Low Molecular Weight Organic Matter Research Articles

Composition, Evolution, and Complexation of Dissolved Organic Matter with Heavy Metals in Landfills

Samples of wastes and leachates were collected from a landfill site and a leachate treatment plant[i.e., equalization basin, anaerobic zone, oxidation ditch, and membrane bioreactor (MBR) section]. Dissolved organic matter (DOM) was extracted from the wastes and leachates, and its composition, evolution, and complexation characteristics with heavy metals were studied using UV-Visible and fluorescence spectroscopy combined with1H nuclear magnetic resonance. The aliphatic compounds were found to be the main substances in DOM in the fresh landfill wastes (<5 a), and the relative content of aromatics and substituent groups, i.e., carbonyl, hydroxyl, and carboxyl functional groups, decreased during the initial process. On the other hand, carbohydrates and organic amines were observed to be the main substances in DOM obtained from the intermediate and old landfill wastes (>5 a), and the relative content of aromatics and substituent groups (carbonyl, hydroxyl, and carboxyl functional groups) increased persistently during the process of organic matter humification. The aliphatics, carbohydrates, and organic amines all existed in DOM from the equalization basin Carbohydrates and aromatic compounds increased rapidly after the anaerobic, aerobiotic, and membrane treatment. However, low molecular weight organic matter and alkyl chain substances decreased during the leachate treatment process and the side chain of the aliphatics was shortened despite the increase in its content. The distribution of zinc in the wastes and leachates was influenced by the complexation with the nitrogen-and oxygen-containing functional groups, whose effect on other metals was not obvious.

Study on the interactions of Ag nanoparticles with low molecular weight organic matter using first principles calculations

Experimental studies on environmental processes such as aggregation, disaggregation, dissolution, surface transformation, and adsorption of engineered nanoparticles (ENPs) in the aquatic systems are reported to be influenced by their interactions with natural organic matter (NOMs) and ENPs inherent physicochemical properties. Herein, density functional theory (DFT), classical lattice dynamics (CLD), and quantum mechanical calculations based on frontier molecular orbital (FMO) theory were applied to elucidate the interactions of ENPs and NOMs. Results were derived for the adsorption energies of formic acid (CH2O2), acetic acid (C2H4O2), and ascorbic acid (C6H8O6) on silver (Ag) ENPs (111) surface – and its shapes, namely: spherical, cylindrical, and different tetrahedron positions (faces, vertices and edges) using the DFT and CLD. Results showed that the adsorption energies increased as the molecular weight of the adsorbate increased; thus C6H8O6 had the highest adsorption energies for surface, spherical- and cylindrical-shaped Ag ENPs. At different positions of tetrahedron Ag ENP (111) surface, results indicated faces exhibited higher adsorption energies compared to the edges; hence, likely to be the most preferred adsorption sites. Overall, results derived from both in silico techniques suggest that Ag ENPs are likely to be easily adsorbed by NOMs with larger molecular mass. In addition, calculations using FMO theory showed a direct relationship with each of the four parameters viz.: the dipole moment (μ), molecular surface area (MSA), absolute electronegativity (χ), and absolute hardness (η) to the molar mass of the adsorbate. Hence, from our theoretical results: μ, MSA, χ, and η properties, and the adsorption energies are likely quantum mechanical descriptors of ENMs adsorption to NOMs in the aquatic systems.

Application of flow cytometry to monitor assimilable organic carbon (AOC) and microbial community changes in water

Flow cytometry is an efficient monitoring tool for rapid cell counting, and can be applied to research on water quality and treatment. In this study, a method that employs flow cytometry and a natural microbial inoculum to determine assimilable organic carbon (AOC) was adapted for use with challenging surface waters that have a high organic and particle content, and subsequently applied in a long term river water study. AOC method optimization showed that river water bacteria could pass through a 0.2μm membrane filter, and therefore membrane filtration combined with heat treatment was required for sample sterilization. Preparation of the natural river inoculum with an acceptable yield value could only be achieved when grown using the natural water source, since growth was limited on different types of inorganic minimal media and in natural spring water. The resulting flow cytometry AOC method was reliable and reproducible, and results were comparable to the standard plate count AOC method. Size exclusion chromatography showed that both high and low molecular weight organic matter fractions were utilized by the natural AOC inoculum. Flow cytometry was used to measure both AOC levels and total cell counts in a long term study to monitor the water quality of a river which was used as a drinking water source. The method could distinguish between high nucleic acid (HNA) and low nucleic acid (LNA) groups of bacteria, and HNA bacteria were found to respond faster than LNA bacteria to seasonal changes in nutrients and water temperature.

Integrated oxidation membrane filtration process – NOM rejection and membrane fouling

The extent and mechanisms by which organic matter in a solution can be retained and foul a membrane largely depends on the molecular weight of the material being filtered and the molecular weight cut-off (MWCO) of the membrane. The present study investigated the effect of the MWCO of a membrane and the molecular weight distribution of natural organic matter (NOM) in a source water on the increase in resistance to the permeate flux over time. Of particular interest was the effect of oxidation, applied prior to membrane filtration, on the predominant fouling mechanism. Oxidation can change the molecular weight distribution of organic matter in raw water, and therefore the ability of a membrane to retain this organic matter.Oxidation, using both ozonation and UV/H2O2, could effectively reduce the extent of fouling for higher MWCO membranes. However, neither oxidation approaches could effectively reduce the extent of fouling for lower MWCO membranes, likely because oxidation could not effectively oxidize lower molecular weight organic matter. Althoug the data indicated that the extent of fouling is increasing with the amount of DOC retained by the membrane, no statistically significant correlation was observed between these parameters. The results suggest that oxidation did not affect the predominant fouling mechanism. However, it did affect the molecular weight distribution of the organic matter retained by the membranes, and as a result, the resistance offered by the foulant cake layer.

Effect of Worm Predation on Changes in Waste Activated Sludge Properties.

This study explored the effects of worm predation on changes in waste activated sludge properties. Results showed that the rate by which worm predation reduced mixed liquor volatile suspended solids (MLVSS) was approximately 23.7% ± 3.1%. Particle size distribution and extracellular polymeric substance (EPS) analyses indicated that the reduction of fine particles and EPS content in sludge predated by worms mainly increased dewaterability and reduced the ratio of MLVSS/mixed liquor suspended solids. Moreover, both mean particle size and protein/carbohydrate ratio increased. The results of three-dimensional excitation-emission matrix and gel filtration chromatogram analyses demonstrated the varied properties of soluble microbial products and EPS were attributed to the worms' selective predation of low molecular-weight organic matter, which facilitated the hydrolysis of macromolecular organic matter.

Novel Ion-Exchange Coagulants Remove More Low Molecular Weight Organics than Traditional Coagulants.

Low molecular weight (MW) charged organic matter is poorly removed by conventional coagulants but contributes to disinfection byproduct formation during chlorination of drinking waters. We hypothesized that CIEX, a new Al-based hybrid coagulant with ion-exchange functional groups, would be new mechanistic approach to remove low MW organic matter during coagulation and would perform better than polyaluminum chloride (PACl) or metal-salt based coagulants. We measured coagulation performance using dissolved organic carbon (DOC) in a high hardness surface water. CIEX achieved excellent turbidity removal and removed 20% to 46% more DOC than FeCl3, Al2(SO4)3, or PACl, depending on dose. The improved DOC removal was attributable to better removal of low MW organic matter (<2 kDa). We further studied removal mechanisms in a model water containing a low MW organic acid (salicylic acid (SA)). CIEX achieved high removal of organic acids (>90% of SA) independent of pH, whereas removal by metal salts was lower (<15%) and was strongly pH dependent. CIEX ion-exchange capability is facilitated by its covalently bound quaternary ammonium group, which conventional coagulants lack. Plus, unlike other cationic polymers that react with chloramines to form N-nitrosodimethylamine (NDMA), CIEX has a low molar yield (9.3 × 10(-7) mol NDMA per mol CIEX-N).

Metaproteomics of aquatic microbial communities in a deep and stratified estuary.

Here we harnessed the power of metaproteomics to assess the metabolic diversity and function of stratified aquatic microbial communities in the deep and expansive Lower St. Lawrence Estuary, located in eastern Canada. Vertical profiling of the microbial communities through the stratified water column revealed differences in metabolic lifestyles and in carbon and nitrogen processing pathways. In productive surface waters, we identified heterotrophic populations involved in the processing of high and low molecular weight organic matter from both terrestrial (e.g. cellulose and xylose) and marine (e.g. organic compatible osmolytes) sources. In the less productive deep waters, chemosynthetic production coupled to nitrification by MG-I Thaumarchaeota and Nitrospina appeared to be a dominant metabolic strategy. Similar to other studies of the coastal ocean, we identified methanol oxidation proteins originating from the common OM43 marine clade. However, we also identified a novel lineage of methanol-oxidizers specifically in the particle-rich bottom (i.e. nepheloid) layer. Membrane transport proteins assigned to the uncultivated MG-II Euryarchaeota were also specifically detected in the nepheloid layer. In total, these results revealed strong vertical structure of microbial taxa and metabolic activities, as well as the presence of specific "nepheloid" taxa that may contribute significantly to coastal ocean nutrient cycling.

Subcritical water extraction of organic matter from sedimentary rocks

Subcritical water extraction of organic matter containing sedimentary rocks at 300°C and 1500psi produces extracts comparable to conventional solvent extraction. Subcritical water extraction of previously solvent extracted samples confirms that high molecular weight organic matter (kerogen) degradation is not occurring and that only low molecular weight organic matter (free compounds) are being accessed in analogy to solvent extraction procedures. The sedimentary rocks chosen for extraction span the classic geochemical organic matter types. A type I organic matter-containing sedimentary rock produces n-alkanes and isoprenoidal hydrocarbons at 300°C and 1500psi that indicate an algal source for the organic matter. Extraction of a rock containing type II organic matter at the same temperature and pressure produces aliphatic hydrocarbons but also aromatic compounds reflecting the increased contributions from terrestrial organic matter in this sample. A type III organic matter-containing sample produces a range of non-polar and polar compounds including polycyclic aromatic hydrocarbons and oxygenated aromatic compounds at 300°C and 1500psi reflecting a dominantly terrestrial origin for the organic materials. Although extraction at 300°C and 1500psi produces extracts that are comparable to solvent extraction, lower temperature steps display differences related to organic solubility. The type I organic matter produces no products below 300°C and 1500psi, reflecting its dominantly aliphatic character, while type II and type III organic matter contribute some polar components to the lower temperature steps, reflecting the chemical heterogeneity of their organic inventory. The separation of polar and non-polar organic compounds by using different temperatures provides the potential for selective extraction that may obviate the need for subsequent preparative chromatography steps. Our results indicate that subcritical water extraction can act as a suitable replacement for conventional solvent extraction of sedimentary rocks, but can also be used for any organic matter containing mineral matrix, including soils and recent sediments, and has the added benefit of tailored extraction for analytes of specific polarities.

Removal of organic matter and disinfection by-products precursors in a hybrid process combining ozonation with ceramic membrane ultrafiltration

The performance of an integrated process including coagulation, ozonation, ceramic ultrafiltration (UF) and biologic activated carbon (BAC) filtration was investigated for the removal of organic matter and disinfection by-products (DBPs) precursors from micro-polluted surface water. A pilot scale plant with the capacity of 120 m3 per day was set up and operated for the treatment of drinking water. Ceramic membranes were used with the filtration area of 50 m2 and a pore size of 60 nm. Dissolved organic matter was divided into five fractions including hydrophobic acid (HoA), base (HoB) and neutral (HoN), weakly hydrophobic acid (WHoA) and hydrophilic matter (HiM) by DAX-8 and XAD-4 resins. The experiment results showed that the removal of organic matter was significantly improved with ozonation in advance. In sum, the integrated process removed 73% of dissolved organic carbon (DOC), 87% of UV254, 77% of trihalomethane (THMs) precursors, 76% of haloacetic acid (HAAs) precursors, 83%of trichloracetic aldehyde (CH) precursor, 77% of dichloroacetonitrile (DCAN) precursor, 51% of trichloroacetonitrile (TCAN) precursor, 96% of 1,1,1-trichloroacetone (TCP) precursor and 63% of trichloronitromethane (TCNM) precursor. Hydrophobic organic matter was converted into hydrophilic organic matter during ozonation/UF, while the organic matter with molecular weight of 1000–3000 Da was remarkably decreased and converted into lower molecular weight organic matter ranged from 200–500 Da. DOC had a close linear relationship with the formation potential of DBPs.

Perchlorate‐induced combustion of organic matter with variable molecular weights: Implications for Mars missions

AbstractInstruments on the Viking landers and Curiosity rover analyzed samples of Mars and detected carbon dioxide and organic compounds of uncertain origin. Mineral‐assisted reactions are leading to uncertainty, particularly those involving perchlorate minerals which thermally decompose to produce chlorine and oxygen which can then react with organic matter to generate organochlorine compounds and carbon dioxide. Although generally considered a problem for interpretation, the release profiles of generated gases can indicate the type of organic matter present. We have performed a set of experiments with perchlorate and organic matter of variable molecular weights. Results indicate that organic susceptibility to thermal degradation and mineral‐assisted reactions is related to molecular weight. Low molecular weight organic matter reacts at lower temperatures than its high molecular weight counterparts. The natural occurrence and association of organic matter with differing molecular weights helps to discriminate between contamination (usually low molecular weight organic matter only) and indigenous carbon (commonly low and high molecular weight organic matter together). Our results can be used to provide insights into data returning from Mars.

초순수 제조 공정에서 역삼투 막의 저농도 유기물 제거

【Ultrapure water (UPW) is water containing nothing but water molecule ( $H_2O$ ). The use of UPW is increasing in many industries such as the thermal and nuclear power plants, petrochemical plants, and semiconductor manufacturers. In order to produce UPW, several unit processes such as ion exchange, reverse osmosis (RO), ultraviolet (UV) oxidation should be efficiently arranged. In particular, RO process should remove not only ions but also low molecular weight (LMW) organic matters in UPW production system. But, the LMW organic matter removal data of RO membranes provided by manufacturers does not seem to be reasonable because they tested the removal in high concentration conditions like 1,000 ppm of isopropyl alcohol (IPA, MW=60.1). In this study, bench-scale experiments were carried out using 4-inches RO modules. IPA was used as a model LMW organic matter with low concentration conditions less than 1 ppm as total organic carbon (TOC). As a result, the IPA removal data by manufacturers turned out to be trustable because the effect of feed concentration on the IPA removal was negligble while the IPA removal efficiency became higher at higher permeate flux.】

Factors affecting the removal of isopropyl alcohol by reverse osmosis membranes for ultrapure water production

Ultrapure water (UPW) is used in the electronic industry for the production of semiconductors, memories, and LCD displays. The two important pollutants for UPW production processes are ions and low-molecular weight (LMW) organic matters. To obtain UPW quality, several unit processes such as ion exchange, ultraviolet (UV) oxidization, and membrane filtration can be used together. Reverse osmosis (RO) which can remove LMW organic matters is one of the key treatment processes for UPW production. In this case, RO feed water contains very little materials such as ions, organic matters, and other pollutants. Thus, we investigated the factors affecting low-concentration LMW organic matter removal by RO membranes in deionized water to simulate the operation condition of RO process for UPW production system. Bench-scale experiments were carried out using four-inch RO elements from four different manufacturers. Isopropyl alcohol (IPA, molecular weight = 60.1) with concentrations less than 1 mg/l was used as a model LMW organic matter. The experimental results reveal that the possible mechanism for the IPA removal is steric hindrance of solutes by the pore structure of membrane. According to the mechanism, the IPA removal efficiency becomes higher at higher permeate flux and lower feed temperature, and RO membrane with higher salt rejection, and lower pure water permeability ensures the higher performance on the removal of IPA.

Sulfate reduction controlled by organic matter availability in deep sediment cores from the saline, alkaline Lake Van (Eastern Anatolia, Turkey)

As part of the International Continental Drilling Program deep lake drilling project PaleoVan, we investigated sulfate reduction (SR) in deep sediment cores of the saline, alkaline (salinity 21.4‰, alkalinity 155 m mEq-1, pH 9.81) Lake Van, Turkey. The cores were retrieved in the Northern Basin (NB) and at Ahlat Ridge (AR) and reached a maximum depth of 220 m. Additionally, 65–75 cm long gravity cores were taken at both sites. SR rates (SRR) were low (≤22 nmol cm-3 day-1) compared to lakes with higher salinity and alkalinity, indicating that salinity and alkalinity are not limiting SR in Lake Van. Both sites differ significantly in rates and depth distribution of SR. In NB, SRR are up to 10 times higher than at AR. SR could be detected down to 19 mblf (meters below lake floor) at NB and down to 13 mblf at AR. Although SRR were lower at AR than at NB, organic matter (OM) concentrations were higher. In contrast, dissolved OM in the pore water at AR contained more macromolecular OM and less low molecular weight OM. We thus suggest, that OM content alone cannot be used to infer microbial activity at Lake Van but that quality of OM has an important impact as well. These differences suggest that biogeochemical processes in lacustrine sediments are reacting very sensitively to small variations in geological, physical, or chemical parameters over relatively short distances.

Photochemical Coupling of Iron Redox Reactions and Transformation of Low-Molecular-Weight Organic Matter

The photoreactions between Fe(III)/Fe(II) and low-molecular-weight organic matter (LMWOM) under solar irradiation have significant implications for many biogeochemical cycles on the Earth and for the fates of environmental pollutants. In this Perspective, we focus on several fundamental aspects of the photochemical processes that couple the redox cycling of iron species and transformation of organic substrates. The primary photoprocesses (e.g., intramolecular electron transfer or photodissociation) are first highlighted by introducing the recently disputed observations on the photolysis of ferrioxalate complexes. The effects of LMWOM and its daughter radicals on the photochemical redox cycling of iron species are discussed with special attention given to the example of Fe–malonate complexes. These processes and mechanisms would provide us some refreshed understanding of environmental photochemistry of LMWOM and the iron species and would be helpful for our assessment of photochemical decontamination of organic pollutants.

Characterization of chromophoric organic matter in effluent from Vitamin C wastewater anaerobic-aerobic treatment

Chroma is not effectively removed from Vitamin C (VC) wastewater by traditional anaerobic-aerobic treatment. This means current treatment does not meet the strict new discharge standard for VC wastewater in China. However, to date, no studies have investigated the removal of chroma from VC wastewater, or characterized the chromophoric organic matter in wastewater. In this study, choromophoric organic matter in effluent from anaerobic-aerobic treatment of Vitamin C wastewater was characterized using high performance gel permeation chromatography (HPGPC), ultrafiltration, and infrared (IR) and ultraviolet-visible (UV/Vis) spectroscopy. Routine water-quality indices were determined, and indicated that the organic matter in the effluent contained nitrogen. The molecular weight of most organic matter in this effluent was below 1000 Da, while the remainder was between 1000–3000 Da. These compounds are likely biodegradation products of high molecular weight organic matter in the effluent, which are raw materials and byproducts from VC production. IR spectra indicated that the low molecular weight (<1000 Da) organic matter and higher molecular weight (1000–3000 Da) organic matter contain similar major functional groups, including -OH, -NH2, -CO-NH2, -C=O-, and -COO−. The effluent was treated using electrolysis, and UV/Vis spectra of this effluent before and after electrolysis indicated that -C=O is an important chroma group in this effluent. Electrolysis can easily break -C=O, and provides a feasible technology for the advanced treatment of anaerobic-aerobic effluent from VC wastewater treatment.

Characterization of algal organic matter and formation of DBPs from chlor(am)ination

The frequent occurrence of algal blooms in drinking water reservoirs causes problems to water supply, one of which is the release of algal organic matter in high concentrations to affect drinking water quality. Algal organic matter, including extracellular organic matter (EOM) and intracellular organic matter (IOM), was characterized. The formation of a variety of disinfection by-products (DBPs) in chlorination and chloramination of EOM, IOM and algal cells was evaluated. Natural organic matter (NOM) isolated from Suwannee River was also studied for comparison. EOM and IOM were rich in organic nitrogen, which consisted of high (over 10 kDa) and low (70–1000 Da) molecular weight (MW) organic matter, whilst the MW of organic carbon in EOM and IOM was relatively lower. IOM had a higher fraction of total organic nitrogen, with larger proportions of higher MW and more hydrophobic contents than did EOM. IOM also contained higher fractions of free amino acids but lower fractions of aliphatic amines than did EOM. During chlorination of EOM and IOM, organic chloramines were first formed and then became undetectable after 1 d. Chlorination of EOM and IOM produced more nitrogenous DBPs (N-DBPs) and haloaldehydes and less carbonaceous DBPs (C-DBPs) than did chlorination of NOM. Organic chloramines were found after 3-d chloramination of EOM and IOM. The amounts of N-DBPs and C-DBPs formed from chloramination of EOM or IOM were much less than that from NOM. EOM produced less DBPs (except for trichloronitromethane) than did IOM and algal cells in chlorination and chloramination.

Improvement in the coagulation performance by combining Al and Fe coagulants in water purification

This study evaluated the beneficial effects on the coagulation process of combining coagulants with Fe and Al in the removal of turbidity and DOC (dissolved organic carbon), and proposed conditions for proper operation of a coagulation process. In addition, the floc characteristics and sludge dewater ability were evaluated. Blended coagulants were more effective than single coagulants at lower concentrations in water purification. The optimal blended ratio for the removal of DOC was 1.45 mM as Al/mM as Fe. Also, blended coagulants were less affected than single coagulants by pH, temperature, and rapid mixing intensity. Based on the results of the change in the apparent molecular weight distribution (AMWD) of DOC in raw and treated water by coagulation, low molecular weight organic matters were removed by 40.7% for the blended coagulant (1.45 mM as Al/mM as Fe). Blended coagulants formed larger flocs than single coagulants did. At pH 6.0, floc strength and sludge dewaterablity were both improved.

Positive roles of biofilm during the operation of membrane bioreactor for water reuse

Generally, membrane biofilm have been believed to be minimized during the operation of membrane bioreactor (MBR) for wastewater treatment and reuse. In this study, positive roles of membrane biofilm in the intermittently aerated MBR system were highlighted. During the long-term operation using real domestic wastewater, membrane biofilm played secondary filtration barrier for both low and high molecular weight organic matters. The biofilm on the membrane surface was responsible for the removal of low molecular weight organic matters by the use of easily degradable organic matters (i.e. <1 kDa) as microbial carbon and energy sources during the filtration. Also, track study showed that the significant denitrification took place by the membrane biofilm, proved by the degradation of carbon source and increase of alkalinity such as inorganic carbon. Nevertheless the necessity of further study, this study will give unique insight into positive roles of membrane biofilm, and also continue to aid both fundamental studies and developments of MBR processes.

Optical properties of low molecular weight and colloidal organic matter: Application of the ultrafiltration permeation model to DOM absorption and fluorescence

Cross-flow ultrafiltration (CFF) is often used to obtain separation and concentration of colloids from bulk natural water samples. Application of the ultrafiltration permeation model allows the quantitative determination of the low molecular weight material (LMW, < 1 kDa) and colloids in bulk dissolved organic matter (DOM) from measurements of time series permeate samples obtained from CFF. Detailed analysis of a Yukon River water sample shows that DOM absorption coefficient and fluorescence follow the permeation model and that the complex spectral optical properties of LMW DOM can be reconstructed from CFF data. A combination of measured and modeled data indicates that the LMW contribution to bulk DOM optical properties obtained from CFF can be grossly underestimated by the use of a low concentration factor (CF, the ratio of initial sample volume to retentate volume). Even at a relatively high CF of 19, optical properties of LMW DOM calculated from measurements of the retentate or integrated permeate would underestimate true values by 5–36%. In the Yukon River sample, LMW dissolved organic carbon represented 26% of the bulk concentration, but only 3–14% of the colored DOM was in the LMW fraction while 31–33% of bulk DOM florescence was due to LMW DOM. The contrasting optical properties of LMW and colloidal DOM support the concept that analysis of bulk DOM absorption and fluorescence properties reveals information about DOM molecular weight.

Ozone, Oxalic Acid, and Organic Matter Molecular Weight – Effects on Coagulation

Abstract Ozonation breaks long chain natural organic matter (NOM) into smaller, more oxygenated compounds such as oxalic acid. The purpose of this study was to evaluate the effects of such transformations on coagulation in high dissolved organic carbon synthetic waters with model particles. Results indicate that the presence of oxalic acid adversely affects the removal of turbidity and organic carbon by coagulation and filtration. The results also show that larger (higher molecular weight) organic matter is easier to remove by coagulation than lower molecular weight organic matter. In both cases, ozonation results in an increase in the optimum coagulant dose or a decrease in the amount of turbidity and TOC removal at a given coagulant dose.