Influence of Dissolved Organic Matter On the Bio-Availability and Toxicity of Metals in Soils and Aquatic Systems

Cations in soil are essential for the growth of plants and micro-organisms. Their availability is dependent on soil organic matter. Soil organic matter (SOM) is heterogeneous comprising amino, aliphatic and phenolic acids, but particularly humic substances. All these substances can complex cations selectively. Mechanisms of complexation with dissolved organic matter are discussed. Such complexation can lead to the apparently contradictory observations that dissolved organic matter (DOM) can either increase the concentration of some less soluble nutrients, making them more available for plant uptake, or make them less available and hence less toxic. the importance of DOM is discussed in relation to soil solution, particularly the rhizosphere, and also in relation to aquatic systems. the latter systems contain mainly dissolved humic substances whereas in the soil, non-humic substances assume a greater importance.

SOM in the rhizosphere is derived from plant, microbial and animal remains but much, especially the water-soluble compounds, are acquired through root exudation. Exudation has important consequences for enhanced nutrient availability as a result of the production of non-humic substances such as amino, aliphatic and phenolic acids. in future, the role of root exudation in relation to DOM and nutrient availability should be investigated more fully, particularly as predicted elevated CO₂ levels are likely to have a major impact on root exudation, nutrient availability, and possibly ecosystem community structure and functioning. It is likely that more information will become available on aquatic systems as more highly sensitive techniques and equipment capable of dealing with low concentrations of DOM in these systems become available.     

Influence of Dissolved Organic Matter On the Bio-Availability and Toxicity of Metals in Soils and Aquatic Systems

Cations in soil are essential for the growth of plants and micro-organisms. Their availability is dependent on soil organic matter. Soil organic matter (SOM) is heterogeneous comprising amino, aliphatic and phenolic acids, but particularly humic substances. All these substances can complex cations selectively. Mechanisms of complexation with dissolved organic matter are discussed. Such complexation can lead to the apparently contradictory observations that dissolved organic matter (DOM) can either increase the concentration of some less soluble nutrients, making them more available for plant uptake, or make them less available and hence less toxic. the importance of DOM is discussed in relation to soil solution, particularly the rhizosphere, and also in relation to aquatic systems. the latter systems contain mainly dissolved humic substances whereas in the soil, non-humic substances assume a greater importance.

SOM in the rhizosphere is derived from plant, microbial and animal remains but much, especially the water-soluble compounds, are acquired through root exudation. Exudation has important consequences for enhanced nutrient availability as a result of the production of non-humic substances such as amino, aliphatic and phenolic acids. in future, the role of root exudation in relation to DOM and nutrient availability should be investigated more fully, particularly as predicted elevated CO₂ levels are likely to have a major impact on root exudation, nutrient availability, and possibly ecosystem community structure and functioning. It is likely that more information will become available on aquatic systems as more highly sensitive techniques and equipment capable of dealing with low concentrations of DOM in these systems become available.     

Der Einfluß physikalischer und chemischer Faktoren auf die Aufnahme in Meerwasser gelöster Aminosäuren durch Aktinien

Changes in abiotic environmental factors do not adversely influence the capacity of Anemonia sulcata (Coelenterata, Anthozoa) to take up dissolved amino acids from sea water; e. g., A. sulcata resorbs also under anaerobic conditions. The influence of temperature on amino acid uptake (Q₁₀=2) indicates that the translocation of the organic molecules through membranes of the ectoderm depends on energy. Uptake of amino acids is possible against a gradient of up to 9×10⁶:1. It can be postulated that L-amino acids (also D-isomers) and glucose are resorbed by different “carrier systems”, since glucose does not influence the uptake of amino acids; however, amino acids can interfere with each other, e. g. phenylalanine/glycine. Blocking of anaerobic glycolysis results in uptake reduction; at the same concentrations “oxidative” blockers have a much smaller effect on amino acid uptake. The possibility of exploiting the surrounding water as an energy source by taking up dissolved organic material is discussed with reference to ecological and evolutionary aspects.     

Use of tritiated substrates in the study of heterotrophy in seawater

An improved method is described for the study of heterotrophic utilization of dissolved organic substances by marine microorganisms. The method is based on the use of ³H-labelled organic substrates of very high specific activity, rather than the conventionally used ¹⁴C-labelled substrates. Direct measurement of the rate of tracer uptake at near ambient concentration can thus be made instead of extrapolation using the Michaelis-Menten equation. The method also permits comparison between the rates of tracer uptake in sub-samples exposed to different physico-chemical conditions (temperature, light, pollutants, etc.) without the necessity of determining the ambient substrate concentration. The method was applied to the determination of D-glucose uptake by nearshore and pelagic natural microbial populations, and was found to be sensitive and convenient.     

Dissolved organic substances during a Phaeocystis pouchetii bloom in the German Bight (North Sea)

Dissolved organic substances (carbohydrates, organic nitrogen, free amino acids) were measured in the German Bight (North Sea) in June, 1981. During and before this survey, sea foam was observed in the east Frisian coastal water and it accumulated on the nearby beaches to an unusually high extent. In this coastal water area, a large Phaeocystis pouchetii Lagerheim bloom and very high concentrations of dissolved organic matter were found. The above dissolved organic substances were all positively correlated to a highly significant degree with P. pouchetii cell numbers in the bloom area. An influence of salinity (or river water) on this correlation could be excluded. Thus, exudation or decomposition products of P. pouchetii were most likely the cause of the unusually high concentrations of dissolved organic matter in the bloom area off the east Frisian coast, where P. pouchetii blooms have been reported for many years. Ammonia concentrations were very low in the P. pouchetii bloom area; this and the accumulation of dissolved organic substances might lead to speculation that decomposition of dissolved organic matter by bacteria could have been reduced due to antibiotic activity of P. pouchetii.     

Physiological energetics of developing embryos and yolk-sac larvae of Atlantic cod (Gadus morhua). I. Respiration and nitrogen metabolism

This paper provides the basis for a general model of catabolic metabolism for developing embryos and yolk-sac larvae of Atlantic cod (Gadus morhua L.). Yolk-dependent routine rates of oxygen consumption, ammonia excretion, and accumulation of ammonium ions were related to quantitative changes in contents of glucose, glycogen, lactate, free amino acids, proteins and lipid classes (lipid classes published separately) in order to determine the rate and sequence of catabolic substrate oxidation that occurs with development at 6.0°C, 34.5 S. The stoichiometric relation of the oxygen consumption and total ammonia production to substrate utilisation indicated that during the first 2 to 3 d of development, glycogen was the sole substrate of oxidative metabolism. After formation of the syncytium, free amino acids (75%) together with polar lipids (13%, mainly phosphatidyl choline) and neutral lipids (9%, mainly triacylglycerol) comprised the metabolic fuels of embryonic development. Following hatch (Day 16 post fertilisation), the fuels were free amino acids (32%), polar lipids (20%, mainly phosphatidyl choline), neutral lipids (17%, mainly triacylglycerol) and proteins (31%). Thus, the catabolic metabolism of endogenously feeding Atlantic cod larvae was predominantly fuelled by amino acids (67%) and lipids (32%), while glycogen only accounted for 1% of the total enthalpy dissipated. It is proposed that the above sequence of catabolic substrate oxidation is also generally applicable to other cold-water fishes which spawn eggs that do not contain oil glubules.     

Huminstoffe in Sedimentporenwässern ausgewählter Bundeswasserstraßen

Humic substances are an important component of organic carbon in natural waters. Their character and properties are determined by the sources and the processes of their origin. Humic substances are not exclusively refractory compounds, but they are involved in several transformation processes in the water. It is not possible to directly analyze humic substances, therefore several methods were applied for their characterization. The presented LC-OCD-technique is a size-exclusion-chromatography with online UV- and carbon detection. Carbon fractions, e.?g. humic substances were differentiated by their molecular size. The portion of humic substances in sediment porewaters of the rivers Elbe, Rhine, Danube, Oder, Müritz-Elde-Waterway was determined. With only a few exceptions it ranges from 50 to 67?% of the dissolved organic carbon. The high molecular weight fraction accounts for 10 to 34?%, and the fraction of the low molecular weight substances was from 7 to 37?%. The ratio between the spectral absorption coefficient (254?nm) and the organic carbon is called SUVA (L/mg × m) and is an inidicator of the proportion of unsaturated bonds in the humic substances. Both high molecular herbal components (e.?g. cellulose, lignin) and biological degradiation products (e.?g. amino acids, sugar) are involved in sediment porewater transformation and degradiation processes. This demonstrates the distribution of the dissolved organic carbon between the fractions.     

Thermodynamische Modelle für die Bioverfügbarkeit und Bioakkumulation organischer Chemikalien

In aquatic systems, the bioavailability of neutral organic xenobioties is goverened by sorption processes with dissolved, colloidal and particulate organic matrices, and in case of ionogenic compounds also by the degree of dissociation or protonation. The assumption of competitive thermodynamic equilibria yields a simple quantitative characterization of the relationship between the total content of a compound and its freely dissolved fraction in aqueous solution. To a first order, the latter is often assumed to be identical with the bioavailable portion of the compound. Thermodynamic considerations lead to the lipophilicity model for the bioconcentration of chemicals dissolved in water, and inclusion of the sorption to sediments as further partitioning process allows a mechanistic interpretation of the bioaccumulation in benthic organisms in terms of a bioconcentration from the interstitial water. For organic acids and bases, recent investigations indicate that the bioavailability of ionic compound portions may be substantially increased by ion pair formation with inorganic species as well as by specific interactions with endogenous macromolecules.     

Feeding by a “nonfeeding” larva: uptake of dissolved amino acids from seawater by lecithotrophic larvae of the gastropod Haliotis rufescens

Larvae of the red abalone (Haliotis rufescens Swainson) are functionally incapable of capturing particulate foods. The aim of this study was to determine whether these larvae could acquire energy from seawater in the form of dissolved organic material. Trochophore and veliger larvae were shown to acquire energy by transporting dissolved organic material from seawater. Both larval stages took up all classes of amino acids tested. The influx of radiolabeled alanine represented the net substrate flux, as determined by direct chemical measurement for both trochophore and veliger larvae. Although veliger larvae have a transport system to take up taurine from seawater, a net efflux was observed for this amino acid. The release of taurine occurred independently of the presence of either taurine or other amino acids in the medium. Transported alanine was used in both anabolic and catabolic pathways. The percent of ¹⁴C-alanine in the trichloroacetic acid-insoluble fraction (macromolecules) of veliger larvae ranged from 21 to 56% of the total radioactivity in the larvae. No lipid biosynthesis was detected from ¹⁴C-labeled alanine. Veliger larvae catabolized 15 to 19% of the total alanine taken up and released it as ¹⁴CO₂. The metabolic rate (oxygen consumption) and the rate of amino acid uptake were both determined for the same group of veliger larvae. The percent contribution that the uptake of amino acids, from a total concentration of 1.6 M, made to the metabolic demand of abalone larvae ranged from 39 to 70%. Thus, these lecithotrophic larvae are not energetically independent of their environment, a result which differs from the current view of energy allocation to nonfeeding larvae.Please address all requests for reprints to Dr. Manahan at the University of Southern California     

Uptake of L-valine and other amino acids by the polychaete Nereis virens

For valine uptake by the polychaete Nereis virens Sars, the kinetic constants were: V _max=355 nmol g^-1 fresh weight h^-1, K _m=20 M. Leucine and some other amino acids acted as partial inhibitors of valine uptake. Valine uptake rate was 78% higher at 21.5 S than at 14 S. The major portion of valine absorbed by the polychaete could be extracted as free valine, with 6.5 to 15.6% being respired, and 3.6 to 9.5% incorporated into proteins. Calculations indicate that 7 to 12% of the metabolism of N. virens may be sustained by uptake of glycine and aspartic acid from natural concentrations. It is suggested that uptake of amino acids by this worm is important in the nitrogen cycling of marine sediments.     

Phototransformation of <Emphasis Type="SmallCaps">l</Emphasis>-tryptophan and formation of humic substances in water

Humic substances are poorly known, though they represent a major pool of non-biotic organic carbon on earth. In particular, there is little knowledge on the formation of humic substances by irradiation of organic matter dissolved in waters. Specifically, it is known that humic substances can be formed from proteins by photochemical processes in surface waters, but the role of single amino acids and their transformation pathways are not yet known. Therefore, here we studied the phototransformation of aqueous l-tryptophan under simulated sunlight. Irradiated l-tryptophan solutions were analyzed by absorption, fluorescence, nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies, chromatography, potentiometry and mass spectrometry (MS). The solutions appeared turbid after irradiation; therefore, nephelometry and dynamic laser light scattering were used to characterize the suspended particles. Results show that about 95% of l-tryptophan was degraded in 8-h irradiation, undergoing deamination and decarboxylation of the amino acidic moieties to release ammonium and formate. The MS signal at m/z 146 suggests the formation of 3-ethylindole, while pH-metric and NMR data revealed the presence of hydroxylated compounds. The phototransformation intermediates of l-tryptophan had fluorescence and absorption spectra similar to those of humic substances, they were able to produce ^·OH upon irradiation and tended to aggregate by both ionic and hydrophobic interactions. Overall, our findings reveal for the first time the nature of products formed upon phototransformation of l-tryptophan. Interestingly, the transformation of l-tryptophan is quite different from that of the previously studied l-tyrosine, although both compounds produce humic-like materials under irradiation.     

High amounts of free aromatic amino acids in the protein-like fluorescence of water-dissolved organic matter

Fluorescence spectroscopy is widely used to study water pollution. The fluorescence of water natural organic matter can be classified into two groups: the protein-like fluorescence originating from aromatic amino acids and the humic fluorescence originating from humic substances. Actually, the precise molecular origin of the protein-like fluorescence is unknown because this fluorescence may be caused by either free amino acids, peptides or proteins. Therefore, we studied the molecular origin of the protein-like fluorescence of Suwannee River natural organic matter and fractions A, B and C + D obtained by size exclusion chromatography/polyacrylamide gel electrophoresis. Fractions were analyzed by reversed-phase high-performance liquid chromatography. The electrophoretic mobilities of fractions varied in the order C + D > B > A and the molecular size in the opposite order. Our results show that the protein-like fluorescence is almost exclusively located in high molecular size fraction A and medium molecular size fraction B. Retention times and fluorescence emission spectra of authentic free aromatic amino acids tyrosine and tryptophan were identical with the retention times and emission spectra of several chromatographic peaks of fractions A and B. More than 50 % of the protein-like fluorescence is due to free aromatic amino acids incorporated in water natural organic matter.     

Die Bedeutung in Meerwasser gelöster Glucose für die Ernährung von Anemonia sulcata (Coelenterata: Anthozoa)

Anemonia sulcata Pennant absorbs and accumulates tritiated D-glucose dissolved in sea water in natural concentrations (80 μg/l). The rate of decrease of glucose concentration in the sea water can best be described by an exponential function, when the concentration of added glucose exceeds 20 to 25 μg/l. The glucose, absorbed through the ectoderm, is immediately metabolized. This is determinable experimentally by tritiated water which is emitted into the sea water. The rate of uptake estimated experimentally was in the range 3 to 4 μg glucose/g wet weight/h, whilst the rate calculated by V _max (maximum absorption rate) was 20 μg/g wet weight/h. The concentration of free glucose in the tentacle tissue is greater by a factor of 10⁵ than that of the medium in which absorption takes place. Absorption is temperature-dependent; the Q₁₀ between 15° and 25°C exceeds 2; translocation is, therefore, energy-dependent. Absorption was diminished by inhibitors, especially by phlorizin. The actinians increase their energy reserves by absorption of glucose (and other dissolved organic substances). The energetic net profit by taking up glucose comprises up to 50% of the energy amount which is equivalent to the oxygen consumption.     

京密引水中天然有机物的形态

用改进的Ｌｅｅｎｈｅｅｒ分离方法，并引入最新的ＸＡＤ－８，ＸＡＤ－４树脂串联技术，将京密引水中有机物定量分离为悬浮和溶解态两大类。后者又进一步分离为憎水有机物、腐殖酸类，ＸＡＤ－４酸和亲水中性有机物等形成。溶解态有机物含量约为３ｍｇＣ／ｌ，其中一半左右为腐殖酸类。ＸＡＤ－４酸占溶解态有机１５－２０％，非极性憎水有机物所占比例很低。     

Studies on the transport of sugars in the holothurian Holothuria scabra

Experiments using ¹⁴C sugars were carried out on the holothurian Holothuria scabra Jäger, in order to assess the role of its perivisceral fluid in the translocation and transportation of dissolved organic materials. The results obtained indicate that the perivisceral fluid plays a significant part. Rates of ¹⁴C glucose, fructose and sucrose uptake were followed in major tissues such as the alimentary canal, haemal system, respiratory tree and body wall. The monosaccharides are absorbed more intensively by digestive and haemal systems, the disaccharide by respiratory tree and body wall. It is, therefore, presumed that tissues in H. scabra selectively absorb sugars depending on their metabolic activity.     

Feeding biology of the brackish-water oncholaimid nematode Adoncholaimus thalassophygas

The brackish-water inhabiting nematode Adoncholaimus thalassophygas (De Man, 1876) may be classified as an omnivore and predator according to the gut contents of the adults. A series of ¹⁴C experiments was conducted to investigate the feeding potential of labelled microorganisms and dissolved ¹⁴C glucose. The observed consistent failure to incorporate ¹⁴C from labelled microorganisms, and its consistent success with dissolved ¹⁴C glucose suggests that dissolved organic matter may be more important than microorganisms as a food source for his nematode. This corresponds also with direct observations of living worms which showed very little uptake of particulate food other than that originating from predation. Defecation and mean gulping rates were low and, therefore, ¹⁴C glucose uptake from solution can hardly be explained by the assumption that large amounts of water are swallowed and passing through the gut. By means of mucus secretion, A. thalassophygas forms compact agglutinations of detrital sediment which are sites of enhanced microbial activity. We suggest that hatched juveniles feed primarily on dissolved organic matter released by the intensive microbial activity within this habitat. Adults retain the ability to utilize dissolved organic matter, and supplement their diet by scavenging on carcasses and occasional predation. Thus, the biology of oncholaimid nematodes may be characterized by an intimate linkage to microbial metabolism, although they do not appear to feed directly upon microorganisms.     

Distributions, cycling and recovery of amino acids in estuarine waters and sediments

Acid hydrolysis of estuarine water samples for the determination of amino acids (AAs) was tested and found to be effective at high (250 μM) nitrate concentrations when the anti-oxidant, ascorbic acid, was added to the samples. Hydrolysable AA concentrations were then determined in surface sediments collected from low and high salinity regions of the Tamar Estuary (UK) during winter 2003 and 2004, and in overlying water when simulated resuspension of sediment particles was performed. Concentrations of AAs in sediment samples comprised <50% of particulate nitrogen, fitting the paradigm that most sedimentary nitrogen is preserved within an organic matrix. When sediment samples were resuspended in overlying water (salinity 17.5), the rapid, measured increase in dissolved AA concentrations almost equalled the reported nitrate concentration in the lower estuary, with the subsequent decrease in the total dissolved AA levels suggested that bacterial uptake was occurring. Our data concur with previous studies on nitrogen desorption from sediments and suggest that an understanding of organic nitrogen cycling will be an important aspect of future effective estuarine management.     

The effect of humic substances on Cu migration in the soil profile

Humic substances (HS) are widely used for diverse purposes. The effect of HS on the metal’s status in contaminated soils is contradictory. The aim of this work was to investigate the Cu migration in soils treated with HS. A model field experiment with the addition of Cu (1.243?mg?Cu/kg) and HS Extra® (potassium humate) was performed. The Cu addition resulted in acidification (by 0.7 pH) after 3 months. The major part of the added Cu remained in the upper 7-cm-thick soil layer; 4% reached the lower soil layer, while only 0.1% were removed beyond the profile. The addition of HS mitigated soil acidification increased the content of Cu bound to solid-phase organic substances and abruptly reduced the Cu activity in the soil liquid phase. Simultaneously, the HS addition increased the water-soluble organic substances (WSOS) by four times, including those in the hydrophilic and hydrophobic fractions, resulting in a twofold increase in the content of soluble Cu. Copper complexes with hydrophilic WSOS mainly reached lysimeters, and hydrophobic organic substances were absorbed by the soil. The HS addition to a slightly acidic soil can accelerate the migration of Cu to adjacent environments.     

Variability of dissolved organic matter in northern adriatic coastal waters

The results obtained in the four seasonal cruises planned in the PRISMA II project are reported. These concern dissolved and colloidal organic carbon, free amino acids and total dissolved carbohydrates and heterotrophic activity. Main factors controlling organic matter degradation, resulting from laboratory tests not planned in the above project, are also discussed. Dissolved organic matter shows seasonal accumulation, which may be markedly different from year to year, and large contributions by colloidal and saccharide components. Heterotrophic activities play an important role in the carbon cycle, although laboratory runs highlight limitations caused by aging of organic matter and phosphorus deficiency.     

VARIABILITY OF DISSOLVED ORGANIC MATTER IN NORTHERN ADRIATIC COASTAL WATERS

The results obtained in the four seasonal cruises planned in the PRISMA II project are reported. These concern dissolved and colloidal organic carbon, free amino acids and total dissolved carbohydrates and heterotrophic activity. Main factors controlling organic matter degradation, resulting from laboratory tests not planned in the above project, are also discussed. Dissolved organic matter shows seasonal accumulation, which may be markedly different from year to year, and large contributions by colloidal and saccharide components. Heterotrophic activities play an important role in the carbon cycle, although laboratory runs highlight limitations caused by aging of organic matter and phosphorus deficiency.