Molecular characterization of effluent organic matter identified by ultrahigh resolution mass spectrometry

Effluent dissolved organic matter (EfOM) collected from the secondary-treated wastewater of the Orange County Sanitation District (OCSD) located in Fountain Valley, California, USA was compared to natural organic matter collected from the Suwannee River (SRNOM), Florida using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Furthermore, the two different treatment processes at OCSD, activated sludge and trickling filter, were separately investigated. The blend of these two effluents was further evaluated after it had passed through the microfiltration process of the Advanced Water Purification Facility (AWPF) at Orange County Water District (OCWD). EfOM contained 872 different m/z peaks that were unambiguously assigned to exact molecular formulae containing a single sulfur atom and carbon, hydrogen and oxygen atoms (CHOS formulae). In contrast, the SRNOM sample only contained 152 CHOS formulae. The trend in CHO molecular compositions was opposite with 2500 CHO formulae assigned for SRNOM but only about 1000 for EfOM. The CHOS-derived mass peaks with highest abundances in EfOM could be attributed to surfactants such as linear alkyl benzene sulfonates (LAS), their co-products dialkyl tetralin sulfonates (DATS) and their biodegraded metabolites such as sulfophenyl carboxylic acids (SPC). The differences between the treatments were found minor with greater differences between sampling dates than treatment methods used.     

Characterization of low molecular weight dissolved natural organic matter along the treatment trait of a waterworks using Fourier transform ion cyclotron resonance mass spectrometry

Dissolved natural organic matter (DOM), particularly the low molecular weight DOM, can affect the performance of water treatment processes and serve as a main precursor of disinfection by-products (DBPs) during chlorination. In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize the low molecular weight DOM along the treatment trait of a conventional drinking water treatment plant. The ESI FT-ICR MS data showed that various C, H, O-only class species were the major components in the source water. According to the van Krevelen diagram analysis, lignin- and tannin-like compounds were the most abundant components. Within an isobaric group, the DOM molecules with a high degree of oxidation (high O/C value) were preferentially removed during coagulation, while those with low degree of oxidation were found to be more reactive toward chlorine. In addition, 357 one-chlorine containing products and 199 two-chlorine containing products formed during chlorination were detected in the chlorination effluent sample at a high confidence level. The chlorinated products can be arranged into series, suggesting that they were originated from C, H, O-only precursor compounds, which were in series related by the replacement of CH₄ against oxygen. For the first time, this study explored the behavior of low molecular weight DOM along a drinking water treatment trait on the molecular level, and revealed the presence of abundant unknown chlorinated products, which are probably rich in carboxylic and phenolic groups, in drinking water.     

Characteristics and fate of organic nitrogen in municipal biological nutrient removal wastewater treatment plants

The aim of this study was to investigate the occurrence and fate of colloidal and dissolved organic nitrogen (CON and DON) across biological nutrient removal (BNR) activated sludge bioreactors. Primary and secondary effluent total nitrogen (TN) measurements and component fractionation, CON and DON concentration profiles across BNR bioreactors, and laboratory batch experiments with the process mixed liquor were carried out at several full-scale BNR plants in northern Poland. The organic nitrogen (ON) components were divided into high CON, low CON, and DON based on sequential filtration through 1.2, 0.45 and 0.1 μm pore-size filters. The average influent DON_0.1μm (<0.1 μm) concentrations ranged from 1.1 g N/m³ to 3.9 g N/m³ and accounted for only 4-13% of total organic nitrogen. In the effluents, however, this contribution increased to 12-45% (the DON_0.1μm concentrations varied in a narrow range of 0.5-1.3 g N/m³). Conversions of ON inside the bioreactors were investigated in more detail in two largest plants, i.e. Gdansk (565,000 PE) and Gdynia (516,000 PE). Inside the two studied bioreactors, the largest reductions of the colloidal fraction were found to occur in the anaerobic and anoxic compartments, whereas an increase of DON_0.1μm concentrations was observed under aerobic conditions in the last compartment. Batch experiments with the process mixed liquor confirmed that DON_0.1μm was explicitly produced in the aerobic phase and significant amounts of ON were converted in the anoxic phase of the experiments.     

Comparison of two fractionation strategies for characterization of wastewater effluent organic matter and diagnosis of membrane fouling

Two fractionation strategies were compared for characterizing organic components in effluent organic matter (EfOM) and natural organic matter (NOM). The first method is widely used and requires sample acidification and then re-neutralization during sequential organic removals onto resins. The second method uses a different suite of separation methods, does not require pH manipulation, and sequentially removes particles, colloids, organic acids, and hydrophobic neutrals without the need for adjusting pH. The NOM samples were dominantly organic acids while EfOM contained a broader distribution of organic functionalities so further evaluation was focused on EfOM. The new method completely removed colloidal matter from EfOM while the conventional fractionation method resulted in an increase in the percentage of EfOM >100 kDa with each fractionation step after filtration. Organic acids were removed in one fractionation step using the new method instead of three steps with the conventional method. The conventional method resulted in increased fouling after the final separation step apparently caused by production of inorganic colloids. The new fractionation method provided a clearer diagnosis that organic acids were the primary cause of fouling even though they were only 14% of EfOM organic carbon. We suggest that the new fractionation method should be considered for diagnosing the effects of NOM or EfOM on the performance of membrane filtration.     

Fate of effluent organic matter and DBP precursors in an effluent-dominated river: A case study of wastewater impact on downstream water quality

The impact of treated wastewater discharges on downstream water quality was evaluated in an effluent-dominated stream in the Southwest USA. The fate and transport of effluent organic matter (EfOM) and disinfection by-product (DBP) precursors was studied. Nitrification and biodegradation were important mechanisms. Changes in DBP formation potential along the river appeared to correlate with dissolved organic carbon (DOC) and organic nitrogen concentrations and specific ultraviolet absorbance. The mean oxidation state of carbon (MOC) decreased in value along the river. MOC decreases paralleled decreases in the biodegradability of residual DOC (i.e., lower biodegradable DOC/DOC ratio). The EfOM was biodegradable by up to 40 percent, both in the stream and in a laboratory reactor, and many DBP precursors (e.g., haloacetonitriles, certain nitrosamines) decreased in concentration. Alternatively, the DBP yields for trihalomethanes or haloacetic acids either remained the same or increased slightly, suggesting that these precursors were part of the recalcitrant organic matter (OM).     

Occurrence and removal of selected organic micropollutants at mechanical, chemical and advanced wastewater treatment plants in Norway

In Norway the combined hydraulic capacity of all domestic wastewater treatment plants is relatively equally distributed between three major treatment plant types; mechanical, chemical, and combined chemical and biological. The Western coast from Lindesnes in the south to the Russian boarder in the North is dominated by mechanical treatment plants, constituting approximately 68% of the treatment capacity in that area. In the present study we report concentrations and removal efficiencies of polycyclic aromatic hydrocarbons (PAHs), nonylphenols, phthalates, polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) found in five Norwegian wastewater treatment plants (WWTPs) applying different levels of treatment. Concentrations of organic micropollutants in the influents to the WWTPs were generally in the low range of what have been reported by others for domestic wastewater in Europe and North-America. More than 90% removal could be obtained for nonylphenols, PBDEs, and the more hydrophobic 4-6 ring PAHs by chemical precipitation, however, biological treatment appeared to be necessary for efficient removal of the less lipophilic 2 and 3 ring PAHs, the medium- to short-chained nonylphenol ethoxylates and diethyl phthalate. SigmaPCB(7) was removed by more than 90% by combined biological/chemical treatment, while removal efficiency by chemical treatment was not possible to estimate due to low inlet concentrations. Low or insignificant removals of PAHs, phthalates and nonylphenols with their ethoxylates were observed at the mechanical WWTP, which was in accordance with the minuscule removal of TOC.     

Occurrence and treatment of wastewater-derived organic nitrogen

Dissolved organic nitrogen (DON) derived from wastewater effluent can participate in reactions that lead to formation of nitrogenous chlorination by-products, membrane fouling, eutrophication, and nitrification issues, so management of DON is important for both wastewater reuse applications and nutrient-sensitive watersheds that receive discharges from treated wastewater. This study documents DON occurrence in full-scale water/wastewater (W/WW) treatment plant effluents and assesses the removal of wastewater-derived DON by several processes (biodegradation, coagulation, softening, and powdered activated carbon [PAC] adsorption) used for advanced treatment in wastewater reuse applications. After varying levels of wastewater treatment, the dominant aqueous nitrogenous species shifts from ammonia to nitrate after aerobic processes and nitrate to DON in tertiary treatment effluents. The fraction of DON in total dissolved nitrogen (TDN) accounts for at most 52% in tertiary treated effluents (median = 13%) and 54% in surface waters impacted by upstream wastewater discharges (median = 31%). The 5-day biodegradability/bioavailability of DON (39%) was higher, on average, than that of dissolved organic carbon (DOC, 26%); however, upon chlorination, the DON removal (3%) decreased significantly. Alum coagulation (with ≥8 mg/L alum per mg/L DOC) and lime softening (with pH 11.3-11.5) removed <25% of DON and DOC without selectivity. PAC adsorption preferentially removed more DOC than DON by 10% on average. The results provided herein hence shed light on approaches for reducing organic nitrogen content in treated wastewater.     

Differences in the molecular composition of fulvic acid size fractions detected by size-exclusion chromatography-on line Fourier transform ion cyclotron resonance (FTICR-) mass spectrometry

Size-exclusion chromatography was coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (SEC-FTICR-MS) to separate a fulvic acid isolate into three size fractions and to determine the elemental composition of fulvic acids in these fractions. Molecular formulas of about 3000 ions in the mass range of 200-700 Da were derived, many of which occur in all three fractions and follow the same system of elemental composition. Product ion spectra generated by SEC coupled to quadrupol-time-of-flight-MS (Q-TOF-MS) confirmed that the ions of all three fractions are basically polycarboxylates with hardly any other functional moiety. However, SEC-FTICR-MS revealed that the ions generated from the high molecular weight (HMW) fraction are enriched in carboxyl groups and are more aromatic as compared with the low molecular weight (LMW) fraction. These findings support the idea that the HMW fulvic acids are formed from LMW fulvic acids. The shift in the relative frequency of ions from the LMW to the HMW fraction is in line with different interaction mechanisms: HMW fulvic acids may be aggregates held together by electrostatic interaction of the carboxylate groups via hydrogen bonds or with polyvalent cations or by hydrophobic interaction of their carbon backbone, or consist of LMW fulvic acids covalently bound to each other or to (aliphatic) alcohols.     

Ammonium nitrogen removal from coking wastewater by chemical precipitation recycle technology

Ammonium nitrogen removal from wastewater has been of considerable concern for several decades. In the present research, we examined chemical precipitation recycle technology (CPRT) for ammonium nitrogen removal from coking wastewater. The pyrolysate resulting from magnesium ammonium phosphate (MAP) pyrogenation in sodium hydroxide (NaOH) solution was recycled for ammonium nitrogen removal from coking wastewater. The objective of this study was to investigate the conditions for MAP pyrogenation and to characterize of MAP pyrolysate for its feasibility in recycling. Furthermore, MAP pyrolysate was characterized by scanning electron microscope (FESEM), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR) as well as X-ray diffraction (XRD). The MAP pyrolysate could be produced at the optimal condition of a hydroxyl (OH⁻) to ammonium molar ratio of 2:1, a heating temperature of 110 °C, and a heating time of 3 h. Surface characterization analysis indicated that the main component of the pyrolysate was amorphous magnesium sodium phosphate (MgNaPO₄). The pyrolysate could be recycled as a magnesium and phosphate source at an optimum pH of 9.5. When the recycle times were increased, the ammonium nitrogen removal ratio gradually decreased if the pyrolysate was used without supplementation. When the recycle times were increased, the ammonium nitrogen removal efficiency was not decreased if the added pyrolysate was supplemented with MgCl₂·6H₂O plus Na₂HPO₄·12H₂O during treatment. A high ammonium nitrogen removal ratio was obtained by using pre-formed MAP as seeding material.     

Effective removal of effluent organic matter (EfOM) from bio-treated coking wastewater by a recyclable aminated hyper-cross-linked polymer

Effluent organic matter (EfOM) is a complex matrix of organic substance mainly from bio-treated sewage effluent and is considered as the main constraint to further advanced treatment. Here a recyclable aminated hyper-cross-linked polymeric adsorbent (NDA-802) featured with aminated functional groups, large specific surface area, and sufficient micropore region was synthesized for effective removal of EfOM from the bio-treated coking wastewater (BTCW), and its removal characteristics was investigated. It was found that hydrophobic fraction was the main constituent (64.8% of DOC) in EfOM of BTCW, and the hydrophobic-neutral fraction had the highest SUVA level (7.06 L mg^?1 m^?1), which were significantly different from that in the domestic wastewater. Column adsorption experiments showed that NDA-802 exhibited much higher removal efficiency of EfOM than other polymeric adsorbents D-301, XAD-4, and XAD-7, and the efficiency could be readily sustained according to continuous 28-cycle batch adsorption–regeneration experiments. Moreover, dissolved organic matter (DOM) fractionation and excitation-emission matrix (EEM) fluorescence spectroscopy study indicated that NDA-802 showed attractive adsorption preference as well as high removal efficiency of hydrophobic and aromatic compounds. Possibly ascribed to the presence of functional aminated groups, relatively large specific surface area and micropore region of the unique polymer, NDA-802 possesses high and sustained efficiency for the removal of EfOM, and provides a potential alternative for the advanced treatment.     

有机碳源及溶解氧对污水脱氮除磷的影响

介绍了有机碳源、溶解氧对常用污水生物脱氮处理工艺（A2O,Carrousel氧化沟,SBR）的影响,指出反硝化除磷、间歇曝气、低氧脱氮除磷技术在处理低碳、高氮磷城市污水方面具有良好的发展前景。     

污水处理厂出水氨氮异常的分析与控制

针对某污水处理厂出水氨氮异常的突发事件,分别对该事件发生的可能原因进行了分析,分别为进水氨氮突然升高和硝化茵流失所致,并根据分析结果采取了针对性的控制措施,取得了良好的效果,可为国内其他污水处理厂应对该类异常现象提供参考。     

Total and methyl mercury transformations and mass loadings within a wastewater treatment plant and the impact of the effluent discharge to an alkaline hypereutrophic lake

Concerns over the fate and bioaccumulation of mercury (Hg) inputs to Onondaga Lake, a hypereutrophic lake in central New York, prompted an investigation into the concentrations and fluxes of Hg discharge from the Onondaga County Metropolitan Wastewater Treatment Plant (METRO WWTP). Discharge of methyl Hg (MeHg) is of concern because it is the form of Hg that readily bioaccumulates along the aquatic food chain. This study incorporated clean protocols for sampling and Hg analysis to evaluate: seasonal patterns in the concentrations of total Hg (THg) and MeHg in the WWTP unit processes; the production of MeHg within the unit processes of the WWTP; the overall fate of THg and MeHg within the WWTP; and the relative impact of the Hg discharged from the WWTP to Onondaga Lake. Concentrations of THg (range: 80-860 ng/L) and MeHg (0.7-17 ng/L) in raw sewage were highly variable, with higher concentrations observed in the summer months. The dynamics of THg though the WWTP were correlated with total suspended solids (TSS). As a result, the majority of the THg removal (55%) occurred during primary treatment. Overall, about 92% of the THg entering the plant was removed as sludge, with volatilization likely a minor component of the overall Hg budget. The transformation of MeHg through the plant differed from THg in that MeHg was not correlated with TSS, and displayed strong seasonal differences between winter (November to April) and summer (May-October) months. During the summer months, substantial net methylation occurred in the activated sludge secondary treatment, resulting in higher MeHg concentrations in secondary effluent. Net demethylation was the dominant mechanism during tertiary treatment, resulting in removal of substantial MeHg from the secondary effluent. The overall MeHg removal efficiency through the plant was about 70% with more efficient removal during summer months. Sediment trap collections made below the epilimnion of Onondaga Lake indicated average deposition rates of 12 μg/m²-day for THg and 0.33 μg/m²-day for MeHg. These deposition rates are more than an order of magnitude higher than the thermocline area normalized external loads from METRO effluent (0.85 μg/m²-day for THg, 0.05 μg/m²-day for MeHg). Our findings indicate that the impact of the discharge from METRO is relatively small, contributing about 10-15% of Hg to the total gross Hg input to the hypolimnion of the lake.     

Quantification and molecular characterization of enteric viruses detected in effluents from two hospital wastewater treatment plants

Hospital wastewater has been described as an important source of spreading pathogenic microorganisms in the environment. However, there are few studies reporting the presence and concentrations of gastroenteric viruses and hepatitis A viruses in these environmental matrices. The aim of this study was to assess the contamination by viruses responsible for acute gastroenteritis and hepatitis derived from hospital wastewater treatment plants (WWTPs). Rotavirus A (RV-A), human adenoviruses (HAdV), norovirus genogroup I and II (NoV GI/GII) and hepatitis A viruses (HAV) were detected and quantified in sewage samples from two WWTPs located in Rio de Janeiro (Brazil) that operates different sewage treatments. WWTP-1 uses an Upflow Anaerobic Sludge Blanket (UASB reactor) and three serial anaerobic filters while WWTP-2 uses aerobic processes, activated sludge with extended aeration and final chlorination of the effluents. Viruses’ detection was investigated by using conventional PCR/RT-PCR, quantitative real-time PCR (qPCR) and partial sequencing of the genome of the viruses detected. Rate of viruses detection ranged from 7% (NoV GI in WWTP-1) to 95% (RV-A in WWTP-2) and genome from all viruses were detected. The most prevalent genotypes were RV-A SG I, HAdV species D and F, NoV GII/4 and HAV subgenotype IA. Mean values of viral loads (genome copies (GC)/ml) obtained in filtered effluents from anaerobic process was 1.9 × 10³ (RV-A), 2.8 × 10³ (HAdV) and 2.4 × 10³ (NoV GII). For chlorinated effluents from activated sludge process, the mean values of viral loads (GC/ml) was 1.2 × 10⁵ (RV-A), 1.4 × 10³ (HAdV), 8.1 × 10² (NoV GII) and 2.8 × 10⁴ (HAV). Data on viral detection in treated effluents of hospital WWTPs confirmed the potential for environmental contamination by viruses and could be useful to establish standards for policies on wastewater management.     

Effects of Fenton treatment on the properties of effluent organic matter and their relationships with the degradation of pharmaceuticals and personal care products

This study examined effects of Fenton oxidation on trace level pharmaceuticals and personal care products (PPCPs) commonly occurring in wastewater. The tested PPCPs included acetaminophen, atenolol, atrazine, carbamazepine, metoprolol, dilantin, DEET, diclofenac, pentoxifylline, oxybenzone, caffeine, fluoxetine, gemfibrozil, ibuprofen, iopromide, naproxen, propranolol, sulfamethoxazole, bisphenol-A and trimethoprim. Transformations of effluent organic matter (EfOM) caused by Fenton oxidation were also quantified. All tested PPCPs, except atrazine and iopromide, were completely removed by Fenton treatment carried out using a 20 mg/L Fe (II) concentration and a 2.5 H₂O₂/Fe (II) molar ratio. Up to 30% on the total carbon concentration was removed during Fenton treatment which was accompanied by the oxidation of EfOM molecules and formation of oxidation products such as oxalic, formic and acetic acids and, less prominently, formaldehyde, acetaldehyde, propionaldehyde and glycolaldehyde. The absorbance of EfOM treated with Fenton reagent at varying Fe (II) concentration and contact time underwent a consistent decrease. The relative decrease of EfOM absorbance was strongly and unambiguously correlated with the removal of all tested PPCPs.     

Seasonal and time variability of heavy metal content and of its chemical forms in sewage sludges from different wastewater treatment plants

Sewage sludges obtained from seven wastewater treatment plants from the province of Salamanca, Spain, were periodically sampled to determine seasonal and time variation of their elemental composition over 2000 to 2002. The aim of this paper was to provide additional insight to evaluate the potential environmental impact following soil incorporation of these materials as amendments. Aqua regia extractable metals (pseudo total content) of Cd, Cr, Cu, Ni, Pb and Zn were determined and furthermore, the main chemical forms of metals within the sludge were evaluated using a five-step fractionation procedure. All the studied sludges displayed high fertility properties due to their richness of OC, P and K. Total mean concentrations of Cd, Cr, Cu, Ni, Pb and Zn in the sludges were within the regulation of the Spanish legislation. Using an multifactor analysis of variance, significant differences between Cr, Cu, Ni, Pb and Zn pseudo total contents (p<0.01) of sludges at different sites were found while the Cd content was statistically similar. Also significant differences were found between these pseudo total contents of heavy metals in samples collected along the time after three years (0.001相似文献   

Determination of proteins and carbohydrates in the effluents from wastewater treatment bioreactors using resonance light-scattering method

A simple and sensitive method was developed for the determination of low-concentration proteins and carbohydrates in the effluents from biological wastewater treatment reactors using resonance light-scattering (RLS) technique. Two ionic dyes, Congo red and Neutral red were, respectively used as an RLS probes for the determination of proteins and carbohydrates. This method is based on the interactions between biomacromolecules and dyes, which cause a substantial increase in the resonance scattering signal of dyes in the wavelength range of 200-650 nm. The characteristics of RLS spectra of the macromolecule-dye complexes, influencing factors, and optimum analytical conditions for the measurement were explored. The method was satisfactorily applied to the measurement of proteins and carbohydrates in the effluents from 10 aerobic or anaerobic bioreactors, and a high sensitivity were achieved.     

Identification and chemical characterization of specific organic indicators in the effluents from chemical production sites

The structural diversity of the wastewater composition was described by the use of detailed non-target screening analyses of industrial effluents from chemical production sites. Determination of the indicative organic compounds acting as potential molecular indicators for industrial emissions from chemical production industries has been possible due to (i) detailed characterisation of industrial contaminants and identification of compounds with high source specificity, (ii) quantitative determination of the organic constituents in the industrial effluents and (iii) the review of their industrial applications. The determination of potential site-specific markers and industrial molecular indicators corresponding to certain production processes (production of starting materials for manufacturing paper and printing inks, powder coatings as well as epichlorohydrin production) was performed in this work.The results of this study allowed significant contributions to the chemical characterisation of industrial contaminants and isolation of indicators that can act as representatives of industrial effluents in the aquatic environment.     

A combined approach for a better understanding of wastewater treatment plants operation: statistical analysis of monitoring database and sludge physico-chemical characterization

Biological wastewater treatment plants (WWTP) are complex systems to assess. Many parameters are recorded daily in WWTP to monitor and control the treatment process, providing huge amounts of registered data. A combined approach of extracting information from the WWTP databases by statistical methods and from the sludge physico-chemical characterization was used here for a better understanding of the WWTP operation. The monitored parameters were analysed by multivariate statistical methods: Principal Components Analysis and multiple partial linear regression. The WWTP operational conditions determine the sludge characteristics. The bacterial activity of the sludge in terms of extra-cellular polymeric substances (EPS) production was assessed using size exclusion chromatography and the internal structure of sludge flocs was observed by confocal laser scanning microscopy. The diagnosis of three paper mill WWTP enabled the identification of an important EPS production, the presence of the nitrification process and the presence of PO₄³⁻ nutrient in WWTP-A. These three main characteristics of WWTP-A were related with a systematically good sludge settling. In WWTP-B and C with bad settling, the bacterial activity was weak.