Evaluation of soils for use as liner materials: a soil chemistry approach

Movement of NH(4)(+) below animal waste lagoons is generally a function of the whole-lagoon seepage rate, soil mineralogy, cations in the lagoon liquor, and selectivity for NH(4)(+) on the soil-exchange sites. Binary exchange reactions (Ca(2+)-K(+), Ca(2+)-NH(4)(+), and K(+)-NH(4)(+)) were conducted on two soils from the Great Plains and with combinations of these soils with bentonite or zeolite added. Binary exchanges were used to predict ternary exchanges Ca(2+)-K(+)-NH(4)(+) following the Rothmund-Kornfeld approach and Gaines-Thomas convention. Potassium and NH(4)(+) were preferred over Ca(2+), and K(+) was preferred over NH(4)(+) in all soils and soils with amendments. Generally, the addition of bentonite did not change cation selectivity over the native soils, whereas the addition of zeolite did. The Rothmund-Kornfeld approach worked well for predicting equivalent fractions of cations on the exchanger phase when only ternary-solution phase compositions were known. Actual swine- and cattle-lagoon solution compositions and the Rothmund-Kornfeld approach were used to project that native soils are predicted to retain 53 and 23%, respectively, of the downward-moving NH(4)(+) on their exchange sites. Additions of bentonite or zeolite to soils under swine lagoons may only slightly improve the equivalent fraction of NH(4)(+) on the exchange sites. Although additions of bentonite or zeolite may not help increase the NH(4)(+) selectivity of a liner material, increases in the overall cation exchange capacity (CEC) of a soil will ultimately decrease the amount of soil needed to adsorb downward-moving NH(4)(+).     

Heavy metal release from contaminated soils: comparison of column leaching and batch extraction results

Heavy metals in soils may adversely affect environmental quality. In this study, we investigated the release of Zn, Cd, Pb, and Cu from four contaminated soils by column leaching and single and sequential batch extractions. Homogeneously packed soil columns were leached with 67 mL/g 10(-2) M CaCl2 to investigate the exchangeable metal pool and subsequently with 1400 mL/g 10(-2) M CaCl2 adjusted to pH 3 to study the potential of metal release in response to soil acidification. In two noncalcareous soils (pH 5.7 and 5.1), exchange by Ca resulted in pronounced release peaks for Zn and Cd that were coupled to the exchange of Mg by Ca, and 40 to 70% of total Zn and Cd contents were rapidly mobilized. These amounts compared well with exchangeable pools determined in single and sequential batch extractions. In two soils with near-neutral pH, the effluent concentrations of Zn and Cd were several orders of magnitude lower and no pronounced elution peaks were observed. This behavior was also observed for Cu and Pb in all four soils. When the soils were leached at pH 3, the column effluent patterns reflected the coupling of CaCO3 dissolution (if present) and other proton buffering reactions, proton-induced metal release, and metal-specific readsorption within the soil column. Varying the flow rate by a factor of five had only minor effects on the release patterns. Overall, Ca exchange and subsequent acidification to pH 3 removed between 65 and 90% of total Zn, Cd, Pb, and Cu from the four contaminated soils.     

Performance of lime-BHA solidified plating sludge in the presence of Na2SiO3 and Na2CO3

This research investigated the performance of lime-BHA (black rice husk ash) solidified plating sludge with 2 wt% NaO from Na(2)SiO(3) and Na(2)CO(3) at the level of 0, 30 and 50 wt%. The sludge was evaluated for strength development, leachability, solution chemistry and microstructure. The lime-BHA solidified plating sludge with Na(2)SiO(3) and Na(2)CO(3) had higher early strength when compared to the control. The addition of Na(2)SiO(3) and Na(2)CO(3) increased the OH(-) concentration and decreased the Ca(2+) and heavy metal ions in solution after the first minute. The XRD patterns showed that the addition of Na(2)SiO(3) resulted in the formation of calcium silicate hydrates, while the addition of Na(2)CO(3) resulted in CaCO(3). The heavy metals from the plating sludge, especially Zn, were immobilized in calcium zincate and calcium zinc silicate forms for the lime-BHA with and without Na(2)SiO(3) solidified wastes, while samples with Na(2)CO(3) contained Zn that was fixed in the form of CaZnCO(3). The cumulative leaching of Fe, Cr and Zn from the lime-BHA solidified plating sludge decreased significantly when activators were added, especially Na(2)CO(3).     

Implications of cation exchange on clay release and colloid-facilitated transport in porous media

Column experiments were conducted to study chemical factors that influence the release of clay (kaolinite and quartz minerals) from saturated Ottawa sand of different sizes (710,360, and 240 microm). A relatively minor enhancement of clay release occurred when the pH was increased (5.8 to 10) or the ionic strength (IS) was decreased to deionized (DI) water. In contrast, clay release was dramatically enhanced when monovalent Na+ was exchanged for multivalent cations (e.g., Ca2+ and Mg2+) on the clay and sand and then the solution IS was reduced to DI water. This solution chemistry sequence decreased the adhesive force acting on the clay as a result of an increase in the magnitude of the clay and sand zeta potential with cation exchange, and expansion of the double layer thickness with a decrease in IS to DI water. The amount of clay release was directly dependent on the Na+ concentration of the exchanging solution and on the initial clay content of the sand (0.026-0.054% of the total mass). These results clearly demonstrated the importance of the order and magnitude of the solution chemistry sequence on clay release. Column results and scanning electron microscope (SEM) images also indicated that the clay was reversibly retained on the sand, despite predictions of irreversible interaction in the primary minimum. One plausible explanation is that adsorbed cations increased the separation distance between the clay-solid interfaces as a result of repulsive hydration forces. A cleaning procedure was subsequently developed to remove clay via cation exchange and IS reduction; SEM images demonstrated the effectiveness of this approach. The transport of Cu2+ was then shown to be dramatically enhanced by an order of magnitude in peak concentration by adsorption on clays that were released following cation exchange and IS reduction.     

Effect of grinding and heating on Ni2+ uptake properties of waste paper sludge

Uptake properties of Ni2+ were examined for unmilled and milled paper sludge calcined at various temperatures to develop a new usage of waste paper sludge. Since paper sludge mainly consists of cellulose ([C6H(10)O5]n) fibers, calcite (CaCO3), kaolinite (Al2Si2O5(OH)4) and talc (Mg3Si(4)O(10)(OH)2), amorphous and crystalline CaO(MgO)-Al(2)O(3)-SiO(2) compounds are formed by calcining paper sludge. Wet and dry milling treatments were performed to accelerate solid-state reaction to form the above mentioned target compounds. The crystalline phases originally present decompose at increasing calcining temperature (up to 800 degrees C) in the order cellulose 相似文献   

The effects of throughfall manipulation on soil leaching in a deciduous forest

The effects of changing precipitation on soil leaching in a deciduous forest were examined by experimentally manipulating throughfall fluxes in the field. In addition to an ambient treatment (AMB), throughfall fluxes were reduced by 33% (DRY treatment) and increased by 33% (WET treatment) using a system of rain gutters and sprinklers on Walker Branch Watershed, Tennessee. Soil leaching was measured with resin lysimeters in the O horizons and with ceramic cup lysimeters in the E (25 cm) and Bt (70 cm) horizons. Large and statistically significant treatment effects on N fluxes were found in the O horizons (lower N fluxes in the DRY and higher N fluxes in the WET treatment). Together with the greater O horizon N content observed in the DRY treatment, this suggested that N was being immobilized at a greater rate in the DRY treatment than in the AMB or WET treatments. No statistically significant treatment effects on soil solution were found in the E horizons with the exception of (Ca2+ + Mg2+) to K+ ratio. Statistically significant treatment effects on electrical conductivity (EC), pH, Ca2+, Mg2+, K+, Na+, SO4(2-), and Cl- were found in the Bt horizons due to differences between the DRY and other treatments. Despite this, calculated fluxes of Ca2+, Mg2+, K+, Na+, SO4(2-), and Cl- were lowest in the DRY treatment. These results suggest that lower precipitation will cause temporary N immobilization in litter and long-term enrichment in soil base cations whereas increased precipitation will cause long-term depletion of soil base cations.     

Effects of oxide coating and selected cations on nitrate reduction by iron metal

Under anoxic conditions, zerovalent iron (Fe(0)) reduces nitrate to ammonium and magnetite (Fe3O4) is produced at near-neutral pH. Nitrate removal was most rapid at low pH (2-4); however, the formation of a black oxide film at pH 5 to 8 temporarily halted or slowed the reaction unless the system was augmented with Fe(2+), Cu(2+), or Al(3+). Bathing the corroding Fe(0) in a Fe(2+) solution greatly enhanced nitrate reduction at near-neutral pH and coincided with the formation of a black precipitate. X-ray diffractometry and scanning electron microscopy confirmed that both the black precipitate and black oxide coating on the iron surface were magnetite. In this system, ferrous iron was determined to be a partial contributor to nitrate removal, but nitrate reduction was not observed in the absence of Fe(0). Nitrate removal was also enhanced by augmenting the Fe(0)-H2O system with Fe(3+), Cu(2+), or Al(3+) but not Ca(2+), Mg(2+), or Zn(2+). Our research indicates that a magnetite coating is not a hindrance to nitrate reduction by Fe(0), provided sufficient aqueous Fe(2+) is present in the system.     

Amelioration of physical strength in waste foundry green sands for reuse as a soil amendment

To avoid increasing costs of landfill disposal, it has become increasingly important for U.S. foundries to identify beneficial reuses for the 8 to 12 million tons of waste foundry sand (WFS) generated annually. A major drawback to the reuse of some WFSs as a soil amendment is their high soil strength, under dry conditions, where root growth may be limited. Fifteen WFSs were analyzed for strength to rupture using lab-formed clods, exchangeable cations (Na, Mg, Ca), metal oxide concentration (Fe, Mn, Al, Si), cation exchange capacity (CEC), and % clay. Several WFS samples from gray iron foundries demonstrated high strength to rupture values (> 1.5 MPa), and could potentially restrict root growth in amended soils. The percentage of Na-bentonite exhibited a positive correlation (R(2) = 0.84) with strength to rupture values. When WFSs containing more Na-bentonite were saturated with 1 mol L(-1) Ca ions, strength values decreased by approximately 70%. Waste foundry sands containing less Na-bentonite were saturated with 1 mol L(-1) Na ions and exhibited a threefold increase in strength. Additions of gypsum (up to 9.6 g kg(-1) sand) to high strength waste foundry sands also caused decreases in strength. These results indicate that high strength WFSs have properties similar to hardsetting soils which are caused by high Na(+) clay content and can be ameliorated by the addition of Ca(2+).     

Release dynamic process identification for a cement based material in various leaching conditions. Part I. Influence of leaching conditions on the release amount

In this paper we investigate at laboratory scale the influence of the liquid/solid leaching conditions on the release of different chemical species from a reference porous material obtained by solidification of PbO and CdO with Portland cement. The pH influence on the dissolution of pollutants and the initial pore solution composition (target elements: Na(+), K(+), Ca(2+), Pb(2+), Cd(2+), SO(4)(2-)) were assessed by applying a methodology consisting of two equilibrium leaching tests, the Acid Neutralization Capacity (ANC) and the Pore Water (PW) tests and geochemical modelling. Samples of the same material were submitted in parallel to four different dynamic leaching tests in order to determine the influence of the sample shape (monolithic or granular) and eluate hydrodynamics (instantaneous L/S ratio, eluate renewal) on the leaching of the target elements. The comparison criteria were the eluate saturation state, the cumulative release and the released flux. Generally, the eluates obtained in the tests applied on granular material were more concentrated, even saturated for the eluate pH value with respect to Ca(2+), Pb(2+) and SO(4)(2-). The consequence of the eluate saturation is the slowing down effect on the dynamic release. The highest released flux was observed for the Monolith Leaching Test (MLT) involving the highest instantaneous L/S ratio and the lowest solid/liquid exchange surface and for which no saturation was observed, except Pb(2+) and SO(4)(2-) in some eluates. The maximum cumulative released-mass was obtained for the Column Leaching Test (CLT) applied on granular material having the highest exchange surface, the lowest instantaneous L/S and a continuous input flow of the leachant. The experimental results demonstrate the significance of the liquid/solid contact type which is also a scenario specific parameter.     

Environmental index for estimating the risk of phosphorus loss in calcareous soils of Manitoba

The degree of phosphorus saturation (DPS) has been used in evaluating the risk of P loss from soil to runoff. While techniques are available for calculating DPS for acid soils, no widely used technique exists for neutral to calcareous soils that are typical of the Northern Great Plains, including Manitoba (Canada) soils. This study aimed to develop techniques of calculating the DPS of neutral to alkaline soils. Four measures of soil labile P and ten indices of P sorption capacity were used to calculate the DPS of 115 Manitoba soils. The various DPS calculated were evaluated using water-extractable ((H2O)) P as an index of P susceptibility to runoff loss. The DPS obtained using Olsen-extractable ((Ols)) P and the Langmuir adsorption maximum (ES(max)) ranged from 0.5 to 31.9% while those obtained from P(Ols) and the single-point adsorption index (P(150)) ranged from 0.9 to 73.9%. Of all the DPS evaluated, those that included P(Ols) and Mehlich 3-extractable ((M3)) P as the numerator with either P(150) or ES(max) as the denominator were fairly well correlated with P(H2O) (r values ranged between 0.45 and 0.63). Along with ES(max) and P(150), a new method of calculating DPS was formulated as the ratio of P(Ols) or P(M3) to Ca(M3) or (Ca + Mg)(M3). We found that the ratio of ammonium oxalate-extractable ((ox)) P to (Al + Fe)(ox), which has been widely used to calculate DPS in acid soils, was not suitable for neutral to alkaline soils of Manitoba. In these neutral to alkaline soils, Ca(M3) or (Ca + Mg)(M3) were better indices of P sorption capacity while P(Ols) and P(M3) provided better estimates of labile soil P. The DPS calculated using Ca(M3) or (Ca + Mg)(M3) were well correlated with P(H2O); however, they were numerically smaller than those obtained from the Langmuir adsorption maximum. As such, a saturation coefficient (alpha) with a value of 0.2 was generated to improve the numerical values of the newly estimated DPS. This new approach can be used to estimate the DPS in neutral and calcareous soils without the need to generate a P adsorption maximum.     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

Sorption of aromatic compounds to clay mineral and model humic substance-clay complex: effects of solute structure and exchangeable cation

Clay minerals and humic substance (HS)-clay complexes are widely distributed in soil environments. Improved predictions on the uptake of organic pollutants by soil require a better understanding of fundamental mechanisms that control the relative contribution from organic and inorganic constituents. Five selected aromatic compounds varying in electronic structure, including nonpolar phenanthrene (PHEN), 1,2,4,5-tetrachlorobenzene (TeCB), polar 1,3-dinitrobenzene (DNB), 2,6-dichlorobenzonitrile (dichlobenil [DNL]), and 1-naphthalenyl methylcarbamate (carbaryl [CBL]), were sorbed separately from aqueous solution to Na(+)-, K(+)-, Cs(+)-, and Ca(2+)-saturated montmorillonites with and without the presence of dissolved HS at pH about 6. Upon normalizing for hydrophobic effects by solute aqueous solubility, the overall trend of sorptive affinity to HS-free K(+)-clay is DNB > DNL, CBL > PHEN, TeCB, indicating preferential adsorption of the polar solutes. With the presence of HS, sorption of PHEN, TeCB, and CBL increases by several times compared with the pure clay, attributed to HS-facilitated hydrophobic partition (PHEN and TeCB) or H-bonding (CBL). The enhanced sorption of PHEN by HS is cation dependent, where Cs(+) shows the strongest facilitative effect. Coadsorption of HS does not affect sorption of DNB and DNL to clays except that of DNB to Ca(2+)-clay because cation-dipole interactions between the polar group (NO(2) or CN) of solute and weakly hydrated exchangeable cations dominate the overall sorption.     

A transport model with coupled ternary exchange and chemisorption retention for hydrazinium cations

A numerical model was developed to describe the fate and transport of hydrazinium (N2H5+) and competing Ca2+ and H+ cations applied in acidic solutions to columns of Ca2+/H+-saturated sandy soil during steady saturated flow conditions. Instantaneous ternary H+-Ca2+-N2H5+ cation exchange using the Gaines-Thomas approach was combined with second-order, irreversible, kinetic chemisorption of exchange-phase N2H5+ ions as major retention mechanisms for N2H5+. Exchange-mediated chemisorption is assumed to occur as chemical binding of N2H5+ ions located on carboxyl-group exchange sites to nearby carbonyl groups, consequently decreasing the effective soil cation exchange capacity (CEC). Comparison of simulated and observed breakthrough curves (BTCs) for concentrations of N2H5+ and Ca2+ ions in column effluent was used in model evaluation. The cation transport model with cation exchange coupled with exchange-mediated chemisorption provided a valid first approximation for N2H5+ transport.     

Soil and tree-ring chemistry response to liming in a sugar maple stand

An evaluation of the impact of dolomitic lime [CaMg(CO3)2] on soils (five years after treatment) and sapwood chemistry (after four growing seasons) was realized for a Ca-deficient sugar maple stand at the lake Clair watershed. The effect on humus chemistry was significant: exchangeable Mg and Ca, effective acidity (EA), base saturation (BSe), pH, and effective cation exchange capacity (CECe) significantly increased, while exchangeable Fe significantly decreased. In the B horizon, liming increased exchangeable Ca, Mg, and Mn concentrations while decreasing other acid cations. No significant temporal trends in element concentrations in tree rings could be detected, although the lime treatment significantly changed the average xylem Mg and Mn concentrations as well as the average Mg/Mn and Ca/Mn ratios of the sapwood. The absence of temporal trends in rings from the last 20 yr implied a significant re-equilibration of elements through the sapwood. Significant relationships were found between averaged xylem Ca/Mn and Mg/Mn ratios and exchangeable humus Ca, Mg, Mn, Al, Fe, and H+ concentration, EA, CECe, and BSe, suggesting that the average xylem Ca/Mn and Mg/Mn ratios are strong indicators of the soil acid-base status.     

A study on oxidative degradation of polyacrylamide in wastewater with UV/FENTON/C4H4O62−

The degradation of polyacrylamide (PAM) in simulate wastewater was studied in UV/Fenton/C₄H₄O₆^2? system. The factors such as molecular ratio of H₂O₂/Fe²⁺/C₄H₄O₆^2?, pH, and the dosage of Fenton reagent that could affect the PAM degradation in the UV/Fenton/C₄H₄O₆^2? system were investigated. The experimental results showed that adding C₄H₄O₆^2? to UV/Fenton system could form photosensitive ferrous complexes, which led to higher degradation efficiency of PAM. The degradation rate of PAM could be up to 95.2% under the following conditions: the concentration of H₂O₂, Fe²⁺, and C₄H₄O₆^2? were 22.5, 2.25, and 2.25 mmol/L, respectively (i.e., molecular ratio of H₂O₂/Fe²⁺/C₄H₄O₆^2? was 10:1:1), the pH value was 3.0.     

Phosphorus sorption by sediments in a southeastern coastal plain in-stream wetland

A close relationship has been reported between sediment organic C (SedOC) content and its P sorption capacity (P(max)) and total P (TP) concentration. Phosphorus sorbed to organically complexed cations is a proposed explanation for this relationship. The objectives of this study were (i) to determine relationships between in-stream wetland SedOC content and both the sediment's P(max) and TP concentrations, and (ii) to ascertain the role of both organically complexed and oxalate-extractable cations on the sediment P(max) and TP values. The sediment's oxalate-extractable Fe (Fe(ox)) and Al (Al(ox)) contents were determined using acidified ammonium oxalate, while sodium pyrophosphate was used to extract organically complexed cations (Al(pryo), Ca(pyro), Fe(pyro), Mg(pyro), and Mn(pyro)). Both the sediment's P(max) and TP contents were strongly correlated with its SedOC concentration (r(2) > 0.90, P < 0.001). Only the Al(ox) contents were significantly correlated with TP and P(max), suggesting that amorphous Al forms have an important role in P sorption. All five pyrophosphate-extracted cations were significantly correlated with SedOC contents. Regression analyses showed that the Al(pyro) accounted for 88% of the variation in sediment P(max) values, whereas a combination of Al(pyro) and Ca(pyro) accounted for 98% of the variation in sediment TP concentrations. Additionally, Al and Ca chelated by SedOC compounds also have an important role in P binding and indicate that a linkage exists between the wetlands SedOC and P(max) content and its ability to accumulate TP. This study identified that two different mechanisms have significant roles in regulating P sorption by sediments in a southeastern Coastal Plain in-stream wetland.     

Sorption of hazardous metals from single and multi-element solutions by saltbush biomass in batch and continuous mode: interference of calcium and magnesium in batch mode

Batch studies were performed to determine the interference of calcium (Ca) and magnesium (Mg) on the sorption of Cu(II), Cd(II), Cr(III), Cr(VI), Pb(II), and Zn(II) [from CuSO(4), K(2)Cr(2)O(7), Pb(NO(3))(2), Cr(NO(3))(3), ZnCl(2), and Cd(NO(3))(2)] by saltbush (Atriplex canescens) biomass. The results demonstrated that Ca and Mg at concentrations of at least 20 times higher than the concentration of most of the target metals did not interfere with the metal binding. The data show that the batch binding capacity from a multimetal solution at pH 5.0 was (micromol/g) about 260 for Cr(III) and Pb, and about 117, 54, and 49 for Cu, Zn, and Cd, respectively. The use of 0.1M HCl allowed the recovery of 85-100% of the bound Cu, Cr(III), and Pb, and more than 37% of the bound Cd and Zn. The column binding capacity for Pb was about 49 micromol/g from both the single and multimetal solutions, while it was, respectively about 35 and 23 micromol/g for Cr(III). The binding capacity for Cu and Zn from the single and multimetal column experiments was 35 micromol/g and less than 10 micromol/g, respectively. The stripping data from the single column experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and Zn, 90% and 74% of the bound Pb and Cr(VI), respectively, and less than 25% of the bound Cd and Cr(III), while the stripping from the multimetal experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and about 74%, 54%, 43%, and 40% of the bound Pb, Zn, Cd, and Cr(III), respectively.     

Chemical extraction methods to assess bioavailable arsenic in soil and solid media

Soil ingestion by children is an important pathway in assessing public health risks associated with exposure to arsenic-contaminated soils. Soil chemical methods are available to extract various pools of soil arsenic, but their ability to measure bioavailable arsenic from soil ingestion is unknown. Arsenic extracted by five commonly used soil extractants was compared with bioavailable arsenic measured in vivo by immature swine (Sus scrofa) dosing trials. Fifteen contaminated soils that contained 233 to 17 500 mg kg(-1) arsenic were studied. Soil extractants were selected to dissolve surficially adsorbed and/or readily soluble arsenic (water, 1 M sodium acetate, 0.1 M Na2HPO4/0.1 M NaH2PO4) and arsenic in Fe and Mn oxide minerals (hydroxylamine hydrochloride, ammonium oxalate). The mean percent of total arsenic extracted was: ammonium oxalate (53.6%) > or = hydroxylamine hydrochloride (51.7%) > phosphate (10.5%), acetate (7.16%) > water (0.15%). The strongest relationship between arsenic determined by soil chemical extraction and in vivo bioavailable arsenic was found for hydroxylamine hydrochloride extractant (r = 0.88, significant at the 0.01 probability level). Comparison of the amount of arsenic extracted by soil methods with bioavailable arsenic showed the following trend: ammonium oxalate, hydroxylamine hydrochloride > in vivo > phosphate, acetate > water. The amount of arsenic dissolved in the stomach (potentially bioavailable) is between surficially adsorbed (extracted by phosphate or acetate) and surficially adsorbed + nonsurficial forms in Fe and Mn oxides (extracted by hydroxylamine hydrochloride or ammonium oxalate). Soil extraction methods that dissolve some of the amorphous Fe, such as hydroxylamine hydrochloride, can be designed to provide closer estimates of bioavailable arsenic.     

Determination of phosphorus speciation in dairy manure using XRD and XANES spectroscopy

Intensive manure application is an important source of diffuse phosphorus (P) pollution. Phosphorus availability from animal manure is influenced by its chemical speciation. The major objective of this study was to investigate the P speciation in raw and anaerobically digested dairy manure with an emphasis on the calcium (Ca) and magnesium (Mg) phosphate phases. Influent and effluent from an on-farm digester in Wisconsin were sampled and sieved, and the 25 to 53 microm size fraction was dried for X-ray powder diffraction (XRD) and P K-edge X-ray absorption near edge structure (XANES) analyses. Struvite (MgNH4PO4.6H2O) was identified in both the raw (influent) and anaerobically digested (effluent) manure using XRD. Qualitative analysis of P K-edge XANES spectra indicated that the Ca orthophosphate phases, except dicalcium phosphate anhydrous (DCPA) or monetite (CaHPO4), were not abundant in dairy manure. Linear combination fitting (LCF) of the P standard compounds showed that 57.0 and 43.0% of P was associated with DCPA and struvite, respectively, in the raw manure. In the anaerobically digested sample, 78.2% of P was present as struvite and 21.8% of P was associated with hydroxylapatite (HAp). The P speciation shifted toward Mg orthophosphates and least soluble Ca orthophosphates following anaerobic digestion. Similarity between the aqueous orthophosphate (aq-PO4), newberyite (MgHPO4.3H2O), and struvite spectra can cause inaccurate P speciation determination when dairy manure is analyzed solely using P K-edge XANES spectroscopy; however, XANES can be used in conjunction with XRD to quantify the distribution of inorganic P species in animal manure.     

Cation-pi bonding: a new perspective on the sorption of polycyclic aromatic hydrocarbons to mineral surfaces

Recent molecular modeling and spectroscopic studies have suggested that relatively strong interactions can occur between aromatic pi donors and metal cations in aqueous solutions. The objective of this study was to characterize potential cation-pi interactions between pi donors and exchangeable cations accumulated at mineral surfaces via both spectroscopic and batch sorption methods. Quadrupolar splitting in deuterium nuclear magnetic resonance ((2)H NMR) spectroscopy for d(2)-dichloromethane, d(6)-benzene, and d(8)-toluene (C(6)D(5)- moiety) in aqueous suspensions of a Na-saturated reference montmorillonite unambiguously indicated the ordering of solute molecules with respect to the clay surface. The half line broadening (Delta nu(1/2)) of (2)H NMR of d(6)-benzene in montmorillonite suspensions showed that soft exchangeable cations generally resulted in more benzene sorption compared with harder cations (e.g., Ag(+) > Cs(+) > Na(+) > Mg(2+), Ba(2+)). In batch sorption experiments, saturating minerals (e.g., porous silica gels, kaolinite, vermiculite, montmorillonite) with a soft transition metal or softer base cations generally increased the polycyclic aromatic hydrocarbon (PAH) sorption relative to harder cations (e.g., Ag(+) > Cs(+) > K(+) > Na(+); Ba(2+) > Mg(2+)). Sorption of phenanthrene to Ag(+)-saturated montmorillonite was much stronger compared with 1,2,4,5-tetrachlorobenzene, a coplanar non-pi donor having slightly higher hydrophobicity. In addition, a strong positive correlation was found between the cation-dependent sorption and surface charge density of the minerals (e.g., vermiculite, montmorillonite > silica gels, kaolinite). These results, coupled with the observations in (2)H NMR experiments with montmorillonite, strongly suggest that cation-pi bonding forms between PAHs and exchangeable cations at mineral surfaces and affects PAH sorption to hydrated mineral surfaces.