We used radiocarbon measurements of dissolved organic carbon (DOC) to resolve sources of riverine carbon within agriculturally dominated landscapes in California. During 2003 and 2004, average Δ14C for DOC was −254‰ in agricultural drains in the Sacramento–San Joaquin Delta, −218‰ in the San Joaquin River, −175‰ in the California State Water Project and −152‰ in the Sacramento River. The age of bulk DOC transiting the rivers of California’s Central Valley is the oldest reported for large rivers and suggests wide-spread loss of soil organic matter caused by agriculture and urbanization. Using DAX 8 adsorbent, we isolated and measured 14C concentrations in hydrophobic acid fractions (HPOA); river samples showed evidence of bomb-pulse carbon with average Δ14C of 91 and 76‰ for the San Joaquin and Sacramento Rivers, respectively, with older HPOA, −204‰, observed in agricultural drains. An operationally defined non-HPOA fraction of DOC was observed in the San Joaquin River with seasonally computed Δ14C values of between −275 and −687‰; the source of this aged material was hypothesized to be physically protected organic-matter in high clay-content soils and agrochemicals (i.e., radiocarbon-dead material) applied to farmlands. Mixing models suggest that the Sacramento River contributes about 50% of the DOC load in the California State Water Project, and agricultural drains contribute approximately one-third of the load. In contrast to studies showing stabilization of soil carbon pools within one or two decades following land conversion, sustained loss of soil organic matter, occurring many decades after the initial agricultural-land conversion, was observed in California’s Central Valley.

Nitric oxide (NO) is an important trace gas and regulator of atmospheric photochemistry. Theory suggests moist soils optimize NO emissions, whereas wet or dry soils constrain them. In drylands, however, NO emissions can be greatest in dry soils and when dry soils are rewet. To understand how aridity and vegetation interact to generate this pattern, we measured NO fluxes in a California grassland, where we manipulated vegetation cover and the length of the dry season and measured [δ(15)-N]NO and [δ(18)-O]NO following rewetting with (15)N-labeled substrates. Plant N uptake reduced NO emissions by limiting N availability. In the absence of plants, soil N pools increased and NO emissions more than doubled. In dry soils, NO-producing substrates concentrated in hydrologically disconnected microsites. Upon rewetting, these concentrated N pools underwent rapid abiotic reaction, producing large NO pulses. Biological processes did not substantially contribute to the initial NO pulse but governed NO emissions within 24 h postwetting. Plants acted as an N sink, limiting NO emissions under optimal soil moisture. When soils were dry, however, the shutdown in plant N uptake, along with the activation of chemical mechanisms and the resuscitation of soil microbial processes upon rewetting, governed N loss. Aridity and vegetation interact to maintain a leaky N cycle during periods when plant N uptake is low, and hydrologically disconnected soils favor both microbial and abiotic NO-producing mechanisms. Under increasing rates of atmospheric N deposition and intensifying droughts, NO gas evasion may become an increasingly important pathway for ecosystem N loss in drylands.

We investigated multiple lines of evidence to determine if observed and paleo-reconstructed changes in acid neutralizing capacity (ANC) in Sierra Nevada lakes were the result of changes in 20th century atmospheric deposition. Spheroidal carbonaceous particles (SCPs) (indicator of anthropogenic atmospheric deposition) and biogenic silica and δ(13)C (productivity proxies) in lake sediments, nitrogen and sulfur emission inventories, climate variables, and long-term hydrochemistry records were compared to reconstructed ANC trends in Moat Lake. The initial decline in ANC at Moat Lake occurred between 1920 and 1930, when hydrogen ion deposition was approximately 74 eq ha(-1) yr(-1), and ANC recovered between 1970 and 2005. Reconstructed ANC in Moat Lake was negatively correlated with SCPs and sulfur dioxide emissions (p = 0.031 and p = 0.009). Reconstructed ANC patterns were not correlated with climate, productivity, or nitrogen oxide emissions. Late 20th century recovery of ANC at Moat Lake is supported by increasing ANC and decreasing sulfate in Emerald Lake between 1983 and 2011 (p < 0.0001). We conclude that ANC depletion at Moat and Emerald lakes was principally caused by acid deposition, and recovery in ANC after 1970 can be attributed to the United States Clean Air Act.