Geology topics

D.S. Ross

Publications and source records attributed to D.S. Ross.

7 recordsLinked to original sources

USGS2008

A quantitative evaluation of the iron-sulfur world and its relevance to life's origins

The significance of Wa??chtersha??user's iron-sulfur world to the origin of life and the limits to its notional autocatalytic cycles are examined in kinetic simulations of the chain polymerization sequence primitive materials ??? amino acids ??? oligomers The simulations were run for the formation of all oligomers up to the 20-mer over a 1 Gy interval from the end of the period of heavy bombardment, during which period life emerged. Upper-limit rate constant estimates developed from the studies of Huber and Wa??chtersha?? user were employed. The simulations showed that oligomer production consistent with life's start within that interval emerges only with an autocatalyst exhibiting a catalytic proficiency comparable to that of contemporary enzymes. The simulations, moreover, ignored likely thermodynamic and statistical burdens which, if included, would have led to the need for catalytic capacities well in excess of those in present-day enzymes. Prebiotic oligomers with such levels of activity are clearly not likely, and it is apparent that the iron-sulfur scheme could not have played a role in life's beginnings. ?? 2008 Mary Ann Liebert, Inc.

Conference Paper↗

USGS2006

The viability of a nonenzymatic reductive citric acid cycle - Kinetics and thermochemistry

The likelihood of a functioning nonenzymatic reductive citric acid cycle, recently proposed as the precursor to biosynthesis on early Earth, is examined on the basis of the kinetics and thermochemistry of the acetate → pyruvate → oxaloacetate → malate sequence. Using data derived from studies of the Pd-catalyzed phosphinate reduction of carbonyl functions it is shown that the rate of conversion of pyruvate to malate with that system would have been much too slow to have played a role in the early chemistry of life, while naturally occurring reduction systems such as the fayalite–magnetite–quartz and pyrrhotite–pyrite–magnetite mineral assemblages would have provided even slower conversions. It is also shown that the production of pyruvate from acetate is too highly endoergic to be driven by a naturally occurring energy source such as pyrophosphate. It is thus highly doubtful that the cycle can operate at suitable rates without enzymes, and most unlikely that it could have participated in the chemistry leading to life.

Origins of Life and Evolution of the Biosphere↗

USGS2006

Cometary impact and amino acid survival - Chemical kinetics and thermochemistry

The Arrhenius parameters for the initiating reactions in butane thermolysis and the formation of soot, reliable to at least 3000 K, have been applied to the question of the survival of amino acids in cometary impacts on early Earth. The pressure/temperature/time course employed here was that developed in hydrocode simulations for kilometer-sized comets (Pierazzo and Chyba, 1999), with attention to the track below 3000 K where it is shown that potential stabilizing effects of high pressure become unimportant kinetically. The question of survival can then be considered without the need for assignment of activation volumes and the related uncertainties in their application to extreme conditions. The exercise shows that the characteristic times for soot formation in the interval fall well below the cooling periods for impacts ranging from fully vertical down to about 9?? above horizontal. Decarboxylation, which emerges as more rapid than soot formation below 2000-3000 K, continues further down to extremely narrow impact angles, and accordingly cometa??ry delivery of amino acids to early Earth is highly unlikely. ?? 2006 American Chemical Society.

Journal of Physical Chemistry A↗

USGS2006

One-day rate measurements for estimating net nitrification potential in humid forest soils

Measurements of net nitrification rates in forest soils have usually been performed by extended sample incubation (2-8 weeks), either in the field or in the lab. Because of disturbance effects, these measurements are only estimates of nitrification potential and shorter incubations may suffice. In three separate studies of northeastern USA forest soil surface horizons, we found that laboratory nitrification rates measured over 1 day related well to those measured over 4 weeks. Soil samples of Oa or A horizons were mixed by hand and the initial extraction of subsamples, using 2 mol L-1 KCl, occurred in the field as soon as feasible after sampling. Soils were kept near field temperature and subsampled again the following day in the laboratory. Rates measured by this method were about three times higher than the 4-week rates. Variability in measured rates was similar over either incubation period. Because NO3- concentrations were usually quite low in the field, average rates from 10 research watersheds could be estimated with only a single, 1-day extraction. Methodological studies showed that the concentration of NH4+ increased slowly during contact time with the KCl extractant and, thus, this contact time should be kept similar during the procedure. This method allows a large number of samples to be rapidly assessed. ?? 2006 Elsevier B.V. All rights reserved.

Forest Ecology and Management↗

USGS2004

Mineralization and nitrification patterns at eight northeastern USA forested research sites

Nitrogen transformation rates in eight northeastern US research sites were measured in soil samples taken in the early season of 2000 and the late season of 2001. Net mineralization and nitrification rates were determined on Oa or A horizon samples by two different sampling methods - intact cores and repeated measurements on composite samples taken from around the cores. Net rates in the composite samples (n=30) showed three different temporal patterns: high net nitrification with minimal NH4+ accumulation, high net nitrification and high NH4+ accumulation, and minimal net nitrification and moderate NH4+ accumulation. The 4-week net rates in intact cores were about half that of the rates from the composite samples but were well related (R2 > 0.70). Composite samples from sites that exhibited high net nitrification were incubated with acetylene and net nitrification was completely stopped, suggesting an autotrophic pathway. Gross mineralization and nitrification (2000 only) rates were estimated using the isotope dilution technique. Gross rates of nitrification and consumption in intact cores were relatively low. Gross rates of mineralization and net rates of nitrification were both related to the soil C/N ratio, with higher rates generally occurring in sites containing Acer saccharum as a dominant or co-dominant species. The comparison of methods suggests that all provide a similar hierarchy of potential rates but that the degree of net nitrification is strongly influenced by the degree of sample disturbance. Differences between sites appear to be related to an interaction of soil (C/N) and vegetation (A. saccharum contribution) characteristics. ?? 2003 Elsevier B.V. All rights reserved.

Forest Ecology and Management↗

USGS2002

The hydrothermolysis of the picrate anion: Kinetics and mechanism

The hydrothermolysis of the picrate anion in aqueous solution has been studied at 260-325??C in liquid water. At starting pH values above 12, the disappearance of picrate begins immediately and is first order in OH-. At lower pH, there is an induction period preceding the disappearance, and over the pH range 6.7-11.9 there is no pH dependence in the developed reaction phase. Added borate and silicate salts promote the reaction, suggesting their acting as nucleophiles at hydrothermal conditions. Nitrite is an initial product, while acetate is a final product and reflective of a vigorous oxidative sequence consuming the intermediate products. A reaction sequence consistent with the results at the lower pH includes initiation of a chain process by displacement of nitrite by water, followed by nucleophilic displacement of nitrite by nitrite such that a nitro group is replaced by an O-N=O group. The ester then rapidly hydrolyzes, and the net reaction is the production of an additional nitrite with each cycle. A simple modeling of this system satisfactorily fits the experimental findings. ?? 2002 Elsevier Science B.V. All rights reserved.

Thermochimica Acta↗

USGS1996

Exchangeable hydrogen explains the pH of spodosol Oa horizons

The chemistry of extremely acid Oa horizons does not conform to traditional pH, Al, and base saturation relationships. Results from two separate studies of northeastern U.S. forested soils were used to investigate relationships between pH in water or dilute salt solutions and other soil characteristics. In Oa horizons with pH below 4, soil pH in dilute CaCl 2 solution was correlated with exchangeable H + measured either by titration ( r = −0.88, P = 0.0001, n = 142) or by electrode ( r = −0.89, P = 0.0001, n = 45). Exchangeable H + expressed as a percentage of the cation-exchange capacity (CEC) was linear with pH and showed similar slopes for data from both studies. For all samples, pHw = 4.21 − 1.80 × H + /CEC ( R 2 = 0.69, n = 194). The reciprocal of the H + /CEC ratio is base saturation with Al added to the bases. Because of the low pH, exchangeable Al does not appear to behave as an acid. Exchangeable H + remains an operationally defined quantity because of the difficulty in separating exchange and hydrolysis reactions. In a variety of neutral-salt extractants, concentrations of H + were correlated with 0.1 M BaCl 2 -exchangeable H + ( r > 0.91, P = 0.0001, n = 26) regardless of the strength of the extract. Nine successive extractions with 0.33 m M CaCl 2 removed more H + than was removed by single batch extractions with either 1 M KCl or 0.1 M BaCl 2 (average H + of 70, 43, and 49 mmol kg −1 , respectively for 26 samples). The data showed little difference in the chemical behavior of Oa horizons from a variety of geographical sites and vegetation types.

Maine, New Hampshire, New York, Vermont↗