Review of organic matter in the Orgueil meteorite

The Orgueil meteorite is a carbonaceous chondrite containing about 3.1% carbon, 5.5% sulfur and 19.9% water. Virtually all of the carbon is present as organic carbon although only about 20% is soluble in common organic solvents; the remainder is in the form of a highly substituted, irregular and aromatic polymer. Detailed methods of analysis have been improved in the past ten years sufficient for the detection of individual compounds in most of the following classes of organic compounds: hydrocarbons, oxygen-, sulfur- and nitrogen-containing organic compounds, optically active species, isotopes, bacteria and organized elements. Ten series of homologous compounds have been observed in the aliphatic hydrocarbons.In the 1950's, when interest was renewed in the Orgueil meteorite, the analytical capabilities may have given a bias toward biogenic agencies for the formation of the organic matter found in the meteorites. Some of the key biochemical compounds for extraterrestrial life are present. There is doubt, however, that these particular compounds are truly indigenous. The possibility that the indigenous organic compounds in the meteorite are present as a result of abiogenic syntheses in the cosmos is becoming more generally accepted.     

Experimental Shock Chemistry of Aqueous Amino Acid Solutions and the Cometary Delivery of Prebiotic Compounds

A series of shock experiments were conducted to assess thefeasibility of the delivery of organic compounds to theEarth via cometary impacts. Aqueous solutions containingnear-saturation levels of amino acids (lysine, norvaline,aminobutyric acid, proline, and phenylalanine) were sealedinside stainless steel capsules and shocked by ballisticimpact with a steel projectile plate accelerated along a12-m-long gun barrel to velocities of 0.5–1.9 km sec^-1. Pressure-temperature-time histories of the shocked fluidswere calculated using 1D hydrodynamical simulations. Maximum conditions experienced by the solutions lasted0.85–2.7 s and ranged from 5.1–21 GPa and 412–870 K. Recovered sample capsules were milled open and liquid wasextracted. Samples were analyzed using high performanceliquid chromatography (HPLC) and mass spectrometry (MS). In all experiments, a large fraction of the amino acidssurvived. We observed differences in kinetic behavior andthe degree of survivability among the amino acids. Aminobutyricacid appeared to be the least reactive, and phenylalanine appeared to be the most reactive of the amino acids. The impact process resulted in the formation of peptide bonds; new compounds included amino acid dimers and cyclic diketopiperazines. In our experiments, and in certain naturally occurring impacts, pressure has a greater influencethan temperature in determining reaction pathways. Our resultssupport the hypothesis that significant concentrations of organic material could survive a natural impact process.     

Natural evidence for chemical and early biological evolution

Meteorites, particularly type II carbonaceous chondrites, provide natural, tangible evidence for chemical evolution, but they do not appear to contain any evidence for biological evolution. On the other hand, some of the oldest sedimentary rocks of the earth have yielded good evidence for early biological evolution; whatever evidence there may be for chemical evolution in these old rocks is generally obscure. Carbonaceous chondrites (types I, II, and III) have been examined for thier content of various kinds of organic compounds. Amino acids have been reported to be present in the three types, but only in type II carbonaceous chondrites (Murray and Murchison) has an indigenous suite of amino acids been found which is apparently free of most terrestrial contaminations. These indigenous compounds are thought to have resulted from extraterrestrial, abiotic, chemical syntheses, and the presence of the amino acids in meteorites provides strong support for the theory of chemical evolution. The geological record of the Swaziland Sequence and Bulawayan System of Southern Africa contains morphological and chemical fossils which indicate that early biological evolution was taking place at least 3.0 to 3.3 aeons ago. Interpretation of the significance of the chemical fossil record has proven to be difficult. At present the occurrence of simple compounds in these very ancient rocks is believed to have little or nothing to do with biochemical processes three aeons ago. The bulk of the reduced carbonaceous material in these rocks, however, probably represents the residue of three billion years old and older organic matter. Isotopic studies of this carbonaceous material may provide chemical evidence for early biological evolution.     

Transport of particulate organic material between salt marsh and estuary

Summary The macrophyte production and the transport of particulate organic matter between march and adjacent estuary have been investigated for a 30 ha salt marsh along the Oosterschelde estuary, The Netherlands.The primary production of macrophytes, measured with Smalley's method, was 837–1030 g dry organic matter.m^–2.year^–1. Measurements of amounts of particulate organic matter transported through one of the main tidal creeks in the salt march resulted in a net import. On average 31% of the material brought in by the flood settled in the marsh. The majority of this material is smaller than 63 m. On the other hand large floating material is exported during storm tides, although the quantity seems to be smaller than that of the suspended material imported.The differences between various marshes with regard to export and import of organic matter are explained in terms of marsh level, primary production, turbulent diffusion, sinking and resuspension of particulate matter and biotic transformations.     

Organic matter chemistry and dynamics in clear-cut and unmanaged hardwood forest ecosystems

Forest harvesting alters the organic matter cycle by changing litter inputs and the decomposition regime. We hypothesized that these changes would result in differences in organic matter chemistry between clear-cut and uncut watershed ecosystems. We studied the chemistry of soil organic matter (SOM), and dissolved organic carbon (DOC) in soil solutions and stream samples in clear-cut and uncut sites at the Hubbard Brook Experimental Forest in New Hampshire using DOC fractionation techniques and solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy.Alkyl-C (aliphatic compounds) and O-alkyl-C (carbohydrates) were the largest C fractions in soil and dissolved organic matter at Hubbard Brook. Alkyl-C ranged from 29–48% of soil C, 25–42% of soil solution C, and 22–42% of streamwater DOC. Carbohydrates comprised 32–49%, 36–43%, and 29–60% of C in soils, solutions, and streamwater, respectively. In both soils and soil solutions, the carbohydrate fraction decreased with increasing soil depth, while the aromaticity of organic matter increased with depth. There were no significant differences in the structural chemistry of SOM between clear-cut and uncut watersheds.The aromatic-C fractions in soil solutions at the clear-cut site ranged from 12–16%, approximately 40% greater than at the uncut site (8.5–11%). Thus, clear-cutting has resulted in the leaching of more highly decomposed organic matter, and depletion of more aliphatic compounds in the soluble organic pool. Because DOC fluxes are small compared to the SOM pool, large differences in soil solution chemistry do not substantially alter the overall composition of SOM. While the organic chemistry of stream DOC varied greatly among 3 sampling dates, there were no obvious clear-cutting effects. Thus, temporal variations in flowpaths and/or in-stream processes appear to be more important than disturbance in regulating the organic carbon chemistry of these streams.     

Water-soluble organic matter in forest soils

By applying a modified gel permeation technique, the molecular-size distribution (MSD) and complexing properties of water-soluble organic matter (WSOM), isolated from the A_h horizon under stands with either Douglas-fir, European beech or Scots pine were established. Both with respect to MSD and complexing properties, the dissolved organic matter was highly similar. WSOM was comprised of compounds apparently high in molecular weight (>1 kDa) and with a complexing capacity of 1.0±0.1 mol mg^–1 carbon as determined for Cu(II) at pH 5.5 and 0.01 M ionic strength. The effect of WSOM on the partitioning of cations between soil solid phase and soil solution was evaluated in several soil batch experiments using loamy sand or sandy soil material. Although a large part of WSOM was sorbed to the soil matrix, Al, Cu, Fe and Pb were solubilized in considerable amounts by complexation. The Mn concentration in the soil solution was also significantly increased but this probably resulted from a redox reaction, with certain constituents of WSOM serving as electron donor. With a decrease in soil pH, cation mobilization by WSOM was significantly lower as a result of increased sorption and a decrease in complexing capacity of the soluble organics. Application of several low MW aliphatic and phenolic acids gave results similar to the results obtained with WSOM.     

The photolytic degradation and oxidation of organic compounds under simulated Martian conditions

Summary Cosmochemical considerations suggest various potential sources for the accumulation of organic matter on Mars. However the Viking Molecular Analysis did not indicate any indigenous organic compounds on the surface of Mars. Their disappearance from the top layer is most likely caused by the combined action of the high solar radiation flux and various oxidizing species in the Martian atmosphere and regolith. In this study the stability of several organic substances and a sample of the Murchison meteorite was tested under simulated Martian conditions. After adsorption on powdered quartz, samples of adenine, glycine and naphthalene were irradiated with UV light at various oxygen concentrations and exposure times. In the absence of oxygen, adenine and glycine appeared stable over the given irradiation period, whereas a definite loss was observed in the case of naphthalene, as well as in the volatilizable and pyrozable content of the Murchison meteorite. The presence of oxygen during UV exposure caused a significant increase in the degradation rate of all samples. It is likely that similar processes have led to the destruction of organic materials on the surface of Mars.     

Synthesis of organic compounds from carbon monoxide and water by UV photolysis

The photolysis of water vapor with carbon monoxide at 1849 Å yields alcohols, aldehydes and organic acids, with an overall quantum yield of 3.3×10^–2. This rather high quantum yield could have led to a contribution of 10¹¹ organic molecules cm^–2 sec^–1 to the pool of organic material on the primitive Earth. The reactions are initiated by the photolysis of water molecules and the resulting hydrogen atoms reduce the carbon monoxide to a variety of one and two carbon compounds. The organic molecules are dissolved in water and thus escape destruction by photolysis. Photolysis of water vapor with carbon dioxide did not yield organic compounds under these conditions.     

The ecological significance of sulfur in the energy dynamics of salt marsh and coastal marine sediments

Sulfur is an important element in the metabolism of salt marshes and subtidal, coastal marine sediments because of its role as an electron acceptor, carrier, and donor. Sulfate is the major electron acceptor for respiration in anoxic marine sediments. Anoxic respiration becomes increasingly important in sediments as total respiration increases, and so sulfate reduction accounts for a higher percentage of total sediment respiration in sediments where total respiration is greater. Thus, sulfate accounts for 25% of total sediment respiration in nearshore sediments (200 m water depth or less) where total respiration rates are 0.1 to 0.3gCm^–1 day^–1 , for 50% to 70% in nearshore sediments with higher rates of total respiration (0.3 to 3gCm^–2 day^–1), and for 70% to 90% in salt marsh sediments where total sediment respiration rates are 2.5 to 5.5gcm^–2 day^–1 .During sulfate reduction, large amounts of energy from the respired organic matter are conserved in inorganic reduced sulfur compounds such as soluble sulfides, thiosulfate, elemental sulfur, iron monosulfides, and pyrite. Only a small percentage of the reduced sulfur formed during sulfate reduction is accreted in marine sediments and salt marshes. When these reduced sulfur compounds are oxidized, energy is released. Chemolithoautotrophic bacteria which catalyze these oxidations can use the energy of oxidation with efficiencies (the ratio of energy fixed in organic biomass to energy released in sulfur oxidation) of up to 21–37% to fix CO₂ and produce new organic biomass.Chemolithoautotrophic bacterial production may represent a significant new formation of organic matter in some marine sediments. In some sediments, chemolithoautotrophic bacterial production may even equal or exceed organoheterotrophic bacterial production. The combined cycle of anaerobic decomposition through sulfate reduction, energy conservation as reduced sulfur compounds; and chemolithoautotrophic production of new organic carbon serves to take relatively low-quality organic matter from throughout the sediments and concentrate the energy as living biomass in a discrete zone near the sediment surface where it can be readily grazed by animals.Contribution from a symposium on the role of sulfur in ecosystem processes held August 10, 1983, at the annual meeting of the A.I.B.S., Grand Forks, ND; Myron Mitchell, convenor.     

DETECTION OF ORGANIC MATTER IN INTERSTELLAR GRAINS

Star formation and the subsequent evolution of planetary systems occurs in dense molecular clouds, which are comprised, in part, of interstellar dust grains gathered from the diffuse interstellar medium (DISM). Radio observations of the interstellar medium reveal the presence of organic molecules in the gas phase and infrared observational studies provide details concerning the solid-state features in dust grains. In particular, a series of absorption bands have been observed near 3.4~2940 cm^–1) towards brightinfrared objects which are seen through large column densities of interstellar dust. Comparisons of organic residues, produced under a variety of laboratory conditions, to the diffuse interstellar medium observations have shown that aliphatic hydrocarbon grains are responsible for the spectral absorption features observed near 3.4 ~2940cm^–1). These hydrocarbons appear to carry the –CH₂– and –CH₃ functional groups in the abundance ratio CH₂/CH₃ ~ 2.5, and theamount of carbon tied up in this component is greater than 4% of the cosmic carbon available. On a galacticscale, the strength of the 3.4 band does notscale linearly with visual extinction, but instead increases more rapidly for objects near the Galactic Center. A similar trend is noted in the strength of the Si–O absorption band near 9.7. The similarbehavior of the C–H and Si–O stretching bands suggests that these two components may be coupled, perhaps in the form of grains with silicate cores and refractory organic mantles. The ubiquity of the hydrocarbon features seen in the near infrared near 3.4throughout our Galaxy and in other galaxies demonstrates the widespread availability of such material for incorporation into the many newly forming planetary systems. The similarity of the 3.4features in any organic material with aliphatic hydrocarbons underscores the need for complete astronomical observational coverage in the 2–30 region, oflines of sight which sample dust in both dense and diffuse interstellar clouds, in order to uniquely specify the composition of interstellar organics. This paper reviews the information available from ground-based observations, although currently the Infrared Satellite Observatory is adding to our body of knowledge on this subject by providing more extensive wavelength coverage. The Murchison carbonaceous meteorite has also been used as an analog to the interstellar observations and has revealed a striking similarity between the light hydrocarbons in the meteorite and the ISM; therefore this review includes comparisons with the meteoritic analog as well as with relevant laboratory residues. Fundamental to the evolution of the biogenic molecules, to the process of planetary system formation, and perhaps to the origin of life, is the connection between the organic material found in the interstellar medium and that incorporated in the most primitive solar system bodies.     

Concentrations and fluxes of organic carbon substrates in the aquatic environment

Data concerning concentrations and fluxes of dissolved organic compounds (DOC) from marine and lacustrine environments are reviewed and discussed. Dissolved free amino acids and carbohydrates comprised the main fraction in the labile organic carbon pool. Dissolved free amino acids in marine waters varied between 3–1400 nM and those of freshwaters between 2.6–4124 nM. Dissolved free carbohydrates varied between 0.4–5000 nM in marine systems and between 14–1111 nM in freshwaters. The turnover times of both substrate pools varied in marine waters between 1.4 hours and 948 days and in freshwaters between 2 hours and 51 days. Measurements of stable^12/13C-ratio and¹⁴C-isotope dating in ocean deep water samples revealed DOC turnover times between 2000–6000 years. Studies on carbon flows within the aquatic food webs revealed that about 50% of photosynthetically fixed carbon was channelled via DOC to the bacterioplankton. Excreted organic carbon varied between 1–70% of photosynthetically fixed carbon in marine waters and between 1–99% in freshwaters. The labile organic carbon pool represented only 10–30% of the DOC. The majority (70–90%) of the DOC was recalcitrant to microbial assimilation. Only 10–20% of the DOC could be easily chemically identified. Most of the large bulk material represented dissolved humic matter and neither the chemical structure nor the ecological function of the DOC is as yet clearly understood.Abbreviations ATP Adenosine Tri-Phosphate - AMS Accelerated Mass Spectrometry - BSA Bovine Serum Albumin - GlAse GlucosidAse activity - DAA Dissolved Amino Acids - DCAA Dissolved Combined Amino Acids - DFAA Dissolved Free Amino Acids - DTAA Dissolved Total Amino Acids - DCHO Dissolved Carbohydrates - DCCHO Dissolved Combined Carbohydrates - DFCHO Dissolved Free Carbohydrates - DTCHO Dissolved Total Carbohydrates - DLCFaAc Dissolved Long Chain Fatty Acids - DSCFaAc Dissolved Short Chain Fatty Acids - DOC Dissolved Organic Carbon - DOM Dissolved Organic Matter - DHM Dissolved Humic Matter - DTPhOH Dissolved Total Phenolic compounds - DCPhOH Dissolved Combined Phenolic compounds - DFPhOH Dissolved Free Phenolic conpounds - EOC Excreted Organic Carbon - HS Humic Substances - HPLC High Performance Liquid Chromatography - HTCO High-Temperature Catalytic Oxidation - (K_t+S_n) Transport Constant + Natural Substrate from Michaelis Menten Kinetics - LOCP Labile Organic Carbon Pool - OM Organic Matter - MEE Microbial Extracellular Enzymes - PER Percent of Extracellular Release - PhDOC Photosynthetically derived Dissolved Organic Carbon - POC Particulate Organic Carbon - ROCP Recalcitrant Organic Carbon Pool - T_t Turnover time - UDOC Utilizable Dissolved Organic Carbon - V_max Maximum Uptake Velocity - WCO Wet Chemical Oxidation Dedicated to Prof. Drs. J. Overbeck on the occasion of his 70th birthday     

Sources of organic carbon in mangrove sediments: variability and possible ecological implications

Mangrove sediments from three different mangrove ecosystems (Coringa Wildlife Sanctuary in the Godavari Delta, Andhra Pradesh, India, and Galle and Pambala, south-west Sri Lanka) were analysed for their organic carbon content, elemental ratios (C:N) and carbon stable isotope composition. Organic carbon content (0.6 – 31.7% dry weight), C/N ratios (7.0 – 27.3) and ¹³C (between –29.4 and –20.6) showed a wide range of values. Lower stocks of organic carbon coincided with low C/N (atom) ratios and less negative ¹³C values, indicating import of marine or estuarine particulate suspended matter. High organic carbon stocks coincided with high C/N ratios and ¹³C values close, but not equal, to those of the mangrove vegetation. The variations observed in this study and published literature data could be adequately described by a simple two-end mixing model, whereby marine/estuarine suspended matter and mangrove litter were taken as end members. Thus, while in some mangrove ecosystems or vegetation zones, organic carbon stocks can be very high and are almost entirely of mangrove origin, there also appear to be cases in which deposited estuarine or marine suspended matter is the dominant source of organic carbon and nitrogen in mangrove sediments. This situation is remarkably similar to that observed in temperate salt marsh ecosystems where the importance of local vascular plant production to the sediment organic carbon pool is equally variable. The observed high variability in organic matter origin is thought to have a major impact on the overall carbon dynamics in intertidal mangrove ecosystems.     

Volatile halogenated organic compounds in European estuaries

Sources, sinks, and distribution patterns ofvolatile halogenated organic compounds (VHOC)in estuaries were investigated during 5 cruises within the BIOGEST programme. Due to their chemical and physical properties (e.g. toxicity, persistence, mobility) these compounds are of considerable environmental concern. A wide range of compounds has been identified and quantified generally ranging from 0.1 ng l^–1 to 350 ng l^–1. Insome samples extraordinarily high values up to4700 ng l^–1 were observed indicatingcontribution from anthropogenic sources.Generally, concentrations of halogenatedcompounds of anthropogenic origin dominatedthose of prevalent natural origin. Data ofselected VHOC are presented in relation tosalinity, particular organic carbon, and totalsuspended matter. Furthermore the observedconcentrations are compared with establishedwater quality regulations. Distributionpatterns of VHOC along the estuary indicatedcommon sources for specific halogenatedcompounds. Decreasing concentrations of mostVHOC along the estuary confirm that degassingto the atmosphere and dilution with sea waterare the dominating processes controlling thefate of these compounds in estuaries.     

The effect of oxygen concentration on the decomposition of organic materials in soil

Summary 1. Techniques are described for relating the oxygen concentrations in the soil water on the surfaces of micro-organisms to their metabolizing activities.2. Studies were made on the decomposition of organic materials in water-saturated crumbs (mean radius 1.55 × 10^–1 cm) of a loam soil.3. Respiration of water-saturated crumbs was not inhibited unless the oxygen concentration was less than about 10^–6 M. Evidence was obtained that above a similar low oxygen concentration there was no inhibition of respiration in soils of widely different type.4. Anaerobic decomposition of the soil organic matter was very slow. Anaerobic decomposition of casein digest was more rapid than that of any other material tested; the products were water soluble and included 83 µ-equivalents of volatile fatty acid per mg of -amino-N decomposed.5. Casein digest percolation of soil crumbs under air resulted in the formation of micro-organisms that respired at 70 per cent of their maximum rate when the oxygen concentration was about 2.7 × 10^–6 M.6. No products of anaerobic casein digest decomposition could be detected on percolating casein digest through soil crumbs when 80 per cent of the soil contained no oxygen and the maximum concentration in any part of the soil was about 3 × 10^–5 M.7. The kinetics of oxygen uptake consequent on the decomposition of casein digest and of other simple organic compounds in soil crumbs were similar and were only slightly affected by reduction of oxygen partial pressure in the atmosphere from 15 to 1.7 cm of mercury.8. It is concluded that change-over from aerobic to anaerobic metabolism of organic materials takes place in widely different soils at an oxygen concentration less than about 3 × 10^–6 M.     

Influence of clay mineral type and organic matter content on the uptake of239Pu and241Am by plants

Summary The uptake of²³⁹Pu and²⁴¹Am from different clay mineral-organic matter-sand mixtures simulating contrasting soil types was examined in growth chamber experiments. The mixtures represented various combinations of organic matter (0, 5 and 10%), kaolinite (11 type) and montomorillonite (21 type) clay minerals, each at the levels of 5, 10 and 25%, and purified quartz sand (as filler).Results indicated a marked reduction in uptake of both²³⁹Pu and²⁴¹Am with increase in organic matter as well as clay content of the mixtures. The Pu Concentration Ratios (CRs) ranged from (2.5–7.0)×10^–3 in the case of kaolinite-organic matter mixtures, and from (0.9–5.5)×10^–3 in the case of montmorillonite-organic matter mixtures. The corresponding values of Am Concentration Ratios (CRs) obtained were (1.9–725.4)×10^–3 in the case of kaolinite-organic matter mixtures, and between (0.7–3.5)×10^–3 for the montmorillonite-organic matter mixtures.Reduction in the uptake of²⁴¹Am with increasing clay content was more pronounced in the montmorillonite clay-organic matter mixtures as compared to that in the case of kaolinite-organic matter mixtures. While similar qualitative reduction in²³⁹Pu CRs with increasing clay content was observed, the reduction was less marked than in the case of²⁴¹Am. The values for Am CRs were higher than the corresponding Pu CRs in kaolinite based mixtures whereas in the case of montmorillonite-organic matter mixtures Pu CRs exceeded the Am CRs.Increasing organic matter content and its interaction with both kaolinite and montmorillonite clay minerals were found to be equally effective in reducing the uptake of²³⁹Pu as well as²⁴¹Am by plants.     

Life on Mars: chemical arguments and clues from Martian meteorites

Primitive terrestrial life – defined as a chemical system able to transfer its molecular information via self-replication and to evolve – probably originated from the evolution of reduced organic molecules in liquid water. Several sources have been proposed for the prebiotic organic molecules: terrestrial primitive atmosphere (methane or carbon dioxide), deep-sea hydrothermal systems, and extraterrestrial meteoritic and cometary dust grains. The study of carbonaceous chondrites, which contain up to 5% by weight of organic matter, has allowed close examination of the delivery of extraterrestrial organic material. Eight proteinaceous amino acids have been identified in the Murchison meteorite among more than 70 amino acids. Engel reported that l-alanine was surprisingly more abundant than d-alanine in the Murchison meteorite. Cronin also found excesses of l-enantiomers for nonprotein amino acids. A large collection of micrometeorites has been recently extracted from Antarctic old blue ice. In the 50- to 100-μm size range, carbonaceous micrometeorites represent 80% of the samples and contain 2% of carbon, on average. They might have brought more carbon than that involved in the present surficial biomass. The early histories of Mars and Earth clearly show similarities. Liquid water was once stable on the surface of Mars, attesting the presence of an atmosphere capable of deccelerating C-rich micrometeorites. Therefore, primitive life may have developed on Mars as well and fossilized microorganisms may still be present in the near subsurface. The Viking missions to Mars in 1976 did not find evidence of either contemporary or past life, but the mass spectrometer on the lander aeroshell determined the atmospheric composition, which has allowed a family of meteorites to be identified as Martian. Although these samples are essentially volcanic in origin, it has been recognized that some of them contain carbonate inclusions and even veins that have a carbon isotopic composition indicative of an origin from Martian atmospheric carbon dioxide. The oxygen isotopic composition of these carbonate deposits allows calculation of the temperature regime existing during formation from a fluid that dissolved the carbon dioxide. As the composition of the fluid is unknown, only a temperature range can be estimated, but this falls between 0° and 90°C, which would seem entirely appropriate for life processes. It was such carbonate veins that were found to host putative microfossils. Irrespective of the existence of features that could be considered to be fossils, carbonate-rich portions of Martian meteorites tend to have material, at more than 1000 ppm, that combusts at a low temperature; i.e., it is an organic form of carbon. Unfortunately, this organic matter does not have a diagnostic isotopic signature so it cannot be unambiguously said to be indigenous to the samples. However, many circumstantial arguments can be made to the effect that it is cogenetic with the carbonate and hence Martian. If it could be proved that the organic matter was preterrestrial, then the isotopic fractionation between it and the carbon is in the right sense for a biological origin. Received: January 22, 1998 / Accepted: February 16, 1998     

Transport of coarse particulate organic matter in an Idaho river,USA

I investigated organic matter transport in the Henry's Fork of the Snake River, Idaho, USA, from August 1987 to November 1988. Mean discharge during the study was 15 m³ s^–1. Screens were used to sample very coarse (> 6 mm) transported aquatic macrophyte material (VCTMM). Drift nets were used to sample coarse (1–6 mm) and fine (0.25–1 mm) transported particulate organic matter (CTOM and FTOM). Mean monthly concentration of VCTMM was 0.064 mg AFDWl^–1 and was significantly higher than CTOM (0.024 mg AFDW l^–1) and FTOM (0.036 mg AFDW l^–1). VCTMM concentration was highest in December (0.163 mg AFDW l^–1) and lowest in May (0.018 mg AFDW l^–1). The sample position along a transect across the channel had a significant effect on the amount of transported organic matter collected in many months. The concentration of debris from individual species tracked the standing stock of that species during the growing season. In Fall, a dramatic increase in VCTMM corresponded to a decrease in macrophyte standing stock. FTOM and CTOM concentrations were highest in January (CTOM: 0.048; FTOM: 0.111 mg AFDW l^–1), lowest in November 1988 (<0.006 mg AFDW l^–1), were not correlated with discharge, and were inversely correlated with the standing stocks of macrophytes upstream, probably because macrophyte beds influenced the retentiveness of the channel. Standing stock of aquatic macrophytes was highest in September–October (5.2 kg wet weight m ^–2) and lowest in February (1.7 kg wet weight m^–2). Annual movement of particulate organic matter past the sampling point was about 45 000 kg AFDW, of which 21 000 kg was VCTMM, 8 000 kg was CPOM, and 16 000 kg was FPOM.     

Seasonal variations in the chemical composition of dissolved organic matter in organic forest floor layer leachates of old-growth Scots pine (Pinus sylvestris L.) and European beech (Fagus sylvatica L.) stands in northeastern Bavaria, Germany

Organic matter dissolved in thepercolation water of forest soils contributeslargely to element cycling and transport ofnatural and anthropogenic compounds. The wayand extent to which these processes areaffected depends on the amount and the chemicalcomposition of soluble organic matter. Becausethe amount of soluble organic matter variesseasonally with changes in the microbialactivity in soil, it seems reasonable to assumethat there may be also seasonal changes in thechemical composition of dissolved organicmatter. We examined dissolved organic matter inthe seepage waters of organic forest floorlayers over a 27-month period (1997–1999) intwo forest ecosystems, a 160-year-old Scotspine (Pinus sylvestris L.) stand and a90-year-old European beech (Fagussylvatica L.) forest. The forest floorleachates were analysed for bulk dissolvedorganic C, C in hydrophilic and hydrophobicdissolved organic matter fractions,lignin-derived phenols (CuO oxidation),hydrolysable neutral carbohydrates and uronicacids, hydrolysable amino sugars, and stablecarbon isotope composition. In addition, westudied the samples by use of liquid-state¹³C-nuclear magnetic resonance (NMR)spectroscopy.For both investigated forest sites we foundthat the dissolved organic carbonconcentrations in forest floor leachates werelargest during summer. They peaked after rainstorms following short dry periods (106–145 mgdissolved organic C l^–1). The proportionsof C in the hydrophilic fractions were largestin winter and spring whereas in summer andautumn more C was found in the hydrophobicfraction. According to liquid-state ¹³C-NMR spectroscopy, summer and autumn samples hadlarger abundances of aromatic and aliphaticstructures as well as larger proportions ofcarboxyl groups whereas the winter and springsamples were dominated by resonances indicatingcarbohydrates. Wet-chemical analyses confirmedthese results. Winter and spring samples wererich in neutral carbohydrates and amino sugars.The summer and autumn samples contained morelignin-derived phenols which were also strongeroxidised than those in the winter and springsamples. Seasonal changes of ¹³C valueswere found to reflect the changes in thechemical composition of dissolved organicmatter. Most negative values occurred whenisotopically light lignin-derived compoundswere abundant and less negative values whencarbohydrates predominated.The different vegetation, age of thestands, and underlying mineral soils resultedin different concentrations of dissolvedorganic carbon and in differences in thedistribution between hydrophobic andhydrophilic organic carbon. Despite of this,the results suggest that the trends in temporalvariations in the composition of dissolvedorganic matter in forest floor seepage waterwere remarkably similar for both sites.Dissolved organic matter in winter and springseems to be mainly controlled by leaching offresh disrupted biomass debris with a largecontribution of bacterial and fungal-derivedcarbohydrates and amino sugars. Dissolvedorganic matter leached from the forest floor insummer and autumn is controlled by thedecomposition processes in the forest floorresulting in the production of stronglyoxidised, water-soluble aromatic and aliphaticcompounds. The chemical composition ofdissolved organic matter in forest floorseepage water in winter and spring indicateslarger mobility, larger biodegradability, andless interaction with metals and organicpollutants than that released during summer andautumn. Thus, the impact of dissolved organicmatter on transport processes may varythroughout the year due to changes in itscomposition.     

Colloidal and dissolved organic matter in lake water: Carbohydrate and amino acid composition,and ability to support bacterial growth

Bacterial utilization of dissolved organic matter (DOM) was studied in water from a humic and a clearwater oligotrophic lake. Indigenous bacteria were inoculated into either 0.2 m natural filtered lake water, or lake water enriched fivefold with colloidal DOM >100 kD but below 0.2 m. Consumption of DOM was followed from changes in concentrations of total dissolved organic carbon (DOC), dissolved combined and free carbohydrates and amino acids (DCCHO and DFCHO, and DCAA and DFAA, respectively) and by uptake of monosaccharide and amino acid radioisotopes. DCCHO and DCAA made up 8% (humic lake) to 33–44% (clear-water lake) of the natural DOC pools, while DFCHO and DFAA contributed at most 1.7% to the DOC pools. Addition of >100 kD DOM increased the DOC concentrations by 50% (clearwater lake) to 92% (humic lake), but it only resulted in a higher bacterial production (by 63%) in the humic lake. During the incubations 13 to 37% of the DOC was assimilated by the bacteria, at estimated growth efficiencies of 4–8%. Despite the measured reduction of DOC, statistically significant changes of specific organic compounds, especially of DCCHO and DCAA, generally did not occur. Probably the presence of high molecular weight DOC interfered with the applied analytical procedures. Addition of radiotracers indicated, however, that DFAA sustained 17–58% and 29–100% of the bacterial carbon and nitrogen requirements, respectively, and that glucose met 1–3% of the bacterial carbon requirements. Thus, our experiments indicate that radiotracers, rather than measurements of concentration changes, should be used in studies of bacterial utilization of DOC in freshwaters with a high content of humic or high molecular weight organic matter.     

Evidence for organic synthesis in high temperature aqueous media — Facts and prognosis

Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range — warm to >400 °C) is responsible for these molecular alterations, expuslion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. Heterocyclic sulfur compounds have been identified in high temperature zones and hydrothermal petroleums of the Guaymas Basin vent systems. They can be interpreted as being synthesized from formaldehyde and sulfur or HS _x ^– in the hydrothermal fluids.Other products from potential synthesis reactions have not yet been found in the natural systems but are expected based on known industrial processes and inferences from experimental simulation data. Various industrial processes have been reviewed and are of relevance to hydrothermal synthesis of organic compounds. The reactivity of organic compounds in hot water (200–350 °C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to >400 °C.Presented in part at the International Society for the Study of the Origin of Life Meeting, Barcelona, Spain, July 1993.