Mass balance modelling of contaminants in river basins: a flexible matrix approach

A novel and flexible approach is described for simulating the behaviour of chemicals in river basins. A number (n) of river reaches are defined and their connectivity is described by entries in an n x n matrix. Changes in segmentation can be readily accommodated by altering the matrix entries, without the need for model revision. Two models are described. The simpler QMX-R model only considers advection and an overall loss due to the combined processes of volatilization, net transfer to sediment and degradation. The rate constant for the overall loss is derived from fugacity calculations for a single segment system. The more rigorous QMX-F model performs fugacity calculations for each segment and explicitly includes the processes of advection, evaporation, water-sediment exchange and degradation in both water and sediment. In this way chemical exposure in all compartments (including equilibrium concentrations in biota) can be estimated. Both models are designed to serve as intermediate-complexity exposure assessment tools for river basins with relatively low data requirements. By considering the spatially explicit nature of emission sources and the changes in concentration which occur with transport in the channel system, the approach offers significant advantages over simple one-segment simulations while being more readily applicable than more sophisticated, highly segmented, GIS-based models.     

Geochemical characterization of acid mine drainage from a waste rock pile, Mine Doyon, Québec, Canada

Water quality in the unsaturated and saturated zones of a waste rock pile containing sulphides was investigated. The main objectives of the project were (1) the evaluation of geochemical trends including the acid mine drainage (AMD)-buffering mechanism and the role of secondary minerals, and (2) the investigation of the use of stable isotopes for the interpretation of physical and geochemical processes in waste rock. Pore water in unsaturated zone was sampled from suction lysimeters and with piezometers in underlying saturated rocks. The investigation revealed strong temporal (dry period vs. recharge period), and spatial (slope vs. central region of pile) variability in the formation of acid mine drainage. The main secondary minerals observed were gypsum and jarosite. There was a higher concentration of gypsum in solid phase at Site TBT than at Site 6, suggesting that part of the gypsum formed at Site 6 in the early stage of AMD has been already dissolved. Formation of secondary minerals contributed to the formation of AMD by opening of foliation planes in waste rock, thus increasing the access of oxidants like O2 and Fe3+ to previously encapsulated pyrite. The behavior of several dissolved species such as Mg, Al, and Fe2+ can be considered as conservative in the leachate. Stable isotopes, deuterium and 18O, indicated internal evaporation within the pile, and were used to trace recharge pulses from snowmelt. Isotope trends for 34S and 18O(SO4) indicated a lack of sulfate reduction and zones of active oxidation of pyrite, respectively. Results of numerical modeling of pyrite oxidation and gas and water transport were consistent with geochemical and isotopic trends and confirmed zones of high evaporation rate within the rock pile close to the slope. The results indicate that physical and chemical processes within the pile are strongly coupled and cannot be considered separately when oxidation rates are high and influence gas transport as a result of heat generation.     

Evaporation behaviour of different organic effluents from open surfaces

Production of large quantities of effluents from different industrial units and the problems of their disposal necessitated this evaporation study. The evaporation of water, sewage water, oil refinery effluent, papermill effluent and liquor distillery effluent was observed in glass beakers when placed (i) in an oven at 60 degrees C and (ii) in screen house for 30 days, by periodically weighing of the beakers. In other experiments, the effect of increasing the frequency of stirring on increasing the evaporation efficiency of the liquor distillery effluent (ELD) was examined in detail. All of the organic effluents except ELD had similar evaporation behaviours as water, but formation of a self-forming film caused the evaporation of ELD to be considerably lower. Resistance to evaporation caused by this film was found to be a decreasing function of the frequency of stirring. This study has a bearing on improving the efficiency of evaporation lagoons, and three stirrings in a day with a manually drawn stirrer in a full-scale lagoon are proposed as a practical and economically viable technique to save 44% of lagoon land in arid and semi-arid regions of the world.     

Fate of hydrophobic organic pollutants in the aquatic environment: a review

The fate of hydrophobic organic pollutants in the aquatic environment is controlled by a variety of physical, chemical and biological processes. Some of the most important are physical transport, chemical and biological transformations, and distribution of these compounds between the various environmental compartments (atmosphere, water, sediments and biota). The major biogeochemical processes that control the fate of hydrophobic organic compounds in the aquatic environment are reviewed. These processes include evaporation, solubilization, interaction with dissolved organic matter, sediment-water partitioning, bioaccumulation and degradation. Physico-chemical parameters used to predict the aquatic fate of such compounds are also discussed.     

Determination and partitioning behavior of perfluoroalkyl carboxylic acids and perfluorooctanesulfonate in water and sediment from Dianchi Lake, China

Perfluorinated compounds (PFCs) have received much attention on their distribution in various matrices including water bodies, precipitations, sediment and biota in different areas globally, however, little attention has been paid to their occurrence and distribution in urban lakes. In this study, water and sediment samples collected from 26 sites in Dianchi Lake, a plateau urban lake in the southwestern part of China were analyzed via high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for ten analytes involving nine perfluoroalkyl carboxylic acids (PFOAs) and perfluorooctanesulfonate (PFOS). Total levels of PFCs were 30.98 ± 32.19 ng L(-1) in water and 0.95 ± 0.63 ng g(-1) in sediment. In water samples PFOA was the dominant PFC contaminant, with concentrations ranging from 3.41 to 35.44 ng L(-1), while in sediments PFOS was the main PFC contaminant at levels from 0.07-0.83 ng g(-1) dry weight. Field-based sediment water distribution coefficients (K(D)) were calculated and corrected for organic carbon content (K(oc)), which reduced variability among samples. The log K(oc) ranged from 2.54 to 3.57 for C8-C12 perfluorinated carboxylic acids, increasing by 0.1-0.4 log units with each additional CF2 moiety. The log K(oc) of PFOS was 3.35 ± 0.32. Magnitudes and trends in log K(D) or log K(oc) appeared to agree well with previously published laboratory data. Results showed that different PFC composition profiles were observed for samples from the lake water and sediments, indicating the presence of dissimilar characteristics of the PFCs compounds, which is important for PFC fate modeling and risk assessment.     

Simulating the temporal changes of OCP pollution in Hangzhou, China

A dynamic fugacity model was applied to simulate the changes of contents and transfer fluxes of hexachlorocyclohexane (HCHs) and dichloro-diphenyl-trichloroethane (DDTs) from 1950s in the environment of Hangzhou, China. The receptors are composed of air, surface water, soils, sediment and biota compartments. The model provides a method to combine loadings of HCHs and DDTs from various sources with a series of physical-chemical processes to estimate concentrations and transport fluxes of HCHs and DDTs. Model results suggested that the calculated concentrations were in line with the observed ones. The highest contents of HCH and DDT in the environment of study area were 523 t and 471 t before 1983, among which about 80.7% HCHs and 93.2% DDTs remained in the soil compartment. From 1984 to now, contents of HCHs and DDTs had decreased to about 0.07% and 0.40% of their highest amount (before 1983), and only about 0.001% and 0.014% will expect to be left in 2020 in the study area according to the model prediction. Before 1983, the main transfer fluxes of HCHs were deposition from air to soil, runoff from soil to water and diffusion from soil to air, but for DDTs the main transfer fluxes were deposition from air to soil and water, and transfer from water to sediment. From 1984 to now, runoff from soil to water and transfer from water to sediment became the dominant processes. Although a large amount of HCHs and DDTs had been applied to the study area, their residue levels in the soils were much lower than those in North China (had lesser HCHs and DDTs application than in South China) at present time, and close to other locations of South China (had similar HCHs and DDTs application level). It can be attributed to the high precipitation and temperature that enhances the processes of wet deposition, evaporation and degradation of OCPs. Sensitivities of the input parameters to the calculated concentrations were evaluated using coefficient-of-variation normalized sensitivity coefficients. The model was also subjected to uncertainty analyses using a Monte Carlo simulation.     

Volatilization of lindance from water in soil-free and flooded soil systems.

Volatilization of 14C-lindane from water in planchets and under flooded soil ecosystem was investigated. Lindane disappeared faster than parathion from planchets. More rapid loss of both insecticides occurred from water than from chloroform. Loss of lindane and parathion was related to measured losses of water by evaporation. During 5-day incubation under flooded soil conditions, disappearance of lindane was faster from open vials than from sealed vials, whereas in nonflooded soil, no volatile loss of the insecticide was evident despite water evaporation. Over 5 day incubation under flooded conditions, greater volatile loss of lindane occurred in sandy soil than in alluvial soil apparanetly due to greater adsorption to the soil colloids decreasing the insecticide concentration in the standing water on the laterite soil. Under identical conditions of water evaporation, lindane loss was directly proportional to its initial concentration in the water. These results suggest that considerable loss of soil applied pesticides can occur by volatilization from the standing water in flooded rice fields, particularly under tropical conditions.     

Flow and transport in unsaturated fractured rock: effects of multiscale heterogeneity of hydrogeologic properties

The heterogeneity of hydrogeologic properties at different scales may have different effects on flow and transport processes in a subsurface system. A model for the unsaturated zone of Yucca Mountain, Nevada, is developed to represent complex heterogeneity at two different scales: (1) layer scale corresponding to geologic layering and (2) local scale. The layer-scale hydrogeologic properties are obtained using inverse modeling, based on the available measurements collected from the Yucca Mountain site. Calibration results show a significant lateral and vertical variability in matrix and fracture properties. Hydrogeologic property distributions in a two-dimensional, vertical cross-section of the site are generated by combining the average layer-scale matrix and fracture properties with local-scale perturbations generated using a stochastic simulation method. The unsaturated water flow and conservative (nonsorbing) tracer transport through the cross-section are simulated for different sets of matrix and fracture property fields. Comparison of simulation results indicates that the local-scale heterogeneity of matrix and fracture properties has a considerable effect on unsaturated flow processes, leading to fast flow paths in fractures and the matrix. These paths shorten the travel time of a conservative tracer from the source (repository) horizon in the unsaturated zone to the water table for small fractions of total released tracer mass. As a result, the local-scale heterogeneity also has a noticeable effect on global tracer transport processes, characterized by an average breakthrough curve at the water table, especially at the early arrival time of tracer mass. However, the effect is not significant at the later time after 20% tracer mass reaches the water table. The simulation results also verify that matrix diffusion plays an important role in overall solute transport processes in the unsaturated zone at Yucca Mountain.     

Transformation pathways of hexachlorocyclopentadiene in the aquatic environment

-- An environmental assessment of the transformation and transport pathways of hexachlorocyclopentadiene (hex) in simulated aquatic ecosystems is presented. Hydrolytic and photolytic disappearance rate constants in distilled and natural waters and in sediment-water systems are given. Sediments in defined sediment-water systems do not significantly affect the disappearance rate constants, compared to distilled water values, for the hydrolytic and photolytic processes. Water solubility, octanol/water partition coefficient, and vapor pressure for hex are also reported and compared with literature values. Fate and transport assessment using an evaluative model indicates that hex will not likely reach substantial steady-state concentrations in the various compartments of the simulated ecosystems. The results also indicate that photolysis and, to a lesser extent, hydrolysis are the predominant degradation processes; export via the water column is the predominant transport process.     

Colloidal mobilization from soil and transport of uranium in (sub)-surface waters

An analytical methodology was developed to characterize the colloidal distribution of trace elements of interest in environmental waters sampled in a same site and enables the different colloidal distributions from waters to be compared. The purpose was to provide consistent information related to the origin and nature of colloids responsible for the transport of trace element(s). The work was motivated by the observed enhanced mobility of uranium in soil. The colloidal size continuum was investigated by a multi-technique approach involving asymmetric flow field-flow fractionation (AF4) coupled with ultraviolet spectroscopy (UV), multi angle light scattering (MALS), and atomic mass spectrometry (ICPMS). To take into consideration the size and shape variability specific to each sample, the size distributions were established from the gyration radii measured from MALS, also considering the size information from standard nanospheres fractionated by AF4. A new parameter called “shape index” was proposed. It expresses the difference in hydrodynamic behavior between analytes and spherical particles taken as reference. Under AF4 diffusion conditions, it can be considered as an evaluator of the deviation from the sphericity of the fractionated analytes. AF4-UV-MALS-ICPMS enabled the dimensional and chemical characteristics of the colloidal size continuum to be obtained. As a “proof of concept”, the developed methodology was applied at a field scale, in a reference study site. In order to have a “dynamic understanding”, the investigation was based on the joint characterization of colloids from surface waters and soil leachates from static and dynamic processes. In the water samples of the study site, the continuum of gyration radius ranged from a few nanometers up to 200 nm. Colloids containing iron, aluminum, and organic carbon were involved in the uranium transport in the soil column and surface waters. The colloidal uranium concentration in the surface water increased from the upstream location (approximately 13 ng (U) L^?1) to the downstream location (approximately 60 ng (U) L^?1).

     

Volatilization of lindane from water in soil‐free and flooded soil systems

Abstract

Volatilization of ¹⁴C‐lindane from water in planchets and under flooded soil ecosystem was investigated. Lindane disappeared faster than parathion from planchets. More rapid loss of both insecticides occurred from water than from chloroform. Loss of lindane and parathion was related to measured losses of water by evaporation. During 5‐day incubation under flooded soil conditions, disappearance of lindane was faster from open vials than from sealed vials, whereas in nonflooded soil, no volatile loss of the insecticide was evident despite water evaporation. Over 5 day incubation under flooded conditions, greater volatile loss of lindane occurred in sandy soil than in alluvial soil apparently due to greater adsorption to the soil colloids decreasing the insecticide concentration in the standing water of the laterite soil. Under identical conditions of water evaporation, lindane loss was directly proportional to its initial concentration in the water. These results suggest that considerable loss of soil applied pesticides can occur by volatilization from the standing water in flooded rice fields, particularly under tropical conditions.     

Enhanced transport of pesticides in a field trial with treated sewage sludge

This study was designed to provide high-density data on spatial distribution of three herbicides with different physiochemical characteristics in a sludge-amended and non-amended control field over the course of an irrigation season. The field experiment was carried out on a sandy loam Hamra Red Mediterranean soil (Rhodoxeralf) at Bet Dagan, Israel. After a single 50 mm irrigation event, the mean centers of mass (COM) in the control field were at 15.6, 14.9, and 17 cm for bromacil, atrazine and terbuthylazine, respectively; in the sludge-amended field, mean COMs were at 28.8, 31.2, and 34.1 cm, respectively. After 500 mm of irrigation in the control field, the COM depth distribution of the three pesticides was inversely correlated with octanol-water (Kow) distribution coefficients and soil sorption coefficients (Koc), and positively correlated with aqueous solubilities. After 500 mm irrigation in the sludge-amended field, the mean terbuthylazine COM was at 19.8 cm versus 13.8 cm for the control field, demonstrating a sustained enhanced effect on terbuthylazine transport. Downward transport of atrazine was also enhanced by sludge amendment, albeit less than terbuthylazine. Bromacil was preferentially accumulated in the upper soil layers of the sludge-amended field as compared with the control field after 500 mm irrigation. The enhanced transport of all three pesticides in the sludge-amended field after a single irrigation event is attributed to development of preferential flow pathways around hydrophobic clods of sludge. Enhanced transport of terbuthylazine, and to a lesser extent, atrazine, throughout the irrigation season, is attributed to their transport as complexes with dissolved, colloidal and suspended organic matter derived from sludge degradation.     

Arsenic speciation and accumulation in evapoconcentrating waters of agricultural evaporation basins

To sustain agricultural productivity, evaporation basins (or ponds) have been widely used for the disposal of agricultural drainage in areas requiring subsurface drainage in the San Joaquin Valley of California, USA. The drainage water contains elevated concentration of trace elements including selenium (Se) and arsenic (As). Unlike Se, little information is available about As, a potentially high risk element. The objective of this study was to characterize the chemical behavior of As and acquire data for better understanding of biogeochemical processes and conditions affecting As fate in evaporation ponds. The study site was a 726 ha evaporation basin facility (containing 10 cells with water flowing in series) in the hydrologically closed Tulare Basin of California. We examined water chemistry, As concentration and speciation along the water flow path between cells as well as within the cells. Arsenic concentrations in the water increased linearly with Cl(-), a conservative ion from evapoconcentration. Reduced As species as arsenite [As(III)] and organic arsenic (org-As) also increased with increases in Cl(-) and salinity. Water samples with elevated EC (i.e., towards the end of flow path) had high dissolved organic matter, low dissolved oxygen, and elevated sulfide concentrations, indicating the development of reducing conditions. We hypothesize that such changes could facilitate the reduction of arsenate [As(V)] to As(III) and org-As. Elevated As in sediment profiles indicate a solid phase sink mechanism, but not significant enough to remove and reduce As concentrations in the water columns. These findings help us better define the processes that affect As in drainage facilities and contribute to our understanding of how As behaves in other regions of the world that have similar climatic and hydrogeochemical conditions.     

Effect of density-driven flow on the through-diffusion experiment

Diffusion is one of the main mechanisms of solute transport in pore water of geologic media. The effective diffusion coefficient of a solute in a rock is usually measured by the through-diffusion experiment. However, in this experiment, the effect of advection, induced by density difference between dense aqueous solution and pure water, has not been considered. To evaluate the effect of density-driven flow, a through-diffusion experiment using Fontainebleau sandstone was conducted for KCl and KI aqueous solutions with various densities. The measured effective diffusion coefficients were positively correlated with the density difference; the effective diffusion coefficient of a 1 M KI solution (density difference, 0.119 g/cm³) was one order of magnitude larger than that of a 0.1 M KCl solution (density difference, 0.005 g/cm³). The result is explained by a theoretical model using a diffusion–advection equation including Darcy's law. Based on the theory, a diagram to evaluate the condition at which the measured effective diffusion coefficient does not include the effect of advection is presented.     

Investigation of hydrogeologic processes in a dipping layer structure: 2. Transport and biodegradation of organics

Numerical simulation tools have been used to study the dominating processes during transport of aromatic hydrocarbons in the unsaturated soil zone. Simulations were based on field observations at an experimental site located on a glacial delta plain with pronounced layered sedimentary structures. A numerical model for transport in the unsaturated zone, SWMS-3D, has been extended to incorporate coupled multispecies transport, microbial degradation following Monod kinetics and gas diffusive transport of oxygen and hydrocarbons. The flow field parameters were derived from previous work using nonreactive tracers. Breakthrough curves (BTC) from the hydrocarbon field experiment were used to determine sorption parameters and Monod kinetic parameters using a fitting procedure. The numerical simulations revealed that the assumption of homogeneous layers resulted in deviations from the field observations. The deviations were more pronounced with incorporation of reactive transport, compared with earlier work on nonreactive transport. To be able to model reasonable BTC, sorption had to be reduced compared to laboratory experiments. The initial biomass and the maximum utilisation rate could be adjusted to capture both the initial lag phase and the overall degradation rate. Nevertheless, local oxygen limitation is predicted by the model, which was not observed in the field experiment. Incorporation of evaporation and diffusive gas transport of the hydrocarbons did not significantly change the local oxygen demand. The main cause of the observed discrepancies between model and field are attributed to channelling as a result of small-scale heterogeneities such as biopores.     

Effect of soil moisture dynamics on dense nonaqueous phase liquid (DNAPL) spill zone architecture in heterogeneous porous media

The amount, location, and form of NAPL in contaminated vadose zones are controlled by the spatial distribution of water saturation and soil permeability, the NAPL spill scenario, water infiltration events, and vapor transport. To evaluate the effects of these processes, we used the three-phase flow simulator STOMP, which includes a new permeability-liquid saturation-capillary pressure (k-S-P) constitutive model. This new constitutive model considers three NAPL forms: free, residual, and trapped. A 2-D vertical cross-section with five stratigraphic layers was assumed, and simulations were performed for seven cases. The conceptual model of the soil heterogeneity was based upon the stratigraphy at the Hanford carbon tetrachloride (CT) spill site. Some cases considered co-disposal of NAPL with large volumes of wastewater, as also occurred at the Hanford CT site. In these cases, the form and location of NAPL were most strongly influenced by high water discharge rates and NAPL evaporation to the atmosphere. In order to investigate the impact of heterogeneity, the hydraulic conductivity within the lower permeability layer was modeled as a realization of a random field having three different classes. For six extreme cases of 100 realizations, the CT mass that reached the water table varied by a factor of two, and was primarily controlled by the degree of lateral connectivity of the low conductivity class within the lowest permeability layer. The grid size at the top boundary had a dramatic impact on NAPL diffusive flux just after the spill event when the NAPL was present near the ground surface. NAPL evaporation with a fine grid spacing at the top boundary decreased CT mass that reached the water table by 74%, compared to the case with a coarse grid spacing, while barometric pumping had a marginal effect for the case of a continuous NAPL spill scenario considered in this work. For low water infiltration rate scenarios, the distribution of water content prior to a NAPL spill event decreased CT mass that reached the water table by 98% and had a significant impact on the formation of trapped NAPL. For all cases simulated, use of the new constitutive model that allows the formation of residual NAPL increased the amount of NAPL retained in the vadose zone. Density-driven advective gas flow from the ground surface controlled vapor migration in strongly anisotropic layers, causing NAPL mass flux to the lower layer to be reduced. These simulations indicate that consideration of the formation of residual and trapped NAPLs and dynamic boundary conditions (e.g., areas, rates, and periods of different NAPL and water discharge and fluctuations of atmospheric pressure) in the context of full three-phase flow are needed, especially for NAPL spill events at the ground surface. In addition, NAPL evaporation, density-driven gas advection, and NAPL vertical movement enhanced by water flow must be considered in order to predict NAPL distribution and migration in the vadose zone.     

Droplet evaporation from porous surfaces; model validation from field and wind tunnel experiments for sand and concrete

The evaporation model of Roberts and Griffiths (1995 Atmospheric Environment 29, 1307–1317) has been subjected to an extensive validation exercise based on a major campaign of field experiments on evaporation from surfaces composed of sand and of concrete. This complements the previous validation which was limited to wind tunnel experiments on sand surfaces. Additionally, the validation using wind tunnel data has been extended to include concrete surfaces. The model describes the constant-rate and falling-rate periods that characterise evaporation from porous media. During the constant-rate period, the evaporation is solely determined by the vapour transport rate into the air. During the falling-rate period, the process in the porous medium is modelled as a receding evaporation front, the overall evaporation rate being determined by the combined effects of vapour transport through the pore network and subsequently into the air. The field trials programme was conducted at sites in the USA and the UK, and examined the evaporation of diethyl malonate droplets from sand and concrete surfaces. Vapour concentrations at several heights in the plume were measured at the centre of a 1 m radius annular source (of width 10 cm) contaminated by uniformly sized droplets (2.4 or 4.1 mm in diameter), key meteorological data being measured at the same time. The evaporation was quantified by coupling concentration and wind speed data. In all, 22 trials were performed on sand and concrete; a further 8 were performed on non-porous surfaces (aluminium foil and slate) as references. The model performance was evaluated against the experimental data in terms of two quantities, the initial evaporation rate of the embedded droplets, and the mass-fraction remaining in the substrate at intervals over the evaporation episode. Overall, the model performance was best in the case of the field experiments for concrete, and the wind tunnel experiments for sand; the performance for wind tunnel experiments for concrete was reasonably good; in the case of the field experiments for sand there was significant underprediction of evaporation rates, though the trends with the determining variables were well predicted.     

Nitrate distribution and denitrification in the saturated zone of paddy field under rice/wheat rotation

Nitrate concentration in well water collected from the wells near farm houses was investigated in the Taihu Lake basin (TBL) of China. Nitrate-N content of the well water ranged from 0.1 to 23 mgNl(-1), and 41% exceeded the criteria (10 mg Nl(-1)). It was found that the difference in well conditions, especially the depth of the well, was the main cause of the difference in the nitrate concentration of well water, i.e. it was higher in shallow well and lower in deeper well. A recommendation was made for local farmers to drill wells deeper than 10 m in order to reduce the risk of high ingestion of nitrate-N in their drinking water. Nitrate distribution and denitrification in the saturated zone of a paddy field under rice/wheat rotation in the TBL were studied. Porous pipes were installed in triplicate at depths of 1.5, 2.0, 2.5, 3.5 and 5 m respectively to collect the soil solution samples. Results showed that nitrate was the predominant N form in soil solution of saturated zone, and it increased from 1.5 to 2.5 m depth, and decreased from 2.5 to 5 m depth. N2O captured in the soil solution was very high comparing with N2O content in air. N2O content was positively correlated with nitrate concentrations in the soil profile. These results indicate that nitrate leached into saturated zone was mainly transformed via denitrification processes. Comparing the sum of inorganic nitrogen with the total nitrogen in soil solution samples collected from those wells at the field, some soluble organic nitrogen was found about 1-2 mg N l(-1) in average.