Aquatic sediments are contaminated by a wide diversity of organic pollutants such as endocrine-disrupting chemicals (EDCs) which encompass a broad range of chemical classes having natural and anthropogenic origins. The use of in vitro bioassays is now widely accepted as an alternative method for their detection in complex samples. However, based on the diversity of EDC chemical properties, their common extraction is difficult and comprehensive validation of extraction methods for a bioanalysis purpose is still weakly documented. In this study, we compared the performance of several organic solvents, i.e., acetone, methanol, dichloromethane, heptane, dichloromethane/acetone (50:50, v/v), dichloromethane/methanol (50:50, v/v), heptane/acetone (50:50, v/v), and heptane/methanol (50:50, v/v), to extract a diversity of active chemicals from a spiked sediment matrix using pressurized liquid extraction. For this purpose, we defined a mixture of 12 EDCs with a wide range of polarity (2 < log Kow < 8) (i.e., estrone, 17β-estradiol, bisphenol A, o,p′DDT, 4-tert-octylphenol, fenofibrate, triphenyl phosphate, clotrimazole, PCB-126, 2,3,7,8 TCDD, benzo[k]fluoranthene, and dibenzo[a,h]anthracene). Working concentrations of each individual compound in the mixture were determined as equipotent concentrations on the basis of the concentration-addition (CA) model applied to in vitro estrogenic, dioxin-like, and pregnane X receptor (PXR)-like activities. Extraction efficiencies based on both chemical and biological analyses were assessed in triplicate in artificial blank sediment spiked with this mixture and in natural sediment contaminated by native EDCs. In both spiked and natural sediment, MeOH/DCM yields the best recovery while heptane was the least efficient solvent. Our study provided the validation of a sediment extraction methodology for EDC bioanalysis purposes, which can be used for comprehensive environmental contamination characterization.

We report on our recent efforts towards identifying bacteria in environmental samples by means of Raman spectroscopy. We established a database of Raman spectra from bacteria submitted to various environmental conditions. This dataset was used to verify that Raman typing is possible from measurements performed in non-ideal conditions. Starting from the same dataset, we then varied the phenotype and matrix diversity content included in the reference library used to train the statistical model. The results show that it is possible to obtain models with an extended coverage of spectral variabilities, compared to environment-specific models trained on spectra from a restricted set of conditions. Broad coverage models are desirable for environmental samples since the exact conditions of the bacteria cannot be controlled.

A simple online headspace solid-phase microextraction (HS-SPME) coupled with the gas chromatography-mass spectrometry (GC-MS) method was developed for simultaneous determination of trace amounts of nine estrogenic odorant alkylphenols and chlorophenols and their derivatives in water samples. The extraction conditions of HS-SPME were optimized including fiber selection, extraction temperature, extraction time, and salt concentration. Results showed that divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most appropriate one among the three selected commercial fibers, and the optimal extraction temperature, time, and salt concentration were 70 °C, 30 min, and 0.25 g/mL, respectively. The developed method was validated and showed good linearity (R ² > 0.989), low limit of detection (LOD, 0.002–0.5 μg/L), and excellent recoveries (76–126 %) with low relative standard deviation (RSD, 0.7–12.9 %). The developed method was finally applied to two surface water samples and some of these target compounds were detected. All these detected compounds were below their odor thresholds, except for 2,4,6-TCAS and 2,4,6-TBAS wherein their concentrations were near their odor thresholds. However, in the two surface water samples, these detected compounds contributed to a certain amount of estrogenicity, which seemed to suggest that more attention should be paid to the issue of estrogenicity rather than to the odor problem.

The effects of plant-bound zinc (Zn) and cadmium (Cd) on element uptake and their interactions in a parasite-host system were investigated in a model experiment. Male Wistar rats were divided into four groups (C, P, TC and TP). Groups TC and TP were infected with the rat tapeworm Hymenolepis diminuta. Groups C and TC were fed a standard rodent mixture (ST-1) and received 10.5 mg of Zn per week, while groups P and TP were fed a mixture supplemented with the Zn- and Cd-hyperaccumulating plant Arabidopsis halleri at a dosage of 236 mg Zn/week and 3.0 mg Cd/week. Rats were euthanized after 6 weeks, and Cd and Zn levels were determined in rat and tapeworm tissue. The results indicate that tapeworm presence did have an effect on Cd and Zn concentrations in the host tissue; the majority of tissues in infected rats had statistically significant lower Zn and Cd concentrations than did uninfected rats. Tapeworms accumulated more zinc and cadmium than did the majority of host tissues. This important finding confirms the ability of tapeworms to accumulate certain elements (heavy metals) from the host body to their own body tissues. Thus, tapeworms can decrease heavy metal concentrations in host tissues.

The Mar Piccolo of Taranto (Ionian Sea, Southern Italy) is a semi-enclosed and strongly polluted basin. For decades, it has been subjected to different anthropogenic impacts. These stressors caused severe sediments contamination with high concentration of different pollutants (PAHs, PCB, heavy metals). In order to assess the current status of sediments contamination, an ecotoxicological investigation combined with chemical analysis (heavy metals, PAH, and PCB) has been performed. In order to derive ecologically relevant conclusions, a multiorganisms and multiend-points approach has been applied, exposing organisms from different trophic levels to elutriate and whole sediment. The battery of bioassays consists of a microalgal growth inhibition test (Dunaliella tertiolecta), acute and sublethal assays (end-points: mortality, immobilization and swimming speed alteration) on crustaceans larvae and juveniles, and rotifers (Amphibalanus amphitrite, Artemia salina, Corophium insidiosum and Brachionus plicatilis), and embryotoxicity test on echinoderms (Paracentrotus lividus). Considering the high levels of sediment contamination highlighted from chemical analysis, an unexpected very low toxic effect was observed, even considering the sublethal end-point (larval swimming speed alteration). The results of this study suggest a very complex contaminants dynamic in the Mar Piccolo sediments that, despite a strong level of contamination, seems to not affect in a proportional manner the biological compartment.

Building a microscale zero-valent iron (mZVI) reaction zone is a promising in situ remediation technology for restoring groundwater contaminated by trichloroethylene (TCE). In order to determine a suitable modifier that could not only overcome gravity sedimentation of mZVI but also improve its remediation efficiency for TCE, the three biopolymers xanthan gum (XG), guargum (GG), and carboxymethyl cellulose (CMC) were employed to coat mZVI for surface modification. The suspension stability of the modified mZVI and its TCE removal efficiency were systematically investigated. The result indicated that XG as a shear-thinning fluid showed the most remarkable efficiency of preventing mZVI from gravity sedimentation and enhancing the TCE removal efficiency by mZVI. In a 480-h experiment, the presence of XG (3 g L⁻¹) increased the TCE removal efficiency by 31.85 %, whereas GG (3 g L⁻¹) and CMC (3 g L⁻¹) merely increased by 15.61 and 9.69 % respectively. The pH value, Eh value, and concentration of ferrous ion as functions of the reaction time were recorded in all the reaction systems, which indicated that XG worked best in buffering the pH value of the solution and inhibiting surface passivation of mZVI.

Heavy metals can be removed from the sludge using bioleaching technologies at thermophilic condition, thereby providing an option for biotreatment of wasted sludge generated from wastewater treatment. The purposes of this study were to establish a molecular biology technique, real-time PCR, for the detection and enumeration of the sulfur-oxidizing bacteria during the thermophilic sludge bioleaching. The 16S rRNA gene for real-time PCR quantification targeted the bioleaching bacteria: Sulfobacillus thermosulfidooxidans, Sulfobacillus acidophilus, and Acidithiobacillus caldus. The specificity and stringency for thermophilic sulfur-oxidizing bacteria were tested before the experiments of monitoring the bacterial community, bacterial number during the thermophilic sludge bioleaching and the future application on testing various environmental samples. The results showed that S. acidophilus was identified as the dominant sulfur-oxidizing bacteria, while A. caldus and S. thermosulfidooxidans occurred in relatively low numbers. The total number of the sulfur-oxidizing bacteria increased during the thermophilic bioleaching process. Meanwhile, the decrease of pH, production of sulfate, degradation of SS/VSS, and solubilization of heavy metal were found to correlate well with the population of thermophilic sulfur-oxidizing bacteria during the bioleaching process. The real-time PCR used in this study is a suitable method to monitor numbers of thermophilic sulfur-oxidizing bacteria during the bioleaching process.

Heavy metals cause serious problems in the environment, and they can be accumulated in organisms, especially in the higher fungi. The concentration of Ni, Cr, Pb, Cd, and Hg in 10 species of edible mushrooms in Medvednica Nature Park, Croatia was therefore determined. In addition, the similarity between the studied species was determined by cluster analysis based on concentrations of the aforementioned metals in the fruiting bodies. The contents of nickel, chromium, lead, cadmium, and mercury in the fruiting bodies of mushrooms were obtained by X-ray fluorescence spectrometry. The highest concentrations of Ni (3.62 mg kg⁻¹), Cr (3.01 mg kg⁻¹), and Cd (2.67 mg kg⁻¹) were determined in Agaricus campestris. The highest concentration of Pb (1.67 mg kg⁻¹) was determined in Macrolepiota procera, and the highest concentration of Hg (2.39 mg kg⁻¹) was determined in Boletus edulis. The concentration of all heavy metals significantly differed (p < 0.001) between examined saprophytic and ectomycorrhizal mushrooms. Considering anatomical part of the fruiting body (cap-stipe), a considerably higher concentration of the analyzed elements was found in the cap for all mushroom species. According to calculated bioconcentration factors, all the examined species were found to be bioexclusors of Ni, Cr, and Pb and bioaccumulators of Cd and Hg. Cluster analysis performed on the basis of the accumulation of the studied metals revealed great phenotypic similarity of mushroom species belonging to the same genus and partial similarity of species of the same ecological affiliation.

Effluents after biochemical treatment contain pollutants that are mostly non-degradable. Based upon previous pilot-scale test results, an industrial-scale electro-oxidation device was built to decompose these refractory materials in the effluent from a park wastewater treatment plant. The electro-oxidation device comprised a ditch-shaped plunger flow electrolysis cell, with mesh-plate Ti/PbO₂ electrodes as the anode and the same size mesh-plate Ti as the cathode. Wastewater flowed vertically through electrodes; the effective volume of the cell was 2.8 m³, and the surface-to-volume ratio was 17.14 m² m⁻³. The optimal current density was 100 A m⁻², and a suitable flow velocity was 14.0 m h⁻¹. The removal efficiencies for chemical oxygen demand and color in the effluent were over 60.0 and 84.0 %, respectively. In addition, the electro-oxidation system offered a good disinfection capability. The specific energy consumption for this industrial-scale device was 43.5 kWh kg COD⁻¹, with a current efficiency of 32.8 %, which was superior to the pilot-scale one. To meet the requirements for emission or reuse, the operation cost was $0.44 per ton of effluent at an average price for electricity of $0.11 kWh⁻¹.

Acid rain can directly or indirectly affect plant physiological functions, especially photosynthesis. The enzyme ATP synthase is the key in photosynthetic energy conversion, and thus, it affects plant photosynthesis. To clarify the mechanism by which acid rain affects photosynthesis, we studied the effects of acid rain on plant growth, photosynthesis, chloroplast ATP synthase activity and gene expression, chloroplast ultrastructure, intracellular H⁺ level, and water content of rice seedlings. Acid rain at pH 4.5 remained the chloroplast structure unchanged but increased the expression of six chloroplast ATP synthase subunits, promoted chloroplast ATP synthase activity, and increased photosynthesis and plant growth. Acid rain at pH 4.0 or less decreased leaf water content, destroyed chloroplast structure, inhibited the expression of six chloroplast ATP synthase subunits, decreased chloroplast ATP synthase activity, and reduced photosynthesis and plant growth. In conclusion, acid rain affected the chloroplast ultrastructure, chloroplast ATPase transcription and activity, and P ₙ by changing the acidity in the cells, and thus influencing the plant growth and development. Finally, the effects of simulated acid rain on the test indices were found to be dose-dependent.