Comparative assessment of treatment technologies for minimizing reverse osmosis concentrate volume for industrial applications: A review.

Desalination of seawater, brackish water, and reclaimed water is becoming increasingly prevalent worldwide to supplement and diversify fresh water supplies. However, particularly for industrial wastewater, the need for environment-friendly and economically viable alternatives for concentrate management is the major impediment to deploying large-scale desalination. This review covers various strategies and technologies for managing reverse osmosis concentrate (ROC) and also includes their disposal, treatment, and potential applications. Developing energy-efficient, economical, and ecologically sound ROC management systems is essential if desalination and wastewater treatment are being implemented for a sustainable water future, particularly for industrial wastewater. The limitations and benefits of various concentrate management strategies are examined in this review. Moreover, it explores the potential of innovative technologies in reducing concentrate volume, enhancing water recovery, eliminating organic pollutants, and extracting valuable resources. This review critically discusses concentrate management approaches and technologies, including disposal, treatment, and reuse, including new technologies for reducing concentrate volume, boosting water recovery, eliminating organic contaminants, recovering valuable commodities, and minimizing energy consumption.

Performance of sulfur-based autotrophic denitrification process for nitrate removal from permeate of an MBR treating textile wastewater and concentrate of a real scale reverse osmosis process.

Textile is one of the industrial sectors generating the highest amount of wastewater with various polluting substances. Lately, water reuse in textile industries, especially, with the reverse osmosis (RO) process following membrane bioreactor (MBR) treatment has been applied more commonly. In this study, an autotrophic sulfur-based denitrifying column performance was evaluated, for the first time, for nitrate reduction from permeate of a lab-scale MBR receiving real textile wastewater and from the concentrate stream of a real scale-RO plant used for recovering water from textile wastewater. Nitrate concentration in the MBR effluent and RO concentrate averaged 35 ± 3 and 12 ± 2 mg-N/L, respectively. With the sulfur-based column bioreactor, quite high (≥90%) denitrification performances were attained both for MBR effluent and RO concentrate up to nitrate loadings of 0.432 and 0.12 g-N/(L.d), respectively. COD present in wastewater was not utilized in the column bioreactor, which illustrates no or minimal contribution of heterotrophic denitrification. Alkalinity concentration in the wastewater was enough to buffer the acid formation during autotrophic denitrification. Sulfate was generated accompanied by nitrate reduction and sulfide was formed at low nitrate loadings. In the batch tests, the denitrification rates for the MBR effluent and RO concentrate were 0.31 and 0.28 g-N/(g-VSS.d), respectively, which were relatively higher than the ones observed for the synthetic nitrate-contaminated groundwater. Autotrophic sulfur-based denitrification is a promising and robust process alternative even for textile RO concentrate with high concentrations of salinity, non-biodegradable COD, and color.

Recovering Phosphate from Complex Wastewater Using Macroporous Cryogel Composited Calcium Silicate Hydrate Nanoparticles.

Since currently used natural, nonrenewable phosphorus resources are estimated to be depleted in the next 30-200 years, phosphorus recovery from any phosphorus-rich residues has attracted great interest. In this study, phosphorus recovery from complex wastewater samples was investigated using continuous adsorption on cryogel column composited calcium silicate hydrate nanoparticles (CSH columns). The results showed that 99.99% of phosphate was recovered from a synthetic water sample (50 mg L-1) using a 5 cm CSH column with a 5 mL min-1 influent flow rate for 6 h while 82.82% and 97.58% of phosphate were recovered from household laundry wastewater (1.84 mg L-1) and reverse osmosis concentrate (26.46 mg L-1), respectively. The adsorption capacity decreased with an increasing flow rate but increased with increasing initial concentration and column height, and the obtained experimental data were better fitted to the Yoon-Nelson model (R2 = 0.7723-0.9643) than to the Adams-Bohart model (R2 = 0.6320-0.8899). The adsorption performance of phosphate was decreased 3.65 times in the presence of carbonate ions at a similar concentration, whereas no effect was obtained from nitrate and sulfate. The results demonstrate the potential of continuous-flow phosphate adsorption on the CSH column for the recovery of phosphate from complex wastewater samples.

Removal of methylisothiazolinone biocide from wastewater by VUV/UV advanced oxidation process: Kinetics, mechanisms and toxicity.

Methylisothiazolinone (MIT) is frequently used as antimicrobial in household and industrial products, and poses ecological and health risks to aquatic organisms and humans. In this study, vacuum ultraviolet (VUV)/ultraviolet (UV) irradiation was found highly efficient for removal of MIT. The rate constant of MIT degradation (kobs) under VUV/UV irradiation was 3.75 µEinstein-1 cm2, which was around 12.5 times higher than that under UV irradiation. The •OH concentration during the VUV/UV process was 1.0 × 10-12 M. The contributions of UV photolysis and •OH oxidation to MIT degradation under VUV/UV irradiation were 7.3% and 92.7%, respectively. The optimum solution pH (6.0-7.1) gave kobs 33%-39% higher than those at pH 3.9 and 9.3. CO32-/HCO3- inhibited MIT degradation and the kobs decreased by 74% when the concentration of CO32-/HCO3- was increased to 1 mM. The order of MIT removal efficiency under VUV/UV irradiation was ultrapure water > secondary effluent > reverse osmosis (RO) concentrate, because of the light screening and •OH quenching effect of actual wastewater. In RO concentrate, the rate constant of MIT degradation under VUV/UV irradiation was 22% higher than that obtained under UV irradiation. The reduction of TOC, UV254, and total fluorescence regional integration of the RO concentrate during VUV/UV process were 7.2%, 34.9%, and 52.3%, respectively. Twelve main transformation products of MIT were identified after VUV/UV degradation. The main degradation mechanisms of MIT were sulfur atom oxidation and hydroxyl addition. Quantitative structure-activity relationship analysis showed that VUV/UV degradation was an efficient method to remove the toxicity of MIT.

Catalytic Ozonation of Organics in Reverse Osmosis Concentrate with Catalysts Based on Activated Carbon.

Acid-washed activated carbon (AC-A), nitric acid modified activated carbon (AC-NO2), aminated activated carbon (AC-NH2) and cerium-loaded activated carbon (Ce/AC) were prepared and characterized by BET procedure, Boehm titration and SEM. Their performances were investigated for the ozonation of p-chlorobenzoic acid (p-CBA) in its solution and organic compounds in reverse osmosis concentrate (ROC). Nitration and amination had little effect on the surface area of catalyst, but increased the concentration of surface acid and basic functional group respectively. After loading Ce, the surface area of the catalyst decreased, and amount of Ce particles were agglomerated on the surface of activated carbon. All the four catalysts can improve the removal rate of the organics in water. Among the four catalysts, Ce/AC shows the highest catalytic activity. The removal rates of p-CBA, TOC and three target pollutants (e.g., tetracycline, metoprolol, atrazine) are 99.6%, 70.38%, 97.76%, 96.21% and 96.03%, respectively. Hydroxyl radical (·OH) was proved to be the core of catalytic reaction mechanism for Ce/AC, with the contribution rate to p-CBA removal of 91.4%. The surface groups and the Ce loaded on AC were the initiator for the rapid generation of ·OH. Electron transfer between electron-rich structures and cerium oxide might be a synergistic effect that can increase catalytic activity of Ce loaded on AC. Catalytic ozonation with Ce/AC is a promising ROC treatment technology due to its efficiency and possibilities for improvement.

Performance of Electrochemical Processes in the Treatment of Reverse Osmosis Concentrates of Sanitary Landfill Leachate.

Electrochemical technologies have been broadly applied in wastewaters treatment, but few studies have focused on comparing the performance of the different electrochemical processes, especially when used to treat highly-polluted streams. The electrochemical treatment of a reverse osmosis concentrate of sanitary landfill leachate was performed by means of electrocoagulation (EC), anodic oxidation (AO) and electro-Fenton (EF) processes, and the use of different electrode materials and experimental conditions was assessed. All the studied processes and experimental conditions were effective in organic load removal. The results obtained showed that EC, with stainless steel electrodes, is the cheapest process, although it presents the disadvantage of sludge formation with high iron content. At high applied current intensity, AO presents the best treatment time/energy consumption ratio, especially if the samples' initial pH is corrected to 3. However, pH correction from natural to 3 deeply decreases nitrogen-containing compounds' removal. For longer treatment time, the EF process with a carbon-felt cathode and a BDD anode, performed at natural iron content and low applied current intensity, is the most favorable solution.

Denitrification and microbial community in MBBR using A. donax as carbon source and biofilm carriers for reverse osmosis concentrate treatment.

In this study, raw Arundo donax (A. donax) pieces were applied as carbon source and biofilm carriers for denitrification in a lab-scale moving bed biofilm reactor (MBBR) for the treatment of reverse osmosis concentrate gathered from local wastewater reuse plant. At stable phase (about 60 days), efficient denitrification performance was obtained with 73.2% ±â€¯19.5% NO3--N average removal and 8.10 ±â€¯3.45 g N/(m3·day) NO3--N average volumetric removal rate. Mass balance analysis showed that 4.84 g A. donax was required to remove 1 g TN. Quantitative real-time PCR analysis results showed that the copy numbers of 16S r-RNA, narG, nirS, nosZ and anammox gene of carrier biofilm and suspended activated sludge in the declination phase (BF2 and AS2) were lower than those of samples in the stable phase (BF1 and AS1), and relatively higher copy numbers of nirS and nirK genes with lower abundance of narG and nosZ genes were observed. High-throughput sequencing analysis was conducted for BF2 and AS2, and similar dominant phyla and classes with different abundance were obtained. The class Gammaproteobacteria affiliated with the phylum Proteobacteria was the most dominant microbial community in both BF2 (52.6%) and AS2 (41.7%). The PICRUSt prediction results indicated that 33 predictive specific genes were related to denitrification process, and the relative abundance of 18 predictive specific genes in BF2 were higher than those in AS2.

Concentrate minimization and water recovery enhancement using pellet precipitator in a reverse osmosis process treating textile wastewater.

Industrial wastewater reuse together with zero or near zero liquid discharges have been a growing trend due to the requirement of sustainable water management mandated by water scarcity and tightening discharge regulations. Studies have been conducted on the reclamation of textile industry wastewater using RO processes. However a lot of scientific attention has been drawn upon limiting the amount of concentrate generated from RO processes, which depends on the concentrations of scale forming ions in the concentrate stream. Hence, this study aims at investigating the applicability of an ultra-filtration (UF) membrane integrated pellet reactor to remove scale forming ions, i.e. Ca2+, Mg2+ and Si from the concentrate of a pilot-scale textile industry RO process, for the first time in the literature. The resulting effluent was further tested in a secondary RO process to decrease concentrate volume and increase total water recovery. The pellet reactor operated at an extremely low hydraulic retention time of 0.1 h removed scale forming ions, i.e. Ca2+, Mg2+, with 90-95% efficiency, which improved the secondary RO process performance up to 92-94% overall water recovery, i.e. near zero liquid discharge was reached. Ozonation of the concentrate partially removed COD and color, which further improved the secondary RO filtration performance.

Electrochemical treatment of concentrate from reverse osmosis of sanitary landfill leachate.

Conventional sanitary landfill leachate treatment has recently been complemented and, in some cases, completely replaced by reverse osmosis technology. Despite the good quality of treated water, the efficiency of the process is low and a large volume of reverse osmosis concentrate has to be either discharged or further treated. In this study, the use of anodic oxidation combined with electro-Fenton processes to treat the concentrate obtained in the reverse osmosis of sanitary landfill leachate was evaluated. The anodic oxidation pretreatment was performed in a pilot plant using an electrochemical cell with boron-doped diamond electrodes. In the electro-Fenton experiments, a boron-doped diamond anode and carbon-felt cathode were used, and the influence of the initial pH and iron concentration were studied. For the experimental conditions, the electro-Fenton assays performed at an initial pH of 3 had higher organic load removal levels, whereas the best nitrogen removal was attained when the electrochemical process was performed at the natural pH of 8.8. The increase in the iron concentration had an adverse impact on treatment under natural pH conditions, but it enhanced the nitrogen removal in the electro-Fenton assays performed at an initial pH of 3. The combined anodic oxidation and electro-Fenton process is useful for treating the reverse osmosis concentrate because it is effective at removing the organic load and nitrogen-containing species. Additionally, this process potentiates the increase in the biodegradability index of the treated effluent.

Novel technologies for reverse osmosis concentrate treatment: a review.

Global water shortages due to droughts and population growth have created increasing interest in water reuse and recycling and, concomitantly, development of effective water treatment processes. Pressured membrane processes, in particular reverse osmosis, have been adopted in water treatment industries and utilities despite the relatively high operational cost and energy consumption. However, emerging contaminants are present in reverse osmosis concentrate in higher concentrations than in the feed water, and have created challenges for treatment of the concentrate. Further, standards and guidelines for assessment and treatment of newly identified contaminants are currently lacking. Research is needed regarding the treatment and disposal of emerging contaminants of concern in reverse osmosis concentrate, in order to develop cost-effective methods for minimizing potential impacts on public health and the environment. This paper reviews treatment options for concentrate from membrane processes. Barriers to emerging treatment options are discussed and novel treatment processes are evaluated based on a literature review.

Inhibition of nitrate reduction by NaCl adsorption on a nano-zero-valent iron surface during a concentrate treatment for water reuse.

Nanoscale zero-valent iron (NZVI) has been considered as a possible material to treat water and wastewater. However, it is necessary to verify the effect of the matrix components in different types of target water. In this study, different effects depending on the sodium chloride (NaCl) concentration on reductions of nitrates and on the characteristics of NZVI were investigated. Although NaCl is known as a promoter of iron corrosion, a high concentration of NaCl (>3 g/L) has a significant inhibition effect on the degree of NZVI reactivity towards nitrate. The experimental results were interpreted by a Langmuir-Hinshelwood-Hougen-Watson reaction in terms of inhibition, and the decreased NZVI reactivity could be explained by the increase in the inhibition constant. As a result of a chloride concentration analysis, it was verified that 7.7-26.5% of chloride was adsorbed onto the surface of NZVI. Moreover, the change of the iron corrosion product under different NaCl concentrations was investigated by a surface analysis of spent NZVI. Magnetite was the main product, with a low NaCl concentration (0.5 g/L), whereas amorphous iron hydroxide was observed at a high concentration (12 g/L). Though the surface was changed to permeable iron hydroxide, the Fe(0) in the core was not completely oxidized. Therefore, the inhibition effect of NaCl could be explained as the competitive adsorption of chloride and nitrate.

Removal of calcium and magnesium ions from reverse osmosis concentrate using a two-stage precipitation with carbonation process.

The reverse osmosis (RO) technique has been extensively employed in the advanced treatment of industrial water and wastewater. However, this process results in the production of a significant quantity of reverse osmosis concentrate (ROC), which contains high levels of salinity and organic contaminants, thereby posing serious environmental problems. This study reported a two-stage precipitation process utilizing quicklime (CaO) and caustic soda (NaOH) in conjunction with air blowing (carbonation) for the removal of Ca2+ and Mg2+ from real brackish water ROC of factory. In stage I, the CaO precipitation-carbonation process was employed to eliminate the majority of Ca2+ from the ROC, while leaving Mg2+ virtually unaffected, yielding high-purity CaCO3 precipitates. In stage II, the NaOH precipitation method was utilized to eliminate the remaining Ca2+ and Mg2+ from the ROC. It was demonstrated that under optimal conditions, the removal rates of Ca2+ and Mg2+ exceeded 97%. Finally, the characterization of precipitates demonstrated the generation of high-purity CaCO3 precipitates in stage I, as well as the formation of CaCO3 and Mg(OH)2 precipitates in stage II. The results confirmed the feasibility of employing the two-stage precipitation with carbonation process to economically treat ROC and enable its reuse, offering valuable insights for the treatment of industrial wastewater.

Comparative study on electro-regeneration of antibiotic-laden activated carbons in reverse osmosis concentrate.

Electro-regeneration is emerging as a new technique to regenerate spent carbon adsorbents through an electrochemical process. In this study, sequential adsorption and electro-regeneration of ciprofloxacin (CIP)-laden carbon were investigated using both pristine and iron (Fe)-doped F400 activated carbon in distilled, deionized (DI) water and reverse osmosis (RO) concentrate water. The impact of reactor flow rate and sequential adsorption/electro-regeneration cycles on the regeneration efficiency were also evaluated. The results indicate that the breakthrough points for both adsorbents in DI water, where 100 % of the CIP molecules were adsorbed, occurred at around 7,800 bed volumes (BVs). Conversely, electro-regeneration for both adsorbents, where 94 % of the CIP molecules were desorbed, took place at 380 BVs. The main distinction between the two activated carbons lies in the initial range of BVs (<400 BVs).Fe doping on F400 appears to enhance its surface selectivity for CIP uptake, which can easily diffuse into the meso/macropore regions of Fe-doped F400. In contrast, pristine F400, being highly microporous, necessitated more contact time to fill its high-energy sites, resulting in a higher affinity for CIP adsorption. Over the four sequential adsorption/electro-regeneration cycles in DI water, a similar regeneration efficiency was observed at 190 BVs. As the flow rate increased from 2 to 6 mL/min, the CIP uptake on pristine F400 decreased in DI water, calculating 138, 74 and 57 mg/g for flow rates of 2, 4, and 6 mL/min, respectively. When the RO concentrate water was compared with DI water, the pristine F400 quickly reached saturation due to pore blockage caused by organic matter in RO concentrate. During electro-regeneration, up to 100 % of adsorbed CIP molecules were desorbed at around 120 BVs in RO concentrate, which is 3X faster than DI water. The effectiveness of this technology can be enhanced by implementing continuous flow systems, thereby improving the overall efficiency of CIP removal in RO concentrate.

Efficiency of ozonation and sulfate radical - AOP for removal of pharmaceuticals, corrosion inhibitors, x-ray contrast media and perfluorinated compounds from reverse osmosis concentrates.

This study investigated the elimination of pharmaceuticals, corrosion inhibitors, x-ray contrast media and perfluorinated compounds from reverse osmosis concentrates during ozonation and UV/persulfate processes. Second-order rate constants for the reactions of candesartan, irbesartan, methyl-benzotriazole, and chloro­benzotriazole with sulfate radical (SO4·-) were determined for the first time. Experiments were conducted in buffered pure water, in buffered water added with the matrix substituents chloride, carbonate, NOM, and reverse osmosis concentrate with spiked micropollutants (MP). UV/persulfate eliminated all MP to a higher extent than ozonation in RO concentrates due to the higher yield of oxidative species and photolytic degradation. Compounds with electron-rich moieties such as carbamazepine, diclofenac, metoprolol, and sulfamethoxazole were completely eliminated with small ozone doses (< 0.5 mg O3 / mg DOC) and with a small fluence (< 5000 J m-2) in UV/persulfate processes. Photosensitive compounds with high reactivity towards hydroxyl radicals (·OH) and SO4·- like the x-ray contrast media Iopamidol, Iohexol, and Amidotrizoic acid were successfully eliminated with a reasonable fluence in UV/persulfate, whereas these compounds persist in ozonation at common ozone dosages. However, much higher fluences and ozone dosages were required for the least reactive compounds like the class of benzotriazoles. Comparing the application of both oxidative processes to the RO concentrate, ozonation has the disadvantage of forming bromate. The energy input of both processes strongly depends on the target compounds to be eliminated. For the elimination of compounds such as sulfamethoxazole, ozonation is a feasible technique, whereas UV/persulfate is better suited for the elimination of recalcitrant compounds such as x-ray contrast media. In general, oxidative process treatment of RO concentrate could be applied to partly abate micropollutants before discharge.

Effective and mechanistic insights into shale gas wastewater reverse osmosis concentrate treatment using ozonation-biological activated carbon process.

Reverse osmosis (RO) plays a pivotal role in shale gas wastewater resource utilization. However, managing the reverse osmosis concentrate (ROC) characterized by high salinity and increased concentrations of organic matter is challenging. In this study, we aimed to elucidate the enhancement effects and mechanisms of pre-ozonation on organic matter removal efficacy in ROC using a biological activated carbon (BAC) system. Our findings revealed that during the stable operation phase, the ozonation (O3 and O3/granular activated carbon)-BAC system removes 43.6-72.2 % of dissolved organic carbon, achieving a 4-7 fold increase in efficiency compared with that in the BAC system alone. Through dynamic analysis of influent and effluent water quality, biofilm performance, and microbial community structure, succession, and function prediction, we elucidated the following primary enhancement mechanisms: 1) pre-ozonation significantly enhances the biodegradability of ROC by 4.5-6 times and diminishes the organic load on the BAC system; 2) pre-ozonation facilitates the selective enrichment of microbes capable of degrading organic compounds in the BAC system, thereby enhancing the biodegradation capacity and stability of the microbial community; and 3) pre-ozonation accelerates the regeneration rate of the granular activated carbon adsorption sites. Collectively, our findings provide valuable insights into treating ROC through pre-oxidation combined with biotreatment.

Electrochemical oxidation of reverse osmosis concentrate using a pilot-scale reactive electrochemical membrane filtration system: Performance and mechanisms.

Scale-up treatment of real wastewater holds the key to promoting the practical application of electrochemical filtration technology. This work used a pilot-scale Ti/Pd reactive electrochemical membrane (REM) system (12 REM modules with a total REM area of 0.144 m2) to treat high-salinity reverse osmosis concentrate (ROC) from a chemical industry park. The pilot-scale Ti/Pd REM system demonstrated effective electrochemical degradation of ROC wastewater, achieving removal efficiencies of 82.3 ± 1.9% for COD and 46.7 ± 5.6% for TN at a membrane flux of 90 L/(m2·h) and a cell voltage of 5 V, with an energy consumption of 0.045 kWh/g-COD. Singlet oxygen (1O2) and reactive chlorine species were identified as the two primary reactive oxygen species generated in the Ti/Pd REM system. Fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) analysis indicated that the pilot-scale Ti/Pd REM treatment effectively oxidized humic acid-like substance and unsaturated aromatic compounds. Overall, the Ti/Pd REM technology shows a promising application potential for the treatment of high-salinity ROC from the chemical industry.

Catalytic ozonation of reverse osmosis concentrate from coking wastewater reuse by surface oxidation over Mn-Ce/γ-Al2O3: Effluent organic matter transformation and its catalytic mechanism.

Degradation of organics in high-salinity wastewater is beneficial to meeting the requirement of zero liquid discharge for coking wastewater treatment. Creating efficient and stable performance catalysts for high-salinity wastewater treatment is vital in catalytic ozonation process. Compared with ozonation alone, Mn and Ce co-doped γ-Al2O3 could remarkably enhance activities of catalytic ozonation for chemical oxygen demand (COD) removal (38.9%) of brine derived from a two-stage reverse osmosis treatment. Experimental and theoretical calculation results indicate that introducing Mn could increase the active points of catalyst surface, and introducing Ce could optimize d-band electronic structures and promote the electron transport capacity, enhancing HO• bound to the catalyst surface ([HO•]ads) generation. [HO•]ads plays key roles for degrading the intermediates and transfer them into low molecular weight organics, and further decrease COD, molecular weights and number of organics in reverse osmosis concentrate. Under the same reaction conditions, the presence of Mn/γ-Al2O3 catalyst can reduce ΔO3/ΔCOD by at least 37.6% compared to ozonation alone. Furthermore, Mn-Ce/γ-Al2O3 catalytic ozonation can reduce the ΔO3/ΔCOD from 2.6 of Mn/γ-Al2O3 catalytic ozonation to 0.9 in the case of achieving similar COD removal. Catalytic ozonation has the potential to treat reverse osmosis concentrate derived from bio-treated coking wastewater reclamation.

Oxidation of the N-containing phosphonate antiscalants NTMP and DTPMP in reverse osmosis concentrates: Reaction kinetics and degradation rate.

N-containing organophosphonate antiscalants such as Aminotris (methylene phosphonic acid) (NTMP/ATMP) and Diethylenetriamine penta(methylene phosphonic acid) (DTPMP) are commonly used in reverse osmosis (RO) to prevent scaling, as well as to increase permeate yields. However, the concentrate in RO still contains antiscalants which can cause adverse effects in the environment such as mobilization of heavy metals. The abatement of antiscalants from RO concentrate can promote the precipitation of oversaturated scale-forming substances and reduce the risk of adverse environmental effects. In the present study, the degradation of NTMP and DTPMP as representatives for N-containing organophosphonate by ozone, hydroxyl radicals (•OH), and sulfate radicals (SO4•-) are studied regarding reaction kinetics and degradation in different matrices. The results show that NTMP and DTPMP react fast with ozone and sulfate radicals (formed in UV/persulfate). Reaction rate constants of ozone showed a strong pH dependency due to the dissociation of the amine. The apparent reaction rates for pH 7 have been determined to be kapp(NTMP + ozone) = 1.44 × 105 M-1 s-1 and kapp(DTPMP + ozone) = 1.16 × 106 M-1 s-1. Reaction kinetics of •OH and SO4•- did not play a distinctive pH dependency (k(•OH) = 109-1010 M-1 s-1 and k(SO4•-) = 107-108 M-1 s-1). Furthermore, real water experiments have shown that ozonation and UV/persulfate are effective tools to abate organophosphonates in RO concentrates. The formation of carcinogenic bromate in ozonation is minimized by the presence of N-containing organophosphonates presumably due to enhanced ozone consumption and scavenging of free bromine.

Oxidation of the nitrogen-free phosphonate antiscalants HEDP and PBTC in reverse osmosis concentrates: Reaction kinetics and degradation rate.

Reverse osmosis (RO) is an advanced technology used to produce potable water from a variety of water sources, including surface water, seawater and wastewater. The yield of the product water from the RO systems is increased by the addition of antiscalants which prevent scaling from calcium and other ions. Removal of antiscalants from RO concentrate can induce the precipitation of oversaturated scale-forming substances, enable additional water recovery from RO concentrates, and reduce the risk of eutrophication after concentrate disposal into the receiving water (e.g., river water). This study aims to provide a better insight into oxidation reactions of the N-free phosphonate antiscalants 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) with ozone, hydroxyl radical (•OH) and sulfate radicals (SO4•-). Ozone barely reacts with HEDP and PBTC at pH 7 (k < 10 M-1s - 1), while second order reaction rates of SO4•- and •OH were determined to be in the range 107-108M - 1s - 1. Sulfate, silicate and chloride matrices increased HEDP ozone degradation rate possibly due to metal complexation effect. Whereas carbonate and chloride hindered PBTC ozone degradation, and natural organic matter (NOM) inhibited both HEDP and PBTC degradation through scavenging of •OH. The SO4•-- radical based oxidation process of HEDP and PBTC is mainly inhibited by carbonate and NOM, interestingly only HEDP degradation is inhibited by chloride whereby the PBTC could not be fully degraded (degradation < 60%). The oxidation of PBTC is in real RO concentrates in both processes limited to 10% degradation, whereas HEDP could be degraded up to 60% with ozone and UV/persulfate application.

Use of reverse osmosis concentrate for mitigating greenhouse gas emissions from pig slurry.

Due to the high global warming potential (GWP) in a short time scale (GWP100 = 28 vs. GWP20 = 86), mitigating CH4 emissions could have an early impact on reducing current global warming effects. The manure storage tank emits a significant amount of CH4, which can diminish the environmental benefit resulting from the anaerobic digestion of manure that can generate renewable energy. In the present study, we added the reverse osmosis concentrate (ROC) rich in salt to the pig slurry (PS) storage tank to reduce CH4 emissions. Simultaneously, pure NaCl was tested at the same concentration to compare and verify the performance of ROC addition. During 40 days of storage, 1.83 kg CH4/ton PS was emitted, which was reduced by 7-75% by the addition of ROC at 1-9 g Na+/L. This decrease was found to be more intensive than that found upon adding pure sodium, which was caused by the presence of sulfate rich in ROC, resulting in synergistic inhibition. The results of the microbial community and activity test showed that sodium directly inhibited methanogenic activity rather than acidogenic activity. In the subsequent biogas production from the stored PS, more CH4 was obtained by ROC addition due to the preservation of organic matter during storage. Overall, 51.2 kg CO2 eq./ton PS was emitted during the storage, while 8 kg CO2 eq./ton PS was reduced by biogas production in the case of control, resulting in a total of 43.2 kg CO2 eq./ton PS. This amount of greenhouse gas emissions was reduced by ROC addition at 5 g Na+/L by 22 and 65 kg CO2 eq./ton PS, considering GWP100 and GWP20 of CH4, respectively, where most of the reduction was achieved during the storage process. To the best of our knowledge, this was the first report using salty waste to reduce GHG emissions in a proper place, e.g., a manure storage tank.