Distribution of metals in different binding phases of estuarine sediments provides chemically significant description of metal–sediment interactions. This study describes the influences of ligand field stabilization energy (LFSE), Jahn–Teller effect, and water exchange rate (k ₋w) on metal distribution in different binding phases of estuarine sediments. It was found that Cu had highest affinity for organic binding phases in the studied sediments followed by Ni and Pb. However, Pb showed strong association with Fe/Mn oxide phases followed by Ni and Cu. Faster k ₋w of Cu (II) (1 × 10⁹ s⁻¹) increased the rate of complex formation of Cu²⁺ ion with ligand in the organic phases. The Cu–ligand (from organic phase) complexes gained extra stability by the Jahn–Teller effect. The combined effects of these two phenomena and high ionic potential increased the association of Cu with the organic phases of the sediments than Ni and Pb. The smaller ionic radii of Ni²⁺ (0.72 Å) than Pb²⁺ (1.20 Å) increase the stability of Ni–ligand complexes in the organic phase of the sediments. High LFSE of Ni(II) (compared with Pb²⁺ ions) also make Ni-organic complexes increasingly stable than Pb. High k ₋w (7 × 10⁹ s⁻¹) of Pb did not help it to associate with organic phases in the sediments. The high concentration of Pb in the Fe/Mn oxyhydroxide binding phase was probably due to co-precipitation of Pb²⁺ and Fe³⁺. High surface area or site availability for Pb²⁺ ion on Fe oxyhydroxide phase was probably responsible for the high concentration of Pb in Fe/Mn oxyhydroxide phase. Increasing concentrations of Cu in organic phases with the increasing Cu loading suggest that enough binding sites were available for Cu in the organic binding phases of the sediments. This study also describes the influence of nature of sedimentary organic carbon (terrestrial and marine derived OC) in controlling these metal distribution and speciation in marine sediment.

A total of 128 surface soil samples were collected, and eight heavy metals, including As, Cd, Cr, Cu, Pb, Ni, Zn, and Hg, were analyzed for their concentrations, potential ecological risks, and human health risks. The mean concentrations of these eight metals were lower than the soil environmental quality standards in China, while they were slightly higher than the background values in Shanxi Province. The enrichment factor, coefficient variation, and potential ecological risk index were used to assess the pollution and eco-risk level of heavy metals, among which, Cd and Hg showed higher pollution levels and potential risks than the others in the studied area. Moreover, multivariate geostatistical analysis suggested that Hg originated mainly from point sources such as industrial emissions, while agricultural activity is the predominant factor for Cd. The human health risk assessment indicated that non-carcinogenic values were below the threshold values. The total carcinogenic risks due to As, Cr, and Ni were within the acceptable range for adults, while for children, they were higher than the threshold value (1.0E−04), indicating that children are facing higher threat to heavy metals in soils. These results provide basic information on heavy metal pollution control and human health risk assessment management in the study regions.

In this study, Hypnum cupressiforme moss bags were used to examine the atmospheric deposition of trace elements in the oil refinery region of Sardinia (Italy) compared with surrounding natural zones. The concentrations of 13 elements [arsenic (As), calcium (Ca), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), sodium (Na), nickel (Ni), lead (Pb), vanadium (V), and zinc (Zn)] were determined using inductively coupled plasma optical emission spectrometry. A significant accumulation of pollutants was detected using active biomonitoring with moss bags compared with a control site. The most relevant contaminants for all of the tested sites were Cr, Cu, Ni, and Zn. Moreover, the accumulation of Cr and Zn in the refinery industrial areas, IA1 and IA2, was more than five times greater than that detected at the control site. Levels of Cd, Mg, and Pb were also higher at all of the monitored sites compared with the control site. Both genomic and proteomic methods were used to study the response of H. cupressiforme to air pollution. No DNA damage or mutations were detected using the amplified fragment length polymorphisms (AFLP) method. At the protein level, 15 gel spots exhibited differential expression profiles between the moss samples collected at the IA1 site and the control site. Furthermore, among the 14 spots that showed a decrease in protein expression, nine were associated with ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) and proteins of the light-harvesting complexes of photosystem (PS) II, three were associated with protein synthesis, and three were stress-related proteins. Thus, some of these proteins may represent good moss biosensors which could be used as pre-alert markers of environmental pollution.

The use of methane and acetate as electron donors for biological reduction of thiosulphate in a 5-L laboratory membrane bioreactor was studied and compared to disproportionation of thiosulphate as competing biological reaction. The reactor was operated for 454 days in semi-batch mode; 30 % of its liquid phase was removed and periodically replenished (days 77, 119, 166, 258, 312 and 385). Although the reactor was operated under conditions favourable to promote thiosulphate reduction coupled to methane oxidation, thiosulphate disproportionation was the dominant microbial process. Pyrosequencing analysis showed that the most abundant microorganisms in the bioreactor were phototrophic green sulphur bacteria (GSB) belonging to the family Chlorobiaceae and thiosulphate-disproportionating bacteria belonging to the genus Desulfocapsa. Even though the reactor system was surrounded with opaque plastic capable of filtering most of the light, the GSB used it to oxidize the hydrogen sulphide produced from thiosulphate disproportionation to elemental sulphur. Interrupting methane and acetate supply did not have any effect on the microbial processes taking place. The ultimate goal of our research was to develop a process that could be applied for thiosulphate and sulphate removal and biogenic sulphide formation for metal precipitation. Even though the system achieved in this study did not accomplish the targeted conversion using methane as electron donor, it does perform microbial conversions which allow to directly obtain elemental sulphur from thiosulphate.

The pathology of cardiovascular disease is multi-faceted, with links to many modifiable and non-modifiable risk factors. Epidemiological evidence now implicates exposure to persistent organic pollutants, such as polychlorinated biphenyls (PCBs), with an increased risk of developing diabetes, hypertension, and obesity; all of which are clinically relevant to the onset and progression of cardiovascular disease. PCBs exert their cardiovascular toxicity either directly or indirectly via multiple mechanisms, which are highly dependent on the type and concentration of PCBs present. However, many PCBs may modulate cellular signaling pathways leading to common detrimental outcomes including induction of chronic oxidative stress, inflammation, and endocrine disruption. With the abundance of potential toxic pollutants increasing globally, it is critical to identify sensible means of decreasing associated disease risks. Emerging evidence now implicates a protective role of lifestyle modifications such as increased exercise and/or nutritional modulation via anti-inflammatory foods, which may help to decrease the vascular toxicity of PCBs. This review will outline the current state of knowledge linking coplanar and non-coplanar PCBs to cardiovascular disease and describe the possible molecular mechanism of this association.

The benzene pollutant in gaseous phase was successfully degraded by using ZnO + Zn₂TiO₄ multicomponent oxide thin films as photocatalysts. The films were obtained with different Ti/Zn ratios (0, 0.20, 0.40, 0.45, 0.50, 0.67, 0.84, and 1) by the sol-gel route. The initial level of benzene concentration was 110 ± 10 ppm. The process was carried out under different conditions of relative humidity (RH): 25, 50, and 80 % in a batch-type reactor, at room temperature. The results show benzene degradation near to 95 % at t = 240 min, where the multicomponent oxide semiconductor has a Ti/Zn ratio of 0.67. Meanwhile, with the TiO₂ thin films, only a degradation of 70 % was reached at the same measurement conditions. This synergistic effect on the photocatalytic activity is a result of the coupling of both semiconductor oxides. An adverse effect on the photocatalytic activity was observed as the relative humidity increases.

This study evaluated the combined effect of pH and metals on the egg fertilization process of two estuarine species, the blue mussel (Mytilus edulis), the oyster (Crassostrea gigas) and a marine species, the sea urchin (Paracentrotus lividus). The success of egg fertilization was examined after exposure of gametes to sediment extracts of various degrees of contamination at pH 6.0, 6.5, 7.0, 7.5 and 8.0. At the pH levels from 6.5 to 8.0, the egg fertilization of the different species demonstrated different sensitivity to metal and/or acidic exposure. In all species, the results revealed that egg fertilization was almost completely inhibited at pH 6.0. The egg fertilization of the blue mussel M. edulis was the least sensitive to the exposure while that of the sea urchin P. lividus demonstrated a concentration-dependent response to the pH levels from 6.5 to 8.0. The results of this study revealed that acidity increased the concentration of several metal ions (Cr, Ni, Cu, Zn, Cd, and Pb) but reduced its availability to the organisms, probably related to the reactivity of the ions with most non-metals or to the competition among metals and other waterborne constituents.

In this study, PUF disk passive air samplers were deployed at eight sites, during two sampling periods, on the Island of Sicily in the Mediterranean basin. Samples were screened for a number of persistent organic pollutants (POPs) including polychlorinated biphenyls (PCBs) (n = 28 congeners), organochlorine pesticides (OCPs) (n = 16 compounds), and polybrominated biphenyl ethers (PBDEs n = 28) using GC-MS. PCB concentrations in air ranged ~10–300 pg m⁻³. The PCB pattern was dominated by lower to middle molecular weight PCBs (Cl₃–₅) and PCB-28 and PCB-52 were the most abundant congeners. α- and γ-Hexachlorocyclohexanes (HCHs) concentrations in air were relatively high ~420 ± 320 (50–1000) and 460 ± 340 (30–1000) pg m⁻³, respectively, with an average α/γ ratio of 1 ± 0.5, indicating a tendency of higher use of lindane than of technical HCH. Among DDTs, only p,p′-DDT 90 ± 15 (~10–800) and p,p′-DDE 60 ± 60 (20–400) were frequently detected. DDT/DDE = 0.4–3.0 (1.0 ± 0.7 for both periods) suggesting past and fresh inputs of DDT at the sampling sites. α-Endosulfan, recently included in Annex A of the Stockholm Convention, fluctuated between 120 ± 50 (50–1000) pg m⁻³. In contrast, PBDE levels were very low (0.2–2 pg m⁻³). Back trajectories of advection suggest that POP levels are mainly related to local sources (primary or secondary) from Sicily (50–70 % contribution of air masses), Southern Italy, and Sardinia (20 %). This study provides new information for POP levels in the atmosphere of the Mediterranean region.

The influence of toluene pollution on the chemical properties and swelling coefficient of root cell walls in alfalfa (Medicago sativa L.) was investigated. Two sets of alfalfa seedlings were selected and one set was treated with 450 mg L⁻¹ toluene in the nutrient solution under hydroponic culture. Thirty days after treatment with toluene, alfalfa plants were harvested and the root cell walls were isolated. Fourier-transform infrared (FTIR) spectroscopy was carried out for the characterization of the root cell walls composition. The cation exchange capacity (CEC) and the swelling coefficient of the root cell walls (K cw) were estimated at various pH values. The toluene contamination significantly reduced the mass of the cell wall material in the alfalfa roots. According to the FTIR spectra, the toluene pollution can change the alfalfa root cell wall properties by reducing the cell wall functional groups. These functional groups are probably related to the proteins and polysaccharides in the cell wall. Also, toluene pollution strongly reduced CEC and K cw of the root cell walls. The results show that the decrease in the active sites of adsorption on the root cell walls as a response to toluene pollution can affect the water flow rate and the mineral nutrients uptake by roots.

A hydrothermal electrocatalytic oxidation (HTECO) method is adopted to treat the biorefractory and toxic 2,4-dichlorophenoxyacetic acid (2,4-D) herbicides wastewater on nano-Pt/Ti electrode in the existence of H₂O₂. Comparisons for the removal of 2,4-D and total organic carbon (TOC) have been carried out between HTECO with individual electrochemical oxidation (EO) and hydrothermal catalytic oxidation (HTCO), showing that high mineralization efficiency was obtained in HTECO process. The possible factors resulting in the high removal efficiency in HTECO process have been studied by investigating the properties of the electrode and solution in hydrothermal condition, the amount of active radicals, the decay kinetic, and evolution of main intermediates of 2,4-D. Thus, an enhanced mechanism for HTECO method for the treatment of herbicides wastewater has been obtained.