Parameterization and evaluation of sulfate adsorption in a dynamic soil chemistry model

Sulfate adsorption was implemented in the dynamic, multi-layer soil chemistry model SAFE. The process is modeled by an isotherm in which sulfate adsorption is considered to be fully reversible and dependent on sulfate concentration as well as pH in soil solution. The isotherm was parameterized by a site-specific series of simple batch experiments at different pH (3.8-5.0) and sulfate concentration (10-260 micromol 1(-1)) levels. Application of the model to the Lake Gardsj6n roof covered site shows that including sulfate adsorption improves the dynamic behavior of the model and sulfate adsorption and desorption delay acidification and recovery of the soil. The modeled adsorbed pool of sulfate at the site reached a maximum level of 700 mmol/m(2) in the late 1980s, well in line with experimental data.     

Modelling long-term cation supply in acidified forest stands

A dynamic soil chemistry model was used to explain the observed decrease in soil base saturation between 1949 and 1984 at three stands in southern Sweden. The results show that acid deposition has caused soil acidification. The model, SAFE (Soil Acidification in Forest Ecosystems), includes the fundamental physical processes such as leaching and accumulation, and chemical processes such as cation exchange, mineral weathering, nutrient uptake and solute equilibrium reactions. The sources and sinks of base cations in the soil system were quantified, showing that weathering, deposition of base cations and depletion of exchangeable base cations supply cations to the soil solution in similar amounts in the upper 1 m during the acidification phase. This demonstrates that budget studies alone cannot be used to distinguish between long-term capacity to resist acidification, represented by weathering, from short-term buffering caused by cation exchange.     

Modelling future soil chemistry at a highly polluted forest site at Istebna in Southern Poland using the "SAFE" model

The multi-layer dynamic model SAFE was applied to the forested catchment Istebna (Southern Poland), to study recovery from acidification. Environmental pollution in the area has been historically high. The model uses data from an intensive monitoring plot established in 1999 in a spruce stand, which was planted in 1880. Observations showed that the soil was depleted of base cations. The measured base saturation in 1999 was between 5 and 8% in the different soil layers. Model predictions assuming full implementation of the UNECE 1999 Gothenburg Protocol and present day base cation deposition show that the base saturation will slowly increase to 20% by 2100. Despite large emission reductions, Istebna still suffers from the very high loads of acidifying input during the past decades. Soil recovery depends on future emissions especially on base cation deposition. The recovery will be even slower if the base cation deposition decreases further.     

Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany

Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well.     

Soil pH and anion abundance affects on copper adsorption

Copper (Cu) input to agricultural soils results from Cu containing pesticides and or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2-9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0-100 mg L(-1) in the equilibration solution, 95-99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl2 or Ca(NO3)2 as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500-2000 mg L(-1), the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2-7.9. In a high pH soil (pH=9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

Adsorption behavior of 2,4-dichlorophenol and pentachlorophenol in an allophanic soil

The adsorption of 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) by a variable-charge soil from southern Chile was studied in a series of batch equilibration experiments. 2,4-DCP and PCP adsorption behavior was evaluated as a function of pH (pH values of 4.5, 6.0 and 7.5) in a 0.1M KCl (25 degrees C) background solution for soil material collected at three different depths (0-20 cm, 20-40 cm, and 40-60 cm). 2,4-DCP and PCP adsorption decreased with increasing soil pH, suggesting that the undissociated species were adsorbed more readily and that electrostatic repulsion may inhibit partitioning as pH increases. The PCP adsorption was greater than observed for 2,4-DCP and decreased with soil depth. Multiple regression analysis between K(d) and various soil properties indicated that the soil organic carbon content is a strong indicator of chlorophenol adsorption, and in addition to organic carbon, the soil pH is an important property controlling adsorption behavior.     

Long term changes in atmospheric N and S throughfall deposition and effects on soil solution chemistry in a Scots pine forest in the Netherlands

In a Scots pine forest the throughfall deposition and the chemical composition of the soil solution was monitored since 1984. (Inter)national legislation measures led to a reduction of the deposition of nitrogen and sulphur. The deposition of sulphur has decreased by approximately 65%. The total mineral-nitrogen deposition has decreased by ca. 25%, which is mainly due to a reduction in ammonium-N deposition (−40%), since nitrate-N deposition has increased (+50%). The nitrogen concentration in the upper mineral soil solution at 10 cm depth has decreased, leading to an improved nutritional balance, which may result in improved tree vitality. In the drainage water at 90 cm depth the fluxes of NO₃⁻ and SO₄²⁻ have decreased, resulting in a reduced leeching of accompanying base cations, thus preserving nutrients in the ecosystem. It may take still several years, however, before this will meet the prerequisite of a sustainable ecosystem.     

Soil pH and Anion Abundance Affects on Copper Adsorption

Abstract

Copper (Cu) input to agricultural soils results from Cu containing pesticides and/or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2–9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0–100 mg L^?1 in the equilibration solution, 95–99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl₂ or Ca(NO₃)₂ as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500–2000 mg L^?1, the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2–7.9. In a high pH soil (pH = 9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

Some models for the adsorption kinetics of pesticides in soil

Abstract

Three models describing adsorption‐desorption kinetics of pesticides in soil, that could be incorporated into computer programs on pesticide movement in soil, were discussed, The first model involved single first‐order rate equations for adsorption and desorption. Results from an analytical and a numerical solution for local equilibration were compared. Concentration‐time relationships for the solution and adsorbed phases were calculated for different rate constants, initial conditions, and partition ratios at equilibrium. The second model described simultaneous adsorption‐desorption equilibration with two mechanisms, both with their own rate constants. After a comparatively fast equilibration with the first mechanism, there was a gradual increase in extent of overall‐adsorption, accompanied with a shift to greater amounts adsorbed by the second mechanism. With the third model, adsorption equilibration occurred by diffusion into a stagnant region. With diffusion distances ranging from 0.1 to 4.0 cm, the time needed for approach to adsorption equilibrium varied from about 0.25 days to about one year. Some of the possibilities of these models were discussed considering published experimental results.     

The effect of dissolved glyphosate upon the sorption of copper by three selected soils

The effect of the pesticide glyphosate (GPS) on adsorption processes of copper onto three soils of different characteristics has been studied. Cu adsorption decreases in general with increasing GPS concentration in solution, due principally to the lower equilibrium pHs, although this is not the only variable affecting copper adsorption. For the same pH values, Cu adsorption is higher in two of the three soils in the presence of GPS, but for the third soil, Cu adsorption is higher in the absence of GPS. This behavior is explained by the possibility of GPS adsorption on these soils and by the formation of Cu-GPS complexes in solution. The soils showing a higher Cu adsorption in the presence of GPS than in its absence for the same pH are able to adsorb this pesticide. In these soils, copper can be adsorbed directly on the soil surfaces, and also through the formation of bonds with GPS previously adsorbed. The third soil was not able to adsorb GPS. Consequently, all the pesticide remained in solution, forming strong Cu complexes with low tendency to be adsorbed on this soil. For this reason, the concentration of free Cu in solution is drastically reduced, and the adsorption of copper on this soil is lower.     

Adsorption, desorption, and mobility of permethrin in Malaysian soils

The adsorption, desorption, and mobility of permethrin in six tropical soils was determined under laboratory and greenhouse conditions. The six soils were selected from vegetable growing areas in Malaysia. Soil organic matter (OM) was positively correlated (r2 = 0.97) with the adsorption of permethrin. The two soils, namely, Teringkap 1 and Lating series with the highest OM (3.2 and 2.9%) released 32.5 and 30.8% of the adsorbed permethrin after four consecutive repetitions of the desorption process, respectively, compared to approximately 75.4% of the Gunung Berinchang soil with the lowest OM (1.0%) under the same conditions. The mobility of permethrin down the soil column was inversely correlated to the organic matter content of the soil. Permethrin residue penetrated only to the 10-15 cm zone in the Teringkap 1 soil with 3.2% OM but penetrated to a depth of more than 20 cm in the other soils. The Berinchang series soil with the lowest OM (1.0%) yielded leachate with 14.8% permethrin, the highest level in leachates from all the soils tested. Therefore, the possibility for permethrin to contaminate underground water may be greater in the presence of low organic matter content, which subsequently allows a higher percentage of permethrin to move downwards through the soil column.     

Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions

We use an inorganic aerosol thermodynamic equilibrium model in a three-dimensional chemical transport model to understand the roles of ammonia chemistry and natural aerosols on the global distribution of aerosols. The thermodynamic equilibrium model partitions gas-phase precursors among modeled aerosol species self-consistently with ambient relative humidity and natural and anthropogenic aerosol emissions during the 1990s.Model simulations show that accounting for aerosol inorganic thermodynamic equilibrium, ammonia chemistry and dust and sea-salt aerosols improve agreement with observed SO₄, NO₃, and NH₄ aerosols especially at North American sites. This study shows that the presence of sea salt, dust aerosol and ammonia chemistry significantly increases sulfate over polluted continental regions. In all regions and seasons, representation of ammonia chemistry is required to obtain reasonable agreement between modeled and observed sulfate and nitrate concentrations. Observed and modeled correlations of sulfate and nitrate with ammonium confirm that the sulfate and nitrate are strongly coupled with ammonium. SO₄ concentrations over East China peak in winter, while North American SO₄ peaks in summer. Seasonal variations of NO₃ and SO₄ are the same in East China. In North America, the seasonal variation is much stronger for NO₃ than SO₄ and peaks in winter.Natural sea salt and dust aerosol significantly alter the regional distributions of other aerosols in three main ways. First, they increase sulfate formation by 10–70% in polluted areas. Second, they increase modeled nitrate over oceans and reduce nitrate over Northern hemisphere continents. Third, they reduce ammonium formation over oceans and increase ammonium over Northern Hemisphere continents. Comparisons of SO₄, NO₃ and NH₄ deposition between pre-industrial, present, and year 2100 scenarios show that the present NO₃ and NH₄ deposition are twice pre-industrial deposition and present SO₄ deposition is almost five times pre-industrial deposition.     

镉溶液污染黏土微观结构演化规律

镉溶液在压实黏土中迁移会引起黏土微观结构的变化。通过一系列扫描电子显微镜与低温氮吸附实验,观察了镉溶液污染黏土的表面微观形貌与孔隙结构的演化规律。扫描电子显微镜观察结果显示,受镉溶液污染严重的土柱上表面孔隙明显,土颗粒之间主要以点-点排列方式为主;而受镉溶液污染较弱的下表面,土颗粒之间主要以片-片状排列为主。低温氮吸附实验结果表明,Z=0 cm、Z=10 cm、Z=20 cm、Z=30 cm处,污染黏土吸附量分别为682.65、631.72、583.25和523.36 cm3/g。随土柱中土层深度的增大,黏土颗粒间微孔增多,二次孔减少,孔隙体积与比表面积减小。镉溶液污染黏土孔隙主要集中在10 nm以下。     

Micro-spatial variation of soil metal pollution and plant recruitment near a copper smelter in Central Chile

Soil chemical changes produced by metal smelters have mainly been studied on a large scale. In terms of plant survival, determination of small scale variability may be more important because less toxic microhabitats may represent safe sites for successful recruitment and thus for plant survival. Three dominant microhabitats (open spaces and areas below the canopy of Sphaeralcea obtusiloba and Baccharis linearis shrubs) were defined in a heavily polluted area near a copper smelter and characterised in terms of microclimate, general soil chemistry, total and extractable metal concentrations in the soil profile (A0 horizon, 0-5 and 15-20 cm depth), and seedling densities. Results indicated a strong variability in microclimate and soil chemistry not only in the soil profile but also among microhabitats. Air/soil temperatures, radiation and wind speed were much lower under the canopy of shrubs, particularly during the plant growth season. Soil acidification was detected on top layers (0-5 cm depth) of all microhabitats while higher concentrations of N, Cu and Cd were detected on litter and top soil layers below shrubs when compared to open spaces; however, high organic matter content below shrubs decreased bioavailability of metals. Plant recruitment was concentrated under shrub canopies; this may be explained as a result of the nursery effect exerted by shrubs in terms of providing a more favourable microclimate, along with better soil conditions in terms of macronutrients and metal bioavailability.     

Distribution of metals in grassland soils following surface applications of sewage sludge

In order to decide on a suitable sampling depth for grassland soil treated with sewage sludge and to assess implications for grazing animals, a field trial on two soils was designed to estimate the distribution of metals in grassland soil profiles following surface applications of sludge. Thus the sites represented permanent grassland where no form of cultivation had taken place. Soil cores were taken using specialised equipment to 30 cm depth and divided into seven sections. Movement from the soil surface to a depth of 10 cm was observed for all of the seven metals, Cd, Cr, Cu, Mo, Ni, Pb and Zn, but most of the metal (60%-100%, mean 87%) remained in the upper 5 cm of soil. It was concluded that sampling to a depth of 5 or 7.5 cm would be most suitable for monitoring long-term grassland treated with surface applications of sludge.     

Adsorption,Desorption, and Mobility of Permethrin in Malaysian Soils

Abstract

The adsorption, desorption, and mobility of permethrin in six tropical soils was determined under laboratory and greenhouse conditions. The six soils were selected from vegetable growing areas in Malaysia. Soil organic matter (OM) was positively correlated (r ² = 0.97) with the adsorption of permethrin. The two soils, namely, Teringkap 1 and Lating series with the highest OM (3.2 and 2.9%) released 32.5 and 30.8% of the adsorbed permethrin after four consecutive repetitions of the desorption process, respectively, compared to approximately 75.4% of the Gunung Berinchang soil with the lowest OM (1.0%) under the same conditions. The mobility of permethrin down the soil column was inversely correlated to the organic matter content of the soil. Permethrin residue penetrated only to the 10–15 cm zone in the Teringkap 1 soil with 3.2% OM but penetrated to a depth of more than 20 cm in the other soils. The Berinchang series soil with the lowest OM (1.0%) yielded leachate with 14.8% permethrin, the highest level in leachates from all the soils tested. Therefore, the possibility for permethrin to contaminate underground water may be greater in the presence of low organic matter content, which subsequently allows a higher percentage of permethrin to move downwards through the soil column.     

Fate of nickel in a lime-stabilized biosolid,a calcareous soil and soil–biosolid mixtures

Soil contamination with anthropogenic metals resulting from biosolid application is widespread around the world. To better predict the environmental fate and mobility of contaminants, it is critical to study the capacity of biosolid-amended soils to retain and release metals. In this paper, nickel adsorption onto a calcareous soil, a lime-stabilized biosolid, and soil–biosolid mixtures (30, 75, and 150 t biosolid/ha) was studied in batch experiments. Sorption experiments showed that (1) Ni adsorption was higher onto the biosolid than the calcareous soil, and (2) biosolid acted as an adsorbent in the biosolid–soil mixtures by increasing Ni retention capacity. The sorption tests were complemented with the estimation of Ni adsorption reversibility by successive applications of extraction solutions with water, calcium (100 mg/L), and oxalic acid (equivalent to 100 mg carbon/L). It has been shown that Ni desorption rates in soil and biosolid-amended soils were lower than 30 % whatever the chemical reagent, indicating that Ni was strongly adsorbed on the different systems. This adsorption/desorption hysteresis effect was particularly significant at the highest biosolid concentration (150 t/ha). Finally, an adsorption empirical model was used to estimate the maximum permissible biosolid application rate using French national guideline. It has been shown that desorption effects should be quantitatively considered to estimate relevant biosolid loadings.     

Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil

Laboratory studies were conducted to characterise four different antibiotic compounds with regard to sorption and mobility in various soil types. Distribution coefficients (Kd values) determined by a batch equilibrium method varied between 0.5 and 0.7 for metronidazole, 0.7 and 1.7 for olaquindox and 8 and 128 for tylosin. Tylosin sorption seems to correlate positively with the soil clay content. No other significant interactions between soil characteristics and sorption were observed. Oxytetracycline was particularly strongly sorbed in all soils investigated, with Kd values between 417 in sand soil and 1026 in sandy loam, and no significant desorption was observed. Soil column leaching experiments indicated large differences in the mobility of the four antibiotic substances, corresponding to their respective sorption capabilities. For the weakly adsorbed substances metronidazole and olaquindox the total amounts added were recovered in the leachate of both sandy loam and sand soils. For the strongly adsorbed oxytetracyline and tylosin nothing was detected in the leachate of any of the soil types, indicating a much lower mobility. Results from defractionation and extraction of the columns (30 cm length) showed that 60-80% of the tylosin added had been leached to a depth of 5 cm in the sandy loam soil and 25 cm in the sand soil.     

SDS改性沸石吸附结晶紫简

以表面活性剂十二烷基硫酸钠（SDS）对沸石进行改性,改性后的沸石对结晶紫溶液进行吸附,以紫外可见分光光度计分析最佳吸附条件。实验结果表明,在30℃,SDS改性沸石投入量为0.25 g;吸附平衡时间为1 h;pH为8的条件下,对含50 mg/L结晶紫染料的去除率可达到92.6%,吸附量达到4.63 mg/g。SDS改性沸石吸附结晶紫的等温吸附曲线与Henry型和Freundlich型均拟合较好。热力学参数计算结果表明,吸附符合自发吸热过程。     

Long-term trends in water chemistry of acid-sensitive Swedish lakes show slow recovery from historic acidification

Long-term (1987–2012) water quality monitoring in 36 acid-sensitive Swedish lakes shows slow recovery from historic acidification. Overall, strong acid anion concentrations declined, primarily as a result of declines in sulfate. Chloride is now the dominant anion in many acid-sensitive lakes. Base cation concentrations have declined less rapidly than strong acid anion concentrations, leading to an increase in charge balance acid neutralizing capacity. In many lakes, modeled organic acidity is now approximately equal to inorganic acidity. The observed trends in water chemistry suggest lakes may not return to reference conditions. Despite declines in acid deposition, many of these lakes are still acidified. Base cation concentrations continue to decline and alkalinity shows only small increases. A changing climate may further delay recovery by increasing dissolved organic carbon concentrations and sea-salt episodes. More intensive forest harvesting may also hamper recovery by reducing the supply of soil base cations.