Natural media such as soil and sediment contain mineralogical and organic components with distinct chemical, surface, and electrostatic properties. To better understand the role of various soil and sediment components on particle transport, columns were packed with quartz sand and natural sediment with added Fe oxyhydroxide coating, illite clay, and peat moss to investigate how these added components influence nTiO₂ retention and transport in geochemically heterogeneous medium. Results showed that nTiO₂ transport was low at pH 5, attributable to the electrostatic attraction between positively-charged nTiO₂ and negatively-charged medium. While illite did not notably affect nTiO₂ transport at pH 5, Fe oxyhydroxide coating increased nTiO₂ transport due to electrostatic repulsion between Fe oxyhydroxide and nTiO₂. Peat moss also increased nTiO₂ transport at pH 5, attributable to the increased DOC concentration, which resulted in higher DOC adsorption to nTiO₂ and intensified electrostatic repulsion between nTiO₂ and the medium. At pH 9, nTiO₂ transport was high due to the electrostatic repulsion between negatively-charged nTiO₂ and medium surfaces. Fe oxyhydroxide coating at pH 9 slightly delayed nTiO₂ transport due to electrostatic attraction, while illite clay and peat moss substantially inhibited nTiO₂ transport via straining/entrapment or electrostatic attraction. Overall, this study demonstrated that pH has a considerable effect on how minerals and organic components of a medium influence nTiO₂ transport. At low pH, electrostatic attraction was the dominant mechanism, therefore, nTiO₂ mobility was low regardless of the differences in mineralogical and organic components. Conversely, nTiO₂ mobility was high at high pH and nTiO₂ retention was dominated by straining/entrapment and sensitive to the mineralogical and organic composition of the medium.

This work has been conducted as an integrated approach to study the behavior of soils to the metals from sludge amendment. Bureau Commun Reference (BCR) methodology was used as an appropriate tool to harvest precious information about heavy metals evolution versus depth before and after sludge treatments. This three-step extraction procedure (i.e., BCR) may clarify the leaching or retention of heavy metals from the amended soils, as well as their risk level. Our results indicated that sludge applications has shown an increasing flux of heavy metals towards amended soils, of which Pb was the most abundant. Heavy metals mobility in control and amended soils showed that main influencing factors are pH and total organic carbon, especially for copper mobility. Almost all of the metals decreased with soil depth, except for Ni. Speciation of heavy metals in sludges showed that about 45% of Pb, Cu and Ni were associated with residual fraction; Cd was mainly bound to reducible fraction. Speciation forms in the control soil indicated that short term application of sludge has remobilized a fraction of heavy metals into their most labile forms (i.e., exchangeable and reducible fraction). Multivariate statistical analysis suggested that Cd, Zn, Pb and Cu preferentially accumulated in organic-rich surface horizons and clay layers where adsorption played an important role as a determining mechanism. Nevertheless, adsorption did not appear to be directly controlled by high pH values (pH > 7). From Cluster Analysis (CA), one can easily recognize that Pb, Zn and Cu movement in soil profiles were significantly affected by pH, especially residual fraction, labile fraction and reducible fraction.

A biofilm reactor was designed with flat ceramic substrates to remove Co(II), Ni(II) and Zn(II) from industrial wastewater. The ceramics were made of clay and nano-rubber with high mechanical resistance. The surface of the ceramic substrate was modified with neutral fiber and nano-hydroxyapatite. A uniform and stable biofilm mass of 320 g with 2 mm of thickness was produced on the modified ceramic after 3 d. The micro-organisms were identified in the biofilm by polymerase chain reaction (PCR) method. Functional groups of biofilms were identified with a Fourier transform infrared spectrometer (FT-IR). Experiments were designed by central composite design (CCD) using the responsive surface method (RSM). The biosorption process was optimized at pH = 5.8, temperature = 22 °C, feed flux of heavy metal wastewater = 225 ml, substrate flow = 30 ml, and retention time = 7.825 h. The kinetic data was analyzed by pseudo first-order and pseudo second-order kinetic models. Isotherm models and thermodynamic parameters were applied to describe the biosorption equilibrium data of the metal ions on the biofilm-ceramic. The maximum biosorption efficiency and capacity of heavy metal ions were about 72% and 57.21 mg, respectively.

Measurement of solute-transport parameters through soils for a wide range of solute- and soil-types is time-consuming, laborious, expensive and practically impossible. So, indirect methods for estimating the transport parameters by pedo-transfer functions are now advancing. This study developed and evaluated an Artificial Neural Network (ANN) model for estimating the transport velocity (V), dispersion coefficient (D) and retardation factor (R) of NaAsO₂, Pb(NO₃)₂, Cd(NO₃)₂, C₉H₉N₃O₂ and CaCl₂ from the basic soil properties. Breakthrough data of the solutes were measured in 14 agricultural soils of Bangladesh by time-domain reflectometry (TDR) in repacked soil columns under unsaturated steady-state water-flow conditions. The transport parameters of the chemicals were determined by analyzing the solute breakthrough data. Bulk density (γ), organic carbon (OC), clay (C) content, pH, median grain diameter (D₅₀) and uniformity coefficient (Cᵤ) of the soils were determined. An ANN model for V, D and R was developed by using data of eight soils, validated/tested with the data of five soils and verified with the data of one soil. Clay content and bulk density of the soils were the most sensitive input variables to the ANN model followed by other soil properties (OC, C, pH, D₅₀ and Cᵤ). The model reliably predicted V, D and R with relative root-mean-square error (RRMSE) of 0.028–0.363, mean error (ME) of – 0.00004 to 0.0005, bias error (BOE%) of 0–0.003 and modeling efficiency (EF) of >0.99. Thus, the ANN model can significantly enhance prediction of pollution transport through soils in terms of cost and effort.

Alprazolam, clonazepam and diazepam are drugs belonging to the benzodiazepine class. These drugs might be important environmental contaminants in aquatic media. A total understanding of behavior and fate of drugs in aquatic environment is not available for these and other drugs. Thus, in this work, a complete optimization of sample treatment and extraction of analytes from sediments and water was described, as well a study of sediment/water distribution comparing it with sample characteristics. Ultrasound for 10 min and 3 steps using 3 mL of extraction solvent were chosen as the stirring form for extraction. A methanol/water (1:1) solution pH 12 was the best extraction solvent. Aiming to eliminate interferences, an addition of 10 μL of NaCl 3.06 mol L⁻¹ was necessary after each step of extraction. Sediment and water samples were characterized, presenting different values on physical-chemical parameters. Six distinct sample sets of water and sediments were spiked with each benzodiazepine and analyzed. Kd values varied from 1.4 to 9.2 L kg⁻¹ for clonazepam, 1.8–11.5 L kg⁻¹ for alprazolam and 2.31–12 L kg⁻¹ for diazepam. A principal component analysis showed high dependence on Kd with sample characteristics mainly related to sediments. In the systems, whose sediments presented high levels of clay, silt and organic matter, the drugs presented a great interaction with the solid part of the system, increasing the Kd value. Koc values varied from 149.25 to 634.13 L kg⁻¹ for clonazepam, 186.57–852.48 L kg⁻¹ for alprazolam, and 194.68–1189.81 L kg⁻¹ for diazepam.

The adsorption of polycyclic aromatic hydrocarbons (PAHs) by components such as elemental carbon (EC), total organic carbon (TOC), and particles is different, and EC and PAHs are good materials for reconstructing historical human activity patterns and pollution conditions. In this study, the effects of EC (soot and char), TOC and particles of different grain size on PAHs in surface sediments were quantitatively analysed, and their historical concentrations in a sediment core from western Taihu Lake were reconstructed. The contents of soot, TOC, clay, EC and char explained 57.2%, 27.6%, 26.0%, 24.0% and 16.4%, respectively, of the PAH concentrations in surface sediments. The correlation between the soot and PAH levels was significantly higher than that between the char, TOC, and clay contents and PAH levels, and PAHs were mainly affected by the local economic development and human activity, as indicated by metrics of population, highway mileage, coal burning, and industrial output. With the development of the economy of the Taihu Lake Basin, the composition of PAHs in the sediments has changed: the proportion of low-molecular-weight PAHs decreased from 42.4% to 17.5%, and that of high-molecular-weight PAHs increased from 58.7% to 82.5%. The concentration of PAHs in pore water from Taihu Lake over the past 100 years was reconstructed and ranged from 43.1 to 961.2 μg L−1, with an average of 180.7 μg L−1. After China's reform and opening up, the concentrations of various PAHs in Taihu Lake changed from safe to chronic pollution levels. The ratios of lead (Pb) isotopes and the diagnostic ratios of PAHs showed that the main sources of PAHs in western Taihu Lake sediments were human activities such as coal and petroleum combustion.

Tetracyclines are a class of antimicrobials frequently found in the environment, and have promoted the proliferation of antibiotic resistance. An unanswered research question is whether tetracycline sorbed to soils is still bioavailable to bacteria and exerts selective pressure on the bacterial community for the development of antibiotic resistance. In this study, bioreporter E. coli MC4100/pTGM strain was used to probe the bioavailability of tetracycline sorbed by smectite clay, a class of common soil minerals. Batch sorption experiments were conducted to prepare clay samples with a wide range of sorbed tetracycline concentration. The bioreporter was incubated with tetracycline-sorbed clay at different clay/solution ratios and water contents, as well as using dialysis tubings to prevent the direct contact between bacterial cells and clay particles. The expression of antibiotic resistance genes from the bioreporter was measured using a flow cytometer as a measurement of bioavailability/selective pressure. The direct contact of bioreporter cells to clay surfaces represented an important pathway facilitating bacterial access to clay-sorbed tetracycline. In clay-water suspensions, reducing solution volume rendered more bacteria to attach to clay surfaces enhancing the bioavailability of clay-sorbed tetracycline. The strong fluorescence emission from bioreporter cells on clay surfaces indicated that clay-sorbed tetracycline was still bioavailable to bacteria. The formation of biofilms on clay surfaces could increase bacterial access to clay-sorbed tetracycline. In addition, desorption of loosely sorbed tetracycline into bulk solution contributed to bacterial exposure and activation of the antibiotic resistance genes. Tetracycline sorbed by soil geosorbents could exert selective pressure on the surrounding microbial communities via bacterial exposure to tetracycline in solution from desorption and to the geosorbent-sorbed tetracycline as well.

Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer media with varying content of material < 0.063 mm in diameter (silt and clay fraction), background solution chemistry, and flow velocity. Breakthrough curves for Ag-ENPs exhibited blocking behavior that frequently produced a delay in arrival time in comparison to a conservative tracer that was dependent on the physicochemical conditions, and then a rapid increase in the effluent concentration of Ag-ENPs. This breakthrough behavior was accurately described using one or two irreversible retention sites that accounted for Langmuirian blocking on one site. Simulated values for the total retention rate coefficient and the maximum solid phase concentration of Ag-ENPs increased with increasing solution ionic strength, cation valence, clay and silt content, decreasing flow velocity, and for polymer-instead of surfactant-stabilized Ag-ENPs. Increased Ag-ENP retention with ionic strength occurred because of compression of the double layer and lower magnitudes in the zeta potential, whereas lower velocities increased the residence time and decreased the hydrodynamics forces. Enhanced Ag-ENP interactions with cation valence and clay were attributed to the creation of cation bridging in the presence of Ca2+. The delay in breakthrough was always more pronounced for polymer-than surfactant-stabilized Ag-ENPs, because of differences in the properties of the stabilizing agents and the magnitude of their zeta-potential was lower. Our results clearly indicate that the long-term transport behavior of Ag-ENPs in natural, silicate dominated aquifer material will be strongly dependent on blocking behavior that changes with the physicochemical conditions and enhanced Ag-ENP transport may occur when retention sites are filled.

Bacteria–phyllosilicate complexes are commonly found in natural environments and are capable of immobilizing trace metals. However, the molecular binding mechanisms of heavy metals to these complex aggregates still remain poorly understood. This study investigated Cd adsorption on Gram-positive Bacillus subtilis, Gram-negative Pseudomonas putida and their binary mixtures with montmorillonite using surface complexation model, Cd K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and isothermal titration calorimetry (ITC). We have shown that larger amounts of Cd are adsorbed by B. subtilis than by P. putida at pH<∼6, and Cd sorption that binding to phosphate groups plays a more important role in P. putida than in B. subtilis. This remind us that we should consider the microbe species when predict the biochemical behavior of trace metals in microbe-bearing environments. The observed Cd adsorption on the binary bacteria–clay composites was more than that predicted based on the component additivity approach. When taking bacteria–clay (1:1 mass ratio) as a representative example, an approximately 68%:32% metal distribution between the bacterial and mineral fraction was found. Both the EXAFS and ITC fits showed that the binding stoichiometry for Cd-carboxyl/phosphate was smaller in the binary mixtures than that in pure bacteria. We proposed that the significant deviations were possibly due to the physical-chemical interaction between the composite fractions that might reduce the agglomeration of the clay grains, increase the negative surface charges, and provide additional bridging of metals ions between bacterial cells and clays.

Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils requires a higher microbial viability and an increased PAH bioavailability. The clay/modified clay-modulated bacterial degradation could deliver a more efficient removal of PAHs in soils depending on the bioavailability of the compounds. In this study, we modified clay minerals (smectite and palygorskite) with mild acid (HCl) and alkali (NaOH) treatments (0.5–3 M), which increased the surface area and pore volume of the products, and removed the impurities without collapsing the crystalline structure of clay minerals. In soil incubation studies, supplements with the clay products increased bacterial growth in the order: 0.5 M HCl ≥ unmodified ≥0.5 M NaOH ≥3 M NaOH ≥3 M HCl for smectite, and 0.5 M HCl ≥3 M NaOH ≥0.5 M NaOH ≥3 M HCl ≥ unmodified for palygorskite. A14C-tracing study showed that the mild acid/alkali-treated clay products increased the PAH biodegradation (5–8%) in the order of 0.5 M HCl ≥ unmodified > 3 M NaOH ≥ 0.5 M NaOH for smectite, and 0.5 M HCl > 0.5 M NaOH ≥ unmodified ≥ 3 M NaOH for palygorskite. The biodegradation was correlated (r = 0.81) with the bioavailable fraction of PAHs and microbial growth as affected particularly by the 0.5 M HCl and 0.5 M NaOH-treated clay minerals. These results could be pivotal in developing a clay-modulated bioremediation technology for cleaning up PAH-contaminated soils and sediments in the field.