Freshwater Organic Matter Research Articles

Differential enrichment mechanism of organic matter in freshwater and salty alkaline lake basins

Differential enrichment mechanism of organic matter in freshwater and salty alkaline lake basins

Periodic membrane fractionation of freshwater organic matter reveals various reactivity patterns during chlorine/chloramine disinfection

Although drinking water disinfection has significantly reduced mortality from waterborne diseases, the formation of potentially harmful disinfection by-products (DBPs) remains a concern today. These DBPs emerge from the reaction of dissolved organic matter (DOM) with chlor(am)ine during disinfection. Identifying these DBP precursors from heterogeneous and complex DOM mixtures is challenging and to address this, a novel membrane fractionation protocol was developed to isolate and identify the organic DBP precursors from fresh water sources. A tight ultrafiltration and nanofiltration membrane were carefully selected to partition DOM into three molecular weight (MW) fractions: high (>20 kDa), medium (0.3–20 kDa) and low (<0.3 kDa) as defined by high performance-size exclusion chromatography- total organic carbon analysis. A mathematical tool was developed to optimize the fractionation protocol. Therefore, ultrafiltration was executed before nanofiltration and the concentration factor was maximized without inducing fouling to obtain the purest fractions. The mathematical tool was also set in place to predict the necessary diafiltration factor for each individual fractionation experiment based on the initial organic matter composition of the surface water allowing the fractionation protocol to be effective at all times. The protocol was applied to surface water samples collected six times across three seasons yielding a fraction enriched in high MW compounds (up to 50 %), a fraction having more than 80 % of medium MW compounds and a fraction only containing low MW compounds. Although the medium MW fraction showed the highest reactivity for the majority of the investigated DBPs, the low MW fraction showed high reactivity for iodinated trihalomethanes during chlorination and for haloacetonitriles during chloramination. The high MW fraction had the lowest reactivity towards DBPs, which can have important implications for a drinking water treatment since this fraction is generally the most effectively removed by e.g. coagulation, while the more important fractions for DBP formation such as the medium and low MW compounds remain in the water until the disinfection step.

Thorough Validation of Optimized Size Exclusion Chromatography-Total Organic Carbon Analysis for Natural Organic Matter in Fresh Waters.

Size exclusion chromatography with total organic carbon detection (HPSEC-TOC) is a widely employed technique for characterizing aquatic natural organic matter (NOM) into high, medium, and low molecular weight fractions. This study validates the suitability of HPSEC-TOC for a simplified yet efficient routine analysis of freshwater and its application within drinking water treatment plants. The investigation highlights key procedural considerations for optimal results and shows the importance of sample preservation by refrigeration with a maximum storage duration of two weeks. Prior to analysis, the removal of inorganic carbon is essential, which is achieved without altering the NOM composition through sample acidification to pH 6 and subsequent N2-purging. The chromatographic separation employs a preparative TSK HW-50S column to achieve a limit of detection of 19.0 µgC dm-3 with an injection volume of 1350 mm-3. The method demonstrates linearity up to 10,000 µgC dm-3. Precision, trueness and recovery assessments are conducted using certified reference materials, model compounds, and real water samples. The relative measurement uncertainty in routine analysis ranges from 3.22% to 5.17%, while the measurement uncertainty on the bias is 8.73%. Overall, the HPSEC-TOC represents a reliable tool for NOM fractions analysis in both treated and untreated ground and surface water.

Dearomatization drives complexity generation in freshwater organic matter

Dissolved organic matter (DOM) is one of the most complex, dynamic and abundant sources of organic carbon, but its chemical reactivity remains uncertain1–3. Greater insights into DOM structural features could facilitate understanding its synthesis, turnover and processing in the global carbon cycle4,5. Here we use complementary multiplicity-edited 13C nuclear magnetic resonance (NMR) spectra to quantify key substructures assembling the carbon skeletons of DOM from four main Amazon rivers and two mid-size Swedish boreal lakes. We find that one type of reaction mechanism, oxidative dearomatization (ODA), widely used in organic synthetic chemistry to create natural product scaffolds6–10, is probably a key driver for generating structural diversity during processing of DOM that are rich in suitable polyphenolic precursor molecules. Our data suggest a high abundance of tetrahedral quaternary carbons bound to one oxygen and three carbon atoms (OCqC3 units). These units are rare in common biomolecules but could be readily produced by ODA of lignin-derived and tannin-derived polyphenols. Tautomerization of (poly)phenols by ODA creates non-planar cyclohexadienones, which are subject to immediate and parallel cycloadditions. This combination leads to a proliferation of structural diversity of DOM compounds from early stages of DOM processing, with an increase in oxygenated aliphatic structures. Overall, we propose that ODA is a key reaction mechanism for complexity acceleration in the processing of DOM molecules, creation of new oxygenated aliphatic molecules and that it could be prevalent in nature.

Geochemical behavior of C, N, and S in sediments of Hangzhou Bay, Southeastern China: implications for the study of paleoclimate and sea-level changes

The correlation between the amount of organic carbon (OC) and sulfur (S) in sediments has been widely used as a paleosalinity indicator to distinguish between marine and freshwater environments. However, whether the ratio of total OC to total S (TOC/TS) can be used to identify unsteady or dynamic marine environments across sedimentary strata is still contended. An HZW1907 sediment core of 80 m in length was successfully collected in the middle of Hangzhou Bay (HZB), serving as one of the few boreholes that are crucial for the study of geologic and geo-environment changes in the coastal regions of eastern China since the Last Glacial Maximum (LGM). Total OC (TOC), stable carbon isotope, and TS of 82 subsamples from the HZW1907 core were analyzed to reconstruct the history of the shallow water biological pump and sulfur preservation record in the bay since the Late Pleistocene. Our results indicate that the samples had low concentrations of TOC (0.21%) and total nitrogen (TN) (0.02%), high mass ratio of TOC/TN (10.8), low δ13C (−24.9‰), low TS content (0.06%), and a high ratio of TOC/TS (9.1) from 33.6 ka BP to 12.3 ka BP, implying that freshwater organic matter (OM), algae, and C3 plant fragments were the main sources of OM in a relatively cold environment. The abundances of TOC, TN, and TS increased to 0.56%, 0.07%, and 0.4%, respectively, while δ13C (−23.9‰) increased and TOC/TS (2.7) decreased in the Holocene sediments, suggesting that seawater began to influence the composition of the sediments of HZB. Climate warming, which is likely to have impacted the results, was experienced from 12.3 ka BP. An OC isotope mixing model indicated that since the Mid-late Holocene, more than 70% of riverine OM accounted for the total OM. The TOC/TS ratio was identified as an effective indicator of seawater intrusion, with C/S ratios of 1–6 being considered to indicate a “sea–land transitional zone” sedimentary environment, a C/S &amp;gt;6 indicating freshwater, and a C/S&amp;lt;1 indicating normal marine facies. These findings provide crucial evidence for using TOC/TS to distinguish freshwater from marine environments and enhance our understanding of past climate changes. Therefore, these geochemical indicators can be used in conjunction with other sedimentary records to obtain accurate results about sedimentary evolution.

Characterization of microplastic-derived dissolved organic matter in freshwater: Effects of light irradiation and polymer types

This study investigated the impacts of light irradiation and polymer types on the leaching behavior of dissolved organic matter (DOM) from microplastics (MPs) in freshwater. Polypropylene had the highest leaching capacity of DOM after photoaging, followed by polystyrene (PS), polyamide (PA) and polyethylene terephthalate (PET). While similarly low levels of DOM were observed in the remaining 5 MP suspensions under UV irradiation and in almost all MP suspensions (except PA) under darkness. These suggest that the photooxidation of some buoyant plastics may influence the carbon cycling of nature waters. Among 9 MP-derived leachates, PET leachates had the highest chromophoric DOM concentration and aromaticity, probably owing to the special benzene rings and carbonyl groups in PET structures and its fast degradation rate. Protein-like substances were the primary fluorescent DOM in MP suspensions (except PS), especially in darkness no other fluorescent substances were found. Considering the bio-labile properties of proteins together, MPs regardless of floating or suspended in an aquatic environment may have prevalent long-term effects on microbial activities. Besides, from monomers to hexamers with newly formed chemical bonds were identified in UV-irradiated MP suspensions. These results will contribute to a deep insight into the potential ecological effects related to MP degradation.

Molecular level seasonality of dissolved organic matter in freshwater and its impact on drinking water treatment

Molecular level seasonality of dissolved organic matter in freshwater and its impact on drinking water treatment

Determining patterns in the composition of dissolved organic matter in fresh waters according to land use and management

In fresh waters, the origins of dissolved organic matter (DOM) have been found to exert a fundamental control on its reactivity, and ultimately, its ecosystem functional role. A detailed understanding of landscape scale factors that control the export of DOM to aquatic ecosystems is, therefore, pivotal if the effects of DOM flux to fresh waters are to be fully understood. In this study we present data from a national sampling campaign across the United Kingdom in which we explore the variability in DOM composition in three broad landscape types defined by similar precipitation, geology, land use and management, hydrology, and nutrient enrichment status. We characterised samples from fifty-one sites, grouping them into one of three major underlying classifications: circumneutral streams underlain by clay and mudstone (referred to as ‘clay’), alkaline streams underlain by Cretaceous Chalk or by Carboniferous or Jurassic Limestone (‘limestone’), and acidic streams in peatland catchments underlain by a range of low permeability lithologies (‘peat’). DOM composition was assessed through organic matter stoichiometry (organic carbon: organic nitrogen; organic carbon: organic phosphorus; C/N(P)DOM) and metrics derived from ultra-violet (UV)/visible spectroscopic analysis of DOM such as specific UV absorption (a254 nm; SUVA254). We found similar SUVA254, C/NDOM and DOM/a254 relationships within classifications, demonstrating that despite a large degree of heterogeneity within environments, catchments with shared environmental character and anthropogenic disturbance export DOM with a similar composition and character. Improving our understanding of DOM characterisation is important to help predict shifts in stream ecosystem function, and ecological responses to enrichment or mitigation efforts and how these may result in species composition shifts and biodiversity loss in freshwater ecosystems.

Sampling, storage and laboratory approaches for dissolved organic matter characterisation in freshwaters: Moving from nutrient fraction to molecular-scale characterisation

Recent research has highlighted the importance of dissolved organic matter (DOM) for ecosystem function and because of this paradigm shift, it has become crucial to not only quantify its contribution to river nutrient loads but also to characterise its composition. There has been a significant research effort utilising optical methods, such as fluorescence and UV–Vis spectrophotometry, in order to start exploring DOM character. However, these methods still lack the granularity to understand the chemical composition at the molecular level, which is vital to properly understanding its functional role in freshwater ecosystems. As a direct result, there has been a shift towards including molecular-scale analyses to investigate the in-stream processing of the material. Alongside this, recent methodological advancements, particularly in mass spectrometry are opening new opportunities for probing one of the most complex environmental mixtures. However, in order to fully exploit these opportunities, it is key that the way that samples are collected, processed and stored is considered carefully such that sample integrity is maintained. There are additional challenges when collecting water samples for analysis at molecular scale, for example the ultra-low concentrations of individual compounds within DOM means that the samples are sensitive to contamination. This paper discusses current sample collection, processing and storage protocols for this C, N and P quantification and characterisation in freshwaters, and proposes a new standardised protocol suitable for both nutrient fraction quantification and molecular scale analyses, based on method development and testing undertaken in our UK Natural Environment Research Council large grant programme, characterising the nature, origins and ecological significance of Dissolved Organic Matter IN freshwater Ecosystems (DOMAINE).

Disruptive effect of artificial light at night on leaf litter consumption, growth and activity of freshwater shredders

Artificial light at night (ALAN) is a globally widespread phenomenon potentially affecting ecosystem processes, such as leaf litter breakdown, which is a source of organic matter in fresh waters. Here, we conducted a long-term experiment to test the effects of ALAN (2 lx) differing in spectral composition: white LEDs and high pressure sodium lamps (HPS) on leaf consumption, growth and activity of two macroinvertebrate species of shredders: Gammarus jazdzewskii and Dikerogammarus villosus (Crustacea, Amphipoda), compared to the undisturbed light-dark cycle. We also tested if the nocturnal illumination would influence the algal community colonising leaves, which is an important component of the leaf-shredder diet. We found that LED light increased the consumption of leaves by both species, which was nearly twice as high as in other treatments, and supressed the growth rate of G. jazdzewskii, whereas the growth of D. villosus was not affected by either light type. Moreover, D. villosus reduced its activity when exposed to ALAN of both types. As ALAN-induced changes in shredder growth and consumption were not associated with their increased activity or decreased food quality, we suggest that LED light may be a source of physiological stress for shredders, raising their energy expenditure, which was compensated by increased food intake. We have shown that LED illumination induces greater effects on wildlife than alternative, narrow wavelength spectrum light sources, such as HPS lamps, and may potentially alter the litter breakdown in aquatic ecosystems. It may accelerate the turnover of leaves by shredders, but on the other hand, it may negatively affect the fitness of macroinvertebrates and thus disturb the leaf processing over a longer term.

P-limitation drives changes in DOM production by aquatic bacteria

Heterotrophic bacteria are key biogeochemical regulators in freshwater systems. Through both decomposition and production of organic matter, bacteria link multiple biogeochemical cycles together. While there has been a significant amount of work done on understanding the role of microbes in the aquatic carbon cycle, important linkages with other biogeochemical cycles will require more information about how organic matter transformations impact other nutrients, such as phosphorus. In this study, we conducted a culture-based laboratory experiment to examine the production of dissolved organic matter (DOM) by heterotrophic bacteria under varied nutrient conditions. In addition to quantifying the production of dissolved organic carbon (DOC), we also measured the production of dissolved organic phosphorus (DOP) and characterized the microbially produced organic matter using optical properties. Results demonstrated that measurable amounts of DOC and DOP were produced by heterotrophic bacteria under nutrient regimes ranging from carbon-limitation to strong phosphorus-limitation. Additionally, optical characterization of DOM revealed that the organic matter produced by bacteria grown under high phosphorus conditions was highly aromatic with similar optical properties to terrestrially derived organic matter. Overall, these findings suggest that heterotrophic bacteria can be important producers of organic matter in freshwaters and that continued trends of increased nutrient concentrations (eutrophication) may fundamentally change the composition of microbially produced organic matter in freshwater systems.

Fouling characteristics of dissolved organic matter in fresh water and seawater compartments of reverse electrodialysis under natural water conditions

The fouling characteristics of dissolved organic matter (DOM) in the fresh water and seawater compartments of the reverse electrodialysis (RED) system were investigated under natural water conditions. The salinity gradient power generation was governed monovalent ions whereas multivalent ions strongly contributed to the fouling formation of the ion-exchange membranes (IEMs). The partial deposition of DOM within the membrane pores during its passage from the fresh water compartment to the seawater compartment facilitated the fouling formation of the IEMs. Despite of the similar DOC losses in fresh water (DOC loss = 20%) and seawater (DOC loss = 22%) through the RED system, the colour variations of the anion-exchange membranes (AEMs) and spacers in contact with fresh water were more noticeable than those in contact with seawater. These results indicate that the deposition of hydrophobic DOM components onto the AEM surfaces water may lead to the increases in the pressure drop of the fresh water compartment and the decreases in the power density of the RED system. Therefore, an appropriate pre-treatment strategy capable of mitigating membrane fouling by hydrophobic DOM components seemed to be indispensable to maintain constantly the performance of the RED system under natural water conditions.

Combined effects of water temperature, grazing snails and terrestrial herbivores on leaf decomposition in urban streams

The decomposition of organic matter in freshwaters, such as leaf litter, can affect global nutrient (e.g., carbon) cycling. This process can be influenced by fast urbanization through increased water temperature, reduced aquatic diversity and changed leaf litter quality traits. In this study, we performed a mesocosm experiment to explore the individual and combined effects of warming (8°C higher and ambient), the presence versus absence of grazing snails (Parafossarulus striatulus), and intraspecific difference of leaf litter quality (intact versus > 40% area of Liriodendron chinense leaves grazed by terrestrial insects) on litter decomposition in urban streams. Litter decomposition rates ranged from 0.019 d−1 to 0.058 d−1 with an average decomposition rate of 0.032 ± 0.002 d−1. All the three factors had significant effects on litter decomposition rate. Warming and the presence of snails accelerated litter decomposition rates by 60% and 35% respectively. Litter decomposition rates of leaves damaged by terrestrial insects were 5% slower than that of intact leaves, because litter quality of terrestrial insect-damaged leaves was lower (i.e., higher specific leaf weight) than intact leaves. For treatments with snails, warming stimulated microbial and snail mediated litter decomposition rates by 35% and 167%, respectively. All combinations of treatments showed additive effects on litter decomposition except for the interaction between warming and snails which showed positive synergistic effects. In addition, neither temperature nor litter quality affected snail growth rate. These results imply that higher water temperature and the presence of abundant snails in urban streams greatly enhanced litter decomposition. Moreover, the effect of pest outbreaks, which resulted in lower litter quality, can cascade to aquatic ecosystems by retarding microbe-mediated litter decomposition. When these factors co-occurred, warming could synergistically interact with snails to speed up the depletion of organic matter, while the effect of leaf quality on litter decomposition may be diminished at high water temperature. These effects could further influence stream food webs and nutrient cycling.

Macrofaunal bioturbation attributes in relation to riverine influence: What can we learn from the Po River lagoonal system (Adriatic Sea)?

Delta areas are highly dynamic transitional areas, important for burial and decomposition of terrestrial and marine organic matter (OM). In these environments, macrofaunal organisms are influenced by fluctuations of fresh OM inputs that modify several aspects of their growth, reproduction and behaviour. Macrofaunal bioturbation activities are significant processes performed by individuals, which directly influence the biogeochemical cycling and thus the ecosystem functioning. To assess the influence of terrigenous/freshwater OM on bioturbation attributes of macrofauna in a lagoonal system, we integrated the bioturbation and irrigation potential (BPc and IPc) community indices and functional traits linked to reworking and ventilation of sediments (using Biological Traits Analysis-BTA). The macrofaunal community was investigated in four lagoons (Caleri, Marinetta-Vallona, Canarin and Scardovari) of the Po River Delta in Italy (northern Adriatic Sea). We examined the macrofaunal biodiversity and bioturbation attributes in relation to grain-size distribution, carbon and nitrogen ratio (C:N), carbon and nitrogen stable isotopes (δ13C and δ15N), and the radionuclides 137Cs and 7Be. The latter were used as proxies of the age of terrigenous/riverine-derived OM. The lowest values of BPc and IPc that corresponded to minimum values of benthic biodiversity were observed at the inner sampling stations of Scardovari. Here, low diversity values were likely ascribed to recent hypoxic/anoxic conditions exacerbated by the low water renewal that characterizes this lagoon, influencing the bioturbation processes. Grain-size fractions were significant drivers of the differences in BPc and IPc, and the major number of taxa in coarse sediments contributed to the highest values of bioturbation indices. A significant difference in IPc between sandy and muddy stations was due to the presence of subsurface deposit feeders with high burrowing depths and blind-ended burrows that enhanced the bio-irrigation in coarse sediments. We observed diverse spatial patterns of trait-categories belonging to sediment reworking activity at stations differently influenced by freshwater OM. Semi-motile and conveyor invertebrates, that are able to move sediment particles through their gut by ingestion and secretion, were dominant nearby the lagoon mouths where OM of freshwater origin was present. High occurrence of motile and biodiffuser invertebrates, that can randomly mix sediments layers, were found at stations characterized by old OM. Macrofaunal sediment reworking and ventilation processes are of paramount importance in the framework of an efficient management and sustainable use of lagoons, often exposed to anoxic and dystrophic events, that are strongly exploited for aquaculture.

Leaf-litter leachate concentration promotes heterotrophy in freshwater biofilms: Understanding consequences of water scarcity

Climate change is increasing overall temporal variability in precipitation resulting in a seasonal water availability, both increasing periods of flooding and water scarcity. During low water availability periods, the concentration of leachates from riparian vegetation increases, subsequently increasing dissolved organic matter (DOM). Moreover, shifts in riparian vegetation by land use changes impact the quantity and quality of DOM. Our objective was to test effects of increasing DOM concentrations from Eucalyptus grandis (one of the most cultivated tree species in the world) leachates on the metabolism (respiration, R; gross primary productivity, GPP) and extracellular enzyme activities (EEAs) of freshwater biofilms. To test effects of DOM concentrations on freshwater biofilm functions, we incubated commercial cellulose sponges in a freshwater pond to allow biofilm colonization, and then exposed biofilms to five different concentrations of leaf-litter leachates of E. grandis for five days. To test if responses to DOM concentrations varied with colonization stage of biofilms, we measured treatment effects on biofilms colonizing standard substrates after one, two, three and four weeks of colonization. Increases in leachates concentrations enhanced biofilm heterotrophy, increasing R rates and decreasing GPP. Leachate concentrations did not affect biofilm EEAs, and changes in biofilm metabolism were not explained by treatment-induced changes in biofilm biomass or stoichiometry. We detected the lowest production:respiration ratios, i.e. more heterotrophic assemblages, with the most concentrated leachate solution and the most advanced biofilm colonization stages. Shifts in quantity of dissolved organic matter in freshwaters may further influence ecosystem metabolism and carbon processing.

Combining asymmetrical flow field-flow fractionation with on- and off-line fluorescence detection to examine biodegradation of riverine dissolved and particulate organic matter

This study demonstrated that asymmetrical flow field-flow fractionation (AF4) coupled with on-line UV and fluorescence detection (FLD) and off-line excitation-emission matrix (EEM) fluorescence spectroscopy can be employed to analyze the influence of microbial metabolic activity on the consumption and production of freshwater organic matter. With the AF4 system, organic matter is on-line enriched during a focusing/relaxation period, which is an essential process prior to separation. Size-fractionated chromophoric and fluorophoric organic materials were simultaneously monitored during the 30-min AF4 separation process. Two fractions of different sizes (dissolved organic matter (DOM) and particulate organic matter (POM)) of freshwater samples from three locations (up-, mid-, and downstream) along the Han River basin of Korea were incubated with the same inoculum for 14 days to analyze fraction-specific alterations in optical properties using AF4-UV-FLD. A comparison of AF4 fractograms obtained from pre- and post-incubation samples revealed that POM-derived DOM were more susceptible to microbial metabolic activity than was DOM. Preferential microbial consumption of protein-like DOM components concurred with enhanced peaks of chromophoric and humic-like fluorescent components, presumably formed as by-products of microbial processing. AF4-UV-FLD combined with off-line identification of microbially processed components using EEM fluorescence spectroscopy provides a powerful tool to study the relationship between microbial activity and composition as well as biodegradability of DOM and POM-derived DOM from different origins, especially for the analysis of chromophoric and fluorophoric organic matter that are consumed and produced by microbial metabolic activity. The proposed AF4 system can be applied to organic matter in freshwater samples having low concentration range (0.3–2.5ppm of total organic carbon) without a pre-concentration procedure.

Contrasting patterns of allochthony among three major groups of crustacean zooplankton in boreal and temperate lakes.

The importance of terrestrial-derived organic matter for lake zooplankton communities remains debated, partly because little is known about the basic pathways by which allochthonous carbon is transferred to zooplankton, and whether these vary among the major taxonomic and functional groups. We quantified allochthony of three zooplankton groups (Cladocera, Calanoida, and Cyclopoida) across 18 lakes in Quebec, spanning broad gradients of dissolved organic matter (DOM) and lake trophy, using a multi-isotope (delta2H + delta13C), multi-source (terrestrial, phytoplanktonic, benthic) approach. All three zooplankton groups had significant levels of allochthony, but differed greatly in their respective patterns across lakes. Allochthony in Calanoida and Cyclopoida was linked to detrital food chains based on particulate organic matter (POM) and on DOM, respectively, whereas in Cladocera it appeared related to both pathways; not surprisingly this latter group had the highest mean allochthony (0.31; compared to 0.18 in Cyclopoida and 0.16 in Calanoida). This study highlights the complexity of the pathways of delivery and transfer of terrestrial organic matter in freshwaters, and underscores the role that microbial food webs play in this transfer.

Distribution of dissolved organic matter in freshwaters using excitation emission fluorescence and Multivariate Curve Resolution

Multivariate Curve Resolution Alternating Least Squares (MCR-ALS) method with the trilinearity constraint is proposed for the analysis of excitation–emission fluorescence data from Dissolved Organic Matter (DOM) in fresh water natural systems, and the results obtained are compared with those obtained with PARAFAC. The effects of different number of components and constraints on the stability of the proposed models are compared. MCR-ALS is shown to be an effective way to characterize and resolve DOM sources in natural fresh water systems from EEM data, with good correlation with experimentally measured DOM concentration values. MATLAB georeferenced mapping is used to illustrate the geographical distribution of resolved DOM contributions. MCR-ALS resolved EEM spectra are used to recognize the corresponding chemical groups assigned to possible DOM sources. Relationships between human activities and the environmental situation of the river system are discussed from these possible DOM sources.

Inter-proxy evidence for the development of the Amazonian mangroves during the Holocene

The dynamics of mangrove forest on the island of Marajo ´ (Ilha de Marajo ´) at the mouth of the river Amazon during the past *7,500 cal. B.P. were studied using multiple proxies, including sedimentary facies, pol- len, d 13 C, d 15 N and C/N ratio, related to 15 sediment samples by 14 C dating. The results allow us to propose a scheme of palaeogeographical development, with changes in vegetation, hydrology and organic matter dynamics. Today, the interior of the island is occupied by varzea freshwater herbaceous vegetation, but during the early to middle Holocene, mangroves with accumulations of estu- arine organic matter colonized the tidal mud flats. This spread of mangroves was caused by post-glacial sea-level rise, which combined with tectonic subsidence, produced a marine transgression. It is likely that the relatively greater marine influence at the studied area was favoured by reduced discharge from the river Amazon, which was itself caused by a dry period that occurred during the early and mid Holocene. During the late Holocene, there was a reduction of mangrove vegetation and the contribution of freshwater organic matter to the area was higher than during the early and mid Holocene. This suggests a decrease in marine influence during the late Holocene which led to a gradual migration of mangrove vegetation from the central region to the northeastern littoral zone of the island, and, consequently, its isolation since at least *1,150 cal. B.P. This was probably a result of lower tidal water salinity caused by a wet period that resulted in greater river discharge during the late Holocene. This work details the contraction of mangrove forest from the north- eastern part of the island of Marajounder the influence of Amazon climatic changes, chronologically and spatially. This allows us to propose a model of successive phases of sediment accumulation and vegetation change, according to the marine-freshwater influence gradient. As demon- strated by this work, the use of a combination of proxies is efficient for establishing a relationship between the chan- ges in estuarine salinity gradient and depositional envi- ronment/vegetation.

An integrated approach to relate Holocene climatic, hydrological, morphological and vegetation changes in the southeastern Amazon region

The geomorphological analysis of the river Tocantins alluvial area was carried out by remote sensing techniques, jointly with studies of sedimentary facies, mineralogy and geochemistry, pollen and spores, C and N isotopes data and radiocarbon dating of a sediment core from a floodplain lake, near the river Tocantins in the southeastern Amazon region. The aim was to identify and discuss the relationship between the main geomorphological processes and climatic factors, as well as their influence on vegetation patterns. The data indicate three phases of sediment and organic matter accumulation associated with vegetation changes during the Holocene: in Phase 1 (>7760 ± 80 cal yrs b.p.), the channel was gradually being disconnected from its main course, accumulating organic matter from terrestrial woody plants; in Phase 2 (>7760 ± 80 to 5145 ± 175 cal yrs b.p.), the very low energy flows allowed the deposition of autochthonous organic mud from suspension. Herbaceous vegetation and a Mauritia palm-swamp dominated the study area, followed by an increase in the contribution of freshwater dissolved organic carbon (DOC) to the lake; Phase 3 (5145 ± 175 cal yrs b.p. until present) records the expansion of ferns and arboreal plants, and greater freshwater organic matter input into the lake with anoxic water conditions. The development of the studied lake occurred by geomorphological changes and the filling process of an abandoned channel according to hydrodynamics and vegetation changes which were probably influenced by climatic changes during the Holocene.