Changes in the Aggregation Behaviour of Zinc Oxide Nanoparticles Influenced by Perfluorooctanoic Acid, Salts, and Humic Acid in Simulated Waters.

The increasing utilization of zinc oxide nanoparticles (ZnO-NPs) in many consumer products is of concern due to their eventual release into the natural environment and induction of potentially adverse impacts. The behaviour and environmental impacts of ZnO-NPs could be altered through their interactions with environmentally coexisting substances. This study investigated the changes in the behaviour of ZnO-NPs in the presence of coexisting organic pollutants (such as perfluorooctanoic acid [PFOA]), natural organic substances (i.e., humic acid [HA]), and electrolytes (i.e., NaCl and CaCl2) in simulated waters. The size, shape, purity, crystallinity, and surface charge of the ZnO-NPs in simulated water after different interaction intervals (such as 1 day, 1 week, 2 weeks, and 3 weeks) at a controlled pH of 7 were examined using various characterization techniques. The results indicated alterations in the size (such as 162.4 nm, 1 day interaction to >10 µm, 3 weeks interaction) and zeta potential (such as -47.2 mV, 1 day interaction to -0.2 mV, 3 weeks interaction) of the ZnO-NPs alone and when PFOA, electrolytes, and HA were present in the suspension. Different influences on the size and surface charge of the nanoparticles were observed for fixed concentrations (5 mM) of the different electrolytes. The presence of HA-dispersed ZnO-NPs affected the zeta potential. Such dispersal effects were also observed in the presence of both PFOA and salts due to their large aliphatic carbon content and complex structure. Cation bridging effects, hydrophobic interactions, hydrogen bonding, electrostatic interactions, and van der Waals forces could be potential interaction forces responsible for the adsorption of PFOA. The presence of organic pollutants (PFOA) and natural organic substances (HA) can transform the surface characteristics and fate of ZnO-NPs in natural and sea waters.

Acute Toxicity and Transgenerational Effects of Perfluorobutane Sulfonate on Caenorhabditis elegans.

Perfluorobutane sulfonate (PFBS), due to its increasing use as an alternative to perfluooctane sulfonate (PFOS), is widely detected in humans and the environment, necessitating the evaluation of its potential ecotoxicological risk. We assessed the toxicity and bioaccumulation potential of PFBS in Caenorhabditis elegans, using lethality, locomotion, reproduction, life span, growth, and chemotactic behavior as the effect parameters. In addition, a total of 6 generations of exposed parent animals were monitored for locomotion, brood, and life span behaviors. Life span and brood size were significantly reduced in parent nematodes (P0) following exposure to ≥0.1 mM PFBS, but these negative effects did not transfer to the progeny. Although there was no remarkable effect on reproduction and life span in parent worms exposed to ≤0.01 mM PFBS, multigenerational exposure at 0.0005 mM significantly affected the F4 and F5 progeny. Furthermore, 0.01 to 2.0 mM of PFBS substantially retarded the locomotion behavior of P0 worms. At higher concentrations such as 1.0 mM, this negative effect on locomotion was transferred to the next generation (F1) but later recovered from F2 progeny onward. Our findings demonstrate for the first time that chronic exposure to PFBS at higher concentrations can cause behavioral toxicity and could be transferred to the progeny. These findings have significant implications for the environmental risk assessment of PFBS. Environ Toxicol Chem 2021;40:1973-1982. © 2021 SETAC.

Sorption-desorption of dimethoate in urban soils and potential environmental impacts.

The environmental fate and impact of dimethoate application in the urban environment were assessed in nine selected soils. The pseudo-second-order kinetics model described the kinetics of dimethoate sorption very well in the urban soils exhibiting two distinct phases, an initial partitioning into clay surfaces and soil organic matter, and eventual diffusion into soil micropores. Dimethoate sorption in the urban soils followed the Freundlich model with an R2 value of 0.94-0.99, suggesting a multi-layered sorption on the heterogeneous surfaces. Sorption of dimethoate in the soils was influenced by clay, silt, organic matter, carboxyl and alkyl groups, and Al and Fe oxides. The undecomposed or incompletely decomposed organic matter present in the soils greatly reduced the sorption and enhanced desorption. The calculated lower values for Freundlich constant (KF) indicate the high mobility of dimethoate in the selected soils. Also, the values of groundwater ubiquity score (GUS), leachability index (LIX), hysteresis index (HI), and coefficient of distribution (Kd) for dimethoate in the soils clearly suggest that the insecticide is prone to leaching out significantly from the soil surface to groundwater. Moreover, the surface runoff from impervious places in the urban environment can be considered as a direct source of groundwater contamination, thereby affecting the quality of potable water besides posing a threat to non-target organisms of ecological importance and food safety. Thus, the present novel study suggests that the application of dimethoate in the urban environment having impervious surfaces must be judicious in order to minimize the potential human and ecological health risks.

Recent Progress in the Abatement of Hazardous Pollutants Using Photocatalytic TiO2-Based Building Materials.

Titanium dioxide (TiO2) has been extensively investigated in interdisciplinary research (such as catalysis, energy, environment, health, etc.) owing to its attractive physico-chemical properties, abundant nature, chemical/environmental stability, low-cost manufacturing, low toxicity, etc. Over time, TiO2-incorporated building/construction materials have been utilized for mitigating potential problems related to the environment and human health issues. However, there are challenges with regards to photocatalytic efficiency improvements, lab to industrial scaling up, and commercial product production. Several innovative approaches/strategies have been evolved towards TiO2 modification with the focus of improving its photocatalytic efficiency. Taking these aspects into consideration, research has focused on the utilization of many of these advanced TiO2 materials towards the development of construction materials such as concrete, mortar, pavements, paints, etc. This topical review focuses explicitly on capturing and highlighting research advancements in the last five years (mainly) (2014-2019) on the utilization of various modified TiO2 materials for the development of practical photocatalytic building materials (PBM). We briefly summarize the prospective applications of TiO2-based building materials (cement, mortar, concretes, paints, coating, etc.) with relevance to the removal of outdoor/indoor NOx and volatile organic compounds, self-cleaning of the surfaces, etc. As a concluding remark, we outline the challenges and make recommendations for the future outlook of further investigations and developments in this prosperous area.

Movement and Fate of 2,4-D in Urban Soils: A Potential Environmental Health Concern.

The fate and movement of 2,4-dichlorophenoxyacetic acid (2,4-D), in terms of sorption-desorption and leaching potential, were evaluated in urban soils following the batch experimental method. The sorption kinetics of 2,4-D in soils followed both "fast" and "slow" sorption processes that could be well described by a pseudo-second-order kinetics model, suggesting that 2,4-D was partitioned into soil organic matter and clay surfaces, and eventually diffused into soil micropores. The sorption isotherms were linear, following both Langmuir and Freundlich models. Partially decomposed or undecomposed organic matter present in urban soils decreased sorption and increased desorption of 2,4-D. Also, sorption of 2,4-D increased with an increase in the contents of clay and Al and Fe oxides, whereas sand and alkaline pH increased the desorption process. The lower calculated K d values suggest that 2,4-D is highly mobile in urban soils than in agricultural soils. The calculated values of groundwater ubiquity score, leachability index, and hysteresis index indicated that the herbicide is highly prone to leach out from surface soil to groundwater which might affect the quality of potable water. The present study clearly suggests that 2,4-D must be judiciously applied in the urban areas in order to minimize the potential health and environmental risks.

Controversies over human health and ecological impacts of glyphosate: Is it to be banned in modern agriculture?

Glyphosate, introduced by Monsanto Company under the commercial name Roundup in 1974, became the extensively used herbicide worldwide in the last few decades. Glyphosate has excellent properties of fast sorption in soil, biodegradation and less toxicity to nontarget organisms. However, glyphosate has been reported to increase the risk of cancer, endocrine-disruption, celiac disease, autism, effect on erythrocytes, leaky-gut syndrome, etc. The reclassification of glyphosate in 2015 as 'probably carcinogenic' under Group 2A by the International Agency for Research on Cancer has been broadly circulated by anti-chemical and environmental advocacy groups claiming for restricted use or ban of glyphosate. In contrast, some comprehensive epidemiological studies involving farmers with long-time exposure to glyphosate in USA and elsewhere coupled with available toxicological data showed no correlation with any kind of carcinogenic or genotoxic threat to humans. Moreover, several investigations confirmed that the surfactant, polyethoxylated tallow amine (POEA), contained in the formulations of glyphosate like Roundup, is responsible for the established adverse impacts on human and ecological health. Subsequent to the evolution of genetically modified glyphosate-resistant crops and the extensive use of glyphosate over the last 45 years, about 38 weed species developed resistance to this herbicide. Consequently, its use in the recent years has been either restricted or banned in 20 countries. This critical review on glyphosate provides an overview of its behaviour, fate, detrimental impacts on ecological and human health, and the development of resistance in weeds and pathogens. Thus, the ultimate objective is to help the authorities and agencies concerned in resolving the existing controversies and in providing the necessary regulations for safer use of the herbicide. In our opinion, glyphosate can be judiciously used in agriculture with the inclusion of safer surfactants in commercial formulations sine POEA, which is toxic by itself is likely to increase the toxicity of glyphosate.

Pesticides in the urban environment: A potential threat that knocks at the door.

Pesticides play a pivotal role in controlling pests and disease infestations not only in urban agriculture but also in non-agricultural settings. Several pesticides like herbicides, insecticides, fungicides, rodenticides, etc. are applied unintentionally at higher concentrations even in small urban areas such as lawns, gardens and impermeable surfaces. Consequent to their indiscriminate use, both extensively and intensively, in the urban areas, contamination of pesticides poses a serious threat to the environment, living organisms and food safety. Although the fate and ecological effects of pesticides and their residues have been thoroughly understood in agricultural soils, information available in the literature on the impact of these contaminants in the urban environment is very limited and fragmentary. In fact, the fate and behaviour of pesticide residues in the urban environment are distinct from those in other ecosystems since the soils in urban areas greatly vary in their physico-chemical properties. Development of sustainable and eco-friendly approaches for remediation of even urban soils contaminated with pesticides is therefore greatly warranted. Thus, the present critical review is the first single source that provides updated knowledge on the sources, nature and extent of pesticide pollution in the urban environment, and the ecological and human health effects of pesticides and their residues. The potential of nano-encapsulation of pesticides for their application in urban settings has also been discussed.

Simultaneous determination of 20 disperse dyes in foodstuffs by ultra high performance liquid chromatography-tandem mass spectrometry.

A reasonable, high sensitive and accurate analytical method for the determination of 20 allergenic disperse dyes in foodstuffs was developed and validated. The obtained results showed that an ultra high liquid performance chromatography system - equipped with tandem quadrupole mass spectrometry (UHPLC-MS/MS) proved to be ideal for the selected method enabling multidimensional processing of the samples. Under optimized conditions, validation results showed excellent linearity (5-1000 µg/L, r2 ≥ 0.997), limits of detection (LODs, 1.1-10.8 µg/kg), recoveries (60.2-110.3%) and precision (RSDs ≤ 12.6%) for the twenty disperse dyes under investigation. The developed method was successfully applied to the analysis of 20 disperse dyes in real foodstuffs demonstrating the validity and applicability of the current method for continuing monitoring of the selected dyes. The proposed UHPLC-MS/MS is thus proved to be a convenient, effective, sensitive and timesaving method for the isolation and determination of allergenic disperse dyes in edible packaging and other foodstuffs.

Sustainable production of biomass and biodiesel by acclimation of non-acidophilic microalgae to acidic conditions.

The overwhelming response towards algal biodiesel production has been well-recognized recently as a sustainable alternative to conventional fuels. Most microalgae cannot grow well at acidic pH. The present study, therefore, investigated whether non-acidophilic microalgae Desmodesmus sp. MAS1 and Heterochlorella sp. MAS3 can be acclimated to extreme-acidic pH for sustainable production of biomass and biodiesel. Growth analysis indicated that both the microalgal strains possessed a passive uptake of CO2 at pH 3.0 with biomass production of 0.25 g dry wt. L-1 in Desmodemus sp. and 0.45 g dry wt. L-1 in Heterochlorella sp.. Flow-cytometry analysis for reactive oxygen species, membrane permeability and neutral-lipids revealed the capabilities of both strains to adapt to the stress imposed by acidic pH. Lipid production was doubled in both the strains when grown at pH 3.0. In-situ transesterification of biomass resulted in 13-15% FAME yield in the selected microalgae, indicating their great potential in biofuel production.

Core-Shell Interface-Oriented Synthesis of Bowl-Structured Hollow Silica Nanospheres Using Self-Assembled ABC Triblock Copolymeric Micelles.

Hollow porous silica nanospheres (HSNs) are emerging classes of cutting-edge nanostructured materials. They have elicited much interest as carriers of active molecule delivery due to their amorphous chemical structure, nontoxic nature, and biocompatibility. Structural development with hierarchical morphology is mostly required to obtain the desired performance. In this context, large through-holes or pore openings on shells are desired so that the postsynthesis loading of active-molecule onto HSNs via a simple immersion method can be facilitated. This study reports the synthesis of HSNs with large through-holes or pore openings on shells, which are subsequently termed bowl-structured hollow porous silica nanospheres (BHSNs). The synthesis of BHSNs was mediated by the core-shell interfaces of the core-shell corona-structured micelles obtained from a commercially available ABC triblock copolymer (polystyrene- b-poly(2-vinylpyridine)- b-poly(ethylene oxide) (PS-P2VP-PEO)). In this synthesis process, polymer@SiO2 composite structure was formed because of the deposition of silica (SiO2) on the micelles' core. The P2VP block played a significant role in the hydrolysis and condensation of the silica precursor, i.e., tetraethylorthosilicate (TEOS) and then maintaining the shell's growth. The PS core of the micelles built the void spaces. Transmission electron microscopy (TEM) images revealed a spherical hollow structure with an average particle size of 41.87 ± 3.28 nm. The average diameter of void spaces was 21.71 ± 1.22 nm, and the shell thickness was 10.17 ± 1.68 nm. According to the TEM image analysis, the average large pore was determined to be 15.95 nm. Scanning electron microscopy (SEM) images further confirmed the presence of large single pores or openings in shells. These were formed as a result of the accumulated ethanol on the PS core acting to prevent the growth of silica.

Trace element dynamics of biosolids-derived microbeads.

This study focused on quantifying and characterising microbeads in biosolids (i.e., treated sewage sludge), and in examining interactions of microbeads with trace elements when biosolids are added to soil. Under laboratory conditions, batch experiments were conducted to investigate the adsorption of Cu onto pure and surface modified microbeads suspended in soil. The ecotoxicity of microbead-metal complexes to soil microbial activities was also investigated by monitoring basal respiration and dehydrogenase activity. Concentrations of the microbeads were 352, 146, 324, and 174 particles kg-1 biosolids for ≤50, 50-100, 100-250, 250-1000 µm size fractions, respectively. The Scanning Electron Microscope (SEM) images illustrated wrinkled and fractured surfaces due to degradation. The adsorption of dissolved organic matter onto microbeads was confirmed through FT-IR microscopy, while using Inductively Coupled Plasma Mass Spectrometer (ICP-MS) the presence of trace metals including Cd (2.34 ng g-1), Cu (180.64 ng g-1), Ni (12.69 ng g-1), Pb (1.17 ng g-1), Sb (14.43 ng g-1), and Zn (178.03 ng g-1) was revealed. Surface modified microbeads were capable of adsorbing Cu compared to the pure microbeads, which may be attributed to the complexation of Cu with dissolved organic matter associated with the microbeads in the matrix. It was further revealed that the biosolids derived microbead-metal complexes decreased soil respiration (up to ∼ 26%) and dehydrogenase activity (up to ∼ 39%). Hence, microbeads reaching biosolids during wastewater treatment are likely to serve as a vector for trace element contamination, transportation, and toxicity when biosolids are applied to soil.

Use of mixed wastewaters from piggery and winery for nutrient removal and lipid production by Chlorella sp. MM3.

The larger-scale generation of piggery and winery wastewaters and consequent eutrophication are quite alarming, necessitating the use of a cost-effective treatment. This study attempted to remediate wastewaters from piggery and winery mixed in the ratios of 20:80, 50:50, 80:20, 100:0 and 0:100, in terms of nutrient removal and subsequent lipid accumulation by soil microalga, Chlorella sp. MM3. The per cent removal of total nitrogen and phosphates by the alga from mixed wastewaters within 10-days ranged between 51 and 89 and 26-49, respectively. As determined by FTIR spectroscopy, the lipid accumulation in the microalgal cells grown in wastewater mixtures ranged between 29 and 51%. Our results suggest that Chlorella sp. MM3 could be a potential candidate for bioremediation of wastewaters derived from piggery farm and winery industry, and that mixing of these wastewaters in 20:80 ratio would be an efficient approach for phycoremediation of mineral-rich effluents and subsequent yield of fairly good amounts of biofuel.

Determination of Total Petroleum Hydrocarbons in Australian Groundwater Through the Improvised Gas Chromatography-Flame Ionization Detection Technique.

Assessment of total petroleum hydrocarbons (TPHs) from contaminated sites demands routine and reliable measurement at trace levels. However, the detection limits of these methods need to be improved. This study developed the programmable temperature vaporization-large volume injection (PTV-LVI) method to quantify TPHs through gas chromatography-flame ionization detection. This configuration enhances the method sensitivity for trace level detections through large volume injections and pre-concentration of analytes along the injection liner. The method was evaluated for the three commonly observed hydrocarbon fractions: C10-C14, C15-C28 and C29-C36. In comparison with conventional injection methods (splitless and pulsed splitless), PTV-LVI showed R2 values > 0.999 with enhanced limits of detection and limits of quantification values. The method was applied to real samples for routine environmental monitoring of TPHs in an Australian contaminated site characterized by refueling station. Analysis of groundwater samples in the area showed a wide range of TPH concentrations as follows: 66-1,546,000 (C10-C14), 216-22,762 (C15-C28) and 105-2,103 (C29-C36) µg/L. This method has detected trace levels, thereby measuring a wider concentration range of TPHs. These more accurate measurements can lead to the appropriate application of risk assessments and remediation techniques.

Characterization and reactivity of iron based nanoparticles synthesized by tea extracts under various atmospheres.

Bio-synthesis of Fe NPs in inert (nitrogen N-Fe NPs) and oxygen (O-Fe NPs) atmospheres employing green tea extracts was investigated through SEM, EDS, XPS and FT-IR techniques. The particle sizes of N-Fe NPs and O-Fe NPs were confirmed by SEM showing 84.7 ± 11.5 nm and 117.8 ± 26.2 nm respectively with subsequent evaluation of the percentage composition of Fe and O by EDS. The XPS results showed that the zero-valent iron and iron oxide nanoparticles were found to be dominant synthesized respectively in nitrogen and oxygen atmospheres. The FT-IR spectra further demonstrated that the surface functional groups of Fe NPs were different by varying the synthesis atmosphere. Fe NPs were used to remove methylene blue (MB) to test the reactivity, and the removal efficiency of MB using N-Fe NPs was 98.7%, while that of O-Fe NPs was only 65.3%. Thus it is clearly demonstrated that the synthesis atmosphere has prominent effects on the formation and catalytic properties of Fe NPs.

Effects of thermal treatments on the characterisation and utilisation of red mud with sawdust additive.

Extremely large amounts of red mud (bauxite residue) are generated globally every year from alumina refining industries, which are being disposed of on engineered landfills. The objective of this study is to investigate the effects of thermal treatments on red mud for development of utilisation strategies. Thermal treatments of red mud samples and their characterisations were investigated under inert (N2) and oxidative (air) conditions with and without sawdust addition at 200-600°C. After calcination, the resulting samples were analysed using thermogravimetric-infrared spectroscopy (TG-IR) for functional group transformations, thermogravimetric analysis (TGA) for thermal loss profiles and X-ray diffraction (XRD) for mineral transformations. The characterisation results showed that in N2 environment, boehmite in red mud was transferred to transition alumina at around 400°C while losing water from structural components. The addition of sawdust for incubation and calcination of red mud in air increased the surface area, whereas that in nitrogen atmosphere lead to reduction of hematite to magnetite at around 500°C. The incorporated carbon materials played a major role in increasing the surface area especially for pore size less than 2.5 nm. This treated red mud with altered mineral composition and improved properties for binding contaminants can be used for environmental remediation and in the process of metal recovery such as iron.