Multi-component adsorption of copper,nickel and zinc from aqueous solutions onto activated carbon prepared from date stones

The removal of Cu²⁺, Ni²⁺, and Zn²⁺ ions from their multi-component aqueous mixture by sorption on activated carbon prepared from date stones was investigated. In the batch tests, experimental parameters were studied, including solution pH, contact time, initial metal ions concentration, and temperature. Adsorption efficiency of the heavy metals was pH-dependent and the maximum adsorption was found to occur at around 5.5 for Cu, Zn, and Ni. The maximum sorption capacities calculated by applying the Langmuir isotherm were 18.68 mg/g for Cu, 16.12 mg/g for Ni, and 12.19 mg/g for Zn. The competitive adsorption studies showed that the adsorption affinity order of the three heavy metals was Cu²⁺?>?Ni²⁺?>?Zn²⁺. The test results using real wastewater indicated that the prepared activated carbon could be used as a cheap adsorbent for the removal of heavy metals in aqueous solutions.     

Soil pH effects on the interactions between dissolved zinc,non-nano- and nano-ZnO with soil bacterial communities

Zinc oxide nanoparticles (ZnO NPs) are used in an array of products and processes, ranging from personal care products to antifouling paints, textiles, food additives, antibacterial agents and environmental remediation processes. Soils are an environment likely to be exposed to manmade nanoparticles due to the practice of applying sewage sludge as a fertiliser or as an organic soil improver. However, understanding on the interactions between soil properties, nanoparticles and the organisms that live within soil is lacking, especially with regards to soil bacterial communities. We studied the effects of nanoparticulate, non-nanoparticulate and ionic zinc (in the form of zinc chloride) on the composition of bacterial communities in soil with a modified pH range (from pH 4.5 to pH 7.2). We observed strong pH-dependent effects on the interaction between bacterial communities and all forms of zinc, with the largest changes in bacterial community composition occurring in soils with low and medium pH levels (pH 4.8 and 5.9). The high pH soil (pH 7.2) was less susceptible to the effects of zinc exposure. At the highest doses of zinc (2500 mg/kg dw soil), both nano and non-nano particulate zinc applications elicited a similar response in the soil bacterial community, and this differed significantly to the ionic zinc salt treatment. The results highlight the importance of considering soil pH in nanotoxicology studies, although further work is needed to determine the exact mechanisms controlling the toxicity and fate and interactions of nanoparticles with soil microbial communities.     

Isolation and characterization of <Emphasis Type="Italic">Bradyrhizobium</Emphasis> sp. SR1 degrading two β-triketone herbicides

In this study, a bacterial strain able to use sulcotrione, a β-triketone herbicide, as sole source of carbon and energy was isolated from soil samples previously treated with this herbicide. Phylogenetic study based on16S rRNA gene sequence showed that the isolate has 100 % of similarity with several Bradyrhizobium and was accordingly designated as Bradyrhizobium sp. SR1. Plasmid profiling revealed the presence of a large plasmid (>50 kb) in SR1 not cured under nonselective conditions. Its transfer to Escherichia coli by electroporation failed to induce β-triketone degrading capacity, suggesting that degrading genes possibly located on this plasmid cannot be expressed in E. coli or that they are not plasmid borne. The evaluation of the SR1 ability to degrade various synthetic (mesotrione and tembotrione) and natural (leptospermone) triketones showed that this strain was also able to degrade mesotrione. Although SR1 was able to entirely dissipate both herbicides, degradation rate of sulcotrione was ten times higher than that of mesotrione, showing a greater affinity of degrading-enzyme system to sulcotrione. Degradation pathway of sulcotrione involved the formation of 2-chloro-4-mesylbenzoic acid (CMBA), previously identified in sulcotrione degradation, and of a new metabolite identified as hydroxy-sulcotrione. Mesotrione degradation pathway leads to the accumulation of 4-methylsulfonyl-2-nitrobenzoic acid (MNBA) and 2-amino-4 methylsulfonylbenzoic acid (AMBA), two well-known metabolites of this herbicide. Along with the dissipation of β-triketones, one could observe the decrease in 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibition, indicating that toxicity was due to parent molecules, and not to the formed metabolites. This is the first report of the isolation of bacterial strain able to transform two β-triketones.     

Production and optimization of biodiesel using mixed immobilized biocatalysts in packed bed reactor

Vegetable oils are used as raw materials for biodiesel production using transesterification reaction. Several methods for the production of biodiesel were developed using chemical (alkali and acidic compounds) and biological catalysts (lipases). Biodiesel production catalyzed by lipases is energy and cost-saving processes and is carried out at normal temperature and pressure. The need for an efficient method for screening larger number of variables has led to the adoption of statistical experimental design. In the present study, packed bed reactor was designed to study with mixed immobilized biocatalysts to have higher productivity under optimum conditions. Contrary to the single-step acyl migration mechanism, a two-step stepwise reaction mechanism involving immobilized Candida rugosa lipase and immobilized Rhizopus oryzae cells was employed for the present work. This method was chosen because enzymatic hydrolysis followed by esterification can tolerate high free fatty acid containing oils. The effects of flow rate and bed height on biodiesel yield were studied using two factors five-level central composite design (CCD) and response surface methodology (RSM). Maximum biodiesel yield of 85 and 81 % was obtained for jatropha oil and karanja oil with the optimum bed height and optimum flow rate of 32.6 cm and 1.35 L/h, and 32.6 cm and 1.36 L/h, respectively.     

Inhibition of residual <Emphasis Type="Italic">n</Emphasis>-hexane in anaerobic digestion of lipid-extracted microalgal wastes and microbial community shift

Converting lipid-extracted microalgal wastes to methane (CH₄) via anaerobic digestion (AD) has the potential to make microalgae-based biodiesel platform more sustainable. However, it is apparent that remaining n-hexane (C₆H₁₄) from lipid extraction could inhibit metabolic pathway of methanogens. To test an inhibitory influence of residual n-hexane, this study conducted a series of batch AD by mixing lipid-extracted Chlorella vulgaris with a wide range of n-hexane concentration (～10 g chemical oxygen demand (COD)/L). Experimental results show that the inhibition of n-hexane on CH₄ yield was negligible up to 2 g COD/L and inhibition to methanogenesis became significant when it was higher than 4 g COD/L based on quantitative mass balance. Inhibition threshold was about 4 g COD/L of n-hexane. Analytical result of microbial community profile revealed that dominance of alkane-degrading sulfate-reducing bacteria (SRB) and syntrophic bacteria increased, while that of methanogens sharply dropped as n-hexane concentration increased. These findings offer a useful guideline of threshold n-hexane concentration and microbial community shift for the AD of lipid-extracted microalgal wastes.     

Potential of <Emphasis Type="Italic">Ranunculus acris</Emphasis> L. for biomonitoring trace element contamination of riverbank soils: photosystem II activity and phenotypic responses for two soil series

Foliar ionome, photosystem II activity, and leaf growth parameters of Ranunculus acris L., a potential biomonitor of trace element (TE) contamination and phytoavailability, were assessed using two riverbank soil series. R. acris was cultivated on two potted soil series obtained by mixing a TE (Cd, Cu, Pb, and Zn)-contaminated technosol with either an uncontaminated sandy riverbank soil (A) or a silty clay one slightly contaminated by TE (B). Trace elements concentrations in the soil-pore water and the leaves, leaf dry weight (DW) yield, total leaf area (TLA), specific leaf area (SLA), and photosystem II activity were measured for both soil series after a 50-day growth period. As soil contamination increased, changes in soluble TE concentrations depended on soil texture. Increase in total soil TE did not affect the leaf DW yield, the TLA, the SLA, and the photosystem II activity of R. acris over the 50-day exposure. The foliar ionome did not reflect the total and soluble TE concentrations in both soil series. Foliar ionome of R. acris was only effective to biomonitor total and soluble soil Na concentrations in both soil series and total and soluble soil Mo concentrations in the soil series B.     

Regulatory effects of dioxin-like and non-dioxin-like PCBs and other AhR ligands on the antioxidant enzymes paraoxonase 1/2/3

Paraoxonase 1 (PON1), an antioxidant enzyme, is believed to play a critical role in many diseases, including cancer. PCBs are widespread environmental contaminants known to induce oxidative stress and cancer and to produce changes in gene expression of various pro-oxidant and antioxidant enzymes. Thus, it appeared of interest to explore whether PCBs may modulate the activity and/or gene expression of PON1 as well. In this study, we compared the effects of dioxin-like and non-dioxin-like PCBs and of various aryl hydrocarbon receptor (AhR) ligands on PON1 regulation and activity in male and female Sprague-Dawley rats. Our results demonstrate that (i) the non-dioxin-like PCB154, PCB155, and PCB184 significantly reduced liver and serum PON1 activities, but only in male rats; (ii) the non-dioxin-like PCB153, the most abundant PCB in many matrices, did not affect PON1 messenger RNA (mRNA) level in the liver but significantly decreased serum PON1 activity in male rats; (iii) PCB126, an AhR ligand and dioxin-like PCB, increased both PON1 activities and gene expression; and (iv) even though three tested AhR ligands induced CYP1A in several tissues to a similar extent, they displayed differential effects on the three PONs and AhR, i.e., PCB126 was an efficacious inducer of PON1, PON2, PON3, and AhR in the liver, while 3-methylcholantrene induced liver AhR and lung PON3, and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), the most potent AhR agonist, increased only PON3 in the lung, at the doses and exposure times used in these studies. These results show that PCBs may have an effect on the antioxidant protection by paraoxonases in exposed populations and that regulation of gene expression through AhR is highly diverse.     

Heavy metal contamination in sediments of an artificial reservoir impacted by long-term mining activity in the Almadén mercury district (Spain)

Sediments from the Castilseras reservoir, located downstream on the Valdeazogues River in the Almadén mercury district, were collected to assess the potential contamination status related to metals(oids) associated with river sediment inputs from several decommissioned mines. Metals(oids) concentrations in the reservoir sediments were investigated using different physical and chemical techniques. The results were analyzed by principal component analysis (PCA) to explain the correlations between the sets of variables. The degree of contamination was evaluated using the enrichment factor (EF) and the geoaccumulation index (Igeo). PCA revealed that the silty fraction is the main metals(oids) carrier in the sediments. Among the potentially harmful elements, there is a group (Al, Cr, Cu, Fe, Mn, Ni, and Zn) that cannot be strictly correlated to the mining activity since their concentrations depend on the lithological and edaphological characteristics of the materials. In contrast, As, Co, Hg, Pb, and S showed significant enrichment and contamination, thus suggesting relevant contributions from the decommissioned mines through fluvial sediment inputs. As far as Hg and S are concerned, the high enrichment levels pose a question concerning the potential environmental risk of transfer of the organic forms of Hg (mainly methylmercury) from the bottom sediments to the aquatic food chain.     

Expression of copper-resistance genes in microbial communities under copper stress and oxic/anoxic conditions

Microorganisms have developed copper-resistance mechanisms in order to survive in contaminated environments. The abundance and expression of the copper-resistance genes cusA and copA, encoding respectively for a Resistance Cell Nodulation protein and for a P-type ATP-ase pump, was assessed along a gradient of copper concentration in microcosms prepared from Seine estuary mudflat sediment. We demonstrated that the abundance of copA and cusA genes decreased with the increase of copper concentration and that cusA gene was up to ten times higher than the copA gene. Only the copA gene was expressed in both oxic and anoxic conditions. The abundance and activity of the microbial community remained constant whatever the concentrations of copper along the gradient. The molecular phylogeny of the two copper-resistance genes was studied and revealed that the increase of copper increased the diversity of copA and cusA gene sequences.     

Occurrence of PPCPs in the marine environment: a review

Little research has been conducted on the occurrence of pharmaceuticals and personal care products (PPCPs) in the marine environment despite being increasingly impacted by these contaminants. This article reviews data on the occurrence of PPCPs in seawater, sediment, and organisms in the marine environment. Data pertaining to 196 pharmaceuticals and 37 personal care products reported from more than 50 marine sites are analyzed while taking sampling strategies and analytical methods into account. Particular attention is focused on the most frequently detected substances at highest concentrations. A snapshot of the most impacted marine sites is provided by comparing the highest concentrations reported for quantified substances. The present review reveals that: (i) PPCPs are widespread in seawater, particularly at sites impacted by anthropogenic activities, and (ii) the most frequently investigated and detected molecules in seawater and sediments are antibiotics, such as erythromycin. Moreover, this review points out other PPCPs of concern, such as ultraviolet filters, and underlines the scarcity of data on those substances despite recent evidence on their occurrence in marine organisms. The exposure of marine organisms in regard to these insufficient data is discussed.