Cation leaching in a sandy forest soil treated with acidified rain

Contribution from Fourth World Wilderness Congress-Acid Rain Symposium, Denver (Estes Park), Colorado, September 11–18, 1987.     

Evaluation of leaching behavior of pendimethalin in sandy loam soil

The mobility of pendimethalin in sandy loam soil was studied in soil columns under laboratory conditions at two application rates, 1.0 and 2.0 kg a.i. ha^???1, with simulated rainfall of 300 mm. The maximum concentration of the herbicide was found in the top 10 cm layer, though it was found distributed in soil at all the depths at both the doses.     

Leaching of nitrogen from calcareous soils in western Iran: a soil leaching column study

Nitrogen (N) leaching has become a matter of worldwide concern. The objectives of this study were: (1) to use soil columns to investigate the leaching of nitrate ( $ {\text{NO}}_3^{ - } $ ), ammonium ( $ {\text{NH}}_4^{ + } $ ), and nitrite ( $ {\text{NO}}_2^{ - } $ ) from calcareous soils that had received an average of 200?kg^?1 N?ha^?1?year^?1 for the previous 30?years and (2) to determine the relationship between soil properties and $ {\text{NO}}_3^{ - } $ , $ {\text{NH}}_4^{ + } $ , and $ {\text{NO}}_2^{ - } $ leaching. The soils used in this study ranged in texture from clay to sandy loam. Leaching experiments were conducted under saturation conditions and consisted of the collection of 1,047–2,524?mL of leachate (12 pore volumes (PVs)), which was equivalent to 534–1,286?mm from rainfall or irrigation. Losses of $ {\text{NO}}_3^{ - } $ ranged from 62 to 437?kg?ha^?1, while losses of $ {\text{NH}}_4^{ + } $ and $ {\text{NO}}_2^{ - } $ ranged from 2.5 to 19.3?kg?ha^?1 and 0.1 to 10.6?kg?ha^?1, respectively. Leaching rates differed between soil samples. The initial and secondary rate of $ {\text{NO}}_3^{ - } $ leaching was determined using an exponential model, and it ranged from 2.8 to 14.7?mg?kg^?1 PV^?1 and 0.11 to 0.32?mg?kg^?1 PV^?1. Greater leaching rates in the initial period could be due to leaching of $ {\text{NO}}_3^{ - } $ in solution, while the secondary leaching might be attributable to the diffusion-controlled transfer of $ {\text{NO}}_3^{ - } $ between mobile and immobile liquid phases. Analysis of variance indicated that the effects of soil type on total $ {\text{NO}}_3^{ - } $ leaching were highly significant (p?<?0.001). The results showed that soil $ {\text{NO}}_3^{ - } $ concentration was positively correlated with the peak concentration of $ {\text{NO}}_3^{ - } $ (r?=?0.86; p?<?0.01) and the total $ {\text{NO}}_3^{ - } $ leached (r?=?0.93; p?<?0.01). In addition, the total $ {\text{NH}}_4^{ + } $ leached was positively correlated with silt (r?=?0.67; p?<?0.05), clay (r?=?0.61; p?<?0.05), and pH (r?=?0.77; p?<?0.01), which suggests that soil parameters might be useful indicators of $ {\text{NO}}_3^{ - } $ and $ {\text{NH}}_4^{ + } $ leaching from calcareous soils. Nitrate leaching from soils could threaten groundwater supplies, so possible strategies for minimizing $ {\text{NO}}_3^{ - } $ leaching losses may need to be considered.     

Leaching behaviour of chlorpyriphos and cypermethrin in sandy loam soil

The mobility of chlorpyriphos and cypermethrin in sandy loam soil was studied in soil columns under laboratory conditions at two application rates, 25 and 50 μg, with simulated rainfall of 300 mm. Residues of chlorpyriphos and cypermethrin in soil and leachate were estimated by gas–liquid chromatography and confirmed by gas chromatography–mass spectrometry. Though maximum concentration of both the insecticides was found in the top 10-cm layer, chlorpyriphos was found distributed in the soil up to a depth of 35 cm and cypermethrin remained up to 15 cm. Results indicated the low mobility of both the insecticides under saturated moisture condition and hence may not contaminate ground water. No residues of any insecticide were detected in the leachate fractions.     

Assessing the soil quality of alpine grasslands in the Qinghai-Tibetan Plateau using a modified soil quality index

Soil degradation has caused various problems on the planet. Human disturbance and land use changes always negatively affect soil quality. In this study, we used a modified soil quality index (SQI) to assess soil quality under differing degrees of human disturbance and land use. The alpine grasslands were studied at different levels of degradation [i.e., severely degraded grassland, heavily degraded grassland, moderately degraded grassland, and non-degraded grassland (NDG)] in a case study conducted in Qinghai-Tibetan Plateau (QTP) to test the feasibility of using the SQI. Fifteen chemical, physical, and biological soil parameters were measured in each type of grassland. Significant variations in SQI were found across the different types of grasslands according to severity of human disturbance and changes in land use. Urease, the ratio of microbial biomass nitrogen to total nitrogen, proteinase, and soil organic carbon were found to be the most important indicators for assessing soil quality. NDG had a higher SQI than the other three types of grasslands. It was concluded that SQI is effective for assessing the soil quality of alpine grasslands in the QTP. The intensity of human disturbance had a negative effect on soil quality in the QTP.     

Mapping nitrate leaching to upper groundwater in the sandy regions of The Netherlands, using conceptual knowledge

The European Community asks its Member States to provide a comprehensive and coherent overview of their groundwater chemical status. It is stated that simple conceptual models are necessary to allow assessments of the risks of failing to meet quality objectives. In The Netherlands two monitoring networks (one for agriculture and one for nature) are operational, providing results which can be used for an overview. Two regression models, based upon simple conceptual models, link measured nitrate concentrations to data from remote sensing images of land use, national forest inventory, national cattle inventory, fertiliser use statistics, atmospheric N deposition, soil maps and weather monitoring. The models are used to draw a nitrate leaching map and to estimate the size of the area exceeding the EU limit value in the early 1990s. The 95% confidence interval for the fraction nature and agricultural areas where the EU limit value for nitrate (50 mg/l) was exceeded amounted to 0.77–0.85 while the lower 97.5% confidence limit for the fraction agricultural area where the EU limit value was exceeded amounted to 0.94. Although the two conceptual models can be regarded as simple, the use of the models to give an overview was experienced as complex.     

Redistribution of zinc, cadmium, and lead among soil fractions in a sandy calcareous soil due to application of poultry litter

This study was conducted to evaluate, using soil columns, the mobilization and redistribution of heavy metals (Zn, Cd, and Pb) among different soil fractions by soluble organic ligands within poultry litter. Uncontaminated soil was amended with Zn, Cd, and Pb to achieve concentration levels of 400, 8, and 200 mg kg⁻¹ soil, respectively. Columns repacked with this amended soil were leached with distilled water, 0.01 M EDTA, 0.01 M CaCl₂, or poultry litter extract (PLE) solutions. After leaching, the soil samples in the columns were sequentially extracted for exchangeable (EXC), carbonate (CARB) organic matter (OM), Mn oxide (MNO), Fe oxide (FEO), and residual (RES) fractions. Considerable mobilization of Zn, Cd, and Pb occurred in soil during EDTA leaching. Leaching with PLE and CaCl₂ solutions significantly decreased Zn and Cd concentrations in the EXC, CARB, and OM fractions. These solutions significantly decreased Pb concentration in the EXC fraction, while PLE solubilized more Pb from EXC fraction than CaCl₂. Thus, the applied poultry litter may change Zn, Cd, and Pb fractions in metal-amended soil and possibly enhance metal mobility.     

Phosphorus geochemistry in a Brazilian semiarid mangrove soil affected by shrimp farm effluents

Wastewater discharge from shrimp farming is one of the main causes of eutrophication in mangrove ecosystems. We investigated the phosphorus (P) geochemistry in mangrove soils affected by shrimp farming effluents by carrying out a seasonal study of two mangrove forests (a control site (CS); a site affected by shrimp farm effluents (SF)). We determined the soil pH, redox potential (Eh), total organic carbon (TOC), total phosphorus (TP), and dissolved P. We also carried out sequential extraction of the P-solid phases. In SF, the effluents affected the soil physicochemical conditions, resulting in lower Eh and higher pH, as well as lower TOC and higher TP than in CS. Organic P forms were dominant in both sites and seasons, although to a lesser extent in SF. The lower TOC in SF was related to the increased microbial activity and organic matter decomposition caused by fertilization. The higher amounts of P oxides in SF suggest that the effluents alter the dominance of iron and sulfate reduction in mangrove soils, generating more reactive Fe that is available for bonding to phosphates. Strong TP losses were recorded in both sites during the dry season, in association with increased amounts of exchangeable and dissolved P. The higher bioavailability of P during the dry season may be attributed to increased mineralization of organic matter and dissolution of Ca-P in response to more oxidizing and acidic conditions. The P loss has significant environmental implications regarding eutrophication and marine productivity.     

Transport of Cryptosporidium parvum oocysts in sandy soil: impact of length scale

The objective of this study was to investigate the impact of length scale (travel distance) on the retention and transport of Cryptosporidium oocysts in a sandy soil. Long columns (1 and 2 meters) and an in situ lysimeter (4 m) were used to allow investigation of larger-scale transport under controlled conditions. Significant retention of oocysts was observed, with the magnitude of removal from solution ranging between 2 to 5 logs. While the removal was greater for longer travel distances (or residence times), the increase was not log-linear. This observation indicates that oocyst transport was not consistent with standard colloid filtration theory. The observed behavior is speculated to arise, at least in part, from intrapopulation variability in oocyst properties. The results of this study indicate that while Cryptosporidium oocysts may be expected to experience significant retention and removal during transport in sandy soil, the magnitude of retention may be less than that which would be predicted by applying standard colloid filtration theory to the results of typical short-column experiments. Thus, a fraction of the oocysts may be more mobile than anticipated and thereby pose a greater than expected risk to groundwater.     

Factors affecting the leaching of lead from UPVC pipes

This paper summarizes the results of a series of studies on the various factors that affect the leaching of lead from unplasticized poly(vinyl chloride) (UPVC) pipes. Factors that were studied include temperature, pH and extractants. Results showed that, for a given UPVC pipe, the rate of leaching of lead depended primarily on temperature and the nature of extractants. While the rate of leaching of lead was quite low with distilled water, it was very much enhanced by the presence of low concentration of anions such as Cl^-, HPO _inf4 ^sup2- HCO _inf3 ^sup- , NO _inf3 ^sup- , SO _inf4 ^sup2- and EDTA. EDTA, being a strong complexing agent, was most effective. Rates of leaching were found to be higher at elevated temperature except in the cases of HPO _inf4 ^sup2- and EDTA. Effect of pH was not pronounced. The temperature at which the UPVC pipes were extruded was found to affect the rate of leaching of lead. Pipes extruded at 190°C were found to have lower rate of leaching than those extruded at 180°C and 170°C. Analysis of the pipes by Scanning Electron Microscopy showed that the distribution of lead in the pipes extruded at 190°C was more uniform than those extruded at 170°C.     

Distribution and fractionation of cadmium, copper, lead, nickel, and zinc in a calcareous sandy soil receiving municipal solid waste

This study was conducted to evaluate the degree of mobility and fractionation of cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) after the addition of municipal solid sewage sludge (MSS) in a sandy calcareous soil. Treatments were (1) soil application of MSS, (2) soil application of enriched municipal solid waste compost (EMSS), and (3) control soil. The MSS application represented a dose of 200 Mg dry weight per hectare. Soil columns were incubated at room temperature for 15 days and irrigated daily with deionized water to make a total of 505 mm. At the end of leaching experiments, soil samples from each column were divided into 14 layers, each being 1 cm down to 10 and 2.5 cm below that and analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, Ni, and Zn. The fractionation of the heavy metals in the top five layers of the surface soil samples was investigated by the sequential extraction method. All soil layers of the columns receiving MSS and EMSS had significantly higher concentrations of DTPA-extractable heavy metals than control soil. The maximum concentration of heavy metals in treated soil was in the surface layer and declined significantly with depth. Sequential extraction results showed that in the treated soil, a major proportion of Cd, Pb, and Ni was associated with organic matter (OM) and exchangeable (EXCH) fractions, and a major proportion of Cu and Zn was associated with residual (RES) and OM fractions. Based on relative percent, Pb, Cd, and Ni in the EXCH fraction was higher than Cu and Zn in soil leached with MSS and EMSS, suggesting that application of this MSS to a sandy calcareous soil, at the loading rate used here, may pose a risk in terms of groundwater contamination with Pb, Cd, and Ni.     

Metal immobilization and phosphorus leaching after stabilization of pyrite ash contaminated soil by phosphate amendments

In this study we would like to show the importance of a holistic approach to evaluation of chemical stabilization using phosphate amendments. An extensive evaluation of metal stabilization in contaminated soil and an evaluation of the leaching of phosphorus induced after treatment were performed. The soil was highly contaminated with Cu (2894 mg kg(-1)), Zn (3884 mg kg(-1)), As (247 mg kg(-1)), Cd (12.6 mg kg(-1)) and Pb (3154 mg kg(-1)). To immobilize the metals, mixtures of soil with phosphate (from H(3)PO(4) and hydroxyapatite (HA) with varying ratios) were prepared with a constant Pb : P molar ratio of 1: 10. The acetic acid extractable concentration of Pb in the mixture with the highest amount of added phosphoric acid (n(H(3)PO(4)) : n(HA) = 3 : 1) was reduced to 1.9% (0.62 mg L(-1)) of the extractable Pb concentration in the untreated soil, but the content of water extractable phosphorus in the samples increased from 0.04 mg L(-1) in the untreated soil sample up to 14.3 mg L(-1) in the same n(H(3)PO(4)) : n(HA) = 3 : 1 mixture. The high increase in arsenic mobility was also observed after phosphate addition. The PBET test showed phosphate induced reduction in Pb bioavailability. In attempting to stabilize Pb in the soil with the minimum treatment-induced leaching of phosphorus, it was found that a mixture of soil with phosphate addition in the molar ratio of H(3)PO(4) : HA of 0.75 : 1 showed the most promising results, with an acetic acid extractable Pb concentration of 1.35 mg L(-1) and a water extractable phosphorus concentration of 1.76 mg L(-1). The time-dependent leaching characteristics of metals and phosphorus for this mixture were evaluated by a column experiment, where irrigation of the soil mixture with the average annual amount of precipitation in Slovenia (1000 mm) was simulated. The phosphorus concentration in the leachates decreased from 2.60 mg L(-1) at the beginning of irrigation to 1.00 mg L(-1) at the end.     

Comparison of linuron degradation in the presence of pesticide mixtures in soil under laboratory conditions

It is widely recognised that complex interactions occur between chemicals in mixtures. In many agricultural situations, the use of tank mixes and complex spray programs is a common practice. Insecticides, fungicides and a herbicide being applied in potato protection were used in this research. Interactions between linuron and insecticides, such as thiamethoxam or clothianidin, and fungicides, such as mancozeb or chlorothalonil, were examined in soil. The degradation rate of linuron in soil during laboratory incubation in six treatments was studied. Mixtures of linuron with mancozeb in sandy loam and clay loam soils had a significant effect on the persistence of this herbicide. For example, for the same herbicide, t _1/2 values for linuron were from 37 days in sandy loam to 44 days in clay loam. These values changed (64–67 days) when thiamethoxam and mancozeb were in soil. When mancozeb was added only, the half-life values were from 59 to 62 days, respectively. Other mixtures with chlorothalonil, thiamethoxam and clothianidin did not have any effect. In order to compare linuron degradation rates in soils, a single first-order model and expanded statistical analysis were used.     

Nitrate and ammonium ions removal from groundwater by a hybrid system of zero-valent iron combined with adsorbents

Nitrate (NO(3)(-)) is a commonly found contaminant in groundwater and surface water. It has created a major water quality problem worldwide. The laboratory batch experiments were conducted to investigate the feasibility of HCl-treated zero-valent iron (Fe(0)) combined with different adsorbents as hybrid systems for simultaneous removal of nitrate (NO(3)(-)) and ammonium (NH(4)(+)) ions from aqueous solution. The maximum NO(3)(-) removal in combined Fe(0)-granular activated carbon (GAC), Fe(0)-filtralite and Fe(0)-sepiolite systems was 86, 96 and 99%, respectively, at 45 °C for 24 h reaction time. The NO(3)(-) removal rate increased with the increase in initial NO(3)(-) concentration. The NO(3)(-) removal efficiency by hybrid systems was in the order of sepiolite > filtralite > GAC. The NH(4)(+) produced during the denitrification process by Fe(0) was successfully removed by the adsorbents, with the removal efficiency in the order of GAC > sepiolite > filtralite. Results of the present study suggest that the use of a hybrid system could be a promising technology for achieving simultaneous removal of NO(3)(-) and NH(4)(+) ions from aqueous solution.     

Long-Term Relationship between Phosphorus Inputs and Wetland Phosphorus Concentrations in a Northern Everglades Marsh

Assessments of long-term relationships between changes innutrient inputs and wetland nutrient concentrations can becomplicated by fluctuations in other environmental factors aswell as by problems typical of long-term monitoring data.Consequently, statistical analysisof these types of data sets requirescareful consideration of environmental covariates, potentialbiases in the monitoring design, and irregularities caused bychanges in field sampling protocols. We evaluated therelationship between anthropogenic phosphorus (P) inputs andwater-column total P (TP) concentrations in a northernEverglades marsh by statistically analyzing available datacollected from several sampling programs over the past 20 years(1978–1997). Canal inputs of agricultural runoff contributemost of the P to the marsh and have produced a zone ofenrichment within the marsh during the past few decades.Regression analyses showed that both canal and marsh TPconcentrations increased during the 1980s and then decreased inthe 1990s. However, the statistical relationship between canal Pinputs and marsh TP, while significant, generally was weakexcept for marsh locations adjacent to the canal. Strongerrelationships existed between marsh TP and hydrologic parameterssuch as marsh water depth, which is controlled by changes inweather patterns and marsh management. In particular, dryconditions during the 1980s may have contributed to observedincreases in marsh P concentrations and the movement of a P`front' further into the marsh. Higher rainfall and water depthsand agricultural best management programs initiated during the1990s have been associated with reduced P concentrations incanal waters entering the marsh. While it is anticipated thatthis reduction eventually will result in lower marsh TPconcentrations, this effect is not yet evident, possibly due tointernal loading of P from enriched marsh soils. Our findingsillustrate some of the environmental factors that can complicateattempts to develop empirical relationships between P inputs andwetland P concentrations and to use such relationships to forecast changesin marsh concentrations based on past monitoring data alone.     

Copper leaching from brake wear debris in standard extraction solutions

Quantification of the copper content of and copper leaching from a disc brake wear debris sample was performed using microwave-assisted acid digestion, the Federal Toxicity Characteristic Leaching Procedure (TCLP), and the State of California Waste Extraction Test (WET). The brake wear debris tested was a composite sample obtained from a brake dynamometer test of one brake pad source material. Comparative digestion studies demonstrated that a modified aqua regia matrix (HNO3:HCl:H2O2 = 1:3:0.5) optimized the digestion effectiveness for determining the total copper content in the brake wear debris. No significant sample heterogeneity within the brake wear debris was observed, based on statistically indistinguishable total copper content results for subsamples with a wide range of sample masses. Upon pooling all subsample results, an overall total copper content for the composite brake wear debris sample was determined to be 10.8% (g/g), with a 95% confidence limit of +/- 0.5% (g/g). Copper leaching increased with decreasing solid-to-liquid ratios in TCLP tests, but was unaffected by the solid-to-liquid ratio in the WET. For a 1:10(4) (g/g) solid-to-liquid ratio, 85% and 99% of the total mass of copper present in the composite brake wear debris sample was leached into solution during the TCLP and WET, respectively. Rate studies also demonstrated that the WET resulted in a faster rate and higher extent of copper leaching relative to the TCLP. Compared to reference copper-containing materials, the composite brake wear debris sample exhibited relatively higher TCLP and WET copper leaching characteristics. The higher copper leaching exhibited by the brake wear debris sample may have resulted from its higher specific surface area and/or from changes in the chemical form of copper that occurred during the braking process.     

Adsorption-desorption and leaching potential of glyphosate and aminomethylphosphonic acid in acidic Malaysian soil amended with cow dung and rice husk ash

This study investigates adsorption-desorption and the leaching potential of glyphosate and aminomethylphosphonic acid (AMPA) in control and amended—addition of cow dung or rice husk ash—acidic Malaysian soil with high oxide mineral content. The addition of cow dung or rice husk ash increased the adsorptive removal of AMPA. The isotherm data of glyphosate and AMPA best fitted the Freundlich model. The constant K_f for glyphosate was high in the control soil (544.873 mg g^?1) followed by soil with cow dung (482.451 mg g^?1) then soil with rice husk ash (418.539 mg g^?1). However, for AMPA, soil with cow dung was high (166.636 mg g^?1) followed by soil with rice husk ash (137.570 mg g^?1) then the control soil (48.446 mg g^?1). The 1/n values for both glyphosate and AMPA adsorptions were <?1 indicating their strong affinity for adsorbents. Desorption of both glyphosate and AMPA occurred only in the control soil. The compounds were not detected in soils with added cow dung or rice husk ash. The addition of cow dung or rice husk ash increased glyphosate mobility. However, ground water ubiquity scores for both control and amended soils were <?2.8. This indicated glyphosate is a transitional herbicide; therefore, its leaching potential in the soil is low, despite the addition of cow dung or rice husk ash. Addition of these wastes decreased the mobility and leaching potential of AMPA. The addition of cow dung or rice husk ash could be beneficial in increasing adsorption and enhancing degradation of these compounds.     

Fractions and leaching characteristics of mercury in coal

A huge amount of coal is always stored in open spaces in coal-fired power plants before combustion. Mercury released from coal by rain or flowing water is an environmental risk and can cause contamination of the soil around the storage area. To better understand mercury pollution and to control mercury emission before combustion, it is necessary to determine the mobility and leaching characteristics of mercury from coal. In this study, we collected ten coal samples from one coal-fired power plant and proposed a sequential extraction procedure to get five fractions of mercury for evaluation. Elemental Hg was found as the most dominant fraction, and sulfate Hg was shown to be the second largest fraction. The mercury in the organic and the soluble fractions were not the major fractions, but they should still be considered because of their high mobility.     

Effects of organic ligands and pH on the leaching of copper from brake wear debris in model environmental solutions

Copper leaching from a disc brake wear debris sample was examined in a variety of aqueous solutions to simulate potential leaching processes during rain events and in surface waters. Synthetic rainwater leached 40% of the total copper present in the brake wear debris into solution after 18 h in batch reactors, which was approximately three times more copper than that extracted by the US Environmental Protection Agency's Synthetic Precipitation Leaching Procedure. Formate and acetate were responsible for the enhanced copper leaching, as demonstrated by higher average amounts of leached copper in synthetic rainwater with- versus without the organic acids (40 versus 31% recovery). This observation suggests leaching tests that do not incorporate the appropriate types and concentrations of organic ligands present in rainwater will likely underestimate copper mobilization from brake wear debris during rain events. Leaching of copper from the brake wear debris ranged from 23 to 40% in solutions containing 3 to 15 mg C L(-1) dissolved humic substances, and was higher still in solutions containing relatively high concentrations of the synthetic metal chelating agent ethylenediaminetetraacetic acid. Static pH tests demonstrated that copper leaching from brake wear debris is highly pH dependent, with more leaching occurring at lower solution pH values. Leaching rate studies revealed that equilibrium generally was not attained within 48 h in the model solutions, indicating that additional copper can be expected to be released in environments where brake wear debris is exposed to long-term leaching processes.