Dissolved and particulate Ag concentrations (AgD and AgP, respectively) were measured in surface water and suspended particulate matter (SPM) along the salinity gradient of the Gironde Estuary, South West France, during three cruises (2008–2009) covering contrasting hydrological conditions, i.e. two cruises during intermediate and one during high freshwater discharge (~740 and ~2,300 m³/s). Silver distribution reflected non-conservative behaviour with 60–70 % of AgP in freshwater particles being desorbed by chlorocomplexation. The amount of AgP desorbed was similar to the so-called reactive, potentially bioavailable AgP fraction (60 ± 4 %) extracted from river SPM by 1 M HCl. Both AgP (0.22 ± 0.05 mg/kg) and AgP/ThP (0.025–0.028) in the residual fraction of fluvial and estuarine SPM were similar to those in SPM from the estuary mouth and in coastal sediments from the shelf off the Gironde Estuary, indicating that chlorocomplexation desorbs the reactive AgP. The data show that desorption of reactive AgP mainly occurs inside the estuary during low and intermediate discharge, whereas expulsion of partially AgP-depleted SPM (AgP/ThP ~0.040) during the flood implies ongoing desorption in the coastal ocean, e.g. in the nearby oyster production areas (Marennes-Oléron Bay). The highest AgD levels (6–8 ng/L) occurred in the mid-salinity range (15–20) of the Gironde Estuary and were decoupled from freshwater discharge. In the maximum turbidity zone, AgD were at minimum, showing that high SPM concentrations (a) induce AgD adsorption in estuarine freshwater and (b) counterbalance AgP desorption in the low salinity range (1–3). Accordingly, Ag behaviour in turbid estuaries appears to be controlled by the balance between salinity and SPM levels. The first estimates of daily AgD net fluxes for the Gironde Estuary (Boyle’s method) showed relatively stable theoretical AgD at zero salinity (Ag D ⁰ = 25–30 ng/L) for the contrasting hydrological situations. Accordingly, AgD net fluxes were very similar for the situations with intermediate discharge (1.7 and 1.6 g/day) and clearly higher during the flood (5.0 g/day) despite incomplete desorption. Applying Ag D ⁰ to the annual freshwater inputs provided an annual net AgD flux (0.64–0.89 t/year in 2008 and 0.56–0.77 t/year in 2009) that was 12–50 times greater than the AgD gross flux. This estimate was consistent with net AgD flux estimates obtained from gross AgP flux considering 60 % desorption in the estuarine salinity gradient.

Fagopyrum esculentum commonly named as buckwheat plant is pseudocereal food crops and healthy herbs but is not known as a bioindicator of environmental condition. In the present study, the effects of ZnO nanoparticles (NPs) and microparticles (MPs) on plant growth, bioaccumulation, and antioxidative enzyme activity in buckwheat were estimated under hydroponic culture. The significant biomass reduction at concentrations of 10–2,000 mg/L was 7.7–26.4 % for the ZnO NP and 11.4–23.5 % for the ZnO MP treatment, (p < 0.05). ZnO NPs were observed in root cells and root cell surface by scanning electron microscopy and transmission electron microscopy analysis. Zn bioaccumulation in plant increased with increasing treatment concentrations. The upward translocation (translocation factor <0.2) of Zn in plant was higher with the ZnO NP treatment than that with the ZnO MP treatment. Additionally, reactive oxygen species generation by ZnO NPs was estimated as the reduced glutathione level and catalase activity, which would be a predictive biomarker of nanotoxicity. The results are the first study to evaluate the phytotoxicity of ZnO NPs to medicinal plant. F. esculentum can be as a good indicator of plant species in NP-polluted environment.

Contaminants in settled indoor dust are potentially health hazardous to human. Thus, identification and quantification of toxic chemicals in settled indoor dust is of great concern. In this study, the levels of major anions ([Formula: see text]), trace metals (Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, As and Pb) and polybromodiphenyl ethers (PBDEs) in settled office and home dust were determined and correlations between the contaminants investigated. Depending on the available materials in both microenvironments, the most possible sources were identified. The results showed that the settled office dusts (n = 6 pooled samples from 85 offices) were more contaminated than home dusts (n = 8 homes). For anions, [Formula: see text] and Cl(-) accounted for 87 and 97 % of the total office and home dust contaminants, respectively. For trace metals, Fe, Cu, Zn and Mn, accounted for 98 % of the contaminants in both office and home dust samples. Fe exhibited the highest percentage of 76.7 and 87.3 % in office and home dust samples, respectively. For PBDEs, the mean concentrations detected in office and home dust ranged between 5.8-86.3 and 1.5-20.6 ng g(-1), respectively. The log-transformed correlation between the total concentrations of trace metals and major anions detected in offices and homes was positive for offices and negative for homes with a statistically significant values (r = 0.73, p < 0.01; r = -0.22, p < 0.01, respectively). The daily exposure rates determined for the most hazardous such as As, Cd, Pb and PBDEs congeners, relative to the individual concentrations reported in the literature in settled indoor dust, were found very lower. Therefore, maybe it is possible to expect less potential health risk. Investigation of formation of coordination compounds between trace metals and PBDEs congeners is possible; however, this requires further study.

A systematic study was carried out to investigate air deposition and to explore the natural distribution and enrichment (contamination) with trace elements in the small area (cca. 13 km²) of an antimony-arsenic-thallium mineralization outcrop at an abandoned mine “Allchar.” The mine is located on the northwestern part of Kožuf Mount, Republic of Macedonia. The locality of Allchar is unique in its mineral composition; besides a very intriguing mineral, lorandite, there are 45 other minerals, some of which are rare. The distribution of 53 elements (with special attention to As, Sb, and Tl) were detected in 69 moss samples from eight various species collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma–mass spectrometry and inductively coupled plasma–atomic emission spectrometry. It was found that the atmospheric deposition for As in the moss samples on or around the Allchar mine is >6.5 times higher and for Tl is 19 times higher compared to values for the samples from the rest of the Allchar area. By the application of multivariate cluster and R-mode factor analyses (FA), five geochemical associations were determined. Cluster and R-mode FA were used to identify and characterize element associations, and five associations of elements were determined by the method of multivariate statistics. F1 (Co, Cr, Fe, Sc, Li, V, Ga, Y, Ni, Mn, Al, La-Lu, Cu, Ge, Be, Bi, and Hf); F2 (As, Tl, Sb, and Mg); F3 (Rb, Cs, and Mo); F4 (Sr, Ba, Hf, Zr, La-Lu, and Bi), and F5 (Cd, Zn, Ag, and Cu).

The planktonic diatom genus Pseudo-nitzschia contains several genetically closely related species. Some of these can produce domoic acid, a potent neurotoxin. Thus, monitoring programs are needed to screen for the presence of these toxic species. Unfortunately, many are impossible to distinguish using light microscopy. Therefore, we assessed the applicability of microarray technology for detection of toxic and non-toxic Pseudo-nitzschia species in the Gulf of Naples (Mediterranean Sea). Here, 11 species have been detected, of which at least 5 are potentially toxic. A total of 49 genus- and species-specific DNA probes were designed in silico against the nuclear LSU and SSU rRNA of 19 species, and spotted on the microarray. The microarray was tested against total RNA of monoclonal cultures of eight species. Only three of the probes designed to be species-specific were indeed so within the limits of our experimental design. To assess the effectiveness of the microarray in detecting Pseudo-nitzschia species in environmental samples, we hybridized total RNA extracted from 11 seasonal plankton samples against microarray slides and compared the observed pattern with plankton counts in light microscopy and with expected hybridization patterns obtained with monoclonal cultures of the observed species. Presence of species in field samples generally resulted in signal patterns on the microarray as observed with RNA extracted from cultures of these species, but many a-specific signals appeared as well. Possible reasons for the numerous cross reactions are discussed. Calibration curves for Pseudo-nitzschia multistriata showed linear relationship between signal strength and cell number.

The aim of this work was to improve the ability of the electro-Fenton process using Fe alginate gel beads for the remediation of wastewater contaminated with synthetic dyes and using a model diazo dye such as Reactive Black 5 (RB5). Batch experiments were conducted to study the effects of main parameters, such as voltage, pH and iron concentration. Dye decolourisation, reduction of chemical oxygen demand (COD) and energy consumption were studied. Central composite face-centred experimental design matrix and response surface methodology were applied to design the experiments and to evaluate the interactive effects of the three studied parameters. A total of 20 experimental runs were set, and the kinetic data were analysed using first-order and second-order models. In all cases, the experimental data were fitted to the empirical second-order model with a suitable degree for the maximum decolourisation of RB5, COD reduction and energy consumption by electro-Fenton–Fe alginate gel beads treatment. Working with the obtained empirical model, the optimisation of the process was carried out. The second-order polynomial regression model suggests that the optimum conditions for attaining maximum decolourisation, COD reduction and energy consumption are voltage, 5.69 V; pH 2.24 and iron concentration, 2.68 mM. Moreover, the fixation of iron on alginate beads suggests that the degradation process can be developed under this electro-Fenton process in repeated batches and in a continuous mode.

The phenomenon of mass occurrence of the lichen Cladonia rei in extremely contaminated post-smelting slag dumps was studied in relation to metal accumulation capacity of this lichen. The research was aimed to evaluate the relationships between element contents in the thalli and in the corresponding substrate. The study was conducted in terms of a wide spectrum of Zn, Cd, Pb and As contents. The concentrations of these elements in the lichen thalli and substrate samples were measured. Various regression models were considered to find the best fitted one that greatly reflects the dependencies. Various Cladonia species and the hyperaccumulator Diploschistes muscorum were also included in the study for comparison purposes. Specific non-linear regression models described by a power function reflected relationships between Zn and Cd contents in C. rei thalli and in the host substrate in the most reliable way. The relationship for As was also noted, but none significant model was found. Contrarily, Pb concentrations in the thalli varied independently of the metal levels in the substrate. Nevertheless, the concentrations of all measured heavy metals in C. rei thalli are relatively low considering the frequently enormous substrate contamination. Different Cladonia species demonstrated a generally similar accumulation capacity and could be considered as weak accumulators. The restrained accumulation pattern may be one of the important attributes of C. rei which facilitates its colonisation of extremely contaminated dumps. This finding highlights ecological importance of this species as stable and resistant pioneer in such affected sites.

The present work investigates the potential use of metal hydroxides sludge (MHS) generated from hot dipping galvanizing plant for adsorption of Congo Red and Naphthol Green B dyes from aqueous solutions. Characterization of MHS included infrared and X-ray fluorescence analysis. The effect of shaking time, initial dye concentration, temperature, adsorbent dosage and pH has been investigated. The results of adsorption experiments indicate that the maximum capacity of Congo Red and Naphthol Green B dyes at equilibrium (q ₑ) and percentage of removal at pH 6 are 40 mg/g, 93 %, and 10 mg/g, 52 %, respectively. Some kinetic models were used to illustrate the adsorption process of Congo Red and Naphthol Green B dyes using MHS waste. Thermodynamic parameters such as (ΔG, ΔS, and ΔH) were also determined.