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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.

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.

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.

Carbonatitic magmatism in subduction zones provides extremely valuable information on the cycling, behavior and storage of deep carbon within the Earth. It may also shed light on insights into crust-mantle interaction and mantle metasomatism within subduction zones. Origin of carbonatite has long been debated: all hypotheses need to reflect the different mineral assemblages and geochemical compositions of carbonatites and their diverse tectonic settings. Here we present a petrological, geochronological, geochemical and isotopic study of carbonatite bodies associated with orogenic peridotites, which occur as stocks or dykes with widths of tens to hundreds of meters in the Luliangshan region, North Qaidam, northern Tibet, China. On the basis of modal olivine (Ol) content, the studied samples were subdivided into two groups: Ol-poor carbonatite and Ol-rich carbonatite. Zircon grains from the Ol-poor carbonatite show detrital features, and yield a wide age spectrum between 400 Ma and 1000 Ma with a pronounced peak at ca. 410–430 Ma. By contrast, oscillatory zoned zircons and inherited cores show two relatively small Neoproterozoic age peaks at ca. 920 and 830 Ma. Zircon grains from the Ol-rich carbonatite sample are also distributed in a wide spectrum between 400 and 1000 Ma, with a pronounced peak at ca. 440 Ma and a slightly inferior peak at ca. 410 Ma. The oscillatory zoned zircons and inherited cores exhibit a smaller Neoproterozoic age peak at ca. 740 Ma. The pronounced peaks ranging from 430 to 410 Ma are consistent with the deep subduction and mantle metasomatic events recorded in associated ultramafic rocks. Both groups of carbonatites are characterized by enrichment of light rare earth elements (LREEs) with high (La/Yb)N values and pronounced negative Eu anomalies. They show high 87Sr/86Sr values (0.708156–0.709004), low 143Nd/144Nd values (0.511932–0.512013) and high δ18OV-SMOW values (+17.9 to +21.3‰). This geochemical and isotopic evidence suggests that these carbonatites were derived from remobilized sedimentary carbonate rocks. We propose that the primary carbonatite magma was formed by partial melting of sedimentary carbonates with mantle contributions. Sedimentary carbonates were subducted into the shallow upper mantle where they melted and formed diapirs that moved upwards through the hot mantle wedge. The case presented provides a rare example of carbonatite originating from sedimentary carbonates with mantle contributions and relevant information on the mantle metasomatism within a subduction zone.

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.

Microbial mat extracellular polymeric substances (EPS) and their fate and transformation in natural waters are unidentified under diurnal condition. EPS from highly saline arid origins were characterised and exposed to natural sunlight conditions to identify its physico-chemical changes over 72 h. Fourier Transform Infrared Spectroscopy (FTIR) and potentiometric titration analyses confirmed the presence of −COOH and –OH functional groups in raw EPS. In addition, size exclusion chromatography (SEC) confirmed the presence of two proteins-sized molecules in the original EPS which were found to degrade upon sunlight exposure. The excitation-emission matrix (EEM) and parallel factor (EEM-PARAFAC) identified two fluorescent components: A combined humic-like and protein-like component, and an individual tyrosine-like component. FTIR in irradiated samples confirmed degradation of EPS by showing presence of the −CH 3 group at 1377 cm −1 . Two proteins-sized molecules identified in SEC were degraded, thereby causing to significant changes in the pH and redox potential (Eh). Correspondingly, three fluorescent components were identified in irradiated samples using EEM-PARAFAC modelling and found to change in their fluorescence intensities upon sunlight exposure. It is therefore suggested that photochemical processes are important for sequential transformation of EPS into various organic substances in surface waters.

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.

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.

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 [Formula: see text] as the dominant anion, whereas Na

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.

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.

The fugacity of CO2 [fCO2 (water)] and air-water CO2 flux were compared between a river-dominated anthropogenically disturbed open estuary, the Hugli and a comparatively pristine mangrove dominated semi-closed marine estuary, the Matla on the east coast of India. Annual mean salinity of the Hugli Estuary (≈ 7.1) was much less compared to the Matla Estuary (≈ 20.0). All the stations of the Hugli Estuary were highly supersaturated with CO2 (annual mean ~ 2200 µatm) whereas, the Matla was marginally oversaturated (annual mean ~ 530 µatm). During the post-monsoon season, the outer station of the Matla Estuary was under saturated with respect to CO2 and acted as a sink. The annual mean CO2 emission from the Hugli Estuary (32.4 mol C m-2 yr-1) was 14 times higher than the Matla Estuary (2.3 mol C m-2 yr-1). CO2 efflux rate from the Hugli Estuary has increased drastically in the last decade, which is attributed to increased runoff from the river-dominated estuary.

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 hydroxyl radical (HO•) is a strong oxidizing agent that can transform dissolved organic matter (DOM) into many intermediate photoproducts and byproducts, which include low molecular weight (LMW) DOM, hydrogen peroxide (H2O2), CO2, dissolved inorganic carbon (DIC: dissolved CO2, H2CO3, HCO3−, and CO32−), NO3−, NH4+, and so on, in surface waters. Furthermore, HO• has a prominent role in the transformation of recalcitrant pollutants into more biodegradable compounds. This chapter discusses the key sources of HO• in natural waters and elucidates the phototransformation pathways of high molecular weight (HMW) and low molecular weight (LMW) DOM induced by HO•. As an example, the photooxidation of methylmercury chloride (MeHgCl) by hydroxyl radicals is discussed along with its reaction mechanism. Among the possible indicators of DOM transformation, the decrease in the fluorescence intensity of autochthonous fulvic acid is discussed based on field observations. The presented results suggest that HO• may be involved in the photooxidation of both HMW and LMW DOM in surface waters.

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.

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.

The main source of energy that drives the dynamics of Earth’s outer spheres, including its climate, is unquestionably the Sun.

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.

The concentration of hydrogen peroxide (H2O2) in natural waters has been determined for the first time in 1925 by Harvey (Harvey 1925), who studied inshore and offshore water from the English Channel.

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