Molecular Characteristics and Formation Mechanisms of Unknown Ozonation Byproducts during the Treatment of Flocculated Nanofiltration Leachate Concentrates Using O3 and UV/O3 Processes.

Both ozone (O3) and UV/O3 treatment processes can effectively remove organic matter in the flocculated membrane filtration concentrate from landfill leachate, but the ozonation byproducts (OBPs) generated in the processes remain unknown. Using electrospray ionization-coupled Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), this study investigated the molecular characteristics of unknown OBPs and their formation mechanisms during the treatment of flocculated nanofiltration concentrate (FNFC) using the O3 and UV/O3 processes. The results showed that after being treated by the O3 and UV/O3 processes, the average value of the oxygen-to-carbon ratio (O/Cavg) in the FNFC organic matter increased substantially from 0.49 to 0.61-0.64 and 0.63-0.71, respectively, with an O3 dosage of 13.4-54.4 mg/min. The main OBPs were CHO and CHON compounds, which were mainly produced through oxygenation (+O2/+O3 and -H2+O2), oxidative deamination (-NH3+O2), decyclopropyl (-C3H4), and deisopropyl (-C3H6) reactions. The hydroxyl radical (•OH) can intensify these reactions, resulting in an abundance of OBPs with a high oxidation degree and low molecular weight. OBPs at five m/z values were fragmented and analyzed with tandem mass spectrometry, and abundant hydroxyl groups, carboxyl groups, and carbonyl groups were tentatively identified, presenting a potential toxicity to aquatic organisms. Due to the high molecular diversity of the OBPs in FNFC, their lower ΔGCoxo compared to natural fulvic acid, and potential toxicity, their impact on the water environment should be given more attention.

Molecular-level transformation of refractory organic matter during flocculation-ultraviolet/peroxymonosulfate treatment of MBR-treated landfill leachate.

Refractory organic matter in membrane bioreactor effluent resulting from landfill leachate treatment has a complex composition. This paper identified the transformation mechanism of organic matter in a flocculation-ultraviolet (UV)/peroxymonosulfate (PMS) system at the molecular level using electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry. The results showed that the flocculation system was able to remove a large amount of dissolved organic matter (DOM) with high oxidation and unsaturation/saturation. UV radiation displayed a relatively strong reactivity for DOM with an electron-rich structure, which it can transform into DOM with lower aromaticity through photolysis and photosensitivity, although the effectiveness of the transformation was poor. In comparison, due to the action of reactive oxygen species, the UV/PMS system can enable reactions such as demethylation, dehydrogenation, decarboxylation, dehydroxylation, ring cleavage, and decarbonylation. It can remove approximately 60% quantity of the total DOM and produce DOM featuring a higher degree of oxidation and saturation than that of the UV system alone. The results showed that the UV/PMS system was a complementary of flocculation in DOM removal from the membrane bioreactor effluent, while the system also resulted in a large number of sulfuric compounds; thus, requiring further evaluation of its ecological effects.

Transformation of dissolved organic matter in landfill leachate during a membrane bioreactor treatment.

In this study, a cutting-edge mass spectrometry (MS) technique, Orbitrap fusion MS with ultrahigh resolution, was used to analyze the molecular composition, chemical properties, formation mechanism, and environmental impact of refractory dissolved organic matter (rDOM) in leachate. The results showed that the bioavailable DOM (bDOM) and rDOM constituents varied substantially during the biological treatment of landfill leachate. Compared with bDOM, the rDOM in leachate had a higher degree of unsaturation, aromaticity, and oxidation, and a larger molecular weight, and contained more organic matter with benzene ring and biphenyl structures. Using high-throughput 16S rRNA sequencing, metagenomics, the Kendrick mass defect (KMD), and a mass difference network (MDiN), it was found that rDOM in leachate is generated through carboxylation (+COO), dehydro-oligomerization (-H2), and chain scission (-CH2) pathways due to the activity of microbes such as Patescibacteria, Chloroflexi, and Proteobacteria. Compared with Suwannee River fulvic acid (SRFA), the rDOM in leachate contained more organics with nitrogen, sulfur, benzene rings, and biphenyls. If the rDOM in leachate enters the environment it will affect the composition of the original organic matter, and its biogeochemical transformation and environmental fate will then need to be monitored and may require special attention.

Novel strategy for controlling colloidal instability during the flocculation pretreatment of landfill leachate.

Flocculation is an economical and effective pretreatment technology for landfill leachate. An iron salt flocculant is often used in landfill leachate pretreatment, but the flocs that are formed are affected by the operation sequence, which subsquently influences flocculation. This study selected three representative landfill leachates (i.e., mature landfill leachate (MLL), biologically treated landfill leachate (BTL), and nanofiltration concentrate leachate (NFCL)). The effect of different operation modes on the removal of organic matter from landfill leachate by flocculation was studied, and a strategy to control colloidal instability is put forward. The results revealed that adjusting the pH value to 9 using NaOH changes the zeta potential of leachate when the leachate and sludge are not separated, which affects electric neutralization in flocculation and colloidal stability. Furthermore, a part of the collected organic matter is released to the leachate again, leading to a decrease in the flocculation pretreatment effect. In this improved flocculation process, the leachate and sludge are first separated, and the pH value of the system is then adjusted to 9. The effect of OH- on electric neutralization is avoided and the remaining Fe3+ can further remove organic matter from leachates. Finally, the UV254 removal efficiencies of MLL, BTL, and NFCL increased by 20.38%, 28.67%, and 22.67%, respectively. In a full-scale application, i.e., an NFCL treatment facility, the UV254 removal efficiency during long-term operation reached 87.50%. Therefore, the colloid instability control strategy this study proposes can provide theoretical and engineering references for the flocculation pretreatment of landfill leachate.

Microbial characteristics of the leachate contaminated soil of an informal landfill site.

Because informal landfills are not constructed in a regulated manner, they will inevitably become a source of leachate pollution to the surrounding environment over time. Microbes are an important part of the soil system, playing a vital role in maintaining the normal functionality of soil. This study investigated the microbial composition and co-occurrence pattern in the leachate contaminated soil of an informal landfill site. The landfill leachate underwent horizontal and vertical migration through the contaminated soil, resulting in significant differences in the microbial compositions of horizontal surface soil (CS) and vertical subsurface soil (DS and ES) compared to uncontaminated soil (S). The microbial diversity of CS, DS, and ES was lower than that of S. Due to the migration of landfill leachate, the microbial composition of the surface soil was substantially changed. The dominant phyla in S included Proteobacteria (26.88%), Chloroflexi (23.68%), Actinobacteroita (17.36%), and Acidobacteroita (16.86%), but in contaminated soils, Firmicutes (35.27-86.68%) were the dominant bacteria. A network analysis indicated that Bacilli, Clostridia, and Thermacetogeniazai of the Firmicutes were the keystone taxa and played a vital role in maintaining the stability of the soil ecosystem. A functional annotation of prokaryotic taxa (FAPROTAX) analysis showed that the microbes involved in the C-, N-, and S-cycles in contaminated soil were significantly different to those in uncontaminated soil. The proportion of (aerobic)-chemoheterotrophy and cellulolysis functional communities in contaminated soils was significantly reduced, while there was an increase in functional communities, such as anammox and denitrification, which are not conducive to soil nitrogen fixation. This negatively affected the maintenance of normal soil ecological functions. This study identified the microbial characteristics in leachate contaminated soil and the results will be beneficial for the remediation of contaminated soil in informal landfill sites.

Molecular insights into the transformation of refractory organic matter in landfill leachate nanofiltration concentrates during a flocculation and O3/H2O2 treatment.

During leachate treatment, molecular information regarding the completely removed, partially removed, less-reactive, increased, and produced parts of dissolved organic matter (DOM) remains unknown. This study applied ESI FT-ICR MS to investigate the transformation characteristics of leachate nanofiltration concentrate (NFC) DOM during a combined flocculation-O3/H2O2 process. The NFC contained 5069 compounds in four main classes (CHO, CHON, CHOS, and CHONS compounds). The DOM number decreased to 4489 during flocculation and to 2903 after the O3/H2O2 process. During flocculation, the completely and partially removed DOM was mainly low-oxygen unsaturated and phenolic compounds. Saturated DOM was produced and remained in the flocculated effluent. During the O3/H2O2 process, the completely and partially removed DOM were mainly low-oxygen unsaturated and phenolic compounds that were mainly in a reduced state. Flocculation can remove many (condensed) aromatic compounds, and methylation and hydrogenation reactions occurred during flocculation. In the O3/H2O2 process, dearomatization, demethylation, carboxylation, and carbonylation reactions further achieved the degradation of DOM that was resistant to flocculation. Overall, the combined flocculation-O3/H2O2 process collectively eliminated a broader range of DOM than the single processes could achieve. The results of this study provide an in-depth understanding of DOM transformation in an NFC treatment.

The molecular differences of young and mature landfill leachates: Molecular composition, chemical property, and structural characteristic.

Landfill leachate is a highly contaminated and complex organic wastewater. It can be categorized into young (YL) and mature leachate (ML) based on the landfill age, with significant differences in the composition of organic matter, resulting from the significant differences in humification degree. To compare the organic composition of YL and ML, ESI FT-ICR MS was applied to systematically investigate their molecular composition, chemical properties, and structural characteristics. The molecular weight of YL organics was lower than that of ML organics. In addition, O/C and H/C distributions of YL and ML organics were significantly different. YL mainly consisted of CHO compounds and aliphatic compounds. ML mainly consisted of CHON compounds and high oxygen highly unsaturated and phenolic compounds. The unsaturation degree of YL organics was expressed by carbon double bond equivalents ((DBE-C)/C = -0.0336) and was not significantly different from that of ML (-0.0241), but nominal oxidation state of carbon (NOSC = -0.8010) and aromaticity (AImod = 0.1254) of YL were significantly lower than of ML (NOSC = -0.0692; AImod = 0.2464). In addition, YL and ML organics were rich in functional groups, but the YL organics contained more straight-chain structures. The ML organics contained fewer straight-chain structures, a larger number of benzene-ring structures, and more oxygen-containing functional groups. The more complex structural properties of ML organics may be the result of the transformation of YL organics after a long series of reactions, including electrocyclization, decarboxylation, and hydrogen abstraction reactions, which eventually increased the humification degree of leachate organic matter.

Microbial community response of the full-scale MBR system for mixed leachates treatment.

In practice, mature landfill leachate and incineration (young) leachate are mixed to improve the biodegradability and enhance biological treatment performance. However, the ratio of mature-to-young leachates greatly influences MBR treatment efficiency and microbial community structure. This study investigated the treatment efficiency and microbial community structure of full-scale MBR systems operated under two mix ratios, mature leachate: young leachate = 7:3 (v/v, denoted as LL) and 3:7 (v/v, denoted as IL). LL group showed lower Cl- and COD concentrations but a higher aromatic organic content comparing to IL group, and the COD and UV254 removals for LL were significantly lower than those for IL by MBR treatment. Microbial community structures were similar in both groups at phylum level, with dominant phyla being Proteobacteria (23.8%-32.3%), Bacteroidetes (15.25%-20.7%), Chloroflexi (10.5%-23.1%), and Patescibacteria (9.9%-13.2%). However, the richness and diversity of LL group were lower, and differences were observed at lower taxonomy levels. Results indicated that salinity mainly changed the structure of microbial community, resulting in greater abundance of salt-tolerant microbials, while refractory organics affected microbial community structure, and also led to decreased diversity and metabolic activity. Therefore, in mixed leachates biological treatment, a higher young leachate ratio is recommended for better organics removal performance. PRACTITIONER POINTS: The trade-off between refractory organics and salinity in mixed leachate treatment should be paid attention. Refractory organics reduced alpha and functional diversities of microorganisms. Mixed leachate with a higher young leachate ratio reached a better organic removal.

A review of the characteristics of Fenton and ozonation systems in landfill leachate treatment.

The development and application of Fenton and ozonation systems in landfill leachate treatment over the last 20 years, and the current research status are reviewed in this paper, with an emphasis on the technical and economic characteristics of Fenton and ozonation systems used to treat different types of landfill leachate. To date, a total of 101 and 78 articles have been published regarding leachate treatment by Fenton and ozonation systems, respectively. These articles considered the use of two systems to treat aged leachate, biologically treated leachate and leachate comprising the concentrated solution resulting from reverse osmosis (RO). The oxidization mechanisms of the two systems used to treat landfill leachate significantly differed in terms of their optimal process parameters (e.g., initial pH value, reagent dosage, and reaction time) and removal efficiency. The Fenton and ozonation systems outperformed persulfate-based advanced oxidation technology in terms of their improved biodegradability of landfill leachate and engineering practicability. The cost of the reagents required to treat landfill leachate by Fenton and ozonation systems accounted for at least 85% of the total operating cost. In contrast to the ozonation system, the Fenton system was more cost-effective when both systems were used to treat the same type of landfill leachate. This study provides a theoretical basis for the operation of Fenton and ozonation systems and also offers technical support for landfill leachate disposal companies that opt to use these technologies.

Preparation of biochar and biochar composites and their application in a Fenton-like process for wastewater decontamination: A review.

Biochar is a carbon-rich material that can be obtained from pyrolysis of solid waste (e.g., agricultural solid waste and sludge from wastewater treatment plants). Biochar features low cost, large specific surface area, and strong adsorption capacity. New biochar composites can be produced via modification and loading of nano particles onto biochar. Biochar can contribute to the dispersion and stabilization of nano particles. In addition, nano particles can increase the number of surface-active sites, which improves the physicochemical properties of the material. Biochar and biochar composites have been applied widely in wastewater treatment, and have significantly enhanced the treatment performance of Fenton-like processes (activation of hydrogen peroxide and persulfate) as an advanced oxidation process for organics removal and wastewater decontamination. This paper reviews the preparation methods for biochar and biochar composites to systematically analyze the influential factors on the preparation process. The paper also comprehensively reviews the mechanisms by which biochar removes different organic pollutants. However, due to the vast number of different biochar feedstocks and their preparation methods, it is difficult to compare the properties of one biochar to another. Guidance if provided for the application of biochar and biochar composites for wastewater decontamination.

Application of membrane separation technology in the treatment of leachate in China: A review.

To comprehensively investigate the application of membrane separation technology in the treatment of landfill leachate in China, the performance of nearly 200 waste management enterprises of different sizes in China were analyzed, with an emphasis on their scale, regional features, processes, and economic characteristics. It was found that membrane separation technologies, mainly nanofiltration (NF), reverse osmosis (RO), and NF + RO, have been used in China since 2004. The treatment capacity of the two most dominant membrane separation technologies, i.e., NF and RO, were both almost 60,000 m3/d in 2018, and both technologies are widely used in landfills and incineration plants. Their distribution is mainly concentrated in eastern and southwestern China, where the amount of municipal solid waste (MSW) is relatively high and the economy is developing rapidly. Membrane separation technology is the preferred technique for the advanced treatment of leachate because more contaminants can be effectively removed by the technology than by other advanced processes. However, the membrane retentate that is produced using this technology-commonly known as leachate concentrate-is heavily contaminated due to the enrichment of almost all the inorganic anions, heavy metals, and organic matter that remain after bioprocessing. An economic cost analysis revealed that the operating cost of membrane separation technology has stabilized and is between 1.77 USD/m3 and 4.90 USD/m3; electricity consumption is the most expensive cost component. This review describes the current problems with the use of membrane separation technology and recommends strategies and solutions for its future use.

Comparison study on microwave irradiation-activated persulfate and hydrogen peroxide systems in the treatment of dinitrodiazophenol industrial wastewater.

In this study, refractory organics in industrial wastewater containing dinitrodiazophenol (DDNP) were treated by microwave (MW) irradiation-activated persulfate (PS) and hydrogen peroxide (H2O2). The organics degradation effect of MW output power, oxidant dosage and initial pH were investigated. Spectral analysis and radical scavenging experiments were used to investigate the degradation pathway and identify reactive oxygen species in the two systems. As the MW output power increased, kobs of both systems increased, but excessively high-power output inhibited organics degradation in the MW-PS system. The impact of initial pH on MW-PS system performance was not obvious compared to that of the MW-H2O2 system (in which alkalinity significantly limited the reaction with organics). Under the same reaction condition, COD removals reached 89.89% (MW-PS) and 54.56% (MW-H2O2) and biodegradability improved from 0.060 to 0.561 (MW-PS) and 0.535 (MW-H2O2). In addition, SO4and ·OHwere identified in the MW-PS system but only ·OHexisted in the MW-H2O2 system, indicating that the MW-PS system could oxidize more types of organics in DDNP wastewater than the MW-H2O2 system. Furthermore, UV-Vis and FITR analyses showed that organics with diazo groups and nitro-groups could be decomposed and intermediate products with C-O-H (which are biodegradable) will be generated. The MW-PS system also produced a better economic benefit than the MW-H2O2 system. Therefore, this study provides valuable references for the use of MW irradiation-activated oxidants to treat DDNP industrial wastewater.

A pilot-scale comparative study of bioreactor landfills for leachate decontamination and municipal solid waste stabilization.

Many studies have sought to optimize operation parameters and enhance the treatment capacity of bioreactor landfills (BL) under ideal laboratory conditions. At pilot scale, conclusions drawn from laboratory-scale experiments will be different due to variations in actual landfill composition and changes in environmental conditions. However, comparative pilot-scale studies of traditional anaerobic landfills (AnL) and BLs are rare. In this study, three pilot-scale landfills, including an AnL, anaerobic BL (AnBL) and semi-aerobic BL (SABL), were monitored to examine the difference in performance at different scales and among types of landfills. Settlement amount followed the order SABL (25.45 cm) > AnBL (18.67 cm) > AnL (14.38 cm). Decomposition of organic matter (i.e., volatile fatty acids) was more rapid in SABL than in the other landfills and no hydrolytic acidification period was observed. Therefore, among the three landfills, SABL entered the methanogenic stage in a much shorter time and MSW stabilization was accelerated due to this landfill's unique combination of aerobic-anoxic-anaerobic ambient. In addition, NH4+-N concentration in leachate from the SABL (~19.96 mg/L) was substantially lower than from AnL (338.28 mg/L) and AnBL (233.22 mg/L), and SABL leachate exhibited the least chloride pollution risk. This study provides theoretical support and strong evidence for using SABLs to treat MSW in practical applications.

Recovery of efficient treatment performance in a semi-aerobic aged refuse biofilter when treating landfill leachate: Washing action using domestic sewage.

Semi-aerobic aged refuse biofilters (SAARB) are known to efficiently remove organic matter, nitrogenous substances, and anions from landfill leachate. However, long-term recirculation of mature landfill leachate inevitably leads to accumulation of pollutants and decreases treatment capacity. In this study, the washing action provided by domestic sewage was used to recover and even enhance the treatment performance of SAARBs treating mature landfill leachate. Three SAARB columns were operated for 300 d after which a "Recirculation-Washing-Recirculation" sequence was followed. In the first recirculation period (22 d), removal of chemical oxygen demand (COD) and total nitrogen (TN) decreased from ca. 90% and 60%, respectively, initially to about 75% and less than 20%, respectively. Thereafter, washing (20 d) of the SAARBs was accomplished by applying domestic sewage. In the subsequent second recirculation period (30 d), the SAARBs were operated at the same hydraulic loading as used initially, but achieved high (ca. 90%) COD and relatively high (ca. 59%-76%) TN removal, including degradation of refractory organic matter such as humic- and fulvic-like substances. Overall, the mechanisms of the treatment performance recovery (including organics degradation and nitrification-denitrification) using domestic sewage can be attributed to three main effects: (1) some accumulated pollutants were washed out, thereby leading to recovery of the adsorption ability of aged refuse; (2) the inhibition of bio-refractory organics stress on microbial activities was mitigated by domestic sewage washing; and (3) the wash out of some accumulated salts (e.g., chloride and sulfate ions) probably helped the microbial activity recover.

Molecular-level insights into the transformation mechanism for refractory organics in landfill leachate when using a combined semi-aerobic aged refuse biofilter and chemical oxidation process.

Landfill leachate contains high concentrations of complex organic matter (OM) that can severely impact the ecological environment. If landfill leachate is to be treated using a combined "biological + advanced treatment" process, the molecular information of OM must be investigated to optimize the operation parameters of the combined process and maximize the removal of organic pollutants. This study applied ultra-high resolution mass spectroscopy to investigate the degradation and transformation characteristics of refractory OM in mature landfill leachate at the molecular level (m/z = 150-800) during biological treatment (i.e., semi-aerobic aged refuse biofilter, SAARB) and subsequent chemical oxidation (i.e., the Fenton process and ozonation). After SAARB treatment, the polycyclic aromatics (aromatic index, AI > 0.66) and polyphenol (0.66 ≥ AI > 0.50) contents increased, and the highly unsaturated phenolic compounds (AI ≤ 0.50 and H/C < 1.5), which have a high bioavailability, were mostly removed. Compared with raw leachate, SAARB effluent (i.e., SAARB leachate) contained fewer organics with short carbon chains, more organics with long carbon chains, an elevated condensation degree for organics and, thus, a considerably reduced biodegradability. Although both the Fenton and ozonation processes could remove many of the polycyclic aromatics and polyphenols, ozone produced considerable amounts of aliphatic compounds with high bioavailability. Compared to ozonation, the Fenton process utilized the hydroxyl radical to non-selectively react with OM and produced better mineralization results.

Improved oxidation of refractory organics in concentrated leachate by a Fe2+-enhanced O3/H2O2 process.

Concentrated leachate from membrane processes, which contains a mass of refractory organics and salt, has become a new problem for wastewater engineers. In this study, removal of organic contaminants in concentrated landfill leachate was investigated by applying the ferrous ion (Fe2+) catalyzed O3/H2O2 process. The maximum chemical oxygen demand (COD) and absorbance at 254 nm (UV254) removal efficiencies under the optimal conditions (initial pH = 3.0, Fe2+ dosage = 6.500 mM, H2O2 dosage = 18.8 mM and O3 dosage = 52.65 mg min-1) were 48.82% and 63.59%, respectively. These were higher than those achieved using the Fe2+/O3, O3/H2O2, and O3 processes, and biodegradability of the leachate was improved significantly. Moreover, compared with other processes, the Fe2+ had a stronger catalytic effect. Molecular distribution analysis and three-dimensional excitation and emission matrix analysis both indicated that the fulvic acid and humic acid in the concentrated leachate were greatly degraded. Ultraviolet-visible spectra showed that the Fe2+/O3/H2O2 process mainly destroyed unsaturated bonds and decreased the aromatic degree of the leachate. The reaction mechanism of the Fe2+/O3/H2O2 process mainly was attributed to three factors: (1) O3 and H2O2 reacting to produce •OH; (2) H2O2 and O3 decomposing into •OH through the oxidation of Fe2+ to Fe3+; and (3) coagulation by Fe (OH)3. The •OH can rapidly degrade recalcitrant organics, and coagulation also increases the removal of organic matter. Therefore, the Fe2+/O3/H2O2 process was an effective method for treating concentrated landfill leachate.

Dinitrodiazophenol industrial wastewater treatment by a sequential ozone Fenton process.

The ozonation process is efficient in degrading aromatic substances and substances with unsaturated bonds, but cannot effectively destroy small-molecule organic compounds, which accumulate. Likewise, the Fenton process is a classic wastewater treatment method, but requires strict pH control and produces secondary pollution when the concentration of organic substances is high. In this study, we applied a 1stO3-2ndFenton sequential process to treat diazodinitrophenol (DDNP) industrial wastewater and provide suitable reaction conditions for Fenton process. For the 1stOzone process, organics removal increased as O3 dosage increased. At optimized operation, the 1stO3 process provided an acidic effluent (pH = 3) and reduced the organics concentration to a level suitable for the 2ndFenton process. Benzene ring substances as well as nitro group and diazo group compounds were greatly degraded in the 1stO3 process and were further mineralized in the 2ndFenton process. Additionally, the biodegradability of DDNP industrial wastewater was greatly improved. This is the first reported time that ozonation and the Fenton process have been integrated sequentially to treat an explosive production wastewater. The study provides a feasible chemical oxidation method for treating DDNP industrial wastewater by simply combining two classic treatment processes.

Degradation of refractory organic contaminants in membrane concentrates from landfill leachate by a combined coagulation-ozonation process.

Landfill leachate is a typical refractory wastewater for which research into rapid and efficient treatment methods has become very topical. In this study, a coagulation-ozonation process was developed to treat the concentrate arising from membrane treatment of landfill leachate. The effect of coagulant type and initial pH on treatment efficiencies was investigated. Results showed that many of organics were effectively removed in the coagulation process. Thereafter, ozone was applied to further treat the coagulation-resistant organic substances. Our results revealed that the degradation rate of these coagulation-resistant substances followed the trend (color number) CN > (light absorbance at 254 nm) UV254 > (chemical oxygen demand) COD, and the residual coagulation-resistant substances were oxidized rapidly in the ozone process. Ozone first destroyed the molecular structure of fulvic acid and the by-products generated, such as protein-like substances. In addition, the molecular weight, organic condensation degree, and concentration of benzene ring compounds were considerably decreased. Moreover, the macro molecular organics (i.e., humic acid and fulvic acid) within the size range 1-100 kDa were effectively degraded and partially transformed into bicarbonate. Overall, the combined coagulation-ozonation process reduced COD, UV254, and CN in the landfill leachate concentrate by 88.32%, 94.37%, and 98.83%, respectively, and thus the biodegradability of the treated leachate also was significantly improved. This excellent performance proved the feasibility of the combined coagulation-ozonation process for the removal of recalcitrant organic substances contained in landfill leachate concentrate, benefiting subsequent biological treatment.

Kinetics study of dinitrodiazophenol industrial wastewater treatment by a microwave-coupled ferrous-activated persulfate process.

In this study, a ferrous-activated persulfate (PS) process induced by microwave (MW) energy was used to treat an industrial wastewater containing dinitrodiazophenol (DDNP). The effect of different operational parameters, such as PS dose, initial pH, MW power, and the mass ratio of ferrous to PS [i.e., n(Fe2+/PS)], on chemical oxygen demand (COD) removal and the pseudo first-order constant k was systematically studied. Results showed that the constant k and COD removal increased considerably with increasing PS dose, MW power, and n(Fe2+/PS); however, the constant k and COD removal decreased proportionally as the initial pH increased from 3 to 11. A base-activated PS system was formed when the initial pH further increased to 13, which resulted in a dramatic increase of k and COD removal. Controlled experiments demonstrated that the synergetic effect of MW, Fe2+, and PS were significant. The value of k was 0.2425 min-1, COD removal was 71.42%, and biodegradability remarkably increased from 0.056 to 0.6712 during treatment by MW-Fe2+/PS at a PS dose of 8 g/L, MW power of 600 W, initial pH of 3, n(Fe2+/PS) of 0.04, and reaction time of 14 min. Spectral analyses showed that the chromophores (including the diazo group and nitro group compounds) and benzene rings were greatly decomposed. Identification tests for reactive oxygen species showed that the predominant oxidizing species in the MW-Fe2+/PS process was the sulfate radical, and that the hydroxyl radical played a lesser role for color number elimination. From the perspective of both treatment efficiency energy consumption, the MW-Fe2+/PS process was confirmed to be an economical and promising pretreatment process for DDNP industrial wastewater.

Degradation of recalcitrant organics in landfill concentrated leachate by a microwave-activated peroxydisulfate process.

A microwave (MW)-activated peroxydisulfate (PDS) process was applied to remove recalcitrant organics in concentrated leachate. In this study, the optimum activation conditions were studied using the absorbance at 254 nm (UV254) and color number removal efficiencies and by comparison of the different processes. The inner oxidation mechanism was investigated by ultraviolet-visible (UV-vis) spectrophotometry and three-dimensional (3D) excitation-emission matrix (EEM) tests. The results show that oxidation effects followed the order MW/PDS > MW/H2O2 > heat/PDS. The efficiencies of chemical oxygen demand (COD) removal, UV254, and color number were 45.50%, 48.95%, and 88.35%, respectively. The biodegradability was enhanced to 0.23 under optimum conditions (initial pH of 3, MW irradiation power of 450 W, PDS dosage of 3.5 g L-1, and reaction time of 10 min). The UV-vis spectra suggest that the humification degree and aromaticity of organics in the concentrated leachate greatly declined in the MW/PDS process. 3D EEM spectra indicate that the molecular weight of organic substances in the concentrated leachate decreased markedly and that the constitution of the organics became simpler after the MW/PDS process. In a word, the MW/PDS process is a promising method for concentrated leachate treatment.