Dissolved Organic Matter Features of Three Adjacent Eastern Mediterranean Urbanized Watersheds

Landscape urbanization broadly affects ecosystems in coastal watersheds, but, until now, the influence of nonpoint source urban inputs on dissolved organic matter (DOM) amount, composition, and source is poorly understood. To understand how DOM composition varied with urbanization, fluorescence excitation-emission matrices (EEMs) were determined for urban and non-urban waters from upstream to downstream sites along three adjacent coastal watersheds that flow into the Mediterranean Sea. Two humic DOM fluorescent components (humic-like and fulvic-like peaks) and two proteinic components (tyrosine-like and tryptophane-like peaks) were identified by EEM fluorescence. The results indicated that urbanization had an important influence on DOM concentration and composition, with urban waters having a high degree of DOM variation due to different land uses surrounding each body of water. Urban waters show a higher DOM fluorescence index (FI), the highest fluorescence intensity of protein-like manifested also by BIX values, and a lower value of the humification index (HIX) than non-urban waters which were dominated by allochthonous inputs. In addition, the EEM was compared in dry and wet season where higher DOM amounts and FI appeared in summer due to autochthonous production coming from algae growth compared to allochthonous input from rainfall dominated in wet season. The concentration of DOC increased from upstream to downstream for the three rivers, especially Beirut River. The increase in DOC values was observed in both dry and wet seasons by 39 and 19 times respectively compared to upstream (0.93 - 0.91 mgC/L).

Characteristics of dissolved organic matter(DOM) in leachate with different landfill ages

The main objective of the study was to investigate the characteristics of dissolved organic matter （DOM） in leachate with different landfill ages through the chemical, spectroscopic, and elemental analysis. Humic acid （HA）, fulvic acid （FA）, and hydrophilic （HyI） fractions were isolated and purified by the XAD-8 resin combined with the cation exchange resin method. The analytical results of fluorescence excitation-emission matrix spectroscopy （EEMs） revealed that the fluorescence peaks were protein-like fluorescence for young landfill leachate, while the fluorescence peaks for medium and old landfill leachate were humic-like and fulvic-like fluorescence, respectively. Elemental analysis showed that carbon, hydrogen, and nitrogen content decreased with landfill age, while the oxygen content increased. Moreover, the nitrogen content in these isolated fractions followed： HA 〉 HyI 〉 FA. The results of elemental analysis, FT-IR, and fluorescence EEMs also confirmed that aromatic carbons and portions of aliphatic functional groups were more abundant in leachate samples with increasing landfill age.

Effect of dissolved organic matter on adsorption and desorption of mercury by soils

Effects of dissolved organic matter (DOM) on adsorption and desorption of Hg were investigated in two kinds of soils, Xanthi-Udic Ferralosols (XUF) and Typic Purpli-Udic Cambosols (TPUC). The DOM was obtained from humus soil (DOMH), rice straw (DOMR), and pig manure (DOMP). The presence of DOM obviously reduced Hg maximum adsorption capacity with up to 40% decreases over the control, being an order of DOMH (250.00 mg/kg)< DOMR (303.03 mg/kg) < DOMP (322.58 mg/kg) < CK (control 416.67 mg/kg) for the...

Sorption of dissolved organic matter and its effects on the atrazine sorption on soils

The dissolved organic matter(DOM), water soluble organic matter derived from sewage sludge was separated into hydrophobic fraction(Ho) and hydrophilic fraction(Hi). The sorption of DOM and its fractions on soils and the effects of DOM sorption on a nonionic pesticide(atrazine(2-chloro-4-ethylamino-6-isopropylamino-1,3,5-trazine)) distribution between soil and water were investigated using a batch equilibrium technique. The total DOM sorption on soils described by the Langmuir equation reached saturation as the DOM concentration increased. The sorption of Ho fit the Freundlich model. In contrast, a negative retention evidently occurred as adding Hi at higher level in tested soils. The sorption of Ho dominated the total DOM sorption and the release of soil organic matter(SOM). Effects of DOM on the atrazine sorption by soils were DOM-concentration dependent and dominated by the interaction of atrazine, DOM, and soil solids. Generally, the presence of DOM with lower concentration promoted atrazine sorption on soils, namely the apparent partitioning constant(K*_d) for atrazine sorption in the presence of DOM was larger than the distribution constant(K_d) without DOM; whereas the presence of DOM with higher concentration inhibited atrazine sorption(i.e., K*_d<K_d). The overall effects of DOM on atrazine sorption in soils might be related to the DOM sorption and the release of soil intrinsic organic matter into aqueous solution. The sorption of Ho on soils promoted the atrazine sorption on soil, while the release of SOM by Hi and the competitive sorption between Hi and atrazine on soil surface led to a decrease of atrazine sorption. Information provided in this work may contribute to a better understanding of the DOM sorption and its impacts on the contaminant soil-water distribution.

Characteristics of dissolved organic matter in lakes with different eutrophic levels in southeastern Hubei Province,China

Dissolved organic matter(DOM)plays a crucial role in both the carbon cycle and geochemical cycles of other nutrient elements,which is of importance to the management and protection of the aquatic environments.To achieve a more comprehensive understanding the characteristics of DOM in the Changjiang(Yangtze)River basin,water samples from four natural lakes(Xiandao,Baoan,Daye,and Qingshan)in southeastern Hubei Province in China with different eutrophication levels were collected and analyzed.The optical characteristics were analyzed using ultraviolet-visible spectrophotometry and excitation-emission matrix spectroscopy coupled with parallel factor analysis.The results show that:(1)two humic-like components(C1 and C2)and two protein-like substances(C3 and C4)of DOM were identified in all waterbodies;(2)C3 originated primarily from the degradation of microalgae and contributed substantially to humic-like components during transformation.C4 was widely present in the Changjiang River basin and its formation was related to microbial activity,rather than algal blooms or seasons.Influenced by the water mixing,the protein-like components were more likely to be transformed by microorganism,whereas humic-like components were more easily to be photobleached;(3)the concentration of DOM and the fluorescence intensity of humic-like components gradually increased with rising lake eutrophication levels.With respect to protein-like components,only C3 showed changes along the eutrophication gradients;(4)DOM showed a high affinity with permanganate index(COD Mn)and chlorophyll a(chl a)while the relationship was variable with phosphorus.This study helps us systematically understand the DOM characteristics,microbial activities,and pollutant transformation in the Changjiang River basin and provides reference to the ecological restoration of aquatic environments.

Fluorescence characteristic changes of dissolved organic matter during municipal solid waste composting

Dissolved organic matter（DOM） of municipal solid waste（MSW） consists of minerals, water, ash and humic substances, and is known to enhance plant growth. In this study, inoculating microbes（Z J, MS） were used in municipal solid wastes composting, and composting implemented a industrialized technology. During composting, dissolved organic matter was extracted from the compost and purified. The spectral characteristics of dissolved organic matter was determined by fluorescence emission, excitation, and synchronous spectroscopy. Fluorescence emission, excitation, and synchronous spectra characterized by different relative fluorescent intensities and peaks over time. Fluorescence spectra were similar to that of fulvic acid in sewage sludge, indicating the presence of dissolved organic matter with aromatic structures and a high degree of molecular polymerization. Compared with the controls with no microbial inoculation, the microbe-inoculated treatments exhibited the increase of aromatic polycondensation, in the following order： MS ＋ ZJ 〉 ZJ 〉 MS 〉 CK.

Binding of pyrene to dissolved organic matters: fractionation and characterization

Based on a modified Leenheer DOM fractionation scheme, fractionation of DOM from the paddy soil was conducted by using XAD-8 resin into hydrophobic bases(HOB), hydrophobic acids(HOA), acid-insoluble matter(AIM), hydrophobic neutrals(HON) and hydrophilic matter(HIM). In total carbon content of DOM, 35.32% were the HIM and only 0.73% the HOB. However, HOA and AIM altogether occupied 53.45%, while the HON fraction represented 10%. The sorption experiments were conducted to determine the sorption capacity of pyrene on unfractionated DOM and its fractions. Elemental analysis, 1H-NMR and FTIR spectra were carried out on unfractionated DOM and its fractions to examine the relationship between the structure of DOM and partition coefficients(K oc). The results showed that HON had a greater affinity for binding pyrene than other fractions. While HON was characterized by large long-chain alkylate (aliphatic structure). AIM exhibited relative higher K oc values than HOA and HIM, due to much aromatic structure in AIM, while the high content of carboxylic groups of HOA and HIM depressed their binding capacity. This study demonstrated HON is a key subcomponents of DOM in binding of pyrene, in other words, aliphalic structure in DOM play an important role in binding of pyrene.

Removal and transformation of dissolved organic matter in secondary effluent during granular activated carbon treatment

This paper focused on the removal and transformation of the dissolved organic matter （DOM） in secondary effluent during the granular activated carbon （GAC） treatment. Using XAD-8/XAD-4 resins, DOM was fractionated into five classes： hydrophobic acid （HPO-A）, hydrophobic neutral （HPO-N）, transphilic acid （TPI-A）, transphilic neutral （TPI-N） and hydrophilic fraction （HPI）. Subsequently, the water quality parameters of dissolved organic carbon （DOC）, absorbance of ultraviolet light at 254 nm （UV-254）, specific ultraviolet light absorbance （SUVA） and trihalomethane formation potential （THMFP） were analyzed for the unfractionated and fractionated water samples. The results showed that the order of the DOC removal with respect to DOM fractions was observed to be HPI〉HPO-A〉HPO-N〉TPI-A〉TPI-N. During the GAC treatment, the THMFP of the unfractionated water samples decreased from 397.4 μg/L to 176.5 μg/L, resulting in a removal efficiency of 55.6%. The removal order of the trilaalomethanes （THMs） precursor was as follows： HPO-A〉TPI-A〉TPI-N〉HPO-N〉HPI. By the GAC treatment, the specific THMFP of HPO-A, TPI-A, TPI-N and the original unfractionated water samples had a noticeable decrease, while that of HPO-N and HPI showed a converse trend. The Fourier transform infrared （FTIR） results showed that the hydroxide groups, carboxylic acids, aliphatic C-H were significantly reduced by GAC treatment.

Multivariate analysis of fluorescence and source identification of dissolved organic matter in Jiaozhou Bay, China

Hierarchical clustering analysis and principal component analysis （PCA） methods were used to assess the similarities and dissimilarities of the entire Excitation-emission matrix spectroscopy （EEMs） data sets of samples collected from Jiaozhou Bay, China. The results demonstrate that multivariate analysis facilitates the complex data treatment and spectral sorting processes, and also enhances the probability to reveal otherwise hidden information concerning the chemical characteristics of the dissolved organic matter （DOM）. The distribution of different water samples as revealed by multivariate results has been used to track the movement of DOM material in the study area, and the interpretation is supported by the results obtained from the numerical simulation model of substance tracing technique, which show that the substance discharged by Haibo River can be distributed in Jiaozhou Bay.

Improved speciation of dissolved organic nitrogen in natural waters: amide hydrolysis with fluorescence derivatization

The objective of this study was to improve primary-amine nitrogen (1°-N) quantification in dissolved organic matter (DOM) originating from natural waters where inorganic forms of N, which may cause analytical interference, are commonly encountered. Efforts were targeted at elucidating organic-N structural criteria influencing the response of organic amines to known colorimetric and fluorescent reagents and exploring the use of divalent metal-assisted amide hydrolysis in combination with fluorescence analyse...

Freeze-induced acceleration of iodide oxidation and consequent iodination of dissolved organic matter to form organoiodine compounds

Freeze-induced acceleration of I–oxidation and the consequent iodination of dissolved organic matter(DOM)contribute to the formation of organoiodine compounds(OICs)in cold regions.The formed OICs may be a potentially important source of risk and are very closely with the environment and human health.Herein,we investigated the acceleration effects of the freeze process on I–oxidation and the formation of OICs.In comparison to reactive iodine species(RIS)formed in aqueous solutions,I–oxidation and RIS formation were greatly enhanced in frozen solution and were affected by pH,and the content of I–and O_(2).Freeze-thaw process further promoted I–oxidation and the concentration of RIS reached 45.7μmol/L after 6 freeze-thaw cycles.The consequent products of DOM iodination were greatly promoted in terms of both concentration and number.The total content of OICs ranged from 0.02 to 2.83μmol/L under various conditions.About 183–1197 OICs were detected by Fourier transform ion cyclotron resonance mass spectrometry,and more than 96.2%contained one or two iodine atoms.Most OICs had aromatic structures and were formed via substitution and addition reactions.Our findings reveal an important formation pathway for OICs and shed light on the biogeochemical cycling of iodine in the natural aquatic environment.

Spatial heterogeneity and compositional profiles of dissolved organic matter in farmland soils across China' Mainland

Dissolved organic matter(DOM) plays an essential role in many geochemical processes,however its complexity, chemical diversity, and molecular composition are poorly understood. Soil samples were collected from 500 vegetable fields in administrative regions of China' Mainland, of which 122 were selected for further investigation. DOM properties were characterized by three-dimensional excitation-emission matrix(3D-EEM) fuorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry(FTICRMS)(field intensity is 15 Tesla). Our results indicated that the main constituents were UVA humic-like substances, humic-like substances, fulvic acid-like substances, and tyrosine-like substances. A total of 10,989 molecular formulae with a mass range of 100.04 to 799.59 Da were detected, covering the mass spectrometric information of the soil samples from 27 different regions. CHO and CHON molecules were dominant in DOM, whereas lignin, tannins,and aromatic substances served as the main components. The results of cluster analysis revealed that the soil properties in Jiangxi Province were considerably different from those in other regions. The key backgrounds of the DOM molecular characteristics in the vegetablefield soil samples across China' Mainland were provided at the molecular level, with large abundance and great variability.

How aromatic dissolved organic matter differs in competitiveness against organic micropollutant adsorption

Activated carbon is employed for the adsorption of organic micropollutants(OMPs)from water,typically present in concentrations ranging from ng L1 to mg L1.However,the efficacy of OMP removal is considerably deteriorated due to competitive adsorption from background dissolved organic matter(DOM),present at substantially higher concentrations in mg L1.Interpreting the characteristics of competitive DOM is crucial in predicting OMP adsorption efficiencies across diverse natural waters.Molecular weight(MW),aromaticity,and polarity influence DOM competitiveness.Although the aromaticity-related metrics,such as UV254,of low MW DOM were proposed to correlate with DOM competitiveness,the method suffers from limitations in understanding the interplay of polarity and aromaticity in determining DOM competitiveness.Here,we elucidate the intricate influence of aromaticity and polarity in low MW DOM competition,spanning from a fraction level to a compound level,by employing direct sample injection liquid chromatography coupled with ultrahigh-resolution Fouriertransform ion cyclotron resonance mass spectrometry.Anion exchange resin pre-treatment eliminated 93%of UV254-active DOM,predominantly aromatic and polar DOM,and only minimally alleviated DOM competition.Molecular characterization revealed that nonpolar molecular formulas(constituting 26%PAC-adsorbable DOM)with medium aromaticity contributed more to the DOM competitiveness.Isomerlevel analysis indicated that the competitiveness of highly aromatic LMW DOM compounds was strongly counterbalanced by increased polarity.Strong aromaticity-derived p-p interaction cannot facilitate the competitive adsorption of hydrophilic DOM compounds.Our results underscore the constraints of depending solely on aromaticity-based approaches as the exclusive interpretive measure for DOM competitiveness.In a broader context,this study demonstrates an effect-oriented DOM analysis,elucidating counterbalancing interactions of DOM molecular properties from fraction to compound level.

Evidence on the causes of the rising levels of COD_(Mn) along the middle route of the South-to-North Diversion Project in China:The role of algal dissolved organic matter

As the biggest inter-basin water transfer scheme in the world,the South-to-North Water Diversion Project(SNWD) was designed to alleviate the water crisis in North China.The main channel of the middle route of the SNWD is of great concern in terms of the drinking water quality.In this study,we tested the hypothesis that the dissolved organic matter(DOM) derived from the planktonic algae causes the rising levels of COD_(Mn) along the middle route by monitoring data on water quality(2015-2019,monthly resolution).The results showed that algal density in the main channel increased along the channel and was significantly correlated with COD_(Mn)(p <0.01).Five fluorescent components of DOM,including tyrosine-like(14.85%),tryptophan-like(22.48%),microbial byproduct-like(26.34%),fulvic acid-like(11.41%),and humic acid-like(24.92%) components,were detected.The level of tyrosine-like components increased along the channel and was significantly correlated with algal density(p<0.01),indicating that algae significantly changed the level of DOM in the channel.Algal decomposition and metabolism were found to be the main mechanisms that drive the changes in COD_(Mn).Therefore,controlling algal density would be an important measure to prevent further increase in CODMn and for the guarantee of excellent water quality.

Three-dimensional fluorescence spectral characterization of soil dissolved organic matters in the fluctuating water-level zone of Kai County,Three Gorges Reservoir

Three-dimensional fluorescence spectroscopy was used to investigate the fluorescent properties of soil dissolved organic matter(DOM)in the water-levelfluctuation zone(WLFZ)of Kai County,Three Gorges Reservoir(TGR).Most of the soil DOM analyzed in this study was found to contain four fluorescence peaks.Peaks A and C represent humic-like fluorescence,whereas peaks B and D represent tryptophan-like fluorescence.Peaks E and F,which represent tyrosine-like fluorescence,only appeared in certain soils.Soil humus was the main source of DOM in soil,and higher concentration of soil DOM was found in the exposed soil than submerged soil.Compared to the peaks A and B,the fluorescence intensities of peaks C and D were strongly influenced by the fluctuating water level.Analysis of fluorescence intensities of different peaks in soil DOM showed that WLFZ soil was not contaminated significantly.Soil DOM contained at least two types of humic-like fluorescence groups and two types of protein-like fluorescence groups.The proportion of the content of peak A in soil organic matter was quite stable.The soil DOM in exposed soil had relatively high humification and aromaticity,and periodic submerging and exposure of soil had an impact on the humification of soil DOM.

Revealing the characteristics of dissolved organic matter in urban runoff at three typical regions via optical indices and molecular composition

Dissolved organic matter(DOM)plays a major role in ecological systems and influences the fate and transportation of many pollutants.Despite the significance of DOM,understanding of how environmental and anthropogenic factors influence its composition and characteristics is limited,especially in urban stormwater runoff.In this article,the chemical properties(pollutant loads,molecular weight,aromaticity,sources,and molecular composition)of DOM in stormwater extracted from three typical end-members(traffic,residential,and campus regions)were characterized by UV–visible(UV–vis)spectroscopy,excitationemission matrix spectroscopy combined with parallel factor analysis(EEM-PARAFAC),and ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry(UPLC-Q-TOF-MS).There are three findings:(1)The basic properties of DOM in stormwater runoff varied obviously from three urban fields,and the effect of initial flush was also apparent.(2)The DOM in residential areas mainly came from autochthonous sources,while allochthonous sources primarily contributed to the DOM in traffic and campus areas.However,it was mainly composed of terrestrial humic-like components with CHO and CHON element composition and HULO and aliphatic formulas.(3)The parameters characterizing DOM were primarily related to terrestrial source and aromaticity,but their correlations varied.Through the combination of optical methods and UPLC-Q-TOF spectrometry,the optical and molecular characteristics of rainwater are effectively revealed,which may provide a solid foundation for the classification management of stormwater runoff in different urban regions.

Ultraviolet humic-like component contributes to riverine dissolved organic matter biodegradation

Biological degradation of dissolved organic matter(DOM)regulates its structure and fate in river ecosystems.Previous views suggested that labile components were dominantly consumed by microbial metabolism.Here we provide new observations that a part of recalcitrant compounds largely contribute to riverine DOM biodegradation.The excitationemission matrix fluorescent spectroscopy combined with peak picking and parallel factor analysis are used to explore component variability during DOM incubation.Humic-like and tryptophan-like DOM are the primary components of riverine DOM,with proportion contributions of 39%–82% and 16%–61% for % of the maximumfluorescence intensity,respectively.After 56 days of aerobic incubation in the dark,large amounts of tyrosine-like DOM generation are observed.Elevated temperature enhances the decomposition of ultraviolet humiclike substance and further stimulates labile DOM bio-mineralization into carbon dioxide.Meanwhile,averaged proportions of amino acid compositions(peak B and T)markedly increase(p<0.05)as the humic-like compositions(peak A,M and C)decrease after DOM incubation,suggesting incomplete degradation of refractory DOM from high-molecular to low-molecular weight compounds.The findings support the new notion of the continuous DOM biodegradation in a mode as“steps by steps”,contributing to a new understanding of carbon cycling for the UN Sustainable Development Goal.

Impact of dissolved organic matter on the photolysis of the ionizable antibiotic norfloxacin

Norfloxacin（NOR）, an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity.Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water — dissolved organic matter（DOM）, which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance（EPR） were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical（U OH） and singlet oxygen（1O2） based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of U OH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and1O2. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored.

Microbial degradation of various types of dissolved organic matter in aquatic ecosystems and its influencing factors

Interactions between chemodiverse dissolved organic matter(DOM)and biodiverse microbes are governed by a myriad of intrinsic and extrinsic factors which are not well understood.Here,we update and bridge the gap of this interdisciplinary theme comprehensively.At an ecosystem level,aquatic ecosystems dominated by algae-sourced DOM(e.g.,eutrophic lake or coastal upwelling areas)harbor more biolabile DOM,such as directly assimilable monomers and readily hydrolysable biopolymers.However,other ecosystems prevailed by DOM supply from soil and vascular plants(e.g.,river or wetland)have more biorefractory DOM,such as low molecular weight(LMW)residue of aliphatic C skeletons and geopolymers.A variety of heterotrophic bacteria,archaea,fungi,phagotrophic protists,and even photoautotrophic phytoplankton shows genomic and/or culturing experimental evidence of being able to process a diverse type of organics.The various biodegradable organics have different chemical structures and chemical bonds such as carbohydrates,amino acids,proteins,lignins,lipids,carboxylic acids,humic acids,hydrocarbons,and nanoplastics.Meanwhile,bio-production of metabolism intermediates and/or biorefractory organics(e.g.,carboxyl-rich alicyclic molecules,CRAM)is observed despite general decay of bulk dissolved organic carbon(DOC)during bioassay experiments.In particular,emerging evidence shows that archaea contribute significantly to biomass in the marine mesopelagic zone and subsurface environments and their abundance often increases with depth in sediments.Furthermore,not only intrinsic factors(e.g.,DOM composition and structure),but also extrinsic ones(e.g.,sunlight and dissolved oxygen)play important roles in interplays between DOM and microbes.

Characterization of natural organic matter in water for optimizing water treatment and minimizing disinfection by-product formation

Introduction Natural organic matter（NOM）present in source water has significant impact on water treatment processes and on the quality of drinking water.NOM is a complex mixture of diverse groups of organic compounds,humic and fulvic acids,proteins,peptides,carbohydrates,and heterogeneous materials