Selected organic pesticides, behavior and removal from domestic wastewater by chemical and physical processes

A study was conducted to evaluate the effectiveness of chemical and physical wastewater treatment processes in removing selected organic pesticides from domestic wastewater. A 3785 m³ day⁻¹ (1 MGD) nominal capacity pilot plant consisting of biological, chemical and physical units was used for the study. Biologically treated domestic wastewater was subjected to chemical coagulation, multimedia filtration, and activated carbon adsorption. Eight sequences of treatment processes were studied. Influent and effluent samples were analyzed for selected chlorinated hydrocarbon pesticides and chlorophenoxy herbicides using EC-GC. Confirmatory tests such as TLC, extraction of p-value and CPU-MS-GC were applied on selected samples. Results of the study provided qualitative and quantitative evaluation of the performance of the treatment processes studied. Qualitatively characteristic profiles consisting of a limited number of refractory organic residues were detected as peaks on EC chromatograms of extracts from each treatment unit. Thirteen compounds were confirmed in the biologically treated wastewater. These included DDT and its metabolites, aldrin, dieldrin, and 2,4-D alkyl esters and salts. Concentration levels of these compounds in wastewaters were at the ng l⁻¹ (part per trillion) level. Chemical coagulation with alum-lime or lime-ferric chloride was found to effect slight reduction of the organic residues detected on EC chromatograms. Quantitatively only DDT compounds were more completely removed by chemical treatment. Multimedia filters had no discernible effect in removing organic residues from biologically and chemically treated wastewater. Activated carbon columns were found to be the most effective means for removing the refractory organic residues detected. However, breakthrough of some organic residues was noted after usage of the carbon for over 1 year. The overall results of the study showed that application of several sequences of treatment processes on domestic wastewater can produce a high quality effluent which is virtually free from EC detectable organic residues.     

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in sewage treatment plants

In this study, the concentrations of PFOS and PFOA in the biological units of various full-scale municipal sewage treatment plants were measured. Samples of influent, primary effluent, aeration tank effluent, final effluent and grab samples of primary, activated, secondary and anaerobically digested sludge were collected by 5 sampling events over one year. The two sewage treatment plants (STPs) selected for this study include plant A receiving 95% domestic wastewater and plant B receiving 60% industrial wastewater and 40% domestic wastewater. PFOS and PFOA were observed at higher concentration in aqueous and sludge samples in plant B than that of plant A. Mass flow of PFOS increased significantly (mean 94.6%) in conventional activated sludge process (CAS) of plant B, while it remained consistent after the secondary treatment in plant A. Mass flow of PFOA increased 41.6% (mean) in CAS of plants A and B and 76.6% in membrane biological reactor (MBR), while it remained unchanged after the treatment of liquid treatment module (LTM). Our results suggest that mass flow of these two compounds remains consistent after treatment of activated sludge process operating at short sludge retention time (SRT). Seasonal variations of PFOS in concentrations of raw sewage were found in plant A, while PFOA did not have significant seasonal variation in both plants A and B.     

A voltammetric electronic tongue as tool for water quality monitoring in wastewater treatment plants

The use of a voltammetric electronic tongue as tool for the prediction of concentration levels of certain water quality parameters from influent and effluent wastewater from a Submerged Anaerobic Membrane Bioreactor pilot plant applied to domestic wastewater treatment is proposed here. The electronic tongue consists of a set of noble (Au, Pt, Rh, Ir, and Ag) and non-noble (Ni, Co and Cu) electrodes that were housed inside a stainless steel cylinder which was used as the body of the electronic tongue system. As a previous step an electrochemical study of the response of the ions sulphate, orthophosphate, acetate, bicarbonate and ammonium was carried out in water using the electrodes contained in the electronic tongue. The second part of the work was devoted to the application of the electronic tongue to the characterization of the influent and effluent waters from the wastewater treatment plant. Partial Least Squares analysis was used to obtain a correlation between the data from the tongue and the pollution parameters measured in the laboratory such as soluble chemical oxygen demand (CODs), soluble biological oxygen demand (BODs), ammonia (NH₄-N), orthophosphate (PO₄-P), Sulphate (SO₄-S), acetic acid (HAC) and alkalinity (Alk). A total of 28 and 11 samples were used in the training and the validation steps, respectively, for both influent and effluent water samples. The electronic tongue showed relatively good predictive power for the determination of BOD, COD, NH₄-N, PO₄-P, SO₄-S, and Alk.     

Fate of endocrine-disrupting chemicals in percolating domestic wastewater effluent

Septic tanks and other on-site systems are a common means of disposing domestic wastewater effluent in Ireland. In assessing site suitability, subsoils below the percolation trench have an important role in attenuating pollutants and hence in protecting groundwater. As part of an investigation into the hydraulic performance of treatment systems at four sites in Ireland with different subsoil characteristics, a series of samples were analysed for endocrine-disrupting chemicals (EDCs), including oestrogens, surfactants and organic oxygen compounds. EDCs were found at all four sites, but only at low concentrations (often below those at which their presence could be confirmed) and generally only in samples known to be percolating effluent. Further research should target oestrogen compounds, as these appear to be present in higher concentrations than the other EDCs and also have greater potency.     

Microbial volatile organic compounds as indicators of fungi. Can an electronic nose detect fungi in indoor environments?

The paper presents a review of several studies on the detection of microbial volatile organic compounds (MVOCs) considered as indicators of fungal contamination. As fungi produce specific profiles, or fingerprints of volatile compounds, the electronic nose technology is a very promising opportunity for rapid and non costly detection of fungi in buildings. E-noses are able to distinguish between mouldy and non-mouldy samples, and also to recognise certain species of fungi. However, two limiting factors may appear decisive for employment of electronic noses in indoor fungi detection: low concentrations of MVOCs and presence of interfering substances in indoor environments.     

Understanding soluble microbial products (SMP) as a component of effluent organic matter (EfOM)

Formation of soluble microbial products (SMP) during biological degradation of organic compounds in a sequencing batch reactor (SBR) was investigated using high performance liquid chromatography--size exclusion chromatography (HPSEC) as well as other organic matter characterization tools. Results showed that carbon compounds in a glucose feed solution were totally transformed to other organic products classified biomass-associated products (BAP). The SMP-BAP contained in the SBR effluent consisted mainly of high-molecular weight (MW) fractions of organic matter, possibly originating from cell lysis. These compounds exhibited a low specific ultraviolet absorbance (SUVA) and a hydrophilic character. In addition, the characteristics of bulk effluent organic matters (EfOM) samples from wastewater treatment facilities were studied. It was observed that EfOM consisted of humic-like and hydrophobic (HPO) compounds, derived from the corresponding drinking water source, in addition to SMP-BAP. A superimposition of SEC chromatograms of the SMP-BAP and humic-like compounds represented a fingerprint of EfOM.     

Simultaneous colour and DON removal from sewage treatment plant effluent: Alum coagulation of melanoidin

The aim of this study was to detect and characterise melanoidin in sewage treatment plant (STP) effluent, and to study the ability of alum coagulation to remove the colour and dissolved organic nitrogen (DON) associated with melanoidin. The melanoidin is non-biodegradable due to the complex cyclic based structure and thus it directly contributes to effluent nitrogen concentrations from the sewage treatment plant (STP). Lowering of effluent total nitrogen limits and the link between colour and chlorinated disinfection by-products have therefore driven a need to understand the structure, properties and treatability of DON species found in STP effluent.The focus of this paper is the refractory coloured, organic nitrogen compound melanoidin. Wetalla STP effluent has relatively high colour (170 mg-PtCo L⁻¹) and DON (2.5 mg L⁻¹) for a biological nutrient removal STP, owing to an industrial supply of melanoidin containing molasses fermentation wastewater. Alum coagulation jar tests were performed on synthetic melanoidin solution, STP effluent containing melanoidin (Wetalla, Toowoomba, Australia) and STP effluent free of melanoidin (Merrimac, Gold Coast, Australia) to examine the treatability of melanoidin and its associated colour and DON content when present in STP effluent.The removal of melanoidin from STP effluent resulted in significant colour and DON reduction. An alum dose of 30 mg L⁻¹ as aluminium was sufficient to reach maximum removal of colour (75%), DON (42%) and dissolved organic carbon (DOC) (30%) present in melanoidin containing STP effluent. Alum was shown to preferentially remove DON with a molecular weight >10 kDa over small molecular weight DON. Fluorescence excitation-emission matrix examination of the humic compounds present in the STP effluent indicated that melanoidin type humic compounds were more readily removed by alum coagulation than other humic compounds.     

Evaluation of the fate of perfluoroalkyl compounds in wastewater treatment plants

Recent studies have shown that the wastewater treatment plant (WWTP) is a significant source of perfluoroalkyl compounds (PFCs) in natural water. In this study, 10 PFCs were analyzed in influent and effluent wastewater and sludge samples in 15 municipal, 4 livestock and 3 industrial WWTPs in Korea. The observed distribution pattern of PFCs differed between the wastewater and sludge samples. Perfluorooctane sulfonate (PFOS) was dominant in the sludge samples with a concentration ranging from 3.3 to 54.1 ng/g, whereas perfluorooctanoic acid (PFOA) was dominant in wastewater and ranged from 2.3 to 615 ng/L and 3.4 to 591 ng/L in influent and effluent wastewater, respectively. Principal component analysis (PCA) results provided an explanation for this variation in PFC distribution patterns in the aqueous and sludge samples. The fates of PFCs in the WWTPs were related with the functional groups. The PFOS concentrations tended to decrease after treatment in most WWTPs, whereas PFOA increased. The different fates of PFOA and PFOS in WWTPs were attributed to the higher organic carbon-normalized distribution coefficient of perfluoroalkylsulfonate (PFASs) than that of the carboxylate analog, indicating the preference of PFASs to partition to sludge. Although industrial WWTPs contained high concentration of PFCs, they are not the main source of PFCs in Korean water environment because of their small release amount. WWTPs located in big cities discharged more PFCs, suggesting household sewage is one of the significant sources of PFCs contamination in the environment.     

A method for measuring haloform formation during wastewater chlorination

An experimental methodology was developed to measure haloform formation in chlorinated wastewater samples using a flexible bag, zero-head space, reactor. A flexible reactor vessel is advantageous when the reaction products are volatile since successive samples can be collected over time without creating a head-space and thereby eliminating partitioning of volatile reaction products from the aqueous phase to the gaseous phase. Grab samples of three kinds of wastewaters; raw wastewater, nitrified secondary effluent, and partially nitrified secondary effluent, were chlorinated at two levels of chlorine doses (Cl₂). The magnitude and rate of total trihalomethane (TTHM) production was estimated based on the formation of chloroform (CHCl₃), bromodichloromethane (CHCl₂Br), dibromochloromethane (CHClBr₂) and bromoform (CHBr₃).     

Characterization of DOM as a function of MW by fluorescence EEM and HPLC-SEC using UVA,DOC, and fluorescence detection

To investigate the composition of dissolved organic matter (DOM) as a function of apparent molecular weight (MW) by rapid analytical methods, high performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) was conducted with sequential on-line detectors consisting of UV, fluorescence, and quantitative DOC measurement. Fluorescence excitation-emission matrix (EEM) spectrophotometry was used to select wavelengths for the HPSEC on-line fluorescence system. The chosen peak maxima locations of excitation-emission wavelengths were 278-353 nm for protein-like substances and 337-423 nm for fulvic-like substances based on an analysis of EEM spectra for various samples and reference materials. This system provides quantitative and qualitative information on the specific MW components of DOM, including proportion of DOC (by DOC measurement), aromaticity (by comparison of UV and DOC measurements), and chemical properties (by fluorescence measurement). It further allows determination of organic matter characteristics (e.g., fulvic-like, protein-like, and polysaccharide-like substances) as a function of MW. Three types of samples (Irvine Ranch ground water (IRWD-GW), Barr Lake surface water (BL-SW), and Hawaii wastewater secondary effluent) were analyzed by the HPSEC-UVA-fluorescence-DOC system. These results were compared with fluorescence EEM for samples fractionated by HPLC-SEC. The DOM fraction in the high apparent MW range (over 10,000g/mol) consisted of polysaccharide-like substances for IRWD-GW and a mixture of polysaccharide-like/protein-like substances for BL-SW and wastewater secondary effluent. Minimal amounts of fulvic-like substances were found in the wastewater secondary effluent sample. The DOM fractions in a medium apparent MW range (5000-1000 g/M) showed higher aromaticity (fulvic in character) than any other fractions for all samples. For the DOM fraction in the low apparent MW range (below 680 g/M), additional aliphatic organic matter was found in IRWD-GW, while BL-SW contained protein-like processes. DOM plays an important role in drinking water and wastewater treatment processes. An enhanced HPSEC technique with multiple on-line detectors enables a better understanding of quantitative and qualitative DOM properties and can help to design and optimize water/wastewater treatment facilities.     

Reactivity and chemical characterization of effluent organic nitrogen from wastewater treatment plants determined by Fourier transform ion cyclotron resonance mass spectrometry

In advanced wastewater treatment plants that achieve high levels of nitrogen (N) removal, up to one-third of the N in effluent is organic, herein referred to as effluent organic N (EON). While we know that inorganic N is highly labile, it is unclear what fraction of EON is bioavailable. In this study, we demonstrate the utility of a method that can be used to examine the reactivity of EON in natural receiving waters to better understand both the ecosystem response and the potential bioavailability of EON. The technique is suitable for analyzing polar organic matter in natural waters; electrospray ionization coupled with Fourier transform mass spectrometry. Bioassays were performed on samples collected at the end of the biological process from two wastewater treatment plants achieving advanced N removal. The samples were concentrated, and then added to natural water samples collected from the oligohaline James River, a major tributary of the Chesapeake Bay. Our results demonstrate that while the lignin-like fraction of the effluent dissolved organic matter (some of which contains N) was conserved, a large portion of aliphatic and aromatic compounds containing N was removed (79-100%) during incubations, while other compounds were produced. Furthermore, the two effluents exhibited differences in the degree of degradation and type of degradation, which can be related both to the various processes employed in the two WWTPs and the dramatic differences in the type of influent they received. These findings suggest that EON is highly reactive in the natural environment and that simple assays examining net consumption or production of bulk dissolved organic N pools are inadequate for assessing the bioavailability of EON.     

污水处理过程中除磷加药智能控制系统及应用研究

应用基于化学除磷模型和在线传感器的智能控制系统对污水处理厂的药剂投加量进行优化控制,以达到污水处理厂一级A总磷排放标准。以广州市某污水处理厂为例,设计了除磷加药智能控制系统的控制策略,拟合出化学除磷公式,以表征智能除磷系统的应用效果。结果表明,在一般城市生活污水的总磷浓度条件下,可以节约除磷药剂量40%~50%,2~3年便可回收控制系统的建设成本。污水处理厂采用该除磷加药智能控制系统后,可以实现在出水水质稳定达标的前提下降低加药量的目标。     

Evaluation of selected ubiquitous contaminants in the aquatic environment and their transformation products. A pilot study of their removal from a sewage treatment plant

A simple method using direct sample injection combined with liquid chromatography tandem mass spectrometry has been developed for the simultaneous analysis of six alkaloid compounds in environmental samples. The target list includes two psychostimulants (nicotine and caffeine), three metabolites (cotinine, nicotinic acid and paraxanthine) and a coffee chemical (trigonelline). The analytical method was evaluated in three different matrices (surface water, influent and effluent wastewater). The method developed showed an adequate sensitivity, below 0.6 μg L⁻¹ for wastewater and 0.1 μg L⁻¹ for river matrices, without any prior treatment of the samples. Finally, the methodology was applied to real samples for evaluation of their removal from a sewage treatment plant and their persistence/fate in the aquatic environment. All compounds studied in this work were detected at all sampling points collected along the Henares River. However, nicotinic acid was only detected three times in treated sewage samples at levels above its detection limit.     

焦化废水中芳香族有机物及杂环化合物在活性污泥法处理中的去除特性

利用完全混合式活性污泥去试验及ＧＣ／ＭＣ分析法，较系统地研究了焦化废水中有机物的去除特性，结果表明：焦化废水是含芳香族液化合物和杂环化合物的典型废水，４种不同运行状态下出水中芳香烃及杂环化合物种类减少，主要由杂环化合物，多环芳烃等难降解有机物及降解中间产物组成；焦化废水中苯酚类及苯类地易降解有机物，吡咯，萘等属于可降解有机物，吡啶，咔唑等属于难降解有机物。     

Indicator compounds for assessment of wastewater effluent contributions to flow and water quality

Numerous studies have reported the presence of trace (i.e., ng/L) organic chemicals in municipal wastewater effluents, but it is unclear which compounds will be useful to evaluate the contribution of effluent to overall river flow or the attenuation processes that occur in receiving streams. This paper presents a new approach that uses a suite of common trace organic chemicals as indicators to assess the degree of impact and attenuation of trace organic chemicals in receiving streams. The utility of the approach was validated by effluent monitoring at ten wastewater treatment plants and two effluent-impacted rivers with short retention times (<17 h). A total of 56 compounds were particularly well suited as potential indicators, occurring frequently in effluent samples at concentrations that were at least five times higher than their limit of quantification. Monitoring data from two effluent-impacted rivers indicated that biotransformation was not important for these two river stretches, whereas photolysis attenuation was possibly important for the shallow river. The application of this approach to receiving waters and water reclamation and reuse systems will allow for more effective allocation of resources in future monitoring programs.     

Pharmaceutical compounds in the wastewater process stream in Northwest Ohio

In order to add to the current state of knowledge regarding occurrence and fate of Pharmaceutical and Personal Care Products (PPCP's) in the environment, influent, effluent and biosolids from three wastewater treatment facilities in Northwest Ohio, USA, and a stream containing effluent discharge from a rural treatment facility were analyzed. The three WWTP facilities vary in size and in community served, but are all Class B facilities. One facility was sampled multiple times in order to assess temporal variability. Twenty compounds including several classes of antibiotics, acidic pharmaceuticals, and prescribed medications were analyzed using ultrasonication extraction, SPE cleanup and liquid chromatography-electrospray ionization tandem mass spectrometry. The highest number of compounds and the greatest concentrations were found in the influent from the largest and most industrial WWTP facility. Short-term temporal variability was minimal at this facility. Many compounds, such as clarithromycin, salicylic acid and gemfibrizol were found at concentrations more than one order of magnitude higher than found in the effluent samples. Effluent waters contained elevated levels of carbamazepine, clindamycin and sulfamethoxazole. Differences in composition and concentration of effluent waters between facilities existed. Biosolid samples from two different facilities were very similar in PPCP composition, although concentrations varied. Ciprofloxacin was found in biosolids at concentrations (up to 46 mug/kg dry mass) lower than values reported elsewhere. Diclofenac survived the WWTP process and was found to persist in stream water incorporating effluent discharge. The low variability within one plant, as compared to the variability found among different wastewater treatment plants locally and in the literature is likely due to differences in population, PPCP usage, plant operations and/or local environment. These data are presented here for comparison with this emerging set of environmental compounds of concern.     

城市污水再生回用的生态毒理问题

介绍和分析了国内外城市污水再生回用的方向、污水厂出水中可能含有的有害物质及其可能造成的生态危害，提出了减少城市污水再生回用生态风险的方法。     

Responses of Hexaplex (Murex) trunculus to selected pollutants

We report the results of a recent survey of the concentration of natural estrogens (17beta-estradiol, 17alpha-estradiol, estrone, estriol) and the synthetic estrogen, 17alpha-ethynylestradiol in representative animal wastes and sewage treatment plant (STP) effluents in the Waikato region of New Zealand. Dairy farm effluent samples showed high levels of estradiol (19-1360 ng/L) and its breakdown product estrone (41-3123 ng/L) compared with piggery or goat farm effluents. The combined load for these estrogens (excluding beta epimer) varied from 60 to >4000 ng/L. The piggery effluent provided the lowest total estrogen load (46 ng/L), with estrone accounting for nearly 60% of the measured estrogens in this sample. The synthetic analogue, 17alpha-ethynylestradiol was detected only in one wastewater treatment plant sample, albeit at trace level. An estrogen receptor competitive binding assay was used to test the biological activity of the samples and confirmed that most agricultural waste samples contain high levels of estrogenic compounds. The potential of these wastes to cause endocrine disruption in the receiving ecosystem is unknown at present.     

Direct and indirect photolysis of sulfamethoxazole and trimethoprim in wastewater treatment plant effluent

The photolysis of two antibacterial compounds, sulfamethoxazole and trimethoprim, was studied in wastewater effluent. The rate of loss of sulfamethoxazole was enhanced in wastewater effluent due to indirect photolysis reactions, specifically reactions with hydroxyl radicals and triplet excited state effluent organic matter. Photolysis in the presence of natural organic matter, however, did not lead to enhanced degradation of sulfamethoxazole. Trimethoprim was also found to be susceptible to indirect photolysis in wastewater effluents, with hydroxyl radical and triplet excited effluent organic matter being the responsible species. Deoxygenation of solutions led to more rapid direct photolysis of sulfamethoxazole and trimethoprim, indicating that direct photolysis proceeds through a triplet excited state, which was verified by demonstrating that trimethoprim is a singlet oxygen sensitizer. In the wastewater effluents tested, photolysis could be apportioned into direct photolysis (48% for sulfamethoxazole, 18% for trimethoprim), reaction with hydroxyl radicals (36% and 62%, respectively) and reaction with triplet excited effluent organic matter (16% and 20%, respectively). These results indicate that allowing photolysis in wastewater stabilization ponds or wastewater treatment wetlands may lead to enhanced pharmaceutical removal prior to discharge and that effluent organic matter has different photoreactivity than natural organic matter.     

采用水解酸化/氧化沟/高效纤维滤池工艺的污水厂设计

某县城经济开发区污水处理厂一期设计规模为1. 5×10⁴m³/d,针对污水厂来水中含有一定比例工业废水的特点,采用水解酸化/氧化沟/高效纤维滤池工艺进行处理。该污水厂于2018年11月投入运行,在进水水质波动较大的情况下,出水COD <50 mg/L,SS <10 mg/L,NH₃-N <3 mg/L,TN <15 mg/L,TP <0. 4 mg/L,能稳定达到《城镇污水处理厂污染物排放标准》(GB 18918—2002)中一级A标准。污水厂厂区工程费用为6 333. 8万元,平均运行成本为0. 78元/m³。介绍了该污水处理厂的设计特点、主要构筑物参数、投资及运行成本,可供类似项目参考。