In former coal transformation plants (coking and gas ones), the major organic contamination of soils is coal tar, mainly composed of polycyclic aromatic compounds (PACs). Air oxidation of a fresh coal tar was chosen to simulate the abiotic natural attenuation impact on PAC-contaminated soils. Water-leaching experiments were subsequently performed on fresh and oxidized coal tars to study the influence of oxidation on dissolved organic matter (DOM) quality and quantity. The characterization of the DOM was performed using a combination of molecular and spectroscopic techniques (high-performance liquid chromatography–size-exclusion chromatography (HPLC-SEC), 3D fluorescence, and gas chromatography coupled with mass spectrometry (GC–MS)) and compared with the DOM from contaminated soils sampled on the field exposed to natural attenuation for several decades. An increase in the oxygenated polycyclic aromatic compound concentrations was observed with abiotic oxidation both in the coal tar and the associated DOM. Polycyclic aromatic hydrocarbon concentrations in the leachates exceeded pure water solubility limits, suggesting that co-solvation with other soluble organic compounds occurred. Furthermore, emission excitation matrix analysis combined with synchronous fluorescence spectra interpretation and size-exclusion chromatography suggests that oxidation induced condensation reactions which were responsible for the formation of higher-molecular weight compounds and potentially mobilized by water. Thus, the current composition of the DOM in aged soils may at least partly result from (1) a depletion in lower-molecular weight compounds of the initial contamination stock and (2) an oxidative condensation leading to the formation of a higher-molecular weight fraction. Abiotic oxidation and water leaching may therefore be a significant combination contributing to the evolution of coal tar-contaminated soils under natural attenuation.

The potential use of biochar from olive mill waste for in situ remediation of metal contaminated soils was evaluated. Biochar was mixed with metal contaminated soil originating from the vicinity of an old zinc smelter. Soil–biochar mixtures were equilibrated for 30 and 90 days. At these time points, Ca(NO₃)₂exchangeable metals were determined, and effects of the biochar amendment on soil toxicity were investigated using plants, bacteria, and earthworms. Bean (Phaseolus vulgaris) growth, metal content, antioxidative enzymes activities, and soluble protein contents were determined. Furthermore, effects on soil microbial communities (activity, diversity, richness) were examined using Biolog ECOplates. After 120 days of soil–biochar equilibration, effects on weight and reproduction of Eisenia foetida were evaluated. With increasing biochar application rate and equilibration period, Ca(NO₃)₂exchangeable metals decreased, and growth of bean plants improved; leaf metal contents reduced, the activities of antioxidative stress enzymes decreased, and soluble protein contents increased. Soil microbial activity, richness, and diversity were augmented. Earthworm mortality lowered, and their growth and reproduction showed increasing trends.

The objective of this work was to study the degradation and mineralization of ethylenethiourea (ETU) in water by ozonation at different pH values and in the presence of hydrogen peroxide. Degradation experiments were performed using an initial ETU concentration of 50 ppm for 180 min with a gas flux of 0.25 dm³ min⁻¹and an O₃production rate of 12.1 mg min⁻¹. Degradation of by-products was monitored by direct injection electrospray ionization mass spectrometry (ESI-MS), ETU concentration was determined by HPLC-UV, and its mineralization was detected by total organic carbon (TOC) analysis. Optimum degradation of ETU in water was observed at pH = 11, whereas at pH = 3, the degradation of ETU was slowest, indicating that the reaction occurred through different mechanisms. The additional effects of hydroxyl radicals formed at the highest pH can be used to explain the results obtained in this study. Peroxone experiments were carried out in the presence of 400 and 800 mg L⁻¹H₂O₂; the degradation of ETU was faster at 400 mg L⁻¹H₂O₂. This was attributed to the scavenging effect of the excess H₂O₂. ETU treatment by ozonation produced several by-products of degradation such as ethylene urea and 2-imidazoline.

Selenium (Se) can alleviate the toxicity of antimony (Sb) in plants; however, the associated mechanisms have not been fully clarified. In this study, we hypothesize that Se can affect the subcellular distribution of Sb to regulate Sb toxicity. To test our hypothesis, two nested hydroponic experiments were performed by using paddy rice (Fengmeizhan). The results showed that Sb exerted toxic effects on the growth of paddy rice, and Se caused beneficial effects that were limited to the shoot growth. In general, Se and Sb mutually showed antagonistic effects on their uptake and concentrations in different subcellular fractions. However, in some cases, the stimulation effects of Sb on the Se concentration in chlorophyll (Chl) and cytosol (Cy) fractions or of Se on the Sb concentration in the cell wall fraction (Cw) were also observed in the shoots, which might suggest that Sb detoxification by Se is also related to the migration of both Se and Sb in cells. Selenium and Sb were primarily concentrated in the Cw and Cy, suggesting the important roles of these two fractions in detoxifying Se and Sb. When paddy rice was subjected to increasing Sb concentrations and a fixed Se concentration, most of the Se in the shoots was sequestered in the Cy (59.81–79.51 % of total Se) and more Se was transferred into the inner cell from Cw; however, in the roots, Se was primarily concentrated in the Cw (53.28–72.10 %). When paddy rice was exposed to increasing Se concentrations with a fixed Sb concentration, the Cw in both the shoots and roots might play an important role in binding Se, especially in the roots where up to 78.92 % of the total Se was sequestered in the Cw.

The weight; testis/body coefficient; levels of LDH, SDH, SODH, G-6PD, and testosterone; cell cycle; and cell apoptosis of the male mice were influenced after being treated with 200 mg/[kg/day] of rare earths suspension for 3 weeks. The “Raman fingerprints” of the human sperm DNA exposed to 0.040 mg/ml CeCl₃ were very different from those of the untreated; the Raman bands at 789 cm⁻¹ (backbone phosphodiester), PO₄ backbone at 1,094 cm⁻¹, methylene deformation mode at 1,221 cm⁻¹, methylene deformation mode at 1,485 cm⁻¹, and amide II at 1,612 cm⁻¹, of which intensities and shifts were changed, might be the diagnostic biomarkers or potential therapeutic targets. The injury mechanism might be that the rare earths influence the oxidative stress and blood testosterone barrier, tangle the big biomolecule concurrently, which might cause the testicular cells and vascular system disorder and/or dysfunction, and at the same time change the physical and chemical properties of the sperm directly.

Microbial processes play a vital important role in the removal of contaminants in constructed wetland (CW). However, the microbial physiology and community structure can be influenced by environmental conditions. In this study, four pilot-scale integrated vertical-flow constructed wetlands (IVCWs) were employed to treat domestic and nitrified wastewaters. The microbial properties, along with their response to wastewater quality characteristics and seasonal variation, were determined. The results showed higher Shannon–Weiner diversity (H) and evenness (E) index of fatty acids (FAs), and relative abundances of signature FAs in down-flow cells and in the systems fed with domestic wastewater (DW). The relative abundances of fungi and gram-negative and aerobic bacteria were greater in up-flow cells. The dominant anaerobic bacteria found in most cells might be accounted for the prevailing anaerobic environment within the wetland beds, which could mean that the system fed with nitrified wastewater (NW) should perform better in nitrogen removal. The redundancy analysis (RDA) showed that pollutant concentrations, especially organic matter, influence the FA compositions greatly, and the most significant difference of microbial community structures was detected in down-flow cells fed with DW and up-flow ones with NW. The branched FAs, which could be used to represent anaerobic bacteria, were observed in down-flow cells treating DW and had a significant positive correlation with chemical oxygen demand (COD) concentration, probably suggesting the important role of anaerobic bacteria in organic matter degradation in the IVCWs. Seasonal variation, however, did not greatly influence the microbial community structure in the IVCWs.

In this study, we investigated Cd, Cr, Cu, Pb, and Zn in the seagrass Posidonia oceanica (L.) Delile leaves and in the brown algae Cystoseira sp. sampled along a 280-km transect in the Tyrrhenian Sea, from the Ustica to Linosa Islands (Sicily, Italy) with the aim to determine their control charts (baseline levels). By applying the Johnson’s (Biometrika 36:149–175, 1949) probabilistic method, we determined the metal concentration overlap ranges in a group of five biomonitors. Here, we propose the use of the indexes of bioaccumulation with respect to the lowest (L′ᵢ) and the highest (Lᵢ) extreme values of the overlap metal concentration ranges. These indexes allow the identification of the most opportune organism (or a suite of them) to better managing particular environmental conditions. Posidonia leaves have generally high Lᵢindexes for Cd, Cu, Pb, and Zn, and this suggests its use as biomonitor for baseline marine areas. Our results confirm the high aptitude of Patella as a good biomonitor for Cd levels in seawater. From this study, Ustica resulted with higher levels of Cd, Cu, Pb, and Zn than the other Sicilian Islands.

The applicability of an in situ electrokinetic process with a parallel electrode configuration was evaluated to treat an As-, Cu-, and Pb-contaminated paddy rice field in full scale (width, 17 m; length, 12.2 m; depth, 1.6 m). A constant voltage of 100 V was supplied and electrodes were spaced 2 m apart. Most As, Cu, and Pb were bound to Fe oxide and the major clay minerals in the test site were kaolinite and muscovite. The electrokinetic system removed 48.7, 48.9, and 54.5 % of As, Cu, and Pb, respectively, from the soil during 24 weeks. The removal of metals in the first layer (0–0.4 m) was higher than that in the other three layers because it was not influenced by groundwater fluctuation. Fractionation analysis showed that As and Pb bound to amorphous Fe and Al oxides decreased mainly, and energy consumption was 1.2 kWh/m³. The standard deviation of metal concentration in the soil was much higher compared to the hexagonal electrode configuration because of a smaller electrical active area; however, the electrode configuration removed similar amounts of metals compared to the hexagonal system. From these results, it was concluded that the electrokinetic process could be effective at remediating As-, Cu-, and Pb-contaminated paddy rice field in situ.

This work aimed to evaluate the effect of surfactants on the removal of aqueous nC₆₀ aggregates by coagulation-filtration process and assess the acute toxicity of filtrates by Microtox test. Three surfactants including cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and Triton X-100 (TX100) were selected representing cationic, anionic, and nonionic types, respectively. Results showed that the change of physicochemical properties of nC₆₀ associating with different types of surfactants determined nC₆₀’s removal efficiency and acute toxicity. CTAB increased the number of large particles. It also changed the zeta potential of nC₆₀ from negative to positive, leading to the low removal rates (17.3–50.2 %) when CTAB concentration was designed in the range of 0.03–1 g/L, and the filtrates showed acute toxicity to bioluminescent bacteria (inhibition rate > 80 %). On the contrary, TX100 obviously increased the proportion of small particles, and it is noteworthy that even less than 1 mg/L of nC₆₀ (20 % of the initial concentration) with TX100 remaining in filtrates could evoke phototoxicity due to reactive oxygen species (ROS) generation under UV irradiation. Compared to CTAB and TX100, SDS exerted an effect on the removal process and toxicity of nC₆₀ only when concentration was beyond the critical micelle concentration (CMC; 2.5 g/L). These findings collectively suggest that characteristics of nC₆₀ are flexible and strongly dependent on surfactant modification, as a result of which these particles could potentially find their way through water treatment route and exert a potential toxicity risk.

A fissured aquifer may be considered as a dense network of fissures separated by low permeability matrix blocks. A conceptual modeling of such a system consists of an infinite number of parallel fractures separated by constant width matrix slabs. While the fissures are assumed to be main flow conduits, the fluid in the porous matrix blocks are considered to be virtually immobile. The mathematical model of the transport of a solute and/or contaminant which assumes a purely convective flow in fissures and diffusion into the matrix blocks consists of two coupled differential equations. An analytical solution of this model for the case of solute entering into the system at a constant concentration has been presented by Skopp and Warrick in Soil Sci Soc Am Proc 38:545-550, 1974. Note however, Skopp and Warrick (Soil Sci Soc Am Proc 38:545-550, 1974) have not considered the additional processes of adsorption and radioactive decay. Unfortunately, their solution had computational limitations as it involved numerical integration of a quite complex expression. Therefore, one had to turn to employing numerical Laplace transform inverters to compute the solutions. This work presents simple real space analytical solutions for the contaminant transport model described above including the adsorption and radioactive decay. The real space solutions have been developed using the method of double Laplace transform and binomial series approximation. An accurate approximate solution has also been presented which converges to the exact solution only after computing three terms in the series full solution. The developed model has been used for 1) assessment of the efficiency of numerical Laplace transform algorithms and 2) investigation of the degree and scale of contamination, and 3) designing remediation schemes for the already contaminated aquifers.