Parallel Factor Research Articles

Effects of mineral adsorption on the molecular composition of soil dissolved organic matter: Evidence from spectral analyses

The adsorption of soil dissolved organic matter (DOM) by minerals is crucial for long-term carbon storage and has been extensively studied. However, the variations in soil DOM composition resulting from adsorption by different minerals have rarely been investigated from a spectral perspective. This study examined the impact of non‑iron (kaolinite) and iron-bearing (ferrihydrite) minerals on the concentration and characteristics of DOM from dark brown soil during a 60-h-long incubation experiment. Soil dissolved organic carbon was removed more efficiently by ferrihydrite (66.2 %) than by kaolinite (14.8 %). UV–Vis spectroscopic analysis indicated that DOM with high aromaticity and molecular weight exhibited a strong affinity for both ferrihydrite and kaolinite. The fluorescence of soil DOM decreased in the ferrihydrite treatment, with a notable reduction in humic-like fluorescent components identified through fluorescent excitation-emission matrix coupled parallel factor analysis. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy revealed that carboxyl groups were critical in DOM adsorption on ferrihydrite, participating in ligand exchange, hydrogen bonding, and electrostatic attraction. This study highlights the important role of iron-bearing minerals in soil carbon sequestration and demonstrates how different mineral alter soil DOM composition, potentially influencing the cycling of organic carbon in terrestrial systems.

Land Use Cover and Flow Condition Affect the Spatial Distribution Characteristics of Fluorescent Dissolved Organic Matter in the Yongding River

Dissolved organic matter (DOM) is involved in many biogeochemical processes and plays an important role in aquatic ecosystems. This study integrated three-dimensional fluorescence excitation–emission matrix (EEM), fluorescence regional integration (FRI), and parallel factor analysis (PARAFAC) to better understand the distribution and component characteristics of DOM in the Yongding River and explore the response of DOM to natural and anthropogenic activities. The results showed that the relative abundance of fulvic-like materials of DOM in the river was the highest, with an average of 68.64%. PARAFAC identified three fluorescent components, namely, C1 (microbial humic-like components), C2 (terrestrial humic-like components), and C3 (protein-like components), and their changes with flow confirmed that the riverine DOM was generally influenced by microbial sources and terrestrial inputs. The upper reaches showed strong autochthonous characteristics and a high humification degree of DOM due to a fast flow rate, while the middle reaches showed biological or aquatic bacterial origin due to a moderate flow rate. The lower reaches of the river showed characteristics of biological and bacterial origin, most strongly influenced by human activities. The findings can help provide a basis for identifying DOM characteristics in the Yongding River basin and understanding the geochemical cycle of DOM at a regional scale.

A novel-approach for identifying sources of fluvial DOM using fluorescence spectroscopy and machine learning model

Rivers are well known as one of the most threatened aquatic environments, whose structure and water quality can be deeply impacted by intensive anthropogenic activities. Despite the fact that anthropogenic influences on river ecosystems could indeed be deduced from the composition and chemistry of fluvial dissolved organic matter (DOM), sources of anthropogenic loading to DOM are still poorly explored. Here, by uniting fluorescence excitation-emission matrices (EEM) and principal component absolute coefficient, four sources of DOM from seventeen rivers in major drainage basins of China could be identified, i.e., originating from municipal sewage, domestic wastewater, livestock wastewater, and natural origins, and thus being defined as MS-DOM, DW-DOM, LW-DOM, NO-DOM, respectively. Based on the random forest model, special nodes in EEM could be traced from four sources, respectively. According to parallel factor analysis, DOM mainly contained protein-like, microbial humic-like, and fulvic-like fluorescence substances, among which protein-like was dominant in MS-DOM and DW-DOM, microbial humic-like in LW-DOM, and fulvic-like in NO-DOM. Based on key peaks and essential nodes in EEM, the identifying source indices were first proposed, which could be introduced to simply distinguish the different anthropogenic-derived sources of fluvial DOM. It was associated with intensity ratios of the key peaks and the essential nodes of EEM spectra from four sources, i.e., municipal sewage (MS-SI: Ex/Em = 280/(335, 410) nm), domestic wastewater (DW-SI: Ex/Em = 280/(340, 410) nm), livestock wastewater (LW-SI: Ex/Em = 235/(345, 380) nm), and natural origins (NO-SI: Ex/Em = 260/(380, 430) nm). By statistical analysis, the high identifying source indices of municipal sewage (>0.5) and natural origins (>0.4) values could be related to MS-DOM and NO-DOM, respectively. The identifying source indices of domestic wastewater with 0.1–0.3 might be linked to DW-DOM and the identifying source indices of livestock wastewater with 0.3–0.4 to LW-DOM. Compared with conventional optical indices, the novel identifying source indices showed remarkable discrimination for the sources of fluvial DOM with different forms of anthropogenic disturbances. Hence the innovative approach could be relatively convenient and accurate to evaluate water quality or pollution risk in river ecosystems.

Investigating the interaction of uranium(VI) with diatoms and their bacterial community: A microscopic and spectroscopic study

Diatoms and bacteria play a vital role in investigating the ecological effects of heavy metals in the environment. Despite separate studies on metal interactions with diatoms and bacteria, there is a significant gap in research regarding heavy metal interactions within a diatom-bacterium system, which closely mirrors natural conditions. In this study, we aim to address this gap by examining the interaction of uranium(VI) (U(VI)) with Achnanthidium saprophilum freshwater diatoms and their natural bacterial community, primarily consisting of four successfully isolated bacterial strains (Acidovorax facilis, Agrobacterium fabrum, Brevundimonas mediterranea, and Pseudomonas peli) from the diatom culture. Uranium (U) bio-association experiments were performed both on the xenic A. saprophilum culture and on the four bacterial isolates. Scanning electron microscopy and transmission electron microscopy coupled with spectrum imaging analysis based on energy-dispersive X-ray spectroscopy revealed a clear co-localization of U and phosphorus both on the surface and inside A. saprophilum diatoms and the associated bacterial cells. Time-resolved laser-induced fluorescence spectroscopy with parallel factor analysis identified similar U(VI) binding motifs both on A. saprophilum diatoms and the four bacterial isolates. This is the first work providing valuable microscopic and spectroscopic data on U localization and speciation within a diatom-bacterium system, demonstrating the contribution of the co-occurring bacteria to the overall interaction with U, a factor non-negligible for future modeling and assessment of radiological effects on living microorganisms.

Probabilistic PARAFAC2.

The Parallel Factor Analysis 2 (PARAFAC2) is a multimodal factor analysis model suitable for analyzing multi-way data when one of the modes has incomparable observation units, for example, because of differences in signal sampling or batch sizes. A fully probabilistic treatment of the PARAFAC2 is desirable to improve robustness to noise and provide a principled approach for determining the number of factors, but challenging because direct model fitting requires that factor loadings be decomposed into a shared matrix specifying how the components are consistently co-expressed across samples and sample-specific orthogonality-constrained component profiles. We develop two probabilistic formulations of the PARAFAC2 model along with variational Bayesian procedures for inference: In the first approach, the mean values of the factor loadings are orthogonal leading to closed form variational updates, and in the second, the factor loadings themselves are orthogonal using a matrix Von Mises-Fisher distribution. We contrast our probabilistic formulations to the conventional direct fitting algorithm based on maximum likelihood on synthetic data and real fluorescence spectroscopy and gas chromatography-mass spectrometry data showing that the probabilistic formulations are more robust to noise and model order misspecification. The probabilistic PARAFAC2, thus, forms a promising framework for modeling multi-way data accounting for uncertainty.

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.

Variations in fluorescence properties of humic acids from calcareous soils amended with different swine manures in a long-term soil experiment.

Molecular properties of soil humic acid (HA) can play an important role in the mechanisms regulating plant nutrient availability. This study explores how the structure of HA is altered by long-term treatment with different forms of swine manure and how these changes may influence nutrient availability. Liquid swine manure (LSM), solid swine manure (SSM), and swine manure compost (SMC) were applied to a calcareous soil over 17 years in a long-term soil fertility study. HA was extracted from site soil samples and analyzed using fluorescence spectroscopic techniques, including a Cu2+ quenching experiment, in order to assess differences in the structure and functionality of the soil organic matter (SOM) resulting from these different treatments. Emission spectra of the SSM-HA and SMC-HA are similar, while the LSM-HA is distinct. Procedures such as parallel factor analysis (PARAFAC) decomposition of emission-excitation matrices showed that structures in the SSM-HA and SMC-HA samples have lower complexity, whereas the structures of LSM-HA are of higher complexity. Interactions with Cu2+ at different pH levels indicate that the LSM-HA shows more dynamic conformational changes as well as stronger interactions and higher quenching efficiency compared to the other treatments. Conversely, SMC-HA demonstrates relatively stable binding constant (Ka) values across different pH levels. The binding constants and quenching efficiency of SSM-HA are significantly affected by changes in pH. This study shows distinct structural characteristics of HA formed under different manure management systems and provides valuable insights into how these variations may impact nutrient dynamics in soils.

Spectral Characteristics of Dissolved Organic Matter in Sediments from Yuanhe River Basin

Dissolved organic matter （DOM） plays an important role in indicating the pollution of the water environment, and sediment is the main source of endogenous pollution of the water environment. Research on the spectral characteristics of DOM in sediments was important for the interpretation of water environment pollution. In this study, UV-visible absorption spectroscopy and three-dimensional fluorescence spectroscopy combined with the parallel factor analysis （PARAFAC） were used to analyze the fluorescent components, sources, and influencing factors of DOM in sediments from the Yuanhe River Basin. The results showed that the average of ω（TN）, ω（TP）, and ω（OM） in sediments from the Yuanhe River Basin were 0.52, 0.66, and 21.22 g·kg-1, respectively. The concentrations of total nitrogen and total phosphorus increased along the flow direction. In addition, the sediment DOM from the Yuanhe River Basin mainly originated from terrestrial sources. The chromophoric DOM concentration and aromaticity of DOM from the downstream reaches were significantly higher than those from the upstream and midstream reaches. Based on PARAFAC, four fluorescent components of DOM in sediments from the Yuanhe River Basin were identified, including three humus-like components （C1, C3, and C4） and one protein-like component （C2）. The sediment DOM was dominated by humus-like materials. Moreover, the fluorescent intensity of the fluorescent components was higher in the downstream reaches. Redundancy analysis revealed that the physicochemical properties of sediments in the mainstream and downstream reaches played a more significant role in the spectral properties of DOM. Phosphorus pollution and the terrestrial humus-like substance of sediment DOM were homologous. These results indicated that the spectral properties of DOM were the indicator of water environmental pollution in the region with strong anthropogenic influence.

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.

Using the Potential Transformation of Dissolved Organic Matter to Understand Carbon Emissions from Inland Rivers.

Understanding the transformation of river dissolved organic matter (DOM) is important for assessing the emissions of greenhouse gases (GHGs) in inland waters. However, the relationships between the variations in DOM components and GHGs remain largely unknown. Here, parallel factor analysis (PARAFAC) was applied to investigate the DOM components in 46 inland rivers in China. We found that the GHG emissions in peri-urban rivers were 1.10-2.15 times greater than those in urban rivers. Microbial and environmental factors (e.g., living cell numbers, microbial activity and pH) explained more than 70% of the total variance in GHG emissions in rivers. DOM variations relationships between different components ware revealed based on compositional data principal component analysis (CoDA-PCA). Microbial-mediated DOM production and degradation were quantified, and the degradation levels in peri-urban rivers were 11.8-25.2% greater than those in urban rivers. Differences in carbon emission potential between urban and peri-urban rivers were related to DOM variances and transformations and were affected by water chemistry (e.g., NH4-N and As). This study clarifies the regulatory effects of DOM composition variations and transformations on GHG emissions, and enhances the understanding of the DOM biogeochemical cycle.

Chromophoric dissolved organic matter traces seasonally changing coastal processes in a river-influenced region of the western Bay of Bengal.

The optical characteristics of colored dissolved organic matter (CDOM) serve as a convenient tool for evaluating coastal processes, e.g., river runoff, anthropogenic inputs, primary production, and bacterial/photochemical processes. We conducted a study on the seasonal and spatial variability of absorbance and fluorescence characteristics of CDOM and nutrients in the coastal waters near the Gauthami estuary of River Godavari, the largest peninsular river of India, for a year. The surface aCDOM(350) showed a significant inverse relation with salinity in the coastal region, indicating a conservative mixing of marine and terrestrial end members. The aCDOM(350) was not conservative in the offshore (100m isobath) waters due to enrichment by secondary sources. Seasonal variability in optical properties indicated diverse sources for CDOM, as revealed by principal component analysis. The excitation-emission matrix (EEM) spectra followed by parallel factor analysis (EEM-PARAFAC) revealed four distinct fluorophores. The tyrosine (B) fluorophore showed a predominant increase in the post-monsoon season (October to January), while tryptophan (T) was relatively more enriched, coincident with nutrient enrichment and transparency increase during the early monsoon phase (July). The biological index (BIX), which reflects recent photosynthetic activity, also displayed relatively higher values during the early monsoon. The humic fluorophores A and M, and humification index (HIX) were relatively enriched during the later phase of monsoon (July-October). HIX was > 4 in a few samples of the offshore region (100-m isobath) and indicated a probable contamination from drill-mud (bentonite) used in hydrocarbon exploration. During the monsoon, the relationship between T and B with CDOM was not evident due to the masking of B fluorescence in intact protein. However, during the post-monsoon (POM) and pre-monsoon (PRM) periods, this masking effect was not observed, likely due to protein degradation via bacterial and photochemical processes, respectively. Temporal variability in nutrients indicated that high ammonium levels were produced during POM (OM bacterial degradation), and high nitrite levels were observed during PRM (due to primary production). This study provides foundational insights into the use of CDOM for understanding the impact of diverse environmental, river discharge, and anthropogenic factors on coastal ecosystems.

Exploring relationships among landfill leachate parameters through multivariate analysis for monitoring purposes.

Elucidating the properties of landfill leachate and the relationships among leachate parameters is crucial for efforts to determine appropriate landfill leachate monitoring activity and management strategies. This study investigated the physical, chemical and optical parameters of leachate in an old Japanese landfill over a 13-month period. The parameters were explored based on their relationships with the maximum fluorescence (Fmax) of three components (microbial humic-like C1, terrestrial humic-like C2 and protein-like C3) deconvoluted from excitation-emission matrix fluorescence spectroscopy coupled with parallel factor analysis. Dissolved organic carbon (DOC), chemical oxygen demand (COD), Cl- and SO42- concentrations and pH ranged from 2.6 to 38.2 mg C L-1, 9 to 324 mg L-1, 14 to 972 mg L-1, 26 to 1554 mg L-1 and 6.9 to 11.6, respectively. Linear regression analysis suggested that the Fmax values of C2 and C3 represented DOC, whereas the Fmax value of C2 alone could serve as a COD indicator. Hierarchical cluster analysis and principal component analysis were employed to successfully categorise leachate samples based on their locations. Higher dissolved organic matter levels were observed in leachate within the old disposal area, whereas elevated levels of inorganic components such as SO42- and Cl- were found in leachate collected from the extended disposal area and at a treatment facility. Statistical analysis provides crucial tools for assessing and managing various areas of a landfill, supporting targeted and effective waste management strategies.

Compositions, sources, and bioavailability of colloidal organic matter in Lake Taihu

Colloidal organic matter (COM) exists ubiquitously in natural waters, and plays a pivotal role in biogeochemical cycles. Lake Taihu is confronted with severe eutrophication and algal blooms. Field investigations were carried out in Lake Taihu and two inflow rivers for two years to identify the source of COM and explore the bioavailability of COM to algae. Compositions and sources of COM were analyzed through UV absorption coefficients and parallel factor analysis of three-dimensional excitation emission matrix spectra (3D EEMs-PARAFAC). Absorption coefficient a(350) of COM in rivers surpassed that in the lake, SUVA254 exhibited noteworthy seasonal variations, and SR indicated a stable autochthonous characteristic. Three components were identified by PARAFAC analysis: tryptophan-like (C1), humic-like (C2), and tyrosine-like (C3). Fluorescence indexes showed that C1 and C3 were mainly autochthonously produced and C2 was derived from allochthonous inputs. The bioassays were conducted to assess the bioavailability of COM to the dominant species, Microcystis aeruginosa. The results showed that colloids supplied rich carbon sources and trace metals, supporting the growth of Microcystis aeruginosa. The specific growth rate, Chl a content, and biological increment of Microcystis aeruginosa in 50 % colloid-added treatment exceeded those in 20 % and 75 % treatments. Simultaneously, the effective quantum yield (Fv/Fm) and the apparent photosynthetic electron transport rate (ETRmax) demonstrated that the photosynthetic activity of Microcystis aeruginosa was higher in 20 % treatment. These findings help in understanding the intricate mechanisms of COM in lake ecosystems, and provide the robust scientific foundation for water management and protection in Lake Taihu.

Fe(III)-mediated changes in microalgae-associated bacterial communities and dissolved organic matter characteristics: A case study for Chlorococcum sp. GD

Trivalent iron ions (Fe(III)) have important effects on aquatic ecosystems, especially on the functional diversity and stability of microorganisms and ecosystems. Here, a cultivable microalgae (Chlorococcum sp. GD) from the natural environment (Shanxi, China) were isolated and identified. A combined high-throughput 16S rRNA gene amplicon sequencing/excitation-emission matrix coupled with parallel factor (EEM-PARAFAC) analysis was used to integrated the results of Fe(III) influence on Chlorococcum sp. GD bacterial community and dissolved organic matter (DOM) characteristics through laboratory experiments. Due to the addition of Fe(III) in the form of ferric nitrate (Fe(NO3)3·9H2O), complexed with EDTA to maintain solubility and bioavailability, the bacterial community was altered. This led to a decrease in the relative abundance of Proteobacteria and Actinobacteria and an increase in the relative abundance of Cyanobacteria, especially under excessive Fe(III) treatment. In addition, the relative contribution of bacterial community dispersal limitation and homogenizing dispersal was 100 %, which may lead to differences in their local adaptation and ecological processes with homogenization of bacterial diversity and loss of function. Excessive Fe(III) caused a significant increase in the abundance of genes involved in the carbon cycle (p < 0.01) and a significant decrease in genes involved in the nitrogen cycle (p < 0.01), further affecting the overall regulatory network of gene expression. This led to an increase in the abundance of genes involved in metabolism, cellular processes, environmental information processing, genetic information processing, and human diseases. The moderate amount of Fe(III) promoted the production of microbial components and accelerated the degree of DOM humification. It is also worth mentioning that excessive Fe(III) inhibited DOM degradation. Overall, this work explored the characteristics of bacterial community and DOM changes in Fe(III)-stressed Chlorococcum sp. GD as an example, which contributes to an in-depth understanding of microbial community diversity and element cycling in aquatic ecosystems.

Changes in combined toxicity of benzophenone-3 and humic acid on Daphnia magna and zebrafish during chlorination disinfection process

Conventional wastewater treatment methods cannot completely remove the ultraviolet (UV) filters or dissolved organic matter. The transformation characteristics of these substances during chlorination disinfection and the varying species-specific toxicities of their combinations remain unclear. Here, Daphnia magna and zebrafish were exposed to benzophenone-3 (BP-3) and humic acid (HA) before and after chlorination disinfection. The results from chemical indicators showed that chlorination treatment decreased UV254 values and changed the intensity of parallel factors in three-dimensional fluorescence. Based on chemical analysis, the chlorine concentration and chlorination time for the toxicity experiments were set at 5 mg/L and 6 h, respectively. Exposure to HA and BP-3 before and after chlorination decreased the heart rate (by 1.37–28.12 %) in both species. However, species-specific responses, including survival rate, swimming distance, and expression of genes related to neurodevelopment, growth, and oxidative stress, were induced by chlorination. Chlorination reduced the impact of HA exposure but worsened the effects of HA and BP-3 co-exposure on D. magna. However, in zebrafish, the toxic effects intensified in most of the exposure groups after chlorination. Correlation analysis showed that the parallel factors of three-dimensional fluorescence were correlated with toxic effects on zebrafish, whereas UV254 was more significantly correlated with toxic effects on D. magna. This study provides insights into the combined toxicity of UV filters and dissolved organic matter in different aquatic organisms during chlorination, which is useful for risk control and optimization of the chlorination process.

Multidimensional Quality Characteristics of Sichuan South-Road Dark Tea and Its Chemical Prediction

The distinctive quality of Sichuan south-road dark tea (SSDT) is gradually disappearing with processing innovation. Here, near-infrared (NIR) spectroscopy (NIRS) and spectrofluorometric techniques were utilized to determine the spectral characteristics of dried SSDT and its brew, respectively. Combined with chemical analysis, the multidimensional quality characteristics of SSDT will be presented. Finally, the NIR spectral fingerprint of dried SSDT was observed, with Kangzhuan (KZ) and Jinjian (JJ) showing a very similar NIR spectrum. The SiPLS models effectively predicted the levels of theabrownin, caffeine, and epigallocatechin gallate, based on the NIR spectrum, with root-mean-square errors of calibration of 0.15, 0.12, and 0.02 for each chemical compound, root-mean-square errors of prediction of 0.20, 0.09, and 0.03, and both corrected and predicted correlation coefficients greater than 0.90. Meanwhile, the fluorescence characteristics of the SSDT brew were identified based on the parallel factor analysis for the fluorescence excitation–emission matrix (EEM). The KZ and JJ brews could be classified with 100% accuracy using extreme-gradient-boosting discriminant analysis. The integration of NIRS and fluorometric EEM seems to be a powerful technique for characterizing SSDTs, and the results can greatly benefit the production and quality control of SSDTs.

Application of tryptophan-like fluorescence index to quantify the trace organic compounds removal in wastewater ozonation

The effectiveness of ozonation, one of the techniques known for destroying organic contaminants from wastewater, depends on the composition of the wastewater matrix. The required ozone (O3) dose is determined based on the target compounds during ozonation. Hydroxyl radicals are quantified using a probe compound. The para-chlorobenzoic acid (pCBA) is typically used as a probe compound to measure hydroxyl radicals. However, real-time measurement is impossible, as the analysis process consumes time and resources. This study aimed to evaluate the spectroscopic characteristics of various organic substances in wastewater ozonation through fluorescence excitation-emission matrix and parallel factor analysis. The study also demonstrated that real-time analyzable tryptophan-like fluorescence (TLF) can be used as a hydroxyl radical index. Importantly, the correlation between para-chlorobenzoic acid and TLF was derived, and the results showed a high correlation (R2 = 0.91), confirming the reliability of our findings. Seven trace organic compounds, classified based on their reactivity with O3 and hydroxyl radicals, were selected as target compounds and treated with O3. The TLF index was used as a model factor for the removal rate of the target compounds. The experimental and model values matched when the O3 dose was below 1.0 g O3/g DOC (RMSE: 0.0445–0.0895).

The Influence of Green Manure Planting on the Spectroscopic Characteristics of Dissolved Organic Matter in Freshwater-Leached Saline–Alkali Soil at Different Depths

This study investigated the influence of green manure planting on the spectroscopic properties of dissolved organic matter (DOM) in saline–alkali soil under freshwater leaching conditions at different soil depths. The UV254, UV253/UV203, α300, α355, SUVA254, SUVA260, and SR ultraviolet parameters indicated reductions in the content of large molecular substances, benzene ring substitution degree, colored dissolved organic matter, aromaticity, and hydrophobic components in the soil leachate DOM with an increasing soil depth. Compared with the non-green manure treatment control, green manure planting mitigated the leaching of dissolved organic matter in soil during saline irrigation, with rape green manure demonstrating superior effectiveness. Utilizing three-dimensional fluorescence combined with parallel factor analysis, this study analyzed three fluorescent components of soil leachate DOM: C1 (visible-light fulvic acid), C2 (humic acid), and C3 (tyrosine-like protein). The combined contribution of the two humic substance components (C1 + C2) was approximately 70%, indicating the dominance of humic substances in leachate DOM. The fluorescence parameters of soil leachate DOM included an average of the fluorescence index (FI) values between 1.4 and 1.9, low humification index (HIX) values consistently below 4, and biological index (BIX) values ranging from 0.8 to 1.0, suggesting a mixed source, low humification degree, poor stability, and moderate self-source characteristics. Compared with the non-green manure treatment control, both the green manure treatments exhibited a relatively higher proportion of biogenic sources and humification degree in soil leachate DOM. This suggests that planting green manure can reduce the relative DOM content under freshwater leaching conditions, increase the proportion of biogenic sources in soil leachate DOM, and enhance soil humification. Planting rapeseed green manure can diminish the leaching of DOM from land sources and augment soil humification.

Optical characterization of black carbon-derived DOM: Implication for the fluorescence detection of fuel combustion products in marine waters

Among pollutants released from shipping, black carbon (BC), also known as soot carbon, is of great interest due to its impacts on climate, air quality, human health and ecosystems. BC emitted from ships may enter marine waters and partially transfer to the seawater dissolved phase. In this study, we investigated the optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) derived from BC particles (DOMBC) emitted by ships, which were compared to those of DOMBC of other origins (diesel-powered industrial machine, biomass burning, urban dust), and to terrestrial and marine DOM (DOMTER, DOMMAR). Ship and diesel DOMBC displayed higher ratios of fluorescence maximum intensity to dissolved organic carbon concentration (Fmax/DOC), higher specific UV absorbance at 254 nm (SUVA254), and lower fluorescence emission wavelengths than the other tested materials. The parallel factor analysis (PARAFAC)-derived fluorophores of the ship and diesel DOMBC exhibited significant correlations with the concentration of dissolved black carbon (DBC), determined using the benzenepolycarboxylic acid (BPCA) method. Based on these results, we propose the Combustion indeX (COX), to help detecting and tracking ship/fuel combustion pollutions in marine waters.

Regulation and microbial response mechanism of nitric oxide to copper-containing swine wastewater treated by Pistia stratiotes

As a signaling molecule, Nitric oxide (NO) has been widely used in abiotic stress mitigation studies.Pistia stratiotes showed a good synergistic removal effect on heavy metals, nitrogen and phosphorus, but the high concentration of copper(Cu) in swine wastewater inhibited the comprehensive removal ability of Pistia stratiotes. At present, it is not clear how the addition of NO regulates the stress resistance mechanism of Pistia stratiotes to copper in swine wastewater, and the microbial response mechanism accompanying this process is not yet clear. Therefore, in the concentration range of 0.31∼4 mg·L−1Cu2+ and NO concentration of 0,0.05 and 0.1 mg L−1, the removal effect of Pistia stratiotes on copper from swine wastewater was studied. The results showed as follows: The treatment of non-available copper in groups M and H increased by 10.67% and 22.31%, respectively, compared with that in group L. The critical point of inhibiting effect of NO on growth rate was 2.03 mg·L−1Cu. By measuring three-dimensional fluorescence spectrum, combined with parallel factor analysis and principal component analysis, it was confirmed that exogenous addition of NO affected the humification degree of dissolved organic matter(DOM) and promoted the chelation of organic matter with copper. With the increase of Cu concentration, the Reyranella and Prosthecobacter with certain copper resistance gradually gained advantages. Redundancy analysis(RDA) showed that Emiticicia had a strong correlation with the removal rates of ammonia nitrogen, total phosphorus and copper in swine wastewater, while hgcI_clade had a strong correlation with the removal rates of total nitrogen. In conclusion, controlling the dosage of NO can effectively improve the tolerance and removal effect of Pistia stratiotes on copper in swine wastewater, which is of great significance for promoting the treatment and resource transformation of swine wastewater.