The influence of weathering and organic matter on heavy metals lability in silicatic, Alpine soils

We investigated the effect of organic matter and weathering on the lability and solid phase speciation of heavy metals (Cd, Cr, Cu, Ni, Pb, Zn) in two contrasting subalpine regions in the Italian Alps. Cr, Ni and Cu could be linked to weathering. This was not the case for Pb. Since organic matter (OM) influences the solid phase speciation of heavy metals, the total organic C and N content, the C and N content of different density fractions of OM and also of the labile (oxidised by H₂O₂) and stable (H₂O₂-resistant) fractions were determined. Soil OM stocks were high and soils on north-facing slopes had more OM than the south-facing sites to which they were paired. Density measurements and the H₂O₂ fractionation indicated that the higher OM content on north-facing sites was due to an accumulation of weakly degraded organic material. Due to higher weathering intensity on north-facing sites, the abundance of the EDTA-extractable heavy metals was higher than on south-facing sites. All EDTA-extractable heavy metals showed a good correlation to the water-soluble phenolic concentrations which indicates that the metals were probably translocated as metal-organic complexes. Pb and Cu correlate not only to the light (density < 1 g/cm³) and labile, organic fraction but also to the heavy (density > 2 g/cm³) and stable fraction. High-mountain ecosystems like the Alps are sensitive to changing environmental conditions such as global warming. A warmer climate and the more favourable conditions it brings for biological activity, especially at cooler sites, will probably lead in the short- to mid-term to an increased loss of accumulated, weakly degraded OM. As the Pb and Cu content is significantly related to the labile organic matter pools, the risk exists that an increase in OM mineralisation could affect the storage capacity and mobility of these metals in soils.     

Removal of inorganic mercury and methylmercury from surface waters following coagulation of dissolved organic matter with metal-based salts

The presence of inorganic mercury (IHg) and methylmercury (MeHg) in surface waters is a health concern worldwide. This study assessed the removal potential use of metal-based coagulants as a means to remove both dissolved IHg and MeHg from natural waters and provides information regarding the importance of Hg associations with the dissolved organic matter (DOM) fraction and metal hydroxides. Previous research indicated coagulants were not effective at removing Hg from solution; however these studies used high concentrations of Hg and did not reflect naturally occurring concentrations of Hg. In this study, water collected from an agricultural drain in the Sacramento-San Joaquin Delta was filtered to isolate the dissolved organic matter (DOM) fraction. The DOM was then treated with a range of coagulant doses to determine the efficacy of removing all forms of Hg from solution. Three industrial-grade coagulants were tested: ferric chloride, ferric sulfate, and polyaluminum chloride. Coagulation removed up to 85% of DOM from solution. In the absence of DOM, all three coagulants released IHg into solution, however in the presence of DOM the coagulants removed up to 97% of IHg and 80% of MeHg. Results suggest that the removal of Hg is mediated by DOM-coagulant interactions. There was a preferential association of IHg with the more aromatic, higher molecular weight fraction of DOM but no such relationship was found for MeHg. This study offers new fundamental insights regarding large-scale removal of Hg at environmentally relevant regarding large-scale removal of Hg at environmentally relevant concentrations.     

Identification and understanding of fouling in low-pressure membrane (MF/UF) filtration by natural organic matter (NOM)

An understanding of natural organic matter (NOM) as a membrane foulant and the behavior of NOM components in low-pressure membrane fouling are needed to provide a basis for appropriate selection and operation of membrane technology for drinking water treatment. Fouling by NOM was investigated by employing several innovative chemical and morphological analyses.

Source (feed) waters with a high hydrophilic (HPI) fraction content of NOM resulted in significant flux decline. Macromolecules of a relatively hydrophilic character (e.g. polysaccharides) were effectively rejected by low-pressure membranes, suggesting that macromolecular compounds and/or colloidal organic matter in the hydrophilic NOM fraction may be a problematic foulant of low-pressure membranes. Moreover, the significant organic fouling that is contributed by polysaccharides and/or proteins in macromolecular and/or colloidal forms depends on molecular shape (structure) as well as size (i.e. molecular weight). More significant flux decline was observed in microfiltration (MF) compared to ultrafiltration (UF) membrane filtration. MF membrane fouling may be caused by pore blockage associated with large (macromolecular) hydrophilic molecules and/or organic colloids. In the case of UF membranes, the flux decline may be caused by sequential or simultaneous processes of surface (gel layer) coverage during filtration. Morphological analyses support the notion that membrane roughness may be considered as a more important factor in membrane fouling by controlling interaction between molecules and the membrane surface, compared to the hydrophobic/hydrophilic character of membranes. Membrane fouling mechanisms are not only a function of membrane type (MF versus UF) but also depend on source (feed) water characteristics.     

In-situ identification of iron electrocoagulation speciation and application for natural organic matter (NOM) removal

In this work, iron speciation in electrocoagulation (EC) was studied to determine the impact of operating parameters on natural organic matter (NOM) removal from natural water. Two electrochemical EC parameters, current density (i) and charge loading rate (CLR), were investigated. Variation of these parameters led to a near unity current efficiency (φ = 0.957 ± 0.03), at any combination of i in a range of 1–25 mA/cm² and CLR in a range of 12–300 C/L/min. Higher i and CLR led to a higher bulk pH and limited the amount of dissolved oxygen (DO) reduced at the cathode surface due to mass transfer limitations. A low i (1 mA/cm²) and intermediate CLR (60 C/L/min) resulted in low bulk DO (<2.5 mg/L), where green rust (GR) was identified by in-situ Raman spectroscopy as the primary crystalline electrochemical product. Longer electrolysis times at higher i led to magnetite (Fe₃O₄) formation. Both higher (300 C/L/min) and lower (12 C/L/min) CLR values led to increased DO and/or increased pH, with lepidocrocite (γ-FeOOH) as the only crystalline species observed. The NOM removal of the three identified species was compared, with conditions leading to GR formation showing the greatest dissolved organic carbon removal, and highest removal of the low apparent molecular weight (<550 Da) chromophoric NOM fraction, determined by high performance size exclusion chromatography.     

Mineralization and biodegradability enhancement of natural organic matter by ozone-VUV in comparison with ozone, VUV, ozone-UV, and UV: Effects of pH and ozone dose

The increase in mineralization and biodegradability of natural organic matter (NOM) by ozone-vacuum ultraviolet (VUV) in comparison with ozone, VUV, ozone-ultraviolet (UV), and UV were investigated. The effects of operating parameters including pH and ozone dose were evaluated. Results showed that the mineralization rate of dissolved organic carbon (DOC) provided by the processes tested was in the following order: ozone-VUV > VUV > ozone-UV > ozone > UV. Among three pH studied (7, 9, and 11), pH 7 provided the highest DOC mineralization rate and biodegradability increase. A synergistic effect was observed when combining ozone with UV or VUV at pH 7 and 9 but not at pH 11. The oxidized NOM samples were separated into six fractions based on polarity (hydrophobic/hydrophilic) and charge (acid/neutral/base) to reveal NOM characteristic changes. Ozone-VUV was effective in mineralizing hydrophobic neutral and acid fractions. The hydrophilic neutral fraction was a major NOM fraction after oxidation (39-87%) and was contributed to by the biodegradable DOC produced during oxidation. High performance size exclusion chromatography results revealed that the combination of UV or VUV with ozone was more effective in the decomposition of high molecular weight compounds than ozone alone.     

Effects of pH, ionic strength, dissolved organic matter, and flow rate on the co-transport of MS2 bacteriophages with kaolinite in gravel aquifer media

Viruses are often associated with colloids in wastewater and could be transported with colloids into groundwater from land disposal of human and animal effluent and sludge, causing contamination of groundwater. To investigate the role of colloids in the transport of viruses in groundwater, experiments were conducted using a 2 m long column packed with heterogeneous gravel aquifer media. Bacteriophage MS2 was used as the model virus and kaolinite as the model colloid. Experimental data were analyzed using Temporal Moment Analysis and Filtration Theory. In the absence of kaolinite colloid, MS2 phage traveled slightly faster than the conservative tracer bromide (Br), with little differences observed between unfiltered and filtered MS2 phage (0.22 μm as the operational cut-off for colloid-free virus). In the presence of kaolinite colloids, MS2 phage breakthrough occurred concurrently with that of the colloidal particles and the time taken to reach the peak virus concentration was reduced, suggesting a colloid-facilitated virus transport in terms of peak-concentration time and velocity. Meanwhile mass recovery and magnitude of concentrations of the phages were significantly reduced, indicating colloid-assisted virus attenuation in terms of concentrations and mass. Decreasing the pH or increasing the ionic strength increased the level of virus attachment to the aquifer media and colloids, and virus transport became more retarded, resulting in lower peak-concentration, lower mass recovery, longer peak-concentration time, and greater apparent collision efficiency. Increasing the concentration of dissolved organic matter (DOM) or flow rate resulted in faster virus transport velocity, higher peak-concentrations and mass recoveries, and lower apparent collision efficiencies. The dual-role of colloids in transport viruses has important implications for risk analysis and remediation of virus-contaminated sites.     

Adsorption of Cu(II) to schwertmannite and goethite in presence of dissolved organic matter

Sorption processes involving secondary iron minerals may significantly contribute to immobilisation of metals in soils and surface waters. In the present work the effect of dissolved organic matter (DOM) from a concentrated bog-water on the adsorption of Cu(II) onto schwertmannite (Fe₈O₈(OH)₆SO₄) and goethite (α-FeOOH) has been studied. The acid/base behaviour of DOM up to pH 6 was explained by assuming a diprotic acid with a density of carboxylate groups of 6.90 μeq (mg C)⁻¹. The resulting acidity constants, recalculated to zero ionic strength were and .The uptake of DOM to schwertmannite and goethite was highest at low pH although adsorption was significant also under mildly alkaline conditions. Adsorption to the two minerals was similar although at high pH more DOM was adsorbed to schwertmannite than to goethite.DOM enhanced the adsorption of Cu(II) at moderately low pH in the goethite system but there was no effect of DOM in the case of schwertmannite. The presence of Cu(II) resulted in a decreased adsorption of DOM to goethite at weakly acidic pH and increased adsorption at high pH. In the case of schwertmannite, Cu(II) did not affect DOM uptake.     

Photocatalytic degradation of carbamazepine, clofibric acid and iomeprol with P25 and Hombikat UV100 in the presence of natural organic matter (NOM) and other organic water constituents

The photocatalytic degradation of natural organic matter (NOM) and organic substance mixtures under simulated solar UV light has been investigated with suspended TiO(2). It could be shown by size-exclusion chromatography that photocatalysis of NOM led to a reduction of the average hydrodynamic radii and presumably of the nominal molecular weight, too. The decrease of the UV/Vis absorption of NOM was faster than the NOM mineralization. This study also focuses on the different abilities of photocatalytic materials (P25 and Hombikat UV100) to decrease persistent substances influenced by the presence of NOM and mixtures of pharmaceuticals or diagnostic agents. In general, the presence of NOM and other organic substances retarded the photocatalysis of a specific persistent substance by the combination of radiation attenuation, competition for active sites and surface deactivation of the catalyst by adsorption. The results of this work prove that photocatalysis is a promising technology to reduce persistent substances like NOM, carbamazepine, clofibric acid, iomeprol and iopromide even if they are present in a complex matrix.     

Identifying the sources and fate of anthropogenically impacted dissolved organic matter (DOM) in urbanized rivers

Anthropogenic activities have dramatically changed the loads and compositions of dissolved organic matter (DOM) in urbanized streams. In this study, the spatial and temporal variations of DOM in the anthropogenically impacted Zhujiang River were investigated by analyzing the water samples in an upstream, urbanized area and downstream of the rivers on different days of one year. The results indicated that the levels of dissolved organic carbon (DOC) and total phosphorus (TP) were unaffected by seasonal changes, but the specific UV₂₅₄ absorbance (SUVA) values and the total nitrogen (TN) content were greater in the winter than those in the summer. Parallel factor (PARAFAC) analysis of the excitation emission matrices (EEM) revealed the presence of three anthropogenically derived components [tryptophan-like (C1) and tyrosine-like proteins (C3) and anthropogenic humic substances (C5)] in the urbanized rivers, and they had greater seasonal and spatial variability than the terrestrial and microbial humic substances (C2 and C4). Cluster analysis revealed that treated wastewater was an important source of DOM in the urbanized streams. Photodegradation experiments indicated that the DOM in the populous area of the rivers had greater photodegradation potentials than that in the downstream region or in the natural waters. Interestingly, that the anthropogenic humic substances (C5) were considerably more photoreactive than the other four PARAFAC components, which exhibited a decrease of 80% after exposure to sunlight for 0.5 d. This study suggests that the treated wastewater could be an important input to the DOM in the urbanized rivers and the naturally occurring photodegradation could help in eliminating the anthropogenic DOM during their transport.     

Comparison of diffusive gradients in thin films and equilibrium dialysis for the determination of Al, Fe(III) and Zn complexed with dissolved organic matter

The distinction between 'free' metals and organically complexed metals in aqueous solutions is important for research involving the mobility or bioavailability of metals in the environment. In this study, the applicability of equilibrium dialysis (molecular weight cut-off = 1000 Da) and diffusive gradients in thin films (DGT) to determine 'free' Al, Fe(III) and Zn in four forest soil solutions was compared. The 'free' metals as measured by both methods, consist of hydrated metal cations and soluble inorganic metal complexes. In addition, dialysis measures any organic complexes < 1000 Da and DGT measures a portion of smaller labile organic complexes. The four soil solutions were prepared by water extraction of an organic soil horizon (H) from a Fimic Anthrosol, and contained either 20 or 75 mg C/l dissolved organic matter at pH 4.0 and pH 7.0. To test the performance of both methods and optimize experimental volume and time, experiments using metal nitrate solutions were carried out. In the solutions at pH 4.0, no significant differences in average 'free' metal contents were found for Al, Fe(III) or Zn. This makes DGT a viable alternative for equilibrium dialysis for the study of the complexation of all three metals in acidic soils. At pH 7.0, again no significant difference between both methods were found for Al and Fe(III), but the DGT results for Zn were significantly higher. This was likely caused by labile organic complexes that were only detected by DGT.     

Spatial and seasonal patterns of fluorescent organic matter in Lake Kinneret (Sea of Galilee) and its catchment basin

Lake Kinneret (Sea of Galilee) is one of the major water resources in Israel. The origin and characteristics of natural organic matter (NOM) in the lake and its tributary rivers were studied using fluorescence excitation emission matrices (EEM) and parallel factor analysis. Two humic-like and one proteinous components were sufficient to describe EEM variability among 167 water samples collected between 2/2005 and 9/2006. The two humic-like components showed different relations in lake and riverine samples. Their vertical distribution in the lake was affected by seasonal stratification and distance from water surface, presumably reflecting the release of humic-like matter from sediments, its production via NOM transformation in the bottom layers, and its photodegradation in the upper layers. Vertical distribution of the proteinous component, indicating biological activity at upper water layers, did not correlate with that of the humic-like components. Dissolved organic carbon concentrations did not show any vertical stratification, emphasizing the power of EEM to explore NOM dynamics.     

Natural organic matter (NOM) removal and structural changes in the bacterial community during artificial groundwater recharge with humic lake water

This study evaluated the removal of natural organic matter (NOM) and structural changes in the microbial community during infiltration of humic lake water at three artificial groundwater recharge (AGR) sites in Finland. The three sites were at waterworks in H?meenlinna, Jyv?skyl? and Tuusula, sites A, B and C, respectively. Site A used groundwater recharge by both basin and sprinkling infiltration, site B used only sprinkling infiltration, and site C used only basin infiltration. Reductions of total organic carbon at sites A, B and C were 91%, 84% and 74%, respectively, in the winter, and 88%, 77% and 73%, respectively, in the summer. The Finnish national recommended value of 2 mg/l for TOC was achieved at all sites and the TOC of natural groundwater at site C was much lower, at 0.6 mg/l. Large molecular fractions of NOM were removed more efficiently than the smaller ones. Total amount of DAPI-stained cells decreased during infiltration at sites A, B and C in winter by 94%, 94% and 75% and in summer by 96%, 97% and 94%, respectively. Bacterial communities in raw waters and extracted groundwaters were diverse with changes occurring during infiltration, which was shown by DNA extraction followed by PCR of 16S rRNA genes and denaturing gradient gel electrophoresis (DGGE) fingerprinting. While the natural groundwater microbial community was diverse, it was different from that of the extracted groundwater in the AGR area. Simultaneous organic carbon removal and the decrease of bacterial counts during infiltration indicated biodegradation. In addition, the changing DGGE profiles during the process of infiltration, demonstrated that changing environmental conditions were reflected by changes in bacterial community composition.     

Stable isotopes of bulk organic matter to trace carbon and nitrogen dynamics in an estuarine ecosystem in Babitonga Bay (Santa Catarina, Brazil)

The biogeochemical processes affecting the transport and cycling of terrestrial organic carbon in coastal and transition areas are still not fully understood. One means of distinguishing between the sources of organic materials contributing to particulate organic matter (POM) in Babitonga Bay waters and sediments is by the direct measurement of δ¹³C of dissolved inorganic carbon (DIC) and δ¹³C and δ¹⁵N in the organic constituents. An isotopic survey was taken from samples collected in the Bay in late spring of 2004. The results indicate that the δ¹³C and δ¹⁵N compositions of OM varied from − 21.7‰ to − 26.2‰ and from + 9.2‰ to − 0.1‰, respectively. δ¹³C from DIC ranges from + 0.04‰ to − 12.7‰. The difference in the isotope compositions enables the determination of three distinct end-members: terrestrial, marine and urban. Moreover, the evaluation of source contribution to the particulate organic matter (POM) in the Bay, enables assessment of the anthropogenic impact. Comparing the depleted values of δ¹³C_DIC and δ¹³C_POC it is possible to further understand the carbon dynamic within Babitonga Bay.     

Effects of chloride,sulfate and natural organic matter (NOM) on the accumulation and release of trace-level inorganic contaminants from corroding iron

This study examined effects of varying levels of anions (chloride and sulfate) and natural organic matter (NOM) on iron release from and accumulation of inorganic contaminants in corrosion scales formed on iron coupons exposed to drinking water. Changes of concentrations of sulfate and chloride were observed to affect iron release and, in lesser extent, the retention of representative inorganic contaminants (vanadium, chromium, nickel, copper, zinc, arsenic, cadmium, lead and uranium); but, effects of NOM were more pronounced. DOC concentration of 1 mg/L caused iron release to increase, with average soluble and total iron concentrations being four and two times, respectively, higher than those in the absence of NOM. In the presence of NOM, the retention of inorganic contaminants by corrosion scales was reduced. This was especially prominent for lead, vanadium, chromium and copper whose retention by the scales decreased from >80% in the absence of NOM to <30% in its presence. Some of the contaminants, notably copper, chromium, zinc and nickel retained on the surface of iron coupons in the presence of DOC largely retained their mobility and were released readily when ambient water chemistry changed. Vanadium, arsenic, cadmium, lead and uranium retained by the scales were largely unsusceptible to changes of NOM and chloride levels. Modeling indicated that the observed effects were associated with the formation of metal–NOM complexes and effects of NOM on the sorption of the inorganic contaminants on solid phases that are typical for iron corrosion in drinking water.     

Characterization of endotoxic indicative organic matter (2-keto-3deoxyoctulosonic acid) in raw and biologically treated domestic wastewater

The aim of this research is to characterize the organic matter showing endotoxicity in domestic wastewater. It is assumed that endotoxicity is caused by lipo-polysaccharide (LPS), particularly large and hydrophobic molecules. In this study, a batch experiment (decay test for 12 h) was conducted to confirm whether LPS is the cause of endotoxicity or not. 2-keto-3deoxyoctulosonic acid (KDO) was used as an indicator of presence of LPS.A size and structural characterization of several samples from raw and domestic wastewater was also carried out in order know which fractions are causing endotoxicity. Endotoxin and KDO patterns were found to be similar, peaking at the same time. Thus, organic matter showing endotoxicity, such as LPS was released in the decay test. Moreover, the organic matter released from bacteria during decay test was partly biodegradable. Results from size characterization (Molecular Weight Distribution) showed that the majority of endotoxin (up to 82%), in domestic sewage and secondary effluents,is composed of molecules larger than 100 kDa and less than 0.1 μm. Similarly, structural characterization (hydrophobic and hydrophilic) showed that the majority of endotoxin, ranging from 59% to 83% of the total endotoxicity, is hydrophobic fractions. Therefore, removing large and hydrophobic molecules from wastewater can be an effective way to achieve a significant decrease in its endotoxicity.     

Biomonitoring of Cd, Cr, Hg and Pb in the Baluarte River basin associated to a mining area (NW Mexico)

With the purpose of knowing seasonal variations of Cd, Cr, Hg and Pb in a river basin with past and present mining activities, elemental concentrations were measured in six fish species and four crustacean species in Baluarte River, from some of the mining sites to the mouth of the river in the Pacific Ocean between May 2005 and March 2006. In fish, highest levels of Cd (0.06 μg g^− 1 dry weight) and Cr (0.01 μg g^− 1) were detected during the dry season in Gobiesox fluviatilis and Agonostomus monticola, respectively; the highest levels of Hg (0.56 μg g^− 1) were detected during the dry season in Guavina guavina and Mugil curema. In relation to Pb, the highest level (1.65 μg g^− 1) was detected in A. monticola during the dry season. In crustaceans, highest levels of Cd (0.05 μg g^− 1) occurred in Macrobrachium occidentale during both seasons; highest concentration of Cr (0.09 μg g^− 1) was also detected in M. occidentale during the dry season. With respect to Hg, highest level (0.20 μg g^− 1) was detected during the rainy season in Macrobrachium americanum; for Pb, the highest concentration (2.4 μg g^− 1) corresponded to Macrobrachium digueti collected in the dry season. Considering average concentrations of trace metals in surficial sediments from all sites, Cd (p < 0.025), Cr (p < 0.10) and Hg (p < 0.15) were significantly higher during the rainy season. Biota sediment accumulation factors above unity were detected mostly in the case of Hg in fish during both seasons. On the basis of the metal levels in fish and crustacean and the provisional tolerable weekly intake of studied elements, people can eat up to 13.99, 0.79 and 2.34 kg of fish in relation to Cd, Hg and Pb, respectively; regarding crustaceans, maximum amounts were 11.33, 2.49 and 2.68 kg of prawns relative to levels of Cd, Hg and Pb, respectively.     

Characterization of copper complexation with natural dissolved organic matter (DOM)--link to acidic moieties of DOM and competition by Ca and Mg

We investigated Cu complexation by three dissolved organic matters (DOMs) collected by reverse osmosis (RO). Alkalimetric titration, pH-stat Cu and Ca titrations, pH edges of Cu–DOM complexation, and Ca/Mg–Cu exchange experiments were investigated at I=10⁻² M for DOM samples of 10 mg C/L. The proton and Cu binding characteristics indicated similarity for all three DOMs. All Cu titrations employed ion selective electrode measurement and indicated the presence of relatively small amounts of strong Cu-binding sites. Four distinct classes of Cu binding sites are required for FITEQL 4.0 to provide good fits to the entire curves. The estimated total Cu binding site density is 4.55 mmol/g C, much less than the total acidity but very close to the phenolic site content. Cu–DOM complexation increases approximately 10-fold per pH unit, even at relatively high pH (>8). We suggest that sites characterized as phenolic based on alkalimetric titration, not carboxyl sites, account for the majority of Cu complexation under natural water conditions, and Cu–DOM complexation is principally through the replacement of H⁺ by Cu²⁺ at the phenolic binding sites. The Cu–H exchange ratio is 1:1 for the first three sites and about 1:2 for the 4th site. This 4-site model describes well the pH dependency of Cu–DOM complexation and provides good estimates of free Cu concentrations throughout wide total copper (Cu_T) and pH ranges. Comparison between Ca–DOM and Cu–DOM complexation demonstrated that (i) Ca–DOM complexation increases much less than an order of magnitude per pH unit and decreases at higher Ca concentration, different from that of Cu–DOM complexation; and (ii) Cu–DOM complexation is highly non-linear, in contrast to the much reduced extent of non-linearity of Ca–DOM complexation. Ca/Mg–Cu exchange experiments showed small competition effect, less than expected by a simple competition model, and the competition tended to reduce with increasing Ca or Mg concentrations. The extent of the competition by Mg and Ca are essentially comparable. Put all together, it suggests that Ca and Mg are preferably bound by carboxyl sites, especially at relatively high concentrations, resulting in a weakened apparent competition effect.     

The contribution of phytoplankton degradation to chromophoric dissolved organic matter (CDOM) in eutrophic shallow lakes: Field and experimental evidence

Eight field campaigns in the eutrophic, shallow, Lake Taihu in the summers from 2005 to 2007, and a phytoplankton degradation experiment of 33 days, were carried out to determine the contribution of phytoplankton degradation to CDOM. Significant and positive correlations were found between the CDOM absorption coefficient at 355 nm [a_CDOM(355)], normalized fluorescence emission (QSU) at 450 nm from excitation at 355 nm [F_n(355)], and the chlorophyll a (Chla) concentration for all eight field campaigns, which indicates that the decomposition and degradation of phytoplankton is an important source of CDOM. In the degradation experiment, the CDOM absorption coefficient increased as phytoplankton broke down during the first 12 days, showing the production of CDOM from phytoplankton. After 12 days, a_CDOM(355) had increased from the initial value 0.41 ± 0.03 m⁻¹ to 1.37 ± 0.03 m⁻¹ (a 234% increase), and the Chla concentration decreased from the initial value of 349.1 ± 11.2 μg/L to 30.4 ± 13.2 μg/L (a 91.3% decrease). The mean daily production rate of CDOM from phytoplankton was 0.08 m⁻¹ for a_CDOM(355). Parallel Factor Analysis (PARAFAC) was used to assess CDOM composition from EEM spectra, and four components were identified: a terrestrial-like humic component, two marine-like humic components, and a protein-like component. The rapid increase in marine-like humic fluorophores (C3 and C4) during the degradation experiment suggests that in situ production of CDOM plays an important role in the dynamics of CDOM. The field campaigns and experimental data in the present study show that phytoplankton can be one of the important CDOM producers in eutrophic shallow lakes.     

The apparent and potential effects of climate change on the inferred concentration of dissolved organic matter in a temperate stream (the Malse River,South Bohemia)

Long-term and seasonal changes in concentration of dissolved organic matter (DOM) and their possible drivers were evaluated for an upland stream in central Europe during 1969-2000. Two periods have been detected within this data set-years with decreased DOM until the middle of 1980s and then years with increased DOM until 2000. Temperature, hydrological regime of runoff from the catchment (namely the amount of interflow), and changes in atmospheric deposition of acidity coincided with the variations in DOM concentrations. The analysis of single runoff events confirmed the relation between the export of increased DOM concentrations from the catchment and interflow. A multiple linear regression model based on monthly averages of temperature and interflow explained 67% of DOM variability. This model suggested a 7% increase in DOM concentration under the scenarios of possible future climate change related to doubled CO(2) concentration in the atmosphere. The scenarios were based on results of several global circulation models.     

The apparent and potential effects of climate change on the inferred concentration of dissolved organic matter in a temperate stream (the Mal e River, South Bohemia)

Long-term and seasonal changes in concentration of dissolved organic matter (DOM) and their possible drivers were evaluated for an upland stream in central Europe during 1969–2000. Two periods have been detected within this data set—years with decreased DOM until the middle of 1980s and then years with increased DOM until 2000. Temperature, hydrological regime of runoff from the catchment (namely the amount of interflow), and changes in atmospheric deposition of acidity coincided with the variations in DOM concentrations. The analysis of single runoff events confirmed the relation between the export of increased DOM concentrations from the catchment and interflow. A multiple linear regression model based on monthly averages of temperature and interflow explained 67% of DOM variability. This model suggested a 7% increase in DOM concentration under the scenarios of possible future climate change related to doubled CO₂ concentration in the atmosphere. The scenarios were based on results of several global circulation models.