Hydrothermal Hot Isostatic Pressing (HHIP)-Experimental Proof of Concept.

A new hydrothermal hot isostatic pressing (HHIP) approach, involving hydrothermal water conditions and no usage of inert gas, was hypothesized and tested on 3D-printed Al-10%Si-0.3%Mg (%Wt) parts. The aluminum-based metal was practically inert at the applied HHIPing conditions of 300-350 MPa and 250-350 °C, which enabled the employment of a long (6-24 h) HHIP treatment with hardly any loss of material (the overall loss due to corrosion was mostly <0.5% w/w). Applying the new approach on the above-mentioned samples resulted in an 85.7% reduction in the AM micro-pores, along with a 90.8% reduction in the pores' surface area at a temperature of 350 °C, which is much lower than the 500-520 °C applied in common argon-based aluminum HIPing treatments, while practically maintaining the as-recieved microstructure. These results show that better mechanical properties can be expected when using the suggested treatment without affecting the material fatigue resistance due to grain growth. The proof of concept presented in this work can pave the way to applying the new HHIPing approach to other AM metal parts.

Should wastewater treatment plants' operational mode radically change to minimize GHG emissions?

The operation of municipal wastewater treatment plants (WWTPs) invariably results in significant emission of greenhouse gases (i.e., CH4, N2O, and CO2) into the atmosphere. We propose to consider a radical change in the way municipal WWTPs are operated, with the aim of minimizing GHG emissions while recycling most of the nutrient mass. The means to this end are to reduce the WWTP energy demand while maximizing the recovery of resources (phosphorus, ammonia, methane). The suggested concept involves operating the activated sludge process at a low sludge retention time (SRT < 2 d), i.e., under conditions that maximize the heterotrophic mass yield and eliminate nitrification. The ammonia concentration that remains in the water (considering N in the excess sludge and struvite production in the sludge-dewatering supernatant line) would be separated from the WWTP effluents using a unique ion-exchange material (ZnHCF), which would be regenerated using a low-volume 4 M NaCl solution. The ammonia would be then stripped at high pH and re-adsorbed by an acidic solution for reuse as fertilizer. The high bacterial yield and lack of nitrification in the aerobic step are expected to boost methane yield 3-4-fold, induce lower oxygen consumption, and most importantly, yield much lower N2O release. An approximate energy mass balance shows the concept to merit further consideration, owing to the potential significant reduction in N2O(g) emissions and recovery of resources. Empirical work followed by LCA is required to corroborate the hypothesis presented herein.

A new approach for eliminating off-flavors from RAS fish, as part of the normal grow-out period.

A new concept is presented for eliminating off-flavor from cold-water RAS-grown fish, while feeding, and as a part of the normal grow-out period. The technology is based on disconnecting the nitrification biofilter, and instead passing the water through an electrolysis system, which both oxidizes the ammonia and disinfects the water, while also removing the off-flavor compounds from the water, which thereby results in the purging of the fish. The purging period was expected to last up to 2 weeks and the fish are fed throughout it. Laboratory and pilot plant experiments were performed to prove the new concept. Lab experiments included quantification of the removal of MIB and geosmin by electrooxidation and stripping, together and separately, in the presence and absence of organic matter. A pilot plant experiment was performed using Rainbow trout to determine the rate at which the off-flavor compounds were removed from the water and the fish flesh (both skin and muscle were tested). The results show that the treatment process eliminated off-flavors in the water after ∼7 days and that the fish were below taste and odor threshold for geosmin and MIB after a maximum of 11 days. Detachment from the biofilter and the fact that the water was vigorously disinfected during the electrooxidation step guaranteed that no further off-flavor compounds would be generated during the operation. Aquacultural-management assessment indicates that RAS farms can increase both their annual production and their income by more than 10%, by implementing the suggested concept as part of the grow-out period.

A Prussian-blue analogue (PBA) ion-chromatography-based technique for selective separation of Rb+ (as RbCl) from brines.

A new general method is presented for separating pure RbCl(s) from solutions rich in Na+ and K+. The method relies on Rb+ adsorption via ion exchange performed by self-synthesized PES coated Zn-Hexa-Cyanoferrate material. The procedure starts by passing the wastewater through an ion exchange column, which is thereafter regenerated with 1 M NH4Cl. If the Rb+ absorbed on the column does not reach a minimal predetermined value (e.g., 8%, eq-based), the ammonia is removed by sublimation and the remaining salts are passed again through a Na+-preadsorbed column. Once the adsorbed Rb+ is substantial (>8%), a chromatography-based separation between Rb+ and Na+/K+ is performed, using a 2nd column, fully pre-adsorbed with NH4+. First, 0.05M NH4+-solution is used to extract Na+ and K+ out of the first column, along with a small Rb+ mass, which is thereafter partly re-adsorbed on the second column, while Na+/K+ ions are not. Once the exiting eluent solution is devoid of the competing ions, 1M NH4+-solution is used to extract all the remaining Rb+ into the regeneration solution, which is thereafter subjected to water evaporation followed by NH3/HCl sublimation to result in pure RbCl(s) product. We used theoretical simulations corroborated by empirical results to present proof of concept for the suggested approach. A detailed cost analysis (Capex and Opex) reveals that the RbCl(s) production cost does not exceed ∼25% of the current salt price.

Removal of contaminants of emerging concern from secondary-effluent reverse osmosis retentates by continuous supercritical water oxidation- parametric study and conceptual design.

The continuous removal of TOC and the degradation efficiency of carbamazepine and 17ß-estradiol were investigated using actual secondary municipal-effluent RO-retentate solutions. A specific set of operating parameters were applied within the supercritical water oxidizing conditions: temperature range 420-480 °C, 25.1 MPa, hydraulic retention time (HRT) of 1-2 min, excess oxidant molar-ratio of 3-10 and presence of a homogenous catalyst (IPA) at 50-100 mg/L. > 99% organic carbon mineralization, along with complete degradation of model pollutants, was observed at 450 °C/1 min/OC= 5-10 and 100 mgIPA/L. The outlet estrone concentration, 1.03 ± 1.14 ng/L, representing estrogenic pollutants, dropped to the "no effect" range. A model for a SCWO plant treating secondary-municipal-effluent-RO-retentate for a city of 100,000 capita-equivalent was developed, based on a shell & tube SCWO flow reactor, showing > 75% energy-efficiency. The model yielded that for the extreme case of a zero caloric-value feed-solution, the total OPEX and CAPEX would be < $6.0 ± 2.5 per m3 of secondary effluents, i.e., two orders of magnitude lower than the reported environmental shadow-price associated with CECs (contaminants of emerging concern). Further work is required on the continuous and efficient separation of the salt-matrix, which can lead to higher overall heat transfer coefficients and enable further reduction in capital costs.

Determining the kinetic constants leading to mineralization of dilute carbamazepine and estradiol-containing solutions under continuous supercritical water oxidation conditions.

Continuous subcritical and supercritical water oxidation experiments were conducted on dilute carbamazepine- and estradiol-containing synthetic solutions used to simulate the removal of model emerging pollutants from secondary municipal effluents. The operating conditions comprised 340-500 °C, retention time of 24-453 s and a stoichiometric oxidant ratio (O.C.) between 4 and 64. The transformation of the various species was determined at the outlet and by modeling a segmented non-isothermal reaction system. Four empirical power law kinetic models were established to represent both the pollutants' degradation and TOC removal efficiencies, using nonlinear multiple regression coupled with bootstrapping and K-fold cross-validation. The mineralization and degradation models for both pollutants yielded a R2 of 67-80.5% vs. the experimental results. Discussion on the various model assumptions revealed that attributing full model deviations to the constant oxygen concentration or to the laminar reactor flow, yielded a deviation of 6% and 15% in the removal efficiencies, respectively. However, the expected deviation of the models was lower than 0.32% at conditions leading to (almost) full mineralization (45-60 s, 480-500 °C and O.C.s of 5-10). The methodologies developed in the study are useful for interpreting future results obtained from SCWO of actual secondary effluent solutions.

Synthesis and characterization of zinc-hexacyanoferrate composite beads for controlling the ammonia concentration in low-temperature live seafood transports.

A new water treatment technology is presented for extending the longevity and increasing the maximal bio-load of container-bound, lucrative live seafood transportations. The technology is designed for removing ammonia and minimizing the bacterial concentration that develop in the water during the transport. This paper focuses on the characteristics of self-synthesized polyether-sulfone (PES) coated Zn-HCF composite beads, which have a high adsorbing capacity for NH4+ in seawater and constitute the heart of the developed technology. Adsorption isotherms show that the operational capacity of the composite material (PES = 20% w/w) at NH4+ concentration of 10 mgN/L at 3.5 °C is ∼3 mgN/g Zn-HCF. The kinetics of the PES-coated beads were shown to be considerably slower than the bare Zn-HCF, but since the retention time in the transport is long (many days), this does not detract from the effectiveness of the adsorption. Simulation experiments with and without live fish showed that the adsorbing material behaved as expected during a 21-d trip and that it did not have any effect on the fish. Repeated adsorption/regeneration (3 and 6 M NaCl) tests proved the composite material's stability and ion-exchange robustness. Electrooxidation of the ammonia in the exhausted regeneration solution was carried out with high efficiency and the treated solution could be used effectively in the following chemical regeneration step. The cost of a treatment unit installed in a 40-foot container was estimated at $40,000 and the ROI at 6 to 12 months.

Cost-effective treatment of swine wastes through recovery of energy and nutrients.

Wastes from concentrated animal feeding operations (CAFOs) are challenging to treat because they are high in organic matter and nutrients. Conventional swine waste treatment options in the U.S., such as uncovered anaerobic lagoons, result in poor effluent quality and greenhouse gas emissions, and implementation of advanced treatment introduces high costs. Therefore, the purpose of this paper is to evaluate the performance and life cycle costs of an alternative system for treating swine CAFO waste, which recovers valuable energy (as biogas) and nutrients (N, P, K+) as saleable fertilizers. The system uses in-vessel anaerobic digestion (AD) for methane production and solids stabilization, followed by struvite precipitation and ion exchange (IX) onto natural zeolites (chabazite or clinoptilolite) for nutrient recovery. An alternative approach that integrated struvite recovery and IX into a single reactor, termed STRIEX, was also investigated. Pilot- and bench-scale reactor experiments were used to evaluate the performance of each stage in the treatment train. Data from these studies were integrated into a life cycle cost analysis (LCCA) to assess the cost-effectiveness of various process alternatives. Significant improvement in water quality, high methane production, and high nutrient recovery (generally over 90%) were observed with both the AD-struvite-IX process and the AD-STRIEX process. The LCCA showed that the STRIEX system can provide considerable financial savings compared to conventional systems. AD, however, incurs high capital costs compared to conventional anaerobic lagoons and may require larger scales to become financially attractive.

Modeling pH variation in reverse osmosis.

The transport of hydronium and hydroxide ions through reverse osmosis membranes constitutes a unique case of ionic species characterized by uncommonly high permeabilities. Combined with electromigration, this leads to complex behavior of permeate pH, e.g., negative rejection, as often observed for monovalent ions in nanofiltration of salt mixtures. In this work we employed a rigorous phenomenological approach combined with chemical equilibrium to describe the trans-membrane transport of hydronium and hydroxide ions along with salt transport and calculate the resulting permeate pH. Starting from the Nernst-Planck equation, a full non-linear transport equation was derived, for which an approximate solution was proposed based on the analytical solution previously developed for trace ions in a dominant salt. Using the developed approximate equation, transport coefficients were deduced from experimental results obtained using a spiral wound reverse osmosis module operated under varying permeate flux (2-11 µm/s), NaCl feed concentrations (0.04-0.18 M) and feed pH values (5.5-9.0). The approximate equation agreed well with the experimental results, corroborating the finding that diffusion and electromigration, rather than a priori neglected convection, were the major contributors to the transport of hydronium and hydroxide. The approach presented here has the potential to improve the predictive capacity of reverse osmosis transport models for acid-base species, thereby improving process design/control.

Reducing the specific energy consumption of 1st-pass SWRO by application of high-flux membranes fed with high-pH, decarbonated seawater.

A new operational approach is presented, which has the potential to substantially cut down on the energy and cost demand associated with seawater reverse osmosis (SWRO) desalination, without changing the currently-installed infrastructure. The approach comprises acidification/decarbonation of the feed seawater followed by high-pH single RO pass using high-flux membranes. Since the limitation imposed by CaCO3(s) precipitation is overcome, the recovery ratio can be significantly increased. This work presents a new operational concept aimed at maximizing the benefits that can be obtained from new low-energy RO membranes available on the market. Results obtained from operating a pilot RO system revealed that following an acidification and decarbonation step, recovery ratio of 56% could be practically attained, along with effluent TDS and boron concentrations of 375 and 0.3 mg/l, respectively (feed water pH was adjusted to pH9.53 following the decarbonation step). The specific energy consumption (SEC) of this operation was calculated to be 5%-10% lower than the SEC typically associated with "conventional" SWRO operation. Two further scenarios were theoretically considered, under which the limiting operational parameter became Mg(OH)2(s) and BaSO4(s) precipitation. It was concluded that despite the fact that higher recovery ratios could be obtained, the high pressure required in these scenarios made them less appealing from both the SEC and cost standpoints. The normalized cost of the suggested approach was found to be ∼$0.07 ± 0.02/m(3) cheaper than the currently-practiced SWRO approach for obtaining product water characterized by TDS < 500 and B < 0.5 mg/l.

Predicting the Rejection of Major Seawater Ions by Spiral-Wound Nanofiltration Membranes.

Seawater nanofiltration (SWNF) generates a softened permeate stream and a retentate stream in which the multivalent ions accumulate, offering opportunities for practical utilization of both streams. This study presents an approach to simulation of SWNF including all major seawater ions (Na(+), Cl(-), Ca(2+), Mg(2+), and SO4(2-)) based on the Nernst-Planck equation, and uses it for permeate and retentate streams composition prediction. The number of degrees of freedom in the system was reduced by assuming a very high ionic permeability for Na(+), which only weakly affected the other parameters in the system. Two alternatives were examined to analyze the importance of concentration dependence of ion permeabilities: The assumption of constant ion permeabilities resulted in a reasonable fit with experimental data. However, for the permeate composition the overall fit was significantly improved (P < 0.0001) when the permeabilities of Ca(2+) and Mg(2+) were allowed to depend on the ratio of their total concentration to Na(+). This type of dependence emphasizes the strong interaction of divalent ions with the membrane and its effect on the membrane fixed charge through screening or charge reversal. When this effect was included, model predictions closely matched the experimental results obtained, corroborating the phenomenological approach proposed in this study.

Optimal sensor placement for detecting organophosphate intrusions into water distribution systems.

Placement of water quality sensors in a water distribution system is a common approach for minimizing contamination intrusion risks. This study incorporates detailed chemistry of organophosphate contaminations into the problem of sensor placement and links quantitative measures of the affected population as a result of such intrusions. The suggested methodology utilizes the stoichiometry and kinetics of the reactions between organophosphate contaminants and free chlorine for predicting the number of affected consumers. This is accomplished through linking a multi-species water quality model and a statistical dose-response model. Three organophosphates (chlorpyrifos, malathion, and parathion) are tested as possible contaminants. Their corresponding by-products were modeled and accounted for in the affected consumers impact calculations. The methodology incorporates a series of randomly generated intrusion events linked to a genetic algorithm for minimizing the contaminants impact through a sensors system. Three example applications are explored for demonstrating the model capabilities through base runs and sensitivity analyses.

A new algorithm for design, operation and cost assessment of struvite (MgNH4PO4) precipitation processes.

Deliberate struvite (MgNH4PO4) precipitation from wastewater streams has been the topic of extensive research in the last two decades and is expected to gather worldwide momentum in the near future as a P-reuse technique. A wide range of operational alternatives has been reported for struvite precipitation, including the application of various Mg(II) sources, two pH elevation techniques and several Mg:P ratios and pH values. The choice of each operational parameter within the struvite precipitation process affects process efficiency, the overall cost and also the choice of other operational parameters. Thus, a comprehensive simulation program that takes all these parameters into account is essential for process design. This paper introduces a systematic decision-supporting tool which accepts a wide range of possible operational parameters, including unconventional Mg(II) sources (i.e. seawater and seawater nanofiltration brines). The study is supplied with a free-of-charge computerized tool (http://tx.technion.ac.il/~agrengn/agr/Struvite_Program.zip) which links two computer platforms (Python and PHREEQC) for executing thermodynamic calculations according to predefined kinetic considerations. The model can be (inter alia) used for optimizing the struvite-fluidized bed reactor process operation with respect to P removal efficiency, struvite purity and economic feasibility of the chosen alternative. The paper describes the algorithm and its underlying assumptions, and shows results (i.e. effluent water quality, cost breakdown and P removal efficiency) of several case studies consisting of typical wastewaters treated at various operational conditions.

Accurate and self-consistent procedure for determining pH in seawater desalination brines and its manifestation in reverse osmosis modeling.

Measuring and modeling pH in concentrated aqueous solutions in an accurate and consistent manner is of paramount importance to many R&D and industrial applications, including RO desalination. Nevertheless, unified definitions and standard procedures have yet to be developed for solutions with ionic strength higher than ∼0.7 M, while implementation of conventional pH determination approaches may lead to significant errors. In this work a systematic yet simple methodology for measuring pH in concentrated solutions (dominated by Na(+)/Cl(-)) was developed and evaluated, with the aim of achieving consistency with the Pitzer ion-interaction approach. Results indicate that the addition of 0.75 M of NaCl to NIST buffers, followed by assigning a new standard pH (calculated based on the Pitzer approach), enabled reducing measured errors to below 0.03 pH units in seawater RO brines (ionic strength up to 2 M). To facilitate its use, the method was developed to be both conceptually and practically analogous to the conventional pH measurement procedure. The method was used to measure the pH of seawater RO retentates obtained at varying recovery ratios. The results matched better the pH values predicted by an accurate RO transport model. Calibrating the model by the measured pH values enabled better boron transport prediction. A Donnan-induced phenomenon, affecting pH in both retentate and permeate streams, was identified and quantified.

Integrated hydraulic and organophosphate pesticide injection simulations for enhancing event detection in water distribution systems.

As a complementary step towards solving the general event detection problem of water distribution systems, injection of the organophosphate pesticides, chlorpyrifos (CP) and parathion (PA), were simulated at various locations within example networks and hydraulic parameters were calculated over 24-h duration. The uniqueness of this study is that the chemical reactions and byproducts of the contaminants' oxidation were also simulated, as well as other indicative water quality parameters such as alkalinity, acidity, pH and the total concentration of free chlorine species. The information on the change in water quality parameters induced by the contaminant injection may facilitate on-line detection of an actual event involving this specific substance and pave the way to development of a generic methodology for detecting events involving introduction of pesticides into water distribution systems. Simulation of the contaminant injection was performed at several nodes within two different networks. For each injection, concentrations of the relevant contaminants' mother and daughter species, free chlorine species and water quality parameters, were simulated at nodes downstream of the injection location. The results indicate that injection of these substances can be detected at certain conditions by a very rapid drop in Cl2, functioning as the indicative parameter, as well as a drop in alkalinity concentration and a small decrease in pH, both functioning as supporting parameters, whose usage may reduce false positive alarms.

Radium and barium removal through blending hydraulic fracturing fluids with acid mine drainage.

Wastewaters generated during hydraulic fracturing of the Marcellus Shale typically contain high concentrations of salts, naturally occurring radioactive material (NORM), and metals, such as barium, that pose environmental and public health risks upon inadequate treatment and disposal. In addition, fresh water scarcity in dry regions or during periods of drought could limit shale gas development. This paper explores the possibility of using alternative water sources and their impact on NORM levels through blending acid mine drainage (AMD) effluent with recycled hydraulic fracturing flowback fluids (HFFFs). We conducted a series of laboratory experiments in which the chemistry and NORM of different mix proportions of AMD and HFFF were examined after reacting for 48 h. The experimental data combined with geochemical modeling and X-ray diffraction analysis suggest that several ions, including sulfate, iron, barium, strontium, and a large portion of radium (60-100%), precipitated into newly formed solids composed mainly of Sr barite within the first ∼ 10 h of mixing. The results imply that blending AMD and HFFF could be an effective management practice for both remediation of the high NORM in the Marcellus HFFF wastewater and beneficial utilization of AMD that is currently contaminating waterways in northeastern U.S.A.

Accurate approach for determining fresh-water carbonate (H2CO3(*)) alkalinity, using a single H3PO4 titration point.

A new, simple and accurate method is introduced for determining H(2)CO(3)(*) alkalinity in fresh waters dominated by the carbonate weak-acid system. The method relies on a single H(3)PO(4) dosage and two pH readings (acidic pH value target: pH~4.0). The computation algorithm is based on the concept that the overall alkalinity mass of a solution does not change upon the addition of a non-proton-accepting species. The accuracy of the new method was assessed batch-wise with both synthetic and actual tap waters and the results were compared to those obtained from two widely used alkalinity analysis methods (titration to pH~4.5 and the Gran titration method). The experimental results, which were deliberately obtained with simple laboratory equipment (glass buret, general-purpose pH electrode, magnetic stirrer) proved the method to be as accurate as the conventional methods at a wide range of alkalinity values (20-400 mg L(-1) as CaCO(3)). Analysis of the relative error attained in the proposed method as a function of the target (acidic) pH showed that at the range 4.0

Chemical stability and extent of isomorphous substitution in ferrites precipitated under ambient temperatures.

The ferrite process is an established method for treating wastewaters containing dissolved toxic metals, using precipitation at temperatures above 65 °C. Various ambient-temperature operation methodologies have also been proposed, but the effects of temperature reduction on product stability, and on the extent of isomorphous substitution (in terms of x in Me(x)Fe(3-x)O(4), Me representing a non-iron metal), have not been adequately quantified. At ambient temperature precipitation, maximal x of Zn(2+), Co(2+), Ni(2+) and Cd(2+) was found in the current study to be approximately 0.73, 0.67, 0.39 and 0.17, respectively. These values are 73% to 50% of the corresponding values attained by precipitation at 90 °C. The chemical stability of the ferrites produced under ambient temperatures was found to deteriorate upon high Me(2+) incorporation levels, in stark contrast with the trend observed in ferrites precipitated at 90 °C. Both observations were ascribed to the increased importance of Fe(2+)-Fe(3+) interaction under ambient conditions in driving spinel ordering. In the presence of high Me to Fe ratio in the initial solution, this interaction is weaker, resulting in impeded dehydration.

Extent and mechanism of metal ion incorporation into precipitated ferrites.

The ability of many noniron metals to be incorporated into the structure of ferrites is being utilized in numerous industrial and environmental applications. The incorporation of some of these metals during Fe(II) oxidation-induced precipitation at moderate temperatures (80-100°C) appears to be limited, for reasons not fully understood, and to extents not always agreed (e.g., Ni(2+), Cr(3+)). In this paper, the incorporation maxima of six metals into the structure of precipitated ferrites (in terms of x in Me(x)Fe(3-)(x)O(4), Me represents a noniron metal) were concluded to be 1.0, 1.0, 0.78, 0.49, 0.35, and 0.0 for Zn(2+), Co(2+), Ni(2+), Al(3+), Cd(2+) and Cr(3+), respectively. With the exception of the much larger Cd(2+), these values were associated with kinetic considerations controlled by the H(2)O exchange rate between the hydration shells surrounding the dissolved metal ion.

A new approach to increasing the efficiency of low-pH Fe-electrocoagulation applications.

Incomplete oxidation of Fe(II) species released from the anode to Fe(III) may impede iron electrocoagulation processes conducted under low dissolved oxygen and/or pH<7 conditions, accompanied by the typically high buffering capacity of wastewater. This paper introduces a new approach to overcome this drawback by applying a second electrochemical cell (Ti/RuO(2) anode and Ti cathode) to be operated in parallel to the electrocoagulation cell. The second unit oxidizes Cl(-) ions invariably present in the water to HOCl, which is capable of oxidizing Fe(II) species at a high rate, irrespective of pH or O(2(aq)) concentration. An electrolytic cell with a Ti/RuO(2) anode and Ti cathode was shown to successively operate in parallel to a sacrificial electrocoagulation cell (Fe anode and Ti cathode) to attain complete Fe(II) conversion to Fe(III) under low-pH conditions, in which, in the absence of the 2nd cell, unwanted Fe(II) species would have dominated the dissolved iron species. Current efficiency for Cl(2) production was 12.4% and 45.7% at 200 and 1000 mg Cl/l, respectively. Under three practical conditions (pH 6, [Cl(-)]=200 mg/l; pH 6, [Cl(-)]=400 mg/l; pH 5, [Cl(-)]=600 mg/l) the power demand of the combined system was 25.29, 12.7 and 8.1 kWh/kg Fe(III)(produced), respectively, suggesting that the presented approach is competitive at [Cl(-)]>∼600 mg/l.