Liyang Yang

Characterization of dissolved organic matter under contrasting hydrologic regimes in a subtropical watershed using PARAFAC model

Dissolved organic matter (DOM) was characterized during five basin-scale investigations (either after storms or in droughts) in Jiulong River, China that is affected by the Asian Monsoon, tropical storms and anthropogenic activities. Dissolved organic carbon concentration, DOM absorption and fluorescence (excitation-emission matrix spectra, EEMs) were measured. Parallel factor analysis (PARAFAC) of EEMs identified three humic-like and two protein-like fluorescent components. DOM concentration was highest at two polluted stations in droughts while lowest in pristine headwaters (station N1). DOM concentration increased most evidently after storms in May, 2009, indicating effective flushing of DOM from land to the river close to the onset of flood season. The protein-like fraction in PARAFAC results decreased after storms in May and June, 2009, highlighting changes in DOM composition and thus its environmental role. Dam constructions likely increased the residence time of DOM in river, making the inflow of DOM during storms have more implications for the riverine (in comparison with estuarine) biogeochemical processes. The effect of storm in August, 2008 after intense DOM flushing during several preceding storms, was not evident. A severe dinoflagellate algal bloom occurred during the extreme drought in the lower watershed, which increased DOM concentration and the protein-like fraction at impacted stations. Different DOM compositions during and after algal bloom were discriminated using the two protein-like components. This study demonstrates the importance of hydrologic regimes and anthropogenic activities on freshwater DOM and its environmental role, which has implications for a number of other rivers that share similar characteristics.

Occurrence and behaviors of fluorescence EEM-PARAFAC components in drinking water and wastewater treatment systems and their applications: a review

Fluorescence excitation emission matrices-parallel factor analysis (EEM-PARAFAC) is a powerful tool for characterizing dissolved organic matter (DOM), and it is applied in a rapidly growing number of studies on drinking water and wastewater treatments. This paper presents an overview of recent findings about the occurrence and behavior of PARAFAC components in drinking water and wastewater treatments, as well as their feasibility for assessing the treatment performance and water quality including disinfection by-product formation potentials (DBPs FPs). A variety of humic-like, protein-like, and unique (e.g., pyrene-like) fluorescent components have been identified, providing valuable insights into the chemical composition of DOM and the effects of various treatment processes in engineered systems. Coagulation/flocculation-clarification preferentially removes humic-like components, and additional treatments such as biological activated carbon filtration, anion exchange, and UV irradiation can further remove DOM from drinking water. In contrast, biological treatments are more effective for protein-like components in wastewater treatments. PARAFAC components have been proven to be valuable as surrogates for conventional water quality parameter, to track the changes of organic matter quantity and quality in drinking water and wastewater treatments. They are also feasible for assessing formations of trihalomethanes and other DBPs and evaluating treatment system performance. Further studies of EEM-PARAFAC for assessing the effects of the raw water quality and variable treatment conditions on the removal of DOM, and the formation potentials of various emerging DBPs, are essential for optimizing the treatment processes to ensure treated water quality.

Critical evaluation of spectroscopic indices for organic matter source tracing via end member mixing analysis based on two contrasting sources

Despite the wide use of absorption and fluorescence spectroscopy for tracking the sources of dissolved organic matter (DOM), there are limited studies on evaluating their source discrimination capabilities at variable solution chemistry (pH, NaCl, Ca(2+), and DOM concentration). For this study, we compared the applicability of several well-known spectroscopic indices via end member mixing analysis based on two contrasting DOM sources (Suwannee River fulvic acid and an algal DOM). The absorption coefficients and the intensities of fluorescent components from parallel factor analysis (PARAFAC) showed linear relationships with increasing algal carbon fraction in the mixture of the two DOMs. In contrast, although they still behaved conservatively, spectral ratio indices such as spectral slopes, ratios of PARAFAC components, humification index, and fluorescence index changed in nonlinear patterns with the mixing ratios. The indices based on PARAFAC results exhibited strong discrimination capabilities, as indicated by high susceptibility to the changes in DOM sources relative to the analytical precision. While variable NaCl concentrations had limited effects, most fluorescence indices were considerably affected by other solution chemistry such as pH, Ca(2+), and DOM level. Our study demonstrated that the applicability of the source discrimination indices should be critically examined especially in the environments with notable changes in the solution chemistry. The solution chemistry effects could be minimized by adjusting samples to a constant condition prior to the measurements or otherwise the effects should be fully taken into account in interpreting the field observations.

Runoff‐mediated seasonal oscillation in the dynamics of dissolved organic matter in different branches of a large bifurcated estuary—The Changjiang Estuary

National Natural Science Foundation of China [41276064, 41076044, 40776041]; Chinese Scholarship Council [2012-3022]

Characterizing treated wastewaters of different industries using clustered fluorescence EEM–PARAFAC and FT-IR spectroscopy: Implications for downstream impact and source identification

The quantity and spectroscopic features of dissolved organic matter (DOM) in treated wastewaters were studied for up to 57 facilities across 12 industrial categories to evaluate the potential influences of the effluents on downstream ecosystems and the feasibility of spectroscopic techniques in discriminating pollution sources. The average dissolved organic carbon (DOC) concentration was 3.30±0.70-73.4±14.0 mg L(-1) for each category, high enough to pollute downstream waterbodies. The average specific UV absorbance at 254 nm (SUVA) for each category spanned a broad range between 0.79±0.24 and 5.35±1.41 L(mg m)(-1), suggesting a variable aromaticity of DOM. Fluorescence excitation emission matrix-parallel factor analysis (EEM-PARAFAC) identified four humic-like and two protein-like components. The EEMs were grouped into seven clusters, five of which were dominated by a single PARAFAC component in each cluster. Fourier transform infrared (FT-IR) spectroscopy revealed notable variations in relative intensities of several characteristic absorbance bands among different wastewaters. The large variability in SUVA, PARAFAC and FT-IR features indicated that the chemical composition of DOM greatly differ among industrial wastewaters, and further implied variable biogeochemical reactivity in downstream waterbodies. The results also suggested the potential of DOM features in discriminating different wastewaters, although the variations within each industrial category were also significant.

Estimating the Concentration and Biodegradability of Organic Matter in 22 Wastewater Treatment Plants Using Fluorescence Excitation Emission Matrices and Parallel Factor Analysis

This study aimed at monitoring the changes of fluorescent components in wastewater samples from 22 Korean biological wastewater treatment plants and exploring their prediction capabilities for total organic carbon (TOC), dissolved organic carbon (DOC), biochemical oxygen demand (BOD), chemical oxygen demand (COD), and the biodegradability of the wastewater using an optical sensing technique based on fluorescence excitation emission matrices and parallel factor analysis (EEM-PARAFAC). Three fluorescent components were identified from the samples by using EEM-PARAFAC, including protein-like (C1), fulvic-like (C2) and humic-like (C3) components. C1 showed the highest removal efficiencies for all the treatment types investigated here (69% ± 26%–81% ± 8%), followed by C2 (37% ± 27%–65% ± 35%), while humic-like component (i.e., C3) tended to be accumulated during the biological treatment processes. The percentage of C1 in total fluorescence (%C1) decreased from 54% ± 8% in the influents to 28% ± 8% in the effluents, while those of C2 and C3 (%C2 and %C3) increased from 43% ± 6% to 62% ± 9% and from 3% ± 7% to 10% ± 8%, respectively. The concentrations of TOC, DOC, BOD, and COD were the most correlated with the fluorescence intensity (Fmax) of C1 (r = 0.790–0.817), as compared with the other two fluorescent components. The prediction capability of C1 for TOC, BOD, and COD were improved by using multiple regression based on Fmax of C1 and suspended solids (SS) (r = 0.856–0.865), both of which can be easily monitored in situ. The biodegradability of organic matter in BOD/COD were significantly correlated with each PARAFAC component and their combinations (r = −0.598–0.613, p < 0.001), with the highest correlation coefficient shown for %C1. The estimation capability was further enhanced by using multiple regressions based on %C1, %C2 and C3/C2 (r = −0.691).

Effects of changing land use on dissolved organic matter in a subtropical river watershed, southeast China

The composition of dissolved organic matter (DOM) is an important determinant for its biogeochemical role in the aquatic environments. Therefore, it is crucial to determine the effects of changing land use on the DOM composition in the river watershed. Water samples were collected from the outlets of 15 sub-watersheds in the subtropical Jiulong River (southeast China) for fluorescence measurements and parallel factor analysis. Two humic-like (C1 and C2) and one protein-like (C3) fluorescent components were identified. Overall, DOM in the Jiulong River watershed was dominated by humic-like materials, probably due to the fact that 69% of the watershed is covered with forest. The 15 sub-watersheds were grouped into four clusters based on the proportion of each fluorescent component in the total fluorescence, suggesting that the DOM composition could be very different among sub-watersheds. There was a strong negative correlation between C2 and C3%. C1% correlated with the water body fraction, likely associated with the aquatic production of C1. C3% correlated positively with the residential area fraction, likely indicating the influence of anthropogenic activities. These results are useful for assessing the effects of land use/land cover changes on the composition and hence biogeochemical roles of DOM in aquatic environments.

Assessing trihalomethanes (THMs) and N-nitrosodimethylamine (NDMA) formation potentials in drinking water treatment plants using fluorescence spectroscopy and parallel factor analysis

The formation of disinfection byproducts (DBPs) is a major challenge in drinking water treatments. This study explored the applicability of fluorescence excitation-emission matrices and parallel factor analysis (EEM-PARAFAC) for assessing the formation potentials (FPs) of trihalomethanes (THMs) and N-nitrosodimethylamine (NDMA), and the treatability of THM and NDMA precursors in nine drinking water treatment plants. Two humic-like and one tryptophan-like components were identified for the samples using PARAFAC. The total THM FP (TTHM FP) correlated strongly with humic-like component C2 (r=0.874), while NDMA FP showed a moderate and significant correlation with the tryptophan-like component C3 (r=0.628). The reduction by conventional treatment was more effective for C2 than C3, and for TTHM FP than NDMA FP. The treatability of DOM and TTHM FP correlated negatively with the absorption spectral slope (S275-295) and biological index (BIX) of the raw water, but it correlated positively with humification index (HIX). Our results demonstrated that PARAFAC components were valuable for assessing DBPs FP in drinking water treatments, and also that the raw water quality could affect the treatment efficiency.

Benthic flux of dissolved organic matter from lake sediment at different redox conditions and the possible effects of biogeochemical processes.

The benthic fluxes of dissolved organic carbon (DOC), chromophoric and fluorescent dissolved organic matter (CDOM and FDOM) were studied for the sediment from an artificial lake, based on laboratory benthic chamber experiments. Conservative estimates for the benthic flux of DOC were 71 ± 142 and 51 ± 101 mg m(-2) day(-1) at hypoxic and oxic conditions, respectively. Two humic-like (C1 and C2), one tryptophan-like (C3), and one microbial humic-like (C4) components were identified from the samples using fluorescence excitation emission matrices and parallel factor analysis (EEM-PARAFAC). During the incubation period, C3 was removed while C4 was accumulated in the overlying water with no significant difference in the trends between the redox conditions. The humification index (HIX) increased with time. The combined results for C3, C4 and HIX suggested that microbial transformation may be an important process affecting the flux behaviors of DOM. In contrast, the overall accumulations of CDOM, C1, and C2 in the overlying water occurred only for the hypoxic condition, which was possibly explained by their enhanced photo-degradation and sorption to redox-sensitive minerals under the oxic condition. Our study demonstrated significant benthic flux of DOM in lake sediment and also the possible involvement of biogeochemical transformation in the processes, providing insight into carbon cycling in inland waters.

Lipid biomarkers and spectroscopic indices for identifying organic matter sources in aquatic environments: A review

Understanding the dynamics of organic matter (OM) and the roles in global and local carbon cycles is challenging to the fields of environmental sciences and biogeochemistry. The accurate identification of OM is an essential element to achieve this goal. Lipids, due to their ubiquitous presence and diagenetic and chemical stability, have long and successfully been used as molecular makers in assessing the sources and the fate of OM in natural environments. In parallel, optical properties of dissolved organic matter (DOM) have been suggested as efficient tools in tracing OM sources. In this review, three representative lipid biomarkers and several common spectroscopic indices were compared for their capabilities to identify OM sources in various aquatic environments. Spectroscopic indices present various benefits in term of the high sensitivity, easy and rapid analysis, and a low cost, providing reliable information on major sources (i.e., autochthonous, allochthonous and anthropogenic) of DOM in given systems investigated. However, for further understanding the associated biogeochemistry (e.g., diagenetic changes in sources), using biomarkers is preferable due to their abilities to identify a wide spectrum of different sources simultaneously as well as their high resolution for mixed OM sources. Thus, a complementary use of both tools is highly recommended for accurately tracking OM sources and the dynamics in aquatic systems, particularly in a watershed affected by multiple sources. Nevertheless, future studies need to be carried out (1) to refine the accuracy of the source assignments in a wide range of settings along with the development of an extensive database encompassing various sources, environmental factors, and geographical locations and (2) to understand how biogeochemical processes reflect the biomarkers and the spectroscopic indices used.