Polarity Dependence of Transport of Pharmaceuticals and Personal Care Products Through Birnessite-Coated Porous Media

Pharmaceuticals and personal care products (PPCPs) have drawn increasing concern of environmental health as they are continuously released into the environment. This study examined the effects of birnessite (δ-MnO2) on the transport and retention of five PPCPs in porous media under steady saturated flow conditions. Considering that natural birnessite occurs as discrete particles and small nodules, birnessite-coated sand was used to mimic the natural regime of birnessite in the environment. Batch isotherm experiments were conducted using uncoated and birnessite-coated sand; results showed that the difference in the affinity of the five PPCPs was correlated to their polarity characteristics. Column experiments were conducted by mixing 0, 10, and 20% birnessite-coated sands with the uncoated sands. These three percentages are equivalent to three contents of manganese (Mn) in the experimental columns (0, 55, and 109 μg Mn g−1 sand). Results suggested that polar compounds (such as bisphenol-A, tetracycline, and ciprofloxacin) had a higher affinity to birnessite-coated sands than the weak polar compounds (such as ibuprofen and carbamazepine) because the polarity was favorable to electrostatic attraction and oxidative reaction. Overall, birnessite decreased the mobility of polar PPCPs but exerted no significant effect on the mobility of weak polar PPCPs under continuous flow conditions. The polarity-based correlation extended traditional electrostatic theory while well interpreting the complicated effects of birnessite on the adsorption and transport of PPCPs, especially neutral or non-dissociated compounds like carbamazepine.

Remediation of Cr(VI)/Cd(ІІ)-Contaminated Groundwater with Simulated Permeable Reaction Barriers Filled with Composite of Sodium Dodecyl Benzene Sulfonate-Modified Maifanite and Anhydride-Modified Fe@SiO2@Polyethyleneimine: Environmental Factors and Effectiveness

A composite material of sodium dodecyl benzene sulfonate- (SDBS-) modified maifanite and anhydride-modified Fe@SiO2@PEI (PEI) was used as an adsorbent for the removal of hexavalent chromium (Cr(VI)) and bivalent cadmium (Cd(II)) from groundwater by using column experiments and simulated PRB test. In this study, the optimum proportion of SDBS-modified maifanite and anhydride-modified Fe@SiO2@PEI was 5 : 1. In the column experiments, it was found that the penetration time increased with the increase of the initial concentrations (30, 60, and 90 mg/L) and the decrease of the flow rates (5.45, 10.9, and 16.35 mL/min) at an influent pH of 6.5 ± 0.3 . It was also obtained that the removal rates of Cr(VI) and Cd(ІІ) reached 99.93% and 99.79% at an initial Cr(VI) and Cd(ІІ) concentration of 30 mg/L with the flow rate of 10.9 mL/min, respectively, at 6 h. Furthermore, excellent removal effectiveness of Cr(VI) and Cd(ІІ) (85.94% and 83.45%, respectively) was still achieved in simulated PRB test at a flow rate of 5.45 mL/min with the heavy metal solution concentration of 5.0 ± 0.5 mg/L (Cr(VI) and Cd(II) concentration were, respectively, 5.0 ± 0 . 5 mg/L); and the adsorbent had not completely failed by the end of the trial. Yoon-Nelson model was successfully applied to predict the breakthrough curves for the assessment of composite material heavy metal removal performance and was in good agreement with the experimental data of the heavy metal removal efficiency. The strong removal ability of the adsorbent could be attributed to the fact that maifanite with a large diameter can provide support and increase the permeability coefficient and porosity and that zero-valent iron (ZVI) can convert Cr(VI) to Cr(III) and improve the adsorption capacity of maifanite. The obtained results suggested that the novel PRB fillers have great significance for preventing and controlling Cr(VI)/Cd(ІІ)-contaminated groundwater.

Effects of Environmental Factors on the Leaching and Immobilization Behavior of Arsenic from Mudstone by Laboratory and In Situ Column Experiments

Hydrothermally altered rocks generated from underground/tunnel projects often produce acidic leachate and release heavy metals and toxic metalloids, such as arsenic (As). The adsorption layer and immobilization methods using natural adsorbents or immobilizer as reasonable countermeasures have been proposed. In this study, two sets of column experiments were conducted, of which one was focused on the laboratory columns and other on the in situ columns, to evaluate the effects of column conditions on leaching of As from excavated rocks and on adsorption or immobilization behavior of As by a river sediment (RS) as a natural adsorbent or immobilizer. A bottom adsorption layer consisting of the RS was constructed under the excavated rock layer or a mixing layer of the excavated rock and river sediment was packed in the column. The results showed that no significant trends in the adsorption and immobilization of As by the RS were observed by comparing laboratory and in situ column experiments because the experimental conditions did not influence significant change in the leachate pH which affects As adsorption or immobilization. However, As leaching concentrations of the in situ experiments were higher than those of the laboratory column experiments. In addition, the lower pH, higher Eh and higher coexisting sulfate ions of the leachate were observed for the in situ columns, compared to the results of the laboratory columns. These results indicate that the leaching concentration of As became higher in the in situ columns, resulting in higher oxidation of sulfide minerals in the rock. This may be due to the differences in conditions, such as temperature and water content, which induce the differences in the rate of oxidation of minerals contained in the rock. On the other hand, since the leachate pH affecting As adsorption or immobilization was not influenced significantly, As adsorption or immobilization effect by the RS were effective for both laboratory and in situ column experiments. These results indicate that both in situ and laboratory column experiments are useful in evaluating leaching and adsorption of As by natural adsorbents, despite the fact that the water content which directly affects the rate of oxidation is sensitive to weathering conditions.

Bioadsorption of lead(II) over the pulp of Acrocomia aculeata

The adsorption of lead in aqueous solution onto Acrocomia aculeata pulp was examined. The pulp was characterized in the presence and absence of lead using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG-DTA), and scanning electron microscopy (SEM). Sulfur and oxygen bonds were responsible for adsorbing lead onto the pulp surface. The TG-DTA profile proved that adding sodium azide increases the pulp�s thermal stability until 200 �C. Adsorption data in batch and column systems were analyzed to understand the pulp adsorption compared to other biomaterials. In the batch experiments, the removal efficiency reached a maximum of 91.9% when a solution of 50 ppm of lead was placed in contact with the pulp for 30 min and fit Freundlich isotherm behavior. In the column experiments, the theoretical maximum adsorption capacity was found to be 11.97 mg g�1; more column data is needed to compare column results to other studies. Further studies to improve the pulp adsorption capacity are needed for it to be a competitive biomaterial for water treatment.

Soil organic carbon mobility in equatorial podzols: soil column experiments

Transfer of organic carbon from topsoil horizons to deeper horizons and to the water table is still little documented, in particular in equatorial environments, despite the high primary productivity of the evergreen forest. Due to its complexing capacity, organic carbon also plays a key role in the transfer of metals in the soil profile and, therefore, in pedogenesis and for metal mobility. Here we focus on equatorial podzols, which are known to play an important role in carbon cycling. We carried out soil column experiments using soil material and percolating solution sampled in an Amazonian podzol area in order to better constrain the conditions of the transfer of organic carbon at depth. The dissolved organic matter (DOM) produced in the topsoil was not able to percolate through the clayey, kaolinitic material from the deep horizons and was retained in it. When it previously percolated through the Bh material, there was production of fulvic-like, protein-like compounds and small carboxylic acids able to percolate through the clayey material and increase the mobility of Al, Fe and Si. Podzolic processes in the Bh can, therefore, produce a DOM likely to be transferred to the deep water table, playing a role in the carbon balances at the profile scale and, owing to its complexing capacity, playing a role in deep horizon pedogenesis and weathering. The order of magnitude of carbon concentration in the solution percolating at depth was around 1.5–2.5 mg L−1. Our findings reveal a fundamental mechanism that favors the formation of very thick kaolinitic saprolites.