Speciation of nickel in Canadian subbituminous and bituminous feed coals, and their ash by-products

The nickel species in the feed coals and ash by-products from seven Canadian power plants (including one with a fluidized bed combuster) burning local subbituminous and bituminous coals with sulfur contents ranging from 0.22 to 3.6% have been examined using nickel XANES spectroscopy. XANES spectroscopy of Ni in coal and coal derived ash is complicated by a poor signal : noise ratio due to fluorescence of the much more abundant iron in the coal. Nevertheless, it has proved possible to show that the Ni environment in coals varies from largely oxidic species to mixtures of Ni-containing oxide and sulfide species. The nickel in one oxidized coal appears to be present as nickel sulfate. Nickel in all bottom and fly ash samples examined appears also to be present largely in oxygen anion environments. With the exception of one fly ash sample, for which the Ni exhibited spectral features similar to those for Ni(2+) in spinel or oxide phases, the nickel in the bottom and fly ash samples appears to exist largely as Ni(2+) in environments similar to those reported for Ni in silicate glasses. The data obtained indicate that the presence of potentially carcinogenic nickel sulfides in ash by-products from combustion of these coals is unlikely.     

Nickel Speciation of Residual Oil Fly Ash and Ambient Particulate Matter Using X-ray Absorption Spectroscopy

ABSTRACT

The chemical speciation of Ni in fly ash produced from ~0.85 wt % S residual (no. 6 fuel) oils in laboratory (7 kW)- and utility (400 MW)-scale combustion systems was investigated using X-ray absorption fine structure (XAFS) spectroscopy, X-ray diffraction (XRD), and acetate extraction [1 M NaOAc-0.5 M HOAc (pH 5) at 25 °C]-anodic stripping voltammetry (ASV). XAFS was also used to determine the Ni speciation of ambient particulate matter (PM) sampled near the 400-MW system. Based on XAFS analyses of bulk fly ash and their corresponding acetate extraction residue, it is estimated that >99% of the total Ni (0.38 wt %) in the experimentally produced fly ash occurs as NiSO₄-xH₂O, whereas >95% of the total Ni (1.70 and 2.25 wt %) in two fly ash samples from the 400-MW system occurs as NiSO₄-xH₂O and Ni-bearing spinel, possibly NiFe₂O₄. Spinel was also detected using XRD. Acetate extracts most of the NiSO₄-xH₂O and concentrates insoluble NiFe₂O₄ in extraction residue. Similar to fly ash, ambient PM contains NiSO₄-xH₂O and NiFe₂O₄;

however, the proportion of NiSO₄-xH₂O relative to NiFe₂O₄ is much greater in the PM. Results from this and previous investigations indicate that residual oil ash produced in the 7-kW combustion system lack insoluble Ni (e.g., NiFe₂O₄) but are enriched in soluble NiSO₄-xH₂O relative to fly ash from utility-scale systems. This difference in Ni speciation is most likely related to the lack of additive [e.g., Mg(OH)₂] injection and residence time in the 7-kW combustion system.     

EPIC tile flow and nitrate loss predictions for three Minnesota cropping systems

Subsurface tile drains are a key source of nitrate N (NO3-N) losses to streams in parts of the north central USA. In this study, the Erosion Productivity Impact Calculator (EPIC) model was evaluated by comparing measured vs. predicted tile flow, tile NO3-N loss, soil profile residual NO3-N, crop N uptake, and yield, using 4 yr of data collected at a site near Lamberton, MN, for three crop rotations: continuous corn (Zea mays L.) or CC, corn-soybean [Glycine max (L.) Merr.] or CS, and continuous alfalfa (Medicago sativa L.) or CA. Initially, EPIC was run using standard Soil Conservation Service (SCS) runoff curve numbers (CN2) for CC and CS; monthly variations were accurately tracked for tile flow (r2 = 0.86 and 0.90) and NO3-N loss (r2 = 0.69 and 0.52). However, average annual CC and CS tile flows were underpredicted by -32 and -34%, and corresponding annual NO3-N losses were underpredicted by -11 and -52%. Predicted average annual tile flows and NO3-N losses generally improved following calibration of the CN2; tile flow underpredictions were -9 and - 12%, whereas NO3-N losses were 0.6 and -54%. Adjusting a N parameter further improved predicted CS NO3-N losses. Predicted monthly tile flows and NO3-N losses for the CA simulation compared poorly with observed values (r2 values of 0.27 and 0.19); the annual drainage volumes and N losses were of similar magnitude to those measured. Overall, EPIC replicated the relative impacts of the three cropping systems on N fate.     

Tillage and nutrient source effects on surface and subsurface water quality at corn planting

This study quantified the effects of tillage (moldboard plowing [MP], ridge tillage [RT]) and nutrient source (manure and commercial fertilizer [urea and triple superphosphate]) on sediment, NH4+ -N, NO3- -N, total P, particulate P, and soluble P losses in surface runoff and subsurface tile drainage from a clay loam soil. Treatment effects were evaluated using simulated rainfall immediately after corn (Zea mays L.) planting, the most vulnerable period for soil erosion and water quality degradation. Sediment, total P, soluble P, and NH4+ -N losses mainly occurred in surface runoff. The NO3- -N losses primarily occurred in subsurface tile drainage. In combined (surface and subsurface) flow, the MP treatment resulted in nearly two times greater sediment loss than RT (P < 0.01). Ridge tillage with urea lost at least 11 times more NH4+ -N than any other treatment (P < 0.01). Ridge tillage with manure also had the most total and soluble P losses of all treatments (P < 0.01). If all water quality parameters were equally important, then moldboard plow with manure would result in least water quality degradation of the combined flow followed by moldboard plow with urea or ridge tillage with urea (equivalent losses) and ridge tillage with manure. Tillage systems that do not incorporate surface residue and amendments appear to be more vulnerable to soluble nutrient losses mainly in surface runoff but also in subsurface drainage (due to macropore flow). Tillage systems that thoroughly mix residue and amendments in surface soil appear to be more prone to sediment and sediment-associated nutrient (particulate P) losses via surface runoff.     

Detrimental effects of carotenoid pigments: the dark side of bright coloration

Carotenoid pigments produce yellow, orange, and red integumentary color displays that can serve as reliable signals of health and condition. In many birds and fish, individuals gain competitive or mating advantages by ingesting and utilizing large quantities of carotenoid pigments. Carotenoid pigments serve as antioxidants, performing important functions as free-radical scavengers. The beneficial effects of carotenoid pigments are well documented, but rarely have researchers considered potential detrimental effects of high-level accumulation of carotenoids. We maintained American goldfinches (Carduelis tristis) on high- or low-carotenoid diets through molt and tested for damage to the liver and skeletal muscle. High intake of carotenoids had no measurable effect on liver enzymes but caused an increase in creatine kinase, an indicator of skeletal muscle breakdown, and a reduction in vertical flight performance, a measure of skeletal muscle integrity. The detrimental effects of high-level carotenoid accumulation were approximately equivalent to the negative effects of removing carotenoids from the diet. The adverse effects observed in this study have important implications for theories of the function and evolution of colorful plumage.