The Henry's law coefficient of 2-nitrophenol over the temperature range 278-303 K

Although 2-nitrophenol has been identified as an important environmental chemical there is scarcity in the literature regarding the temperature dependence of its Henry's law coefficient, H. Here a bubble purge method was used to measure H for 2-nitrophenol over the temperature range 278-303 K. A novel approach in the data treatment allowed correction of the data for non-equilibrium partitioning in the apparatus to obtain the true equilibrium H value. The experimentally derived temperature-dependent expression for H of 2-nitrophenol is lnH (M atm(-1)) = (6290/T (K)) - 16.6. The standard enthalpy and entropy of gas-to-liquid transfer for 2-nitrophenol in aqueous solution are -52.3 +/- 8.1 kJ mol(-1) and -138 +/- 28 J mol(-1) K(-1), respectively. (Errors are 95% confidence intervals.)     

Metals in sediments and the edible cockle Cerastoderma edule from two Moroccan Atlantic lagoons: Moulay Bou Selham and Sidi Moussa.

Metals (Cd, Cu, Pb and Zn) were determined over a 3-year period in sediments and bivales Cerastoderma edule from two lagoon ecosystems on the Moroccan Atlantic coastline, Moulay Bou Selham and Sidi Moussa. Sediment metal concentrations were seasonally influenced, and were highest, generally, in winter--possibly signifying an increased contribution from run-off from adjacent arable land and roads. Neither site can be considered highly contaminated; however, Cd was enriched at Sidi Moussa, probably as a result of waste discharge from phosphate industries 20 km along the coast to the northeast. This ability to act as a sink for metals at distance from sources demonstrates the need for surveillance in these sensitive environments. Copper and Zn concentrations in edible cockles C. edule appear to be regulated over the concentration ranges currently found in lagoon sediments. In contrast, body burdens of Pb and, to a lesser extent Cd, reflect sediment levels and might be useful in future risk assessments. Metal concentrations Cerastoderma edule are seasonally related to the reproductive cycle, however, and sample timing will need to be standardised in future monitoring exercises.     

Microcosm studies of microbial degradation in a coal tar distillate plume

Investigation of a groundwater plume containing up to 24 g l(-1) phenolic compounds suggested that over a period of nearly 50 years, little degradation had occurred despite the presence of a microbial community and electron acceptors within the core of the plume. In order to study the effect of contaminant concentration on degradation behaviour, laboratory microcosm experiments were performed under aerobic and anaerobic conditions at four different concentrations obtained by diluting contaminated with uncontaminated groundwater. The microcosms contained groundwater with total phenols at ca. 200, 250, 660 and 5000 mg l(-1), and aquifer sediment that had been acclimatised within the plume for several months. The microcosms were operated for a period of 390-400 days along with sterile controls to ascertain whether degradation was microbially mediated or abiotic. Under aerobic conditions, degradation only occurred at concentrations up to 660 mg l(-1) total phenols. At phenol concentrations below 250 mg l(-1) a benzoquinone intermediate, thought to originate from the degradation of 2,5-dimethylphenol, was isolated and identified. This suggested an unusual degradative pathway for this compound; its aerobic degradation more commonly proceeding via catecholic intermediates. Under anaerobic conditions, degradation only occurred in the most dilute microcosm (total phenols 195 mg l(-1)) with a loss of p-cresol accompanied by a nonstoichiometric decrease in nitrate and sulphate. By inference, iron(III) from the sediment may also have been used as a terminal electron acceptor, in which case the amount of biologically available iron released was calculated as 1.07 mg Fe(III)/g of sediment. The study shows that natural attenuation is likely to be stimulated by dilution of the plume.     

Economic comparison of emission control systems for glass manufacturing furnaces with heat recovery

Glass manufacturing, like other process industries, is faced with air pollution compliance problems due to ever stricter emission limits. Several waste gas cleaning equipment options are available for air pollution control (APC) in glass plants, the most common arrangements being based on electrostatic precipitator (ESP) or fabric filter (FF) dust collectors and semi-wet or dry processes for acid gas removal. However, several counteracting aspects affect the choice of gas cleaning technologies, which are confirmed by the discrepancies encountered in actual suppliers' bids. In this paper, the main pollution control options are analyzed by carrying out a critical comparison under the cost-effectiveness point of view to select the lowest cost arrangement considering capital investment, operating expenses, and energy-saving revenues from heat recovery processes. The analysis is carried out with reference to a case study involving actual float glass production lines at Pilkington plants in Italy.     

Long-range transport and re-circulation of pollutants in the western Mediterranean during the project Regional Cycles of Air Pollution in the West-Central Mediterranean Area

During the warm season (March–September), high ozone concentrations have been reported at the coastal and mountain monitoring stations of the eastern Iberia coast (Millán et al., J. Geophys. Res. 102 (D7) 8811, J. Appl. Meteorol. 4 (2000) 487). The vegetation protection threshold of current Directive 92/72/EEC and the World Health Organisation guideline for the protection of crops and semi-natural vegetation are systematically exceeded during the whole period. The main objective of the present study is to search for the origin of these chronic pollution levels: to search for the reason(s) for such high O₃ concentrations during such a long period. A mesoscale model is used to reproduce the diurnal cycle of winds and stability/layering over the Western Mediterranean Basin (WMB), at a sufficient space/temporal resolution, under a typical recursive synoptic condition during the warm season: data from the flight tracks of the European Project—Regional Cycles of Air Pollution in the West-Central Mediterranean Area—are used to substantiate the model results. Times of residence and the final distribution of pollutants entering the WMB are estimated using single-particle Lagrangian trajectories and a multiple-particle dispersion model. Our results show that the marine boundary layer and the lower troposphere in the region between the Balearic Islands and eastern Iberia are subject to a flow regime that tends to accumulate pollutants within large circulations, covering the entire western basin. We have also shown a diurnal pulsation of the Tramontana/Mistral wind regime, which can transport new pollutants into the area (background concentrations of 50–65 ppb of O₃ of continental European origin) that are added to local emissions and re-circulated within the coastal breezes at eastern Iberia for periods of more than five days. Local emissions and wind configuration contribute to increase the O₃ concentrations up to 100 ppb and even more.     

Resistant sorption of in situ chlorobenzenes and a polychlorinated biphenyl in river Rhine suspended matter

The desorption kinetics of in situ chlorobenzenes (dichlorobenzenes, pentachlorobenzene and hexachlorobenzene) and 2,4,4^′-trichlorobiphenyl (PCB-28) were measured with a gas-purge technique for river Rhine suspended matter sampled in Lobith, The Netherlands. This suspended matter is the main source of sediment accumulation in lake Ketelmeer. In lake Ketelmeer sediment earlier observations showed that slow and very slow fractions dominate the desorption profile.

For the river Rhine suspended matter, only for PCB-28 a fast desorbing fraction of around 1.6% could be detected. The observed rate constants were on the average 0.2 h⁻¹ for fast desorption, 0.004 h⁻¹ for slow desorption, and 0.00022 h⁻¹ for very slow desorption. These values are in agreement with previous findings for the sediment from lake Ketelmeer and with available literature data on fast, slow, and very slow desorption kinetics.

The results from this study show the similarity of desorption profiles between river Rhine suspended matter, and the top layer sediment from lake Ketelmeer. This indicates that slow and very slow fractions are already present in material forming the top layer of lake Ketelmeer, and were not formed after deposition of this material in the lake. The absence of detectable fast fractions for most compounds could be caused by the absence of recent pollution of the suspended matter. But, the observations may also be explained by a rapid disappearance of compounds from the fast fraction due to a combination of a high affinity of very slow sites for these compounds, and their relatively high volatility.     

Baseline levels of PCDD/Fs in soil and herbage samples collected in the vicinity of a new hazardous waste incinerator in Catalonia,Spain

The construction in Constantí (Catalonia, Spain) of a new hazardous waste incinerator (HWI), which is the first one in Spain, finished in 1999. In order to determine the temporal variation (1996–1998) in the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the vicinity of the new HWI, 40 soil and 40 herbage samples were collected (1998) at the same sampling points in which samples had been taken two years before (1996). Each sample was analyzed for PCDDs and PCDFs by high resolution gas chromatography/high resolution mass spectrometry. In the 1996 survey, PCDD/F concentrations in soils ranged from 0.13 to 24.20 ng I-TEQ/kg (d.m.), with median and mean values of 0.67 and 1.68 ng I-TEQ/kg (d.m.), respectively. In the present study, PCDD/F concentrations ranged from 0.12 to 17.20 ng I-TEQ/kg (d.m.), with a median value of 0.75 ng I-TEQ/kg (d.m.) and a mean value of 1.59 ng I-TEQ/kg (d.m.). In turn, in the present study PCDD/F concentrations in vegetation ranged from 0.14 to 2.01 ng I-TEQ/kg (d.m.) (median and mean values: 0.23 and 0.31 ng I-TEQ/kg, respectively), while in the 1996 survey PCDD/F concentrations ranged from 0.24 to 1.22 ng I-TEQ/kg (d.m.) (median and mean values: 0.53 and 0.61 ng I-TEQ/kg, respectively). According to the present (1998) and the previous (1996) levels of PCDD/Fs found in soils and vegetation, the area under potential influence of the new facility shows a rather low contamination by these compounds. The current results should be useful to establish the environmental impact of the HWI.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Application of the Microtox test and pollution indices to the study of water toxicity in the Albufera Natural Park (Valencia, Spain)

The toxic effects of waters collected from irrigation channels in a Mediterranean wetland (Albufera Natural Park, Valencia, Spain) were tested with the Microtox assay and compared with six pollution indices (PIs) defined from analytical parameters. Chemical oxygen demand (COD), biological oxygen demand (BOD), nutrients, heavy metals and pesticides were measured. The bioassay result (concentrations of the water sample (% V/V) that reduced light emission to 10%, 20% and 50%, EC10, EC20 and EC50, respectively (ECs)) was compared with the PIs. This comparison has demonstrated a general agreement between ECs and PIs, except in the case of irrigation channels affected by herbicides used in rice farming (molinate and thiobencarb). No pronounced inhibition was detected in the bioluminescence in relation to the eutrophic parameters in the irrigation waters for EC50 values, indicating that this parameter does not suffice to detect eutrophic waters. Data derived from irrigation water pollution and bioassay were assembled by multivariate statistical techniques (principal component analysis). These components were associated with various contamination sources.     

Contaminant residues in seabird eggs from the Canadian Arctic. II. Spatial trends and evidence from stable isotopes for intercolony differences

Eggs of glaucous gulls (Larus hyperboreus), black-legged kittiwakes (Rissa tridactyla), thick-billed murres (Uria lomvia) and black guillemots (Cepphus grylle) were collected from several sites throughout the Canadian Arctic. Samples were analyzed for organochlorines as well as mercury and selenium. Glaucous gulls breeding at sites in the High Arctic showed higher levels of organochlorine contamination than those in the western Low Arctic. This was likely due to dietary differences among colonies as suggested by stable isotope data, although different overwintering areas may also play a role. Levels of sigmaPCB, sigmaDDT, sigmaCHLOR, sigmaCBz and dieldrin were significantly lower in thick-billed murres from Prince Leopold Island in the High Arctic compared with colonies in the eastcrn Low Arctic. This difference was likely due to the combined effects of different atmospheric deposition patterns in the High and Low Arctic and different overwintering areas since murres from Prince Leopold Island may winter farther north than murres from the other colonies sampled. Eggs from colonies at higher latitudes generally contained higher concentrations of mercury. The trophic and dietary differences/similarities suggested by stable-nitrogen and carbon isotope data in this study were useful in explaining the spatial patterns of contaminant concentrations observed among colonies of seabirds such as the glaucous gull and the black-legged kittiwake where variation in latitudinal atmospheric deposition patterns and different overwintering grounds did not appear to be confounding factors.