Urban horticulture is of growing importance in developing and developed countries around the world; however, contamination of urban horticultural products can exceed the precautionary values, posing significant human health risks due to dietary exposure to high levels of the pollutants. In this study, samples of rhizosphere soil and corresponding vegetables have been collected from an urban garden in Ilorin, Nigeria, to assess the contamination level of trace metals as well as the health risk, associated with dietary intake of contaminated vegetables, in adult sub-population. The range of Cu, Pb, and Cd in garden topsoil was 14.0-52.50, 33.00-121.40, and 1.00-4.50 mg/kg, respectively. The metals sources were both anthropogenic and lithogenous, though the long-term accumulation of trace metals in the soil led to significant soil-plant transfer as evident in the levels of metals in some of the vegetables. The estimated daily intakes (EDI) of Cu and Pb through vegetable consumption were far below the recommended tolerable daily intakes (TDI) and the hazard quotient (HQ) values were within the safe zone for the adult population. In contrast, the EDI of Cd for the vegetables was several folds greater than the TDI, thus greatly contributing to a high hazard index (HI>1.0), observed in all vegetables. Therefore, risk assessment of trace metal ingestion through consumption of the vegetables in the adult sub-population depicts serious health hazards with Cd, mainly contributing to vegetable contamination in the studied area.

Biochar is a promising material used in soil amendment and carbon nanotubes may enter soil due to its increasing application. These carbonaceous materials may change the bioavailability of pollutants in soil. In this concern, 0.5% w/w multi-walled carbon nanotubes (MWCNTs) and 3 corn-straw biochars acquired at different pyrolyzing temperatures were used in soil amendment and their influences on the bioavailability of hexabromocyclododecanes (HBCDs), a brominated flame retardant, to 2 ecologically different earthworm species were studied. The amendment of 4 carbonaceous materials all reduced the bioaccumulation of HBCDs in earthworms by 18.2%–67.3%, which varied depending on the type of carbonaceous materials and the pyrolyzing temperature of biochars. The reduction in HBCDs uptake by Eisenia fetida (an epigeic species) was greater than by Metaphire guillelmi (an anecic species). The 2 earthworm species both showed bioaccumulative selectivity on certain HBCD diastereoisomer and enantiomer in the amended soils, which was similar to that in the control soil. Moreover, Tenax-assisted HBCDs desorption test was carried out for the simulation of their bioavailability. The rapid desorption fraction (Frap), total desorption (15 d), and 24 h desorption all correlated well with the uptake of HBCDs in the earthworms, suggesting that the 24 h-desorption, due to its easy availability, can be a good proxy to predict the bioavailability of HBCDs to earthworms in soil.

Vanadium(V) is present in trace amounts in most plants and widely distributed in soils. However, the environmental toxicity of V compound in soils is controversial. A greenhouse study with soybean from germination to bean production under exposure to pentavalent V [V(V)] was conducted to elucidate the interaction of plants and V fractions in soils and to evaluate the toxicity of V at different plant growth stages. Soybean growth has no effect on non-specific-bond and specific-bond fractions of V in soils, but V fractionation occurred in more extraction-resistant phases at high V concentrations. High concentrations of V(V) postponed the germination and growth of the soybeans. Bean production was less than half of that of the control at 500 mg kg⁻¹ spiked V(V). For the 0 mg kg⁻¹ spiked V(V) treated plants, the root was not the main location where V was retained. Vanadium in the soils at ≤ 250 mg kg⁻¹ did not significantly affect the V concentration in the shoot and leaf of soybeans. With the increase in V concentration in soil, V concentrations in roots increased, whereas those in beans and pods decreased. From vegetative growth to the reproductive growth, the soybeans adsorbed more V and accumulated more V in the roots, with <20% transported to the aboveground parts. Hence, the analysis of V concentration in vegetative tissues or beans may not be a useful indicator for V pollution in soil. Meanwhile, the ratio of V concentration in cell wall to the total V concentration in the root increased with the increase in V(V) concentration in soils. Our results revealed that high concentrations of V inhibited soybean germination and biomass production. However, plants may produce self-defense systems to endure V toxicity.

Recent work identified the need for site-specific Pb bioaccessibility evaluation and scaled contaminant modeling. Pb heterogeneity has made bioaccessibility characterization difficult, and complicated distribution models. Using field testing, bioaccessibility measurement, Integrated Exposure Uptake and Biokinetic (IEUBK) modeling, and geospatial techniques, we propose a framework for conducting applied risk-based, multiscale assessment. This framework was tested and implemented in Burlington, VT, an area of old housing stock and high Pb burden (up to 15 000 mg kg−1) derived primarily from paint. After analyzing local soil samples for total and bioaccessible Pb, it was determined that bioaccessible and total Pb were well correlated in this area, through which an average bioaccessibility parameter was derived approximating Pb bioaccessibility for this soil type and Pb impact. This parameter was used with the IEUBK to recommend the local limit for residential soil Pb be reduced from 400 to 360 mg kg−1, taking into consideration the lowering of the blood lead level threshold for Pb poisoning from 10 to 5 μg dL−1 by the Centers for Disease Control (CDC). Geospatial investigation incorporated samples collected during this investigation and samples from a high school summer science academy, and relied on three techniques, used at different scales: kriging of total and background Pb alone, kriging of total and background Pb with housing age as a well-sampled, well-correlated secondary variable (cokriging), and inverse distance weighting of total and bioaccessible Pb. Modeling at different scales allowed for characterization of Pb impact at single sites as well as citywide. Model maps show positive correlation between areas of older housing and areas of high Pb burden, as well as potential at different scales for reducing the effects of Pb heterogeneity.

Metals are ubiquitous and normally co-occur as mixtures in soil, but there remains much to do regarding the development of appropriate models which incorporate mixture interactions and bioavailability to estimate their phytotoxicity and phytoaccumulation. Here, we developed a probability-based electrostatic toxicity model (ETM) and a Langmuir-type electrostatic uptake model (EUM) to predict and normalize toxicity and uptake of zinc-copper mixtures in Hordeum vulgare L. in different soils. For model development, the electrical potential (ψ0) and metal ion activities ({M2+}0) at the cell-membrane surface was computed based on plant physiological properties and soil solution chemistry. Single metal toxicity correlated more closely to their corresponding {M2+}0 than to ion activities in soil solution or total soil metal concentrations. The ETM explained up to 89% of the variance in mixture toxicity across different soils. Incorporation of ψ0 into the EUM improved the model's ability for predicting metal uptake. Besides, cell-surface H+ appeared to significantly inhibit copper uptake via competition or other mechanisms, beyond its effect upon ψ0. Our results for the first time demonstrate that electrostatic theory can be used to predict and reconcile mixture toxicity and uptake data in different soils, indicating the potential of electrostatic-based models in risk assessment of multimetal-contaminated soils.

Widespread use of insecticides for the control of urban pests such as ants, termites, and spiders has resulted in contamination and toxicity in urban aquatic ecosystems in different regions of the world. Passive samplers are a convenient and integrative tool for in situ monitoring of trace contaminants in surface water. However, the performance of a passive sampler depends closely on its affinity for the target analytes, making passive samplers highly specific to the types of contaminants being monitored. The goal of this study was to develop a passive sampler compatible with a wide range of insecticides, including the strongly hydrophobic pyrethroids and the weakly hydrophobic fipronil and organophosphates. Of six candidate polymeric thin films, polyurethane film (PU) was identified to be the best at enriching the test compounds. The inclusion of stable isotope labeled analogs as performance reference compounds (PRCs) further allowed the use of PU film for pyrethroids under non-equilibrium conditions. The PU sampler was tested in a large aquarium with circulatory water flow, and also deployed at multiple sites in surface streams in southern California. The concentrations of pesticides derived from the PU sampler ranged from 0.5 to 18.5 ng/L, which were generally lower than the total chemical concentration measured by grab samples, suggesting that suspended particles and dissolved organic matter in water rendered them less available. The influence of suspended particles and dissolved organic matter on bioavailability was more pronounced for pyrethroids than for fipronils. The results show that the developed PU film sampler, when coupled with PRCs, may be used for rapid and sensitive in-situ monitoring of a wide range of insecticides in surface water.

Use of titanium dioxide nanoparticles (TiO2 NPs) has become a part of our daily life and the high environmental concentrations predicted to accumulate in aquatic ecosystems are cause for concern. Although TiO2 has only limited reactivity, at the nanoscale level its physico-chemical properties and toxicity are different compared with bulk material. Phytoplankton is a key trophic level in fresh and marine ecosystems, and the toxicity provoked by these nanoparticles can affect the structure and functioning of ecosystems. Two microalgae species, one freshwater (Chlamydomonas reinhardtii) and the other marine (Phaeodactylum tricornutum), have been selected for testing the toxicity of TiO2 in NP and conventional bulk form and, given its photo-catalytic properties, the effect of UV-A was also checked. Growth inhibition, quantum yield reduction, increase of intracellular ROS production, membrane cell damage and production of exo-polymeric substances (EPS) were selected as variables to measure.TiO2 NPs and bulk TiO2 show a relationship between the size of agglomerates and time in freshwater and saltwater, but not in ultrapure water. Under two treatments, UV-A (6 h per day) and no UV-A exposure, NPs triggered stronger cytotoxic responses than bulk material. TiO2 NPs were also associated with greater production of reactive oxygen species and damage to membrane. However, microalgae exposed to TiO2 NPs and bulk TiO2 under UV-A were found to be more sensitive than in the visible light condition. The marine species (P. tricornutum) was more sensitive than the freshwater species, and higher Ti internalization was measured. Exopolymeric substances (EPS) were released from microalgae in the culture media, in the presence of TiO2 in both forms. This may be a possible defense mechanism by these cells, which would enhance processes of homoagglomeration and settling, and thus reduce bioavailability.

AgCl and Ag2S prevalently exist in the environment as minerals and/or the chlorination and sulfidation products of ionic silver and elemental silver nanoparticles (AgNPs). In this work, we investigated the chemical transformation of AgCl and Ag2S under simulated sunlight (in water) and incineration (in sludge and simulated municipal solid waste, SMSW). In the presence of natural organic matter, AgCl in river water was observed to be transformed into AgNPs under simulated sunlight, while photo-reduction of Ag2S could not take place under the same experimental conditions. During the course of incineration, pure Ag2S was transformed into elemental silver while AgCl remained stable; however, both Ag2S in sludge and AgCl in SMSW can be transformed to elemental silver under incineration, evident by the results of X-ray absorption spectroscopy and scanning electron microscopy measurements. Incineration temperature played an important role in the transformation of Ag2S and AgCl into elemental silver. These results suggest that chemical transformations of Ag2S and AgCl into elemental silver could be a possible source of naturally occurring or unintentionally produced AgNPs, affecting the fate, transport, bioavailability and toxicity of silver. Therefore, it is necessary to include the contributions of this transformation process when assessing the risk of ionic silver/AgNPs and the utilization and management of incineration residues.

The effects of two Pteris vittata L. accessions and a polycyclic aromatic hydrocarbon (PAH)-degrading bacterium (Alcaligenes sp.) on arsenic (As) uptake and phenanthrene dissipation were studied. The Alcaligenes sp. survived in the rhizosphere and improved soil As bioavailability with co-exposure. However, bacterial inoculation altered Pteris vittata L. stress tolerance, and substantially affected the As distribution in the rhizosphere of the two P. vittata accessions. Bacterial inoculation was beneficial to protect the Guangxi accession against the toxic effects, and significantly increased plant As and phenanthrene removal ratios by 27.8% and 2.89%, respectively. In contrast, As removal was reduced by 29.8% in the Hunan accession, when compared with corresponding non-inoculated treatments. We conclude that plant genotype selection is critically important for successful microorganism-assisted phytoremediation of soil co-contaminated with As and PAHs, and appropriate genotype selection may enhance remediation efficiency.

This study sought to evaluate the toxicological effects of graphene oxide (GO) through tests with Danio rerio (zebrafish) embryos, considering the influence of the base washing treatment and the interaction with natural organic matter (i.e., humic acid, HA). A commercial sample of GO was refluxed with NaOH to remove oxidation debris (OD) byproducts, which resulted in a base washed GO sample (bw-GO). This process decreased the total oxygenated groups in bw-GO and its stability in water compared to GO. When tested in the presence of HA, both GO and bw-GO stabilities were enhanced in water. Although the embryo exposure showed no acute toxicity or malformation, the larvae exposed to GO showed a reduction in their overall length and acetylcholinesterase activity. In the presence of HA, GO also inhibited acid phosphatase activity. Our findings indicate a mitigation of material toxicity after OD removal. The difference in the biological effects may be related to the materials’ bioavailability and biophysicochemical interactions. This study reports for the first time the critical influence of OD on the GO material biological reactivity and HA interaction, providing new data for nanomaterial environmental risk assessment and sustainable nanotechnology.