A new approach for parameterizing dissolved organic matter (DOM) ultraviolet-visible absorption spectra is presented. Two distinct spectral slope regions (275–295 nm and 350–400 nm) within log-transformed absorption spectra were used to compare DOM from contrasting water types, ranging from wetlands (Great Dismal Swamp and Suwannee River) to photobleached oceanic water (Atlantic Ocean). On the basis of DOM size-fractionation studies (ultrafiltration and gel filtration chromatography), the slope of the 275–295-nm region and the ratio of these slopes (SR; 275–295-nm slope : 350–400-nm slope) were related to DOM molecular weight (MW) and to photochemically induced shifts in MW. Dark aerobic microbial alteration of chromophoric DOM (CDOM) resulted in spectral slope changes opposite of those caused by photochemistry. Along an axial transect in the Delaware Estuary, large variations in SR were measured, probably due to mixing, photodegradation, and microbial alteration of CDOM as terrestrially derived DOM transited through the estuary. Further, SR varied by over a factor of 13 between DOM-rich wetland waters and Sargasso Sea surface waters. Currently, there is no consensus on a wavelength range for log-transformed absorption spectra. We propose that the 275–295-nm slope be routinely reported in future DOM studies, as it can be measured with high precision, it facilitates comparison among dissimilar water types including CDOM-rich wetland and CDOM-poor marine waters, and it appears to be a good proxy for DOM MW.

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Absorption spectral slopes and slope ratios as indicators of molecular weight, source, and photobleaching of chromophoric dissolved organic matter

Marine dissolved organic matter (DOM) is a complex mixture of molecules found throughout the world's oceans. It plays a key role in the export, distribution, and sequestration of carbon in the oceanic water column, posited to be a source of atmospheric climate regulation. Biogeochemistry of Marine Dissolved Organic Matter, Second Edition, focuses on the chemical constituents of DOM and its biogeochemical, biological, and ecological significance in the global ocean, and provides a single, unique source for the references, information, and informed judgments of the community of marine biogeochemists. Presented by some of the world's leading scientists, this revised edition reports on the major advances in this area and includes new chapters covering the role of DOM in ancient ocean carbon cycles, the long term stability of marine DOM, the biophysical dynamics of DOM, fluvial DOM qualities and fate, and the Mediterranean Sea. Biogeochemistry of Marine Dissolved Organic Matter, Second Edition, is an extremely useful resource that helps people interested in the largest pool of active carbon on the planet (DOC) get a firm grounding on the general paradigms and many of the relevant references on this topic. * Features up-to-date knowledge of DOM, including five new chapters* The only published work to synthesize recent research on dissolved organic carbon in the Mediterranean Sea* Includes chapters that address inputs from freshwater terrestrial DOM

Biogeochemistry of marine dissolved organic matter

Advances in spectroscopic techniques have led to an increase in the use of optical properties (absorbance and fluorescence) to assess dissolved organic matter (DOM) composition and infer sources and processing. However, little information is available to assess the impact of biological and photolytic processing on the optical properties of original DOM source materials. Over a 3.5 month laboratory study, we measured changes in commonly used optical properties and indices in DOM leached from peat soil, plants, and algae following biological and photochemical degradation to determine whether they provide unique signatures that can be linked to original DOM source. Changes in individual optical parameters varied by source material and process, with biodegradation and photodegradation often causing values to shift in opposite directions. Although values for different source materials frequently overlapped, multivariate statistical analyses showed that unique optical signatures could be linked to original DOM source material, with 17 optical properties determined by discriminant analysis to be significant (p < 0.05) in distinguishing between DOM source and environmental processing. These results demonstrate that inferring source material from optical properties is possible when parameters are evaluated in combination even after extensive biological and photochemical alteration.

https://aslopubs.onlinelibrary.wiley.com/doi/epdf/10.1002/lno.10270

Optical properties of dissolved organic matter (DOM): Effects of biological and photolytic degradation

The fluorescent properties of dissolved organic matter (DOM) are often studied in order to infer DOM characteristics in aquatic environments, including source, quantity, composition, and behavior. While a potentially powerful technique, a single widely implemented standard method for correcting and presenting fluorescence measurements is lacking, leading to difficulties when comparing data collected by different research groups. This paper reports on a large-scale interlaboratory comparison in which natural samples and well-characterized fluorophores were analyzed in 20 laboratories in the U.S., Europe, and Australia. Shortcomings were evident in several areas, including data quality-assurance, the accuracy of spectral correction factors used to correct EEMs, and the treatment of optically dense samples. Data corrected by participants according to individual laboratory procedures were more variable than when corrected under a standard protocol. Wavelength dependency in measurement precision and accuracy were observed within and between instruments, even in corrected data. In an effort to reduce future occurrences of similar problems, algorithms for correcting and calibrating EEMs are described in detail, and MATLAB scripts for implementing the study's protocol are provided. Combined with the recent expansion of spectral fluorescence standards, this approach will serve to increase the intercomparability of DOM fluorescence studies.

Measurement of Dissolved Organic Matter Fluorescence in Aquatic Environments: An Interlaboratory Comparison

Surface water samples were collected from 43 streams distributed throughout watersheds of mixed land use in southern Ontario, Canada. Absorbance and fluorescence spectroscopy with parallel factor analysis (PARAFAC) was used to characterize dissolved organic matter (DOM). DOM characteristics were related to environmental variables, microbial activity indicators (bacterial production and extracellular leucine aminopeptidase activity), and riparian land use to understand better how these factors influence DOM in streams. PARAFAC produced a six-component model (C1 to C6). Temperature correlated with each PARAFAC component, suggesting that water source, drainage area, and light penetration broadly affected DOM characteristics. C1 and C2 represented terrestrial, humic-like DOM fluorophore groups and comprised 41–65% of stream DOM fluorescence. C5, a tryptophan-like component, related negatively to a humification index but positively to leucine-aminopeptidase activity and recently produced DOM, suggesting that C5 consisted of autochthonous, microbially produced DOM. C3, C4, and C6 showed signs of quinone-like, humic-like, and microbial transformable fluorophores. The distribution of these potentially redox-active PARAFAC components indicated that DOM was in a more reduced state in streams with higher bacterial production and agricultural land use than in streams with increased wetlands area, which had greater relative abundance of the oxidized quinone-like component. Anthropogenic land use and microbial activity altered the quantity and quality of DOM exported from human-affected streams from that observed in forest- and wetland-dominated streams. DOM in agriculturally affected streams was likely more labile and accessible to the microbial community than DOM in wetland streams, which supported low rates of microbial activity.

https://aslopubs.onlinelibrary.wiley.com/doi/pdf/10.4319/lo.2010.55.3.1159

Unraveling the role of land use and microbial activity in shaping dissolved organic matter characteristics in stream ecosystems

Specific UV absorbance (SUVA) is defined as the UV absorbance of a water sample at a given wavelength normalized for dissolved organic carbon (DOC) concentration. Our data indicate that SUVA, determined at 254 nm, is strongly correlated with percent aromaticity as determined by 13C NMR for 13 organic matter isolates obtained from a variety of aquatic environments. SUVA, therefore, is shown to be a useful parameter for estimating the dissolved aromatic carbon content in aquatic systems. Experiments involving the reactivity of DOC with chlorine and tetra- methylammonium hydroxide (TMAH), however, show a wide range of reactivity for samples with similar SUVA values. These results indicate that, while SUVA measurements are good predictors of general chemical characteristics of DOC, they do not provide information about reactivity of DOC derived from different types of source materials. Sample pH, nitrate, and iron were found to influence SUVA measurements.

Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon.

Accurate determinations of total (TOC), dissolved (DOC) and particulate (POC) organic carbon concentrations are critical for understanding the geochemical, environmental, and ecological roles of aquatic organic matter. Of particular significance for the drinking water industry, TOC measurements are the basis for compliance with US EPA regulations. The results of an interlaboratory comparison designed to identify problems associated with the determination of organic matter concentrations in drinking water supplies are presented. The study involved 31 laboratories and a variety of commercially available analytical instruments. All participating laboratories performed well on samples of potassium hydrogen phthalate (KHP), a compound commonly used as a standard in carbon analysis. However, problems associated with the oxidation of difficult to oxidize compounds, such as dodecylbenzene sulfonic acid and caffeine, were noted. Humic substances
posed fewer problems for analysts. Particulate organic matter (POM) in the form of polystyrene beads, freeze-dried bacteria and pulverized leaf material were the most difficult for all analysts, with a wide range of performances reported. The POM results indicate that the methods surveyed in this study are inappropriate for the accurate determination of POC and TOC concentration. Finally, several analysts had difficulty in efficiently separating inorganic carbon from KHP solutions, thereby biasing DOC results.

James L Weishaar

Papers

Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon.

Assessment of relative accuracy in the determination of organic matter concentrations in aquatic systems.