Kinematic wave approximation to solute transport along preferred flow paths in soils

A routing procedure is introduced which accounts for the loss of a conservative solute tracer from preferred paths during macropore flow. Water flow is treated as a series of kinematic waves from which the tracer is lost due to mixing previously stored soil water, and an expression for solute loss is added to a previously developed model. The model parameters are estimated through experiments at three different input rates applied to a column of a macroporous forest soil.The results of seven experimental runs indicate that solute losses are consistently highest at the early stages of infiltration and drainage flow. An empirical relationship is proposed which links the frequency distribution of the flow parameter with that for solute loss from the preferred path during transient water flow and solute transport.     

Modelling dissolution of multi-component non-aqueous phase liquids using Pareto distributions

A distributed-site non-aqueous phase liquid (NAPL) dissolution model that can capture the physical process of dissolution is presented. The model uses a Pareto distribution of effective interfacial area and a correlation for the mass transfer. Model parameters are obtained using a formal constrained non-linear optimisation technique. The model is applied on effluent data from two soil column experiments. The results of the Pareto distributed site model, with only two parameters to fit, were compared to two-site and multi-site models as well as the beta distributed site model. The Pareto distributed-site model produces equal or smaller error estimates than the other models.     

An axisymmetric diffusion experiment for the determination of diffusion and sorption coefficients of rock samples

Diffusion anisotropy is a critical property in predicting migration of substances in sedimentary formations with very low permeability. The diffusion anisotropy of sedimentary rocks has been evaluated mainly from laboratory diffusion experiments, in which the directional diffusivities are separately estimated by through-diffusion experiments using different rock samples, or concurrently by in-diffusion experiments in which only the tracer profile in a rock block is measured. To estimate the diffusion anisotropy from a single rock sample, this study proposes an axisymmetric diffusion test, in which tracer diffuses between a cylindrical rock sample and a surrounding solution reservoir. The tracer diffusion between the sample and reservoir can be monitored from the reservoir tracer concentrations, and the tracer profile could also be obtained after dismantling the sample. Semi-analytical solutions are derived for tracer concentrations in both the reservoir and sample, accounting for an anisotropic diffusion tensor of rank two as well as the dilution effects from sampling and replacement of reservoir solution. The transient and steady-state analyses were examined experimentally and numerically for different experimental configurations, but without the need for tracer profiling. These experimental configurations are tested for in- and out-diffusion experiments using Koetoi and Wakkanai mudstones and Shirahama sandstone, and are scrutinized by a numerical approach to identify favorable conditions for parameter estimation. The analysis reveals the difficulty in estimating diffusion anisotropy; test configurations are proposed for enhanced identifiability of diffusion anisotropy. Moreover, it is demonstrated that the axisymmetric diffusion test is efficient in obtaining the sorption parameter from both steady-state and transient data, and in determining the effective diffusion coefficient if isotropic diffusion is assumed. Moreover, measuring reservoir concentrations in an axisymmetric diffusion experiment coupled with tracer profiling may be a promising approach to estimate of diffusion anisotropy of sedimentary rocks.     

Diffusive partitioning tracer test for the quantification of nonaqueous phase liquid (NAPL) in the vadose zone: Performance evaluation for heterogeneous NAPL distribution

A partitioning tracer test based on gas-phase diffusion in the vadose zone yields estimates of the residual nonaqueous phase liquid (NAPL) saturation. The present paper investigates this technique further by studying diffusive tracer breakthrough curves in the vadose zone for a heterogeneous NAPL distribution. Tracer experiments were performed in a lysimeter with a horizontal layer of artificial kerosene embedded in unsaturated sand. Tracer disappearance curves at the injection point and tracer breakthrough curves at some distance from the injection point were measured inside and outside of the NAPL layer. A numerical code was used to generate independent model predictions based on the physicochemical sand, NAPL, and tracer properties. The measured and modeled tracer breakthrough curves were in good agreement confirming the validity of important modeling assumptions such as negligible sorption of chlorofluorocarbon (CFC) tracers to the uncontaminated sand and their fast reversible partitioning between the soil air and the NAPL phase. Subsequently, the model was used to investigate different configurations of NAPL contamination. The experimental and model results show that the tracer disappearance curves of a single-well diffusive partitioning tracer test (DPTT) are dominated by the near-field presence of NAPL around the tip of the soil gas probe. In contrast, breakthrough curves of inter-well tracer tests reflect the NAPL saturation in between the probes, although there is no unique interpretation of the tracer signals if the NAPL distribution is heterogeneous. Numerical modeling is useful for the planning of a DPTT application. Simulations suggest that several cubic meters of soil can be investigated with a single inter-well partitioning tracer test of 24-hour duration by placing the injection point in the center of the investigated soil volume and probes at up to 1 m distance for the monitoring of gaseous tracers.     

Water and solute movement in soil as influenced by macropore characteristics: 2. Macropore tortuosity

The paper describes the results of a laboratory study on the effects of macropore tortuosity on breakthrough curves BTCs and solute distribution in a Forman loam (fine loamy-mixed Udic Haploborolls) soil. BTC were obtained using 2-D columns (slab) containing artificial macropores of five different tortuosity levels. The BTCs were run under a constant hydraulic head of 0.08 m over an initially air dry soil. The input solutions contained 1190 mg l⁻¹ of potassium bromide, 10 mg l⁻¹ of Rhodamine WT, and 100 mg l⁻¹ of FD&C Blue #1. A soil column without macropores served as a control. The displacement of a non-adsorbed tracer was not affected by the tortuosity level. An increase in macropore tortuosity progressively increased the breakthrough time, increased the apparent retardation coefficient (R′), decreased the depth to the center of mass of a given adsorbed tracer, and increased the anisotropy in tracer distribution profile. The relative importance of macropore tortuosity increased with an increase in the adsorption coefficient of the tracer. Compared to macropore continuity, the macropore tortuosity had greater impact on solute distribution profile than in its leaching.     

Effects of water content on reactive transport of 85Sr in Chernobyl sand columns

It is known that under unsaturated conditions, the transport of solutes can deviate from ideal advective-dispersive behaviour even for macroscopically homogeneous porous materials. Causes may include physical non-equilibrium, sorption kinetics, non-linear sorption, and the irregular distribution of sorption sites. We have performed laboratory experiments designed to identify the processes responsible for the non-ideality of radioactive Sr transport observed under unsaturated flow conditions in an Aeolian sandy deposit from the Chernobyl exclusion zone. Miscible displacement experiments were carried out at various water contents and corresponding flow rates in a laboratory model system. Results of our experiments have shown that breakthrough curves of a conservative tracer exhibit a higher degree of asymmetry when the water content decreases than at saturated water content and same Darcy velocity. It is possible that velocity variations caused by heterogeneities at the macroscopic scale are responsible for this situation. Another explanation is that molecular diffusion drives the solute mass transfer between mobile and immobile water regions, but the surface of contact between these water regions is small. At very low concentrations, representative of a radioactive Sr contamination of the pore water, sorption and physical disequilibrium dominate the radioactive Sr transport under unsaturated flow conditions. A sorption reaction is described by a cation exchange mechanism calibrated under fully saturated conditions. The sorption capacity, as well as the exchange coefficients are not affected by desaturation. The number of accessible exchange sites was calculated on the basis that the solid remained in contact with water and that the fraction of solid phase in contact with mobile water is numerically equal to the proportion of mobile water to total water content. That means that for this type of sandy soil, the nature of mineral phases is the same in advective and non-advective domains. So sorption reaction parameters can be estimated from more easily conducted saturated experiments, but hydrodynamic behaviour must be characterized by conservative tracer experiments under unsaturated flow conditions.     

Application of HYDRUS 1D model for assessment of phenol–soil adsorption dynamics

Laboratory-scale batch, vertical, and horizontal column experiments were conducted to investigate the attenuative capacity of a fine-grained clayey soil of local origin in the surrounding of a steel plant wastewater discharge site in West Bengal, India, for removal of phenol. Linear, Langmuir, and Freundlich isotherm plots from batch experimental data revealed that Freundlich isotherm model was reasonably fitted (R ²?=?0.94). The breakthrough column experiments were also carried out with different soil bed heights (5, 10, and 15 cm) under uniform flow to study the hydraulic movements of phenol by evaluating time concentration flow behavior using bromide as a tracer. The horizontal migration test was also conducted in the laboratory using adsorptive phenol and nonreactive bromide tracer to explore the movement of solute in a horizontal distance. The hydrodynamic dispersion coefficients (D) in the vertical and horizontal directions in the soil were estimated using nonlinear least-square parameter optimization method in CXTFIT model. In addition, the equilibrium convection dispersion model in HYDRUS 1D was also examined to simulate the fate and transport of phenol in vertical and horizontal directions using Freundlich isotherm constants and estimated hydrodynamic parameters as input in the model. The model efficacy and validation were examined through statistical parameters such as the coefficient of determination (R ²), root mean square error and design of index (d).     

A field experiment with variable-suction multi-compartment samplers to measure the spatio-temporal distribution of solute leaching in an agricultural soil

Solutes spread out in time and space as they move downwards from the soil surface with infiltrating water. Solute monitoring in the field is often limited to observations of resident concentrations, while flux concentrations govern the movement of solutes in soils. A recently developed multi-compartment sampler is capable of measuring fluxes at a high spatial resolution with minimal disturbance of the local pressure head field. The objective of this paper is to use this sampler to quantify the spatial and temporal variation of solute leaching below the root zone in an agricultural field under natural rainfall in winter and spring. We placed two samplers at 31 and 25 cm depth in an agricultural field, leaving the soil above undisturbed. Each sampler contained 100 separate cells of 31 × 31 mm. Water fluxes were measured every 5 min for each cell. We monitored leaching of a chloride pulse under natural rainfall by frequently extracting the collected leachate while leaving the samplers buried in situ. This experiment was followed by a dye tracer experiment. This setting yielded information that widely surpassed the information that can be provided by separate anionic and dye tracer trials, and solute transport monitoring by coring or suction cups. The detailed information provided by the samplers showed that percolation at the sampling depth started much faster (approximately 3 h after the start of rainfall) in initially wet soil (pressure head above − 65 cm) than in drier soil (more than 14 h at pressure heads below − 80 cm). At any time, 25% of the drainage passed through 5–6% of the sampled area, reflecting the effect of heterogeneity on the flow paths. The amount of solute carried by individual cells varied over four orders of magnitude. The lateral concentration differences were limited though. This suggests a convective–dispersive regime despite the short vertical travel distance. On the other hand, the dilution index indicates a slight tendency towards stochastic–convective transport at this depth. There was no evidence in the observed drainage patterns and dye stained profiles of significant disturbance of the flow field by the samplers.     

Modelling field-scale cadmium transport below the root zone of a sewage sludge amended soil in an arid region in Central Iran

Addition of trace metals such as cadmium to soils in metal-rich sewage sludge may result in contamination of soil and groundwater. This study addresses the plot-scale transport of Cd derived from sewage sludge in a layered clay soil in an arid region of central Iran. Sewage sludge was enriched by Cd at rates of 38 and 80 mg kg(-1) and applied to experimental soil plots using a complete random block design with three replicates. Cadmium concentration was measured as a function of depth after 185 and 617 days. HYDRUS-1D and MACRO codes were calibrated for Cd transport in the site treated with 80 mg kg(-1) sewage sludge. Model parameters were estimated by inverse modelling using the SUFI-2 procedure. The site treated with 38 mg kg(-1) cadmium was used to test the calibrated models. Both convection-dispersion equation (CDE) and non-equilibrium CDE in HYDRUS-1D produced reasonable calibration results. However, the estimated Freundlich sorption constants were significantly smaller than those measured in a batch study. A site tracer experiment revealed the existence of substantial macropore flow. For this reason we applied MACRO to account for this process. The calibration and test results with MACRO were as good as those obtained by HYDRUS-1D with the difference that adsorption constants were much closer to the measured ones. This indicates that in HYDRUS-1D, the adsorption parameters were underestimated in order to allow a deeper transport of Cd which had actually occurred due to macropore flow. A 20-year simulation scenario depicting the long-term effect of sludge application indicated small risk of groundwater contamination. However, high concentration of Cd near the soil surface raises a concern about the crop Cd uptake which should be further investigated.     

Electrokinetic ion transport through unsaturated soil: 1. Theory, model development, and testing

An electromigration transport model for non-reactive ion transport in unsaturated soil was developed and tested against laboratory experiments. This model assumed the electric potential field was constant with respect to time, an assumption valid for highly buffered soil, or when the electrode electrolysis reactions are neutralized. The model also assumed constant moisture contents and temperature with respect to time, and that electroosmotic and hydraulic transport of water through the soil was negligible. A functional relationship between ionic mobility and the electrolyte concentration was estimated using the chemical activity coefficient. Tortuosity was calculated from a mathematical relationship fitted to the electrical conductivity of the bulk pore water and soil moisture data. The functional relationship between ionic mobility, pore-water concentration, and tortuosity as a function of moisture content allowed the model to predict ion transport in heterogeneous unsaturated soils. The model was tested against laboratory measurements assessing anionic electromigration as a function of moisture content. In the test cell, a strip of soil was spiked with red dye No 40 and monitored for a 24-h period while a 10-mA current was maintained between the electrodes. Electromigration velocities predicted by the electromigration transport model were in agreement with laboratory experimental results. Both laboratory-measured and model-predicted dye migration results indicated a maximum transport velocity at moisture contents less than saturation due to competing effects between current density and tortuosity as moisture content decreases.     

Transport and degradation of propyleneglycol and potassium acetate in the unsaturated zone

De-icing chemicals used during the winter season are potential pollutants for the groundwater underneath the new main airport of Norway. Several field experiments examining the transport and degradation of propyleneglycol (PG), potassium acetate (KAc) and non-reactive tracers were performed in a lysimeter trench under natural snowmelting conditions. Chemicals were applied underneath the snow cover and the transport in a heterogeneous coarse sandy soil was examined by extracting soil water from 30 or 40 suction cups placed at five depths between 0.4 and 2.4 m depth. Transport and degradation was analysed by spatial moment calculations. The de-icing chemicals showed the same basic displacement as chemically inactive tracers, an initial fast transport during the melting period followed by a period of stagnation throughout the summer season. PG seemed to be displaced to greater depths compared to non-reactive tracer after the first application. However, computer simulations of transport and degradation in a heterogeneous unsaturated soil showed that decreasing degradation constants with depth can generate a downward movement of the centre of mass without any flow occurring in the system. Potassium acetate showed some adsorption, with calculated retardation factors of approximately 1.3 and 1.2. The degradation rate constant for PG was calculated to be 0.015 day-1 in 1994 and increased to 0.047 day-1 in the second application made in 1995. The degradation rate constant for acetate was estimated to be 0.02 day-1. Increased manganese concentrations seem to be a good indicator of degradation of PG and Ac.     

Rapid transport from the surface to wells in fractured rock: a unique infiltration tracer experiment

A unique infiltration tracer experiment was performed whereby a fluorescent dye was applied to the land surface in an agricultural field, near Perth, Ontario, Canada, to simulate the transport of solutes to two pumped monitoring wells drilled into the granitic gneiss aquifer. This experiment, interpreted using the discrete-fracture capability of the numerical model HydroGeoSphere, showed that solute transport from the surface through thin soil (less than 2m) to wells in fractured bedrock can be extremely rapid (on the order of hours). Also, it was demonstrated that maximum concentrations of contaminants originating from the ground surface will not necessarily be the highest in the shallow aquifer horizon. These are important considerations for both private and government-owned drinking water systems that draw water from shallow fractured bedrock aquifers. This research illustrates the extreme importance of protecting drinking water at the source.     

The effect of surface-active solutes on water flow and contaminant transport in variably saturated porous media with capillary fringe effects

Organic contaminants that decrease the surface tension of water (surfactants) can have an effect on unsaturated flow through porous media due to the dependence of capillary pressure on surface tension. We used an intermediate-scale 2D flow cell (2.44 x 1.53 x 0.108 m) packed with a fine silica sand to investigate surfactant-induced flow perturbations. Surfactant solution (7% 1-butanol and dye tracer) was applied at a constant rate at a point source located on the soil surface above an unconfined synthetic aquifer with ambient groundwater flow and a capillary fringe of approximately 55 cm. A glass plate allowed for visual flow and transport observations. Thirty instrumentation stations consist of time domain reflectometry probes and tensiometers measured in-situ moisture content and pressure head, respectively. As surfactant solution was applied at the point source, a transient flow perturbation associated with the advance of the surfactant solution was observed. Above the top of the capillary fringe the advance of the surfactant solution caused a visible drainage front that radiated from the point source. Upon reaching the capillary fringe, the drainage front caused a localized depression of the capillary fringe below the point source because the air-entry pressure decreased in proportion to the decrease in surface tension caused by the surfactant. Eventually, a new capillary fringe height was established. The height of the depressed capillary fringe was proportional to height of the initial capillary fringe multiplied by the relative surface tension of the surfactant solution. The horizontal transport of surfactant in the depressed capillary fringe, driven primarily by the ambient groundwater flow, caused the propagation of a wedge-shaped drying front in the downgradient direction. Comparison of dye transport during the surfactant experiment to dye transport in an experiment without surfactant indicated that because surfactant-induced drainage decreased the storage capacity of the vadose zone, the dye breakthrough time to the water table was more than twice as fast when the contaminant solution contained surfactant. The extensive propagation of the drying front and the effect of vadose zone drainage on contaminant breakthrough time suggest the importance of considering surface tension effects on unsaturated flow and transport in systems containing surface-active organic contaminants or systems, where surfactants are used for remediation of the vadose zone or unconfined aquifers.     

Consistent interpretation of the results of through-, out-diffusion and tracer profile analysis for trace anion diffusion in compacted montmorillonite

Literature data for anion diffusion in compacted swelling clays contain systematic inconsistencies when the results of through-diffusion tests are compared with those of out-diffusion or tracer profile analysis. In the present work we investigated whether these inconsistencies can be explained by taking into account heterogeneities in the compacted samples; in particular increased porosities at the clay boundaries. Based on the combined results of out-diffusion, tracer profile analysis and the spatial distribution of the electrolyte anion in the clay, we conclude that the inconsistencies can indeed be resolved by taking into account a heterogeneous distribution of the total and the anion-accessible porosity. This, by definition, leads to a position dependence of the effective diffusion coefficient. Neglecting these effects results in a rather subordinate systematic error in the determination of effective diffusion coefficients of anions from through-diffusion tests with clay thicknesses in the centimetre range. However, stronger errors in terms of absolute values and conceptual interpretation may be introduced in out-diffusion tests and profile analyses of the diffused tracer. We recommend that anion diffusion tests should be accompanied by measurements of the total and anion-accessible porosity as a function of position in the direction of diffusion.     

A screening method for preliminary assessment of risk to groundwater from land-applied chemicals

A simple mathematical model for initial screening is presented that can aid in evaluating the relative risk to groundwater from applying nonpolar synthetic organic chemicals to soil. The basic premise is that the magnitude of the quotient of the chemical concentration of the water entering the aquifer and the maximum allowable concentration (as established by EPA or Health Departments) represents the health risk of a chemical. The chemical concentration of the soil water is estimated based on conservative, simplifying assumptions and requires only readily available data such as: basic soil properties (organic matter and saturated hydraulic conductivity), organic chemical properties (octanol-water partition coefficient and degradation rate) and environmental factors (recharge rate and depth to groundwater).The methodology was applied to assess the relative risk of organic chemicals in municipal sewage sludge and pesticides applied to agricultural land. The results are realistic.     

An inverse system for incorporation of conditioning to pressure and streamline-based calibration

A streamline-based history matching technique is employed to perform fast and efficient permeability identification and to integrate tracer data into an inverse model. To incorporate tracer data into the inverse model, a given tracer breakthrough curve is interpreted as cumulative breakthrough along independent streamlines. Permeabilities are modified along each streamline to match the tracer breakthrough curve. In this way, there is no explicit computation of sensitivity coefficients, nor any matrix inversion. However, this approach is incomplete by itself. Since the modifications occur along the streamlines, the identified permeability distribution is often incompatible with the actual permeability distribution. Thus, streamlines should be positioned correctly before the streamline-based method is applied. To accomplish this, geostatistical methods such as kriging and sequential Gaussian simulation (SGS) are implemented to provide an appropriate disposition of streamlines at the beginning of the inverse process. Then, permeabilities are iteratively calibrated in a conventional grid system to satisfy pressure and permeability observation data, and simultaneously modified along streamlines to match tracer data. The two independent optimization processes assist mutually and lead to stable convergence to a minimum. By applying the proposed inverse system to synthetic reference fields, it is observed that identified fields satisfactorily reproduce the permeability distribution of the reference fields. In addition, the pressure distributions of the identified and the reference fields are fairly alike, and the identified tracer breakthrough curves are well fitted to those of the reference fields. With regard to spatial patterns of transport behaviors, the streamlines of the identified fields show similar trajectories to those of the reference fields, and the time of flight distributions of the inversed fields are also analogous to those of the reference fields. The proposed inverse system is capable of estimating the future performance of a two-dimensional aquifer from a constrained number of permeability and pressure observation data accompanied by tracer data.     

The field campaigns of the European Tracer Experiment (ETEX): overview and results

As part of the European Tracer Experiment (ETEX) two successful atmospheric experiments were carried out in October and November, 1994. Perfluorocarbon (PFC) tracers were released into the atmosphere in Monterfil, Brittany, and air samples were taken at 168 stations in 17 European countries for 72 h after the release. Upper air tracer measurements were made from three aircraft. During the first experiment a westerly air flow transported the tracer plume north-eastwards across Europe. During the second release the flow was eastwards. The results from the ground sampling network allowed the determination of the cloud evolution as far as Sweden, Poland and Bulgaria. This demonstrated that the PFT technique can be successfully applied in long-range tracer experiments up to 2000 km. Typical background concentrations of the tracer used are around 5–7 fl ?^-1 in ambient air. Concentrations in the plume ranged from 10 to above 200 fl/?^-1. The tracer release characteristics, the tracer concentrations at the ground and in upper air, the routine and additional meteorological observations at the ground level and in upper air, trajectories derived from constant-level balloons and the meteorological input fields for long-range transport models are assembled in the ETEX database. The ETEX database is accessible via the Internet. Here, an overview is given of the design of the experiment, the methods used and the data obtained.     

Airflow dispersion in unsaturated soil

Dispersion data is abundant for water flow in the saturated zone but is lacking for airflow in unsaturated soil. However, for remediation processes such as soil vapour extraction, characterization of airflow dispersion is necessary for improved modelling and prediction capabilities. Accordingly, gas-phase tracer experiments were conducted in five soils ranging from uniform sand to clay at air-dried and wetted conditions. The disturbed soils were placed in one-dimensional stainless steel columns, with sulfur hexafluoride used as the inert tracer. The tested interstitial velocities were typical of those present in the vicinity of a soil vapour extraction well, while wetting varied according to the water-holding capacity of the soils. Results gave dispersivities that varied between 0.42 and 2.6 cm, which are typical of values in the literature. In air-dried soils, dispersion was found to increase with the pore size variability of the soil. For wetted soils, particle shape was an important factor at low water contents, while at high water contents, the proportion of macroporous space filled with water was important. The relative importance of diffusion decreased with increasing interstitial velocity and water content and was, in general, found to be minor compared to mechanical mixing across all conditions studied.     

Spatial and temporal distribution of the leaching of surface applied tracers from an irrigated monolith of a loamy vineyard soil

Fresh water scarcity is an increasing problem worldwide. Strategies to alleviate water scarcity include the use of low-quality water for irrigation. The risk of groundwater contamination by pollutants in this water is affected by soil heterogeneity and preferential flow. These risk factors can be assessed by measuring the spatio-temporal redistribution of uniformly applied water and solutes. We placed a soil monolith (height 29 cm) from an Australian vineyard on a 100-cell multi-compartment sampler (MCS). At this vineyard, treated wastewater is used in response to the severe shortage of water in the summer. We studied the leaching risk associated with heterogeneous or preferential flow by irrigating the soil column with 24 applications to simulate one year. We applied simulated rainfall as well as wastewater (which contained chloride) during summer while relying on rainfall only in winter. We compared the chloride leaching with the leaching of bromide, which was applied during one of the applications as a pulse. During the entire simulated year, leaching of solutes from the monolith was measured. The results indicate that the assumption of uniform flow would underestimate the risk for the fresh groundwater reserves: 25 % of the solutes are transported though 6 % of the soil’s cross-section. The spatial distribution of drainage and solute leaching varied little during the experiment. Consequently, the mass flux density pattern of the bromide pulse was comparable to that of the repeatedly applied chloride. However, the MCS data suggested lateral ‘escape’ from chloride to non-mobile areas, which means in the long run, considerable quantities of these solutes can build up in areas that do not receive irrigation water.     

Soil concentrations and source apportionment of polybrominated diphenyl ethers (PBDEs) and trace elements around a heavily industrialized area in Kocaeli,Turkey

Air pollutants are transported by dry deposition, wet deposition, and gas exchange accumulated in soil. Therefore, soil is an important environmental medium reflecting the level and the spatial distribution of air pollutants such as polybrominated diphenyl ethers (PBDEs) and heavy metals. Soil concentrations of seven PBDE congeners and 21 trace elements were determined in a heavily industrialized region (Dilovasi) in Kocaeli, Turkey. At all sites, Σ₇PBDE concentrations ranged from 0.70 to 203 with a mean value of 26.3 μg kg^?1 (dry weight). The congener profiles and mass inventories of PBDEs and their interactions with soil organic matter (SOM) were also investigated. BDE-209 was the dominant congener at all sites, followed by BDE-99 and/or -47. The estimated inventory of PBDEs for the Dilovasi district was 310 kg. However, there are several additional industrial regions in Kocaeli city. Considering the total land area, the potential inventory would be much larger for this city. The relationship between the PBDE concentrations in soil and SOM content indicated that factors other than soil properties have a greater influence on soil concentrations. Crustal enrichment factors (EFs) were determined; correlation analysis and factor analysis (FA) were also applied to generated data set to identify and apportion the sources polluting the soil. Sn, Mn, Ca, As, Zn, Pb, and Cd had significantly high average EF values, indicating that their soil concentrations were mainly influenced by anthropogenic activities. In FA, six factors were extracted with a cumulative variance of 84.4 % and industrial activities and traffic were found to be the main factors affecting the soil profile.