Evaluating 50 years of time-series soil radiocarbon data: towards routine calculation of robust C residence times

In 1959, Athol Rafter began a substantial programme of monitoring the flow of ¹⁴C produced by atmospheric thermonuclear tests through New Zealand’s atmosphere, biosphere and soil. By building on the original measurements through ongoing sampling, a database of over 500 soil radiocarbon measurements spanning 50 years has now been compiled. The datasets, including an 11-point time series, allow strong focus on the robust quantification of residence times ranging from years to decades. We describe key aspects of the dataset, including the ability to identify critical assumptions inherent in calculating soil C residence times. The 3 most critical assumptions relate to: (1) the proportion of old C (“fraction passive”), (2) the lag time between photosynthesis and C entering the modeled pool, and (3) changes in the rates of C input (i.e., steady state). We demonstrate the ability to compare residence times in contrasting sites, such Andisols and non-Andisols, and the ability to calculate residence times across a range of soil depths. We use ¹⁴C in a two-box model to quantify soil carbon turnover parameters in deforested dairy pastures under similar climate in the Tokomaru silt loam (non-Andisol) versus the Egmont black loam (Andisol), originally sampled in 1962, 1965 and 1969, and resampled again in 2008. The ¹⁴C-based residence times of the main soil C pool in surface soil (~8 cm) are ~9 years in the Tokomaru soils compared to ~17 years for the Egmont soils. This difference represents nearly a doubling of soil C residence time, and roughly explains the doubling of the soil C stock. Passive soil C comprises 15% of the soil C pool in Tokomaru soils versus 27% in Egmont soils. A similar difference in residence times is found in a second surface soil comparison between the Bruntwood soil (Andisol) and the Te Kowhai soil (non-Andisol) with residence times of 18 and 27 years, respectively. The comparisons support evidence that C dynamics do differ in Andisols versus non-Andisols, as a result of both the mineral allophane and Al complexation. Expanding our calculations beyond surface soil, we show that thickening the calculation depth by combining horizons allows robust residence times to be calculated at a range of depths. Overall, the large and systematically collected dataset demonstrate that soil C residence times of the main soil C pool can be routinely calculated using ¹⁴C wherever samples collected 10 or more years apart in New Zealand grassland soils are available, and presumably under similar circumstances in other soils worldwide.     

Stereotactic Body Radiation Therapy for Primary and Metastatic Liver Tumors

OBJECTIVES: The full potential of stereotactic body radiation therapy (SBRT), in the treatment of unresectable intrahepatic malignancies, has yet to be realized as our experience is still limited. Thus, we evaluated SBRT outcomes for primary and metastatic liver tumors, with the goal of identifying factors that may aid in optimization of therapy. METHODS: From2005 to 2010, 62 patients with 106 primary and metastatic liver tumors were treated with SBRT to a median biologic effective dose (BED) of 100 Gy (42.6-180). The majority of patients received either three (47%) or five fractions (48%). Median gross tumor volume (GTV) was 8.8 cm³ (0.2-222.4). RESULTS: With a median followup of 18 months (0.46-46.8), freedom from local progression (FFLP) was observed in 97 of 106 treated tumors, with 1- and 2-year FFLP rates of 93% and 82%. Median overall survival (OS) for all patients was 25.2 months, with 1- and 2-year OS of 81%and 52%. Neither BED nor GTV significantly predicted for FFLP. Local failure was associated with a higher risk of death [hazard ratio (HR) = 5.1, P = .0007]. One Child-Pugh Class B patient developed radiationinduced liver disease. There were no other significant toxicities. CONCLUSIONS: SBRT provides excellent local control for both primary and metastatic liver lesions with minimal toxicity. Future studies should focus on appropriate selection of patients and on careful assessment of liver function to maximize both the safety and efficacy of treatment.     

Long-term changes in temperate marine fish assemblages are driven by a small subset of species

The species composition of plant and animal assemblages across the globe has changed substantially over the past century. How do the dynamics of individual species cause this change? We classified species into seven unique categories of temporal dynamics based on the ordered sequence of presences and absences that each species contributes to an assemblage time series. We applied this framework to 14,434 species trajectories comprising 280 assemblages of temperate marine fishes surveyed annually for 20 or more years. Although 90% of the assemblages diverged in species composition from the baseline year, this compositional change was largely driven by only 8% of the species' trajectories. Quantifying the reorganization of assemblages based on species shared temporal dynamics should facilitate the task of monitoring and restoring biodiversity. We suggest ways in which our framework could provide informative measures of compositional change, as well as leverage future research on pattern and process in ecological systems.     

Loss of CDK5RAP2 affects neural but not non-neural mESC differentiation into cardiomyocytes

Biallelic mutations in the gene encoding centrosomal CDK5RAP2 lead to autosomal recessive primary microcephaly (MCPH), a disorder characterized by pronounced reduction in volume of otherwise architectonical normal brains and intellectual deficit. The current model for the microcephaly phenotype in MCPH invokes a premature shift from symmetric to asymmetric neural progenitor-cell divisions with a subsequent depletion of the progenitor pool. The isolated neural phenotype, despite the ubiquitous expression of CDK5RAP2, and reports of progressive microcephaly in individual MCPH cases prompted us to investigate neural and non-neural differentiation of Cdk5rap2-depleted and control murine embryonic stem cells (mESC). We demonstrate an accumulating proliferation defect of neurally differentiating Cdk5rap2-depleted mESC and cell death of proliferative and early postmitotic cells. A similar effect does not occur in non-neural differentiation into beating cardiomyocytes, which is in line with the lack of non-central nervous system features in MCPH patients. Our data suggest that MCPH is not only caused by premature differentiation of progenitors, but also by reduced propagation and survival of neural progenitors.     

Pentacycloundecane lactam vs lactone norstatine type protease HIV inhibitors: binding energy calculations and DFT study

Background

Novel pentacycloundecane (PCU)-lactone-CO-EAIS peptide inhibitors were designed, synthesized, and evaluated against wild-type C-South African (C-SA) HIV-1 protease. Three compounds are reported herein, two of which displayed IC₅₀ values of less than 1.00 μM. A comparative MM-PB(GB)SA binding free energy of solvation values of PCU-lactam and lactone models and their enantiomers as well as the PCU-lactam-NH-EAIS and lactone-CO-EAIS peptide inhibitors and their corresponding diastereomers complexed with South African HIV protease (C-SA) was performed. This will enable us to rationalize the considerable difference between inhibitory concentration (IC₅₀) of PCU-lactam-NH-EAIS and PCU-lactone-CO-EAIS peptides.

Results

The PCU-lactam model exhibited more negative calculated binding free energies of solvation than the PCU-lactone model. The same trend was observed for the PCU-peptide inhibitors, which correspond to the experimental activities for the PCU-lactam-NH-EAIS peptide (IC₅₀ = 0.076 μM) and the PCU-lactone-CO-EAIS peptide inhibitors (IC₅₀ = 0.850 μM). Furthermore, a density functional theory (DFT) study on the natural atomic charges of the nitrogen and oxygen atoms of the three PCU-lactam, PCU-lactim and PCU-lactone models were performed using natural bond orbital (NBO) analysis. Electrostatic potential maps were also used to visualize the electron density around electron-rich regions. The asymmetry parameter (η) and quadrupole coupling constant (χ) values of the nitrogen and oxygen nuclei of the model compounds were calculated at the same level of theory. Electronic molecular properties including polarizability and electric dipole moments were also calculated and compared. The Gibbs theoretical free solvation energies of solvation (∆G_solv) were also considered.

Conclusions

A general trend is observed that the lactam species appears to have a larger negative charge distribution around the heteroatoms, larger quadrupole constant, dipole moment and better solvation energy, in comparison to the PCU-lactone model. It can be argued that these characteristics will ensure better eletronic interaction between the lactam and the receptor, corresponding to the observed HIV protease activities in terms of experimental IC₅₀ data.

Electronic supplementary material

The online version of this article (doi:10.1186/s12929-015-0115-5) contains supplementary material, which is available to authorized users.     

Microbial biomass,respiration and diversity in ultramafic soils of West Dome,New Zealand

Ultramafic soils are colonised by plant communities adapted to naturally elevated heavy metal content but it is not known whether soil microbial communities are similarly adapted to heavy metals. We measured microbial properties of six ultramafic soils that ranged in heavy metal content to test whether microbial diversity would decrease and respiratory quotient (microbial respiration:biomass) increase due to the stress imposed by increasing metal content. Soil samples were collected from beneath Nothofagus solandri var. cliffortioides tall forest, tall Leptospermum scoparium shrubland, open Leptospermum scoparium shrubland, an open Leptospermum scoparium shrubland with the rare ultramafic endemic Celmisia spedenii, a mixed divaricate shrubland, and a red tussock (Chionochloa rubra) grassland on the Dun Mountain Ophiolite belt, New Zealand. Samples were analysed for catabolic evenness using the catabolic response profile technique, microbial biomass, microbial respiration, and soil properties (pH, total carbon, total nitrogen, magnesium and total or extractable chromium and nickel). The sites differed in base saturation, pH and concentrations of metals, particularly magnesium, chromium and nickel, properties that are a major determinant of the plant communities that develop. Microbial biomass and respiration, catabolic evenness (range of 19.1 to 22.7) and the respiratory quotient were not correlated to any of the measured soil chemical properties. Factor analysis of the respiratory responses showed that the microbial communities under each vegetation type were distinct. The second factor extracted was correlated to total carbon (r ²=0.62, P<0.01), basal respiration (r ²=0.55, P<0.01) and microbial biomass (r ²=0.65, P<0.01). Increasing metals concentrations had no direct impact on microbial diversity, biomass, respiration or community energetics. However, we suggest that metal concentrations may have exerted an indirect effect on the structure of the microbial communities through control of the vegetation community and litter inputs of carbon to the soil.     

High‐Temperature Treatment of Li‐Rich Cathode Materials with Ammonia: Improved Capacity and Mean Voltage Stability during Cycling

Li‐rich electrode materials of the family x Li₂MnO₃·(1?x )LiNi_a Co_b Mn_c O₂ (a + b + c = 1) suffer a voltage fade upon cycling that limits their utilization in commercial batteries despite their extremely high discharge capacity, ≈250 mA h g^?1. Li‐rich, 0.35Li₂MnO₃·0.65LiNi_0.35Mn_0.45Co_0.20O₂, is exposed to NH₃ at 400 °C, producing materials with improved characteristics: enhanced electrode capacity and a limited average voltage fade during 100 cycles in half cells versus Li. Three main changes caused by NH₃ treatment are established. First, a general bulk reduction of Co and Mn is observed via X‐ray photoelectron spectroscopy and X‐ray absorption near edge structure. Next, a structural rearrangement lowers the coordination number of Co? O and Mn? O bonds, as well as formation of a surface spinel‐like structure. Additionally, Li⁺ removal from the bulk causes the formation of surface LiOH, Li₂CO₃, and Li₂O. These structural and surface changes can enhance the voltage and capacity stability of the Li‐rich material electrodes after moderate NH₃ treatment times of 1–2 h.