Nonlinear rise in Greenland runoff in response to post-industrial Arctic warming.

The Greenland ice sheet (GrIS) is a growing contributor to global sea-level rise1, with recent ice mass loss dominated by surface meltwater runoff2,3. Satellite observations reveal positive trends in GrIS surface melt extent4, but melt variability, intensity and runoff remain uncertain before the satellite era. Here we present the first continuous, multi-century and observationally constrained record of GrIS surface melt intensity and runoff, revealing that the magnitude of recent GrIS melting is exceptional over at least the last 350 years. We develop this record through stratigraphic analysis of central west Greenland ice cores, and demonstrate that measurements of refrozen melt layers in percolation zone ice cores can be used to quantifiably, and reproducibly, reconstruct past melt rates. We show significant (P < 0.01) and spatially extensive correlations between these ice-core-derived melt records and modelled melt rates5,6 and satellite-derived melt duration4 across Greenland more broadly, enabling the reconstruction of past ice-sheet-scale surface melt intensity and runoff. We find that the initiation of increases in GrIS melting closely follow the onset of industrial-era Arctic warming in the mid-1800s, but that the magnitude of GrIS melting has only recently emerged beyond the range of natural variability. Owing to a nonlinear response of surface melting to increasing summer air temperatures, continued atmospheric warming will lead to rapid increases in GrIS runoff and sea-level contributions.

Cis/Trans Energetics in Epoxide, Thiirane, Aziridine and Phosphirane Containing Cyclopentanols: Effects of Intramolecular OH⋯O, S, N and P Contacts.

A recent computational analysis of the stabilizing intramolecular OH⋯O contact in 1,2-dialkyl-2,3-epoxycyclopentanol diastereomers has been extended to thiiriane, aziridine and phosphirane analogues. Density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2) and CCSD(T) coupled-cluster computations with simple methyl and ethyl substituents indicate that electronic energies of the c i s isomers are lowered by roughly 3 to 4 kcal mol-1 when the OH group of these cyclopentanol systems forms an intramolecular contact with the O, S, N or P atom on the adjacent carbon. The results also suggest that S and P can participate in these stabilizing intramolecular interactions as effectively as O and N in constrained molecular environments. The stabilizing intramolecular OH⋯O, OH⋯S, OH⋯N and OH⋯P contacts also increase the covalent OH bond length and significantly decrease the OH stretching vibrational frequency in every system with shifts typically on the order of -41 cm-1.

14 examples of how LLMs can transform materials science and chemistry: a reflection on a large language model hackathon.

Large-language models (LLMs) such as GPT-4 caught the interest of many scientists. Recent studies suggested that these models could be useful in chemistry and materials science. To explore these possibilities, we organized a hackathon. This article chronicles the projects built as part of this hackathon. Participants employed LLMs for various applications, including predicting properties of molecules and materials, designing novel interfaces for tools, extracting knowledge from unstructured data, and developing new educational applications. The diverse topics and the fact that working prototypes could be generated in less than two days highlight that LLMs will profoundly impact the future of our fields. The rich collection of ideas and projects also indicates that the applications of LLMs are not limited to materials science and chemistry but offer potential benefits to a wide range of scientific disciplines.

Aerobic biotransformation of alkyl branched aromatic alkanoic naphthenic acids via two different pathways by a new isolate of Mycobacterium.

Naphthenic acids (NAs) are complex mixtures of carboxylic acids found in weathered crude oils and oil sands, and are toxic, corrosive and persistent. However, little is known about the microorganisms and mechanisms involved in NA degradation. We isolated a sediment bacterium (designated strain IS2.3), with 100% 16S rRNA gene sequence identity to Mycobacterium aurum, which degraded synthetic NAs (4'-n-butylphenyl)-4-butanoic acid (n-BPBA) and (4'-t-butylphenyl)-4-butanoic acid (t-BPBA). n-BPBA was readily oxidized with almost complete degradation (96.8% ± 0.3) compared with t-BPBA (77.8% ± 3.7 degraded) by day 49. Cell counts increased fourfold by day 14 but decreased after day 14 for both n- and t-BPBA. At day 14, (4'-butylphenyl)ethanoic acid (BPEA) metabolites were detected. Additional metabolites produced during t-BPBA degradation were identified by mass spectrometry of derivatives as (4'-carboxy-t-butylphenyl)-4-butanoic acid and (4'-carboxy-t-butylphenyl)ethanoic acid; suggesting that strain IS2.3 used omega oxidation of t-BPEA to oxidize the tert-butyl side-chain to produce (4'-carboxy-t-butylphenyl)ethanoic acid, as the primary route for biodegradation. However, strain IS2.3 also produced this metabolite through initial omega oxidation of the tert-butyl side-chain of t-BPBA, followed by beta-oxidation of the alkanoic acid side-chain. In conclusion, an isolate belonging to the genus Mycobacterium degraded highly branched aromatic NAs via two different pathways.

Greenland Ice Mapping Project: Ice Flow Velocity Variation at sub-monthly to decadal time scales.

We describe several new ice velocity maps produced by the Greenland Ice Mapping Project (GIMP) using Landsat 8 and Copernicus Sentinel 1A/B data. We then focus on several sites where we analyse these data in conjunction with earlier data from this project, which extend back to the year 2000. At Jakobshavn Isbrae and Koge Bugt, we find good agreement when comparing results from different sensors. In a change from recent behaviour, Jakobshavn Isbrae began slowing substantially in 2017, with a mid-summer peak that was even slower than some previous winter minimums. Over the last decade, we identify two major slowdown events at Koge Bugt that coincide with short-term advances of the terminus. We also examined populations of glaciers in northwest and southwest Greenland to produce a record of speedup since 2000. Collectively these glaciers continue to speed up, but there are regional differences in the timing of periods of peak speedup. In addition, we computed trends in winter flow speed for much of the southwest margin of the ice sheet and find little in the way of statistically significant change over the period covered by our data. Finally, although consistency of the data generally is good through time and across sensors, our analysis indicates substantial differences can arise in regions with high strain rates (e.g., shear margins) where sensor resolution can become a factor. For applications such as constraining model inversions, users should factor in the impact that the data's resolution has on their results.

On the use of nanomechanical atomic force microscopy to characterise oil-exposed surfaces.

Oil-exposed surfaces are susceptible to carbonaceous deposits (CDs). In turn, deposits are responsible for fouling, compromising performance and reducing profitability across the hydrocarbon value chain. An understanding of the deposition behaviour of these organic molecules is therefore imperative. In this paper we address the question of understanding the deposition in upstream operation, where the CDs are known to be asphaltenes, the heaviest fraction of oil. Systematic characterisation of fouled oil-exposed surfaces constitutes an initial step towards that direction and it is a challenging task in itself. We demonstrate the use of Atomic Force Microscopy (AFM) to map surface mechanical properties and how they can be used to determine differences between deposit types. We also demonstrate that the use of an adhesion inhibitor (AI) has a dramatic effect not only on the morphology but also on the mechanical properties of asphaltene deposits.

A Complete Map of Greenland Ice Velocity Derived from Satellite Data Collected over 20 Years.

While numerous maps of Greenland ice flow velocity exist, most have gaps in coverage and/or accuracy is limited. We processed a large volume of synthetic aperture radar (SAR) and Landsat 8 imagery collected between 1995 and 2015 to produce a nearly complete map of ice flow velocity for Greenland at a far greater accuracy than most prior products. We evaluated the accuracy of this map by comparing it with a variety of measured and estimated velocities. For the slow-moving interior of the ice sheet, where estimates are determined from interferometric phase, the errors are ~2 m a-1 or better. For coastal areas, where estimates are determined entirely from speckle- or feature-tracking methods, errors are 2-3 m a-1, which is in good agreement with the estimated formal errors. Especially for the slow-moving majority of the ice sheet, this map provides an important source of data for numerous types of glaciological studies.

A SAR Record of Early 21st Century Change in Greenland.

Glaciers in Greenland are changing rapidly. To better understand these changes, we have produced a series of seven synthetic-aperture-radar (SAR) backscatter mosaics for seven winters during the period from 2000 to 2013. Six of the mosaics were created using RADARSAT Fine-Beam data and the seventh used ALOS PALSAR Fine-Beam Single-Polarization data. The RADARSAT mosaics are radiometrically calibrated and capture changes in the backscatter coefficient related to melt and other events, particularly the strong melting in the summer of 2012. Comparison of features in the ascending-orbit ALOS mosaic and the descending-orbit RADARSAT mosaics indicate that in areas of smooth to moderate topography their locations are consistent to within a few 10s of meters. The locations of features identifiable in the RADARAT mosaics, which were collected with the same imaging parameters, generally agree to within better than the 20-m posting of the data. With such geometric accuracy, these data establish a record of change in Greenland for the early part of the 21st Century, thus providing a baseline that can be compared with new radar and optical data sets.

The effect of oil sands process-affected water and model naphthenic acids on photosynthesis and growth in Emiliania huxleyi and Chlorella vulgaris.

Naphthenic acids (NAs) are among the most toxic organic pollutants present in oil sands process waters (OSPW) and enter marine and freshwater environments through natural and anthropogenic sources. We investigated the effects of the acid extractable organic (AEO) fraction of OSPW and individual surrogate NAs, on maximum photosynthetic efficiency of photosystem II (PSII) (FV/FM) and cell growth in Emiliania huxleyi and Chlorella vulgaris as representative marine and freshwater phytoplankton. Whilst FV/FM in E. huxleyi and C. vulgaris was not inhibited by AEO, exposure to two surrogate NAs: (4'-n-butylphenyl)-4-butanoic acid (n-BPBA) and (4'-tert-butylphenyl)-4-butanoic acid (tert-BPBA), caused complete inhibition of FV/FM in E. huxleyi (≥10 mg L(-1)n-BPBA; ≥50 mg L(-1)tert-BPBA) but not in C. vulgaris. Growth rates and cell abundances in E. huxleyi were also reduced when exposed to ≥10 mg L(-1)n- and tert-BPBA; however, higher concentrations of n- and tert-BPBA (100 mg L(-1)) were required to reduce cell growth in C. vulgaris. AEO at ≥10 mg L(-1) stimulated E. huxleyi growth rate (p ≤ 0.002), yet had no apparent effect on C. vulgaris. In conclusion, E. huxleyi was generally more sensitive to NAs than C. vulgaris. This report provides a better understanding of the physiological responses of phytoplankton to NAs which will enable improved monitoring of NA pollution in aquatic ecosystems in the future.

Microbial biodegradation of aromatic alkanoic naphthenic acids is affected by the degree of alkyl side chain branching.

Naphthenic acids (NAs) occur naturally in oil sands and enter the environment through natural and anthropogenic processes. NAs comprise toxic carboxylic acids that are difficult to degrade. Information on NA biodegradation mechanisms is limited, and there are no studies on alkyl branched aromatic alkanoic acid biodegradation, despite their contribution to NA toxicity and recalcitrance. Increased alkyl side chain branching has been proposed to explain NA recalcitrance. Using soil enrichments, we examined the biodegradation of four aromatic alkanoic acid isomers that differed in alkyl side chain branching: (4'-n-butylphenyl)-4-butanoic acid (n-BPBA, least branched); (4'-iso-butylphenyl)-4-butanoic acid (iso-BPBA); (4'-sec-butylphenyl)-4-butanoic acid (sec-BPBA) and (4'-tert-butylphenyl)-4-butanoic acid (tert-BPBA, most branched). n-BPBA was completely metabolized within 49 days. Mass spectral analysis confirmed that the more branched isomers iso-, sec- and tert-BPBA were transformed to their butylphenylethanoic acid (BPEA) counterparts at 14 days. The BPEA metabolites were generally less toxic than BPBAs as determined by Microtox assay. n-BPEA was further transformed to a diacid, showing that carboxylation of the alkyl side chain occurred. In each case, biodegradation of the carboxyl side chain proceeded through beta-oxidation, which depended on the degree of alkyl side chain branching, and a BPBA degradation pathway is proposed. Comparison of 16S rRNA gene sequences at days 0 and 49 showed an increase and high abundance at day 49 of Pseudomonas (sec-BPBA), Burkholderia (n-, iso-, tert-BPBA) and Sphingomonas (n-, sec-BPBA).

Seasonal speedup along the western flank of the Greenland Ice Sheet.

It has been widely hypothesized that a warmer climate in Greenland would increase the volume of lubricating surface meltwater reaching the ice-bedrock interface, accelerating ice flow and increasing mass loss. We have assembled a data set that provides a synoptic-scale view, spanning ice-sheet to outlet-glacier flow, with which to evaluate this hypothesis. On the ice sheet, these data reveal summer speedups (50 to 100%) consistent with, but somewhat larger than, earlier observations. The relative speedup of outlet glaciers, however, is far smaller (<15%). Furthermore, the dominant seasonal influence on Jakobshavn Isbrae's flow is the calving front's annual advance and retreat. With other effects producing outlet-glacier speedups an order of magnitude larger, seasonal melt's influence on ice flow is likely confined to those regions dominated by ice-sheet flow.

Structure elucidation of C80, C81 and C82 isoprenoid tetraacids responsible for naphthenate deposition in crude oil production.

A series of C(80) isoprenoid 20-bis-16,16'-biphytanyl tetraacids has previously been found to be responsible for calcium naphthenate scaling in crude oil processing. This paper describes the structure elucidation by high-field NMR spectroscopy of the structures of the series of homologous C(80) tetraacids containing 4-8 five-membered rings. In addition, the structures of methyl-substituted C(81) and C(82) analogues containing 7 and 8 five-membered rings have been determined for the first time. The biosynthetic implications are discussed.

Analysis of 'ARN' naphthenic acids by high temperature gas chromatography and high performance liquid chromatography.

Examination by high temperature GC (HTGC) of the methyl esters of the so-called 'ARN' naphthenic acids from crude oils of North Sea UK, Norwegian Sea and West African oilfields revealed the distributions of resolved 4-8 ring C80 tetra acids and trace amounts of other acids. Whilst all three oils contained apparently the same major acids, the proportions of each differed, possibly reflecting the growth temperatures of the archaebacteria from which the acids are assumed to have originated. The structures of the 4, 5, 7 and 8 ring acids are tentatively assigned by comparison with the known 6 ring acid and related natural products and an HPLC method for the isolation of the individual acids is described. ESI-MS of individual acids isolated by preparative HPLC established the elution order of the 4-8 ring acids on the HPLC and HTGC systems and revealed the presence of previously unreported acids tentatively identified as C81 and C82 7 and 8 ring analogues.

Role of catalase and oxyR in the viable but nonculturable state of Vibrio vulnificus.

Vibrio vulnificus has proven difficult to culture from water or shellfish during winter months, which is attributed to the viable but nonculturable (VBNC) state. Because reactive oxygen species were found to be involved in the low temperature-induced entrance of V. vulnificus into this state, we generated an oxyR mutant which lacks catalase activity. This strain is nonculturable on solid media even at ambient temperature, due to the presence of H(2)O(2) in such media. Low temperature incubation of the parent resulted in loss of catalase activity, making the cells H(2)O(2) sensitive, and paralleling the loss of culturability (entry into the VBNC state). Thus, cells of V. vulnificus in the VBNC state are likely exhibiting this response to low in situ temperature and only when the artificial condition of laboratory culture is attempted are the cells nonculturable due to cold-induced loss of catalase activity. To our knowledge, this is the first study providing direct evidence for the metabolic basis of nonculturability and the viable but nonculturable state.