Rapid start-up and operational characteristics of partial denitrification coupled with anammox driven by innovative strategies.

The Partial Denitrification-Anammox (PD/A) process established a low-consumption, efficient and sustainable pathway for complete nitrogen removal, which is of great interest to the industry. Rapid initiation and stable operation of the PD/A systems were the main issues limiting its engineering application in wastewater nitrogen removal. A PD/A system was initiated in a continuous stirred-tank reactors (CSTRs) in the presence of low concentration of organic matter, and the effects of organic matter types and COD/NO3--N ratios on the performance of the PD/A system, and microbial community characteristics were explored. The results showed that low concentrations of organic matter could promote the rapid initiation of the Anammox process and then the strategy of gradually replacing NO2--N with NO3--N could successfully initiate the PD/A system at 70 days. The type of organic matter had a significant effect on the initiation of the Anammox and the establishment of the PD/A system. Compared to glucose, sodium acetate was more favorable for rapid start-up and the synergy among microorganisms, and organic matter was lower, with an optimal COD/NO3--N ratio of 3.0. Microorganisms differed in their sensitivity to environmental factors. The relative abundance of Planctomycetota and Proteobacteria in R2 was 51 %, with the presence of three typical anammox bacteria, Candidatus_Brocadia, Candidatus_Kuenenia, and Candidatus_Jettenia in the system. This study provides a new strategy for the rapid initiation and stable operation of the PD/A process.

Waste iron scraps promote anammox bacteria to resist inorganic carbon limitation.

The anaerobic ammonium oxidation (anammox) process is adversely affected by the limitation of inorganic carbon (IC). In this research, a new technique was introduced to assist anammox biomass in counteracting the adverse effects of IC limitation by incorporating waste iron scraps (WIS), a cheap and easily accessible byproduct of lathe cutting. Results demonstrated that reducing the influent IC/TN ratio from 0.08-0.09 to 0.04 resulted in a 20 % decrease in the nitrogen removal rate (NRR) for the control reactor, with an average specific anammox activity (SAA) of 0.65 g N/g VSS/day. Nevertheless, the performance of the WIS-assisted anammox reactor remained robust despite the reduction in IC supply. In fact, the NRR and SAA of the WIS-assisted reactor exhibited substantial improvements, reaching approximately 1.86 kg/(m3·day) and 0.98 g N/g VSS/day, respectively. These values surpassed those achieved by the control reactor by approximately 39 % and 51 %, respectively. The microbial analysis confirmed that the WIS addition significantly stimulated the proliferation of anammox bacteria (dominated by Candidatus Kuenenia) under IC limitation. The anammox gene abundances in the WIS-assisted anammox reactor were 3-4 times higher than those in the control reactor. Functional genes prediction based on the KEGG database revealed that the addition of WIS significantly enhanced the relative abundances of genes associated with nitrogen metabolism, IC fixation, and central carbon metabolism. Together, the results suggested that WIS promoted carbon dioxide fixation of anammox species to resist IC limitation. This study provided a promising approach for effectively treating high ammonium-strength wastewater using anammox under IC limitation.

Achieving smartphone-based colorimetric assay for Hg2+ with a bimetallic site strategy based on Hg2+-triggered oxidase-like catalytic activity of NSC/Co6Ni3S8 nanocomposite.

Modulation of the nanozyme's catalytic activity is crucial for its real applications in detecting target analytes. Herein, we fabricated the nanocomposite (NSC/Co6Ni3S8) of N, S co-doped carbon and Co6Ni3S8 by a facile sol-gel approach. Compared to NSC/Ni9S8, NSC/Co6Ni3S8 with bimetallic active sites displayed better enzyme-mimetic activity. This nanocomposite could catalyze O2 to form ·O2- and oxidize colorless 3, 3', 5, 5'-tetramethylbenzidine (TMB) into blue oxTMB. The other two free radicals (h+ and ·OH) played minor roles during the catalytic reaction. Hg2+ could integrate with S2- to form HgS and the surface charges of O2 were transferred to Hg2+ to promote O2 adsorption. DFT theoretical calculations highlight that the main reasons for the enhancing effect of Hg2+ on color development results from electron transfer and increased adsorption energy of O2 molecules onto the surface of NSC/Co6Ni3S8. By employing the oxidase-like activity of NSC/Co6Ni3S8 and Hg2+-triggered promoting effect, a colorimetric sensing platform was established for Hg2+ assay with a linear range of 10-200 µg/L and detection limit of 3 µg/L. Through integration with a smartphone-based APP "Thing Identify" software, a visual colorimetric assay for Hg2+ was constructed with a detection limit of 5 µg/L. Compared to the data detected by the mercury vapor meter, the relative recoveries of 92.4-108.1% evidenced the higher accuracy of this smartphone-based visual detection. Overall, the NSC/Co6Ni3S8-based colorimetric assay is convenient, rapid, and visual, and can be applied for routine monitoring of Hg2+ in real-world waters under outdoor conditions.

Dietary cadmium health risk assessment for the Chinese population.

Cadmium (Cd) has high rates of soil-to-plant transference, coupled with its non-biodegradability and persistence; long-term management of Cd in agriculture is thus required to ensure better soil and food security and safety. Identifications of regions with high soil Cd concentration or high dietary Cd intakes are critical public health priorities. Human health risk assessment for dietary Cd intake was thus undertaken by employing three approaches: FCA (food chain approach), TDA (total diet approach), and FQA (food quality approach). The correlation between green/total vegetable consumption rates and dietary Cd intake from vegetables was statistically significant. For consumption, the hazard quotients (HQs) calculated by FCA and TDA were all less than 1 except for Hunan and Sichuan province. For rice consumption, the HQs derived by FCA or TDA approach for eight provinces exceeded 1. Residents in Hubei, Guangxi, Jilin, Zhejiang, Liaoning, Shanghai, Sichuan, and Guangxi were more vulnerable due to their notable higher consumption rates.Weighted rankings of the health risk levels were determined to derive the comparative risk management priority. For Cd intake from vegetables, four provinces/cities have high relative priority; for Cd intake from grains, three provinces have high relative priority. The comparative risk management priority for Hunan and Sichuan was high for dietary intake from vegetables or rice. Weighted average HQs were derived to determine the integrated dietary Cd intake health risk levels for dietary intake from vegetables or grains. The risk levels for Hunan, Guangxi, Sichuan, and Zhejiang are high, so effective measures should be taken to reduce Cd dietary intakes to ensure health protection.It is envisaged that the methodology employed in this study could provide useful insights into how various approaches can be integrated to determine human health risk levels for Cd intake, so more effective and targeted measures can be taken accordingly for the relevant regions.

Microbial ecological responses of partial nitritation/anammox granular sludge to real water matrices and its potential application.

Granular sludges are commonly microbial aggregates used to apply partial nitritation/anammox (PN/A) processes during efficient biological nitrogen removal from ammonium-rich wastewater. Considering keystone taxa of anammox bacteria (AnAOB) in granules and their sensitivity to unfavorable environments, it is essential to investigate microbial responses of autotrophic PN/A granules to real water matrices containing organic and inorganic pollutants. In this study, tap water, surface water, and biotreated wastewater effluents were fed into a series of continuous PN/A granular reactors, respectively, and the differentiation in functional activity, sludge morphology, microbial community structure, and nitrogen metabolic pathways was analyzed by integrating kinetic batch testing, size characterization, and metagenomic sequencing. The results showed that feeding of biotreated wastewater effluents causes significant decreases in nitrogen removal activity and washout of AnAOB (dominated by Candidatus Kuenenia) from autotrophic PN/A granules due to the accumulation of heavy metals and formation of cavities. Microbial co-occurrence networks and nitrogen cycle-related genes provided evidence for the high dependence of symbiotic heterotrophs (such as Proteobacteria, Chloroflexi, and Bacteroidetes) on anammox metabolism. The enhancement of Nitrosomonas nitritation in the granules would be considered as an important contributor to greenhouse gas (N2O) emissions from real water matrices. In a novel view on the application of microbial responses, we suggest a bioassay of PN/A granules by size characterization of red-color cores in ecological risk assessment of water environments.

Analysis of bacterial community distribution characteristics in the downstream section of a cross confluence in a polluted urban channel.

Channel confluences are common in urban rivers and caused complex hydrodynamic conditions in the downstream section, significantly influencing the distribution of pollutants and the microbial community. So far, the principles of bacterial community assembly and their linkages with environmental factors are poorly understood. In the present study, the hydrodynamic and pollution conditions were investigated in a typical channel confluence of an urban river in the Yangtze River delta area, China, and their impacts on the bacterial community structure in the water and sediment were characterized using 16S rRNA gene high-throughput sequencing technology. Based on the results, the flow velocity was the crucial factor influencing the dispersal of nutrients, organic compounds, and bacterial communities in the river water. Moreover, the sediments exhibited higher α-diversity and bacterial richness for nitrogen and sulfur cycling than the water. In addition to flow velocity, the contents of total organic carbon, total phosphorus, and heavy metals determined the sediment bacterial communities at varying depths. The predictive analysis of functional gene category indicated differences between the water and sediment communities in metabolic potentials and pathogen risk and provided guidance for water pollution control and the eco-remediation of urban rivers.

Metal-free graphene-based catalytic membranes for persulfate activation toward organic pollutant removal: a review.

Owing to their ultrathin two-dimensional structure and efficient catalytic ability for persulfate activation, graphene-based nanocarbons exhibit considerable application potential in fabricating carbonaceous composite membranes for in situ catalytic oxidation to remove organic pollutants. This approach offers significant advantages over conventional batch systems. However, the relationships between the physicochemical properties of carbon mats and performance of graphene-based catalytic membranes in water purification remain ambiguous. Herein, we summarize the main mechanisms of in situ catalytic oxidation and the facile fabrication strategies of carbonaceous composite membranes. Different factors influencing the performance of graphene-based catalytic membranes are comprehensively discussed. The defective level, heteroatom doping, and stacking morphology of carbon mats and operational conditions during filtration play critical roles in the oxidative degradation of target pollutants. Long-term operation leads to the deterioration of catalytic activity and transmembrane pressure, especially in the complex water matrix. Finally, the present challenges and future perspectives are presented to improve the anti-fouling performance and catalytic stability of membranes and develop scalable fabrication methods to promote the engineering applications of in situ catalytic oxidation in real water purification.

Greenhouse gas emission benefits of adopting new energy vehicles in Suzhou City, China: A case study.

The promotion of new energy in light-duty vehicles (LDVs) is considered as an effective approach for achieving low-carbon road transport targets. In this study, life cycle assessment was performed for five typical vehicle models in Suzhou City (fourth largest LDV stock in China): internal combustion engine vehicle (ICEV), hybrid electric vehicle (HEV), plug-in electric vehicle (PHEV), battery electric vehicle (BEV) and hydrogen fuel cell vehicle (HFCV). Their energy consumption, and greenhouse gas (GHG) and air pollutant emissions during vehicle and fuel cycles in 2020 were examined using the Greenhouse gases, Regulated Emissions, and Energy Use in Transportation (GREET) model. GHG emission reduction potential of LDV fleet was projected under various scenarios for 2021-2040. The results showed that BEVs exhibited advantages for replacing ICEVs over HEVs, PHEVs and HFCVs, taking into account China's road electrification policy. The GHG emission intensity of BEVs in 2040 was estimated to be 19-34% of ICEVs in 2020, with a deep decarbonized electricity mix and improved vehicle efficiency. For the aggressive Sustainable Development Scenario, the GHG emissions of LDVs would peak before 2026, ahead of China's target by 2030, and the ~ 100% share of EVs in 2040 would result in a lower GHG emissions, equivalent to the 2010 level. It highlights the importance of early action, green electricity mix, and public transport development in reducing GHG emissions of large LDV fleet.

[Characterization of Sludge Morphology and Bacterial Community Evolution in the Rapid Activation of Freeze-stored PN/A Granular Sludge].

Inoculating granular sludge is an alternative method for the quick start-up of a high-performance autotrophic nitrogen removal reactor. In order to establish the response relationship between sludge activation and reactor performance, the freeze-stored granular sludge was inoculated into a continuous-flow reactor, and a control strategy of the high loading rate and high hydraulic selective pressure was carried out in this study. As a result, a one-stage partial nitritation/ANAMMOX process was started up in 34 days, and the removal efficiency of total nitrogen was over 83%, with a removal loading rate of total nitrogen of 1.67 kg·(m3·d)-1. During this period, the Image pro-plus software was employed to analyze the evolution of the characteristic dimensions of particles. A good linear positive correlation (R2=0.988) between the projected area of the erythrine zone in the inner layer and the specific nitrogen removal rate of granules was found, which provide a simple method to estimate the activity of the PN/A granules. The results of MiSeq high-throughput sequencing showed that the enrichment of aerobic ammonia-oxidizing bacteria (Nitrosomonas) and the wash-out of heterotrophic bacteria (such as Denitratisoma and Haliangium, etc.) were achieved in the start-up of the reactor. Meanwhile, the improvement in granular compactness was in favor of activating anaerobic ammonia oxidizing bacteria (Candidatus_Kuenenia, abundance>30%) that colonized the inner layer of the granules.

Carbonaceous composite membranes for peroxydisulfate activation to remove sulfamethoxazole in a real water matrix.

In this study, we fabricated carbonaceous composite membranes by loading integrated mats of nitrogen-doped graphene, reduced graphene oxide, and carbon nanotubes (NG/rGO/CNTs) on a nylon microfiltration substrate and employed it for in-situ catalytic oxidation by activating peroxydisulfate (PDS) for the removal of sulfamethoxazole (SMX) in a real water matrix. The impact of coexisting organics on the performance of carbonaceous catalysis was investigated in the continuous filtration mode. Reusability testing and radical quenching experiments revealed that the non-radical pathways of surface-activated persulfate mainly contributed to SMX degradation. A stable SMX removal flux (rSMX) of 22.15 mg m-2·h-1 was obtained in 24 h when tap water was filtered continuously under a low pressure of 1.78 bar and in a short contact time of 1.4 s, which was slightly lower than the rSMX of 23.03 mg m-2·h-1 performed with deionized water as the control group. In addition, higher contents of protein-, fulvic acid-, and humic acid-like organics resulted in membrane fouling and significantly suppressed SMX removal during long-term filtration. Changes in the production of sulfate ions and the Raman spectra of carbon mats indicated that organics prevent the structural defects of the carbon matrix from participating in PDS activation. Moreover, NG/rGO/CNTs composite membranes coupled with activated persulfate oxidation exhibited good self-cleaning ability, because membrane fouling could be partly reversed by restoring filtration pressure during operation. This study provides a novel and effective oxidation strategy for efficient SMX removal in water purification, allowing the application of carbonaceous catalysis for the selective degradation of emerging contaminants.

[Effects of Cold Acclimation on the Activity of Autotrophic Nitrogen Removal in Granular Sludge and Its Bacterial Population Structure].

Cold acclimation is an effective approach for improving the nitrogen removal performance and operational stability of partial nitritation/ANAMMOX (PN/A) combined processes at low temperatures. To explore the specific effects of cold acclimation on the characteristics of sludge, differentiations in temperature sensitivity, granular morphology, composition of extracellular polymer substance (EPS), and bacterial community structure between PN/A granular sludges cultivated at medium-high temperature (30℃) and acclimated to low temperature (15℃) were investigated in this study. The results of reaction thermodynamics showed that the nitrogen removal performance of the granules acclimated to low temperature (GL) was significantly higher than that of those cultivated at medium-high temperature (GH) under the low temperature (10-20℃), and the apparent activation energy (Ea) of total inorganic nitrogen removal for the former was decreased by 28.4%. Compared with GH, GL had a smaller average particle size of 25.8% and higher EPS contents of 16.6%, resulting in a significant lower settling property. Based on the high-throughput sequencing results, GL exhibited a higher diversity of bacterial community, and a lower relative abundance ratio (0.04) of aerobic ammonium-oxidizing bacteria (Nitrosomonas) and anaerobic ammonium-oxidizing bacteria (Candidatus_Kuenenia) than 0.34 for GH. It indicated that the PN/A granules held a strong ability to retain slow-growing autotrophic bacteria in the system, even under low temperatures. These findings could provide meaningful references for analyzing the self-adaption mechanisms of PN/A sludge to low temperature conditions and promote the industrial application of combined processes.

The in situ catalytic oxidation of sulfamethoxazole via peroxydisufate activation operated in a NG/rGO/CNTs composite membrane filtration.

Metal-free carbonaceous composite membranes have been proven to effectively drive novel in situ catalytic oxidation for the degradation of organic pollutants via persulfates activation. In this study, nitrogen-doped graphene (NG) was employed as a modifier to enhance the catalytic activity of the carbon mats by assembly with reduced graphene oxide (rGO) and carbon nanotubes (CNTs) on the top of a nylon supporter. The morphology and performance of the NG/rGO/CNTs composite membrane were compared to those obtained without the addition of NG (rGO/CNTs). Owing to the larger nanochannels for water delivery and stronger hydrophobicity on the surface, the NG/rGO/CNTs composite membrane shows a superior low-pressure filtration performance in favor of energy-saving operation. For the in situ catalytic oxidation of the NG/rGO/CNTs composite membrane through the activation of peroxydisufate (PDS), the average removal rate of sulfamethoxazole (SMX), one of frequently detected sulfonamide antibiotics in water, can reach 21.7 mg·m-2·h-1 under continuous filtration mode, which was 17% more rapid than that of the rGO/CNTs, resulting in significant detoxifying of the oxidation intermediates. Owing to the addition of NG into the carbon mats, the reactive nitrogen-doped sites identified by X-Ray photoelectron spectroscopy (XPS), such as pyridinic and graphitic N, played important roles in PDS activation, while both the radical and non-radical pathways were involved in in situ catalytic oxidation. According to the experimental evidence of the effects that solution environment has on the SMX removal and transmembrane pressure, the NG/rGO/CNTs composite membrane shows a relatively high resistance to changes in the solution pH, chloride ion inhibition, and background organics fouling. These results suggest a new approach to the application of activated persulfate oxidation in water treatment, such that improvements to the reaction stability warrant further investigation.

Conversion of full nitritation to partial nitritation/anammox in a continuous granular reactor for low-strength ammonium wastewater treatment at 20 °C.

The feasibility of converting full nitritation to partial nitritation/anammox (PN/A) at ambient temperature (20 °C) was investigated in a continuous granular reactor. The process was conducted without anammox bacteria inoculation for the treatment of 70 mg L-1 of low-strength ammonium nitrogen wastewater. Following the stepwise increase of the nitrogen loading rate from 0.84 to 1.30 kg N m-3 d-1 in 320 days of operation, the removal efficiency of total inorganic nitrogen (TIN) exceeded 80% under oxygen-limiting conditions. The mature PN/A granules, which had a compact structure and abundant biomass, exhibited a specific TIN removal rate of 0.11 g N g-1 VSS d-1 and a settling velocity of 70.2 m h-1. This was comparable with that obtained at above 30 °C in previous reports. High-throughput pyrosequencing results revealed that the co-enrichment of aerobic and anaerobic ammonium-oxidizing bacteria identified as genera Nitrosomonas and Candidatus Kuenenia, which prompted a hybrid competition for oxygen and nitrite with nitrite-oxidizing bacteria (NOB). However, the overgrowth of novel NOB Candidatus Nitrotoga adapted to low temperatures and low nitrite concentration could potentially deteriorate the one-stage PN/A process by exhausting residual bulk ammonium under long-term excessive aeration.

[Adaptability of Completely Autotrophic Nitrogen Removal over Granular Sludge to Low-Strength at Low Temperature].

A single-stage PN-ANAMMOX (PN/A) granular sludge cultured at room temperature was used to investigate the completely autotrophic nitrogen removal efficiency and microbial community structure of low-strength wastewater based on the completely autotrophic nitrogen removal over nitrite in granular sludge at a low temperature. The results showed that at the low temperature (15±1)℃, the ammonia nitrogen load was maintained at 1.29 kg ·(m3 ·d)-1, and the ammonia nitrogen concentration in the injection was gradually reduced from 70 mg ·L-1 to 40 mg ·L-1. DO/TAN was controlled at 0.22-0.25. The total nitrogen removal rate was maintained at (85±4)%, and the average TN concentration in the effluent was 8.9 mg ·L-1. There was no significant proliferation of nitrite-oxidizing bacteria (NOB) during the operation period, and the Nitrospira abundance was less than 1%. Elutriation of the floc sludge and the control of low DO/TAN values can be used as effective control strategies to inhibit NOB proliferation. Through completely autotrophic nitrogen removal over nitrite in granular sludge operated under low-temperature and low-substrate conditions, the particle size became smaller, and the color changed from brown red to brown yellow. The total amount of PS decreased slightly, and the ratio of PN/PS stabilized at 2.5-3.0. Planctomycetes and Proteobacteria dominated the community, and Candidatus_Kuenenia and Candidatus_Brocadia were two AMX bacteria in the sludge.

[Analysis of Rapid Start-up and Mixed Nutritional Nitrogen Removal Performance of Complete Autotrophic Granular Sludge].

A rapid start of the completely autotrophic nitrogen removal over nitrite (CANON) process based on granular sludge and efficient nitrogen removal under mixotrophic conditions are important steps in a continuous flow reactor for CANON engineering applications. In this study, an aged CANON granular sludge was mechanically crushed to 0.3 mm as inoculum in an airlift internal-loop reactor (AIR) to achieve simultaneous COD removal and mixotrophic denitrification of the single-stage granular sludge. The system achieved stable partial nitrification by controlling DO after 26 days of startup. Granulation and anaerobic ammonia oxidation were then promoted by shortening the HRT to increase the ammonia nitrogen load to 5.65 kg ·(m3 ·d)-1. The total nitrogen removal rate reached 58% on the 68th day. Subsequently, the C/N ratio of influent was increased from 0 to 0.25 and 0.5, which promoted the synergistic growth of AOB, AMX, and heterotrophic microorganisms. The removal rates of ammonia and total nitrogen were 95% and 85% respectively, and the removal of COD reached approximately 80%. The activity of NOB such as Nitrospira was effectively inhibited as the COD concentration was increased. q(NH4+-N) and q(TN) were stable at 0.4 g ·(g ·h)-1 and 0.34 g ·(g ·h)-1, respectively, while q(NO3--N) was approximately 0.02 g ·(g ·h)-1. Microbial diversity was observed using MiSeq high-throughput sequencing. It showed that organic carbon had no significant effect on the abundance of Nitrosomomas and Candidutus_Kuenenia, while increasing the abundance of Candidutus_Brocadia and Denitratisoma in the sludge. This study provides ideas for the rapid start of continuous flow CANON granular sludge process to treat wastewater with low C/N ratio.

[Impact of Hydraulic Retention Time on Performance of Partial Nitrification Granular Sludge in Continuous Stirred-Tank Reactor].

The effects of different hydraulic retention time (HRT) on short-cut nitrification granular sludge were studied in a continuous stirred-tank reactor (CSTR) by maintaining stable influent ammonia nitrogen load. Particle size distribution, extracellular polymeric substances (EPS), and functional bacterial kinetics were analyzed. The morphology of granular sludge, the performance of the CSTR, and the activity of functional microorganisms were investigated. The high throughout sequencing technology of MiSeq was employed to analyze the structure of the microbial community in sludge. The results showed that the ammonia nitrogen removal rate in the reactor was gradually increased from 80% to 95%, and the nitrite accumulation rate was always over 85% when the HRT was decreased from 4 h to 1 h. Particle size distribution of granular sludge was greatly influenced by HRT. The mass fraction of granules with a diameter smaller than 0.3 mm and larger than 1.6 mm was gradually declined, whereas the mass fraction of granules with a diameter between 0.3 mm and 0.8 mm was increased when HRT was shortened from 4 h to 1 h. The dominating proportion of granules with a diameter between 0.3 mm and 0.8 mm reached about 50% when HRT was 1 h. The impact of HRT on the activity of functional microorganisms was studied, and HRT activity was found to be closely related to the size of granular sludge. Proteobacteria were dominant in the system. AOB enrichment was represented by Nitrosomonas, which was more than 56%. Shortening HRT is beneficial for the enrichment of AOB.

[Start-up of a Three-stage PN/A Granular Sludge Reactor for Treating Wastewater with High Concentrations of Ammonia].

In order to apply partial nitritation-ANAMMOX (PN/A) technology to treat wastewater with high concentrations of ammonia, autotrophic nitrogen-removing granular sludge was crushed and inoculated into a three-stage continuous flow reactor. The nitrogen loading rate (NLR), dissolved oxygen (DO) concentration, and free ammonia (FA) levels in each compartment of the reactor were controlled over a 106-day period. Results showed that the nitritation process occurred with the inoculated granules during the initial phase. A limited aeration strategy was employed in the reactor at relatively high NLRs. Given the effective suppression of nitrite-oxidizing bacteria and the prevention of ANAMMOX bacteria from high DO conditions, the compact structure and nitrogen-removal activity of the granules could be improved. When the ammonia-nitrogen concentration was increased in the influent to 350 mg·L-1, the adverse impacts of high FA concentrations on the functional microbe activity in the first compartment should be eliminated. This occurs by reducing the influent pH and alkalinity dosage. This occurs by reducing the influent pH and degree of alkalinity. As a result, a total nitrogen removal rate of 7.2 kg·(m3·d)-1 was achieved in the reactor, which is 50 to 100 times higher than that of conventional activated sludge systems. The consistent improvement in the nitrogen-removal activity of the granules was demonstrated by batch testing at different aeration intensities. This showed that activity was greatest in the first compartment, which showed the highest granular maturity. In addition, a clear linear correlation (R2>0.97) was observed between the amount of extracellular polymeric substance and the specific nitrogen removal rate. This indicated that the dense granules played a positive role in enhancing the performance of the reactor.

Switchable hydrophilicity solvent based and solidification-assisted liquid-phase microextraction combined with GFAAS for quantification of trace soluble lead in raw bovine and derivative milk products.

A novel microextraction method was developed by combining CO2-controlled switchable hydrophilicity solvent (SHS) with solidification of the aqueous phase (SAP), referred to as CSHS-SAP. It was applied for pre-concentration/extraction of the complexes of Pb-ammonium pyrrolidine dithiocarbamate (APDC) prior to GFAAS detection in raw bovine milk and milk products (whole-fat, half-skimmed and skimmed milks). In the CSHS-SAP microextraction, a clear interface was easily formed, and convenient and complete collection was achieved by directly transferring the SHS phase into a vial, which overcame the shortcomings of blurred interface and difficult collection of SHS phase using CSHS-based microextraction. SAP led to the increase of extraction recoveries for Pb2+ by 8-11%. Some important factors were optimised using a one-factor-at-a-time approach: 800 µL of N,N-dimethylbutylamine and water at a ratio of 1:1 as SHS, 1.0 g L-1 APDC as chelating agent, sample pH = 6.0, 0.6 mL of 1.0 mol L-1 NaOH, solidification time of 70 min and 300 µL of 0.5 mol L-1 HNO3 for back extraction. Under optimised conditions, limits of detection were as low as 0.01-0.02 µg kg-1 and enrichment factors reached more than 23-fold. Inter- and intra-day precisions had relative standard deviations of 3.6-6.4%. With the CSHS-SAP/GFAAS method Pb2+ was detected at 0.5-1.8 µg kg-1 in four bovine raw milk samples, which were collected from Hubei and Henan Provincial oil-producing area, China. However, Pb2+ was below the LOD in all of the local milk products. Overall, the newly developed CSHS-SAP/GFAAS method is convenient, efficient and robust, giving it great potential for rapid and accurate analysis of trace Pb2+ in liquid milks.

[Start-up Performance and Sludge Characteristics of Single-stage Autotrophic Nitrogen Removal System with Granular Sludge at Low Ammonia Nitrogen Concentration at Room Temperature].

The start-up and stable operation of single-stage autotrophic nitrogen removal process under low ammonia nitrogen substrate at room temperature appears as the premise and basis for the application in municipal wastewater treatment. In this study, the PN/A (partial nitritation and ANAMMOX) granular sludge for long-term storage was inoculated into an air-lift bioreactor to investigate the nitrogen removal performance during the start-up of single-stage partial nitritation and ANAMMOX process under the following conditions:temperature at (23±2)℃, pH at 7.7-8.0. Synthetic wastewater with ammonia nitrogen concentration of 70 mg·L-1 was used as influent. By stepwise shortening hydraulic retention time (HRT) (1.1 h→0.9 h→0.7 h→0.5 h) and increasing ammonia nitrogen loading rate[1.53 kg·(m3·d)-1→1.87 kg·(m3·d)-1→2.40 kg·(m3·d)-1→3.36 kg·(m3·d)-1], the bioactivity as the synergy between the ammonia oxidizing bacteria (AOB) and anaerobic oxidizing bacteria (AMX) were gradually restored. After 95 d operation and regulation, the process was successfully established and the removal rate of NH4+-N and TN were 85% and 69%, respectively. According to the performance of sludge at each stage, the nitrite oxidizing bacteria (NOB) were selectively inhibited by controlling dissolved oxygen strictly. The average particle size gradually increased and finally was reached to 1.30 mm after the sludge was adapted to the environment. The profile of the mature autotrophic granular sludge was smooth and clear, SEM showed that the center of granular sludge formed a cavity with porous structure on the surface, the sludge morphology consisted mainly of cocci, with a small amount of bacilli and short bacilli. The major component of EPS in granular sludge was protein (81.48%) indicating that it had a good settling performance.

Magnetic solid phase extraction of sulfonamides based on carboxylated magnetic graphene oxide nanoparticles in environmental waters.

A magnetic nano-adsorbent material was prepared by functionalizing carboxylic group onto the granule surface of magnetic graphene oxide nanoparticles (CMGO), using in-situ co-precipitating method. The surface morphology was characterized by SEM and TEM. The CMGO was selected as the adsorbent for the magnetic solid phase extraction (MSPE) of sulfonamides (SAs) from environmental water samples, and the eluted analytes were determined by ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). A series of experimental parameters were optimized to improve the extraction efficiency such as amount of CMGO, extraction time, pH, ionic strength of the sample solution and desorption conditions. When the pH of water sample was 4.00, the extraction recoveries (ERs) for SAs were over 82.0% with 15.0 mg CMGO adsorption for 20 min. Under the optimized extraction conditions, linear range was obtained with coefficients of determination (R2)≥0.9983. The limits of detection for this proposed method were in the range of 0.49-1.59 ng/L, and the enrichment factors were 1320-1702 for eight SAs. The newly developed method was successfully applied to the analysis of trace SAs in real-world water samples, which provided satisfactory ERs in the range of 82.0-106.2% with RSDs less than 7.2%. Overall, it shows a great potential for the concentration of trace amine organic pollutions in complex matrices.