Three-dimensional patterns of moisture, water repellency, bromide and pH in a sandy soil

Soil water repellency might lead to preferential flow of water and solutes through the unsaturated zone of soils. To study this process in a water repellent sandy field soil, a bromide tracer had been applied on a 2.2 m long and 0.4 m wide plot. The bromide application rate was 8 g/m², and the plot was sampled using 100 cm³ steel cylinders after 52 mm of rainfall in 12 days. A total of seven layers were sampled to a depth of 74 cm. Each layer was sampled at 240 locations in a 40 by 6 grid. All samples were used for the determination of soil water content, degree of actual and potential water repellency, bromide concentration and pH. The spatial distribution of these properties was visualized three-dimensionally and compared. The degree of water repellency, bromide concentration, and pH distribution bore close resemblance to the fingered flow induced soil water content distribution. The degree of potential water repellency was relatively low in places with such fingers. Actual water repellency occurred between the fingers at the dry spots. Bromide was not found, or only in very low concentrations, in such places. Bromide depth profiles clearly indicated the occurrence of diverging flow in the wetter subsoil. Most likely, manuring activities during the last decades resulted in relatively high pH values in the topsoil, and in the subsoil along the recurring fingered flow pathways.     

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.     

Geostatistical analysis of soil hydrologic properties in a field plot

A 91-m transect was set up in an irrigated field near Las Cruces, New Mexico to obtain soil water tension and water content data to investigate their spatial variability. A total of 455 sampling points were monitored along a grid consisting of 91 stations placed 1 m apart by 5 depths per station (at 0.3, 0.6, 0.9, 1.2 and 1.5 m below the surface). Post-irrigation tension and wetness measurements were recorded over 45 days at 11 time periods. Soil water tension was measured with tensiometers using a hand-held pressure transducer. A neutron probe was used to obtain volumetric water content. Using the observed wetness and tension data, unsaturated hydraulic conductivity values were derived (using a cubic spline function to estimate the gradient), and an exponential model was used to fit the calculated conductivity-tension curves to obtain hydraulic conductivity parameter values. The spatial and temporal variability of wetness, tension, saturated hydraulic conductivity and pore-size distribution parameters, and texture at the 0.3-m depth were examined using geostatistical techniques.The exponential model was found to inadequately describe the hydraulic conductivity/tension relationship for the full range of tension, particularly in the tension range near saturation. The derived values of the saturated hydraulic conductivity parameter were much greater than expected and do not correspond to reasonable saturated hydraulic conductivity values.All of the soil parameters studied exhibited large spatial variability horizontally and vertically in the field. Ranges of dependence determined from semivariogram analysis over the 44-day drainage period are 3–32 m for wetness, 6–34 m for soil water tension, 5–35 m for natural log of saturated hydraulic conductivity parameters, 5–11 m for pore-size distribution parameter, and 8–24 m for percent sand, silt and clay at the 0.3 m depth. An alternate hole-effect model is suggested to describe the texture semivariograms.It was determined that the variance of volumetric water content generally increased at each depth over the measured time periods, which is consistent with certain past field studies and a stochastic analysis of unsaturated flow in heterogeneous soils. Future research is recommended relating soil texture to soil hydrologic parameters with the goal of predicting soil behavior with less extensive sampling schemes.     

Transport of atmospheric fine particulate matter: part 2--findings from recent field programs on the intraurban variability in fine particulate matter

Air quality field data, collected as part of the fine particulate matter Supersites Program and other field measurements programs, have been used to assess the degree of intraurban variability for various physical and chemical properties of ambient fine particulate matter. Spatial patterns vary from nearly homogeneous to quite heterogeneous, depending on the city, parameter of interest, and the approach or method used to define spatial variability. Secondary formation, which is often regional in nature, drives fine particulate matter mass and the relevant chemical components toward high intraurban spatial homogeneity. Those particulate matter components that are dominated by primary emissions within the urban area, such as black carbon and several trace elements, tend to exhibit greater spatial heterogeneity. A variety of study designs and data analysis approaches have been used to characterize intraurban variability. High temporal correlation does not imply spatial homogeneity. For example, there can be high temporal correlation but with spatial heterogeneity manifested as smooth spatial gradients, often emanating from areas of high emissions such as the urban core or industrial zones.     

Model and input uncertainty in multi-media fate modeling: benzo[a]pyrene concentrations in Europe

This paper evaluates the contribution of (i) uncertainty in substance properties, (ii) lack of spatial variability, (iii) intermodel differences and (iv) neglecting sorption to black carbon (BC) to the uncertainty of Benzo[a]pyrene (BaP) concentrations in European air, soil and fresh water predicted by the multi-media fate model Simplebox. Uncertainty in substance properties was quantified using probabilistic modeling. The influence of spatial variability was quantified by estimating variation in predicted concentrations with three spatially explicit fate models (Impact 2002, EVn BETR and BETR Global). Intermodel differences were quantified by comparing concentration estimates of Simplebox, Impact 2002, EVn BETR and the European part of BETR Global. Finally, predictions of a BC-inclusive version of Simplebox were compared with predictions of a BC-exclusive version. For air concentrations of BaP, the lack of spatial variability in emissions was most influential. For freshwater concentrations of BaP, intermodel differences and lack of spatial variability in dimensions of fresh water bodies were the dominant sources of uncertainty. For soil, all sources of uncertainty were of comparable magnitude. Our results indicate that uncertainty in Simplebox can be as large as three orders of magnitude for BaP concentrations in the environment and would be substantially underestimated by focusing on one source of uncertainty only.     

Transport of Atmospheric Fine Particulate Matter: Part 2—Findings from Recent Field Programs on the Intraurban Variability in Fine Particulate Matter

Abstract

Air quality field data, collected as part of the fine particulate matter Supersites Program and other field measurements programs, have been used to assess the degree of intraurban variability for various physical and chemical properties of ambient fine particulate matter. Spatial patterns vary from nearly homogeneous to quite heterogeneous, depending on the city, parameter of interest, and the approach or method used to define spatial variability. Secondary formation, which is often regional in nature, drives fine particulate matter mass and the relevant chemical components toward high intraurban spatial homogeneity. Those particulate matter components that are dominated by primary emissions within the urban area, such as black carbon and several trace elements, tend to exhibit greater spatial heterogeneity. A variety of study designs and data analysis approaches have been used to characterize intraurban variability. High temporal correlation does not imply spatial homogeneity. For example, there can be high temporal correlation but with spatial heterogeneity manifested as smooth spatial gradients, often emanating from areas of high emissions such as the urban core or industrial zones.     

Variability of pesticide exposure in a stream mesocosm system: macrophyte-dominated vs. non-vegetated sections

For flowing water bodies no information is available about patterns of contaminant distribution in flowing water compared to macrophyte-dominated structures. The aim of the study was to examine temporal dynamic and spatial cross-channel variability of pulse exposure of the insecticide thiacloprid in outdoor stream mesocosms. Two distinct cross-channel sections have been considered: macrophyte-dominated littoral and non-vegetated midstream. Median disappearance time ranged from 17 to 43 h (water phase, midstream). We showed that during the exposure pulse (10h) thiacloprid concentrations in the macrophyte-dominated section were 20-60% lower than those in the non-vegetated section. This suggests that spatial variability in contaminant concentrations, particularly in streams containing macrophytes, should be taken into account to enable a more realistic assessment of (i) exposure and associated effects and (ii) mass transport of pesticides and other chemicals into river systems (e.g. losses with surface runoff).     

Soil burdens of persistent organic pollutants - Their levels, fate and risk. Part II. Are there any trends in PCDD/F levels in mountain soils?

Good quality data apt for an assessment of temporal trends of polychlorinated dibenzo-p-dioxins and furans (PCDDs/Fs) in soils are difficult to obtain since there is a general lack of information on their residues in soils. Variability of soil profiles, non-homogeneity of samples, and often also inconsistency of applied sampling procedures further complicate this problem. To assess spatial and temporal trends of contamination, three soil sampling campaigns have been performed over the period of 12 years at the mountain forest sites in the Czech Republic. Relation between the air, needle and soil contaminations was addressed in addition to time-related variability of soil. It has been confirmed that soil is a good matrix for evaluation of spatial distribution of persistent organic pollutants (POPs) but difficult for establishment of temporal trends. A slow rate of the soil-forming processes and their site-specificity was generally the major source of uncertainties.     

Operator-splitting errors in coupled reactive transport codes for transient variably saturated flow and contaminant transport in layered soil profiles

One possible way of integrating subsurface flow and transport processes with (bio)geochemical reactions is to couple by means of an operator-splitting approach two completely separate codes, one for variably-saturated flow and solute transport and one for equilibrium and kinetic biogeochemical reactions. This paper evaluates the accuracy of the operator-splitting approach for multicomponent systems for typical soil environmental problems involving transient atmospheric boundary conditions (precipitation, evapotranspiration) and layered soil profiles. The recently developed HP1 code was used to solve the coupled transport and chemical equations. For steady-state flow conditions, the accuracy was found to be mainly a function of the adopted spatial discretization and to a lesser extent of the temporal discretization. For transient flow situations, the accuracy depended in a complex manner on grid discretization, time stepping and the main flow conditions (infiltration versus evaporation). Whereas a finer grid size reduced the numerical errors during steady-state flow or the main infiltration periods, the errors sometimes slightly increased (generally less than 50%) when a finer grid size was used during periods with a high evapotranspiration demand (leading to high pressure head gradients near the soil surface). This indicates that operator-splitting errors are most significant during periods with high evaporative boundary conditions. The operator-splitting errors could be decreased by constraining the time step using the performance index (the product of the grid Peclet and Courant numbers) during infiltration, or the maximum time step during evapotranspiration. Several test problems were used to provide guidance for optimal spatial and temporal discretization.     

Spatial and temporal variability in urban fine particulate matter concentrations

Identification of hot spots for urban fine particulate matter (PM(2.5)) concentrations is complicated by the significant contributions from regional atmospheric transport and the dependence of spatial and temporal variability on averaging time. We focus on PM(2.5) patterns in New York City, which includes significant local sources, street canyons, and upwind contributions to concentrations. A literature synthesis demonstrates that long-term (e.g., one-year) average PM(2.5) concentrations at a small number of widely-distributed monitoring sites would not show substantial variability, whereas short-term (e.g., 1-h) average measurements with high spatial density would show significant variability. Statistical analyses of ambient monitoring data as a function of wind speed and direction reinforce the significance of regional transport but show evidence of local contributions. We conclude that current monitor siting may not adequately capture PM(2.5) variability in an urban area, especially in a mega-city, reinforcing the necessity of dispersion modeling and methods for analyzing high-resolution monitoring observations.     

Sequencing diurnal air flow patterns for ozone exposure assessment around Houston,Texas

Understanding the human health impacts of ground level ozone requires detailed knowledge of its spatial–temporal distribution beyond that provided by surface monitoring networks. Here, a novel methodology based on unsupervised multivariate statistical techniques has been developed and used to identify the transport and dispersion patterns of tropospheric ozone. The hierarchical clustering method is used to visualize air flow patterns at two time scales relevant for ozone buildup. Sequentially executed statistical methods consider hourly 1-h surface wind field measurements. First, clustering is performed at the hourly time scale to identify 1-h surface flow patterns. Then, sequencing is performed at the daily time scale to identify groups of days sharing similar diurnal cycles for the surface flow. Selection of appropriate numbers of air flow patterns allows inference of regional transport and dispersion patterns for understanding population exposure to ozone. The methods are applied to the Houston, Galveston, and Beaumont-Port Arthur, TX study domain. Representative hourly wind field patterns are determined for the entire 2004 ozone season. Then, sequencing is performed for the 32 days in exceedance of the NAAQS for 8-h ozone. Four diurnal flow patterns capturing different ozone exceedance scenarios are isolated; each scenario is associated with a distinct spatial distribution for atmospheric pollutants.     

Characterization of subsoil heterogeneity, estimation of grain size distribution and hydraulic conductivity at the Krauthausen test site using Cone Penetration Test

A Cone Penetration Test (CPT) survey with a high spatial resolution was performed in order to investigate the stratigraphy as well as the spatial variability of various soil properties of the Krauthausen test site. Analyses of the CPT measurements showed the subsurface to be dominated by a planar layered structure. Variogram analysis of the various CPT parameters disclosed that within each layer the soil properties have an anisotropic spatial correlation structure. A correlation analysis of the measured CPT data and co-located grain size distributions from soil samples was performed. Since the correlation coefficients were greater equal to 0.7, a reliable empirical relationship between the data sets could be developed. Based on this empirical relationship grain size distributions were estimated at CPT locations. The statistical processing of estimated and measured grain size distributions with respect to their spatial correlation structure disclosed good agreement between the data sets. The estimated grain size distributions from CPT data were used to estimate the hydraulic conductivity in the aquifer. The results provide detailed information of the spatial heterogeneity of the hydraulic conductivity at Krauthausen test site. The validation of these results, using a prior investigation of hydraulic conductivity statistics, suggests the CPT a fast and inexpensive tool for the estimation of three dimensional hydraulic conductivity fields with sufficient accuracy.     

Screening variability and change of soil moisture under wide-ranging climate conditions: Snow dynamics effects

Soil moisture influences and is influenced by water, climate, and ecosystem conditions, affecting associated ecosystem services in the landscape. This paper couples snow storage-melting dynamics with an analytical modeling approach to screening basin-scale, long-term soil moisture variability and change in a changing climate. This coupling enables assessment of both spatial differences and temporal changes across a wide range of hydro-climatic conditions. Model application is exemplified for two major Swedish hydrological basins, Norrström and Piteälven. These are located along a steep temperature gradient and have experienced different hydro-climatic changes over the time period of study, 1950–2009. Spatially, average intra-annual variability of soil moisture differs considerably between the basins due to their temperature-related differences in snow dynamics. With regard to temporal change, the long-term average state and intra-annual variability of soil moisture have not changed much, while inter-annual variability has changed considerably in response to hydro-climatic changes experienced so far in each basin.     

Prediction of overall persistence and long-range transport potential with multimedia fate models: robustness and sensitivity of results

The hazard indicators persistence (P) and long-range transport potential (LRTP) are used in chemicals assessment to characterize chemicals with regard to the temporal and spatial extent of their environmental exposure. They are often calculated based on the results of multimedia fate models. The environmental and substance-specific input parameters of such models are subject to a range of methodological uncertainties and also influenced by natural variability. We employed probabilistic uncertainty analysis to quantify variance in P and LRTP predictions for chemicals with different partitioning and transport behavior. Variance found in the results is so large that it prevents a clear distinction between chemicals. Additionally, only small improvements are observed when evaluating the results relative to a benchmark chemical. This can be explained by the dominance of substance-specific parameters and the only small direct influence of environmental parameters on P and LRTP as model outcomes. The findings underline the importance of learning how environmental conditions cause variability in substance behavior for improved substance ranking and classification.     

Entrapment and dissolution of DNAPLs in heterogeneous porous media

Two-dimensional multiphase flow and transport simulators were refined and used to numerically investigate the entrapment and dissolution behavior of tetrachloroethylene (PCE) in heterogeneous porous media containing spatial variations in wettability. Measured hydraulic properties, residual saturations, and dissolution parameters were employed in these simulations. Entrapment was quantified using experimentally verified hydraulic property and residual saturation models that account for hysteresis and wettability variations. The nonequilibrium dissolution of PCE was modeled using independent estimates of the film mass transfer coefficient and interfacial area for entrapped and continuous (PCE pools or films) saturations. Flow simulations demonstrate that the spatial distribution of PCE is highly dependent on subsurface wettability characteristics that create differences in PCE retention mechanisms and the presence of subsurface capillary barriers. For a given soil texture, the maximum and minimum PCE infiltration depth was obtained when the sand had intermediate (an organic-wet mass fraction of 25%) and strong (water- or organic-wet) wettability conditions, respectively. In heterogeneous systems, subsurface wettability variations were also found to enhance or diminish the performance of soil texture-induced capillary barriers. The dissolution behavior of PCE was found to depend on the soil wettability and the spatial PCE distribution. Shorter dissolution times tended to occur when PCE was distributed over large regions due to an increased access of flowing water to the PCE. In heterogeneous systems, capillary barriers that produced high PCE saturations tended to exhibit longer dissolution times.     

The use of tree-rings and foliage as an archive of volcanogenic cation deposition

Tree cores (Pinus nigra ssp. laricio) and leaves (Castanea sativa) from the flanks of Mount Etna, Sicily were analysed by ICP-MS to investigate whether volcanogenic cations within plant material provide an archive of a volcano's temporal and spatial depositional influence. There is significant compositional variability both within and between trees, but no systematic dendrochemical correlation with periods of effusive, explosive or increased degassing activity. Dendrochemistry does not provide a record of persistent but fluctuating volcanic activity. Foliar levels of bioaccumulated cations correspond to modelled plume transport patterns, and map short-term volcanic fumigation. Around the flanks of the volcano foliar variation is greater for volatile cations (Cs, Cd, Pb) than for lithophilic cations (Ba, Sr), consistent with trace-metal supply from volcanic aerosol during quiescent periods.     

高原地区铬渣污染场地污染特性研究

在我国高原地区某铬渣污染场地进行钻孔取样,分析场地工程地质特性,对场地铬的污染状况及空间分布特征进行研究。结果表明:场地地质结构较单一,地下水丰富,土质的渗透性强,渗透系数在1.78×10-3~0.243 cm/s之间;场地铬污染严重,总铬与六价铬的浓度最大值分别为22 485.6 mg/kg和7 495.2 mg/kg,地下水中六价铬的浓度最大值为107.2 mg/L;通过剖面铬浓度分析:铬在纵向上浓度分布受土壤质地的影响,均呈现表层4 m浓度较高,4 m以下浓度较低且变化较小的规律。由Kriging插值法绘的铬浓度分布等值线图可清晰看出场地表层土表现出向沟谷位置迁移趋势,地下水中残留的铬向地下水流场方向迁移。     

Mapping field spatial distribution patterns of isoproturon-mineralizing activity over a three-year winter wheat/rape seed/barley rotation

The temporal and spatial variability of the activity of soil microorganisms able to mineralize the herbicide isoproturon (IPU) pesticide was investigated over a three-year long crop rotation between 2008 and 2010. Isoproturon mineralization was higher in 2008, when winter wheat was treated with this herbicide, than in 2009 and 2010, when rape seed and barley were treated with different herbicides. Under laboratory conditions, we showed that isoproturon mineralization was not promoted by sulfonylurea herbicide applied on barley crop in 2010. IPU mineralization was shown to be highly variable at the field scale in years 2009 and 2010. Principal component analyses and analyses of similarities revealed that soil pH and equivalent humidity, and to a lesser extent soil organic matter content and cation exchange capacity (CEC) were the main drivers of isoproturon-mineralizing activity variance. Using a rather simple model that yields the rate of isoproturon mineralization as a function of soil pH and equivalent humidity, we explained up to 85% of the variance observed. Mapping field-scale distribution of isoproturon mineralization over the three-year survey indicated higher variability in 2009 and in 2010 as compared to 2008, suggesting that isoproturon treatment applied to winter wheat promoted isoproturon mineralization activity and reduced its spatial variability. Field-scale distribution of isoproturon mineralization showed important similarity to the distribution of soil pH, equivalent humidity and to a lesser extent to soil organic matter and cation exchange capacity (CEC) thereby confirming our model.