Improved methods for isolating and validating indigenous biomarkers in Precambrian rocks

Hydrocarbon biomarkers in highly mature Precambrian rocks have the potential to provide important information about the diversity ecology, and evolution of early life, but studying them presents special analytical challenges. Extractable hydrocarbons are present in Archean and most Paleoproterozoic sedimentary rocks in such trace concentration that even slight contamination from petroleum-derived materials in situ or during drilling, storage, sampling, handling and laboratory analysis would compromise the results and, thereby, any consequent inferences. Here we report protocols that we have developed for the analysis of cores from several recently completed deep-time scientific drilling initiatives. By paying special attention to cutting, cleaning, crushing and extraction, it is possible to significantly reduce laboratory blanks to acceptable levels. When these methods are utilized, meaningful variations in the patterns of biomarkers over stratigraphic and lithologic boundaries provide compelling evidence for syngeneity.     

Volcanoes as possible indicators of tectonic stress orientation — Aleutians and Alaska

A new method for obtaining from volcanic surface features the orientations of the principal tectonic stresses is applied to Aleutian and Alaskan volcanoes. The underlying concept for this method is that flank eruptions for polygenetic volcanoes can be regarded as the result of a large-scale natural magmafracturing experiment. The method essentially relies on the recognition of the preferred orientation of radial and parallel dike swarms, primarily using the distribution of monogenetic craters including flank volcanoes. Since dikes tend to propagate in a direction normal to the minimum principal stress (T-axis), the method primarily yields the direction of the maximum horizontal compression (MHC) of regional origin. The direction of the MHC may correspond to either the maximum (P-axis) or intermediate (B-axis) principal stress.The direction of MHC obtained at 20 volcanoes in the Aleutian arc coincides well with the direction of convergence between the Pacific and North American plates. This result provides evidence that in the island arc the inferred direction of MHC is parallel to the maximum principal tectonic stress. In the back-arc region, general E-W trends of MHC are obtained from seven volcanic fields on islands on the Bering Sea shelf and the mainland coast of Alaska. These volcanic fields consist mostly of clusters of monogenetic volcanoes of alkali basalt. In the back-arc region, the trends of MHC may correspond to an E-W intermediate, a vertical maximum, and a N-S minimum principal stress.Implications for the tectonics of island arcs and back-arc regions are: (1) volcanic belts of some island arcs, including the Aleutian arc, are under compressional deviatoric stress in the direction of plate convergence. It is improbable that such arcs would split along the volcanic axis to form actively spreading marginal basins. (2) This compressional stress at the arc, probably generated by underthrusting, appears to be transmitted across the entire arc structure, but is apparently replaced within several hundred kilometers by a stress system characterized by horizontal extension (tensional deviatoric stress) in the back-arc region. (3) The volcanoes associated with these two stress systems differ in type (polygenetic vs. monogenetic) and in the chemistry of their magmas (andesitic vs. basaltic). These differences and the regional differences in orientation of the principal tectonic stresses suggest that the back-arc stress system has its own source at considerable depth beneath the crust.Lamont-Doherty Geological Observatory Contribution No. 2503.     

Self-organization of recent rhythmic iron-manganese precipitations in underground mines in the Harz mountains

A recent early diagenetic banded iron-manganese mud has been forming underground in a closed lead-zinc mine for approximately 40 years. The processes leading to the banded structure of the precipitate were studied during a period of 2 years. Therefore, 19 physical and chemical parameters were measured regularly in short intervals. The resulting time series were analysed with respect to the data sets of the monthly chemical analyses of the descendent mine water, the daily rainfall and the mineral content. The results reveal that the precipitated material undergoes internal self-organization due to interaction of redox, colloid-chemical, microbial, electrical and ripening processes, and not exclusively produced by seasonal fluctuations of material input. Thus, the primary banding of the material, caused by externally forced fluctuations of the redox conditions within the mine water, is reorganized after a short time. The finally observed bands are controlled by non-linear coupling of reaction and transport processes within the mud. A genetic model for the banded mineralization was developed and verified by numerical simulation.     

Quantitative phosphorus measurement: A field test procedure for archaeological site analysis at Piedras Negras,Guatemala

Currently there is a wide interest in the use of chemical analyses for the evaluation of anthropogenically altered soils and other archaeological deposits. Because soil phosphorus levels increase in areas of human habitation, and leave a permanent signature that can only be removed by erosion of the soil itself, phosphorus mapping has become a popular field procedure to indicate areas of habitation where overt evidence of ancient occupance is absent. We have developed a methodology to obtain accurate acid‐extractable phosphorus concentrations (mg/kg) in calcareous soils under the primitive field conditions of Piedras Negras, Guatemala. Predicated on Mehlich‐II acid extractant and colorimetric methods, this procedure processed 36 samples per hour at very low cost per sample. Based on eight replicate measurements of a group of samples, the coefficient of variation of the procedure was 8.3%. Subsequent analysis of 35 soil samples in a controlled laboratory revealed a moderate correlation of 0.44 between the Mehlich‐extractable phosphorus and total phosphorus. The correlation was 0.91 between the Mehlich procedure and Olsen bicarbonate extractable phosphorus, indicating that Mehlich‐based results are similar to those obtainable using a traditional extractable phosphorus method on soils of neutral to alkaline pH. There was a moderate correlation between Mehlich P and ring‐test rating (r = 0.42). The wider dynamic range of the Mehlich extraction, coupled with the use of a battery‐operated colorimeter, facilitated the finding of a refuse midden within an area of phosphate enriched soils. Further tests indicated that phosphorus concentrations measured in the field deviated by only 7% from those made under controlled laboratory conditions. © 2000 John Wiley & Sons, Inc.     

Biomass-Cover Relationship for Eelgrass Meadows

Eelgrass meadows play key roles in coastal ecosystems, and the extent of the standing biomass is focal to address ecosystem functioning. Eelgrass cover is commonly assessed in marine monitoring programs while biomass sampling is destructive and expensive. Therefore, we have proposed a functional relationship that translates eelgrass cover into aboveground biomass using site-specific information on Secchi depth or light attenuation. The relationship was estimated by non-linear regression on 791 combined observations of eelgrass cover and biomass from eight different coastal sites in Denmark. Eelgrass biomass initially increased with cover and flattened out as cover exceeded 40–50 % due to increased self-shading. Decreasing light energy with depth reduced the eelgrass biomass potential (assessed at 100 % cover), and this reduction was stronger for coastal sites with lower water transparency. Moreover, the biomass potential varied seasonally from around 110–140 g DW m^?2 in spring months to a peak of 241 g DW m^?2 in August, consistent with other seasonal studies. The model explained 56 % of the variation in log-transformed biomasses, but significant variation between coastal sites still remained, deviating between ?23 and 39 % from the mean relationship. These site-specific deviations could be due to differences in losses related to grazing, drifting algae and epiphytes, better light capture by dense canopies, as well as differences in how well light conditions within eelgrass meadows are represented by actual measurements of Secchi depth and light attenuation. The relationship can be employed to estimate eelgrass biomass of entire coastal ecosystems from observations of eelgrass cover and depth.     

Nanostructure, composition and mechanisms of bivalve shell growth

Freshwater and marine cultured pearls form via identical processes to the shells of bivalves and can therefore serve as models for the biomineralization of bivalve shells in general. Their nanostructure consists of membrane-coated granules (vesicles) which contain amorphous calcium carbonate (ACC) at the beginning of the biomineralization sequence, preceding the crystallization of aragonite and vaterite. In contrast to the commonly accepted view, crystallization of ACC occurs rapidly and within the granular nano-compartments mediated by organic molecules much earlier than platelet formation. The interlamellar organic sheets in nacre that form the platelet structure of nacre themselves form by self-organization after the crystallization process of CaCO₃ is completed and, thus, cannot serve as a nucleation template for aragonite. Pores in the organic sheets are postulated to be a result of this process rather than to represent the pathways for CaCO₃ through pre-existing interlamellar sheets. The amorphous phase has the highest concentrations of Mg (5.8 mol%), Mn (6.6 mol%), S (4.7 mol%) and P (1 mol%) of the three CaCO₃-polymorphs. Mg/Ca and Mn/Ca ratios are found to decrease in the order ACC > vaterite > aragonite, corresponding to decreasing organic content in the different phases. This, as well as an observed enrichment of Mg in the organic-rich growth-banding of the pearls, suggests an at least partially organic speciation of Mg and Mn in bivalves and may be responsible for the observed physiological influence on Mg/Ca and Mn/Ca ratios in bivalves as a proxy for environmental parameters.     

High Sensitivity Analysis of Trace Element-Poor Geological Reference Glasses by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS)

Fifty-two trace elements in NIST SRM 614, 616 and MPI-DING BM90/21-G glass reference materials as well as in NIST SRM 612, USGS BCR2-G and other MPI-DING reference glasses (KL2-G, GOR132-G, GOR128-G, ATHO-G, Tl-G, StHs6/80-G and ML3B-G) were determined by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Accurate ultra-low trace element abundances in the NIST SRM 614, 616 and BM90/21-G reference glasses down to lower ng g⁻¹ levels were determined with relative standard deviations (RSD) of less than 10%. Limits of detection using He as carrier gas were up to two times lower than with Ar and were 0.004 to 0.12 μg g⁻¹ for elements of lower mass numbers (amu < 85) and 0.002 to 0.06 μg g⁻¹ for elements having amu < 85. The measured concentrations generally agree within 15% with previous studies except for B in NIST SRM 614 and 616, which appears to be heterogeneously distributed, and Co, Zn, Ga and Ag in NIST SRM 616 for which the existing data set is too small to evaluate the discrepancies. New values for As (0.593 μg g⁻¹), Ag (0.361 μg g⁻¹) and Cd (0.566 μg g⁻¹) in NIST SRM 614 and new values for Na (94864 μg g⁻¹) and As (0.276 μg g⁻¹) in NIST SRM 616 are reported.     

Solute and geothermal flux monitoring using electrical conductivity in the Madison,Firehole, and Gibbon Rivers,Yellowstone National Park

The thermal output from the Yellowstone magma chamber can be estimated from the Cl flux in the major rivers in Yellowstone National Park; and by utilizing continuous discharge and electrical conductivity measurements the Cl flux can be calculated. The relationship between electrical conductivity and concentrations of Cl and other geothermal solutes (Na, SO₄, F, HCO₃, SiO₂, K, Li, B, and As) was quantified at monitoring sites along the Madison, Gibbon, and Firehole Rivers, which receive discharge from some of the largest and most active geothermal areas in Yellowstone. Except for some trace elements, most solutes behave conservatively and the ratios between geothermal solute concentrations are constant in the Madison, Gibbon, and Firehole Rivers. Hence, dissolved concentrations of Cl, Na, SO₄, F, HCO₃, SiO₂, K, Li, Ca, B and As correlate well with conductivity (R² > 0.9 for most solutes) and most exhibit linear trends. The 2011 flux for Cl, SO₄, F and HCO₃ determined using automated conductivity sensors and discharge data from nearby USGS gaging stations is in good agreement with those of previous years (1983–1994 and 1997–2008) at each of the monitoring sites. Continuous conductivity monitoring provides a cost- and labor-effective alternative to existing protocols whereby flux is estimated through manual collection of numerous water samples and subsequent chemical analysis. Electrical conductivity data also yield insights into a variety of topics of research interest at Yellowstone and elsewhere: (1) Geyser eruptions are easily identified and the solute flux quantified with conductivity data. (2) Short-term heavy rain events can produce conductivity anomalies due to dissolution of efflorescent salts that are temporarily trapped in and around geyser basins during low-flow periods. During a major rain event in October 2010, 180,000 kg of additional solute was measured in the Madison River. (3) The output of thermal water from the Gibbon River appears to have increased by about 0.2%/a in recent years, while the output of thermal water for the Firehole River shows a decrease of about 10% from 1983 to 2011. Confirmation of these trends will require continuing Cl flux monitoring over the coming decades.