NOM) on the dissolution and stability of AgNPs were investigated in synthetic and natural freshwaters for 7 days. In synthetic freshwater, the aggregation of AgNPs occurred due to the compression of the electric double layer, accompanied by the dissolution of AgNPs. However, once oxygen was removed, the highest dissolved Ag (Agdis) concentration decreased from 356.5 μg/L to 272.1 μg/L, the pH of the AgNP suspensions increased from less than 7.6 to more than 8.4, and AgNPs were regenerated by the reduction of released Ag+ by citrate. The addition of NOM mitigated aggregation, inhibited oxidative dissolution and induced the transformation of AgNPs into Ag2S due to the formation of NOM-adsorbed layers, the reduction of Ag+ by NOM, and the high affinity of sulfur-enriched species in NOM for Ag. Likewise, in oxygen-depleted natural freshwaters, the inhibition of oxidative dissolution was obtained in comparison with oxygenated freshwaters, showing a decrease in the maximum Agdis concentration from 137.6 and 57.0 μg/L to 83.3 and 42.4 μg/L from two natural freshwater sites. Our results suggested that aggregation and dissolution of AgNPs in aquatic environments depend on the chemical composition, where oxygen-depleted freshwaters more significantly increase the colloidal stability. In comparison with oxic conditions, anoxic conditions were more favorable to the regeneration of AgNPs by reducing species (e.g., citrate and NOM) and enhanced the stability of nanoparticles. This indicates that some AgNPs will be more stable for long periods in oxygen-deprived freshwaters, and pose more serious environmental risks than that in oxygenated freshwaters.

Metal-based nanoparticles (MNPs) may be translocated and biochemically modified in vivo, which may influence the fate of MNPs in the environment. Here, synchrotron-based techniques were used to investigate the behavior of CuO NPs in rice plants exposed to 100 mg/L CuO NPs for 14 days. Micro X-ray fluorescence (μ-XRF) and micro X-ray absorption near edge structure (μ-XANES) analysis revealed that CuO NPs moved into the root epidermis, exodermis, and cortex, and they ultimately reached the endodermis but could not easily pass the Casparian strip; however, the formation of lateral roots provided a potential pathway for MNPs to enter the stele. Moreover, bulk-XANES data showed that CuO NPs were transported from the roots to the leaves, and that Cu (II) combined with cysteine, citrate, and phosphate ligands and was even reduced to Cu (I). CuO NPs and Cu-citrate were observed in the root cells using soft X-ray scanning transmission microscopy (STXM).

This study aims to investigate effects of freshwater components in order to predict agglomeration behavior of silver nanoparticles coated with citrate (AgNP-Cit), polyvinylpyrrolidone (AgNP-PVP), and of TiO2 nanoparticles. Agglomeration studies were conducted in various media based on combinations of ions, natural organic matter (humic, fulvic acid) and surfactants (sodium dodecyl sulfate, alkyl ethoxylate), at a constant ionic strength of 10 mM over time for up to 1 week. Agglomeration level of AgNP-Cit and TiO2 was mostly dependent on the concentration of Ca2+ in media, and their size strongly increased to micrometer scale over 1 week. However, AgNP-Cit and TiO2 were stabilized to particle size around 500 nm in the presence of NOM, surfactants and carbonate over 1 week. AgNP-PVP maintained their original size in all media except in the presence of Mg2+ ions which led to significant agglomeration. Behavior of these engineered nanoparticles was similar in a natural freshwater medium.

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1 + QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth. Kinetically defined metal fractions mimic mobility aspects of heavy metals.

Since humans spend more than 90% of their time in indoor environments, indoor exposure can be an important non-dietary pathway to hazardous organic contaminants. It is thus important to characterize the chemical composition of indoor dust to assess the total contaminant exposure and estimate human health risks. The aim of this investigation was to perform a comprehensive chemical characterization of indoor dust. First, the robustness of an adopted extraction method using ultrasonication was evaluated for 85 target compounds. Thereafter, a workflow combining target analysis, suspect screening analysis (SSA) and nontarget analysis (NTA) was applied to dust samples from different indoor environments. Chemical analysis was performed using both gas chromatography and liquid chromatography coupled with high resolution mass spectrometry. Although suppressing matrix effects were prominent, target analysis enabled the quantification of organophosphate/brominated flame retardants (OPFRs/BFRs), liquid crystal monomers (LCMs), toluene diisocyanate, bisphenols, pesticides and tributyl citrate. The SSA confirmed the presence of OPFRs but also enabled the detection of polyethylene glycols (PEGs) and phthalates/parabens. The combination of hierarchical cluster analysis and scaled mass defect plots in the NTA workflow confirmed the presence of the above mentioned compounds, as well as detect other contaminants such as tetrabromobisphenol A, triclocarban, diclofenac and 3,5,6-trichloro-2-pyridinol, which were further confirmed using pure standards.

Remediation of heavy metal contaminated soils remains a global challenge. Here, low-molecular-weight organic acids were used to extract Cu and Zn from polluted soils, and the extracted heavy metals were subsequently adsorbed by activated carbon electrodes. The electrochemical adsorption mechanism as well as the influence of pH, organic acid type and voltage were investigated, and the soil remediation effect was further evaluated by the cultivation of rape. After extraction by citrate at initial pH 8.3 and electrochemical adsorption at 0.9 V for 7 d, the concentrations of total and bioavailable Cu in soils decreased from 1090 to 281 to 391 and 52 mg kg⁻¹, and those of Zn decreased from 262 to 39 to 208 and 30 mg kg⁻¹, respectively. Cu and Zn ions were mainly electrochemically adsorbed on the carbon cathode and anode, respectively, resulting in decreases of their concentrations to below 1 mg L⁻¹ in the leachate. The presence of organic acids improved the remediation performance in the order of citrate > oxalate > acetate. The decrease in the initial pH of citrate solution enhanced the removal rate of Zn, while seemed to have no effect on that of Cu. The removal capacity for heavy metals decreased with decreasing cell voltage from 0.9 to 0.3 V. In the rape cultivation experiment, the Cu and Zn contents in shoot and root were decreased by more than 50%, validating the soil remediation effect. The present work proposes a facile method for heavy metal removal from contaminated soils.

We used replicated paddy microcosm systems to estimate the tropic transfer of citrate-coated silver nanoparticles (AgNP citrate), polyvinylpyrrolidone (PVP)-coated AgNP (AgNP PVP), and silver ions (AgNO₃) for 14 days under two exposure regimes (a single high-dose exposure; 60 μg L⁻¹ and a sequential low-dose exposure at 1 h, 4 days and 9 days; 20 μg L⁻¹ × 3 = 60 μg L⁻¹). Most Ag ions from AgNO₃ had dispersed in the water and precipitated partly on the sediment, whereas the two Ag NPs rapidly coagulated and precipitated on the sediment. The bioconcentration factors (BCFs) of Ag from AgNPs and AgNO₃ in Chinese muddy loaches and biofilms were higher than those of river snails in both exposure conditions. These BCFs were more prominent for 14 days exposure (7.30 for Chinese muddy loach; 4.48 for biofilm) in the low-dose group than in the single high-dose group. Their retention of AgNPs and Ag ions differed between the two exposure conditions, and uptake and elimination kinetics of Ag significantly differed between AgNP citrate and AgNP PVP in the sequential low-dose exposure. Stable isotopes analyses indicated that the trophic levels between Chinese muddy loaches and biofilms and between river snails and biofilms were 2.37 and 2.27, respectively. The biomagnification factors (BMFs) of AgNPs and AgNO₃ between Chinese muddy loaches and biofilms were significantly higher than those between river snails and biofilms under both exposure settings. The BMFs of AgNP citrate and AgNO₃ between Chinese muddy loaches and biofilms were greater than those of AgNP PVP for 14 days in the single high-dose group, whereas the BMFs of AgNP PVP were greater than those of AgNP citrate and AgNO₃ in the sequential low-dose group. These microcosm data suggest that AgNPs have the potential to impact on ecological receptors and food chains.

The quality of indoor environment has received considerable attention owing to the declining outdoor human activities and the associated public health issues. The prolonged exposure of children in childcare facilities or the occupational exposure of adults to indoor environmental triggers can be a culprit of the pathophysiology of several commonly observed idiopathic syndromes. In this study, concentrations of potentially toxic plasticizers (phthalates as well as non-phthalates) were investigated in 28 dust samples collected from three different indoor environments across the USA. The mean concentrations of non-phthalate plasticizers [acetyl tri-n-butyl citrate (ATBC), di-(2-ethylhexyl) adipate (DEHA), and di-isobutyl adipate (DIBA)] were found at 0.51–880 μg/g for the first time in indoor dust samples from childcare facilities, homes, and salons across the USA. The observed concentrations of these replacement non-phthalate plasticizer were as high as di-(2-ethylhexyl) phthalate, the most frequently detected phthalate plasticizer at highest concentration worldwide, in most of indoor dust samples. The estimated daily intakes of total phthalates (n = 7) by children and toddlers through indoor dust in childcare facilities were 1.6 times higher than the non-phthalate plasticizers (n = 3), whereas estimated daily intake of total non-phthalates for all age groups at homes were 1.9 times higher than the phthalate plasticizers. This study reveals, for the first time, a more elevated (∼3 folds) occupational intake of phthalate and non-phthalate plasticizers through the indoor dust at salons (214 and 285 ng/kg‐bw/day, respectively) than at homes in the USA.