Parallel Factor Analysis Model Research Articles

A new approach to three-dimensional monitoring of surface changes in lakes: application of three-way data analysis model in Lake Burdur, Turkey.

Lakes are areas of ecological significance that host a wide range of living species. Therefore, monitoring changes in lake surfaces is critical for ecosystem preservation. Since conventional methods based on one-dimensional data analysis have limited capacity to analyze complex systems, they may not always produce the desired results in examining surface change. In this regard, a novel approach based on a three-way analysis model of a multi-temporal dataset was improved for the first time to monitor surface changes in Lake Burdur between 2014 and 2023 in terms of latitude, longitude, and year modes. The newly proposed approach, based on the deconvolution of a multi-temporal data series, provided a new way and an alternative approach with a three-dimensional perspective for the simultaneous prediction of changes in latitude, longitude, and relative quantity profiles of Lake Burdur between 2014 and 2023. The proposed approach is based on the parallel factor analysis (PARAFAC) modeling of the multi-temporal datasets. The change in the lake surface as water levels were monitored from latitudinal and longitudinal profiles was obtained by applying the PARAFAC model to the multi-temporal data array. In the same model, the change in lake water surface over the years was determined from the relative quantity profile. The results obtained from the three-way analysis model were compared with the results provided by the conventional method. It was concluded that the findings of this study could provide valuable information to researchers and policymakers in developing effective strategies to analyze changes in lake surfaces in future studies.

Determination of DEET, Icaridin, and IR3535 in insect repellents using excitation-emission matrix (EEM) fluorescence spectroscopy and multiway calibration

Due to rising temperatures in recent years, there has been an increase in outbreaks of arboviral diseases like Dengue, chikungunya, Zika, and yellow fever, which are primarily transmitted by two Aedes mosquitos. The outbreak has sparked significant concern among the population and prompted countries to heighten their precautions, specially by increasing the use of insects repellents. Regarding the regulatory demands of these products, this study develops a novel analytical method for the determination of DEET, Icaridin, and IR3535 in insect repellents combining excitation-emission matrix (EEM) fluorescence spectroscopy with higher-order multivariate calibration techniques. For this purpose, a dataset comprising 21 samples containing the studied active ingredients was used to construct Parallel Factor Analysis (PARAFAC) and Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) models. As a result, DEET, Icaridin, and IR3535 were quantified with a RMSEP lower than 1.84% for PARAFAC and below 11.30% for MCR-ALS. The EJCR test confirmed the accuracy of the proposed methods, which agreed with the high-performance liquid chromatography reference method at a 95% confidence level. These findings suggest that developing multiway calibration models using EEM proves to be accurate and cost-effective for quality control in repellent-based products.

Fluorescent EEM-PARAFAC considerations of Aldrich humic acid salt as an aquatic or terrestrial organic matter surrogate

The fluorescence of “long dead” terrestrially sourced organic carbon (Aldrich humic acid salt) was compared to “recently dead or excreted” aquatically sourced organic carbon (ornamental pond). This research eliminated the “living” (biologically active) category of organic carbon (by azide treatment and filtration) which prevented organic matter continuing to metabolize due to microbial activity during storage and analysis. The focus in this context is on the diagenetic (fulvic and humic) substances, which are considered the most recalcitrant organic carbon forms in water treatment. The purposes of this research were to investigate (a) what excitation-emission matrix (EEM) spectroscopy and PARAllel FACtor (PARAFAC) analysis (EEM-PARAFAC) modeling reveals about the limitations to the use of terrestrially derived Aldrich Humic Acid as an aquatic organic matter surrogate, (b) potential flaws observed in EEM spectra and incorrect PARAFAC component assignments gathered in contemporaneous studies, and (c) how EEM-PARAFAC modeling can be used to illustrate the continuum in organic matter aging or maturity. Additionally, to expand the analysis, data were compared to previously published PARAFAC models derived from other freshwater sources. An important result of this research was discovery of a PARAFAC component peak observed at the emission (EM) wavelength at 540 nm in Aldrich Humic Acid which has been rarely noted in the literature, and not previously recognized for its potential importance. This research implies that Aldrich humic acid should only be used as an aquatic surrogate with caution, and that it can be a surrogate for terrestrial soil or ore samples.

Spatial differences of dissolved organic matter composition and humification in an artificial lake.

The depth-dependent dynamics of dissolved organic matter (DOM) structure and humification in an artificial lake limits the understanding of lake eutrophication and carbon cycling. Using fluorescence regional integration (FRI) and parallel factor analysis (PARAFAC) models to analyze the 3D fluorescence spectroscopy dataset, we revealed the depth-dependent structure and vertical distribution of DOM in the estuarine and center regions of Lake Hongfeng. The percentage fluorescence response (Pi,n) showed humic acid is an important part of DOM in Lake Hongfeng. Fluorescence results show that the fulvic-like and protein-like materials in HF1-DOM located at the estuarine position showed greater variation in the middle stage, probably due to human influence and sediment suspension. Fluorescence index (PI+II+IV,n/PIII+V,n and FIC4/FIC3) can be used to indicate the degree of humification of DOM in artificial lakes. Results of each index show that the estuary is more affected by human activities, and the humification degree is significantly lower than that of the center of the lake. The evaluation index system of the humification degree of artificial lake established in this study can effectively predict the eutrophication state of the typical area of artificial lake and deeply understand the possible important influence of human activities on the carbon cycle of lake.

MacroPARAFAC for handling rowwise and cellwise outliers in incomplete multiway data

Multiway data extend two-way matrices into higher-dimensional tensors, often explored through dimensional reduction techniques. In this paper, we study the Parallel Factor Analysis (PARAFAC) model for handling multiway data, representing it more compactly through a concise set of loading matrices and scores. We assume that the data may be incomplete and could contain both rowwise and cellwise outliers, signifying cases that deviate from the majority and outlying cells dispersed throughout the data array. To address these challenges, we present a novel algorithm designed to robustly estimate both loadings and scores. Additionally, we introduce an enhanced outlier map to distinguish various patterns of outlying behavior. Through simulations and the analysis of fluorescence Excitation-Emission Matrix (EEM) data, we demonstrate the robustness of our approach. Our results underscore the effectiveness of diagnostic tools in identifying and interpreting unusual patterns within the data.

Molecular composition of Beijing PM2.5 Brown carbon associated with fluorescence revealed by gas chromatography time-of-flight mass spectrometry and parallel factor analysis

Brown carbon (BrC), the important component of carbonaceous aerosol, attracted much attention for its complex chemical composition which affect its light absorption, fluorescent properties, and atmospheric reactions. In this study, we revealed for the first time the molecular composition of non-polar/low-polar organic matters contributing to fluorescence of Beijing PM2.5 from 2016 to 2018. Firstly, excitation-emission matrix (EEM) spectra of the 122 PM2.5 samples were analyzed and supported by gas chromatography-time of flight mass spectrometry (GC-ToF-MS) and partial least squares regression model, 400 BrC molecules associated with fluorescence were screened out among which 44 were the newly ones. Secondly, six chromophores (C1–C6) were identified by applying parallel factor analysis (PARAFAC) model, which represented categories of compounds consistent with the ToF results. Then, the specific molecule composition of each chromophore was achieved by combining GC-ToF-MS and EEM-PARAFAC. For example, indeno[1,2,3-cd]pyrene is a new fluorescent molecule which contributed high in C3 (high oxygenated humic-like chromophore) and C5 (fluorescein chromophore). The results can, on one side, enrich the database of fluorescent molecular composition, which turns out to be similar as that of light-absorption; on the other side and more importantly, provide chemical characteristics of BrC fluorescent chromophores on the level of molecule.

Stemflow dissolved organic matter in mixed temperate forests: temporal and interspecific variation of optical indices and development of a stemflow-specific PARAFAC model

Stemflow is a conduit for the transport of canopy-derived dissolved organic matter (DOM) to the forest floor. This study examined the character of stemflow DOM for four tree species over four phenophases (leafless, emergence, leafed, and senescence for deciduous species and leafed-winter, emergence, leafed- spring/summer, and senescence for coniferous species) occurring in temperate forests; namely, Betula lenta L. (sweet birch), Fagus grandifolia Ehrh. (American beech), Liriodendron tulipifera L. (yellow poplar), and Pinus rigida Mill. (pitch pine). American beech exhibited the lowest average specific UV absorbance at 254 nm (SUVA254) values, while yellow poplar displayed the highest values. SUVA254 values were largest in senescence and smallest in emergence. The spectral slope ratio was lower for pitch pine than the deciduous tree species. Humification index (HIX) values decreased across all species during the emergence phenophase. The developed and validated stemflow-specific four-component parallel factor analysis (PARAFAC) model demonstrated the combined influence of interspecific and temporal fluctuations on the composition of humic and protein-like substances within stemflow. By separating and examining stemflow DOM independent of throughfall, our study provides fresh insights into the spatiotemporal dynamics of stemflow inputs to near-trunk soils that may inform hot spots and hot moments theories.

Assessing the spatiotemporal variability of dissolved organic matter fluorescence composition in the Lake George, NY watershed

Lake George (LG) is a temperate, oligotrophic, medium-sized lake (114 km2) located in northeastern New York State (U.S.). Lakes are highly understudied environments where extensive dissolved organic matter (DOM) processing occurs. With this study we establish the foundation for researching the organic biogeochemistry of the LG watershed, in particular, the numerous tributaries flowing into the lake. Collected were 213 samples from 64 tributaries and 12 lake locations. Some of the tributaries had unique wastewater, agricultural, or wetland influences. We employed fluorescence spectroscopy, a common biogeochemical technique, to characterize the fluorescent DOM (FDOM) component. We developed a parallel factor analysis (PARAFAC) model for the deconvolution of FDOM data allowing to depict six underlying FDOM constituents, which varied in source and biogeochemical reactivity on spatiotemporal scales. Tributary DOM, in comparison to lake DOM, was much more aromatic, of larger molecular weight, more humic, and contained less protein-like material. The distribution of humic and protein-like PARAFAC components was impacted by land-use and wastewater influences. Supporting characterization of the chromophoric DOM (CDOM) and total DOM (on dissolved organic carbon basis) allowed differentiating the influence of wetlands, which could not be depicted by spatiotemporally assessing the variability of PARAFAC components. Temporal assessment revealed minor variabilities in tributary DOM quantity and quality except in cases of point sources such as wastewater treatment facilities. Overall, this primer study establishes baseline understanding of the baseflow levels of DOM constituents in the LG watershed, and more broadly, presents a PARAFAC model for the deconvolution of fluorescence spectra of DOM from temperate and oligotrophic lake watersheds such as LG.

Linking Dissolved Organic Matter Composition to Landscape Properties in Wetlands Across the United States of America

AbstractWetlands are integral to the global carbon cycle, serving as both a source and a sink for organic carbon. Their potential for carbon storage will likely change in the coming decades in response to higher temperatures and variable precipitation patterns. We characterized the dissolved organic carbon (DOC) and dissolved organic matter (DOM) composition from 12 different wetland sites across the USA spanning gradients in climate, landcover, sampling depth, and hydroperiod for comparison to DOM in other inland waters. Using absorption spectroscopy, parallel factor analysis modeling, and ultra‐high resolution mass spectroscopy, we identified differences in DOM sourcing and processing by geographic site. Wetland DOM composition was driven primarily by differences in landcover where forested sites contained greater aromatic and oxygenated DOM content compared to grassland/herbaceous sites which were more aliphatic and enriched in N and S molecular formulae. Furthermore, surface and porewater DOM was also influenced by properties such as soil type, organic matter content, and precipitation. Surface water DOM was relatively enriched in oxygenated higher molecular weight formulae representing HUPHigh O/C compounds than porewaters, whose DOM composition suggests abiotic sulfurization from dissolved inorganic sulfide. Finally, we identified a group of persistent molecular formulae (3,489) present across all sites and sampling depths (i.e., the signature of wetland DOM) that are likely important for riverine‐to‐coastal DOM transport. As anthropogenic disturbances continue to impact temperate wetlands, this study highlights drivers of DOM composition fundamental for understanding how wetland organic carbon will change, and thus its role in biogeochemical cycling.

The deciphering of microplastics-derived fluorescent dissolved organic matter in urban lakes, canals, and rivers using parallel factor analysis modelingand mimic experiment.

The aim of the study is to investigate the leaching of fluorescent dissolved organic matter (fDOM) from microplastics. In addition, this study identifies the connection between fDOM and microplastics in the aquatic environment. Three-dimensional excitation-emission matrix identified five fluorophores, that is, peak A, M, T, Tuv, and Wuv, and the parallel factor analysis modeling identified five components, that is, tryptophan-like, p-hydroxy acetophenone, humic acid (C-like), detergent-like, and fulvic acid (M-like) in the urban surface water. Mimic experiments using commonly used synthetic plastic (like microplastics) in Mili-Q water under solar radiation and dark environments demonstrate the release of fDOM from plastic. Two fluorophore peaks were observed at Ex/Em = 250/302 nm and Ex/Em = 260/333 nm for the expanded polystyrene plastic polymer and one fluorophore peak at Ex/Em = 260/333 nm for the low-density polyethylene. Fluorophore and component intensity exhibited notable associations with microplastics in the aquatic environment. These findings indicated that the characteristics and dynamics of fDOM in urban surface water are influenced by microplastics. PRACTITIONER POINTS: Fluorescent dissolved organic matters were identified in urban surface waters. Expanded polystyrene (EPS) had shown two fluorophores at Em/Ex = 250/302 and Em/Ex = 260/333. Low-density polyethylene (LDPE) had one fluorophore at Em/Ex = 260/333. Fluorophore and component intensity in the aquatic settings exhibited associations with microplastics.

Geospatial Variability of Fluorescent Dissolved Organic Matter in Urban Watersheds: Relationships with Land Cover and Wastewater Infrastructure.

We investigated the fluorescent dissolved organic matter (FDOM) composition in two watersheds with variable land cover and wastewater infrastructure, including sanitary sewers and septic systems. A four-component parallel factor analysis model was constructed from 295 excitation-emission matrices recorded for stream samples to examine relationships between FDOM and geospatial parameters. The contributions of humic acid- and fulvic acid-like fluorescence components (e.g., C1, C2, C3) were fairly consistent across a 12 month period for the 27 sampling sites. In contrast, the protein-like fluorescence component (C4) and a related ratiometric wastewater indicator (C4/C3) exhibited high variability in urban tributaries, suggesting that some sites were impacted by leaking sewer infrastructure. Principal component analysis indicated that urban areas clustered with impervious surfaces and sanitary sewer density, and cross-covariance analysis identified strong positive correlations between C4, impervious surfaces, and sanitary sewer density at short lag distances. The presence of wastewater was confirmed by detection of sucralose (up to 1,660 ng L-1) and caffeine (up to 1,740 ng L-1). Our findings not only highlight the potential for C4 to serve as an indicator of nearby, compromised sanitary sewer infrastructure, but also suggest that geospatial data can be used to predict areas vulnerable to wastewater contamination.

Biochar and hydrochar application influence soil ammonia volatilization and the dissolved organic matter in salt-affected soils

Biochar, which including pyrochar (PBC) and hydrochar (HBC), has been tested as a soil enhancer to improve saline soils. However, the effects of PBC and HBC application on ammonia (NH3) volatilization and dissolved organic matter (DOM) in saline paddy soils are poorly understood. In this research, marsh moss-derived PBC and HBC biochar types were applied to paddy saline soils at 0.5 % (w/w) and 1.5 % (w/w) rates to assess their impact on soil NH3 volatilization and DOM using a soil column experiment. The results revealed that soil NH3 volatilization significantly increased by 56.1 % in the treatment with 1.5 % (w/w) HBC compared to the control without PBC or HBC. Conversely, PBC and the lower application rate of HBC led to decrease in NH3 volatilization ranging from 2.4 % to 12.1 %. Floodwater EC is a dominant factor in NH3 emission. Furthermore, the fluorescence intensities of the four fractions (all humic substances) were found to be significantly higher in the 1.5 % (w/w) HBC treatment applied compared to the other treatments, as indicated by parallel factor analysis modeling. This study highlights the potential for soil NH3 losses and DOM leaching in saline paddy soils due to the high application rate of HBC. These findings offer valuable insights into the effects of PBC and HBC on rice paddy saline soil ecosystems.

Development of dissolved organic matter-based indicators to understand the degradation of organic contaminants in reverse osmosis concentrate from potable reuse systems

Reverse osmosis (RO)-based treatment of municipal wastewater effluent allows for potable reuse, but this process generates reverse osmosis concentrate (ROC) that needs further treatment before disposal. This study investigated the application of UV-based advanced oxidation processes (AOPs) to degrade nine contaminants of emerging concern (CECs) from real ROC waste streams, using UV-only and UV-AOPs with hydrogen peroxide, free chlorine, and persulfate. Dissolved organic matter (DOM) in ROC was characterized using fluorescence excitation emission matrix data and analyzed by a four-component parallel factor (PARAFAC) analysis model. UV-only treatment showed considerable removal of CECs that displayed high values of quantum yields and molar absorption coefficients. UV-AOP treatment of ROC exhibited heavy scavenging of reactive species during CEC degradation. A probe-based approach established that hydroxyl radical was the dominant reactive species in all UV-AOPs. A kinetic analysis of PARAFAC components of DOM showed that the visible humic-like and protein-like components exhibited the higher reaction kinetics compared to UV humic-like and nutrient-like components. The strong linear correlation of protein-like component and seven of the nine CECs across multiple AOPs indicated that they have similar reactivity, enabling the establishment of chemical-reactivity based surrogates for prediction CEC fate in ROC wastes.

Compositional and optical characteristics of aqueous brown carbon and HULIS in the eastern Indo-Gangetic Plain using a coupled EEM PARAFAC, FT-IR and 1H NMR approach

This study provides insights into the fluorophoric composition of aqueous brown carbon (BrCaq) and chemically-separated humic-like substances (HULIS): neutral HULIS (HULIS-n; at pH = 7) and acidic HULIS (HULIS-a; at pH = 2) on a seasonal and day-night basis in the eastern Indo-Gangetic Plain (IGP), India. A coupled approach including excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC) model, Fourier-transformed infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy was employed to understand the links between structural, compositional and fluorophoric characteristics of BrCaq and HULIS fractions. HULIS fluorophores (HULISfluoro) with varying oxidation states transported from the northwest IGP were dominant during biomass burning seasons (post-monsoon and winter), while protein-like fluorophores (PRLISfluoro) from marine emissions showed large contributions during summer. HULIS-n moieties were mostly primary in nature with higher conjugation, while HULIS-a were associated with secondarily formed and aged species with a larger contribution from degradation products. A substantial presence of tyrosine-like proteins in both chemically-separated HULIS fractions indicated that atmospheric HULIS is not entirely humic or fulvic-like in the eastern IGP. Finally, the dominance of H-C-O groups across seasons suggested consistent fossil fuel signatures along with season-specific influence of photodegradable cellulose from marine organisms in the summer and biomass burning in the post-monsoon and winter.

Monitoring ascorbic acid oxidation with H2O2 and analyzing the food supplement product using parallel factor analysis model of kinetic UV absorption measurements

Ascorbic acid is a functional compound in maintaining the physiological processes of humans who acquire it from dietary sources, and also functions as an antioxidant. Therefore, the quantitation, and degradation of ascorbic acid in the food matrix and its interaction with coexisting components is a very important issue in terms of food safety and human health. Classical analytical methods may not give the expected results in the analysis of more advanced and complex food products obtained with the developing production technology. In this perspective, the parallel factor analysis (PARAFAC) model using kinetic UV absorption measurements was improved for the co-estimation of the kinetics and quantification of ascorbic acid in a food supplement product, which is a commercial effervescent preparation without requiring a prior separation step. The proposed three-way analysis strategy was validated and applied to the analysis of the relevant samples. For example, in the test samples, percent recovery and relative standard deviation were found to be 99.4 % and 1.36 %, respectively. The proposed chemometric strategy would be an alternative approach with a good selectivity for estimating the kinetics and quantification of ascorbic acid in a commercial supplementary product. The assay results of the PARAFAC model was checked by using ultra-performance liquid chromatography (UPLC).

Driving mechanism of water replenishment on DOM composition and eutrophic status changes of lake in arid and semi-arid regions of loess area

Water replenishment can be a key factor in driving lake eutrophication status. In arid and semi-arid regions of China, water replenishment for a lake has been widely carried out for not only improving water environmental quality, but also maintaining ecological system function. However, it is still unclear in terms of mechanism by which water replenishment drives lake eutrophication status. In this study, fluorescence excitation-emission matrix spectroscopy (EEMs) combined with multiple statistical analysis models (including parallel factor analysis, correlation analysis, redundancy analysis, and partial least squares structural equation modeling) was utilized to reveal potential driving mechanism and causality between water replenishment, dissolved organic matter (DOM) fractions and eutrophic status of Lake Shahu in China. Based on variations of DOM fractions, fulvic-like substances could be accumulated during the replenishment period, while nutrients carried along the replenishment might conduce to increase microbial activities during the non-replenishment period. This should be contributed to an alteration of prominent component from fulvic-like substances to tyrosine-like substances during the replenishment period to non-replenishment period. According to partial least squares structural equation modeling, two potential indirect paths were finally revealed, i.e., water replenishment derived the eutrophic status of Lake Shahu: water replenishment → microbial activity → algae → eutrophication, and water replenishment → microbial activity → eutrophication. This supposed that the water replenishment should indirectly drive the algae and eutrophication of the lake by promoting the transformation of DOM fractions. In addition, natural conditions could indirectly contribute to the eutrophication of the lake through impacting the algae growth. These findings should be conducive to trace the alteration of DOM fractions in lakes by water replenishment and in recognizing potential driving mechanisms of water replenishment on eutrophication of lakes by changing DOM fractions. This could provide basic theoretical support for policymakers to regulate and treat the eutrophication of lakes.

Effects of paddy irrigation-drainage system on water quality and productivity of small rivers in the Himi region of Toyama, Central Japan

The aim of this study was to clarify the impact of differences between historical and recently introduced irrigation and drainage management systems on water quality in the rivers around paddy fields. We investigated the seasonal variation in nutrients concentration and dissolved organic carbon (DOC) components in single- (used for intake only) and dual-purpose (used for both intake and drainage) channels during a 4-year period in the Himi region of Toyama, Central Japan. The system of dual-purpose channel has traditionally been used in the region of this study. A total of 197 three-dimensional excitation-emission matrix (3DEEM) fluorescence spectra of DOM in waters were applied for the parallel factor analysis (PARAFAC) modeling. Based on the 3DEEM and PARAFAC, the abundance of terrestrial humic-like components in the dual-purpose channel was significantly higher than that in the single-purpose channel. The even long-chain n-fatty acids derived associated with rice cropping in sediments of the dual-purpose channels were 22−30-fold higher than that of the single-purpose channel. In addition, the turbidity values of the river waters had significantly positive linear correlations with concentrations of K+, DOC, and humic-like components. These observations indicate that the dissolved nutrient concentrations in the river water were higher in the dual-purpose channel compared to those of the single-purpose channel, which may be supplied by leaching from the inflow of soil particles from the paddy fields. During the mid-irrigation period, the quantity of epiphytic chlorophyll a on artificial substrate tiles in the dual-purpose channel were 3.1–4.1-fold higher than that in the single-purpose channel. This study clear that the input of paddy drainage during the irrigation season significantly changes the DOC components in river waters and irrigation management is strongly linked to the primary production in agricultural channels. Therefore, it is important to consider the impact of the introduction of different irrigation and drainage management systems on water quality and productivity in order to maintain the riverine ecosystems around rice paddies, which are based on historical water use systems.

Exploring impacts of water-extractable organic matter on pre-ozonation followed by nanofiltration process: Insights from pH variations on DBPs formation

This study investigated the influence of pH (4–10) on the treatment of water-extractable organic matter (WEOM), and the associated disinfection by-products (DBPs) formation potential (FP), during the pre-ozonation/nanofiltration treatment process. At alkaline pH (9–10), a rapid decline in water flux (> 50 %) and higher membrane rejection was observed, as a consequence of the increased electrostatic repulsion forces between the membrane surface and organic species. Parallel factor analysis (PARAFAC) modeling and size exclusion chromatography (SEC) provides detailed insights into the WEOM compositional behavior at different pH levels. Ozonation at higher pH significantly reduced the apparent molecular weight (MW) of WEOM in the 4000–7000 Da range by transforming the large MW (humic-like) substances into small hydrophilic fractions. Fluorescence components C1 (humic-like) and C2 (fulvic-like) exhibited a predominant increase/decrease in concentration for all pH conditions during pre-ozonation and nanofiltration treatment process, however, the C3 (protein-like) component was found highly associated with the reversible and irreversible membrane foulants. The ratio C1/C2 provided a strong correlation with the formation of total trihalomethanes (THMs) (R2 = 0.9277) and total haloacetic acids (HAAs) (R2 = 0.5796). The formation potential of THMs increased, and HAAs decreased, with the increase of feed water pH. Ozonation markedly reduced the formation of THMs by up to 40 % at higher pH levels, but increased the formation of brominated-HAAs by shifting the formation potential of DBPs towards brominated precursors.

Semi-Blind Joint Channel and Symbol Estimation for IRS-Assisted MIMO Systems

Intelligent reflecting surface (IRS) is a promising technology for the <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$6^\mathrm{th}$</tex-math></inline-formula> generation of wireless systems, realizing the smart radio environment concept. This paper presents a novel tensor-based receiver for IRS-assisted multiple-input multipleoutput communications capable of jointly estimating the channels and the transmitted data streams in a semi-blind fashion. Assuming a fully passive IRS architecture and introducing a simple space-time coding scheme at the transmitter, the received signal model can be advantageously built using the PARATUCK tensor model, which can be seen as a hybrid of parallel factor analysis and Tucker models. A semi-blind receiver is derived by exploiting the algebraic structure of the PARATUCK tensor model. We first formulate a semi-blind receiver based on a trilinear alternating least squares method that iteratively estimates the two involved-IRS-base station and user terminal-IRS-communication channels and the transmitted symbol matrix. We discuss identifiability conditions that ensure the joint semi-blind recovery of the involved channel and symbol matrices and propose a joint design of the coding and IRS reflection matrices to optimize the receiver performance. We also formulate an enhanced two-stage semiblind receiver that efficiently exploits the direct link to refine the channel and symbol estimates iteratively. In particular, we discuss the impact of an imperfect IRS absorption (residual reflection) on the performance of the proposed receiver. Numerical results are proposed for performance evaluation in several system settings in terms of the normalized mean squared error of the estimated channels and the achieved symbol error rate, corroborating the merits of the proposed semi-blind receiver in comparison to competing methods.

Seasonal and diel modulation of DOM in a mangrove-dominated estuary.

Rivers and estuaries are the main links between continents and oceans. The Paraíba do Sul River is among the most important rivers of the southeastern Brazilian region, carrying an average of 0.08 Tg of dissolved organic matter (DOM) to the ocean but has been facing significant changes in river discharge. In this study, we aimed to provide insights into the sources and transformations of chromophoric dissolved organic matter (CDOM) and fluorescent dissolved organic matter (FDOM) sources across a salinity gradient under changing river discharge scenarios. Three spatial surveys were performed covering the entire salinity gradient of the main estuarine channel and surrounding mangrove waters under contrasting river discharge (178 to 1240 m3 s-1), and diel sampling was conducted in the mangrove tidal creek. The characterization of DOM through the parallel factor analysis (PARAFAC) model identified six components across the river-ocean gradient and mangrove creek: terrestrial origin (C1 - fulvic acid and C2 and C3 - humic-like), protein-like (C4), tryptophan-like (C5), and tyrosine-like (C6). Our results showed a shift in DOM composition and contribution along the salinity gradient, from terrestrial (C3) to autochthonous (C5 and C6) signatures. The October-17 dry campaign was characterized by a higher proportion of microbial protein-like component C4 and a lower contribution of humic-like components compared to February-17 and March-18 across the salinity gradient with an increase in the mixing zone. The DOM compositions of the February 17 dry and March 18 wet campaigns were similar. Additionally, the March-18 wet campaign, marked by the highest river discharge, showed higher inputs of terrestrial DOM (C1-C3 components) compared to February-17 in the estuary, which allowed DOM to be transported rather than transformed. The mangrove diel study showed that tidal fluctuations are also an important driver of carbon input to the mangrove creek with a possible impact on DOM composition in estuarine waters.