The variation of mass and disinfection by-product formation potential of dissolved organic matter fractions along a conventional surface water treatment plant

Dissolved organic matter (DOM) influences many aspects of water treatment, including the formation of potentially harmful disinfection by-products (DBPs) when disinfectants are applied. DOM from a conventional surface water treatment plant (WTP) in Northern New Jersey was isolated and fractionated using resin adsorption chromatography into six different fractions. These fractions are operationally categorized as hydrophobic acid, hydrophobic neutral, hydrophobic base, hydrophilic acid, hydrophilic neutral and hydrophilic base. The hydrophilic acid fraction was found to be the most abundant fraction in the source water. The hydrophilic neutral, hydrophilic acid and hydrophobic acid fractions had the highest removal efficiency through the WTP (about 65%). The variation and removal effectiveness of each fraction along the WTP was studied. Seven-day chlorine DBP formation potential (FP) tests were performed on all DOM fractions through the WTP. For the source water studied, the hydrophilic acid fraction was found to be the most reactive precursor to the trihalomethane (THM) formation. The hydrophobic neutral fraction was found to be the fraction of concern with respect to the FP of haloacetic acids (HAAs) class of DBPs. The FP of each fraction's class of DBPs was found to be amenable for reduction along the treatment train, specifically by coagulation/sedimentation. The fractionated approach concept showed to be very beneficial in the study of DBP precursors and their effective removal by physical and chemical treatment.     

Evaluation of disinfection by-products formation during chlorination and chloramination of dissolved natural organic matter fractions isolated from a filtered river water

Dissolved natural organic matter (DOM) in a filtered river water was isolated and fractionated into six different fractions. Trihalomethanes (THMs) and haloacetic acids (HAAs) formed from these isolated DOM fractions during chlorination and chloramination were determined. Results show that the hydrophobic acid, hydrophilic acid, hydrophilic base and hydrophobic neutral are major precursors of THMs and HAAs. There exist good correlations between the values of specific ultraviolet absorbance at 254nm of the individual DOM fractions and their disinfection by-products formation potential, indicating that aromatic moieties are responsible for disinfection by-products formation for both hydrophobic and hydrophilic DOM fractions. Chloramination of the DOM fractions yields much less THMs and HAAs than chlorination. For the dominant DOM fraction (i.e. hydrophobic acid) in the water, the yields of THMs and HAAs increase more significantly in chlorination than those in chloramination with the increase of disinfectant dosage, contact time and dissolved organic carbon content.     

Fast quantification of humic substances and organic matter by direct analysis of sediments using DRIFT spectroscopy

A simple method based on diffuse reflectance coupled with infrared Fourier transform spectroscopy (DRIFTS) has been developed for the quantification and the characterization of sedimentary (or soil, peat, etc.) humic substances. Under optimized conditions, the quantification of humic substances or total organic matter is possible with DRIFTS at a frequency of 2930 cm(-1) using whole dry sediment samples. A study of the operational parameters that affect the DRIFTS signal shows the importance of normalizing analysis conditions, especially the diffuse reflectance accessory alignment, the particle size and compaction, and the homogeneity of the powdered samples, to obtain reproducible quantitative analyses. The quantification of total humic substances by DRIFTS correlates well with the concentrations determined using classical extraction methods. DRIFTS analysis requires only a few minutes instead of tedious extractions of humic substances. Moreover, the distribution of total organic matter and of fulvic acids, humic acids, and humin can also be obtained. Analysis of natural samples indicates that a calibration using humic material representative of the studied area provides the most accurate quantification. The fast screening of organic matter fractions by DRIFTS on intact natural samples provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.     

Degradation of natural organic matter in surface water using vacuum-UV irradiation

The use of vacuum-UV (VUV) radiation to degrade natural organic matter (NOM) and the main variables affecting the efficiency of this process were investigated using an annular photoreactor. After 180 min of irradiation with VUV, the total organic carbon (TOC) decreased from 4.95 ppm to 0.3 ppm. Also, decadic absorption coefficients of the water at 185 nm and 254 nm decreased from 3.2 cm(-1) to 2.85 cm(-1), and 0.225 cm(-1) to 0 cm(-1), respectively. The reactor operation was kinetically controlled for Reynolds numbers greater than 600, changes of pH between 5 and 9 had little effect, and increases in alkalinity decreased the process efficacy. Additionally, H(2)O(2)/VUV and VUV processes were compared to H(2)O(2)/UV and UV processes, where the formers showed greater effectiveness with complete mineralization of NOM as opposed to partial oxidation with H(2)O(2)/UV, and no mineralization with UV alone. Modeling and analysis of the photon flux and absorption in the reactor showed that 99% of the 185 nm radiation was absorbed by the water in the reactor. In comparison, only 48% of the 254 nm radiation was absorbed by the water. The overall quantum efficiency of the mineralization for VUV was 0.10 for 50% TOC reduction.     

Modified dissolved organic matter fractionation technique for natural water

A technique to fractionate dissolved organic materials (DOMs) from low DOM water (<5mg/l) was developed by using triple columns of DAX-8 adsorption resin, one column of AG-MP-50 cationic resin, and another column of WA 10 weak anionic resin in sequence. The procedure was then applied to fractionate water samples obtained at various sampling locations throughout two surface water treatment plants (WTPs) in central New Jersey to study its effectiveness, DOM occurrence, and variation along treatment units. The treatment plants utilize different treatment methods, hence producing variability in DOM fractions suitable for examining the procedure's effectiveness. This procedure was compared with current fractionation protocols and proved to be accurate in fractionation of low DOM water.     

Effect of bromide ion on isolated fractions of dissolved organic matter in secondary effluent during chlorination

The role of bromide ion in the trihalomethane (THM) formation and structure of dissolved organic matter (DOM) during chlorination of the secondary effluent taken from the Wenchang Wastewater Treatment Plant (Harbin, China) was investigated. DOM was fractionated using XAD resins into five fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). The patterns of individual THM species with increased bromide concentrations were similar for all DOM fractions. The THM speciation as well as halogen fraction for these five fractions followed similar trends with the Br(-)/Cl(2) ratio. Chlorination resulted in decreased ultraviolet (UV) absorbance across wavelengths from 250 to 280 nm for DOM fractions whether bromide ions existed or not, and bromide addition led to lower differential UV absorbance values. Fourier-transform infrared (FT-IR) results indicated that chlorination, whether bromide ions existed or not, resulted in the near elimination of aromatic CH and amide peaks, increased CO absorption intensity and occurrence of CO and CCl peaks for HPO-A, HPO-N, TPI-A and TPI-N. Furthermore, bromide addition in chlorination led to the occurrence of CBr peak for all four fractions.     

Characterization of isolated fractions of dissolved organic matter from sewage treatment plant and the related disinfection by-products formation potential

Dissolved organic matter (DOM) in effluent from a conventional sewage treatment plant was isolated using resin adsorbents into six classes: hydrophobic bases (HoB), hydrophobic acids (HoA) and hydrophobic neutrals (HoN); hydrophilic bases (HiB), hydrophilic acids (HiA) and hydrophilic neutrals (HiN). Organic acids were the most abundant fractions of DOM. Hydrophobic organics especially hydrophobic acids were found to have higher overall disinfection by-products formation potential (DBPFP). Moreover, the potential decreased as the sequence of acids, neutrals and bases. Ultraviolet spectrophotometry at 254nm (UV(254)), fluorescence spectroscopy, size exclusion chromatography and Fourier transform infrared spectroscopy (FTIR) were employed to characterize DOM fractions. And the relationship between the characteristics of DOM fractions and the related DBPFP was discussed in detail. It was found that UV(254) to DOC ratio (SUVA) exhibited a positive correlation with haloacetic acids (HAAs) formation potential whereas distinctive linear correlation was not observed between SUVA and trihalomethanes (THMs) formation potential. Of the fluorescence organics contained in DOM, humic acids exhibited higher chlorine reactivity than fulvic acids. Smaller molecules of humic acids produced more DBPs. Furthermore, a combination of aromatic moieties and aliphatic structures with nu(C_O) groups contributed largely to the formation of DBPs.     

The evolution of organic matter in space

Carbon, and molecules made from it, have already been observed in the early Universe. During cosmic time, many galaxies undergo intense periods of star formation, during which heavy elements like carbon, oxygen, nitrogen, silicon and iron are produced. Also, many complex molecules, from carbon monoxide to polycyclic aromatic hydrocarbons, are detected in these systems, like they are for our own Galaxy. Interstellar molecular clouds and circumstellar envelopes are factories of complex molecular synthesis. A surprisingly high number of molecules that are used in contemporary biochemistry on the Earth are found in the interstellar medium, planetary atmospheres and surfaces, comets, asteroids and meteorites and interplanetary dust particles. Large quantities of extra-terrestrial material were delivered via comets and asteroids to young planetary surfaces during the heavy bombardment phase. Monitoring the formation and evolution of organic matter in space is crucial in order to determine the prebiotic reservoirs available to the early Earth. It is equally important to reveal abiotic routes to prebiotic molecules in the Earth environments. Materials from both carbon sources (extra-terrestrial and endogenous) may have contributed to biochemical pathways on the Earth leading to life's origin. The research avenues discussed also guide us to extend our knowledge to other habitable worlds.     

Reduction of organic matter and trihalomethane formation potential in reclaimed water from treated industrial estate wastewater by coagulation

Raw water from treated industrial estate wastewater in northern Thailand was used in jar-test coagulation experiments with variations of separate alum and ferric chloride dosages from 10 to 80 mg/L at pH conditions ranging from 5 to 6.5. Natural organic matter (NOM) surrogates and trihalomethane formation potential (THMFP) were determined to study their reduction. The obtained results showed that total organic carbon (TOC) were gradually reduced from the average value of about 6.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Moreover, dissolved organic carbon (DOC) were reduced from an average value of 5.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Specific ultraviolet absorption (SUVA) were decreased from an average value of approximately 4.7 L/mgm to a level of about 2 L/mgm by alum and ferric chloride dosages of approximately 20 mg/L. In addition, chlorine demands at 1 day reaction were the same as those of 7-day demands with a correlation coefficient of 0.98 (n = 10, correlation significant at the 0.01 level). Interestingly, chloroform of approximately 65 and 60% of total THMFP was found as the predominant THMFP species in treated industrial estate wastewater and reclaimed water, respectively, in comparison with other THM species. Maximum THMFP percentage removal of 25 and 28 by using alum and ferric chloride dosages of about 80 mg/L at pH 5.5 and 5 were obtained, respectively, at the examined conditions.     

Solubility enhancement of PCDD/F in the presence of dissolved humic matter

From previous studies, we, the authors collected and arranged the octanol-water partition coefficients (K(ow)), water solubility (S0), and dissolved humic matter (DHM)-water partition coefficients (K(oc)) for 95 organic compounds, and presented the correlations between each physical property. The K(oc) and K(ow) of dioxins estimated were significantly increased while S0 was decreased on increasing the chlorine number. In the presence of DHM, solubility enhancement (Sw/S0, Sw is the actual solubility in the presence of DHM) in highly chlorinated PCDD/F such as HpCDDs and OCDD is higher than that in low chlorinated ones. It means that dioxins abundant wastes (fly ash) should not be codisposed with organic abundant wastes (sewage sludge, food waste or bottom ash, etc.) to minimize the leachability of dioxins.     

Implantation of organic matter through water onto solid substrates by a laser induced molecular jet

Organic molecular dots were successfully produced by means of a nano second pulsed dye laser on glass and indium tin oxide (ITO) substrates, with sizes of several hundred nanometres. The method involves the transfer of organic molecules from the source Coumarin 6 (C6) and poly [2-methoxy, 5-(2′-ethyl-hexyloxy)-p-phenylene-venylene] (MEH-PPV) films onto a target material through a water filled space-gap using a laser induced molecular jet (LIMJ). In this way, the organic dots of Coumarin 6 and MEH-PPV molecules were successfully implanted onto the glass and ITO targets. The present results demonstrate the possibility to significantly improve photo electronic or photoelectric devices such as novel photonic crystal and molecular device sensors, and so on.     

Compositional and functional features of humic acid-like fractions from vermicomposting of sewage sludge and cow dung

The chemical changes occurring in five different substrates of sewage sludge spiked with different proportions of cow dung after vermicomposting with Eisenia foetida for 90 days were investigated. Their humic acid-like (HAL) fractions were isolated to determine the elemental and functional composition, and structural and functional characteristics using ultraviolet/visible, Fourier transform infrared (FT-IR) and fluorescence spectroscopies and scanning electron microscopy. After vermicomposting, the total organic C and C/N ratio decreased, and the total extractable C and humic acid (HA) C increased in all substrates. In the HAL fractions, the C and H contents, C/N and C/O and aliphatic structures, proteinaceous components and carbohydrates decreased, while the O and N and acidic functional group contents and C/H ratio, aromaticity and polycondensation structures increased. Further, the results suggest that the addition of cow dung to sewage sludge could improve the quality of organic matter humification of the substrates. The structures of HAL fractions in vermicomposts resembled those typical of soil HA, especially the vermicompost of cow dung alone. Scanning electron microscopy showed the microstructure of HAL fraction in final product became close-grained and lumpy. Overall results indicate that vermicomposting was an efficient technology for promoting organic matter (OM) humification in sewage sludge and cow dung alone, as well as in mixtures of both materials, improving their quality and environmental safety as a soil OM resource for utilization as soil amendments.     

Thermal desorption/pyrolysis coupled with photoionization time-of-flight mass spectrometry for the analysis of molecular organic compounds and oligomeric and polymeric fractions in urban particulate matter

Atmospheric aerosols are subject to be responsible for human health effects. In this context, besides mass and number concentration of particles, their chemical composition has gained interest recently. However, knowledge about the organic content of particulate matter is still relatively scarce; i.e., only 10-40% of compounds present in the aerosol are as yet identified. By means of a newly developed measurement technique, thermal desorption/photoionization time-of-flight mass spectrometry (TOFMS), organic species evolved from urban aerosol samples collected at Augsburg, Germany, are analyzed. Thereby, compounds desorbed according to a temperature protocol following procedures for OC/EC analysis (120, 250, and 340 degrees C as desorbing temperatures) are ionized by soft, fragmentationless resonance multiphoton ionization (REMPI) and single photon ionization (SPI), respectively. With REMPI-TOFMS, a large variety of PAH is detectable. A comprehensive analysis is enabled by adding SPI-TOFMS, which gives access to aliphatic and carbonylic hydrocarbons as well as alkanoic acids and esters. Analysis of the data showed a high abundance of phenol and guiacol as well as retene, which are known markers for wood combustion. Similar patterns were found with ash from spruce wood combustion. An increase of volatile substances at 340 degrees C gave rise to the suggestion that these compounds are re-formed by pyrolytic decomposition reactions from oligomeric, polymeric, and polyfunctional oxygenated species. This was corroborated by the investigation of the behavior of cellulose acetate, which exhibited a similar pattern in its SPI-TOFMS spectrum at 340 degrees C as the aerosol. More thorough investigations of urban aerosol and source material with respect to problems such as the mass closure of carbonaceous material, indications for source apportionment, and allotment of organic species on a molecular level to fractions of organic and elemental carbon seem feasible with this measurement method.     

Passive sampler for dissolved organic matter in freshwater environments

A passive sampler for the isolation of dissolved organic matter (DOM) from freshwater environments is described. The sampler consists of a molecular weight selective membrane (1000 kDa) and an anion exchange resin (diethylaminoethylcellulose (DEAE-cellulose)). NMR indicates the samplers isolate DOM that is nearly indistinguishable from that isolated using the batch DEAE-cellulose procedure. In a comparative study DOM isolated from Lake Ontario cost approximately 0.30 dollars/mg to isolate using the passive samplers while DOM isolated using the traditional batch procedure cost approximately 8-10 dollars/mg. The samplers have been shown to be effective in a range of freshwater environments including a large inland lake (Lake Ontario), fast flowing tributary, and wetland. Large amounts (gram quantities of DOM) can be easily isolated by increasing the size or number of samplers deployed. Samplers are easy to construct, negate the need for pressure filtering, and also permit a range of temporal and spatial experiments that would be very difficult or impossible to perform using conventional approaches. For example, DOM can be monitored on a regular basis at numerous different locations, or samplers could be set at different depths in large lakes. Furthermore, they could potentially be deployed into hard to reach environments such as wells, groundwater aquifers, etc., and as they are easy to use, they can be mailed to colleagues or included with expeditions going to difficult to reach places such as the Arctic and Antarctic.     

Effects of organic complexing ligands and soil organic matter on the metal adsorption/migration in soil

Abstract

The adsorption of heavy metals on soil from the Neihu Landfill Site in Taipei City was investigated in order to assess the ground water pollution problems. The effects of soil organic matter and the behaviors of organic complexing ligands like EDTA and humic acid to the overall adsorption process were studied and discussed. In explaining the results, the pH of soil system and the properties of the soil/aqueous interface were chosen as two significant and interacting factors for discussion. The concept of the specific adsorption mechanism was also demonstrated and discussed. The results showed that the complexing ligands existing in soil liquid phase have more influences than natural organic matter does. The competitive sequences of different organic matter contents indicated that organic functional sites preferentially bind with Cu and Cd. The presence of EDTA and humic acid which formed ligandlike complexes will reduce Cd adsorption efficiency. These effects will induce mobility and the fate of heavy metals in soils, such as bioavailability.     

Molecular size distribution of dissolved organic matter in water of the Pearl River and trihalomethane formation characteristics with chlorine and chlorine dioxide treatments

River water sample was collected from Guangzhou section of the Pearl River to investigate soluble organic fractions and formation of trihalomethane (THMs) after chlorine and chlorine dioxide treatments. The water sample was passed through Amicon YC-05, YM-1, YM-3, YM-10, YM-30, YM-100 and ZM-500 series membranes after a pre-treatment. The molecular weight distribution and the specific ultra-violet absorbance (SUVA(254)) of each fraction obtained from membrane were analyzed, and these fractions were further disinfected with chlorine and chlorine dioxide. The results showed that reverse osmosis (RO) fraction contained mainly dissolved organic matter (DOM) from the water sample, suggesting that the water has been highly contaminated by anthropogenic activities. Meanwhile, the THMs concentration and SUVA(254) increased gradually as the molecular weight of the obtained fractions reduced, indicating that the low molecular weight DOM was the major THMs precursor in the disinfection process with chlorine and chlorine dioxide. The results suggest that THMs in source water of Pearl River could be effectively reduced when pollution of human activity is greatly controlled. Between the two disinfection processes tested, chlorine dioxide produced less THMs than chlorine in this study.     

Quantitation in the solid-state 13C NMR analysis of soil and organic soil fractions

13C CP-MAS and DP-MAS spin-counting experiments have been carried out on an absolute basis for a specific whole soil and its humin, humic acid, and fulvic acid fractions, as well as a sample of the soil that was treated with 2% HF(aq). The results confirm previous conclusions that a substantial fraction of the carbon content indicated by classic elemental analysis is missed in some samples, especially whole soil and humin, by both CP-MAS and DP-MAS 13C NMR methods, and that the problem is more serious for CP-MAS than for DP-MAS. This study also confirms the fact that treatment of soil organic matter with 2% HF(aq) dramatically reduces this problem but may generate some structural uncertainties associated with significant structural alterations that accompany the HF(aq) treatment, as indicated by the 13C NMR data. The relationship between the "missing carbon" problem and the concentration of paramagnetic centers, especially Fe(III) centers, is explored in substantial detail.     

ACF阳极氧化法去除水中腐殖酸的研究

以活性炭纤维毡为阳极,不锈钢片为阴极,采用电化学氧化法处理了含腐殖酸的水溶液.结果显示,该方法可有效去除水中的腐殖酸,对于初始浓度为50mg/L的腐殖酸溶液,在适宜条件下电解120min后,腐殖酸和COD去除率可分别高达93.81%和92.60%.实验考察了溶液pH值、电流密度、支持电解质浓度、腐殖酸的初始浓度和阳极材...     

Utilization of ICP/OES for the determination of trace metal binding to different humic fractions

In this study, the use of inductively coupled plasma/optical emission spectrometry (ICP/OES) to determine multi-metal binding to three biomasses, Sphagnum peat moss, humin and humic acids is reported. All the investigations were performed under part per billion (ppb) concentrations. Batch pH profile experiments were performed using multi-metal solutions of Cd(II), Cu(II), Pb(II), Ni(II), Cr(III) and Cr(VI). The results showed that at pH 2 and 3, the metal affinity of the three biomasses exposed to the multi-metal solution that included Cr(III) presented the following order: Cu(II), Pb(II)>Ni(II)>Cr(III)>Cd(II). On the other hand, when Cr(VI) was in the heavy metal mixture, Sphagnum peat moss and humin showed the following affinity: Cu(II), Pb(II)>Ni(II)>Cr(VI)>Cd(II); however, the affinity of the humic acids was: Cu(II)>Pb(II), Cr(VI)>Ni(II)>Cd(II). The results demonstrated that pH values of 4 and 5 were the most favorable for the heavy metal binding process. At pH 5, all the metals, except for Cr(VI), were bound between 90 and 100% to the three biomasses. However, the binding capacity of humic acids decreased at pH 6 in the presence of Cr(VI). The results showed that the ICP/OES permits the determination of heavy metal binding to organic matter at ppb concentration. These results will be very useful in understanding the role of humic substances in the fate and transport of heavy metals, and thus could provide information to develop new methodologies for the removal of low concentrations of toxic heavy metals from contaminated waters.