The detailed molecular composition of laboratory generated limonene ozonolysis secondary organic aerosol (SOA) was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Approximately 1200 molecular formulas were identified in the SOA over the mass range of 140 to 850 Da. Four characteristic groups of high relative abundance species were observed; they indicate an array of accretion products that retain a large fraction of the limonene skeleton. The identified molecular formulas of each of the groups are related to one another by CH₂, O and CH₂O homologous series. The CH₂ and O homologous series of the low molecular weight (MW) SOA (<i>m/z</i> < 300) are explained with a combination of functionalization and fragmentation of radical intermediates and reactive uptake of gas-phase carbonyls. They include isomerization and elimination reactions of Criegee radicals, reactions between alkyl peroxy radicals, and scission of alkoxy radicals resulting from the Criegee radicals. The presence of compounds with 10–15 carbon atoms in the first group (e.g. C₁₁H₁₈O₆) provides evidence for SOA formation by the reactive uptake of gas-phase carbonyls during limonene ozonolysis. The high MW compounds (<i>m/z</i> > 300) were found to constitute a significant number fraction of the identified SOA components. The formation of high MW compounds was evaluated by molecular formula trends, fragmentation analysis of select high MW compounds and a comprehensive reaction matrix including the identified low MW SOA, hydroperoxides and Criegee radicals as building blocks. Although the formation of high MW SOA may occur via a variety of radical and non-radical reaction channels, the combined approach indicates a greater importance of the non-condensation reactions over aldol and ester condensation reaction channels. Among these hemi-acetal reactions appear to be most dominant followed by hydroperoxide and Criegee reaction channels

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Stable isotope ratios of hydrogen and oxygen have been applied to water cycle research for over 60 years. Over the past two decades, however, new data, data compilations, and quantitative methods have supported the application of isotopic data to address large-scale water cycle problems. Recent results have demonstrated the impact of climate variation on atmospheric water cycling, provided constraints on continental- to global-scale land-atmosphere water vapor fluxes, revealed biases in the sources of runoff in hydrological models, and illustrated regional patterns of water use and management by people. In the past decade, global isotopic observations have spurred new debate over the role of soils in the water cycle, with potential to impact both ecological and hydrological theory. Many components of the water cycle remain underrepresented in isotopic databases. Increasing accessibility of analyses and improved platforms for data sharing will refine and grow the breadth of these contributions in the future. ▪ Isotope ratios in water integrate information on hydrological processes over scales from cities to the globe. ▪ Tracing water with isotopes helps reveal the processes that govern variability in the water cycle and may govern future global changes. ▪ Improvements in instrumentation, data sharing, and quantitative analysis have advanced isotopic water cycle science over the past 20 years.

Stable isotope ratios of H and O are widely used to identify the source of water, e.g., in aquifers, river runoff, soils, plant xylem, and plant-based beverages. In situations where the sampled water is partially evaporated, its isotope values will have evolved along an evaporation line (EL) in δH/δO space, and back-correction along the EL to its intersection with a meteoric water line (MWL) has been used to estimate the source water's isotope ratios. Here, we review the theory underlying isotopic estimation of source water for evaporated samples (iSW). We note potential for bias from a commonly used regression-based approach for EL slope estimation and suggest that a model-based approach may be preferable if assumptions of the regression approach are not valid. We then introduce a mathematical framework that eliminates the need to explicitly estimate the EL-MWL intersection, simplifying iSW analysis and facilitating more rigorous uncertainty estimation. We apply this approach to data from the US EPA's 2007 National Lakes Assessment. We find that data for most lakes are consistent with a water source similar to annual runoff, estimated from monthly precipitation and evaporation within the lake basin. Strong evidence for both summer- and winter-biased sources exists, however, with winter bias pervasive in most snow-prone regions. The new analytical framework should improve the rigor of iSW in ecohydrology and related sciences, and our initial results from US lakes suggest that previous interpretations of lakes as unbiased isotope integrators may only be valid in certain climate regimes.

Local meteoric water lines (LMWLs) represent the site‐specific long‐term covariation of hydrogen and oxygen stable isotope ratios. LMWLs have practical utility as a hydrologic framework and as benchmarks for evaluating hydroclimatic processes in isotope‐enabled climate models. In this manuscript, we characterize the global distribution of LMWLs and compare them to LMWLs from model data. To evaluate the sensitivity of the covariance of stable isotope ratios to data set length, we paired time series rarifaction with Bayesian ellipse estimation. We then applied a threshold of 48 months and estimated LMWLs at 398 sites in 25 Köppen climate classes using orthogonal distance regression. Slopes ranged from 4.8 to 10.9, with an average of 7.64 ± 0.64. Intercepts ranged from −24‰ to 27‰, with an average of 6.85 ± 6.2‰. We identified three processes: (1) subcloud evaporation of rain, (2) atmospheric remoistening by rainfall evaporation, and (3) conditions of snow formation as important controls on slopes and intercepts in arid, humid, and seasonally snowy regions, respectively. We compared observational LMWLs with those from a suite of isotope‐enabled climate models. At arid and snowy sites, model data produced higher slopes and intercepts than observational data. At humid sites, model data exhibited dampened variability in slopes and intercepts relative to observational data. These results indicate potential for improvement in the precipitation and/or isotope parameterizations of raindrop evaporation, advection of reevaporated water, evapotranspiration fractionation, and supersaturation in mixed‐phase clouds. This meta‐analysis demonstrates LMWLs utility for identifying specific hydroclimatic and isotopic processes in observations and models.