Evaluation of ecological disturbance and intrinsic bioremediation potential of pulp mill-contaminated lake sediment using key enzymes as probes

A rapid protocol was developed to measure 10 different enzymic activities from a large number of 1-cm-sliced freshly collected lake sediments. Layers heavily polluted by organic halogens (4900 mg Cl kg(-1)) revealed severe depression of phosphatase, sulfatase, leucine-aminopeptidase, chitinase, acetate esterase and butyrate esterase activities as compared to layers above and below the most polluted zone. alpha-Glucosidase, beta-glucosidase, beta-xylosidase and palmitate esterase were less affected. Methane oxidation potential was dramatically depressed in the polluted strata whereas tetrachloromethane dehalogenating activity was observed in the polluted sediment only. The sediment layers formed after the chlorine discharges into the lake had diminished to 1/10, and showed restoration of the activities close to those observed in non-recipient sediment, in spite of the persisting presence of >1000 mg of organic chlorine (kg dry wt)(-1). We conclude that certain enzymic activities involved in breakdown or oxidation of organic matter in the sediments are useful probes for assessing the degree of ecological damage and its potential for restoration in recipient lakes of industrial discharges.     

Catalytic and electrocatalytic hydrogenolysis of brominated diphenyl ethers

Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental contaminants due to their use as additive flame-retardants. Conventional catalytic hydrogenolysis in methanol solution and electrocatalytic hydrogenolysis in aqueous methanol were examined as methods for debrominating mono- and di-bromodiphenyl ethers, as well as a commercial penta-PBDE mixture, in each case using palladium on alumina as the catalyst. Electrocatalytic hydrogenolysis employed a divided flow-through batch cell, with reticulated vitreous carbon cathodes and IrO2/Ti dimensionally stable anodes. Both methods gave efficient sequential debromination, with essentially complete removal of bromine from the PBDEs, but the electrocatalytic method was limited by the poor solubility of PBDEs in aqueous methanol.     

Removal of nitrogen and phosphate from wastewater by addition of bittern

Removal of nitrogen and phosphate through crystallization of struvite (MgNH(4)PO(4).6H(2)O) has gained increasing interest. Since wastewaters tend to be low in magnesium relative to ammonia and phosphates, addition of this mineral is usually required to effect the struvite crystallization process. The present study evaluated the feasibility of using bittern, a byproduct of salt manufacture, as a low-cost source of magnesium ions. High reaction rates were observed; the extent of nitrogen and phosphorus removals did not change beyond 10 min. Phosphorus removals from pure solutions with bittern added were equivalent to those obtained with MgCl(2) or seawater. Nitrogen removals with bittern were somewhat lower than with the alternate Mg(2+) sources, however. Application of bittern to biologically treated wastewater from a swine farm achieved high phosphate removal, but ammonia removals were limited by imbalance in the nitrogen:phosphorus ratio.     

Diflubenzuron residue and persistence on an oak forest after aerial application

Abstract

A twenty hectare forest block in central Pennsylvania was aerially sprayed with diflubenzuron (Dimilin 25W®) at the dose of 33.23g A.I./ha in 9.4 litres/ha. Leaf samples were collected from the upper and lower canopies of 27 oaks and understory within this block on the day of spray, May 29, 1991. Canopy leaves were also collected on May 31, June 10, July 29 and September 26, 1991.

Recovery of diflubenzuron residues on fortified canopy‐leaf and litter‐leaf samples using analytical techniques employed in this study averaged 87.4% (SE = 7.5%) and 66.2% (SE = 8.2%), respectively.

On the day of spray, diflubenzuron residues on the upper canopy, lower canopy and understory averaged 81.18, 39.65 and 8.35 ng/cm², respectively. Diflubenzuron residues on canopy‐leaf samples collected 2, 12, 61 and 120 days post‐spray averaged 14.83 (SE = 10.19), 16.75 (SE = 9.95), 12.84 (SE = 8.25) and 11.20 (SE = 7.52) ng/cm², respectively. Diflubenzuron residues on litter‐leaf samples collected after leaf senescence ‐ 169 and 323 days post spray contained measurable amounts of diflubenzuron in 51 and 59% of the samples, respectively. Of the samples with measurable amounts of diflubenzuron, residues averaged 1.36 (SE = 2.44) and 0.65 ng/cm² (SE = 0.73) respectively.     

Aquatic fate assessment of the polycyclic musk fragrance HHCB. Scenario and variability analysis in accordance with the EU risk assessment guidelines

By means of the environmental fate and distribution models laid down in the Technical Guidance Documents (TGD) and implemented in the European Union System for the Evaluation of Substances (EUSES) environmental concentrations of the polycyclic musk fragrance HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-[g]-2- benzopyrane; trade name: e.g. Galaxolide) were calculated for the aquatic environment under consideration of various scenarios. The results were then compared to monitoring data from the region of North Rhine-Westphalia (River Ruhr). An uncertainty analysis was carried out to determine sensitive parameters, to integrate environmental variability and to confirm the model's calculations. The standard scenario of EUSES overestimates the measured concentrations, which confirms the conservative nature of the calculations. The regional-specific scenarios lead to lower deviations from the measured values than the standard scenario. Deviations range from one to two orders of magnitude in the effluent of sewage treatment plants; they amount to one order of magnitude for surface water concentrations on a local scale and conform to monitoring data on a regional scale. The use of measured bioconcentration factors for fish instead of estimated ones reduces deviations remarkably. The investigation reveals that unrealistic worst-case calculations of HHCB can at best be ameliorated by the application of more realistic emission rates and measured bioconcentration factors. The use of regional-specific parameters also diminishes the deviations of the calculations from the measured concentrations.     

Clonal variation in heavy metal accumulation and biomass production in a poplar coppice culture. II. Vertical distribution and phytoextraction potential

Short rotation coppice cultures (SRC) are intensively managed, high-density plantations of multi-shoot trees. In April 1996, an SRC field trial with 17 different poplar clones was established in Boom (Belgium) on a former waste disposal site. In December 1996 and January 2001, all shoots were cut back to a height of 5 cm to create a coppice culture. For six clones, wood and bark were sampled at the bottom, middle and top of a shoot in August and November 2002. No significant height effect of metal concentration was found, but for wood, metal concentrations generally increased toward the top of the shoot in August, and decreased toward the top of the shoot in November. Phytoextraction potential of a clone was primarily determined by metal concentration and by biomass production. Shoot size and number of shoots per stool were less important, as a high biomass production could be achieved by producing a few large shoots or many smaller shoots. Clone Fritzi Pauley accumulated 1.4 kg ha(-1) of Al over two years; Wolterson and Balsam Spire showed a relatively high accumulation of Cd and Zn, i.e. averaging, respectively 47 and 57 g ha(-1) for Cd and 2.4 and 2.0 kg ha(-1) for Zn over two years.     

Reactions of compost-derived humic substances with lead, copper, cadmium, and zinc

Thermodynamic stability constants of the formation of complexes from the reactions of humic substances with various metals are usually used as parameters to judge the reactivities of both humic substances and metals. However, in calculating the thermodynamic stability constants, complicated processes for the acquisition of activities of components in reactions are absolutely inevitable. In this study, we investigated the average conditional concentration quotients of the complexes formed from the reaction of metals with humic substances and the relations of these quotients to thermodynamic stability constants. The characterized humic substances including HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) extracted from a swine compost were prepared to react with Pb, Cu, Cd, and Zn at 25 degrees C and at pH 4.00 and 6.50. Reactions of HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) with the four metals were carried out at 1:0.1, 1:0.5, 1:1, 1:5, and 1:10 ligand:metal stoichiometry. The concentrations of the free ions of Pb, Cu, Cd, and Zn in the reaction systems of metal-HA suspensions and metal-FA solutions were measured by anodic stripping voltammetry (ASV). The sequence of the average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals was FA(MW<1,000)>FA(MW>1,000)>HA(MW>1,000), showing the relative reactivities of the fractions of swine compost-derived humic substances. The sequence of reacting metals with humic substances was Pb>Cu>Cd>Zn, which is in good agreement with the sequence reported by judging the thermodynamic stability constants. The average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals were thus useful parameters that can be directly related to thermodynamic stability constants and other parameters.