Matter In Freshwaters 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

Potential deterioration of chemical water quality due to trace metal adsorption onto tire and road wear particles – Environmentally representative experiments

Tire wear particles are an increasing issue in particle emissions to the environment. Germany-wide approximately 100,000 t tire wear particles are emitted every year into the environment which are estimated to be one third of the microplastic emissions. Up to 20% are estimated to reach inland surface waters. Their behavior in the aquatic environment is understudied. Tire wear particles have an overly hydrophobic surface that is capable of adsorbing substances like trace elements. In this study we investigated the adsorption and desorption of trace metals onto and from the particle surface of tire-related samples in water samples of the Freiberger Mulde, a river with naturally elevated concentration of trace elements. The priority trace metals Cr, Ni, Zn, Cd and Pb show a significant adsorption onto the particle surface of tire-related samples. Tire wear particles themselves revealed adsorption of mainly Ni, Cd and Pb. Regarding the German classification for suspended matter in freshwaters, an endangering of the chemical water quality is expected due to the adsorption process and not due to the particles themselves. Upcoming electromobility is expected to increase the Zn (increased tire abrasion) and decrease the Cu amount (reduced brake abrasion) released to freshwaters.

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.

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.

Tracing particulate matter and associated microorganisms in freshwaters

Sediment resuspension represents a key process in all natural aquatic systems, owing to its role in nutrient cycling and transport of potential contaminants. Although suspended solids are generally accepted as an important quality parameter, current monitoring programs cover quantitative aspects only. Established methodologies do not provide information on origin, fate, and risks associated with uncontrolled inputs of solids in waters. Here we discuss the analytical approaches to assess the occurrence and ecological relevance of resuspended particulate matter in freshwaters, with a focus on the dynamics of associated contaminants and microorganisms. Triggered by the identification of specific physical–chemical traits and community structure of particle-associated microorganisms, recent findings suggest that a quantitative determination of microorganisms can be reasonably used to trace the origin of particulate matter by means of nucleic acid-based assays in different aquatic systems.

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.

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.

Stable isotope analysis of organic carbon in small (µg C) samples and dissolved organic matter using a GasBench preparation device

The stable isotopes of organic matter can provide valuable information on carbon cycling dynamics, microbial metabolisms, and past climates. Since bulk measurements may mask dynamic changes to critical portions of the organic pool, researchers are increasingly isolating individual compounds for isotopic analysis. The amount of carbon isolated is frequently small, requiring specialized equipment for its analysis. We present a simple and accurate method to measure the δ(13)C values of µg-amounts of organic compounds and dissolved organic matter in freshwaters using wet oxidation and a GasBench II preparation device. Samples containing 3 µg C can be analyzed with a precision of <0.4‰. For samples containing 1.2 µg C, the precision is <0.8‰. The blank is estimated to be ~0.2 µg C. The accuracy of the method is demonstrated for a wide range of compounds including those that are difficult to oxidize such as humic acid and phthalic acid. The δ(13)C values of DOC from river and riparian ground water determined by this method are comparable with those determined with an elemental analyzer on freeze-dried samples of DOC. The low detection limit and the ease with which it can be combined with isolation techniques such as liquid chromatography make this technique attractive for the off-line analysis of organic compounds, and open new possibilities for the development of methodologies for compound-specific carbon isotope analysis of complex mixtures separated by HPLC.

Size distribution of methylmercury associated with particulate and dissolved organic matter in freshwaters

Water samples were collected from 20 wetland, river and lake sites across Eastern Ontario and Western Quebec to investigate the distribution of methylmercury (MeHg) associated with various size fractions of dissolved organic matter (DOM). Tangential Flow UltraFiltration (TUF) was used to fractionate DOM by nominal molecular size (<0.2 μm, <300 kDa, <30 kDa, <5 kDa and <1 kDa). DOM fluorescence (DOM FL) and absorbance (DOC Abs) were used to quantify DOM photoreactivity and aromaticity in each sample. Significant differences in the size-associated distribution of MeHg, Dissolved Organic Carbon (DOC), DOM FL, and DOM Abs were observed between wetlands, rivers, and lakes. The low molecular weight (LMW) fraction (<5 kDa) in wetlands contained the majority of MeHg (70.0 ± 13.8%), DOC (56.1 ± 9.4%), and DOM FL (77.4 ± 7.5%). DOM FL was also high in the LMW fraction for rivers (60.6 ± 25%) and lakes (75.2 ± 16.9%). Mean MeHg concentrations in the LMW fraction of lakes (41 ± 26 pg L − 1 ) and rivers (32 ± 19 pg L − 1 ) were substantial but much lower than wetlands. Rivers had the highest percentage of methylmercury (38.0 ± 23.5%) in the particulate (>0.2 µm) fraction. This research highlights the importance of low molecular weight dissolved organic matter in methylmercury fate. For example, a large proportion of MeHg was found in the LMW weight fractions (mean = 47.3 ± 25.4%) of the wetlands, rivers, and lakes in this study.

Oxygen release compound as a chemical treatment for nutrient rich estuary sediments and water

The objectives of this work were: (i) to evaluate the efficacy of Oxygen Release Compound (ORC®), oxygen providing agent that enhance the oxidation of organic matter in fresh water, marine water, and sediment; and (ii) to explore the potential aquatic toxicity that might be generated due to its use. A bench scale laboratory experiments were conducted using five different water sources (2 freshwater, 2 marine water and a deionised water). During the assay, flasks of 1 L capacity were dosed with artificial sediment and ORC® and kept at room temperature for 10 days. Temperature, pH, DO, UV254, TOC and Mg were periodically measured. The potential aquatic toxicity that might be generated as a by-product of ORC® use was performed. The experimental results reveal that ORC® is indeed effective in releasing oxygen over a long period of time and it is also effective for the remediation of natural waters enriched with organic matter. The toxicity test shows that ORC® treatment did not create any biological toxicity in freshwater samples (IC50 < 1 Toxicity Unit – TU). However, marine water samples reveal a high toxicity and had IC50 > 1 TU. The study proves that ORC® was an appropriate technology that can safely be used to treat natural waters enriched with nutrient and natural organic matter.

The Chemical Speciation of Fe(III) in Freshwaters

Dialysis and chemical speciation modelling have been used to calculate activities of Fe3+ for a range of UK surface waters of varying chemistry (pH 4.3–8.0; dissolved organic carbon 1.7–40.3 mg l-1) at 283K. The resulting activities were regressed against pH to give the empirical model: log aFe3+ = 2.76(±0.53) – 2.63(±0.08)•pH Predicted Fe3+ activities are consistent with a solid–solution equilibrium with hydrous ferric oxide. However, the apparent solubility of the solid phase decreases as pH decreases, consistent with some previous studies on Fe(III) solubility in the laboratory. The empirical model was used to predict concentrations of Fe in dialysates and ultrafiltrates of globally distributed surface and soil/ground waters. The predictions were improved greatly by the incorporation of a temperature correction for aFe3+, consistent with the temperature–dependence of previously reported hydrous ferric oxide solubility. The empirical model, incorporating temperature effects, may be used to make generic predictions of the ratio of free and complexed Fe(III) to dissolved organic matter in freshwaters. Comparison of such ratios with observed Fe : dissolved organic matter ratios allows an assessment to be made of the amounts of Fe present as Fe(II) or colloidal Fe(III), where no separate measurements have been made.

Copper Binding by Dissolved Organic Matter in Freshwaters in Kenya

The binding of Cu2+ to dissolved organic matter in eight different natural water samples obtained from different locations in Kenya was studied by potentiometric titration method. The DOC contents of the eight natural water samples ranged from 2.71 to 374 mg/L. The water samples were adjusted to a uniform background electrolyte concentration of 0.5 M NaNO(3) and pH 6 and the temperature maintained at 20 degrees C during the assay. A Nernst equation E (mV) = -32.175 pCu + 305.5 (R (2) = 0.9996) obtained for the Cu2+ calibration standards (10(-4)-10(-6) M) was used to determine the concentration of free and bound Cu2+, respectively. The bound [Cu2+] varied by a factor of 2, ranging from 2.67 x 10(-3) mol/kg DOC (in a high DOC alkaline lake water sample) to 3.2962 x 10(-1) mol/kg (in a low DOC river water sample). The binding constants (Log K) varied by a factor of 2 and ranged from 3.43 to 5.57. The percentage binding ranged from 87% to almost 100% in the eight natural water samples. A Suwannee River Fulvic Acid standard sample (40 mg/L DOC) was used for comparison and for validation of the method.