Characterization of biomass pyrolysis vapors with molecular beam, single photon ionization time-of-flight mass spectrometry

A single photon ionization, molecular beam sampling, reflectron time-of-flight mass spectrometer (SPI/MBTOFMS) has been developed and used to study pyrolysis products from a selection of biomass materials. Spectra are characterized by high resolution and decreased fragmentation compared to electron-impact ionization mass spectra from related molecular beam mass spectrometer systems equipped with quadrupole mass analyzers.     

Prediction of Pb speciation in concentrated and dilute nutrient solutions

Despite the presence of numerous studies in the literature examining the phytotoxicity of Pb, there is a lack of precise quantitative data on limiting concentrations of Pb for plant growth. Using the PhreeqcI chemical equilibrium model, simulations were conducted to examine the speciation of Pb in concentrated and dilute nutrient solutions. Due to the higher P concentration of Hoagland's solution (1000microM), precipitation of chloropyromorphite (Pb5(PO4)3Cl) was predicted to occur at lower pH values, and at lower Pb concentrations, than for a dilute nutrient solution (2microM P). Although nutrient solutions prepared in the glasshouse were supersaturated (and Pb concentrations were substantially higher than predicted by modeling), they confirmed the importance of the P concentration in influencing the precipitation of Pb. Given the low solubility of Pb-phosphates, nutrient solutions with low P concentrations should be utilized, and plant growth should be related to measured Pb concentrations rather than to the quantity of Pb initially added.     

The dynamics of dissolved nitrogen in a blanket peat dominated catchment

Precipitation, soil solution and drainage water were collected from a blanket peat catchment at Moor House National Nature Reserve in the Northern Pennine Uplands, UK, an area of moderately high N deposition. Two tributaries of the main stream were also sampled. Between 1993 and 1995 samples were analysed for NH4+ and NO3- and for part of the period for organic N. Inputs of N in precipitation exceeded outputs in stream water. Organic N represented a small proportion of N inputs while inputs of inorganic N averaged 10.2 kg ha(-1) a(-1). Soil solution from 10 cm depth in the peat was dominated by organic N whereas at 50 cm NH4+ slightly exceeded organic N. NO3- was rarely detected at either depth except during a period of exceptionally warm and dry weather in 1995. Output fluxes in stream water of organic N (5.7 to 6.5 kg ha(-1) a(-1)) were much greater than those of inorganic N (0.6 to 2.2 kg ha(-1) a(-1)). Inorganic N in streams was predominantly NO3- except in the smallest stream which had the largest concentrations of NH4+. This suggests that N transformations, particularly nitrification, may be taking place in the mineral soils adjacent to the streams or within the stream channel of the larger catchment.     

The disposal of a lime water treatment residue on soil and spoil material from a coalmine: a glasshouse investigation

Eragrostis tef (Zucc.), Cenchrus ciliaris L., and Digitaria eriantha Steud. were grown in a soil (Psammentic Haplustalf) and spoil material from a coalmine both treated with a lime water treatment residue (WTR) at rates of 0, 50, 100, 200, and 400 g kg(-1). The yield of the grasses, from the sum of the three harvests, and concentrations of B, Ca, Cu, K, Fe, Mg, Mn, N, Na, P, and Zn in foliage from the second harvest were determined. The yield of grasses grown in the soil decreased exponentially as WTR application increased. The yields of C. ciliaris, D. eriantha, and E. tef (in the 400 g kg(-1) WTR treated soil) decreased by 74.4, 78.7, and 59.8%, respectively, when compared with the control treatments. In the spoil, the yield of E. tef and D. eriantha decreased by 13.6% and and D. eriantha by 23.9%, while an increase was observed for C. ciliaris (45.4%), at the highest WTR application rate. No relationship existed between yield of E. tef and WTR application rate when grown in the spoil, while a weak negative linear relationship (p < 0.05) was found for D. eriantha and a positive linear relationship existed for C. ciliaris. Magnesium concentrations of the grasses were positively correlated to WTR application rate. Grasses grown in the soil had higher Na concentrations, while those grown in the spoil typically had higher B, N, and Zn concentrations. The decreases in yield were attributed to nutrient deficiencies (notably Zn), induced by high WTR application rates that led to high substrate pH. Disposal of high rates of WTR on the mine materials was not recommended.     

Desorption kinetics for selected PCB congeners from river sediments

Desorption of PCBs from sediment can significantly affect the ultimate fate and effects of PCBs in aquatic systems. Using a gas purging technique to strip soluble and sorbed polychlorinated biphenyls (PCBs) from solutions and sediment suspensions, Henry's law constants, approach to equilibrium, and desorption rate constants for four PCB congeners were measured. Henry's law constants were on the order of 10⁻⁴ m³ atm mole⁻¹. Desorption rate constants measured for a predominantly kaolinitic, low-organic carbon sediment were on the order of 0.03–0.1 days⁻¹. In contrast, desorption rate constants measured for a sediment composed of montmorillonite with a 3% organic carbon content were on the order of 0.009–0.04 days⁻¹. Desorption data suggest that equilibration times for PCBs with low chlorine content are on the order of six weeks, and months to years for PCBs with a significantly higher chlorine content.     

Relationships between aqueous solubility and octanol-water partition coefficients

The physical chemical equations relating solubility to octanol water partition coefficient are presented and used to develop a new correlation between these quantities which includes a melting point (fugacity ratio) correction. The correlation is satisfactory for 45 organic compounds but it is not applicable to organic acids. When applied to very high molecular weight (> 290) compounds the correlation is less satisfactory; either it is believed because the data are inaccurate or because the tendency for these compounds to partition into organic phases is less than expected. This may have profound environmental implications.     

Atmospheric transport of atrazine: a simple device for its detection

Thin-layer chromatography plates were exposed at three different locations in Bavaria for 3-week periods during the growing season of maize. The adsorption of traces of atrazine was detected by thin-layer chromatography, GC-MS, and by an enzyme immunoassay. It was restricted to the sowing season, which coincides with the application of atrazine. The herbicide could not be detected after this time. The simplicity of the adsorption device, combined with a serological assay, render this procedure suitable for detecting airborne organic pollutants.