Patrick G. Hatcher

Bulk chemical characteristics of dissolved organic matter in the ocean.

Dissolved organic matter (DOM) is the largest reservoir of reduced carbon in the oceans. The nature of DOM is poorly understood, in part, because it has been difficult to isolate sufficient amounts of representative material for analysis. Tangential-flow ultrafiltration was shown to recover milligram amounts of >1000 daltons of DOM from seawater collected at three depths in the North Pacific Ocean. These isolates represented 22 to 33 percent of the total DOM and included essentially all colloidal material. The elemental, carbohydrate, and carbon-type (by 13C nuclear magnetic resonance) compositions of the isolates indicated that the relative abundance of polysaccharides was high (∼50 percent) in surface water and decreased to ∼25 percent in deeper samples. Polysaccharides thus appear to be more abundant and reactive components of seawater DOM than has been recognized.

Comparison of quantification methods to measure fire‐derived (black/elemental) carbon in soils and sediments using reference materials from soil, water, sediment and the atmosphere

Black carbon (BC), the product of incomplete combustion of fossil fuels and biomass (called elemental carbon (EC) in atmospheric sciences), was quantified in 12 different materials by 17 laboratories from different disciplines, using seven different methods. The materials were divided into three classes: (1) potentially interfering materials, (2) laboratory-produced BC-rich materials, and (3) BC-containing environmental matrices (from soil, water, sediment, and atmosphere). This is the first comprehensive intercomparison of this type (multimethod, multilab, and multisample), focusing mainly on methods used for soil and sediment BC studies. Results for the potentially interfering materials (which by definition contained no fire-derived organic carbon) highlighted situations where individual methods may overestimate BC concentrations. Results for the BC-rich materials (one soot and two chars) showed that some of the methods identified most of the carbon in all three materials as BC, whereas other methods identified only soot carbon as BC. The different methods also gave widely different BC contents for the environmental matrices. However, these variations could be understood in the light of the findings for the other two groups of materials, i.e., that some methods incorrectly identify non-BC carbon as BC, and that the detection efficiency of each technique varies across the BC continuum. We found that atmospheric BC quantification methods are not ideal for soil and sediment studies as in their methodology these incorporate the definition of BC as light-absorbing material irrespective of its origin, leading to biases when applied to terrestrial and sedimentary materials. This study shows that any attempt to merge data generated via different methods must consider the different, operationally defined analytical windows of the BC continuum detected by each technique, as well as the limitations and potential biases of each technique. A major goal of this ring trial was to provide a basis on which to choose between the different BC quantification methods in soil and sediment studies. In this paper we summarize the advantages and disadvantages of each method. In future studies, we strongly recommend the evaluation of all methods analyzing for BC in soils and sediments against the set of BC reference materials analyzed here.

The molecularly-uncharacterized component of nonliving organic matter in natural environments.

Molecularly-uncharacterized organic matter comprises most reduced carbon in soils, sediments and natural waters. The origins, reactions and fates of these ubiquitous materials are relatively obscure, in large part because the rich vein of geochemical information that typically derives from detailed structural and stereochemical analysis is yet to be tapped. This discussion highlights current knowledge about the origins and characteristics of molecularly uncharacterized organic matter in the environment and outlines possible means by which this structurally uncharted frontier might best be explored.

Degradation of carbohydrates and lignins in buried woods

Spruce, alder, and oak woods deposited in coastal sediments were characterized versus their modern counterparts by quantification of individual neutral sugars and lignin-derived phenols as well as by scanning electron microscopy, 13C NMR, and elemental analysis. The buried spruce wood from a 2500 yr old deposit was unaltered whereas an alder wood from the same horizon and an oak wood from an open ocean sediment were profoundly degraded. Individual sugar and lignin phenol analyses indicate that at least 90 and 98 wt% of the initial total polysaccharides in the buried alder and oak woods, respectively, have been degraded along with 15–25 wt% of the lignin. At least 75% of the degraded biopolymer has been physically lost from these samples. This evidence is supported by the SEM, 13C NMR and elemental analyses, all of which indicate selective loss of the carbohydrate moiety. The following order of stability was observed for the major biochemical constituents of both buried hardwoods: vanillyl and p-hydroxyl lignin structural units > syringyl lignin structural units > pectin > α-cellulose > hemicellulose. This sequence can be explained by selective preservation of the compound middle lamella regions of the wood cell walls. The magnitude and selectivity of the indicated diagenetic reactions are sufficient to cause major changes in the chemical compositions of wood-rich sedimentary organic mixtures and to provide a potentially large in situ nutrient source.

Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods, ambers and coals

Cyclic terpenoids present in the solvent extractable material of fossil woods, ambers and brown coals have been analyzed. The sample series chosen consisted of wood remains preserved in Holocene to Jurassic sediments and a set of of ambers from the Philippines (copalite), Israel, Canada and Dominican Republic. The brown coals selected were from the Fortuna Garsdorf Mine and Miocene formations on Fiji. The fossil wood extracts contained dominant diterpenoid or sesquiterpenoid skeletons, and aromatized species were present at high concentrations, with a major amount of two-ring aromatic compounds. Tricyclic diterpenoids were the predominant compounds in the ambers. Aromatized derivatives were the major components, consisting of one or two aromatic ring species with the abietane and occasionally pimarane skeletons. The saturated structures were comprised primarily of the abietane and pimarane skeletons having from three to five carbon (C1, C2, etc.) substituents. Kaurane and phyllocladane isomers were present in only minor amounts. Bicyclic sesquiterpenoids as saturated and partial or fully aromatized forms were also common in these samples, but only traces of sesterterpenoids and triterpenoid derivatives were found. The brown coal extracts were composed of major amounts of one- and two-ring aromatized terpenoids, with a greater proportion of triterpenoid derivatives than in the case of the woods and ambers. This was especially noticeable for the German coal, where the triterpenoids were predominant. Open C-ring aromatized structures were also present in this coal. Steroid compounds were not detectable, but some hopanes were found as minor components in the German brown coal. An overview of the skeletal structure classes identified in each sample, as well as the general mass spectrometric characteristics of the unknown compounds are included in the present paper. It can be concluded from these structural distributions that aromatization is the main process for the transformation of terrestrial cyclic terpenoids during diagenesis, constituting a general pathway for all terpenoids.

A new rapid technique for the characterization of lignin in vascular plants: thermochemolysis with tetramethylammonium hydroxide (TMAH)

Abstract Flash pyrolysis in the presence of tetramethylammonium hydroxide (TMAH) has been utilized for the characterization of lignin in a gymnosperm (pine), angiosperm (alder), and nonwoody ( Juncus effusus L.) vascular plant tissue. The gymnosperm tissue yielded primarily methylated guaiacyl derivatives resulting from cleavage of lignin β-O-4 bonds and subsequent methylation of acidic hydroxy groups. The angiosperm tissue also yielded guaiacyl-type compounds in addition to an analogous suite of methylated syringyl lignin derivatives. The nonwoody angiosperm yielded methylated cinnamyl lignin derivatives in addition to methylated guaiacyl and syringyl compounds. Analysis of alder wood with this technique at a low temperature of 310°C has demonstrated that the dominant reaction with TMAH is mainly a thermally assisted chemolytic degradation rather than degradation induced by pyrolytic bond cleavage. Accordingly, we now call the technique TMAH thermochemolysis.

The organic geochemistry of coal: from plant materials to coal

Coalification is a process that transforms plant remains under the influence of time, temperature, and possibly pressure to a black, generally lustrous solid organic fossil fuel having a very complex chemistry. Although much has been learned in the past two centuries on coal chemistry, we still have little knowledge of the way plant materials undergo these transformations. The problem has been the existence of adequate characterization tools. The advent of some new tools for structural elucidation of macromolecules has led to some revised thinking on coalification. Originally thought to be a process involving the full degradation of plant remains and subsequent reconstitution of these remains, the general consensus today is that the process involves a selective preservation of certain resistant plant components followed by some minor reorganization of the biopolymers that survive. The major components of plants do degrade, and the resistant ones often constitute only a small fraction of the original mass of the plant materials. This paper examines the most recent literature concerning coalification and focuses on the chemistry associated with coalification of certain recognizable plant remains that have been at the center of research activity for the past two decades. Thus, we examine the recent knowledge of the chemistry of resistant biopolymers in extant and fossil wood, cuticles, resins, spores, and algae, knowledge that has been assembled to establish the reaction pathways towards coal macromolecules.

Lignin degradation in wood-feeding insects

The aromatic polymer lignin protects plants from most forms of microbial attack. Despite the fact that a significant fraction of all lignocellulose degraded passes through arthropod guts, the fate of lignin in these systems is not known. Using tetramethylammonium hydroxide thermochemolysis, we show lignin degradation by two insect species, the Asian longhorned beetle (Anoplophora glabripennis) and the Pacific dampwood termite (Zootermopsis angusticollis). In both the beetle and termite, significant levels of propyl side-chain oxidation (depolymerization) and demethylation of ring methoxyl groups is detected; for the termite, ring hydroxylation is also observed. In addition, culture-independent fungal gut community analysis of A. glabripennis identified a single species of fungus in the Fusarium solani/Nectria haematococca species complex. This is a soft-rot fungus that may be contributing to wood degradation. These results transform our understanding of lignin degradation by wood-feeding insects.

Chemical structural studies of natural lignin by dipolar dephasing solid-state 13C nuclear magnetic resonance

Abstract Two natural lignins, one from a gymnosperm wood the other from angiosperm wood, were examined by conventional solid-state and dipolar dephasing 13 C nuclear magnetic resonance (NMR) techniques. The results obtained from both techniques show that the structure of natural lignins is consistent with models of softwood and hardwood lignin. The dipolar dephasing NMR data provide a measure of the degree of substitution on aromatic rings which is consistent with the models.

Comparison of two thermochemolytic methods for the analysis of lignin in decomposing gymnosperm wood: the CuO oxidation method and the method of thermochemolysis with tetramethylammonium hydroxide (TMAH)

Abstract Comparison of the new TMAH thermochemolysis procedure with the traditional CuO oxidation procedure for lignin characterization in gymnosperm wood and soil formed from degraded gymnosperm wood indicates that an excellent agreement exists between the two methods, especially with regard to the yield of lignin monomers. Moreover, the TMAH procedure appears to be more sensitive for calculation of benzenecarboxylic acid/benzaldehyde ( Ad Al ) ratios, displaying a larger dynamic range than that observed by CuO oxidation. If one considers the simplicity with which the TMAH procedure is carried out, this technique is much more suited to routine analyses of large numbers of samples.