In this study, the phototoxicity of cadmium sulfide (CdS), molybdenum disulfide (MoS2), and tungsten disulfide (WS2) nanoparticles (NPs) toward Escherichia coli (E. coli) under UV irradiation (365 nm) was investigated. At the same mass concentration of NPs, the toxicity of three NPs decreased in the order of CdS > MoS2 > WS2. For example, the death rates of E. coli exposed to 50 mg/L CdS, MoS2, and WS2 were 96.7%, 38.5%, and 31.2%, respectively. Transmission electron microscope and laser scanning confocal microscope images of E. coli exposed to three NPs showed the damage of cell walls and release of intracellular components. The CdS-treated cell wall was more extensively damaged than those of MoS2-treated and WS2-treated bacteria. WS2 and MoS2 generated superoxide radical (O2⁻), singlet oxygen (¹O2), and hydroxyl radical under UV irradiation, CdS produced only O2⁻ and ¹O2. CdS and WS2 released ions under UV irradiation, while MoS2 did not. Reactive oxygen species (ROS) generation and toxic ion release jointly resulted in the antibacterial activities of CdS and WS2. ROS generation was the dominant toxic mechanism of MoS2 toward the bacteria. This study highlighted the importance of considering the hazardous effect of sulfide NPs after their release into natural waters under light irradiation condition.

Microplastic pollution of marine environment is receiving increased publicity over the last few years. The present survey is, according to our knowledge, the survey with the largest sample size analyzed, to date. In total, 1337 specimens of fish were examined for the presence of plastic microlitter representing 28 species and 14 families. In addition, samples of seawater and sediment were also analysed for the quantification of microplastic in the same region. Samples of water/sediment were collected from 18 locations along the Mediterranean coast of Turkey. 94% of all collected plastic microlitter from the sea was in the size range between 0.1 and 2.5 mm, while the occurrence of other sizes was rare. The quantity of microplastic particles in surface water samples ranged from 16 339 to 520 213 per km2. Fish were collected from 10 locations from which 8 were either shared with or situated in the proximity of water/sediment sampling locations. A total of 1822 microplastic particles were extracted from stomach and intestines of fish. Majority of ingested particles were represented by fibers (70%) and hard plastic (20.8%), while the share of other groups: nylon (2.7%), rubber (0.8%) and miscellaneous plastic (5.5%) were low. The blue color of plastic was the most dominant color. 34% of all examined fish had microplastic in the stomach. On average, fish which had microplastic contained 1.80 particle per stomach. 41% of all fish had microplastic in the intestines with an average of 1.81 particle per fish. 771 specimens contained microplastic in either stomach and/or intestines representing 58% of the total sample with an average of 2.36 particles per fish. Microplastic was found in all species/families that had sample size of at least 2 individuals. The number of particles present in either stomach or intestines ranged between 1 and 35. Ingested microparticles had an average diameter ±SD of 656 ± 803 μm, however particles as small as 9 μm were detected. The trophic level of fish species had no influence whatsoever on the amount of ingested microplastic. Pelagic fish ingested more microplastic than demersal species. In general, fish that ingested higher number of microplastic particles originated from the sites that also had a higher particle count in the seawater and sediment.

Land application of biochar has been increasingly recommended as a powerful strategy for carbon sequestration and soil remediation. However, the biochar particles, especially those in the nanoscale range, may migrate or carry the inherent contaminants along the soil profile, posing a potential risk to the groundwater. This study investigated the transport and retention of wood chip-derived biochar nanoparticles (NPs) in water-saturated columns packed with a paddy soil. The environmentally-relevant soil solution chemistry including ionic strength (0.10–50 mM), electrolyte type (NaCl and CaCl2), and natural organic matter (0–10 mg L−1 humic acid) were tested to elucidate their effects on the biochar NPs transport. Higher mobility of biochar NPs was observed in the soil at lower ionic strengths, with CaCl2 electrolyte being more effective than NaCl in decreasing biochar NPs transport. The retained biochar NPs in NaCl was re-entrained (∼57.7%) upon lowering transient pore-water ionic strength, indicating that biochar NPs were reversibly retained in the secondary minimum. In contrast, negligible re-entrainment of biochar NPs occurred in CaCl2 due to the primary minimum and/or particle aggregation. Humic acid increased the mobility of biochar NPs, likely due to enhanced electrosteric repulsive interactions. The transport behaviors of biochar NPs can be well interpreted by a two-site kinetic retention model that assumes reversible retention for one site, and irreversible retention for the other site. Our findings indicated that the transport of wood chip biochar NPs is significant in the paddy soil, highlighting the importance of understanding the mobility of biochar NPs in natural soils for accurately assessing their environmental impacts.

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.

Little is known about pollution in urban snow and how aerosol and gaseous air pollutants interact with the urban snowpack. Here we investigate interactions of exhaust pollution with snow at low ambient temperature using fresh snow in a temperature-controlled chamber. A gasoline-powered engine from a modern light duty vehicle generated the exhaust and was operated in homogeneous and stratified engine regimes. We determined that, within a timescale of 30 min, snow takes up from the exhaust a large mass of organic pollutants and aerosol particles, which were observed by electron microscopy, mass spectrometry and aerosol sizers. Specifically, the concentration of total organic carbon in the exposed snow increased from 0.948 ± 0.009 to 1.828 ± 0.001 mg/L (homogeneous engine regime) and from 0.275 ± 0.005 to 0.514 ± 0.008 mg/L (stratified engine regime). The concentrations of benzene, toluene and 13 out of 16 measured polycyclic aromatic hydrocarbons (PAHs), particularly naphthalene, benz[a]anthracene, chrysene and benzo[a]pyrene in snow increased upon exposure from near the detection limit to 0.529 ± 0.058, 1.840 ± 0.200, 0.176 ± 0.020, 0.020 ± 0.005, 0.025 ± 0.005 and 0.028 ± 0.005 ng/kg, respectively, for the homogeneous regime. After contact with snow, 50–400 nm particles were present with higher relative abundance compared to the smaller nanoparticles (<50 nm), for the homogeneous regime. The lowering of temperature from 25 ± 1 °C to (−8) – (−10) ± 1 °C decreased the median mode diameter of the exhaust aerosol particles from 69 nm to 57 nm (p < 0.1) and addition of snow to 51 nm (p < 0.1) for the stratified regime, but increased it from 20 nm to 27 nm (p < 0.1) for the homogeneous regime. Future studies should focus on cycling of exhaust-derived pollutants between the atmosphere and cryosphere. The role of the effects we discovered should be evaluated as part of assessment of pollutant loads and exposures in regions with a defined winter season.

Batch and saturated soil column experiments were conducted to investigate sorption and mobility of two ¹⁴C-labeled contaminants, the hydrophobic chlordecone (CLD) and the sulfadiazine (SDZ), in the absence or presence of functionalized multi-walled carbon nanotubes (MWCNTs). The transport behaviors of CLD, SDZ, and MWCNTs were studied at environmentally relevant concentrations (0.1–10 mg L⁻¹) and they were applied in the column studies at different times. The breakthrough curves and retention profiles were simulated using a numerical model that accounted for the advective-dispersive transport of all compounds, attachment/detachment of MWCNTs, equilibrium and kinetic sorption of contaminants, and co-transport of contaminants with MWCNTs. The experimental results indicated that the presence of mobile MWCNTs facilitated remobilization of previously deposited CLD and its co-transport into deeper soil layers, while retained MWCNTs enhanced SDZ deposition in the topsoil layers due to the increased adsorption capacity of the soil. The modeling results then demonstrated that the mobility of engineered nanoparticles (ENPs) in the environment and the high affinity and entrapment of contaminants to ENPs were the main reasons for ENP-facilitated contaminant transport. On the other hand, immobile MWCNTs had a less significant impact on the contaminant transport, even though they were still able to enhance the adsorption capacity of the soil.

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.

Widely used titanium dioxide (TiO2) nanoparticles are likely to accumulate ultimately in sediments and potentially pose a risk to water ecosystems. This study evaluated the effect of TiO2 nanoparticles on the photodissolution of particulate organic matter (POM) through fluorescence spectroscopy. Excitation-emission matrices and parallel factor analyses revealed that the fluorescent characteristics of produced dissolved organic matter (DOM) during photodissolution of suspended sediment and synthetic particulate organic matter (SPOM) were primarily humic-like. SPOM particles appeared to simulate well the photodissolution of suspended sediment. Quasi-complete increases in fluorescence intensity and chromophoric DOM (CDOM) abundance were reached after 90, 60, and 50 min irradiation for TiO2 concentrations of 0, 2, and 5 mg L−1, respectively. The faster increment of fluorescence intensity and CDOM abundance indicated the photocatalytic dissolution of SPOM, as opposite charges between TiO2 and SPOM at pH = 4 favored the adsorption of TiO2 onto SPOM. For sediments, the CDOM abundance and fluorescence intensity decreased with increasing TiO2 concentration, resulting from the photocatalytic degradation of photoproduced DOM from sediments. These results demonstrated that pH plays an important role in the photocatalytic dissolution of POM by TiO2. Therefore, appropriate pH controls should be implemented when TiO2 are used to treat sediments contaminated with organic pollutants. Finally, with increasing use of TiO2, its accumulation in sediments may affect the fate of carbon, nutrients, and heavy metals in shallow-water ecosystems.

This work tested a new remediation technology for in-situ degradation of estrogens by delivering a new class of stabilized manganese oxide (MnO2) nanoparticles in contaminated soils. The nanoparticles were prepared using a food-grade carboxymethyl cellulose (CMC) as a stabilizer, which was able to facilitate particle delivery into soil. The effectiveness of the technology was tested using 17β-estradiol (E2) as a model estrogen and three sandy loams (SL1, SL2, and SL3) as model soils. Column transport tests showed that the nanoparticles can be delivered in the three soils, though retention of the nanoparticles varied. The nanoparticle retention is strongly dependent on the injection pore velocity. The treatment effectiveness is highly dependent upon the mass transfer rates of both the nanoparticles and contaminants. When the E2-laden soils were treated with 22–130 pore volumes of a 0.174 g/L MnO(2) nanoparticle suspension, up to 88% of water leachable E2 was degraded. The nanoparticles were more effective for soils that offer moderate desorption rates of E2. Decreasing injection velocity or increasing MnO(2) concentration facilitate E2 degradation. The nanoparticles-based technology appears promising for in-situ oxidation of endocrine disruptors in groundwater.

Rapidly growing global population adds significant strains on the fresh water resources. Consequently, saline water is increasingly tapped for crop irrigation. Meanwhile, rapid advancement of nanotechnology is introducing more and more engineered nanoparticles into the environment and in agricultural soils. While some negative effects of ENPs on plant health at very high concentrations have been reported, more beneficial effects of ENPs at relatively low concentrations are increasingly noticed, opening doors for potential applications of nanotechnology in agriculture. In particular, we found that cerium oxide nanoparticles (CeO2NPs) improved plant photosynthesis in salt stressed plants. Due to the close connections between salt stress tolerance and the root anatomical structures, we postulated that CeO2NPs could modify plant root anatomy and improve plant salt stress tolerance. This study aimed at testing the hypothesis with Brassica napus in the presence of CeO2NPs (0, 500 mg kg−1 dry sand) and/or NaCl (0, 50 mM) in a growth chamber. Free hand sections of fresh roots were taken every seven days for three weeks and the suberin lamellae development was examined under a fluorescence microscope. The results confirmed the hypothesis that CeO2NPs modified the formation of the apoplastic barriers in Brassica roots. In salt stressed plants, CeO2NPs shortened the root apoplastic barriers which allowed more Na+ transport to shoots and less accumulation of Na+ in plant roots. The altered Na+ fluxes and transport led to better physiological performance of Brassica and may lead to new applications of nanotechnology in agriculture.