Thermal stability of ladderane lipids as determined by hydrous pyrolysis

Anaerobic ammonium oxidation (anammox) has been recognized as a major process resulting in loss of fixed inorganic nitrogen in the marine environment. Ladderane lipids, membrane lipids unique to anammox bacteria, have been used as markers for the detection of anammox in marine settings. However, the fate of ladderane lipids after sediment burial and maturation is unknown. In this study, anammox bacterial cell material was artificially matured by hydrous pyrolysis at constant temperatures ranging from 120 to 365 °C for 72 h to study the stability of ladderane lipids during progressive dia- and catagenesis. HPLC-MS/MS analysis revealed that structural alterations of ladderane lipids already occurred at 120 °C. At temperatures >140 °C, ladderane lipids were absent and only more thermally stable products could be detected, i.e., ladderane derivatives in which some of the cyclobutane rings were opened. These diagenetic products of ladderane lipids were still detectable up to temperatures of 260 °C using GC-MS. Thus, ladderane lipids are unlikely to occur in ancient sediments and sedimentary rocks, but specific diagenetic products of ladderane lipids will likely be present in sediments and sedimentary rocks of relatively low maturity (i.e., C₃₁ hopane 22S/(22S + 22R) ratio <0.2 or ββ/(αβ + βα + ββ) ratio of >0.5).     

Dissolved carbon and 33-133-133-1anomalies in the water column caused by hydrocarbon seeps on the northwestern Gulf of Mexico slope

Alkalinity, dissolved inorganic carbon (DIC), and ¹³C profiles from seep sites on the northwestern Gulf of Mexico upper slope show anomalously negative ¹³C values of up to –4.5 PDB, increased levels of DIC of up to 2.45 mmole/liter, and slight alkalinity rises of up to 2.54 meq/liter, relative to water column profiles from a seep-free site (0.63, 2.04 mmole/liter, and 2.39 meq/liter). The observed DIC enrichments coupled with the¹³C-depletions are attributed to the release of CO₂ by microbial oxidation of crude oil in the seep environment, and its migration into the water column. The ¹³C composition of the migrating CO₂ is estimated to be –26.0 on the basis of dissolved carbon inventory. Manifestation of DIC and ¹³C anomalies in the water column caused by hydrocarbon seepage holds promise to be useful for hydrocarbon reconnaissance surveys over large offshore tracts on account of the simplicity of sampling acquisition, and rapidity of analytical techniques in the laboratory.     

Contaminant concentrations and toxicity of sea-surface microlayer near Los Angeles, California

Sea-surface microlayer samples were collected from six nearshore areas receiving different amounts of anthropogenic inputs. The samples were analyzed for selected trace metals, chlorinated hydrocarbons, and polycyclic aromatic hydrocarbons. The relative toxicities of the samples were determined with fish embryo bioassays.Contaminant concentrations generally increased from offshore to the inshore stations. Contaminant concentrations were several orders of magnitude higher in microlayer samples from the highly industrialized Los Angeles and Long Beach harbors compared to samples from a site 15km offshore. Microlayer samples from the inshore stations were significantly more toxic, and induced significantly more developmental abnormalities and chromosome aberrations, than samples from the offshore stations.     

Source(s) and cycling of the nonhydrolyzable organic fraction of oceanic particles

A major fraction of particulate organic carbon (POC) in the deep ocean remains molecularly uncharacterized. In an effort to determine the chemical characteristics and source(s) of sinking POC, we studied a nonhydrolyzable fraction of sinking POC using ¹³C NMR (nuclear magnetic resonance) spectroscopy and analytical pyrolysis. ¹³C NMR spectra and products from analytical pyrolysis of the nonhydrolyzable fraction exhibit a strongly aliphatic character that is distinct from that of bulk POC. The aliphatic nature of this fraction is consistent with its low stable carbon isotope values. We hypothesize that the nonhydrolyzable fraction derives to a significant extent from a refractory component of organisms that selectively accumulates, resulting in its manifestation as a major part of POC sinking to the deep ocean and in underlying sediments.     

Channel geometry of mountain streams in New Zealand

A dataset of 21 study reaches in the Porter and Kowai rivers (eastern side of the South Island), and 13 study reaches in Camp Creek and adjacent catchments (western side of the South Island) was used to examine downstream hydraulic geometry of mountain streams in New Zealand. Streams in the eastern and western regions both exhibit well-developed downstream hydraulic geometry, as indicated by strong correlations between channel top width, bankfull depth, mean velocity, and bankfull discharge. Exponents for the hydraulic geometry relations are similar to average values for rivers worldwide. Factors such as colluvial sediment input to the channels, colluvial processes along the channels, tectonic uplift, and discontinuous bedrock exposure along the channels might be expected to complicate adjustment of channel geometry to downstream increases in discharge. The presence of well-developed downstream hydraulic geometry relations despite these complicating factors is interpreted to indicate that the ratio of hydraulic driving forces to substrate resisting forces is sufficiently large to permit channel adjustment to relatively frequent discharges.     

Sugarloaf Mountain,central Arizona,USA: A small-scale example of Miocene basalt-rhyolite magma mixing to yield andesitic magmas

Sugarloaf Mountain is a 200-m high volcanic landform in central Arizona, USA, within the transition from the southern Basin and Range to the Colorado Plateau. It is composed of Miocene alkalic basalt (47.2–49.1?wt.% SiO₂; 6.7–7.7?wt.% MgO) and overlying andesite and dacite lavas (61.4–63.9?wt.% SiO₂; 3.5–4.7?wt.% MgO). Sugarloaf Mountain therefore offers an opportunity to evaluate the origin of andesite magmas with respect to coexisting basalt. Important for evaluating Sugarloaf basalt and andesite (plus dacite) is that the andesites contain basaltic minerals olivine (cores Fo_76-86) and clinopyroxene (～Fs_9-18Wo_35-44) coexisting with Na-plagioclase (An_48-28Or_1.4–7), quartz, amphibole, and minor orthopyroxene, biotite, and sanidine. Noteworthy is that andesite mineral textures include reaction and spongy zones and embayments in and on Na-plagioclase and quartz phenocrysts, where some reacted Na-plagioclases have higher-An mantles, plus some similarly reacted and embayed olivine, clinopyroxene, and amphibole phenocrysts.Fractional crystallization of Sugarloaf basaltic magmas cannot alone yield the andesites because their ～61 to 64?wt.% SiO₂ is attended by incompatible REE and HFSE abundances lower than in the basalts (e.g., Ce 77–105 in andesites vs 114–166?ppm in basalts; Zr 149–173 vs 183–237; Nb 21–25 vs 34–42). On the other hand, andesite mineral assemblages, textures, and compositions are consistent with basaltic magmas having mixed with rhyolitic magmas, provided the rhyolite(s) had relatively low REE and HFSE abundances. Linear binary mixing calculations yield good first approximation results for producing andesitic compositions from Sugarloaf basalt compositions and a central Arizona low-REE, low-HFSE rhyolite. For example, mixing proportions 52:48 of Sugarloaf basalt and low incompatible-element rhyolite yields a hybrid composition that matches Sugarloaf andesite well ? although we do not claim to have exact endmembers, but rather, viable proxies. Additionally, the observed mineral textures are all consistent with hot basalt magma mixing into rhyolite magma. Compositional differences among the phenocrysts of Na-plagioclase, clinopyroxene, and amphibole in the andesites suggest several mixing events, and amphibole thermobarometry calculates depths corresponding to 8–16?km and 850° to 980?°C. The amphibole P-T observed for a rather tight compositional range of andesite compositions is consistent with the gathering of several different basalt-rhyolite hybrids into a homogenizing ‘collection' zone prior to eruptions. We interpret Sugarloaf Mountain to represent basalt-rhyolite mixings on a relatively small scale as part of the large scale Miocene (～20 to 15 Ma) magmatism of central Arizona. A particular qualification for this example of hybridization, however, is that the rhyolite endmember have relatively low REE and HFSE abundances.     

Daily variability of dissolved inorganic radiocarbon at three sites in the surface ocean

We report radiocarbon measurements of dissolved inorganic carbon (DIC) in surface water samples collected daily during cruises to the central North Pacific, the Sargasso Sea and the Southern Ocean. The ranges of Δ¹⁴C measurements for each cruise (11–30‰) were larger than the total uncertainty (7.8‰, 2-sigma) of the measurements. The variability is attributed to changes in the upper water mass that took place at each site over a two to four week period. These results indicate that variability of surface Δ¹⁴C values is larger than the analytical precision, because of patchiness that exists in the DIC Δ¹⁴C signature of the surface ocean. This additional variability can affect estimates of geochemical parameters such as the air–sea CO₂ exchange rate using radiocarbon.     

Constraining the propagation of bomb-radiocarbon through the dissolved organic carbon (DOC) pool in the northeast Pacific Ocean

This study extends the 1991-1995 records of marine dissolved organic carbon (DOC) concentrations and Δ¹⁴C values at hydrographic Station M (34°50′N, 123°00′W) with new measurements from a frozen (-20 °C) archive of samples collected between April 1998 and October 2004. The magnitudes and synchronicity of major Δ¹⁴C anomalies throughout the time-series imply transport of DOC from the surface ocean to depths of at least 450 m on the timescale of months. Keeling plots of all measurements at Station M predict a continuum of possible background DOC compositions containing at least 21 μM of -1000‰ (i.e., ≥57,000 ¹⁴C years) DOC, but are more consistent with mean deep DOC (38 μM, -549‰; i.e., 6,400 ¹⁴C years). These results and coral records of surface dissolved inorganic carbon (DIC) Δ¹⁴C were used to estimate pre-bomb DOC Δ¹⁴C depth profiles. The combined results indicate that bomb-¹⁴C has penetrated the DOC pool to depths of ≥450 m, though the signal at that depth is obscured by short-term variability.     

Modeling regional landslide susceptibility using dynamic soil moisture profiles

A landslide susceptibility mapping study was performed using dynamic hillslope hydrology. The modified infinite slope stability model that directly includes vadose zone soil moisture (SM) was applied at Cleveland Corral, California, US and Krishnabhir, Dhading, Nepal. The variable infiltration capacity (VIC-3L) model simulated vadose zone soil moisture and the wetness index hydrologic model simulated groundwater (GW). The GW model predictions had a 75% NASH-Sutcliffe efficiency when compared to California’s in-situ GW measurements. The model performed best during the wet season. Using predicted GW and VIC-3L vadose zone SM, the developed landslide susceptibility maps showed very good agreement with mapped landslides at each study region. Previous quasi-dynamic model predictions of Nepal’s hazardous areas during extreme rainfall events were enhanced to improve the spatial characterization and provide the timing of hazardous conditions.