Nitrogenous disinfection byproducts formation and nitrogen origin exploration during chloramination of nitrogenous organic compounds

Formation of nitrogenous disinfection by-products (N-DBPs) of cyanogen chloride (CNCl), dichloroacetonitrile (DCAN) and chloropicrin was evaluated during chloramination of several selected groups of nitrogenous organic (organic-N) compounds, including α-amino acids, amines, dipeptides, purines, and pyrimidines, The intermediates generated, reaction pathways, and nitrogen origin in N-DBPs were explored as well. CNCl was observed in chloramination of all tested organic-N compounds, with glycine giving the highest yields. DCAN was formed during chloramination of glutamic acid, cytosine, cysteine, and tryptophan. Chloramination of most organic-N compounds except for cysteine and glutamic acid generated chloropicrin. Aldehydes and nitriles were identified as the intermediates by negative mode electrospray ionization mass spectrometry during reactions of NH₂Cl and organic-N compounds. Labeled ¹⁵N-monochloramine (¹⁵NH₂Cl) techniques showed that nitrogen in N-DBPs may originate from both NH₂Cl and organic-N compounds and the nitrogen partition percentages vary as functions of reactants and pH.     

Ultrafiltration membrane fouling by extracellular organic matters (EOM) of Microcystis aeruginosa in stationary phase: influences of interfacial characteristics of foulants and fouling mechanisms

This paper focused on the membrane fouling caused by extracellular organic matters (EOM) which was extracted from lab-cultured Microcystis aeruginosa in stationary phase. The characteristics of EOM such as molecular weight distribution, hydrophobicity and fluorescence were measured. It was found that high molecular weight (MW) and hydrophilic organics accounted for the major parts of algal EOM which was comprised of protein-like, polysaccharide-like and humic-like substances. Ultrafiltration (UF) experiments were carried out in a stirring cell and hydrophobic polyethersulfone (PES) membranes which carried negative charge were used. Prefiltration, calcium addition and XAD fractionation were employed to change the interfacial characteristics of EOM. Then the effects of these interfacial characteristics on flux decline, reversibility and mass balance of organics were compared. Algal EOM proved to cause serious membrane fouling during UF. The fraction of algal EOM between 0.45 μm and 100 kDa contributed a significant portion of the fouling. Hydrophobic organics in EOM tended to adhere to membrane surface causing irreversible fouling, while the cake layer formed by hydrophilic organics caused greater resistance to water flow due to hydrophilic interaction such as hydrogen bond and led to faster flux decline during UF. The results also indicated that the algal EOM was negatively charged and the electrostatic repulsion could prevent organics from adhering to membrane surface. In term of fouling mechanisms, cake layer formation, hydrophobic adhesion and pore plugging were the main mechanisms for membrane fouling caused by algal EOM.     

A comparison of the role of two blue-green algae in THM and HAA formation

The contribution of two blue-green algae species, Anabaena flos-aquae and Microcystis aeruginosa, to the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was investigated. The experiments examined the formation potential of these disinfection by-products (DBPs) from both algae cells and extracellular organic matter (EOM) during four algal growth phases. Algal cells and EOM of Anabaena and Microcystis exhibited a high potential for DBP formation. Yields of total THMs (TTHM) and total HAAs (THAA) were closely related to the growth phase. Reactivity of EOM from Anabaena was slightly higher than corresponding cells, while the opposite result was found for Microcystis. Specific DBP yields (yield/unit C) of Anabaena were in the range of 2-11 μmol/mmol C for TTHM and 2-17 μmol/mmol C for THAA, while those of Microcystis were slightly higher. With regard to the distributions of individual THM and HAA compounds, differences were observed between the algae species and also between cells and EOM. The presence of bromide shifted the dominant compounds from HAAs to THMs.     

Characterization of dissolved extracellular organic matter (dEOM) and bound extracellular organic matter (bEOM) of Microcystis aeruginosa and their impacts on UF membrane fouling

Extracellular organic matter (EOM) of cyanobacteria was classified into the dissolved EOM (dEOM) which was released into culture solution and the bound EOM (bEOM) which surrounded the cells. The dEOM and bEOM extracted from Microcystis aeruginosa in stationary phase were used to study their characteristic differences and then their impacts on ultrafiltration (UF) membrane fouling. Component analyses showed that dEOM was comprised of proteins, polysaccharides and humic-like substances, while that bEOM contained only proteins and polysaccharides. Additionally, polysaccharides dominated in dEOM with a polysaccharide/DOC ratio of 1.11 mg mg⁻¹, while proteins were the primary components of bEOM with a protein/DOC ratio of 1.08 mg mg⁻¹. Results of size fractionation and XAD resin fractionation revealed that bEOM was mainly distributed in the high-MW and hydrophobic fractions, while that dEOM was more hydrophilic. Result of UF experiments indicated that dEOM which had a higher organic content and stronger hydrophilicity caused more severe flux decline and reversible fouling, and that bEOM led to slower flux decline but more irreversible fouling due to less electrostatic repulsive and more hydrophobic adhesion. The impacts of these two kinds of EOM on the UF fouling caused by cyanobacterial cells were also investigated. It was found that both flux decline and irreversible membrane fouling caused by the cells were aggravated when cells were together with EOM, especially for bEOM which might increase the surface hydrophobicity of the cells.     

Occurrence of dissolved and particle-bound taste and odor compounds in Swiss lake waters

The occurrence of algal taste and odor (T&O) compounds was investigated in three Swiss lakes which exhibit different nutrient levels from eutrophic to oligotrophic (Lake Greifensee, Lake Zurich and Lake Lucerne). Apart from dissolved T&O compounds, the study also encompassed particle-bound compounds, i.e., compounds that can be released from damaged algal cells during drinking water treatment. A combined instrumental (SPME-GC-MS) and sensory method was applied that allowed to detect and quantify T&O compounds in natural waters in the sub ppt to low ppt-range.In addition to the prominent T&O compounds geosmin and 2-methyl-isoborneol (MIB), four other T&O compounds could be detected in the lake waters, though all at relatively low concentrations (maximum concentrations of geosmin 19 ng L⁻¹, MIB 3 ng L⁻¹, β-ionone 27 ng L⁻¹, β-cyclocitral 7 ng L⁻¹, 2-isobutyl-3-methoxypyrazine 2 ng L⁻¹, 2-isopropyl-3-methoxypyrazine 16 ng L⁻¹). The concentration peaks typically occurred in the epilimnion during summer concurrent with a high phytoplankton biomass. Consistently, the concentration levels for most of the compounds varied substantially between the three lakes and generally decreased in the order eutrophic Lake Greifensee > mesotrophic Lake Zurich > oligotrophic Lake Lucerne. Furthermore, our data revealed that the occurrence of β-ionone was largely influenced by Planktothrix rubescens. This is the first time that a correlation between β-ionone and this cyanobacterium has been reported for natural waters.     

Delayed influence of dam storage and discharge on the determination of seasonal proliferations of Microcystis aeruginosa and Stephanodiscus hantzschii in a regulated river system of the lower Nakdong River (South Korea)

This study presents the relationship between the dam hydrology and phytoplankton proliferations in a regulated river system in East Asia. A long-term ecological study reveals that multi-purpose dam regulation on river flow in the Nakdong River (South Korea) affects proliferating patterns of phytoplankton, especially during summer (June-August) and winter (December-next February) as Microcystis aeruginosa and Stephanodiscus hantzschii, respectively, dominate each season by over 80%. Eutrophication was observed in the lower Nakdong River (South Korea) (mean+/-standard deviation: nitrate-N, 2.8+/-0.9 mg L(-1); phosphate-P, 40.3+/-31.3 microg L(-1); chlorophyll a, 45.2+/-84.9 microg L(-1); n=449), and the limnological characteristics responded to climatic variations such as monsoon and summer typhoons. The river basin experiences concentrated rainfall during the rainy season (June-September, over ca. 60% of total annual rainfall). Correlation and cross-correlation for time-delayed relationship revealed the hydrological environments (i.e., quantity of dam storage and discharge) had significantly negative relationship with the population dynamics of the two bloom-forming species for up to the next 2 years. S. hantzschii had clearer relationship with dam storage and discharge, which might be due to the seasonality exhibited by the species. The results support the necessity of "smart flow control" which may enable destruction of bloom formation by the two species with an adequate pulse of discharge generated by upstream dams in the far-east Asian river systems. This would increase the efficiency of water resource management system.     

Characterization of PEI-modified biomass and biosorption of Cu(II), Pb(II) and Ni(II)

The objective of this work is to develop a surface-modified biosorbent with enhanced sorption capacity for heavy metal ions. The biomass of Penicillium chrysogenum was modified with polyethylenimine (PEI) and then crosslinked with glutaraldehyde. The crosslinked PEI was chemically bonded on the biomass surface through the amine and carboxylate groups on the pristine biomass. The presence of the amine group was confirmed by X-ray photon spectroscopy (XPS) and Fourier transform infrared (FTIR) analysis, and the concentration of the amine groups on the biomass surface was found to be 2 mmol/g through potentiometric titration. The rugged morphology of the biomass surface after the modification was observed by scanning electron microscope (SEM). Compared with the pristine biomass, the modified biomass with amine groups showed a significant increase in sorption capacity for three metal ions, namely, copper, lead and nickel. The sorption isotherms of the biomass for three metals were well described by Langmuir equation, with a maximum sorption at 92 mg copper, 204 mg lead and 55 mg nickel per g biomass. The binding sites for the three metals attributed to the amine groups on the biomass surface were verified by FTIR analysis.