Influence of plants on the chemical extractability and biodegradability of 2,4-dichlorophenol in soil

This study investigated the fate and behaviour of [UL-(14)C] 2,4-dichlorophenol (DCP) in planted (Lolium perenne L.) and unplanted soils over 57 days. Extractability of [UL-(14)C] 2,4-DCP associated activity was measured using calcium chloride (CaCl(2)), acetonitrile-water and dichloromethane (DCM) extractions. Biodegradability of [UL-(14)C] 2,4-DCP associated activity was assessed through measurement of (14)CO(2) production by a degrader inoculum (Burkholderia sp.). Although extractability and mineralisation of [UL-(14)C] 2,4-DCP associated activity decreased significantly in both planted and unplanted soils, plants appeared to enhance the sequestration process. After 57 days, in unplanted soil, 27% of the remaining [UL-(14)C] 2,4-DCP associated activity was mineralised by Burkholderia sp., and 13%, 48%, and 38% of (14)C-activity were extracted by CaCl(2), acetonitrile-water and DCM, respectively. However, after 57 days, in planted soils, only 10% of the [UL-(14)C] 2,4-DCP associated activity was available for mineralisation, whilst extractability was reduced to 2% by CaCl(2), 17% by acetonitrile-water and 11% by DCM. This may be due to the effect of plants on soil moisture conditions, which leads to modification of the soil structure and trapping of the compound. However, the influence of plants on soil biological and chemical properties may also play a role in the ageing process.     

Determination of toxic cyclic heptapeptides by liquid chromatography with detection using ultra-violet, protein phosphatase assay and tandem mass spectrometry

Microcystins, toxic cyclic heptapeptides and nodularin-R, a toxic cyclic pentapeptide, were determined using liquid chromatography (LC) with detection using photo-diode array ultra-violet (PDA-UV) and protein phosphatase (PP) assay. Positive fractions were analysed for toxins using collision-induced dissociation (CID) and tandem MS/MS experiments which were carried out simultaneously using electrospray ion-trap instrumentation. Reversed-phase liquid chromatography (LC) using an acetonitrile/water gradient was used for the LC-MS(2) determination of six microcystins standards and nodularin. The molecular related ion species, [M+H](+)([M+2H](2+) in the case of MC-RR), were used as the precursor ions for MS(2) experiments. Optimum calibration and reproducibility data were obtained for MC-LR using LC-MS(2); 0.1-5.0 microg/ml, r2 = 0.992 (n = 3); % RSD < or =7.3 at 0.25 microg MC-LR/ml (n = 3). The detection limit (S/N = 3) was better than 0.1 ng. Water samples for microcystin analysis were first screened using protein phosphatase (PP) assays and positives were concentrated using C-18 solid-phase extraction. The developed method was applied to examine a lake in Ireland contaminated by Microcystis sp. and MC-LR and MC-LA were identified.     

Semicontinuous PM2.5 sulfate and nitrate measurements at an urban and a rural location in New York: PMTACS-NY summer 2001 and 2002 campaigns

Several collocated semicontinuous instruments measuring particulate matter with particle sizes < or =2.5 microm (PM2.5) sulfate (SO4(2-)) and nitrate (NO3-) were intercompared during two intensive field campaigns as part of the PM2.5 Technology Assessment and Characterization Study. The summer 2001 urban campaign in Queens, NY, and the summer 2002 rural campaign in upstate New York (Whiteface Mountain) hosted an operation of an Aerosol Mass Spectrometer, Ambient Particulate Sulfate and Nitrate Monitors, a Continuous Ambient Sulfate Monitor, and a Particle-Into-Liquid Sampler with Ion Chromatographs (PILS-IC). These instruments provided near real-time particulate SO4(2-) and NO3- mass concentration data, allowing the study of particulate SO4(2-)/NO3- diurnal patterns and detection of short-term events. Typical particulate SO4(2-) concentrations were comparable at both sites (ranging from 0 to 20 microg/m3), while ambient urban particulate NO3- concentrations ranged from 0 to 11 microg/m3 and rural NO3- concentration was typically less than 1 microg/m3. Results of the intercomparisons of the semicontinuous measurements are presented, as are results of the comparisons between the semicontinuous and time-integrated filter-based measurements. The comparisons at both sites, in most cases, indicated similar performance characteristics. In addition, charge balance calculations, based on major soluble ionic components of atmospheric aerosol from the PILS-IC and the filter measurements, indicated slightly acidic aerosol at both locations.     

Performance of anaerobic waste activated sludge digesters after microwave pretreatment.

Effects of microwave pretreatment on waste activated sludge (WAS) in mesophilic semicontinuous digesters with acclimatized inoculum at solids retention times (SRTs) of 5, 10, and 20 days are presented. Batch digesters determined optimum microwave temperature, intensity, WAS concentration, and percentage of WAS pretreated for highest WAS solubilization (soluble to total chemical oxygen demand ratio [SCOD:TCOD]) and biogas production. Pretreatment results indicated the potential to damage floc structure and release 4.2-, 4.5-, and 3.6-fold higher soluble proteins, sugars, and SCOD:TCODs compared with controls, with nucleic acid release. Pretreatment increased dewaterability and bioavailability of WAS with 20% higher biogas production compared with controls in batch digestion. In semicontinuous digesters, relative (to control) improvements in removals dramatically increased, as SRT was shortened from 20 to 10 to 5 days, with 23 and 26% higher volatile solids removals for WAS pretreated to 96 degrees C by microwave and conventional heating at a 5-day SRT.     

Contribution of vehicle emissions from an attached garage to residential indoor air pollution levels

The infiltration of vehicle emissions into a house from the attached garage was studied for 16 homes of differing designs using the same extensively characterized vehicle at each home. Before the in-home measurement program, the cold-start and hot-start tailpipe emissions and hot-soak evaporative emissions from a 1993 Buick Regal were measured using standard vehicle emissions measurement methods. The emissions were chemically characterized for methane, nonmethane hydrocarbons (NMHC), and carbonyl compounds. The in-home measurements occurred over two winter seasons (1997-1998 and 1998-1999) in Ottawa, Ontario, Canada. Samples of indoor air and garage atmosphere were characterized for carbon monoxide, carbon dioxide, methane, NMHC, and carbonyl compounds. During the second year, real-time measurements of carbon, carbon dioxide, and total hydrocarbons were made to determine when and for how long the emissions plume infiltrates the house. Chemical mass balance modeling results using 31 NMHC species suggest that between 9 and 71% of the concentrations measured in the house during the hot-soak test and between 13 and 85% of the concentrations measured in the house during the cold-start test could be attributed to vehicle emissions infiltrating from the garage. In contrast, increases in carbonyl compound concentrations caused by the vehicle were difficult to detect above the already significant levels found in the houses.     

Modelling the atmospheric fate and seasonality of polycyclic aromatic hydrocarbons in the UK

This paper presents the results from an exercise in atmospheric contaminant fate modelling, which had three main objectives: (1) to investigate the balance between estimated national atmospheric emissions of six selected PAHs and observed ambient measurements for the UK, as a means of testing the current emission estimates; (2) to investigate the potential influence of seasonally dependent environmental fate processes on the observed seasonality of air concentrations; and (3) after undertaking the first two objectives, to make inferences about the likely magnitude of seasonal differences in sources. When addressing objective 1 with annually averaged emissions data, it appeared that the UK PAH atmospheric emissions inventory was reasonably reliable for fluorene, fluoranthene, pyrene, benzo[a]pyrene and benzo[ghi]perylene--but not so for phenanthrene. However, more detailed analysis of the seasonality in environmental processes which may influence ambient levels, showed that the directions and/or magnitudes of the predicted seasonality did not coincide with field observations. This indicates either that our understanding of the environmental fate and behaviour of PAHs is still limited, and/or that there are uncertainties in the emissions inventories. It is suggested that better quantification of PAH sources is needed. For 3- and 4-ringed compounds, this should focus on those sources which increase with temperature, such as volatilisation from soil, water, vegetation and urban surfaces, and possible microbially-mediated formation mechanisms. The study also suggests that the contributions of inefficient, diffusive combustion processes (e.g. domestic coal/wood burning) may be underestimated as a source of the toxicologically significant higher molecular weight species in the winter. It is concluded that many signatory countries to the UNECE POPs protocol (which requires them to reduce national PAH emissions to 1990 levels) will experience difficulties in demonstrating compliance, because source inventories for 1990 and contemporary situations are clearly subject to major uncertainties.     

Soil functional responses to excess nitrogen inputs at global scale

There is little evidence that nitrogen (N) cycling in the highly weathered, low-phosphorus (P), acidic soils found in Southern Hemisphere continents will differ greatly from that in North America and Europe. Evidence from the 'south' shows: the similarity in forms and temporal patterns in losses of N from different land uses; that the C:N ratios of the forest floor/litter layer from different continents are strongly predictive of a range of processes on a global scale; that generalizations based on Northern Hemisphere experience of the impact of N additions to 'P-limited' ecosystems are likely to fail for southern ecosystems where anatomical and physiological adaptation of native plants to low-P soils makes questionable the concept of 'P-limitation'; that the greatest threats in the 'south' are probably changes in land use that may greatly increase N inputs and turnover; that localized increases in N inputs produce similar effects to those seen in the 'north'.     

Genetic effects of air pollution on forest tree species of the Carpathian Mountains

The effects of air pollution on the genetic structure of Norway spruce, European silver fir and European beech were studied at four polluted sites in Slovakia, Romania and Czech Republic. In order to reduce potential effects of site heterogeneity on the health condition, pair-wise sampling of pollution-tolerant and sensitive trees was applied. Genotypes of sampled trees were determined at 21 isozyme gene loci of spruce, 18 loci of fir and 15 loci of beech. In comparison with Norway spruce, fewer genetic differences were revealed in beech and almost no differentiation between pollution-tolerant and sensitive trees was observed in fir. In adult stands of Norway spruce, sensitive trees exhibited higher genetic multiplicity and diversity. The decline of pollution-sensitive trees may result thus in a gradual genetic depletion of pollution-exposed populations of Norway spruce through the loss of less frequent alleles with potential adaptive significance to altered stressing regimes in the future. Comparison of the subsets of sensitive and tolerant Norway spruce individuals as determined by presence or absence of discolorations ("spruce yellowing") revealed different heterozygosity at 3 out of 11 polymorphic loci.     

Spatial distribution of atmospheric PAHs and PCNs along a north-south Atlantic transect

Ship-board air samples collected between The Netherlands and South Africa in January-February 2001 were analysed for polycyclic aromatic hydrocarbons (PAHs) and polychlorinated naphthalenes (PCNs). The highest PAH concentrations occurred in the European samples, and in samples close to West Africa and South Africa. Consistently low PAH concentrations were measured in the southern hemisphere open ocean samples (190-680 pg/m3). The highest PCN concentrations occurred in the European samples, but high values were also detected off the West African coast, and in the sample taken closest to South Africa. Data are presented for diurnal cycles taken in the remote South Atlantic. The day:night ratios of phenanthrene, 1-methylphenanthrene and fluoranthene were typically approximately 1.5-2.5:1. The mechanism(s) causing this observation is/are not understood at present, but dynamic environmental process(es) is/are implicated.     

An operational assessment of the application of the relative reduction factors in the demonstration of attainment of the 8-hr ozone National Ambient Air Quality Standard

The U.S. Environmental Protection Agency in 1997 revised the 1-hr ozone (O3) National Ambient Air Quality Standard (NAAQS) to one based on an 8-hr average, resulting in potential nonattainment status for substantial portions of the eastern United States. The regulatory process provides for the development of a state implementation plan that includes a demonstration that the projected future O3 concentrations will be at or below the NAAQS based on photochemical modeling and analytical techniques. In this study, four photochemical modeling systems, based on two photochemical models, Community Model for Air Quality and the Comprehensive Air Quality Model with extensions, and two emissions processing models, Sparse Matrix Optimization Kernel for Emissions and Emissions Modeling System, were applied to the eastern United States, with emphasis on the northeastern Ozone Transport Region in terms of their response to oxides of nitrogen and volatile organic carbon-focused controls on the estimated design values. With the 8-hr O3 NAAQS set as a bright-line test, it was found that a given area could be termed as being in or out of attainment of the NAAQS depending upon the modeling system. This suggests the need to provide an estimate of model-to-model uncertainty in the relative reduction factor (RRF) for a better understanding of the uncertainty in projecting the status of an area's attainment. Results indicate that the model-to-model differences considered in this study introduce