Reduced Graphene Oxide/Waste-Derived TiO2 Composite Membranes: Preliminary Study of a New Material for Hybrid Wastewater Treatment.

This work reports the preliminary results of the development of composite self-assembling membranes obtained by the combination of reduced graphene oxide (rGO) with commercial Degussa P25 titanium dioxide (TiO2). The purpose is to demonstrate the possibility of combining, in the same self-standing material, the capability to treat wastewater containing both inorganic and organic pollutants by exploiting the established ability of rGO to capture metal ions together with that of TiO2 to degrade organic substances. Moreover, this study also investigates the potential photocatalytic properties of tionite (TIO), to demonstrate the feasibility of replacing commercial TiO2 with such waste-derived TiO2-containing material, fulfilling a circular economy approach. Thus, rGO-TiO2 and rGO-TIO composite membranes, 1:1 by weight, were prepared and characterized by SEM-EDX, XRD, thermogravimetry, as well as by Raman and UV-Vis spectroscopies to verify the effective and homogeneous integration of the two components. Then, they were tested towards 3-mg L-1 aqueous synthetic solutions of Fe3+ and Cu2+ ions to evaluate their metal adsorption ability, with values of the order of 0.1-0.2 mmol gmembrane-1, comparable or even slightly higher than those of pristine rGO. Finally, the ability of the composites to degrade a common organic pesticide, i.e., Imidacloprid®, was assessed in preliminary photocatalysis experiments, in which maximum degradation efficiencies of 25% (after 3 h) for rGO-TiO2 and of 21% (after 1 h) for rGO-TIO were found. The result of tionite-containing membranes is particularly promising and worthy of further investigation, given that the anatase content of tionite is roughly 1/6 of the one in commercial TiO2.

Combining Coagulation and Electrocoagulation with UVA-LED Photo-Fenton to Improve the Efficiency and Reduce the Cost of Mature Landfill Leachate Treatment.

This study focused on the reduction of the treatment cost of mature landfill leachate (LL) by enhancing the coagulation pre-treatment before a UVA-LED photo-Fenton process. A more efficient advanced coagulation pretreatment was designed by combining conventional coagulation (CC) and electro-coagulation (EC). Regardless of the order in which the two coagulations were applied, the combination achieved more than 73% color removal, 80% COD removal, and 27% SUVA removal. However, the coagulation order had a great influence on both final pH and total dissolved iron, which were key parameters for the UVA-LED photo-Fenton post-treatment. CC (pH = 5; 2 g L-1 of FeCl36H2O) followed by EC (pH = 5; 10 mA cm-2) resulted in a pH of 6.4 and 100 mg L-1 of dissolved iron, whereas EC (pH = 4; 10 mA cm-2) followed by CC (pH = 6; 1 g L-1 FeCl36H2O) led to a final pH of 3.4 and 210 mg L-1 dissolved iron. This last combination was therefore considered better for the posterior photo-Fenton treatment. Results at the best cost-efficient [H2O2]:COD ratio of 1.063 showed a high treatment efficiency, namely the removal of 99% of the color, 89% of the COD, and 60% of the SUVA. Conductivity was reduced by 17%, and biodegradability increased to BOD5:COD = 0.40. With this proposed treatment, a final COD of only 453 mg O2 L-1 was obtained at a treatment cost of EUR 3.42 kg COD-1.

Environmentally friendly synthesized and magnetically recoverable designed ferrite photo-catalysts for wastewater treatment applications.

Fenton processes are promising wastewater treatment alternatives for bio-recalcitrant compounds. Three different methods (i.e., reverse microemulsion, sol-gel, and combustion) were designed to synthesize environmentally friendly ferrites as magnetically recoverable catalysts to be applied for the decomposition of two pharmaceuticals (ciprofloxacin and carbamazepine) that are frequently detected in water bodies. The catalysts were used in a heterogeneous solar photo-Fenton treatment to save the cost of applying high-energy UV radiation sources, and was performed under a slightly basic pH to avoid metal leaching and adding salts for pH adjustment. All the developed catalysts resulted in the effective treatment of ciprofloxacin and carbamazepine in both synthetic and real domestic wastewater. In particular, the sol-gel synthesized ferrite was more magnetic and more suitable for reuse. The degradation pathways of both compounds were elucidated for this treatment. The degradation of ciprofloxacin involved attacks to the quinolone and piperazine rings. The degradation pathway of carbamazepine involved the formation of hydroxyl carbamazepine and dihydroxy carbamazepine before yielding acridine by hydrogen abstraction, decarboxylation, and amine cleavage, which would be further oxidized.

The application of advanced oxidation technologies to the treatment of effluents from the pulp and paper industry: a review.

The paper industry is adopting zero liquid effluent technologies to reduce freshwater use and meet environmental regulations, which implies closure of water circuits and the progressive accumulation of pollutants that must be removed before water reuse and final wastewater discharge. The traditional water treatment technologies that are used in paper mills (such as dissolved air flotation or biological treatment) are not able to remove recalcitrant contaminants. Therefore, advanced water treatment technologies, such as advanced oxidation processes (AOPs), are being included in industrial wastewater treatment chains aiming to either improve water biodegradability or its final quality. A comprehensive review of the current state of the art regarding the use of AOPs for the treatment of the organic load of effluents from the paper industry is herein addressed considering mature and emerging treatments for a sustainable water use in this sector. Wastewater composition, which is highly dependent on the raw materials being used in the mills, the selected AOP itself, and its combination with other technologies, will determine the viability of the treatment. In general, all AOPs have been reported to achieve good organic removal efficiencies (COD removal >40%, and about an extra 20% if AOPs are combined with biological stages). Particularly, ozonation has been the most extensively reported and successfully implemented AOP at an industrial scale for effluent treatment or reuse within pulp and paper mills, although Fenton processes (photo-Fenton particularly) have actually addressed better oxidative results (COD removal ≈ 65-75%) at a lab scale, but still need further development at a large scale.

Variation in photosynthetic performance and hydraulic architecture across European beech (Fagus sylvatica L.) populations supports the case for local adaptation to water stress.

The aim of this study was to provide new insights into how intraspecific variability in the response of key functional traits to drought dictates the interplay between gas-exchange parameters and the hydraulic architecture of European beech (Fagus sylvatica L.). Considering the relationships between hydraulic and leaf functional traits, we tested whether local adaptation to water stress occurs in this species. To address these objectives, we conducted a glasshouse experiment in which 2-year-old saplings from six beech populations were subjected to different watering treatments. These populations encompassed central and marginal areas of the range, with variation in macro- and microclimatic water availability. The results highlight subtle but significant differences among populations in their functional response to drought. Interpopulation differences in hydraulic traits suggest that vulnerability to cavitation is higher in populations with higher sensitivity to drought. However, there was no clear relationship between variables related to hydraulic efficiency, such as xylem-specific hydraulic conductivity or stomatal conductance, and those that reflect resistance to xylem cavitation (i.e., Ψ(12), the water potential corresponding to a 12% loss of stem hydraulic conductivity). The results suggest that while a trade-off between photosynthetic capacity at the leaf level and hydraulic function of xylem could be established across populations, it functions independently of the compromise between safety and efficiency of the hydraulic system with regard to water use at the interpopulation level.

The hydraulic conductance of Fraxinus ornus leaves is constrained by soil water availability and coordinated with gas exchange rates.

Leaf hydraulic conductance (Kleaf) is known to be an important determinant of plant gas exchange and photosynthesis. Little is known about the long-term impact of different environmental factors on the hydraulic construction of leaves and its eventual consequences on leaf gas exchange. In this study, we investigate the impact of soil water availability on Kleaf of Fraxinus ornus L. as well as the influence of Kleaf on gas exchange rates and plant water status. With this aim, Kleaf, leaf conductance to water vapour (gL), leaf water potential (Psileaf) and leaf mass per area (LMA) were measured in F. ornus trees, growing in 21 different sites with contrasting water availability. Plants growing in arid sites had lower Kleaf, gL and Psileaf than those growing in sites with higher water availability. On the contrary, LMA was similar in the two groups. The Kleaf values recorded in sites with two different levels of soil water availability were constantly different from each other regardless of the amount of precipitation recorded over 20 days before measurements. Moreover, Kleaf was correlated with gL values. Our data suggest that down-regulation of Kleaf is a component of adaptation of plants to drought-prone habitats. Low Kleaf implies reduced gas exchange which may, in turn, influence the climatic conditions on a local/regional scale. It is concluded that leaf hydraulics and its changes in response to resource availability should receive greater attention in studies aimed at modelling biosphere-atmosphere interactions.

Ion-mediated enhancement of xylem hydraulic conductivity is not always suppressed by the presence of Ca2+ in the sap.

The physiological significance of ion-mediated enhancement of xylem hydraulic conductivity (K(h)) in planta has recently been questioned. The phenomenon has been suggested to be an artefact caused by the use of deionized water as a reference fluid during measurements of the impact of different ions on K(h). In the present study, ion-mediated changes in K(h) were measured in twigs of five woody species during perfusion with 25 mM KCl compared with different reference fluids like deionized water, a commercial mineral water containing different ions (including 0.5 mM Ca(2+)), and a 1 mM CaCl(2) solution. Both fully hydrated twigs and twigs with about 50% loss of hydraulic conductivity due to cavitation-induced embolism were tested. Adding 25 mM KCl to the three reference fluids caused K(h) to increase by about 20%. The KCl-mediated increase of K(h) was even larger (up to 100%) in embolized twigs. The presence of Ca(2+) in the reference solution decreased, but not suppressed, the KCl-mediated enhancement of K(h) in fully hydrated twigs of three species, but not in the other two species tested. Ca(2+) did not affect the K(h) response to KCl in embolized twigs. These data suggest that the recently reported suppression of the 'ionic effect' by the presence of calcium in the xylem sap is not a general phenomenon and that ion-mediated changes of K(h) may play a role in planta partially to compensate for cavitation-induced loss of xylem hydraulic conductivity.

Reduced content of homogalacturonan does not alter the ion-mediated increase in xylem hydraulic conductivity in tobacco.

Xylem hydraulic conductivity (K(s)) in stems of tobacco (Nicotiana tabacum) wild-type SR1 was compared to that of PG7 and PG16, two transgenic lines with increased levels of expression of the gene encoding the Aspergillus niger endopolygalacturonase (AnPGII). Activity of AnPGII removes in planta blocks of homogalacturonan (HG) with deesterified carboxyls, thus increasing the degree of neutrality of pectins. The effect of K+ was tested in increasing stem K(s) using model plants with more neutral polysaccharides in primary walls and, hence, in intervessel pit membranes. K(s) measured with deionized water was compared to that with KCl solutions at increasing concentrations (DeltaK(s), %). Plants transformed for HG degree of neutrality showed a dwarfed phenotype, but DeltaK(s) did not differ among the three experimental groups. The ion-mediated hydraulic effect saturated at a KCl concentration of 25 mm in SR1 plants. All the three tobacco lines showed DeltaK(s) of around +12.5% and +17.0% when perfused with 10 and 25 mm KCl, respectively. Because modification of HG content did not influence ion-mediated hydraulic enhancement, we suggest that pectin components other than HG, like rhamnogalacturonan-I and/or rhamnogalacturonan-II, might play important roles in the hydrogel behavior of pit membranes.

Ion-mediated increase in the hydraulic conductivity of Laurel stems: role of pits and consequences for the impact of cavitation on water transport.

Changes in hydraulic conductivity (K(h)) were measured in stems of Laurus nobilis L. during perfusion with KCl, NaCl or sucrose solutions. Ionic solutes induced marked increase of K(h) with respect to deionized water but sucrose had no effect. The kinetics of KCl-induced K(h) increase was measured together with changes in [K(+)] of the perfused solution. K(h) increases were paralleled by increases in the [K(+)](out)/[K(+)](in) ratio. Samples of different lengths or with increasing percentage loss of conductivity (PLC) due to xylem cavitation were tested, with the aim of increasing radial flow through intervessel pits. KCl solutions enhanced the K(h) of 12-cm-long samples with a concentration-dependent effect up to 100 mm KCl. DeltaK(h) increased from 3 to 30% in 1.5- and 12-cm-long samples, respectively and remained constant for longer samples. Increasing PLC induced an exponential increase in DeltaK(h). PLC measured with KCl solutions was significantly less than that measured with deionized water, suggesting that measurements of PLC can be affected by the composition of the perfused solution. Experiments support the hypothesis that the 'ionic effect' is mediated by physico-chemical changes of pectins of the pit membranes and raise the possibility that plants might alter the ionic composition of the xylem sap to alleviate the hydraulic impact of cavitation.

Is rootstock-induced dwarfing in olive an effect of reduced plant hydraulic efficiency?

We investigated the hydraulic architecture of young olive trees either self-rooted or grafted on rootstocks with contrasting size-controlling potential. Clones of Olea europea L. (Olive) cv 'Leccino' inducing vigorous scion growth (Leccino 'Minerva', LM) or scion dwarfing (Leccino 'Dwarf', LD) were studied in different scion/rootstock combinations (LD, LM, LD/LD, LM/LM, LD/LM and LM/LD). Shoots growing on LD root systems developed about 50% less leaf surface area than shoots growing on LM root systems. Root systems accounted for 60-70% of plant hydraulic resistance (R), whereas hydraulic resistance of the graft union was negligible. Hydraulic conductance (K = 1/R) of LD root systems was up to 2.5 times less than that of LM root systems. Total leaf surface area (A(L)) was closely and positively related to root hydraulic conductance so that whole-plant hydraulic conductance scaled by A(L) did not differ between experimental groups. Accordingly, maximum transpiration rate and minimum leaf water potential did not differ significantly among experimental groups. We conclude that reduced root hydraulic conductance may explain rootstock-induced dwarfing in olive.

Application of a physical input-output table to evaluate the development and sustainability of continental water resources in Spain.

Continental waters are complex resources in terms of a measurable physical quantity, and measuring them requires a good knowledge of total water availability. In this research, an accounting physical input-output table (PIOT) was applied to evaluate total water resources and gross annual availabilities at each stage of the natural-artificial water cycle. These stages are considered subsystems of a continental water resource system describing water transfers for an average year within 13 administrative basins of Spain. Water transfers between various subsystems are characterized by internal flows decreasing the water resource availabilities. The PIOT analysis establishes these internal flows, and the origins and final uses of the total resources for each subsystem. The input-output balance registered an unsustainable negative net accumulation in eight water basins. The PIOT analysis also allowed the calculation of significant indicators such as water resource developments (RDI) and their sustainable use (SUI). RDI and SUI demonstrate that groundwater is a critical resource affecting the environment (e.g., wetlands in the upper Guadiana) and the water supply (e.g., irrigation in the Segura basin). The results of this model suggest that above-/below-ground hydrological links are important when decisions have to be made in order to provide a satisfactory supply of water in Spain. The model integrates the different water basins under territorial criteria, and therefore it may be useful for the Spanish National Hydrological Plan.

Reuse of waste materials as growing media for ornamental plants.

The use of different waste materials: pine bark, coconut fibre and sewage sludge as substrates in the production of ornamental plants was studied, with an special interest on the suitability of coconut fibre as growing substrate for conifer plants. The plant species tested were Pinus pinea, Cupressus arizonica and C. sempervirens and the substrate mixtures were: (1) pine bark, (2) pine bark with 15% of sewage sludge compost, (3) pine bark with 30% of sewage sludge compost, (4) coconut fibre, (5) coconut fibre with 15% of sewage sludge compost and (6) coconut fibre with 30% of sewage sludge compost. Substrates were physically and chemically well characterized, and 75-cm plants were grown on them for one year. Plant and substrate status were periodically tested along the experiment. As biosolid recycling is the main objective of the present work, the mixtures with 30% of composted sewage sludge will be the most convenient substrate to use. For C. sempervirens and C. arizonica, a mixture between pine bark or coconut fibre and 30% of biosolid compost in volume gave the best results, but the lower cost of the pine bark than the coconut fibre substrate indicated the use of the PB+30% CSS. For P. pinea the research of new combinations between waste products is recommended to attain better results.

Resistance to water flow through leaves of Coffea arabica is dominated by extra-vascular tissues.

The leaf hydraulic conductance (Kleaf) of Coffea arabica L. was measured for shoots exposed to non-lethal temperature stress or to a freeze-thaw cycle, and compared with Kleaf of non-stressed samples (controls). Exposure to temperatures below 6°C for 1 h caused measurable damage to the functional integrity of cell membranes as shown by increased membrane leakiness to electrolytes. A 1 : 1 relationship was found to exist between relative electrolyte leakage and relative Kleaf suggesting that membrane damage caused Kleaf to increase. Low temperatures did not cause membrane disruption as shown by the comparison of chilled samples with frozen-thawed ones. In frozen leaves, membranes were extensively disrupted and both electrolyte leakiness and Kleaf increased 5-fold. Low temperatures did not induce alterations of the hydraulic properties of the leaf vascular system, as revealed by measurements of Kleaf after up to 500 cuttings of minor veins were made in the leaf blade of control and chilled leaves. Calculations showed that 62-75% of leaf hydraulic resistance resided in the extra-vascular water pathway. Results are discussed within the frame work of our current understanding of leaf hydraulic architecture as well as in terms of plant adaptation to extremes in temperature.

Kinetics of recovery of leaf hydraulic conductance and vein functionality from cavitation-induced embolism in sunflower.

The kinetics of leaf vein recovery from cavitation-induced embolism was studied in plants of sunflower cv. Margot, together with the impact of vein embolism on the overall leaf hydraulic conductance (Kleaf). During the air-dehydration of leaves to leaf water potentials (Psi L) of -1.25 MPa, Kleaf was found to decrease by about 46% with respect to values recorded in well-hydrated leaves. When leaves, previously dehydrated to Psi L= -1.1 MPa (corresponding to the turgor loss point), were put in contact with water, Kleaf recovered completely in 10 min and so did leaf water potential. Functional vein density was estimated in both dehydrating and rehydrating leaves in terms of total length of red-stained veins infiltrated with a Phloxine B solution per unit leaf surface area. Veins were found to embolize (unstained) with kinetics showing a linear relationship with Kleaf so that about a 70% loss of functional veins corresponded with a Kleaf loss of 46%. Cavitated veins recovered from embolism within 10 min from the beginning of leaf rehydration. These data indicate that: (a) leaves of sunflower underwent substantial vein embolism during dehydration; (b) vein embolism and leaf hydraulic efficiency apparently recovered from dehydration completely and rapidly upon rehydration; (c) vein refilling occurred while conduits were still at more negative xylem pressures than those required for spontaneous bubble dissolution on the basis of Henry's law. The possible consistent contribution of vital mechanisms for vein refilling is discussed.

Xylem cavitation, leaf growth and leaf water potential in Eucalyptus globulus clones under well-watered and drought conditions.

Leaf growth, predawn leaf water potential (Ψpd), evapotranspiration, stem maximum permeability, and its percentage loss of hydraulic conductivity (PLC) were measured in rooted cuttings of selected clones of Eucalyptus globulus Labill. subjected to well-watered and drought conditions. Drought significantly reduced evapotranspiration, leaf growth and maximum permeability. E. globulus clones lost up to 70% of conductivity at values of Ψpd less negative than -1 MPa. PLC values higher than 85% could not be measured without causing leaf shedding. The coefficient related to the slope of the vulnerability curves ranged from 1.52-2.23. The lowest value was measured in the most drought-resistant clone, as estimated from field trials. Plants from this clone displayed higher drought-induced reductions in maximum permeability than plants from other clones, had significantly smaller leaves and maintained higher values of predawn leaf water potential as soil water content (SWC) declined.