Sorptive and desorptive fractionation of dissolved organic matter by mineral soil matrices

Interactions of dissolved organic matter (DOM) with soil minerals, such as metal oxides and clays, involve various sorption mechanisms and may lead to sorptive fractionation of certain organic moieties. While sorption of DOM to soil minerals typically involves a degree of irreversibility, it is unclear which structural components of DOM correspond to the irreversibly bound fraction and which factors may be considered determinants. To assist in elucidating that, the current study aimed at investigating fractionation of DOM during sorption and desorption processes in soil. Batch DOM sorption and desorption experiments were conducted with organic matter poor, alkaline soils. Fourier-transform infrared (FTIR) and UV-Vis spectroscopy were used to analyze bulk DOM, sorbed DOM, and desorbed DOM fractions. Sorptive fractionation resulted mainly from the preferential uptake of aromatic, carboxylic, and phenolic moieties of DOM. Soil metal-oxide content positively affected DOM sorption and binding of some specific carboxylate and phenolate functional groups. Desorptive fractionation of DOM was expressed by the irreversible-binding nature of some carboxylic moieties, whereas other bound carboxylic moieties were readily desorbed. Inner-sphere, as opposed to outer-sphere, ligand-exchange complexation mechanisms may be responsible for these irreversible, as opposed to reversible, interactions, respectively. The interaction of aliphatic DOM constituents with soil, presumably through weak van der Waals forces, was minor and increased with increasing proportion of clay minerals in the soil. Revealing the nature of DOM-fractionation processes is of great importance to understanding carbon stabilization mechanisms in soils, as well as the overall fate of contaminants that might be associated with DOM.     

Desorption kinetics of arsenate from kaolinite as influenced by pH

Arsenic is highly toxic and therefore represents a potential threat to the environment and human health. The mobility and bioavailability of arsenic in soil is mostly controlled by adsorption and desorption reactions. Even though adsorption and traditional batch desorption experiments provide information about the environmental fate of As, the equilibrium conditions imposed in these studies would usually not be reached in the natural environment. Flow-through desorption techniques, where the desorbed species are removed from the substrate, can therefore be used to provide information about the rate and mechanisms of As desorption. The effect of pH on As adsorption reactions is relatively well understood; however, desorption of As and the effect of pH on As desorption remain unexplored. Desorption of As(V) (the most dominant arsenic species in aerated soils) was therefore investigated using batch and flow-through desorption experiments. Traditional batch desorption experiments underestimated the desorption rate of As(V) from kaolinite. The pH had a large effect on the amount of As(V) desorbed from kaolinite, with both an increase and a decrease in pH (from the initial pH 6.4) enhancing As(V) desorption. Modeling desorption over time revealed that the pH can influence As(V) desorption over extended periods of time.     

Solubility of antimony and other elements in samples taken from shooting ranges

The aim of this study was to determine whether or not Sb and other elements (Ni, Cu, Bi, Tl, and Hg) originating from Pb alloy (2-5 wt. % Sb) bullets become more soluble as a result of weathering and what mechanisms possibly control their solubility. Samples were taken from bank material behind the targets at seven Swiss shooting ranges. The samples were dried, sieved, analyzed, and subjected to leaching experiments. Total average concentrations of Sb ranged from 0.5 to 13.8 g kg(-1). In the leaching experiments, Sb was almost exclusively present in solution as the oxidized species Sb(V) in concentrations of up to 5 mg L(-1). The Ca mineral Ca[Sb(OH)6]2 is suggested to control dissolved Sb(V) concentrations in soils at high concentrations. Oxalate extractions suggested that approximately 50% of Sb [predominantly Sb(V)] in the <0.5-mm fraction was adsorbed to Fe (hydr)oxides and possibly other minerals, such as calcite, that are soluble at pH 2. However, it is possible that only a fraction of the oxalate-extractable Sb(V) is reversibly bound to mineral surfaces. It was concluded that the release of Sb is significant and considerably higher than the other elements under investigation and that the mechanisms controlling Sb mobility should be further investigated.     

Sorption of iron-cyanide complexes on goethite in the presence of sulfate and desorption with phosphate and chloride

Soils are contaminated with potentially toxic iron-cyanide complexes by some industrial activities. The influence of sulfate on the sorption of the iron-cyanide complexes ferricyanide, [Fe(CN)6]3-, and ferrocyanide, [Fe(CN)6]4-, on goethite was investigated in batch experiments. The experiments were conducted as influenced by pH and varying sulfate/iron-cyanide complex concentration ratios. Furthermore, the desorption of iron-cyanide complexes sorbed on goethite was studied using phosphate and chloride solutions as influenced by pH and anion concentration. Over the whole pH range (pH 3.5 to 8), ferricyanide and sulfate showed similar affinities for the goethite surface. The extent of ferricyanide sorption strongly depended on sulfate concentrations and vice versa. In contrast, ferrocyanide sorption was only decreased (approximately 12%) by sulfate additions at pH 3.5. Ferricyanide was completely desorbed by 1 M chloride, ferrocyanide not at all. Unbuffered phosphate solutions (pH 8.3) desorbed both iron-cyanide complexes completely. Even in 70-fold excess, pH-adjusted phosphate solutions could not desorb ferrocyanide completely at pH 3.5. For ferricyanide we propose a sorption mechanism that is similar to the sulfate sorption mechanism, including outer-sphere and weak inner-sphere surface complexes on goethite. Ferrocyanide appears to form inner-sphere surface complexes. Additionally, we assume that ferrocyanide precipitates probably as a Berlin Blue-like phase at pH 3.5. Hence, ferrocyanide should be less mobile in the soil environment than ferricyanide or sulfate.     

Adsorption of isoxaflutole degradates to aluminum and iron hydrous oxides

Isoxaflutole is a preemergence herbicide that has been marketed as a substitute for atrazine. It is rapidly transformed to a more stable and soluble diketonitrile degradate (DKN) after field application and can further degrade to a benzoic acid degradate (BA) within soil. However, no previous research has been conducted to investigate DKN and BA sorption to metal oxide minerals. The primary objective of this research was to elucidate the interactions of DKN and BA with synthetic hydrous aluminum and iron oxides (HAO and HFO, respectively) to understand how variably charged minerals may influence adsorption of these compounds in soil. The herbicide degradates did adsorb to HAO and HFO, and the data were well described by the Freundlich model (R2 > 0.91), with Nvalues ranging from 0.89 to 1.2. Adsorption isotherms and Kd values demonstrate that BA is adsorbed to HFO to a greater extent than other degradate-mineral combinations that were studied. The degree of hysteresis between adsorption/desorption isotherms was characterized as slight (hysteresis index values < 1.7), suggesting weak DKN and BA retention to HFO and HAO oxide surfaces. Degradate adsorption was observed to greatly diminish as suspension pH increased. Attenuated total reflectance-Fourier transform infrared spectra show no evidence that DKN or BA adsorb to mineral surfaces as inner-sphere complexes under hydrated conditions. Instead DKN and BA adsorb to positively charged metal oxide surfaces as outer-sphere or diffuse ion swarm complexes via electrostatic attraction. This research indicates that metal oxides may serve as important retardants for DKN and BA migration through acidic soils enriched with aluminum and iron oxides.     

Uptake and release of phosphorus from overland flow in a stream environment

Phosphorus runoff from agricultural fields has been linked to fresh-water eutrophication. However, edge-of-field P losses can be modified by benthic sediments during stream flow by physiochemical processes associated with Al, Fe, and Ca, and by biological assimilation. We investigated fluvial P when exposed to stream-bed sediments (top 3 cm) collected from seven sites representing forested and agricultural areas (pasture and cultivated), in a mixed-land-use watershed. Sediment was placed in a 10-m-long, 0.2-m-wide fluvarium to a 3-cm depth and water was recirculated over the sediment at 2 L s(-1) and 5% slope. When overland flow (4 mg dissolved reactive phosphorus [DRP] and 9 mg total phosphorus [TP] L(-1)) from manured soils was first recirculated, P uptake was associated with Al and Fe hydrous oxides for sediments from forested areas (pH 5.2-5.4) and by Ca for sediments from agricultural areas (pH 6.5-7.2). A large increase (up to 200%) in readily available P NH4Cl fraction was noted. After 24 h, DRP concentration in channel flow was related to sediment solution P concentration at which no net sorption or desorption of P occurs (EPC0) (r2 = 0.77), indicating quasi-equilibrium. When fresh water (approximately 0.005 mg P L(-1) mean base flow DRP at seven sites) was recirculated over the sediments for 24 h, P release kinetics followed an exponential function. Microbial biomass P accounted for 34 to 43% of sediment P uptake from manure-rich overland flow. Although abiotic sediment processes played a dominant role in determining P uptake, biotic process are clearly important and both should be considered along with the location and management of landscape inputs for remedial strategies to be effective.     

Geochemical partitioning of copper, lead, and zinc in benthic, estuarine sediment profiles

The geochemical partitioning of copper (Cu), lead (Pb), and zinc (Zn) was examined in benthic sediment profiles (0- to 20-cm depth interval) composed of relatively coarse (65-90% sand-sized particles), noncohesive, suboxic material (Eh +120 to +260 mV). Total Cu, Pb, and Zn concentrations ranged from 8.3 to 194, 16.3 to 74.8, and 30.1 to 220 mg/kg, respectively, and were related to vertical trends in sediment texture. The observed distribution coefficients describing solid-solution partitioning were in the range of 100 to 1000 L/kg. The geochemical partitioning of solid-phase Cu, Pb, and Zn between six operationally defined fractions was examined with a sequential extraction scheme. The association of Cu, Pb, and Zn with amorphous oxides, crystalline oxides, and organic matter was linearly dependent on the abundance of each respective phase. For retention by amorphous oxide minerals, the observed stoichiometry ranged from 5.2 to 23.7 mg/g for Cu, 12.8 to 21.5 mg/g for Pb, and 23.1 to 85.7 mg/g for Zn. Corresponding values for association with crystalline oxides were an order of magnitude less than those for amorphous oxides, indicating a lesser affinity of trace metals for crystalline oxides. The stoichiometric relationships describing association with organic matter ranged from 17.6 to 54.0 mg/g for Cu, 6.1 to 9.6 mg/g for Pb, and 6.4 to 16.4 mg/g for Zn. The results from this study provide an insight into processes controlling trace metal partitioning in coarse-textured, suboxic, estuarine sediments.     

Speciation of phosphorus in phosphorus-enriched agricultural soils using X-ray absorption near-edge structure spectroscopy and chemical fractionation

Knowledge of phosphorus (P) species in P-rich soils is useful for assessing P mobility and potential transfer to ground water and surface waters. Soil P was studied using synchrotron X-ray absorption near-edge structure (XANES) spectroscopy (a nondestructive chemical-speciation technique) and sequential chemical fractionation. The objective was to determine the chemical speciation of P in long-term-fertilized, P-rich soils differing in pH, clay, and organic matter contents. Samples of three slightly acidic (pH 5.5-6.2) and two slightly alkaline (pH 7.4-7.6) soils were collected from A or B horizons in two distinct agrosystems in the province of Québec, Canada. The soils contained between 800 and 2100 mg total P kg(-1). Distinct XANES features for Ca-phosphate mineral standards and for standards of adsorbed phosphate made it possible to differentiate these forms of P in the soil samples. The XANES results indicated that phosphate adsorbed on Fe- or Al-oxide minerals was present in all soils, with a higher proportion in acidic than in slightly alkaline samples. Calcium phosphate also occurred in all soils, regardless of pH. In agreement with chemical fractionation results, XANES data showed that Ca-phosphates were the dominant P forms in one acidic (pH 5.5) and in the two slightly alkaline (pH 7.4-7.6) soil samples. X-ray absorption near-edge structure spectroscopy directly identified certain forms of soil P, while chemical fractionation provided indirect supporting data and gave insights on additional forms of P such as organic pools that were not accounted for by the XANES analyses.     

Interactions of chlorpyrifos with colloidal materials in aqueous systems

An understanding of sorptive processes is key to describing the fate of chlorpyrifos [O,O-diethyl-O-(3, 5, 6-trichloro-2-pyridyl) phosphorothioate] in aquatic environments. The objectives of this study were to evaluate isotherms for adsorption and desorption of chlorpyrifos on colloidal materials and to advance understanding of interaction mechanisms between chlorpyrifos and colloidal materials. Six Ca-saturated reference smectites, one Ca-saturated humic acid (Ca-humate), and one suspended sediment sample, collected from the Upper Cedar River, Iowa, were studied. A batch equilibration technique was employed to quantify adsorption and desorption isotherms for chlorpyrifos over the 0 to 100 microg L(-1) concentration range in a 0.01 M CaCl(2) background. Large differences in sorption affinity and variation in desorption hysteresis were found among the smectites. Neither chlorpyrifos adsorption nor its desorption were correlated with cation exchange capacity, surface area, or surface charge density of the smectites. The evidence suggests that physical interaction between chlorpyrifos and smectites is the dominant mechanism for adsorption of chlorpyrifos in aqueous systems. Chlorpyrifos was very strongly sorbed on Ca-humate and was not desorbed from the Ca-humate back into the aqueous solution. Chlorpyrifos was moderately sorbed on river sediment, and a large adsorption-desorption hysteresis was also found. The study implies that the nature of both organic and inorganic materials in suspended sediment can influence the adsorption-desorption behavior of chlorpyrifos in aqueous systems.     

Can assessing for potential contribution of soil organic and inorganic components for butachlor sorption be improved?

Sorption of butachlor to various types of common soil components was investigated. Six pure minerals (montmorillonite [Mont], kaolinite [Kaol], Ca homoionic montmorillonite [Ca-Mont] and kaolinite [Ca-Kaol], amorphous hydrated Al and Fe oxides [AHOs-Al, AHOs-Fe]), four soil alkali-extractable pure humic acids (HAs), and the four corresponding HAs originated real unmodified and HO-treated soils were selected as the representative sorbents. Results showed that the HAs played a crucial role, and clay minerals (especially Mont) also showed an important effect in butachlor sorption. The AHOs may likely influence only in a mediator way by enhancing the availability of sorption domains of HAs. By removing 78% (on average) of the total organic carbon (TOC) from the soils with HO, the content ratio of clay to TOC (RCO) increased by an average of 367% and became >60. This change simultaneously decreased the sorption capacity of soils (40%, on average). Considering that the surface sorption domain on clay minerals may be highly exposed and more competitive after the partial removal of soil organic matter (SOM), this reaffirmed the potential contribution from clay minerals. It can thus be inferred that in the real soil where SOM and clay minerals are associated, the coating of clay minerals may have weakened the partition function of SOM or blocked some sorption domain within SOM, resulting in a decreased sorption of butachlor. Therefore, clay minerals, especially 2:1 type expanding minerals, may play a dual function vs. SOM content for the sorption of butachlor in soil.     

Imazaquin adsorbed on pillared clay and crystal violet-montmorillonite complexes for reduced leaching in soil

Ground water pollution due to herbicide leaching has become a serious environmental problem. Imazaquin [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid] is an herbicide used to control broadleaf weeds in legume crops. Imazaquin is negatively charged at the basic pH of calcareous soils and exhibits high leaching potential in soils. Our aim was to design formulation of imazaquin to reduce herbicide leaching. Imazaquin sorption on pillared clay (PC) and crystal violet (CV)-montmorillonite complexes was studied. The CV-montmorillonite complexes become positively charged with adsorption of CV above the cation exchange capacity (CEC) of montmorillonite, and thus can sorb imazaquin. The Langmuir equation provides a good fit to isotherms of imazaquin sorption on PC and CV-montmorillonite complexes, but for charged complexes an equation that combines electrostatics with specific binding was preferred. Maximal imazaquin sorption was 17.3 mmol kg-1 for PC and 22.2 mmol kg-1 for CV-montmorillonite complexes. The extents of imazaquin desorption into water were 21% for PC and 5% for CV-clay complexes. The presence of anions decreased imazaquin sorption on both sorbents in the sequence phosphate > acetate > sulfate. Reduction of imazaquin sorption by the anions and the extent of its desorption in electrolyte solutions were higher for PC than for CV-clay complexes. Leaching of imazaquin from CV-montmorillonite formulations through soil (Rhodoxeralf) columns was two times less than from PC formulations and four times less than that of technical imazaquin. The CV-montmorillonite complexes at a loading above the CEC appear to be suitable for preparation of organo-clay-imazaquin formulations that may reduce herbicide leaching significantly.     

Magnesium-rich minerals in sediment and suspended particulates of South Florida water bodies: implications for turbidity

Fine sediments in shallow water bodies such as Lake Okeechobee are prone to resuspension. Predominantly inorganic "mud" sediment that covers approximately 670 km2 of the lake has been recognized as a persistent source of turbidity. The objective of this study was to determine if mineral components of sediments in Lake Okeechobee and water conveyances of the northern Everglades also occur as suspended sediment and hence constitute a potential abiotic contributor to turbidity. Sediment samples were collected from nine stations within the lake and eight locations north of Water Conservation Area 2A in the Everglades. Water samples were also collected at selected locations. The silt and clay mineralogy of sediment and suspended particles was determined using X-ray diffraction, thermogravimetry, scanning-electron microscopy, energy-dispersive X-ray elemental microanalysis, and high-resolution transmission-electron microscopy. Clay fractions of the lake sediment contained the Mg silicate minerals sepiolite and palygorskite, along with smectite, dolomite, calcite, and kaolinite. Sediment silt fractions were dominated by carbonates and/or quartz, with smaller amounts of Ca phosphates and sepiolite. Mineralogy of the mud sediment was similar to that reported for geologic phosphate deposits. This suggests that the mud sediment might have accumulated by stream transport of minerals from these deposits. Suspended solids and mud-sediment mineralogy were similar, except that smectite was more abundant in suspended solids. Everglade samples also contained Mg-rich minerals. The small size, low density, and fibrous or platy nature of the prevalent mud sediment minerals make them an abiotic, hydrodynamically sensitive source of persistent turbidity in a shallow lake. Mitigation efforts focused exclusively on P-induced biogeochemical processes do not address the origin or effects of these minerals. Ecological management issues such as turbidity control, P retention, geologic P input, and suitability of dredging are related to mud-sediment properties and provenance.     

Structural and sorption characteristics of adsorbed humic acid on clay minerals

Clay-humic complexes are commonly distributed in natural environments. They play very important roles in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study examined the structural changes of humic acid (HA) after adsorption by clay minerals and determined phenanthrene sorption by clay-humic complexes. Solid- and liquid-state 13C nuclear magnetic resonance (NMR), for the first time, provided direct evidence for HA fractionation during adsorption on mineral surfaces, that is, aliphatic fractions were preferentially adsorbed by clay minerals while aromatic fractions were left in the solution. The ratio of UV absorbance of HA at 465 and 665 nm (E4 to E6 ratio), which is related to aromaticity, corroborated with the NMR results. For both montmorillonite and kaolinite, adsorbed HA fractions had higher sorption linearity (N) and affinity (K(oc)) than the source HA. The K(oc) of adsorbed HA for the clay-humic complexes could be up to several times higher than that of the source HA. This large increase may be contributed by the low polarity of the bound HA. Moreover, for each mineral, the N values of adsorbed HA increased with increasing HA loading. It is believed that HA may develop a more condensed structure on mineral surface at lower HA loading level due to the stronger interactions between HA and mineral surface as a result of close contacts.     

Total Contents and Sequential Extraction of Heavy Metals in Soils Irrigated with Wastewater,Akaki, Ethiopia

The Akaki River, laden with untreated wastes from domestic, industrial, and commercial sources, serves as a source of water for irrigating vegetable farms. The purpose of this study is to identify the impact of waste-water irrigation on the level of heavy metals and to predict their potential mobility and bioavailability. Zn and V had the highest, whereas Hg the lowest, concentrations observed in the soils. The average contents of As, Co, Cr, Cu, Ni, Zn, V, and Hg of both soils; and Pb and Se from Fluvisol surpassed the mean + 2 SD of the corresponding levels reported for their uncontaminated counterparts. Apparently, irrigation with waste water for the last few decades has contributed to the observed higher concentrations of the above elements in the study soils (Vertisol and Fluvisol) when compared to uncontaminated Vertisol and Fluvisol. On the other hand, Vertisol accommodated comparatively higher average levels of Cr, Cu, Ni, Zn, etc V, and Cd, whereas high contents of Pb and Se were observed in Fluvisol. Alternatively, comparable levels of Co and Hg were found in either soil. Except for Ni, Cr, and Cd in contaminated Vertisol, heavy metals in the soils were not significantly affected by the depth (0–20 and 30–50 cm). When the same element from the two soils was compared, the levels of Cr, Cu, Ni, Pb, Se, Zn, V, Cd at 0–20 cm; and Cr, Ni, Cu, Cd, and Zn at 30–50 cm were significantly different. Organic carbon (in both soils), CEC (Fluvisol), and clay (Vertisol) exhibited significant positive correspondences with the total heavy metal levels. Conversely, Se and Hg contents revealed perceptible associations with carbonate and pH. The exchangeable fraction was dominated by Hg and Cd, whereas the carbonate fraction was abounded with Cd, Pb, and Co. conversely, V and Pb displayed strong affinity to reducible fraction, where as Cr, Cu, Zn, and Ni dominated the oxidizable fraction. Cr, Hg, Se, and Zn (in both soils) showed preference to the residual fraction. Generally, a considerable proportion of the total levels of many of the heavy metals resided in non residual fractions. The enhanced lability is generally expected to follow the order: Cd > Co > Pb > Cu > Ni > Se > V and Pb > Cd > Co > Cu > Ni > Zn in Vertisol and Fluvisol, respectively. For the similar wastewater application, the soil variables influence the status and the distribution of the associated heavy metals among the different soil fractions in the study soils. Among heavy metals that presented relatively elevated levels and with potential mobility, Co, Cu, Ni (either soil), V (Vertisol), Pb, and Zn (Fluvisol) could pose health threat through their introduction into the food chain in the wastewater irrigated soils.     

Adsorption and transport of arsenic(V) in experimental subsurface systems

The adsorption and transport of As(V) in a heterogeneous, iron oxide-containing soil was investigated in batch and column laboratory experiments. The As(V) adsorbed rapidly to the soil over the first 48 h, but continued to adsorb slowly over the next several weeks, clearly indicating the potential for rate-limited transport. The equilibrium As(V) adsorption isotherm was markedly nonlinear, further indicating the potential for nonideal transport. A model developed for the adsorption of As(V) to hydrous ferric oxide (HFO) was able to predict the pH-dependent adsorption of As(V) to the soil in batch experiments within 0.116 to 0.726 root mean square error (RMSE). Arsenic(V) was significantly retarded in column transport experiments. The column transport experiments were modeled using the one-dimensional advection-dispersion equation, considering both linear and nonlinear adsorption equilibrium. Although the nonlinear local equilibrium model (NLLE, RMSE = 0.273) predicted the data better than the linear local equilibrium model (LLE, RMSE = 0.317), As(V) breakthrough occurred more rapidly than predicted by either model due to adsorption nonequilibrium. However, due to the presence of an irreversible or slowly desorbing fraction, the peak aqueous As(V) concentration (0.624 mg L(-1)) and the total amount of As(V) recovered (44%) was lower than predicted based on the two equilibrium models (NLLE and LLE). For the conditions used in this study [1 mg L(-1) As(V), pH 4.5 and 9,0-0.25 mM PO4, 0.53-1.6 cm min(-1) pore water velocity], the effect on As(V) mobility and recovery increased in the order pH < pore water velocity < PO4.     

Potential negative consequences of adding phosphorus-based fertilizers to immobilize lead in soil

A study of the potential negative consequences of adding phosphate (P)-based fertilizers as amendments to immobilize lead (Pb) in contaminated soils was conducted. Lead-contaminated firing range soils also contained elevated concentrations of antimony (Sb), a common Pb hardening agent, and some arsenic (As) of unknown (possibly background) origin. After amending the soils with triple superphosphate, a relatively soluble P source, column leaching experiments revealed elevated concentrations of Sb, As, and Pb in the leachate, reflecting an initial spike in soluble Pb and a particularly dramatic increase in Sb and As mobility. Minimal As, Sb, and Pb leaching was observed during column tests performed on non-amended control soils. In vitro extractions tests were performed to assess changes in Pb, As, and Sb bioaccessibility on P amendment. Lead bioaccessibility was systematically lowered with increasing P dosage, but there was much less of an effect on As and Sb bioaccessibility than on mobility. Our results indicate that although P amendments may aid in lowering the bioaccessibility of soil-bound Pb, it may also produce an initial increase in Pb mobility and a significant release of Sb and As from the soil, dramatically increasing their mobility and to a lesser extent their bioavailability.     

Vivianite precipitation and phosphate sorption following iron reduction in anoxic soils

Phosphorus retention in lowland soils depends on redox conditions. The aim of this study was to evaluate how the Fe(III) reduction degree affects phosphate adsorption and precipitation. Two similarly P-saturated, ferric Fe-rich lowland soils, a sandy and a peat soil, were incubated under anaerobic conditions. M?ssbauer spectroscopy demonstrated that Fe(III) in the sandy soil was present as goethite and phyllosilicates, whereas Fe(III) in the peat soil was mainly present as polynuclear, Fe-humic complexes. Following anoxic incubation, extensive formation of Fe(II) in the solids occurred. After 100 d, the Fe(II) production reached its maximum and 34% of the citrate-bicarbonate-dithionite extractable Fe (Fe(CBD)) was reduced to Fe(II) in the sandy soil. The peat soil showed a much faster reduction of Fe(III) and the maximum reduction of 89% of Fe(CBD) was reached after 200 d. Neoformation of a metavivianite/vivianite phase under anoxic conditions was identified by X-ray diffraction in the peat. The sandy soil exhibited small changes in the point of zero net sorption (EPC?) and P(i) desorption with increasing Fe(III) reduction, whereas in the peat soil P desorption increased from 80 to 3100 μmol kg?1 and EPC? increased from 1.7 to 83 μM, after 322 d of anoxic incubation. The fast Fe(III) reduction made the peat soils particularly vulnerable to changes in redox conditions. However, the precipitation of vivianite/metavivianite minerals may control soluble P(i) concentrations to between 2 and 3 μM in the long term if the soil is not disturbed.     

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.     

The supply behaviour of state mining enterprises: A case study of the Jordanian phosphate industry

An important feature of export-oriented production in mineral-rich developing countries for almost three decades after 1960 was the growth of state-owned enterprises. For the phosphate industry, this was reflected in the expansion of companies such as Office Cherifienne des Phosphate (OCP) in Morocco and the Jordan Phosphate Mines Company (JPMC). There was a strategic importance of the industry for these nations and the large capital outlays necessary for phosphate and fertilizer production expansion often required considerable government assistance because of the perceived high risks of private investment in the industry.     

Accumulation, release, and solubility of arsenic, molybdenum, and vanadium in wetland sediments

This study was undertaken to determine the fate of As, Mo, and V (trace elements, TEs) in the sediments of a constructed wetland in use for the remediation of potentially toxic trace element-contaminated agricultural drainwater. After three years of wetland operation, sediment cores were collected to determine changes in TE concentrations as a function of depth and the effects of varying water column depth. All TE concentrations were highest in the top 2 to 4 cm and decreased with depth. Molybdenum accumulated in the wetland sediments, up to levels of 32.5 +/- 4.6, 30.2 +/- 8.9, and 59.3 +/- 26.1 mg kg(-1) in the top 1 cm of sediment at water depths of 15, 30, and 60 cm, respectively. In the top 2 cm of sediment, As accumulated (28.2 +/- 3.0 mg kg(-1)) only at the 60-cm water depth. Below 2 cm, as much as 10 mg kg(-1) of As was lost from the sediment at all water depths. In most cases, V concentrations decreased in the sediment. In this wetland system, the lowest redox potentials were found near the sediment surface and increased with depth. Thus, in general As, Mo, and V concentrations in the sediment were highest under more reducing conditions and lowest under more oxidizing conditions. Most of the accumulated Mo (73%) became water soluble on drying of samples. This has important implications for systems undergoing changes in redox status; for instance, if these wetland sediments are dried, potentially large amounts of Mo may be solubilized.