Emission Matrix-parallel Factor Analysis Research Articles

Evaluation of Groundwater Infiltration in Sewer Networks Using Fluorescence Spectroscopy

Diagnosing water infiltration is imperative to assess the integrity and operation performance of sewer networks, which is challenging and costly due to the complex nature of these networks. This study proposes a simple approach to evaluate the extent of groundwater infiltration via a fluorescence spectroscopy method, i.e., the identification and quantification of the fluorescent signature components of the dissolved organic matter sewage. A newly built sewer network in Shantou, Southern China, was selected for the case study, and a mass balance method based on water quality characteristic factors (total phosphorus and NH4+-N) was applied in parallel for comparison. The results showed that the mass balance method was substantially influenced by fluctuations in sewage and external water concentrations, rendering it unreliable due to the extensive data and calculations required. Conversely, three-dimensional excitation–emission matrix–parallel factor analysis enabled the identification of terrestrial humus compounds as the signatures of underground water sources. The estimation indicates that the groundwater proportion across the four surveyed inspection wells along the pipeline network ranged from 10.8 ± 2.5% to 9.6 ± 3.5%, conforming to the allowable groundwater infiltration limits set for municipal sewage pipelines (10–15%). This study presents a simple method for the in-depth analysis of groundwater infiltration in urban sewage networks, providing valuable insights into maintaining water quality and network integrity.

Air nanobubble water improves plant uptake and tolerance toward cadmium in phytoremediation

Heavy metal contamination continues to be a persistent environmental problem. To address this issue, this study evaluated the impact of air nanobubbles (NBs) in water on the uptake of heavy metals by Alternanthera philoxeroides (A. philoxeroides), a common aquatic plant in China known for its rapid growth, strong vitality, and high capacity for heavy metal remediation. This study found that diluted air NBs (25% concentration) boosted cadmium uptake of A. philoxeroides by 17.39%. They also enhanced plant growth (25–50%) and photosynthetic pigments (10–20%) even at low cadmium levels (0.1 mM). Furthermore, the incorporation of 25% air NBs has been demonstrated to significantly amplify the performance of key antioxidant enzymes, such as superoxide dismutase and catalase, alongside heightened levels of crucial antioxidants such as malondialdehyde. This heightened activity of antioxidant defenses offers a compelling explanation for the potential amelioration of cadmium toxicity and concurrent enhancements in overall plant growth rates. Notably, a comprehensive analysis utilizing the excitation emission matrix–parallel factor analysis (EEM-PARAFAC) technique has revealed alterations in the composition of rhizosphere dissolved organic matter due to the presence of NBs. This ncomposition change of the rhizosphere dissolved organic mattermposition has subsequently exerted an influence on plant complexation processes and the subsequent uptake of cadmium. This study demonstrates that the strategic implementation of air NBs in water systems holds the potential to significantly enhance the plant's ability to detoxify cadmium and improve the uptake of heavy metals during phytoremediation processes.

Effects of organic additives on spectroscopic and molecular-level features of photo-induced dissolved organic matter from microplastics

The environmental occurrence and impact of dissolved organic matter leached from microplastics (MP-DOM) has been the subject of increased research interest. Commercial plastics, which typically contain additives, are subject to natural weathering processes and can eventually lose their additives. However, the effects of organic additives in commercial microplastics (MPs) on the release of MP-DOM under UV irradiation remain poorly understood. In this study, four polymer MPs (polyethylene; PE, polypropylene; PP, polystyrene; PS, polyvinylchloride; PVC) and four commercial MPs, including a PE zip bag, a PP facial mask, a PVC sheet, Styrofoam, were subjected to leaching under UV irradiation, and the MP-DOM was characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and fluorescence excitation emission matrix-parallel factor analysis (EEM-PARAFAC). Although UV light promoted the leaching of MP-DOM from both MP groups, the amount released was more pronounced for the polymer MPs than for the commercial MPs. The commercial MP-DOM was characterized by a prominent protein/phenol-like component (C1), while a humic-like component (C2) prevailed in the polymer MPs. FT-ICR-MS identified a higher number of unique molecular formulas for the commercial than for the polymer MP-DOM. The unique molecular formulas of commercial MP-DOM included known organic additives and other breakdown products, while the polymer MP-DOM featured more pronounced unsaturated carbon structures in its identified unique formulas. Several molecular-level parameters showed significant correlations with fluorescence properties, such as CHO formulas (%) with C1 and condensed aromatic structure (CAS-like, %) with C2, suggesting the potential application of fluorescent components as an optical descriptor for the complex molecular-level composition. This study also revealed the possible high environmental reactivity of both polymer MPs and fully weathered plastics due to the unsaturated structures generated in sunlit environments.

Pyrolysis temperature dependent effects of biochar on shifting fluorescence spectrum characteristics of soil dissolved organic matter under warming

Biochar generally shift the content and molecular composition of soil dissolved organic matter (DOM) which represent the reactive components and have essential roles in coupling elemental cycling in soil. However, it is not clear how the effects of biochar on soil DOM composition is shifted under warming. This causes a knowledge gap to fully understand the fate of SOM affected by biochar application in a warming climate. To fill this gap, we conducted a simulated climate warming incubation of soil to study the influence of biochar with different pyrolysis temperatures and feedstock types on soil DOM components composition. Three-dimensional fluorescence spectrum analysis combining excitation emission matrix-parallel factor analysis (EEM-PARAFAC), fluorescence region integral (FRI), UV–vis spectrometry, principal component analysis (PCA), clustering analysis, Pearson correlation and multi-factor analysis of variance on fluorescence parameters (including FRI on Region I-V, FI, HIX, BIX, H/P) and soil DOC and DON content were analyzed for this purpose. Results showed that biochar shifted soil DOM composition and enhanced soil humification, which was dominantly pyrolysis-temperature dependent. Biochar shifted the soil DOM components composition probably through mediating soil microbial processing rather than direct input of their pristine DOM, and the influence of biochar on soil microbial processing was pyrolysis-temperature dependent and highly affected by warming. Medium-temperature biochar was more efficient for enhancing soil humification, by accelerating the transformation of protein-like components into humic-like components. Soil DOM composition presented a rapid response to warming, and long-term incubation may eliminate the effects of warming on shifting soil DOM composition. By revealing the heterogeneous effects of biochar with different pyrolysis temperatures on fluorescence characteristics of soil DOM components, our study provides a hint for the essential role of biochar on enhancing soil humification, and also suggests a vulnerability of biochar for soil carbon sequestration under warming.

Release of adsorbed copper and carbon during Fe(Ⅱ) catalytic conversion of ferrihydrite-humic acid coprecipitation under acidic condition: Mechanism and properties

The mobility of copper (Cu) may be significantly impacted during the conversion of ferrihydrite-humic acid (Fh-HA) coprecipitates. However, the environmental behavior of the adsorbed Cu in Fh-HA coprecipitation and the kinetic process of organic carbon (C) during the Fe(Ⅱ)-catalyzed Fh-HA coprecipitates conversion remains unclear. In this study, a series of Fh-HA coprecipitates with various C/Fe molar ratios were synthesized. Furthermore, the effects of the Fe(Ⅱ) mediated Fh and Fh-HA conversion processes on Cu mobility and carbon release characteristics under acidic condition were investigated. The results show that the specific surface area of Fh-HA is reduced as compared to pure Fh, which impedes the conversion of Fe minerals and increases the release of Cu to the solution. The rate of conversion can be accelerated by increasing the Fe(II) concentration, resulting in the retention of Cu in the mineral structure. As compared to artificial HA, Elliott soil humic acid (ESHA) coprecipitated with Fh resulted in a reduced Cu release. According to results of the fluorescence excitation emission matrix-parallel factor analysis, the "release-resorption" process of carbon occurred during conversion and low molecular weight HA related to the biological activity was the main source of the released organic carbon. The major functional groups were C-O functional groups and phenolic hydroxyl groups, and Cu was involved in the formation of Fe-O-Cu after conversion. The findings of this study provide crucial information for comprehending the biogeochemical process of Cu associated with Fh and Fh-HA coprecipitates.

Spectral change of dissolved organic matter after extracted by solid-phase extraction and its feasibility in predicting the acute toxicity of polar organic pollutants in textile wastewater.

Spectroscopic parameters can be used as proxies to effectively trace the occurrence of organic trace contaminants, but their suitability for predicting the toxicity of discharged industrial wastewater with similar spectra is still unknown. In this study, the organic contaminants in treated textile wastewater were subdivided and extracted by four commonly-used solid-phase extraction (SPE) cartridges, and the resulting spectral change and toxicity of textile effluent were analyzed and compared. After SPE, the spectra of the percolates from the four cartridges showed obvious differences with respect to the substances causing the spectral changes and being more readily adsorbed by the WAX cartridges. Non-target screening results showed source differences in organic micropollutants, which were one of the main contributors leading to their spectral properties and spectral variations after SPE in the effluents. Two fluorescence parameters (C1 and humic-like) identified by the excitation emission matrix-parallel factor analysis (EEM-PARAFAC) were closely correlated to the toxicity endpoints for Scenedesmus obliquus (inhibition ratios of cell growth and Chlorophyll-a synthesis), which can be applied to quantitatively predict the change of toxicity effect caused by polar organic pollutants. The results would provide novel insights into the spectral feature analysis and toxicity prediction of the residual DOM in industrial wastewater.

Molecular compositions and optical properties of water-soluble brown carbon during the autumn and winter in Guangzhou, China

Brown carbon (BrC) has attracted increasing attention due to its significant effects on the atmospheric environment and climate. In this study, we investigated the seasonal variations of the optical and molecular properties of water-soluble BrC in Guangzhou and the key factors affecting its light absorption and fluorescence properties. The mass absorption efficiency at 365 nm (MAE365) indicated that water-soluble BrC had a stronger light absorption capacity in winter than in autumn. An excitation emission matrix-parallel factor analysis (EEM-PARAFAC) identified four fluorescent components (C1–C4) in the water-soluble organic compound (WSOC) fraction, of which the humic-like components (C1, C2, and C4) were the dominant fluorophores. More C1 and C4 components were detected in autumn WSOC, whereas more C3 component in winter WSOC, which was mainly due to the differences in the sources and oxidation processes of WSOC in different seasons. The molecular composition of WSOC also indicated significant seasonal variations as revealed by an electrospray ionization ultrahigh-resolution mass spectrometry (ESI-UHRMS) analysis. The autumn WSOC had a higher degree of oxidation, whereas the winter WSOC had a higher aromaticity. Furthermore, a principal component analysis (PCA) and the Pearson correlation coefficients indicated that the light absorption of water-soluble BrC over Guangzhou was mainly affected by their aromaticity and N-containing species, with aromatic CHO and CHON compounds being the most important chromophores. The fluorescent components C1 and C4 were characterized by a relatively high oxidation level, which may be more relevant to aged organic aerosols with a high aromaticity and oxidation. The fluorescent component C3 may be more relevant to the primary emission of organic aerosols or fresh organic aerosols with low oxidation, and some non-nitrogen-containing species also had associations with previously assigned protein-like components (C3).

Fluorescence Spectral Characteristics of Dissolved Organic Matter in Songhua Lake Sediment

Dissolved organic matter (DOM) has a significant impact on the main pollution indicators of the lake (e.g., COD), and sediment is the main source of pollution in the lake. Research on the fluorescence spectral characteristics of DOM in sediments is important to reveal the mechanism of lake pollution. In this study, sediments were collected from 20 sites in Songhua Lake. The DOM components in the sediment were analyzed using the excitation emission matrix-parallel factor analysis (EEM-PARAFAC) technique, and the properties of the sediment DOM were clarified via spectroscopy. Additionally, the relationship between DOM and eutrophication of the water column was explored. The results showed that four components were identified from the sediment DOM of Songhua Lake:humic-like C1 (330/415 nm), C2 (255/440 nm), C3 (365/470 nm), and protein-like C4 (280/355 nm). The high HIX and low BIX indicated that the source of sediment DOM was mainly terrestrial and included some biological sources. The spatial distribution of the fluorescence intensity of the four components was relatively similar, showing that the fluorescence intensity was higher in the upstream (S1-S7) than that in the downstream (S8-S20). The massive deposition of suspended particulate matter (SPM) carried by the three rivers (Huifa River, Songhua River, and Jiao River) was the main reason for this spatial distribution. Eutrophication status in the water column of Songhua Lake was similar to the fluorescence intensity distribution of sediment DOM. Meanwhile, there was a strong correlation between eutrophication level and sediment DOM fluorescence intensity in the downstream water column of Songhua Lake.

Relative contributions of different sources to DOM in Erhai Lake as revealed by PLS-PM

Dissolved organic matter (DOM) is a complex mixture of organic molecules that plays an important role in freshwater lake ecosystems. Excitation emission matrix–parallel factor analysis (EEM-PARAFAC) is an important tool for the identification and source analysis of DOM but is still inadequate for studying the differences and quantifying the contributions of different sources. Here, based on the maximum fluorescence intensities (Fmax) of the four fluorescent components (e.g., protein-like component C1, and the humic-like components C2, C3, C4) identified by EEM-PARAFAC, combined with large-scale data obtained from observations at Erhai Lake, we used partial least squares path modeling (PLS-PM) to improve the understanding of the migration and transformation mechanisms of DOM. The results showed that the phytoplankton and trophic state had greater impacts on DOM, while the impacts of sediment and inflow rivers were less significant. The results of the models that used nitrogen nutrients (N) and phosphorus nutrients (P) to separately indicate the trophic state suggested that the driving force of P on DOM was stronger than that of N in Erhai Lake. Among the four fluorescent components, the protein-like component with the largest relative proportion (41.98%) was mainly affected by phytoplankton, which was consistent with the autogenic characteristics obtained through spontaneous source index (BIX). The duality of the humic-like components was consistent with the duality of DOM through fluorescent index (FI). C3 had a higher sensitivity to the trophic state than the other components, and C2 received the greatest positive contribution from the rivers entering the lake. These results provide an improved insight into the influence of different sources on the behavior of DOM and demonstrate the potential of using PLS-PM to study the complex driving mechanism of aquatic biogeochemical parameters.

Insight into interactions of polystyrene microplastics with different types and compositions of dissolved organic matter

Microplastics (MPs), as newly emerging pollutants, may interact with dissolved organic matter (DOM) widely present in the environment after entering the environment, thereby influencing the migration and transformation of MPs. The interaction characteristics and mechanism between DOM and MPs are restricted by many factors, and the current mechanism remains unclear. Thus, we explored the combination of MP with different types and compositions of DOM (fulvic acid (FA) and humic acid (HA)). Adsorption experiments revealed that MP has high adsorption affinity for all four DOMs, particularly FA. Meanwhile, the affinity of MP-DOM was also examined using excitation–emission matrix (EEM) analyses and fluorescence quenching method (excitation emission matrix-parallel factor analysis (EEM-PARAFAC)). Aromatic substances and hydrophobic substances dominate all DOM samples. For all DOM types tested, the quenching curve varies considerably with the type and compositions of DOM. In addition, three fluorescent components exhibited significant fluorescence quenching over time. The interaction mechanism of MPs and DOM at the molecular level was further elucidated by utilizing two-dimensional (2D) Fourier transformation infrared (FTIR) correlation spectroscopy (COS) analysis, which revealed that the oxygen-containing functional group in MPs was the most preferred DOM binding structure. This work was facilitated to explore the environmental behavior of MPs and formation of secondary MPs under natural conditions.

典型冷暖季沉水植物凋落物分解特性及沉积物微生物群落变化

PDF HTML阅读 XML下载 导出引用 引用提醒 典型冷暖季沉水植物凋落物分解特性及沉积物微生物群落变化 DOI: 10.5846/stxb202106281715 作者: 作者单位: 作者简介: 通讯作者: 中图分类号: 基金项目: 国家水体污染控制与治理科技重大专项（2018ZX07110003）；国家自然科学基金项目（31670467） Decomposition characteristics of typical warm season and cold season submerged plant litters and change of microbial community in sediment Author: Affiliation: Fund Project: National Major Science and Technology Program-“Water Body Pollution Control and Remediation” (2018ZX07110003), National Natural Science Foundation of China (31670467) 摘要 | 图/表 | 访问统计 | 参考文献 | 相似文献 | 引证文献 | 资源附件 | 文章评论 摘要:为研究湿地沉水植物腐败分解对水体的污染状况，选择典型沉水植物金鱼藻（暖季植物）和菹草（冷季植物）进行了为期60 d的凋落物分解实验。结果表明金鱼藻和菹草凋落物分解规律相似，0-15 d快速分解，15-60 d缓慢分解，60 d凋落物失重率分别达到60.43%和66.72%。菹草的有机物释放量明显高于金鱼藻，N和P释放量相反，分解释放的N主要是NH+4-N和有机氮。三维荧光光谱（EEMs）结合平行因子分析法解析出一种类色氨酸物质C2和3种类腐殖质物质C1、C3、C4，易降解的类色氨酸有机物先增加后减少，难降解的类富里酸和类腐殖酸有机物逐渐增加。EEMs和四种组分的最大荧光强度百分比表明，溶解性有机物（DOM）在0-15 d以易降解有机物为主，15-60 d以难降解有机物为主。两种植物凋落物分解释放的DOM含量及特性不同，整体上呈低腐殖化特征，可能是水中难降解DOM的一个重要来源。植物凋落物的分解促进了沉积物中微生物的丰富度，降低了微生物的多样性；参与分解的主要微生物包括4 d时的Pseudomonas属（26%-35%）、15 d和30 d时的Malikia属（>8%）和Bacillus属（2.6%-9%），分解难降解有机物的微生物逐渐增加，如Flavobacterium属；沉积物中微生物群落结构的变化受营养物质可利用性变化的影响。分析发现植物凋落物分解对水质的影响具有阶段性，0-15 d，N和P释放量增加暂时导致了水质恶化；15-60 d，N和P释放量降低，难降解有机物含量逐渐增加，可能会加剧水体甚至是沉积物的腐殖化程度。因此，在植物衰亡期应及时打捞或者做好植物平衡收割管理，避免因植物大量腐败导致水质恶化。 Abstract:In order to study the pollution of submerged plant litter decomposition in wetland, a 60-days litter decomposition experiment was carried out with typical submerged plants, including Ceratophyllum demersum L. (warm season plant) and Potamogeton crispus L. (cold season plant). The results showed that decomposition process of both plant litters was similar, a fast decomposition from 0 to 15 d followed by slow decomposition from 15 to 60 d. The mass loss of plant litters on 60 d reached 60.43% and 66.72%, respectively. More organic matters were obviously released from Potamogeton crispus L. than those from Ceratophyllum demersum L., while nitrogen and phosphorus release was the opposite. The nitrogen released was mainly ammonia nitrogen and organic nitrogen. Excitation emission matrix parallel factor analysis identified four kinds of fluorescence components:tryptophan-like C2, and three kinds of humus-like C1, C3, C4. The easily biodegradable tryptophan-like organic matters increased first and then decreased, while the difficult biodegradable fulvic acid-like and humic acid-like organic matters increased gradually. Three-dimensional fluorescence spectra and the maximum fluorescence intensity percentages of the four components showed that dissolved organic matter (DOM) was dominated by easily degradable organic compounds during 0-15 d and by refractory organic compounds during 15-60 d. The contents and characteristics of DOM released during the decomposition of plant litters were different, showing a low humification feature on the whole, which may be an important endogenous source of difficult biodegradable DOM in water. The decomposition of plant litters improved the microbial richness and decreased the microbial diversity in sediments. The main microorganisms included Pseudomonas (26%-35%) at 4 d, Malikia (>8%) and Bacillus (2.6%-9%) at 15 d and 30 d for decomposition, while the microorganisms that decomposed the refractory organic matter increased gradually, such as Flavobacterium. Changes in microbial community structure in sediments were influenced by changes in the availability of nutrients. The results showed that the effects of plant litter decomposition on water quality were phased. The release nitrogen and phosphorus increased during 0-15 d, which led to the deterioration of water quality temporarily; during 15-60 d, nitrogen and phosphorus release decreased, while refractory organic matter content increased gradually, which may exacerbate the humification degree of water and even sediment. Therefore, in the decay period of plant litters, it is necessary to salvage plant litters in time or manage plant harvesting rationally to avoid the deterioration of water quality caused by plant litter decay. 参考文献 相似文献 引证文献

The Estimation of Chemical Oxygen Demand of Erhai Lake Basin and Its Links with DOM Fluorescent Components Using Machine Learning

Water quality estimation tools based on real-time monitoring are essential for the effective management of organic pollution in watersheds. This study aims to monitor changes in the levels of chemical oxygen demand (COD, CODMn) and dissolved organic matter (DOM) in Erhai Lake Basin, exploring their relationships and the ability of DOM to estimate COD and CODMn. Excitation emission matrix–parallel factor analysis (EEM–PARAFAC) of DOM identified protein-like component (C1) and humic-like components (C2, C3, C4). Combined with random forest (RF), maximum fluorescence intensity (Fmax) values of components were selected as estimation parameters to establish models. Results proved that the COD of rivers was more sensitive to the reduction in C1 and C2, while CODMn was more sensitive to C4. The DOM of Erhai Lake thrived by internal sources, and the relationship between COD, CODMn, and DOM of Erhai Lake was more complicated than rivers (inflow rivers of Erhai Lake). Models for rivers achieved good estimations, and by adding dissolved oxygen and water temperature, the estimation ability of COD models for Erhai Lake was significantly improved. This study demonstrates that DOM-based machine learning can be used as an alternative tool for real-time monitoring of organic pollution and deepening the understanding of the relationship between COD, CODMn, and DOM, and provide a scientific basis for water quality management.

The relationship between the molecular composition of dissolved organic matter and bioavailability of digestate during anaerobic digestion process: Characteristics, transformation and the key molecular interval

In this study, swine wastewater (SW) and cow wastewater (CW) were used for anaerobic digestion (AD). We found the bioavailability of dissolved organic matter (DOM) was affected by the molecular weight ranges and molecular composition during the AD process. The organic substance in the small molecular range (0–5 kDa) accumulated due to a larger molecular fraction (>10 kDa) degradation, which enhanced the bioavailability of the DOM. Moreover, based on the excitation emission matrix-parallel factor (EEM-PARAFAC) analysis, the protein-like component in 0–5 kDa molecular size and humic-like component over 5 kDa are significantly positively correlated with DOM bioavailability. This study indicated that increasing the hydrolysis of larger organic matter and humification degree of molecular weights>5 kDa are critical solutions to improving the bioavailability of DOM. These conclusions can help explain the molecular mechanisms of DOM transformation and the AD process of livestock wastewater.

The spectral characteristics of biochar-derived dissolved organic matter at different pyrolysis temperatures

Comprehensive assessment of the dissolved organic matter (DOM) released from biochar is essential because it affects the migration and transformation of pollutants. The pyrolysis temperature and feedstock are the main factors affecting the amount and structure of DOM released from biochar. In this study, biochar-derived DOM was produced from three feedstocks at five temperatures (200–600 °C), and the effects of the pyrolysis temperature and feedstock on its components were investigated using UV–vis, Synchronous fluorescence, excitation emission matrix-parallel factor (EEM-PARAFAC) analysis and Fourier transform infrared-two-dimensional-correlation spectroscopy (FTIR-2D-COS). It was found that the biochar-derived DOM contents of the fruit peel and dewatered sludge biochar gradually decreased with increasing pyrolysis temperature; however, the DOM content of fresh human manure biochar increased at 600 °C, and a higher DOM content was obtained at low temperatures. The SUVA254 and SUVA260 shown that most of the aromatic substances in the DOM existed in the hydrophobic fraction. Moreover, the DOM mainly contained humic acid-like substances and protein-like substances. As the pyrolysis temperature increased, the protein-like and humic acid substances exhibited opposite trends, with higher protein-like contents at high temperatures. In addition, based on the FTIR-2D-COS analysis, the variations in the functional groups of the DOM depended on the pyrolysis temperature and the type of feedstock. This study highlights the importance of combining multiple optical techniques to evaluate biochar-derived DOM and provides valuable information for biochar applications.

Treatment of iodine-containing water by the UV/NH2Cl process: Dissolved organic matters transformation, iodinated trihalomethane formation and toxicity variation

UV/NH2Cl process is becoming increasingly important for water treatment, while its impact on iodine-containing water remains unknown. In this study, the structure transformation of dissolved organic matters (DOMs), generation of iodinated trihalomethanes (I-THMs), and variation of acute toxicity were evaulated during the UV/NH2Cl treatment of iodine-containing water. The combination of exciation emission matrix-parallel factor analysis and two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy showed that fulvic-like fraction of DOM was more susceptible to UV/NH2Cl process and particularly iodo and polysaccharide groups gave the fastest resopnses. Consequently, UV fluence lower than 60 mJ/cm2 promoted the production of I-THMs, while excessive UV exhausted NH2Cl and reactive iodine species and subsequently reduced I-THM generation. Moreover, DOM concentration and source, NH2Cl dosage, and I− concentration had significant impacts on I-THM formation in the UV/NH2Cl process. Additionally, a positive correlation was found between acute toxicity variation and I-THM formation when treating iodine-containing waters with UV/NH2Cl. These results together provide a comprehensive understanding on UV/NH2Cl treatment of iodine-containing water.

Correlating the chemical properties and bioavailability of dissolved organic matter released from hydrochar of walnut shells

Large amounts of lignocellulosic biomass are discarded, whereas the carbon source of sewage is deficient. This situation greatly impairs the efficiency of wastewater treatment. To address this concern, we evaluate the feasibility of using hydrochar as a potential carbon source by systematically investigating the effects of hydrothermal carbonization (HTC) conditions on the composition, content, and chemical structure of dissolved organic matter (DOM) released from hydrochar. Results show that the most important factor that affects the properties of hydrochar and DOM is temperature, followed by heating rate. Under optimal HTC conditions, the growth of Bacillus subtilis increased by 18.32% in hydrochar aqueous solution in comparison with the 6.64% growth of the untreated biomass group. Excitation emission matrix–parallel factor analysis and UV–vis analyses confirm that the DOM released by hydrochar produced at a low temperature mainly contains protein substances, which promote the growth of microorganisms. The DOM released by hydrochar at a high temperature mainly contains humic substances with an aromatic structure; such substances are toxic to microorganisms. This study demonstrates that hydrochar obtained under optimized conditions can be a potential carbon source of wastewater treatment plants.

Applying EEM- PARAFAC Analysis With Quantitative Real-Time PCR to Monitor Methanogenic Activity of High-Solid Anaerobic Digestion of Rice Straw.

The methanogenic activity is an important indicator to assess the efficiency of high-solid anaerobic digestion. However, it is not yet elucidated clearly how to detect the parameter rapidly and reliably in the rice straw feeding reactor. Co-inoculated with ruminal digesta and anaerobic sludge, the digestion performance was studied at three different organic loading rates (OLRs). The excitation emission matrix–parallel factor analysis (EEM–PARAFAC) was used to detect dynamic changes in the characteristic of fluorescence components. Our results revealed that CH4 productivity reached 280.90 mL/g volatile solid (VS) with a 54.39% CH4 content under the OLR of 2.26 g/(L⋅d), which amount to 80.29% of its theoretical value. At the OLR of 2.47 g/(L⋅d), the average accumulated NH4+ concentration was 1082.63 mg/L, which resulted in the hydrogenotrophic Methanobacteriales decreasing from 1.70 × 109 to 1.04 × 106 copies/g in the solid residues, whereas the acetotrophic Methanosarcinales increased from 7.89 × 106 to 9.44 × 106 copies/g. The dynamics of the methanogenic community consequently influenced the bioconversion efficiency of rice straw, and CH4 productivity was reduced to 256.54 mL/g VS. The three fluorescent components, at the excitation/emission wavelength of 420 nm/470 nm, 340 nm/430 nm, and 280 nm/340 nm, were decomposed by PARAFAC model in the digestate. Fluorescence intensities of coenzyme F420 and NADH reflected the dynamic changes of CH4-producing activity and anaerobic digestion efficiency, respectively. The coenzyme F420, unique to hydrogenotrophic methanogens, was correlated with methane yield, suggesting they played a dominant role in the anaerobic reactor. This study demonstrates that the EEM–PARAFAC combined with Q-PCR can be used to characterize methanogenic activity variation during the high-solid anaerobic digestion of rice straw with 15% total solid (TS).

EEM–PARAFAC characterization of dissolved organic matter and its relationship with disinfection by-products formation potential in drinking water sources of northeastern China

Dissolved organic matter (DOM) is the precursor of disinfection by-products (DBPs) which is widely found in the aquatic environment. The analysis of DOM in raw water is helpful to evaluate the formation potentials of DBPs. However, there is relatively little research on the DOM identification of raw water in northern China. In this study, the variation in DOM in M reservoir water in one year by fluorescence excitation–emission matrix-parallel factor analysis (EEM–PARAFAC) was investigated to evaluate the DBP formation potential (DBPFP). The results suggested that five components, namely, two humic-like substances (C2, C3), two fulvic-like substances (C1, C4) and one protein-like substance (C5), were identified in the DOM of M reservoir water. The content of DOM in autumn and winter was higher than that in spring and summer. The source of DOM in the water body of M reservoir was mainly from terrestrial source, but less from aquatic source. The source, types and humification degree of DOM affect the formation of DBPs. The formation potential of DBPs had the following order: trihalomethanes (THMs) > dichloroacetic acid (TCAA) > trichloroacetic acid (DCAA) > chloral hydrate (CH). The formation potentials of THM and TCAA were strongly correlated with C2 (rTHM = 0.805, rTCAA = 0.857). The formation potential of CH has a good correlation with C1 (r = 0.722). The formation of DCAA has a good correlation with C4 (r = 0.787). DOM and DBPFP were negatively correlated with the biological index (BIX) and fluorescence index (FI) of the raw water, and positively correlated with the humification index (HIX).

Copper-binding properties of microplastic-derived dissolved organic matter revealed by fluorescence spectroscopy and two-dimensional correlation spectroscopy

Despite numerous studies on microplastics (MPs), little attention has been paid to the dissolved organic substances leached from MPs and their environmental fate. In this study, we explored the copper-binding characteristics of MP-derived dissolved organic matter (MP-DOM) leached from several MP types, including commercial polypropylene, polyvinylchloride, and expanded polystyrene, under dark and UV irradiation conditions. The copper-binding affinity of MP-DOM was examined using fluorescence quenching method based on different fluorophores identified via the excitation emission matrix-parallel factor analysis (EEM-PARAFAC). The heterogeneous distribution of binding sites across the functional groups of MP-DOM was further elucidated by utilizing two-dimensional correlation spectroscopy (2D-COS) based on Fourier transform infrared spectroscopy (FTIR). Phenol/protein-like fluorescence prevailed in all MP-DOM samples, whereas humic-like fluorescence was more pronounced in the irradiated MP-DOM. For all tested plastic types, two plastic-derived fluorescent components (C2 and C3) exhibited substantial fluorescence quenching with increasing copper concentrations. The calculated stability constants showed larger differences between the two leaching conditions than between the three MP types with higher log KM values for the UV-irradiated (4.08–5.36) than dark-treated MP-DOM (1.05–3.60). The binding constants were comparable to those of natural organic matter with aquatic/terrestrial origins. The 2D-COS results further revealed that the oxygen-containing structures in MP-DOM generated by UV irradiation might be responsible for the higher binding affinity of the irradiated MP-DOM. This is the first study demonstrating the environmental reactivity of MP-DOM towards metal binding, highlighting the importance of leaching conditions for the metal-binding behavior of MP-DOM.

High cadmium pollution from sediments in a eutrophic lake caused by dissolved organic matter complexation and reduction of manganese oxide

Eutrophication and metal pollution are global environmental problems. The risk of metal pollution is high in the eutrophic lakes because of high mobility of metal in sediments. However, the mechanism of cadmium (Cd) mobility in sediments is still unclear. Here we study the mobilization of Cd in sediments from the eutrophic Lake Taihu via monthly field monitoring of mobile Cd using diffusive gradient in thin films (DGT) and high resolution dialysis (HR-Peeper) techniques. We found a high mobility of Cd in sediments in February and March, resulting from reductive dissolution of Mn oxide mediation by high microbial activities, as shown by the similarities in distribution patterns of DGT-labile Cd and Mn. A two orders of magnitude increase in dissolved Cd concentrations (about 28 μg L−1) was observed in May and June, with dissolved Cd concentrations in overlying water about 110 times higher than the criteria continuous concentration set by Environmental Protection Agency. Hourly changes were found to coincide and correlate between dissolved Cd and dissolved organic matter (DOM) under simulated anaerobic conditions, strongly suggesting that the sudden outbreak of Cd pollution observed in the field resulted from the complexation of DOM with Cd in sediments. This was further supported by the NICA-Donnan model that more than 71% of dissolved Cd in the pore water in May and June was present as Cd-DOM complexes. Three components of DOM including humic-, tryptophan-, and tyrosine-like components in the sediments in June was identified using the fluorescence excitation emission matrix-parallel factor analysis. We found that Cd was stable complexed with tyrosine-like component. The Fourier transform infrared and two-dimensional correlation spectroscopy further revealed that Cd was bound to phenolic OH, alkene CC, alcoholic CO, aromatic CH, and alkene CH groups. Our study effectively promotes the understanding of Cd mobilization in sediments and highlights the risk of sudden Cd pollution events in the eutrophic lakes.