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 (S_R; 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 S_R were measured, probably due to mixing, photodegradation, and microbial alteration of CDOM as terrestrially derived DOM transited through the estuary. Further, S_R 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.

Plastic contamination of the environment is a global problem whose magnitude justifies the consideration of plastics as emergent geomaterials with chemistries not previously seen in Earth’s history. At the elemental level, plastics are predominantly carbon. The comparison of plastic stocks and fluxes to those of carbon reveals that the quantities of plastics present in some ecosystems rival the quantity of natural organic carbon and suggests that geochemists should now consider plastics in their analyses. Acknowledging plastics as geomaterials and adopting geochemical insights and methods can expedite our understanding of plastics in the Earth system. Plastics also can be used as global-scale tracers to advance Earth system science.

Congo River water was filtered and then irradiated for 57 d in a solar simulator, resulting in extensive photodegradation of dissolved organic matter (DOM). Whole‐water (i.e., unfractionated) DOM was analyzed pre‐ and post‐irradiation using ultrahigh resolution Fourier transform ion cyclotron mass spectrometry (FT‐ICR MS), revealing the following three pools of DOM classified based upon their photoreactivity: (1) photo‐resistant, (2) photo‐labile, and (3) photo‐produced. Photo‐resistant DOM was heterogeneous, with most molecular classes represented, although only a small number of aromatics and no condensed aromatics were identified. The photoproduced pool was dominated by aliphatic compounds, although it included a small number of aromatics, including condensed aromatics. Aromatic compounds were the most photoreactive, with > 90% being lost upon irradiation. Photochemistry also resulted in a significant drop in the number of molecules identified and a decrease in their structural diversity. The FT‐ICR MS signatures of two classes of refractory organic matter, black carbon and carboxylic‐rich alicyclic molecules (CRAM), were present in the sample prior to irradiation, indicating that the Congo River could be a significant exporter of recalcitrant DOM to the ocean. All black carbon‐like molecules identified in the initial sample were lost during irradiation. Molecular signatures consistent with CRAM were also highly photo‐labile, demonstrating that environmental solar irradiation levels are capable of removing these refractory compounds from aquatic systems. Irradiation also shifted the molecular signature of terrestrial DOM toward that of marine DOM, thereby complicating the task of tracking terrestrial DOM in the ocean.

Dissolving Charcoal: Biomass burning produces 40 to 250 million tons of charcoal per year worldwide. Much of this is preserved in soils and sediments for thousands of years. However, the estimated production rate of charcoal is significantly larger than that of decomposition, and Jaffe et al. (p. 345 ; see the Perspective by Masiello and Louchouarn ) calculate that a large fraction of the charcoal produced by fires is lost from the land through dissolution and transport to the oceans.

Climate change induced permafrost thaw in the Arctic is mobilizing ancient dissolved organic carbon (DOC) into headwater streams; however, DOC exported from the mouth of major arctic rivers appears predominantly modern. Here we highlight that ancient (>20,000 years B.P.) permafrost DOC is rapidly utilized by microbes (~50% DOC loss in <7 days) and that permafrost DOC decay rates (0.12 to 0.19 day⁻¹) exceed those for DOC in a major arctic river (Kolyma: 0.09 day⁻¹). Permafrost DOC exhibited unique molecular signatures, including high levels of aliphatics that were rapidly utilized by microbes. As microbes processed permafrost DOC, its distinctive chemical signatures were degraded and converged toward those of DOC in the Kolyma River. The extreme biolability of permafrost DOC and the rapid loss of its distinct molecular signature may explain the apparent contradiction between observed permafrost DOC release to headwaters and the lack of a permafrost signal in DOC exported via major arctic rivers to the ocean.