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.

Organic matter, as an electron donor, plays a vital role in As mobilization mediated by microorganisms during reductive dissolution of Fe/Mn oxides in shallow aquifers. However, the specific types and sources of organic matter involved in biogeochemical processes accelerating As mobilization are still controversial. Both sediment and groundwater samples were collected at different depths from aquifers of the Hetao Basin, a typical inland basin hosting high As groundwater. Sedimentary lipids and their compound-specific carbon isotope ratios were analyzed to evaluate characteristics and sources of organic matter. Results show that sedimentary As were well correlated with Fe and Mn oxides, suggesting that As exist as Fe/Mn oxide bound forms. Groundwater As far exceeded the drinking water guide value of 10 μg/L. Moreover, As concentrations in shallow groundwater were relatively higher. Lipids in clay were mainly originated from terrestrial higher plants, while that in fine sand samples were derived from terrestrial higher plants, microorganism and petroleum. Shallow fine sand samples were also characterized by evident in-situ biodegradation. Compound-specific carbon isotope compositions of sedimentary lipids showed that short-chain n-alkanes and n-alkanoic acids had more positive δ13C values compared to long-chain compounds, especially in shallow fine sand samples. δ13CTOC were also low in shallow fine sand samples. These results jointly indicate that these lipids in shallow fine sand samples acted as carbon source for indigenous microorganism and the short-chain components were particularly more vulnerable to biodegradation, which may contribute to high As concentrations in shallow groundwater. The new findings provide the first evidence that short chain length n-alkyl compounds afforded a source of potential electron donors for microbially mediated As mobilization process in the shallow aquifers.

Since the introduction of standardized nematode toxicity assays by the American Society for Testing and Materials (ASTM) and International Organization for Standardization (ISO), many studies have reported their use. Given that the currently used standardized nematode toxicity assays have certain limitations, in this study, we examined the use of a novel nematode offspring counting assay for evaluating soil ecotoxicity based on a previous soil-agar isolation method used to recover live adult nematodes. In this new assay, adult Caenorhabditis elegans were exposed to soil using a standardized toxicity assay procedure, and the resulting offspring in test soils attracted by a microbial food source in agar plates were counted. This method differs from previously used assays in terms of its endpoint, namely, the number of nematode offspring. The applicability of the bioassay was demonstrated using metal-spiked soils, which revealed metal concentration-dependent responses, and with 36 field soil samples characterized by different physicochemical properties and containing various metals. Principal component analysis revealed that texture fraction (clay, sand, and silt) and electrical conductivity values were the main factors influencing the nematode offspring counting assay, and these findings warrant further investigation. The nematode offspring counting assay is a rapid and simple process that can provide multi-directional toxicity assessment when used in conjunction with other standard methods.

This study is the first quantitative report on petroleum biomarkers from the coral reefs systems of the Persian Gulf. 120 reef surface sediment samples from ten fragile coral reef ecosystems were collected and analyzed for grain size, biogenic elements, elemental ratios, and petroleum biomarkers (n-alkanes, PAHs¹ and Hopanes) to assess the sources and early diagenesis of sedimentary organic matter. The mean grain size of the reef sediments ranged from 13.56 to 37.11% (Clay), 26.92 to 51.73% (Sand) and 35.97 to 43.85% (Silt). TOC² (3.35–9.72 mg.g⁻¹) and TON³ (0.4–1.10 mg.g⁻¹) were identified as influencing factors on the accumulation of petroleum hydrocarbons, whilst BC⁴ (1.08–3.28 mg.g⁻¹) and TIN⁵ (0.13–0.86) did not exhibit any determining effect. Although BC and TIN demonstrated heterogeneous spatial distribution, TOC and TON indicated homogenous distribution with continually upward trend in concentration from the east to west ward of the Gulf. The mean calculated TOC/TN ratios vacillated according to the stations (p < 0.05) from 2.96 at Shidvar Island to 8.64 at Hengam Island. The high TOC/TN ratios were observed in the Hengam (8.64), Kharg (8.04) and Siri (6.29), respectively, suggesting a predominant marine origin. The mean concentrations of ∑C11–35n-alkanes, ∑30 PAHs and ∑9Hopanes were found in the ranges of 385–937 μg.g⁻¹dw, (overall mean:590 μg.g⁻¹dw), 326–793 ng.g⁻¹dw (499 ng.g⁻¹dw), 88 to 568 ng.g⁻¹ d (258 ng.g⁻¹dw), respectively. Higher concentrations of detected petroleum biomarkers in reef sediments were chiefly distributed near main industrial areas, Kharg, Lavan and Siri, whilst the lower concentrations were in Hormoz and Qeshm. In addition, one-way ANOVA⁶ analysis demonstrated considerably significant differences (p < 0.05) among concentration of detected total petroleum hydrocarbons between most sampling locations. Some sampling sites especially Kharg, Lavan, Siri and Lark indicated higher concentration of n-alkanes due to the higher maintenance of organic matter by high clay content in the sediments. Furthermore, most sediment samples, except for Hormoz, Qeshm and Hengam showed an even carbon preference for n-alkanes which could be correlated to bacterial input. NPMDS⁷ analysis also demonstrated that among the congeners of petroleum biomarkers, n-C12,n-C14, n-C16,n-C18 and n-C20 for n-alkanes, Phe⁸ and Naph⁹ along with their Alkyl homologues for PAHs (2–3 rings accounted for 60%) and C30αβ and C29αβ for Hopanes were discriminated from their other congeners in the whole study area. Our results based on the PCA¹⁰ analysis and diagnostic indices of AHs¹¹ and PAHs along with ring classification of PAHs, in addition, the ubiquitous presence of UCM,¹² and Hopanes revealed that the main sources of the pollution were petroleum and petroleum combustion mainly from offshore oil exploration and extraction, discharge of pollutants from shipping activities.