Fractionation of fulvic acids: characteristics and complexation with copper

Two fulvic acid samples isolated from Suwannee river (International Humic Substance Society) and Feeitsuey reservoir were subjected to gel filtration chromatography (GFC) for molecular size fractionation. The GFC-eluted samples were separated into three groups corresponding to the molecular weight ranges: < 220, 220-1000, and 1000-4000. Fluorescence quenching techniques were employed for determining the conditional stability coefficient and kinetic parameters of copper complexation with the three fractions of fulvic acids. Experimental conditions were pH 6, 5 x 10(-5)m total copper and 5 mg C litre(-1) of fulvic acids. The conditional stability coefficients of the fulvic acid fractions were in the order of 0.9-3.3 x 10(5)m(-1), and the forward and reverse rate constants were in the order of 6.9-12.4 x 10(3)m(-1) s(-1) and 3.5-8.0 x 10(-2) s(-1). Information could be useful in modelling copper transport in the hydrosphere.     

Management options to limit nitrate leaching from grassland

Nitrate leaching can be reduced by the adoption of less intensive grassland systems which, though requiring a greater land area to achieve the same agricultural output, result in less nitrate leaching per unit of production than do intensively managed grasslands. The economic penalties associated with reductions in output can be partly offset by greater reliance on symbiotic nitrogen fixation and the use of clover-based swards in place of synthetic N fertilisers. Alternatively, specific measures can be adopted to improve the efficiency of nitrogen use in intensively managed systems in order to maintain high outputs but with reduced losses. Controls should take account of other forms of loss and flows of nitrogen between grassland and other components of the whole-farm system and, in most instances, should result in an overall reduction in nitrogen inputs. Removing stock from the fields earlier in the grazing season will reduce the accumulation of high concentrations of potentially leachable nitrate in the soil of grazed pastures but will increase the quantity of manure produced by housed animals and the need to recycle this effectively. Supplementing grass diets with low-nitrogen forages such as maize silage will reduce the quantity of nitrogen excreted by livestock but may increase the potential for nitrate leaching elsewhere on the farm if changes to cropping patterns involve more frequent cultivation of grassland. Improved utilisation by the sward of nitrogen in animal excreta and manures and released by mineralisation of soil organic matter will permit equivalent reductions to be made in fertiliser inputs, provided that adequate information is available about the supply of nitrogen from these non-fertiliser sources.     

Pharmacokinetic model of dioxin and furan levels in adipose tissue from Sawmill work involving chlorophenate fungicides

Sawmill workers in British Columbia (B.C.), Canada, have been exposed to chlorophenate fungicides which are known to be contaminated with polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Due to concern about the potential of these workers to have significant body burdens of PCDD/Fs, and the absence of measurements in these worker, a single-compartment pharmacokinetic model was developed to estimate the concentration of PCDD/Fs in the fat tissue of the sawmill workers. Data from a large cohort of B.C. sawmill workers and literature-based data on chlorophenate exposures and PCDD/F concentrations in chlorophenates were used in Monte Carlo simulations to predict a PCDD/F body burden distribution. The median concentrations of HxCDF and HpCDF predicted using the model for the B.C. sawmill worker population exceeded the range measured in unexposed populations. PeCDF and OCDF concentrations exceeded the range measured in unexposed populations at the 70th percentile of the model-predicted distribution, and PeCDD at the 90th percentile. The primary limitation of the model was the scarcity of input data about actual dermal and inhalation exposures to chlorophenates.     

Growth and nutrition of Quercus rubra L. seedlings and mature trees after three seasons of ozone exposure

Seedling growth and nutritional status have been shown to be sensitive to ozone, but the influence of multi-season ozone exposure on mature tree growth and nutrition has not been examined. To determine if seedlings and mature trees were similarly affected by ozone exposure, growth and nutrient concentrations in northern red oak (Quercus rubra L.) 4-year-old seedlings and 32-year-old mature trees were examined after treatment with subambient, ambient and twice ambient concentrations of ozone for three growing seasons. SUM00 values summed over the three growing seasons were 147, 255 and 507 ppm-h, respectively, for the subambient, ambient and twice ambient exposures. For mature trees, no influence of ozone treatment on lower stem diameter growth, stem growth within the mid-canopy and foliar biomass was observed. Seedling height was increased by ozone, but biomass and diameter were unaffected. A reduction in the specific leaf weight of leaves in response to ozone coincident with the loss of recurrent flushing was observed in seedlings. Ozone exposure reduced foliar nitrogen concentrations and increased woody tissue nutrient concentrations in seedlings and mature trees at the end of the third growing season. These results suggest an influence of ozone on retranslocation processes in seedlings and mature trees.     

Biomonitoring of air pollutants from traffic and industries employing Ramalina ecklonii (Spreng.) Mey. and Flot. in Córdoba, Argentina

The lichen Ramalina ecklonii (Spreng.) Mey. and Flot. was transplanted to 29 biomonitoring sites in the southeastern area of Córdoba, Argentina and tested for chlorophyll a, phaeophytin a, conjugated dienes concentration, malondialdehyde, soluble protein content and sulfur accumulation. The biomonitoring sites were determined according to (i) vehicular traffic levels, and (ii) industrial density, i.e. number and type of industries (small and medium) close to each of the sites. Each of the two groups were then broken down into three categories which provided a basis for performance analysis and quantification of the chemical parameters in the biomonitor. A pollution index (P.I.) was calculated based on the ratio of phaeophytin a to chlorophyll a and ratio of sulfur, malonaldehyde and conjugated dienes in transplanted specimens to sulfur, malonaldehyde and conjugated dienes in the freshly picked specimens. Significant differences were observed in sulfur content and P.I. in lichen samples that had been transplanted to sites with different vehicular traffic levels. At the same time, significant differences in the phaeophytin a concentration, phaeophytin a/chlorophyll a ratio and P.I. were observed at sites characterized by different levels of industrial density (all with low-to-medium traffic).     

The impact of SO2 and SO2 + ascorbic acid treatments on growth and partitioning of dry matter in Trigonella foenum-graecum L

To study the impact of SO(2) and SO(2) + ascorbic acid on growth and partitioning of dry matter in Trigonella foenum-graecum L., two-week-old plants were exposed to SO(2) for 2 h daily over a 42 day period. One of the exposed sets was treated with ascorbic acid. Plants were grown in a wire house and unexposed plants were used as controls for comparison. The parameters measured, such as dry weights of leaf, stem and root per plant, were found to be lower in the exposed sets than in the controls. The reductions were greater in dry weights of stem and root as compared with weights of leaves, indicating that the partitioning of the dry matter was altered. Greater amounts of soluble sugars and starch in the leaves of exposed plants, compared with the stem, also revealed that translocation was hampered. Reductions were greater in fruiting than in flowering, suggesting that fruit abortion was high. Although ascorbic acid treatment could mitigate the effect of SO(2), the differences were not found to be statistically significant. Significant changes were seen in fruit yield, suggesting that the effect of ascorbic acid is cumulative. The impact of SO(2) and SO(2) + ascorbic acid on partitioning of dry matter to different 'sinks' is discussed.     

Organic carbon concentration profiles in recent cave sediments: records of agricultural pollution or diagenesis?

Recent (<7 years old) cave sediments in Speedwell Cavern, Derbyshire, show an approximately exponential decay of organic carbon with depth. This phenomenon was thought to be due to one of two causes: (i) changing agricultural practice within the catchment feeding the cave, especially the increased use of sewage sludge and animal slurry as fertilizer; (ii) a relatively constant organic carbon concentration over time in the input sediment, with subsequent carbon mineralization during diagenesis. Carbon isotope composition of the organic material and the evolution of H/C ratio with depth indicate that the latter hypothesis is correct and that the profiles result from microbial diagenesis, not increased organic carbon inputs. By comparison with sediment of known (7 years) age, temporal decay constants for organic matter can be derived; these lie between rates previously determined for organic matter decomposition in marine sediments and soils. The H/C ratio of organic matter can be modelled as a function of time and proceeds in a similar fashion to soil organic material.     

Sequential extraction analysis of heavy metals using a chelating agent (NTA) to counteract resorption

The geochemical partitioning of Pb, Ni and Zn in contaminated quartz-rich sediment and soil samples was characterized by sequential extraction analysis in the presence and absence of nitrilotriacetic acid (NTA). With NTA, levels of metals recovered are higher in the earlier steps and lower in the later steps of the procedure. This suggests that post-extraction resorption is effectively counteracted by chelation, thereby improving the accuracy of the method. An NTA concentration of 200 mg liter(-1) appears to be sufficient for counteracting resorption without causing significant dissolution of non-targeted phases in the samples studied. However, experiments using reference materials spiked with solutions containing Pb, Ni, Cu and Zn suggest that resorption will remain a problem when large amounts of strong sorbents such as organic matter are present. The results also show that although post-extraction resorption does occur in the absence of NTA, the magnitude of resorption is small (<20 to 30% of the summed total of metal present in the sample) in quartz-rich sediments.     

Persistent organochlorines in beluga whales (Delphinapterus leucas) from the St Lawrence River estuary--I. Concentrations and patterns of specific PCBs, chlorinated pesticides and polychlorinated dibenzo-p-dioxins and dibenzofurans

Blubber samples from beluga whales (Delphinapterus leucas) in the St Lawrence River estuary were analysed for PCB congeners (ortho- and non-ortho-substituted) and other persistent organochlorines as well as chlorinated dibenzo-dioxins/furans (PCDD/Fs). Major individual components (mean concentrations > 1 microg g(-1)) were 4,4'-DDE, -DDD and -DDT, T12 (a toxaphene-related compound), trans-nonachlor, oxychlordane, mirex, HCB, tris(p-chlorophenyl) methane and dieldrin. Concentrations of SigmaPCBs (8.3-412 microg g(-1)), SigmaDDT (3.36-389 microg g(-1)) and mirex (0.18-6.8 microg g(-1)) were particularly elevated relative to other odontocetes in Canadian waters. SigmaDDT, PCBs (as Aroclor), mirex and T12 concentrations were positively correlated with age of adult females (> 10 years) but only weakly, or not significantly, correlated with age of adult males. PCDD/Fs were present at low ng kg(-1) levels and consisted mainly of penta- and hexachlorofurans, and hepta- and octachlorodioxin. CB126 (3,3',4,4',5-PCB) was the most prominent non-ortho-substituted PCB congener in beluga blubber. Total TCDD toxic equivalents averaged 330 ng kg(-1) in females and 1400 ng kg(-1) in males and were dominated by CB126, and the mono-ortho-substituted congeners CB105 and CB118. Biomagnification factors (BMFs) for mirex and SigmaPCB from fish to beluga ranged from 11 to 16, and were similar to BMFs in Arctic animals, indicating that elevated levels in St Lawrence animals are a consequence of relatively high levels of recalcitrant organochlorines in prey of the beluga in the St Lawrence river system.