Search

The migration of particles smaller than 2 µm in soil pores is responsible for the preferential transfer of various contaminants and for soil textural differentiation in luvisols. Aggregation vs. dispersion mechanisms of clay particles are suspected to play a major role in this migration process. However, these mechanisms have mostly been studied with respect to pure and well-crystallized clay minerals rather than pedogenetic particles and have often been performed under physicochemical conditions, which are poorly representative of soil conditions. We studied the respective impacts of ph and Ca concentration on aggregation and dispersion behavior of clay particles in a luvisol under conditions encountered in the soil solution. Both static and dynamic approaches were followed in studying particle interactions and dynamics under transient phenomena. Based on these experiments, we have drawn a phase diagram for soil clays as a function of pH and Ca concentrations and have identified mechanisms associated with the formation of these different phases. We find that soil particle behavior in suspensions is similar to that recorded for model clays in that they are driven by both ph and Ca concentrations. These two parameters are interrelated and tend to favor aggregation at higher Ca concentrations and/or lower pH. These effects are reversible over the gravitational water time scale, with the exception of dilution-induced dispersion. In situating these physicochemical mechanisms within a literature review of rainwater and soil solution chemistries, we determine the expected role of these mechanisms on the transport of particles in gravitational soil water. [ABSTRACT FROM AUTHOR]

Abstract: The bacterial reverse mutation test, recommended by the Organization for Economic Co-operation and Development (OECD) to determine genotoxicity of chemical compounds, has been recently used by several authors to investigate nanoparticles. Surprisingly, test results have been negative, whereas in vitro mammalian cell tests often give positive genotoxic responses. In the present study, we used the fluctuation test procedure with the Salmonella typhimurium strains TA97a, TA98, TA100 and TA102 to determine the mutagenic potential of TiO2 nanoparticles (NP-TiO2) and showed that, when it is used conventionally, this test is not suitable for nanoparticle genotoxicity assessment. Indeed, the medium used during exposure prevents electrostatic interactions between bacterial cells and nanoparticles, leading to false-negative responses. We showed that a simple pre-exposure of bacteria to NP-TiO2 in a low ionic strength solution (NaCl 10mM) at a pH below the nanoparticle isoelectric points (pH 5.5) can strongly improve the accuracy of the test. Thus, based on these improvements, we have demonstrated the genotoxicity of the engineered NP-TiO2 tested and a NP-TiO2 byproduct from a sunscreen nanocomposite. It was also shown that strain TA102 is more sensitive than the other strains, suggesting an oxidative stress-mediated mechanism of genotoxicity. [Copyright &y& Elsevier]

The increasing production of nanomaterials will in turn increase the release of nanosized byproducts to the environment. The aim of this study was to evaluate the behaviour, uptake and ecotoxicity of TiO2 byproducts in the earthworm Eisenia fetida. Worms were exposed to suspensions containing 0.1, 1 and 10 mg/L of byproducts for 24 h. Size of TiO2 byproducts showed aggregation of particles up to 700 μm with laser diffraction. Only worms exposed at 10 mg/L showed bioaccumulation of titanium (ICP-AES), increasing expression of metallothionein and superoxide dismutase mRNA (Real-time PCR) and induction of apoptotic activity (Apostain and TUNEL). TiO2 byproducts did not induce cytotoxicity on cœlomocytes, but a significant decrease of phagocytosis was observed starting from 0.1 mg/L. In conclusion, bioaccumulation of byproducts and their production of reactive oxygen species could be responsible for the alteration of the antioxidant system in worms. [Copyright &y& Elsevier]

Mineral sunscreen nanocomposites, based on a nano-TiO2 core, coated with aluminium hydroxide and dimethicone films, were submitted to an artificial ageing process. The resulting Altered TiO2 Nanocomposites (ATN) were then tested in the liquid phase on the plant model Vicia faba, which was exposed 48 h to three nominal concentrations: 5, 25 and 50 mg ATN/L. Plant growth, photosystem II maximum quantum yield, genotoxicity (micronucleus test) and phytochelatins levels showed no change compared to controls. Oxidative stress biomarkers remained unchanged in shoots while in roots, glutathione reductase activity decreased at 50 mg ATN/L and ascorbate peroxidase activity decreased for 5 and 25 mg ATN/L. Nevertheless, despite the weak response of biological endpoints, ICP-MS measurements revealed high Ti and Al concentrations in roots, and X-ray fluorescence micro-spectroscopy revealed titanium internalization in superficial root tissues. Eventual long-term effects on plants may occur. [Copyright &y& Elsevier]

This work investigates the physical–chemical evolution during artificial aging in water of four commercialized sunscreens containing TiO2-based nanocomposites. Sunscreens were analyzed in terms of mineralogy and TiO2 concentration. The residues formed after aging were characterized in size, shape, chemistry and surface properties. The results showed that a significant fraction of nano-TiO2 residues was released from all sunscreens, despite their heterogeneous behaviors. A stable dispersion of submicronic aggregates of nanoparticles was generated, representing up to 38w/w% of the amount of sunscreen, and containing up to 30% of the total nano-TiO2 initially present in the creams. The stability of the dispersion was tested as a function of salt concentration, revealing that in seawater conditions, a major part of these nano-TiO2 residues will aggregate and sediment. These results were put in perspective with consumption and life cycle of sunscreens to estimate the amount of nano-TiO2 potentially released into AQUATIC environment. [Copyright &y& Elsevier]

Aging in water of a TiO2-based nanocomposite used in sunscreen cosmetics has been studied as a function of light and time. It consisted initially in a TiO2 core, coated with Al(OH)3 and polydimethylsiloxane (PDMS) layers. Size measurement, coating alteration, and surface charge were followed by laser diffraction, TEM/EDS, ICP-AES and electrophoretic mobility measurement. The nanocomposite rapidly underwent progressive dispersion in the aqueous phase, enabled by the dissolution of the PDMS layer. A stable suspension of colloidal byproducts from 50 to 700nm in size was formed. Their positively charged Al(OH)3 surface was evidenced with an isoelectric point around 7–8, controlling the dispersion stability. The critical coagulation concentrations measured with NaCl and CaCl2 was 2 × 10−2 and 8 × 10−3 M respectively. The presence of natural organic matter affected the colloidal stability according to the NOM/byproduct ratio. A 2 wt% ratio favored bridging flocculation, whereas a 20 wt% ratio induced sterical stabilization. [Copyright &y& Elsevier]

Located in a semi-arid to arid region, Morocco is confronting increasing water scarcity challenges. In the circular economy paradigm, the reuse of treated wastewater in agriculture is currently considered a possible solution to mitigate water shortage and pollution problems. In recent years, Morocco has made significative progress in urban wastewater treatment under the National Wastewater Program (PNA). However, rural sanitation has undergone significant delays. Therefore, an alternative technology for wastewater treatment and reuse in rural areas is investigated in this review, considering the region's economic, social, and regulatory characteristics. Constructed wetlands (CWs) are a simple, sustainable, and cost-effective technology that has yet to be fully explored in Morocco. CWs, indeed, appear to be suitable for the treatment and reuse of wastewater in remote rural areas if they can produce effluent that meets the standards of agricultural irrigation. In this review, 29 studies covering 16 countries and different types of wastewater were collected and studied to assess the treatment efficiency of different types of CWs under different design and operational parameters, as well as their potential application in agricultural reuse. The results demonstrated that the removal efficiency of conventional contamination such as organic matter and suspended solids is generally high. CWs also demonstrated a remarkable capacity to remove heavy metals and emerging contaminants such as pharmaceuticals, care products, etc. The removal of microbial contamination, on the other hand, is challenging, and does not satisfy the standards all the time. However, it can be improved using hybrid constructed wetlands or by adding polishing treatment. In addition, several studies reported that CWs managed to produce effluent that met the requirements of wastewater reuse in agriculture of different countries or organisations including Morocco. [ABSTRACT FROM AUTHOR]

Sunscreens are emulsions of water and oil that contain filters capable of protecting against the detrimental effects of ultraviolet radiation (UV). The widespread use of cosmetic products based on nanoparticulate UV filters has increased concerns regarding their safety and compatibility with both the environment and human health. In the present work, we evaluated the effects of titanium dioxide nanoparticle (TiO2 NP)-based UV filters with three different surface coatings on the development and immunity of the sea urchin, Paracentrotus lividus. A wide range of NP concentrations was analyzed, corresponding to different levels of dilution starting from the original cosmetic dispersion. Variations in surface coating, concentration, particle shape, and pre-dispersant medium (i.e., water or oil) influenced the embryonic development without producing a relevant developmental impairment. The most common embryonic abnormalities were related to the skeletal growth and the presence of a few cells, which were presumably involved in the particle uptake. Adult P. lividus immune cells exposed to silica-coated TiO2 NP-based filters showed a broad metabolic plasticity based on the biosynthesis of metabolites that mediate inflammation, phagocytosis, and antioxidant response. The results presented here highlight the biosafety of the TiO2 NP-based UV filters toward sea urchin, and the importance of developing safer-by-design sunscreens. [ABSTRACT FROM AUTHOR]

Engineered nanoparticle (ENP) fate models developed to date — aimed at predicting ENP concentration in the aqueous environment — have limited applicability because they employ constant environmental conditions along the modeled system or a highly specific environmental representation; both approaches do not show the effects of spatial and/or temporal variability. To address this conceptual gap, we developed a novel modeling strategy that: 1) incorporates spatial variability in environmental conditions in an existing ENP fate model; and 2) analyzes the effect of a wide range of randomly sampled environmental conditions (representing variations in water chemistry). This approach was employed to investigate the transport of nano-TiO 2 in the Lower Rhône River (France) under numerous sets of environmental conditions. The predicted spatial concentration profiles of nano-TiO 2 were then grouped according to their similarity by using cluster analysis. The analysis resulted in a small number of clusters representing groups of spatial concentration profiles. All clusters show nano-TiO 2 accumulation in the sediment layer, supporting results from previous studies. Analysis of the characteristic features of each cluster demonstrated a strong association between the water conditions in regions close to the ENP emission source and the cluster membership of the corresponding spatial concentration profiles. In particular, water compositions favoring heteroaggregation between the ENPs and suspended particulate matter resulted in clusters of low variability. These conditions are, therefore, reliable predictors of the eventual fate of the modeled ENPs. The conclusions from this study are also valid for ENP fate in other large river systems. Our results, therefore, shift the focus of future modeling and experimental research of ENP environmental fate to the water characteristic in regions near the expected ENP emission sources. Under conditions favoring heteroaggregation in these regions, the fate of the ENPs can be readily predicted. [ABSTRACT FROM AUTHOR]

Water flow and TiO 2 nanoparticle (NP) transfer in a fractured hard-rock aquifer were studied in a tracer test experiment at a pilot site in Brittany, France. Results from the Br tracer test show that the schist aquifer can be represented by a two-layer medium comprising i) fractures with low longitudinal dispersivity in which water and solute transport is relatively fast, and ii) a network of small fissures with high longitudinal dispersivity in which transport is slower. Although a large amount of NPs was retained within the aquifer, a significant TiO 2 concentration was measured in a well 15 m downstream of the NP injection well, clearly confirming the potential for TiO 2 NPs to be transported in groundwater. The Ti concentration profile in the downstream well was modelled using a two-layer medium approach. The delay used for the TiO 2 NPs simulation compared to the Br concentration profiles in the downstream well indicate that the aggregated TiO 2 NPs interacted with the rock. Unlike Br, NPs do not penetrate the entire pore network during transfer because of electrostatic interactions between NP aggregates and the rock and also to the aggregate size and the hydrodynamic conditions, especially where the porosity is very low; NPs with a weak negative charge can be attached onto the rock surface, and more particularly onto the positively charged iron oxyhydroxides coating the main pathways due to natural denitrification. Nevertheless, TiO 2 NPs are mobile and transfer within fracture and fissure media. Any modification of the aquifer's chemical conditions is likely to impact the groundwater pH and, the nitrate content and the denitrification process, and thus affect NP aggregation and attachment. [ABSTRACT FROM AUTHOR]

Interdisciplinarity is of first importance to evaluate the risks associated with nanotechnology. The reasons are that nanomaterials are very new materials that combine nano-sizes and new reactivities. The complexity comes from the very low concentrations of nanomaterials in the environmental medium, the transformations of the nanomaterials due to the reactivity of the surface, the transfer in the environmental media, particularly in the presence of liquid water (soils, sediments, surface water), which implies an association with natural colloids (organic or minerals) and blockage in some compartments. These properties govern the hazard that strongly depends on exposure and speciation. [ABSTRACT FROM AUTHOR]

Organic UV filters are emerging contaminants in personal care products such as sunscreens. The toxicity of numerous of these UV filter compounds has been demonstrated in several marine taxa. However, whilst the biological impact has already been largely demonstrated, the anthropogenic drivers leading to UV filter contamination still need to be identified. In this work, a survey was conducted on a site of the French Atlantic Coast (i) to describe beachgoers' behaviours (sunscreen use and beach frequentation), (ii) provide an estimation of the UV filters released at sea and (iii) highlight the effect of air temperature on these behaviours and on the release of UV filters. In parallel with these estimations of the UV filters released at sea, in situ chemical measurements were performed. By comparing the results of both approaches, this interdisciplinary work provides an insight of how the observations of beachgoers' behaviour modulations and attendance level fluctuations could be used to prevent UV filter contaminations and ultimately manage the ecotoxicological risk., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

There is increasing evidence that sunscreen, more specifically the organic ultra-violet filters (O-UVFs), are toxic for aquatic organisms. In the present study, we simulated an environmental sunscreen exposure on the teleost fish, Chelon auratus. The first objective was to assess their spatial avoidance of environmental concentrations of sunscreen products (i.e. a few μg.L -1 of O-UVFs). Our results showed that the fish did not avoid the contaminated area. Therefore, the second objective was to evaluate the toxicological impacts of such pollutants after 35 days exposure to concentrations of a few μg.L -1 of O-UVFs. At the individual level, O-UVFs increased the hepatosomatic index which could suggest pathological alterations of the liver or the initiation of the detoxification processes. At the cellular level, a significant increase of malondialdehyde was measured in the muscle of fish exposed to O-UVFs which suggests a failure of antioxidant defences and/or an excess of reactive oxygen species., 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. Published by Elsevier Ltd.)

Aquatic environments have been found to be contaminated with a variety of inorganic and organic UV filters. This includes novel nano-sized titanium dioxide (TiO 2 ) composite particles, which have been increasingly developed and incorporated into commercial sunscreens in recent years. So far, relatively little is known about the effects of this novel class of UV filters on aquatic life. Therefore, this study aimed to determine and compare the toxicity of three such nanoparticulate TiO 2 UV filters with different surface coatings, namely Eusolex® T-Avo (SiO 2 -coated), T-Lite™ SF (Al(OH) 3 /PDMS-coated), and Eusolex® T-S (Al 2 O 3 /stearic acid-coated) either alone, or in the presence of selected organic UV filters (octinoxate, avobenzone, octocrylene), toward fish using RTgill-W1 cell cultures as an in vitro experimental model. Besides standard exposure protocols, alternative approaches (i.e., exposure to water accommodated fractions (WAFs), hanging-drop exposure) were explored to account for nanoparticle (NP)-specific fate in the medium and obtain additional/complementary information on their toxicity in different conditions. The AlamarBlue, CFDA-AM and Neutral Red Retention (NR) assays were used to measure effects on different cellular endpoints. Transmission electron microscopy (TEM) was used to examine NP uptake. Our results showed that none of the TiO 2 NP UV filters were cytotoxic at the concentrations tested (0.1-10 µg/mL; 24 h) but there were differences in their uptake by the cells. Thus, only the hydrophilic T-AVO was detected inside cells, but the hydrophobic T-Lite SF and T-S were not. In addition, our results show that the presence of NPs (or the used dispersant) tended to decrease organic UV filter toxicity. The level of combination effect depended on both NP-type (surface chemistry) and concentration, suggesting that the reduced toxicity resulted from reduced availability of the organic UV filters due to their adsorption to the NP surface. Thus, mixtures of TiO 2 NP UV filters and organic UV filters may have a different toxicological profile compared to the single substances, but probably do not pose an increased hazard., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Tobias Lammel reports financial support was provided by Swedish Research Council Formas. Tobias Lammel reports financial support was provided by German Research Foundation. Tobias Lammel reports financial support was provided by Stiftelsen Wilhelm och Martina Lundgrens Vetenskapsfond. Tobias Lammel reports financial support was provided by Helge Axelsson Johnsons Stiftelse., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Nanoparticulate mineral UV filters, such as titanium dioxide (TiO 2 ) nanocomposites, are being increasingly used in sunscreens as an alternative to organic UV filters. However, there is still a lack of understanding regarding their fate and behavior in aquatic environments and potential environmental impacts after being released from a bather's skin during recreational activities. In this work, we assessed the release, fate, and transformation of two commercial nanocomposite TiO 2 UV filters, one hydrophobic and one hydrophilic, in ultrapure water and simulated fresh- and seawater. The hydrophobic TiO 2 nanocomposite, T-SA, was coated with a primary Al 2 O 3 photopassivation layer and a secondary stearic acid layer, while the hydrophilic TiO 2 nanocomposite, T-SiO 2 , was coated with a single SiO 2 photopassivation layer. The influence of the sunscreen formulation was examined by dispersing the TiO 2 nanocomposites in their typical continuous phase (i.e., oil for T-SA and water for T-SiO 2 ) before introduction into the aqueous system. After 48 h of aqueous aging and 48 h of settling, 88-99% of the hydrophobic T-SA remained floating on top of the water column in all aqueous systems. On the other hand, 100% of the hydrophilic T-SiO 2 settled out of the water column in the fresh- and seawaters. With respect to the photopassivation coatings, no loss of the T-SA Al 2 O 3 layer was detected after aqueous aging, but 99-100% dissolution of the SiO 2 layer on the T-SiO 2 nanocomposite was observed after 48 h in the fresh- and seawaters. This dissolution left behind T-SiO 2 by-products exhibiting a photocatalytic activity similar to that of bare rutile TiO 2 . Overall, the results demonstrated that the TiO 2 surface coating and sunscreen formulation type drive environmental behavior and fate and that loss of the passivation layer can result in potentially harmful, photoactive by-products. These insights will help guide regulations and assist manufacturers in developing more environmentally safe sunscreens., 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 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The increasingly frequent detection of resistant organic micropollutants in waters calls for better treatment of these molecules that are recognized to be dangerous for human health and the environment. As an alternative to conventional adsorbent material such as activated carbon, silica-clay nanocomposites were synthesized for the removal of pharmaceuticals in contaminated water. Their efficiency with respect to carbamazepine, ciprofloxacin, danofloxacin, doxycycline, and sulfamethoxazole was assessed in model water and real groundwater spiked with the five contaminants. Results showed that the efficacy of contaminant removal depends on the chemical properties of the micropollutants. Among the adsorbents tested, the nanocomposite made of 95% clay and 5% SiO 2 NPs was the most efficient and was easily recovered from solution after treatment compared with pure clay, for example. The composite is thus a good candidate in terms of operating costs and environmental sustainability for the removal of organic contaminants.

In order to assess the release of UV filters from the sunscreen used by beachgoers into seawater within the bathing zone, a field campaign was carried out during the summer of 2017 at three beaches in Marseille, along the French Mediterranean coast. A social survey analyzed beachgoer attendance, the quantities and types of suncare products used and the bathing frequencies, while the bathing water was analyzed spatially and temporally so as to quantify both mineral and organic UV filters directly released and recovered. During the peak recreational time at the three beaches, both mineral and organic UV filters were detected in higher concentrations in the bathing area than offshore. In general, higher concentrations were recovered in the water top surface layer than in the water column, giving respectively 100-900 and 20-50 μg/L for TiO 2 , 10-15 and 1-3 μg/L for ZnO, 40-420 and 30-150 ng/L for octocrylene, and 10-15 and 10-350 ng/L for avobenzone. More than 75% of the 471 interviewees reported bathing every time they go to the beach, with 68% using a suncare product 2.6 times on average. From these data we estimated that an average mass of 52 kg/day or 1.4 t/month of suncare products are possibly released into bathing water for a beach attended by 3000 people daily. The mass ratio of UV filters in such products typically ranges from 0.03 to 0.1, allowing us to propose theoretical maximum concentrations in the beach water. Our recovery of measured UV filter concentrations in seawater compared to the theoretical concentrations revealed two distinct scenarios for the mineral and organic filters. While up to 49% of the mineral filters used by beachgoers may be released into the seawater, the organic filters were minimally recovered in the environment, most likely due to internalization through the skin barrier or partial photodegradation., (Copyright © 2019 The Authors. Published by Elsevier B.V. All rights reserved.)

Short-term, aqueous aging of a commercial nanocomposite TiO 2 UV filter with a protective SiO 2 shell was examined in abiotic simulated fresh- and seawater. Under these conditions, the SiO 2 layer was quantitatively removed (∼88-98%) within 96 hours, as determined using inductively coupled plasma-atomic emission spectroscopy (ICP-AES). While these bulk ICP-AES analyses suggested almost identical SiO 2 shell degradation after aging in fresh- and seawater, surface sensitive 29 Si dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (SSNMR), with signal enhancements of 5-10× compared to standard SSNMR, was able to distinguish differences in the aged nanocomposites at the molecular level. DNP-SSNMR revealed that the attachment of the silica layer to the underlying TiO 2 core rested on substantial Si-O-Ti bond formation, bonds which were preserved after freshwater aging, yet barely present after aging in seawater. The removal of the protective SiO 2 layer is due to ionic strength accelerated dissolution, which could present significant consequences to aqueous environments when the photoactive TiO 2 core becomes exposed. This work demonstrates the importance of characterizing aged nanocomposites not only on the bulk scale, but also on the molecular level by employing surface sensitive techniques, such as DNP-NMR. Molecular level details on surface transformation and elemental speciation will be crucial for improving the environmental safety of nanocomposites., Competing Interests: The authors declare that there is no conflict of interest to report., (This journal is © The Royal Society of Chemistry.)

Predicting nanoparticle (NP) fate in the environment continues to remain a challenge, especially for natural surface water systems, where NPs can hetero-aggregate with natural organic and mineral suspended matter. Here we present the interactions and aggregation behavior of TiO 2 NPs with natural organic matter (NOM) in a natural lake water. NP fate in a synthetic water of the same pH and ionic composition was also tested in the presence and absence of NOM analogs to gain insight into the different stabilizing effects of each NOM type. Several complementary analytical techniques were utilized to assess lake NOM composition, including pyrolysis-gas chromatography-mass spectrometry, gel permeation chromatography, the polarity rapid-assessment method, and Nanoparticle Tracking Analysis. In the natural lake water, the TiO 2 NPs preferentially interacted with mostly anionic NOM of high and medium molecular weight (~1200-1450 and 400-520 Da). Specifically, strong interactions with proteins and polyhydroxy aromatics were observed. NP fate and stability were determined in both raw lake water containing mineral particulate matter and total NOM (NOM tot ) and filtered lake water containing only NOM <0.8 μm (NOM <0.8 ), with different aggregation profiles observed over time. Additionally, three times the number of TiO 2 NPs remained in suspension when only NOM <0.8 was present compared to the unfiltered water containing mineral particulate matter and NOM tot . These results demonstrate the contrasting NP fates in the aquatic environment according to the presence of NOM tot vs. NOM <0.8 and further suggest that the use of pure NOM analogs may not accurately represent NP interactions and fate in the natural system., (Copyright © 2018 Elsevier B.V. All rights reserved.)