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Fluorescence (excitation-emission matrices, EEMs) spectroscopy coupled with PARAFAC (parallel factor) modelling and UV-Vis (ultraviolet visible) spectra were used to ascertain the sources, distribution and biogeochemical transformation of dissolved organic matter (DOM) in the Duliujian River catchment. Dissolved organic carbon (DOC), chromophoric dissolved organic matter (a335) (CDOM), and hydrophobic components (a260) were higher in summer than in other seasons with 53.3 m−1, while aromaticity (SUVA254) was higher in spring. Four fluorescent components, namely terrestrial humic acid (HA)-like (A/C), terrestrial fulvic acid (FA)-like (A/M), autochthonous fulvic acid (FA)-like (A/M), and protein-like substances (Tuv/T), were identified using EEM-PARAFAC modelling in this river catchment. The results demonstrated that terrestrial HA-like substances enhance its contents in summer ARE compared with BRE, whilst terrestrial FA-like substances were newly input in summer ARE, which was entirely absent upstream and downstream, suggesting that rain events could significantly input the terrestrial soil-derived DOM in the ambient downward catchments. Autochthonous FA-like substances in summer BRE could derive from phytoplankton in the downstream waters. The results also showed that DOM from wetland exhibited lower fluorescent intensity of humic-like peak A/C and fulvic-like peak A/M, molecular weight (SR) and humification index (HIX) during the low-flow season. Built-up land, cropland, and unused land displayed higher a335 (CDOM). A higher proportion of forest and industrial land in the SCs showed higher SUVA254 values. Humic-like moiety, molecular weight and aromaticity were more responsive to land use during stormflow in summer. Rainfall could increase the export of soil DOM from cropland and unused land, which influences the spatial variation of HIX. The results in this study highlighted that terrestrial DOM has a significant influence on the biogeochemical alterations of DOM compositions and thus water quality in the downward watershed catchments, which might significantly vary according to the land-use types and their alterations by human activities.

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.

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.

The production of fluorescent dissolved organic matter (FDOM) produced from phytoplankton and its subsequent degradation both of which occur constantly under diurnal-day time sunlight and by night time dark-microbial processes, 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, but not in lower temperature months. In July, extracellular polymeric substances (EPS), an early-state DOM, were produced from phytoplankton in early morning (06:00–09:00), then 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 night time (02:00–06:00). Such transformations occurred simultaneously with the fluctuating production of nutrients (NH4+, NO3−, NO2−, PO43− and dissolved Si), dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and the two isotopes (δ15N and δ18O) of NO3−. The FDOM components identified by fluorescence excitation-emission matrix (EEM) spectroscopy combined with parallel factor (PARAFAC) analysis consisted of EPS, autochthonous humic-like substances (AHLS) of C and M types distinctly, a combined form of C and M types of AHLS, protein-like substances (PLS), newly-released PLS, tryptophan-like substances (TLS), tyrosine-like substances (TYLS), a combined form of TYLS and phenylalanine-like substances (PALS), as well as 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.

Superoxide, produced photochemically as well as microbially, is an important reactant present in seawater and a major source of hydrogen peroxide. Superoxide decay may occur through catalyzed or uncatalyzed dismutation forming H2O2 and O2, through oxidation to O2, or through reduction into H2O2. Under definite circumstances, the redox processes that are different from dismutation could produce or consume H+, thereby altering the pH of seawater. In order to alter the pH, these processes have to involve, together with O2•, redox couples that exchange e and H+ in a ratio other than 1:1. This potential pH modification is dependent on several factors, including the extent of H+ imbalance, the rate of formation/transformation of superoxide (which reaches a steady-state concentration in seawater), and the alkalinity of seawater (which varies globally from 2.10 to 2.45 mmol L1 and buffers the pH variations). In the present study, an estimate of the possible pH changes associated with photochemically-produced superoxide in the global ocean has been provided. Among the important approximations that were required to perform the calculations, one was that it was not possible to include the microbially generated O2•, as a geographic distribution of microbial processes is not available. Unfortunately, the microbial production of O2• is comparable to or at certain times even higher than its photochemical production. Despite the above-stated and certain other limitations, it may be inferred that the tropical and equatorial oceans, because of the high O2• photoproduction rates, would be having the highest potential of undergoing pH variations (up to 0.005 pH units in ten years). Along the tropical/equatorial latitude belt, at comparable sunlight irradiance, such variations are expected to be the largest (0.005 pH units) in the Indian Ocean due to a relatively low alkalinity, in the range of 2.2–2.3 mmol L1. The lowest variations (0.003–0.004 pH units) are expected in the Atlantic Ocean, because of a relatively high alkalinity in the range of 2.3–2.4 mmol L1. The main requirement for the O2• chemistry to impact the pH of seawater significantly is that the H+-imbalance reactions should be maintained for a sufficiently long period of time. The pH effect is most probably to be operational in the river-impacted coastal areas (potential candidates are the areas affected by the following rivers: Ganges, Mekong, Irrawaddy, Zambezi, Amazon River, Orinoco, Mississippi, and Rio Grande), which are characterized by a continuous flow of redox-active organic compounds into the seawater.

Estimates of biogeochemical processes and the proportion of N2O production in the aquatic system of impoundments are important to quantify nitrogen cycling, particularly during stratification perio...

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 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.

This study explored the stratigraphic distribution and soil/shallow aquifer characteristics surrounding a chromium ore processing residue (COPR) dumpsite at a former chemical factory in China. Total Cr levels in top soils (5–10 cm) nearby the COPR dumpsite were in the range of 8571.4–10711.4 mg/kg. Shallow aquifers (1–6 m) nearby the COPR dumpsite showed a maximum total Cr level of 9756.7 mg/kg. The concentrations of Cr(VI) in groundwater nearby the COPR dumpsite were 766.9–1347.5 mg/L. These results display that the top soils, shallow aquifers, and groundwater of the study site are severely polluted by Cr(VI). Then, three aquifers (silt, clay, and silty clay), respectively, collected from the depth of 1.4–2.4 m, 2.4–4.8 m, and 4.8–11.00 m were first used to evaluate the adsorption characteristics and transport behavior of Cr(VI) in shallow aquifers by both batch and column experiments. The adsorption of Cr(VI) on tested aquifers was well described by pseudo-second-order equation and Freundlich model. The adsorption capacities of Cr(VI) on three aquifers followed the order: clay > silty clay > silt. The kinetics proved that Cr(VI) is not easily adsorbed by the aquifer mediums but transports with groundwater. Thermodynamics indicated that Cr(VI) adsorption on tested aquifers was feasible, spontaneous, and endothermic. Cr(VI) adsorption on tested aquifers decreased with increasing pH. Furthermore, the transport of Cr(VI) in adsorption columns followed the sequence of clay

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.

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.

Ocean acidification, a complex phenomenon that lowers seawater pH, is the net outcome of several contributions. They include the dissolution of increasing atmospheric CO2 that adds up with dissolved inorganic carbon (dissolved CO2, H2CO3, HCO3−, and CO32−) generated upon mineralization of primary producers (PP) and dissolved organic matter (DOM). The aquatic processes leading to inorganic carbon are substantially affected by increased DOM and nutrients via terrestrial runoff, acidic rainfall, increased PP and algal blooms, nitrification, denitrification, sulfate reduction, global warming (GW), and by atmospheric CO2 itself through enhanced photosynthesis. They are consecutively associated with enhanced ocean acidification, hypoxia in acidified deeper seawater, pathogens, algal toxins, oxidative stress by reactive oxygen species, and thermal stress caused by longer stratification periods as an effect of GW. We discuss the mechanistic insights into the aforementioned processes and pH changes, with particular focus on processes taking place with different timescales (including the diurnal one) in surface and subsurface seawater. This review also discusses these collective influences to assess their potential detrimental effects to marine organisms, and of ecosystem processes and services. Our review of the effects operating in synergy with ocean acidification will provide a broad insight into the potential impact of acidification itself on biological processes. The foreseen danger to marine organisms by acidification is in fact expected to be amplified by several concurrent and interacting phenomena.

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.

Biological degradation of terrestrially derived macromolecules including lignin and cellulose has been shown to produce a large number of environmentally relevant phenolic compounds. It has demonstrated that extracellular superoxide (O2  ) is produced by heterotrophic bacteria that are common in lakes, soil, hydrothermal vents, marine sediments, estuaries and oceans. Rates of superoxide production normalized to the proportion of metabolically active cells vary between 0.02  0.02 amol cell −1 hour −1 (mean ± standard error) and 19.4  5.2 amol cell −1 hour −1 . Such findings provide insights into the mechanism of two key and yet unclear processes, including the biological degradation of particulate organic matter (POM) that can form dissolved organic substances, and the structural diversification of dissolved organic substances originated from POM such as plant material or algal biomass.

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.

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 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.

Chemical properties and reactivity of fluorescent dissolved organic matter (FDOM) are examined in this paper. They are key issues to understand the biogeochemical processes in the aquatic environments. Typically, FDOM undergoes photochemical transformation and is recalcitrant to microbial degradation, except for the aromatic amino acids that are microbiologically degraded under dark conditions. Experimental results demonstrate that the fluorescence intensity of various FDOM components is depleted upon irradiation (in the hours to 70 days time scale), approximately by 20‐85% for fulvic acid, by 12‐95% for fluorescent whitening agents (FWAs) or commercial detergents, and by 5‐60% for trytophan. Microbial degradation is able to decompose the amino acid tryptophan and similar compounds, by approximately 13‐24% in unfiltered river waters, 67% in unfiltered sewerage samples, and 11% in filtered river samples. The photoreactivity of FDOM is greatly decreased when passing from freshwater (river and lakes) to marine waters, but deep waters in lakes or marine environments are often more sensitive to photodegradation processes than surface waters. The high reactivity of FDOM toward photodegradation could be understood on the basis of its (however complex) chemical structure, considering that many FDOM components can undergo photoionization or otherwise photosensitized oxidation under sunlight. The controlling factors to the photochemical and microbial degradation of FDOM for a variety of waters are extensively discussed. One of the important functions of FDOM is the formation of complexes with transition metals in the aquatic environments, and this review discusses the mechanisms by which FDOM interacts with metals. Further investigations on FDOM, namely the identification of still unknown FDOM components, the metal-FDOM interactions as well as the photochemical and microbial reactivity will give invaluable information on the DOM dynamics in the aquatic environments.

l ‐1 in the epilimnion and 1.4‐41.0 µg l ‐1 in hypolimnion with the maximum level in July when water temperature (WT) was the highest of the year. DOC concentrations were significantly correlated with Chl a and WT. Chl a was well correlated with WT in the epilimnion of Lake Hongfeng, suggesting that biological activities might be a major DOC source in the lake waters. DOC concentrations were weakly correlated or not correlated with fulvic acid-like fluorescence in the epilimnion, but they were significantly correlated with tryptophan-like fluorescence, indicating that the tryptophan-like fluorescent material was from new DOM in the lakes during the summer period. But these correlations were often insignificant or absent in the waters of Lake Baihua except peaks T and TUV, which may be caused by the input of organic contaminants from the industrial activities near Lake Baihua. This study may assist to better understand the sources of lake DOM and the effects of organic matter pollution on the biogeochemical cycling of DOM in lake environments.

Nanming River, the largest urban river in Guizhou Province, southwestern China plateau, has been severely polluted for decades. This study characterizes the organic materials and their sources in the upstream and downstream waters by dissolved organic carbon (DOC), excitation emission matrix (EEM) spectroscopy, parallel factor (PARAFAC) analysis and photo-microbial experiments. DOC concentrations were low (47–120 μM C) upstream and relatively high (146–462 μM C) downstream. The PARAFAC studies on the sample EEM spectra demonstrated that the upstream dissolved organic matter (DOM) was mostly composed of one component that had a fulvic acid-like substance; downstream DOM was composed of two components with mixtures of tryptophan-like and fulvic acid-like substances. From the results of the sewerage drainage samples collected along the bank of the river, it is evident that both household detergent-like and protein-like or tryptophan-like substances are predominantly present, indicating that untreated sewerage effluents are the major sources of organic matter pollution in Nanming River. The degradation experiments conducted on river, sewerage drainage and commercial detergent samples demonstrated that the detergent-like and tryptophan-like substances are both photochemically and microbiologically more decomposable than fulvic acid-like materials under sunlight and dark incubations. These results suggest that the input of the untreated sewerage effluents along the streams is the major pollution source in Nanming River, and the fluorescent DOM was efficiently affected by both photochemical and microbial processes.

Fluorescent dissolved organic matters (FDOM) in the groundwater-river-lake environments were investigated using three-dimensional excitation-emission matrix (EEM) and measuring the dissolved organic carbon (DOC), inorganic anions and electric conductivity (EC) in shallow groundwater, river and lake waters. DOC concentrations were high and largely varied in groundwater, 16–328 μM C (mean 109 ± 88 μM C), and in river waters, 43–271 μM C (mean 158 ± 62 μM C) and were very low in the lake Biwa waters, 89–97 μM C (mean 93 ± 2 μM C). The fluorescence properties of EEM showed that the fulvic-like components (peak C, peak A and peak M) were dominated in groundwater and river waters, but protein-like components (peak T) was in lake waters. The peak C was observed at $$ {{\text{Ex}}} \mathord{\left/ {\vphantom {{{\text{Ex}}} {{\text{Em}}}}} \right. \kern-\nulldelimiterspace} {{\text{Em}}} = {320 \pm 9} \mathord{\left/ {\vphantom {{320 \pm 9} {424 \pm 5}}} \right. \kern-\nulldelimiterspace} {424 \pm 5}\;{\text{nm}} $$ in groundwater, and 340 ± 5/432 ± 4 nm in river waters, but the lake waters detected the two peaks, 347 ± 7/441 ± 11 nm (peak C) as a minor peak and 304 ± 2/421 ± 8 nm (peak M) as a major peak. Emission wavelength of peak T was observed to shorten in wavelengths from groundwater to river and then lake waters. Peak T in lake waters showed at shorter in wavelengths (279 ± 2/338 ± 11 nm) at the middle point of Lake Biwa compared to those of lake shore site (283 ± 3/350 ± 7 nm). Photo-irradiation experiment on upstream waters suggested the changes in the fluorescence peaks of fulvic acid-like substances in lake waters, which might be caused by photo-degradation. DOC concentration was significantly correlated with inorganic anions and EC in river waters. However, such correlations were not observed in groundwater. Anion concentrations in lake waters were low with respect to DOC concentration. These results showed that the optical and chemical properties of FDOM are characteristically varied among groundwater, river and lake waters, indicating the impacts of environments to various FDOM at the same watershed level.

Distributions of molecular size and fluorescence properties of dissolved organic matter (DOM) in the Lake Biwa and Lake Baikal watersheds were investigated using the cross-flow ultrafiltration technique and three-dimensional fluorescence measurements. From the fluorescence properties, protein-like substances were usually found in the 0.1 μm-GF/F fraction (the Durapore membrane retentate of the GF/F filtrate) of the lake DOM. The results indicated autochthonous production of protein-like organic-matters in the lake environment. Fulvic acid (FA)-like components were composed of two fractions with respect to fluorescence properties and molecular size. Two FA-like fluorescence peaks, which showed different fluorescence peak positions in the excitation-emission matrix (EEM), were partly fractionated by the molecular size of 5000 daltons (5 kDa). The FA-like fluorescence peak position of the

Photodegradation of dissolved organic matter (DOM), collected from two upstream and one downstream sites in the Lake Biwa watershed in Japan, was investigated using fluorescence properties of three-dimensional excitation emission matrix (3-D EEM). Solar irradiation caused a decrease in the dissolved organic carbon (DOC) concentration and in the fluorescence peak intensity (FI) of fulvic acid (FA)- and protein-like substances in DOM. Mineralization of DOC during an irradiation period (13 days) was observed to be higher in upstream samples (32-36%) compared to that in downstream sample (16%). DOC concentration in samples stored in the dark significantly decreased in the downstream sample (16%), while those in upstream samples hardly decreased (1-8%). The FI of FA-like substance decreased by 72-84% during 13-days irradiation (integrated solar intensity = 176 MJ m-2). The protein-like fluorescence was only observed in the downstream sample and the net decrease in the FI was 59% in the irradiated sample. The first-order reaction kinetics was applied to analyze the photodegradation of DOM. Two-step photodegradation was suggested for the fluorescent DOM (FDOM), while not for the DOC. Results obtained here suggested that FA-like FDOM is more susceptible to photodegradation compared with those of protein-like substances and DOC.

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.

Quantitative and qualitative characterizations of dissolved organic matter (DOM) were carried out at the watershed level in central Japan by measuring dissolved organic carbon (DOC) concentration and the three-dimensional excitation–emission matrix (3-D EEM). DOC concentration was low (mean 37 ± 19 µM C) in the upstream waters, whereas, in general, it increased toward the downstream areas (mean 92 ± 47 µM C). Significant variations in DOC concentration were detected among rivers and channels. DOC concentration in the epilimnion of Lake Biwa increased during the summer period and decreased during the winter period. The lake hypolimnion has lower DOC concentration (mean 87 ± 7 µM C) compared with the epilimnion (107 ± 15 µM C). Fulvic acid (FA)-like substances in the DOM were directly characterized by 3-D EEM. The fluorescence peak for upstream DOM was found in regions with longer wavelengths (excitation/emission 386 ± 6/476 ± 5 nm) compared with downstream and lake DOM (351 ± 12/446 ± 15 nm and 341 ± 6/434 ± 6 nm, respectively). The DOC concentration is correlated with fluorescence peak intensity of FA-like substances in DOM in river waters. Such a relationship was not found in lake DOM. A blueshift of the fluorescence peak from upstream to lake DOM was observed. A decrease in fluorescence intensities was also detected during the summer period. These results may suggest that the degradation of FA-like substances in DOM occurs from natural solar irradiation. Protein-like fluorescence was significantly detected in the lake epilimnion during the summer period. A linear relationship between DOC concentration and protein-like fluorescence indicated that an autochthonous input of DOM gave rise to the increase in DOC concentration in the lake epilimnion during the summer. These results may suggest that the 3-D EEM can be used as a tool for the investigation of DOM dynamics at the watershed level with concurrent measurement of DOC concentration and the fluorescence properties of fulvic acid-like and protein-like substances.

Dynamics and optical nature of fluorescent dissolved organic matter (FDOM) were investigated in two rivers (Kurose and Ohta) in Hiroshima prefecture, Japan during 2002-2003, by measuring dissolved organic carbon (DOC) and three-dimensional excitation emission matrix fluorescence (3-D EEM). In monthly collected samples, DOC varied from 43 to 146 μM C at upstream sites in both rivers, and from 130 to 349 μM C and from 45 to 164 μM C in Kurose and Ohta downstream, respectively. The 3-D EEM of FDOM in the river waters identified three characteristic peaks, indicating the occurrence of fulvic acids (peak F), fluorescent whitening agents (peak W), and protein-like substances (peak T). The upstream FDOM in the both river waters and the downstream FDOM in the Ohta river contained the peaks F and T, identified by comparing with that of the Suwannee River Fulvic Acid (SRFA) and tryptophan and their photo-irradiated standards. The 3-D EEM of FDOM in Kurose downstream waters, however, contained the peaks W and T. The ratio of fluorescence intensity for peak F or W to DOC (FI/DOC-index) was estimated to be high (2.00 ± 0.51 to 2.09 ± 0.38 QSU (quinine sulphate unit)/μM C) at Kurose downstream compared to Ohta rivers (0.73 ± 0.35 to 0.74 ± 0.38 QSU/μM C) and to the Kurose River upstream (0.55 ± 0.22 to 0.65 ± 0.21 QSU/μM C), and the absolute FI values were several times higher in Kurose downstream waters than Kurose upstream and Ohta river waters. Moreover, the studies on the photo irradiation experiments of the standard FDOMs indicated that the peak W is easily photo-decomposed while the peak F appears to be photo-resistant. These results indicate that the chemical properties of FDOM in the Kurose downstream waters are different from those in the Kurose upstream and Ohta river waters.

Of the 2508 water samples analyzed in 10 districts of Bangladesh, 51%, on an average, contained arsenic levels of 0.05 to 2.50 mg/l. 95% of nail, 96% of hair, and 94% of urine samples contained arsenic above the normal level. Approximately 3.58 million people out of a total of 17.92 million who are drinking water containing arsenic levels >0.20 mg/l are potentially exposed to high risk of health hazard. Eight thousand and five hundred arsenic patients are identified; they are suffering from various skin lesions, gangrene in leg, skin, lung, bladder, liver, and renal cancer. A big portion of the total population is highly vulnerable to various internal cancers. Lowest arsenic concentration in drinking water producing dermatological disease is found to be 0.103 mg/l. However, the exposure time to develop arsenicosis varies from case to case reflecting its dependence on arsenic level in drinking water and food, nutritional status, genetic variant of human being, and compounding factors. This study has determined the high intensity of fluorescent humic substances in drinking water containing elevated concentrations of arsenic and very low concentrations of heavy metals. The synergistic/antagonistic effect of fluorescent compounds present in drinking water may aggravate the toxicity of arsenic. Geochemical study suggests that arsenic may be released from both reductive dissolution of Fe and Mn (oxy)hydroxide and microbial oxidation of organic matter. Keywords: Arsenic in groundwater, Skin lesions, Health risk, Heavy metals, Humic substances

Dissolved organic matter (DOM), of allochthonous and autochthonous origin, is a heterogeneous mixture of organic compounds, with molecular weights ranging from less than 100 to over 300,000 Da in natural waters. The DOM components are involved into key biogeochemical processes such as global carbon cycle, nutrient dynamics, photosynthesis, biological activity and finally as energy sources in the aquatic environments. Among the DOM components, only a limited fraction of organic compounds show fluorescence properties. These compounds are termed the fluorescent DOM (FDOM). In the pioneering works conducted by Kalle and Duursma, the fluorescence of terrestrial humic substances served as a tracer of soil organic matter in freshwater and seawater environments. The fluorescence of humic substances has then been used to distinguish the mixing of river water with seawater as well as their sources.

Solar radiation is a universal and regular phenomenon in biosphere that is vital for all life in the Earth’s crust. It maintains all the physical, chemical and biological processes of organic matter and dissolved organic matter (DOM) in natural waters.

Hydroxyl radical (HO•) is a short-lived free radical, and it is the most potent oxidizing transient among the reactive oxygen species. It is an effective, nonselective and strong oxidant that is ubiquitously formed in natural sunlit surface waters (rivers, lakes and seawater and so on), rain, dew, cloud, fog, snow, aerosol, and in all living organisms.

Organic matter (OM) in water is composed of two major fractions: dissolved and non-dissolved, defined on the basis of the isolation technique using filters (0.1–0.7 μm). Dissolved organic matter (DOM) is the fraction of organic substances that passes the filter, while particulate organic matter (POM) remains on the filter (Danielsson 1982; Kennedy et al. 1974; Liu et al. 2007; Mostofa et al. 2009a). DOM is generally originated from three major sources: (i) allochthonous Dissolved Organic Matter in Natural Waters

Complexation of the metal ions (M) with dissolved organic matter (DOM), i.e. M-DOM formation is of fundamental importance in metal ion chemistry and can control the occurrence of free toxic metals, the transport or migration of metals, acid–base balance and solubility in water, occurrence of the photo-Fenton reaction in surface water, biological effects, the bioavailability and toxicity to organisms in water, sediment and soil environments.

This chapter will give a general overview on the sources and nature of colored and CDOM, biogeochemical functions of CDOM, optical variables, chromophores in the CDOM, and the theory of CDOM absorbance in natural waters. Moreover, the controlling factors of CDOM that are most important in natural waters will be discussed. Two key factors such as photoinduced and microbial changes in CDOM are also discussed. Finally, a discussion is devoted to the importance of CDOM in natural waters.

Environmental context. Hydrogen peroxide (H2O2) and organic peroxides (ROOH) are ubiquitously present in natural waters and primarily essential for several redox reactions. This study examines the effects of various dissolved organic substances on the formation of H2O2 and ROOH and their relationship with different water quality parameters in two Japanese rivers. This study suggests that fulvic acid is primarily responsible for production of H2O2 and ROOH in river waters. Abstract. Hydrogen peroxide (H2O2) and organic peroxides (ROOH) were examined in water samples collected from the upstream and downstream sites of two Japanese rivers (the Kurose and the Ohta). H2O2 concentrations during monthly measurements varied between 6 and 213 nM in the Kurose River and 33 and 188 nM in the Ohta River. ROOH varied between 0 and 73 nM in the Kurose River and 1 and 80 nM in the Ohta. Concentrations of peroxides were higher during the summer months than in winter. H2O2 concentrations correlated well with the measured content of dissolved organic carbon and/or the fluorescence intensity of the fluorescent dissolved organic matter (FDOM) in the water from these rivers, which suggested that the dissolved organic matter and FDOM are the major sources of H2O2. Further characterisation of FDOM components by excitation emission matrix spectroscopy and parallel factor (PARAFAC) analysis indicated that fulvic acid is a dominant source of H2O2 in river waters, which accounted for 23–70% of H2O2 production in the Ohta River, 25–61% in the upstream and 28–63% in the downstream waters of the Kurose River, respectively. A fluorescent whitening agent and its photoproduct (4-biphenyl carboxaldehyde) together contributed 3–7% of H2O2 production in the downstream waters of the Kurose River. Tryptophan-like substances were a minor source of H2O2 (

The three-dimensional excitation emission matrix (EEM) fluorescence spectroscopy was employed to investigate the interaction of extracellular polymeric substances (EPS) from natural biofilm with Hg(II). The EEM spectra demonstrated that EPS with molecular weight over 14 kDa had two protein-like fluorescence peaks. The fluorescence intensity at both peaks was strongly dependent on the solution pH in the absence and presence of Hg(II), with the maximal fluorescence intensity at neutral pH. Fluorescence of both protein-like peaks was significantly quenched by Hg(II). The values of conditional stability constants (log K(a)=3.28-4.48) derived from modified Stern-Volmer equation are approximate to those for humic substances and dissolved organic matter (DOM), indicating that fluorescent components in EPS have strong binding capacity for Hg(II). Our findings suggest that EPS from biofilm is a class of important organic ligands for complexation with Hg(II) and may significantly affect the chemical forms, mobility, bioavailability and ecotoxicity of heavy metals in the aquatic environment.

O acidification is typically caused by production of carbonic acid (H2CO3) through the dissolution of increasing atmospheric CO2, which adds to CO2 plus DIC (dissolved CO2, H2CO3, HCO3 −, and CO3 2−) produced in seawater by several processes including biological ones (primary production followed by respiration). Acidification can decrease the saturation states of carbonate minerals, which may considerably endanger the dynamics, structure and biodiversity of coral reefs and other marine calcifying organisms. The consequence is the decline in the early development stages of shellfish, coral reefs, or other marine calcifiers, with impacts on fertilization, sexual reproduction, cleavage, larval settlement, survival and growth, finally causing a substantial population decline. Decline in shellfish or coral reefs, which form the foundation of marine ecosystems, would markedly affect the whole food webs and marine population dynamics. Despite the apparent straightforwardness of such a scenario, the actual determination of the impact of atmospheric CO2 on seawater pH is a difficult task. This happens primarily because of the relatively small pH changes, unless very long time spans are taken into account. Moreover, pH modifications can also take place at a local scale because of several possible confounding factors, of which we will show the potential role of superoxide chemistry. Among additional causes for seawater pH variation, one is the acidification connected with eutrophication phenomena that have increased worldwide since the last few decades. Indeed, changes in land-use practices can induce the release of high amounts of nutrients and terrestrial organic matter (OM) to coastal seawaters, including dissolved OM (DOM) and particulate OM (POM). The transformation of organic P and N into phosphate and nitrate because of microbial or photochemical processes can cause a significant decrease of the alkalinity of coastal seawater and, therefore, a decrease in pH. Another possibility (although limited in space and time) is the elevated production of CO2 and DIC during harmful algal blooms, which can significantly alter the pH of seawater as long as they are operational. Eutrophication phenomena and algal blooms can both be enhanced by global warming, which causes an increase of surface seawater temperature and leads to a longer summer stratification period. In warm, sunlit surface seawater the photochemical and biological processes that are involved in the degradation of DOM and POM can be strongly enhanced, leading to increased production of CO2 and of anionic species that decrease the alkalinity of seawater. The third possible issue is connected with atmospheric acid rain, most notably involving HNO3 and H2SO4 that can directly lower the seawater pH. All such processes are usually limited to the coastal areas that are most affected by eutrophication phenomena, while acid rains are not expected to have a comparatively important impact on the pH of the open ocean. Within this context, an additional factor of potential importance is represented by the chemistry of superoxide. The radical ion O2 −• is produced by various sources including extracellular generation by heterotrophic bacteria that are commonly detected in lakes, soil, hydrothermal vents, marine sediments, estuaries, and oceans. Rates of superoxide production normalized to the proportion of metabolically active cells are found to vary between 0.02 ± 0.02 amol cell−1 hour−1 (mean ± standard error) and 19.4 ± 5.2 amol cell−1 hour−1. Such production rates could lead to an alteration of seawater pH because of H consumption upon dismutation of superoxide (2 O2 −• + 2H → H2O2 + O2). The latter process is catalyzed by redox-active metals such as Cu(I/II) and Fe(II/ III) and possibly (but still controversially) by organic compounds with redox-capable moieties. With a biological generation rate of O2 −• prudentially assumed to be 0.2 pmol dm−3 s−1, which is only 10% of that reported by Diaz et al., based on superoxide dismutation alone one can have a H consumption rate of ∼6 μmol dm−3 year−1. A simplified seawater model shows that the process would be able to compensate for an acidification rate of 0.1−0.3 pH units year−1 Viewpoint