Molecular Weight Distribution of Dissolved Organic Matter in Lake Hongfeng Determined by High Performance Size Exclusion Chromatography (HPSEC) With On-Line UV-Vis Absorbance and Fluorescence Detection

The molecular weight distribution (MWD) of dissolved organic matter (DOM) in lake waters from Lake Hongfeng was examined using high performance size exclusion chromatography (HPSEC) with UV-vis absorbance and fluorescence detection. The elution curves obtained by absorbance and fluorescence techniques expressed similar patterns, with the exception of diminishing of large fraction and the peaks behind several seconds in fluorescence chromatograms. According to its molecular weight (MW), DOM in water samples is divided into several fractions: large ({>3.5} kDa); medium-large ({3.5}-{2.0} kDa); medium ({2.0}-{1.0} kDa) and small ({<1.0} kDa). The average molecular weight was calculated using the elution curve detected by UV-vis absorbance and fluorescence detection techniques. The results showed that the weight-average molecular weight (Mw) and number-average molecular weight (Mn) calculated by UV-vis absorbance techniques range from 1750 to 2050 Dalton and from 1450 to 1850 Dalton, respectively. And the Mw and Mn obtained by fluorescence detection are lower by 50 to 400 Dalton. As a reference, the molecular weight of Fluka humic acid (FHA) is larger than that of water samples by about 200 Dalton. The average molecular weight of DOM for water samples collected in March and July was compared. The results revealed that the molecular weight is lower for water samples obtained in July than that obtained in March, indicating the ambient environment has an influence on the molecular weight, including photo-degradation and biological activity.

Effect of Dissolved Organic Matter on Titanium Dioxide Nanoparticles in Aquatic Environment:Molecular Weight Fractions

At present,a growing number of consumer products contain engineered nanoparticle TiO2(nano⁃TiO2),which has resulted in the consequences of nano⁃TiO2 entering the aquatic environment directly or indirectly at some stage.The fate of nano⁃TiO2 in the aquatic environment has become the key factor which affects its safety application and nanoecotoxicology.This paper aims to investigate how the dissolved organic matters(DOM),especially the molecular weight fractions in the aquatic environment,affect the aggregation,stability,and fate of nano⁃TiO2,and the interaction mechanism of DOM and nano⁃TiO2.Results of dynamic light scattering(DLS)showed that the molecular weight of DOM molecules caused different aggregation rates of nano⁃TiO2 in aqueous solution.Fourier Transform infrared spectroscopy(FTIR)results indicated the molecular structure is characteristics of DOM fractions and the mechanisms of bonds formation between DOM and nano⁃TiO2.Results of three⁃dimensional excitation⁃emission matrices(3D⁃EEM)confirmed the FTIR results and implied the increase of the stability of theπ-πconjugated system in the presence of DOM.In addition,low molecular weight of DOM fractions appeared to show more affinity with nano⁃TiO2 than high molecular weight fractions.

Bioactivity profile of dissolved organic matter and its relation to molecular composition

Dissolved organic matter(DOM)occupies a huge and uncharted molecular space.Given its properties,DOM can be presented as a promising biotechnological resource.However,research into bioactivities of DOM is still in early stages.In this study,the biotechnological potential of terrestrial and marine DOM,its molecular composition and their relationships are investigated.Samples were screened for their in vitro antibacterial,antifungal,anticancer and antioxidant activities.Antibacterial activity was detected against Staphylococcus aureus in almost all DOM samples,with freshwater DOM showing the lowest IC50 values.Most samples also inhibited Staphylococcus epidermidis,and four DOM extracts showed up to fourfold higher potency than the reference drug.Antifungal activity was limited to only porewater DOM towards human dermatophyte Trichophyton rubrum.No significant in vitro anticancer activity was observed.Low antioxidant potential was exerted.The molecular characterization by FT-ICR MS allowed a broad compositional overview.Three main distinguished groups have been identified by PCoA analyses.Antibacterial activities are related to high aromaticity content and highly-unsaturated molecular formulae(O-poor).Antifungal effect is correlated with highly-unsaturated molecular formulae(O-rich).Antioxidant activity is positively related to the presence of double bonds and polyphenols.This study evidenced for the first time antibacterial and antifungal activity in DOM with potential applications in cosmeceutical,pharmaceutical and aquaculture industry.The lack of cytotoxicity and the almost unlimited presence of this organic material may open new avenues in future marine bioprospect-ing efforts.

Characterization of dissolved organic matter fractions from Lake Hongfeng, Southwestern China Plateau

With XAD-series and ion exchange resins, dissolved organic matter （DOM） from Lake Hongfeng in Southwestern China Plateau was isolated into 6 fractions, i.e., humic acid （HA）, fulvic acid （FA）, hydrophobic neutrals （HON）, hydrophilic acids （HIA）, hydrophilic bases （HIB） and hydrophilic neutrals （HIN）. Those fractions were characterized by high performance size exclusion chromatography, fluorescence spectroscopy and UV absorbance. Among the 6 fractions, FA was predominant and accounted for 51% of the total DOM. The weight-average （Mw） and number-averaged （Mn） molecular weight of these fractions ranged from 1688 to 2355 Da and from 1338 to 1928 Da, respectively. A strong correlation was observed between specific UV absorbance at 280 nm, E2/E3 （absorbance at 250 nm to 365 nm）, and the molecular weight for DOM fractions. UV-Vis fulvic-like fluorescence peaks were found in all fractions. Proteinlike fluorescence peaks existed in HON may indicate that microbial activity was severely in Lake Hongfeng. There was a significant relationship between fluorescence intensities and specific UV absorbance at 254 nm for those DOM fractions, suggesting their similar luminescence characteristics. The values of fluorescence index （f450/500） indicated that hydrophobic fractions may derive from terrestrial sources, and the hydrophilic fractions from microbial and terrestrial origins. Those results suggest that there were inter-relationships between molecular weight, fluorescence and absorbance characteristics, and also subtle consistencies between the hydrophilic and hydrophobic properties and the sources for these 6 fractions from Lake Hongfeng.

Characteristics and distribution of low molecular weight organic acids in the sediment porewaters in Bosten Lake, China

The composition and vertical profiles of low molecular-weight organic acids （LMWOAs） and the contribution of them to dissolved organic matter （DOM） in sediment porewaters in Bosten Lake, Xinjiang, China were investigated. The results showed that total concentration of LMWOAs was up to 94.5 μmol/L and their proportion in DOM was 5.6%, suggesting that LMWOAs were important chemical components in DOM in lake sediment porewaters. Among the seven LMWOAs, pyruvic and acetic acid had the highest concentrations with 26.30 and 8.31 μmol/L, accounting for 51.4% and 14.92% of LMWOAs, respectively. Trifluoroacetic and sorbic acid had the lowest concentrations, indicating that the compositions of LMWOAs in relative reducing environments were largely different from those reported in glacier, atmosphere and soils. The concentrations of lactic, acetic, formic, sorbic and oxalic acid decreased with increasing depth, probably relating to stronger microbial activities in the initial stage of early diagenesis. Trifluoroacetic acid was mainly anthropogenic with its concentration, showing a diusive trend from the surface to bottom sediments. The concentrations of lactic acid and nitrate generally showed a consistent profile. The increasing concentration of pyruvic acid in the vertical profile was just opposite to that of sulfate, revealing a significant negative relationship between them. Oxalic acid remained constant except for an obvious peak at 6 cm depth. The results indicated the diversities in sources and behaviors for various LMWOAs during early diagenesis in sediments.

Relationship between fluorescence characteristics and molecular weight distribution of natural dissolved organic matter in Lake Hongfeng and Lake Baihua,China

Dissolved organic matter (DOM) is one of the most interesting and difficult problems in recent years due to its important functions in the ecological and environmental system and the complexity of its chemical composition and structure. It is well ac- cepted that fluorescence characteristics and mo- lecular weight distribution are two important pa- rameters in the DOM characterization. However, the relationship between them is still unknown. In this study, fluorescence and molecular weight distribution of DOM in Lake Hongfeng, Lake Baihua and their rivers, and their relationship were investigated using the combination of fluorescence spectroscopy and high-performance size exclusion chromatography (HPSEC) with on-line UV absorbance and fluores- cence detectors. The results show that there were two obvious humic-like fluorescence peaks (Peaks A and B) in DOM from lake water. But there was an- other obvious protein-like fluorescence peak (Peak C) in DOM from river water. The humic-like fluorescence material consisted of DOM fraction with smaller mo- lecular weight, ranging from 1.0 to 3.0 kDa, while the protein-like fluorescence material mainly consisted of DOM fraction with MW larger than 2.0 kDa. The cal- culation of MW using HPSEC was related to the UV absorbance wavelength chosen.

Effect of dissolved phosphorus on alkaline phosphatase activity in marine microalgae

Alkaline phosphatase activity (APA) and dissolved phosphorus were monitored during the batch cultures of two bone microalgae. Results indicate that variation of APA was in the shape of 'S' curve. Different specs of dissolved phaphorus had different effects on APA. The concentrations of dis solved inorganic phosphorus (DIP) and and molecular dissolved organic phosphorus (SDOP) had a sig nificant effect on APA, while the concentration of large molecular dissolved organic phosphorus (LDOP) had a little effect on APA., and the increase of APA could accelerate the decomposing of LDOP in the medium. Results also show that algae species and abundance had why a little effect on APA.

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.

Application of Fourier transform ion cyclotron resonance mass spectrometry in molecular characterization of dissolved organic matter

Dissolved organic matter(DOM)plays an important role in the global carbon cycle,and an in-depth analysis of its chemical composition is fundamental to the study of its environmental and biogeochemical behavior and significance.DOM is a complex mixture of organic substances,and determining its molecular composition is a long-standing challenge in the field of analytical chemistry.The development and application of Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS)has enabled the identification of the chemical composition of DOM at the molecular level.This paper summarizes progress made in the molecular characterization of DOM based on the FT-ICR MS technique,including DOM sample pretreatment methods,mass spectrometry ionization techniques,data acquisition,data processing and presentation,and molecular structure characterization.Focusing on the work done by the instrument at the State Key Laboratory of Heavy Oil Processing in the China University of Petroleum,Beijing,we introduce applications of FT-ICR MS in the fields of earth science,environmental science and engineering,and look ahead to further research directions in the future.

Diverse molecular compositions of dissolved organic matter derived from different composts using ESI FT-ICR MS

Dissolved organic matter(DOM)derived from various composts can promote significant changes of soil properties.However,little is known about the DOM compositions and their similarities and differences at the molecular level.In this study,the molecular compositions of DOM derived from kitchen waste compost(KWC),green waste compost(GWC),manure waste compost(MWC),and sewage sludge compost(SSC)were characterized by electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry(ESI FT-ICR MS).The molecular formulas were classified into four subcategories:CHO,CHON,CHOS,and CHONS.The KWC,MWC,and SSC DOM represented the highest fraction(35.8%-47.4%)of CHON subcategory,while the GWC DOM represented the highest fraction(68.4%)of CHO subcategory.The GWC DOM was recognized as the nitrogen-and sulfurdeficient compounds that were less saturated,more aromatic,and more oxidized compared with other samples.Further analysis of the oxygen,nitrogen-containing(N-containing),and sulfur-containing(S-containing)functional groups in the four subcategories revealed higher organic molecular complexity.Comparison of the similarities and differences of the four samples revealed 22.8%ubiquitous formulas and 17.4%,11.1%,10.7%,and 6.3%unique formulas of GWC,KWC,SSC,and MWC DOM,respectively,suggesting a large proportion of ubiquitous DOM as well as unique,source-specific molecular signatures.The findings presented herein provide new insight into the molecular characterization of DOM derived from various composts and demonstrated the potential role of these different compounds for agricultural utilization.

Molecular signatures of soil-derived dissolved organic matter constrained by mineral weathering

Dissolved organic matter(DOM)in soils drives biogeochemical cycling and soil functions in different directions depending on its molecular signature.Notably,there is a distinct paucity of information concerning how the molecular signatures of soil DOM vary with different degrees of weathering across wide geographic scales.Herein,we resolved the DOM molecular signatures from 22 diverse Chinese reference soils and linked them with soil organic matter and weathering-related mineralogical properties.The mixed-effects models revealed that the yields of DOM were determined by soil organic carbon content,whereas the molecular signature of DOM was primarily constrained by the weathering-related dimension.The soil weathering index showed a positive effect on the lability and a negative effect on the aromaticity of DOM.Specifically,DOM in highly weathered acidic soils featured more amino sugars,carbohydrates,and aliphatics,as well as less O-rich polyphenols and condensed aromatics,thereby conferring a higher DOM biolability and lower DOM aromaticity.This study highlights the dominance of the weathering-related dimension in constraining the molecular signatures and potential functions of DOM in soils across a wide geographic scale.

好氧堆肥污泥农用后溶解性有机质释放特征

研究污泥农用后溶解有机质(DOM)的释放特征,有助于评价和预测土壤中共存污染物的环境行为和效应。以河南省洛阳市某污泥处理厂好氧堆肥后的市政污泥作为样本,利用扫描电子显微镜(SEM)、总有机碳分析仪、紫外-可见吸收光谱(UV-Vis)、凝胶渗透色谱(GPC)、三维荧光光谱(3D-EEM)、傅里叶变换红外光谱(FTIR)和核磁共振波谱(NMR)等表征技术,研究污泥农用后释放DOM的浓度、分子量、组成和结构等性质的演变特征。结果表明,污泥还田60 d内,释放的DOM微观形貌上存在较大变化,由致密块状物变为不规则松散物质;污泥农用后释放溶解性有机碳(DOC)量在4.25~6.22 mg·g^(-1)污泥范围,呈现先上升后稳步下降的趋势;释放过程中,污泥DOM的分子量和芳香性等性质也存在显著的变化:污泥DOM重均分子量由0.5 d时2674 g·mol^(-1)的逐渐升高为60 d的129026 g·mol^(-1);污泥还田后释放的DOM分子中芳香性物质逐渐积累;3D-EEM结合平行因子分析(PARAFAC)模型分析污泥释放DOM中的荧光物质,发现DOM中荧光物质主要为类富里酸和类腐殖质,释放过程中,类腐殖质逐渐积累,DOM整体上呈现腐殖化趋势;FTIR图谱表征污泥DOM脂肪族烷烃类物质的减少和芳香烃物质生成。污泥还田后释放DOM数量和性质变化,显著改变土壤中共存污染物环境行为和生态效应。该研究可为评估和预测污泥农用后产生的环境影响提供理论依据,也对市政污泥的资源化利用具有一定指导意义。

天然气净化厂废水处理过程中溶解性有机物的变化

溶解性有机物(DOM)是废水达标排放标准的重要考虑因素,综合分析废水中DOM的分子组成是对其高效去除的前提。以某天然气净化厂废水为研究对象,采用傅里叶变换离子回旋共振质谱法(FT-ICR MS)和三维荧光光谱(3D-EEMs)从分子层面深入分析氧化过程中DOM的荧光性质、分子组成、质荷比、分子转化。EEM结果表明,废水中主要以类腐殖质物质为主,其次为富里酸类物质。O_(3)/H_(2)O_(2)氧化降低了类腐殖质物质的荧光强度,但DOM降解受限于臭氧与富含电子有机物的反应特性;而O_(3)/H_(2)O_(2)-Fenton联合氧化能大幅降低总荧光强度,有效去除类腐殖质。FT-ICR MS结果表明,O_(3)/H_(2)O_(2)氧化去除了部分CHO类、CHON类DOM,但对CHOS类、CHONS类DOM的去除效果欠佳。多环芳烃和高度不饱和的化合物被臭氧降解为脂肪族类化合物,增加了CHO类DOM含氧量。O_(3)/H_(2)O_(2)-Fenton氧化对CHOS类、CHONS类DOM具有较好的去除效果,去除了大部分多酚化合物,生成具有含氧量更低和饱和度更高的DOM。同时,联合氧化极大地缓解了超滤膜污染,去除了大部分可逆污染和不可逆污染。

亚铁活化过硫酸盐体系对水体溶解性有机质分子转化的影响

亚铁活化过硫酸盐(PS/Fe^(2+))高级氧化是修复有机污染水体的常用技术,在修复过程中会诱导水体中溶解性有机质(DOM)分子结构转变。为研究PS/Fe^(2+)体系中DOM的分子转化特性,选取腐殖酸(HA)、富里酸(FA)和天然有机质(NOM)3种不同种类的DOM为研究对象,利用光谱和高分辨率质谱对比分析了PS/Fe^(2+)反应前后DOM的理化特性和分子结构特征。结果表明:①与热或碱活化PS体系相比,PS/Fe^(2+)反应后DOM芳香度、分子数和分子量显著下降。②反应后,DOM中残留了含C、H和O的木质素和单宁类物质,去除了O/C<0.6的低氧化程度分子,生成了富含氮和硫的高氧化程度分子。③PS/Fe^(2+)体系去除了DOM中的不饱和态分子(49.3%~94.0%),生成饱和态物质的数量、类型因DOM种类表现出明显差异。研究显示,PS/Fe^(2+)体系在自由基氧化与络合作用的共同介导下显著增加了DOM的分子转化程度,进而可能影响共存污染物的环境行为。

多次低剂量应用草酸促进芹菜减磷生产

针对蔬菜作物生长期一次性低剂量应用草酸土壤磷素活化作用时效短和一次性高剂量应用草酸风险较大的缺点,选用多次低剂量灌溉应用草酸的方法,以期持续、安全地活化设施菜地土壤盈余磷素,推动设施蔬菜减磷生产。选用速效磷含量分别为88.6和46.1mg·kg^(−1)的两个设施菜地土壤(分别简称土壤A和土壤B)开展室内浅层土壤(深度为1 cm)培养试验、无植物和种植芹菜的盆栽土壤(深度17 cm)温室试验,探究多次低剂量应用草酸活化土壤磷素及促进芹菜生产效果。土壤培养试验揭示多次低剂量灌溉应用草酸(每次草酸应用0.36 g·kg^(−1),共5次,每次间隔10 d)均可以持续、平稳地提高土壤A和土壤B的水溶性无机磷(DIP)的含量。无植物的盆栽土壤试验则显示在土壤A中多次低剂量灌溉应用草酸的土壤磷素活化作用集中在0~10 cm土层,特别是0~5 cm土层。盆栽芹菜试验多次应用草酸(芹菜定植30 d应用草酸4次,每次0、0.18或者0.36 g·kg^(−1),每次间隔10 d)的结果显示,土壤A和土壤B施磷分别减量70%和54%的前提下,两个草酸应用剂量均提高芹菜收获时两个土壤0~5 cm土层的DIP含量,在土壤A中增幅显著(分别为92.0%和165%),在土壤B中仅较高草酸剂量下显著增加64.5%;较高草酸剂量的芹菜增产效果不明显,较低草酸剂量的增产效果显著(20.0%~33.6%,P<0.05),在土壤B中更为明显。多次低剂量灌溉应用草酸在其它土壤-蔬菜系统中的效果及风险有待研究。

Characterization of the dissolved organic matter in sewage effluent of sequence batch reactor： the impact of carbon source

Dissolved organic matter （DOM） transforma- tion in sequence batch reactor （SBR） fed with carbon sources of different biodegradability was investigated. During the biologic degradation process, the low mole- cular weight （MW） fraction （〈 1 kDa） gradually decreased, while the refractory compounds with higher aromaticity were aggregated. Size exclusion chromatogra- phy （SEC） and fluorescence of excitation emission matrices （EEM） demonstrated that more biopolymers （polysaccharides or proteins） and humic-like substances were presented in the extracellular polymeric substance （EPS） extracted from the SBR fed with sodium acetate or glucose, while the EPS from SBR fed with slowly biodegradable dissolved organic carbon （DOC） substrate- starch had relatively less biopolymers. Comparing the EfOM in sewage effluent of three SBRs, the effluent from SBR fed with starch is more aromatic. Organic carbon with MW 〉 1 kDa as well as the hydrophobic fraction in DOM gradually increased with the carbon sources changing from sodium acetate to glucose and starch. The DOC fractiona- tion and the EEM all demonstrated that EfOM from the effluent of the SBR fed with starch contained more fulvic acid-like substances comparing with the SBR fed with sodium acetate and glucose.

Effect of dissolved organic matter on mercury release from water body

Dissolved organic matter（DOM） plays an important role in the process of mercury release from water body.In this study,the influence of DOM from different sources（DOMR,DOMS and DOMH,extracted from rice straw,compost and humic soil respectively） on mercury reduction was investigated.The molecular weight distribution and chemical composition of DOM from each source were determined using ultrafiltration membrane technique and elemental analysis respectively.The result showed that mercury release from DOM-added samples was much lower than the control;the lowest mercury release flux was observed in the treatment of DOMH,25.02% of the control,followed by DOMS and DOMR,62.46% and 64.95% of the control,respectively.The higher saturation degree and lower molecular weight of DOMH was responsible for the highest inhibition degree on the mercury release.The link between DOMH,concentration and mercury flux was also estimated and the result showed that mercury flux was increased with DOMH at lower concentration,while decreased with DOMH at higher concentration.Different mechanism dominated the influence of DOM on mercury release with variation of DOM concentration.

Factors controlling N-nitrosodimethylamine （NDMA） formation from dissolved organic matter

The formation of cancinogenic nitrosamines, esp. N-nitrosodimethylamine （NDMA） in water and wastewater treatment plants has drawn much attention in recent years. Dissolved organic matter from the transported Luan River water as water source of Tianjin was fractionated with different XAD resins and a series of ultra-filtration membranes with molecular weight （MW） cut-offs of 5k Da, 3k Da, and lk Da, respectively. The NDMA yields from the raw water and each fraction were measured to investigate their role in NDMA yield. Results indicated that the hydrophilic fraction had a higher NDMA yield than those of hydrophobic fraction and transphilic fraction. The fraction with MW below lk Da had a higher NDMA yield than that with larger MW. NDMA formation increased as the dissolved organic carbon （DOC） to dissolved organic nitrogen （DON） ratio decreased, which indicated that DON might serve as the real important precursor for NDMA. The correlation between NDMA yield and specific ultraviolet absorbance at 254nm （SUVA254） suggested that the latter might not represent the specific precursors for NDMA in the water. Besides the water quality, the influences of pH, disinfectant dosage, and disinfection contact time on the formation of NDMA were also examined. These results will help water treatment plants establish measures to control this harmful disinfection by-product.

蘑菇渣和稻秸堆肥中不同分子量水溶性有机物含量分布和光谱特征

分子量(MW)是影响堆肥溶解性有机物(DOM)化学性质和环境行为等的重要因素,目前关于堆肥DOM的MW分布等认识仍不清晰。以蘑菇渣堆肥(MRC)和水稻秸秆堆肥(RSC)中DOM为研究对象,采用超滤分级技术对堆肥DOM中不同MW组分进行分级定量和化学表征,进而探究不同堆肥DOM中MW组分的分布和光谱特征。DOC结果显示,MRC和RSC中DOM均以>10 kDa的高分子量(HMW)组分组成为主,分别富集有80%和71%的DOC(溶解性有机碳),而中等分子量(5~10 kDa,MMW)和低分子量(<5 kDa,LMW)组分分别占总DOC的12%~15%和9%~15%,表明HMW是决定腐熟堆肥DOM的化学组成和分子结构的关键物质。光谱特征参数(如SUVA_(254)、E_(2)/E_(3)和HIX)结果显示,不同MW的DOM的芳香化程度和腐殖化程度均呈现相同的趋势,即HMW>MMW>LMW;而BIX和FI值则呈现与之相反的分布规律。结果表明堆肥DOM中HMW(高分子组分)组分富集了较多的芳香环等不饱和共轭结构,而MMW和LMW组分具有更高的自生源贡献。三维荧光-平行因子分析结果显示,堆肥DOM及其MW组分主要由3种类腐殖质(C1—C3)和1种类蛋白质(C4)构成。其中,MRC和RSC中的HMW组分均以长波类腐殖酸(C3)组成为主,其含量分别占HMW组分总荧光强度的34%和85%;而两类堆肥中MMW和LMW组分则以类富里酸(C1,41%~53%)和短波类腐殖酸(C2,25%~36%)组成为主。红外光谱(FTIR)结果表明,堆肥DOM中HMW组分含有更多的疏水性苯环结构,而MMW和LMW组分则具有较多的亲水性含氧官能团(如羰基、羧基等)。研究结果促进了对堆肥DOM化学组成和分子结构的认识,为进一步评价堆肥腐熟和稳定化程度及其环境行为等提供了重要的数据参考。

Chemodiversity of soil dissolved organic matter affected by contrasting microplastics from different types of polymers

Chemodiversity of dissolved organic matter(DOM)is a crucial factor controlling soil nutrient availability,greenhouse gas emissions,and pollutant migration.Microplastics(MPs)are widespread pollutants in terrestrial ecosystems in many regions.However,the effects of MPs on DOM chemodiversity are not sufficiently understood,particularly under different types of polymers.Using UV-Vis spectroscopy,3D fluorescence spectroscopy,and Fourier-transform ion cyclotron resonance mass spectrometry,the effects of three prevalent MPs[polyethylene,polystyrene,and polyvinyl chloride(PVC)]on the chemical properties and composition of soil DOM were investigated via a 310-d soil incubation experiment.The results showed that MPs reduced the aromatic and hydrophobic soil DOM components by more than 20%,with PVC MPs having the greatest effect.Furthermore,as MP contents increase,the humification level of soil DOM significantly decreases.MPs increased DOM molecules with no heteroatom by 8.3%-14.0%,but decreased DOM molecules with nitrogen content by 17.0%-47.8%.This may be because MPs cause positive“priming effect,”resulting in the breakdown of bioavailable components in soil DOM.This is also related to MPs changing microbial richness and diversity and enriching microbial communities involved in lignin compositions degradation.In the presence of MPs,soil DOM chemodiversity depended on soil pH,electrical conductivity,dissolved organic carbon,soil organic matter,bacterial Shannon,and fungal Chao index.Specifically,DOM in MP-contaminated soils featured more lipids and less condensed aromatics and proteins/amino sugars,thereby conferring a lower DOM aromaticity and higher lability.