Mining and smelting activities have contaminated the environment with trace metals (TMs) at a worldwide scale for at least two millennia. A combination of chemical approaches and active biomonitoring was performed to analyse the environmental availability and bioavailability of TM palaeo-pollution in a former PbAg mining district in the Vosges Mountains, France. Along a soil TM contamination gradient that covered eight stations, including two archaeological mining sites, the toxicokinetics of six TMs (Pb, Cd, As, Ag, Co, Sb) in the snail Cantareus aspersus revealed that palaeo-pollution from the studied sites remains bioavailable. This study provides the first data on the accumulation kinetics of Ag and Co for C. aspersus. The environmental availability of the TMs was estimated with three chemical extraction methods (aqua regia, EDTA 50 mM, CaCl2 10 mM). Univariate regression analyses showed that EDTA extraction is the best method for estimating the bioavailability of Pb, As, Ag, Co and Sb to snails. None of the three extractants was efficient for Cd. A multivariate analysis of bioaccumulation data revealed that TM bioavailability and transfer were modulated by exposure sources (soil, humus and vegetation) rather than by soil physico-chemical characteristics. Hence, although the deposition of mining wastes dates back several centuries, these wastes still represent a source of contamination that must be considered to develop relevant site management and environmental risk assessment.

Phytoextraction is one of the most promising technologies for the remediation of metal contaminated soils. Changes in soil metal availability during phytoremediation have direct effects on removal efficiency and can also illustrate the interactive mechanisms between hyperaccumulators and metal contaminated soils. In the present study the changes in metal availability, desorption kinetics and speciation in four metal-contaminated soils during repeated phytoextraction by the zinc/cadmium hyperaccumulator Sedum plumbizincicola (S. plumbizincicola) over three years were investigated by chemical extraction and the DGT-induced fluxes in soils (DIFS) model. The available metal fractions (i.e. metal in the soil solution extracted by CaCl2 and by EDTA) decreased greatly by >84% after phytoextraction in acid soils and the deceases were dramatic at the initial stages of phytoextraction. However, the decreases in metal extractable by CaCl2 and EDTA in calcareous soils were not significant or quite low. Large decreases in metal desorption rate constants evaluated by DIFS were found in calcareous soils. Sequential extraction indicated that the acid-soluble metal fraction was easily removed by S. plumbizincicola from acid soils but not from calcareous soils. Reducible and oxidisable metal fractions showed discernible decreases in acid and calcareous soils, indicating that S. plumbizincicola can mobilize non-labile metal for uptake but the residual metal cannot be removed. The results indicate that phytoextraction significantly decreases metal availability by reducing metal pool sizes and/or desorption rates and that S. plumbizincicola plays an important role in the mobilization of less active metal fractions during repeated phytoextraction.

A pot experiment was conducted to investigate the effects of biochars on the availability of heavy metals (Cd, Cu, Mn, Ni, Pb, and Zn) to ryegrass in an alkaline contaminated soil. Biochars only slightly decreased or even increased the availability of heavy metals assesses by chemical extractant (a mixture of 0.05 mol L−1 ethylenediaminetetraacetic acid disodium, 0.01 mol L−1 CaCl2, and 0.1 mol L−1 triethanolamine). The significantly positive correlation between most chemical-extractable heavy metals and the ash content in biochars indicated the positive role of ash in this extraction. Biochars significantly reduced the plant uptake of heavy metals, excluding Mn. The absence of a positive correlation between the chemical-extractable heavy metals and the plant uptake counterparts (except for Mn) indicates that chemical extractability is probably not a reliable indicator to predict the phytoavailability of most heavy metals in alkaline soils treated with biochars. The obviously negative correlation between the plant uptake of heavy metals (except for Mn) and the (O + N)/C and H/C indicates that biochars with more polar groups, which were produced at lower temperatures, had higher efficiency for reducing the phytoavailability of heavy metals. The significantly negative correlations between the plant uptake of Mn and ryegrass biomass indicated the “dilution effect” caused by the improvement of biomass. These observations will be helpful for designing biochars as soil amendments to reduce the availability of heavy metals to plants in soils, especially in alkaline soils.

The influence of bacteria on the transport and deposition behaviors of carbon nanotubes (CNTs) in quartz sand was examined in both NaCl (5 and 25 mM ionic strength) and CaCl2 (0.3 and 1.2 mM ionic strength) solutions at unadjusted pH (5.6–5.8) by direct comparison of both breakthrough curves and retained profiles in both the presence and absence of bacteria. Two types of widely utilized CNTs, i.e., carboxyl- and hydroxyl-functionalized multi-walled carbon nanotubes (MWCNT-COOH and MWCNT-OH, respectively), were employed as model CNTs and Escherichia coli was utilized as the model bacterium. The results showed that, for both types of MWCNTs under all examined conditions, the breakthrough curves were higher in the presence of bacteria, while the retained profiles were lower, indicating that the co-presence of bacteria in suspension increased the transport and decreased the deposition of MWCNTs in porous media, regardless of ionic strength or ion valence. Complementary characterizations and extra column tests demonstrated that competition by bacteria for deposition sites on the quartz sand surfaces was a major (and possibly the sole) contributor to the enhanced MWCNTs transport in porous media.

With the development and application of graphene oxides (GO), the potential toxicity and environmental behavior of GO has become one of the most forefront environmental problems. Herein, a novel nanoscale layered double hydroxides (glycerinum-modified nanocrystallined Mg/Al layered double hydroxides, LDH-Gl), layered double oxides (calcined LDH-Gl, LDO-Gl) and metallic oxide (TiO2) were synthesized and applied as superior coagulants for the efficient removal of GO from aqueous solutions. Coagulation of GO as a function of coagulant contents, pH, ionic strength, GO contents, temperature and co-existing ions were studied and compared, and the results showed that the maximum coagulation capacities of GO were LDO-Gl (448.3 mg g−1) > TiO2 (365.7 mg g−1) > LDH-Gl (339.1 mg g−1) at pH 5.5, which were significantly higher than those of bentonite, Al2O3, CaCl2 or other natural materials due to their stronger reaction active and interfacial effect. The presence of SO32− and HCO3− inhibited the coagulation of GO on LDH-Gl and LDO-Gl significantly, while other cations (K+, Mg2+, Ca2+, Ni2+, Al3+) or anion (Cl−) had slightly effect on GO coagulation. The interaction mechanism of GO coagulation on LDO-Gl and TiO2 might due to the electrostatic interactions and strong surface complexation, while the main driving force of GO coagulation on LDH-Gl might be attributed to electrostatic interaction and hydrogen bond, which were further evidenced by TEM, SEM, FT-IR and XRD analysis. The results of natural environmental simulation showed that LDO-Gl, TiO2 or other kinds of natural metallic oxides could be superior coagulants for the efficient elimination of GO or other toxic nanomaterials from aqueous solutions in real environmental pollution cleanup.

Dissolved organic matters (DOMs) extracted from wheat straw (SDOM) and cow manure (MDOM) were used to investigate their effects on the suspension stability and aggregation of multi-walled carbon nanotubes (MWCNTs). Two types of DOM can effectively disperse and stabilize the MWCNTs. At initial MWCNT concentration of 500 mg/L, suspended MWCNT concentration ranged from 8.0 to 17.9 mg/L as DOM were varied from 50 to 200 mg/L dissolved organic carbon (DOC). The critical coagulation concentration (CCC) values were estimated to be 41.4 mM NaCl and 5.3 mM CaCl2 in the absence of DOM. The presence of SDOM and MDOM significantly retarded the aggregation rate of MWCNTs. The CCC values increased to 120 mM NaCl and 14.8 mM CaCl2 at SDOM concentration of 20 mg/L DOC. Due to its higher aromaticity and molecular weight, MDOM showed higher ability to stabilize MWCNTs, with CCC values of 201 mM and 15.8 mM at 20 mg/L DOC. These findings revealed that DOMs originated from agricultural wastes will have great impact on the dispersion and stabilization of MWCNTs, thus their fate in the aquatic environment.

The increasing use of herbicides in sugarcane production has increased environmental concern regarding the fate of these compounds, especially when they are used in mixtures. Among the various processes that determine the behavior of molecules in the environment, leaching stands out. In this context, the aim of this study was to evaluate the leaching of a mixture of hexazinone, sulfometuron-methyl, and diuron in soils with contrasting textures. A completely randomized experimental design containing three replications in a 2 × 6 factorial arrangement was used, with two soils (alfisol–Paleudult, sandy clay texture and ultisol–typic Hapludalf, sandy loam texture) and six depths (0–0.05, 0.05–0.10, 0.10–0.15, 0.15–0.20, 0.20–0.25, and 0.25–0.30 m). Three glass columns of 50 cm were used for each soil. The dose used was 391.0 + 33.35 + 1386.9 g a.i. ha⁻¹ of hexazinone, sulfometuron-methyl and diuron, respectively. After applying the mixture to the top of each column, rainfall simulation with 200 mm of 0.01 mol L⁻¹ CaCl₂ solution was applied for 48 h. The leachates were collected at 6, 12, 24, 36, and 48 h. The chromatographic determinations of the herbicides were performed by high-performance liquid chromatography (HPLC) with a UV-Vis detector. For hexazinone, the highest percentage recovery in the soil with a sandy clay texture occurred at a depth of 0.10–0.15 m, with 40 % recovered, while in the soil with a sandy loam texture, the most part was recovered at a depth of 0.25–0.30 m. Diuron demonstrated little mobility in the soil and was detected in most cases only in the surface layer (up to 0.10 m) in both soils. Sulfometuron-methyl, in soil with a sandy clay texture, was detected to a depth of 0.15–0.20 m with the highest concentration found at a depth of 0–0.05 m, while in sandy loam soil, a higher concentration was found at a depth of 0.10–0.15 m; this herbicide was detected down to 0.25–0.30 m. These results show that the soil texture directly influences the leaching of hexazinone, sulfometuron-methyl, and diuron.

Elevated plant-available cadmium (Cd) in soils results in contamination to cacao (Theobroma cacao L) beans. Effectiveness of vermicompost and zeolite in reducing available Cd in three cacao-growing soils was studied under laboratory conditions. Sorption–desorption experiments were conducted in soils and amendments. Cadmium was added at 0 or 5 mg kg⁻¹ (spiked), then, amendments were incorporated at 0, 0.5, or 2 %. Amended soils were incubated at room temperature for 28 days. Plant-available Cd was determined using 0.01 M CaCl₂ (WSE) and Mehlich 3 (M3) extraction procedures in subsamples taken from individual bags at six time intervals. Soils and amendments displayed different sorption characteristics and a better fit was attained with Freundlich model (R ² > 0.82). Amendments were ineffective in reducing extractable Cd in non-spiked soils. In Cd-spiked soils, vermicompost at 2 % significantly reduced WSE-Cd (P < 0.01) from 3.36, 0.54, and 0.38 mg kg⁻¹ to values lower that instrument’s detection in all the three soils and significantly diminished M3-extractable Cd (P < 0.05) from 4.62 to 4.11 mg kg⁻¹ in only one soil. Vermicompost at 0.5 % significantly decreased WSE-Cd (P < 0.01) from 3.04 and 0.31 to 1.69 and 0.20 mg kg⁻¹, respectively, in two soils with low sorption capacity for Cd. In contrast, zeolite failed to reduce WSE- or M3-extractable Cd in all studied soils. A negative correlation occurred between soil pH and WSE-Cd (r > −0.89, P < 0.01). The decrease in WSE-Cd appears to be associated with the increase in pH of the vermicompost-amended soils.

Accumulation of divalent manganese (Mn) and its toxicity in the green alga Scenedesmus quadricauda was studied at circumneutral pH (6.5). A comparison of two applied concentrations (10 or 100 μM) of MnCl₂, MnSO₄, and Mn(NO₃)₂ indicated that mainly sulfate evoked higher Mn accumulation. On the other hand, nitrate rather depleted antioxidative enzyme activities (APX, CAT, SOD), leading to an increase in ROS formation as proven by fluorescence microscopy. Subsequent experiments revealed that increase in pH (from 4.5 to 9.5) increased also Mn content but typically depleted amounts of reduced glutathione and phytochelatin 2. We also measured the size of particles formed from the manganese salts at pH 9.5. Competitive experiment between Ca/K salts (CaCl₂, CaSO₄, Ca(NO₃)₂, KCl, K₂SO₄, KNO₃) and Mn (as Mn sulfate) showed a negative relation between Ca and Mn amount but KNO₃ stimulated Mn accumulation. Microscopy revealed that mainly K salts elevated plasma membrane damage (Acridine orange staining). Data indicate that not only pH but also accompanying anion affects Mn accumulation and that Ca salts may affect Mn toxicity.

For the purpose of clarifying the chemical nature of fly ashes, the raw fly ashes were collected from the stacks of 17 fixed sources consisting of 15 municipal waste incinerators, a metal melting factory, and a cement plant all of which are located in the western Japan from Nov. 2000 to Jan. 2007. The municipal waste incinerators were successfully classified into four groups in terms of the relative mass ratios between chloride, potassium, and sodium. Sodium, potassium, and calcium were found abundantly in fly ashes collected from all four types of municipal waste incinerators. The theoretical estimation of chlorine form suggested that the form of NaCI, KCl, MgCl, and CaCl₂ accounted for approximately 55 % of total chlorine in raw fly ash. Trace heavy metals (i.e., Zn, Mn, Pb, Cu, Cr, Ni, and V) were preferentially enriched in the ambient PM₂.₅ which was strongly influenced by regional stationary sources (including municipal waste incinerators). The water-soluble OC to TC fraction in the fly ashes of municipal waste incinerator, metal furnace, and cement plant was estimated as 56.8, 79.0, and 89.6 %, respectively.