DOC leaching from a coniferous forest floor: modeling a manipulation experiment

The DyDOC model simulates the C dynamics of forest soils, including the production and transport of dissolved organic matter (DOM), on the basis of soil hydrology, metabolic processes, and sorption reactions. The model recognizes three main pools of soil C: litter, substrate (an intermediate transformation product), and humic substances. The model was used to simulate the behavior of C in the O horizon of soil under a Norway spruce stand at Asa, Sweden, that had been subjected to experimental manipulations (addition and removal) of above‐ground litter inputs and to removal of the Oi and Oe layers. Initially, the model was calibrated using results for the control plots and was able to reproduce the observed total soil C pool and ¹⁴C content, DOC flux and DO¹⁴C content, and the pool of litter C, together with the assumed content of C in humic substances (20% of the total soil C), and the assumed distribution of DOC between hydrophilic and hydrophobic fractions. The constant describing DOC exchange between micro‐ and macropores was estimated from short‐term variations in DOC concentration. When the calibrated model was used to predict the effects of litter and soil manipulations, it underestimated the additional DOC export (up to 33%) caused by litter addition, and underestimated the 22% reduction in DOC export caused by litter withdrawal. Therefore, an additional metabolic process, the direct conversion of litter to DOC, was added to the model. The addition of this process permitted reasonably accurate simulation of the results of the manipulation experiments, without affecting the goodness‐of‐fit in the model calibration. The results suggest that, under normal conditions, DOC exported from the Asa forest floor is a mixture of compounds derived from soil C pools with a range of residence times. Approximately equal amounts come from the litter pool (turnover time 4.6 yr), the substrate pool (26 yr), and the humic‐substances pool (36 yr).     

Bioconcentration of Dioxins and Furans in Vegetation

Information sources for bioconcentration factors (BCFs) from the existing technical literature include models based on K _ow and/or regulatory agency guidance from agencies such as USEPA. Since magnitude assignments of BCFs influence the degree of conservativeness implicit in risk assessments, the BCF magnitudes for a contaminated site in Ontario, Canada, were assessed from field measurements for dioxins and furans from soil to vegetation and are compared with BCFs from the literature. It is demonstrated that observed BCFs for dioxins and furans from the field study are generally much higher (3 to 575 times for 15 compounds and 2,770 times for Octa CDF) than those computed by the USEPA method and are higher by a factor of 3 to 650 (for eight compounds) computed by the K _ow model. These findings indicate that use of model-based BCFs may result in underestimation of the risk or hazard.     

Incorporation of Chromate into Calcium Carbonate Structure During Coprecipitation

To rigorously assess treatment technologies and establish regulatory framework for chromate-contaminated site remediation, it is useful to know the exact chromium speciation in soil matrices. In an earlier study, Thornton, E. C., & Amonette, J. E. (1999). Hydrogen sulfide gas treatment of Cr(VI)-contaminated sediment samples from a plating-waste disposal site – implications for in-situ remediation. Environmental Science & Technology, 33, 4096–4101, reported that some chromate in the bulk particles was not accessible to gaseous reductants or solution-phase extractants, based on XANES studies. We hypothesized that part of this non-extractable chromate may reside in the structure of minerals such as calcium carbonate. To test this hypothesis, a number of calcium carbonate precipitates were prepared in the presence of various concentrations of chromate during the precipitation, which could coprecipitate chromate, or by adding chromate after the precipitation was completed. Hydrochloric acid was used to dissolve calcium carbonate and therefore extract the coprecipitated and surface attached chromate. The results showed that the coprecipitated chromate was non-extractable by hot alkaline solution or phosphate buffer, but could be solubilized by HCl in proportional to the amount of calcium carbonate dissolved. The X-ray diffraction experiments revealed that the coprecipitation of chromate with calcium carbonate had an influence on its crystal structure: The higher the chromate concentration, the greater the ratio of vaterite to calcite.     

Chronic toxicity of tributyltin to Chesapeake bay biota

Chronic tributyltin toxicity experiments were conducted with the following Chesapeake Bay organisms: amphipod, Gammarus sp.; juvenile Atlantic menhaden, Brevoortia tyrannus and larval inland silverside, Menidia beryllina. TBT concentrations ranging from 29 to 579 ng L^?1 did not significantly affect survival of the benthic amphipod, Gammarus sp. after 24-d exposures. The weight of Gammarus exposed to control conditions was 2.8 times greater than the weight of these test organisms exposed to 579 ng L^?1 TBT. Twenty-eight day exposures to TBT concentrations of 93 and 490 ng L^?1 did not significantly affect survival of juvenile B. tyrannus or larval M. beryllina. Histological examinations of B. tyrannus did not demonstrate absolute effects resulting from TBT exposure due to extensive variation between individuals. Various morphometric measurements of M. beryllina after TBT exposure did not demonstrate significant effects. However, significant reductions in growth were reported for M. beryllina at both TBT concentrations. Environmental concentrations of TBT in Chesapeake Bay and possible effects on the above biota are discussed.     

Dual positive and negative regulation of wingless signaling by adenomatous polyposis coli

The evolutionarily conserved Wnt/Wingless signal transduction pathway directs cell proliferation, cell fate, and cell death during development in metazoans and is inappropriately activated in several types of cancer. The majority of colorectal carcinomas contain truncating mutations in the adenomatous polyposis coli (APC) tumor suppressor, a negative regulator of Wnt/Wingless signaling. Here, we demonstrate that Drosophila Apc homologs also have an activating role in both physiological and ectopic Wingless signaling. The Apc amino terminus is important for its activating function, whereas the beta-catenin binding sites are dispensable. Apc likely promotes Wingless transduction through down-regulation of Axin, a negative regulator of Wingless signaling. Given the evolutionary conservation of APC in Wnt signal transduction, an activating role may also be present in vertebrates with relevance to development and cancer.     

Low-frequency signals in long tree-ring chronologies for reconstructing past temperature variability

Preserving multicentennial climate variability in long tree-ring records is critically important for reconstructing the full range of temperature variability over the past 1000 years. This allows the putative "Medieval Warm Period" (MWP) to be described and to be compared with 20th-century warming in modeling and attribution studies. We demonstrate that carefully selected tree-ring chronologies from 14 sites in the Northern Hemisphere (NH) extratropics can preserve such coherent large-scale, multicentennial temperature trends if proper methods of analysis are used. In addition, we show that the average of these chronologies supports the large-scale occurrence of the MWP over the NH extratropics.     

Tyrosinase reactivity in a model complex: an alternative hydroxylation mechanism

The binuclear copper enzyme tyrosinase activates O2 to form a mu-eta2:eta2-peroxodicopper(II) complex, which oxidizes phenols to catechols. Here, a synthetic mu-eta2:eta2-peroxodicopper(II) complex, with an absorption spectrum similar to that of the enzymatic active oxidant, is reported to rapidly hydroxylate phenolates at -80 degrees C. Upon phenolate addition at extreme temperature in solution (-120 degrees C), a reactive intermediate consistent with a bis-mu-oxodicopper(III)-phenolate complex, with the O-O bond fully cleaved, is observed experimentally. The subsequent hydroxylation step has the hallmarks of an electrophilic aromatic substitution mechanism, similar to tyrosinase. Overall, the evidence for sequential O-O bond cleavage and C-O bond formation in this synthetic complex suggests an alternative intimate mechanism to the concerted or late stage O-O bond scission generally accepted for the phenol hydroxylation reaction performed by tyrosinase.     

Phosphofructokinase 1 glycosylation regulates cell growth and metabolism

Cancer cells must satisfy the metabolic demands of rapid cell growth within a continually changing microenvironment. We demonstrated that the dynamic posttranslational modification of proteins by O-linked β-N-acetylglucosamine (O-GlcNAcylation) is a key metabolic regulator of glucose metabolism. O-GlcNAcylation was induced at serine 529 of phosphofructokinase 1 (PFK1) in response to hypoxia. Glycosylation inhibited PFK1 activity and redirected glucose flux through the pentose phosphate pathway, thereby conferring a selective growth advantage on cancer cells. Blocking glycosylation of PFK1 at serine 529 reduced cancer cell proliferation in vitro and impaired tumor formation in vivo. These studies reveal a previously uncharacterized mechanism for the regulation of metabolic pathways in cancer and a possible target for therapeutic intervention.     

Regeneration of ammonia borane spent fuel by direct reaction with hydrazine and liquid ammonia

Ammonia borane (H(3)N-BH(3), AB) is a lightweight material containing a high density of hydrogen (H(2)) that can be readily liberated for use in fuel cell-powered applications. However, in the absence of a straightforward, efficient method for regenerating AB from dehydrogenated polymeric spent fuel, its full potential as a viable H(2) storage material will not be realized. We demonstrate that the spent fuel type derived from the removal of greater than two equivalents of H(2) per molecule of AB (i.e., polyborazylene, PB) can be converted back to AB nearly quantitatively by 24-hour treatment with hydrazine (N(2)H(4)) in liquid ammonia (NH(3)) at 40°C in a sealed pressure vessel.