Quantification of Metals and Semimetals in Carbon‐Rich Rocks: A New Sequential Protocol Including Extraction from Humic Substances

We have developed a new sequential extraction technique that does not require complex procedures and is efficient in determining metal and semimetal contents of carbon‐rich rocks. Six geological reference materials (SBC‐1, SCHS‐1, SCo‐1, SDO‐1, SGR‐1b and SLg‐1) and an in‐house black shale (SH‐1) were selected to test the method, which consists of four main digestion steps involving: (a) dilute HCl acid; (b) NaOH; (c) aqua regia; and (d) hydrofluoric acid. Compared with traditional aqua regia + hydrofluoric acid attack, this new protocol recovers more of the moderately volatile elements during early extraction of humic substances. In addition when compared with reference values, those for most elements are in agreement within uncertainty. Furthermore, this new protocol reveals important information on the partitioning of elements; for instance, steps one and two indicate which elements are associated with carbonates and organic phases from fulvic and humic acid extractions, whereas step three provides results for which elements are associated with sulfide minerals and step four indicates which elements remained in the silicate and oxide phases.     

Oxygen sites in hydrous aluminosilicate glasses: the role of Al-O-Al and H2O

We describe here high-field ¹⁷O magic-angle-spinning (MAS) and triple-quantum MAS (3QMAS) NMR spectra for several alkali silicate and Na, K, and Ca aluminosilicate glasses containing up to 10 wt.% water. The H₂O site appears to have a large quadrupolar coupling constant, and its chemical shift increases from Na- to K- glasses, suggesting significant cation-H₂O interactions. In ¹⁷O one-pulse MAS and 3QMAS and ²⁷Al one-pulse NMR experiments, major differences were seen between spectra for anhydrous and hydrous calcium aluminosilicate glasses. The changes in the ¹⁷O MAS spectra can be explained by the addition of an H₂O peak and to the disappearance of an Al-O-Al peak from the ¹⁷O NMR spectrum for the hydrous glass. The ²⁷Al results are consistent with this interpretation.     

Control of the variability of nutrients and suspended sediments in a gulf coast estuary by climatic forcing and spring discharge of the Atchafalaya River

Water column nutrients (nitrate, ammonium, soluble reactive phosphate, total Kjeldahl nitrogen, and total phosphorus) and suspended sediments (SS) were measured during one 44-h and two 28-h periods in March 1982 at two stations in Fourleague Bay, Louisiana, which is located at the mouth of the Atchafalaya River, a distributary of the Mississippi River. River water (a source of nitrate, total Kjeldahl nitrogen, total phosphorus, and suspended sediments to Fourleague Bay) flows into the upper reaches of the bay during high tide and frontal overrunning conditions with northerly and westerly winds. During one sampling period, decreasing wind speed and the rising tide resulted in Atchafalaya River water inundating the bay and nitrate concentrations in the upper bay increasing from 30–70 μM to 90–118 μM. Significant variations in nutrients associated with the movement of water masses from the river, marshes, and Gulf of Mexico occurred over several different time scales. Tidal transport occurred over 25-h periods, while frontal passages occurred at 3-d to 5-d intervals. Variability in nutrient and suspended sediment concentrations over these relatively short time scales can be as great as seasonal variability in the bay.     

Sympatric seagrass shrimp show similar structure and selection along the seashore: a comparison of two cryptic Phycomenes zostericola lineages

Small crustaceans are diverse and abundant in seagrass habitats and provide many ecological services. Further information is needed about their long‐ and short‐term response to habitat fragmentation and loss. Shrimp specimens were sampled from coastal seagrasses: latitudes 9°–27° S (Torres Strait to Moreton Bay, Queensland, Australia) and longitudes 141°–153° E (Weipa to Moreton Bay, Queensland, Australia). The seagrass shrimp Phycomenes zostericola (Caridea: Decapoda) underwent phylogeographic analysis using mitochondrial and nuclear sequence data. Lineage relationships were investigated and two deeply divergent sympatric lineages of P. zostericola were discovered in northern samples. The two lineages display vastly different demographic histories in spite of similar overall phylogeographic patterns. The two lineages appear to be in secondary contact with each other, detailing independent histories of sea level change, long distance colonisation and habitat fragmentation. Their regional structure is evidence that the potential for dispersal is only realised under specific environmental conditions. Nuclear data, used to determine reproductive status between lineages, instead displayed a non‐random latitudinal geographic distribution suggesting directional selection, possibly in response to ocean temperatures. The differences between the two deeply divergent lineages highlight the importance of understanding variability among cryptic taxa and their response to habitat change.     

Benthic metabolism and nutrient cycling along an estuarine salinity gradient

Benthic metabolism and nutrient exchange across the sediment-water interface were examined over an annual cycle at four sites along a freshwater to marine transect in the Parker River-Plum Island Sound estuary in northeastern Massachusetts, U.S. Sediment organic carbon content was highest at the freshwater site (10.3%) and decreased along the salinity gradient to 0.2% in the sandy sediments at the marine end of the estuary. C:N ratios were highest in the mid estuary (23:1) and lowest near the sea (11:1). Chlorophyll a in the surface sediments was high along the entire length of the estuary (39–57 mg chlorophyll a m⁻²) but especially so in the sandy marine sediments (172 mg chlorophyll a m⁻²). Chlorophyll a to phaeophytin ratios suggested most chlorophyll is detrital, except at the sandy marine site. Porewater sulfide values varied seasonally and between sites, reflecting both changes in sulfate availability as overlying water salinity changed and sediment metabolism. Patterns of sediment redox potential followed those of sulfide. Porewater profiles of inorganic N and P reflected strong seasonal patterns in remineralization, accumulation, and release. Highest porewater NH₄ ⁺ values were found in upper and mid estuarine sediments, occasionally exceeding 1 mM N. Porewater nitrate was frequently absent, except in the sandy marine sediments where concentrations of 8 μM were often observed. Annual average respiration was lowest at the marine site (13 mmol O₂ m⁻² d⁻¹ and 21 mmol TCO₂ m⁻² d⁻¹) and highest in the mid estuary (130 mmol O₂ m⁻² d⁻¹ and 170 mmol TCO₂ m⁻² d⁻¹) where clam densities were also high. N₂O and CH₄ fluxes were low at all stations throughout the year: Over the course, of a year, sediments varied from being sources to sinks of dissolved organic C and N, with the overall spatial pattern related closely to sediment organic content. There was little correlation between PO₄ ³⁻ flux and metabolism, which we attribute to geochemical processes. At the two sites having the lowest salinities, PO₄ ³⁻ flux was directed into the sediments. On average, between 22% and 32% of total system metabolism was attributable to the benthos. The mid estuary site was an exception, as benthic metabolism accounted for 95% of the total, which is attributable to high densities of filter-feeding clams. Benthic remineralization supplied from less than 1% to over 190% of the N requirements and 0% to 21% of the P requirements of primary producers in this system. Estimates of denitrification calculated from stoichiometry of C and N fluxes ranged from 0% for the upper and mid estuary site to 35% for the freshwater site to 100% of sediment organic N remineralization at the marine site. We hypothesize that low values in the upper and mid estuary are attributable to enhanced NH₄ ⁺ fluxes during summer due to desorption of exchangeable ammonium from rising porewater salinity. NH₄ ⁺ desorption during summer may be a mechanism that maintains high rates of pelagic primary production at a time of low inorganic N inputs from the watershed.     

Long-term impact of the proglacial lake Jökulsárlón on the flow velocity and stability of Breiðamerkurjökull glacier,Iceland

Proglacial lakes are becoming ubiquitous at the termini of many glaciers worldwide due to continued climate warming and glacier retreat, and such lakes have important consequences for the dynamics and future stability of these glaciers. In light of this, we quantified decadal changes in glacier velocity since 1991 using satellite remote sensing for Breiðamerkurjökull, a large lake-terminating glacier in Iceland. We investigated its frontal retreat, lake area change and ice surface elevation change, combined with bed topography data, to understand its recent rapid retreat and future stability. We observed highly spatially variable velocity change from 1991 to 2015, with a substantial increase in peak velocity observed at the terminus of the lake-terminating eastern arm from ~1.00 ± 0.36 m day⁻¹ in 1991 to 3.50 ± 0.25 m day⁻¹ in 2015, with mean velocities remaining elevated from 2008 onwards. This is in stark comparison to the predominately land-terminating arms, which saw no discernible change in their velocity over the same period. We also observed a substantial increase in the area of the main proglacial lake (Jökulsárlón) since 1982 of ~20 km², equating to an annual growth rate of 0.55 km² year⁻¹. Over the same period, the eastern arm retreated by ~3.50 km, which is significantly greater than the other arms. Such discrepancies between the different arms are due to the growth and, importantly, depth increase of Jökulsárlón, as the eastern arm has retreated into its ~300 m-deep reverse-sloping subglacial trough. We suggest that this growth in lake area, forced initially by rising air temperatures, combined with the increase in lake depth, triggered an increase in flow acceleration, leading to further rapid retreat and the initiation of a positive feedback mechanism. These findings may have important implications for how increased melt and calving forced by climate change will affect the future stability of large soft-bedded, reverse-sloped, subaqueous-terminating glaciers elsewhere. © 2020 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd     

Direct application of compound-specific radiocarbon analysis of leaf waxes to establish lacustrine sediment chronology

This study demonstrates use of compound-specific radiocarbon analysis (CSRA) for dating Holocene lacustrine sediments from carbonate-hosted Ordy Pond, O‘ahu, Hawai‘i. Long-chain odd-numbered normal alkanes (n-alkanes), biomarkers characteristic of terrestrial higher plants, were ubiquitous in Ordy Pond sediments. The δ¹³C of individual n-alkanes ranged from −29.9 to −25.5‰, within the expected range for n-alkanes synthesized by land plants using the C₃ or C₄ carbon fixation pathway. The ¹⁴C ages of n-alkanes determined by CSRA showed remarkably good agreement with ¹⁴C dates of rare plant macrofossils obtained from nearby sedimentary horizons. In general, CSRA of n-alkanes successfully refined the age-control of the sediments. The sum of n-alkanes in each sample produced 70–170 μg of carbon (C), however, greater age errors were confirmed for samples containing less than 80 μg of C. The ¹⁴C age of n-alkanes from one particular sedimentary horizon was 4,155 years older than the value expected from the refined age-control, resulting in an apparent and arguable age discrepancy. Several lines of evidence suggest that this particular sample was contaminated by introduction of ¹⁴C-free C during preparative capillary gas chromatography. This study simultaneously highlighted the promising potential of CSRA for paleo-applications and the risks of contamination associated with micro-scale ¹⁴C measurement of individual organic compounds.