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Thermal decomposition of cycloheptane was studied using flash pyrolysis coupled with vacuum ultraviolet (118.2 nm) single photon ionization time-of-flight mass spectrometry at temperatures ranging from 295 K to 1380 K. C-C bond breaking of cycloheptane leading to the 1,7-heptyl diradical was considered as the initiation step. The 1,7-heptyl diradical could readily isomerize to 1-heptene and decompose into several fragments, with dissociation to •C₄H₉and •C₃H₅as the predominant product channel. The 1,7-heptyl diradical could undergo direct dissociation, as evidenced by the production of the C₅H₁₀species. Quantum chemistry calculations at UCCSD(T)/cc-pVDZ//UB3LYP/cc-pVDZ level of theory on the initial reaction pathways of cycloheptane were also carried out to support the experimental observations. Other possible initiation channels, as well as some secondary reaction products, were also identified.

Soil erosion and sedimentation problems remain a major water quality concern for making watershed management policies in the Mississippi River Basin (MRB). It is unclear whether the observed decreasing trend of stream suspended sediment loading to the mouth of the MRB over the last eight decades truly reflects a decline in upland soil erosion in this large basin. Here, we improved a distributed regional land surface model, the Dynamic Land Ecosystem Model, to evaluate how climate and land use changes have impacted soil erosion and sediment yield over the entire MRB during the past century. Model results indicate that total sediment yield significantly increased during 1980–2018, despite no significant increase in annual precipitation and runoff. The increased soil erosion and sediment yield are mainly driven by intensified extreme precipitation (EP). Spatially, we found notable intensified EP events in the cropland‐dominated Midwest region, resulting in a substantial increase in soil erosion and sediment yield. Land use change played a critical role in determining sediment yield from the 1910s to the 1930s, thereafter, climate variability increasingly became the dominant driver of soil erosion, which peaked in the 2010s. This study highlights the increasing influences of extreme climate in affecting soil erosion and sedimentation, thus, water quality. Therefore, existing forest and cropland Best Management Practices should be revisited to confront the impacts of climate change on water quality in the MRB.

Human‐induced nitrogen–phosphorus (N, P) imbalance in terrestrial ecosystems can lead to disproportionate N and P loading to aquatic ecosystems, subsequently shifting the elemental ratio in estuaries and coastal oceans and impacting both the structure and functioning of aquatic ecosystems. The N:P ratio of nutrient loading to the Gulf of Mexico from the Mississippi River Basin increased before the late 1980s driven by the enhanced usage of N fertilizer over P fertilizer, whereafter the N:P loading ratio started to decrease although the N:P ratio of fertilizer application did not exhibit a similar trend. Here, we hypothesize that different release rates of soil legacy nutrients might contribute to the decreasing N:P loading ratio. Our study used a data‐model integration framework to evaluate N and P dynamics and the potential for long‐term accumulation or release of internal soil nutrient legacy stores to alter the ratio of N and P transported down the rivers. We show that the longer residence time of P in terrestrial ecosystems results in a much slower release of P to coastal oceans than N. If contemporary nutrient sources were reduced or suspended, P loading sustained by soil legacy P would decrease much slower than that of N, causing a decrease in the N and P loading ratio. The longer residence time of P in terrestrial ecosystems and the increasingly important role of soil legacy nutrients as a loading source may explain the decreasing N:P loading ratio in the Mississippi River Basin. Our study underscores a promising prospect for N loading control and the urgency to integrate soil P legacy into sustainable nutrient management strategies for aquatic ecosystem health and water security.