Elizabeth C. Minor

Using two-dimensional correlations of 13C NMR and FTIR to investigate changes in the chemical composition of dissolved organic matter along an estuarine transect.

Applying two-dimensional correlation spectroscopy to (13)C NMR and FTIR spectra of the high molecular-weight dissolved organic matter (HMW-DOM) isolated along an Elizabeth River/Chesapeake Bay salinity transect shows that HMW-DOM consists of three major components that have different biogeochemical reactivities. The first appears to be a heteropolysaccharide (HPS) component and its contribution to carbon increases as we approach the marine offshore. The second appears to be composed of carboxyl-rich compounds (CRC); its carbon percentage decreases. The third component contains the major functional group of amide/amino sugar (AMS) and its carbon percentage stays almost constant along the salinity transect. It seems that the HPS and CRC are present in many aquatic environments at different relative ratios. The 2D-correlation maps reveal that each of these components is composed of dynamic mixtures of compounds that share similar backbone structures but have significant functional group differences. Two-dimensional (2D) correlation spectroscopy is a powerful new biogeochemical tool to track the changes in complex organic matter as a function of space, time, or environmental effects.

Structural characterization of dissolved organic matter: a review of current techniques for isolation and analysis

Natural dissolved organic matter (DOM) in aquatic systems plays many environmental roles: providing building blocks and energy for aquatic biota, acting as a sunscreen in surface water, and interacting with anthropogenic compounds to affect their ultimate fate in the environment. Such interactions are a function of DOM composition, which is difficult to ascertain due to its heterogeneity and the co-occurring matrix effects in most aquatic samples. This review focuses on current approaches to the chemical structural characterization of DOM, ranging from those applicable to bulk samples and in situ analyses (UV-visible spectrophotometry and fluorescence spectroscopy) through the concentration/isolation of DOM followed by the application of one or more analytical techniques, to the detailed separation and analysis of individual compounds or compound classes. Also provided is a brief overview of the main techniques used to characterize isolated DOM: mass spectrometry (MS), nuclear magnetic resonance mass spectrometry (NMR) and Fourier transform infrared spectroscopy (FTIR).

Estuarine/marine UDOM as characterized by size-exclusion chromatography and organic mass spectrometry

High performance size-exclusion chromatography (HPSEC) and direct temperature-resolved mass spectrometry (DT-MS) were used to explore molecular weight distributions and molecular level characteristics within marine/estuarine ultrafiltered dissolved organic matter (UDOM, >1 kDa) collected from the lower Chesapeake Bay, USA and the Oosterschelde estuary, The Netherlands. Initial HPSEC characterization indicates that the overall size distribution is similar in all the UDOM samples; however, there are distinct variations among the samples, especially in the low molecular weight region. As a preliminary study of molecular level variations with apparent molecular size, the Oosterschelde UDOM sample was separated into molecular weight fractions using HPSEC. These fractions were then analyzed by DT-MS. The size fractions within the UDOM sample yielded distinctly different mass spectra; the larger size classes were enriched in aminosugars, deoxysugars, and methylated sugars while the smaller size classes were enriched in hexose sugars. There is also evidence that hexose sugars appear in at least two structures with highly different molecular weights and potentially highly different source and sink functions within the marine water column.

Evaluating the photoalteration of estuarine dissolved organic matter using direct temperature-resolved mass spectrometry and UV-visible spectroscopy

Abstract.Direct temperature-resolved mass spectrometry (DT-MS) was used to evaluate the molecular-level photodegradation of dissolved organic matter (DOM) isolated from three sites in a Chesapeake Bay subestuary (swamp- and marsh-influenced up-river, midestuarine, and bay mouth). From each site, filtered (<0.1 or <0.2 μm) water samples were irradiated in solarsimulated ultraviolet light followed by isolation of the DOM using C18-solid-phase extraction and subsequent DT-MS analysis. To provide background DOM photoreactivity data for the water samples, we also determined dissolved inorganic carbon (DIC) photoproduction and chromophoric dissolved organic matter (CDOM) photobleaching. DIC photoproduction was correlated with initial DOM light absorbance, initial dissolved organic carbon (DOC) concentration, and photobleaching. Changes in DT-MS characteristics within the extracts (in particular, the loss of an “aromatic” signal believed to be from reworked terrestrial material) were found to correlate linearly with the absorbance of the corresponding water samples. A relationship between photobleaching and DT-MS characteristics was also observed, with the upstream samples asymptotically approaching a constant “molecular-level” value as photobleaching increased. Both relationships appeared to be independent of absorbance wavelength in the ultraviolet. Following irradiation, the swamp/marsh-dominated upstream samples resembled the down-stream samples in terms of absorption spectra and MS-determined molecular-level characteristics. These shifts indicate that terrestrially-derived DOM may be more difficult to differentiate from marine DOM upon photodegradation, which has implications regarding evaluating the terrestrial impact within the marine DOM pool.

Microscale characterization of algal and related particulate organic matter by direct temperature-resolved mass spectrometry

Abstract In this paper we report a preliminary investigation of laboratory algal cultures and natural populations of marine particles utilizing Direct (i.e. “in-source”) Temperature-resolved Mass spectrometry (DT-MS). With this technique the potential exists to characterize microgram quantities of particulate organic matter (POM) at the molecular level. Two particular aspects of the approach set DT-MS apart from previous pyrolysis (Py)-MS investigations. First, temperature resolution allows characterization of both desorption (biolipid) and pyrolysis (biopolymeric) products in a single measurement. Second, an improved sample inlet configuration enables compounds exhibiting a broad range of polarities and molecular weights to be transmitted to the analyzer. The above features, coupled with the rapid analysis time (typically 5 min/sample) and amenability to statistical data reduction procedures, renders DT-MS well suited for profiling or mapping molecular-level variations in POM composition at a spatial and temporal resolution hitherto impractical using conventional biochemical assays. To illustrate the versatility of the approach and extent of (bio)chemical information available from DT-MS, we have analyzed a series of algal cultures together with selected POM samples collected in sediment traps and filtered from hydrocasts. We have also exploited the inherent sensitivity of DT-MS, to obtain information on compositional variability between and, more significantly, within particle size classes. Results of the latter, which was attained by conducting DT-MS measurements on particles sorted by flow cytometry, reveal substantial internal variations in chemical composition.

Estimation of carbonate, total organic carbon, and biogenic silica content by FTIR and XRF techniques in lacustrine sediments

AbstractMajor components of lacustrine sediments, such as carbonates, organic matter, and biogenic silica, provide significant paleoenvironmental information about lake systems. Fourier transform infrared spectroscopy (FTIR) and scanning X-ray fluorescence (XRF) techniques are fast, cost effective, efficient methods to determine the relative abundances of these components. We investigate the potential of these techniques using sediments from two large lakes, Lake Malawi in Africa and Lake Qinghai in China. Our results show statistically significant correlations of conventionally measured concentrations of carbonate (%CaCO3), total organic carbon (%TOC), and biogenic silica (%BSi), with absorbance in the corresponding FTIR spectral regions and with XRF elemental ratios including calcium:titanium (Ca/Ti), incoherent:coherent X-ray scatter intensities (Inc/Coh), and silicon:titanium (Si/Ti), respectively. The correlation coefficients (R) range from 0.66 to 0.96 for comparisons of FTIR results and conventional measurements, and from 0.70 to 0.90 for XRF results and conventional measurements. Both FTIR and XRF techniques exhibit great potential for rapid assessment of inorganic and organic contents of lacustrine sediments. However, the relationship between XRF-ratios or FTIR-absorbances and abundances of corresponding sedimentary components can vary with sediment source and lithology.

DOM characteristics along the continuum from river to receiving basin: a comparison of freshwater and saline transects

The chemical characteristics of bulk (sterile-filtered) and high molecular-weight dissolved organic matter (HMW DOM) were analyzed for freshwater (St. Louis River, Minnesota to Lake Superior) and saline (Elizabeth River, Virginia to Chesapeake Bay) river-to-receiving basin transects. Dissolved organic carbon concentrations and UV–Visible spectroscopy of bulk DOM demonstrated a reduction in organic carbon, colored DOM and aromatic compounds downstream in both transects. The proportion of DOM recoverable via ultrafiltration as HMW material also decreased downstream in both transects, although there was an offset in recoveries between the transects that may be explained by the effects of ionic strength and/or differences in ultrafiltration technique. The analysis of HMW DOM by Fourier transform infrared spectroscopy illustrated similar trends between transects, with a general shift from aromatic/carboxylic compounds nearshore to aliphatic/carbohydrate materials offshore. The parallel changes observed along saline and freshwater transects imply that similar processes play significant roles in the down-gradient alteration of DOM and that ionic strength or pH changes cause second-order effects.

Estuarine organic matter composition as probed by direct temperature-resolved mass spectrometry and traditional geochemical techniques

Abstract Estuarine modification of terrestrial and riverine/estuarine organic matter may strongly affect the eventual preservation of reduced carbon in world oceans and is also important in nutrient and contaminant cycling. In this study multiple size classes of organic matter (including particles and dissolved fractions, POM and DOM) from a transect down the Delaware River/Bay system were collected and analyzed. Variations in chemical characteristics were identified using direct temperature-resolved mass spectrometry (DT-MS) and wet chemical techniques coupled with discriminant analysis and canonical correlations analysis. These comparative measures illustrate the complementary nature of traditional versus more recent mass spectrometry approaches. Within the estuary system, organic matter size class, rather than sample location, is found to be the major source of molecular-level variation. POM is enriched in proteins, nucleic acids, fatty acids, chlorophyll, and sterols, whereas DOM is enriched in aminosugar, furfural, and alkylphenol moieties. In positive ammonia chemical ionization DT-MS studies, which focus on the sugar components in POM and DOM, riverine very high molecular weight DOM (>30 kDa,

Changes in the molecular-level characteristics of sinking marine particles with water column depth

Abstract Over the past decade, sinking particulate organic matter (POM) samples from depth profiles in the equatorial Pacific have been analyzed by multiple techniques to evaluate the organic matter preservation mechanisms most dominant in the oceanic water column. How the samples were analyzed strongly influenced which organic matter preservation scheme appeared to dominate. Bulk functional group analysis by solid-state 13C-NMR showed that organic matter composition varied very little in light of the extreme degree of remineralization (>98%) that occurred with water column depth. This indicates preservation by a physical mechanism, such as sorption to mineral grains or protection within a mineral aggregate. However, detailed lipid studies of the characterizable fraction showed that selective preservation was important, with lipid structure being correlated with preservation over depth. However, the characterizable fraction decreases greatly with depth. Therefore, in this paper, direct temperature-resolved mass spectrometry (DT-MS), was used to further characterize POM, with the assumption that this approach could “see” a substantial proportion of the “uncharacterized” organic matter. DT-MS, which provides compositional information at an intermediate level between the detailed wet chemical studies and one-dimensional solid-state C13-NMR, also indicates an intermediate view between the mechanistic extremes of selective preservation and physical protection.

Changes in dissolved organic matter characteristics in Chincoteague Bay during a bloom of the pelagophyte Aureococcus anophagefferens

Aureococcus anophagefferens, the pelagophyte responsible for brown tide blooms, occurs in coastal bays along the northeast coast of the United States. This species was identified in Chincoteague Bay, Maryland, in 1997 and has bloomed there since at least 1998. Time series of dissolved organic matter (DOM) concentrations and characteristics are presented for two sites in Chincoteague Bay: one that experienced a brown tide bloom in 2002 and one that did not. Characteristics of the bulk DOM pool were obtained using dissolved organic carbon (DOC) and ultraviolet-visible (UV-Vis) measurements (spectral slope and specific UV absorbance). High molecular weight DOM (HMW-DOM) was characterized in terms of DOC concentration, carbon: nitrogen (C:N) ratio, isotopic signature, and molecular-level characteristics as determined by direct temperature resolved mass spectrometry (DT-MS). Compositional changes in the DOM pool are associated with brown tide blooms, although a direct relationship between DOM characteristics and bloom development could not be confirmed. DOC measurements suggest that during the brown tide bloom, HMW-DOM was released into the surface water. UV-Vis analysis on the bulk DOM and molecular-level characterization of the HMW-DOM using DT-MS show that this material was optically active and more aromatic in nature. Based upon C:N ratio and HMW-DOC measurements, it appears that this HMW-DOM was more nitrogen enriched. Whether this material was released as exudates or was due to lysis ofA. anophagefferens could not be determined.