Investigating the different transformations of tetracycline using birnessite under different reaction conditions and various humic acids.

Prior studies have successfully used manganese oxides to facilitate the transformation of tetracycline in aqueous solution. To further understand the kinetic and the transformation pathway of tetracycline via birnessite (δ-MnO2) under different conditions, experiments were conducted at pH levels of 3, 6, and 9 in the presence or absence of Aldrich humic acid (ADHA). Tetracycline removal followed the pseudo-second-order reaction model in all investigated cases, and the removal efficiency (g mg-1 h -1) followed the following trend: pH 3 (0.45/0.27) > pH 6 (0.036/0.087) > pH 9 (0.036/0.103) in the absence/presence of ADHA. Liquid chromatography-mass spectrometry/mass spectrometry results identified five main transformation products at m/z 495, 477, 493, 459, and 415, produced by the transformation reactions, including hydration, oxidation, desaturation, and oxy reduction. Notably, in the presence of ADHA at pH 3, products with higher toxicity secondary (m/z 477 and 495) were reduced, while less toxicity products (m/z 459 and 415) were enhanced. The experiments utilizing tetracycline and δ-MnO2 with varied humic acids (HA) revealed that HA with high polar organic carbon groups, such as O-alkyl, exhibited higher removal efficiency at pH 6. This research offers the first comprehensive insights into the pathway transformations of tetracycline via δ-MnO2 under different pH conditions and HA types. For further understanding, future work should investigate the binding of HA, TTC, and/or Mn2+ and the oxidation capacity of MnO2 after the reaction to clarify Mn2+ elution mechanisms.

Fluorescence spectroscopy in the detection and management of disinfection by-product precursors in drinking water treatment processes: A review.

Monitoring and prevention of the formation of disinfection by-products (DBPs) is paramount in drinking water treatment plants (DWTP) to ensure human health safety. This review provides an overview of how fluorescence techniques are developed to predict DBP formation and to evaluate the reduction of fluorescence components and DBPs following individual DWTP processes. Evidence has shown that common DBPs, nitrogenous DBPs and specific emerging DBPs exhibit positive linear relationships with terrestrial, anthropogenic, tryptophan-like, and eutrophic humic-like fluorescence. Due to the interrelationships of both regulated and emerging DBP types with fluorescence components, the limitations arise when attempting to predict emerging DBPs solely through linear relationships. Monitoring the reduction of DBP precursors after each treatment process can be achieved by studying the relationship between fluorescence components and DBPs. During the coagulation process, highest reduction rates are observed for terrestrial humic-like fluorescence. Advanced treatments such as granular, powdered, silver-impregnated activated carbon, magnetic ion exchange resins, and reverse osmosis, have revealed a significant reduction of fluorescent DBP precursors, ranging from 53% to 100%. During chlorination, the reduction rate follows the order: terrestrial humic-like > microbial humic-like > protein/tryptophan-like fluorescence. This review provides insights into the reduction of fluorescence signatures following individual DWTP processes, which offers information regarding DBP formation. These insights could assist in optimizing the treatment process to more effectively manage DBP formation. For the identification of emerging DBP generation, the utilization of advanced models is imperative to precisely predict emerging DBPs and to more accurately trace DBP precursors within DWTPs.

Changes in structural characteristics of humic and fulvic acids under chlorination and their association with trihalomethanes and haloacetic acids formation.

The effects of chlorination on 16 humic and fulvic acids (HAs and FAs, respectively) extracted from six different soil samples from Korea and two purchased soil samples (Canadian peat moss, Elliott Silt Loam Soil) were investigated to identify the changes in their structural characteristics and their effects on trihalomethane formation potential (THMFP) and haloacetic acid formation potential. The effect of chlorination was also investigated in fractionated samples (Aldrich HA, F1-F5) based on molecular weight (MW). Total organic carbon (TOC), specific UV absorbance (SUVA), fulvic-like fluorescence (%FLF), terrestrial humic-like fluorescence (%THLF), weight-average molecular weight (MWw), and carbon structures (13C NMR) were measured for each sample before and after chlorination, and factors relating to the chlorination mechanism were examined using principal component analysis (PCA). The results showed that the changes in the structural characteristics and the disinfection by-product formation of chlorinated HA and FA differed critically. For chlorinated HA, TOC and %FLF decreased due to oxidation, whereas %THLF was reduced via incorporation; MW also affected the structural changes and THMFP generation. In the PCA results, high SUVA, low MW, low N/C, and low O groups of aromatic C were associated with high THMFP production in HA, whereas low O groups of aliphatic C in FA were associated with both oxidation and incorporation in terms of THMFP. These results elucidate the mechanisms associated with the effects of chlorination in HA and FA and will support the prediction of THMFP generation in HA and FA based on their specific structural characteristics.

Influence of soil conditions on dissolved organic matter leached from forest and wetland soils: a controlled growth chamber study.

This study investigated the effects of various soil conditions, including drying-rewetting, nitrogen deposition, and temperature rise, on the quantities and the composition of dissolved organic matter leached from forest and wetland soils. A set of forest and wetland soils with and without the nitrogen deposition were incubated in the growth chambers under three different temperatures. The moisture contents were kept constant, except for two-week drying intervals. Comparisons between the original and the treated samples revealed that drying-rewetting was a crucial environmental factor driving changes in the amount of dissolved organic carbon (DOC). The DOC was also notably increased by the nitrogen deposition to the dry forest soil and was affected by the temperature of the dry wetland soil. A parallel factor (PARAFAC) analysis identified three sub-fractions of the fluorescent dissolved organic matter (FDOM) from the fluorescence excitation-emission matrices (EEMs), and their compositions depended on drying-rewetting. The data as a whole, including the DOC and PARAFAC components and other optical indices, were possibly explained by the two main variables, which were closely related with the PARAFAC components and DOC based on principal component analysis (PCA). Our results suggested that the DOC and PARAFAC component information could provide a comprehensive interpretation of the changes in the soil-leached DOM in response to the different environmental conditions.

Changes in the dissolved organic matter leaching from soil under severe temperature and N-deposition.

In this study, we conducted growth chamber experiments using three types of soil (wetland, rice paddy, and forest) under the conditions of a severe increase in the temperature and N-deposition in order to investigate how extreme weather influences the characteristics of the dissolved organic matter (DOM) leaching from different soil types. This leachate controls the quantity and quality of DOM in surface water systems. After 5 months of incubation, the dissolved organic carbon (DOC) concentrations decreased in the range of 21.1 to 88.9 %, while the specific UV absorption (SUVA) values increased substantially in the range of 19.9 to 319.9 % for all of the samples. Higher increases in the SUVA values were observed at higher temperatures, whereas the opposite trend was observed for samples with N-addition. The parallel factor analysis (PARAFAC) results showed that four fluorescence components: terrestrial humic-like (component 1 (C1)), microbial humic-like (component 2 (C2)), protein-like (component 3 (C3)), and anthropogenic humic-like (component 4 (C4)) constituted the fluorescence matrices of soil samples. During the experiment, labile DOM from the soils was consumed and transformed into resistant aromatic carbon structures and less biodegradable components via microbial processes. The principle component analysis (PCA) results indicated that severe temperatures and N-deposition could enhance the contribution of the aromatic carbon compounds and humic-like components in the soil samples.

Improving the application of laser-induced breakdown spectroscopy for the determination of total carbon in soils.

The increase of atmospheric greenhouse gases such as CO2 has caused noticeable climate change. Since increased CO2 may contribute to carbon storage in terrestrial ecosystems through the CO2 cycle between the atmosphere and vegetation, it is necessary to improve methods for measuring C in soil. In this study, we determined the total carbon concentrations of soils using a highly sensitive and rapid method, laser-induced breakdown spectroscopy. The presence of C has been measured by detecting signal at the wavelength of 247.86 nm. The obstacle of Fe interference at the C measurement wavelength of 247.86 nm was reduced by selecting the optimal delay time of 1.4 µs. The ratio of peak intensities (areas) at 247.86 nm for C and 248.20 nm for Fe was then successfully applied to the calibration curve. In addition, to dismiss the problem of measuring the C lines at 247.86 nm, 193.03 nm has been used to observe C emission. Both the 193.03- and 247.86-nm lines provided significant linear calibrations. The 193.03-nm lines presented stronger relative accuracies in predicting the lower C concentrations of the unknown samples than that one at 247.86 nm.

Influence of upstream land use on dissolved organic matter and trihalomethane formation potential in watersheds for two different seasons.

Different land uses of upstream catchments may affect the quantity and the quality of dissolved organic matter (DOM) in watersheds, but the influence may differ by season. In this study, we examined concentrations and selected spectroscopic properties of DOM and the propensity to form trihalomethanes (THMs) for 19 different middle-sized watersheds across the Han River basin in Korea. Sampling was conducted for non-storm events during pre-monsoon (May) and monsoon seasons (July). The anthropogenic land uses including agricultural and residential areas occupied 2.3 to 49.4% of the upstream catchments of the watersheds. Non-aromatic, labile, and less condensed DOM structures were more abundant in the monsoon season. Parallel factor analysis (PARAFAC) modeling with fluorescence data demonstrated that a combination of three different fluorescence components could explain the seasonal and the spatial distributions of DOM characteristics. Terrestrial humic-like fluorescence was the most abundant component for all the DOM samples, while protein-like fluorescence became more pronounced for the monsoon season. THM concentrations did not differ between the two seasons. Observed seasonal differences in the concentrations and the characteristics of DOM suggested a greater contribution of groundwater to the streams in watersheds in the monsoon versus the pre-monsoon season. Significant correlations among anthropogenic land use, microbial humic-like fluorescence, and the propensity to form THMs were found only for the pre-monsoon season. Principal component analysis (PCA) demonstrated that, regardless of the season, anthropogenic land uses increased the concentrations of DOM and nutrients but that their effects on the DOM properties were not evident for the monsoon season.

Tracing the sources of refractory dissolved organic matter in a large artificial lake using multiple analytical tools.

Structural and chemical characteristics of refractory dissolved organic matter (RDOM) from seven different sources (algae, leaf litter, reed, compost, field soil, paddy water, treated sewage) were examined using multiple analytical tools, and they were compared with those of RDOM in a large artificial lake (Lake Paldang, Korea). Treated sewage, paddy water, and field soil were distinguished from the other sources investigated by their relatively low specific UV absorbance (SUVA) values and more pronounced fulvic-like versus humic-like fluorescence of the RDOM samples. Microbial derived RDOM from algae and treated sewage showed relatively low apparent molecular weight and a higher fraction of hydrophilic bases relative to the total hydrophilic fraction. For the biopolymer types, the presence of polyhydroxy aromatics with the high abundance of proteins was observed only for vascular plant-based RDOM (i.e., leaf litter and reed). Molecular weight values exhibited positive correlations with the SUVA and the hydrophobic content among the different RDOM, suggesting that hydrophobic and condensed aromatic structures may be the main components of high molecular weight RDOM. Principal component analysis revealed that approximately 77% of the variance in the RDOM characteristics might be explained by the source difference (i.e., terrestrial and microbial derived) and a tendency of further microbial transformation. Combined results demonstrated that the properties of the lake RDOM were largely affected by the upstream sources of field soil, paddy water, and treated sewage, which are characterized by low molecular weight UV-absorbing and non-aromatic structures with relatively high resistance to further degradation.

Multivariate analysis for spatial distribution of dissolved organic matters in a large river-type dam reservoir.

In contrast to extensive studies of dissolved organic matters (DOM) in natural lakes, the distributions and the characteristics of DOM in artificial dam reservoirs have not been well documented despite a growing demand for the construction worldwide. For this study, spatial variations in the concentrations and the characteristics of DOM in Lake Paldang, a large river-type dam reservoir, were investigated using the concentrations, the specific UV absorbance (SUVA), the synchronous fluorescence spectra and the molecular weight (MW(w)) values. In addition, environmental factors determining the DOM spatial distribution were examined based on a principal component analysis (PCA). Variations in the DOM characteristics were greater than those for the concentrations (1.1-2.4 mg C/L). In contrast to typical lakes, vertical variations with a depth were much smaller than those observed among horizontal sampling sites within the reservoir. Irrespective of the depth, four individual sampling locations were easily distinguished by comparison of some selected DOM characteristics. The protein-like fluorescence (PLF), MW(w) and SUVA values observed at the location near the dam exceeded the corresponding values for the sampling locations near major influent rivers, suggesting that, even for the river-type dam reservoir, the downstream DOM characteristics may be governed by in-lake DOM production processes such as the release from sediments and algal activities. The results of principal component analysis (PCA) revealed that approximately 61% of the variance in DOM distribution might be explained by allochthonous/autochthonous carbon sources and predominant presence of either total nitrogen or total phosphorous over the other.