We investigated the competitive effects of different fractions of wastewater treatment plant effluent organic matter (EfOM) on adsorption of an organic micro pollutant (OMP), propranolol (PRO), in a fixed bed column packed with magnetic tyre char (MTC). The results showed that the presence of EfOM inhibited PRO adsorption in wastewater leading to decreased PRO adsorption capacity from 5.86 to 2.03 mg/g due to competitive effects and pore blockage by smaller EfOM fractions. Characterization of EfOM using size exclusion chromatography (LC-OCD) showed that the principal factor controlling EfOM adsorption was pore size distribution. Low molecular weight neutrals had the highest adsorption onto MTC while humic substances were the least interfering fraction. Effect of important parameters such as contact time, linear velocity and bed height/diameter ratio on MTC performance was studied in large-lab scale columns. Linear velocity and contact time were found to be effective in increasing adsorption capacity of PRO on MTC and delaying breakthrough time. Increase in linear velocity from 0.64 cm/min to 1.29 cm/min increased mass transfer and dispersion, resulting in considerable rise of adsorbed amount (5.86 mg/g to 22.58 mg/g) and increase in breakthrough time (15.8–62.7 h). Efficiency of non-equilibrium Hydrus model considering dispersion and mass transfer mechanism was demonstrated for real wastewater and scale up purposes. Ball milling for degradation of adsorbed PRO and regeneration of MTC resulted in 79% degradation of PRO was achieved after 5 h milling (550 rpm), while the addition of quartz sand increased the efficiency to 92%.

Inhalation of respirable silica particles can cause serious lung diseases (e.g., silicosis and lung cancer), and the toxicity of respirable silica is highly dependent on its crystal form. Common combustion processes such as coal and biomass burning can provide high temperature environments that may alter the crystal forms of silica and thus affect its toxic effects. Although crystalline silica (i.e., quartz, tridymite, and cristobalite) were widely found at different temperatures during the burning processes, the sources and crystal transformation pathways of silica in the burning processes are still not well understood. Here, we investigate the crystal transformation of silica in the coal and biomass combustion processes and clarify the detailed transformation pathways of silica for the first time. Specifically, in coal burning process, amorphous silica can transform into quartz and cristobalite starting at 1100 °C, and quartz transforms into cristobalite starting at 1200 °C; in biomass burning process, amorphous silica can transform into cristobalite starting at 800 °C, and cristobalite transforms into tridymite starting at 1000 °C. These transformation temperatures are significantly lower than those predicted by the classic theory due to possibly the catalysis of coexisting metal elements (e.g., aluminum, iron, and potassium). Our results not only enable a deeper understanding on the combustion-induced crystal transformation of silica, but also contribute to the mitigation of population exposure to respirable silica.

In acidic medium, hazardous heavy metals of lead-zinc tailing (LZT) are easily leachable and mobilizable. Thus, the hazard, amount, form, and complexity of the leached heavy metals under acidic precipitation become a major environmental concern. This work investigates the gangue minerals, toxicity, speciation, leaching characteristics of heavy metals in LZT under simulated acid rain, as well as immobilization effects and mechanisms using a sustainable binder. In LZT, dolomite, quartz, calcite, and muscovite are the main gangue minerals, tiny hazardous metallic minerals were absorbed in the surface. The results revealed that Pb, Zn, Cr, and Cd were the predominant harmful elements, particularly Pb and Zn. Zn is leached completely and is the concerned hazardous element under simulated acid rain. In the acid rain neutralization ability test, the amount of leachable Pb, Cr, Ca, and Si maintained in equilibrium, leached Zn, Cd, Al, and Mg depended on the addition of acid. Pb and Ca were sedimented in residues. Immobilization of Pb, Zn, Cr, and Cd depended on the stability of Ca(OH)₂/C–S–H of hydrates, and 70% LZTHP after curing 7 days can be used for some practical engineering projects. This work opens up deeply understandings for the leached heavy metals under acidic precipitation and improves the sustainable and safe in the field of immobilization of heavy metals.

The sedimentary history of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) over the past 140 years in a lake sediment core from Huixian karst wetland was reconstructed. The total PAHs and OCPs concentrations ranged from 40.0 to 210 ng g⁻¹ and 0.98 to 31.4 ng g⁻¹, respectively. The vertical distribution of PAHs and OCPs in different stages was great consistent with the history of regional socio-economic development and the usage of OCPs. As the indicators of socio-economic development, gross domestic product (GDP), population, energy consumption, highway mileage, and private vehicles correlated with the PAHs concentrations, indicating the impact of human activities on PAHs levels. The PAHs and OCPs concentrations were also affected by environmental changes in the wetland, as reconstructed by total organic carbon (TOC), sand, silt, clay, quartz, and calcite in sediments. Redundancy analysis (RDA) results showed TOC was the dominant factor to explain the concentrations of PAHs and OCPs with the explanation of 86.7% and 43.5%, respectively. In addition, TOC content had significantly positive correlation with PAHs (0.96, p < 0.01) and OCPs (0.78, p < 0.01). In particular, the significantly positive correlation (p < 0.05) between calcite and PAHs and OCPs inferred that karstification might play an important role in the migration of PAHs and OCPs in the karst area. Therefore, the lake in Huixian wetland tended to be a sink more than a source of PAHs and OCPs influenced by the increasing TOC content and karstification under climate warming.

PM₂.₅ and PM₁₀ fugitive dust samples from multiple sources (construction, demolition, industrial, agricultural fields, and bare ground) were collected in triplicate for each size bin, from 18 distinct locations in and around Bhopal, central India. The dust samples were dried, sieved, and re-suspended in a chamber fitted with a suitable sampling system, to collect PM₂.₅ and PM₁₀ samples onto Teflon and Quartz filters. The filters were subjected to gravimetric and chemical analyses. Trace elements, water-soluble ions, and thermal-optical carbon fractions were quantified using a variety of analyses. These species were then used to develop PM₁₀ and PM₂.₅ chemical source profiles of the fugitive dust sources. As expected, crustal species were abundant in all source categories. For industrial dust, Fe contribution to mass in both size fractions was about 11.4% and above the upper continental crustal abundance. Further, the source profiles generated for each source were different from their counterparts in the US EPA SPECIATE database and profiles reported in literature. Thus, it will be useful to utilize profiles generated in this study to enhance receptor model performance for the study region. However, collinearity analysis of the profiles revealed that PM₁₀ agricultural and bare ground dust; and PM₂.₅ construction and demolition dust profile pairs may not be separated by receptor models. Finally, a human health risk assessment revealed that construction and industrial dust may pose significant risk to the population. The Incremental Lifetime Cancer Risk (ILCR) metric revealed that adults (2 × 10⁻⁵) and children (1 × 10⁻⁵) were susceptible to cancer risk from exposure to metals in PM₂.₅ fugitive dust. Further, children were more vulnerable than adults. This finding merits further investigation of oxidation state and solubility/bioavailability of Cr and Ni in fugitive dusts.

The release of fine particles from biochar materials applied in the environment may have important environmental implications, such as mobilization of environmental contaminants. In natural environments biochar fine particles can undergo various transformation processes, which may change their surface chemistry and consequently, the mobility of the particles. Here, we show that sulfide reduction can significantly alter the transport of wheat-straw- and pine-wood-derived biochar fine particles in saturated porous media. Counterintuitively, the sulfide-reduced biochar particles exhibited greater mobility in artificial groundwater than their non-reduced counterparts, even though reduction led to decrease of surface charge negativity and increase of hydrophobicity (from the removal of surface O-functional groups), both should favor particle deposition, as predicted based on extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) theory. Using transport experiments conducted in single-cation background solutions containing K⁺, Mg²⁺ or Ca²⁺ under different pH conditions, we show that the surprisingly greater mobility of sulfide-reduced biochar particles was attributable to the removal of surface carboxyl groups during reduction, as this markedly alleviated particle deposition through cation bridging, wherein Ca²⁺ acted as the bridging agent in linking the surface O-functional groups of biochar particles and quartz sand. These findings show the critical roles of surface properties in dictating the mobility of biochar fine particles and call for further understanding of their transport properties, which apparently cannot be simply extrapolated based on the findings of other (engineered) carbonaceous nanomaterials.

The removal of arsenic from groundwater is an important issue for environmental safety and human health. Research focused on the comparative assessment of arsenic removal from arsenic-bearing groundwater and arsenic-containing-synthetic water (2 mg/L) using natural magnetic material (NMM) (rock) and synthesized magnetic material (SMM) by Bacillus pasteurii and humic acid. The arsenic-bearing groundwater (97.56 ± 0.05 μg/L) exceed the WHO limit (10 μg/L) of arsenic concentration for drinking water. The NMM contains dominantly magnetite, hematite, ferrihydrate, coesite, quartz, and stishovite. The NMM of natural rock exhibited the existence of iron (6.25–8.86% Fe₃O₄), which is widespread and important component in sedimentary rocks. The investigation on vibrating sample magnetometers (VSM) of NMM and SMM demonstrated the typical magnetization properties, which can be separated after arsenic removal process. The thermogravimetric analysis (TGA) of SMM displayed the existence of organic matter decomposition during particle synthesis. The TEM and SEM exhibited the nanoparticle particle formation within the range of 10–39 nm (10–20 nm particle Fe₃O₄ through B. pasteurii). FTIR spectrum (before and after removal of arsenic) indicated the existence and binding nature in between arsenic and iron. >90% of arsenic was removed from arsenic-bearing groundwater using Fe₃O₄, Fe₃O₄ (N₂-Environment), Fe₃O₄ with humic acid, and Fe₃O₄ with B. pasteurii after 25 min, 8 min, 13 min and 120 min, respectively. In case of NMM in Site-A, the arsenic removal was observed very fast as 85–87% within 30 s, whereas 95–99%, 93–95% and 88–91% removal detected using the sample of Site-A, Site-B, and Site-C respectively, after 120 min at natural pH (8.31 ± 0.05) of arsenic-bearing groundwater. Thus, NMM, (ecofriendly green material), can be applicable for arsenic removal from arsenic-bearing groundwater.

The increasing production and use of graphene-based nanomaterials (e.g., graphene oxide (GO) and reduced graphene oxide (RGO)) will lead to their environmental release. To date, transport of RGOs in saturated porous media is poorly understood. Here, we examined the transport behaviors of three RGO materials obtained by reducing a GO product with commonly used reducing agents – N₂H₄, NaBH₄ and L-ascorbic acid (referred to as N₂H₄-RGO, NaBH₄-RGO and VC-RGO, respectively). When the dominant background cation was Na⁺, K⁺ or Mg²⁺, the mobility of the RGOs and GO in saturated quartz sand correlated well with their surface C/O ratio. Interestingly, the lower mobility of the more reduced materials (the ones with higher C/O values) was not only the results of their less negative surface charges and larger particle sizes, but also the outcome of their greater hydrophobicity, in line with the calculated extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) profiles. Counterintuitively, when the background cation was Ca²⁺, the least reduced material among the three RGOs, VC-RGO, exhibited the lowest mobility. Analysis of electrophoretic and aggregation properties, as well as pH-effect experiments, indicated that the surprisingly low mobility of VC-RGO was attributable to the strong cation-bridging effect (primarily Ca²⁺-bridging between RGO and quartz sand) associated with this material, as VC-RGO contained the highest amount of surface carboxyl group (a strong metal-binding moiety). Notably, enhanced attachment (due to increased hydrophobic effect and cation-bridging) and particle aggregation appeared to work synergistically to increase RGO retention, as the attachment of large RGO aggregates significantly enhanced particle straining by narrowing the flow path. These observations reveal a largely overlooked link between the mobility of graphene-based materials and their key physicochemical properties.

Evaluating the fate and transport of nanoparticles (NPs) in the subsurface environment is critical for predicting the potential risks to both of the human health and environmental safety. It is believed that numerous environmental factors conspire to control the transport dynamics of nanoparticles, yet the effects of organic phosphates on nanoparticles transport remain largely unknown. In this work, we quantified the transport process of TiO2 nanoparticle (nTiO2) and their retention patterns in water-saturated sand columns under various myo-inositol hexakisphosphate (IHP) or phosphate (Pi) concentrations (0–180 μM P), ferrihydrite coating fractions (λ, 0–30%), ionic strengths (1–50 mM KCl), and pH values (4–8). The transport of nTiO2 was enhanced at increased P concentration due to the enhanced colloidal stability. As compared with Pi at the equivalent P level, IHP showed stronger effect on the electrokinetic properties of nTiO2 particles due to its relatively more negative charge and higher adsorption affinity, thereby facilitating the nTiO2 transport (and thus reduced retention) in porous media. At the IHP concentration of 5 μM, the retention of nTiO2 increased with increasing λ and ionic strength, while decreased with pH. In addition, the retention profiles of nTiO2 showed a typical hyperexponential pattern for most scenarios mainly due to the unfavorable attachment, and can be well described by a hybrid mathematical model that coupled convection dispersion equations with a two-site kinetic model and DLVO theory. These quantitative estimations revealed the importance of IHP on affecting the transport of nTiO2 typically in phosphorus-enriched environments. It provides new insights into advanced understanding of the co-transport of nanoparticles and phosphorus in natural systems, essential for both nanoparticle exposure and water eutrophication.

The transport and retention behavior of polymer- (PVP-AgNP) and surfactant-stabilized (AgPURE) silver nanoparticles in carbonate-dominated saturated and unconsolidated porous media was studied at the laboratory scale. Initial column experiments were conducted to investigate the influence of chemical heterogeneity (CH) and nano-scale surface roughness (NR) arising from mixtures of clean, positively charged calcium carbonate sand (CCS), and negatively charged quartz sands. Additional column experiments were performed to elucidate the impact of CH and NR arising from the presence and absence of soil organic matter (SOM) on a natural carbonate-dominated aquifer material. The role of the nanoparticle capping agent was examined under all conditions tested in the column experiments. Nanoparticle transport was well described using a numerical model that facilitated blocking on one or two retention sites. Results demonstrate that an increase in CCS content in the artificially mixed porous medium leads to delayed breakthrough of the AgNPs, although AgPURE was much less affected by the CCS content than PVP-AgNPs. Interestingly, only a small portion of the solid surface area contributed to AgNP retention, even on positively charged CCS, due to the presence of NR which weakened the adhesive interaction. The presence of SOM enhanced the retention of AgPURE on the natural carbonate-dominated aquifer material, which can be a result of hydrophobic or hydrophilic interactions or due to cation bridging. Surprisingly, SOM had no significant impact on PVP-AgNP retention, which suggests that a reduction in electrostatic repulsion due to the presence of SOM outweighs the relative importance of other binding mechanisms. Our findings are important for future studies related to AgNP transport in shallow unconsolidated calcareous and siliceous carbonate sands.