Pesticide modelling for a small catchment using SWAT-2000

Pesticides in stream flow from the 142 ha Colworth catchment in Bedfordshire, UK were monitored from October 1999 to December 2000. About 47% of the catchment is tile-drained and different pesticides and cropping patterns have recently been evaluated in terms of their effect on nutrient and pesticide losses to the stream. The data from Colworth were used to test soil and water assessment tool (SWAT) 2000 predictions of pesticide concentrations at the catchment outlet. A sound model set-up to carry out pesticide modelling was created by means of hydrological modelling with proper simulation of crop growth and evapotranspiration. The pesticides terbuthylazine, terbutryn, cyanazine and bentazone were modelled. There was close agreement between SWAT-predicted pesticide concentration values and observations. Scenario trials were conducted to explore management options for reducing pesticide loads arriving at the catchment outlet. The results obtained indicate that SWAT can be used as a tool to understand pesticide behavior at the catchment scale.     

Climate variability, vulnerability, and coping mechanism in Alaknanda catchment, Central Himalaya, India

A study was carried out to discover trends in the rainfall and temperature pattern of the Alaknanda catchment in the Central Himalaya. Data on the annual rainfall, monsoon rainfall for the last decade, and average annual temperatures over the last few decades were analyzed. Nonparametric methods (Mann-Kendall and Sen's method) were employed to identify trends. The Mann-Kendall test shows a decline in rainfall and rise in temperature, and these trends were found to be statistically significant at the 95% confidence level for both transects. Sen's method also confirms this trend. This aspect has to be considered seriously for the simple reason that if the same trend continues in the future, more chances of drought are expected. The impact of climate change has been well perceived by the people of the catchment, and a coping mechanism has been developed at the local level.     

Spatial variability of throughfall fluxes in a spruce forest

The spatial variability of throughfall deposition of H(+), Ca(2+), Mg(2+), Na(+), K(+), Cl(-), NO(3)(-), NH(4)(+), O(4)(2-) to a Norway spruce (Picea abies (L.) Karst.) forest was intensively examined during the period October 1986 to October 1987. Large systematic spatial variability of the atmospheric deposition within the forest was observed. The flux of throughfall water was higher away from the trunk compared to the flux close to the trunk. In contrast to this, the deposition of all substances was considerably higher close to the trunk compared to the deposition at the periphery of the canopy. A linear decrease in deposition as a function of the distance from the nearest tree trunk was found. Further, the deposition varied quite dramatically between trees according to their size. The observed spatial variability in throughfall may be due to variabilities in the processes taking part in altering the distribution and composition of the precipitated water as it moves through the canopy. The influence of these processes of precipitation, wash-off, dry deposition and canopy exchange is discussed, and it is found that both increased dry deposition and canopy exchange in the tree tops contribute to the higher solute fluxes found close to the tree trunk.     

典型污染场地中滴滴涕浓度空间变异性研究

利用经典统计学和地统计学相结合的方法,以某滴滴涕(DDT)粉剂生产企业为例,对污染场地中表层和地下5m处土样DDT浓度的空间变异性进行了研究。结果表明:表层和地下5m处土样DDT浓度经过对数转化后均通过了柯尔莫哥洛夫-斯蜜诺夫检验(K-S检验),能够很好地服从正态分布;表层和地下5m处土样DDT浓度的半变异函数拟合符合高斯模型,决定系数分别为0.8973和0.9348,由空间自相关引起的空间变异性分别占系统总变异性的99.11%和83.12%;用克里格插值法制出的DDT浓度等值线图能直观地反映表层和地下5m处土样DDT浓度的空间分布特征,DDT浓度呈现以原粉生产车间为中心向四周扩散的趋势,地下5m处土样DDT浓度空间分布与表层基本一致。     

Pesticide concentrations in agricultural storm drainage inlets of a small Swiss catchment

Agricultural pesticides transported to surface waters pose a major risk for aquatic ecosystems. Modelling studies indicate that the inlets of agricultural storm drainage systems can considerably increase the connectivity of surface runoff and pesticides to surface waters. These model results have however not yet been validated with field measurements. In this study, we measured discharge and concentrations of 51 pesticides in four out of 158 storm drainage inlets of a small Swiss agricultural catchment (2.8 km²) and in the receiving stream. For this, we performed an event-triggered sampling during 19 rain events and collected plot-specific pesticide application data. Our results show that agricultural storm drainage inlets strongly influence surface runoff and pesticide transport in the study catchment. The concentrations of single pesticides in inlets amounted up to 62 µg/L. During some rain events, transport through single inlets caused more than 10% of the stream load of certain pesticides. An extrapolation to the entire catchment suggests that during selected events on average 30 to 70% of the load in the stream was transported through inlets. Pesticide applications on fields with surface runoff or spray drift potential to inlets led to increased concentrations in the corresponding inlets. Overall, this study corroborates the relevance of such inlets for pesticide transport by establishing a connectivity between fields and surface waters, and by their potential to deliver substantial pesticide loads to surface waters.

     

Climate change impacts on the leaching of a heavy metal contamination in a small lowland catchment

The Keersop catchment (43km(2)) in the south of The Netherlands has been contaminated by the emissions of four zinc ore smelters. The objective of this study was to assess the effects of future projected climate change on the hydrology and the leaching of heavy metals (i.e. Cd and Zn) in the catchment. The numerical, quasi-2D, unsaturated zone Soil Water Atmosphere Plant model was used with 100-year simulated daily time series of precipitation and potential evapotranspiration. The time series are representative of stationary climates for the periods 1961-1990 ("baseline") and 2071-2100 ("future"). The time series of future climate were obtained by downscaling the results of eight regional climate model (RCM) experiments, driven by the SRES A2 emissions scenario, using change factors for a series of climate statistics and applying them to stochastic weather generator models. The time series are characterized by increased precipitation in winter, less precipitation in summer, and higher air temperatures (between 2°C and 5°C) throughout the year. Future climate scenarios project higher evapotranspiration rates, more irrigation, less drainage, lower discharge rates and lower groundwater levels, due to increased evapotranspiration and a slowing down of the groundwater system. As a result, lower concentrations of Cd and Zn in surface water are projected. The reduced leaching of heavy metals, due to drying of the catchment, showed a positive impact on a limited aspect of surface water quality.     

Quantitative chemical composition and characteristics of aerosols over western India: One-year record of temporal variability

One-year quantitative chemical data set consisting of water-soluble constituents (NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl^?, NO₃^?, SO₄^2? and HCO₃^?), crustal and trace elements (Al, Fe, Ca, Mg, K, Mn, Zn, Pb) and carbonaceous species (OC, EC) in ambient aerosols, collected over an urban site located in a high-dust semi-arid region of western India, reveals excellent linear relationship (r² = 0.92; slope = 0.96 ± 0.05) between gravimetrically assessed TSP (total suspended particulates) and chemically analyzed aerosol mass. The TSP abundance ranging from 60 to 250 μg m^?3, over a period of 12 months (January–December), is dominated by mineral dust (～70%); whereas contribution from sea-salts, anthropogenic and carbonaceous species exhibits significant temporal variability depending upon the wind regimes. The mineral dust is enriched in Ca, Mg and Fe with respect to upper continental crust (UCC); whereas Zn and Pb exhibit a characteristic anthropogenic source and high enrichment factors. The carbonaceous species show significant seasonality; with dominance of OC (range: 4.6–28 μg m^?3; average: 12.8 μg m^?3; SD: 6.8) and minor contribution from EC (range: 0.3–4.4 μg m^?3; average: 2.4 μg m^?3; SD: 1.4). The observed concentrations are significantly lower than those reported for the metro cities in South Asia but the OC/EC ratios (range: 4.3–35; average: 8.3; SD: 5.7) are significantly higher than the characteristic ratio (～2–4) reported for the urban atmosphere. Such quantitative chemical characterization of aerosols is essential in assessing their role in atmospheric chemistry and climate change. This study could also be useful in understanding the physical and optical aerosol properties documented from the same site and thus, in validating regional climate models.     

Spatial variability in the degradation rate of isoproturon in soil

Thirty samples of soil were taken at 50-m intersections on a grid pattern over an area of 250 x 200 m within a single field with nominally uniform soil characteristics. Incubations of isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) under standard conditions (15 degrees C; -33 kPa soil water potential) indicated considerable variation in degradation rate of the herbicide, with the time to 50% loss (DT50) varying from 6.5 to 30 days. The kinetics of degradation also varied between the sub-samples of soil. In many of them, there was an exponential decline in isoproturon residues; in others, exponential loss was followed by more rapid rates of decline; in a few soil samples, rapid rates of loss began shortly after the start of the incubations. In more detailed studies with soils from a smaller number of sub-sites (20), measurements were again made of isoproturon degradation rate, and the soils were analysed for organic matter content, pH, and nutrient status (N, P, K). Measurements were also made of isoproturon adsorption by the soils and of soil microbial biomass. Patterns of microbial metabolism were assessed using 95 substrates in Biolog GN plates. Soils showing rapid biodegradation were generally of higher pH and contained more available potassium than those showing slower degradation rates. They also had a larger microbial biomass and greater microbial metabolic diversity as determined by substrate utilisation on Biolog GN plates. The implications of the results for the efficacy and environmental behaviour of isoproturon are discussed.     

Spatial variability of ammonium and nitrate in soils near a poultry farm

This paper assesses the distribution of ammonium (NH4+) and nitrate (NO3-) nitrogen deposition in native bushland soil adjacent to an open ventilated poultry farm. The farm is located in Thirlmere 150 km south west of Sydney, Australia. A total of 104 geographically referenced soil cores were obtained from the study area. Soil pH, electrical conductivity (EC), NH4(+) - and NO3(-)-nitrogen concentrations were analysed for variable trends at three depths, i.e. 0-30, 30-60, and 60-90 cm. Significantly higher concentrations of the two nitrogen forms and EC were observed nearer to the farm in the surface soil samples (0-30 cm). The distribution of NH4+, NO3- and EC were all correlated in surface samples throughout the study area. There was no indication of NH4+ and NO3- leaching within soil profile sampled and it appears that weeds and native vegetation had utilised the accumulated nitrogen. The level of N deposition adjacent to the poultry farm decreased downwind due to dispersion of plume and to the buffering effects from the bushland.     

Spatial variability of sediment ecotoxicity in a large storm water detention basin

Detention basins are valuable facilities for urban storm water management, from both the standpoint of flood control and the trapping of pollutants. Studies performed on storm water have shown that suspended solids often constitute the main vector of pollutants (heavy metals, polycyclic aromatic hydrocarbon (PAH), etc.). In order to characterise the ecotoxicity of urban sediments from storm water detention basins, the sediments accumulated over a 6-year period were sampled at five different points through the surface of a large detention basin localised in the east of Lyon, France. A specific ecotoxicological test battery was implemented on the solid phase (raw sediment) and the liquid phase (interstitial water of sediments). The results of the study validated the method formulated for the ecotoxicological characterization of urban sediments. They show that the ecotoxicological effect of the sediments over the basin is heterogeneous and greater in areas often flooded. They also show the relationship between, on one hand, the physical and chemical characteristics of the sediments and, on the other hand, their ecotoxicity. Lastly, they contribute to a better understanding of the dynamics of the pollution close to the bottom of detention basins, which can be useful for improving their design. The results of this research raise particularly the issue of using oil separators on the surface of detention basins.     

Assessing pesticide concentrations and fluxes in the stream of a small vineyard catchment - Effect of sampling frequency

This study reports on the occurrence and behaviour of six pesticides and one metabolite in a small stream draining a vineyard catchment. Base flow and flood events were monitored in order to assess the variability of pesticide concentrations according to the season and to evaluate the role of sampling frequency on the evaluation of fluxes estimates. Results showed that dissolved pesticide concentrations displayed a strong temporal and spatial variability. A large mobilisation of pesticides was observed during floods, with total dissolved pesticide fluxes per event ranging from 5.7 × 10⁻³ g/Ha to 0.34 g/Ha. These results highlight the major role of floods in the transport of pesticides in this small stream which contributed to more than 89% of the total load of diuron during August 2007. The evaluation of pesticide loads using different sampling strategies and method calculation, showed that grab sampling largely underestimated pesticide concentrations and fluxes transiting through the stream.     

Natural and pre-treatments induced variability in the chemical composition and morphology of lichens and mosses selected for active monitoring of airborne elements

To enhance the reliability of the moss and lichen transplant technique for active biomonitoring of trace metals in urban environments, we evaluated the natural variability in the chemical composition of the (epilithic and epiphytic) moss Hypnum cupressiforme and the epiphytic lichen Pseudevernia furfuracea from two reference areas in NE Italy. Green shoots of epilithic mosses and lobes of epiphytic lichens from larch branches showed rather homogenous composition and were selected for the exposure in nylon bags. As different physico-chemical pre-treatments are usually applied to selected cryptogamic material before its exposure, we also evaluated the effects of oven-drying at 120 degrees C for 24h, washing in 1N HNO3 solution, and in 0.5% NH4 oxalate solution at 85 degrees C for 15 h on the chemical composition and morphology of water-washed moss shoots and lichen lobes. Pre-treatments remarkably changed the chemical composition of selected materials but not their surface morphology.     

Spatial and temporal variability in outdoor,indoor, and personal PM2.5 exposure

Outdoor, indoor and personal PM_2.5 measurements were made in a population of nonsmoking adults from three communities in the Minneapolis–St. Paul metropolitan area between April and November 1999. Thirty-two healthy adult subjects (23 females, 9 males; mean age 42±10, range: 24–64 yr) were monitored for 2–15 days during the spring, summer, and fall monitoring seasons. Twenty-four hour average gravimetric PM_2.5 samples were collected using a federal reference monitor (Anderson RAAS2.5-300) located at outdoor (O) central sites in the Battle Creek (BCK), East St. Paul (ESP) and Phillips (PHI) communities. Concurrent 24-h average indoor (I) and personal (P), and a limited number of outdoor-at-home (O@H) samples were collected using inertial impactors (PEM™ Model 200, MSP, Inc). The O (geometric mean {GM}=8.6; n=271; range: 1.0–41 μg/m³) were lower than I concentrations (GM=10.7; n=294; range 1.3–131 μg/m³), which were lower than P concentrations (GM=19.0; n=332; range 2.2–298 μg/m³). Correlation coefficients between O concentrations in the three communities were high and measured GM O levels in BCK were significantly lower than ESP, most likely because of local sources, but GM concentrations in PHI were not significantly different from BCK or ESP. On days with paired samples (n=29), O concentrations were significantly lower (mean difference 2.9 μg/m³; p=0.026) than O@H measurements (GM=11.3; range: 3.5–33.8 μg/m³), likely due to local sources in communities. Observed I and P concentrations were more variable, probably because of residential central air conditioning and hours of household ventilation for I and P, and occupational and environmental tobacco smoke exposures outside the residence for P. Across all individuals and days the median PM_2.5 “personal cloud” was 5.7 μg/m³, but the mean of the average for each participant was 15.7 μg/m³, with very low values in participants who did not work outside the home and much higher values in subjects with active lifestyles. Across all households and individuals the correlation between P and O concentrations was not significant, but the overall I–O correlation (0.27) and P–I correlation (0.51) were significant (p<0.05). Relatively little spatial variability was observed in O PM_2.5 concentrations across the three communities compared to the variability associated with I and P samples, and the measured O levels were relatively low compared to other large metropolitan areas in the United States.     

Spatial variability of PM2.5 in urban areas in the United States

Data from the U.S. Environmental Protection Agency's Aerometric Information Retrieval System (now known as the Air Quality System) database for 1999 and 2000 have been used to characterize the spatial variability of concentrations of particulate matter with aerodynamic diameter < or = 2.5 microg (PM2.5) in 27 urban areas across the United States. Different measures were used to quantify the degree of uniformity of PM2.5 concentrations in the urban areas characterized. It was observed that PM2.5 concentrations varied to differing degrees in the urban areas examined. Analyses of several urban areas in the Southeast indicated high correlations between site pairs and spatial uniformity in concentration fields. Considerable spatial variation was found in other regions, especially in the West. Even within urban areas in which all site pairs were highly correlated, a variable degree of heterogeneity in PM2.5 concentrations was found. Thus, even though concentrations at pairs of sites were highly correlated, their concentrations were not necessarily the same. These findings indicate that the potential for exposure misclassification errors in time-series epidemiologic studies exists.     

Measurements of the chemical composition of stratiform clouds

Measurements are reported of the chemical composition of the liquid water and interstitial air in warm (> 0°C), non-precipitating stratus and strato-cumulus clouds at various locations in the eastern United States. Inorganic ionic composition of the cloud water was generally dominated by H⁺, NH₄⁺, NO₃⁻ and SO₄²⁻, similar to the composition of precipitation in this region of the U.S. Concentrations of the corresponding interstitial aerosol species and gaseous HNO₃ were invariably low in comparison to concentrations of the respective ionic species in cloudwater. In contrast, the concentration of NO_x (i.e. NO + NO₂ + organic nitrates) was invariably comparable to or in excess of that of cloudwater nitrate. Sulfur dioxide was found at varying concentrations relative to cloudwater sulfate. In many cases, the SO₂ concentration was quite low (< 0.2 ppb) even in the presence of substantial quantities of cloudwater SO₄²⁻ (> 1 ppb equivalent gas-phase concentration), suggesting large fractional conversion and incorporation into cloudwater. In other cases, in which dilute SO₂ plumes (pso, > 5 ppb) were observed in the cloud interstitial air, the gaseous SO₂ concentration substantially exceeded the cloudwater sulfate concentration.Concentrations of H₂O₂ in cloudwater were found to exhibit strong inverse correlation with interstitial SO₂. Appreciable concentrations of SO₂ in cloud interstitial air and H₂O₂ in cloudwater were only rarely observed to coexist, for the most part only one or the other being present above the limit of detection. These observations are consistent with aqueous-phase oxidation of SO₂ by H₂O₂, as has been inferred previously on the basis of laboratory kinetic studies, and with the hypothesis that depending on relative concentrations, either of these species can be a limiting reagent for in-cloud SO₂ oxidation. The uptake of NO_x as cloudwater nitrate is less complete than the uptake of SO₂ as sulfate, and evidence for the occurrence of similar in-cloud processes causing the conversion of NO or NO₂ to cloudwater nitrate has not been found.     

Spatial variability of arsenic and chromium in the soil water at a former wood preserving site

Contamination of industrial sites by wood preservatives such as chromated copper arsenate (CCA) may pose a serious threat to groundwater quality. The objective of this study was to characterise the spatial variability of As and Cr concentrations in the solid phase and in the soil water at a former wood impregnation plant and to reveal the fundamental transport processes. The soil was sampled down to a depth of 2m. The soil water was extracted in situ from the vadose zone over a period of 10 months at depths of 1 and 1.5m, using large horizontally installed suction tubes. Groundwater was sampled from a depth of 4.5m. Results showed that arsenic and chromium had accumulated in the upper region of the profile and exhibited a high spatial variability (As: 21-621 mg kg(-1); Cr: 74-2872 mg kg(-1)). Concentrations in the soil water were high (mean As 167 microg L(-1); Cr: 62 microg L(-1)) and also showed a distinct spatial variability, covering concentration ranges up to three orders of magnitude. The variability was caused by the severe water-repellency of the surface soil, induced by the concurrent application of creosote wood preservatives, which leads to strong preferential flow as evident from a dye experiment. In contrast to soil water concentrations, only low As concentrations (<12 microg L(-1)) were detected in the groundwater. High Cr concentrations in the groundwater (approx. 300 microg L(-1)), however, illustrated the pronounced mobility of chromium. Our study shows that at sites with a heterogeneous flow system in the vadose zone a disparity between flux-averaged and volume-averaged concentrations may occur, and sampling of soil water might not be adequate for assessing groundwater concentrations. In these cases long-term monitoring of the groundwater appears to be the best strategy for a groundwater risk assessment.     

The chemical composition of snow at a rural upland site in Mid-wales

The chemical composition of samples of freshly fallen snow and snow in standing accumulations several days old have been determined for an upland rural site in Mid-Wales. Fresh snow has a lower solute content than incident rainfall at an equivalent time of year, which may be related to the weather conditions, specifically wind direction, during periods of snowfall. The concentrations of solutes in standing snow drifts appear to increase with time and mechanisms by which this might occur are discussed.     

Spatial and temporal variability of sediment deposition on artificial-lawn traps in a floodplain of the River Elbe

Artificial-lawn mats were used as sediment traps in floodplains to measure sediment input and composition during flood events. To estimate the natural variability, 10 traps were installed during two flood waves at three different morphological units in a meander loop of the River Elbe. The geochemical composition of deposited and suspended matter was compared. The sediment input showed weak correlations with concentration and composition of river water. It also correlated poorly with flood duration and level as well as distance of trap position from the main river. This is due to the high variability of the inundation, different morphological conditions and the variability of sources. The composition of the deposits and the suspended matter in the river water was comparable. Hence, for the investigated river reach, the expected pollution of the floodplain sediments can be derived from the pollution of the suspended matter in the river during the flood wave.     

Real-time measurements of the chemical composition of size-resolved particles during a Santa Ana wind episode,California USA

Size-resolved particle composition, mass and number concentrations, aerosol scattering coefficients, and prevailing meteorological conditions were measured at the Ellen Browning Scripps Memorial Pier located in La Jolla, California on 15 December 1998. Aerosol particles were sampled using a field transportable aerosol time-of-flight mass spectrometer, allowing for the continuous detection and characterization of single particles from a polydisperse sample. An extensive and rapid change in the chemical composition of aerosol particles with aerodynamic diameters between 1.0 and 2.5 μm has been observed during the onset of a Santa Ana Winds condition. Coincident with the observed change in meteorological conditions, a substantial decrease in sea salt particles corresponds to an increase in dust and carbon-containing particles. This paper examines observations of the rapid changes occurring in the chemical composition of single aerosol particles and demonstrates the new types of information that can be obtained by measuring single particle size and composition with high temporal resolution.