Monod kinetics rather than a first-order degradation model explains atrazine fate in soil mini-columns: Implications for pesticide fate modelling

Pesticide transport models commonly assume first-order pesticide degradation kinetics for describing reactive transport in soil. This assumption was assessed in mini-column studies with associated batch degradation tests. Soil mini-columns were irrigated with atrazine in two intermittent steps of about 30 days separated by 161 days application of artificial rain water. Atrazine concentration in the effluent peaked to that of the influent concentration after initial break-through but sharply decreased while influx was sustained, suggesting a degradation lag phase. The same pattern was displayed in the second step but peak height and percentage of atrazine recovered in the effluent were lower. A Monod model with biomass decay was successfully calibrated to this data. The model was successfully evaluated against batch degradation data and mini-column experiments at lower flow rate. The study suggested that first-order degradation models may underestimate risk of pesticide leaching if the pesticide degradation potential needs amplification during degradation.     

Implications of high altitude desert dust transport from Western Sahara to Nile Delta during biomass burning season

The air over major cities and rural regions of the Nile Delta is highly polluted during autumn which is the biomass burning season, locally known as black cloud. Previous studies have attributed the increased pollution levels during the black cloud season to the biomass or open burning of agricultural waste, vehicular, industrial emissions, and secondary aerosols. However, new multi-sensor observations (column and vertical profiles) from satellites, dust transport models and associated meteorology present a different picture of the autumn pollution. Here we show, for the first time, the evidence of long range transport of dust at high altitude (2.5-6 km) from Western Sahara and its deposition over the Nile Delta region unlike current Models. The desert dust is found to be a major contributor to the local air quality which was previously considered to be due to pollution from biomass burning enhanced by the dominant northerly winds coming from Europe.     

Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 2. Formation, bioaccumulation and elimination of hydroxylated metabolites

The uptake, elimination and transformation of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, and then depurated over a five-month period. Methoxylated (MeO-) and hydroxylated (OH-) PBDEs were determined in fish plasma exposed to PBDEs and compared to those obtained in control fish. While all MeO- and some OH- congeners identified in fish plasma were found to originate from non-metabolic sources, several OH- congeners, i.e., OH-tetraBDEs and OH-pentaBDEs, were found to originate from fish metabolism. Among these, 4′-OH-BDE-49 was identified as a BDE-47 metabolite. Congener 4′-OH-BDE-101, identified here for the first time, may be the result of BDE-99 metabolic transformation. Our results unequivocally showed that PBDEs are metabolised in juvenile sole via the formation of OH- metabolites. However, this was not a major biotransformation route compared to biotransformation through debromination.     

Benzyl-penicillin (Penicillin G) transformation in aqueous solution at low temperature under controlled laboratory conditions

Antibiotics are released into the environment in a variety of ways: via wastewater effluent as a result of incomplete metabolism in the body after use in human therapy, as runoff after use in agriculture, through improper disposal by private households or hospitals or through insufficient removal by water treatment plants. Unlike in most European countries, in Arctic regions effluents are not suitably treated prior to their release into the aquatic environment. Also, many of the scattered human settlements in remote regions of the Arctic do not possess sewage treatment facilities and pharmaceutical residues therefore enter the aqueous environment untreated. Only limited data are available on the biodegradation of antibiotics under Arctic conditions. However, such information is needed to estimate the potential harm of antibiotics for the environment. Pen-G is used in this study since it is a widely prescribed antibiotic compound whose environmental properties have not yet been investigated in detail. Thus, for a very first assessment, the OECD approved biodegradation Zahn-Wellens test (ZWT, OECD 302 B) was used to study biodegradation and non-biotic elimination of the antibiotic Benzyl-penicillin (Pen-G) at different temperatures (5°C, 12.5°C and 20°C). The testing period was extended from the OECD standard of 28-42d. In addition to dissolved organic carbon (DOC), Pen-G levels and major transformation products were recorded continuously by LC-ion-trap-MS/MS. DOC monitoring revealed considerable temperature dependence for the degradation process of Pen-G. DOC loss was slowest at 5°C and considerably faster at 12.5°C and 20°C. In the initial step of degradation it was found that Pen-G was hydrolyzed. This hydrolyzed Pen-G was subsequently further degraded by decarboxylation, the result of which was 2-(5,5-dimethyl-1,3-thiazolidin-2-yl)-2-(2-phenylacetamido)acetic acid. Furthermore, direct elimination of 2-phenyl-acetaldehyde from the hydrolyzed and decarboxylated Pen-G also led to the formation of 2-[amino(carboxy)methyl]-5,5-dimethyl-1,3-thiazolidone-4-carboxylic acid. Since biodegradation slows down considerably at a low temperature, the resulting transformation products had considerably longer residence times at 5°C compared to higher temperature conditions within the 42-d experiment. The results presented here clearly demonstrate that a risk assessment for pharmaceuticals present in low ambient temperature environments (i.e. the Arctic) cannot be based on test results obtained under standard laboratory conditions (i.e. 20°C ambient temperatures).     

Nocturnal boundary layer characteristics and land breeze development in Houston,Texas during TexAQS II

The nocturnal boundary layer in Houston, Texas was studied using a high temporal and vertical resolution tethersonde system on four nights during the Texas Air Quality Study II (TexAQS II) in August and September 2006. The launch site was on the University of Houston campus located approximately 4 km from downtown Houston. Of particular interest was the evolution of the nocturnal surface inversion and the wind flows within the boundary layer. The land–sea breeze oscillation in Houston has important implications for air quality as the cycle can impact ozone concentrations through pollutant advection and recirculation. The results showed that a weakly stable surface inversion averaging in depth between 145 and 200 m AGL formed on each of the experiment nights, typically within 2–3 h after sunset. Tethersonde vertical winds were compared with two other Houston data sets (High Resolution Doppler Lidar and radar wind profiler) from locations near the coastline and good agreement was found, albeit with a temporal lag at the tethersonde site. This comparison revealed development of a land breeze on three nights which began near the coastline and propagated inland both horizontally and vertically with time. The vertical temperature structure was significantly modified on one night at the tethersonde site after the land breeze wind shift, exhibiting near-adiabatic profiles below 100 m AGL.     

Variation in biogenic volatile organic compound emission pattern of Fagus sylvatica L. due to aphid infection

Volatile organic compounds (VOCs) have been the focus of interest to understand atmospheric processes and their consequences in formation of ozone or aerosol particles; therefore, VOCs contribute to climate change. In this study, biogenic VOCs (BVOCs) emitted from Fagus sylvatica L. trees were measured in a dynamic enclosure system. In total 18 compounds were identified: 11 monoterpenes (MT), an oxygenated MT, a homoterpene (C₁₄H₁₈), 3 sesquiterpenes (SQT), isoprene and methyl salicylate. The frequency distribution of the compounds was tested to determine a relation with the presence of the aphid Phyllaphis fagi L. It was found that linalool, (E)-β-ocimene, α-farnesene and a homoterpene identified as (E)-4,8-dimethyl-1,3,7-nonatriene (DMNT), were present in significantly more samples when infection was present on the trees. The observed emission spectrum from F. sylvatica L. shifted from MT to linalool, α-farnesene, (E)-β-ocimene and DMNT due to the aphid infection. Sabinene was quantitatively the most prevalent compound in both, non-infected and infected samples. In the presence of aphids α-farnesene and linalool became the second and third most important BVOC emitted. According to our investigation, the emission fingerprint is expected to be more complex than commonly presumed.     

Comparison of land-use regression models between Great Britain and the Netherlands

Land-use regression models have increasingly been applied for air pollution mapping at typically the city level. Though models generally predict spatial variability well, the structure of models differs widely between studies. The observed differences in the models may be due to artefacts of data and methodology or underlying differences in source or dispersion characteristics. If the former, more standardised methods using common data sets could be beneficial. We compared land-use regression models for NO₂ and PM_10, developed with a consistent protocol in Great Britain (GB) and the Netherlands (NL).Models were constructed on the basis of 2001 annual mean concentrations from the national air quality networks. Predictor variables used for modelling related to traffic, population, land use and topography. Four sets of models were developed for each country. First, predictor variables derived from data sets common to both countries were used in a pooled analysis, including an indicator for country and interaction terms between country and the identified predictor variables. Second, the common data sets were used to develop individual baseline models for each country. Third, the country-specific baseline models were applied after calibration in the other country to explore transferability. The fourth model was developed using the best possible predictor variables for each country.A common model for GB and NL explained NO₂ concentrations well (adjusted R² 0.64), with no significant differences in intercept and slopes between the two countries. The country-specific model developed on common variables for NL but not GB improved the prediction.The performance of models based upon common data was only slightly worse than models optimised with local data. Models transferred to the other country performed substantially worse than the country-specific models. In conclusion, care is needed both in transferring models across different study areas, and in developing large inter-regional LUR models.     

Ground-level ozone in the Pearl River Delta region: Analysis of data from a recently established regional air quality monitoring network

The ambient air quality monitoring data of 2006 and 2007 from a recently established Pearl River Delta (PRD) regional air quality monitoring network are analyzed to investigate the characteristics of ground-level ozone in the region. Four sites covering urban, suburban, rural and coastal areas are selected as representatives for detailed analysis in this paper. The results show that there are distinct seasonal and diurnal cycles in ground-level ozone across the PRD region. Low ozone concentrations are generally observed in summer, while high O₃ levels are typically found in autumn. The O₃ diurnal variations in the urban areas are larger than those at the rural sites. The O₃ concentrations showed no statistically significant difference between weekend and weekdays in contrast to the findings in many other urban areas in the world. The average ozone concentrations are lower in urban areas compared to the sites outside urban centers. Back trajectories are used to show the major air-mass transport patterns and to examine the changes in ozone from the respective upwind sites to a site in the center of the PRD (Wanqingsha). The results show higher average ozone concentrations at the upwind sites in the continental and coastal air masses, but higher 1 h-max O₃ concentrations (by 8–16 ppbv) at the center PRD site under each of air-mass category, suggesting that the ozone pollution in the PRD region exhibits both regional and super-regional characteristics.     

The wind speed dependence of the concentrations of airborne particulate matter and NOx

The wind speed dependence of concentrations of PM₁₀, chloride, sulphate, nitrate, organic carbon, elemental carbon, particle number and NO_x has been determined at three separate sites, Marylebone Road (kerbside), North Kensington (urban background) and Harwell (rural). The data are best described by a general dilution term multiplied by up to three separate source-related terms which we interpret as representing long-range transport sources, discrete local (including area) sources and marine sources respectively. Using this approach, the various particulate metrics can be quantitatively disaggregated according to the contributions of the three source types. The behaviour of nitrate is anomalous, probably due to an influence of wind speed upon the dissociation of ammonium nitrate.     

Improved land cover and emission factors for modeling biogenic volatile organic compounds emissions from Hong Kong

This paper describes a study of local biogenic volatile organic compounds (BVOC) emissions from the Hong Kong Special Administrative Region (HKSAR). An improved land cover and emission factor database was developed to estimate Hong Kong emissions using MEGAN, a BVOC emission model developed by Guenther et al. (2006). Field surveys of plant species composition and laboratory measurements of emission factors were combined with other data to improve existing land cover and emission factor data. The BVOC emissions from Hong Kong were calculated for 12 consecutive years from 1995 to 2006. For the year 2006, the total annual BVOC emissions were determined to be 12,400 metric tons or 9.82 × 10⁹ g C (BVOC carbon). Isoprene emission accounts for 72%, monoterpene emissions account for 8%, and other VOCs emissions account for the remaining 20%. As expected, seasonal variation results in a higher emission in the summer and a lower emission in the winter, with emission predominantly in day time. A high emission of isoprene occurs for regions, such as Lowest Forest-NT North, dominated by broadleaf trees. The spatial variation of total BVOC is similar to the isoprene spatial variation due to its high contribution. The year to year variability in emissions due to weather was small over the twelve-year period (?1.4%, 2006 to 1995 trendline), but an increasing trend in the annual variation due to an increase in forest land cover can be observed (+7%, 2006 to 1995 trendline). The results of this study demonstrate the importance of accurate land cover inputs for biogenic emission models and indicate that land cover change should be considered for these models.