The retention of organic pollutant (OP) in soils is commonly attributed to interactions with soil organic matter (SOM), perhaps overlooking substantial involvement of soil minerals. In this study, 36 soil samples with far-ranging ratios of clay to organic carbon were used to examine contribution of minerals on soil sorption of pentachlorophenol (PCP) and phenanthrene (PHE). Sorption isotherms (n = 216) were fit individually using three typical sorption models, with the most fitted Kd values screened out for quantification of the net mineral contribution to total sorption via development of mathematical model accounting for associations between minerals and SOM. Two mineral-relevant parameters [adsorption distribution coefficient (Kmin) and mineral contribution index (MCI)] were simultaneously defined. Previously reported soil sorption data of PCP, PHE and butachlor (13, 12 and 46, respectively) were also extracted and included to improve the credibility of mathematic model. The average MCI values were calculated as 0.421, 0.405 and 0.512 in PCP, PHE and butachlor treated soils, respectively, very close to or even over than the minerals dominant critical value (0.5). This suggested the significant, or even predominant, contribution of minerals – as compared to SOM. Significant dependence of MCI with four conventional parameters of soil property further offered the possibility to roughly evaluate mineral contributions based on estimated threshold values of soil property parameters (especially TOC). This study provides an accessible approach for predicting the contribution of minerals in soil OP retention, especially highlighting their predominant roles vs. SOM in regulating OP removal in most of subsurface soil or contaminated brownfields where organic carbon content of soil was very low, that was not like what previously believed.

This study investigated the relationship between lead (Pb) speciation determined using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy in <10 μm particulate matter (PM₁₀) from mining/smelting impacted Australian soils (PP, BHK5, BHK6, BHK10 and BHK11) and inhalation exposure using two simulated lung fluids [Hatch’s solution, pH 7.4 and artificial lysosomal fluid (ALF), pH 4.5]. Additionally, elemental composition of Pb rich regions in PP PM₁₀ and the post-bioaccessibility assay residuals were assessed using a combination of Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX) to provide insights into how extraction using simulated lung fluids may influence Pb speciation in vitro. Correlation between Pb speciation (weighted %) and bioaccessibility (%) was assessed using Pearson r (α = 0.1 and 0.05). Lead concentration in PM₁₀ samples ranged from 782 mg/kg (BHK6) to 7796 mg/kg (PP). Results of EXAFS analysis revealed that PP PM₁₀ was dominated by Pb adsorbed onto clay/oxide, while the four BHK PM₁₀ samples showed variability in the weighted % of Pb adsorbed onto clay/oxide and organic matter bound Pb, Pb phosphate, anglesite and galena. When bioaccessibility was assessed using different in vitro inhalation assays, results varied between samples and between assays, Pb bioaccessibility in Hatch’s solution ranged from 24.4 to 48.4%, while in ALF, values were significantly higher (72.9–96.3%; p < 0.05). When using Hatch’s solution, bioaccessibility outcomes positively correlated to anglesite (r:0.6246, p:0.0361) and negatively correlated to Pb phosphate (r: -0.9610, p:0.0041), organic bound Pb (r: -0.7079, p: 0.0578), Pb phosphate + galena + plumbojarosite (r: -0.9350, p: 0.0099). No correlation was observed between Pb bioaccessibility (%) using Hatch’s solution and weighted % of Pb adsorbed onto clay/oxide and between bioaccessibility (%) using ALF and any Pb species. SEM and EDX analysis revealed that a layer of O–Pb–Ca–P–Si–Al–Fe formed during the in vitro extraction using Hatch’s solution.

Chemically oxidative removal of polycyclic aromatic hydrocarbons (PAHs) in soil is related to their occurrence state. Whether the heterogeneity of natural organic matter has an effect on the occurrence of PAHs in soil and, if there is an effect, on the oxidative removal efficiency of PAHs remains unknown. In this study, the removal efficiencies of 16 priority PAHs aged in humic acids (HAs) of different soil aggregate fractions by various oxidants were investigated by combining soil fractionation and microreaction experiments. Results showed that the accumulations of PAHs in particulate HA (P-HA) and microaggregate occluded HA (MO-HA) mainly occurred in the early period of the aging time frame. In contrast, PAH accumulation in non-aggregated silt and clay associated HA (NASCA-HA) was relatively slow and tended to saturate in the late period of the aging time frame. The cumulative contents of PAHs throughout the entire aging period in MO-HA and NASCA-HA were significantly greater than that in P-HA. The aged PAHs in P-HA and NASCA-HA exhibited the highest and lowest removal efficiencies, respectively. This ranking was mainly governed by the molecular size and polarity of HAs. Sodium persulfate and potassium permanganate had the highest removal efficiencies in total PAHs in HAs, with average efficiencies of 85.8% and 79.1%, respectively, in P-HA. Hydrogen peroxide had the lowest degradation efficiency in PAHs. In particular, the degradation efficiency of total PAHs in NASCA-HA was lowered to 31.0%. PAH congeners in HAs showed a large difference in oxidative removal efficiency. Low-ring PAH was more easily degraded than medium- and high-ring PAHs, and in most treatments, fluoranthene and pyrene in the medium ring and benzo[a]pyrene in the high ring demonstrated higher efficiencies than other PAHs with the same number of rings. Our findings are useful in promoting the accurate and green remediation of PAH-contaminated soils.

Sulfide-rich tailings produced by mineral processing are prone to oxidation and cause many pollution problems in the surrounding environment; therefore, this issue has become a focus of attention. The Tongling Shuimuchong tailings reservoir contains a large amount of sulfide minerals, especially pyrrhotite and pyrite. This reservoir features obvious oxidation in the surface layer, and the slab is very hard. Mineralogical and environmental geochemical analyses were performed on tailings with different degrees of oxidation in the Shuimuchong tailings reservoir to investigate the influence of the formation of the hard oxidized layer on environmental pollution in the tailings pond. The samples were first subjected to particle-size analysis. The shallow tailings were mainly composed of medium particle; the proportions of coarse particle and fine tailings particles were equal; and the proportions of clay and silt were less than those of the other size fractions. Mineralogical analysis showed that pyrrhotite and pyrite were replaced by residual structures in the oxide layer. The secondary minerals goethite, hematite and jarosite were attached to the edges and fractures of sulfide minerals. The samples were geochemically analyzed to determine the total concentrations of 5 elements, the pH and the major anions. The maximum SO₄²⁻ concentrations of 33,970 and 32,749 mg/kg were observed at a depth of 40 cm in profiles 1 and 2, respectively. Metal sulfide mineral oxidation in the tailings lowered the pH of the materials to values less than 4. The concentration of HCO₃⁻ (122–635 mg/kg) in the tailings samples was very low, and the concentration of CO₃²⁻ was zero. As (53.2–133.7 mg/kg), Pb (24.2–307.5 mg/kg) and Hg (0.03–0.06 mg/kg) were concentrated in the highly oxidized layer at the surface; the Cd content (0.23–10.5 mg/kg) increased with decreasing oxidation degree of the tailings; and the Cr content (38.0–54.9 mg/kg) fluctuated around a certain value.

Tetracycline (TC) can enter the human body via the soil-vegetable-human food chain; therefore, it is necessary to understand the toxicity of TC to humans through vegetables grown on contaminated soils. The present study combined an enzyme-linked immunosorbent assay method and an HL-7702 cell model and assessed the bioavailability and toxicity of TC from pak choi (Brassica campestris L. ssp. chinensis) grown on TC-contaminated soils. The results showed that the degradation rate of TC in black soil was significantly higher than that in purplish clay, while the results for TC uptake in pak choi were opposite. The bioaccessibility of TC was found to be higher in pak choi grown on purplish clay (5.67–7.59%) than in that grown on black soil (5.22–6.77%). It is suggested that soil properties contribute to the uptake of TC by pak choi. More fertile soil contained lower TC concentrations and thus mediated lower TC toxicity to humans. It may seem comforting that TC concentrations in the edible parts of pak choi are often found to be below safe limits. However, the TC diagnosis method showed that even moderate increases in TC concentrations in pak choi may induce oxidative stress, liver injury, mitochondrial cristae and rough endoplasmic reticulum swelling, and early apoptosis in liver cells HL-7702. The pak choi grown in purplish clay showed higher TC cytotoxicity than that grown in black soil. The TC cytotoxicity of raw pak choi was found to be higher than that of cooked pak choi. These results provide direct evidence of effective ways to prevent TC toxicity in humans.

Copper oxide nanoparticles (CuO NPs) is one of the most commonly used metal oxide nanoparticles for commercial and industrial products. An increase in the manufacturing and use of the CuO NPs based products has increased the likelihood of their release into the aquatic environment. This has attracted major attention among researchers to explore their impact in human as well as environmental systems. CuO NPs, once released into the environment interact with the biotic and abiotic constituents of the ecosystem. Hence the objective of the study was to provide a holistic understanding of the effect of abiotic factors on the stability and aggregation of CuO NPs and its correlation with their effect on the development of zebrafish embryo. It has been observed that the bioavailability of CuO NPs decrease in presence of humic acid (HA) and heteroagglomeration of CuO NPs occurs with clay minerals. CuO NPs, CuO NPs + HA and CuO NPs + Clay significantly altered the expression of genes involved in development of dorsoventral axis and neural network of zebrafish embryos. However, the presence of HA with clay showed protective effect on zebrafish embryo development. These findings provide new insights into the interaction of NPs with abiotic factors and combined effects of such complexes on developing zebrafish embryos genetic markers.

Chemical compositions of streambed biofilms from a major river of central Japan (the Kushida River) were obtained, with data of associated sediments (fine-grained fractions < 63 μm) and dissolved components of waters, in order to provide preliminary information about biogeochemical significance of streambed biofilms. During the sampling period (July 31st to August 3rd, 2013), dissolved components of the river waters were influenced by the dam reservoir. Concentrations of NO₃⁻, silica (as Si), SO₄²⁻, PO₄³⁻ and Ca²⁺ decreased across the dam, whereas Fe and Mn increased across the dam, and then decreased downstream rapidly. Streambed biofilms contain significant amount of non-nutrient elements such as Al (up to 21% as Al₂O₃ on water and others-free basis), indicating that they are contaminated as siliciclatic (silt and clay) materials. Siliciclastic materials in the biofilms are basically compositionally similar to fine-grained (<63 μm) fractions of streambed sediments. However, some elements such as Ca, P, Mn, and Zn are markedly enriched in the biofilms. Particularly, Mn concentrations in the biofilm samples collected just below the dam reservoir are very high (∼4.0 wt %), probably due to accumulation from the discharged water. Concentrations of trace elements such as P, Cr, Cu, Zn and V appear to be controlled by amounts of Fe-oxides and/or Mn-oxides in biofilms. Numbers of factors are involved in controlling chemical compositions of streambed biofilms, including amount of contaminated siliciclastics, authigenic mineral formation, adsorption of dissolved materials and microbial metabolisms. As demonstrated by this study, systematic analyses including major elements and comparison with associated sediments and waters could reveal biogeochemistry of this complex system.

The present study for the first time demonstrated the interactions of metal oxide (MO) nano-pollutants (CuO and Al2O3-NPs) with tissues and cellular DNA of tomato plants grown in soil sand: silt: clay (667:190:143) and Hoagland-hydroponic system and assessed the hazardous effects of NPs on cell physiology and biochemistry. Results of SEM equipped with EDX revealed attachment of variably shaped CuO-NPs (18 nm) and Al2O3-NPs (21 nm) on roots, and internalization followed by translocation in plants by ICP-MS and TEM. Significant variations in foliage surface area, chlorophyll, proteins, LPO, and antioxidant enzymes were recorded. Roots and shoots accumulated 225.8 ± 8.9 and 70.5 ± 4 μgAl g−1 DW, whereas Cu accumulation was 341.6 ± 14.3 (roots) and 146.9 ± 8.1 μg g−1 DW (shoots) which was significant (p ≤ 0.0005) as compared to control. The total soluble protein content in roots, shoots, and leaves collected from Al2O3-NPs treated plants increased by 120, 80, and 132%, respectively while in CuO-NPs treatments, the increase was 68 (roots), 36 (shoots), and 86% (leaves) over control. The level of antioxidant enzymes in plant tissues was significantly (p ≤ 0.05) higher at 2000 μg ml−1 of MONPs over control. A dose-dependent increase in reactive oxygen species (ROS), biphasic change of lower and higher fluorescence in mitochondria due to dissipation of mitochondrial membrane potential (ΔΨm) and membrane defects using propidium iodide were observed. Comparatively, CuO-NPs induced higher toxicity than Al2O3-NPs. Perceptible changes in proteins (amide-I & II), cellulose, glucose, galactose and other carbohydrates were observed under FT-IR. The binding studies with TmDNA showed fluorescence quenching of EtBr-TmDNA and acridine orange-TmDNA complex only by CuO-NPs with -ΔG and +ΔH and +ΔS values. However, Al2O3-NPs induced lesser change in TmDNA conformation. Conclusively, the results are novel in better demonstrating the mechanistic basis of nano-phyto-toxicity and are important which could be used to develop strategies for safe disposal of Al2O3-NPs and CuO-NPs.

Compacted clay is widely used as capillary barriers in landfill final cover system. Recently, biochar amended clay (BAC) has been proposed as a sustainable alternative cover material. However, the effects of biochar on saturated hydraulic conductivity (kₛₐₜ) of clay with high degree of compaction is not yet understood. The present study aims to investigate the effects of biochar on kₛₐₜ of compacted kaolin clay. Soil specimens were prepared by amending kaolin clay with biochar derived from peanut-shell at 0, 5 and 20% (w/w). The kₛₐₜ of soil specimens was measured using a flexible water permeameter. The effects of biochar on the microstructure of the compacted clay was also investigated using MIP. Adding 5% and 20% of biochar increased the kₛₐₜ of compacted kaolin clay from 1.2 × 10⁻⁹ to 2.1 × 10⁻⁹ and 1.3 × 10⁻⁸ ms⁻¹, respectively. The increase in kₛₐₜ of clay was due to the shift in pore size distribution of compacted biochar-amended clay (BAC). MIP results revealed that adding 20% of biochar shifted the dominant pore diameter of clay from 0.01–0.1 μm (meso– and macropores) to 0.1–4 μm (macropores). Results reported in this communication revealed that biochar application increased the kₛₐₜ of compacted clay, and the increment was positively correlated to the biochar percentage.

The use of the soil can alter its functionality and influence the (bio)availability of any contaminants present. Our study considers two types of agricultural soils, rainfed and olive soils, managed according to conventional practices that apply contaminants directly to the soil (fertilizers, pesticides, fungicides, etc.) and receive contaminants from the atmosphere (traffic, industry, etc.); and a forest soil that is not subject to these agricultural practices. In this scenario, we consider a mixture of 16 trace elements (As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, Sb, Sn, V and Zn), since their interactions with the soil can produce synergistic and/or antagonistic effects that are not considered in most studies. We studied whether the content and (bio)availability of low concentrations of a mixture of trace elements affect the soil functionality in terms of the activity of some key enzymes We analysed the total, potentially and immediately available fractions, the soil parameters and soil enzyme activity. The results show that the functionality of the soils studied was affected despite the low concentrations of trace elements. The highest concentrations of total trace elements and available fractions were found in forest soils compared to the other two uses. Soil enzyme activity is best explained by the potentially available fraction of a mixture of trace elements and physico-chemical soil variables. In our study, pH, total nitrogen, organic carbon and fine mineral particles (silt and clay) had an influence on soil enzyme activity and the (bio)available fractions of trace elements.