Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg⁻¹) compared to soil B (22.03 mg kg⁻¹). The simazine adsorption distribution coefficients (K_d) were 9.32 L kg⁻¹ for soil A and 7.74 L kg⁻¹ for soil B. The simazine adsorption enthalpy in soil A was −21.0 kJ mol⁻¹ while in soil B the adsorption enthalpy value was −11.5 kJ mol⁻¹. These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine–organic matter interactions and in soil B by simazine–clay interactions. The understanding of simazine sorption–desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.     

Column- and catchment-scale transport of cadmium: effect of dissolved organic matter

In the Ellen catchment on the Pinjarra Plain, NE of Perth in Western Australia, cadmium from fertilisers is starting to leach from soils. About 70% of surface soils in the Ellen catchment are sandy and often on top of a shallow ephemeral water table. Adsorption of Cd in the sandy soils of the Ellen catchment was studied by batch adsorption and by leaching small columns of soil. Adsorption of Cd increases linearly with increasing soil organic matter content and exponentially with increasing pH. Cadmium is significantly mobilised in the sandy soils by dissolved organic matter.The capacity of most of the sandy soils in the Ellen catchment to adsorb phosphate from fertiliser has been saturated. Resulting concentrations in Ellen Brook average 500 μg L⁻¹ P. Cadmium is adsorbed more strongly in the sandy soils than phosphate and is just starting to leach into Ellen Brook. From a comparison of Cd/P ratios in water, soils and fertiliser, cadmium concentrations in Ellen Brook are estimated to be at 10–30% of their maximum for complete breakthrough from soils. Present concentrations of Cd in Ellen Brook average 0.1 μg L⁻¹ and are estimated to approach the maximum for complete breakthrough in 100 yr. Maximum Cd concentrations in Ellen Brook could range from 0.6 to 2 μg L⁻¹, depending on rates of input with fertiliser and future increases in agricultural land use in the catchment.Breakthrough curves, resulting from leaching Cd through small columns of sandy soil, indicate that adsorption significantly increases the effective hydrodynamic dispersion of Cd. Longitudinal dispersivities, measured at pore-water velocities of 0.7–14 m day⁻¹, were 5 cm for Cd and 0.1–0.2 cm for chloride. The much greater dispersion of Cd in the sandy soils than of chloride is shown not to be caused by non-equilibrium adsorption.     

The contribution of dry deposited ammonia and sulphur dioxide to the composition of precipitation from continuously open gauges

A series of experiments using bulk precipitation collectors of the type used in the UK precipitation chemistry network measured the amounts of NH₄⁺, SO₄²⁻ and other ions that could be washed from funnels (diameter 15 cm) exposed to a wide range of NH₃ and SO₂ concentrations over periods from hours to days. In dry conditions, the average deposition flux of NH₃ was between 50 and 120 nmol NH₄⁺ funnel⁻¹ d⁻¹ (0.1–0.3 kg N ha⁻¹ yr⁻¹), and was independent of the concentration of NH₃. Dry deposition of NH₃ to wet funnels at small NH₃ concentrations was almost 5 times that to dry funnels under the same conditions (average 240 nmol funnel⁻¹ d⁻¹; 0.7 kg ha⁻¹ yr⁻¹), and increased with increasing NH₃ concentrations. The amount of NH₄⁺ ions remaining on the funnel surface was inversely proportional to the vapour pressure deficit during the experiment. This result was interpreted as a dependence on the duration of surface wetness, with greater deposition of NH₄⁺ when evaporation rates of surface water were small.The amount of SO₂ deposited on funnel surfaces was closely related to the amount of NH₃ deposited, in both wet and dry conditions, but was not strongly correlated with the SO₂ concentration. At low NH₃ and SO₂ concentrations the average deposition to dry funnels was 70 nmol SO₄²⁻ funnel⁻¹ d⁻¹ (0.5 kg ha⁻¹ yr⁻¹), and to wet funnels was approximately 2.5 times larger. The results are interpreted in terms of the balance between the rate of evaporation of surface water, and the rate of oxidation of SO₂, which leads to the ‘fixing’ of NH₄⁺ ions on the surface as involatile salts.It is predicted that dry deposition of NH₃ to funnel surfaces across the UK Secondary Network could account for as much as one-half of the measured bulk wet deposition at sites where wet deposition of NH₄–N is small. The amount of dry deposition depends on how long and how often funnel surfaces are wetted by rain or dew, and on the air concentrations of NH₃. These predictions are based on funnels being wetted only once per day. More frequent wetting would increase the contribution from dry deposition, and the consequent overestimate of wet deposition of NH₄–N across the UK by using data obtained from bulk collectors. To some extent this overestimate may be offset by microbial degradation and loss of NH₄–N in weekly bulk precipitation samples during collection and storage.     

Time aggregation of nitrogen leaching in relation to critical threshold values

Leaching of nitrate contributes to the deterioration of groundwater and can consequently have a negative influence on the quality of our drinking water. Critical threshold values for nitrogen leaching are established to preserve groundwater quality. A critical threshold value for nitrate leaching of 50 mg 1⁻¹ (11.3 mg N 1⁻¹), similar to the drinking water standard, serves as a threshold value for European countries. However, the temporal aggregation scale on which this threshold value should be considered is unknown. A well tested simulation model was used to evaluate the exceedance of the threshold value at different time aggregation levels, ranging from one day till 30 yr. For three different soil structure types within one soil type and a selected fertilisation regime, the aggregated nitrogen leaching over 30 yr was 11.4, 19.2 and 10.6 mg 1⁻¹. Considering an aggregation level of one day, the critical threshold value of 11.3 mg N 1⁻¹ was exceeded 2973, 5801 and 2556 times, respectively, for the three structure types during 30 yr. By considering other time aggregation levels, a clear relation resulted between time aggregation level and the number of time elements during which the critical level was exceeded. Results strongly indicate that a critical threshold value for leaching should include an associated time-aggregation level.     

Atmospheric deposition and canopy exchange processes in alpine forest ecosystems (northern Italy)

Throughfall and bulk precipitation chemistry were studied for five years (June 1994–May 1999) at two high elevation forest sites (Val Gerola and Val Masino) which were known to differ in terms of tree health, as assessed by live crown condition. The ion concentration of bulk precipitation samples did not differ significantly between sites, except for Mg²⁺, while the throughfall concentrations differed in the measured values of H⁺, N-NO₃⁻, Cl⁻, Na⁺, K⁺, DOC and weak organic acids. The results of the application of the canopy exchange model indicated a higher contribution from the dry deposition of N-NO₃⁻, N-NH₄⁺ and H⁺ at Val Gerola, where the damage symptoms were more evident. In addition, the canopy leaching of Ca²⁺, K⁺ and weak organic acids were 47%, 21% and 27% higher at Val Gerola than at Val Masino. Annual SO₄²⁻ deposition fluxes (21.3 kg ha⁻¹ yr⁻¹ at Val Masino and 23.6 kg ha⁻¹ yr⁻¹ at Val Gerola) were similar to those reported for moderately polluted European and U.S. sites. Annual N loads were 13.6 and 13.1 kg ha⁻¹ yr⁻¹ in the bulk input, and 15.0 and 18.0 kg ha⁻¹ yr⁻¹ in throughfall inputs, at Val Masino and Val Gerola, respectively. The contribution of the organic fraction to the total N atmospheric deposition load is significant, constituting 17% of the bulk flux and 40% of the throughfall flux. Measured nitrogen loads exceed the critical nutrient loads by several kg N ha⁻¹ at both stations. In particular the nitrogen throughfall load at Val Gerola was about 3 times higher than the critical values.     

Arsenic concentration in porewater of an alkaline coal ash disposal site: Roles of siderite precipitation/dissolution and soil cover

The geochemical behavior of As in porewaters of an alkaline coal ash disposal site was investigated using multilevel samplers. The disposal site was in operation from 1983 until 1994 and was covered with 0.3–0.5 m thick soils in 2001 when this study was initiated. Sequential extraction analyses and batch leaching experiments were also performed using the coal ash samples collected from the disposal site. The results suggest the important roles of siderite (FeCO₃) precipitation/dissolution and soil cover, which have been ignored previously. Arsenic levels in the porewater were very low (average of 10 μg L⁻¹) when the site was covered with soil due to coprecipitation with siderite. The soil cover enabled the creation of anoxic conditions, which raised the Fe concentration by the reductive dissolution of Fe-(hydr)oxides. Because of the high alkalinity generated from the alkaline coal ash, even a small increase in the Fe concentration (0.66 mg L⁻¹ on average) could cause siderite precipitation. When the soil cover was removed, however, an oxidizing condition was created and triggered the precipitation of dissolved Fe as (hydr)oxides. As a result, the dissolution of previously precipitated As-rich siderite caused higher As concentration in the porewater (average of 345 μg L⁻¹).     

Mercury in United Kingdom topsoils; concentrations, pools, and Critical Limit exceedances

The median total mercury concentration in 898 UK rural topsoils, sampled between 1998 and 2008, was 0.095 μg g⁻¹. Approximate adjustment for unreactive metal produced an estimate of 0.052 μg g⁻¹ for reactive Hg. The highest concentrations were in the north and west, where organic-rich soils with low bulk densities dominate, but the spatial pattern was quite different if soil Hg pools (mg m⁻²) were considered, the highest values being near to the industrial north of England and London. Possible toxic effects of Hg were best evaluated by comparison with soil Critical Limits expressed as ratios of Hg to soil organic matter, or soil solution Hg²⁺ concentrations, estimated by chemical speciation modelling. Only a few percent of the rural UK soils showed exceedance, and this also applied to rural soils from the whole of Europe. UK urban and industrial soils had higher Hg concentrations and more cases of exceedance.     

Mercury deposition/accumulation rates in the vicinity of a lead smelter as recorded by a peat deposit

Mercury (Hg) concentration profiles and historical accumulation rates were determined in three ²¹⁰Pb-dated cores from a peat deposit in the vicinity of a lead (Pb) smelter at Příbram, Czech Republic. The Hg concentrations in peat samples ranged from 66 to 701 μg kg⁻¹. Cumulative Hg inventories from each core (for the past 150 yr) varied by a factor of 1.4 (13.6–18.5 mg Hg m⁻²), indicating variations of net Hg accumulation rate within the peat deposit. Historical changes in vegetation cover (leading to variable interception by trees) are probably responsible for this variation in space and time. The uncorrected Hg accumulation rates peaked between the 1960s and 1980s (up to 226 μg m⁻² yr⁻¹). Recent findings show that Hg records from peat tend to overestimate historical levels of Hg deposition. Therefore we used the mass loss compensation factor (MLCF) to normalize Hg accumulation rates. These corrected Hg accumulation rates were significantly lower (maximum 129 μg m⁻² yr⁻¹) and better corresponded to changes in historical smelter emissions, which were highest in the 1960s. The agreement between the corrected Hg accumulation rates in the uppermost peat sections (2–38 μg m⁻² yr⁻¹) and biomonitoring of atmospheric deposition by mosses in several recent years (4.7–34.4 μg m⁻² yr⁻¹) shows the usefulness of MLCF application on Hg accumulation in peat archives. However, the MLCF correction was unsuitable for Pb. The recent Pb deposition rates obtained by an independent biomonitoring study using mosses (0.5–127 mg m⁻² yr⁻¹) were better correlated with net Pb accumulation rates recorded in peat (7–145 mg m⁻² yr⁻¹) than with corrected rates obtained by the MLCF approach (1–28 mg m⁻² yr⁻¹).     

Depleted N carryover, leaching and uptake for three years of irrigated corn

Deep percolation of nitrate can contribute to the deterioration of groundwater resources. Leaching of nitrate is a complex process affected by fertilizer and irrigation practices, efficiency of N use by the crop, and how the soil's water holding capacity and water transmission properties are affected by soil texture. Depleted (¹⁵NH₄)₂SO₄ fertilizer at N rates of 0, 125, 250 and 375 kg ha⁻¹ was applied annually for 3 years to continuous corn grown within three different water regimes. This time period and the labeled N permitted an evaluation of N use efficiency by the crop and NO₃ leaching and carryover on a Weld silty clay loam, a fine-textured soil, typical of the “hardland” soils of the semi-arid Great Plains. Three water regimes, W₁ ( 1.5 ET), W₂ ( ET) and W₃ ( 0.8 ET), were used. Beneath each plot within each water regime, Duke-Haise vacuum trough extractors were installed under undisturbed soil profiles at 1.22-m depth to measure weekly percolate and the NO₃ concentration in the percolate. The corn was harvested in the fall in the dent stage to measure the total above-ground biomass N uptake. Soil profiles (1.8 m) were sampled annually in the fall after crop harvest to determine NO₃---N in the soil or carryover.Great variability was encountered in measuring the amount of extractor water and its NO₃ content under each water regime, which made estimates of N03 leaching losses unreliable. Also, the variability demonstrates formidable problems in quantifying percolation losses with vacuum trough extractors under undisturbed fine-textured soil profiles. With the highest N rate of 376 kg ha⁻¹ yr⁻¹ and within the water regime W₁, where leaching was expected to be greatest, only 1% of the cumulative labeled N applied was found in extractor waters and most movement of the labeled N into extractors occurred the third year. The 125-kg-ha⁻¹ yr⁻¹ fertilizer N rate significantly increased the crop yield over the unfertilized plots without increasing residual NO₃---N accumulation; whereas fertilizer N rates of > 125 kg ha⁻¹ yr⁻¹ did not appreciably increase plant yields over the 125-kg-ha⁻¹-N rate, but did appreciably increase residual NO₃.     

Nitric oxide and nitrous oxide emission from Hungarian forest soils; linked with atmospheric N-deposition

Studies of forest nitrogen (N) budgets generally measure inputs from the atmosphere in wet and dry deposition and outputs via hydrologic export. Although denitrification has been shown to be important in many wetland ecosystems, emission of N oxides from forest soils is an important, and often overlooked, component of an ecosystem N budget. During 1 year (2002–03), emissions of nitric oxide (NO) and nitrous oxide (N₂O) were measured from Sessile oak and Norway spruce forest soils in northeast Hungary. Accumulation in small static chambers followed by gas chromatography-mass spectrometry detection was used for the estimation of N₂O emission flux. Because there are rapid chemical reactions of NO and ozone, small dynamic chambers were used for in situ NO flux measurements. Average soil emissions of NO were 1.2 and 2.1 μg N m⁻² h⁻¹, and for N₂O were 15 and 20 μg N m⁻² h⁻¹, for spruce and oak soils, respectively. Due to the relatively high soil water content, and low C/N ratio in soil, denitrification processes dominate, resulting in an order of magnitude greater N₂O emission rate compared to NO. The previously determined N balance between the atmosphere and the forest ecosystem was re-calculated using these soil emission figures. The total (dry+wet) atmospheric N-deposition to the soil was 1.42 and 1.59 g N m⁻² yr⁻¹ for spruce and oak, respectively, while the soil emissions are 0.14 and 0.20 g N m⁻² yr⁻¹. Thus, about 10–13% of N compounds deposited to the soil, mostly as and , were transformed in the soil and emitted back to the atmosphere, mostly as greenhouse gas (N₂O).     

Spatial character of polychlorinated biphenyls from soil and respirable particulate matter in Taiyuan, China

As one of China’s great metropolises, Taiyuan is affected by heavy chemical industry and manufacture of chemical products, and faces pollution from polychlorinated biphenyls (PCBs). Therefore, this study was conducted to determine the PCB concentrations in various environmental media in Taiyuan. We collected 15 soil samples, 34 respirable particulate matter (PM) samples (17 of PM_2.5 and 17 of PM₁₀) from urban areas of Taiyuan, and measured a total of 144 PCB congeners (including some coeluting PCB congeners). The total PCB concentrations were 51–4.7 × 10³ pg g⁻¹ in soil, 27–1.4 × 10² pg m⁻³ in PM_2.5 and 16–1.9 × 10² pg m⁻³ in PM₁₀. Of the PCB homologues, the dominant PCBs detected in the various media were all tri-CBs. Soil was relatively the most polluted media. Furthermore, principal-component analysis revealed that the major PCB source in Taiyuan may be associated with the main commercial PCB through long-range transmission. Toxic equivalency (TEQ) concentrations (based on ten dioxin-like PCBs) ranged from N.D. to 5.9 × 10⁻³ pg-WHO TEQ g⁻¹ in soil, 2.0 × 10⁻⁴–3.4 × 10⁻³ pg-WHO TEQ m⁻³ and 1.0 × 10⁻⁴–1.2 × 10⁻³ pg-WHO TEQ m⁻³ in PM_2.5 and PM₁₀, respectively. In previous studies, PCBs were not a severe component of contaminant in Taiyuan; however, this study suggested there is a potential threat of human exposure to PCBs for residents of Taiyuan.     

Development of steady-state phosphate concentrations in septic system plumes

Long-term monitoring of PO₄⁻³ behaviour in a well-defined septic system plume on calcareous sand (Cambridge site) shows that, after 17 yr of system operation, a distinct PO₄⁻³ plume (PO₄⁻³−P > 1 mg L⁻¹) is present extending 20 m downgradient from the infiltration bed. The PO₄³⁻ plume migration velocity is 1 m yr⁻¹, reflecting retardation by a factor of 20 compared to the groundwater velocity. During monitoring between years 10 to 17, an expanding steady-state zone was noted below the infiltration bed where PO₄³⁻ −P levels remained consistently near 4 mg L⁻¹, a value 25% lower than the average effluent value (6.3 mg L⁻¹). The pattern of attenuation — a 25% mass loss in the 2-m-thick vadose zone, then little further attenuation along the flowpath — is suggestive of a condition of equilibrium with a controlling phosphate mineral phase. Chemical equilibrium modelling shows supersaturation with respect to hydroxylapatite and variscite. Four other field sites are identified from the literature and from our work where similar steady-state PO₄³⁻ zones are present in septic system plumes. In these, steady-state levels range from 15% to 68% of effluent values, with lower concentrations observed in the more acidic plumes, again indicative of a mineral solubility control, possibly variscite.PO₄³⁻ behaviour in these plumes suggests that, although P migration velocity is controlled by the processes of sorption, the magnitude of PO₄³⁻ that is present is governed by the constraints of phosphate mineral solubility. When septic systems on sands are located relatively close to sensitive surface water bodies and when long-term downgradient impact is the primary concern, more attention should be focused on the geochemical conditions that control PO₄³⁻ mineral solubility rather than only on the sorption characteristics of the sediment.     

Terricolous alpine lichens are sensitive to both load and concentration of applied nitrogen and have potential as bioindicators of nitrogen deposition

The influence of applied nitrogen (N) concentration and load on thallus chemistry and growth of five terricolous alpine lichen species was investigated in a three-month N addition study. Thallus N content was influenced by both concentration and load; but the relative importance of these parameters varied between species. Growth was most affected by concentration. Thresholds for effects observed in this study support a low critical load for terricolous lichen communities (<7.5 kg N ha⁻¹ y⁻¹) and suggest that concentrations of N currently encountered in UK cloudwater may have detrimental effects on the growth of sensitive species. The significance of N concentration effects on sensitive species also highlights the need to avoid artificially high concentrations when designing N addition experiments. Given the sensitivity of some species to extremely low loads and concentrations of N we suggest that terricolous lichens have potential as indicators of deposition and impact in northern and alpine ecosystems.     

Assessing the Impacts of Long-Range Sulfur and Nitrogen Deposition on Arctic and Sub-Arctic Ecosystems

For more than a decade, anthropogenic sulfur (S) and nitrogen (N) deposition has been identified as a key pollutant in the Arctic. In this study new critical loads of acidity (S and N) were estimated for terrestrial ecosystems north of 60° latitude by applying the Simple Mass Balance (SMB) model using two critical chemical criteria (Al/Bc = 1 and ANC_le = 0). Critical loads were exceeded in large areas of northern Europe and the Norilsk region in western Siberia during the 1990s, with the more stringent criterion (ANC_le = 0) showing the larger area of exceedance. However, modeled deposition estimates indicate that mean concentrations of sulfur oxides and total S deposition within the Arctic almost halved between 1990 and 2000. The modeled exceeded area is much reduced when currently agreed emission reductions are applied, and almost disappears under the implementation of maximum technically feasible reductions by 2020. In northern North America there was no exceedance under any of the deposition scenarios applied. Modeled N deposition was less than 5 kg ha⁻¹ y⁻¹ almost across the entire study area for all scenarios; and therefore empirical critical loads for the eutrophying impact of nitrogen are unlikely to be exceeded. The reduction in critical load exceedances is supported by observed improvements in surface water quality, whereas the observed extensive damage of terrestrial vegetation around the mining and smelter complexes in the area is mainly caused by direct impacts of air pollution and metals.     

Critical Limits for Hg(II) in soils, derived from chronic toxicity data

Published chronic toxicity data for Hg(II) added to soils were assembled and evaluated to produce a data set comprising 52 chronic end-points, five each for plants and invertebrates and 42 for microbes. With end-points expressed in terms of added soil Hg(II) contents, Critical Limits were derived from the 5th percentiles of species sensitivity distributions, values of 0.13 μg (g soil)⁻¹ and 3.3 μg (g soil organic matter)⁻¹ being obtained. The latter value exceeds the currently recommended Critical Limit, used to determine Hg(II) Critical Loads in Europe, of 0.5 μg (g soil organic matter)⁻¹. We also applied the WHAM/Model VI chemical speciation model to estimate concentrations of Hg²⁺ in soil solution, and derived an approximate Critical Limit Function (CLF) that includes pH; log [Hg²⁺]_crit = −2.15 pH −17.10. Because they take soil properties into account, the soil organic matter-based limit and the CLF provide the best assessment of toxic threat for different soils. For differing representative soils, each predicts a range of up to 100-fold in the dry weight-based content of mercury that corresponds to the Critical Limit.     

Contamination in Ontario farmstead domestic wells and its association with agriculture:: 1. Results from drinking water wells

Groundwater provides about 30% of water requirements in Ontario, but farm families depend almost entirely on private wells. Major potential contaminants on farms are nitrate (NO₃⁻), pathogenic microorganisms, pesticides and petroleum derivatives. A survey of farm drinking-water wells was conducted throughout the Province of Ontario, Canada, in 1991 and 1992 and tested for these contaminants. The main objectives of the survey were to determine the quality and safety of drinking water for farm families, and determine the effect of agricultural management on groundwater quality at a provincial scale. Four farm wells were chosen in each township where >50% of the land area was used for agricultural production. Elsewhere one well per township was usually sampled. Within each township the types of farming activity and dominant soils were additional criteria for selection. The network comprised 1292 of the estimated 500,000 water-wells in Ontario, and the study conformed to a stratified random survey. A subset of 160 wells, chosen by farm type, soil, and the presence or absence of a fuel storage tank, was investigated for the presence of petroleum derivatives: benzene, toluene, ethyl benzene, and xylene. About 40% of farm wells tested contained one or more of the target contaminants above the maximum acceptable concentration; 34% of wells had more than the maximum acceptable number of coliform bacteria, 14% contained NO₃⁻-N concentrations above 10 mg l⁻¹ limit and about 7% were contaminated with both bacteria and NO₃⁻. Only six wells contained pesticide residues above the interim maximum acceptable concentration (IMAC), but pesticides were detected in 7% of wells in winter and in 11% in summer. No wells contained detectable petroleum derivatives. These results for NO₃⁻ contamination were not significantly different from those reported for a survey of Ontario wells for the period 1950–1954, but the frequency of contamination by Escherichia coli was greater in the present study. None of the point sources investigated contributed significantly to the NO₃⁻ contamination. The percentage of wells contaminated by coliform bacteria decreased significantly with increasing separation of the well from the feedlot or exercise yard on livestock farms. A full statistical model including the type of well construction, depth, age and soil hydrologic group was developed to describe the frequency of NO₃⁻ contamination.     

Petroleum mass removal from low permeability sediment using air sparging/soil vapor extraction: impact of continuous or pulsed operation

Air sparging and soil vapor extraction (AS/SVE) are innovative remediation techniques that utilize volatilization and microbial degradation to remediate petroleum spills from soils and groundwater. This in situ study investigated the use of AS/SVE to remediate a gasoline spill from a leaking underground storage tank (UST) in the low permeability, clayey soil of the Appalachian Piedmont. The objectives of this study were to evaluate AS/SVE in low permeability soils by quantifying petroleum mass removal rates, monitoring vadose zone contaminant levels, and comparing the mass extraction rates of continuous AS/SVE to 8 and 24 h pulsed operation. The objectives were met by collecting AS/SVE exhaust gas samples and vadose zone air from multi-depth soil vapor probes. Samples were analyzed for O₂, CO₂, BTEX (benzene, toluene, ethylbenzene, xylene), and total combustible hydrocarbon (TCH) concentrations using portable hand meters and gas chromatography. Continuous AS/SVE was effective in removing 608 kg of petroleum hydrocarbons from low permeability soil in 44 days (14.3 kg day⁻¹). Mass removal rates ranged from 2.6 times higher to 5.1 times lower than other AS/SVE studies performed in sandy sediments. BTEX levels in the vadose zone were reduced from about 5 ppm to 1 ppm. Ten pulsed AS/SVE tests removed 78 kg in 23 days and the mean mass removal rate (17.6 kg day⁻¹) was significantly higher than the last 15 days of continuous extraction. Pulsed operation may be preferable to continuous operation because of increased mass removal and decreased energy consumption.     

Diffusion of HTO, Cl and I in Opalinus Clay samples from Mont Terri: Effect of confining pressure

Diffusion coefficients (T=23±2 °C) and accessible porosities for HTO, ³⁶Cl⁻ and ¹²⁵I⁻ were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na⁺ and Cl⁻ as the main components (I=0.42 M).The measured values of the effective diffusion coefficients (D_e) and rock capacity factors (α) are: D_e=1.2–1.5×10⁻¹¹ m² s⁻¹ and α=0.09–0.11 for HTO, D_e=4.0–5.5×10⁻¹² m² s⁻¹ and α=0.05 for ³⁶Cl⁻ and D_e=3.2–4.6×10⁻¹² m² s⁻¹ and α=0.07–0.10 for ¹²⁵I⁻. For non-sorbing tracers (HTO, ³⁶Cl) the rock capacity factor α is equal to the diffusion-accessible porosity . The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of 17% for HTO, 28% for ³⁶Cl⁻ and 30% for ¹²⁵I⁻. Moreover, the diffusion coefficients for ³⁶Cl⁻ and ¹²⁵I⁻ are smaller than for HTO, which is consistent with an effect arising from anion exclusion.The diffusion coefficients of HTO and ¹²⁵I⁻ measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.     

Nitrate reduction during ground-water recharge, Southern High Plains, Texas

In arid and semi-arid environments, artificial recharge or reuse of wastewater may be desirable for water conservation, but NO₃⁻ contamination of underlying aquifers can result. On the semi-arid Southern High Plains (USA), industrial wastewater, sewage, and feedlot runoff have been retained in dozens of playas, depressions that focus recharge to the regionally important High Plains (Ogallala) aquifer. Analyses of ground water, playa-basin core extracts, and soil gas in an 860-km² area of Texas suggest that reduction during recharge limits NO₃⁻ loading to ground water. Tritium and Cl⁻ concentrations in ground water corroborate prior findings of focused recharge through playas and ditches. Typical δ¹⁵N values in ground water (>12.5‰) and correlations between δ¹⁵N and ln C_NO⁻3–N suggest denitrification, but O₂ concentrations ≥3.24 mg l⁻¹ indicate that NO₃⁻ reduction in ground water is unlikely. The presence of denitrifying and NO₃⁻-respiring bacteria in cores, typical soil–gas δ¹⁵N values <0‰, and decreases in NO₃⁻–N/Cl⁻ and SO₄²⁻/Cl⁻ ratios with depth in cores suggest that reduction occurs in the upper vadose zone beneath playas. Reduction may occur beneath flooded playas or within anaerobic microsites beneath dry playas. However, NO₃⁻–N concentrations in ground water can still exceed drinking-water standards, as observed in the vicinity of one playa that received wastewater. Therefore, continued ground-water monitoring in the vicinity of other such basins is warranted.     

Influence of tidal regime on the distribution of trace metals in a contaminated tidal freshwater marsh soil colonized with common reed (Phragmites australis)

A historical input of trace metals into tidal marshes fringing the river Scheldt may be a cause for concern. Nevertheless, the specific physicochemical form, rather than the total concentration, determines the ecotoxicological risk of metals in the soil. In this study the effect of tidal regime on the distribution of trace metals in different compartments of the soil was investigated. As, Cd, Cu and Zn concentrations in sediment, pore water and in roots were determined along a depth profile. Total sediment metal concentrations were similar at different sites, reflecting pollution history. Pore water metal concentrations were generally higher under less flooded conditions (mean is (2.32 ± 0.08) × 10⁻³ mg Cd L⁻¹ and (1.53 ± 0.03) × 10⁻³ mg Cd L⁻¹). Metal concentrations associated with roots (mean is 202.47 ± 2.83 mg Cd kg⁻¹ and 69.39 ± 0.99 mg Cd kg⁻¹) were up to 10 times higher than sediment (mean is 20.48 ± 0.19 mg Cd kg⁻¹ and 20.42 ± 0.21 mg Cd kg⁻¹) metal concentrations and higher under dryer conditions. Despite high metal concentrations associated with roots, the major part of the metals in the marsh soil is still associated with the sediment as the overall biomass of roots is small compared to the sediment.