Selective recovery of boron, cobalt, gallium and germanium from seawater solar saltworks brines using N-methylglucamine sorbents: Column operation performance.

The European Union (EU) identified a list of Critical Raw Materials (CRMs) crucial for its economy, aiming to find alternative sources. Seawater is a promising option as it contains almost all elements, although most at low concentrations. However, to the present, the CRMs' recovery from seawater is technically and economically unfeasible. Other alternatives to implement sea mining might be preferred, such as reverse osmosis brines or saltworks bitterns (after sodium chloride crystallisation). The CRMs' extraction in a selective way can be achieved using highly selective recovery processes, such as chelating sorbents. This study focuses on extracting Trace Elements (TEs) from solar saltworks brines, including boron, cobalt, gallium and germanium, using commercial N-methylglucamine sorbents (S108, CRB03, CRB05). The application of these sorbents has shown potential for boron recovery, but their selectivity for cobalt, gallium, and germanium requires further investigation. This research aims to assess these sorbents' kinetics and column mode performance for TEs recovery from synthetic bitterns. Boron and germanium were rapidly sorbed, reaching equilibrium (>90 %) within 1 h, except for S108, which took 2 h. In column mode, 20-25 pore volumes of bittern were treated to remove boron and germanium, but competition from other elements reduced treatment capacity. An acidic elution (1 M hydrochloric acid) allowed to elute them (>90 %), reaching concentration factors for germanium and boron of 35 and 11, respectively, while cobalt and gallium had less affinity for the sorbents. In addition, the experiments performed were fitted by a mass transfer model to determine the equilibrium constants and selectivities. Therefore, bittern mining has been proven as a secondary/alternative source to obtain CRMs, which can lead the EU to a position in which its dependence on other countries to obtain these raw materials would be decreased.

Search for Gamma-Ray Spectral Lines from Dark Matter Annihilation up to 100 TeV toward the Galactic Center with MAGIC.

Linelike features in TeV γ rays constitute a "smoking gun" for TeV-scale particle dark matter and new physics. Probing the Galactic Center region with ground-based Cherenkov telescopes enables the search for TeV spectral features in immediate association with a dense dark matter reservoir at a sensitivity out of reach for satellite γ-ray detectors, and direct detection and collider experiments. We report on 223 hours of observations of the Galactic Center region with the MAGIC stereoscopic telescope system reaching γ-ray energies up to 100 TeV. We improved the sensitivity to spectral lines at high energies using large-zenith-angle observations and a novel background modeling method within a maximum-likelihood analysis in the energy domain. No linelike spectral feature is found in our analysis. Therefore, we constrain the cross section for dark matter annihilation into two photons to ⟨σv⟩≲5×10^{-28} cm^{3} s^{-1} at 1 TeV and ⟨σv⟩≲1×10^{-25} cm^{3} s^{-1} at 100 TeV, achieving the best limits to date for a dark matter mass above 20 TeV and a cuspy dark matter profile at the Galactic Center. Finally, we use the derived limits for both cuspy and cored dark matter profiles to constrain supersymmetric wino models.

Nitrogen flow analysis in Spain: Perspectives to increase sustainability.

Nitrogen (N) is a macronutrient that, together with P and K, is vital for improving agricultural yields, but its excessive use in crop fertilisation and presence in treated wastewater and sludge are generating emissions both into the atmosphere and into natural water bodies, which leads to eutrophication events. The Haber-Bosch process is energy-intensive and it is the main chemical route to produce reactive nitrogen for the production of fertilisers. Furthermore, there is a strong dependence on imports of reactive nitrogen in Spain and Europe. For these reasons, it is necessary to propose sustainable alternatives that allow solving environmental and supply problems, in addition to proposing efficient management schemes that fit into the circular economy approach. In this context, a nitrogen flow analysis (NFA) was carried out for Spain with the year 2016 as reference. To assess some interactions and flows of N, specific sub-models were also considered for the agriculture and waste management systems. For the food and non-food flow systems, country-specific data were considered. The sectors covered were crop production (CP), animal production (AP), food processing (FP), non-food production (NF) and human consumption (HC). The results reveal a total annual import of 2142 kt N/y, of which 43 % accumulated in stocks of soils and water bodies (913 kt N/y). The largest proportion of losses was associated with emissions from agriculture (724 kt N/y to water bodies and 132 kt N/y accumulated in soils), followed by industry emissions to the atmosphere (122 kt N/y). Wastewater treatment plants (WWTPs) received around 67 kt N/y, of which 26 % was removed as biosolids and 20 % of these biosolids were recovered to be used for fertilising applications. The 49 kt N/y discharged in the final treated effluent represented 79 % of the total loss of reactive nitrogen to water bodies. In addition, an analysis of N-use efficiency and the actions required for its improvement in Spain, as well as the impact of the current diet on the N cycle, was carried out.

Mining minerals and critical raw materials from bittern: Understanding metal ions fate in saltwork ponds.

Seawater represents a potential resource for raw materials extraction. Although NaCl is the most representative mineral extracted other valuable compounds such as Mg, Li, Sr, Rb and B and elements at trace level (Cs, Co, In, Sc, Ga and Ge) are also contained in this "liquid mine". Most of them are considered as Critical Raw Materials by the European Union. Solar saltworks, providing concentration factors of up-to 20 to 40, offer a perfect platform for the development of minerals and metal recovery schemes taking benefit of the concentration and purification achieved along the evaporation saltwork ponds. However, the geochemistry of these elements in this environment has not been yet thoroughly evaluated. Their knowledge could enable the deployment of technologies capable to achieve the recovery of valuable minerals. The high ionic strengths expected (0.5-7 mol/kg) and the chemical complexity of the solutions imply that only numerical geochemical codes, as PHREEQC, and the use of Pitzer model to estimate the activity coefficients of the different species in solution can be adopted to provide valuable description of the systems. In the present work, for the first time, PHREEQC Pitzer code database was extended to include the target minor and trace elements using Trapani saltworks (Sicily, Italy) as a case study system. The model was able to predict: i) the purity in halite and the major impurities contained, mainly Ca, Mg and sulphate species; ii) the fate of minor components as B, Sr, Cs, Co, Ge and Ga along the evaporation ponds. The results obtained pose a fundamental step in critical raw materials mining from seawater brine, for process intensification and combination with desalination.

Techno-economic assessment of decentralized polishing schemes for municipal water reclamation and reuse in the industrial sector in costal semiarid regions: The case of Barcelona (Spain).

This study demonstrates the techno-economic reliability of an innovative fit-for-use treatment train to boost municipal reclaimed water reuse fore industrial uses in the Barcelona Metropolitan Area (BMA). The relatively high conductivity (2090 µS/cm) and hardness (454 mg/L) of reclaimed water in the BMA (e.g. Water Reclamation Plant (WRP) of El Baix Llobregat, Barcelona, Spain), together with the restrictive water quality demands in industrial uses, claims for the implementation of advanced reclamation schemes based on desalination technologies such as reverse osmosis (RO). The study assesses the benefits of two potential pre-treatments of the RO stage: (i) ultrafiltration (UF) or (ii) an innovative high-performance nano-structured polymeric adsorbent (CNM); in which a permeability decline of 5% was observed when CNM was used as a pre-treatment, while a stable permeability of RO was found when was fed by the UF effluent. On the other hand, generic cost curves have been calculated for the technologies evaluated and were applied to estimate capital and operational expenditures (CAPEX and OPEX) for the scale-up in three different industrial sites (e.g., chemical, waste management and electro-coating industries). The economic assessment indicates that the use of municipal reclaimed water is economically competitive in front of the use of tap water in the BMA, providing savings between 0.13 and 0.52 €/m3 for the waste management industry and between 0.49 and 0.98 €/m3 for the electrocoating industry. On the other hand, the use of groundwater in one of the industrial sites and its relatively low cost implied that, although it is necessary a RO, the current cost of water is significantly lower.

Integration of membrane processes for the recovery and separation of polyphenols from winery and olive mill wastes using green solvent-based processing.

Winery and olive mill industries generate large amounts of wastes causing important environmental problems. The main aim of this work is the evaluation of different membrane separation processes like microfiltration, ultrafiltration, nanofiltration, and reverse osmosis for the recovery of polyphenols from winery and olive mill wastes in aqueous solutions. Membrane processes were tested separately in a closed-loop system, and by an integration in a concentration mode sequential design (open-loop). Feed flow rate was varied from 1 to 10 mL min-1, and permeate samples were taken in order to measure the polyphenols concentration. The separation and concentration efficiency were evaluated in terms of total polyphenol content, and by polyphenols families (hydroxybenzoic acids (HB), hydroxycinnamic acids (HC), and flavonoids (F)), using high performance liquid chromatography. Results showed that MF and UF membranes removed suspended solids and colloids from the extracts. NF was useful for polyphenols separation (HB rejections were lower than for HC and F: HB rejections of 50 and 63% for lees filters and olive pomace extracts, respectively), and RO membranes were able to concentrate polyphenols streams (86 and 95% rejection from lees filters and olive pomace, respectively). Membranes sequential designs for lees filters and olive pomace extracts, using a selective membrane train composed by UF, NF and RO membranes, were able to obtain polyphenol rich streams and high-quality water streams for reuse purposes.

Recovery of rare earth elements from acidic mine waters: An unknown secondary resource.

Acidic mine Drainage (AMD) is still considered one of the greatest mining sustainability challenges due to the large volumes of wastes generated and the high associated treatment cost. New regulation initiatives on sustainable development, circular economy and the need for strategic elements as Rare Earth Elements (REE) may overcome the traditional research initiatives directed to developing low cost treatment options and to develop research initiatives to identify the potential benefit of considering such AMD as a potential secondary resource. As an example, this study develops the integration of a three-stage process where REE are selectively separated from base metals (e.g. Fe, Al, Mn, Ca, Mg, Cd, Pb) and then concentrate to produce a rich REE by-product recovered as REE-phosphates. Selective separation of Fe (>99%) was achieved by total oxidation to Fe(III) and subsequent precipitation as schwertmannite at pH 3,6 ± 0.2. REE were then extracted from AMD using a sulfonic ion-exchange resin to produce concentrated REE sulfuric solutions up to 0.25 gREE/L. In a final stage selective separation of REE from Al(III), Ca(II) and Mg(II) and transitions elements (Cu, Zn, Ni) was achieved by precipitation with phosphate solutions under optimized pH control and total phosphate concentration. XRD analysis identified low-crystalline minerals. By using a thermal treatment the presence of PrPO4(s) and Cheralite (CePO4(s)) where Ce is substituted by La and Ca and Xenotime (YPO4(s)) were found as main minerals AlPO4(s) Ca,MgYPO4(s) were also identified.

Integration of membrane distillation as volume reduction technology for in-land desalination brines management: Pre-treatments and scaling limitations.

Management of in-land reverse osmosis (RO) desalination brines generated from surface brackish waters is a current challenge. Among the different near-Zero and Zero Liquid Discharge (ZLD) alternatives, Membrane Distillation (MD), in which the transport of water is thermally driven, appears as an attractive technology if a residual heat source is available. The aim of this study was to identify the limits of Direct Contact MD (DCMD) pre-treatments such as acidification and aeration, or the combination of both to quantify the scaling reduction potential when treating a RO brine from surface brackish water. Experimental data were used to evaluate the effectiveness of DCMD to achieve the highest concentration factors, depending on the chosen pre-treatment. Additionally, an economic analysis of the operational cost, taking as case study a site where the current management of the brine is the discharge to the sea, was also carried out. Results showed that pre-treatments enhanced MD performance by increasing the concentration factor achieved and highest volume reductions (about 3 times) were reached with the combination of acidification and aeration pre-treatments. Both processes reduced the precipitation potential of CaCO3(s) by reducing the total inorganic carbon (>90%); however, CaSO4·2H2O(s) precipitated. Results also indicated that even if a waste heat source is available, brine disposal into the sea is the cheapest option, while ZLD alternatives were not attractive in the current regulatory framework since their cost was higher than the discharge to the sea. Other options related to the Minimal Liquid Discharge may be more economically attractive.

Valorisation options for Zn and Cu recovery from metal influenced acid mine waters through selective precipitation and ion-exchange processes: promotion of on-site/off-site management options.

Acid mine waters (AMWs), generated in the processing of polymetallic sulphides, contain copper and zinc as the main valuable transition metal ions, which are typically removed by liming, due to their great environmental impact. In this context, this work proposes the integration of selective precipitation (SP) and ion-exchange (IX) processes for the separation and recovery of both valuable metals to encourage on-site and off-site management options promoting valorisation routes. Thus, the main objectives of this work were (i) the selective removal of Fe(III) and Al(III), using NaOH under pH control (pH < 5) to avoid the precipitation of Cu(II) and Zn(II) and (ii) the evaluation of a solvent-impregnated resin (Lewatit VP OC 1026, named VP1026) and a cation IX resin (Lewatit TP 207, named TP207) for the sequential extraction of both metal ions from AMW (batch and column experiments). Results indicated that the metallic pollution load was mostly removed during the SP process of Fe(III) (>99%) and Al(III) (>90%) as hydroxylsulphates (e.g., schwertmannite and basaluminite). The metal extraction profiles were determined for both metals from pH 1 to pH 5 by batch experiments, and indicated that the best extraction of Zn(II) was obtained using VP1026, being higher than 96% (pH = 2.6-2.8), whereas TP207 extraction performance was optimal for Cu(II) extraction (>99%) at pH = 3-4. Moreover, in dynamic experiments using a fixed-bed configuration, it was possible to separate and concentrate Zn(II) (concentration factor = 10) and Cu(II) (concentration factor = 40) using VP1026 and TP207, respectively. Overall, the integration of SP and IX processes showed a great potential in the separation and recovery of valuable metals from mine waters to promote a circular economy, based on the management proposal for non-ferrous metallurgical industries. The recovered Zn-rich and Cu-rich sulphuric concentrated streams were theoretically evaluated for further on-site or off-site re-use treatments (e.g., electrowinning, precipitation, crystallization).

Arsenic impact on the valorisation schemes of acidic mine waters of the Iberian Pyrite Belt: Integration of selective precipitation and spiral-wound nanofiltration processes.

Arsenic and selenium presence in acid mine waters (AMWs) limits their disposal due to environmental regulations. The focus to solve the economic infeasibility is directed to sustainable solutions, promoting resource recovery. In fact, rare earth elements (REEs) recovery is proposed in most of the Iberian Pyrite Belt AMWs. However, the presence of arsenic and selenium may impact in the REEs recovery. Among different alternatives, nanofiltration (NF) provides a concentration stage on REEs recovery, reduces the nominal flow and removes hazardous species. In this work, Iberian Pyrite Belt AMWs with up to 10 mg/L REEs, containing arsenic (2 mg/L), were treated with a NF membrane. Firstly, AMWs were pre-treated with H2O2/NaOH, to oxidise Fe(II) to Fe(II) and As(III) to As(V), promoting their removal and avoiding their potential precipitation at the membrane. Subsequently, NF pressure effect (6-20 bar) was studied, removing metals (>95 %), whereas arsenic rejections ranged from 60 to 71 %. Then, water recovery potential was evaluated at 10, 15 and 22 bar by reproducing a 10-stages NF plant. Results showed that the proposed treatment could be an alternative for arsenic and selenium removal (70 µg/L and 0.5 µg/L permeate concentrations, respectively) to achieve mining discharge limits according to regulations.

Bounds on Lorentz Invariance Violation from MAGIC Observation of GRB 190114C.

On January 14, 2019, the Major Atmospheric Gamma Imaging Cherenkov telescopes detected GRB 190114C above 0.2 TeV, recording the most energetic photons ever observed from a gamma-ray burst. We use this unique observation to probe an energy dependence of the speed of light in vacuo for photons as predicted by several quantum gravity models. Based on a set of assumptions on the possible intrinsic spectral and temporal evolution, we obtain competitive lower limits on the quadratic leading order of speed of light modification.

From nanofiltration membrane permeances to design projections for the remediation and valorisation of acid mine waters.

Acidic Mine Waters (AMWs) are characterised by high acidity (pH < 3) as H2SO4 and elevated contents of metals (Al, Fe, Cu, Zn), including rare earth elements (REEs). Due to the exhaustion of minable REE containing-minerals, AMWs are increasingly regarded as an alternative source of REEs. Among the different alternatives for the pre-concentration of AMWs required to make the REE extraction possible, nanofiltration (NF) membranes emerge as a promising technology because they not only successfully reject multivalent ions (metals), allowing its concentration in the retentate stream, but also permit the transport of monovalent ones, such as H+ and HSO4-, allowing the recovery of sulphuric acid in the permeate. Despite this potential of NF, there is still a lack of modelling tools for predicting the performance of NF membranes because of its dependence on solution composition, membrane properties and interaction between both. In this study, a prediction tool based on the Solution-Electro-Diffusion model (including the effect of solution composition) was developed and experimentally validated for the application of two polyamide-based NF membranes (NF270 and Desal DL) for the recovery of REEs and H2SO4 from three different synthetic solutions mimicking AMWs (pH 1.0, 60 mg/L REEs and, 25-600 mg/L Al, Cu, Ca and Zn) differing in their Fe concentration (0-2125 mg/L). Metals were effectively rejected (>98%), whereas H2SO4 was transported across the membrane (H+ rejections <30%). The mathematical model was able to predict the performance of both membranes as well as the potential scaling events associated with Fe and Al hydroxides and hydroxy-sulphates.

Integration of liquid-liquid membrane contactors and electrodialysis for ammonium recovery and concentration as a liquid fertilizer.

The accumulation of ammonia in water bodies can cause eutrophication and reduce water quality. Furthermore, 80% of the ammonia in the world is consumed as fertilizer, which makes it a resource that can be recovered under the circular economy concept. Then, ammonia from wastewater can be valorised for agricultural applications. Liquid-liquid membrane contactors (LLMCs) have been postulated as a novel and eco-friendly technology for ammonia recovery, because they can convert dissolved ammonia into ammonium salts by an acid stripping solution. The concentration of the ammonium salt produced is limited by the co-transport of water in LLMC. Further concentration by electrodialysis (ED) is presented as a solution to overcome this problem. In this work, ammonia streams with different initial ammonia concentrations (1.7-4.0 g/L) were treated by LLMCs to produce liquid ammonium salt fertilizers (as NH4NO3 and NH4H2PO4). Then, these ammonium solutions were concentrated by ED in order to achieve the nitrogen content required for direct application in agriculture for fertigation. After the LLMC process, the fertilizer obtained was composed of approximately 5.1% or 10.1% (w/w) nitrogen, depending on the initial ammonia concentration. After that, it was possible to concentrate these ammonium salts by a factor of 1.6 ± 0.3 using ED with an optimal energy consumption of 0.21 ± 0.08 kWh/kg ammonium salt and 93.1 ± 4.2% of faradaic yield. This gave a liquid fertilizer composed of 15.6% (w/w) nitrogen as NH4NO3. Overall, it was possible to integrate two innovative membrane technologies for the valorisation and concentration of nutrients from ammonia wastewater streams.

Techno-economic evaluation and comparison of PAC-MBR and ozonation-UV revamping for organic micro-pollutants removal from urban reclaimed wastewater.

The presence of sewage-borne Organic Micro-Pollutants (OMP) in Wastewater Treatment Plants (WWTP) effluents represents an increasing concern when water is reclaimed for irrigation or even indirect potable reuse. During eighteen months, an innovative hybrid water reclamation scheme based on a Membrane Biological Reactor (MBR) enhanced with Powder Activated Carbon (PAC) was operated at pilot-scale (70 m3/d) in order to compare it with state-of-the art Wastewater Reclamation System (WWRS) also revamped with a final step of ozonation-UV. Removal of persistent OMP, water quality and treatment costs were evaluated and compared for the different treatment schemes. OMP removal efficiency results for the different schemes concluded that established technologies, such as physico-chemical and filtration systems as well as MBR, do not remove significantly (>15%) the most recalcitrant compounds. The upgrading of these two systems through the addition of ozonation-UV step and PAC dosing allowed improving average recalcitrant OMP removal to 85 ±â€¯2 and 75 ±â€¯5%, respectively. In term of costs, PAC-MBR represents an increase of 37% of costs regarding conventional systems but presents improvements of 50% reduction in space and water quality. On the other hand, ozonation requires up to a 15% increase of foot-print; nevertheless, represents lower costs and lower carbon footprint. Ozonation-UV seems to be the best option for upgrading existing facilities, while PAC-MBR should be considered when space represents a critical limitation and produced water is reused for high water quality purposes.

New concepts on carbon redirection in wastewater treatment plants: A review.

Wastewater treatment plants (WWTPs) are no longer considered pollution removal systems but rather resources (nutrients and energy) recovery plants. Legislation imposing more stringent effluent requirements and the need energy self-sufficient or even energy-positive plants are the main drivers for the research and development of new WWTP configurations. While a lot of effort has been focused on developing new processes for nutrient recovery, limited efforts have been allocated to maximizing energy recovery from the organic load. Within this context, high-rate activated sludge (HRAS) is the most promising alternative technology to redirect carbon (organic compounds) towards energy as biogas. This is a critical review of the last decade's development of new alternatives for carbon redirection to improve the energy balance of WWTPs on both the laboratory and the industrial scale.

Simultaneous ammonium and phosphate recovery and stabilization from urban sewage sludge anaerobic digestates using reactive sorbents.

The use of low-cost inorganic sorbents as a new sustainable strategy to enhance the valorization of nutrients (N-P-K), from the urban water cycle (e.g., side streams from sewage sludge anaerobic digestion), in agriculture applications is presented. The simultaneous recovery and stabilization of ammonium and phosphate by using a mixture of two reactive sorbents (Na and K zeolites and magnesium oxide) was evaluated. The nutrients stabilization process, favoured at alkaline pH values, is carried out by a) the precipitation of phosphate ions with magnesium and/or ammonium ions and b) the sorption of ammonium by Na- and K-zeolites. MgO(s) promoted the stabilization of phosphate as bobierrite (Mg3(PO4)2(s)) or struvite (MgNH4PO4(s)) depending on the applied dose. Doses with the stoichiometric molar ratio of Mg/P promote the formation of bobierrite, while molar ratios higher than 3 favour the formation of struvite. Na zeolites (NaP1-NA, NaP1-IQE) demonstrated efficiency on ammonium stabilization between 60±2 (for 15gZ/L) to 90±3% (for 50gZ/L). The ammonium recovery efficiency is limited by the zeolite sorption capacity. If the target of the fertilizing criteria should include K, then the use of a K-zeolite (e.g., 5AH-IQE) provides a good solution. The optimum pH for the precipitation of struvite and bobierrite is 9.5 and the optimum pH for ammonium removal is between 4 and 8.5. N is present in higher concentrations (up 0.7-1gNH4+/L) when pH is ranged between 8.2 and 8.6. The ammonium recovery ratios were better than those previously reported using only magnesium oxide or even a more expensive reagent as newberrite (MgHPO4(s)). The recovery mechanisms described generate low-solubility stabilized nutrients forms that potentially can be applied as slow-release fertilizers in agriculture. Thus, the use in agriculture of blends of digested sludge with low-solubility stabilized nutrients forms will improve soils quality properties in terms of organic matter and nutrients availability.

Fluorescence spectroscopy and parallel factor analysis as a dissolved organic monitoring tool to assess treatment performance in drinking water trains.

Fluorescence excitation emission matrix (FEEM) spectroscopy was used to evaluate its applicability as a tool to track dissolved organic matter (DOM) in a drinking water treatment plant (DWTP) that incorporates a conventional line (consisting in ozonation and GAC filtration) and a membrane-based line (consisting in ultrafiltration, reverse osmosis and mineralization) working in parallel. Seven sampling points within the different process stages were characterized monthly during 2014. A global Parallel Factor Analysis (PARAFAC) was used to pull out underlying organic fractions from the fluorescence spectra. Accordingly a five components model was selected to describe the system and the pros and cons of the model were discussed by analysis of the residuals. Among the five fluorescent components, those associated to humic-like matter (C1, C3 and C4) showed a similar season variability in the river water feeding the DWTP (which resembled that of UV254 and TOC), whereas the two components associated to protein-like matter (C2 and C5) exhibited a different behavior. The maximum fluorescence intensity values (Fmax) were used to quantify DOM removals across the plant. Compared to the conventional line, water from the UF/RO membrane-based line showed between 6 and 14 times lower fluorescence intensity signal for the humic-like components and between 1 and 3 for the protein-like components as compared to the conventional line. The differences in DOM composition due to seasonal variations and along the treatment trains point out the suitability of using fluorescence measurements over other parameters such as UV254 as a monitoring tool to help optimize operation conditions of each treatment stage and improve produced water quality in a DWTP.

Recovery of ammonia from domestic wastewater effluents as liquid fertilizers by integration of natural zeolites and hollow fibre membrane contactors.

The integration of up-concentration processes to increase the efficiency of primary sedimentation, as a solution to achieve energy neutral wastewater treatment plants, requires further post-treatment due to the missing ammonium removal stage. This study evaluated the use of zeolites as a post-treatment step, an alternative to the biological removal process. A natural granular clinoptilolite zeolite was evaluated as a sorbent media to remove low levels (up to 100mg-N/L) of ammonium from treated wastewater using batch and fixed bed columns. After being activated to the Na-form (Z-Na), the granular zeolite shown an ammonium exchange capacity of 29±0.8mgN-NH4+/g in single ammonium solutions and 23±0.8mgN-NH4+/g in treated wastewater simulating up-concentration effluent at pH=8. The equilibrium removal data were well described by the Langmuir isotherm. The ammonium adsorption into zeolites is a very fast process when compared with polymeric materials (zeolite particle diffusion coefficient around 3×10-12m2/s). Column experiments with solutions containing 100mgN-NH4+/L provide effective sorption and elution rates with concentration factors between 20 and 30 in consecutive operation cycles. The loaded zeolite was regenerated using 2g NaOH/L solution and the rich ammonium/ammonia concentrates 2-3g/L in NaOH were used in a liquid-liquid membrane contactor system in a closed-loop configuration with nitric and phosphoric acid as stripping solutions. The ammonia recovery ratio exceeded 98%. Ammonia nitrate and di-ammonium phosphate concentrated solutions reached up to 2-5% wt. of N.

Reverse osmosis membrane composition, structure and performance modification by bisulphite, iron(III), bromide and chlorite exposure.

Reverse osmosis (RO) membrane exposure to bisulphite, chlorite, bromide and iron(III) was assessed in terms of membrane composition, structure and performance. Membrane composition was determined by Rutherford backscattering spectrometry (RBS) and membrane performance was assessed by water and chloride permeation, using a modified version of the solution-diffusion model. Iron(III) dosage in presence of bisulphite led to an autooxidation of the latter, probably generating free radicals which damaged the membrane. It comprised a significant raise in chloride passage (chloride permeation coefficient increased 5.3-5.1 fold compared to the virgin membrane under the conditions studied) rapidly. No major differences in terms of water permeability and membrane composition were observed. Nevertheless, an increase in the size of the network pores, and a raise in the fraction of aggregate pores of the polyamide (PA) layer were identified, but no amide bond cleavage was observed. These structural changes were therefore, in accordance with the transport properties observed.

Characterization of water dissolved organic matter under woody vegetation patches in semi-arid Mediterranean soils.

Woody patches in semiarid environments favor the establishment of other plants. Facilitation may be favored by an increase in soil fertility. Dissolved organic matter (DOM), is the most active fraction of soil organic matter and may contain compounds affecting plant establishment, as allelochemicals, hormone-like substances and metal carriers. However, information on DOM contents and composition in these environments is scarce. In this paper, we study the impact of woody patches on DOM in Stipa tenacissima L. steppes and discuss its implications for community dynamics. DOM under patch- and inter-patch areas, was analyzed for elemental composition, UV-Vis indices and organic acid content. Element concentration and composition in DOM, and organic acid concentration were similar in patch- and inter-patch areas. Yet, soils under patches were richer in DOC, aromatic species and organic acids (particularly fumaric acid) than soils in inter-patch areas. Dominant species affected organic matter concentration and quality in complex ways. Thus, patches dominated by Ephedra fragilis showed higher concentrations of TOC and aromatics than those dominated by other species. Rhamnus lycioides patches showed the highest accumulation of fumaric acid, which may contribute to its successful recruitment rate and expansion in the area. Our results show substantial differences in the amount and composition of DOM and specific compounds affecting soil functionality and plant dynamics. Further studies on the effects of such changes on seedling performance are needed to increase our understanding of plant-plant interactions in semiarid environments.