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Lack of safe water availability and access to clean water cause a higher risk of infectious diseases and other diseases as well. Heavy metals (HMs) are inorganic pollutants that cause severe threats to humans, animals, and the environment. Therefore, an effective HM removal technology is urgently needed. In the present study, a customized bipolar membrane electrodialysis process was used to remove HMs from aqueous solutions. The impacts of the feed ionic strength, applied electrical potential, and the type and concentration of HMs (Cd2+, Co2+, Cr3+, Cu2+, and Ni2+) on the process performance were investigated. The results showed that feed solution pH changes occurred in four stages: it first decreased linearly before stabilizing in the acidic pH range, followed by an increase and stabilization in the basic range of the pH scale. HM speciation in the basic pH range revealed the presence of anionic HM species. The presence of HMs on anion exchange membranes confirmed the contribution of these membranes for HM removal in the base channels of the process. While no clear trend was seen in the ionic strength solution, the maximum HM removal was observed when 1.5 g/L NaCl was used. The initial HM concentration showed a linear increase in HMs removal of up to 30 mg/L. A similar trend was seen with an increase in the applied electrical potential of up to 15 V. In general, the amount of HMs removed increased in the following order: Cd2+ ˃ Ni2+ ˃ Co2+ ˃ Cu2+ ˃ Cr3+. Under some operational conditions, however, the removed amount of Cu2+, Co2+, and Ni2+ was similar. The mass balance and SEM-EDX results revealed that the removed HMs were sorbed onto the membranes. In conclusion, this process efficiently separates HMs from aqueous solutions. It showed the features of diluate pH adjustment, reduction in the overall stack electrical resistance, and contribution of anion exchange membranes in multivalent cation removal. The mechanisms involved in HMs removal were diffusion and migration from the bulk solution, followed by their sorption on both cation and anion exchange membranes.

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The impact of ciprofloxacin (CIP) in the partial nitrification and anammox biofilm system was investigated by multivariate analysis, focusing on size-fractionated organic components. The CIP dose of 10 µg/L did not inhibit the total nitrogen (TN) removal efficiency, even though the abundance of antibiotic resistant genes (ARGs) (i.e., qnrD, qnrB, qnrA, qnrS, and arcA) was elevated. However, a gradual higher CIP dosing up to 100 µg/L inhibited the TN removal efficiency, while the abundance of ARGs was still increased. Moreover, both the TN removal efficiency and the abundant ARGs were dwindled at 470 µg/L of CIP. As the CIP dose increased from 0 to 100 µg/L, the abundance of high molecular weight (MW) fractions (14,000 to 87,000 Da; 1000 to 14,000 Da) and humic/fulvic acid-like components in the soluble extracellular polymeric substances (HSS) decreased, with more increases of low MW (84-1000 Da; less than 84 Da) fractions and soluble microbial by-products in soluble extracellular polymeric substances (SMPS). Continuously increasing the CIP dose till 470 µg/L, an inverse trend of the changes of these organic components was noted, along with clear reductions of the microbial diversity and richness, and the abundance of key functional genes responsible for nitrogen removal. The predominance of functional gene amoA (related with ammonia oxidizing bacteria) was more significantly with more distribution of SMPS with relatively low MW and less distribution of HSS with relatively high MW, as well as polymer decomposing microorganisms such as Bryobacteraceae and the unclassified Saprospirales.

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The role of humic substances (HS) during sludge treatment has been the focus in recent years. Quantification of HS in sludge dissolved organic matter (DOM) and the chemical and structural characterization of HS data are the prerequisite for understanding their role during different sludge treatment processes. Currently, a number of published articles inadequately acknowledge fundamental principles of analysis methods both in terms of experimental approach and data analysis. Therefore, a more comprehensive and detailed description of the experimental methods and the data analysis are needed. In this study, the current used methods for HS quantification in DOM of sludge had been tested for different calibration and sludge DOM samples. The results indicated that the current methods showed overestimated and contradictory results for HS quantification in sludge DOM. To be specific, using the modified Lowry method, different values were obtained depending on the humic acids used for calibration, and false negative results were observed for some sludge samples. By using the relative amount of HS (based on dissolved organic carbon (DOC)) to total sludge DOM (based on DOC), variations among the results of different analysis methods for the same sample were high. According to the calculated Bray-Curtis dissimilarity indexes, the results for HS quantification obtained by three-dimensional excitation emission matrix (3D-EEM), either with spectra analysis methods by peak picking, fluorescence region integration (both region volume and area integration), or PARAllel FACtor analysis showed higher degrees of dissimilarity to those quantified by size exclusion liquid chromatography or XAD-8 method. The selection of fluorescence regions for HS seemed to be the determining factor for overestimation obtained by the 3D-EEM technique. In future work, strategies, like a consistent terminology of HS, the use of an internal standard sample, and the related standardized operation for HS quantification in sludge DOM need to be established.

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Hydrolysis of particulate organic matter is known to be a limiting step in biological wastewater treatment. In this work, we used an experimental set-up, which allowed the parallel observation of hydrolysis product formation on the one side and utilization on the other side. The hydrolysis products are characterized by using size exclusion chromatography with online carbon and UV (254 nm) detection. The used particles (size: 25-250 µm) originated from municipal wastewater. Here, it is shown that the concentration of high molecular weight organic matter increases over the first three days. During this time, bacteria grow and produce the required enzymes to perform the further degradation. The oxygen utilization rate (OUR) on the other side continuously develops, confirming the presence of easily biodegradable organic matter. In parallel, the amount of bacteria and extracellular polymeric substances (EPS) undergoes a certain dynamics, which was visualized by using confocal laser scanning images.

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Dissolved organic matter (DOM) of sludge is a heterogeneous mixture of high to low molecular weight organic substances which is including proteinaceous compounds, carbohydrates, humic substances, lipids, lignins, organic acids, organic micropollutants and other biological derived substances generated during wastewater treatment. This paper reviews definition, composition, quantification, and transformation of DOM during different sludge treatments, and the complex interplay of DOM with microbial communities. In anaerobic digestion, anaerobic digestion-refractory organic matter, particularly compounds showing polycyclic steroid-like, alkane and aromatic structures can be generated after pretreatment. During dewatering, the DOM fraction of low molecular weight proteins (< 20,000 Dalton) is the key parameter deteriorating sludge dewaterability. During composting, decomposition and polymerization of DOM occur, followed by the formation of humic substances. During landfill treatment, the composition of DOM, particularly humic substances, are related with leachate quality. Finally, suggestions are proposed for a better understanding of the transformation and degradation of DOM during sludge treatment. Future work in sludge studies needs the establishment and implementation of definitions for sample handling and the standardization of DOM methods for analysis, including sample preparation and fractionation, and data integration. A more detailed knowledge of DOM in sludge facilitates the operation and optimization of sludge treatment technologies.

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The Maji ya Chai River in Northern Tanzania, a fluoride-rich tropical area, shows a seasonal variation of natural organic matter (NOM) and fluoride concentration. Water samples collected monthly during one year from two locations of the River were characterized. High levels of precipitation in the rainy seasons increased the total organic carbon (TOC) concentration to as high as 36 mgC L-1 and diluted the fluoride concentration from a dry season high of 24 mg L-1 to <4 mg L-1. A black water swamp in the Maji ya Chai River catchment was confirmed as the main source of NOM, fluoride, salinity, and inorganic carbon entering the River in the rainy season. The water samples were filtered by a number of nanofiltration/reverse osmosis (NF/RO) membranes to identify the retention mechanisms and the impact of varying water quality on treatability. While the denser membranes removed fluoride due to size exclusion, for the membranes with bigger pore radius charge repulsion was the dominant mechanism of fluoride retention. Regardless of the seasonal conditions a TOC concentration <2 mgC L-1 was achieved by all membranes at 50% recovery, as NF/RO membranes remove TOC mainly by size exclusion. Two swamp water samples, containing high TOC (79 and 183 mgC L-1), were filtered to determine the characteristics of NOM which permeate the NF/RO membranes. Liquid chromatography organic carbon detection (LC-OCD) was used to characterize the fractions in the permeates, consisting of about 1% of the original NOM. The average molecular weight of the permeate humic substances (HS) was more than four times larger than the membrane molecular weight cut-off. This suggests that large HS can permeate the NF/RO membranes through diffusion. Moreover, the relatively high aromaticity of the permeate HS (1.7-5.2 L mg-1 m-1) indicated the high content of hydrophobic-aromatic fractions.

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This work aims to correlate signals of LED UV/fluorescence sensor with the degradation of dissolved organic matter (DOM) and trace-level organic contaminants (TOrCs) during ozonation process. Six sets of bench-scale ozonation kinetic experiments incorporated with three different water matrices and 14 TOrCs of different reactivity (group I âˆ¼ V) were conducted. Calibrated by tryptophan and humic substances standards and verified by the lab benchtop spectroscopy, the newly developed portable/online LED sensor, which measures the UV280 absorbance, protein-like and humic-like fluorescence simultaneously, was feasible to monitor chromophores and fluorophores with good sensitivity and accuracy. The liquid chromatography with organic carbon detector combined with 2D synchronous correlation analysis further demonstrated how the DOM components of large molecular weight were transformed into small moieties as a function of the decrease of humic-like fluorescence. For TOrCs, their removal rates were well correlated with the decrease of the LED UV/fluorescence signals, and their elimination patterns were mainly determined by their reactivity with O3 and hydroxyl radicals. At approximately 50% reduction of humic-like fluorescence almost complete oxidation of TOrCs of group I and II was reached, a similar removal percentage (25-75%) of TOrCs of group III and IV, and a poor removal percentage (<25%) of group V. This study might contribute to the smart control of advanced oxidation processes for the water and wastewater treatment in the future.

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Trihalomethanes (THM) are the most typical disinfection by-products (DBPs) found in public swimming pool water. DBPs are produced when organic and inorganic matter in water reacts with chemical disinfectants. The irregular contribution of substances from pool visitors and long contact time with disinfectant make the forecast of THM in pool water a challenge. In this work occurrence of THM in a public indoor swimming pool was investigated and correlated with the dissolved organic carbon (DOC). Daily sampling of pool water for 26 days showed a positive correlation between DOC and THM with a time delay of about two days, while THM and DOC didn't directly correlate with the number of visitors. Based on the results and mass-balance in the pool water, a simple simulation model for estimating THM concentration in indoor swimming pool water was proposed. Formation of THM from DOC, volatilization into air and elimination by pool water treatment were included in the simulation. Formation ratio of THM gained from laboratory analysis using native pool water and information from field study in an indoor swimming pool reduced the uncertainty of the simulation. The simulation was validated by measurements in the swimming pool for 50 days. The simulated results were in good compliance with measured results. This work provides a useful and simple method for predicting THM concentration and its accumulation trend for long term in indoor swimming pool water.

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Mass transfer and biological transformation phenomena in the capillary fringe were studied using phenol, salicylic acid, benzenesulfonic acid, and the iodinated X-ray contrast agent iomeprol as model organic compounds and the microorganism strain Pseudomonas fluorescens. Three experimental approaches were used: Batch experiments (uniform water saturation and transport by diffusion), in static columns (with a gradient of water saturation and advective transport in the capillaries) and in a flow-through cell (with a gradient of water saturation and transport by horizontal and vertical flow: 2-dimension flow-through microcosm). The reactors employed for the experiments were filled with quartz sand of defined particle size distribution (dp=200...600 µm, porosity ε=0.42). Batch experiments showed that phenol and salicylic acid have a high, whereas benzenesulfonic acid and iomeprol have a quite low potential for biodegradation under aerobic conditions and in a matrix nearly close to water saturation. Batch experiments under anoxic conditions with nitrate as electron acceptor revealed that the biodegradation of the model compounds was lower than under aerobic conditions. Nevertheless, the experiments showed that the moisture content was also responsible for an optimized transport in the liquid phase of a porous medium. Biodegradation in the capillary fringe was found to be influenced by both the moisture content and availability of the dissolved substrate, as seen in static column experiments. The gas-liquid mass transfer of oxygen also played an important role for the biological activity. In static column experiments under aerobic conditions, the highest biodegradation was found in the capillary fringe (e.g. ßt/ß0 (phenol)=0 after t=6 d) relative to the zone below the water table and unsaturated zone. The highest biodegradation occurred in the flow-through cell experiment where the height of the capillary fringe was largest.

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A full-scale (110 ML/d) potable water treatment plant (WTP) based on the MIEX process, an innovative new process based on a strong base anion-exchange resin with magnetic properties, has been operating in Perth Western Australia since 2001. This plant has been configured so that a combined MIEX-coagulation (MIEX-C) process can be operated in parallel with a conventional enhanced coagulation (EC) process, allowing comparison of the performance of the two processes. Here, we report the use of size exclusion chromatography (SEC) to compare the removal of different apparent molecular weight (AMW) fractions of DOC by the two processes. Water was sampled from five key locations within the WTP, and SEC was carried out using three different on-line detector systems, DOC-specific detection, UV absorbance detection at lambda = 254 nm, and fluorescence detection (lambda(ex) = 282 nm; lambda(em) = 353 nm). This approach provided information on the chemical nature of the DOC comprising the various AMW fractions. The study showed that the MIEX-C process outperformed the EC process with greater removal of DOC in each of the eight separate AMW fractions identified. While EC preferentially removed the fractions of highest AMW, and those exhibiting the greatest aromatic (humic) character, MIEX-C removed DOC across all AMW fractions and did not appear to discriminate as strongly on the basis of differences in aromatic character or AMW. The results demonstrate the benefits of combining these complementary treatment processes. The study also demonstrates the utility of SEC coupled with multiple detection systems in determining the characteristics of various AMW components of DOC.

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Recorded molecular weights (MWs) for humic substances (HS) range from a few hundred to millions of daltons. For purposes of defining HS as a specific class of chemical compounds, it is of particular importance to ascertain if this broad range of MWs can be attributed to actual variability in molecular properties or is simply an artifact of the analytical techniques used to characterize HS. The main objectives of this study were (1)to establish if a preferential range of MWs exists for HS and (2) to determine any consistent MW properties of HS. To reach the goal, we have undertaken an approach to measure under standardized conditions the MW characteristics of a large set of HS from different natural environments. Seventy-seven humic materials were isolated from freshwater, soil, peat, and coal, such that each possessed a different fractional composition: humic acid (HA), fulvic acid (FA), and a nonfractionated mixture of HA and FA (HF). Size exclusion chromatography (SEC) was used as the analytical technique to determine molecular weight characteristics. The MW distributions were characterized by number (Mn) and weight (Mw) average MW, and by polydispersity. The complete range of Mw values varied within 4.7-30.4 kDa. The maximum Mw values were observed for peat HF and soil HA, whereas the smallest weights were measured for river water HF. Maximum values of polydispersity (3.5-4.4) were seen for peat HF and soil HA, while much lower values (1.6-3.1) were found for all preparations isolated with XAD-resins. Statistical evaluation showed consistent Mw and Mn variations with the HS source, while polydispersity was mostly a function of the isolation procedure used. A conclusion was made that HS have a preferential range of MW values that could characterize them as a specific class of chemical compounds.

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