Reproductive toxicity of PFOA, PFOS and their substitutes: A review based on epidemiological and toxicological evidence.

Per- and polyfluoroalkyl substances (PFAS) have already drawn a lot of attention for their accumulation and reproductive toxicity in organisms. Perfluorooctanoic acid (PFOA) and perfluorooctanoic sulfonate (PFOS), two representative PFAS, are toxic to humans and animals. Due to their widespread use in environmental media with multiple toxicities, PFOA and PFOS have been banned in numerous countries, and many substitutes have been produced to meet market requirements. Unfortunately, most alternatives to PFOA and PFOS have proven to be cumulative and highly toxic. Of the reported multiple organ toxicities, reproductive toxicity deserves special attention. It has been confirmed through epidemiological studies that PFOS and PFOA are not only associated with reduced testosterone levels in humans, but also with an association with damage to the integrity of the blood testicular barrier. In addition, for women, PFOA and PFOS are correlated with abnormal sex hormone levels, and increase the risk of infertility and abnormal menstrual cycle. Nevertheless, there is controversial evidence on the epidemiological relationship that exists between PFOA and PFOS as well as sperm quality and reproductive hormones, while the evidence from animal studies is relatively consistent. Based on the published papers, the potential toxicity mechanisms for PFOA, PFOS and their substitutes were reviewed. For males, PFOA and PFOS may produce reproductive toxicity in the following five ways: (1) Apoptosis and autophagy in spermatogenic cells; (2) Apoptosis and differentiation disorders of Leydig cells; (3) Oxidative stress in sperm and disturbance of Ca2+ channels in sperm membrane; (4) Degradation of delicate intercellular junctions between Sertoli cells; (5) Activation of brain nuclei and shift of hypothalamic metabolome. For females, PFOA and PFOS may produce reproductive toxicity in the following five ways: (1) Damage to oocytes through oxidative stress; (2) Inhibition of corpus luteum function; (3) Inhibition of steroid hormone synthesis; (4) Damage to follicles by affecting gap junction intercellular communication (GJIC); (5) Inhibition of placental function. Besides, PFAS substitutes show similar reproductive toxicity with PFOA and PFOS, and are even more toxic to the placenta. Finally, based on the existing knowledge, future developments and direction of efforts in this field are suggested.

Trigred motif 36 regulates neuroendocrine differentiation of prostate cancer via HK2 ubiquitination and GPx4 deficiency.

Neuroendocrine prostate cancer (NEPC), the most lethal subtype of castration-resistant prostate cancer (PCa), may evolve from the neuroendocrine differentiation (NED) of PCa cells. However, the molecular mechanism that triggers NED is unknown. Trigred motif 36 (TRIM36), a member of the TRIM protein family, exhibits oncogenic or anti-oncogenic roles in various cancers. We have previously reported that TRIM36 is highly expressed to inhibit the invasion and proliferation of PCa. In the present study, we first found that TRIM36 was lowly expressed in NEPC and its overexpression suppressed the NED of PCa. Next, based on proteomic analysis, we found that TRIM36 inhibited the glycolysis pathway through suppressing hexokinase 2 (HK2), a crucial glycolytic enzyme catalyzing the conversion of glucose to glucose-6-phosphate. TRIM36 specifically bound to HK2 through lysine 48 (lys48)-mediated ubiquitination of HK2. Moreover, TRIM36-mediated ubiquitination degradation of HK2 downregulated the level of glutathione peroxidase 4 (GPx4), a process that contributed to ferroptosis. In conclusion, TRIM36 can inhibit glycolysis via lys48-mediated HK2 ubiquitination to reduce GPX4 expression and activate ferroptosis, thereby inhibiting the NED in PCa. Targeting TRIM36 might be a promising approach to retard NED and treat NEPC.

Simple and Sensitive Method for Synchronous Quantification of Regulated and Unregulated Priority Disinfection Byproducts in Drinking Water.

Due to their elevated concentrations in drinking water, compared to other emerging environmental contaminants, disinfection byproducts (DBPs) have become a global concern. To address this, we have created a simple and sensitive method for simultaneously measuring 9 classes of DBPs. Haloacetic acids (HAAs) and iodo-acetic acids (IAAs) are determined using silylation derivatization, replacing diazomethane or acidic methanol derivatization with a more environmentally friendly and simpler treatment process that also offers greater sensitivity. Mono-/di-haloacetaldehydes (mono-/di-HALs) are directly analyzed without derivatization, along with trihalomethanes (THMs), iodo-THMs, haloketones, haloacetonitriles, haloacetamides, and halonitromethanes. Of the 50 DBPs studied, recoveries for most were 70-130%, LOQs for most were 0.01-0.05 µg/L, and relative standard deviations were <30%. We subsequently applied this method to 13 home tap water samples. Total concentrations of 9 classes of DBPs were 39.6-79.2 µg/L, in which unregulated priority DBPs contributed 42% of total DBP concentrations and 97% of total calculated cytotoxicity, highlighting the importance of monitoring their presence in drinking water. Br-DBPs were the dominant contributors to total DBPs (54%) and total calculated cytotoxicity (92%). Nitrogenous DBPs contributed 25% of total DBPs while inducing 57% of total calculated cytotoxicity. HALs were the most important toxicity drivers (40%), particularly four mono-/di-HALs, which induced 28% of total calculated cytotoxicity. This simple and sensitive method allows the synchronous analysis of 9 classes of regulated and unregulated priority DBPs and overcomes the weaknesses of some other methods especially for HAAs/IAAs and mono-/di-HALs, providing a useful tool for research on regulated and unregulated priority DBPs.

Transformation of Algal Toxins during the Oxidation/Disinfection Processes of Drinking Water: From Structure to Toxicity.

With the increase of algal blooms worldwide, drinking water resources are threatened by the release of various algal toxins, which can be hepatotoxic, cytotoxic, or neurotoxic. Because of their ubiquitous occurrence in global waters and incomplete removal in conventional drinking water treatment, oxidation/disinfection processes have become promising alternative treatment options to destroy both the structures and toxicity of algal toxins. This Review first summarizes the occurrence and regulation of algal toxins in source water and drinking water. Then, the transformation kinetics, disinfection byproducts (DBPs)/transformation products (TPs), pathways, and toxicity of algal toxins in water oxidation/disinfection processes, including treatment by ozonation, chlorination, chloramination, ultraviolet-based advanced oxidation process, and permanganate, are reviewed. For most algal toxins, hydroxyl radicals (HO•) exhibit the highest oxidation rate, followed by ozone and free chlorine. Under practical applications, ozone and chlorine can degrade most algal toxins to meet water quality standards. However, the transformation of the parent structures of algal toxins by oxidation/disinfection processes does not guarantee a reduction in toxicity, and the formation of toxic TPs should also be considered, especially during chlorination. Notably, the toxicity variation of algal toxins is associated with the chemical moiety responsible for toxicity (e.g., Adda moiety in microcystin-LR and uracil moiety in cylindrospermopsin). Moreover, the formation of known halogenated DBPs after chlorination indicates that toxicity in drinking water may shift from toxicity contributed by algal toxins to toxicity contributed by DBPs. To achieve the simultaneous toxicity reduction of algal toxins and their TPs, optimized oxidation/disinfection processes are warranted in future research, not only for meeting water quality standards but also for effective reduction of toxicity of algal toxins.

Unravelling High-Molecular-Weight DBP Toxicity Drivers in Chlorinated and Chloraminated Drinking Water: Effect-Directed Analysis of Molecular Weight Fractions.

As disinfection byproducts (DBPs) are ubiquitous sources of chemical exposure in disinfected drinking water, identifying unknown DBPs, especially unknown drivers of toxicity, is one of the major challenges in the safe supply of drinking water. While >700 low-molecular-weight DBPs have been identified, the molecular composition of high-molecular-weight DBPs remains poorly understood. Moreover, due to the absence of chemical standards for most DBPs, it is difficult to assess toxicity contributions for new DBPs identified. Based on effect-directed analysis, this study combined predictive cytotoxicity and quantitative genotoxicity analyses and Fourier transform ion cyclotron resonance mass spectrometry (21 T FT-ICR-MS) identification to resolve molecular weight fractions that induce toxicity in chloraminated and chlorinated drinking waters, along with the molecular composition of these DBP drivers. Fractionation using ultrafiltration membranes allowed the investigation of <1 kD, 1-3 kD, 3-5 kD, and >5 kD molecular weight fractions. Thiol reactivity based predictive cytotoxicity and single-cell gel electrophoresis based genotoxicity assays revealed that the <1 kD fraction for both chloraminated and chlorinated waters exhibited the highest levels of predictive cytotoxicity and direct genotoxicity. The <1 kD target fraction was used for subsequent molecular composition identification. Ultrahigh-resolution MS identified singly charged species (as evidenced by the 1 Da spacing in 13C isotopologues), including 3599 chlorine-containing DBPs in the <1 kD fraction with the empirical formulas CHOCl, CHOCl2, and CHOCl3, with a relative abundance order of CHOCl > CHOCl2 ≫ CHOCl3. Interestingly, more high-molecular-weight CHOCl1-3 DBPs were identified in the chloraminated vs chlorinated waters. This may be due to slower reactions of NH2Cl. Most of the DBPs formed in chloraminated waters were composed of high-molecular-weight Cl-DBPs (up to 1 kD) rather than known low-molecular-weight DBPs. Moreover, with the increase of chlorine number in the high-molecular-weight DBPs detected, the O/C ratio exhibited an increasing trend, while the modified aromaticity index (AImod) showed an opposite trend. In drinking water treatment processes, the removal of natural organic matter fractions with high O/C ratio and high AImod value should be strengthened to minimize the formation of known and unknown DBPs.

Overlooked Iodo-Disinfection Byproduct Formation When Cooking Pasta with Iodized Table Salt.

Iodized table salt provides iodide that is essential for health. However, during cooking, we found that chloramine residuals in tap water can react with iodide in table salt and organic matter in pasta to form iodinated disinfection byproducts (I-DBPs). While naturally occurring iodide in source waters is known to react with chloramine and dissolved organic carbon (e.g., humic acid) during the treatment of drinking water, this is the first study to investigate I-DBP formation from cooking real food with iodized table salt and chloraminated tap water. Matrix effects from the pasta posed an analytical challenge, necessitating the development of a new method for sensitive and reproducible measurements. The optimized method utilized sample cleanup with Captiva EMR-Lipid sorbent, extraction with ethyl acetate, standard addition calibration, and analysis using gas chromatography (GC)-mass spectrometry (MS)/MS. Using this method, seven I-DBPs, including six iodo-trihalomethanes (I-THMs) and iodoacetonitrile, were detected when iodized table salt was used to cook pasta, while no I-DBPs were formed with Kosher or Himalayan salts. Total I-THM levels of 11.1 ng/g in pasta combined with cooking water were measured, with triiodomethane and chlorodiiodomethane dominant, at 6.7 and 1.3 ng/g, respectively. Calculated cytotoxicity and genotoxicity of I-THMs for the pasta with cooking water were 126- and 18-fold, respectively, compared to the corresponding chloraminated tap water. However, when the cooked pasta was separated (strained) from the pasta water, chlorodiiodomethane was the dominant I-THM, and lower levels of total I-THMs (retaining 30% of the I-THMs) and calculated toxicity were observed. This study highlights an overlooked source of exposure to toxic I-DBPs. At the same time, the formation of I-DBPs can be avoided by boiling the pasta without a lid and adding iodized salt after cooking.

Interactions between H2O2 and dissolved organic matter during granular activated carbon-based residual H2O2 quenching from the upstream UV/H2O2 process.

Granular activated carbon (GAC) filtration can be employed to synchronously quench residual H2O2 from the upstream UV/H2O2 process and further degrade dissolved organic matter (DOM). In this study, rapid small-scale column tests (RSSCTs) were performed to clarify the mechanisms underlying the interactions between H2O2 and DOM during the GAC-based H2O2 quenching process. It was observed that GAC can catalytically decompose H2O2, with a long-lasting high efficiency (>80% for approximately 50,000 empty-bed volumes). DOM inhibited GAC-based H2O2 quenching via a pore-blocking effect, especially at high concentrations (10 mg/L), with the adsorbed DOM molecules being oxidized by the continuously generated ·OH; this further deteriorated the H2O2 quenching efficiency. In batch experiments, H2O2 could enhance DOM adsorption by GAC; however, in RSSCTs, it deteriorated DOM removal. This observation could be attributed to the different ·OH exposure in these two systems. It was also observed that aging with H2O2 and DOM altered the morphology, specific surface area, pore volume, and the surface functional groups of GAC, owing to the oxidation effect of H2O2 and ·OH on the GAC surface as well as the effect of DOM. Additionally, the changes in the content of persistent free radicals in the GAC samples were insignificant following different aging processes. This work contributes to enhancing understanding regarding the UV/H2O2-GAC filtration scheme, and promoting the application in drinking water treatment.

Formation of halonitromethanes from methylamine in the presence of bromide during UV/Cl2 disinfection.

The UV/Cl2 process is commonly used to achieve a multiple-barrier disinfection and maintain residuals. The study chose methylamine as a precursor to study the formation of high-toxic halonitromethanes (HNMs) in the presence of bromide ions (Br-) during UV/Cl2 disinfection. The maximum yield of HNMs increased first and then decreased with increasing concentration of Br-. An excessively high concentration of Br- induced the maximum yield of HNMs in advance. The maximum bromine incorporation factor (BIF) increased, while the maximum bromine utilization factor (BUF) decreased with the increase of Br- concentration. The maximum yield of HNMs decreased as pH value increased from 6.0 to 8.0 due to the deprotonation process. The BUF value remained relatively higher under an acidic condition, while pH value had no evident influence on the BIF value. The maximum yield of HNMs and value of BUF maximized at a Cl2:Br- ratio of 12.5, whereas the BIF value remained relatively higher at low Cl2:Br- ratios (2.5 and 5). The amino group in methylamine was first halogenated, and then released into solution as inorganic nitrogen by the rupture of C-N bond or transformed to nitro group by oxidation and elimination pathways. The maximum yield of HNMs in real waters was higher than that in pure water due to the high content of dissolved organic carbon. Two real waters were sampled to verify the law of HNMs formation. This study helps to understand the HNMs formation (especially brominated species) when the UV/Cl2 process is adopted as a disinfection technique.

Formation control of bromate and trihalomethanes during ozonation of bromide-containing water with chemical addition: Hydrogen peroxide or ammonia?

To ensure the safety of drinking water, ozone (O3) has been extensively applied in drinking water treatment plants to further remove natural organic matter (NOM). However, the surface water and groundwater near the coastal areas often contain high concentrations of bromide ion (Br-). Considering the risk of bromate (BrO3-) formation in ozonation of the sand-filtered water, the inhibitory efficiencies of hydrogen peroxide (H2O2) and ammonia (NH3) on BrO3- formation during ozonation process were compared. The addition of H2O2 effectively inhibited BrO3- formation at an initial Br- concentration amended to 350 µg/L. The inhibition efficiencies reached 59.6 and 100% when the mass ratio of H2O2/O3 was 0.25 and > 0.5, respectively. The UV254 and total organic carbon (TOC) also decreased after adding H2O2, while the formation potential of trihalomethanes (THMsFP) increased especially in subsequent chlorination process at a low dose of H2O2. To control the formation of both BrO3- and THMs, a relatively large dose of O3 and a high ratio of H2O2/O3were generally needed. NH3 addition inhibited BrO3- formation when the background ammonia nitrogen (NH3N) concentration was low. There was no significant correlation between BrO3- inhibition efficiency and NH3 dose, and a small amount of NH3N (0.2 mg/L) could obviously inhibit BrO3- formation. The oxidation of NOM seemed unaffected by NH3 addition, and the structure of NOM reflected by synchronous fluorescence (SF) scanning remained almost unchanged before and after adding NH3. Considering the formation of BrO3- and THMs, the optimal dose of NH3 was suggested to be 0.5 mg/L.

Disinfection by-product (DBP) research in China: Are we on the track?

Disinfection by-products (DBPs) formed during water disinfection has drawn significant public concern due to its toxicity. Since the first discovery of the trihalomethanes in 1974, continued effort has been devoted on DBPs worldwide to investigate the formation mechanism, levels, toxicity and control measures in drinking water. This review summarizes the main achievements on DBP research in China, which included: (1) the investigation of known DBP occurrence in drinking water of China; (2) the enhanced removal of DBP precursor by water treatment process; (3) the disinfection optimization to minimize DBP formation; and (4) the identification of unknown DBPs in drinking water. Although the research of DBPs in China cover the whole formation process of DBPs, there is still a challenge in effectively controlling the drinking water quality risk induced by DBPs, an integrated research framework including chemistry, toxicology, engineering, and epidemiology is especially crucial.

Role of TSP-1 as prognostic marker in various cancers: a systematic review and meta-analysis.

BACKGROUND: Published studies present conflicting data regarding the impact of Thrombospondin-1 (TSP-1) expression on prognosis of various cancers. We performed this meta-analysis to illustrate the preliminary predictive value of TSP-1. METHODS: Twenty-four studies with a total of 2379 patients were included. A comprehensive literature search was performed by using PubMed, Cochrane Library, Web of Science, Embase, and hand searches were also conducted of relevant bibliographies. Pooled hazard ratios (HRs) with 95% confidence intervals (CIs) for patient survival and disease recurrence were initially identified to explore relationships between TSP-1 expression and patient prognosis. RESULTS: A total of 24 eligible studies were included in this meta-analysis. Our results showed that high level of TSP-1 was correlated significantly with poor overall survival (OS) (HR = 1.40, 95% CI: 1.17 ~ 1.68; P<0.001). However, high TSP-1 expression predicted no significant impact on progression-free survival (PFS)/ metastasis-free survival (MFS) (HR = 1.35, 95%CI: 0.87-2.10; P = 0.176) and disease-free survival (DFS)/ recurrence-free survival (RFS) (HR = 1.40, 95%CI: 0.77-2.53; P = 0.271). In addition, we performed subgroup analyses which showed that high TSP-1 expression predicted poor prognosis in breast cancer and gynecological cancer. Additionally, the relatively small number of studies on PFS/MFS and DFS/RFS is a limitation. The data extracted through Kaplan-Meier curves may not be accurate. Moreover, only English articles were included in this article, which may lead to deviations in the results. CONCLUSIONS: Our findings indicated high TSP-1 expression may act as a promising biomarker of poor prognosis in cancers, especially in breast cancer and gynecological cancer.

Formation of Iodinated Disinfection Byproducts (I-DBPs) in Drinking Water: Emerging Concerns and Current Issues.

Formation of iodinated disinfection byproducts (I-DBPs) in drinking water has become an emerging concern. Compared to chlorine- and bromine-containing DBPs, I-DBPs are more toxic, have different precursors and formation mechanisms, and are unregulated. In this Account, we focus on recent research in the formation of known and unknown I-DBPs in drinking water. We present the state-of-the-art understanding of known I-DBPs for the six groups reported to date, including iodinated methanes, acids, acetamides, acetonitriles, acetaldehyde, and phenols. I-DBP concentrations in drinking water generally range from ng L-1 to low-µg L-1. The toxicological effects of I-DBPs are summarized and compared with those of chlorinated and brominated DBPs. I-DBPs are almost always more cytotoxic and genotoxic than their chlorinated and brominated analogues. Iodoacetic acid is the most genotoxic of all DBPs studied to date, and diiodoacetamide and iodoacetamide are the most cytotoxic. We discuss I-DBP formation mechanisms during oxidation, disinfection, and distribution of drinking water, focusing on inorganic and organic iodine sources, oxidation kinetics of iodide, and formation pathways. Naturally occurring iodide, iodate, and iodinated organic compounds are regarded as important sources of I-DBPs. The apparent second-order rate constant and half-lives for oxidation of iodide or hypoiodous acid by various oxidants are highly variable, which is a key factor governing the iodine fate during drinking water treatment. In distribution systems, residual iodide and disinfectants can participate in reactions involving heterogeneous chemical oxidation, reduction, adsorption, and catalysis, which may eventually affect I-DBP levels in finished drinking water. The identification of unknown I-DBPs and total organic iodine analysis is also summarized in this Account, which provides a more complete picture of I-DBP formation in drinking water. As organic DBP precursors are difficult to completely remove during the drinking water treatment process, the removal of iodide provides a cost-effective solution for the control of I-DBP formation. This Account not only serves as a reference for future epidemiological studies to better assess human health risks due to exposure to I-DBPs in drinking water but also helps drinking water utilities, researchers, regulators, and the general public understand the formed species, levels, and formation mechanisms of I-DBPs in drinking water.

Organic Amines Enhance the Formation of Iodinated Trihalomethanes during Chlorination of Iodide-Containing Waters.

The effects of organic amines (OAs) including glycine (Gly), sarcosine (Sar), and triethanolamine (Tea), representing primary, secondary, and tertiary amines, respectively, on iodinated trihalomethanes (I-THMs) formation during chlorination of iodide (I-)-containing waters were investigated. The total concentration of I-THMs formed in the co-presence of an OA and natural organic matter (NOM) was more than 3 times the sum of those formed in the presence of an OA alone and NOM alone, as OAs competed for free chlorine (FC) to form organic chloramines. Taking Gly as an example, the transformation of I- was determined. In the absence of NOM, the yields of iodate (IO3-) were 89%, 60%, and nearly 0 at [Gly]o/[FC]o = 0:1, 3:4, and 1:1, but 0, 2%, and 43% for hypoiodous acid (HOI), respectively. In the presence of NOM, as [Gly]o/[FC]o increased from 0:1 to 1:1, the yield of IO3- decreased from 66% to 0, while that of I-THMs increased from 2.9% to 16.1%. The competition of FC by OAs inhibited the oxidation of HOI to IO3-, and the formed organic chloramines can oxidize I- to HOI, thus promoting I-DBPs formation. Finally, the enhanced I-THMs formation was verified in real waters.

Formation of trihalomethanes in swimming pool waters using sodium dichloroisocyanurate as an alternative disinfectant.

Disinfection is essential to preventing infection caused by microbial pathogens in swimming pool water. The most commonly used disinfection methods are chlorine disinfectant, including sodium hypochlorite (NaOCl) and sodium dichloroisocyanurate (SDIC, C3O3N3Cl2Na) with characteristics of available chlorine formation and stability. In this study, we estimate the formation of trihalomethanes (THM4) in indoor swimming pools filled with seawater that adopt these disinfection methods, and we investigated the factors influencing the formation of THM4. Formation of THM4 by free chlorine (FC) and SDIC respectively is 327.8 µg L-1 and 307.6 µg L-1; Br-THMs is 226.7 µg L-1 for FC, 198 µg L-1 for SDIC. SDIC has less THM4 formation than FC in the same molar Br- dosage (10 µM) and total chlorine dosage (20 µM), and bromoform is the main Br-THMs species. The occurrence of THM4 is inhibited at high dosages of natural organic matter and Br-. The total Br-THMs increase from 75 µg L-1 to 189.7 µg L-1 and from 64.6 µg L-1 to 190 µg L-1 by FC and SDIC at pH 5.0-9.0, both of which are highly dependent on pH. In real water, similar results were found in Br--containing water (1 mg-Br- L-1).

Nitrogen removal performance of anaerobic ammonia oxidation (ANAMMOX) in presence of organic matter.

A sequencing batch reactor (SBR) was used to test the nitrogen removal performance of anaerobic ammonium oxidation (ANAMMOX) in presence of organic matter. Mesophilic operation (30 ± 0.5 °C) was performed with influent pH 7.5. The results showed, independent of organic matter species, ANAMMOX reaction was promoted when COD was lower than 80 mg/L. However, specific ANAMMOX activity decreased with increasing organic matter content. Ammonium removal efficiency decreased to 80% when COD of sodium succinate, sodium potassium tartrate, peptone and lactose were 192.5, 210, 225 and 325 mg/L, respectively. The stoichiometry ratio resulting from different OM differed largely and R1 could be as an indicator for OM inhibition. When COD concentration was 240 mg/L, the loss of SAA resulting from lactose, peptone, sodium potassium tartrate and sodium succinate were 28, 36, 50 and 55%, respectively. Sodium succinate had the highest inhibitory effect on SAA. When ANAMMOX process was used to treat wastewater containing OM, the modified Logistic model could be employed to predict the NREmax.

Effect of influent substrate ratio on anammox granular sludge: performance and kinetics.

Effect of influent substrate ratio on anammox process was studied in sequencing batch reactor. Operating temperature was fixed at 35 ± 1 °C. Influent pH and hydraulic retention time were 7.5 and 6 h, respectively. When influent NO2--N/NH4+-N was no more than 2.0, total nitrogen removal rate (TNRR) increased whereas NH4+-N removal rate stabilized at 0.32 kg/(m3 d). ΔNO2--N/ΔNH4+-N increased with enhancing NO2--N/NH4+-N. When NO2--N/NH4+-N was 4.5, ΔNO2--N/ΔNH4+-N was 1.98, which was much higher than theoretical value (1.32). The IC50 of NO2--N was 289 mg/L and anammox activity was inhibited at high NO2--N/NH4+-N ratio. With regard to influent NH4+-N/NO2--N, the maximum NH4+-N removal rate was 0.36 kg/(m3 d), which occurred at the ratio of 4.0. Anammox activity was inhibited when influent NH4+-N/NO2--N was higher than 5.0. With influent NO3--N/NH4+-N of 2.5-6.5, NH4+-N removal rate and NRR were stabilized at 0.33 and 0.40 kg/(m3 d), respectively. When the ratio was higher than 6.5, nitrogen removal would be worsened. The inhibitory threshold concentration of NO2--N was lower than NH4+-N and NO3--N. Anammox bacteria were more sensitive to NO2--N than NH4+-N and NO3--N. TNRR would be enhanced with increasing nitrogen loading rate, but sludge floatation occurred at high nitrogen loading shock. The Han-Levenspiel could be applied to simulate nitrogen removal resulting from NO2--N inhibition.

Nitrogen removal performance and operation strategy of anammox process under temperature shock.

Sequencing batch reactors were used to study anaerobic ammonium oxidation (anammox) process under temperature shock. Both long-term (15-35 °C) and short-term (10-50 °C) temperature effects on nitrogen removal performance were performed. In reactor operation test, the results indicated that ammonium removal rate decreased from 0.35 kg/(m3 day) gradually to 0.059 kg/(m3 day) when temperature dropped from 35 to 15 °C. Although bacteria morphology was not modified, sludge settling velocity decreased with decreasing temperature. In batch test, apparent activation energy (Ea) increased with decreasing temperature, which suggested the activity decrease of anaerobic ammonium oxidizing bacteria (AAOB). Low temperature inhibited AAOB and weakened nitrogen removal performance. The cardinal temperature model with inflection was first used to describe temperature effect on anammox process. Simulated results revealed that anammox reaction could occur at 10.52-50.15 °C with maximum specific anammox activity of 0.50 kg/(kg day) at 36.72 °C. The cold acclimatization of AAOB could be achieved and glycine betaine could slightly improve nitrogen removal performance at low temperature.

Performance and kinetics of ANAMMOX granular sludge with pH shock in a sequencing batch reactor.

As an efficient and cost-effective nitrogen removal process, anaerobic ammonium oxidation (ANAMMOX) could be well operated at suitable pH condition. However, pH shock occurred in different kinds of wastewater and affected ANANNOX process greatly. The present research aimed at studying the performance and kinetics of ANAMMOX granular sludge with pH shock. When influent pH was below 7.5, effluent [Formula: see text]-N and [Formula: see text]-N increased with decreasing pH. At Ph 6.0, effluent [Formula: see text]-N approached 100 mg/L, and the ratios of [Formula: see text] approached 2.2 and 1.3, respectively. Both greatly deviated from theoretical values. When influent pH was above 7.5, effluent [Formula: see text]-N and [Formula: see text]-N increased with increasing pH. At pH 9.0, ammonium removal rate (ARR) and nitrite removal rate (NRR) decreased to 0.011 ± 0.004 and 0.035 ± 0.004 kg/(m3·d), respectively. Besides, [Formula: see text]-N:[Formula: see text]-N deviated from theoretical value. Longer recovery time from pH 9.0 than from pH 6.0 indicated that alkaline surroundings inhibited anaerobic ammonium oxidizing bacteria (AAOB) greater. The sludge settling velocity was 2.15 cm/s at pH 7.5. However, it decreased to 2.02 cm/s when pH was 9.0. Acidic pH had little effect on sludge size, but disintegration of ANAMMOX granule was achieved with pH of 9.0. The Bell-shaped (A) model and the Ratkowsky model were more applicable to simulate the effect resulting from pH shock on ANAMMOX activity (R2 > 0.95), and both could describe ANAMMOX activity well with pH shock. They indicated that qmax was 0.37 kg [Formula: see text]-N/(kgMLSS·d) at the optimum pH value (7.47) in present study. The minimum pH during which ANAMMOX occurred was 5.68 while the maximum pH for ANAMMOX reaction was 9.26. Based on nitrogen removal performance with different pH, strongly acidic (pH ≤ 6.5) or alkaline (pH ≥ 8.5) inhibited ANAMMOX process. Besides, ANAMMOX appeared to be more susceptible to alkaline wastewater. Compared to extremely acidic condition (low pH), extremely alkaline condition (high pH) affected ANAMMOX granules much more.

Occurrence and removal of antibiotics in ecological and conventional wastewater treatment processes: A field study.

The occurrence and removal of 19 antibiotics (including four macrolides, eight sulfonamides, three fluoroquinolones, three tetracyclines, and trimethoprim) were investigated in two ecological (constructed wetland (CW) and stabilization pond (SP)) and two conventional wastewater treatment processes (activated sludge (AS) and micro-power biofilm (MP)) in a county of eastern China. All target antibiotics were detected in the influent and effluent samples with detection frequencies of >90%. Clarithromycin, ofloxacin, roxithromycin and erythromycin-H2O were the dominant antibiotics with maximum concentrations reaching up to 6524, 5411, 964 and 957 ng/L, respectively; while the concentrations of tiamulin, sulfamerazine, sulfathiazole, sulfamethazine, sulfamethizole and sulfisoxazole were below 10 ng/L. Although the mean effluent concentrations of target antibiotics were obviously lower than the influent ones (except ciprofloxacin), their removals were usually incomplete. Principal component analysis showed that the AS and CW outperformed the MP and SP processes and the AS performed better than the CW process in terms of antibiotics removal. Both the AS and CW processes exhibited higher removal efficiencies in summer than in winter, indicating biological degradation could play an important role in antibiotics removal. Because of the incomplete removal, the total concentration of detected antibiotics increased in the mixing and downstream sections of a local river receiving the effluent from a typical wastewater treatment facility practicing AS process. Nowadays, ecological wastewater treatment processes are being rapidly planned and constructed in rural areas of China; however, the discharge of residual antibiotics to the aquatic environment may highlight a necessity for optimizing or upgrading their design and operation.