Isolation of dissolved organic matter from aqueous solution by precipitation with FeCl3: mechanisms and significance in environmental perspectives.

Ferric ions can bind strongly with dissolved organic matter (DOM), including humic acids (HA), fulvic acids (FA), and protein-like substances, whereas isolation of Fe-DOM precipitates (Fe-DOMP) and their biochemical characteristics remain unclear. In this work FeCl3 was used to isolate DOM components from various sources, including river, lake, soil, cow dung, and standard tryptophan and tyrosine, through precipitation at pH 7.5-8.5. The Fe-DOMP contribute to total DOM by approximately 38.6-93.8% of FA, 76.2% of HA and 25.0-30.4% of tryptophan and tyrosine, whilst fluorescence spectra allowed to monitor/discriminate the various DOM fractions in the samples. The relative intensity of the main infrared peaks such as 3406‒3383 cm-1 (aromatic OH), 1689‒1635 cm-1 (‒COOH), 1523-1504 cm-1 (amide) and 1176-1033 cm-1 (‒S=O) show either to decline or disappear in Fe‒DOMP. These results suggest the occurrence of Fe bonds with various functional groups of DOM, indicating the formation of π-d electron bonding systems of different strengths in Fe‒DOMP. The novel method used for isolation of Fe-DOMP shows promising in opening a new frontier both at laboratory and industrial purposes. Furthermore, results obtained may provide a better understanding of metal-organic complexes involved in the regulation of the long-term stabilization/sequestration of DOM in soils and waters.

Spatiotemporal optical properties of dissolved organic matter in a sluice-controlled coastal plain river with both salinity and trophic gradients.

Due to the combined effect of sluices and sea tide, the sluice-controlled coastal plain river would be characterized by both trophic state and salinity gradients, affecting the spatiotemporal optical properties of dissolved organic matter (DOM). In this study, we investigated the spatiotemporal variation of water quality parameters and optical properties of DOM in the Haihe River, a representative sluice-controlled coastal plain river in Tianjin, China. A significant salinity gradient and four trophic states were observed in the water body of the Haihe River. Two humic- and one protein-like substances were identified from the DOM by the three-dimensional fluorescence spectra combined with the parallel factor (PARAFAC) analysis. Pearson's correlation analysis and redundancy analysis (RDA) showed that the salinity significantly affected the abundance of chromophoric DOM (CDOM) but did not cause significant changes in the fluorescence optical characteristics. In addition, the effect of Trophic state index (TSI) on the CDOM abundance was greater than that on the fluorescence intensity of fluorescent dissolved organic matter (FDOM). In the water body with both salinity and trophic state gradients, TSI posed a greater influence than salinity on the CDOM abundance. Our results fill the research gap in spatiotemporal DOM characteristics and water quality variation in water bodies with both salinity and trophic state gradients. These results are beneficial for clarifying the joint influence of saline intrusion and sluices on the DOM characteristics and water quality in sluice-controlled coastal plain rivers.

Fluorescence and molecular signatures of dissolved organic matter to monitor and assess its multiple sources from a polluted river in the farming-pastoral ecotone of northern China.

The sources and composition of dissolved organic matter (DOM) in rivers are critical to water quality and aquatic ecosystems. Studies on detailed composition of organic matter in rivers in the farming-pastoral ecotone are relatively limited in the research community. To better understand the characteristics and dynamics of DOM, Yang River in North China was selected as the study area because of its profound influences on the farming-pastoral ecotone nearby. A combination of fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) techniques revealed that the DOM composition of Yang River is driven by land use. DOM in Yang River is predominantly imported from allochthonous inputs, together with agricultural runoff, pastureland, and urban sewage, causing a comprehensive impact on DOM. In detail, DOM associated with cropland inputs was dominated by lignin-like species, with higher nitrogen content. In comparison, DOM related to grassland is more diverse and susceptible to degradation. An increase in urban areas led to an increase in sulfur-containing compounds, while their oxygen, nitrogen, and aromaticity contents were significantly lower than those in cropland. Interestingly, urban-influenced lignin-like compounds may be associated with the effluents from the pulp and paper mill. Additionally, synthetic surfactants from the lower section of the river were also structurally identified by tandem mass spectrometry. Overall, this study could provide valuable insights into the DOM sources and their transformation dynamics at a molecular level, which could be an indicator for riverine water quality management and be applied to other farming-pastoral ecotones straightforward.

Optical properties of dissolved organic matter in Japanese rivers and contributions to photoformation of reactive oxygen species.

The optical properties of dissolved organic matter (DOM) from five rivers (Kokubu, Kurose, Ohta, Yamato, and Yodo) in Japan were investigated and contributions of DOM to photoformation of three reactive oxygen species (ROS) (hydroxyl radicals (OH), nitric oxide radicals (NO), and singlet oxygen (1O2)) were assessed. The lowest and highest mean dissolved organic carbon concentrations were for the Ohta River (0.95 (mg C) L-1) and Yamato River (2.85 (mg C) L-1), respectively, and the concentrations correlated with some optical parameters. Absorption ratios (e.g., the E2:E3 and A280/A350 ratios) and the spectral slope S275-295 indicated that DOM from the Yodo and Kokubu rivers had the lowest and highest molecular weights, respectively. PARAFAC models and DOM excitation-emission matrices were used to assess the sources and fates of DOM in the rivers. The PARAFAC model indicated that the main types of fluorescent DOM in the rivers were terrestrial humic-like (TH-L) and tryptophan-like (TP-L) substances. The Kokubu River contained other compounds such as fluorescent whitening agents, autochthonous humic-like substances, and extracellular polymeric substances. Statistically significant relationships between the dissolved organic carbon and TH-L, TP-L, and extracellular polymeric substance concentrations suggested that TH-L, TP-L, and extracellular polymeric substances are important contributors to total DOM in the rivers. TH-L and TP-L substances strongly contribute to ROS photoformation, but TH-L substances play roles in both ROS generation and scavenging. Comprehensive models for estimating the photoformation rates of different ROS (in M s-1) were established by integrating the contributions of the relevant major and minor sources. Examples are ROH (10-12) = 21.0 [NO2-]_µM + 0.460 [TH-L]_QSU + 10.9, RNO (10-12) = 67.9 [NO2-]_µM + 35.2 [a300]_m-1 - 2.51 [TH-L]_QSU - 0.765 [TP-L]_QSU - 8.14, and R1O2 (10-9) = 3.81 [a300]_m-1 - 0.101 [TP-L]_QSU + 11.1.

Salinity-induced fluorescent dissolved organic matter influence co-contamination, quality and risk to human health of tube well water, southeast coastal Bangladesh.

Salinity in the drinking water of coastal Bangladesh results from a severe socio-economic, environmental and human health safety crisis. In this paper, we analyzed 120 tube well water samples from southeast coastal Bangladesh for eight trace metals (TMs). Contamination, quality and risk of TMs to human health of tube well water influenced by salinity-induced fluorescent dissolved organic matter (FDOM) were assessed using multiple pollution indices, GW quality index (GWQI), traditional health risk, and PARAFAC models. The mean values of EC, Fe, Cd, Cr, and As surpassed the limit set by local and international standards with significant spatial variations. The results of the GWQI showed that 52.5% of the samples were within the moderate-poor quality range in the study region. PARAFAC modeling identified three groundwater FDOM constituents with a coupling of humic acid (HA), fulvic acid (FA), and degraded fulvic acid (DFA)-like substances. Moreover, the positive correlations among EC, TMs, HA, FA, and DFA proved that salinity-induced FDOM had significant contributions to the dissolution potential of contaminants in the aquifer, hence increased the mobilization of TMs. Health risk models suggested that children are more susceptible to the non-carcinogenic and carcinogenic risks than adults at the community level. The carcinogenic risks of Cd, As, Pb, and Cr via oral exposure pathway indicated the highest carcinogenic risks for both adults and children. The findings also indicated that the salinity-derived FDOM-TMs complex is the key driver to groundwater co-contaminations and elevated health impacts. Besides, high concentrations of Fe and As are the key causal issues for sustainable water safety. Thus, strict water management and monitoring plans require preventing these contaminants for sustainable community well-being in the coastal region.

The impacts of reservoirs on the sources and transport of riverine organic carbon in the karst area: A multi-tracer study.

Reservoirs have been constructed as clean energy sources in recent decades with various environmental impacts. Karst rivers typically exhibit high dissolved inorganic carbon (DIC) concentrations, whether and how reservoirs affect carbon cycling, especially organic carbon (OC)-related biogeochemical processes in karst rivers, are unclear. To fill this knowledge gap, multiple tracer methods (including fluorescence excitation-emission matrix (EEM), ultraviolet (UV) absorption, and stable carbon (δ13C) and radiocarbon (Δ14C) isotopes) were utilized to track composition and property changes of both particulate OC (POC) and dissolved OC (DOC) along river-transition-reservoir transects in the Southwest China karst area. The changes in chemical properties indicated that from the river to the reservoir, terrestrial POC is largely replaced by phytoplankton-derived OC, while gradual coloured dissolved organic matter (CDOM) removal and addition of phytoplankton-derived OC to the DOC pool occurred as water flowed to the reservoir. Higher primary production in the transition area than that in the reservoir area was observed, which may be caused by nutrient released from suspended particles. Within the reservoir, the production surpassed degradation in the upper 5 m, resulting in a net DIC transformation into DOC and POC and terrestrial DOM degradation. The primary production was then gradually weakened and microbial degradation became more important down the profile. It is estimated that ~3.1-6.3 mg L-1 (~15.5-31.5 mg-C m-2 (~10-21%)) DIC was integrated into the OC pool through the biological carbon pump (BCP) process in the upper 5 m in the transition and reservoir areas. Our results emphasize the reservoir impact on riverine OC transport, and due to their characteristics, karst areas exhibit a higher BCP potential which is sensitive to human activities (more nutrient are provided) than non-karst areas.

Photo-ammonification of low molecular weight dissolved organic nitrogen by direct and indirect photolysis.

The photo-ammonification process plays a crucial role in the transformation of dissolved organic nitrogen (DON) to dissolved inorganic nitrogen (DIN). However, previous studies have primarily focused on DON biotransformation than on abiotic processes. This study investigated the photo-ammonification process of nine model low molecular weight (LMW) DON molecules (e.g., amino acids, nucleotides, and urea) under the influence of different light sources. The results showed that photo-ammonification of model DON was mainly induced by UV light, while negligible contribution by visible light was found. Depending on their molecular structures, amino acids yielded different ammonia amounts, whereas negligible photo-ammonification was observed for nucleotides and urea. As for the reactive species, OH promoted ammonia yields of all the model amino acids; 3CDOM⁎ contributed to the photo-ammonification of six amino acids; 1O2 only had a positive impact on ammonification of tryptophan, histidine, and tyrosine; and CO3- accelerated ammonia generation from histidine and methionine. In natural water samples, tryptophan, tyrosine, histidine, and methionine generated significant ammonia. OH and 1O2 were speculated as the contributing reactive species based on kinetic studies as well as significant fluorescent humic-like and tyrosine-like substances degradation in irradiated samples compared to the raw samples characterized by the EEM-PARAFAC analysis. The negative linear correlations between photo-ammonification rates and the ELUMO-EHOMO of the amino acids emphasized the importance of the role of the molecular structure. Overall, these results revealed the LMW DON photo-ammonification mechanism in sunlit surface waters and highlighted its significance in the nitrogen biogeochemical cycle as well as water quality management.

New insights into mechanisms of sunlight- and dark-mediated high-temperature accelerated diurnal production-degradation of fluorescent DOM in lake waters.

The production of fluorescent dissolved organic matter (FDOM) by phytoplankton and its subsequent degradation, both of which occur constantly under diurnal-day time sunlight and by night time dark-microbial respiration processes in the upper layer of surface waters, influence markedly several biogeochemical processes and functions in aquatic environments and can be feasibly related to global warming (GW). In this work sunlight-mediated high-temperature was shown to accelerate the production of FDOM, but also its complete disappearance over a 24-h diurnal period in July at the highest air and water temperatures (respectively, 41.1 and 33.5 °C), differently from lower temperature months. Extracellular polymeric substances (EPS), an early-state DOM, were produced by phytoplankton in July in the early morning (6:00-9:00), then they were degraded into four FDOM components over midday (10:00-15:00), which was followed by simultaneous production and almost complete degradation of FDOM with reformation of EPS during the night (2:00-6:00). Such transformations occurred simultaneously with the fluctuating production of nutrients, dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and the two isotopes (δ15N and δ18O) of NO3-. It was estimated that complete degradation of FDOM in July was associated with mineralization of approximately 15% of the initial DOC, which showed a nighttime minimum (00:00) in comparison to a maximum at 13:00. FDOM identified by excitation-emission matrix spectroscopy combined with parallel factor analysis consisted of EPS, autochthonous humic-like substances (AHLS) of C- and M-types, a combined form of C- and M-types of AHLS, protein-like substances (PLS), newly-released PLS, tryptophan-like substances, tyrosine-like substances (TYLS), a combined form of TYLS and phenylalanine-like substances (PALS), and their degradation products. Finally, stepwise degradation and production processes are synthesized in a pathway for FDOM components production and their subsequent transformation under different diurnal temperature conditions, which provided a broader paradigm for future impacts on GW-mediated DOM dynamics in lake water.

Insights into solubility of soil humic substances and their fluorescence characterisation in three characteristic soils.

Soil humic substances (HS) are involved in almost all biogeochemical processes and functions in soils, thus their extraction from aiming to their characterization is very important. However, many factors that influence HS extraction from soil still need further studies. The aim of this work was to assess and quantify comparatively the solubility of soil HS as a function of extraction time, various extractants, solid to liquid ratio and sequential extraction. In this work three different soils, i.e. a forest, a maize and a paddy soil, were examined to assess the solubility of soil HS based on their fluorescence (excitation-emission matrix, EEM) features and changes in nutrient (NO3--N, PO43--P and dissolved Si) contents using multiple extraction approaches (time-dependent, various extractants, solid to liquid ratio, and sequential extraction). Three fluorescent components, i.e. humic acids-like (HA-like), fulvic acids-like (FA-like), and protein-like fluorophores (PLF), were identified by parallel factor (PARAFAC) analysis of EEM spectra of the various soil extracts. The solubility of HS, dissolved organic carbon (DOC) and nutrients were shown to increase with extraction time, except for PLF. The FA-like fraction disappeared completely in KCl extracts of all three soils, suggesting the inefficiency of salt extraction. Conversely, HS and nutrients solubility substantially increased in alkaline extracts, and dissolved Si was correlated significantly with the fluorescent intensities of HA-like and FA-like, thus confirming the well-known typical process of alkaline dissolution of HS bound to phytolith and silicate minerals. The relative solubility of HS and nutrients was higher at lower solid to liquid ratio (1:250-1:100), whereas their maximum yields was achieved at high solid to liquid ratio (1:10) for all three soils. Sequential extraction results showed that the first water extraction step contributed 42-55% of HS, which suggested that a single extraction was insufficient to recover HS. In conclusion, water and alkaline extraction could provide, respectively, the labile and insoluble complexed HS existing in soil.

Spatial Variations of Trace Metals and Their Complexation Behavior with DOM in the Water of Dianchi Lake, China.

The dynamics of trace metals and the complexation behavior related to organic matter in the interface between water and sediment would influence water quality and evolution in the lake system. This study characterized the distribution of trace metals and the optical properties of dissolved organic matter (DOM) on the surface, and the underlying and pore water of Dianchi Lake (DC) to understand the origin of metals and complexation mechanisms to DOM. Some species of trace metals were detected and Al, Ti, Fe, Zn, Sr and Ba were found to be the main types of metals in the aquatic environment of DC. Ti, Fe, Sr and Ba predominated in water above the depositional layer. Al, Ti, Fe and Sr were the most abundant metallic types in pore water. Mn and Zn were the main type found at the southern lake site, reflecting the contribution of pollution from an inflowing river. The correlations between DOM and metals suggested that both originated from the major source as particulate organic matter (POM), associated with weathering of Ca-, Mg-carbonate detritus and Fe- or Mn-bearing minerals. High dynamics of DOM and hydrochemical conditions would change most metal contents and speciation in different water compartments. Proportions of trace metals in dissolved organic carbon (DOC) in natural waters were correlated with both DOM molecular weight and structure, different metals were regulated by different organic properties, and the same metal also had specific binding characteristic with DOM in various water compartments. This study highlighted the interrelation of DOM and metals, as well as the pivotal role that organic matter and nutrients played during input, migrations and transformations of metals, thereby reflecting water quality evolution in the lake systems.

Hydrogeochemistry and δ13CDIC and δ18OH2O composition of three Chinese Tibetan Plateau lakes.

This study established the hydrochemistry and stable isotope variations in three lakes, namely brackish Zigetang Co, freshwater Cona and Ranwu lakes located in the central and southeastern Tibetan Plateau of China. Vertical profile fluctuations in the water column, such as temperature and dissolved oxygen (DO) concentration, displayed significant differences which were linked to the thermocline. The hydrochemistry of the three lakes showed that [Formula: see text] as the dominant anion, whereas Na+ is the main cation in Zigetang Co and Cona lake and Ca2+ is the prevailing cation in Ranwu lake. In Zigetang Co, K+ and Na+ concentrations decreased by 42 % from 1999 to 2012, caused by the enlargement of the lake area, documented by field investigations carried out in 1998, 2002, 2006 and 2012. The δ13CDIC and δ18OH2O values analysed from the three lakes varied from -6.0 to 2.0 ‰, and from -14.8 to -6.4 ‰, respectively. The closed Zigetang lake showed higher δ13CDIC and δ18OH2O values compared to those of the rivers, the semi-closed Cona and open Ranwu lakes. The δ13CDIC values of lake water in Zigetang Co were mainly controlled by CO2 exchange between lake water and atmosphere; the δ18OH2O values were dominated by the evaporation/freshwater input ratios.

Environmental characteristics and changes of sediment pore water dissolved organic matter in four Chinese lakes.

Sediment pore waters were examined in four Chinese lakes (Bosten, Qinghai, Chenghai and Dianchi) to characterise the sources of dissolved organic matter (DOM) and their microbial changes in the sediment depth profiles. Parallel factor (PARAFAC) modelling on the sample fluorescence spectra confirmed that the pore water DOM was mostly composed of two components with a mixture of both allochthonous and autochthonous fulvic acid-like substances in three lakes, except Lake Dianchi, and protein-like components in Lake Bosten. However, DOM in Lake Dianchi was composed of three components, including a fulvic acid-like, and two unidentified components, which could originate from mixed sources of either sewerage-impacted allochthonous or autochthonous organic matter (OM). Dissolved organic carbon (DOC) concentrations were typically high (583-7410 µM C) and fluctuated and increased vertically in the depth profile. The fluorescence intensity of the fulvic acid-like substance and absorbance at 254 nm increased vertically in the sediment pore waters of three lakes. A significant relationship between DOC and the fluorescence intensity of the fulvic acid-like component in the sediment pore waters of three lakes, except Lake Dianchi, suggested that the fulvic acid-like component could significantly contribute to total DOM and could originate via complex microbial processes in early diagenesis on OM (ca. phytoplankton, terrestrial plant material) in these lakes. Pore water DOM components could therefore be a useful indicator to assess the DOM sources of the lake sediment during sedimentation over the past several decades, which have been heavily affected by ambient terrestrial vegetation and human activities.

Photo-flocculation of microbial mat extracellular polymeric substances and their transformation into transparent exopolymer particles: Chemical and spectroscopic evidences.

Upon exposure to sunlight extracellular polymeric substances (EPS) were partially transformed into transparent exopolymer particles (TEP) and unstable flocs of different sizes without the addition of any precursors. Parallel factor (PARAFAC) modelling of the sample fluorescence spectra identified humic-like and protein-like or tyrosine-like components in both untreated and irradiated EPS samples. After 58 hours of solar irradiation, humic-like substances were entirely decomposed, while the regenerated protein-like substance from EPS was the key component in the irradiated samples. Degradation and reformation of EPS occurred which was confirmed by the results of size exclusion chromatography, dissolved organic carbon, total protein and total polysaccharide analyses. Irradiated EPS was composed of -COOH or C = O (amide I band) and -NH and -CN (amide II band), while Fourier transform infrared spectroscopy (FTIR) of TEP revealed more acidic -COOH and -C-O groups, indicating typical acidic protein-like TEP. The regenerated protein-like substances could form complexes with free metals originating from degraded EPS in irradiated samples, which could be responsible for the formation of TEP/floc in the aqueous media. These results suggest that TEP/floc formation from EPS could occur by a complexation mechanism between dissolved organic matter and metals, thereby causing ionic charge neutralisation upon sunlight exposure.

Simultaneous photoinduced generation of Fe(2+) and H2O2 in rivers: An indicator for photo-Fenton reaction.

The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical (HO) that is produced by the reaction of simultaneous photo-induced generation of Fe(2)(+)-dissolved organic matter (DOM) with H2O2 in sunlit surface waters as well as in the treatment of organic pollutants in the advanced oxidation processes (AOPs). Concentrations of both H2O2 and Fe(2)(+)-DOM were dependent on time and total solar intensity flux, and their levels were highest in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset. H2O2 and Fe(2)(+)-DOM concentrations during monthly readings were also found higher in comparison with the diurnal samples, shortly before sunrise or after sunset. A π-electron bonding system is formed between Fe and the functional groups in DOM (Fe-DOM), through electron donation from the functional groups of DOM to an empty d-orbital of Fe. The π-electron is loosely bound and is highly susceptible to a rapid excitation upon light exposure that will provide better understanding of the formation of aqueous electrons, superoxide radical anions, H2O2 and finally, photo-Fenton reactions, too. Our results imply that simultaneous generation of H2O2 and Fe(2)(+)-DOM upon sunlight exposure during the daytime is most likely to be the key photo-Fenton reaction pathway, taking place in surface waters.

Co-occurrence of arsenic and fluoride in the groundwater of Punjab, Pakistan: source discrimination and health risk assessment.

The present study discusses elevated groundwater arsenic (As) and fluoride (F(-)) concentrations in Mailsi, Punjab, Pakistan, and links these elevated concentrations to health risks for the local residents. The results indicate that groundwater samples of two areas of Mailsi, Punjab were severely contaminated with As (5.9-507 ppb) and F(-) (5.5-29.6 ppm), as these values exceeded the permissible limits of World Health Organization (10 ppb for As and 1.5 ppm for F(-)). The groundwater samples were categorized by redox state. The major process controlling the As levels in groundwater was the adsorption of As onto PO4 (3-) at high pH. High alkalinity and low Ca(2+) and Mg(2+) concentrations promoted the higher F(-) and As concentrations in the groundwater. A positive correlation was observed between F(-) and As concentrations (r = 0.37; n = 52) and other major ions found in the groundwater of the studied area. The mineral saturation indices calculated by PHREEQC 2.1 suggested that a majority of samples were oversaturated with calcite and fluorite, leading to the dissolution of fluoride minerals at alkaline pH. Local inhabitants exhibited arsenicosis and fluorosis after exposure to environmental concentration doses of As and F(-). Estimated daily intake (EDI) and target hazard quotient (THQ) highlighted the risk factors borne by local residents. Multivariate statistical analysis further revealed that both geologic origins and anthropogenic activities contributed to As and F(-) contamination in the groundwater. We propose that pollutants originate, in part, from coal combusted at brick factories, and agricultural activities. Once generated, these pollutants were mobilized by the alkaline nature of the groundwater.

Sources, factors, mechanisms and possible solutions to pollutants in marine ecosystems.

Algal toxins or red-tide toxins produced during algal blooms are naturally-derived toxic emerging contaminants (ECs) that may kill organisms, including humans, through contaminated fish or seafood. Other ECs produced either naturally or anthropogenically ultimately flow into marine waters. Pharmaceuticals are also an important pollution source, mostly due to overproduction and incorrect disposal. Ship breaking and recycle industries (SBRIs) can also release various pollutants and substantially deteriorate habitats and marine biodiversity. Overfishing is significantly increasing due to the global food crisis, caused by an increasing world population. Organic matter (OM) pollution and global warming (GW) are key factors that exacerbate these challenges (e.g. algal blooms), to which acidification in marine waters should be added as well. Sources, factors, mechanisms and possible remedial measures of these challenges to marine ecosystems are discussed, including their eventual impact on all forms of life including humans.