Pedogenic and biogenic alkaline‐extracted silicon distributions along a temperate land‐use gradient

The primary source of dissolved silicon (Si: DSi) is the weathering of silicate minerals. In recent years, it has been shown that Si cycling through vegetation creates a more soluble Si pool in the soil, as amorphous Si (ASi) deposits in plants (phytoliths) are returned to the soil through litter. Amorphous Si accumulation in soils depends on a number of factors, including land use. In addition to the biogenic ASi fraction, soils contain other non‐biogenic amorphous and sorbed Si fractions that could contribute significantly to DSi export to rivers, but hitherto these Si fractions have been difficult to separate from each other with traditionally applied extraction methods. The objective of this paper is to understand better how land use affects the distribution of the different extractable Si fractions. We re‐analysed samples from the land‐use gradient studied previously by Clymans et al. ( 2011 ) with a continuous Si and aluminium (Al) extraction technique. Different extractable Si fractions of biogenic or pedogenic origin were successfully separated on the basis of their dissolution in alkaline solutions (Na₂CO₃ and NaOH) and Si:Al ratios. We show that forests store almost all alkaline extractable Si (AlkExSi) in the pedogenic fraction while the importance of phytoliths increases with human disturbance to become the dominant fraction in the AlkExSi pool at the arable site. The pedogenic AlkExSi pool is also more reactive than the phytolith‐bound Si. Conversely, pastures and croplands tend to preserve phytoliths in the soil, which are less reactive, decreasing the potential of DSi export relative to forested ecosystems.     

Ammonium fluoride extraction for determining inorganic sulphur in acid forest soils

Current methods for determining inorganic sulphur (S) in aerated mineral soil horizons often result in underestimates. To overcome this defect we developed a new method combining a batch extraction with 0.5 m NH₄F solution at a soil:solution ratio of 1:5 with a subsequent analysis of the mobilized SO₄^2– by ion chromatography. The ammonium fluoride extraction enables us to characterize inorganic sulphate in non‐calcareous forest soils. It is more efficient than conventional procedures in which inorganic S is extracted with phosphate or bicarbonate solution. In contrast to the extraction with strongly alkaline reagents (NaOH, KOH, LiOH), the NH₄⁺–NH₃ buffer system in NH₄F prevents the pH of the suspension from exceeding 9.0 and thus the undesired conversion of organic S into SO₄^2– by auto‐oxidation and hydrolysis of ester sulphate. In a comparison we demonstrated that the inorganic S in six German forest soils is underestimated by up to 50% or 200 kg S ha^?1 in the uppermost 60 cm, if it is assessed by extraction with 0.016 m KH₂PO₄ or 0.5 m NaHCO₃ instead of 0.5 m NH₄F. Conversely, the pool of ester sulphate is overestimated almost threefold.     

Soil organic phosphorus in tropical forests: an assessment of the NaOH–EDTA extraction procedure for quantitative analysis by solution 31P NMR spectroscopy

The extraction of soil organic phosphorus by the NaOH–EDTA procedure was assessed in detail for a tropical forest soil (clay‐loam, pH 4.3, total carbon 2.7%). Optimum conditions for the quantification of soil organic phosphorus and characterization of its composition by solution ³¹P NMR spectroscopy were extraction in a solution containing 0.25 m NaOH and 50 mm Na₂EDTA in a 1:20 solid to solution ratio for 4 hours at ambient laboratory temperature. Replicate analyses yielded a coefficient of variation of 3% for organic phosphorus as a proportion of the spectral area. There was no significant difference in total phosphorus extraction from fresh and air‐dried soil, although slightly more organic phosphorus and less paramagnetic ions were extracted from dried soil. The procedure was not improved by changing the concentration of NaOH or EDTA, extraction time, or solid to solution ratio. Pre‐extraction with HCl or Na₂EDTA did not increase subsequent organic phosphorus extraction in NaOH–EDTA or improve spectral resolution in solution ³¹P NMR spectroscopy. Post‐extraction treatment with Chelex resin did not improve spectral resolution, but removed small concentrations of phosphorus from the extracts. Increasing the pH of NaOH–EDTA extracts (up to 1.0 m NaOH) increased the concentration of phosphate monoesters, but decreased DNA to an undetectable level, indicating its hydrolysis in strong alkali. The standardized NaOH–EDTA extraction procedure is therefore recommended for the analysis of organic phosphorus in tropical forest soils.     

Evaluation of anion exchange membranes to estimate bioavailable phosphorus in native grasslands of semi‐arid Northwestern Australia

Abstract

Anion exchange membranes (AEMs) were used to assess the P status of semi‐arid sub‐tropical soils of high P sorption capacity from the Pilbara region in northwestern Australia. We determined the most appropriate procedure for using AEMs in these soils using a factorial of extraction ratios and shaking times and compared the method with extraction by water. Significantly more inorganic P (Pi) was extracted by the membranes (AEM‐Pi) than by water, and the amount extracted increased with extraction time but was generally independent of the extraction ratio. Maximum AEM‐Pi was 3.61 μg g^‐1 after eight hour extraction. The AEM procedure was compared with traditional extraction procedures using 0.5 M sodium bicarbonate (NaHCO₃) and 0.1 M sodium hydroxide (NaOH) to assess ability to detect spatial heterogeneity. The amount of Pi extracted decreased in the order: AEM>NaOH>NaHCO_3* The AEM method detected a significant effect of depth on Pi (P=0.0001), while the NaOH method detected both site and treatment effects (P<0.05). Inorganic P extracted by NaHCO₃ did not vary by site, treatment, or depth. Coefficients of variation were generally least using the AEM method. We recommend that studies of spatial and temporal dynamics of P on highly‐weathered soils in semi‐arid regions include measurement of both AEM‐Pi and NaOH‐extractable Pi.     

Availability of P from 32P-labelled endogenous soil P and 33P-labelled fertilizer in an alkaline soil producing cotton in Australia

Yield responses of irrigated, field‐grown cotton to phosphorus fertilizer application in Australia have been variable. In an attempt to understand better this variability, the distribution of fertilizer P within soil P fractions was identified using ³²P and ³³P radioisotopes. The soil chosen, an alkaline, grey, cracking clay (Vertosol), was representative of those used for growing cotton in Australia. Chang and Jackson fractionation of soil P from samples collected within 1 h of application indicated that 49, 7 and 13% of the P fertilizer was present as 0.5 m NH₄F, 0.1 m NaOH and 1 m H₂SO₄ extractable P, respectively. Over 89% of the P fertilizer was recovered as Colwell extractable P in these samples, suggesting that the majority of these reaction products was in a highly plant‐available form. Fertilizer‐P remained in an available form within the band 51 days after application, and 68% of the applied fertilizer‐P was recovered as Colwell‐P (1071 mg kg^?1). The Colwell‐P concentration in the band was 35 times that in the unfertilized soil. Thus, the variability in crop response to P fertilizer application in these soils is not a consequence of fertilizer‐P becoming unavailable to plants. These results confirm the suitability of the Colwell (1963) sodium bicarbonate extraction method for measuring available P in these soils.     

Exchangeability of phosphate extracted by four chemical methods

Isotopically exchangeable phosphate (P) is a major source of P for plants. In practice, however, plant‐available P is assessed by chemical extractions solubilizing a mixture of P forms the availability of which is ill defined. We undertook an isotopic approach to assess the exchangeability of P extracted by (1) CO₂‐saturated water (P‐CO₂), (2) ammonium acetate EDTA (P‐AAEDTA), and (3) sodium bicarbonate (P‐NaHCO₃) compared to the exchangeability of P extracted by water. Five topsoils with similar P‐fertilization histories but different soil properties were studied. Phosphorus was extracted from soils labeled with carrier‐free ³³P after 1 week of incubation, and the specific activity (SA = ³³P / ³¹P) of the extracts was compared with the SA of P extracted by water to calculate the amount of P isotopically exchangeable that had been solubilized during the extraction. P‐CO₂ extracted between 20 and 100 times less P than P‐AAEDTA and P‐NaHCO₃. The SA of P‐CO₂ was not different from the SA of water‐extractable P, showing that P‐CO₂ solubilized similar forms of P as water and that these forms can be considered as available. The SA of P extracted by the two other methods ranged between 25% and 63% for P‐AAEDTA and 66% and 92% for P‐NaHCO₃ of the SA of water‐extractable P. The fraction of exchangeable P extracted by AAEDTA decreased linearly with increasing soil pH, suggesting that this method dissolves slowly or non‐exchangeable P from calcium phosphates.     

A preliminary comparison of the ammonium acetate‐edta soil phosphorus extraction method to the bray‐1 and olsen soil phosphorus extraction methods

Abstract

The ammonium acetate (NH₄OAc)‐EDTA soil phosphorus (P) extraction method was compared to either the Bray‐1 soil P extraction method for non‐calcareous soils or the Olsen soil P extraction method for calcareous soils to predict com and wheat plant tissue P concentration and grain yield responses. The NH₄OAc‐EDTA method predicted yield and tissue P concentration responses to P fertilizer applications more accurately than the Olsen method at three of five sites. Both the Bray‐1 and NH₄OAc‐EDTA methods were successful in predicting corn and wheat yield responses to P fertilizer applications in non‐ calcareous soils in many locations. However, a direct comparison of extracted soil P levels showed that the NH₄OAc‐EDTA method extracted soil P at levels which were more closely related to the Bray‐1 method than the Olsen method.     

Organic and Inorganic Forms of Phosphorus in a Calcareous Soil Planted with Four Species of Eucalyptus in Southern Iran

The objectives of the present study were to evaluate the effect of four eucalyptus species on (i) selected surface soil properties and (ii) the distribution of inorganic and organic phosphorus (P_i and P_o) fractions. Soil samples were collected from soil 0–20 cm deep beneath and between trees. The P_i forms were determined by sequential extraction with sodium bicarbonate (NaHCO₃‐P), ammonium acetate (NH₄OAc) (OAc‐P), ammonium fluoride (NH₄F‐P), sodium hydroxide (NaOH)–sodium carbonate (Na₂CO₃) (HC‐P), citrate dithionite (CD‐P), and sulfuric acid (H₂SO₄) (H₂SO₄‐P). The P_o forms were sequentially extracted with NaHCO₃ (NaHCO₃‐P_o), NaOH (NaOH‐P_o), and H₂SO₄ (H₂SO4‐P_o). The NaOH‐P_o was subdivided into moderately stable (NaOH‐P_om) and highly stable P_o (NaOH‐P_os). Organic matter, clay and silt contents, total nitrogen, and available potassium of the soil beneath the trees increased. The OAc‐P and HC‐P forms beneath the trees were less than of that between them, which shows that these fractions probably are labile inorganic P pools. The NaHCO₃‐P_o and NaOH‐P_os forms were greater beneath the trees than those of interspaces, whereas NaOH‐P_om and H₂SO₄‐P_o were not affected by plantation.     

Extraction of mobile element fractions in forest soils using ammonium nitrate and ammonium chloride

The extraction of earth alkaline and alkali metals (Ca, Mg, K, Na), heavy metals (Mn, Fe, Cu, Zn, Cd, Pb) and Al by 1 M NH₄NO₃ and 0.5 M NH₄Cl was compared for soil samples (texture: silt loam, clay loam) with a wide range of pH(CaCl₂) and organic carbon (OC) from a forest area in W Germany. For each of these elements, close and highly significant correlations could be observed between the results from both methods in organic and mineral soil horizons. The contents of the base cations were almost convertible one‐to‐one. However, for all heavy metals NH₄Cl extracted clearly larger amounts, which was mainly due to their tendency to form soluble chloro complexes with chloride ions from the NH₄Cl solution. This tendency is very distinct in the case of Cd, Pb, and Fe, but also influences the results of Mn and Zn. In the case of Cd and Mn, and to a lower degree also in the case of Pb, Fe, and Zn, the effect of the chloro complexes shows a significant pH dependency. Especially for Cd, but also for Pb, Fe, Mn, Zn, the agreement between both methods increased, when pH(CaCl₂) values and/or contents of OC were taken into account. In comparison to NH₄Cl, NH₄NO₃ proved to be chemically less reactive and, thus, more suitable for the extraction of comparable fractions of mobile heavy metals. Since both methods lead to similar and closely correlated results with regard to base cations and Al, the use of NH₄NO₃ is also recommended for the extraction of mobile/exchangeable alkali, earth alkaline, and Al ions in soils and for the estimation of their contribution to the effective cation‐exchange capacity (CEC). Consequently, we suggest to determine the mobile/exchangeable fraction of all elements using the NH₄NO₃ method. However, the applicability of the NH₄NO₃ method to other soils still needs to be investigated.     

The effect of Zinc application on the methods which can be used to determine available Iron content of soils

This research was carried out in order to find out the effect of zinc application on the methods which can be used to determine available iron content of paddy soils. For this purpose, an experiment was carried out in greenhouse conditions by growing maize. The effect of increasing rates of zinc application on biological indexes of maize plants was determined. Eight chemical extraction methods for available iron content of soils were used and these methods are: 0.005 M DTPA+0.01 M CaCl₂+0.1 M TEA; 0.005 N HCl+0.025 N H₂SO₄; 1 N NH₄Oac; 0.01 N Na₂EDTA+1 N NH₄Oac; 2 N MgCl₂; 0.01 M Na₂EDTA +1 M (NH₄)₂CO₃; 0.01 N Na₂EDTA and 0.005 M DTPA+NH₄HCO₃. The relationships between biological indexes and chemical extraction methods were determined at the end of the experiment. The highest correlation coefficient was determined with the method 0.005 M DTPA+0.01 M CaCl₂+0.1 M TEA. The iron content of maize plants decreased with zinc application and dry matter content increased with zinc application.     

Assessment of potentially reactive pools of aluminum in Andisols using a five-step sequential extraction procedure

A five-step sequential extraction procedure was developed for the partitioning of soil aluminum (Al) into five fractions: exchangeable, weakly organic bound, strongly organic bound, inorganic non-crystalline and crystalline. The results obtained by the sequential extraction method for Al were compared with those estimated from single extractions using identical operating conditions applied in each individual sequential fraction. The Al content in the extracts was measured by inductively coupled plasma optical emission spectrometry. The results indicated that the first four steps [potassium chloride (KCl), copper chloride (CuCl₂), sodium pyrophosphate (Na₄P₂O₇), acid ammonium oxalate ((NH₄)₂C₂O₄)] in the sequential procedure could be as effective as single extraction methods at estimating exchangeable Al, weakly organic bound Al, strongly organic bound Al, and non-crystalline Al. However, the crystalline Al content by sequential procedure was not in agreement with single extraction procedures. Further, the sequential extractions resulted in more consistent estimates of the aluminum/silicon (Al/Si) molar ratio and allophane and crystalline Al contents than single extractions method. Results of X-ray diffraction on the soil samples confirm the presence of appreciable amounts of at least three types of crystalline minerals, including gibbsite, vermiculite or halloysite. Our result implies that the sequential method can be more reliable in estimating the various Al forms in Andisols.     

SIZE FRACTIONATION, DISSOLUTION ANALYSIS, AND INFRA-RED SPECTROSCOPY OF HUMUS COMPLEXES IN ANDO SOILS

Eight samples of Ando soil A₁ and buried A₁ horizons of different ages were fractionated into clay-, silt-, and sand-size separates, and the yields and carbon contents of these separates were determined. The clay-size separates were subjected to two series of successive extractions, 1) 0.1 M Na₄ P₂ O₇/2% Na₂ CO₃/0.5 M NaOH and 2) dithionite-citrate/2% Na₂ CO₃/0.5 M NaOH; and to difference infra-red spectroscopy for identification of the extracted constituents. The result indicated that humus evolves from forms with a very low complexing ability for Al and Fe into forms that complex Al and Fe in the A₁ horizon, and that humus further interacts with allophane-like constituents, allophane and imogolite in the buried A₁ horizon. These reactions between humus and inorganic constituents result in formation of silt- and sand-size aggregates which are stable to sonic wave treatment, but are broken down into finer particles upon boiling with H₂ O₂.     

EXTRACTORS FOR ESTIMATING PLANT AVAILABLE SILICON FROM POTENTIAL SILICON FERTILIZER SOURCES

Methods to quantify plant available silicon (Si) from Si-based slags for use as fertilizers are not well defined. Although it is possible to estimate total Si from a potential Si fertilizer source; this approach does not represent how much Si is available for uptake by the plant. In this study, Si was extracted from ten sources [Wollastonite W10; calcium silicate slag from the US; calcium silicate from Canada; magnesium silicate; Excellerator; silican gel; 00-00-12 + Si (liquid source) and three types of potassium silicate with different concentrations in the liquid form, K53; K120 and AgSil^TM25] using each of the following seven methods: hydrochloric acid (HCl) plus hydrofluoric acid (HF) extraction, leaching column; sodium carbonate (Na₂CO₃–10 g L^?1) + ammonium nitrate (NH₄NO₃–16 g L^?1); citric acid (50 g dm^?3 or 5%); hydrochloric acid (0.5 N); neutral ammonium citrate (NAC); and resin (Amberlite IRC-50, pK 6.1). All the Si-containing products were added to pots at rates equal to 600 kg ha^?1 of Si based on the total Si extracted. Poa trivialis cv. ‘Darkhorse’ was grown for 24 days with these sources to determine Si plant uptake. Based on the correlation coefficients, the best extractor for available Si in solid fertilizer was determined to be Na₂CO₃ + NH₄NO₃, while for liquid fertilizers, the total Si (HCl + HF) was found to be the best. Consequently, regulatory agencies now have two extractors for estimating the plant available Si from fertilizers depending on the physical property of the material (solid or liquid).     

Deep‐freezing pretreatment and time of extraction of soil samples for inorganic nitrogen determination

Abstract

Soil samples for inorganic nitrogen (N) determination are usually deep‐frozen to prevent microbial transformations of N between sampling and analysis. For analysis, frozen soils are thawed, which may also lead to transformations of N. A specially manufactured mill for grinding frozen soil was tested to minimize these transformations. Whether the time of extraction of the samples could be extended to 20 hr to better accomondate routine work and to make the clay aggregates to disperse better during extraction was also investigated. Freezing of the samples did not produce different results to fresh soils from ammonium nitrogen (NH₄ ⁺‐N) or nitrate nitrogen (NO₃ ^‐‐N) determination. Thawing of the samples increased the concentration of NO₃ ^‐‐N in the extracts and grinding increased that of NH₄ ⁺‐N. When either thawing or grinding was applied, the total inorganic nitrogen concentration was about the same. Thawing of the ground samples increased concentrations of NO₃’‐N and NH₄ ⁺‐N in the extracts. Extending the time of extraction from 0.5 or 1 hr to 20 hr increased the concentration of NH₄ ⁺‐N in the extracts, while NO₃ ^‐‐N content was also increased slightly. It was concluded that sample pretreatment may cause serious errors in the determination of inorganic N even by methods which have proven most successful to prevent microbial transformations of nitrogen, unless the soils are extracted immediately after sampling. The period of extraction should not exceed two hours.     

Characterization and implication of phytolith-associated potassium in rice straw and paddy soils

Rice straw contains up to 2.3% K in dry matter, including potassium (K) subcompartmented in phytoliths, complex siliceous structures formed in plant tissue via precipitation of Si. Rice straw is usually returned to the soil as a conventional practice to sustain soil nutrients, and therefore, the K pool accompanied with rice straw phytoliths is also cycled. Based on phytoliths obtained by ashing of rice straw at 400 °C and dissolution experiments using batch extraction in combination with physical separation of phytoliths by heavy liquid, this study evaluated the phytolith K(phytK) pool in rice straw and aged phytoliths in paddy soils. Entrapped organic matter containing K within phytolith silica cells was visualized by X-ray tomographic microscopy, and releases of this phytK pool accompanying phytolith dissolution were quantified. A 1% Na₂CO₃ solution, which has been commonly used to extract amorphous Si and to quantify soil phytoliths, showed obvious responses for K derived from phytolith dissolution, indicating that the Na₂CO₃ method can be developed for measurement of phytK. In 13 soil samples, Na₂CO₃-dissolvable K content assignable to phytK was 0.55 ± 0.39 g kg^?1 in the puddled horizon, suggesting the phytK pool is of high significance for the management of K in paddy soils.     

Extractability of previously‐applied zinc as influenced by properties of calcareous soils

Abstract

The recovery of applied zinc (Zn) by plants is relatively small. Coupled with lack of leaching, this leads to accumulation of Zn in topsoil which may result in unfavorable growth conditions for the subsequent plants. Different extractants may be used for assessing the Zn status of soils previously treated with Zn sources. The extractability of retained Zn is influenced by soil properties. This experiment was conducted to study the influence of selected properties of calcareous soils on extractability of Zn by three popular Zn soil tests. Twenty samples from surface horizons (0–20 cm) of highly calcareous soils of southern Iran (pH 7.9 to 8.5; calcium carbonate equivalent 16 to 58%) previously treated with three levels of Zn (0, 10, and 20 mg Zn kg^‐1 soil as ZnSO₄#lb7H₂O) in triplicate and under one crop of corn (Zea mays L.) were extracted with DTPA, EDTA‐(NH₄)₂CO₃ and Na₂‐EDTA. Extractability (EXT) in a particular extractant was defined as the slope of the regression line, relating extractable Zn of each soil to the rate of applied Zn, multiplied by 100. The EXT values of soils ranged from 24.9 to 73.0% for DTPA, 47.2 to 84.4% for EDTA‐(NH₄)₂CO₃, and 28.2 to 56.7% for Na₂‐EDTA. Stepwise regression equations showed that cation exchange capacity (CEC) and calcium carbonate equivalent (CCE) followed by clay content were the most influential soil properties in EXT of retained Zn of highly calcareous soils. The EXT values decreased with increase in CEC, and CCE but increased with increase in clay.     

Association of cadmium,zinc, copper,and nickel with components in naturally heavy metal‐rich soils studied by parallel and sequential extractions

Abstract

In this study, a new parallel and sequential extraction procedure was proposed to investigate the solubility of metals [cadmium (Cd), zinc (Zn), copper (Cu), and nickel (Ni)] and their association with soil components in naturally metal‐rich soils of Norway. Two different soils, alum shale (clay loam) and moraine (loam), developed on alum shale minerals were used. Each soil had two pH levels. For parallel and successive extractions, H₂O, 0.1M NH₄OAc (soil pH), 0.3M NH₄OAc (soil pH), 1M NH₄OAc (soil pH), and 1M NH₄OAc (pH 5.0) were used. A significant amount of Cd was extracted by NH₄O Ac related to concentration of NH₄OAc in the extracting solution. The amounts of Zn, Cu, and Ni extracted by these reagents were almost negligible except with 1M NH₄OAc (pH 5.0). Thus these metals were strongly bound to soil components. A seven step sequential extraction procedure was applied to evaluate the association of metals with soil constituents. The extractions were performed sequentially by extracting the soil with reagents having an increasing dissolution strength: 1M NH₄OAc (soil pH), 1M NH₄OAc (pH 5.0), 1M NH₂OH.HCl (in 25% HOAc), 1M NH₂OH.HCl (in 0.1M HNO₃), 30% H₂O₂ (in 0.1M HNO₃), 30% H₂O₂ (1M HNO₃), and aqua regia. In both soils at both pH levels investigated, appreciable percentages of total Cd (20–50%) were found associated with the NH₄OAc extractable fraction (mobile fraction). For Zn, Cu, and Ni, the percentage of total metal extracted with NH₄OAc was low (<4%), but it increased significantly by introducing a reducing agent (NH₂OH.HCl). The NH₂OH.HCl‐extractable fraction was the greatest fraction (>60%) for all four metals examined. These results suggest that among the metals studied, only Cd was easily desorbed from soil and should be considered mobile and potentially bioavailable. Other metals (Zn, Cu, and Ni) were strongly associated with the soil components and should be considered less available to plants. Using the sequential fractionation technique as a measure of availability, mobility and potential bioavailability of these four metals in the alum shale soils were: Cd>Zn>Ni>Cu.     

Remediation of Lead Contaminated Soil by EDTA. I. Batch and Column Studies

Extraction using ethylenediaminetetraacetic acid (EDTA), and other chelates has been demonstrated to be an effective method of removal of Pb from many contaminated soils. However, column leaching of Pb from alkaline soils with EDTA has been problematic due to extremely low soil permeability. The first purpose of this study was to develop batch extraction procedures and methods of analysis of batch extraction data to provide Pb solubility information which can be used to model the column extraction of Pb from soils. The second purpose was to determine the effect of the addition of KOH and CaCl₂ to K₂H₂EDTA extract solution on both hydraulic conductivity and Pb removal. A Pb-contaminated soil sample was collected from an abandoned battery recycling facility. Both batch shaker extractions and column leaching experiments were completed using 5 different EDTA extract solutions. When only CaCl₂ was added to EDTA no change in the amount of Pb removed by batch extraction was observed. As expected, lead solubility was observed to decrease as pH was increased by the addition of KOH. However, Pb solubility was only slightly decreased by the addition of both CaCl₂ and KOH. The amount of time required to leach 6.0 L of extraction solution through the soil columns varied from 2 to 33 days. The addition of CaCl₂ and/or KOH resulted in increased soil hydraulic conductivity relative to the EDTA-only solution. The hydraulic conductivity was related to residual calcium carbonate content, suggesting that dissolution of CaCO₃ and subsequent production of CO₂ gas in the soil pores was partially responsible for the observed reductions in soil permeability. However, Pb removal was diminished with the addition of CaCl₂ and KOH because of the decreased Pb solubility and also kinetic limitations associated with the shorter residence time of the extract solution in the column.     

Characterization of phosphorus in sub-alpine forest and adjacent grassland soils by chemical extraction and phosphorus-31 nuclear magnetic resonance spectroscopy

We used chemical extraction methods and ³¹P-nuclear magnetic resonance (NMR) to investigate the effects of vegetation on the amount and structural composition of phosphorous (P) in the sub-alpine soils of central Taiwan. Chemical extraction methods were used to measure inorganic P (Pi) and organic P (Po) in main soil horizons. The soil P composition was assessed by ³¹P-NMR spectroscopy on alkaline EDTA–NaOH extracts. According to the results of chemical extractions, the forest soil had a higher amount of Pi than the grassland soil, which might be a result of the mineralization of Po. ³¹P-NMR spectra showed inorganic orthophosphate (up to 67%) and orthophosphate monoesters (up to 75%) as the major forms of P extracted in forest and grassland soils, respectively. Smaller proportions of orthophosphate diesters and trace amounts of phosphonates and pyrophosphate were found. With possible hydrolysis of P compounds during chemical extraction and slight systemic error in the processes of extraction with NMR, the results from NMR analysis are, in general, consistent with those of chemical extraction.     

Chemical forms and sorption of copper and zinc in soils of central Chile

Abstract

Soil samples from a field irrigated with untreated industrial and municipal wastewater for several decades and from a field not receiving wastewater (control) were analyzed for total copper (Cu) and zinc (Zn) and for the amount of these elements removed in sequential extractions with MgCl₂, NaOAc, NH₂OH#lbHCl, 6H₂O₂‐HNO₃‐NH₄OAc, and HNO₃‐HF‐HCl. Organically‐bound Cu forms predominated in the wastewater‐affected soil while in the control soil both residual and organic forms yielded the same proportion of Cu. Distribution of Zn was different in the diverse fractions, and in the polluted soil the reducible and the residual forms predominated while in the control soil the residual form accounted for the highest proportion of recovered Zn. Sequential extraction of Cu from a copper sulfate‐treated soil incubated for 32 days at constant temperature resulted in the same proportional distribution of Cu forms in the polluted soil. In the control soil the oxidizable form decreased and the residual one increased noticeably. The two‐surface Langmuir adsorption model was used to adjust data and to interpret Cu and Zn adsorption by soils excepting Cu sorption by the polluted soil, where the one‐surface model was applied.