Colloid-sized microplastics (MPs) are ubiquitous in aquatic environments and can share the same transport route together with various crystalline, poorly crystalline and freshly formed iron oxides. However, the colloidal interactions between these colloid constituents are not fully understood. This study was designed to investigate the colloidal properties of polystyrene microplastics (PSMPs) under the influence of haematite, goethite, ferrihydrite and freshly formed Fe oxide (FFFO). Dynamic light scattering was coupled with a test tube method to observe changes in the surface charge and colloidal dynamics of suspensions of PSMPs and Fe oxides. The overall effects on the aggregation of PSMPs are found to decrease in the following order: FFFO > ferrihydrite > goethite > haematite. The effects of these Fe oxides are found to strongly depend on pH. While the crystalline oxides play a dominant role in the acidic environment, poorly crystalline oxides show greater effects on PSMP aggregation in an alkaline environment. Heteroaggregation due to decreasing electrostatic interactions is the major mechanism that governs the colloidal dynamics of PSMPs and Fe oxides. It can be inferred that the copresence of Fe oxides and MPs can delay the transport of MPs or even change the destination for MPs.

Goethite is a common iron hydroxide, which can be substituted by manganese (Mn) in the goethite structure. It is important to investigate the immobilization of uranium(VI) on Mn-substituted goethite (Mn-Goe) to understand the fate and migration of uranium in soils and sediments. In this study, the sorption of uranium(VI) by Mn-Goe was investigated as a function of pH, adsorbent dosage, contact time, and initial uranium concentration in batch experiments. Several material analysis techniques were used to characterize manganese substituted materials. Results indicated that Mn was successfully introduced into the goethite structure, the length of particles increased gradually, the surface clearly exhibited higher roughness with increasing Mn content, and that uranium(VI) sorption of synthetic Mn-Goe appeared to be higher than that of goethite. The sorption kinetics supported the results presented by the pseudo-second-order model. The sorption capacity of uranium on Mn-Goe was circa 77 mg g⁻¹ at pH = 4.0 and 25 °C. Fourier transform-infrared spectroscopy (FT-IR) analyses revealed that uranium ions were adsorbed through functional groups containing oxygen on the Mn-Goe structure. The enhancement of Mn-substitution for the uranium(VI) sorption capacity of goethite was revealed. This study suggests that goethite and Mn-Goe can both play a significant role in controlling the mobility and transport of uranium(VI) in the subsurface environment, which is helpful for material development in environmental remediation.

Multi-walled carbon nanotubes (MWCNTs) are increasing used in commercial applications and may be released into the environment with anionic surfactants, such as sodium dodecylbenzenesulfonate (SDBS), in sewer discharge. Little research has examined the transport, retention, and remobilization of MWCNTs in the presence or absence of SDBS in porous media with controlled chemical heterogeneity, and batch and column scale studies were therefore undertaken to address this gap in knowledge. The adsorption isotherms of SDBS on quartz sand (QS), goethite coated quartz sand (GQS), and MWCNTs were determined. Adsorption of SDBS (MWCNTs » GQS > QS) decreased zeta potentials for these materials, and produced a charge reversal for goethite. Transport of MWCNTs (5 mg L⁻¹) dramatically decreased with an increase in the fraction of GQS from 0 to 0.1 in the absence of SDBS. Conversely, co-injection of SDBS (10 and 50 mg L⁻¹) and MWCNTs radically increased the transport of MWCNTs when the GQS fraction was 0, 0.1, and 0.3, especially at a higher SDBS concentration, and altered the shape of retention profile. Mathematical modeling revealed that competitive blocking was not the dominant mechanism for the SDBS enhancement of MWCNT transport. Rather, SDBS sorption increased MWCNT transport by increasing electrostatic and/or steric interactions, or creating reversible interactions on rough surfaces. Sequential injection of pulses of MWCNTs and SDBS in sand (0.1 GQS fraction) indicated that SDBS could mobilize some of retained MWCNTs from the top to deeper sand layers, but only a small amount of released MWCNTs were recovered in the effluent. SDBS therefore had a much smaller influence on MWCNT transport in sequential injection than in co-injection, presumably because of a greater energy barrier to MWCNT release than retention. This research sheds novel insight on the roles of competitive blocking, chemical heterogeneity and nanoscale roughness, and injection sequence on MWCNT retention and release.

A massive and dense textured layer (ca. 35–50 cm thick) of hardpan was uncovered at the top layer, which capped the unweathered sulfidic Cu-Pb-Zn tailings in depth and physically supported gravelly soil root zones sustaining native vegetation for more than a decade. For the purpose of understanding functional roles of the hardpan layer in the cover profile, the present study has characterized the microstructures of the hardpan profile at different depth compared with the tailings underneath the hardpans. A suit of microspectroscopic technologies was deployed to examine the hardpan samples, including field emission-scanning electron microscopy coupled with energy dispersive spectroscopy (FE-SEM-EDS), X-ray diffraction (XRD) and synchrotron-based X-ray absorption fine structure spectroscopy (XAFS). The XRD and Fe K-edge XAFS analysis revealed that pyrite in the tailings had been largely oxidised, while goethite and ferrihydrite had extensively accumulated in the hardpan. The percentage of Fe-phyllosilicates (e.g., biotite and illite) decreased within the hardpan profile compared to the unweathered tailings beneath the hardpan. The FE-SEM-EDS analysis showed that the fine-grained Ca-sulfate (possibly gypsum) evaporites appeared as platelet-shaped that deposited around pyrite, dolomite, and crystalline gypsum particles, while Fe-Si gels exhibited a needle-like texture that aggregated minerals together and produced contiguous coating on pyrite surfaces. These microstructural findings suggest that the weathering of pyrite and Fe-phyllosilicates coupled with dolomite dissolution may have contributed to the formation of Ca-sulfate/gypsum evaporites and Fe-Si gels. These findings have among the first to uncover the microstructure of hardpan formed at the top layer of sulfidic Cu-Pb-Zn tailings, which physically capped the unweathered tailings in depth and supported root zones and native vegetation under semi-arid climatic conditions.

The behaviour of arsenic (As) from geogenic soil exposed to aerobic conditions is critical to predict the impact of As on the environment, which processes remain unresolved. The current study examined the depth profile of As in geologically derived subsoil cores from Hong Kong and investigated the mobilization, plant availability, and bioaccessibility of As in As-contaminated soil at different depths (0–45.8 m). Results indicated significant heterogeneity, with high levels of As in three layers of soil reaching up to 505 mg/kg at a depth of 5 m, 404 mg/kg at a depth of 15 m, and 1510 mg/kg at a depth of 27–32 m. Arsenic in porewater samples was <11.5 μg/L in the study site. X-ray absorption spectroscopy (XAS) indicated that main As species in soil was arsenate (As(V)), as adsorbed fraction to Fe oxides (41–69% on goethite and 0–8% on ferrihydrite) or the mineral form scorodite (30–57%). Sequential extraction procedure demonstrated that 0.5 ± 0.4% of As was exchangeable. Aerobic incubation experiments exhibited that a very small amount (0.14–0.48 mg/kg) of As was desorbed from the soil because of the stable As(V) complex structure on abundant Fe oxides (mainly goethite), where indigenous microbes partly (59 ± 18%) contributed to the release of As comparing with the sterilized control. Furthermore, no As toxicity in the soil was observed with the growth of ryegrass. The bioaccessibility of As was <27% in the surface soil using simplified bioaccessibility extraction test. Our systematic evaluation indicated that As in the geogenic soil profile from Hong Kong is relatively stable exposing to aerobic environment. Nevertheless, children and workers should avoid incidental contact with excavated soil, because high concentration of As was present in the digestive solution (<0.1–268 μg/L).

A chronological sequence of urban soils 3–92 years old was studied to determine the effects of time on morphogenesis, artifact weathering, and the geochemical partitioning of Pb. Key chronofunctions determined are an increase in ˆA horizon Development Index (defined herein based on soil color) and water-soluble Pb, and a decrease in pH and C/N, with increasing soil age. Key artifact weathering reactions are: 1) portlandite in mortar altered to calcite, 2) ferrite in wrought-iron altered to ferrihydrite and goethite, and 3) carbonaceous materials altered to water-soluble organic substances. Mortar and wrought-iron were found to be Pb-bearing, but weather to produce immobilizing agents. Hence, they are both a source and a sink for Pb. The origin and mobilization of water-soluble Pb is complex and probably includes microbial extracellular polymeric substances, biodegraded soil organic matter, and solubilized organic substances derived from carbonaceous anthropogenic microparticles (soot, char and coal-related wastes).

Critical factors leading to arsenic release and attenuation from the shallow subsurface were studied with multidisciplinary approach in the natural gold–arsenic geochemical anomaly at Mokrsko (Czech Republic). The results show that microbial reduction promotes arsenic release from Fe(III) (hydr)oxides and Fe(III) arsenates, thereby enhancing dissolved arsenic in the shallow groundwater at average concentration of 7.76 mg/L. In the organic-rich aggregates and wood particles, however, microbial sulfate reduction triggers the formation of realgar deposits, leading to accumulation of As in the distinct organic-rich patches of the shallow subsurface. We conclude that precipitation of realgar in the shallow subsurface of soil/sediment depends on specific and non-trivial combination of water and rock chemistry, microbial community composition and spatial organisation of the subsurface zone, where speciation in saturated environments varied on a centimeter scale from reduced (decomposed wood, H2S and realgar present) to oxidized (goethite and arsenate minerals are present).

Understanding the arsenic (As) enrichment mechanisms in the subsurface environment relies on a systematic investigation of As valence species and their partitioning with the Fe (oxyhydr)oxide phases in the subsoil profile. The present study explored the distribution, speciation, partitioning, and (im)mobilization of As associated with Fe in four subsoil cores (∼30 m depth) from Hong Kong using sequential chemical extraction and X-ray absorption near edge spectroscopy. The subsoil profiles exhibited relatively high concentrations of As at 26.1–982 mg/kg (median of 112 mg/kg), and the As was dominated by As(V) (85–96%) and primarily associated with the residual fraction (50.7–94.7%). A small amount of As (0.002–13.2 mg/kg) was easily mobilized from the four subsoil profiles, and a concentration of water-soluble As higher than 100 μg/L was observed for only some subsoil layers. The molar ratios of As:Fe in the oxalate-extractable Fe fraction ranged from 1.2 to 76.5 mmol/mol (median of 11.1 mmol/mol), revealing the participation of poorly crystalline Fe (oxyhydr)oxides in immobilizing most of the high geogenic As. The primary phases of ferric (oxyhydr)oxides were characterized as ferrihydrite (16–53%), lepidocrocite (0–32%), and goethite (0–62%), and these phases contributed to the sufficient ability of the subsoil to sequester 45.3–100% (median of 98.8%) of the exogenous As(V) (1.0 mg/L) in adsorption experiments. In contrast to As(V), exogenous As(III) showed a lower removal percentage (3.9–79.1%, median of 45.1%). The study revealed that the chemical speciation of As and Fe in the subsoil profiles is useful for predicting the immobilization of high geogenic As in the region, which is also helpful for the safe utilization of As-containing soil during land development worldwide.

Sulfidized nanoscale zero-valent iron (S-nZVI) is a promising material for in situ soil remediation. However, its transformation (i.e., aging) and effects on the microbial community in soil ecosystems are largely unknown. In this study, S-nZVI having low (S-nZVI (L)) and high sulfur-doping (S-nZVI (H)) were incubated in soil microcosms and bare nZVI was used as a control. Their aged products were characterized using microspectroscopic analyses and the changes in the corresponding soil microbial community were determined using high-throughput sequencing analyses. The results indicate that severe corrosion of both bare and S-nZVI occurred over 56 days of aging with significant morphological and mineral changes. Magnetite, lepidocrocite, and goethite were detected as the main aged products. In addition, sulfate ions, pyrite, and iron polysulfide were formed in the aged products of S-nZVI. Cr(VI) removal test results indicated that S-nZVI(L) achieved the best results after aging, likely because of the optimal FeS arrangement on its nanoparticle surfaces. The presence of nZVI and S-nZVI increased the abundance of some magnetotactic microorganisms and altered bacterial and fungal community structures and compositions. Moreover, the addition of S-nZVI enriched some bacterial and fungal genera related to sulfur cycling because of the presence of sulfide-bearing material. The findings reveal the transformation of S-nZVI during aging and its effects on microbial communities in soil ecosystems, thereby helping to the evaluation of S-nZVI application in soil remediation.

Nanoscale zero-valent iron (nZVI) is the main nanomaterial used in environmental remediation processes. The present study aims to evaluate the life cycle sustainability of nZVI production methods applied in environmental remediation. Three production methods of nZVI were selected for analysis: milling, liquid reduction with sodium borohydride, and chemical reduction with hydrogen gas (in two approaches: considering the goethite and hematite synthesis and after using in nZVI production and, using goethite and hematite particles already synthesized for nZVI production). The life cycle sustainability assessment was carried out based on a multi-criteria and multi-attribute analysis. The multi-criteria analysis was used to determine impact category preferences of different specialists in sustainability and remediation, and calculate the sustainability score through a linear additive model. Finally, a Monte Carlo simulation was used to quantify the results uncertainty. The functional unit considered was 1.00 kg of nZVI produced. The milling method and the hydrogen gas method in approach considering the use goethite and hematite particles already synthesized were the most sustainable. Moreover, the sustainability index was found to be influenced by the considered location scenarios as well as the perspectives of the different specialists, which was essential in producing a more accurate and comprehensive evaluation of the aforementioned sustainability methods. Overall, this study significantly contributed to applications of the state-of-the-art life cycle sustainability assessment in studies regarding nanomaterials, employing a simple methodology that included an analysis of different specialists. In addition, this is the first article that uses life cycle sustainability assessment in nanomaterials.