Salt marsh pond biogeochemistry changes hourly-to-yearly but does not scale with dimensions or geospatial position

Author Posting. © American Geophysical Union, 2020. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Biogeosciences 125(10), (2020): e2020JG005664, doi:10.1029/2020JG005664.Shallow ponds are expanding in many salt marshes with potential impacts on ecosystem functioning. Determining how pond characteristics change over time and scale with physical dimensions and other spatial predictors could facilitate incorporation of ponds into projections of ecosystem change. We evaluated scaling relationships across six differently sized ponds in three regions of the high marshes within the Plum Island Ecosystems‐Long Term Ecological Research site (MA, USA). We further characterized diel fluctuations in surface water chemistry in two ponds to understand short‐term processes that affect emergent properties (e.g., habitat suitability). Primary producers drove oxygen levels to supersaturation during the day, while nighttime respiration resulted in hypoxic to anoxic conditions. Diel swings in oxygen were mirrored by pH and resulted in successive shifts in redox‐sensitive metabolisms, as indicated by nitrate consumption at dusk followed by peaks in ammonium and then sulfide overnight. Abundances of macroalgae and Ruppia maritima correlated with whole‐pond oxygen metabolism rates, but not with surface area (SA), volume (V), or SA:V. Moreover, there were no clear patterns in primary producer abundances, surface water chemistry, or pond metabolism rates across marsh regions supplied by different tidal creeks or that differed in distance to upland borders or creekbanks. Comparisons with data from 2 years prior demonstrate that plant communities and biogeochemical processes are not in steady state. Factors contributing to variability between ponds and years are unclear but likely include infrequent tidal exchange. Temporal and spatial variability and the absence of scaling relationships complicate the integration of high marsh ponds into ecosystem biogeochemical models.Thanks to S. McNichol, S. Jayne, E. Neel, and PIE‐LTER (NSF‐OCE1238212) for field assistance; I. Forbrich for meteorological data (Giblin & Forbrich, 2018); J. Jennings for dissolved nutrient analyses; J. Seewald for ion chromatograph access; and G. Mariotti for elevation data. C. Wilson and an anonymous reviewer provided comments that greatly improved our manuscript. A. C. S. was supported by NSF (OCE1233678), NOAA (NA14NOS4190145), and Sea Grant (NA14OAR4170104) awards, and A. D. by the MIT Undergraduate Research Opportunities Program.2021-03-1

Mortality and pulmonary complications in patients undergoing surgery with perioperative SARS-CoV-2 infection: an international cohort study

Background: The impact of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) on postoperative recovery needs to be understood to inform clinical decision making during and after the COVID-19 pandemic. This study reports 30-day mortality and pulmonary complication rates in patients with perioperative SARS-CoV-2 infection. Methods: This international, multicentre, cohort study at 235 hospitals in 24 countries included all patients undergoing surgery who had SARS-CoV-2 infection confirmed within 7 days before or 30 days after surgery. The primary outcome measure was 30-day postoperative mortality and was assessed in all enrolled patients. The main secondary outcome measure was pulmonary complications, defined as pneumonia, acute respiratory distress syndrome, or unexpected postoperative ventilation. Findings: This analysis includes 1128 patients who had surgery between Jan 1 and March 31, 2020, of whom 835 (74·0%) had emergency surgery and 280 (24·8%) had elective surgery. SARS-CoV-2 infection was confirmed preoperatively in 294 (26·1%) patients. 30-day mortality was 23·8% (268 of 1128). Pulmonary complications occurred in 577 (51·2%) of 1128 patients; 30-day mortality in these patients was 38·0% (219 of 577), accounting for 81·7% (219 of 268) of all deaths. In adjusted analyses, 30-day mortality was associated with male sex (odds ratio 1·75 [95% CI 1·28–2·40], p\textless0·0001), age 70 years or older versus younger than 70 years (2·30 [1·65–3·22], p\textless0·0001), American Society of Anesthesiologists grades 3–5 versus grades 1–2 (2·35 [1·57–3·53], p\textless0·0001), malignant versus benign or obstetric diagnosis (1·55 [1·01–2·39], p=0·046), emergency versus elective surgery (1·67 [1·06–2·63], p=0·026), and major versus minor surgery (1·52 [1·01–2·31], p=0·047). Interpretation: Postoperative pulmonary complications occur in half of patients with perioperative SARS-CoV-2 infection and are associated with high mortality. Thresholds for surgery during the COVID-19 pandemic should be higher than during normal practice, particularly in men aged 70 years and older. Consideration should be given for postponing non-urgent procedures and promoting non-operative treatment to delay or avoid the need for surgery. Funding: National Institute for Health Research (NIHR), Association of Coloproctology of Great Britain and Ireland, Bowel and Cancer Research, Bowel Disease Research Foundation, Association of Upper Gastrointestinal Surgeons, British Association of Surgical Oncology, British Gynaecological Cancer Society, European Society of Coloproctology, NIHR Academy, Sarcoma UK, Vascular Society for Great Britain and Ireland, and Yorkshire Cancer Research

Iron-Catalyzed Cross-Coupling of Unactivated Secondary Alkyl Thio Ethers and Sulfones with Aryl Grignard Reagents

The first systematic investigation of unactivated aliphatic sulfur compounds as electrophiles in transition-metal-catalyzed cross-coupling are described. Initial studies focused on discerning the structural and electronic features of the organosulfur substrate that enable the challenging oxidative addition to the C­(sp³)–S bond. Through extensive optimization efforts, an Fe­(acac)₃-catalyzed cross-coupling of unactivated alkyl aryl thio ethers with aryl Grignard reagents was realized in which a nitrogen “directing group” on the S-aryl moiety of the thio ether served a critical role in facilitating the oxidative addition step. In addition, alkyl phenyl sulfones were found to be effective electrophiles in the Fe­(acac)₃-catalyzed cross-coupling with aryl Grignard reagents. For the latter class of electrophile, a thorough assessment of the various reaction parameters revealed a dramatic enhancement in reaction efficiency with an excess of TMEDA (8.0 equiv). The optimized reaction protocol was used to evaluate the scope of the method with respect to both the organomagnesium nucleophile and sulfone electrophile