Use of Artificial Neural Networks as a Predictive Tool of Dissolved Oxygen Present in Surface Water Discharged in the Coastal Lagoon of the Mar Menor (Murcia, Spain).

The Mar Menor is a Mediterranean coastal saltwater lagoon (Murcia, Spain) that represents a unique ecosystem of vital importance for the area, from both an economic and ecological point of view. During the last decades, the intense agricultural activity has caused episodes of eutrophication due to the contribution of inorganic nutrients, especially nitrates. For this reason, it is important to control the quality of the water discharged into the Mar Menor lagoon, which can be performed through the measurement of dissolved oxygen (DO). Therefore, this article aimed to predict the DO in the water discharged into this lagoon through the El Albujón watercourse, for which two theoretical models consisting of a multiple linear regression (MLR) and a back-propagation neural network (RPROP) were developed. Data of temperature, pH, nitrates, chlorides, sulphates, electrical conductivity, phosphates and DO at the mouth of this watercourse, between January 2014 and January 2021, were used. A preliminary statistical study was performed to discard the variables with the lowest influence on DO. Finally, both theoretical models were compared by means of the coefficient of determination (R2), the root mean square errors (RMSE) and the mean absolute error (MAE), concluding that the neural network made a more accurate prediction of DO.

Application of Concretes Made with Glass Powder Binder at High Replacement Rates.

Glass is a material that can be reused, except for a small part that, due to its residual characteristics, cannot be reused and becomes a nonbiodegradable waste to accumulate in landfills. The chemical composition and pozzolanic properties of waste glass are encouraging for the use of these wastes in the cement and concrete industries and for providing technically and environmentally viable solutions. In this study, we propose the production of deactivated concretes with a high content of glass powder in the binder. The substitution percentage of glass powder for cement used in this work was between 70% and 80%. Consistency, air content, bulk density, workability, compression strength, and permeability tests were performed. Regarding compressive strength, the results obtained at 90 days for percentages of cement substitution by glass powder of 70 and 80%, respectively, were 14.2 and 8.6. The chemical analysis of leachates showed concentrations of Fe, Cu, V, Ni, and Mo, in mg L-1, of 1.57, 1.38, 0.85, 0.95, and 0.44, respectively. The results obtained, compared with the relevant legislation, have proved that the inclusion of glass powder in a high percentage of substitution and with a granulometry of 20 µm in the manufacture of deactivated concretes is feasible for exterior pavements.

A Gnotobiotic Model to Examine Plant and Microbiome Contributions to Survival under Arsenic Stress.

So far, the relative importance of the plant and its microbiome in the development of early stages of plant seedling growth under arsenic stress has not been studied. To test the role of endophytic bacteria in increasing plant success under arsenic stress, gnotobiotic seeds of J. montana were inoculated with two endophytic bacteria: Pantoea conspicua MC-K1 (PGPB and As resistant bacteria) and Arthrobacter sp. MC-D3A (non-helper and non-As resistant bacteria) and an endobacteria mixture. In holobiotic seedlings (with seed-vectored microbes intact), neither the capacity of germination nor development of roots and lateral hairs was affected at 125 µM As(V). However, in gnotobiotic seedlings, the plants are negatively impacted by absence of a microbiome and presence of arsenic, resulting in reduced growth of roots and root hairs. The inoculation of a single PGPB (P. conspicua-MCK1) shows a tendency to the recovery of the plant, both in arsenic enriched and arsenic-free media, while the inoculation with Arthrobacter sp. does not help in the recovery of the plants. Inoculation with a bacterial mixture allows recovery of plants in arsenic free media; however, plants did not recover under arsenic stress, probably because of a bacterial interaction in the mixture.

Controlled Synthesis and Microstructural Properties of Sol-Gel TiO2 Nanoparticles for Photocatalytic Cement Composites.

Titania nanoparticles are intensely studied for photodegradation applications. Control of nanoscale morphology and microstructural properties of these materials is critical for photocatalytic performance. Uniform anatase-type TiO2 nanoparticles were prepared by the sol-gel process using titanium isopropoxide as precursor. Controlled annealing up to 400 ℃ established crystallization and particle size ranging between 20 and 30 nm. Detailed thermal examination reveals that anatase phase transformation into rutile is affected by the annealing temperature and by the initial particle size. The anatase to rutile phase transformation occurs in the nanoparticles at 550 ℃. The Total Reflection X-ray Fluorescence (TXRF) study of the anatase nanoparticles shows a shift towards higher energy in the Ka Ti line of 10 eV, related to structural defects. These features were discussed in the photocatalytic behavior of several cement-based materials modified with the so-prepared anatase nanoparticles. The photocatalytic activity of the anatase-type TiO2/cement mortar system is evaluated from the degradation of Methylene Blue (MB) under UV irradiation, monitored through the absorbance at 665 nm. The results show that the photocatalytic composites exhibit up to 76.6% degradation efficiency. Mechanical testing of the nano-TiO2 modified cementitious composites evinces a moderate reinforcement of the strength properties at long ages.

Rapid metal extractability tests from polluted mining soils by ultrasound probe sonication and microwave-assisted extraction systems.

Ultrasonic probe sonication (UPS) and microwave-assisted extraction (MAE) were used for rapid single extraction of Cd, Cr, Cu, Ni, Pb, and Zn from soils polluted by former mining activities (Mónica Mine, Bustarviejo, NW Madrid, Spain), using 0.01 mol L-1 calcium chloride (CaCl2), 0.43 mol L-1 acetic acid (CH3COOH), and 0.05 mol L-1 ethylenediaminetetraacetic acid (EDTA) at pH 7 as extracting agents. The optimum extraction conditions by UPS consisted of an extraction time of 2 min for both CaCl2 and EDTA extractions and 15 min for CH3COOH extraction, at 30% ultrasound (US) amplitude, whereas in the case of MAE, they consisted of 5 min at 50 °C for both CaCl2 and EDTA extractions and 15 min at 120 °C for CH3COOH extraction. Extractable concentrations were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The proposed methods were compared with a reduced version of the corresponding single extraction procedures proposed by the Standards, Measurements and Testing Programme (SM&T). The results obtained showed a great variability on extraction percentages, depending on the metal, the total concentration level and the soil sample, reaching high values in some areas. However, the correlation analysis showed that total concentration is the most relevant factor for element extractability in these soil samples. From the results obtained, the application of the accelerated extraction procedures, such as MAE and UPS, could be considered a useful approach to evaluate rapidly the extractability of the metals studied.

Stability of toxic arsenic species and arsenosugars found in the dry alga Hijiki and its water extracts.

The achievement of reliable results in speciation analysis requires not only sensitive techniques but also sureness of species stability. Therefore, it is necessary to carry out stability studies because it is important to know with absolute certainty that there is not any species transformation during sample treatment and/or storage. Although several procedures have been recommended for the preservation of species integrity, there is no general agreement, as arsenic species stability depends on the sample matrix, the concentration level and the sample treatment procedure, so it is necessary to assess the arsenic species stability for each case. Thus, the present paper reports the stability tests of arsenic species carried out on the commercially available edible alga Hijiki (Hizikia fusiformis), from Japan, in both the dry sample and its water extracts, which were stored in amber glass and polystyrene containers at -18 and +4°C in the dark. Extractions were carried out with deionized water by microwave-assisted extraction, at a temperature of 90°C and three extraction steps of 5 min each, whereas arsenic speciation analysis was performed by anion exchange high performance liquid chromatography-photo-oxidation-hydride generation-atomic fluorescence spectrometry. The results obtained for the dry alga showed that the arsenic species present in it (arsenate (As(V)), dimethylarsinic acid (DMA) and the arsenosugars glycerol (Gly-sug), phosphate (PO4-sug), sulfonate (SO3-sug) and sulfate (SO4-sug)) were stable for at least 12 months when the sample was stored in polystyrene containers at +20°C in the dark. Regarding water extracts, the best storage conditions consisted of the use of polystyrene containers and a temperature of +4°C, for a maximum storage time of seven days. Therefore, the immediate analysis of Hijiki water extracts would not be necessary, and they could be stored for one week before analysis, ensuring arsenic species stability. This information about species integrity in extracts is especially useful when the sample treatment for arsenic species extraction is time-consuming.

Levels of toxic arsenic species in native terrestrial plants from soils polluted by former mining activities.

Ten native terrestrial plants from soils polluted by former mining activities (Mónica mine, NW Madrid, Spain), with high total arsenic concentration levels (up to 3500 µg g(-1)), have been studied to determine the fraction of arsenic present as toxic forms (inorganic and methylated species), which present a higher mobility and therefore the potential risk associated with their reintegration into the environment is high. Roots and aboveground parts were analyzed separately to assess possible transformations from translocation processes. Extractions were carried out with deionized water by microwave-assisted extraction at a temperature of 90 °C and three extraction steps of 7.5 min each. Total extracted arsenic concentrations were determined by inductively coupled plasma atomic emission spectrometry, showing extraction percentages from 9 to 39% (calculated as the ratio between total extracted arsenic (Asext) and total arsenic (AsT) concentrations in plants). Speciation studies, performed by high performance liquid chromatography-photo-oxidation-hydride generation-atomic fluorescence spectrometry, showed the main presence of arsenate (As(v)) (up to 350 µg g(-1)), followed by arsenite (As(iii)), in both plant parts. Monomethylarsonic acid (MMA) and trimethylarsine oxide (TMAO) were also found only in some plants. On the other hand, the use of 0.5 mol L(-1) acetic acid as an extractant led to higher extraction percentages (33-87%), but lower column recoveries, probably due to the extraction of arsenic compounds different to the toxic free ions studied, which may come from biotransformation mechanisms carried out by plants to reduce arsenic toxicity. However, As(v) concentrations increased up to 800 µg g(-1) in acid medium, indicating the probable release of As(v) from organoarsenic compounds and therefore a higher potential risk for the environment.