First inter-laboratory comparison exercise for the determination of anticancer drugs in aqueous samples

The results of an inter-laboratory comparison exercise to determine cytostatic anticancer drug residues in surface water, hospital wastewater and wastewater treatment plant effluent are reported. To obtain a critical number of participants, an invitation was sent out to potential laboratories identified to have the necessary knowledge and instrumentation. Nine laboratories worldwide confirmed their participation in the exercise. The compounds selected (based on the extent of use and laboratories capabilities) included cyclophosphamide, ifosfamide, 5-fluorouracil, gemcitabine, etoposide, methotrexate and cisplatinum. Samples of spiked waste (hospital and wastewater treatment plant effluent) and surface water, and additional non-spiked hospital wastewater, were prepared by the organising laboratory (Jo?ef Stefan Institute) and sent out to each participant partner for analysis. All analytical methods included solid phase extraction (SPE) and the use of surrogate/internal standards for quantification. Chemical analysis was performed using either liquid or gas chromatography mass (MS) or tandem mass (MS/MS) spectrometry. Cisplatinum was determined using inductively coupled plasma mass spectrometry (ICP-MS). A required minimum contribution of five laboratories meant that only cyclophosphamide, ifosfamide, methotrexate and etoposide could be included in the statistical evaluation. z-score and Q test revealed 3 and 4 outliers using classical and robust approach, respectively. The smallest absolute differences between the spiked values and the measured values were observed in the surface water matrix. The highest within-laboratory repeatability was observed for methotrexate in all three matrices (CV?≤?12 %). Overall, inter-laboratory reproducibility was poor for all compounds and matrices (CV 27–143 %) with the only exception being methotrexate measured in the spiked hospital wastewater (CV?=?8 %). Random and total errors were identified by means of Youden plots.     

Mercury species accumulation and trophic transfer in biological systems using the Almadén mining district (Ciudad Real,Spain) as a case of study

The impact of mercury (Hg) pollution in the terrestrial environments and the terrestrial food chains including the impact on human food consumption is still greatly under-investigated. In particular, studies including Hg speciation and detoxification strategies in terrestrial animals are almost non-existing, but these are key information with important implications for human beings. Therefore, in this work, we report on Hg species (inorganic mercury, iHg, and monomethylmercury, MeHg) distribution among terrestrial animal tissues obtained from a real-world Hg exposure scenario (Almadén mining district, Spain). Thus, we studied Hg species (iHg and MeHg) and total selenium (Se) content in liver and kidney of red deer (Cervus elaphus; n?=?41) and wild boar (Sus scrofa; n?=?16). Similar mercury species distribution was found for both red deer and wild boar. Major differences were found between tissues; thus, in kidney, iHg was clearly the predominant species (more than 81 %), while in liver, the species distribution was less homogeneous with a percentage of MeHg up to 46 % in some cases. Therefore, Hg accumulation and MeHg transfer were evident in terrestrial ecosystems. The interaction between total Se and Hg species has been evaluated by tissue and by animal species. Similar relationships were found in kidney for both Hg species in red deer and wild boar. However, in liver, there were differences between animals. The possible underlying mechanisms are discussed.     

A novel application of concentrated solar thermal energy in foundries

Scrap preheating in foundries is a technology that saves melting energy, leading to economic and environmental benefits. The proposed method in this paper utilizes solar thermal energy for preheating scrap, effected through a parabolic trough concentrator that focuses sunlight onto a receiver which carries the metallic scrap. Scraps of various thicknesses were placed on the receiver to study the heat absorption by them. Experimental results revealed the pattern with which heat is gained by the scrap, the efficiency of the process and how it is affected as the scrap gains heat. The inferences from them gave practical guidelines on handling scraps for best possible energy savings. Based on the experiments conducted, preheat of up to 160 °C and a maximum efficiency of 70 % and a minimum efficiency of 40 % could be achieved across the time elapsed and heat gained by the scrap. Calculations show that this technology has the potential to save around 8 % of the energy consumption in foundries. Cumulative benefits are very encouraging: 180.45 million kWh of energy savings and 203,905 t of carbon emissions cut per year across the globe. This research reveals immense scope for this technology to be adopted by foundries throughout the world.     

Phytoplankton dynamics with a special emphasis on harmful algal blooms in the Mar Piccolo of Taranto (Ionian Sea,Italy)

The response of phytoplankton assemblages to the closure of urban sewage outfalls (USOs) was examined for the Mar Piccolo of Taranto (Mediterranean Sea), a productive semi-enclosed coastal marine ecosystem devoted to shellfish farming. Phytoplankton dynamics were investigated in relation to environmental variables, with a particular emphasis on harmful algal blooms (HABs). Recent analyses evidenced a general reduction of the inorganic nutrient loads, except for nitrates and silicates. Also phytoplankton biomass (chlorophyll a) and abundances were characterized by a decrease of the values, except for the inner area of the basin (second inlet). The phytoplankton composition changed, with nano-sized species, indicators of oligotrophic conditions, becoming dominant over micro-sized species. If the closure of the USOs affected phytoplankton dynamics, however, it did not preserve the Mar Piccolo from HABs and anoxia crises. About 25 harmful species have been detected throughout the years, such as the potentially domoic acid producers Pseudo-nitzschia cf. galaxiae and P seudo-nitzschia cf. multistriata, identified for the first time in these waters. The presence of HABs represents a threat for human health and aquaculture. Urgent initiatives are needed to improve the communication with authorities responsible for environmental protection, economic development, and public health for a sustainable mussel culture in the Mar Piccolo.     

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.