Interactive effects of CO2 and O3 on a ponderosa pine plant/litter/soil mesocosm.

To study individual and combined impacts of two important atmospheric trace gases, CO2 and O3, on C and N cycling in forest ecosystems; a multi-year experiment using a small-scale ponderosa pine (Pinus ponderosa Laws.) seedling/soil/litter system was initiated in April 1998. The experiment was conducted in outdoor, sun-lit chambers where aboveground and belowground ecological processes could be studied in detail. This paper describes the approach and methodology used, and presents preliminary data for the first two growing seasons. CO2 treatments were ambient and elevated (ambient + 280 ppm). O3 treatments were elevated (hourly averages to 159 ppb, cumulative exposure > 60 ppb O3, SUM 06 approximately 10.37 ppm h), and a low control level (nearly all hourly averages <40 ppb. SUM 06 approximately 0.07 ppm h). Significant (P < 0.05) individual and interactive effects occurred with elevated CO2 and elevated O3. Elevated CO2 increased needle-level net photosynthetic rates over both seasons. Following the first season, the highest photosynthetic rates were for trees which had previously received elevated O3 in addition to elevated CO2. Elevated CO2 increased seedling stem diameters, with the greatest increase at low O3. Elevated CO2 decreased current year needle % N in the summer. For 1-year-old needles measured in the fall there was a decrease in % N with elevated CO2 at low O3, but an increase in % N with elevated CO2 at elevated O3. Nitrogen fixation (measured by acetylene reduction) was low in ponderosa pine litter and there were no significant CO2 or O3 effects. Neither elevated CO2 nor elevated O3 affected standing root biomass or root length density. Elevated O3 decreased the % N in coarse-fine (1-2 mm diameter) but not in fine (< 1 mm diameter) roots. Both elevated CO2 and elevated O3 tended to increase the number of fungal colony forming units (CFUs) in the AC soil horizon, and elevated O3 tended to decrease bacterial CFUs in the C soil horizon. Thus, after two growing seasons we showed interactive effects of O3 and CO2 in combination, in addition to responses to CO2 or O3 alone for a ponderosa pine plant/litter/soil system.     

Effects of nitrogen and phosphorus limitation on the activated sludge biomass in a kraft mill biotreatment system.

Unlike wastewater, pulp and paper mill effluents are generally severely deficient in bioavailable nitrogen and phosphorus. The influence of nitrogen and phosphorus limitations on steady-state or typical pulp and paper mill activated sludge floc properties and performance was studied using a bioreactor-fed synthetic raw mill effluent and seeded with mill activated sludge. Limitation of either nitrogen or phosphorus decreased growth, five-day biochemical oxygen demand, and suspended solids removal. Nitrogen limitation greatly enhanced activated sludge floc poly-beta3-hydroxybutyrate (PHB), but not carbohydrate or extracellular polymeric substances (EPS). In contrast, phosphorus limitation increased total floc carbohydrate and EPS, but not PHB. The flocs showed little ability to store either nitrogen or phosphorus. Nitrogen limitation, but not phosphorus limitation, produced much more negative net floc surface charge, increasing fines, while phosphorus limitation, but not nitrogen limitation, increased the floc bound water content and surface hydrophobicity and decreased fines.     

Construction demolition wastes, Waelz slag and MSWI bottom ash: a comparative technical analysis as material for road construction

The objective of the study is to analyze the technical suitability of using secondary materials from three waste flows (construction and demolition waste (CDW), Waelz slag and municipal solid waste incineration (MSWI) bottom ash), under the regulations and standards governing the use of materials for road construction. A detailed technical characterization of the materials was carried out according to Spanish General Technical Specifications for Road Construction (PG3). The results show that Waelz slag can be adequate for using in granular structural layers, while CDW fits better as granular material in roadbeds. Likewise, fresh MSWI bottom ash can be used as roadbed material as long as it does not contain a high concentration of soluble salts. This paper also discusses the adequacy of using certain traditional test methods for natural soils when characterizing secondary materials for use as aggregates in road construction.     

Use of whole-body and subcellular Cu residues of Lumbriculus variegatus to predict waterborne Cu toxicity to both L. variegatus and Chironomus riparius in fresh water

We tested the use of whole-body and subcellular Cu residues (biologically-active (BAM) and inactive compartments (BIM)), of the oligochaete Lumbriculus variegatus to predict Cu toxicity in fresh water. The critical whole-body residue associated with 50% mortality (CBR₅₀) was constant (38.2-55.6 μg g⁻¹ fresh wt.) across water hardness (38-117 mg L⁻¹ as CaCO₃) and exposure times during the chronic exposure. The critical subcellular residue (CSR₅₀) in metal-rich granules (part of BIM) associated with 50% mortality was approximately 5 μg g⁻¹ fresh wt., indicating that Cu bioavailability is correlated with toxicity:subcellular residue is a better predictor of Cu toxicity than whole-body residue. There was a strong correlation between the whole-body residue of L. variegatus (biomonitor) and survival of Chironomus riparius (relatively sensitive species) in a hard water Cu co-exposure. The CBR₅₀ in L. variegatus for predicting mortality of C. riparius was 29.1-45.7 μg g⁻¹ fresh wt., which was consistent within the experimental period; therefore use of Cu residue in an accumulator species to predict bioavailability of Cu to a sensitive species is a promising approach.     

Formation of dioxins (PCDDs/PCDFs) by dioxin-free fly ash as a catalyst and relation with several chlorine-sources

Simplified thermal formation experiments have been conducted using dioxin-free fly ash as a catalyst with many kinds of combustible samples such as newspaper, kerosene, paraffin, PE (polyethylene), PP (polypropylene) and PVC. Chlorine sources were PVC, NaCl and HCl. The combustion of samples containing chlorine in the absence of dioxin-free fly ash produced dioxins at a low level although HCl was present in the gas stream. On the other hand, the combustion of samples without chlorine with dioxin-free fly ash increased dioxins formation to a level around 10 times higher than that upon heating dioxin-free fly ash alone. This result is considered to be due to the presence of metal chloride in the fly ash and hydrocarbons in the gas stream. The combustion of samples containing either an organic or inorganic chlorine source or using a HCl stream with dioxin-free fly ash increased dioxin level dramatically.     

Anaerobic digestion of linear alkyl benzene sulfonates: biodegradation kinetics and metabolite analysis

In the present work the effect of the alkyl chain length and the position of the sulfophenyl substituent of the linear alkylbenzene sulfonates (LAS) on their anaerobic biodegradability have been investigated. Degradation kinetics of the linear alkyl benzene sulfonates homologues, 2C₁₀LAS, 2C₁₂LAS and 2C₁₄LAS, have been studied. It has been also investigated the effect of the isomer type on the degradation rate of the LAS molecule through the comparative study of the 2C₁₀LAS and 5C₁₀LAS isomers. Batch anaerobic biodegradation tests were performed using sludge from the anaerobic digester of a wastewater treatment plant as microorganisms source. Ultimate biodegradation was evaluated from the biogas production whereas primary biodegradation was determined by specific analysis of the surfactant. LAS homologues and isomers showed a negligible primary biodegradation under anaerobic conditions. Furthermore, analysis of sulfophenyl carboxilates (SPC) by LC–MS indicated a low and constant level of these LAS degradation metabolites over the test period. These data are consistent with a minimal transformation of the LAS parent molecule in the anaerobic digesters. On the other hand, the addition of the shortest alkyl chain length homologues, decyl and dodecylbenzene sulfonates, reduces the biogas production whereas the most hydrophobic homologue, the tetradecylbenzene sulfonate, enhances the biogas production. This LAS homologue seems to increase the availability of organic compounds sorbed on the anaerobic sludge promoting their biodegradation.     

Comparison of spontaneous antibiotic resistance frequency of Salmonella Typhimurium growth in glucose amended continuous culture at slow and fast dilution rates

The objective of the study was to determine the frequency of spontaneous acquisition of resistance to select antibiotics by Salmonella Typhimurium (ST) when grown in glucose amended continuous flow culture at slow (D = 0.025 h(-1)) or fast (D = 0.27 h(-1)) dilution rates. The bacterium was grown in LB minimal medium (pH 6.25) containing no antibiotics. Upon achieving steady state, samples were plated to tryptic soy agar (TSA) alone or supplemented (per ml) with 2 and 16 microg oxytetracycline, 4 and 16 microg tetracycline, 2 and 64 microg kanamycin, and 0.25 and 2 microg enrofloxacin. Regardless of growth rate, CFU of resistant ST from the TSA containing antibiotics was less than 2 x 10(1) except for 2 microg kanamycin and 0.25 microg enrofloxacin treatments (higher than 1 x 10(9) and 4 x 10(7) CFU of resistant ST for trials 1 and 2, respectively). Frequency of recovering resistant ST from the TSA containing the higher antibiotic concentrations was less than 1 in 10(9) for all antibiotics, but was higher on the media containing 2 microg kanamycin and 0.25 microg enrofloxacin at both slow and fast growth rates. In general, minimal susceptibility differences were detected for isolates from slow and fast dilution rates.     

Copper regulation and homeostasis of Daphnia magna and Pseudokirchneriella subcapitata: influence of acclimation

This study aimed to evaluate (1) the capacity of the green alga Pseudokirchneriella subcapitata and the waterflea Daphnia magna to regulate copper when exposed to environmentally realistic copper concentrations and (2) the influence of multi-generation acclimation to these copper concentrations on copper bioaccumulation and homeostasis. Based on bioconcentration factors, active copper regulation was observed in algae up to 5 microg Cu L(-1) and in daphnids up to 35 mug Cu L(-1). Constant body copper concentrations (13+/-4 microg Cu g DW(-1)) were observed in algae exposed to 1 through 5 microg Cu L(-1) and in daphnids exposed to 1 through 12 microg Cu L(-1). At higher exposure concentrations, there was an increase in internal body copper concentration, while no increase was observed in bioconcentration factors, suggesting the presence of a storage mechanism. At copper concentrations of 100 microg Cu L(-1) (P. subcapitata) and 150 microg Cu L(-1) (D. magna), the significant increases observed in body copper concentrations and in bioconcentration factors may be related to a failure of this regulation mechanism. For both organisms, internal body copper concentrations lower than 13 microg Cu g DW(-1) may result in copper deficiency. For P. subcapitata acclimated to 0.5 and 100 microg Cu L(-1), body copper concentrations ranged (mean+/-standard deviation) between 5+/-2 microg Cu g DW(-1) and 1300+/-197 microg Cu g DW(-1), respectively. For D. magna, this value ranged between 9+/-2 microg Cu g DW(-1) and 175+/-17 microg Cu g DW(-1) for daphnids acclimated to 0.5 and 150 microg Cu L(-1). Multi-generation acclimation to copper concentrations >or =12 microg Cu L(-1) resulted in a decrease (up to 40%) in body copper concentrations for both organisms compared to the body copper concentration of the first generation. It can be concluded that there is an indication that P. subcapitata and D. magna can regulate their whole body copper concentration to maintain copper homeostasis within their optimal copper range and acclimation enhances these mechanisms.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).