Comparison of Seven SO4-S Extraction Methods for Analysis by Turbidimetry or ICP Spectrometry

Soil sulfur (S) analyses for fertilizer recommendations in the northern Great Plains often do not reflect crop S requirements. Seven SO₄-S extraction methods with S determination by either turbidometry or inductively coupled plasma emission spectroscopy including Ca(H₂PO₄)₂ and KH₂PO₄ (both containing 500 ug/l P), 0.25 M KCl (40 ºC) and 0.25 M KCl (room temperature), H₂O, DTPA, and Mehlich 3 extractants. Three horizon depths of three soils from a previous field study were used for these comparisons. Average standard deviations for turbidometric determinations were 4.3 times greater than ICP determinations. With turbidometry, S values were H₂O > KH₂PO₄ > Ca(H₂PO₄)₂ > KCl (40 ºC) = KCl, while with ICP, the values were Mehlich 3 > KCl (40 ºC) = KCl > DTPA (diethylenetriaminepentaacetic acid) > KH₂PO₄ > H₂O > Ca(H₂PO₄)₂. Extraction with KCl at room temperature with ICP determination appears to show promise, but further method evaluation is necessary before it can be recommended as a SO₄-S test method.     

Development of a New Soil Extractant for Simultaneous Phosphorus,Ammonium, and Nitrate Analysis

Abstract

A new soil extractant (H³A) with the ability to extract NH₄, NO₃, and P from soil was developed and tested against 32 soils, which varied greatly in clay content, organic carbon (C), and soil pH. The extractant (H³A) eliminates the need for separate phosphorus (P) extractants for acid and calcareous soils and maintains the extract pH, on average, within one unit of the soil pH. The extractant is composed of organic root exudates, lithium citrate, and two synthetic chelators (DTPA, EDTA). The new soil extractant was tested against Mehlich 3, Olsen, and water for extractable P, and 1 M KCl and water‐extractable NH₄ and NO₂/NO₃. The pH of the extractant after adding soil, shaking, and filtration was measured for each soil sample (5 extractants×2 reps×32 soils=320 samples) and was shown to be highly influential on extractable P but has no effect on extractable NH₄ or NO₂/NO₃. H³A was highly correlated with soil‐extractable inorganic N (NH₄, NO₂/NO₃) from both water (r=0.98) and 1 M KCl (r=0.97), as well as being significantly correlated with water (r=0.71), Mehlich 3 (r=0.83), and Olsen (r=0.84) for extractable P.     

Extractability and dissolution kinetics of pure and soil-added synthesized aluminium hydroxy sulphate minerals

Various extractants used in current analytical procedures for the fractionation of sulphur (S) in soils were compared with respect to their ability to dissolve Al hydroxy sulphate minerals of defined composition (basaluminite, K alunite, mixtures of basaluminite and Na alunite). The minerals were synthesized and aged in the laboratory at 20°C and 50°C. The dissolution kinetics at 20°C of these Al hydroxy sulphates in deionized water, 0.02M HCl and 0.02M NaOH were also investigated. The dissolution stability of the Al hydroxy sulphate minerals increased in the order basaluminite < K alunite < Na alunite. The dissolving power of the reagents used increased in the order H₂O ≤ 0.016M KH₂PO₄? 0.02M HCl ≈ acidic NH₄ oxalate ≈ 0.5M NaHCO₃ < Na₂ CO₃/NaHCO₃ < 0.1M NH₄F < 0.5M NH₄F < 0.05M NaOH ≤ 0.05M LiOH. In Al hydroxy sulphate-containing soils, inorganic S is probably understimated and ester sulphate S overestimated, if the inorganic S pool is assessed by extraction with KH₂PO₄, Ca(H₂PO₄)₂ or NaHCO₃ solutions. The dissolution of all studied Al hydroxy sulphates, particularly that of K and Na alunite, in H₂O and 0.02 M HCl is strongly delayed by kinetic restraints. Thus it seems unlikely that Al³⁺ or SO^2?₄ activites in soil solutions are strictly regulated by precipitation/dissolution equilibria of these minerals except for horizons with extraordinarily slow seepage water movement.     

Fractionation and distribution of selenium in soils

Abstract

A modified selenium (Se) fractionation procedure was used to study Se distribution in three soils (two silt loams and one silty clay). This sequential procedure consisted of: i) 0.2 M potassium sulfate (K₂SO₄)‐soluble fraction, ii) 0.1 M potassium dihydrogen phosphate (KH₂PO₄)‐exchangeable fraction, iii) 0.5 M ammonium hydroxide (NH₃H₂O)‐soluble fraction, iv) 6 M hydrochloric acid (HCl)‐extractable fraction, and v) residual fraction digested with perchloric (HClO₄) and sulfuric (H₂SO₄) acids. The fractionation procedure had high recovery rates (92.5 to 106%). The Se distribution in soil was controlled by soil properties, such as pH, oxide, clay, and calcium carbonate (CaCO₃) contents. In the untreated soil samples, residual Se fraction was dominant. In the Se‐enriched soils, the silty clay had significantly more Se in the NH₃H₂O and residual fractions while in the two silt loams the largest were KH₂PO₄ and residual fractions. The Se availability in the two silt loams was higher than in the silty clay. The Se availability pattern in the untreated soils was: unavailable (HCl + residual fractions) >> potentially available (KH₂PO₄ + NH₃H₂O fractions) > available (K₂SO₄ fraction), while in the Se‐enriched soils it was potentially available > unavailable > available.     

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.     

Optimizing soil dissolved organic matter extraction by grey relational analysis

Dissolved organic matter(DOM) in soil plays an important role in the fate and transport of contaminants.It is typically composed of many compounds,but the effect of different extraction factors on the abundance of different DOM components is unknown.In this study,DOM was extracted from three soils(paddy field,vegetable field and forest soils) with various extraction time,liquid to solid ratios(LSRs),extractant types,and extractant concentrations.The LSR had a significant effect on DOM content,which increased by 0.5–4.0 times among the three soils when LSR increased from 2:1 to 10:1(P 0.05).Dissolved organic matter content increased by 4%–53% when extraction time increased from 10 to 300 min(P 0.05).Extractant concentration had different effects on DOM content depending on the extractant.Higher concentrations of KCl promoted DOM extraction,while higher concentrations of KH_2PO_4 inhibited DOM extraction.Therefore,grey relational analysis was used to further quantitatively evaluate the effect of extraction time,LSR,and extractant concentration on DOM,using KCl as an extractant.For the paddy field and forest soils,the impact of these three factors on DOM extraction efficiency was in the following order:KCl concentration LSR extraction time.However,the effect was different for the vegetable field soil:LSR extraction time KCl concentration.Taking all these factors into account,1.50 mol L~(-1) KCl and an LSR of 10:1 with a shaking time of 300 min was recommended as the most appropriate method for soil DOM extraction.     

Evaluation of extractants for predicting availability of sulphur to mustard in inceptisols

Abstract

Mustard (Brassica juncea) is an important oilseed crop of northern India, which is widely grown in Delhi and adjoining States. This crop has a relatively high requirement of sulphur (S), and is sensitive to S‐deficiency. For predicting response of mustard to S application, several extractants have been tried with variable results. Since selection of a promising extractant for a particular soil needs careful consideration, the present investigation was planned to select the most promising extractant to predict the availability of S to mustard grown on Inceptisols of Delhi. For this purpose, a greenhouse experiment was conducted with twenty soils (two from each often important soil series from the cultivated alluvial soil belt of Delhi. Nine extractants, commonly used for estimating the availability of S, were evaluated and S in soil extract and in plant digest was estimated using the turbiditimetric method. The results indicate that the phosphate salt methods extracted comparatively more S than other extractants. The amount of S extracted by these extractants was found in the following order: KH₂PO₄‐500 ppm P>Ca(H₂PO₄)₂‐500 ppm P>0.001 M HCl>NaOAc+HOAc>heat soluble S>0.15% CaCl₂>l% NaCl> water soluble S>NH₄OAc+HOAc. Simple correlation coefficients of the amounts of S extracted by different extractants and the forms of S with the plant parameters were worked out. To determine the combined effect of soil characteristics on S extraction by different extractants, stepwise multiple regression analysis was carried out. Based on this study, the suitability of the extractants for mustard crops in Inceptisols of Delhi may be arranged as follows: 0.15% CaCl₂>water soluble S>0.001 M HCl>Ca(H₂PO₄)₂‐500 ppm>1%NaCl>NH₄OAc+HOAc>NaOAc+HOAc>KH₂PO₄‐500 ppm P>heat soluble S.     

Sorption of Phosphorus from Swine,Dairy, and Poultry Manures

In most phosphorus (P) sorption studies, P is added as an inorganic salt to a predefined background solution such as calcium chloride (CaCl₂) or potassium chloride (KCl); however, in many regions, the application of P to agricultural fields is in the form of animal manure. The purpose of this study, therefore, was to compare the sorption behavior of dissolved reactive P (DRP) in monopotassium phosphate (KH₂PO₄)–amended CaCl₂ and KCl solutions with sorption behavior of DRP in three different animal manure extracts. Phosphorus single‐point isotherms (PSI) were conducted on eight soils with the following solutions: KH₂PO₄‐amended 0.01 M CaCl₂ solution, KH₂PO₄‐amended 0.03 M KCl solution, water‐extracted dairy manure, water‐extracted poultry litter, and swine lagoon effluent. The PSI values for the dairy manure extract were significantly lower than the CaCl₂ solution for all eight soils and lower than the KCl solution for six soils. The PSI values were significantly higher, on the other hand, for poultry litter extract and swine effluent than the inorganic solutions in four and five of the soils, respectively. Our observations that the sorption of DRP in manure solutions differs significantly from that of KH₂PO₄‐amended CaCl₂ and KCl solutions indicates that manure application rates based on sorption data collected from inorganic P salt experiments may be inaccurate.     

Development of an express method for measuring soil nitrate,phosphate, potassium,and pH for future in-field application

Background

In practical farming, there is often a need for short-term availability of information on the soil nutrient status.

Aims

To develop a new express method for the extraction of major plant-available nutrients and measurement of soil nutrients. In future, this method shall serve for in-field measurements of soil samples with an ion-sensitive field-effect transistor (ISFET).

Methods

Various extraction conditions such as type of extractant, soil-to-solution ratio, time, and intensity were investigated on a broad selection of dried soil samples in the laboratory. Based on 83 field-moist soil samples with varying clay contents, these conditions were compared to standard laboratory methods.

Results

With increasing extraction time, the nutrient concentrations increased. When the soil-to-solution ratio was reduced, a greater share of nutrients was extracted, independent of soil type. H₂O and 0.01 M CaCl₂ and standard calcium-acetate-lactate (CAL) solution proved to be too weak in the short period to reach the ISFET sensor measurement range. Higher concentrated CAL solutions performed much better. Finally, a 5-min CaCl₂ extraction followed by the removal of an aliquot for the determination of soil pH and NO₃⁻ was found to be effective. The remaining solution was then mixed with 0.20 M CAL solution for the analysis of H₂PO₄⁻ and K⁺ at 10 min of extra extraction time. This extraction method showed very good correlations with the values based on the German laboratory reference methods for pH (R² = 0.91) and for nitrate (R² = 0.95). For phosphorus and potassium, we obtained an R² of 0.70 and 0.81, respectively, for all soils. When soils were grouped according to clay content higher correlations were found.

Conclusions

A new express method based on a wet-chemical approach with a soil preparation procedure was successfully developed and validated. This seems to be a valuable basis for future in-field measurements via ISFET.     

Sulphate Adsorption in Soils of North and Northeast Iran

Abstract

Gypsum (CaSO₄ · 2H₂O) is used in agriculture both as a source of calcium (Ca) and sulphate (SO₄ ^2?) and as an amendment to improve soil structure. The effect of gypsum on the adsorption of SO₄ ^2? in irrigated and nonirrigated soils was examined. Almost all of the indigenous sulphate (SO₄) in a range of Golesthan and North Khorasan soils with moderate pH values (>6) was found to be present in the soil solution and, as a consequence, was highly susceptible to leaching. The adsorption of sulphate to the soils receiving no gypsum was greater with correlation coefficient of r=0.91 at 0 kg S ha^?1 as compared to the soils received 40 kg ha^?1 of gypsum as fertilizer with the value of r=0.88 in Golesthan Province. The same trend was observed in Khorasan Province with r=0.79 and r=0.75 with soils receiving 0 and 40 kg S ha^?1, respectively. The results were more pronounced in irrigated fields for both provinces. The amount of sulphate adsorption in Golesthan Province soils was comparatively greater than soils of Khorasan Province. The results raise questions regarding the efficiency of SO⁴‐containing fertilizers in correcting and preventing S deficiency in situations where leaching is a concern.     

Extraction of water‐soluble organic matter from mineral horizons of forest soils

Dissolved organic matter (DOM) is involved in many important biogeochemical processes in soil. As its collection is laborious, very often water‐soluble organic matter (WSOM) obtained by extracting organic or mineral soil horizons with a dilute salt solution has been used as a substitute of DOM. We extracted WSOM (measured as water‐soluble organic C, WSOC) from seven mineral horizons of three forest soils from North‐Rhine Westphalia, Germany, with demineralized H₂O, 0.01 M CaCl₂, and 0.5 M K₂SO₄. We investigated the quantitative and qualitative effects of the extractants on WSOM and compared it with DOM collected with ceramic suction cups from the same horizons. The amounts of WSOC extracted differed significantly between both the extractants and the horizons. With two exceptions, K₂SO₄ extracted the largest amounts of WSOC (up to 126 mg C kg^–1) followed by H₂O followed by CaCl₂. The H₂O extracts revealed by far the highest molar UV absorptivities at 254 nm (up to 5834 L mol^–1 cm^–1) compared to the salt solutions which is attributed to solubilization of highly aromatic compounds. The amounts of WSOC extracted did not depend on the amounts of Fe and Al oxides as well as on soil organic C and pH. Water‐soluble organic matter extracted by K₂SO₄ bore the largest similarity to DOM due to relatively analogue molar absorptivities. Therefore, we recommend to use this extractant when trying to obtain a substitute for DOM, but as WSOM extraction is a rate‐limited process, the suitability of extraction procedures to obtain a surrogate of DOM remains ambiguous.     

Extractable Concentrations of Cobalt from Serpentine Soils with Several Single‐Extraction Procedures

In this study, we selected three soil pedons on the shoulder, backslope, and footslope along a serpentine toposequence to measure cobalt (Co) extractability using six single‐extraction procedures. These extraction procedures are distilled water, 0.11 M acetic acid in the first step of the BCR sequential extraction (BCR1), 1 M ammonium acetate (NH₄OAc; pH 7.0), 0.01 M calcium chloride (CaCl₂), diethylenetriamine pentaacetic acid (DTPA), and 0.1 M hydrochloric acid (HCl). Although the Co concentrations in the water extracts of the study soils ranged from 0.15 to 0.93 mg kg^?1, those with HCl extraction can be up to 22.1 mg kg^?1. The extractable Co concentrations in the study soils demonstrate that the extraction capacity is in the order HCl > DTPA > CaCl₂ ? NH₄OAc > BCR1 > H₂O. The percentages of extractable Co after applying the six single‐extraction procedures reveal that Co mobility is greatest in the soils on the backslope, moderate on the footslope, and least mobile on the shoulder.     

pH对磷钾铝石形成的影响

Effects of column temperature and flow rate on separation of organic acids were studied by determining nine low-molecular-weight organic acids on reversed-phase C18 column using high performace liquid chromatography(HPLC) with a wavelength of UV(ultraviolet)214 nm and a mobile phase of 18 mmol L^-1 KH2PO4 buffer solution (pH2.1).The thermal stabiltiy of organic acids was determined by comparing the recoveries of organic acids in different temperature treatments.The relationships between column temperature,flow rate or solvent pH and retention time were analyzed.At low solvent pH,separatioin efficiency of organic acids was increased by raising the flow rate of the solvent because of lowering the retention time or organic acids.High column temperature was unfavorable for the separation of organic acids.The separating effect can be enhanced through reducing column temperature in organic acid determination due to increasing retention time.High thermal stability of organic acids with low concentrations was observed at temperature of 40℃-45℃,Sensitivity and separation effect of organic acid determination by HPLC were clearly improved by a combination of raising flow rate and lowering column temperature at low solvent pH.     

Effect of bone chars on phosphorus‐cadmium‐interactions as evaluated by three extraction procedures

Foreseen P shortage and contamination problems have stimulated the search for renewable and contaminant‐free P‐fertilizers and amendments that immobilize Cd. We investigated the P‐dissolution and Cd‐immobilizing effect of bone char (pyrolyzed de‐fatted bone chips; BC) and bone char with added reduced S compounds (BC^plus). Five soils varying in pH and low to high Cd‐contamination were incubated with slow‐release P‐fertilizers (BC and BC^plus) and the fast P‐release diammonium phosphate (DAP), and extracted with NH₄NO₃‐, NaHCO₃‐solutions, and H₂O. The P‐concentrations obtained by the three extractants were well correlated and NH₄NO₃ well suited to simultaneously assess the P‐ and Cd‐solubility. The addition of BC increased pH in all soils whereas BC^plus and DAP lowered the pH in soils with pH > 5. Similar trends for NH₄NO₃‐P differences between treatments and control were observed for BC and BC^plus during the incubation period, although BC^plus resulted in much larger P‐concentrations. The highest Cd‐immobilization efficiency was obtained in BC‐treated soils. The addition of BC^plus and DAP decreased the Cd‐concentrations until 34 d of incubation in all soils and remained effective in Cd‐immobilizing in soils that showed a pH raise over 145 d of incubation. Thus, the results indicate that surface modification of BC may promote the P‐dissolution along with a concomitant Cd‐immobilization largely through its pH‐effect but this must be confirmed in studies under non‐equilibrium conditions.     

Inorganic sulphate extraction from SO2-impacted Andosols

Sulphate sorption on to the surface of short‐range ordered minerals and precipitation of Al‐hydroxy sulphate contribute to the acid neutralizing capacity of soils. The correct measurement of total inorganic sulphate is thus essential in soils that are accumulating SO₄^2– anions. We extracted SO₄^2– by various solutions, namely 0.005 m Ca(NO₃)₂, 0.016 m KH₂PO₄, 0.5 m NH₄F and 0.2 m acidic NH₄‐oxalate (pH 3), from Vitric and Eutric Andosols exposed to prolonged deposition of acid and SO₂ from an active volcano (Masaya, Nicaragua). We attributed sulphate extractable by KH₂PO₄ (20–3030 mg kg^?1) to anion‐exchangeable SO₄^2–, which was much smaller than NH₄F‐ and oxalate‐extractable SO₄^2– (400–9680 and 410–10 480 mg kg^?1, respectively). Our results suggest the occurrence of a sparingly soluble Al‐hydroxy‐mineral phase extractable by both NH₄F and oxalate. The formation of Al‐hydroxy minerals would result from the combination of enhanced weathering caused by strong acid loading and simultaneous occurrence of large SO₄^2– concentrations in soil solution. Oxalate extracted slightly more inorganic SO₄^2– than did NH₄F, this additional amount of SO₄^2– correlating strongly with oxalate‐extractable Si and Fe contents. Preferential occlusion of SO₄^2– by short‐range ordered minerals, especially ferrihydrite, explains this behaviour. If we exclude the contribution of occluded sulphate then oxalate and NH₄F mobilize similar amounts of SO₄^2– and are believed to mobilize all of the inorganic SO₄^2– pool.     

Chemical fractionation,water solubility and temporal distribution of sheep faecal sulphur fractions in grazed pastures receiving long‐term sulphate fertilization

Abstract

Although over 40% of excretal S is returned to intensively sheep ‐grazed pastures as faecal S, limited information is available on faecal S fractions, their water solubility and temporal distribution. This study reports results obtained from sheep faeces returned to grazed pastures which have received long‐term annual sulphate applications for 15–20 years. Five freshly‐voided sheep faecal samples (<100 g moist faeces per sample) per sampling were randomly collected at approximately one month intervals over a one‐year growing season. Faeces were fractionated into total S, inorganic SO₄ ^2‐, ester SO₄ ^2‐, Hi‐reducible S and C‐bonded S. Results obtained showed that faecal total S, ester SO₄ ^2‐ Hi‐reducible S and C‐bonded S fractions varied significantly throughout the year. Carbon‐bonded S was the dominant (>80%) faecal S fraction, regardless of faecal total S content or the time of year faecal samples were deposited. Faecal ester SO₄ ^2‐ and inorganic _SO₄ ^2‐fractions accounted for 3.3–7.1% and 0.1–14% of faecal total S respectively. Thus approximately 3.4–21.1% of faecal total S was estimated to be potentially leached or readily available to pasture plants. The Hi‐reducible faecal S fraction was significantly‐correlated (r = 0.59***; *** = P ≤ 0.001) with HCl‐extractable faecal inorganic S, which was considered to represent faecal total SO₄ ^2‐ (ester SO₄ ^2‐ and inorganic SO₄ ^2‐ fractions).

The solubility of different faecal S fractions was determined by sequential extraction of ground (< 1 mm) faeces three times (30 minutes per extraction) with water or 0.01 M Ca(H₂PO₄)₂ solution (1: 5 ratio of faecal DM: extractant). Both amounts of water‐extractable and Ca(H₂PO₄)‐extractable faecal S fractions were found to vary significantly throughout the year. Ca(H₂PO₄)₂ tended to extract more inorganic faecal S than water, attributed to the presence of phosphate and the low pH (pH=4) of Ca(H₂PO₄)₂ extractant. A significant proportion (15–25%) of faecal S was extracted by water and most (70%) of this water‐extractable faecal S was in the organic S fraction. Water‐extractable inorganic faecal S probably originated from the faecal total SO₄ ^2‐ fraction as shown by their significant correlation (r = 0.45** ‐0.63***; ** = P≤ 0.01; *** = P≤ 0.001). Some of the faecal S in water extracts may also originate from the faecal C‐bonded S fraction, as a significant correlation was obtained between C‐bonded faecal S and either water‐extractable faecal organic S (r = 0.53–0.57***; *** = P ≤ 0.001) or water‐extractable faecal inorganic S (r = 0.40–0.41*; * = P ≤ 0.05).

Significant amounts of faecal inorganic SO₄ ^2‐ and ester SO₄ ^2‐ fractions were removed by Ca(H₂PO₄)₂ extractant. The Ca(H₂PO₄)₂‐extractable faecal inorganic S was significantly correlated (r = 0.73***^; *** = P ≤ 0.001) with water‐extractable faecal inorganic S.     

Quantification of individual phosphorus species in sediment: a sequential conversion and extraction method

Common sequential phosphorus (P) extraction methods are not specific to particular chemical species and have several limitations. This work presents the first chemical method for quantification of individual mineral and sorbed P species. It was developed by combining a conversion technique with a sequential extraction procedure. Mangrove sediments with different characteristics were incubated in pH‐adjusted 0.01 M CaCl₂ with and without reference material additions of octacalcium phosphate (Ca₈H₂(PO₄)₆·5H₂O; OCP), hydroxyapatite (Ca₅(PO₄)₃OH), strengite (FePO₄·2H₂O) or variscite (AlPO₄·2H₂O). The changes in soluble phosphate concentration were measured in the supernatant solution, while pH‐induced variations in P composition were determined by subsequent sequential extraction of the sediments. Dissolved phosphate concentration was controlled by adsorption below pH 7.8. Above this pH, soluble phosphate concentration was governed by OCP, which was qualitatively determined by plotting the experimental values of pH + pH₂PO₄ and pH – 0.5 pCa on a solubility diagram including the isotherms of known crystalline phosphate compounds. In contrast to the often‐predicted slow dissolution rate of crystalline phosphates in soils or sediments, drastic changes in P composition by dissolution, precipitation and adsorption processes were detected after 7 days. These were mainly not observed indirectly by changes in dissolved phosphate through adsorption effects, but were determined quantitatively by subsequent sequential extraction, thus enabling the quantification of individual species. Evaluation of the method was performed by standard addition experiments. Besides P species quantification, the method provides the means for other applications, such as the determination of P mineral dissolution kinetics in soils and sediments, the prediction of P composition in changing environmental settings and the refinement of theoretical models of phosphate solubility in soil and sedimentary environments.     

Evaluation of soil sulfate extractants and methods of analysis for plant available sulfur

Abstract

A steady decline in sulfur additions to Atlantic Canadian soils has prompted the need for an accurate method of determining their plant available sulfur status. Three soils were extracted with five soil extractants ‐ 0.01M Ca(H2PO₄)₂‐H₂O in 2M HOAc, 0.1M CaCl₂, Bray‐1 and de‐ionized water. The soil extracts were analyzed for sulfur or sulfate using inductively coupled argon plasma emission spectrometry (ICAP), AutoAnalyzer (AAN), anion exchange‐high performance liquid chromatography (HPLC‐CD) or atomic absorption spectroscopy (AAS). Results were compared with plant response of sulfur treatments to red clover, ryegrass, canola and wheat in a growth room. Instrument reproducibility and crop response indicated the ideal method of determining plant available soil sulfur was HPLC‐CD using the extractant Ca(H2PO₄)₂‐H₂O.     

Remediation of a Magnesium‐Contaminated Soil by Chemical Amendments and Leaching

The deposition of magnesium (Mg)‐rich dust from magnesite mining activities has resulted in serious land degradation. However, the main factors limiting plant growth in Mg‐contaminated soils are unclear. Moreover, little information is available on the remediation of Mg‐contaminated soils. In this study, remediation of soils contaminated with Mg‐rich dust was investigated in a pot experiment using maize as the indicator plant. There were five treatments: (i) control; (ii) leaching; (iii) application of CaCl₂; (iv) leaching + CaCl₂ application; and (v) application of Ca(H₂PO₄)₂ · H₂O. Soil properties and growth of maize (Zea mays L.) seedlings were measured. Leaching alone significantly decreased soluble Mg concentration. Leaching + CaCl₂ application greatly increased exchangeable Ca concentration and decreased soil pH by 0·3 units. Application of CaCl₂ alone increased soluble Mg concentration sharply, which directly inhibited the germination of maize seeds. Application of Ca(H₂PO₄)₂ · H₂O significantly increased the concentrations of exchangeable Ca and available phosphorus and decreased soil pH by 1·7 units. The biomass of maize seedlings increased in the order of control = leaching < leaching + CaCl₂ < < Ca(H₂PO₄)₂ · H₂O. These results suggested that the plant growth in Mg‐contaminated soils was limited primarily by Ca deficiency and secondarily by high soil pH when exchangeable Ca was sufficient. High soil pH suppressed plant growth probably mainly by inhibiting phosphate uptake from the soil. Applying acid Ca salt with low solubility is an attractive option for the remediation of Mg‐contaminated soils. Copyright © 2015 John Wiley & Sons, Ltd.     

Short‐Term Effect of Lime,Phosphorus, and Iron Amendments on Water‐Extractable Lead and Arsenic in Orchard Soils

Abstract

Lead arsenate was extensively used to control insects in apple and plum orchards in the 1900s. Continuous use of lead arsenate resulted in elevated soil levels of lead (Pb) and arsenic (As). There are concerns that As and Pb will become solubilized upon a change in land use. In situ chemical stabilization practices, such as the use of phosphate‐phosphorus (P), have been investigated as a possible method for reducing the solubility, mobility, and potential toxicity of Pb and As in these soils. The objective of this study was to determine the effectiveness of calcium carbonate (lime), P, and iron (Fe) amendments in reducing the solubility of As and Pb in lead‐arsenate‐treated soils over time. Under controlled conditions, two orchard soils, Thurmont loam (Hapludults) and Burch loam (Haploxerolls), were amended with reagent‐grade calcium carbonate (CaCO₃), iron hydroxide [Fe(OH)₃], and potassium phosphate (KH₂PO₄) and incubated for 16 weeks at 26°C. The experimental results suggested that the inorganic P increased competitive sorption between H₂PO₄ ^? and dihydrogen arsenate (H₂AsO₄ ^?), resulting in greater desorption of As in both Thurmont and Burch soils. Therefore, addition of lime, potassium phosphate, and Fe to lead‐arsenate‐contaminated soils could increase the risk of loss of soluble As and Pb from surface soil and potentially increase these metal species in runoff and movement to groundwater.